PLASTIC FILMS IN FOOD

PACKAGING
PLASTICS DESIGN LIBRARY (PDL)
PDL HANDBOOK SERIES
Series Editor: Sina Ebnesajjad, PhD
President, FluoroConsultants Group, LLC
Chadds Ford, PA, USA
www.FluoroConsultants.com
The PDL Handbook Series is aimed at a wide range of engineers and other professionals working in the plastics industry, and related
sectors using plastics and adhesives.
PDL is a series of data books, reference works and practical guides covering plastics engineering, applications, processing, and
manufacturing, and applied aspects of polymer science, elastomers and adhesives.
Recent titles in the series
Brandau, Bottles, Preforms and Closures, Second Edition
ISBN: 9781437735260
Brandau, Stretch Blow Molding, Second Edition
ISBN: 9781437735277
Ebnesajjad, Handbook of Adhesives and Surface Preparation
ISBN: 9781437744613
Grot, Fluorinated Ionomers, Second Edition
ISBN: 9781437744576
Kutz, Applied Plastics Engineering Handbook
ISBN: 9781437735147
Kutz, PEEK Biomaterials Handbook
ISBN: 9781437744637
McKeen, Permeability Properties of plastics and Elastomers, Third edition
ISBN: 9781437734690
Sastri, Plastics in Medical Devices
ISBN: 9780815520276
Wagner, Multilayer Flexible Packaging
ISBN: 9780815520214
Woishnis & Ebnesajjad, Chemical Resistance of Thermoplastics (2 volume set)
ISBN: 9781455778966
McKeen, The Effect of Sterilization on Plastics and Elastomers
ISBN: 9781455725984
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or
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Copyright r 2012 Elsevier Inc. All rights reserved.
 PLASTIC FILMS IN FOOD
PACKAGING
Materials, Technology, and Applications

Edited by

Sina Ebnesajjad
President, Fluoroconsultants Group, LLC

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 Contents

Preface ................................................................................................................................................................. xiii

1 Introduction to Use of Plastics in Food Packaging .................................................................... 1

1.1 Background ................................................................................................................................................. 1
1.2 Polyolefins................................................................................................................................................... 1
1.2.1 Polyethylene...................................................................................................................................... 2
1.2.2 Polypropylene ................................................................................................................................... 4
1.2.3 Specialty Polyolefins ........................................................................................................................ 4
1.3 Polyester ...................................................................................................................................................... 5
1.3.1 Specialty Polyesters .......................................................................................................................... 5
1.4 Polystyrene .................................................................................................................................................. 7
1.5 Polyvinyl Chloride ...................................................................................................................................... 7
1.6 Polyvinylidene Chloride ............................................................................................................................. 8
1.7 Polyamide.................................................................................................................................................... 8
1.7.1 Nylon 6 ............................................................................................................................................. 8
1.7.2 Nylon 12 ........................................................................................................................................... 9
1.7.3 Nylon 66 ......................................................................................................................................... 10
1.7.4 Nylon 66/610 .................................................................................................................................. 10
1.7.5 Nylon 6/12 ...................................................................................................................................... 10
1.7.6 Polyamide 6/69 (Nylon 6/69) ......................................................................................................... 11
1.7.7 Amorphous Polyamides.................................................................................................................. 11
1.8 Ethylene
Vinyl Alcohol Copolymer ....................................................................................................... 11
1.9 Renewable Resource and Biodegradable Polymers ................................................................................. 12
1.9.1 Ethyl Cellulose................................................................................................................................ 14
1.9.2 Polycaprolactone............................................................................................................................. 14
1.9.3 Polylactic Acid................................................................................................................................ 14
1.9.4 Poly-3-hydroxybutyrate .................................................................................................................. 15
1.10 Summary ................................................................................................................................................. 15
References ........................................................................................................................................................ 15

2 Polypropylene Films.................................................................................................................... 17
2.1 Unoriented Film ........................................................................................................................................ 17
2.2 Cast Film ................................................................................................................................................... 17
2.3 Biaxially Oriented Film ............................................................................................................................ 18
References ........................................................................................................................................................ 20

3 PE-Based Multilayer Film Structures ......................................................................................... 21

3.1 Introduction ............................................................................................................................................... 21
3.2 Polymer Selection ..................................................................................................................................... 24
3.3 Mechanical Properties............................................................................................................................... 26
3.4 Barrier Properties ...................................................................................................................................... 27
3.5 Polymer Sealability ................................................................................................................................... 31
3.6 Adhesive Polymers ................................................................................................................................... 33
3.7 Applications for Flexible Packaging Film Structures .............................................................................. 35

v
vi CONTENTS

3.7.1 Medical Packaging.......................................................................................................................... 36

3.7.2 Food Packaging............................................................................................................................... 38
3.8 Summary ................................................................................................................................................... 49
References ........................................................................................................................................................ 50

4 Biaxially Oriented Films for Packaging Applications ............................................................... 53

4.1 Introduction ............................................................................................................................................... 53
4.2 Orienting Technologies............................................................................................................................. 53
4.3 Oriented Film Types—Applications......................................................................................................... 56
4.3.1 BOPP Films .................................................................................................................................... 56
4.3.2 BOPET Films.................................................................................................................................. 62
4.3.3 BOPA Films.................................................................................................................................... 64
4.3.4 Biaxially Oriented Polystyrene Films ............................................................................................ 66
4.3.5 Other Biaxially Oriented Films ...................................................................................................... 66
4.3.6 Film Oriented in Transverse Direction .......................................................................................... 68
4.4 Trends for Oriented Films ........................................................................................................................ 69
References ........................................................................................................................................................ 69

5 Development of High-Barrier Film for Food Packaging ........................................................... 71

5.1 Introduction ............................................................................................................................................... 71
5.2 Background ............................................................................................................................................... 72
5.3 Improvement of Barrier Properties of Films............................................................................................ 74
5.4 Review of Permeation............................................................................................................................... 77
5.5 Multilayer Flexible Packaging Structures ................................................................................................ 78
5.6 Measurement of Barrier Properties of Films............................................................................................ 86
5.6.1 Oxygen Test Methods..................................................................................................................... 86
5.6.2 Water Vapor Test Methods ............................................................................................................ 89
5.6.3 Carbon Dioxide Test Methods ....................................................................................................... 90
References ........................................................................................................................................................ 91

6 Applications of Polypropylene Films......................................................................................... 93

6.1 Automotive Applications .......................................................................................................................... 93
6.1.1 Exterior Automotive Applications ................................................................................................. 93
6.1.2 Interior Automotive Applications................................................................................................... 96
6.1.3 Under-the-Hood Automotive Applications .................................................................................... 98
6.2 Medical Applications ................................................................................................................................ 98
6.3 Appliances............................................................................................................................................... 100
6.3.1 Small Appliances .......................................................................................................................... 100
6.3.2 Large Appliances .......................................................................................................................... 102
6.4 Textiles and Nonwovens......................................................................................................................... 104
6.4.1 Floor Coverings and Home Furnishings ...................................................................................... 104
6.4.2 Automotive ................................................................................................................................... 104
6.4.3 Apparel.......................................................................................................................................... 104
6.4.4 Industrial Applications and Geotextiles ....................................................................................... 106
6.4.5 Nonwovens.................................................................................................................................... 106
6.5 Packaging ................................................................................................................................................ 106
6.5.1 Plastics Versus Other Packaging Materials.................................................................................. 106
6.5.2 Use of Polypropylene in Packaging ............................................................................................. 108
6.5.3 High-Crystallinity and High-Melt-Strength Grades..................................................................... 109
6.5.4 Clarified Polypropylene................................................................................................................ 109
CONTENTS vii

6.5.5 Metallocene Polypropylene .......................................................................................................... 109

6.5.6 Rigid Packaging............................................................................................................................ 110
6.5.7 Film ............................................................................................................................................... 112
6.5.8 Barrier Packaging ......................................................................................................................... 114
6.6 Consumer Products ................................................................................................................................. 114
6.7 Building and Construction ...................................................................................................................... 117
References ...................................................................................................................................................... 118

7 Emerging Technologies in Food Packaging: Overview ......................................................... 121

7.1 Introduction ............................................................................................................................................. 121
7.2 Innovations in Food Processing and Packaging..................................................................................... 122
7.3 Food Packaging Technologies ................................................................................................................ 122
7.3.1 Extra Active Functions of Packaging Systems ............................................................................ 122
7.3.2 Modified Atmosphere Packaging ................................................................................................. 123
7.3.3 Edible Films and Coatings ........................................................................................................... 123
7.4 New Food Processing Technologies....................................................................................................... 124
7.5 Future Trends in Food Packaging........................................................................................................... 124
References ...................................................................................................................................................... 125

8 Introduction to Active Food Packaging Technologies ........................................................... 127

8.1 Introduction ............................................................................................................................................. 127
8.2 Drivers for Choice of Active Packaging ................................................................................................ 128
8.2.1 Economic Advantage.................................................................................................................... 128
8.2.2 Process Engineering Limitations.................................................................................................. 129
8.2.3 Time-Dependent Processes........................................................................................................... 129
8.2.4 Secondary Effects ......................................................................................................................... 130
8.2.5 Environmental Impacts................................................................................................................. 130
8.2.6 Enhanced Convenience................................................................................................................. 130
8.3 Forms of Active Packaging .................................................................................................................... 131
8.3.1 Localized Effects .......................................................................................................................... 131
8.3.2 Whole-Package Activity............................................................................................................... 131
8.3.3 Edible Coatings............................................................................................................................. 132
8.4 History of Active Packaging................................................................................................................... 132
8.4.1 Active Packaging for Processed Foods and Beverages ............................................................... 132
8.5 Impact on Packaging Materials and Processes....................................................................................... 135
8.5.1 Material Properties........................................................................................................................ 135
8.5.2 Process Adaptation ....................................................................................................................... 135
8.6 Active Packaging and the Distribution Chain........................................................................................ 136
8.7 Regulatory Environment ......................................................................................................................... 136
References ...................................................................................................................................................... 137

9 Oxygen-Scavenging Packaging................................................................................................ 139

9.1 Introduction ............................................................................................................................................. 139
9.2 Reviews ................................................................................................................................................... 139
9.3 History ..................................................................................................................................................... 139
9.3.1 Package Inserts ............................................................................................................................. 140
9.3.2 Packaging Materials as Oxygen Scavengers................................................................................ 141
9.4 Application to Food and Beverage Packaging ....................................................................................... 145
9.5 Future Opportunities ............................................................................................................................... 147
References ...................................................................................................................................................... 148
viii CONTENTS

10 Antimicrobial Packaging Systems ......................................................................................... 151

10.1 Introduction ......................................................................................................................................... 151
10.2 Food Safety ......................................................................................................................................... 151
10.2.1 Spoilage of Food Products...................................................................................................... 151
10.2.2 Food-Borne Illness .................................................................................................................. 151
10.2.3 Malicious Tampering and Bioterrorism ................................................................................. 152
10.3 Antimicrobial Packaging..................................................................................................................... 152
10.4 Antimicrobial Agents .......................................................................................................................... 153
10.4.1 Chemical Antimicrobial Agents ............................................................................................. 153
10.4.2 Natural Antimicrobial Agents................................................................................................. 155
10.4.3 Probiotics................................................................................................................................. 155
10.5 System Design..................................................................................................................................... 156
10.5.1 Antimicrobial Mechanisms ..................................................................................................... 156
10.5.2 Microbiocidal .......................................................................................................................... 156
10.5.3 Microbiostatic.......................................................................................................................... 163
10.5.4 Functioning Modes and Volatility .......................................................................................... 163
10.5.5 Nonvolatile Migration............................................................................................................. 164
10.5.6 Volatile Migration................................................................................................................... 164
10.5.7 Nonmigration and Absorption ................................................................................................ 165
10.5.8 Shapes and Compositions of Systems .................................................................................... 165
10.6 Commercialization .............................................................................................................................. 166
10.6.1 Technical Factors .................................................................................................................... 166
10.6.2 Regulatory, Marketing, and Political Factors......................................................................... 173
References .................................................................................................................................................... 174

11 Damage Reduction to Food Products During Transportation and Handling ..................... 181
11.1 Introduction ......................................................................................................................................... 181
11.2 Functions of Packaging....................................................................................................................... 181
11.2.1 Containment ............................................................................................................................ 181
11.2.2 Protection................................................................................................................................. 182
11.2.3 Communication ....................................................................................................................... 183
11.2.4 Utility....................................................................................................................................... 183
11.3 Food Product Categories..................................................................................................................... 184
11.3.1 Meats ....................................................................................................................................... 184
11.3.2 Seafood.................................................................................................................................... 185
11.3.3 Vegetables and Fruits.............................................................................................................. 186
11.3.4 Processed Versus Nonprocessed............................................................................................. 187
11.4 Food Product Distribution Environment............................................................................................. 187
11.4.1 Harvesting ............................................................................................................................... 187
11.4.2 Packing .................................................................................................................................... 188
11.4.3 Shipping................................................................................................................................... 188
11.4.4 Storage and Shelf Life ............................................................................................................ 188
11.5 Major Causes of Food Spoilage/Damage in Supply Chain ............................................................... 189
11.5.1 Microbiological Spoilage ........................................................................................................ 189
11.5.2 Biochemical............................................................................................................................. 189
11.5.3 Chemical.................................................................................................................................. 189
11.5.4 Macrobiological Spoilage ....................................................................................................... 189
11.5.5 Physical ................................................................................................................................... 189
11.6 Packaging Materials ............................................................................................................................ 189
11.6.1 Paper........................................................................................................................................ 190
11.6.2 Plastic ...................................................................................................................................... 191
CONTENTS ix

11.6.3 Metal........................................................................................................................................ 192

11.6.4 Glass ........................................................................................................................................ 192
11.7 “Smart” Packaging .............................................................................................................................. 193
11.7.1 Active Packaging .................................................................................................................... 193
11.7.2 Modified Atmosphere Packaging ........................................................................................... 193
11.7.3 Controlled Atmosphere Packaging ......................................................................................... 194
11.7.4 Intelligent Packaging............................................................................................................... 194
11.8 Trends in Protective Food Packaging of 2000 and Beyond .............................................................. 194
11.8.1 Food Packaging Trends........................................................................................................... 194
11.8.2 Damage Reduction Trends...................................................................................................... 196
References .................................................................................................................................................... 197

12 Food Packaging Machinery .................................................................................................... 199

12.1 Introduction ......................................................................................................................................... 199
12.1.1 Containment ............................................................................................................................ 199
12.1.2 Protection................................................................................................................................. 199
12.1.3 Communication ....................................................................................................................... 199
12.1.4 Utility....................................................................................................................................... 199
12.2 Filling Machines.................................................................................................................................. 201
12.3 Volumetric Fillers ............................................................................................................................... 201
12.3.1 Piston Fillers............................................................................................................................ 201
12.3.2 Diaphragm Fillers.................................................................................................................... 202
12.3.3 Timed Flow Fillers.................................................................................................................. 202
12.3.4 Auger Fillers............................................................................................................................ 202
12.4 Weight Filling ..................................................................................................................................... 203
12.4.1 Net Weight Fillers................................................................................................................... 204
12.4.2 Gross Weight Fillers ............................................................................................................... 204
12.5 In-Line or Rotary Fillers ..................................................................................................................... 204
12.5.1 In-Line Fillers.......................................................................................................................... 204
12.5.2 Rotary Fillers........................................................................................................................... 205
12.6 Cap Application Machines.................................................................................................................. 205
12.6.1 Chucks and Clutches............................................................................................................... 207
12.6.2 Chuck-Type Press-On Cappers............................................................................................... 207
12.6.3 Roller-Type Press-On Cappers ............................................................................................... 207
12.7 Induction Cap Sealing......................................................................................................................... 207
12.8 Flexible Packaging .............................................................................................................................. 209
12.9 Form-Fill-Seal Equipment .................................................................................................................. 209
12.9.1 Vffs Equipment ....................................................................................................................... 209
12.9.2 Hffs Equipment ....................................................................................................................... 210
12.9.3 Tffs Equipment........................................................................................................................ 210
12.10 Canning Machinery ............................................................................................................................ 211
12.11 Carton Filling and Closing Machinery............................................................................................... 212
12.11.1 Carton Filling........................................................................................................................ 212
12.12 Metal Detectors .................................................................................................................................. 213
12.12.1 Typical Metal Detectors ....................................................................................................... 214

13 Compostable Polymer Properties and Packaging Applications.......................................... 217

13.1 Introduction ......................................................................................................................................... 217
13.2 Biodegradable Polymers from Renewable Resources........................................................................ 218
13.2.1 Poly(lactic acid) ...................................................................................................................... 218
13.2.2 Polyhydroxyalkanoates ........................................................................................................... 220
x CONTENTS

13.2.3 Thermoplastic Starch .............................................................................................................. 225

13.2.4 Other Compostable Polymers from Renewable Resources.................................................... 227
13.3 Biodegradable Polymers from Petrochemical Sources ...................................................................... 232
13.3.1 Aliphatic Polyesters and Copolyesters ................................................................................... 232
13.3.2 Aromatic Polyesters and Copolyesters ................................................................................... 233
13.3.3 Poly(caprolactone) .................................................................................................................. 236
13.3.4 Poly(esteramide)s .................................................................................................................... 236
13.3.5 Poly(vinyl alcohol).................................................................................................................. 238
13.4 Blends......................................................................................................................................... 239
13.5 Summary.............................................................................................................................................. 242
13.5.1 Major Markets of Compostable Polymer Materials............................................................... 243
References .................................................................................................................................................... 243

14 Waste Management for Polymers in Food Packaging Industries........................................ 249

14.1 Biodegradable Synthetic Copolymers and Composites ..................................................................... 249
14.1.1 Novel Biodegradable Copolyamides Based on Diacids, Diamines,
and α-Amino Acids ................................................................................................................ 249
14.1.2 Novel Biodegradable Copolyesteramides from ε-Caprolactone
and Various PA Salts .............................................................................................................. 250
14.1.3 Novel Star-Shaped Copolylactides ......................................................................................... 251
14.1.4 Biodegradable Composite Materials....................................................................................... 251
14.1.5 Natural
Synthetic Polymer Blends........................................................................................ 252
14.1.6 Partially Degradable Blends ................................................................................................... 252
14.2 Chitosan
Poly(Vinyl Alcohol) Blends .............................................................................................. 253
14.3 Landfill ................................................................................................................................................ 254
14.4 Incineration.......................................................................................................................................... 255
14.5 Pyrolysis .............................................................................................................................................. 255
14.6 Reuse and Recovery............................................................................................................................ 256
14.7 Composting.......................................................................................................................................... 257
14.8 Recycling............................................................................................................................................. 259
14.8.1 Plastic Recycling..................................................................................................................... 261
14.8.2 Sorting ..................................................................................................................................... 271
14.8.3 Preparation for Recycling ....................................................................................................... 282
14.8.4 Mechanical Recycling............................................................................................................. 282
14.8.5 Feedstock Recycling ............................................................................................................... 284
14.8.6 Chemical Recycling ................................................................................................................ 288
14.8.7 Radiation Technology ............................................................................................................. 289
14.9 The Issue of Contamination on Recycling ......................................................................................... 290
14.9.1 Environmental Impacts of Waste Management Processes..................................................... 293
References .................................................................................................................................................... 294
Relevant Websites........................................................................................................................................ 310

15 Polymer Blending for Packaging Applications ..................................................................... 311

15.1 Introduction ......................................................................................................................................... 311
15.2 Why Blend?......................................................................................................................................... 311
15.3 Blending Processes.............................................................................................................................. 312
15.3.1 Pellet Premixing ...................................................................................................................... 313
15.3.2 Melt Blending.......................................................................................................................... 314
15.4 Physics of Blending ............................................................................................................................ 317
15.5 Thermodynamics ................................................................................................................................. 317
CONTENTS xi

15.6 Morphology Development in Immiscible Blends .............................................................................. 321

15.7 Morphology Development in Blown Film ......................................................................................... 333
15.7.1 Viscosity Ratio ........................................................................................................................ 333
15.7.2 Interfacial Tension .................................................................................................................. 333
15.7.3 Minor Phase Concentration in Blend ..................................................................................... 333
15.7.4 Polymer Elasticity (Non-Newtonian Behavior) ..................................................................... 333
15.7.5 Extruder RPM ......................................................................................................................... 334
15.7.6 Extruder Temperature ............................................................................................................. 334
15.7.7 Shear Stress in Extruder, Adapter, and Die ........................................................................... 334
15.7.8 Screw Design .......................................................................................................................... 334
15.7.9 Draw Ratio .............................................................................................................................. 334
15.7.10 Frost Line Height and Process Time .................................................................................... 335
15.8 Dispersion of Rigid Particles and Nanocomposites ........................................................................... 335
15.9 Rheology of Polymer Blends.............................................................................................................. 337
15.10 Conclusion......................................................................................................................................... 338
References .................................................................................................................................................... 339

16 A Survey of Regulatory Aspects of Food Packaging ........................................................... 345

16.1 Introduction ......................................................................................................................................... 345
16.1.1 Bisphenol A............................................................................................................................. 345
16.2 Determining the Regulatory Status of Components of a Food Contact Material
in the United States ............................................................................................................................. 346
16.2.1 Food Contact Formulation (FCF) Compliance Notification.................................................. 348
16.3 Regulatory Report: FDA’s FCS Notification Program ...................................................................... 348
16.3.1 Definitions, History, and Scope.............................................................................................. 348
16.3.2 The Notification Process......................................................................................................... 349
16.3.3 Increasing the Odds of Success .............................................................................................. 350
16.3.4 FCS Formulations ................................................................................................................... 351
16.4 Preservation of Foods by Irradiation .................................................................................................. 351
16.4.1 FDA Regulations for Treatment of Foods with Radiation .................................................... 352
16.4.2 Title 21 CFR 179. Subpart B: Radiation and Radiation Sources .......................................... 353
16.4.3 Title 21 CFR 179. Subpart C: Packaging Materials for Irradiated Foods............................. 357
16.5 Regulatory Aspects of Recycled Plastics—US FDA View ............................................................... 359
16.5.1 Introduction ............................................................................................................................. 359
16.5.2 Use of Recycled Plastics in Food Packaging: Chemistry Considerations............................. 360
16.5.3 Surrogate Contaminant Testing .............................................................................................. 364
16.5.4 Plastic Containers from Nonfood-Contact Applications as Feedstock.................................. 366
16.5.5 The Use of an Effective Barrier ............................................................................................. 368
16.5.6 Elimination of Data Recommendations for 3 Recycling Processes
for PET and PEN .................................................................................................................... 369
16.6 EU Legislation on Food Contact Plastics........................................................................................... 369
16.6.1 EU Regulation No. 10/2011 on Plastic Materials Intended to Come
into Contact with Food ........................................................................................................... 369
16.6.2 Consolidating Paragraphs........................................................................................................ 369
16.6.3 Chapter I: General Provisions................................................................................................. 376
16.6.4 Chapter II: Compositional Requirements ............................................................................... 378
16.6.5 Chapter III: Specific Provisions for Certain Materials and Articles ..................................... 380
16.6.6 Chapter IV: Declaration of Compliance and Documentation................................................ 381
16.6.7 Chapter V: Compliance .......................................................................................................... 381
16.6.8 Chapter VI: Final Provisions .................................................................................................. 382
xii CONTENTS

16.7 European Union Legislation for Recycled Plastics............................................................................ 383

16.8 Questions and Answers on Recycled Plastics in Food Contact Materials ........................................ 383
Acknowledgment ......................................................................................................................................... 384
Appendix: Model of the Sorption of Surrogate Contaminants into Plastic................................................ 384
References .................................................................................................................................................... 386
Further Reading............................................................................................................................................ 388
Index ................................................................................................................................................................... 389
 Preface

Almost everyone deals with foods packaged in To be a candidate for use in food packaging appli-
plastic containers on a daily basis. Plastic bags and cations, a plastic must possess a few attributes.
packages have proliferated around the world, They include mechanical strength to allow the
including remote locations such as Himalayan package food to withstand the rigors of handling,
peaks. There are many reasons for the inception of transportation, storage, refrigeration, and consumer
plastic food packaging. There are also many func- interactions, abrasion, and irradiation. The plastic
tions which these packages must fulfill depending must also have the appropriate thermal stability for
on the type of food being protected. thermal processing such as retort and sterilization
Once upon a time, people were sustained by processes. These characteristics and proper package
locally grown, seasonal food and what could be design usually prevent concealed tampering.
safely transported within no longer than the maxi- The size of food markets is massive globally.
mum time before spoilage. The increase in the Packaged foods are not only common in the developed
population of the earth has long outgrown the capac- economies but have become commonplace in the
ity of local products to meet the needs of nearby developing world. Packaged foods are increasingly
populations. Large cities have virtually no local available in the third-world countries of Africa, Asia,
growth areas. and South America. For example, the size of grocery
The ease of travel, efficient transportation, and business is over $500 billion annually in the United
information systems have exposed people from one States, most of which is offered in packaged form.
corner of the earth to foods from vast distances This book brings together the key applications,
away. Marketing by food suppliers and sellers has technologies, machinery, and waste management
given rise to a demand for food variety. Access to practices for packaging foodstuffs using plastic films.
an astonishing array of foods from the four corners The selections address questions related to the film
of the world is no longer considered a luxury. grades, types of packages for different types of foods,
There are several requirements which food pack- packaging technologies, machinery, and waste man-
aging must meet. The foremost function of a package agement. Additionally, the book provides a review of
is protection of food products. Packages protect food the new technologies for packaging foodstuffs. A
from the loss of nutrients, functional properties, color, reader with an interest in food packaging would save
aroma, taste, and preserve the general appearance substantially because the contents of this book gather
expected by consumers. A good package should the salient aspects of several recent books from which
create an acceptable barrier between the food and materials have been drawn.
external environment; particularly water vapor, oxy- This book contains three new chapters.
gen, and microorganisms. The shelf life, the length Chapter 1 is an introduction to the use of plastics
of time that product remains in acceptable conditions in food packaging. Chapter 2 covers the deve-
for use, strongly depends on the barrier ability of a lopment of barrier films for food packaging.
package. Chapter 16 presents a survey of numerous regula-
The second function of the package is to transport tions which govern food packaging in the United
the product in a convenient manner. Finally, a good States of America and the European Union. The
package should provide clear information about the combination of new chapters and the selected
food to consumers and attract them to buy it. Food chapters from other books render this title unique
packaging disregarding of the material of packaging among all the titles available on the subject of
is intended to protect the food from contamination food packaging in the market.
and preserve the quality of the food between I would like to offer my deepest thanks to
manufacturing and retail sales and consumption. Pamela L. Langhorn, who is a partner at the firm

xiii
xiv PREFACE

of Keller and Heckman in Washington, DC, for I am indebted to Matthew Deans, the Senior
reviewing Chapter 16. Pamela is one of the Publisher of William Andrew, for his leadership and
foremost experts in the food packaging laws with invaluable support. Thanks to Matthew’s wisdom
a global purview. She made numerous corrections, and guidance Plastics Design Library continues to
suggestions, and upgrades to this chapter for which grow in both the number of titles and the breadth of
I am most grateful. subject matters it offers.
I would like to thank all the authors who have The support provided by Frank Hellwig, Associate
contributed to this book: C. Maier, T. Calafut, T.I. Acquisition Editor, for the preparation of the manu-
Butler, B.A. Morris, J. Breil, J.H. Han, M.L. Rooney, script and publication was invaluable and is most
J. Singh, P. Singh, H.A. Hughes, E. Rudnik, and appreciated.
I.S. Arvanitoyannis.
Special thanks go to my friends Dr. Larry Sina Ebnesajjad
McKeen for authoring Chapter 1 and Dr. Maryam September 2012
Fereydoon, the coauthor of Chapter 5.
 1 Introduction to Use of Plastics in Food Packaging
L.W. McKeen

Packaging film is very thin plastic and the basic • A trend toward conversion to biodegradable,
component of plastic and elastomer materials is poly- sustainable, and recyclable flexible packaging
mer. This chapter is narrowly focused on the com- materials to improve the environmental foot-
mercial plastic films used in packaging. Generally, print of packaging.
films are used as barriers; they keep dirt, germs, • Flexible packaging films being made thinner
liquids or gases on one side of the film. Nearly any to reduce costs and minimize waste after use,
plastic can be made in film form, but this chapter which also drives the need for higher perform-
will discuss only those that are used for packaging on ing materials.
a commercial basis. By definition, flexible packaging
includes bags, envelopes, pouches, sachets, and • Flexible packaging products will replace bot-
wraps made of easily yielding materials such as film, tles and containers for a range of food and
foil, or paper sheeting which, when filled and sealed, beverage products.
acquires pliable shape. This chapter also will not
cover multilayer films which are commercially very The following sections will look at the chemistry
important but covered in another chapter. of various plastics used in flexible packaging films.
Polymeric packaging materials are used to sur- The discussion will include chemical structures and
round a package completely, securing its contents where flexible films made of those materials are used.
from gases and vapors, moisture, and biological
effects of the outside environment, while providing
a pleasing and often decorative appearance. Water 1.2 Polyolefins
vapor and atmospheric gases if allowed to permeate Polymers made from hydrocarbon monomers
in or out of a package can alter the taste, color, and that contain a carbon
carbon double bond through
nutritional content of the packaged good. The which the polymer is made by addition polymeriza-
effects of gas and vapors on food are complex and tion are called polyolefins. An alkene, also called
comprise a major branch of food science. The fol- an olefin, is a chemical compound made of only
lowing is a brief overview. Additional details in carbon and hydrogen atoms containing at least one
terms of typical film properties and permeation carbon-to-carbon double bond. The simplest
properties are available in the literature (McKeen alkenes, with only one double bond and no other
2011, 2012). functional groups, form a homologous series of
hydrocarbons with the general formula CnH2n. The
two simplest alkenes of this series are ethylene and
1.1 Background propylene. When these are polymerized, they form
polyethylene and polypropylene, which are the two
The global flexible packaging market is very of the plastics that account for the bulk of the plas-
large, as is shown in Table 1.1 for 2009. The tic film packaging market. There are other specialty
table shows that polyethylenes and polypropylenes polyolefins that are made into very low-volume
make up the bulk of the market. The six plastic specialty films.
types listed in the table account for over three quar- Polyolefins are made by addition polymerization
ters of the total packaging films produced. The (sometimes called chain-growth polymerization). A
growth rate is expected to be about 4% annually chain reaction adds new monomer units to the grow-
until 2016. Other key market drivers and trends ing polymer molecule, one at a time through double
identified for flexible packaging include: bonds in the monomers. This is shown in Figure 1.1.

Ebnesajjad: Plastic Films in Food Packaging. DOI: http://dx.doi.org/10.1016/B978-1-4557-3112-1.00001-6

© 2013 Elsevier Inc. All rights reserved. 1
2 PLASTIC FILMS IN FOOD PACKAGING

Table 1.1 Global Flexible Packaging—2009

Material Millions of Tons (MMT) %

Polyethylenes (PE) 4.8 32.6
Polypropylenes (PP) 4.7 32
Biaxial-orientated polyethylene terephthalate (BoPET) 0.4 3
Polyvinyl chloride (PVC) 0.3 2.1
Polyamide, nylon (PA) 0.6 3.9
Ethylene
vinyl alcohol (EVOH) 0.4 2.6
Total plastics 11.3 76.2
Paper, Aluminum foil, Cellulosics 3.5 23.8
Source: PIRA International.

H R1 H R2 H R1 H R2

m C C +n C C C C C C

H H H H H H H H
n+m

Figure 1.1 Addition polymerization.

The structures of some of the monomers used to H H H CH3

make polyethylene, polypropylene, and the other C C C C
polyolefins discussed here are shown in Figure 1.2.
H H H H
Structures of the polymers may be found in the
appropriate sections contain the data for those
Ethylene Propylene
materials.
H H

1.2.1 Polyethylene C C CH3 H3C CH2

The structure of polyethylene is given in Figure 1.1 H CH2 CH CH CH2

where both R1 and R2 are replaced by H. There are
several types of polyethylene, which are classified CH3
mostly by their density. There are several ASTM
standards that are used to describe polyethylene 4-Methylpentene-1 Butene-1
including ASTM D2103—10 Standard Specification
for Polyethylene Film and Sheeting. According H 2C
to ASTM D1248—12 Standard Specification for CH
H2C CH
Polyethylene Plastics Extrusion Materials for Wire CH
and Cable, the basic types or classifications of poly- H2C CH
ethylene are as follows: Norbornene

• Ultra low-density polyethylene (ULDPE), poly- Figure 1.2 Chemical structures of the monomers
mers with densities ranging from 0.890 to used to make the polyolefins polyethylene, and
0.905 g/cm3, contains comonomer. polypropylene.
1: INTRODUCTION TO USE OF PLASTICS IN FOOD PACKAGING 3

• Very low-density polyethylene (VLDPE), Branching affects the crystallinity. A diagram of a

polymers with densities ranging from 0.905 to representation of the crystal structure of polyethyl-
0.915 g/cm3, contains comonomer. ene is shown in Figure 1.4. One can imagine how
• Linear low-density polyethylene (LLDPE), branching in the polymer chain can disrupt the crys-
polymers with densities ranging from 0.915 to talline regions. The crystalline regions are the highly
0.935 g/cm3, contains comonomer. ordered areas in the shaded rectangles of Figure 1.4.
A high degree of branching would reduce the size
• Low-density polyethylene (LDPE), polymers of the crystalline regions, which leads to lower
with densities ranging from about 0.915 to crystallinity.
0.935 g/cm3 (further specification ASTM Film applications and uses of polyethylene
D4635—08a Standard Specification for include:
Polyethylene Films Made from Low-Density
Polyethylene for General Use and Packaging • ULDPE—Heavy-duty sacks, turf bags, con-
Applications). sumer bags, packaging for cheese, meat, cof-
• Medium-density polyethylene (MDPE), poly- fee, and detergents, silage wrap, mulch films,
mers with densities ranging from 0.926 to and extruded membranes.
0.940 g/cm3, may or may not contain comono- • LDPE—Food packaging (bread bags, baked
mer (further specification ASTM D3981—09a goods, light-duty produce bags, etc.); light- to
Standard Specification for Polyethylene Films heavy-duty bags; textile packaging (shirts,
Made from Medium-Density Polyethylene for sweaters, etc.).
General Use and Packaging Applications).
• LLDPE—Agricultural films, saran wrap, and
• High-density polyethylene (HDPE), polymers bubble wrap.
with densities ranging from 0.940 to 0.970 g/
cm3, may or may not contain comonomer. • MDPE—Specialty merchandise bags; mailing
envelopes; heavy-duty shipping sacks; pallet
Figure 1.3 shows the differences in the structures shrink films; fresh-cut produce packaging.
graphically. The differences in the branches in • HDPE—Food packaging: dairy products and
terms of number and length affect the density and bottled water, cosmetics, medical products,
melting points of some of the types. and household chemicals.

Figure 1.3 Graphical depictions of polyethylene Figure 1.4 Graphical diagram of polyethylene
types. crystal structure.
4 PLASTIC FILMS IN FOOD PACKAGING

1.2.2 Polypropylene Applications and uses of polypropylene include:

The structure of polypropylene is given in • Homopolymer: Thermoforming, slit film, and
Figure 1.1 where both R1 and R2 are replaced by oriented fibers.
CH3. Polypropylene can be made in a number of
ways. The way it is produced can affect its physical • Random copolymer: Food, household chemi-
properties. It can also have very small amounts of cals, beauty-aid products, clear containers,
comonomers, which will alter its structure and and hot-fill applications.
properties. The three main types of polypropylene • Impact copolymers: film, sheet, and profiles.
generally available are:

• Homopolymers are made in a single reactor

with propylene and a catalyst. It is the stiffest
of the three propylene types and has the highest
1.2.3 Specialty Polyolefins
tensile strength at yield. In the natural state (no Two specialty polyolefins with packing applica-
colorant added), it is translucent and has excel- tions are discussed in the next two sections.
lent see-through or contact clarity with liquids.
In comparison to the other two types it has less
impact resistance, especially below 0 C.
Polybutene-1
• Random copolymer (homophasic copolymer) is
made in a single reactor with a small amount of Polybutene-1 (PB-1) is made from 1-butene, as
ethylene (, 5%) added, which disrupts the crys- shown in Figure 1.5. PB-1 resins are high-
tallinity of the polymer allowing this type to be molecular-weight isotactic, semicrystalline ther-
the clearest. It is also the most flexible with the moplastic polyolefins. Some products contain
lowest tensile strength of the three. It has better small amounts of comonomers, ethylene and/or
room temperature impact than homopolymer propylene.
but shares the same relatively poor impact resis- PB-1 has high flexibility and creep resistance
tance at low temperatures. over a wide temperature range. Applications and
uses include two main fields:
• Impact copolymers (heterophasic copolymer),
also known as block copolymers, are made in a • Peelable easy-to-open packaging where PB-1
two reactor system, in which the homopolymer is used as blend component predominantly in
matrix is made in the first reactor and then trans- polyethylene to tailor peel strength and peel
ferred to the second reactor, where ethylene and quality, mainly in alimentary consumer pack-
propylene are polymerized to create ethylene aging and medical packaging.
propylene rubber in the form of microscopic
nodules dispersed in the homopolymer matrix • Lowering seal-initiation temperature of high-
phase. These nodules impart impact resistance at speed packaging polypropylene-based films.
both ambient and low temperatures to the com- Blending PB-1 into polypropylene achieves
pound. This type has intermediate stiffness heat sealing temperatures as low as 65 C,
and tensile strength and is quite cloudy. In gen- maintaining a broad sealing window and good
eral, the more ethylene monomer is added, the optical film properties.
greater the impact resistance, with correspond-
ingly lower stiffness and tensile strength.
CH3
ASTM Standards related to polypropylene films H3C CH2 H2C
include:
CH CH2 CH CH2
n
• ASTM D2103—10 Standard Specification for 1-Butene Polybutene-1
Polyethylene Film and Sheeting.
• ASTM D2673—09 Standard Specification for Figure 1.5 Structure of 1-butene monomer and PB-
Oriented Polypropylene Film. 1 polymer.
1: INTRODUCTION TO USE OF PLASTICS IN FOOD PACKAGING 5

4-Methylpentene-1-Based Polyolefin • Low density,

4-Methylpentene-1-based polyolefin (PMP) is a • Extremely low water absorption,
lightweight, functional polymer that displays a • Excellent water vapor barrier properties,
unique combination of physical properties and char-
• High rigidity, strength, and hardness,
acteristics due to its distinctive molecular structure,
which includes a bulky side chain as shown in • Variable heat deflection temperature up to
Figure 1.6. PMP possesses many characteristics 170 C,
inherent in traditional polyolefins such as excellent • Very good resistance to acids and alkalis.
electrical insulating properties and strong hydroly-
sis resistance. Moreover, it features low dielectric, Applications and uses: COC is used as a core
superb clarity, transparency, gas permeability, and layer in push-through packaging, either in five-
heat and chemical resistance and release qualities. layer coextruded or three-layer laminated film
Applications and uses include: structures. It is also used as flexible and rigid pack-
aging for food and consumer items.
• Paper coatings and baking cartons,
• Release film and release paper,
• High-frequency films, 1.3 Polyester
• Food packaging such as gas permeable Polyethylene terephthalate (PET) is the most
packages for fruit and vegetables. common thermoplastic polyester packaging film
and is often called just “polyester”. PET exists both
as an amorphous (transparent) and as a semicrystal-
Cyclic Olefin Copolymer
line (opaque and white) thermoplastic material.
Cyclic olefin copolymer (COC) is an amorphous Semicrystalline PET has good strength, ductility,
polyolefin made by reaction of ethylene and norbor- stiffness, and hardness. Amorphous PET has better
nene in varying ratios. Its structure is given in ductility but less stiffness and hardness. It absorbs
Figure 1.7. The norbornene structure in Figure 1.7 is very little water. Its structure is shown in
designated “Y”. The properties can be customized Figure 1.8.
by changing the ratio of the monomers found in the Applications and uses: Roasting bags, audio/video
polymer. COC is amorphous, so it is transparent. tapes, release liner, stamping foil, and label overlay.
Other performance benefits include:
1.3.1 Specialty Polyesters
While PET is by far the most common polyester
H3C CH3
CH packaging film, there are many other polyesters
also offered. These specialty films are described in
CH2 the following sections.
CH CH2
Polyethylene Napthalate
n
Polyethylene napthalate (PEN) is similar to PET
Figure 1.6 Structure of PMP. but has better temperature resistance, strength,
hydrolysis resistance, dimensional stability, and low
oligomer extraction. It is particularly stable when
CH2 CH2 CH CH
X CH2
O O
HC CH
O CH2 CH2 O C C

CH2 CH2
Y n

Figure 1.7 Chemical structure of COCs. Figure 1.8 Chemical structure of PET.
6 PLASTIC FILMS IN FOOD PACKAGING

exposed to sterilization processes. The structure of oriented, it forms a high-strength material, with
this polyester is shown in Figure 1.9. relatively uniform properties and low fibrillation.
Significant commercial markets have been devel- Also, its high-temperature capability enables it to
oped for its application in textile and industrial meet the needs of thermally demanding applica-
fibers, films, and foamed articles, containers for tions, such as films for printed wiring boards.
carbonated beverages, water and other liquids, and
thermoformed applications.
Polybutylene Terephthalate
Liquid Crystalline Polymers Polybutylene terephthalate (PBT) is semicrystal-
Liquid crystalline films are high-performance line, white or off-white polyester similar in both
specialty films. Though their structures vary, they composition and properties to PET. It has some-
are highly aromatic as shown in Figure 1.10. what lower strength and stiffness than PET, is a lit-
Liquid crystalline polymer (LCP) films and tle softer but has higher impact strength and similar
sheets are well suited for many medical, chemical, chemical resistance. As it crystallizes more rapidly
electronic, beverage, and food packaging applica- than PET, it tends to be preferred for industrial
tions. They are more impermeable to water vapor, scale molding. Its structure is shown in Figure 1.11.
oxygen, carbon dioxide, and other gases than typi- PBT is a dimensionally stable, sterilizable film
cal barrier resins. When LCP film is biaxially with good optical quality, even after sterilization.

O
Polycarbonate
O C O
Polycarbonate (PC) is another polyester film. Its
C O CH2 CH2
structure is shown in Figure 1.12.
PC performance properties include:
n

Figure 1.9 Structure of PEN. • Very impact resistant and is virtually unbreak-
able and remains tough at low temperatures,
• “Clear as glass” clarity,
O • High heat resistance,
C • Dimensional stability,
• Resistant to ultraviolet light, allowing exterior
use,
O C O • Flame retardant.
O n
This film offers high heat resistance and superior
Figure 1.10 Chemical structure of Ticona Vectras dimensional stability and finds uses in packaging of
A950 LCP. medical devices.

O O

C C O CH2 CH2 CH2 CH2 O

Figure 1.11 Chemical structure of PBT polyester.

1: INTRODUCTION TO USE OF PLASTICS IN FOOD PACKAGING 7

1.5 Polyvinyl Chloride

CH3 O
Polyvinyl chloride (PVC) is a flexible or rigid
O C O C
material that is chemically nonreactive. Rigid PVC
CH3 is easily machined, heat formed, welded, and even
n solvent cemented. PVC can also be machined using
standard metal working tools and finished to close
Figure 1.12 Chemical structure of PC polyester.
tolerances and finishes without great difficulty.
PVC resins are normally mixed with other additives
such as impact modifiers and stabilizers, providing
Polycyclohexylene-Dimethylene hundreds of PVC-based materials with a variety of
Terephthalate engineering properties.
Polycyclohexylene-dimethylene terephthalate
(PCT) is high-temperature polyester that possesses
the chemical resistance, processability, and dimen-
CH2 CH2
sional stability of PET and PBT. However, the ali-
phatic cyclic ring shown in Figure 1.13 imparts O O CH2 CH CH CH2
added heat resistance. This puts it between the
C C O CH2 CH2 O
common polyesters and the LCP polyesters
described in the previous sections. n
Applications and uses include bags, rigid medi-
cal and blister packaging. Figure 1.13 Chemical structure of PCT polyester.

1.4 Polystyrene
Polystyrene (PS) is the simplest plastic based on CH CH2
styrene. Its structure is shown in Figure 1.14.
There are three general forms of PS film:

• General purpose PS,

• Oriented PS, n
• High impact (HIPS).
Figure 1.14 Chemical structure of PS.
One of the most important plastics is high impact
PS or HIPS. This is a PS matrix that is imbedded
with an impact modifier, which is basically a
rubber-like polymer such as polybutadiene. This is Polystyrene phase Polybutadiene phase
shown in Figure 1.15.
Applications and uses: General Purpose—Yogurt,
cream, butter, meat trays, egg cartons, fruit and
vegetable trays, as well as cakes, croissants, and
cookies. Medical and packaging/disposables, bakery
packaging, and large and small appliances, medical
and packaging/disposables, particularly where clar-
ity is required, window envelope patches and labels.
Oriented—Oriented-PS films can be printed and
laminated to foams for food-service plates and trays
offering improved esthetics. The films can also be
used as a laminate to PS sheet for a high gloss shine
for bakery and convenience food items. Figure 1.15 The structure of HIPS.
8 PLASTIC FILMS IN FOOD PACKAGING

There are three broad classifications for rigid sheet structures as a barrier layer in medical pack-
PVC compounds: Type I, Type II, and CPVC. aging, and packaging of foods such as fresh red
Type II differs from Type I due to greater impact meats, cheese, and sausages. Coatings are often
values but lower chemical resistance. CPVC has applied to prevent specific gas transmission.
greater high temperature resistance. These materials
are considered “unplasticized” because they are less
flexible than the plasticized formulations. 1.7 Polyamide
Applications and uses: Packaging is a major
market for PVC. Rigid grades are blown into bot- High-molecular weight polyamides are com-
tles and made into sheets for thermoforming boxes monly known as nylon. Polyamides are crystalline
and blister packs. Flexible PVC compounds are polymers typically produced by the condensation of
used in food packaging applications because of a diacid and a diamine. There are several types,
their strength, transparency, processability, and low and each type is often described by a number, such
raw material cost. as nylon 66 or polyamide 66 (PA66). The numeric
suffixes refer to the number of carbon atoms pres-
ent in the molecular structures of the amine and
1.6 Polyvinylidene Chloride acid respectively (or a single suffix if the amine
and acid groups are part of the same molecule).
Polyvinylidene chloride (PVDC) resin, the struc-
The polyamide plastic materials discussed in this
ture of which is shown in Figure 1.16, is usually a
book and the monomers used to make them are
copolymer of vinylidene chloride with vinyl chlo-
given in Table 1.2.
ride or other monomers. PVDC is commonly
The general reaction is shown in Figure 1.17.
known as Sarant.
Applications and uses: Monolayer films for food
wrap and medical packaging, coextruded films and 1.7.1 Nylon 6
Nylon 6 begins as pure caprolactam which is a
ring-structured molecule. This is unique in that the
H Cl
ring is opened and the molecule polymerizes with
itself. Since caprolactam has six carbon atoms, the
C C polyamide that is produced is called nylon 6,
which is nearly the same as Nylon 66 described in
H Cl Section 1.7.3. The structure of Nylon 6 is shown
n
in Figure 1.18 with the repeating unit in the
Figure 1.16 Structure of PVDC homopolymer. brackets.

Table 1.2 Monomers Used to Make Specific Polyamides/Nylons

Polyamide/Nylon Type Monomers Used to Make

Nylon 6 (PA6) Caprolactam
Nylon 11 (PA11) Aminoundecanoic acid
Nylon 12 (PA12) Aminolauric acid
Nylon 66 (PA66) 1,6-Hexamethylene diamine and adipic acid
Nylon 610 (PA610) 1,6-Hexamethylene diamine and sebacic acid
Nylon 612 (PA612) 1,6-Hexamethylene diamine and 1,12-dodecanedioic acid
Nylon 666 (PA6/66) Copolymer based on nylon 6 and nylon 66
Nylon 46 (PA46) 1,4-Diaminobutane and adipic acid
Polyamide amorphous (6-3-T) Trimethyl hexamethylene diamine and terephthalic acid
Polyphthalamide (PPA) Any diamine and isophthalic acid and/or terephthalic acid
1: INTRODUCTION TO USE OF PLASTICS IN FOOD PACKAGING 9

Some of the Nylon 6 characteristics are as with itself to produce the polyamide containing
follows: twelve carbons between the two nitrogen atoms of
the two amide groups. Its structure is shown in
• Outstanding balance of mechanical properties. Figure 1.19.
• Outstanding toughness in equilibrium mois- The properties of semicrystalline polyamides are
ture content. determined by the concentration of amide groups in
the macromolecules. Polyamide 12 has the lowest
• Outstanding chemical resistance and oil resis- amide group concentration of all commercially
tance. available polyamides thereby substantially promot-
• Outstanding long-term heat resistance (at a ing its characteristics:
long-term continuous maximum temperature
ranging between 80 C and 150 C). • Lowest moisture absorption (B2%),
• Offers low gasoline permeability and out- • Good to excellent resistance against greases,
standing gas barrier properties. oils, fuels, hydraulic fluids, various solvents,
• Highest rate of water absorption and highest salt solutions, and other chemicals,
equilibrium water content (8% or more). • Low coefficient of sliding friction,
• Excellent surface finish even when reinforced. • Lowest strength and heat resistance of any
• Poor chemical resistance to strong acids and polyamide unmodified.
bases.
Applications and uses: Grilamid L 25 is used for
Films can be made by extrusion, extrusion coat- sausage skins for precooked sausages and packag-
ing, and blown film; polyamide films can be easily ing films for deep-frozen goods.
thermoformed and biaxially stretched.
Applications and uses: Multilayer packaging—
food and medical, cover/base, pouch, and solid films. O H

C N
N
1.7.2 Nylon 12
H
Nylon 12 has only one monomer, aminolauric n
acid. It has the necessary amine group on one end
and the acid group on the other. It polymerizes Figure 1.19 Chemical structure of nylon 12.

HO O O O

R + H2N R' NH2 C R C N R' N + H2O

O OH H H
n

Figure 1.17 Generalized polyamide reaction.

O H O

C N C
N C N

H O H

Figure 1.18 Chemical structure of nylon 6.

10 PLASTIC FILMS IN FOOD PACKAGING

1.7.3 Nylon 66 cheese, and coffee. Also used in wrapping fine art,
potable water, and electrical applications.
The structure of Nylon 66 is shown in Figure 1.20.
Some of the Nylon 66 characteristics are as
follows:
1.7.4 Nylon 66/610
• Outstanding balance of mechanical properties. Nylon 66/610 is a copolymer made from hexam-
• Outstanding toughness in equilibrium mois- ethylenediamine, adipic acid, and sebacic acid. Its
ture content. structure is represented in Figure 1.21.
Applications and uses: Flexible packaging for
• Outstanding chemical resistance and oil foodstuff and medical packaging such as IV bags.
resistance.
• Outstanding long-term heat resistance (at a
long-term continuous maximum temperature
ranging between 80 C and 150 C). 1.7.5 Nylon 6/12
• Offers low gasoline permeability and out- The structure of Nylon 6/12 is given in
standing gas barrier properties. Figure 1.22.
Some of the Nylon 6/12 characteristics are as
• High water absorption. follows:
• Poor chemical resistance to strong acids and
bases. • High impact strength,
• Very good resistance to greases, oils, fuels,
Applications and uses: Packaging meat and hydraulic fluids, water, alkalis, and saline,
cheese, industrial end uses, pouch and primal bag,
stiff packages, snacks, condiments, shredded • Low coefficients of sliding friction and high
abrasion resistance, even when running dry,
• Heat deflection temperature (melting point
O H O nearly 40 C higher than Nylon 12),
C N C • Tensile and flexural strength,
N C N
• Outstanding recovery at high wet strength.
H O H
n
Applications: Multilayer food packaging and boil
Figure 1.20 Chemical structure of nylon 66. in bag.

O O

C CH2 CH2 NH CH2 CH2 CH2 C CH2 CH2 NH CH2 CH2 CH2 CH2 CH2
NH CH2 CH2 C CH2 CH2 CH2 NH CH2 CH2 C CH2 CH2 CH2 CH2 CH2

O O
n

Figure 1.21 Structure of polyamide 66/610.

H O H

N C N
N C

H O
n

Figure 1.22 Chemical structure of nylon 6/12.

1: INTRODUCTION TO USE OF PLASTICS IN FOOD PACKAGING 11

1.7.6 Polyamide 6/69 (Nylon 6/69) copolymers will result in a product that behaves like
an amorphous polymer. These blends retain all of the
This resin is specifically suited for applications advantages of the Selars PA resin with some of the
requiring superior toughness and abrasion resis- mechanical property advantages of semicrystalline
tance. Applications and uses: Flexible packaging polyamide.
for foodstuffs, especially for packaging of ripening Applications and Uses: Used as a monolayer or
cheeses, shrinkable packaging of meat, cheese, sau- as a component of multilayer flexible films in meat
sage, and fish. and cheese packages as well as rigid packaging.
Multilayer or monolayer types are used in transpar-
1.7.7 Amorphous Polyamides ent hollow vessels (bottles), packaging films, and
deep-drawn plates.
Amorphous polyamides are designed to give no
crystallinity to the polymer structure. An example
is shown in Figure 1.23. 1.8 Ethylene
Vinyl Alcohol
The tertiary butyl group attached to the amine Copolymer
molecule is bulky and disrupts this molecule’s abil-
ity to crystallize. This particular amorphous poly- Ethylene
vinyl alcohol (EVOH) is a copolymer
amide is sometimes designated as Nylon 6-3-T. of ethylene and vinyl alcohol. Its structure is shown
Amorphous polymers can have properties that dif- in Figure 1.25. These materials are highly crystal-
fer significantly from crystalline types, one of line and are produced with various levels of ethyl-
which is optical transparency. ene content.
Some of the amorphous polyamide characteris- EVOH film has many desirable properties that
tics are as follows: are summarized as follows:

• Crystal-clear, high optical transparency, • Antistatic Properties: Since EVOH resin is a

• High mechanical stability, highly antistatic polymer, dust is prevented
from building up on the package when used
• High heat deflection temperature, as a surface layer.
• High impact strength, • Luster and Transparency: EVOH resins pro-
• Good chemical resistance compared to other duce a high gloss and low haze, resulting in
plastics, outstanding clarity characteristics. The use of
• Good electrical properties, EVOH resin as the outer surface of a package
provides excellent sparkle for improved pack-
• Low mold shrinkage. age appearance.
Another amorphous polyamide is called Nylon • Printability: With an
OH group in its molec-
6I/6T and is a mixture of the two polyamide seg- ular chain, the EVOH resin surface can be
ments shown in Figure 1.24. easily printed without special treatment.
Blending even low percentages (20%) of Selars • Resistance to Oil and Organic Solvents: EVOH
PA (PA 6I/6T) with nylon 6, nylon 66, and polyamide resins resist oils and organic solvents, making

H H

C C N N

O O
H3C CH3

CH3
n

Figure 1.23 Chemical structure of amorphous polyamide, nylon 6-3-T.

12 PLASTIC FILMS IN FOOD PACKAGING

them particularly suitable for packaging oily Flexible packaging: Processed meats, bag-in-box,
foods, edible oils, mineral oils, agricultural pes- red meat, cereal, pesticides, and agrichemicals.
ticides, and organic solvents.
• Weather Resistance: EVOH resins display
excellent weatherability. Even when exposed 1.9 Renewable Resource and
to outdoor conditions, the polymer retains its
color and does not become yellow or opaque. Biodegradable Polymers
Mechanical property changes are minimal, This section covers those polymers that are pro-
demonstrating an overall high resistance to duced from renewable resource raw materials such
weather effects. as corn, or that are biodegradable or compostable.
• Permeability: EVOH resins offer outstanding This is a developing area in packaging materials
gas (oxygen, carbon dioxide, nitrogen, and and though there are a relatively limited number of
helium) barrier properties, and maintain their polymers used commercially, they will certainly
barrier property over a wide range of humid- become more numerous and more common in the
ity. The oxygen-barrier properties of EVOH future.
vary according to the ethylene content in Biodegradable plastics are made out of ingredi-
the polymer. Packages containing EVOH ents that can be metabolized by naturally occurring
resins can effectively retain fragrances and microorganisms in the environment. Some
preserve the aroma of the contents within the petroleum-based plastics will biodegrade eventu-
package. At the same time, undesirable odors ally, but that process usually takes a very long time
are prevented from entering or leaving the and contributes to global warming through the
package. release of carbon dioxide.
Petroleum-based plastic is derived from oil, a
Film processing methods include monolayer film limited resource. The plastic present in renewable
extrusion (blown or cast), coextruded film extrusion raw materials biodegrades much faster and can be
(blown or cast), coextrusion blow-molding, profile almost carbon neutral. Renewable plastic is derived
coextrusion, and coating. from natural plant products such as corn, oats,
Applications and uses: Rigid packaging for wood, or other plants, which helps ensure the sus-
entrees, edible oils, juice, cosmetics, pharmaceuti- tainability of the earth. Polylactic acid (PLA) is the
cals, heating pipe, automotive plastic fuel tanks, most widely researched and used 100% biodegrad-
and packaging for condiments and toothpaste. able plastic packaging polymer currently, and is

H
H
N
N C C N
N C C
H O O
H O O
X Z

Figure 1.24 Structure of segments in polyamide 6I/6T.

H2C CH2 + H2C CH CH2 CH2 CH CH2

n
OH OH m
Ethylene Vinyl alcohol EVOH

Figure 1.25 The structure of EVOH copolymer.

1: INTRODUCTION TO USE OF PLASTICS IN FOOD PACKAGING 13

made entirely from corn-based cornstarch. Details Several interesting green polymers are discussed
on PLA are included in Section 1.9.3. in the next few paragraphs. These are ones for which
Cellophanet is a polymeric cellulose film made no public permeation data have been identified.
from the cellulose obtained from wood, cotton, Polyanhydrides are currently used mainly in the
hemp, or other sources. There are several modifica- medical device and pharmaceutical industry (Jain
tions made to cellulose called polysaccharides (cel- et al., 2005). Figure 1.26 shows the generalized
lulose esters) that are common including cellulose structure of an anhydride polymer and two polyan-
acetate, nitrocellulose, carboxymethyl cellulose hydrides that are used to encapsulate certain drugs.
(CMC), and ethyl cellulose. Details on cellophane Poly(bis-carboxyphenoxypropane) (pCCP) is rela-
and its derivatives are included in the sections tively slow to degrade. Poly(sebacic anhydride)
which follow this one. (pSA) degrades rapidly. Separately, neither of these
Polycaprolactone (PCL) is biodegradable polyes- materials can be used, but if a copolymer is made
ter that is often mixed with starch. Details on PLA in which 20% of the structure is pCCP and 80% is
are included in Section 1.9.3. pSA, the overall properties meet the needs of the
Polyhydroxyalkanoates (PHAs) are naturally pro- drug. Polyanhydrides are now being offered for
duced and include poly-3-hydroxybutyrate (PHB or general uses.
PH3B), polyhydroxyvalerate (PHV), and polyhy- Polyglycolic acid (PGA) and its copolymers
droxyhexanoate (PHH); A PHA copolymer called have found limited use as absorbable sutures and
poly(3-hydroxybutyrate-co-3-hydroxyvalerate) are being evaluated in the biomedical field, where
(PHBV) is less stiff and tougher, and may be used its rapid degradation is useful. That rapid degrada-
as packaging material. tion has limited its use in other applications. There

O O

C C
R1 O R2

General anhydride structure

O O

C C
O

CH2 CH2
O CH2 O

pCCP

C CH2 CH2 CH2 CH2 CH2

O CH2 CH2 CH2 CH2 CH2 C

O n

pSA

Figure 1.26 Polyanhydride chemical structures.

14 PLASTIC FILMS IN FOOD PACKAGING

has been patent activity on PGA films (Kawakami 1.9.3 Polylactic Acid
et al., 1998). The structure of PGA is shown in
Figure 1.27. PLA is derived from renewable resources, such
The following sections contain details of several as corn starch or sugarcane. PLA polymers are con-
of the more common biosourced/biodegradable sidered biodegradable and compostable. PLA is a
polymers used in packaging applications. thermoplastic, high-strength, high-modulus polymer
that can be made annually from renewable sources
to yield articles for use in either the industrial pack-
aging field or the biocompatible/bioabsorbable med-
1.9.1 Ethyl Cellulose ical device market. Bacterial fermentation is used
Ethyl cellulose is similar in structure to cellulose to make lactic acid, which is then converted to the
and cellulose acetate but some of the hydroxyl lactide dimer to remove the water molecule which
(
OH) functional groups are replaced on the cellu- would otherwise limit the ability to make high-
lose by the ethoxy group (
O
CH2
CH3). The molecular weight polymer. The lactide dimer,
structure of ethyl cellulose is shown in Figure 1.28. after the water is removed, can be polymerized
Applications and uses: Pharmaceutical applica- without producing water. This process is shown in
tions, cosmetics, nail polish, vitamin coatings, print- Figure 1.30.
ing inks, specialty coatings, and food packaging. Applications and uses: It is being evaluated as a
material for tissue engineering, loose-fill packaging,
compost bags, and food packaging.
1.9.2 Polycaprolactone
PCL is a biodegradable polyester with a low
melting point of around 60 C and a glass transition
temperature of about 260 C. PCL is prepared by
ring opening polymerization of ε-caprolactone O CH2
using a catalyst such as stannous octanoate. The
H2C CH3 EtO
structure of PCL is shown in Figure 1.29.
PCL is degraded by hydrolysis of its ester lin- CH O CH O
kages under physiological conditions (such as in the
human body) and has therefore received a great O CH CH O CH CH
deal of attention for use as an implantable bio- CH CH CH CH
material. In particular it is especially interesting for
the preparation of long-term implantable devices. HO OEt HO CH2
A variety of drugs have been encapsulated within
EtO
PCL beads for controlled release and targeted
drug delivery. PCL is often mixed with starch n
to obtain a good biodegradable material at a low
price.
Applications and uses: The mix of PCL and where OEt or EtO = O CH2 CH3
starch has been successfully used for making trash
bags in Korea (Yukong Company). Figure 1.28 Structure of ethyl cellulose.

O
H CH2 O
O C H O CH2 CH2 C
CH2 CH2 CH2
O
n n

Figure 1.27 PGA chemical structures. Figure 1.29 Structure of PCL.

1: INTRODUCTION TO USE OF PLASTICS IN FOOD PACKAGING 15

CH3 O CH3
H3C OH H3C
CH O
CH O CH OH
CH C
−Water CH
HO C CH O C
O
HO O C CH3
O CH3 O
n
O

Lactic acid Cyclic lactide monomer PLA

Figure 1.30 Conversion of lactic acid to PLA.

1.9.4 Poly-3-hydroxybutyrate
CH3 O
PHAs are naturally produced and include PHB
O CH CH2 C or PH3B, PHV, and PHH. A PHA copolymer called
PHBV is less stiff and tougher, and it may be used
n
as packaging material. Chemical structures of some
PH3B of these polymers are shown in Figure 1.31.

CH3 O H2C CH3 O

O CH CH2 C O CH CH2 C
1.10 Summary
Thin film packaging is an important market and
n
even though it is mature, new technical develop-
PHBV ments are expected in the years to come.

H2C CH3 O
References
O CH CH2 C
Jain, J.P., Modi, S., Domb, A.J., Kumar, N., 2005.
n Role of polyanhydrides as localized drug carriers.
PHV J. Controlled Release 103, 541
563.
Kawakami, Y., Sato, N., Hoshino, M., Kouyama,
Figure 1.31 Structures of several PHAs.
T., Shiiki, Z., 1998, Oriented polyglycolic acid
film and production process thereof. US Patent
5853639.
McKeen, L.W., 2011. Permeability Properties of
Plastics and Elastomers, Third ed. Elsevier.
McKeen, L.W., 2012. Film Properties of Plastics
and Elastomers, Third ed. Elsevier.
This page intentionally left blank
 2 Polypropylene Films
Teresa Calafut

Polypropylene film is one of the most versatile excellent impact strength, and low moisture perme-
packaging materials. It is economical due to its low ability but provide only poor barriers to gases, such
density and is replacing other materials, such as as oxygen and carbon dioxide, some perfumes, and
polyethylene, polyvinyl chloride, polyester, and cel- oil such as peppermint oil. Clarity of unoriented ran-
lophane, in packaging applications. Almost 90% of dom copolymer film is moderate and is affected by
plastic packaging is used in food applications; other processing conditions. Because its physical proper-
applications include film packaging for stationery ties are balanced, unoriented film is easier to pro-
products, cigarettes, and textiles (Goddard, 1993; cess on bag-making equipment than cast-oriented
Graves, 1995; Shell Polypropylene Film Grade film, and slitting and sealing is easier in the trans-
Resins Guide, 1992). verse direction. Applications include packaging for
Both random copolymers and homopolymers are shirts, hosiery, bread, and produce, used as a
used in film production. Films can be unoriented, uni- strength and barrier layer in disposable diapers, and
axially oriented, or biaxially oriented and are defined used in electrical capacitors (Barnetson, 1996;
as sheet materials that are less than 0.254 mm Fortilene Polypropylene Properties, Processing, and
(10 mil) in thickness; thicker films are referred to as Design Manual, 1981; Himont, 1992; Miller et al.,
sheets. Resins with melt-flow indexes of B2
8 g/ 1991; Moore, 1996; Polymers in Contact with Food,
10 min are generally used in films, although higher 1991; Thompson et al., 1987).
melt-flow rate resins are also used. Higher melt-flow
resins are used in cast film processes (Fortilene
Polypropylene Properties, Processing, and Design
Manual (1981); Capshew (1997). 2.2 Cast Film
Cast processes are usually used to produce uniaxi-
ally oriented film, oriented in the machine direction.
2.1 Unoriented Film Physical properties of the film depend on the degree
of orientation, and a film is produced with different
Unoriented polypropylene films can be produced surface properties on each side. Oriented cast poly-
by casting or blown film processes. Chill roll casting propylene film is clear and glossy, with high tensile
and tubular water quenching are commonly used. strength. It is about three times stiffer and stronger
Conventional air quenching, widely used for polyeth- than low-density polyethylene film. Cast film pro-
ylene, produces brittle films with poor clarity in poly- vides good moisture barrier properties and scuff resis-
propylene; however, newer polypropylene resins and tance at low cost. Low-temperature brittleness is a
copolymers developed for air-quenched processes problem with homopolymer polypropylene film; this
can provide economical alternatives to polyethylene. can be overcome by the use of a copolymer resin
The tubular water-quench process is commonly used (Fortilene Polypropylene Properties, Processing, and
to produce monolayer film (Barnetson, 1996; Design Manual, 1981; Graves, 1995).
Fortilene Polypropylene Properties, Processing, and A water bath is sometimes used instead of a chill
Design Manual, 1981; Himont, 1992; Miller et al., or casting roll; the water bath process quenches the
1991; Moore, 1996; Polymers in Contact with Food, melt on both sides at the same time, producing a
1991; Thompson et al., 1987). film with the same surface properties on each side.
Unoriented films have a very soft hand and are The machine direction orientation in the water bath
easily heat sealed. They exhibit good heat stability, process is somewhat different than that obtained
low flexural moduli, excellent puncture resistance, using the casting roll, and the very rapid quenching

Ebnesajjad: Plastic Films in Food Packaging. DOI: http://dx.doi.org/10.1016/B978-1-4557-3112-1.00002-8

© 1998 Elsevier Inc. All rights reserved. Reproduced from a chapter in: Maier, Polypropylene — The Definitive User’s Guide and Databook (1998). 17
18 PLASTIC FILMS IN FOOD PACKAGING

lowers the crystallinity, producing a tougher film adjustable. It is a widely used process, more com-
(Fortilene Polypropylene Properties, Processing, mon than the tubular process, and a glossy, trans-
and Design Manual, 1981). parent film is produced. Biaxial orientation results
Tear initiation, by impact, puncture, or ripping, is in increased toughness, increased stiffness,
difficult in oriented polypropylene (OPP) films; once enhanced clarity, improved oil and grease resis-
initiated, however, the resistance to tear propagation tance, and enhanced barrier properties to water
is low. Tear strength depends on grade and process vapor and oxygen. Impact resistance, low-
conditions and on whether the tear propagates in the temperature impact resistance, and flexcrack resis-
machine or transverse direction. A tear strip is usu- tance are substantially modified. BOPP films are
ally incorporated in OPP film packs to facilitate used in food packaging and are replacing cello-
opening (Barnetson, 1996; Fortilene Polypropylene phane in applications such as snack and tobacco
Properties, Processing, and Design Manual, 1981). packaging due to favorable properties and low cost
(Fortilene Polypropylene Properties, Processing,
and Design Manual, 1981; Goddard, 1993).
2.3 Biaxially Oriented Film Oriented films can be used as heat-shrinkable
films in shrink-wrap applications or can be heat set
Biaxially oriented polypropylene (BOPP) film is to provide dimensional stability. Heat sealing is dif-
film stretched in both machine and transverse direc- ficult in BOPP films, but can be made easier by
tions, producing molecular chain orientation in two either coating the film after processing with a heat-
directions. BOPP film is produced by a tubular pro- sealable material (such as polyvinylidene chloride)
cess, in which a tubular bubble is inflated, or a ten- or by coextrusion with one or more copolymers
ter frame process, in which a thick extruded sheet before processing to produce layers of film.
is heated to its softening point (not to the melting Copolymers used in sealing layers must have high
point) and is mechanically stretched by 300
400%. gloss and clarity and should have low sealing tem-
Stretching in the tenter frame process is usually peratures to prevent distortion of the oriented poly-
4.5:1 in the machine direction and 8.0:1 in the mer during sealing. Random copolymers containing
transverse direction, although these ratios are fully 3
7% ethylene are often used as sealing layers; the

Table 2.1 Properties of OPP Films

ASTM Test Cast, Uniaxial Biaxial

Property Method Orientation Orientation
Area factor in 2/lb./1 mil film
30,400
31,300 30,600
3
Specific gravity (g/cm ) D1505 0.885
0.905 0.902
0.907
Tensile strength (psi) D882 4500
7000 7500
40,000
Elongation (%) D882 550
1000 352475
Tear strength (g/mil propagation) D1922 25 MD 600 TD 3
10
Fold endurance D2176 Very high Excellent
24 h % water absorption D570 0.005 0.005
Water vapor transmission rate (g/mil/ E96 0.7 0.25
100 in.2/24 h at 100 F)
Oxygen permeability (cm3/100 in.2/mil/24 h/ D1434 150
240 160
atm. at 77 F)
Heat-sealing temperature range ( F)
285
400

Gloss (%)
90 95
Haze (%)
1
2 1
2
MD, machine direction; TD, transverse direction.
Table 2.2 Properties of Novolen Cast Filma
Block
Property Unit Test Method Copolymer Random Copolymer Homopolymer
Grade 2309KX 3200 MCX 3520 LX 1125N 1127MX 1325L
Additives None None Antiblock Slip, Slip, Slip,
agents antiblock antiblock antiblock
agents agents agents
Melt flow g/10 min ISO 1133 4 8 5 11 8 5
rate
Gloss 20 % DIN 67530 5 130 130 110 95 115
Haze % ASTM 1003 28 0.5 0.3 2.3 3.0 1.7
Tensile Machine MPa DIN 53455 55 37 32 42 44 35
strength at direction
break Transverse MPa DIN 53455 36 35 30 38 40 33
direction
Elongation Machine % DIN 53455 750 730 750 680 700 750
at break direction
Transverse % DIN 53455 720 750 760 720 730 780
direction
Dart drop g ASTM 1709 500 450 . 800 280 300 800
impact
resistance
F50
Modulus of Machine MPa DIN 53121 650 480 300 700 680 370
elasticity in direction
flexure Transverse MPa DIN 53121 640 470 310 670 650 350
direction
Coefficient DIN 53375 0.90 Not Not 0.25 0.17 0.13
of friction measurable measurable
a
50 μm gauge; Data was obtained using film specimens prepared by internal standards. Film properties depend considerably on processing conditions. This must be taken into account when
comparing these data with data obtained under different processing conditions.
20 PLASTIC FILMS IN FOOD PACKAGING

lower melting point (, 132 C; ,270 F) results in a Fortilene Polypropylene Properties, Processing, and
30% increase in line speeds, and they can be Design Manual, 1981. Supplier Design Guide.
recycled with no significant loss of strength or clar- Soltex.
ity. Coating or coextrusion increases the barrier prop- Goddard, R., 1993. Reference Book (ISBN 0-902799-
erties of BOPP film, decreasing its permeability to 34-7). Packaging Materials. Pira—The Research
gases. Common barrier polymers are ethylene vinyl Association.
alcohol, polyvinylidene chloride, and polyamide; five Graves, V., 1995. Reference Book (M603.1.6).
or more layers may be coextruded or laminated, or Polypropylene: A Commodity Plastic Reaches
the barrier polymer can be dispersed in the matrix Record Highs in 1994 Production, Modern
polymer (Fortilene Polypropylene Properties, Plastics Encyclopedia 1996. McGraw-Hill.
Processing, and Design Manual, 1981; Goddard, Himont, 1992. Seize the Opportunity to Open New
1993; Polymers in Contact with Food, 1991). Markets and Reduce Costs, Supplier Marketing
Some typical properties of cast, uniaxially ori- Literature (PL-007). Himont.
ented film, and BOPP films are listed in Table 2.1. Miller, R.C., Blair, R.H., Vernon, W.D., Walsh, T.S.,
Properties of films made using Novolen (BASF) 1991. Reference Book (M603.1.2). Polypropylene,
homopolymers, random copolymers, and block Modern Plastics Encyclopedia 1992. McGraw-Hill.
copolymers are listed in Table 2.2 (Fortilene Moore, E.P., 1996. Reference Book (ISBN 3-446-
Polypropylene Properties, Processing, and Design 18176-8). Fabrication Processes, Polypropylene
Manual, 1981; Novolen Polypropylene (PP), 1992; Handbook. Carl Hanser Verlag.
Thompson et al., 1987). Novolen Polypropylene (PP), 1992. Supplier
Technical Report (F 573e). BASF Plastics.
Polymers in Contact with Food, 1991. In: Conference
References Proceedings (ISBN 0 90 2348 66 3). Rapra
Technology Ltd.
Barnetson, A., 1996. Monograph (ISBN 1-85957- Shell Polypropylene Film Grade Resins Guide,
068-2). Plastic Materials for Packaging. Rapra 1992. Supplier Technical Report (SC: 1209
93).
Technology Limited Ltd. Shell Chemical Company.
Capshew, C., 1997. Reference Book (vol. 73, No. 12). Thompson, W.R., Bortolini, W., Young, D.R.,
Polypropylene: A Commodity Plastic Reaches Davies, J.K., 1987. Reference Book (M603.1).
Record Highs in 1995 Production, Modern Plastics Polypropylene, Modern Plastics Encyclopedia
Encyclopedia 1997 McGraw-Hill. 1988. McGraw-Hill.
 3 PE-Based Multilayer Film Structures
Thomas I. Butler1 and Barry A. Morris2
1 2
Blown Film Technology, LLC, Lake Jackson, TX, USA; DuPont Packaging and Industrial Polymers, Wilmington, DE, USA

3.1 Introduction food packaging films to the heavy-duty shipping

bag market.
Flexible packaging is used to deliver a product Coextrusion can reduce the number of process
from the manufacturer or distributor to the retailer operations required when several polymers are
or ultimate consumer and protect that product dur- needed to obtain the desired properties (Smith,
ing shipping, display, and storage. Multilayer flexi- 1975). Eliminating process steps saves labor, equip-
ble packaging is the combining of two or more ment overhead, and reduces turnaround time.
layers into a composite web or tube that provides The more operations that can be combined into a
functional, protective, or decorative properties. The single process means more space available for
introduction of new polymers, the development of other equipment and less scrap generated with mul-
new processing equipment technology, and the tiple process steps (Schrenk and Finch, 1981).
emergence of new packaging applications have Coextrusion can eliminate the use of solvent-based
resulted in good growth rates in coextruded and adhesives. This may provide some raw material
laminated structures. Whatever the application or cost savings and, with increasing regulations on
use, polymer materials are selected and the entire solvent use and disposal, the incineration or recov-
packaging structure is designed to meet the perfor- ery cost could be high.
mance requirements specific to that particular The number of polymers available for extrusion
application. These could include one or more of the have increased in recent years (Schrenk and
following: Veazey, 1984). There are several polymers to
choose from with various attributes, such as:
• specific performance properties,
• reduced cost, • high barrier
• reduced number of processes. • selected permeation rate
• adhesion
The requirement for specific performance prop- • high-strength sealing
erties sometimes cannot be met by one polymer or
even with polymer blends extruded in a monolayer • easy opening (peelable) sealing
film. Blending may not be desirable if the polymers • low-temperature sealing
are incompatible. Coextrusion with a high-strength • high hot tack sealing
or high-barrier polymer can allow significant down
gauging while maintaining or improving key prop- • high tensile strength
erties. Heat-seal polymers can be incorporated into • high impact strength
a film structure to improve packaging line effi- • high tear strength
ciency or speed.
• high modulus
Multilayer flexible packaging structures can
lower the cost of many film structures by reducing • high-temperature resistance
the amounts of the expensive polymer used, • low-temperature impact
increasing the less costly polymers, using recycled
• high clarity
material, or reducing film thickness. Competitive
advantages can be achieved for many film struc- • abrasion resistance
tures, ranging from the high technology barrier • chemical resistance

Ebnesajjad: Plastic Films in Food Packaging. DOI: http://dx.doi.org/10.1016/B978-1-4557-3112-1.00003-X

© 2013 Elsevier Inc. All rights reserved. Adapted from a chapter in: Wagner, Multilayer Flexible Packaging (2009). 21
22 PLASTIC FILMS IN FOOD PACKAGING

• low taste and odor Polymer films may be manufactured by blown

• high cling film or cast film extrusion or by extrusion coating a
polymer onto another substrate, such as paper or
• low slip aluminum foil. Blown films are made by melting
• stabilized and pumping polymer through an annular die
• degradable (Potts, 1987). Cast films are made by melting and
pumping polymer through a flat die. The extrusion
• antistatic
coating process is similar to the cast film process
• antifog except that the molten polymer is coated directly
• pigmented onto another material. The manufacturing process
selected is governed by factors such as
• thermoformable.

This list of polymer performance attributes will • the job size,

continue to grow as application requirements are • the packaging material to be made,
identified. • the end-user packaging performance require-
A critical factor in developing successful flexible ments,
packaging applications has always been a good
understanding of the target application. The perfor-
• the equipment availability.
mance properties required by the application and
Cast film extrusion typically operates at much
economic comparisons should be evaluated against
higher output rates than blown film, so for larger
the many alternative structures. Performance
volume production, it has an advantage with high-
requirements may include all user requirements in
usage single-use films such as stretch film. Blown
the chain of use. For consumers, this may mean
film extrusion typically runs at a lower rate and
that the packaging
may result in film with improved physical proper-
• protects the product, ties. Blown film also allows for bubble-size adjust-
ment and thus the film width produced. This is a
• identifies the product, key advantage when many different film widths
• is easy to open. must be produced on the same machine. There are
many existing coextrusion processes, ranging from
For retailers, the packaging may provide two-layer to eleven-layer capability.
The coextrusion process is used to combine mul-
• eye-catching graphics that help sell the prod- tiple materials into a single film (Karagiannis et al.,
uct, and 1987; Schrenk, 1978, 1984). Both blown films and
• the proper physical form for display cast films may be coextruded in three, five, seven,
purposes. nine, or more layers. The combination of multiple
materials in a single film is a cost-effective means
For the packager, flexible packaging may need of combining the performance properties of several
to provide polymers in a single film (Soutar, 1989). One
example would be the coextrusion of a barrier poly-
• high packaging speeds, mer such as ethylene vinyl alcohol (EVOH) or
polyvinylidene chloride (PVDC) with a sealant
• low scrap rates,
resin such as linear low-density polyethylene
• meet the functional requirements for protect- (LLDPE), ethylene vinyl acetate (EVA), or a poly-
ing the product inside the package. olefin plastomer (POP). Coextrusion is widely used
in producing high-performance packaging films,
Specific performance requirements will vary such as those used to package foods. It is also
greatly from one package to another, but in every increasingly used to produce industrial films, such
case, meeting the performance requirements will as stretch film.
help assure proper protection of the goods being As coextrusion technology has evolved over the
packaged. past 30 years, the number of layers has increased
3: PE-BASED MULTILAYER FILM STRUCTURES 23

(Arvedson, 1984). Whereas 5
10 years ago a five- tenter frame process. Oriented polyethylene (PE)
layer line was state of the art, now it is common to films are usually manufactured using a double bubble
see seven-layer and higher lines installed (Bode, process. Polyvinyl chloride (PVC) films may also be
1986; Gates, 1987, 1989). In addition to the advan- oriented. Some oriented films are cross-linked further
tages described earlier of combining different poly- to enhance their performance. Compared to other
mer materials, the extra layer capability gives the films, oriented films typically provide improved opti-
converter greater flexibility and control over its cal properties, higher stiffness, and increased shrink-
process (Gates, 1988; Wright, 1983). For example, age during packaging, which leads to improved
if a five-layer line was designed to produce five package appearance. Coextruded barrier films may
layers of equal thickness, it may be a challenge to also be oriented, typically using a double bubble pro-
produce an unbalanced structure such as a barrier cess. Applications include shrink bags and sausage
cereal liner: (60% high-density polyethylene casings.
(HDPE)/5% tie/5% EVOH/5% tie/25% EVA) Layer multiplication technology, developed at
(Arvedson, 1984). The line may have to be slowed Dow Chemical in the 1980s (Im and Schrenk,
down to achieve the desired HDPE thickness 1988; Schrenk, 1975; Schrenk et al., 1992a,b) and
because of extruder output limitations. At low line used primarily for optical films (Alfey and Schenk,
speed, however, controlling the thin layer thickness 1973; Pointing et al., 2009), is starting to see appli-
can be difficult since the extruders may be over- cation in packaging structures. The concept
sized. Making the same structure on a seven- or involves forming the layers in a coextrusion feed-
nine-layer line is easier. The HDPE layer can be block, dividing them vertically and stacking the
split into more than one layer and fed by multiple layers on top of one another, as shown in
extruders, allowing for greater output and control Figure 3.1. Each multiplier module results in a dou-
over the process. bling of the number of layers. By adding several
Another advantage of greater layer capability is modules in series, hundreds of layers have been
the ability to split barrier layers into two or more achieved. Improved strength and barrier properties
layers (Ossmann, 1986). For example, a simple have been claimed (Bernal-Lara et al., 2005; Kerns
polyamide (PA) barrier film (PA/tie/LLDPE) may et al., 1999; Mueller et al., 1997; Oliver, 2009;
be split into (PA/tie/PA/tie/LLDPE). Separating the Schirmer et al., 2010; Wang et al., 2000). For
barrier layers insures barrier continuity—if a pin- example, researchers at Case Western Reserve
hole develops in one layer, the second layer still show an increase in oxygen barrier of polyethylene
may be intact. Thin layer orientation and property oxide (PEO) of 100 times or more when the layer
nonlinearity with thickness suggest that two thin dimensions reach the nanometer domain. They
layers may have better barrier performance than a attribute this to changes in the crystalline structure
single layer of the same total thickness (DeLassus, (Wang et al., 2000). Time will tell whether this can
1985). be applied to more conventional polymers used in
Polymer films may be stretched, or oriented, packaging.
to impart improved properties useful for packaging While originally developed for flat die coex cast
applications. Oriented film is produced by a double sheet or film extrusion, recently Schirmer (1998,
bubble or tenter frame process. A thick film 2002) and Dow Chemical (Dooley et al., 2011)
or sheet is manufactured, typically 250
1000 μm have introduced blown film versions. Zumbrunnen
(10
40 mil), and is subsequently oriented (stretched) of Clemson University has been promoting technol-
in a semisolid state to many times its original dimen- ogy based on chaotic advection that supposedly
sions (Finch, 1986). The multiple step production is reproducibly creates unique morphologies, includ-
normally done in a continuous operation (Sacharuk, ing microlayers of barrier and other polymers
1988). The sheet stretching or orientation may occur (Zumbrunnen and Zumbrunnen, 2009). As some of
sequentially in the machine and transverse directions the original Dow patents have now expired, equip-
or the stretching may occur simultaneously in both ment suppliers have begun to promote their own
directions. After orienting, the films are typically versions in the market.
12.5
25 μm (0.5
1.0 mil) thick. The film is typi- Lamination is used to combine two or more
cally supplied in roll form. Biaxially oriented poly- films into a single packaging structure (Djordjevic,
propylene (BOPP) is most often manufactured by a 1988). It allows materials that cannot be coextruded
24 PLASTIC FILMS IN FOOD PACKAGING

to be combined. An example would be an aluminum are also used for nuts and salty snacks. Metalized
foil and a PE sealant film lamination. More compli- films may be coated to provide sealability or may
cated laminations may include different polymer be laminated to another polymer film to provide
films, paper, and foil. Laminations are usually either improved properties, such as seal integrity. Other
adhesive laminations or extrusion laminations. In coatings, whether to provide barrier properties or
adhesive laminations, the substrates are combined other functionality, may also be applied to polymer
using an adhesive material (Djordjevic, 1989). In films used in flexible packaging.
extrusion laminations, the substrates are adhered
together using a molten polymer; often low-density 3.2 Polymer Selection
polyethylene (LDPE) is used as the adhesive layer.
Lamination can also protect the printing ink by plac- Polymers are selected for the specific perfor-
ing it between layers, thus providing superior gra- mance that they provide and are combined in the
phics for surface-printed packages. For example, final package design to meet all the requirements
glossy stand-up pouches have a reverse-printed outer for the specific application in which they are being
layer laminated to structural and sealant materials. used. Often, there are many different material com-
Laminations are also used to provide oxygen, mois- binations or film constructions that will meet an
ture, or light barrier. The barrier functionality may application’s minimum performance requirements
be provided by foil or a barrier polymer such as (Veazey, 1983). In these cases, the packaging struc-
EVOH or PVDC. Most high-value processed meat ture selected may be based on considerations such
and cheese packages are laminations. This allows as availability from multiple suppliers or ability to
various materials to be combined into the packaging provide differentiation over competitive packaging.
structure and for superior graphic properties when For example, a box with an inner liner or a stand-
using reverse printing. Since laminations are more up pouch may be used, each combination providing
costly than coextruded or monolayer films, lamina- the minimum requirements for product protection
tions are generally reserved for use in higher value and safety. One consumer goods company may
applications. select a box and inner liner and another consumer
Metallization is used to apply a thin coating, typ- goods company may elect to package their product
ically aluminum, to a polymer film. This provides in a stand-up pouch for the same product; or one
improved oxygen and water barrier properties as manufacturer may choose to use a stand-up pouch
well as forming a light barrier. The major use for and another manufacturer may choose to use a
metalized film is potato chip bags. Metalized films pillow pouch for the same product.

Die
Layer
multipliers Extruder A

Feedblock
B

Sheet or film Skin layer

Extruder B

Recombine Stack Divide Feedstream

Figure 3.1 Schematic of layer multiplication technology. Source: Taken from Dooley et al. (2011).
3: PE-BASED MULTILAYER FILM STRUCTURES 25

Polymers are chosen for individual layers to • machinability

achieve specific performance properties. For exam- • economics.
ple, polymers could be selected to contribute to the
film’s An individual layer could consist of virgin poly-
mer, blends of polymers, regrind/recycled material,
• tensile strength or high levels of additives (Daniels, 1985). Most
• permeation resistance thermoplastic polymers can be coextruded together.
• sealability PE is the largest thermoplastic used in flexible
packaging applications. There are many PE homo-
• adhesion polymers and copolymers that are available for use.
• optics Some common polymers used in flexible packaging
• formability structures are included in Table 3.1.

Table 3.1 Common Polymers Used for Flexible Packaging Applications

Polymer Name Abbreviation Density (g/cm3)

Ethylene acrylic acid EAA 0.925
0.950
Ethylene carbon monoxide ECO 0.930
Ethylene ethyl acrylate EEA 0.925
0.950
Partially neutralized ethylene (meth)acrylic acid (ionomer) ION 0.940
0.950
Ethylene methacrylic acid EMAA 0.925
0.950
Ethylene methyl acrylate EMA 0.930
0.950
Ethylene vinyl acetate EVA 0.925
0.945
Ethylene vinyl alcohol EVOH 1.14
1.16
Maleic anhydride grafted polyethylene PE-g-MAH 0.91
0.940
High-density polyethylene HDPE 0.940
0.965
High-molecular weight HDPE HMW
HDPE 0.940
0.962
Linear low-density polyethylene LLDPE 0.915
0.940
Low-density polyethylene LDPE 0.915
0.925
Medium-density polyethylene MDPE 0.925
0.940
Metallocene polyethylene m-LLDPE 0.865
0.960
Polyolefin plastomer/elastomer POP/POE 0.856
0.915
Enhanced polyethylene EPE 0.900
0.925
Polyamide (nylon) PA 1.12
1.14
Polybutylene PB 0.909
Polycarbonate PC 1.2
Polyethylene terephthalate PET 1.3
Polypropylene PP 0.89
0.902
Polystyrene PS 1.04
Polyvinyl chloride PVC 1.16
Polyvinylidene chloride PVDC 1.7
Ultralow-density polyethylene ULDPE 0.90
0.915
26 PLASTIC FILMS IN FOOD PACKAGING

Some of the key performance requirements for 3.3 Mechanical Properties

high-performance flexible packaging include the
following: Most published film data sheets are developed
from monolayer films. A coextruded structure’s
• Barrier properties: to keep oxygen, water, light, mechanical strength may be estimated using the
flavor, or grease from entering or leaving the law of mixtures as shown in Eq. (3.1), i.e. the sum-
package. Barrier properties may be character- mation of the tensile strength per unit layer thick-
ized by measuring the oxygen and water vapor ness, multiplied by its thickness, divided by the
permeation through the packaging material. total thickness.
• Selective permeability: to allow oxygen and P
n
carbon dioxide to permeate through the pack- ðt1  M1 Þ 1 ðt2  M2 Þ 1 ti  Mi
i53
age at a calculated rate to extend the shelf life M5 P
n (3.1)
of fresh-cut produce. Oxygen, carbon dioxide, t1 1 t2 1 ti
i53
and water vapor permeability are frequently
measured and specified. where
• Abuse resistance: to prevent damage to the
packaging material and its contents during M 5 estimate of coextruded film mechanical
shipping and storage. Abuse resistance may property,
include puncture resistance, tear strength, ti 5 polymer layer thickness of layer i,
impact strength, and modulus. Some packages
require good toughness at refrigerated or Mi 5 polymer mechanical property/unit thickness
freezer temperatures. of layer i,
• Sealability: to allow packages to be made at n 5 number of layers.
high packaging speeds and keep the product
secure by preventing the package seams from Determining multilayer film properties with
failing. Sealability may be characterized by Eq. (3.1) does not account for any interactions (pos-
heat-seal and hot tack strength, heat-seal and itive or negative) between layers, or the influence
hot tack initiation temperatures, seal-through- of fabrication variables or orientation. Sometimes
contamination performance, caulkability, and unfavorable interactions can lead to interlayer
seal integrity. Hot tack refers to the seal strength destruction, such as when a very ductile layer is
while still in the molten state. It is critically adhered to a brittle layer, resulting in the film exhi-
important for packages where the product drops biting the properties of the brittle layer
into the package while the seal is still partly (Hessenbruch, 1988). Figure 3.2 shows the effect of
molten, but also for horizontally filled packages a LDPE core versus a HDPE core in a three-layer
involving gussets where the spring-back nature coextrusion structure (A/B/A) with increasing
of the folded film creates an opening force. LLDPE polymer content in the skin layers, on dart
Caulkability refers to the ability of the sealant impact.
material to flow, filling in gaps around folds, In the first case, the dart impact strength is a lin-
wrinkles, or product contaminants. ear function of LLDPE content and can be approxi-
mated by the law of mixtures. However, in the
• Machinability: to allow the packaging films to second case, dart impact strength is nonlinear and
be easily run on high-speed automatic packag- is disproportionately negatively influenced by the
ing equipment. Machineability is governed HDPE content. The LLDPE polymer is a highly
largely by film modulus, film thickness, seal elastic material, which allows it to absorb high
properties, and coefficient of friction. levels of impact energy. The LDPE, while not as
• Consumer appeal: package appearance is an elastic as LLDPE, does not detract from the impact
important factor driving product preference by strength. HDPE is more brittle than the LLDPE
consumers. Appeal is largely related to print polymer and tends to form localized stress concen-
quality and package gloss. Film thickness and tration sites resulting in lower dart impact values
modulus may also impact consumer appeal. for the film structure.
3: PE-BASED MULTILAYER FILM STRUCTURES 27

Dart impact strength converting process can impact stiffness. In some

Influence of core layer polymer A/B.A Coextrusion
cases, extrusion laminating two stiff films may
350
build in greater stiffness than adhesive lamination,
300 since extrusion lamination allows the layers to be
Dart impact f50m (g)

250 separated further apart.

200

150

100
3.4 Barrier Properties
LLDPE/LDPE/LLDPE
50 LLDPE/HDPE/LLDPE
Flexible packaging films are used to provide bar-
0
rier to gases such as the following:
0 20 40 60 80 100
LLDPE in film (%) • oxygen
A layer 1.0MI, 0.920g/cm3 LLDPE
B1 layer 0.7MI, 0.965g/cm3 HDPE
Total output = LB/HR/in.
Film thickness = 1.5mil • nitrogen
B2 layer 2.0MI, 0.918g/cm3 HDPE BUR = 2.5
• carbon dioxide
Figure 3.2 Influence of polymer in core layer. • water vapor.

Other applications may require taste and odor

Another reason that mechanical property data resistance properties. Permeation occurs in polymer
from monolayer film can be misleading is because films and this mechanism allows interaction with
some properties have a bias versus tested thickness; the environment. Molecules may permeate through
that is, there may not be a linear relationship a package in a three-step process. First, the mole-
between the mechanical property and film thick- cules must dissolve into the film structure. Then
ness. Also, the film-making process itself can the molecules will diffuse through the film layers.
impart differences between coextruded films and And, finally, the molecule will desorb on the oppo-
monolayer films. For example, the stress history site side. The molecule can move either from out-
may differ due to quenching differences between side the film into the package or from inside to
mono- and multilayer films, resulting in differences outside. This permeation happens due to a concen-
in orientation and properties (Morris, 1998). tration or pressure gradient and is sensitive to tem-
Therefore, the law of mixtures for coextruded films perature and, for many polymers, relative humidity.
may be used for estimates, and film properties The permeation rate of a material through a poly-
should be measured. mer is a function of the diffusivity at steady state
Film stiffness affects times solubility in the polymer, as shown in
Eq. (3.2). Diffusivity is also a function of solubility
• machinability on packaging equipment, especially at the low solubility levels.
• wrinkling,
• the handling or feel of the final package, and P5D  S (3.2)

• in some cases, the package function (e.g. a where

stand-up pouch).
P 5 permeability of a material through a polymer
Multilayer film stiffness is a function of the stiff- (g/s-cm),
ness (modulus), thickness, and position of each
layer. Morris and Vansant (1997) showed that the D 5 diffusivity of a material through a polymer
outermost layers in a multilayer film have the (cm2/s),
greatest impact on stiffness. Like an I beam, sepa- S 5 solubility coefficient of a material in a poly-
rating stiff layers in a structure is an effective way mer (g/cm3).
to impart stiffness to it. Thus, using a stiff sealant
layer can help build in stiffness and allow the total Permeation rates are usually measured at steady-
structure to be down gauged. Furthermore, the state conditions. The adsorption of a material can
28 PLASTIC FILMS IN FOOD PACKAGING

significantly influence the permeation rates, and if Table 3.2 shows a sample calculation of moisture
the adsorption mechanisms are of sufficiently long transmission rates based on permeability factors for
duration, this may prevent steady-state conditions a three-layer film typical for a cereal liner applica-
from being reached during the expected shelf tion using Eqs (3.3) and (3.4). This apparent two-
life of the package. Thus, in these instances, the layer film is a typical cereal liner structure that is
polymer location in a film structure could influ- generally made on a three-layer blown film line
ence actual permeation rates during a package’s with the HDPE layer split into two layers due to
shelf life. extruder size limitations.
The gas transmission rate at steady state through For many high-barrier films, the overall perme-
a given polymer is inversely proportional to the ability rate is controlled by the highest barrier poly-
layer thickness. The permeation coefficient through mer. Permeability rates are sensitive to temperature
a multilayer film structure may be estimated by and will increase as ambient temperature increases
summing the permeation resistance of each layer, and follow the Arrhenius equation. Some polymer’s
as shown in Eq. (3.3): permeability rates are also a function of relative
humidity and increase with increasing relative
1 f1 f2 fn humidity. Table 3.3 lists some oxygen permeability
5 1 1?1 (3.3)
P P1 P2 Pn data for various polymers ranked from the lowest
to the highest measured at 1.0 mil, 23 C, and 0%
where relative humidity.
Table 3.4 lists the moisture transmission rate
P 5 coextruded film permeation coefficient, data for various polymers from the lowest perme-
ation to the highest, measured at 1.0 mil, 100 F
fn 5 polymer n layer thickness ratio, (37.8 C), and 90% relative humidity.
Pn 5 polymer n permeation coefficient. Understanding the package environment during
filling, processing, distribution, and storage is
The actual transmission through a coextruded required to determine the permeation needs of a
film is then calculated as shown in Eq. (3.4). multilayer flexible package. Inadequate understand-
ing of the product barrier requirements poses a
P
TM 5 (3.4) design problem in predicting shelf life from gas
tt transmission data. Packagers must rely on extensive
shelf-life testing of individual food products to
where evaluate barrier film performance requirements.
Taste and aroma barrier can be very important in
TM 5 transmission of film, some packaging applications. It is not possible to
tt 5 total thickness of coextruded film. predict from common gas transmission data the

Table 3.2 Sample Calculation of Moisture Transmission Rate

HDPE HDPE EVA
0.9 0.8 0.3 mil
45% 40% 15%
P(HDPE) 5 0.6 g 3 mil/100 in. /day2

P(EVA) 5 2.0 g 3 mil/100 in.2/day

1/P 5 [(0.45/0.6) 1 (0.4/0.6) 1 (0.15/2.0)] 5 1.49
P 5 0.67
TM 5 0.674/2.0 5 0.34 g/100 in.2/day moisture transmission
Basis at steady state conditions
3: PE-BASED MULTILAYER FILM STRUCTURES 29

polymer’s aroma and flavor barrier to other chemi- where

cals. The chemical component’s molecular size and
solubility will determine the permeation rates in the TR 5 transmission rate of a gas through film
polymer. (cm3/(day 3 atm)),
Economics is a critical concern in all flexible P 5 permeability coefficient of a gas through
packaging applications. Many factors are involved polymer (cm3 3 mil/(100 in 2 3 day 3 atm)),
in determining the value a polymer is providing.
For example, when comparing the cost of two bar- t 5 thickness of polymer (mill),
rier polymers, the comparison should be based on A 5 surface area of polymer exposed to a gas
an equal transmission rate and package surface (in.2).
areas at the target application conditions (tempera-
ture and humidity). Use Eq. (3.5) to determine the Table 3.5 shows the calculations required to
best barrier polymer value: compare two barrier polymers. First, the equivalent
thickness of each polymer that will provide the
A 1 same barrier property is determined using Eq. (3.5).
TR 5 P   (3.5)
100 t Then, the cost of each polymer is determined

Table 3.3 Oxygen Permeability Coefficients for Various Polymers

Oxygen Permeability Coefficients

1. 0 mil, 73 F (23 C), 0% RH
Polymer Type Oxygen Permeability Coefficient (cm3 3 mil/100 in.2 3 day 3 atm)
PVOH 0.03
0.06 (Plastics Design Library Staff, 1995)
EVOH 0.02
PVDC 0.15
PA 2.6
PET 3.5
PVC 5
20
PLA 30 (Auras et al., 2003; Cabedo et al., 2005)
PP 150
HDPE 150
EAA 200
500
EMAA 200
500
ION 200
500
PS 350
PB 385
LDPE 420
LLDPE 440
EPE 500
800
EVA 600
1000
EMA 600
1000
ULDPE 600
950
POP/POE 600
2000
30 PLASTIC FILMS IN FOOD PACKAGING

based on the equivalent barrier properties. The data The oil resistance of a polymer is influenced by
needed are as follows: its polarity and crystallinity. Polar polymers, such as
PA and polyester, have good oil resistance. Among
• the required transmission rate (TR), polyolefins and ethylene copolymers, polypropylene
• permeability coefficient (P1 and P2), (PP) and HDPE generally have the best oil resis-
tance due to their high crystallinity. For PE, when
• package surface area (A). the density is reduced by introducing comonomers,

Table 3.4 Moisture Permeability Coefficients

Moisture Vapor Transmission Rates (MVTR): 1.0 mil, 100 F (37.8 C), 90% RH
Polymer Type MVTR (g 3 mil/100 in.2 3 day)
PVDC 0.10
PP 0.7
HDPE 0.4
0.8
LLDPE 0.8
1.2
ULDPE 1.2
1.5
LDPE 1.0
1.2
PB 1.0
1.2
EVA 1.0
5.5
EAA 1.0
1.6
EMAA 1.0
1.6
ION 1.0
1.6
EMA 1.0
9.0
POP 1.3
2.0
EPE 0.9
1.2
POE 2.0
3.0
PET 2.0
3.3
PVC 0.9
5.1
EVOH 2.0
4.5
PS 7.0
10.0
PA 10.0
20.0
PLA 40 (Auras et al., 2003)

Table 3.5 Calculation of the Most Cost-Effective Barrier Polymer

Polymer Thickness Package Cost

A t1
1 t 1 5 P1  100  1
TR C Polymer 1 5 1000  A  ρPolymer 1  $Polymer 1
A t2
2 t2 5 P2  100  TR
1
C Polymer 2 5 1000  A  ρPolymer 2  $Polymer 2

tn 5 required polymer thickness (mil); Pn 5 permeability coefficient; A 5 package area (in.2); ρn 5 polymer density
(lb/in3); TR 5 transmission rate required to protect package contents; Cn 5 polymer cost per package; $n 5 polymer
n price ($/lb).
3: PE-BASED MULTILAYER FILM STRUCTURES 31

its oil resistance decreases. An exception is iono- and are often used as sealants; generally, the higher
mers, which have excellent oil and grease resistance the copolymer content, the lower the seal-initiation
because of their polarity. Oil penetration generally temperature. Stehling and Meka (1994) showed that
increases with increasing temperature. the fusion seal-initiation temperature and the tem-
perature for maximum seal strength of polyolefins
and ethylene copolymers strongly correlate with
3.5 Polymer Sealability their crystallinities. The seal interface strength is
due to molecular chain interpenetration across the
Heat sealability is a critical property for many interface. Only after the polymer fully melts does
packaging applications. Figure 3.3 shows a typical enough penetration occur to ensure maximum seal
heat-seal strength as a function of seal-bar tempera- strength. Qureshi et al. (2001) show that the molecu-
ture. A polymer that exhibits low-temperature seal- lar architecture of LLDPE plays a role: homoge-
ability and maintains seal integrity over a broad seal neous copolymers have a more rapid seal strength
temperature, dwell time, and seal pressure can signif- increase than do heterogeneous (Zieger
Natta)
icantly increase packaging line speeds, improve effi- polymers, presumably due to their faster diffusion
ciencies, and minimize seal failures. Such a polymer rates. They estimate that, for PE to achieve its
may be unacceptable, however, for packages requir- maximum seal strength, its chains must penetrate a
ing heat resistance, as in applications such as retort, distance on the order of its radius of gyration, a
boil-in-bag, or microwave cooking. characteristic length scale of the polymer molecule
Heat-seal properties are influenced by a poly- in its random coiled configuration. Morris (2002)
mer’s thermal and rheological properties as well as found that ionomers only require penetration of a
factors such as the following (Halle, 1989): fraction of their radius of gyration to establish
maximum seal strength. He attributes this to the
• seal-bar temperatures longer range ionic forces present in ionomers. These
• seal-bar pressure same forces, however, contribute to slower diffusion
• dwell time rates for ionomers.
Morris also looked at the interrelationship
• sealing bar configuration between seal-bar temperature, dwell time, and
• package design. package design on heat-seal performance (Morris,
2002). Thicker packaging structures require longer
Table 3.6 shows some heat-seal data that com- dwell times for a given seal-bar temperature to
pares the minimum seal-bar temperature required to reach the same heat-seal strength as thinner struc-
obtain a 3.5 N/cm (2.0 lb/in.) seal strength for tures. Nominally, this is due to heat transfer consid-
monolayer films at the prescribed conditions. erations; it takes longer for the heat to transfer
Ethylene copolymers have low melting temperatures through thicker films. Simple heat transfer model-
ing was not enough to account for seal performance
differences. By coupling a polymer diffusion model
with heat transfer analysis, Morris (2002) was
able to predict packaging performance. He found
that, at least for the slowly diffusing ionomers, seal
strength increases at the interface after the heat-seal
jaws are removed as the film slowly cools to room
temperature.
ti tm tmx Another critical sealability property is hot tack
TEMPERATURE
strength; the ability to maintain seal integrity while
still hot and a load is applied. Hot tack is important
ti = Initiation temperature for fusion seal
tm = Temperature for maximum seal strength
in vertical form/fill/seal (VFFS) machines since the
tmx = Maximum temperature for seal product weight puts a force on the bottom seal
while it is still hot (Van Ness, 1983). It can also be
Figure 3.3 Heat-seal strength versus seal-bar important in horizontal form/fill/seal (HFFS) appli-
temperature. cations, particularly in gusseted areas where the
32 PLASTIC FILMS IN FOOD PACKAGING

films are folded. A film’s dead fold or “spring- tack curve shape. Some POPs have very high maxi-
back” nature exerts an opening force that must be mum hot tack strengths near their melting points
countered by good hot tack strength to avoid chan- that tail off quickly at higher temperatures. Strain-
nel leakers. Hot tack derives from two competing induced crystallization in these homogeneous poly-
mechanisms. The first is polymer diffusion and mers has been proposed for the unusually high hot
penetration; as in the case for heat-seal perfor- tack strength (Qureshi et al., 2001). Poor hot tack
mance, strength at the interface is built by polymer strength at elevated temperatures is due to lower
interdiffusion and entanglement. The second is melt melt strength. Heterogeneous LLDPE and ultralow-
strength, which is related to polymer viscosity. density polyethylene (ULDPE) tend to have broader
Diffusion increases with increasing temperature, hot tack curves. Broader yet are acid copolymers
whereas melt strength decreases. Thus, hot tack and, finally, ionomers, which have exceptionally
strength versus sealing temperature typically goes
through a maximum. Figure 3.4 compares hot tack 8
ionomer

DTC hot tack, (N/15mm)

for ionomer versus POP. Ionomer has a broad hot 7
pop
tack range and POP has a narrow hot tack range. 6
The maximum hot tack strength, the peak hot 5
tack temperature, and the hot tack range can all be 4
consequential in end use. The hot tack range versus 3
temperature can be particularly important since it 2
indicates how much flexibility packers may have in 1
their packaging operation. Often, seal-bar tempera- 0
50 75 100 125 150 175 200 225 250 275
tures are not well controlled or the line speed is
Jaw temperature (C)
ramped up and down during the day, which affects
the seal-bar temperature. The molecular architec- Figure 3.4 Hot tack performance. Source: From
ture and polymer chemistry play a role in the hot De Garavilla (1995).

Table 3.6 Polymer Thermal and Sealing Properties

Melting Vicat Softening Fusion Seal

Polymer Type Point,  C (F) Point,  C (F) Temperaturea,  C (F)
EMA (20%) 80 (176) 59 (138) 82 (189)
3
POP (0.902 g/cm ) 94 (201) 80 (176) 88 (190)
EVA (12%) 90 (194) 81 (178) 91 (195)
ION 93 (200) 72 (161) 99 (210)
EAA (9% AA) 98 (208) 83 (181) 93 (200)
3
ULDPE (0.912 g/cm ) 121 (250) 105 (221) 101 (215)
3
LDPE (0.920 g/cm ) 110 (230) 92 (198) 107 (225)
3
LLDPE (0.920 g/cm ) 122 (252) 110 (230) 118 (245)
3
HDPE (0.960 g/cm ) 135 (275) 125 (257) 121 (250)
PP 168 (334) 133 (271) 149 (300)
b
PS 120 (248)
PVDC 160 (320)b
EVOH 160 (320)
PA 216 (420)
PC 154 (310)
a
Hot tack sealer, 50-μm (2.0-mil) film with 50-μm (2.0-mil) PET backing, 0.5-s dwell, 275-kPa (40-psi) pressure.
b
Tg.
3: PE-BASED MULTILAYER FILM STRUCTURES 33

high melt strength due to their unique ionic mor- over the product life cycle, there must be sufficient
phology (Morris and Chen, 2003). adhesion between the layers. Interlayer adhesion is
Caulking or flow into cavities formed by wrin- affected by
kles or gussets is sometimes required. Polymer
flow is characterized by its viscosity, which is a • the structure design,
function of temperature and shear rate. Higher seal- • the individual layer properties,
ing temperatures result in more flow and caulking.
However, if the temperature is too high, the sealant • the process by which it is put together,
may be squeezed out of the seal area, resulting in • the manner in which it is used (Morris, 1992).
poor seal performance. Heat sealing is generally a
very low shear process. The zero shear viscosity at The structure design and, in particular, the indi-
the sealing temperature is a good starting point vidual layers’ compatibility will determine whether
when comparing different polymers for their ability specialized adhesive polymers or tie layers are
to caulk. Melt index, a flow measure typically used needed (Potts, 1987). For two polymers to bond to
in the industry, is only a crude indicator for caulk- one another, they first must come into intimate con-
ing since it does not account for a polymer’s vis- tact. In coextrusion, this is achieved as the molten
cosity as a function of temperature and shear rate. polymer streams are combined in the die or feed-
Seal-bar pressure is another heat-seal variable block. For coatings and laminations, this requires
we have not discussed yet. A general guideline is good wetting, which is a function of viscosity,
to use just enough pressure to get by. Some pres- polarity, and surface tension. Once good contact is
sure is needed to ensure the film surfaces are in achieved, molecular segments may diffuse across
intimate contact for interfacial penetration to occur. the interface provided
Too much pressure, however, may result in
squeeze-out of the sealant from the seal area. • the molecules are compatible,
In some packaging applications, such as potato • the polymers are above their glass transition
chip pouches, an easy opening seal is desired. or melting temperature to allow chain segment
There are three general methods used to control the mobility,
seal strength for easy-open or peel
seal
performance:
• there is sufficient time and temperature for
diffusion to occur.
• an interfacial peel
seal mechanism where the
As discussed above, diffusion is the primary
sealant is often blended with another polymer
mechanism for heat sealing a sealant to itself. Even
that “contaminates” the seal strength,
if conditions are not favorable for diffusion, good
• a delamination peel
seal mechanism, some- adhesion can be obtained as a result of chemical
times known as a “burst” peel where adjusting reaction at the interface.
the sealant layer adhesion to the adjacent Table 3.7 gives some examples of the adhesion
layer controls the seal strength. The opening between some typical layer combinations found in
force tears through the sealant layer and the coextruded packaging films. For those cases where
seal fails along the sealant/adjacent layer adhesion is poor, specialized adhesive polymers or
interface, tie resins have been developed (Guillotte and
• a cohesive failure mechanism where some- Wright, 1983). Tie resins are typically a polyolefin
thing is blended into the polymer to ensure or ethylene copolymer matrix resin, with chemical
the failure is within the sealant layer during functionality and sometimes a toughener added. The
opening. matrix resin is chosen for its compatibility with one
bonded layer to take advantage of the diffusion
mechanism in adhesion. In Figure 3.5, PE is being
3.6 Adhesive Polymers adhered to PA. In this case, the matrix resin can be
PE, EVA, or other ethylene copolymer that bonds to
For a coextruded structure to function during the PE layer. Chemical functionality is incorporated
manufacture, packaging, distribution, and storage into the adhesive polymer via copolymerization,
34 PLASTIC FILMS IN FOOD PACKAGING

grafting reaction, or alloying. Some common exam- structure apart in a peel strength test. Peel strength
ples of chemical functionality are given in is a function of fracture energy or energy to create
Table 3.8. In the example in Figure 3.5, either acid new surfaces as the peel front advances. At the
or anhydride functionality is typically chosen. The advancing edge, the adhesive deforms, creating an
acid or anhydride groups react with the PA amine energy loss that contributes to the measured frac-
end groups to achieve good adhesion. Finally, vari- ture energy. Increasing the adhesive thickness may
ous tie resin manufacturers often blend in proprie- increase the deformation zone, thereby increasing
tary modifiers, such as rubber, that impact the tie the fracture energy. It may also increase the energy
resin physical properties and its peel strength perfor- to bend the peel arm during the peel test, although
mance. The most common tie resins used today are this effect is small for flexible films. In theory, the
anhydride-modified polyolefins for bonding to PA fracture energy will increase with increasing thick-
and EVOH in barrier film structures. ness until a critical value is reached where the
When selecting an appropriate tie resin, several deformation zone becomes small compared to the
factors come into play besides the adhesion perfor- thickness. At this point, the fracture energy plateaus
mance. The adhesive must comply with appropriate (Wu, 1982). In many flexible packaging structures,
government regulations, such as Food and Drug the adhesive thickness is below this critical thick-
Administration (FDA) regulations for food packag- ness so that reducing thickness reduces the peel
ing in the United States. It must have proper flow strength performance. There are also practical lim-
properties for the given converting process and suf- its on how low the thickness can be for a given
ficiently match the flow properties of adjacent converting process and still ensure adhesive layer
layers to avoid flow instabilities during coextrusion.
The tie resin may also be called upon to impart
other properties, such as moisture barrier, tough-
ness, or clarity. Selecting an appropriate tie resin
matrix will often accomplish this. For example, an
PE PA
HDPE-based tie resin will have a lower moisture
vapor transmission rate (MVTR) than one based on
EVA. Finally, as with any polymer, the product
quality and consistency is important for achieving
good performance. Adhesive is based on Adhesive contains
Tie resin thickness in the packaging structure ethylene copolymer to anhydride or acid
promote diffusion with groups for chemical
can influence adhesion performance, as can coating PE interaction with PA
thickness in extrusion coating (Morris, 2008a).
Adhesion is most often measured by pulling the Figure 3.5 Coextrusion adhesive technology.

Table 3.7 Chart of Adhesion Between Polymers

Polymer HDPE PP PS PA EVOH PVDC PC

LDPE G P P P P P P
LLDPE G G P P P P P
ECO F P X P P G F
EVA G G G P P G F
EMA G G X P P G F
EAA F P P G P P P
ION (Na) P P P P P P P
ION (Zn) P P P G P P P
PE-g-MAH G P P G G P F
G 5 good, F 5 fair, P 5 poor, X 5 no data.
3: PE-BASED MULTILAYER FILM STRUCTURES 35

continuity. For most processes, 2
3 μm (0.1 mil) is modulus of the tie resin, he was able to
the lower adhesive layer thickness limit. develop a single relationship that describes
How the film is fabricated can have a significant the effect of processing and material para-
impact on adhesion. Typically, less orientation and meters on peel strength in both blown and
greater contact time at higher temperatures favor cast film (Morris, 2008b).
adhesion. Several processing parameters are impor- • Orientation decreases adhesion. Increasing
tant for optimizing adhesion performance (Guillotte blow-up ratio in blown film, or increasing
and Wright, 1983): draw-down ratio in cast film, can reduce
adhesion. Orientation processes such as dou-
• Adhesion generally increases with increasing ble bubble processes can substantially reduce
processing temperatures. Both diffusion and adhesion by increasing stress, reducing thick-
chemical interaction are favored at higher ness, and creating new interfacial area
temperatures. (decreasing bond density).
• Increasing melt contact time generally • Thermoforming can reduce adhesion by some
improves adhesion. Combination technology of the same mechanisms as orientation.
(feedblock or die design), the order in which
layers are brought together, and die land Finally, the manner in which the structure is used
length can affect adhesion. can impact adhesion (Morris, 1992). End-use stor-
• Increasing line speed generally reduces adhe- age conditions (temperature, RH) and the environ-
sion. In studying the blown film process, ment the package is subjected to, both physical (e.g.
Morris (1996a,b) found that the peel strength cook-in meats, post-packaging sterilization or pas-
of an anhydride-modified polyolefin to EVOH teurization) and chemical, can alter adhesion. The
increased ten-fold by changing the process product itself can contain chemical species that
time, which is inversely related to line speed. migrate to the interface and destroy adhesive bonds.
He attributed this to a decrease in stress A well-known example is the effect an acid species
imparted during quenching. Morris (2008b,c) in orange juice and condiments has on LDPE or
found similar behavior in coextrusion cast EAA adhesion to foil (Olafsson and Hildingsson,
film and coextrusion coating, although the 1994; Olafsson et al., 1993a,b, 1995; Pieper, 1994;
nature of the process time versus peel strength Schroeder et al., 1990). It is critically important to
behavior suggests time for reaction may play test structures under conditions that closely simulate
a role. He related the differences between the end use before finalizing a packaging structure.
blown and cast film/extrusion coating back to
fundamental differences in the time and tem-
perature at which new interfacial area is cre- 3.7 Applications for Flexible
ated during drawing of the resin in the Packaging Film Structures
processes (Morris, 2008c). By scaling the pro-
cess time by the characteristic relaxation time Packages may be formed in-line by several techni-
of the tie resin and the peel strength by the ques or may be supplied to the packer as preformed

Table 3.8 List of Commonly Used Functional Groups in Tie Resins

Functionality Adheres to
Acid PA, Al foil
Anhydride PA, EVOH
VA PVDC, PP, PET
Acrylate Some inks, PET, PP
Epoxy PET
Silane Glass
36 PLASTIC FILMS IN FOOD PACKAGING

pouches or bags. Packaging may be created by • towelettes—OPET/print/LDPE/Al/ION and

wrapping or shrinking a basic film around a bundle variations
of goods. In-line packaging forming examples • condoms—similar structures as towelettes
include VFFS, HFFS, and thermoform/fill/seal. In
VFFS operations, film from a roll is guided through • laminates for toothpaste tubes—PE-film/
rollers and then shaped by a forming collar into a (LDPE-EAA)/Al/(EAA/LDPE)/PE-film
tube. The film moves in a vertical direction (down) • stand-up pouches—OPET/print/adh/m-OPP/
over a filling tube. A vertical seal is made, forming adh/(LLDPE
HDPE
LLDPE) and variations.
the film into a continuous tube. As the film con-
tinues through the machine, a horizontal seal is
made, perpendicular to the film machine direction, 3.7.1 Medical Packaging
forming the bottom-end seal of the bag being
formed and the top seal of the previously filled A wide variety of structures are used in the med-
bag. The product is dropped into the partially ical packaging area (Table 3.9). The structure
formed bag, advanced to the seal bars, and the next requirements include
bottom- and top-end seal is made. The process may
operate in a step-wise or continuous manner. One • sterilization capability,
example of a product normally packaged on VFFS • microbial barrier,
equipment is fresh-cut produce. In HFFS opera- • linear tear properties,
tions, the film moves in a horizontal direction
during the packaging step, reducing the need for • puncture resistance.
high hot tack strength. One application that typi-
cally uses HFFS equipment is chunk cheese. In Sterilization methods used for medical packaging
thermoform/fill/seal operations, a bottom web is film include ethylene oxide gas or radiation. The
formed, product is added, and the top web, which package is typically a forming web and a nonwoven
is normally flat, is sealed to the bottom web. fabric (like TYVEKs) that lets the ethylene oxide
Thermoform/fill/seal packaging is frequently used in and out of the package. Medical packaging usu-
for bacon and processed meats. Stand-up pouches ally does not require oxygen barrier properties, so
and other types of packaging may be formed in- EVOH is normally not required in medical packag-
line with the filling equipment, or may be fully or ing structures. Coextrusion processes are growing
partially prefabricated prior to the filling step. in this market. Blown film, cast film, and extrusion
Markets for flexible packaging films have con- coating processes are used in producing flexible
tinued to grow in many applications. PE and the packaging structures for medical packaging applica-
various copolymers account for more than 75% of tions. Films ranging from three layers to eleven
the flexible packaging film. Some major market layers are now available. These markets are typi-
segments where coextruded film is used include the cally small and require many years to meet the
following (Keymark Associates North American required qualifications.
Flexible Packaging Strategies, 2002): The forming webs were historically three-layer
EVA and ionomer films, as shown in the syringe
• medical packaging package in Figure 3.6. Heavy gauge films were
sometimes produced by combining a three-layer
• food packaging film to form six layers. Newer film structures have
• heavy-duty shipping bags seen more layers being used and incorporating PA
• stretch wrap to replace ionomer in film structures to address
economic issues.
• trash bags Consumer and industrial heath care packaging
• condiments—OPET/print/LDPE/Al/EAA/ includes the following:
LDPE and variations
• aseptic packaging OJ—juice boxes—print/ • medical disposables
LDPE/paperboard/LDPE/Al/EMAA/LDPE and • surgical instruments—structures similar to
variations disposables
 3: PE-BASED MULTILAYER FILM STRUCTURES
Table 3.9 Medical Device Packaging Structures

Gauge
Layers (%) (μm)
Three-layer structure
EVA ION EVA 20j60j20 50
400
ION EAA EVA 30j30j40 50
400
Paper PE Foil Lamination
Five-layer structure
LLDPE Tie PA Tie LLDPE 40j5j10j5j40 50
400
m- Tie PA Tie m-LLDPE 40j5j10j5j40 50
400
LLDPE
LLDPE Tie PA Tie PA 70j5j10j5j10 50
400
LDPE Paper LDPE Foil LDPE Lamination
PET Adh LDPE EVA ION Lamination
Seven-layer structure
LLDPE Tie PA EVOH PA Tie LLDPE 30j5j10j10j10j5j30 50
400
Nine-layer structure
PE Tie PA Tie PE Tie PA Tie PE 20j5j10j5j20j5j10j5j20 50
400
LLDPE LDPE Tie PA EVOH PA Tie LDPE LLDPE 10/15/10/10/10//10/10/15/ 50
400
10

37
38 PLASTIC FILMS IN FOOD PACKAGING

• resterilization packaging • have excellent optical properties,

• syringes and hypodermic needles • shrink at low temperature to prevent product
• forming web damage,
• nonforming web • impart good softness and elasticity,
• sutures • provide excellent oxygen, moisture, odor, and
• pharmaceutical grease barrier protection,
• condoms and towelettes. • prevent freezer burn,
• facilitate using individual cuts by food pre-
Lidding stock is normally produced by extrusion parers,
coating and/or lamination processes and combines
paper, polymers, and foil to form multilayer struc- • help reduce purge loss,
tures. Sachets for condom and towelette packaging • extend shelf life,
typically use the structure OPET/print/LDPE/Al/ • offer easy disposal,
ION and variations, with ionomers used as the seal-
• have good machinability,
ant for its chemical flex crack resistance.
• have an oxygen transmission rate (OTR)
less than 1.0 cm3/100 in.2 day atm (nonfrozen
3.7.2 Food Packaging
only).
Primal Meat Packaging (Shrink)
Packaging primal and subprimal meat requires a A shrinkable film used in this application is a
package that must: PVDC barrier film with the sealant layer designed
to provide toughness and puncture resistance. These
• provide high shrinkage to fully collapse around films must be oriented to provide acceptable
irregular shapes, shrink properties using a double bubble process.
Table 3.10 shows some typical film structures used
in shrink film for primal and subprimal meat
packaging.

Processed Meat Packaging

Processed and cook-in meat such as luncheon
meat, ham, bologna and salami are packaged in
barrier films that are designed to keep oxygen
from entering the package. This extends shelf life
and gives the retailer extended product display
time. It also allows consumers to keep the product
in their refrigerator, unopened, for some time after
Figure 3.6 Multilayer film used for syringe package. purchase. These packages are often printed with

Table 3.10 Primal and Subprimal Meat Packaging

Five-Layer Structure Layers (%) Gauge (μm)

ULDPE EVA PVDC EVA ULDPE 40j5j10j5j40 50
120
m-LLDPE EVA PVDC EVA m-LLDPE 40j5j10j5j40 50
120
m-LLDPE LLDPE Tie EVOH PA 30j40j10j10j10 50
120
ION LLDPE Tie EVOH PA 30j40j10j10j10 200
300
ION EVA LLDPE PVDC oriented-PA 20j30j35j5j10 50
100
Note: /PVDC/ is an adhesive lamination with PVDC.
3: PE-BASED MULTILAYER FILM STRUCTURES 39

eye-catching graphics to increase sales. These films requiring aroma or taste barrier properties will con-
may contain tain either PA or EVOH polymers. (Table 3.13).

• a barrier polymer, Snack Food Packaging

• printing surface, such as polyethylene tere- Potato chips are often packaged in structures that
phthalate (PET) or PA, that also provides ther-
contain metalized films (Table 3.14). Polymer film
mal resistance during sealing and helps
metallization provides an oxygen barrier, moisture
provide abuse resistance during distribution,
barrier, and light barrier. The light barrier is to pro-
• LLDPE or ULDPE toughness layers, tect the potato chips from ultraviolet radiation that
• a sealant layer that could be LLDPE, a POP, initializes an oxidation mechanism. Seal strength
or an ionomer. must be optimized to provide a secure package that
can be easily opened by the consumer. Seal integ-
The processed meat package comprises a form- rity and consumer appeal are also critical.
ing film and a backing film. The forming film is
thermoformed to the meat product shape. In addi- Salty Snack Packaging
tion, low oxygen permeability, abuse resistance,
and seal integrity are critical to maintaining the Salty snacks are frequently high in fat content
proper atmosphere inside the package. Optical and may require a package that provides an oxygen
properties, such as high gloss and high clarity, are barrier in order to prevent the fat in the food from
important on the backing film where reverse- going rancid. They may also require grease resis-
printed PET is used to create consumer appeal. tance to keep the package from leaving an oily
Barrier requirements for processed meats range spot. Salty snacks may be packaged in barrier films
from 0.2 to 1.0 cm3/100 in.2 day atm for OTR and containing foil, a metalized polymer film, or a bar-
0.2
0.5 g/100 in.2 day for water vapor transmission rier polymer such as EVOH or PVDC and are gas
rates (WVTR). Table 3.11 shows some typical film flushed with nitrogen to maintain a low oxygen
structures used in processed meat packaging. concentration inside the package (Table 3.15).

Bakery
Poultry/Fish Packaging
Moisture barrier is normally the critical property
Moisture barrier properties are more critical. The
in bakery applications. Polymers used for moisture
packages are normally vacuum packaged
barrier include LDPE, LLDPE, HDPE, or PP.
(Figure 3.7) with a good sealant polymer such as
Typically, EVA polymers are used for sealability
EVA, ionomer, or LLDPE (Table 3.12).
and optics. Applications, such as the cake mix
pouch, will require aroma, taste, and moisture bar-
Cereal Box Liners rier properties. PA is used for taste and aroma
barrier. In bread bags, the LLDPE polymer’s tough-
Cereal box liners (Figure 3.8) also require good
ness allows down gauging, while LDPE allows
moisture barrier properties to provide good taste
good optics and printability (Table 3.16).
and freshness protection. HDPE polymers are typi-
cally used to provide a moisture barrier. Sealant
polymers such as EVA, ionomer, POP, or blends Cheese Packaging
are used for low-temperature seals, form-fill-seal Most cheese sold in the United States is prepack-
packaging, and easy opening seals. Certain products aged in flexible packaging. The cheese packaging
have additional requirements, such as puncture includes
resistance to keep the product from poking through
the packaging film, and flavor and aroma barrier • individually wrapped slices (IWS) of pro-
for highly flavored cereals. Heat-seal-initiation tem- cessed cheese,
peratures of 90 C and below are commonly
required. MVTRs less than or equal to 0.1 g/ • chunk cheese,
100 in.2 day atm are often required. Packages • shredded cheese.
40 PLASTIC FILMS IN FOOD PACKAGING

Table 3.11 Processed Meat Packaging Film Structures

Product Structure Layers (%) Gauge (μm)

Ground beef
LLDPE/Tie/PA (75/5/20) 150
200
LLDPE/Tie/EVOH/PA (75/5/10/10) 150
200
LLDPE/Tie/PA/EVOH/PA/Tie/LLDPE (25/10/10/10/10/10/25) 40
150
Barrier overwrap
m-LLDPE/LLDPE/Tie/EVOH (30/40/10/10/10) 150
200
m-LLDPE/LDPE/LDPE/Tie/PA/EVOH/PA (20/15/15/10/15/10/15) 150
200
Chub films
LLDPE/PVDC//PA (75//5//20) 150
200
Foodservice portion: steaks/chops/roasts
Forming web
LLDPE/Tie/EVOH/PA (75/5/5/15) 150
200
ION/Tie/EVOH/PA (75/5/5/15) 150
200
LLDPE/Tie/PA (75/5/20) 150
200
ION/PA (80/20) 150
200
ION/EVA//PVDC/PA (60/10//5/25) 150
200
LLDPE/Tie/PA/EVOH/PA/Tie/LLDPE (25/10/10/10/10/10/25) 150
200
Nonforming web
LLDPE/Tie/EVOH/PA (70/10/10/10) 50
80
ION/Tie/EVOH/PA (70/10/10/10) 50
80
LLDPE//PVDC//o-PET (85//5//10) 50
80
ION//PVDC//o-PET (85//5//10) 50
80
ION/Tie/PA (80/10/10) 50
80
LLDPE/Tie/PA/EVOH/PA/Tie/LLDPE (25/10/10/10/10/10/25) 50
80
Skin packaging forming web
ION/Tie/EVOH//Tie/EVA (35/10/10//10/35) 150
250
Skin packaging nonforming web
ION/Tie/EVOH//Tie/EVA (35/10/10//10/35) 50
80
Luncheon meat
Forming web
LLDPE/Tie/EVOH/PA (75/5/5/15) 150
200
ION/Tie/EVOH/PA (75/5/5/15) 150
200
m-LLDPE/Tie/EVOH/PA (75/5/5/15) 150
200
LLDPE/Tie/PA/EVOH/PA/Tie/LLDPE (25/10/10/10/10/10/25) 150
200
Nonforming web
LLDPE/EVA/PVDC//o-PET (60/10/5//25) 50
100
m-LLDPE/Tie/EVOH//o-PET (60/10/5//25) 50
100
(Continued )
3: PE-BASED MULTILAYER FILM STRUCTURES 41

Table 3.11 (Continued)

Product Structure Layers (%) Gauge (μm)

ION/Tie/EVOH//o-PET (60/10/5//25) 50
100
LLDPE/Tie/EVOH/PA (60/10/5/25) 50
100
LLDPE//PVDC//o-PA (60/10//5//25) 50
100
LLDPE/Tie/PA/EVOH/PA (60/10/10/10/10) 50
100
LLDPE/Tie/PA/EVOH/PA/Tie/LLDPE (25/10/10/10/10/10/25) 50
100
Frankfurters
Forming web
LLDPE/Tie/EVOH/PA (75/5/5/15) 150
200
m-LLDPE/EVOH/PA (75/5/5/15) 150
200
ION/EVOH/PA (75/5/5/15) 150
200
LLDPE/Tie/PA/EVOH/PA/Tie/LLDPE (25/10/10/10/10/10/25) 150
200
ION/Tie/PA/EVOH/PA/Tie/PA (15/20/10/5/10/25/15) 150
200
LLDPE/Tie/PA/EVOH/PA/Tie/PA (20/15/10/5/10/25/15) 150
200
ION/Tie/PA/EVOH/PA/Tie/PP (15/20/10/5/10/25/15) 150
200
Nonforming web
LLDPE-EVA//PVDC//o-PA (60/25//5//10) 50
100
m-LLDPE/Tie/EVOH/o-PET (60/15/10/15) 50
100
ION//PVDC//o-PET (85//5//10) 50
100
LLDPE/Tie/PA/EVOH/PA/Tie/LLDPE (25/10/10/10/10/10/25) 50
100
ION/PE/o-PET (25/50/25) 50
100
ION/Tie/EVOH/Tie/PE/o-PET (15/10/10/10/40/15) 50
100
Sausage
Forming web
LLDPE/LDPE/Tie/EVOH/PA/Tie/EVA (30/5/10/10/10/5/30) 150
200
m-LLDPE/Tie/EVOH/PA (75/5/5/15) 150
200
ION/Tie/EVOH/PA (75/5/5/15) 150
200
LLDPE/Tie/PA/EVOH/PA/Tie/LLDPE (25/10/10/10/10/10/25) 150
200
ION/Tie/PA/EVOH/PA/Tie/PA (15/20/10/5/10/25/15) 150
200
LLDPE/Tie/PA/EVOH/PA/Tie/PA (20/15/10/5/10/25/15) 150
200
ION/Tie/PA/EVOH/PA/Tie/PP (15/20/10/5/10/25/15) 150
200
LLDPE/Tie/EVOH//o-PET (60/15/10//15) 50
100
m-LLDPE/Tie/EVOH/PA (60/15/10/15) 50
100
LLDPE/Tie/PA/EVOH/PA/Tie/LLDPE (25/10/10/10/10/10/25) 50
100
Shrink bags
EVA/EVOH/EVA (48/5/47) 50
80
EVA/PVDC/EVA (48/5/47) 50
80
(Continued )
42 PLASTIC FILMS IN FOOD PACKAGING

Table 3.11 (Continued)

Product Structure Layers (%) Gauge (μm)

Ham
Forming web
LLDPE/Tie/EVOH/PA (60/15/10/15) 150
200
ION/Tie/EVOH/PA (60/15/10/15) 150
200
LLDPE/Tie/PA/EVOH/PA/Tie/LLDPE (25/10/10/10/10/10/25) 50
100
Nonforming web
LLDPE//PVDC//PA (70//5//25) 50
80
ION//PVDC//PA (70//5//25) 50
80
LLDPE//PVDC//o-PET (70//5//25) 50
80
ION//PVDC//o-PET (70//5//25) 50
80
LLDPE/Tie/PA/EVOH/PA/Tie/LLDPE (25/10/10/10/10/10/25) 50
100
Shrink bags
EVA/EVOH/EVA (48/5/47) 50
80
EVA/PVDC/EVA (48/5/47) 50
80
m-LLDPE/Tie/EVOH/Tie/m-LLDPE (30/10/10/10/30) 50
80
Bacon
ION/Tie/EVOH/PA (50/10/10/30) 50
100
ION/PE/PA (15/50/35) 50
100
ION/Tie/PA/EVOH/PA/Tie/PA (20/20/10/5/10/20/15) 50
100
Deli meats
Shrink bags
EVA/EVOH/EVA (48/5/47) 50
80
EVA/PVDC/EVA (48/5/47) 50
80
m-LLDPE/Tie/EVOH/Tie/m-LLDPE (30/10/10/10/30) 50
80
Forming web
LLDPE/Tie/EVOH/PA (80/5/5/10) 200
250
ION/Tie/EVOH/PA (80/5/5/10) 200
250
LLDPE/Tie/PA/EVOH/PA/Tie/LLDPE (25/10/10/10/10/10/25) 50
100
Nonforming web
LLDPE//Tie/PA/EVOH/EVA (40//10/10/20/30) 50
80
ION/Tie/EVOH/PA (60/15/10/15) 50
80
LLDPE/Tie/PA/EVOH/PA/Tie/LLDPE (25/10/10/10/10/10/25) 50
100
Casings
LLDPE//o-PA (70//30) 50
80
LLDPE//o-PA//PVDC (70//20//10) 50
80
3: PE-BASED MULTILAYER FILM STRUCTURES 43

Both chunk cheese and shredded cheese require (Table 3.18). If oxygen barrier is required for long
substantial oxygen barrier to prevent mold growth shelf life, then PA could be used.
and spoilage. EVOH, PVDC, or PVOH (poly vinyl
alcohol) may provide the oxygen barrier. While
EVOH is generally coextruded into the film struc- Frozen Food
ture, PVDC or PVOH may be coated on a film via Frozen foods (Figure 3.9) are packaged in a vari-
a coating process. Cheese packaging also requires ety of packaging types. Examples of frozen foods
excellent seal integrity and abuse resistance to pre- packaged in flexible packaging include
vent the controlled atmosphere inside the package
from being lost. Cheese packages are often lamina- • frozen fruits,
tions made with reverse-printed outer webs contain-
ing PET or PA for superior graphical presentation. • vegetables,
They may also be extrusion coated structures where • French fries,
the sealant layer has been extrusion coated onto the • individually quick frozen chicken breasts.
outer layer. Sealant layers may consist of EVA, an
ionomer, or a POP. Low heat seal-initiation temper- Many frozen foods are packaged in surface-
ature (90 C or below) and good seal-through- printed PE films. Some higher value-added items
contamination performance are required. Processed are packaged in laminations, which may be shaped
cheese typically requires films with an OTR of into stand-up pouches. Most frozen food bags are
0.6
1.0 cm3/100 in.2 day atm and WVTR of 1.0 g/ made on standard VFFS machinery.
100 in.2 day (Table 3.17). Key requirements for frozen food packaging are
An acrylic, PVOH-coated, OPP film is also used
in cheese packaging in both extrusion and adhesive • low-temperature toughness,
laminations. It is an ExxonMobil product called
Bicor AOH. Acrylic is coated on one side and • modulus,
PVOH on the other side. • high hot tack strength,
• high-seal strength.
Milk Pouches
LLDPE or LDPE/LLDPE blends provide the
sealant in both milk powder and liquid pouches

Figure 3.7 Poultry packaging. Figure 3.8 Cereal boxes.

Table 3.12 Poultry/Fish Packaging

Seven-Layer Structure Layers (%) Gauge (μm)

LLDPE/Tie/PA/EVOH/PA/Tie/LLDPE 25j10j10j10j10j10j25 40
150
LLDPE/Tie/PA/EVOH/PA/Tie/Ion 25j10j10j10j10j10j25 40
150
44 PLASTIC FILMS IN FOOD PACKAGING

Some packages are clear and require good clar- packaging. Stiffness must be adequate for high-
ity, while others are pigmented and require good speed packaging, and packaging films must have
gloss. LLDPE, ULDPE, EVA, and POP resins tear and puncture strength high enough to prevent
are all commonly used in creating frozen food package damage during transportation and storage

Table 3.13 Cereal Packaging

Market Structure Layers (%) Gauge (μm)

Bag-in-box
HDPE/HDPE/EVA 45 j45 j10 40
60
HDPE/HDPE/ION 45 j45 j10 40
60
Bag-in-box (peelable seal)
HDPE/HDPE/EVA 1 ION 45 j45 j10 40
60
Bag-in-box (barrier bag)
HDPE/Tie/EVOH/Tie/EVA 60 j10j10j10 j10 40
60
HDPE/Tie/PA/Tie/EVA 60 j10j10j10 j10 40
60

Table 3.14 Snack Food Packaging Films

Structure Layers (%) Gauge (μm)

Potato chips (OTR 2.0, MVTR 0.02)
o-PP//met o-PP 50 jj 50 20
60
o-PP//LDPE//met o-PP 25jj 50 jj25 20
60
EVA/HDPE//met o-PP 15j 70 jj15 40
80
Tortilla and corn chips (OTR ,2.0, MVTR ,0.35)
o-PP//LDPE//o-PP 25jj 50 jj25 20
60
o-PP//PVDC//o-PP 50 //p/5jj 45 20
60
Pretzels (OTR ,2.0, MVTR ,0.5)
o-PP//LDPE//o-PET 25jj 50 jj25 30
80
o-PP//LDPE//o-PP 25jj 50 jj25 30
80
o-PP//PVDC//o-PP 45 jj5jj 50 30
60
Meat snacks
LDPE//PVDC//o-PET 45 jj5jj 50 30
60
LLDPE/Tie/EVOH/PA 60 j10j10j10j10 40
80
p, primer.

Table 3.15 Snack Nuts Packaging

Structure Layers (%) Gauge (μm)

o-PP//LDPE//o-PP 20jj60jj20 40
60
o-PP//LDPE//Foil//LDPE 10jj20jj5jj65 40
60
3: PE-BASED MULTILAYER FILM STRUCTURES 45

(Table 3.19). Stand-up pouches and self-venting dioxide permeability, seal integrity, machinability,
(microwave) technologies are also used for frozen and consumer appeal. Consumer appeal includes
food packaging these days. both feel and appearance. Feel is generally deter-
mined by film thickness and modulus while appear-
ance is governed by print quality and film optical
Fresh-Cut Produce
properties, such as clarity, haze, and gloss. In order
Key performance requirements for fresh-cut pro- to extend the shelf life of the produce being pack-
duce packaging include proper oxygen and carbon aged, films must provide the proper oxygen

Table 3.16 Bakery Packaging

Structure Layers (%) Gauge (μm)

cPP/PP/cPP 10j80j10 30
60
EVA/PP 20j80 30
60
HDPE/EAA/PA/EAA 70j10j10j10 30
70
LLDPE/PP/LLDPE 10j80j10 30
60
LLDPE/Tie/PA/EVOH/PA 30j10j20j10j20 100
160

Table 3.17 Cheese Packaging

Structure Layers (%) Gauge (μm)

Natural chuck cheese pouches
LLDPE/Tie/EVOH//o-PET 75 j10jj15 40
60
LLDPE//PVDC//o-PP 75 j10jj15 50
60
LLDPE//PVDC//o-PET 75 j10jj15 45
50
EVA//PVDC 95 jj5 50
60
LLDPE//PVDC//o-PA 75 j10jj15 45
50
Vacuum bags for aging
EVA//PVDC//o-PA 85 jj5jj10 40
100
LLDPE/Tie/PA 80 j10j10 40
100
EVA/Tie/PA 80 j10j10 40
100
Shredded cheese
PVDC//PA//LDPE 5jj20jj 75 80
100
PVDC//PET//LDPE 5jj20jj 75 80
100
PA/EVOH/Tie/LDPE 10j10j10j 70 80
100
Processed cheese slices
o-PP//EVA 50jj 50 20
PP/EVA 20j 80 35
40

Table 3.18 Milk Packaging

Structure Layers (%) Gauge (μm)

LLDPE/Tie/PA/Tie/LLDPE 35j10j10j10j35 40
70
HDPE/(LDPE 1 LLDPE) 40j60 40
80
46 PLASTIC FILMS IN FOOD PACKAGING

permeability that is matched to the packed produce biaxially oriented PA for toughness, foil for oxygen
respiration rate. Cut produce respires after harvesting, barrier, and a PP sealant film. These pouches may
consuming oxygen and giving off carbon dioxide. By contain items like tuna, pet food, and soup. The
controlling the permeation of gases through the pack- food items are held at elevated temperature after
age, the environment inside the package is controlled, packaging, so the packages must remain intact at
respiration is slowed, and shelf life is extended. The elevated temperatures. In addition to temperature
bags must have complete seal integrity in order to resistance, toughness, seal strength, and barrier
prevent the unplanned transfer of gases between properties are critically important.
the bags and the environment. Bags may contain
PP, LLDPE, ULDPE, EVA, or POP. OTR require-
ments vary widely depending on the produce being Edible Oil Packaging
packaged, but common items range from about The packaging of cooking oil uses PA to provide
100 cm3/100 in.2 day atm for Caesar salad mixes, oxygen barrier properties. Ethylene acrylic acid is
150
200 cm3/100 in.2 day atm for iceberg salad typically used as the sealant layer. The seal type
mixes, and 200
350 cm3/100 in.2 day atm for spe- determines the PA layer location (Table 3.20).
cialty salad mixes such as baby greens and exotic let-
tuces. Perforation may be used to obtain high Bag-in-Box
transmission rates for some applications.
Coextruded films containing oxygen barrier
polymers are replacing some metalizing laminates
Retortable Pouches where flex crack resistance is required. LLDPE or
A growing flexible packaging is in the replace- EVA polymers are used as sealants (Table 3.21).
ment of metal cans with retortable pouches. These
pouches are typically laminations containing
Stretch Wrap
Stretch film, or stretch/cling film, is used to unit-
ize goods for transportation. A thin film is
stretched, either by machine or by hand, and
wrapped around packages to hold the goods
together. The film clings to itself and to the pallet,
securing the load. In its most common form,
stretch/cling film is applied to a stacked pallet
using a power pre-stretch pallet wrapper in an auto-
mated operation (Figure 3.10). In this operation, the
film is stretched, between 100% and 300%, by roll-
ers turning at different speeds and is then applied to
a loaded pallet that sits atop a moving turntable.
Machine wrap film is typically supplied on rolls
that are 20- or 30-in. (51- or 76-cm) wide. Hand
wrap film is supplied on smaller rolls. Stretch/cling
Figure 3.9 Frozen food packaging. films may be manufactured by either a cast film or
blown film process. Most stretch/cling films are

Table 3.19 Frozen Food Packaging

Structure Layers (%) Gauge (μm)

EVA/LLDPE/EVA 15j 70 j15 40
80
PET//Tie//LDPE/ION 15jj5jj 40j 40 40
80
m-LLDPE/LLDPE/m-LLDPE 15j 70 j15 40
80
HDPE/MDPE/EVA 15j 70 j15 40
80
3: PE-BASED MULTILAYER FILM STRUCTURES 47

coextruded structures containing three to seven • pet food

layers. Most cast film lines are now being installed • fertilizer
with five-layer capability, and blown film coex-
truded films are typically three layers. LLDPE is • chemicals
the primary component of most stretch films. For • topsoil
specialized applications, coextrusions containing • bark mulch
minor PP, EVA, POP, m-LLDPE, EPE, or ULDPE
• compressed bales of fiberglass insulation.
layers may be employed (Table 3.22). For most
stretch film structures, a resin with good inherent
When filled they weigh 40 pounds (18 kg) or
cling is used on either one or both surface layers.
more. Heavy-duty shipping sacks may be supplied
A tackifier, such as poly-isobutylene, can also be
as preformed bags or as roll stock, which is formed
added to the structure to provide the desired cling
into bags in a continuous VFFS operation. Special
force. Stretch film is used to unitize entire or par-
machinery is required to form heavy-duty shipping
tial pallets stacked with products such as resin
sacks on VFFS machinery in a high-speed continu-
bags, fertilizer bags, consumer goods, and food
ous operation. These bags need moderate coeffi-
products during distribution. Most stretch film is
cient of friction (COF) because they must easily
removed by the retailer prior to displaying the
pass through the packaging equipment, but stacked
packaged items for sale. Stretch films must have
bags must not slide off each other. Bags filled with
the following:

• good cling
• stretchability
• load retention
• puncture resistance.

Heavy-Duty Bags (Shipping Bags)

Heavy-duty shipping sacks are used to transport
items such as the following:

• resin
• salt Figure 3.10 Rotary pallet stretch cling wrapper.

Table 3.20 Edible Oil Packaging

Structure Layers (%) Gauge (μm)

PA/Tie/EAA 10j15j75 50
150
EAA/Tie/PA/Tie/EAA 30j10j10j10j35 50
150
EAA/PA/EAA 40j20j40 50
150

Table 3.21 Bag-in-Box

Structure Layers (%) Gauge (μm)

LLDPE/Tie/PA/Tie/LLDPE 35j10j10j10j35 40
80
EVA/Tie/PA/Tie/EVA 35j10j10j10j35 40
80
LLDPE/Tie/EVOH/Tie/LLDPE 35j10j10j10j35 40
80
48 PLASTIC FILMS IN FOOD PACKAGING

hot products, such as salt, must also withstand the typically made on high-stalk HDPE blown film
filling temperatures without excessive stretching or coextrusion lines.
dimpling. Film toughness and creep resistance are
also important in many heavy-duty shipping sack
applications. LLDPE has allowed significant gauge
High-Clarity Shrink Film (Oriented)
reduction. LDPE is used to reduce creep and Oriented, high-clarity shrink film is used to pro-
improve processability. HDPE and PP are used for tect and display high-value consumer goods. It is
stiffness and higher end-use temperature resistance. distinguished from regular shrink film by its super-
EVA polymers are used for low-temperature seal- ior clarity and appearance as well as increased
ability in form-fill-seal applications (Table 3.23). shrinkage properties and higher stiffness. Goods are
packaged by wrapping the film loosely around the
goods, sealing the film to make a completely
Trash Bags enclosed bag, and then shrinking the film in a
LLDPE introduction is accelerated using coextru- shrink tunnel or oven. Small holes may be poked in
sion in trash (or refuse) bags (Table 3.24). Down the film before wrapping to allow air to escape
gauging and using recycled material allows for while the film is shrinking. As in industrial shrink
improved economics and addresses environmental film, heat causes the polymer molecules to relax,
concerns. High-molecular weight HDPE polymers causing the film to return to its original unoriented
are also finding increased usage due to further size and shrink tightly around the packaged goods.
down-gauging opportunities. This is the largest Since the polymer molecules in oriented shrink
coextruded film market segment. film are much more highly oriented, greater shrink-
age may be obtained. Boxed software and statio-
nery products are often wrapped with high-clarity
Grocery Sacks (Merchandize Bags) shrink film. Ice-cream cartons and other food pro-
High-molecular weight HDPE coextruded with ducts are also wrapped in high-clarity shrink film.
LLDPE provides improved sealability with good Optical properties, seal properties, shrinkage, and
down-gauging potential (Table 3.25). This film is holding force are key requirements for oriented

Table 3.22 Stretch Cling Pallet Wrap

Structure Layers (%) Gauge (μm)

Stretch cling film
EVA/ULDPE/LLDPE 10j 80 j10 15
30
ULDPE/LLDPE/ULDPE 10j 80 j10 15
30
ULDPE/LLDPE/m-LLDPE/LLDPE/ULDPE 10j25j30j25j10 15
30
One-side cling film
m-LLDPE/LLDPE/LMDPE 10j 80 j10 15
30
EMA/LLDPE/PP 10j 80 j10 15
30
POP/LLDPE/PP 10j 80 j10 15
30
ULDPE/LLDPE/LLDPE/e-LLDPE/PP 10j20j30j30j10 10
30

Table 3.23 Heavy-Duty Bags

Structure Layers (%) Gauge (μm)

LLDPE/EPE/LLDPE 1 LDPE 20j60j20 100
200
EPE/PP/EPE 20j60j20 100
200
3: PE-BASED MULTILAYER FILM STRUCTURES 49

shrink film. These structures are normally biaxially properties, some markets may have other barriers to
oriented films of LLDPE and PP (Table 3.26). entry such as qualification cost, experience in the
market, or lack of business relationships. These con-
siderations must be evaluated. The multilayer coex-
3.8 Summary trusion line design requires knowledge of the
specific structures and polymers to be produced. It
It is critical for the flexible packaging film pro- is recommended that mutual discussions with the
ducers to understand their market. Even within a equipment supplier and polymer suppliers be made
given market segment, there are usually several to insure that proper consideration is given to all
film structures that are used. The film producers critical aspects.
must evaluate the alternative film structures to New applications continue to be developed for
determine the best fit for the market identified and multilayer films, and film structures continue to
for their production capabilities. Market trends evolve as new market drivers come into play. The
should be analyzed to determine strategy. The mar- structures highlighted in this chapter are intended
ket studies will dictate which coextrusion/lamina- only as examples and may not represent where
tion equipment design will be optimum. Economic packaging is headed in the future. For example,
evaluation of each market should include the cost sustainability has recently garnered attention in the
incurred in scrap recycle (or disposal). The average marketplace. For packaging, this may mean a num-
production run size and the polymer changes will ber of things, such as down gauging to reduce the
determine the off-spec film produced. A new con- carbon footprint or the use of new biosourced or
sideration for today’s marketplace may also include biodegradable polymers. No matter what the market
some thoughts into after-use disposal of the multi- driver, the principles developed in this chapter
layer film. The design and testing of multilayer remain true. Combining high-performance polymers
film, particularly in the barrier films, will require and low-cost polymers will expand market opportu-
more manpower and overhead costs than typical nities. Understanding how to combine easily the
monolayer film. properties of new polymers and knowledge of the
The markets identified for multilayer flexible market needs and trends will lead to development
packaging should value higher performance proper- of more coextrusion applications.
ties and high-value films. In addition to performance Table 3.27 gives a list of conversion factors.

Table 3.24 Trash Bag Coextrusion Structures

Structure Layers (%) Gauge (μm)

LLDPE/LLDPE 50j50 15
70
LLDPE/RECYCLE/LLDPE 33j34j33 15
70
LLDPE/HMW
HDPE/LLDPE 10j80j10 15
25

Table 3.25 Grocery Bags

Structure Layers (%) Gauge (μm)

LLDPE/HMW
HDPE/LLDPE 10j80j10 12
20

Table 3.26 High-Clarity Shrink Film

Structure Layers (%) Gauge (μm)

PP/LLDPE/PP 25j50j25 15
25
50 PLASTIC FILMS IN FOOD PACKAGING

Table 3.27 Conversion Factors

Property To Convert from: To: Multiply by:

3 3
Density g/cm lb/ft 62.43
2
Pressure lb/in. MPa 0.00689
Output lb/h kg/h 0.45359
Output lb/h g/s 0.125997
Length in. mm 25.4
Specific output lb/h/in.-c kg/h/mm-c 0.017858
Specific output lb/h/in.-c kg/h/mm-d 0.05622
Viscosity poise Pa-s 0.1
2
Viscosity poise lb-s/in. 1.45E-05
2
Stress lb/in. kPa 6.8947
Stress lb/in.2 dynes/cm2 68947
MVTR g 3 mil/100 in. /day
2
g 3 mm/m /day 2
0.394
Permeability cm 3 mil/100 in. /day/atm
3 2
cm 3 mm/mm /s/atm
3 2
4.56E-12
Permeability cm 3 mil/100 in. /day/atm
3 2
cm 3 mil/m /day/atm
3 2
15.5
Weight lb kg 0.4536
Peel or seal strength lb/in. g/in. 454
Peel or seal strength g/in. N/15 mm 0.0058

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Conference, Society of Plastics Engineers. Marcel Dekker, New York, NY.
Schrenk, W.J., 1978. Interfacial flow instability in mul- Zumbrunnen, M.L., Zumbrunnen, D.A., 2009.
tilayer coextrusion. Polymer. Eng. Sci. 18 (8), 620. A new blown film die for controllably forming
Schrenk, W.J., 1984. Flat die coextrusion of film and and extruding micro-layers, polymer blends and
sheet by the feedblock method. In: TAPPI PL&C composites. In: SPE ANTEC, Technical Papers,
Conference, TAPPI Press, Atlanta, GA, p. 269. Society of Plastics Engineers.
 4 Biaxially Oriented Films for Packaging Applications
Jürgen Breil
Brückner Maschinenbeau GmbH & Co. KG/Germany

4.1 Introduction orientation of plastic films represents a refinement

process which is applicable for almost all plastics.
Oriented plastic films for packaging applications Semicrystalline plastics in particular, such as poly-
are industrially produced in large quantities. As propylene (PP) and polyester, also have their crys-
such, the majority are biaxially oriented, which tallinity augmented by the stretching process, which
means that stretching is applied in both directions in considerably improves the mechanical strength.
order to improve the film characteristics in the A similar improvement in properties as a result of
machine direction as well as in the transverse direc- the biaxial orientation process is also observed for
tion (Briston and Katan, 1989). These characteristics many other polymers (polyethylene terephthalate
ideally meet the demands on modern flexible pack- (PET), polyamide (PA), polystyrene (PS), etc.). The
aging. As illustrated in Figure 4.1, flexible packag- exceptional mechanical properties in combination
ing has to fulfill a protective function and allow with the barrier and optical properties and compara-
product design in line with economic and, increas- bly low raw material costs have led to the fact that
ingly, environmental aspects. The required packag- BOPP, biaxially oriented polyethylene terephthalate
ing product protection is attained by the excellent (BOPET), and biaxially oriented polyamide (BOPA)
barrier properties against gases (water vapor, oxy- films account for the largest and most significant
gen, and others) as well as good quality seals. The share among stretched films, which have a large
required product appearance is attained by share in packaging applications.
high-gloss and transparent thin packaging film as
well as by excellent printability. The requirements
for sought-after economic packaging are met by
4.2 Orienting Technologies
good material utilization and the fulfillment of the In orienting technologies, one can, in general, differ-
demand for high-speed packaging lines. Environmental entiate between the orientation draw direction and
aspects, which play an ever-increasing role, can the related stretching process. The existing stretching
be satisfied by utilizing environmentally friendly processes (longitudinal and transverse stretching,
materials (such as polyolefin), as well as the opti- sequential-biaxial stretching, and simultaneous-biaxial
mum raw material yield, thus ensuring maximum stretching) do not depict competitive, but rather sup-
packaging effect with minimum material cost. plementary, features used to attain specific film charac-
The extent to which biaxial orientation improves teristics. As such, the required stretching equipment
properties is shown in Figure 4.2 using biaxially varies depending on the process. Stretching in the
oriented polypropylene (BOPP) in comparison to machine direction is normally done by means of a
nonoriented cast polypropylene (CPP) as an exam- machine direction orienter (MDO) via rolls with
ple. Along with a significant increase in the increasing speeds. Typical products are, for example,
mechanical properties (Young’s modulus, tensile tear strips or PP adhesive tapes. For all transverse-
strength), a considerable improvement in the optical oriented films, the stretching process takes place by
(haze, gloss) as well as the barrier properties can be means of a transverse direction orienter (TDO), where
observed. The overall improved barrier properties the film is fixed on both ends and, upon passing
attained are due to the orientation of the molecule through an oven at various temperatures, is stretched in
chains which, for a nonoriented polymer, are ran- a transverse direction. Typical examples of transverse
dom, whereas in the stretching process, a clear stretched film types are shrink sleeves, where shrink-
molecule-chain orientation occurs. As such, biaxial age merely occurs in the transverse direction. Biaxial

Ebnesajjad: Plastic Films in Food Packaging. DOI: http://dx.doi.org/10.1016/B978-1-4557-3112-1.00004-1

© 2013 Elsevier Inc. All rights reserved. Adapted from a chapter in: Wagner, Multilayer Flexible Packaging (2009). 53
54 PLASTIC FILMS IN FOOD PACKAGING

Premotion
· Optics
· Printing
- Brand identification
- Attractiveness

Flexible
packaging

Protection Health/Environment
· Mechanical · FDA regulations
· Water Vapour · Environmently
· Gas (O2, CO2, ...) friendly production
· Light · Minimum raw -
· Aroma, taste material consumption
· Seal intergrity · Disposal

Economics
· Cost-effective production
· Inexpensive raw materials
· Suitable for fast packaging
machines

Figure 4.1 Flexible packaging requirements for protection, promotion, health/environment and economics.

3500
CPP
BOPP 600 600 80

70

4
850
250 10 1500

560
150 160
1,6 5

50 60 200
30 100

MD TD MD TD H2O O2 CO2 N2
Tensile strength Elongation Haze Glass g25µm cm225µm
(N/mm2) at break (%) (%) m2dbar
m2d
(%)

Mechanical properties Optical properties Barrier properties

Figure 4.2 Property improvement for biaxially stretched PP (BOPP) versus cast PP (CPP).

orientation, in the machine and transverse directions, tapes, labels, and industrial films are manufactured
can be done either sequentially or simultaneously. In with this process. Simultaneous orientation is possible
the sequential process, an MDO and a tenter frame are with the tenter and the blown process (Figure 4.3). The
utilized successively (Hansen et al., 1989; Tobita et al., blown process is a so-called double- or triple-bubble
1999). This process has the widest prevalence for all technology where, initially, a tube is extruded, then
stretched film types. All types of packaging films, rapidly cooled, and then heated to the stretching
4: BIAXIALLY ORIENTED FILMS FOR PACKAGING APPLICATIONS 55

Sequential stretching Simultaneous stretching

MDO/Tenter Tenter systems Double bubble

Paragraph

Spindle

LISIMR

Figure 4.3 Biaxial orientation technologies.

Three-Layer Coextruded BOPP

· Film width from 4,2m up to 10,4
· Production speed up to 550m/min
· Film thickness 10–80µm
· Line output from 700 up to 6000kg/h

Figure 4.4 Sequential-biaxial stretching line.

temperature. A synchronous increase of the draw-off

speed and bubble expansion by internal pressure results
in the required simultaneous orientation process.
Sequential stretching first in the machine direc-
tion and then in the transverse direction utilizing
an MDO and a TDO is the most prevalent process
in use today. Figure 4.4 is a cut-away view of a
three-layer coextruded BOPP line that shows the
main extruder, two coextruders, die and casting
station, MDO, TDO, gauging station, treatment,
and full width winder. Figure 4.5 shows a finished Figure 4.5 Finished 10 m BOPP mill roll.
56 PLASTIC FILMS IN FOOD PACKAGING

LISIM® Technology
Enhancement of film properties
· Enhanced mechanical properties

· Customized shrink properties

· Superior barrier properties

Aroma
H2O
O2

· High sealling properties

Figure 4.6 Enhanced film property possibilities with LISIMs.

10,4 m mill roll after being removed from the winder. will now be explained further. In most cases, ori-
Today, the state of the art for BOPP lines features: ented films for packaging applications are further
processed. The most significant converting processes
• working width 10,4 m, are vacuum coating (metallizing, SiOx, AlOx), offline
• speed 530 m/min, coating (acrylic, polyvinylidene chloride, polyvinyl
alcohol, etc.), lamination with other oriented films,
• output capacity 6000 kg/h.
polyethylene (PE) sealing layers and printing (front
The trend to even higher output capacities will printing, reverse printing). Such downstream proces-
continue in the future. sing will not be discussed in this chapter. Considering
Simultaneous orienting (LISIMs technology; the market for oriented films in general, the various
Breil, 2002) represents an alternative to the preva- raw materials used can be distinguished. Figure 4.7
lent sequential orientation and offers the following shows a breakdown of oriented films manufactured
advantages (Figure 4.6): worldwide. A comparison of the properties of the
most common biaxially oriented film types, BOPP,
• Improved film properties (shrinkage, mechanical, BOPET, and BOPA, is given in Table 4.1. The given
barrier, sealing, etc.), thickness refers to the most common film types. The
various film types mainly differ with regard to their
• High productivity in comparison to mechani-
mechanical, thermal and barrier characteristics and
cal simultaneous systems (speed, width).
these determine the particular application. Also, other
LISIMs technology is available and proven in properties, like thermal resistance or electrical prop-
production scale for BOPP, BOPET, and BOPA. erties, differentiate the film types and predestine
them for specific applications.

4.3 Oriented Film Types— 4.3.1 BOPP Films

Applications
With a worldwide consumption of over 6 million
In addition to the orientation technology outlined tons, BOPP films constitute by far the largest share
previously, the film products and their applications in biaxially oriented film. Its applications are very
4: BIAXIALLY ORIENTED FILMS FOR PACKAGING APPLICATIONS 57

Breakdown of raw materials used for oriented films (2011)

3% 1% 2% 1%
35% 58%

PP PET PS PVC PA Others

Worldwide production capacity

Raw material PP PET PS PVC PA Others Total
x1000tpa 10.250 6.150 603 170 267 230 17.670

Figure 4.7 Production capacity for biaxially oriented film.

Table 4.1 Film Properties of Common Biaxially Oriented Films

Mechanical Properties Unit 20 μm BOPP 12 μm BOPET 15 μm BOPA

2
Tensile strength MD N/mm 140 230 250
2
E-Modulus TD N/mm 280 260 280
2
MD N/mm 2000 4400 3500
2
TD N/mm 3500 5200 3800
Elongation MD % 220 110 110
TD % 70 90 100
Impact strength kg/cm 5 5 15
Tear propagation g 3.5 3.5 7.5
 
Thermal shrinkage % 5% at 135 C 2% at 190 C 2% at 160 C
Density g/cm3 0.91 1.393 1.16
2
Yield m /kg 55 59 58
3 2
OTR cm /m /d 1600 90 40
2
WVTR g/m /d 6.0 8.5 270
300
Surface tension dyn 40 50
55 50
55

diverse and can basically be split into packaging Coextruded films containing three, five or seven
applications, not only in the food sector but also in layers are available, where three-layer coextruded
the nonfood sector. Figure 4.8 shows a few of these film has the largest share. The core layer of PP
applications which play an important role in every- homopolymer is coextruded with the outer PP
day life. A classification of such applications can copolymer layers (Figure 4.10). The outer layers
be made in terms of the thickness range and the have a lower melting point thus ensuring that the
number of layers. The thinnest films are required sealing process necessary for packaging applica-
for electrical applications, such as capacitor film, tions can take place at temperatures that do not
with a thickness of at least 2,7 μm. The thickest deform the main layer. The surface layers essen-
films are used within the synthetic paper sector, up tially serve to define:
to 180 μm. As shown, films with a thickness range
between 15 and 35 μm are widely applied in vari- • the sliding characteristics—friction value,
ous packaging applications (Figure 4.9). surface roughness,
58 PLASTIC FILMS IN FOOD PACKAGING

Figure 4.8 Examples for BOPP film applications.

Industrial Laminated Electrical General General Pearlized Packaging Synthetic

tapes metallized purposes purpose purpose and white purposes paper

30–40μm 10–50μm 3–20μm 15–50μm 12–40μm 30–40μm 30–80μm 30–100μm

Pressure Brochures Cable Flower Lamination Food

Laminatio Catalogs
sensitives tapes catalogues insolution overwrappings (composite film) packaging
bakeries,
Box sealing Print Textiles Food
Capacitors Texties cheese, noodles Manuals
tapes laminatiion (shirt packaging) packaging
Masking Carton Metalizing Hygiene
Release films Cosmeties Release films
tapes boxes (crisps, snacks) articles
Caometic Cigarette Packaging
Labels
boxes Stationary overwrappings bags
goods: Shrinkable
Restaurant photo albums, flims Release films Maps
menus envelope (cosmetics)
Food windows, ...
packaging
Twist films
(sweets)
Mat films
(book covers)

Three-Layer heat 5–7 Layer heat- Mineral

Plain film
sealable film sealable film polymer filled

Figure 4.9 Overview of BOPP film applications.

• sealing properties, • stiffness,

• surface treatment for printing coating adhe- • barrier properties.
sion and metallizing properties,
For some applications, five-layer films and, in
• hot tack, certain cases, even seven-layer films are used
• antistatic, (Wellenhofer 1979). The advantages of five-layer
• optical properties (haze, gloss), technology are, on the one hand, improved charac-
teristics, such as better optical, gloss, transparent,
• whiteness,
opaque properties, as well as cost advantages;
4: BIAXIALLY ORIENTED FILMS FOR PACKAGING APPLICATIONS 59

Three-layer transparent film

Heat-sealable skin layers

Transparent core layers

Five-layer cavitated film

Heat-sealable skin layers

Voided core layer

Intermediate layers

Figure 4.10 Typical BOPP film structures.

Film type Thickness Examples for end-use application

category (μm)

Wrap-around White voided film, both sides high

35–50
labels gloss, one side treated

Wrap-around White voided metallized film,

35
labels High-gloss surfaces, very high yield

White voided metallized film, heat

Food packaging 35 sealable, high protection against
light (ice cream)
White voided film, both sides heat
Food packaging 30–50 sealable, high protection against
light

Business cards,
40–80 Synthetic paper
maps, bags

Paper lamination 15–40 Matt film

Figure 4.11 Five-layer film applications for BOPP.

expensive additives are predominantly added in the • More cost-effective structures without impair-
thinner intermediate layers. Five-layer film struc- ing the optical film quality by using higher
tures allow for more flexibility by implementing levels of recycled material and reducing the
intermediate layers between the main layers and amount of additives,
skin layers. The following benefits can be obtained: • Increase the seal properties by adding low-
sealing copolymer onto a comparatively thick
• Use of special masterbatches for the main, PP copolymer layer as an intermediate layer.
intermediate, and skin layers to change optical
properties: An overview of five-layer applications is given
• a high-opacity film, for example, white in Figure 4.11.
opaque films, As one example, Figure 4.12 shows the struc-
• provide high-gloss or matte surfaces. ture, advantages, applications, and seal strength
60 PLASTIC FILMS IN FOOD PACKAGING

Structure Application

A: Copolymer/coroma
treated surface
B: PP
C: PP core layer
D: Copolymer
E: Low-SIT sealant

Advantages
6
· High seal integrity 5.5

Seal strength (NJ15mm)

5-layer
5
· High-packaging speed 4.5
4
3.5
3 3-layer
2.5
2
1.5
1
0.5
0
90 95 100 105 110 115 120 125 130 135 140 145
Sealing-law temperature (°C)

Figure 4.12 Five-layer low-SIT BOPP film structure.

Structure Application

Metallized surface

A: High surface.
energy polymer
B: Adhesive layer
C: PP core layer
D: PP
E: Co-polymer

Advantages
· Excellent gas and aroma barrier
- OTR: 0.15 (cm3/m2dbar) 23°C/75%
- WVTR: 0.2 (g/m2 d) 38°C/90% r.F.
· Good sealability
· Good optics

Figure 4.13 Five-layer metallized UHB BOPP film structure and advantages.

versus sealing-jaw temperature for a five-layer this particular product design, the first surface is a
low-seal-initiation temperature (SIT) BOPP film. polymer with a high surface energy (PA, ethylene
A very high-seal strength and sealed seam rigidity vinyl alcohol (EVOH), and others). This polymer
is achieved with this structure. This characteristic requires a tie or adhesive layer to bond to the
is vitally important for many packaging applica- PP main layer. The fourth layer is also PP and is
tions, since both the film and the sealed seam covered with a heat-sealable copolymer skin. The
quality provide the necessary product protection. metallized properties of this structure, compared
Another example of the diversity of five-layer to PP homopolymer or PP copolymer surfaces,
structures is given in Figure 4.13 which represents show a much better adhesion strength and metallized
an ultra-high-barrier (UHB) metallized film. In surface uniformity. The combination of the barrier
4: BIAXIALLY ORIENTED FILMS FOR PACKAGING APPLICATIONS 61

Structure Application

A: Skin
B: PP blend
C: Tie layer
D: Barrier layer
E: Tie layer
F: PP blend
G: Skin

Advantages
· Superior oxygen barrier <2cm3/m2bar
· Excellent optics
· Low-temperature sealing properties

Figure 4.14 Seven-layer transparent barrier film.

properties of the skin layer and metallization results stretching ratios, and, furthermore, the implementa-
in 300 times better oxygen-barrier values than tion of the sequential orientation process. For the
obtained by standard metallized BOPP films. The simultaneous orientation process, however, it is
UHB metallized film example shows that, when possible to stretch all types of EVOH with an
suitable barrier materials are combined, the overall ethylene content of 24
47%. Although the barrier
barrier characteristics (OTR and WVTR) can be sub- properties of the EVOH types are increased, in
stantially enhanced. Metallized film also provides view of the orientation process, it is still the case
a light barrier and UV protection. that EVOH with a high ethylene content has con-
There is also a demand for transparent barrier siderably poorer barrier properties. This is illus-
films which is being satisfied by clear barrier coat- trated in Figure 4.15 showing an evaluation of the
ings, but this is also possible to realize by coextru- oxygen barrier in various EVOH types and orien-
sion, i.e. with seven-layer structures. Seven-layer tation with area-stretching ratio of almost 50. It
technology is particularly suitable for such films, can therefore be concluded that the use of EVOH
since it is possible to attain the required barrier types with an ethylene content of not more than
values without metallizing. In this case, a barrier 33% is particularly beneficial, since a good oxy-
material preferentially EVOH is applied in the mid- gen barrier of less than 2 cm3/m2/d bar can be
dle of the main layer imbedded between the tie attained with thin layers of 2 μm thickness. This
layers. Furthermore, such symmetrical film layer value can easily compete with other high-barrier
configuration has the advantage that the occurrence film types, which are off-line coated. The exam-
of curling becomes less likely. A typical seven- ples of multilayer BOPP films demonstrate the
layer configuration is shown in Figure 4.14. Such wide variability of structures achievable by imple-
seven-layer structures with the application of vari- menting coextrusion technology. This also applies to
ous polymers, such as PP and EVOH, can be manu- other film types such as BOPET and BOPA. There is
factured with sequential and with simultaneous a strong trend to enhance the barrier properties further
orientation technology. However, upon selection of with a minimum of packaging material, so there is no
the types of raw material to be used, one has to doubt that coextruded oriented films will continue
bear in mind the divergence of the various process with stable growth rates.
requirements for the particular stretching process. BOPP films are widespread, not only in transpar-
The available types of EVOH resin show a distinct ent applications but also as white opaque film types
correlation between the ethylene content and the which are mainly used for packaging and labeling.
stretchability on the one hand and, on the other Inorganic additives (e.g., calcium carbonate) are
hand, with the barrier values. Generally, it can be implemented in the polymer matrix (Jabarin,
said that a higher ethylene content implicates a 1993). These particles lead to an initial flaking/
less-complicated orientation process, permits higher separation from the polymer matrix during machine
62 PLASTIC FILMS IN FOOD PACKAGING

Seven-layer barrier film

influence of EVOH-ethylene content on OTR-values
4,5
Sequential
4
3,5 Stretching ratio MD XTD=7x7

(cm3x20µm/m2xdxbar)
OTR 23°C@75%RH
Stretching temperature=160°C
3 Stretching speed=400%/s
2,5
2
1,5
1
0,5
Simultaneous
0
25 30 35 40 45 50
Ethylene content (%)

Figure 4.15 Evaluation of the oxygen barrier with the use of various EVOH types.

Top View

Formation of vacuoles

Y Microscopic hollow space

Z
Pigment

X
Polymer
Side
Top
"Pearl effect" due to varying refractive indices

Figure 4.16 Cavitated BOPP film mechanism.

direction orientation, so that, during consequential order to attain good printability. Figure 4.17 shows a
transverse direction orientation, small cavities occur 100 μm synthetic paper cross section showing the cal-
(Figure 4.16). These so-called vacuoles cause the cium carbonate particles, the cavities, and the
light to be refracted in varying ways such that nondensity-reduced skin layers. Synthetic paper is
the required pearl effect arises. At the same time, frequently coated in further processing in order to
the density reduction increases the yield proportion- attain a better absorption and a quicker drying of the
ally. Both aspects are mainly used for confectionary, printing inks.
chocolate bars, ice cream, etc. Synthetic paper takes a
special role among cavitated BOPP films. The effect
of vacuole formation during orientation is also made 4.3.2 BOPET Films
use of, where a larger density range of 0.6
0.9 g/cm3 BOPET films, with a consumption of approxi-
can be produced. Applications for synthetic paper are mately 2 million tons per year, are the second most
extremely wide-ranging and cover a large thickness common oriented film, following BOPP. In the past,
range (Table 4.2). Three-layer and five-layer films BOPP films dominated in packaging applications and
are coextruded where the surface is optimized in BOPET films dominated in technical applications.
4: BIAXIALLY ORIENTED FILMS FOR PACKAGING APPLICATIONS 63

Table 4.2 Thickness Range for Synthetic Paper

Thickness (μm) Recommended Applications

50
180 Pressure sensitive, cut and stack, and wrap-around labels; release liners, posters,
and ink-jet printing base
75
100 Pressure sensitive, wrap-around and in-mold labels
75
200 Cut and stack and wrap-around labels, posters, maps, shopping bags, business
cards, calendars, and banners
75
250 Labels, books, posters, and calendars
75
400 Maps, posters, tags, cards, charts, menus, phone cards, calendars, and banners
130
700 Carriers, files, and folders
250
1000 Cards, tags, book covers, folders, charts, and maps

Three-layer coextruded, thickness 100μm These characteristics reflect the specific beneficial
features for the various applications accordingly
(Figure 4.18). Variants ensue from the different
stretching processes, recipes, coextrusion, and coating
processes. In the sequential stretching process,
the longitudinal
transverse (MD/TD) process is
dominant (Tsunashima et al., 1999). However, the
transverse
longitudinal (TD/MD) and longitudi-
nal
transverse
longitudinal (MD/TD/MD) pro-
cesses are also applied. For the MD/TD/MD process,
higher stiffness values in machine direction can be
achieved. The simultaneous stretching process is
applied to very thin films, for example, for capacitor
Figure 4.17 Cross section of 100 μm BOPP films, and contact-free stretching technology is also
synthetic paper. used for thicker film with high-quality optical uses.
In view of the good stiffness values and sliding prop-
Biaxially oriented polyester film, with its high rigid erties in the packaging sector, the benefits, such as
properties, was ideal as a carrier film for magnetic excellent machinability plus good printability and
tapes, floppy disks, and capacitors. Since this mag- optical appearance, are applied. With coextrusion,
netic recording medium has been replaced by optical sealable or matte surfaces can be attained
data media, this application has nearly disappeared in (Figure 4.19). Furthermore, a frequently applied
a short time. At the same time, however, an increase advantage of coextrusion technology is the applica-
in the prevalence of BOPET films in the packaging tion of inorganic additives in the thin outer layers, in
industry has taken place, resulting in a worldwide order to adjust the required friction coefficient with-
growth of 4
5%. out having a negative influence on the transparency.
The basic characteristics are: In-line coating processes are also widespread which
ensure optimum printing ink adhesion. A common
• high mechanical strength, downstream processing phase of BOPET film is met-
allizing, which is mainly used to improve the barrier
• good temperature and chemical resistance, properties, but also to attain an attractive visual
• dimensional stability over a broad temperature appearance. For numerous food wrappings, the bar-
range, rier properties, in terms of oxygen and aroma, are
• adjustable friction coefficient, particularly vital criteria to ensure that the required
minimum shelf life is attained. With metallizing, an
• excellent optical clarity, oxygen permeation value of ,1 cm3/m2/d bar can be
• good printability. reached (Figure 4.20).
64 PLASTIC FILMS IN FOOD PACKAGING

Packaging Metallized Electrical Graphic arts Other

Magnetic tapes Magnetic use
as laminates films purposes and X-ray applications
6–12µm 6–76µm
8–25µm 6–19µm 0,5–350µm 20–200µm 10–125µm

Food Metallic yarns X-ray

Audio tapes Audio tapes Cable wrapping Adhesive tapes
packaging fashion photo film
Electro
Video tapes Video tapes Pouches Packaging Micro films Green houses
insulation
Cassettes, Computer Fatty and Hot foil Slot liners
Litho films Stiffeners
computer tapes tapes oily foods stamping motor insulation
Micro cassette Floppy Coffee bags Solar control
Capacitors Graphic arts Release films
tapes disks (under vacuum) mirrors
Shrinkable Wall covering Flexible Drafting films
Carbon ribbon Label cards
films decoration circuits engineering
Medical supplies Thermal Overhead
A-PER/C-PET transfer tapes projection

photo resist

Prepress

Tensilized film Balanced film

Figure 4.18 BOPET film applications.

Trends in BOPET films—packaging grades

· Co-extrusion process allows wider application window
Skin A: additives for better winding, converting

Core: clear and recycled polymer

Skin B: Skin B: Skin B:

increase barrier Heat sealable using Mattfilm with
properties, i.e., PEN i.e., PET-G fillers

Figure 4.19 Coextruded structures in BOPET.

Biaxially oriented polyester packaging films are 4.3.3 BOPA Films

frequently laminated with BOPP, PE film, alumi-
num foil, or other packaging material. A typical With a worldwide consumption of 250,000 tons
laminate structure is shown in Figure 4.21 as an per annum, BOPA films represent a small specialty
example coffee wrapping. The polyester film is segment, predominantly used in the packaging
reverse-side printed and laminated with aluminum sector (Goetz, 2005). In view of the excellent punc-
foil as a barrier layer and polyethylene film as a ture resistance along with good oxygen and aroma
sealing layer. Good transparency, high gloss, and barriers, BOPA is primarily used for flexible wrap-
the print quality are thus reflected in the image pings for sausages, cheese, fish, and liquid contents
appearance. (Figure 4.22). Thickness is normally in the range of
12
25 μm with a dominant fraction of 15 μm.
4: BIAXIALLY ORIENTED FILMS FOR PACKAGING APPLICATIONS 65

Transmission rates for oxygen and water vapour

10,000

1000 PP
BOPP

OTR (cm3/m2dbar)
100
PET

10 BOPP-met BOPET

BOPET-met
0.1

0.01
0.1 1 10 100
WVTR (g/m2d)

Figure 4.20 Comparison of transmission rates for PP and PET.

Structure
Triex-Laminate, i.e., for coffee, tea, peanuts, cosmetics
· Coffee
- PET12-alufoil-PE60
· Coffee bag
- OPP30-reverse print-PET12met-PE60
· Peanuts
- PET12-alufoil-PE60
· Cosmetics sachets
- PET12-alufoil-PE40

40–60μm sealable PE
Adhesive
7 or 9μm alufoil
Adhesive
Reverse printing
PET film 12 μm

Figure 4.21 Typical packaging lamination structures with BOPET film.

Typical applications

· Frozen foods

· Cooked foods

· Pickled vegetables

· Agricultural products

· Aquatic products

· Medical products

· Designer balloons

Figure 4.22 Typical applications of BOPA film.

66 PLASTIC FILMS IN FOOD PACKAGING

Special applications, such as gas-filled balloons, are 4.3.4 Biaxially Oriented

primarily made from metallized thin BOPA film
Polystyrene Films
(10
12 μm).
In principle, all the above-mentioned stretching The worldwide market demand for biaxially
processes are suitable for manufacturing BOPA oriented polystyrene (BOPS) film amounts to approx-
films, so that sequential, simultaneous and double- imately 600,000 tons per annum and is basically split
bubble lines are used. Sequential stretching lines into two market segments (Nentwig, 1994). Thinner
with longitudinal
transverse process and a working 30
150 μm films are suited for applications such
width of 4
5 m are widely abundant. as envelope windows and separating film for photo
For packaging applications, BOPA films are albums, and thicker 150
800 μm films are mainly
laminated with other films, mainly PE, in order to cover applications such as deep-draw vacuum pack-
ensure sealability in bag manufacture. Typical lami- aging film (Figures 4.22, 4.24, and 4.25). Thinner
nate structures are shown in Figure 4.23. film types very often require a matte surface, and
deep-draw applications require high transparency
and luster. In addition, a good deep-draw perfor-
mance has to be ensured and can be adjusted via
the stretching parameters.
Converting: multilayer film BOPS films are produced exclusively by the
Cheese PE 40–50μm sequential process (longitudinal
transverse). In order
· Cheese slices
OPA 15μm
to make the cast sheet, a roll stack is used to ensure
· Block hard cheese
that the thick film has optimum surface quality.

OPET 12μm
Meat
OPA 15μm
4.3.5 Other Biaxially
· Minced meat
Oriented Films
PE 50μm
Besides the oriented films previously discussed
PE 60μm (BOPP, BOPET, BOPA, and BOPS), various other
Crisp and Snacks
· Peanuts
OPA 15μm specialty film types need to be mentioned.
Coex OPP 30μm Biaxially oriented polyethylene (BOPE) films are
solely in use as shrink film applications, where there
Figure 4.23 Typical packaging lamination are many different products varying in layer structure,
structures with BOPA film. recipe, and process parameters. In principle, each

Figure 4.24 Examples of BOPS film applications.

4: BIAXIALLY ORIENTED FILMS FOR PACKAGING APPLICATIONS 67

application has its own tailored shrink values, shrink monoaxially and biaxially oriented and yields
forces, strengths, and barriers. Barrier properties an attractive property spectrum (Figure 4.26). In
preferably are attained by coextrusion with EVOH. particular, the excellent visual appearance has
For the production of BOPE shrink films, the double- made it an interesting alternative for packaging.
bubble process is almost solely used. Furthermore, the deadfold characteristics should
Oriented films from renewable resins represent be noted which are a prerequisite for twist wrap.
another quite new film type on the market at pres- Compared with other packaging films, the water
ent and are biodegradable. Polylactide (PLA) is the vapor barrier, however, is considerably inferior,
major resin used since it has attractive properties although to some extent this can be compensated
and is already available in large quantities. The for by metallizing or SiOx coating. Further uses
raw material is primarily corn. PLA film can be ensue in view of the permeability for water vapor

Thin film (30–150μm) Thermoforming film(150–800μm)

Printing base film— Cake and pie domes Sandwich containers

Envelope windows
labels, inserts,
twist wrap
displays Fresh product
Biscuit and containers
Recipe cards candy trays
Page protectors Salad trays
Pressure-sensitive
coating and metallizing Medical devices
Microwave
oven packs
Graphic arts film Deli tubs
Laminations
Chocolate box
Fast-food containers inserts
Photo albums
Transparencies Portion control
packaging Display packs for
fresh flowers

Display blister packs Clear cup lids

Figure 4.25 BOPS film applications.

Product features

Optical properties
· High transparency
· Exceptional surface gloss

Converting features
· Twistable with excellent deadfold
· Both sides sealable
· Low-sealing temperature
and high seal strength
· Thermoformatble
· Printable
· Adhesive or thermolaminatable
to paper/board

Figure 4.26 Product features for biodegradable polymers (PLA).

68 PLASTIC FILMS IN FOOD PACKAGING

· Bags for bread and other bakeries

· Packaging for fresh food—agricultural products

(high WVTR works like anti-fog and can enhance
shelf life, high stiffness suggest freshness)

· Packaging for cheese and butter

(deadfold retention)

· Bags for cheese and salami

(enables riping—longer shelf life)

· Shrink sleeve film

and high-modulus label films

Figure 4.27 PLA film applications.

Figure 4.28 Shrink film applications.

and, thus, such a characteristic is most suited for transverse direction. These are used solely as shrink
bread and vegetable packaging (Figure 4.27). films where it is necessary that the films only
shrink in the transverse direction and machine
4.3.6 Film Oriented in Transverse direction shrink is not required. Such films are,
to a large extent, used as sleeves and this anisotro-
Direction pic shrink behavior is required in order that the
A relatively large and strongly growing market container-contours appear clearly, and the desired
segment is represented by films oriented in the print is attained (Figure 4.28).
4: BIAXIALLY ORIENTED FILMS FOR PACKAGING APPLICATIONS 69

80

70

60
OPET
Shrinkage (%) 50
OPVC
OPS
40
OPP
30

20

10

0
50 55 60 65 70 75 80 85 90 95 100
Temperature (°C)

Figure 4.29 TD shrinkage versus temperature for four shrink films.

Shrink values of up to 80% in the transverse direc- line scale that all functions of a complex triplex lam-
tion can be attained, whereas full body sleeves can inate could be attained by a coextruded stretched
also be attained for containers with strong contours. film manufactured in one process step. In view of
Polyvinyl chloride, PS, PET-G, and PP materials limited crude oil resources, coupled with ever-
are used where, in terms of shrinkage, the different increasing oil prices, plastics manufactured from
characteristics of these materials become apparent crude oil bases are also subject to price increases.
(Figure 4.29). This, accordingly, gives a boost for alternative mate-
rials and thus the possibility of cost-efficient produc-
tion on an industrial scale. The production of
4.4 Trends for Oriented Films suitable stretchable films for packaging applications
from such alternative raw materials is evident in the
Basically, oriented films are most suitable for
PLA example. One can predict that much research
meeting the trends in the packaging sector set by
and development will be performed within this sec-
politics, society, and the industry. Packaging regu-
tor in the near future.
lations, compel the industry to give consideration
not only to the material and manufacturing costs
but also to the disposal costs and in future perhaps
to the CO2 footprint. This induces one to use mini- References
mum packaging material to achieve maximum pro-
tection with packaging. These goals can only be Breil, J., 2002. Added value speciality films pro-
reached with high-strength materials to reduce duced with sequential and simultaneous stretching
thickness while meeting the protection and barrier lines. In: 18th Annual Maack World Congress,
functions, plus operational properties that ensure Speciality Plastic Films, 29
30 October 2002,
high-speed packaging. With sophisticated orienting Switzerland, Zurich.
processes (e.g., simultaneous stretching technol- Breil J., Lund, R., 2008. Development of new
ogy), a significant increase of strength and barrier BOPP barrier films by coextrusion and simulta-
can be attained for all plastics. Furthermore, future neous biaxial orientation, September, Portsmouth,
potential in terms of packaging can be further VA, Tappi place Conference.
developed, for example, by the substitution of alu- Briston, J.H., Katan, L.L., 1989. Plastic Films, third
minum foil with transparent or metallized high- ed. Longman Scientific and Technical, Harlow.
barrier stretched film. Another large potential lies Goetz, W., 2005. Polyamide resin for BOPA film.
within the integration of many-function layers in Polyamide 2005, Maack Conference, Dusseldorf.
the production process of oriented films, so that Hansen, F., Knappe, W., Potente, H., 1989.
complex processing steps can be waived (Breil and Handbuch der Kunststoff-Extrusionstechnik. Carl
Lund, 2008). For example, it was proven in pilot Hanser Verlag, Munich.
70 PLASTIC FILMS IN FOOD PACKAGING

Nentwig, J., 1994. Polystyrol, Kunststoff Folien, properties of biaxially oriented film. In: Kanai,
Herstellung—Eigenschaften—Anwendung. Carl T., Campbell, G.A. (Eds.), Film Processing. Carl
Hanser Verlag, Munich. Hanser Verlag, Munich.
Tobita, K., Miki, T., Takeuchi, N., 1999. Biaxially Wellenhofer, P., 1979. Monoaxiales und biaxiales
oriented film. In: Kanai, T., Campbell, G.A. (Eds.), Recken mit besonderer Berücksichtigung des
Film Processing. Carl Hanser Verlag, Munich. biaxialen Flachfolienstreckens. In: Folien, G.
Tsunashima, K., Toyoda, K., Yoshii, T., 1999. (Ed.), Vliesstoffe aus Polypropylen. VDI-Verlag,
Stretching conditions, orientation and physical Dusseldorf.
 5 Development of High-Barrier Film for Food Packaging
Maryam Fereydoon1 and Sina Ebnesajjad 2
1
École Polytechnique de Montréal, Montreal, Quebec, Canada; 2President, FluoroConsultants Group, LLC

The first and most important function of pack- Under steady-state conditions, the permeability
age is the protection of food products. Packages coefficient is defined as “the rate at which a quan-
protect food from the loss of nutrients, functional tity of permeant passes through a unit surface area
properties, color, aroma, taste, and preserve the of polymer in unit time having unit thickness with a
general appearance expected by consumers. A unit pressure difference across the sample” (Selke,
good package should create an acceptable barrier 1997). The number of permeant molecules that pen-
between the food and external environment, partic- etrate into a package depends on the characteristics
ularly with respect to water vapor, oxygen, and of the polymer, the characteristics of the penetrat-
microorganisms. The shelf life, the length of time ing molecules, their interaction and cross-effects,
that product remains in an acceptable condition for the temperature, and the permeant concentration
use, strongly depends on barrier capability of a inside and surrounding the package. However, the
package. The second function of the package is to gas transport coefficients vary according to the
transport the product in a convenient manner. nature of the polymer (chemical structure), polymer
Finally a good package should provide clear infor- properties such as the degree of crystallinity, and in
mation about the food to consumers and attract some cases the thermal and mechanical histories of
them to buy it. Food packaging, regardless of its plastic films. Orientation also has a major influence
material, is intended to protect the food from con- on the barrier properties and mechanical perfor-
tamination and preserve the quality of the food mances of both semicrystalline and amorphous
from manufacturing to retail sales and consump- polymers. According to this fact, it is possible to
tion. For use in packaging applications, a polymer improve the barrier properties of the polymers by
needs some attributes such as mechanical strength inducing the orientation of the polymer molecules
to allow the packaged food to withstand the rigors during the process or post-processing of the films.
of handling, transportation, storage, refrigeration Oriented films are significantly stronger than unor-
and consumer handling, abrasion, and irradiation. iented ones.
Food packaging also needs appropriate thermal sta- Actually, monolayer films are not able to bring
bility for thermal processing such as retort and ster- all the properties required for the food packaging.
ilization process. The focus of this chapter is on In addition, single-layer films are generally quite
the barrier properties aimed at the preservation of permeable to a variety of gases. Barrier films are
the quality of food. usually multilayer films that have been designed to
be impervious to gas migration. Multilayer films
are widely used for food packaging applications
5.1 Introduction and can be produced by thermal lamination, coat-
ing, or coextrusion technologies. Combining differ-
The barrier property of a polymer refers to its ent polymers in order to design a multilayer film
ability to transfer a permeant through it. When a structure with excellent barrier property to gas (usu-
polymer is exposed to a permeant having different ally water vapor and oxygen) and high mechanical
concentrations on its two sides, the permeant passes and optical performance without significant cost
through the polymer by net effect from the high- increase is the main challenge in food packaging
concentration to the low-concentration side in three industries.
steps: sorption to polymer, diffusion, and desorp- Over the past decades, plastic packaging materials
tion from polymer (Figure 5.1). have been optimized to match product-specific

Ebnesajjad: Plastic Films in Food Packaging. DOI: http://dx.doi.org/10.1016/B978-1-4557-3112-1.00005-3

© 2013 Elsevier Inc. All rights reserved. 71
72 PLASTIC FILMS IN FOOD PACKAGING

sensitivities and minimize environmental impacts. contamination, delay spoilage, and permit some
Therefore, packaging materials are sometimes very enzymatic activity to improve tenderness and
complex. In the area of packaging, particularly food decrease weight loss. In cooked, cured, packaged
packaging, multiple layer films have been developed food products, factors such as percentage residual
by incorporating one or more layers of the same oxygen, oxygen transmission rate (OTR) of the
polymer or different types of polymers blended or packaging material, storage temperature, light
coextruded together to provide good transparency, intensity, and product composition are critical fac-
excellent mechanical performance such as tensile and tors affecting quality, stability and ultimately con-
impact strengths, gas barrier properties, moisture bar- sumer acceptance. Exposure to light in combination
rier property, optical properties, and thermal and with even low levels of oxygen in food packages
dimensional stability. Application examples include may facilitate microbial growth, thereby causing a
packaging for meat, potato chips, cheese, snack significant reduction in the shelf life of foods.
foods, and pharmaceuticals. Although oxygen-sensitive foods can be packaged
Interest in the use of intelligent and active pack- accordingly using vacuum packaging, such techni-
aging systems for food packaging has increased ques do not always facilitate complete removal of
recently. The most common food quality defects oxygen. Oxygen that is transferred through the
caused by microorganisms are associated with packaging film or is trapped within the product
water vapor and oxygen entry into the packaged cannot be removed by these techniques. Oxygen
food. Loss of moisture and flavor that are trans- scavengers and oxygen absorbing systems improve
ferred out of some foods also results in a loss of product quality and shelf life by absorbing the
quality. Active packaging refers to the incorpo- residual oxygen after the packing.
ration of certain additives into packaging systems The function of carbon dioxide in a packaging
(whether slack within the pack, attached to the environment is to reduce microbial growth.
inside of packaging materials, or incorporated Therefore, a carbon dioxide-generating system can
within the packaging materials themselves) with the be viewed as a technique complimentary to oxygen
purpose of improving the shelf life and quality of scavenging. In some cases, releasing of carbon
food. Active packaging systems include oxygen dioxide by simultaneously consuming oxygen is
scavengers, moisture control agents, and antimicro- desirable. In such cases, systems are based on either
bial packaging technologies. Intelligent packaging ferrous carbonate or a mixture of ascorbic acid and
systems are those that monitor the condition of sodium bicarbonate.
packaged foods to give information regarding the Intelligent packaging, defined as systems that
quality of the packaged food during transport and check the condition of packaged foods to give
storage. In some cases such as fresh food packag- information about the quality of the packaged food
ing, intelligent packaging is carried out to avoid during transport and storage, is another category of
packaging of interest recently. Intelligent packaging
concepts involve the use of sensors and indicators
that consist of a receptor and a transducer. The
Permeable material
receptor receives the physical or chemical informa-
tion and transforms it into a form of energy. The
Sorption information can be measured by the transducer.
The transducer is a device capable of transforming
the energy carrying the physical or chemical infor-
Diffusion
Desorption
mation about the product into a useful analytical
signal that can be monitored.

Net transfer
5.2 Background
High concentration Low concentration
Generally, categories of packaging are classified
Figure 5.1 Permeation of a substance through a according to the function of the package, including
plastic packaging material (Selke, 1997). its barrier properties, strength, ability to withstand
5: DEVELOPMENT OF HIGH-BARRIER FILM FOR FOOD PACKAGING 73

abuse during filling and shipping, sealability, opti- damage due to external forces. The polymers that
cal and clarity properties, and so on. The material are typically used as the abuse layer are polypro-
used to structure design the package is classified pylene (PP), high-density polyethylene (HDPE),
according to the package function. For example, linear low-density polyethylene (LLDPE), polyam-
from the point of view of barrier function of the ide (PA), and polyethylene terephthalate (PET).
package, there are two categories of films. The first The sealant layer of the multilayer structure pro-
category is the films that are used as barriers; they vides a hermetic seal to protect the product.
keep liquid or gasses on one side of the film. The Copolymers consisting of ethylene are often used
second category consists of films that are used as as sealants because of their low melting points.
membranes that allow certain materials to pass However, the polymers with low temperature heat
through the membrane but block others. Barrier sealants, such as low-density polyethylene (LDPE),
film applications include packaging, coating, ethylene vinyl acetate (EVA), LLDPE, metallocene
gloves, containers, hoses, and tubing. Generally, polyethylene (mPE) plastomers, acid copolymers,
packaging materials may be classified into three and ionomers, are used as the seal layer. The selec-
categories: flexible, semirigid, and rigid. tion of the best sealant for a given application
depends on what the sealant needs to contribute to
• Flexible materials’ applications may include the overall performance of the package. These fea-
wraps, lidding, pouches, or bags, and its films tures may include seal initiation temperature, hot
are of a thickness equal to or less than tack over a wide temperature range, caulkability,
0.127 mm (5 mil). clarity, puncture resistance, stiffness, tensile
• Semirigid materials are thicker than strength, and compatibility with adhesive layers.
0.127 mm. They are usually formed as sheets. In the core layer, the polymers with low gas perme-
ability are used, such as aliphatic polyamide 6, aro-
• Rigid materials’ applications may include matic polyamide MXD6, ethylene vinyl alcohol
trays, boxes, or crates, and are composed of (EVOH), or polyvinylidene chloride (PVDC).
thick films or rigid polymers. Beverage pack- Special tie resins or adhesive layers are used to
aging mostly is in the rigid category, which combine the outer layers, skin layers, and core
covers a broad range of applications. layers via coextrusion or lamination. Table 5.1
shows OTR of a number of plastic films that are
To design a flexible film structure of a multi- well known in the market as good oxygen barriers.
layer to meet packaging requirements, particularly The data indicate orders of magnitude differences
for food packaging applications, materials are among the oxygen barrier properties of different
selected according to the package function and cost plastic films.
consideration, and cost to the environment is In the design of a multilayer structure, the selec-
another main consideration in package design. tion of material for each layer is done according
At the same time, the package must be cost- to the preferred functional requirements of the
effective. Costs include the cost of materials and package. Many food products need to be protected
packing waste as well as costs to the environment. against the gain or loss of moisture. Materials such
Finally, the package structure must satisfy the con- as coated cellophane, polyethylene (PE), PP, poly-
sumers’ desire in the aspects of sustainability, vinylidene chloride (PVC), and polyester films are
safety, and legislation. However, the performance excellent barriers to water vapor and are used to
of a package should be determined by the market obstruct the transmission of water vapor through
potential for any particular product. the film. These materials are often used on the out-
Most food packages have multilayer construc- side (and inside) layers of multilayer films. It
tions to achieve the desired functional requirements should be noted, however, that even the most
of the package in a cost-effective manner. impermeable of these films has a measurable
Generally speaking, in any multilayer structure sev- permeability.
eral layers are seen. The outer layer of a multilayer Other products such as fresh vegetables need to
structure consists of an abuse-resistant layer. The breathe; so to avoid condensation of water, materi-
purpose of using such a layer in the design of a als such as polyolefin plastomers and certain grades
package is to protect or preserve its contents from of cellophane are used for these applications. The
74 PLASTIC FILMS IN FOOD PACKAGING

Table 5.1 High Oxygen Barrier Polymers (Giles and Bain, 2000)

Oxygen Permeability Oxygen Permeability

Material (cm3  mm/m2/day atm, 0% RH) (cm3  mm/m2/day atm, 100% RH)
LCP 0.003 0.003
PVDC 0.004 0.004
EVOH 0.003 0.25
MXD6 0.09 0.1
PA6 0.5 1.3
PET 1.5 1.5
PEN 0.3 0.3

rate of water vapor transmission (WVT) will its functional groups which influences the mecha-
depend upon the vapor pressure gradient across the nism of diffusion in macromolecular compounds.
film. Dry contents in a humid environment would Table 5.2 shows the water transmission rate of a
absorb moisture, wet contents in a dry environment number of plastic films. The data indicate orders of
would lose moisture, and if the relative humidity magnitude differences in the moisture barrier prop-
(RH) inside and outside the package are equal, erties of different plastic films. For example, the
there will be no transmission even through the most water vapor transmission rate (WVTR) of polycar-
permeable of films. bonate (PC) is greater than that of polyvinylidene
Oxygen, carbon dioxide, and nitrogen within a chloride (PVC).
package often must be controlled. If oxygen is
allowed into a package, it may speed up the degra-
dation of organic materials by initiating or acceler- 5.3 Improvement of Barrier
ating the decay process. Uncontrolled, this will Properties of Films
promote staleness and loss of nutritive value. In the
case of fresh meat, a high rate of oxygen transmis- Developing high-barrier films has been the main
sion is required to maintain its bright red color. To challenge for film suppliers. Surface modification,
meet this special requirement, special grades of cel- crystallization and orientation, blending, and incor-
lophane, PEs, and nitriles have been developed to poration of nanoparticles as an impermeable phase
provide the low WVT needed to avoid drying the have been suggested by researchers for the
meat while providing high oxygen transmission to improvement of barrier properties.
maintain the color. Typically, it is difficult to obtain all the desirable
This phenomenon of high transmission of oxy- barrier properties from a single film layer. Polymer
gen combined with low transmission of water suppliers and the plastic film manufacturers have
seems paradoxical but is very critical to these spe- long recognized the need for multilayered, lami-
cialized needs. The reverse characteristics apply to nated, coextruded, coated, and metalized films to
PA and other films that have a relatively high per- meet the varied requirements of food packaging.
meability to water vapor but a low permeability to High-barrier packaging can comprise several differ-
oxygen, nitrogen, and carbon dioxide. Other films ent layers and various types of resins, which pro-
have high (or low) transmission rates for all gases vide advanced properties for such things as
as well as for water vapor. extended shelf life and the ability to let in certain
The oxygen barrier property of some films is gases to change product coloring.
strongly affected somehow by the water vapor. Surface modification is one method for improv-
In order to prevent the moisture effect, the barrier ing barrier properties. Transparent silicon oxide
layer would be sandwiched between two layers that (SiOx) coating on polymers such as PET, PP, PA,
have high water vapor barrier properties (Poisson polyethylene naphthalate (PEN), and polyvinyl
et al., 2008; Thellen et al., 2009). The interaction alcohol (PVA) films have been greatly investigated
of water with a polymer depends on the polarity of by researchers (Giles and Bain, 2000). Many
5: DEVELOPMENT OF HIGH-BARRIER FILM FOR FOOD PACKAGING 75

Table 5.2 Water Vapor Transmission Rate of Plastic Films

Water Vapor Transmission

Material Rate, g (25 μm)/m2/day
Polycarbonate 170.5
Biaxially oriented polyamide 6 158.1
Biaxially oriented PET 131.8
Rubber-modified acrylonitrile copolymer 94.6
Amorphous PA 50
Rigid polyvinyl chloride 46.5
PET 20.2
Ethylene vinyl alcohol 21.7
124
Biaxially oriented PET 18.6
LDPE 17.7
PP 10.7
BOPP 5.9
HDPE 5.9
s
Saran PVDC polyvinylidene chloride 0.93
3.4

researchers are interested in surface modification on polymers, especially PET, by the PECD (plasma
through SiOx coating for food packaging, medical electrochemical deposition) technique has been
devices, and beverage packaging applications widely used to dramatically improve gas barrier
because of its transparency, water resistance, recy- properties in food packaging. The main disadvan-
clability, retortability, microwave use, and excellent tage of this method is that high-barrier films are
barrier properties. Two techniques have been used not transparent (Abbas et al., 2005; Hasebe et al.,
for SiOx coating: physical vapor deposition (PVD) 2007; Shirakura et al., 2006). Another technology
and plasma-enhanced chemical vapor deposition in surface modification is the deposition of inorga-
(PECVD). PECVD was preferable because it can nic
organic materials formulated through sol
gel
be used to deposit materials at low temperatures, chemistry as coating layers on polymers. It has
with excellent coverage at a higher deposition rate, been shown that high density cross-linking epoxy-
creating better adhesion and less brittle failure than amine cross-linked1 silicon sol
gel created excel-
films produced by PVD (Giles and Bain, 2000). lent barrier protection coating (Vreugdenhil et al.,
From the industrial point of view, PVDC, well 2008). Metalized film under very high vacuum at
known as a high-barrier polymer, is coated on the high temperatures is the other technique to improve
surface of polymer films in order to improve the barrier properties of the film. This technique
oxygen barrier property. In Table 5.3, the OTRs of has the capability to improve barrier properties of
a number of plastic films that are PA6/PVDC and films such as PET, PP, LDPE, PC, and biaxially
PP/PVDC coated are compared. The data indicate oriented PA. The main disadvantage of this method
orders of magnitude differences in the oxygen bar- is that it affects opacity. Epoxy-amine coating is
rier properties of different plastic films compared the technique that some companies have used to
to the films coated with PVDC. For example, the improve barrier properties; Graham Packaging and
oxygen permeation of oriented PP is comparable Crown Cork & Seal used this coating technique in
with PP-coated PVDC. PET bottles and used have Bairocade in PET bot-
Another surface modification technology that has tles for packaging beer.
been used for the improvement of barrier properties
in film packaging is carbon deposition by plasma 1
The three cross-linkers used are diethylenetriamine (DETA),
technique. Diamond-like carbon (DLC) deposition ethylenediamine (EDA), and N-aminoethylpiperazine (AEP).
76 PLASTIC FILMS IN FOOD PACKAGING

In fact, surface modification methods are expen- Among nanofillers, clay minerals have been used in
sive and not appropriate for food packaging indus- a variety of polymers to reduce oxygen permeabil-
tries. Furthermore, crack formation at the surface ity. The improvement in barrier properties is based
during stretching of the coated products causes bar- on the tortuosity (Figure 5.2), in which the per-
rier properties to deteriorate. meant must travel a longer diffusive path in the
Blending is a way to produce barrier materials presence of clay fillers in the polymer matrix
by bringing desired properties of different polymers (Aleperstein et al., 2005; Artzi et al., 2004, 2005;
together. Blending is a less costly technology than Bharadwaj, 2001; Chang et al., 2001; Cussler et al.,
coextrusion or coinjection. However, blends are dif- 1988; Krook et al., 2002, 2005).
ficult to recycle. In the blending technique, barrier It is well known that the strength and stiffness of
properties are strongly influenced by the morphol- films increase and permeability decreases as their
ogy of the product. The main challenge in blending density goes up. For example, biaxially oriented
is to have a favorable morphology at a reasonable polypropylene (BOPP) film has become one of the
cost. Some of the blends that have been developed most popular high-growth films in the world mar-
for barrier applications in the packaging field are ket. The oxygen transmission of BOPP was shown
EVOH in PP (Faisant et al., 1998), EVOH in PA to be modifiable by vapor deposition of melamine,
(De Petris et al., 1998), PA in PP (Citterio et al., which formed a transparent uniform layer on poly-
1999), PA in PET (Hu et al., 2004), or PEN in PET meric films. The vapor-deposited melamine mole-
(Wu et al., 2006). cules underwent a large number of cooperative
Inclusion of nanoparticles is an effective and
practical method of improving barrier properties of
polymeric materials. Adding any kind of imperme-
Dispersed
able fillers improves the barrier properties of mate- nanoclay Oxygen out
rials. Using nanoscale filler particles with a high
surface area to thickness aspect ratio, in order
to reduce the cost combined with good process
ability, has received much more attention recently
(Alexandre et al., 2006; Dennis et al., 2001;
Filippone et al., 2010; Fornes and Paul, 2004; Liu
Tortuous path Oxygen in
et al., 2003; Okada et al., 1988; Tianxi et al.,
2003). Dispersion of nanosized particles within the
polymer matrix has been widely used in the past Figure 5.2 Schematic showing silicate layers effect
few years in order to reduce oxygen permeability. on permeation by increasing tortuosity path.

Table 5.3 High Oxygen Barrier Films (Giles and Bain, 2000)

Oxygen Permeability Oxygen Permeability

Film (20 μm at 20 C) (cm3  m2/day atm, 0% RH) (cm3  m2/day atm, 85% RH)
EVOH 32% ethylene 0.13 1.5
EVOH 44% ethylene 1.3 3.3
MXD6 3 3.6
PA6/PVDC coated 7 7
PP/PVDC coated 11 11
OPA6 (oriented 25 65
polyamide [PA] 6)
OPET (oriented 60 60
polyethylene terephthalate)
OPP (oriented polypropylene) 2000 2000
5: DEVELOPMENT OF HIGH-BARRIER FILM FOR FOOD PACKAGING 77

hydrogen bond interactions leading to a coherent Multilayer plastics film

layer consisting of an infinite network (Lazić et al.,
2010). Metallization as a means of reducing mois-
ture permeation through films such as PET is quite Room environment Package Food product
wall
well known. Metallization of 13 micron polyester
reduces the WVTR by two orders of magnitude
(Cumberbatch, 1995).
When deciding which barrier film is correct for
your application, the following factors must be con-
sidered (Barrier Films, 2012):

1. What kind of microclimate do you wish to

maintain? Most films control moisture well,
but oxygen transmission varies.
2. For how long do you wish to maintain the Figure 5.3 Mechanism of permeation of water
microclimate? There is no reason to use the vapor.
most effective film if you need to only main-
tain a controlled atmosphere for a few days, In its simplest form, permeation can be
but long-term storage demands better barrier expressed as a product of the solubility and diffu-
properties. sion coefficients of the permeant in the polymer.
Permeation of a gas can be calculated from
3. How will you maintain the microclimate? An Eq. (5.1). This equation is derived from Fick’s first
active system is more forgiving than one law of mass transfer. Permeation concerns the
based on absorbents. movement of a species through the molecules of
4. Do you wish to make visual inspections of another species, e.g., a gas through a polymer. It
the enclosed objects? Films vary in clarity does not take into account transport of material
and color, and some are opaque. through cracks, voids, and general physical flaws in
5. Will a difference in material costs matter? the structure of the second species such as the poly-
While materials are usually the least expen- mer. Both phenomena result in the migration of
sive part of a project, cost savings could be chemicals through the structure. This means that
substantial in a large project. after an appropriate plastic material has been
selected to meet the permeation requirements of a
process, the equipment must be fabricated carefully
to avoid flaws in the polymer structure.
5.4 Review of Permeation
P 5 DUS (5.1)
Permeation or the barrier property of a plastic
refers to its abilities of transferring something where P (cm3/s cm atm) is the permeability of the
through it. When a polymer is exposed to a per- gas, D (cm3/s) is the diffusion coefficient, and
meant with different concentration on two sides, S (cm3/cm3 atm) is the solubility coefficient.
the permeant passes through the polymer by net Several factors affect the permeation rate in a
effect from high-concentration to low-concentration semicrystalline polymer. Temperature increase
side in three steps: sorption to polymer, diffusion, raises the permeation rate nearly exponentially
and desorption from polymer. It is a significant (Figure 5.4). Solubility of the liquid permeants
consideration in the selection of a plastic material, increases in the polymer at higher temperatures
because permeation follows a solution-diffusion while gas solubility decreases. At above the glass
mechanism. The gas absorbs at the entering face transition temperature, the segmental mobility of
and dissolves at the high-pressure side of the mate- the polymer chains increases, thus creating larger
rial, diffuses through the polymer phase, and des- “holes” for the passage of permeant molecules. The
orbs or evaporates at the low-pressure side permeation rate follows the Arrhenius equation
(Figure 5.3). (Eq. (5.2)), albeit with some limitations.
78 PLASTIC FILMS IN FOOD PACKAGING

Permeation rate (g/m2 /day)

Permeation rate

an
ki
ic
-F
on
n

N
kia
Fic

Permeant concentration

Figure 5.4 Fickian and non-Fickian permeation

behaviors.
Temperature (C)

P 5 P0 Ueð2Ea =RTÞ (5.2) Figure 5.5 Effect of temperature on permeation

rate through a plastic film.
Permeation rate of gases increases at higher par-
tial pressures. For liquids, permeation rates rise
with an increase in the concentration of the per- 5.5 Multilayer Flexible Packaging
meant. Unless the permeant species are highly solu- Structures
ble in the polymer, the permeation rate increases
linearly with pressure, concentration, and the area Layer-multiplying coextrusion represents an
of permeation. Significant errors can occur when advanced polymer processing technique for com-
testing at elevated temperatures close to the glass bining two or more polymers in a layered configu-
transition temperature (Tg) of the plastic film ration with controlled structure. It is a continuous
(Figure 5.5). Table 5.4 provides data for permeation processing technique capable of producing films
rate constant (P0) and activation energy (Ea) of sev- economically. Coextrusion is an industrial process
eral polymers used in packaging Figure 5.6. used to produce sheets and films that are
The permeation rate decreases sharply at higher suitable for food packaging. In this process, two or
film thickness, as illustrated in Figure 5.7, for WVT more polymers are extruded simultaneously from
through a typical hydrophobic plastic film. While the individual extruders. The melted polymers are
permeation rate is high at a low thickness and delivered from extruders to a feedblock to be
decreases near exponentially with increase in the shaped and combined. Then, the melt flow is
thickness, after a critical thickness is reached, the directed to the die to spread, become thin, and dis-
effect of thickness is diminished and the permeation tribute uniformly to form the coextruded film. The
rate reaches a plateau. At lower thicknesses, the effect main problem in coextrusion is to simultaneously
of surface structure begins to play a significant role process polymers of different rheological proper-
in the permeation. A more oriented (ordered) surface ties, which may cause problems such as interfacial
will inhibit permeation. In general, other factors such instability and encapsulation that significantly
as the chemical and physical characteristics of the affect the quality of the product (Wanger, 2010).
polymer affect the permeation rate significantly. Multilayer film structures that provide high-
Chemical affinity of the polymer for the permeant, barrier levels to oxygen, water vapor, aromas/
intermolecular forces such as van der Waals and flavors, and/or UV light for food applications usu-
hydrogen bonding forces, degree of crystallinity, and ally contain a combination of barrier, bulk, and
degree of cross-linking are the influential variables. sealant films. Structures that use aluminum foils as
In summary, it can be seen clearly that film a barrier or graphic substrate are usually excluded
thickness of the package, polymer type, and ambi- from this group. The thickness of the entire struc-
ent conditions of the use/storage environment influ- ture is usually less than 0.25 mm (0.010 in.),
ence the transfer of gases and vapor into and out of including the printed layer, bulk, barrier, tie, and
the food package. sealant layers.
5: DEVELOPMENT OF HIGH-BARRIER FILM FOR FOOD PACKAGING 79

Table 5.4 Permeation Constant and Activation Energy for Polymer Films and Permeants (Selke, 1997)

P 3 1014
Polymer Permeant 
T ( C) (cm3 cm cm22 s21 Pa21) Ea (kJ mol21)
HDPE
0.964 density Oxygen 25 3.023 35.1
Carbon dioxide 25 2.70 30.2
Water vapor 25 90

LDPE
0.914 density Oxygen 25 21.6 42.6
Carbon dioxide 25 94.5 38.9
Water vapor 25 675 33.4
PA6 Oxygen 30 0.285 43.5
Carbon dioxide 20 0.66 40.6
Water vapor 25 1,328

PET
Crystalline Oxygen 25 0.263 32.3
Carbon dioxide 25 1.275 18.4
Water vapor 25 975. 2.9
Amorphous Oxygen 25 0.443 37.6
Carbon dioxide 25 2.25 27.6
PVC
Oxygen 25 0.340 55.6
Carbon dioxide 25 1.178 56.9
Water vapor 25 2,060 22.9
PVDC
Oxygen 30 0.040 66.5
Carbon dioxide 30 0.225 51.4
Water vapor 25 3.75 46.0
PVOH (polyvinyl alcohol)
Oxygen 25 0.067

Carbon dioxide 25 0.090

(cm3 cm/cm2 s Pa) 3 (2.224 3 1015) 5 cm3 mil/100 in.2/24 h atm.

A single layer capable of working as a barrier layer plastics, such as PE, which are used to con-
film is very rare. The true value is created when struct multilayer structures, have been listed.
the barrier film is a component that enables the
effective performance of the final packaging film. Barrier layers
Lists of polymers used to manufacture common 1. EVOH copolymer
barrier, bulk, tie layer, or sealant films have been Oxygen barrier, flavor/aroma barrier
provided in the following paragraphs (Wanger, 2. Polyamide (PA6)
2010). The specific action of each barrier material Oxygen barrier, aroma barrier, and
has been described. Different subtypes of the bulk some oil barrier
80 PLASTIC FILMS IN FOOD PACKAGING

9. Ionomer
Oil barrier and chemical barrier for
some agents
10. Liquid crystal polymer (LCP)
In (permeation rate)

Bulk layer
1. PE
Tg High density (HD), linear low density
(LLD), low density (LD), very low den-
sity (VLD)
Extrapolated values at
elevated temperatures 2. PP
HoPP (homopolymer PP), CoPP (ethyl-
ene-propylene copolymer), Ter-PP
1/T(1/K) (ethylene-propylene-butene terpolymer)
3. Acrylates
Figure 5.6 Arrhenius plot of permeation rate
Ethyl methyl acrylate (EMA)
(McKeen, 2012).
Ethylene butyl acrylate (EBA)
Ethylene ethyl acrylate (EEA)
0.40
Poly(methyl methacrylate) (PMMA)
Ethylene/methylmethacrylate (EMMA)
0.35
4. EVA: low, medium, and high VA content
0.30 5. Polystyrene (PS), high impact PS (HIPS),
general purpose PS (GPPS)
Transmission rate

0.25
Sealant (also adhesive or tie) layer
(g/in.2/24 h)

1. Ionomers of acid copolymers

0.20
2. Acid copolymer EAA (ethylene acrylic
0.15 acid) or EMAA (ethylene methacrylic acid)
3. VLDPE (very low-density polyethylene)
0.10 4. EVA or EMA (ethyl methacrylate) blends
with LLDPE
0.05 5. CoPP/Ter-PP, EVA, EMA, LLDPE,
mLLDPE (metallocene Linear Low
0.00
0 50 100 150 200 250 300
Density Polyethylene)
Thickness (μm) 6. LDPE or PP

Figure 5.7 Effect of thickness of WVTR through a

A multilayer film is generally constructed by
hydrophobic plastic film.
coextrusion, coating, lamination, or metallization of
a substrate. Food barrier structures often include
3. Semicrystalline PAs (polyamide MXD6) components such as polyvinylidene chloride coat-
Gas (O2, CO2) barrier, aroma barrier ing, which acts both as a barrier and a sealant/tie
4. Polyesters (PET) layer, ethyl vinyl alcohol copolymer film (tie
Moisture barrier, some flavor/aroma layer), PA, metalized films, or additives such as
barrier, and some chemical barrier aluminum and silicon oxides.
5. Poly vinylidene chloride (PVDC) The main manufacturing technology to produce
Moisture, oxygen, flavor, aroma, and multilayer flexible packaging films is coextrusion
some chemical barrier (Figure 5.4), which is used in the following processes:
6. PEN
7. HDPE 1. Film blowing,
Moisture barrier
8. PP 2. Film casting (,10 mil or ,0.25 mm),
Moisture barrier 3. Extrusion coating and laminating.
5: DEVELOPMENT OF HIGH-BARRIER FILM FOR FOOD PACKAGING 81

Coextruding polymers is no simple matter. In the significantly affect the quality of the product. It
food industry, they have their compatibility issues, should be considered that the polymer that is used as
and in the polymer processing industry, the com- thin skin layer in a coextruded multilayer film toler-
plexity is taken to a higher level (Wanger, 2010). ates higher shear rate than the polymer used in the
The benefits of combining materials by coextrusion, core layer.
however, far outweigh the challenges associated Coextrusion layer instability is called “melt dis-
with such an endeavor. Coextrusion provides solu- turbance” and is related to the flow of the layer
tions to meet product functionality. A variety of polymers with different rheological properties in
film properties must be taken into consideration the die and also to other processing conditions.
when designing a food packaging film. Some of Interfacial instability is an unsteady-state process
those properties relate to the surface characteristics, condition in which the interface position between
while others pertain to the entire thickness/body of two neighbor layers changes. Interface distortion
the film. Surface characteristics typically include causes uniformity in the thickness of layers.
coefficient of friction (COF), gloss, haze (surface Interfacial instability in a multilayer film signifi-
induced), and sealability, as well as surface tension cantly affects the clarity of the film. As the level of
and chemical receptivity, which are important for instability increases, the interface can begin to
materials to be printed. The important characteris- become wavy (Ganpule and Khomami, 1999). By
tics of the bulk layer include tensile properties, elon- increasing the instability at interface, the waves are
gation, internally induced haze, transparency, color, propagated and the surface becomes deformed. The
impact strength, and a variety of other parameters. layer instability is known as zig-zag, arrow heads,
Figure 5.8 is a flow diagram of a coextrusion fish scales, or chevron, depending on its severity.
feedblock where three extruders are employed to Generally, interfacial instability in a coextrusion
produce a three-layer asymmetrical structure. This system creates differences in elasticity between
particular design has a barrier on the outside with a resins based on storage modulus (G0 ). So for
tie layer to provide adhesion to the bulk layer resin inhabitation of interfacial instability, selection of
Figures 5.8 and 5.9. polymers for different layers and also the selection
In coextrusion process, viscosity dependence of of processing conditions should be done such that
polymer on extrusion temperature and shear-thinning the elasticity ratio approaches one (Khomami and
behavior of non-Newtonian polymers must be care- Ranjbaran, 1997).
fully considered; otherwise serious problems will Interfacial instability is determined by the fol-
occur during the film processing that will lowing factors:

• Layer thickness,
• Viscosity ratio,
• Elasticity ratio,
1
• Interfacial tension.

2 Interfacial instability can be eliminated by

3 (Wanger, 2010):

• lowering the shear stress by lowering extru-

sion rate,
• increasing the melt or die temperature,
three-layered coextrusion with barrier
layer outside body layer
• increasing the die gap (reducing the stress),
1 Main extruder • lowering the polymer viscosity in skin layer
2 Satellite extruder (Adhesive)
3 Satellite extruder (Barrier layer)
by resin replacement,
• increasing the skin layer thickness,
Figure 5.8 Flow diagram of a coextrusion feedblock
using three extruders to produce a three-layer • selecting optimum processing conditions,
asymmetrical structure (Wanger, 2010). • changing the choice of polymeric material.
82 PLASTIC FILMS IN FOOD PACKAGING

Applesauce cups
PP
Bynel® adhesive
EVOH
Bynel® adhesive
PP

(a)

Toothpaste tubes (all plastic)

LDPE
Bynel® adhesive
EVOH
Bynel® adhesive
LDPE

(b)

Cereal box liners

HDPE
Bynel® adhesive
EVOH
Bynel® adhesive
Pealable seal blend with Surlyn®
(ionomer) or Elvax®
EVA

(c)

Condiment packets
PET
LDPE
Foil
Nucrel® ethylene-acrylic
acid copolymer

(d)

Figure 5.9 Examples of the structures of multilayered packaging film. Materials made by DuPont were
selected as examples to assist the reader in finding additional information. [McKeen, L.W., 2012. Permeability
Properties of Plastics and Elastomers. Elsevier, Oxford.]
5: DEVELOPMENT OF HIGH-BARRIER FILM FOR FOOD PACKAGING 83

Cook-in poultry or ham

PA
Nucrel® ethylene-acrylic
acid copolymer

(e)

Frozen seafood
Surlyn® (ionomer)
Nucrel® ethylene-acrylic
acid copolymer

(f)

Granola bars
Paper
LDPE
Foil
Surlyn® (ionomer)

(g)

Hot dog package Top seal

PET
Surlyn® (ionomer)

Bottom
Surlyn® (ionomer)
Bynel® adhesive
EVOH
Bynel® adhesive
PA

(h)

Figure 5.9 (Continued)

84 PLASTIC FILMS IN FOOD PACKAGING

Restaurant jelly cups Top seal

PET
Primer
LDPE
Appeel® lidding sealant resins

(i)

Juice boxes
Paper
LDPE
Nucrel® ethylene-acrylic acid copolymer
Foil
Nucrel® ethylene-acrylic acid copolymer
LDPE

(j)

Juice cartons
Paper board
LDPE
Bynel® adhesive
PA
Bynel® adhesive
LDPE

(k)

Ketchup squeeze tubes

PP
Bynel® adhesive
EVOH
Bynel® adhesive
PP

(l)

Figure 5.9 (Continued)

5: DEVELOPMENT OF HIGH-BARRIER FILM FOR FOOD PACKAGING 85

Wine/liquid cartons
Elvax® EVA
Metalized PET
Elvax® EVA

(m)

Single-serve noodle cups Lidding film

Paper
Primer
Foil
LDPE
Appeel® lidding sealant resins

Surlyn® cup (PS)

(n)

Peanuts
Oriented polypropylene (OPP)
Bynel® adhesive
HDPE
Surlyn® (ionomer)

(o)

Produce packages (such as mushrooms)

OPP
LDPE
EVA

(p)

Figure 5.9 (Continued)

86 PLASTIC FILMS IN FOOD PACKAGING

So for reducing the interfacial instabilities in a based on experience, must be used to correlate
coextrusion process, optimization of processing packaging performance with OTR. It is suitable as
conditions, proper design of die, control of process, a common method of testing, provided that the
and polymer selection for matching rheology seem same sampling procedures, standardization proce-
to be necessary. dures, test conditions, and acceptance criteria are
Another significant problem in coextrusion pro- followed.
cess is encapsulation. In the feedblock channel, This test method provides a procedure for the
there is the shear profile. Respectively, there is a determination of the steady-state rate of transmis-
viscosity distribution across the channel. Viscosity sion of oxygen gas through plastics in the form
of the individual layers decreases from center to of film, sheeting, laminates, coextrusions, or
wall channel because the shear rate is high near the plastic-coated papers or fabrics. It provides for
wall and the viscosity of flows at the center of the the determination of (1) oxygen gas transmission
channel is low as a result of shear rate dropping to rate (O2GTR), (2) the permeance of the film to
zero. Therefore, when we stack polymers in a lay- oxygen gas (PO2), and (3) oxygen permeability
ered coextrusion flow, we should ensure that the coefficient (P0 O2) in the case of homogeneous
viscosity of the individual layers decreases as the materials.
flow channel wall is approached. If this is not done,
the layers will attempt to rearrange themselves to
place the lowest viscosity layer on the outside of ASTM F1307: Standard Test Method for
flow against the wall where the shear rate is high- OTR through Dry Packages Using a
est, to lower the shear stress in the system. These
Coulometric Sensor
flow problems, where the viscosities are not prop-
erly stacked, lead to layer rearrangement or encap- This test method covers a procedure for the
sulation. Encapsulation is mainly caused when the determination of the steady-state rate of transmis-
viscosity ratio at neighbor layers is high. It is sion of oxygen gas into packages. More specifi-
strongly dependent on viscosity ratio and thickness cally, the method is applicable to packages that in
of less viscous fluid. If the viscosity and thickness normal use will enclose a dry environment.
of less viscous fluid are increased, the encapsula-
tion rate is increased.
ASTM F1927 Standard
O2GTR at a given temperature and percentage
5.6 Measurement of Barrier relative humidity (%RH) are important determi-
Properties of Films nants of the packaging protection afforded by bar-
rier materials. It is not the only determinant, and
A number of standard methods are available to additional tests, based on experience, must be used
measure the permeation of oxygen, water vapor, to correlate packaging performance with O2GTR.
and carbon dioxide through plastic films. These It is suitable as a common method of testing, pro-
methods are issued by standards organizations such vided that the same sampling procedures, standardi-
as American Society for Testing Materials zation procedures, test conditions, and acceptance
(ASTM International) and International Standards criteria are followed.
Organization (ISO). Table 5.5 gives a listing of This test method gives a procedure for the deter-
some of the common permeation and transmission mination of the rate of transmission of oxygen gas,
measurement methods. at steady state and at a given temperature and %RH
level, through film, sheeting, laminates, coextru-
sions, or plastic-coated papers or fabrics. This test
5.6.1 Oxygen Test Methods method extends the common practice in dealing
with zero humidity or, at best, an assumed humid-
ASTM D3985 OTR ity. Humidity plays an important role in the O2GTR
The OTR is an important determinant of the of many materials. This test method provides for
packaging protection provided by barrier materials. the determination of O2GTR, the permeability of
It is not the sole determinant, and additional tests, the film to oxygen gas (PO2), the permeation
5: DEVELOPMENT OF HIGH-BARRIER FILM FOR FOOD PACKAGING 87

Table 5.5 Test Methods for Measurement of Barrier Properties of Plastic Films

Method
Designation Title What Is Measured?
Oxygen
ASTM D3985 Method for determination of oxygen Measurement of O2 transmission
transmission rate through films, sheets, laminates, etc.
ASTM F1307 Method for determination of oxygen Measurement of steady-state rate of
transmission rate through dry packages transmission of oxygen gas into
using a Coulometric sensor packages
ASTM F1927 Method for determination of O2GTR, Determination of the rate of
permeability, and permeance at transmission of O2 gas, at steady state,
controlled relative humidity through at a given temperature, and %RH level,
barrier materials using a coulometric through film, sheeting, laminates, etc.
detector
JIS K 7126 Method for determining the gas Determination of the gas transmission
transmission rate of any plastic material rate of any plastic material in the form
in the form of film, sheeting, laminate, of film, sheeting, laminate, etc.
etc.
DIN-53380 Testing of plastics—Determination of Oxygen-specific carrier gas method for
Part 3 gas transmissions rate testing of plastic films and plastics
moldings
ISO
14663-2 Determination of steady-state rate of Determination of steady-state rate of
transmission of oxygen transmission of oxygen gas through
ethylene/vinyl alcohol copolymer in the
form of film
Water vapor
ASTM F1249 Test method for determination of Obtain reliable values for the water
O2GTR, permeability, and permeance vapor transmission rate (WVTR) of
at controlled RH through barrier plastic film and sheeting. The WVTR
materials using a coulometric detector is an important property of packaging
materials and can be directly related
to shelf life and packaged product
stability
ASTM D6701 Test method for determining WVTRs Covers a procedure for determining the
through nonwoven and plastic barriers rate of water vapor transmission (WVT)
(withdrawn) ranging between 500 and 100,000 g/m2/
day through nonwoven and plastic
barrier materials. The method is
applicable to films, barriers consisting of
single or multilayer synthetic or natural
polymers, nonwoven fabric, and
nonwoven fabrics coated with films up
to 3 mm (0.1 in.) in thickness
ASTM E 398 Test method for determination of Covers a procedure for determining the
O2GTR, permeability, and permeance rate of WVT ranging between 500 and
at controlled RH through barrier 100,000 g/m2/day through nonwoven
materials using a Coulometric detector and plastic barrier materials. The
method is applicable to films, barriers
consisting of single or multilayer
(Continued )
88 PLASTIC FILMS IN FOOD PACKAGING

Table 5.5 (Continued)

Method
Designation Title What Is Measured?
synthetic or natural polymers,
nonwoven fabric, and nonwoven fabrics
coated with films up to 3 mm (0.1 in.) in
thickness
JIS K-7129 Plastics—film and sheeting— Specifies an instrumental method
determination of WVTR by instrumental for determining the WVTR of plastic
method film, plastic sheeting, and multilayer
structures including plastics that
have smooth surfaces without any
embossed portions, using a
humidity detection sensor method,
infrared detection sensor method,
and gas chromatographic
sensor method
ISO
15106-2 Plastics—film and sheeting— Specifies an instrumental method for
determination of WVTR—Part 2: determining the WVTR of plastic film,
infrared detection sensor method plastic sheeting, and multilayer
structures including plastics, using an
infrared detection sensor. The method
provides rapid measurement over a
wide range of WVTRs.
TAPPI T-557 WVTR through plastic film and sheeting Covers a procedure for determining the
using a modulated infrared sensor rate of WVT through flexible barrier
materials. The method is applicable to
sheets and films up to 2.54 mm (0.1 in.)
in thickness, consisting of single or
multilayer synthetic or natural polymers
and foils, including coated materials. It
provides for the determination of (1)
WVTR, (2) the permeance of the film to
water vapor, and (3) for homogeneous
materials, water vapor permeability
coefficient
Carbon dioxide
ASTM F2476 Method for the determination of CO2TR Determination of the steady-state
through barrier materials using an rate of transmission of carbon dioxide
infrared detector gas through plastics in the form of
film, sheeting, laminates, coextrusions,
or plastic-coated papers or fabrics. It
provides for the determination of (1)
CO2TR, (2) the permeation of the
film to carbon dioxide gas (PCO2), and
(3) carbon dioxide permeability
coefficient (PvCO2) in the case of
homogeneous materials.
DIN-53380 Testing of plastics—determination of Testing of plastics: carbon
Part 4 gas transmissions rate dioxide
specific infrared absorption
method for testing of plastic films and
plastic moldings
5: DEVELOPMENT OF HIGH-BARRIER FILM FOR FOOD PACKAGING 89

coefficient of the film to its thickness (PO2), and standardization procedures, test conditions, and
the oxygen permeability coefficient (PO2) in the acceptance criteria.
case of homogeneous materials at given tempera- This test method gives a procedure for deter-
ture and %RH level(s). mining the rate of WVT through flexible barrier
materials. The method is applicable to sheets and
films up to 3 mm (0.1 in.) in thickness and consist-
JIS K 7126 ing of single or multilayer synthetic or natural poly-
Japanese Industrial Standards (JIS) are developed mers and foils, including coated materials. It
by the JIS Committee. The letter K stands for provides for the determination of (1) WVTR, (2)
chemical engineering
related standards. JIS K the permeance of the film to water vapor, and (3)
7126 specifies a method for determining the gas for homogeneous materials, water vapor permeabil-
transmission rate of any plastic material in the form ity coefficient.
of film, sheeting, laminate, coextruded material, or
flexible plastic-coated material under a differential ASTM D6701: Standard Test Method for
pressure. Determining WVTRs through Nonwoven
and Plastic Barriers (Withdrawn)
This test method covers a procedure for deter-
DIN-53380 Part 3: Testing of
mining the rate of WVT, ranging from 500 to
Plastics—Determination of Gas 100,000 g/m2/day, through nonwoven and plastic
Transmissions Rate barrier materials. The method is applicable to films,
This is an oxygen-specific carrier gas method for barriers consisting of single or multilayer synthetic
the testing of plastic films and plastic moldings. or natural polymers, nonwoven fabric, and nonwo-
ven fabrics coated with films up to 3 mm (0.1 in.)
in thickness. This test method provides for the
ISO-14663-2: Determination of Steady- determination of (1) WVTR and (2) the permeation
State Rate of Transmission of Oxygen to water vapor.
Gas through Ethylene/Vinyl Alcohol
Copolymer in the Form of Film Using a ASTM E 398: Standard Test Method for
Coulometric Sensor and Is Standardized WVTR of Sheet Materials Using Dynamic
by the ISO-14663-2:1999 RH Measurement
The O2GTR is usually expressed in cubic centi- The WVTR, under known and carefully con-
trolled conditions, may be used to evaluate the
meters (at 0 C under standard atmospheric pres-
sure) per m2 per 24 h under a pressure difference of vapor barrier qualities of a sheet. Direct correlation
1 atm (cm3/m2/24 h atm). of values obtained under different conditions of test
temperature and RH will be valid provided the bar-
rier material under test does not undergo changes in
5.6.2 Water Vapor Test Methods solid state (such as a crystalline transition or melt-
ASTM F1249: Standard Test Method for ing point) at or between the conditions of test.
This test method covers dynamic evaluation
WVTR through Plastic Film and
of the rate of transfer of water vapor through a
Sheeting Using a Modulated Infrared flexible barrier material and allows conversion to
Sensor the generally recognized units of WVT, as
The purpose of this test method is to obtain reli- obtained by various other test methods including
able values for the WVTR of plastic film and sheet- the gravimetric method described in Test Methods
ing. WVTR is an important property of packaging E 96/E 96M.
materials and can be directly related to shelf life This test method is limited to flexible barrier
and packaged product stability. sheet materials composed of either completely
Data from this test method is suitable as a ref- hydrophobic materials or combinations of hydro-
eree method of testing, provided that the purchaser phobic and hydrophilic materials having at least
and seller have agreed on sampling procedures, one surface that is hydrophobic.
90 PLASTIC FILMS IN FOOD PACKAGING

The minimum test value obtained by this test The method is applicable to sheets and films up to
method is limited by the leakage of water vapor 2.54 mm (0.1 in.) in thickness and consisting of
past the clamping seals of the test instrument. single or multilayer synthetic or natural polymers
A reasonable value may be approximately and foils, including coated materials. It provides
0.01 g/24 h m2 for any WVTR method, including for the determination of (1) WVTR, (2) the per-
the desiccant procedure of Test Methods E 96/E meance of the film to water vapor, and (3) for
96M at 37.8 C and 90% RH. This limit can be homogeneous materials, water vapor permeability
checked for each instrument with an impervious coefficient.
specimen such as aluminum foil. Calibration pro-
cedures can compensate for the leakage rate if
so stated. 5.6.3 Carbon Dioxide Test
This test method is not suitable for referee testing Methods
but is suitable for control testing and material com-
parison. Several other ASTM test methods are avail- ASTM F2476: Test Method for the
able to test a similar property. This test method is Determination of Carbon Dioxide Gas
unique in that it closely duplicates typical product Transmission Rate (CO2TR) through
storage where a transfer of moisture from a package Barrier Materials Using an Infrared
into the environment is allowed to proceed without Detector
constantly sweeping the environmental side with dry
CO2TR is an important determinant of the pack-
gas. Methods with constantly swept dry sides include
aging protection afforded by barrier materials. It is
Test Methods F1249, F372, and F1770.
not, however, the only determinant, and additional
tests, based on experience, must be used to corre-
late packaging performance with CO2TR. It is
JIS K-7129: Plastics—Film and suitable as a referee method of testing, provided
Sheeting—Determination of that purchaser and seller have agreed on sampling
WVTR—Instrumental Method procedures, standardization procedures, test condi-
This standard specifies an instrumental method tions, and acceptance criteria.
for determining the WVTR of plastic film, plastic This method covers a procedure for the determi-
sheeting, and multilayer structures including plas- nation of the steady-state rate of transmission of
tics that have smooth surfaces without any carbon dioxide gas through plastics in the form of
embossed portions using a humidity detection sen- film, sheeting, laminates, coextrusions, or plastic-
sor method, infrared detection sensor method, and coated papers or fabrics. It provides for the deter-
gas chromatographic sensor method. mination of (1) CO2TR, (2) the permeation of the
film to carbon dioxide gas (PCO2), and (3) carbon
ISO-15106-2: Plastics—Film and dioxide permeability coefficient (PvCO2) in the
Sheeting—Determination of WVTR—Part case of homogeneous materials.
2: Infrared Detection Sensor Method
ISO-15106-2 method specifies an instrumental DIN-53380 Part 4: Testing of Plastics—
method for determining the WVTR of plastic film, Determination of Gas Transmissions Rate
plastic sheeting, and multilayer structures including
plastics using an infrared detection sensor. The Testing of plastics: Carbon dioxide
specific
method provides rapid measurement over a wide infrared absorption method for testing of plastic
range of WVTRs. films and plastic moldings.
Designing a multilayer film for coextrusion
requires consideration of a variety of factors
TAPPI T-557: WVTR through Plastic Film
including:
and Sheeting using a Modulated
Infrared Sensor 1. Physical properties such as tensile, elonga-
This test method is a procedure for determining tion, flexure, stiffness, hardness, toughness,
the rate of WVT through flexible barrier materials. puncture, COF, sealability, and peelability.
5: DEVELOPMENT OF HIGH-BARRIER FILM FOR FOOD PACKAGING 91

2. Barrier properties to agents such as oxygen, Dennis, H.R., et al., 2001. Effect of melt processing
moisture, oil, chemical, aroma/fragrance, and conditions on the extent of exfoliation in
carbon dioxide. organoclay-based nanocomposites. Polymer 42,
3. Additives such as colorants, mineral fillers, 9513
9522.
surface friction modifier, property modifiers, Faisant, J.B., et al., 1998. Morphology, thermome-
melt fracture inhibitors, and scavengers. chanical and barrier properties of polypropylene-
ethylene vinyl alcohol blends. Polymer 39 (3),
533
545.
References Filippone, G., et al., 2010. Using organoclay to pro-
mote morphology refinement and co-continuity in
Abbas, G.A., et al., 2005. Structural investigation high-density polyethylene/polyamide 6 blends—
and gas barrier performance of diamond-like car- effect of filler content and polymer matrix compo-
bon based films on polymer substrates. Carbon sition. Polymer 51, 3956
3965.
43, 303
309. Fornes, T.D., Paul, D.R., 2004. Structure and prop-
Aleperstein, D., et al., 2005. Experimental and erties of nanocomposites based on nylon-11 and
computational investigation of EVOH/clay nano- -12 compared with those based on nylon-6.
composites. J. Appl. Polym. Sci. 97, 2060
2066. Macromolecules 37, 7698
7709.
Alexandre, B., et al., 2006. Nanocomposite-based Ganpule, H.K., Khomami, B., 1999. An investiga-
polyamide 12/montmorillonite: relationships tion of interfacial instabilities in the superposed
between structures and transport properties. channel flow of viscoelastic fluids. J. Non-
Desalination 199, 164
166. Newtonian Fluid Mech. 81 (1
2), 27
69.
Artzi, N., Narkis, M., Siegmann, A., 2004. EVOH/ Giles, G.A., Bain, D.R., 2000. Materials and
Clay Nanocomposites Produced by Dynamic Development of Plastics Packaging for the
Melt Mixing. John Wiley & Sons. Consumer Market. Sheffield Academic Press,
Artzi, N., et al., 2005. The effect of extrusion Sheffield.
processing conditions on EVOH/clay nanocom- Hasebe, T., et al., 2007. Recent advances in
posites at low organo-clay contents. Polym. diamond-like carbon films in the medical and
Compos. 26, 343
351. food packing fields. New Diamond Front. Carbon
Barrier Films, 2012. Available from: ,www.keep- Technol. 17, 263
279.
safe.com.. Hu, Y., et al., 2004. Oxygen barrier enhancement
Bharadwaj, R.K., 2001. Modeling the barrier prop- of pet by blending with an aromatic polyamide.
erties of polymer-layered silicate nanocompo- In: ANTEC 2004—Annual Technical Conference
sites. Macromolecules 34, 9189
9192. Proceedings, May 16
20, 2004. Society of
Chang, J.-H., et al., 2001. Preparation and charac- Plastics Engineers, Chicago, IL.
terization of polyimide nanocomposites with dif- Khomami, B., Ranjbaran, M.M., 1997.
ferent organo-montmorillonites. Polym. Eng. Sci. Experimental studies of interfacial instabilities in
41, 1514
1520. multilayer pressure-driven flow of polymeric
Citterio, C., et al., 1999. Physico-chemical charac- melts. Rheol. Acta 36 (4), 345
366.
terization of compatibilized poly(propylene)/ Krook, M., et al., 2002. Barrier and mechanical prop-
aromatic polyamide blends, Macromolecular erties of montmorillonite/polyesteramide nanocom-
Materials and Engineering 270 (1), 22
27. posites. Polym. Eng. Sci. 42, 1238
1246.
Cumberbatch, G.M., 1995. High barrier metalized Krook, M., Morgan, G., Hedenqvist, M.S., 2005.
polyester films for packaging applications. Barrier and mechanical properties of injection
In: TAPPI Polymers, Laminations and Coatings molded montmorillonite/polyesteramide nano-
Conference, Atlanta, GA. composites. Polym. Eng. Sci. 45, 135
141.
Cussler, E.L., et al., 1988. Barrier membranes. Lazić, V.L., et al., 2010. Barrier properties of
J. Membr. Sci. 38, 161
174. coated and laminated polyolefin films for food
De Petris, S., et al., 1998. Study of blends of nylon 6 packaging. Acta Phys. Pol. A 117 (5), 855
858.
with EVOH and carboxyl-modified EVOH and a Liu, T., et al., 2003. Preparation and characteriza-
preliminary approach to films for packaging appli- tion of nylon 11/organoclay nanocomposites.
cations. J. Appl. Polym. Sci. 68 (4), 637
648. Polymer 44, 3529
3535.
92 PLASTIC FILMS IN FOOD PACKAGING

McKeen, L.W., 2012. Permeability Properties of for high oxygen barrier packaging applications.
Plastics and Elastomers. Elsevier, Oxford. J. Membr. Sci. 340 (1
2), 45
51.
Okada, A., Fukushima, Y., Kawasumi, M., Inagaki, Tianxi, L., et al., 2003. Preparation and characteri-
S., Usuki, A., Sugiyama, S., et al., 1988. Composite zation of nylon 11/organoclay nanocomposites.
material and process for manufacturing same. US Polymer 44, 3529
3535.
Patent 4739007. Vreugdenhil, A.J., et al., 2008. The role of crosslin-
Poisson, C., et al., 2008. Mechanical, optical and kers in epoxy-amine crosslinked silicon sol
gel
barrier properties of PA6/nanoclay-based single- barrier protection coatings. Thin Solid Films 517
and multilayer blown films. Polym. Polym. (2), 538
543.
Compos. 16 (6), 349
358. Wanger, J.R., 2010. Hand Book of Multilayer Flexible
Selke, S.E.M., 1997. Understanding Plastic Packaging Technology and Applications for Food,
Packaging Technology. Hanser, New York, NY. Personal Care and Over-the Counter Pharmaceutical
Shirakura, A., et al., 2006. Diamond-like carbon Industries. Elsevier, Burlington, VA.
films for PET bottles and medical applications. Wu, W., et al., 2006. Morphology and barrier mech-
Thin Solid Films, 494 (1-2), 84
91. anism of biaxially oriented poly(ethylene tere-
Thellen, C., et al., 2009. Co-extrusion of multilayer phthalate)/poly(ethylene 2,6-naphthalate) blends.
poly(m-xylylene adipimide) nanocomposite films J. Appl. Polym. Sci. 101, 1309
1316.
 6 Applications of Polypropylene Films
Teresa Calafut

Polypropylene is used in components of automo- (UV)-stabilized polypropylenes, reinforced or unre-

biles and large and small appliances, packaging inforced, and foamed grades are usually used in
films and containers, medical devices, and textiles. bumpers. Elastomer-modified grades in fascia pro-
A good balance of properties, which can be tailored vide a balance of toughness and rigidity in order
to a wide range of fabrication methods and applica- to meet current regulations. Bumper fascia must
tions, and its low cost make it useful in many dif- have good rigidity and maximum impact resistance,
ferent industries. even at low temperatures (Figures 6.1 and 6.2)
(Inform—Hostalen PP, 1996; Libert and Rosenthal,
1992; Williams, 1992).
6.1 Automotive Applications Stampable glass mat-reinforced (GMT) polypro-
pylene homopolymer can be used in bumper beams,
Polypropylene is used throughout the automo- depending on the application. GMT is composed of
bile—in interiors, exteriors, and under the hood. It continuous, unidirectional glass fibers that can be
is used in the automobile industry more than any arranged in a particular direction to meet demand-
other single polymer, and its usage is increasing. In ing performance requirements. In the Jaguar saloon,
the Opel Astra, 68% of the thermoplastic compo- the bumper beam is used mainly as a carrier for the
nents are composed of polypropylene, compared to cosmetic cover; replacement of steel by GMT,
10% polyamide, 6% acrylonitrile butadiene styrene appropriate for this application, can result in
(ABS), 4% polyethylene, and 12% of other thermo- 30
40% weight savings and B40% reduction in
plastics. In Ford models, use of polypropylene has tooling costs, and the cost of corrosion prevention
increased from an average of 5.5 kg (12.1 lb) in is eliminated (Inform—Hostalen PP, 1996; Libert
1980, to 8.0 kg (17.6 lb) in 1985, to 17.0 kg (37.4) and Rosenthal, 1992; Williams, 1992).
in 1990 (Dufton, 1992; Williams, 1992). Modern bumpers are integrated into the car
Mineral- and glass-reinforced polypropylenes, body, painted the color of the car, and adjusted to
polypropylene homopolymers and copolymers, ther- fit the contours of the load-bearing structure.
moplastic vulcanizates, and polypropylene foams Primers are necessary to promote adhesion of the
are used in applications ranging from structural paint to the bumper surface, and a surface treatment
components and energy-absorbing media to interior such as flame treatment may be required (Inform—
trim, carpeting, and fluid containers. The wide use Hostalen PP, 1996; Libert and Rosenthal, 1992;
and versatility of polypropylene in automotive Williams, 1992).
applications facilitates mechanical recycling, since Automobile manufacturers that use polypropyl-
less material separation is required, and the resin ene bumpers include Ford (Orion, Escort), Peugeot
maintains good mechanical properties after repro- (405), Volvo, Opel, and BMW. Polypropylene/
cessing (Libert and Rosenthal, 1992; Royle, 1992). EPDM (ethylene propylene diene monomer) blends
used in the Opel Omega provide impact resistance
6.1.1 Exterior Automotive (at temperatures as low as 230 C (222  F)), UV
resistance, high dimensional accuracy, high-quality
Applications surface finish, and excellent weathering and chemi-
Automobile bumpers are commonly made using cal resistance properties. The bumpers are light-
polypropylene. Plastic bumper systems generally weight and easily painted, and special grades are
consist of an inner beam, an energy-absorbent available that result in low shrinkage, necessary
core, and a fascia. Elastomer-modified, ultraviolet when painted and unpainted bumpers are produced

Ebnesajjad: Plastic Films in Food Packaging. DOI: http://dx.doi.org/10.1016/B978-1-4557-3112-1.00006-5

© 1998 Elsevier Inc. All rights reserved. Reproduced from a chapter in: Maier, Polypropylene — The Definitive User’s Guide and Databook (1998). 93
94 PLASTIC FILMS IN FOOD PACKAGING

from the same injection mold. Resins have low ther- The Hoechst Magazine, 1992; Inform—Automotive
mal expansion (expansion coefficient of 50 2 80 3 Industry, 1995; Inform—Hostalen PP, 1996).
1025 K21) in order to accommodate the small gaps Expanded polypropylene (EPP) foam is used in
(“zero-gap” concept) between the bumper and body the bumper core on the 1997 Buick Park Avenue
parts present in modern automotive design. A poly- (Figure 6.4a). EPP is more resilient and is 30%
propylene bumper is shown in Figure 6.3 (Future— lighter than other cushioning materials with the

Polypropylene block copolymers

High-impact applications
14

12
Notched Izod −30°C (kJ/m3)

Bumpers (Fascias)

10

8
Interior applications
Trim, door panels
6 Others

Battery cases
2
700 900 1100 1300 1500
Flexural modulus (MPa)

Figure 6.1 Rigidity and impact strength necessary for high-impact automotive applications. Bumper fascia
requires good rigidity and maximum impact resistance; good rigidity and high-impact resistance are necessary
for battery cases. In interior applications, trim, door panels, and lower interior parts require rigidity and good
impact resistance; rigid block copolymers are usually used. Dashboards, commonly made from blends of
polypropylene/EPDM/talc, require rigidity, high heat-deflection temperatures, and good impact resistance for
sun-exposed parts. Parts in the upper half of the car interior, usually made from homopolymer or block
copolymer and talc, require high rigidity (.3000 MPa; 435,110 psi) (Libert and Rosenthal, 1992).

High-impact applications
0
Ductile/brittle transition temperature (°C)

−10

−20 Interior applications

−30
Battery cases

−40
Bumpers (fascias)

−50
800 1000 1200 1400
Flexural modulus (MPa)

Figure 6.2 Impact resistance of automobile applications at low temperatures. Exterior bumper fascias require
maximum impact resistance at low temperatures. A high level of impact strength is required for battery cases;
for interior applications, low-temperature impact resistance is not as critical (Libert and Rosenthal, 1992).
6: APPLICATIONS OF POLYPROPYLENE FILMS 95

same performance properties. Due to a high ratio

of impact strength to density, thinner walls can be
used on the bumper cores, resulting in greater
styling flexibility. Other uses of EPP foam in
automotive applications are shown in Figure 6.4b
(Neopolen).
Other exterior automotive applications include
mirror housings, side protective strips, underbody
trim, hubcaps, bumper brackets, spoilers, wind-
screens, air inlet grilles for bumpers, radiator
grilles, and wheel arch linings. In the Opel Astra,
polypropylene is used in the front and rear bumpers,
spoilers, tailgate linings, and sill trim for the boot.
The 1997 Mercury Mountaineer uses a “gouge-
Figure 6.3 A bumper made from talc-reinforced, resistant” grade of enhanced or high-crystallinity
elastomer-modified polypropylene (Hostacom, polypropylene (Mytex) in the side body panels, repla-
Hoechst) (Inform—Hostalen PP, 1996). cing thermoplastic polyurethane elastomer (TPU)

(a)

Bumper cores

Tool caddies

Sound barriers
"C" pillar

Head-impact energy absorbers

Door liners
Side-impact energy absorbers
Passenger seating
Armrests
"A" pillar
Sun visors
Knee bolsters
Instrument panel components
Firewalls
Heat shields
(b) Bumper cores

Figure 6.4 Automotive applications for EPP foam (EPP, BASF). (a) A bumper for the Buick Park Avenue and
(b) interior and exterior automotive uses of EPP foam (Neopolen).
96 PLASTIC FILMS IN FOOD PACKAGING

UV exposure and humidity, cracking, crazing, color

changes, or other effects should not be apparent
after testing. Other tests include color fastness,
abrasion resistance, fluid resistance, and flammabil-
ity. Components within a specific radius of the
driver cannot break into pieces with sharp, jagged
surfaces on impact, and the component should be
esthetically pleasing, with no rattles or squeaks dur-
ing operation (Williams, 1992).
Figure 6.5 The side rubbing or protector strip Interior automotive applications generally use a
on the Audi A4, produced from a polypropylene talc-filled, impact-modified grade of polypropylene.
mineral-reinforced thermoplastic elastomer Applications of polypropylene include doorpost
(Hostacom, Hoechst). The strip is painted to match cladding and pockets, air ducts, heater/air-condi-
the color of the car, and no metal insert is used tioning unit casings, armatures for fascia panels and
(Inform—Automotive Industry, 1995). center consoles, and carpeting. Polypropylene is
used for fascia panels on the Ford Fiesta and Escort
(Dufton, 1992; Future—The Hoechst Magazine, and the Opel Vectra and has been used in instru-
1992; Inform—Automotive Industry, 1995). ment panels, consoles, quarter panels, and pillars in
The Opel Omega uses a recyclable polypropyl- Chrysler, Ford, and GM vehicles since the early
ene/EPDM thermoplastic elastomer for the side 1990s (Barnetson, 1997; Williams, 1992).
protective strip, which protects the doors from dam- Polypropylene provides a good price-to-performance
age. The easy-flowing material is bonded to a gal- ratio, weight reduction, recyclability, improved acoustic
vanized steel profile and fixed to the car with damping compared to other polymers such as ABS,
double-sided adhesive tape. The resin has a low and reduced windscreen fogging. Windscreen fogging
coefficient of thermal expansion and excellent is generally due to migration of volatile components
weathering resistance. The Audi A4 uses a mineral- from the polymer resin. The low stiffness of polypro-
reinforced thermoplastic elastomer, with no metal pylene makes thicker, bulkier moldings necessary,
insert, for the side rubbing strip (Figure 6.5). The so that direct replacement of other plastics is not possi-
painted strip is fixed to the car with adhesive tape ble without expensive tool and design modifications
(Dufton, 1992; Future—The Hoechst Magazine, (Barnetson, 1997; Czerski, 1992; Williams, 1992).
1992; Inform—Automotive Industry, 1995). Talc-filled polypropylenes generally have poor
Polypropylene rearview mirror housings are used scratch resistance; however, coated grades are avail-
in the Renault Clio and Twingo and the Peugeot able that do not exhibit the usual white marks after
106. Rearview mirror housings require materials flexing or scuffing. Marking occurs when mechani-
with adequate mechanical strength, even at low tem- cal damage to the surface disturbs the resin’s surface
peratures, resistance to cleaning agents and UV radi- layer, resulting in changes in light reflection and
ation, and the ability to withstand high winds and exposure of talc particles; whitening and increases
vibration (Future—The Hoechst Magazine, 1992). in gloss occur in the affected area. Whitening is
most noticeable on dark moldings or finely textured
6.1.2 Interior Automotive surfaces; colors exhibit increased gloss (Barnetson,
1997; Czerski, 1992; Williams, 1992).
Applications Volkswagen uses 20% talc-reinforced polypro-
Although the performance requirements of inte- pylene for the pillar trim of the Polo (Figure 6.6).
rior trim components are less demanding than exte- The material displays good flowability and retains
rior applications, interior automotive components toughness even at low temperatures. In the Opel
must also comply with esthetic and safety require- Omega, the textile surface of the A pillar is pro-
ments. Environmental aging tests subject the inte- duced by backmolding the textile trim with
rior component to temperature extremes of 240 C mineral-reinforced polypropylene. Scratch-resistant
(240 F) to 75 C (167 F) for components below grades are used in the central console of the Volvo
waist level and up to 105 C (221 F) for compo- S40/V40 (polypropylene/EPDM), in the dashboard
nents in sunlight (above waist level), in addition to carrier and facing and the glove box lid of the
6: APPLICATIONS OF POLYPROPYLENE FILMS 97

Mercedes Benz Sprinter (reinforced polypropylene), lights for the Ford Mondeo is made from a white-
and in the tailgate trim material on the Audi A4 colored grade of polypropylene due to good light-
(block copolymer) (Future—The Hoechst Magazine, absorbing properties that shield the lights from
1992; Inform—Automotive Industry, 1995; Inform— each other. Polypropylene is being used to replace
Hostalen PP, 1996). ABS, polyamide (PA), and polycarbonate (PC) due
Other applications include fascia in the Opel to its recyclability, rigidity, low warpage, and flow-
Corsa and Tigra (Figure 6.7); tailgate and side trim, ability (Dufton, 1992; Future—The Hoechst
hand grips, doorpost trim, and the center console Magazine, 1992; Inform—Hostalen PP, 1996).
on the Opel Astra; and speaker housings in the In the BMW 3 series, polypropylene is used in
Ford Mondeo and Fiesta (40% mineral-reinforced). door handles (Figure 6.8), door pockets, trim and
The housing for the warning, control, and indicator parcel shelves. The resin provides a balanced rigid-
ity/toughness ratio, good scratch resistance, low
thermal expansion, sound-deadening properties, and
recyclability. In Volvo trucks, polypropylene is
used in the three-part center console with storage
trays, A and B pillar trim, and door tread. Truck
materials must withstand much harsher conditions
than those in cars, due to vehicle vibrations and
increased driver use. The polypropylene components,
designed for hard wear, deaden sound, and vibra-
tions, are UV resistant and have a touch-friendly fin-
ish (Inform—Automotive Industry, 1995).
Cross-linked, foamed blends of polypropylene
and polyethylene sheetstock are widely used in
Japan as padding in car interiors in door trim
Figure 6.6 Pillar trim of the Volkswagon Polo, panels, inserts, instrument panels, glove box doors,
made with 20% talc-reinforced polypropylene roof liners, pillars, and seatbacks. Polypropylene
(Hostacom, Hoechst) (Future—The Hoechst contributes durability, high thermal stability, and
Magazine, 1992). mechanical stiffness, while polyethylene provides
elongation, ductility, and softness. The blends,
which are foamed after cross-linking, may provide
a substitute for polyvinyl chloride (PVC) foams
(Smock, 1997).

Figure 6.7 Fascia on the Opel Corsa, made from Figure 6.8 Polypropylene door handles on
40% mineral-reinforced polypropylene (Hostacom, the BMW 3 series (Hostacom, Hoechst)
Hoechst) (Inform—Automotive Industry, 1995). (Inform—Automotive Industry, 1995).
98 PLASTIC FILMS IN FOOD PACKAGING

Dashboards made entirely of polypropylene are and glass fiber-reinforced grades and have high
being developed. Currently, most dashboards are a dimensional stability, good heat resistance and low-
three-layer structure consisting of a glass-filled temperature stability, good processability, and good
polypropylene beam, a polyurethane foam core, and chemical resistance. Due to their toughness, the
a PVC skin cover. An example of an all- housings can be installed by snapfitting, making dis-
polypropylene dashboard includes a beam of talc- mantling and recycling easier (Inform—Automotive
reinforced homopolymer or copolymer, a core of Industry, 1995; Inform—Hostalen PP, 1996).
EPP (BASF), and a rubber-modified block copoly- Heater housings for the Mercedes C class are made
mer skin cover. Ferro is developing a foamable of 40% mineral-reinforced polypropylene. Use of this
polypropylene with a small amount of metallocene material has reduced fogging and eliminated the
polypropylene (mPP) added for a softer feel and unpleasant odor that entered new car interiors along
more flexIbility and heat resistance in the dash- with the heated air. The housing is dimensionally and
board core (Barnetson, 1997; Czerski, 1992). heat stable and reduces transmission of structural-
borne sound (Inform—Automotive Industry, 1995).
6.1.3 Under-the-Hood Automotive Polypropylene used in ventilation grilles
exhibits good weathering resistance, and the grilles
Applications retain their visual appearance even after several
The most severe environment in the automobile years. The polypropylene spoiler on the Peugeot
is the engine compartment; temperatures can range 406 remains UV resistant and dimensionally
from 240 C (240 F) to 140 C (280 F), and parts stable under severe heat; in addition, the good flow-
are exposed to vibrations and to chemical attack by ability of the resin makes production easier. The
lubricants and fuels. Heat resistance has become Opel Astra uses polypropylene in air cleaner hous-
even more important in recent years due to the ten- ings, air ducts, coolant, washer, brake fluid reser-
dency of engine compartments to become more voirs, battery casings, and fan mounts. Two-part
enclosed, causing higher temperatures (Dufton, polypropylene structural ducts in the 1997 Ford
1992; Inform—Automotive Industry, 1995). Flareside truck replaced ABS, resulting in lower
The largest amount of polypropylene in under- cost and improved sound-deadening properties.
the-hood applications is used for battery cases. The ducts can be hot plate welded. Several under-
Polymer properties required for battery cases include the-hood applications of polypropylene are shown
good rigidity and a high level of impact resistance, in Figure 6.9 (Barnetson, 1997; Dufton, 1992;
especially at low temperatures (Figures 6.1 and 6.2). Inform—Hostalen PP, 1996).
Other applications include fluid reservoirs (water,
antifreeze, brake fluid, etc.), headlamp housings, air
ducts, fans and brackets, fan wheels, air filter hous- 6.2 Medical Applications
ings, charcoal canisters, radiator frames, steering rod
covers, cable ducts, timing chain covers, heater Polypropylene is used in a variety of medical
housings, and central electric housings. GMT mate- applications—medical devices; drug delivery sys-
rials are used in semistructural applications such as tems; nonwoven fabrics; packaging for medical
battery trays, engine shields, and support panels for devices, solutions, and drugs; and other applications.
radiator and fan housings; polypropylene, PBT, or It is used in disposable and prefilled syringes, sam-
PC/PBT is used as the thermoplastic material, ple cups, diagnostic cuvettes, centrifuge tubes, par-
depending on the heat resistance required for the enteral kit parts, needle shields, connectors, surgical
component (Dufton, 1992; Libert and Rosenthal, trays, infectious waste containers and bags, drapes,
1992; The Hostalen PP, 1996). clamps, spine support boards, and blow-molded con-
In the Mercedes Benz E class, reinforced poly- tainers. Other uses include contact lens molding
propylene is used in the radiator frame, the air cups, needle disposal containers, phlebotomy needle
intake grille, the radiator tank cover, the housing of holders, infant feeding tubes, medication spoons,
the central electrical components, the lid of the cool- analytical test strips, and blood oxygenator mem-
ing water compensation reservoir, the heating and branes. Syndiotactic polypropylene is frequently
ventilation housings, and the headlight housings. preferred for applications such as blood bags and
Headlight housings are generally made from talc- sterile garments. It is more transparent than isotactic
6: APPLICATIONS OF POLYPROPYLENE FILMS 99

(c)

(a)

(d)

(e)
(b)

Figure 6.9 Under-the-hood applications of polypropylene ((a)
(d) made from Hostacom from Hoechst
and (e) from Amoco). (a) Headlight housing, (b) heater housing, (c) ventilation grid, (d) draft deflector,
and (e) battery case, fan (Amoco Polypropylene Homopolymers, 1992; Inform—Hostalen PP, 1996).

polypropylene and is more resistant to gamma steril- is estimated that over 150 million pounds of poly-
ization (Ewen, 1997; Performance Polyolefins, propylene is used per year in medical devices, with
1991; Portnoy, 1994a; Precision Woven Screening the largest fraction (over 70 million pounds per
Media, 1997). year) used for disposable hypodermic syringes and
Tamper-resistant/evident closures can be inex- other small parts. Polypropylene thermoplastic elas-
pensively injection molded from polypropylene, tomers and thermoplastic vulcanizates are gaining
and waste containers and bags extruded from poly- in popularity for medical applications as replace-
propylene can be sterilized. Clamps, connectors, ments for rubber and urethane in applications such
and closures for solution bottles can be made by as wound dressings, drainage bags, and gloves.
injection molding using the “living hinge” property Cost reduction, in addition to allergic reactions to
of polypropylene. Living hinges can be flexed over latex proteins and biocompatibility concerns about
a million times before failure for a description the use of natural rubber, has led to increased use
of living hinges in polypropylene) (Performance of these materials (Boschert, 1997; Performance
Polyolefins, 1991; Portnoy, 1994a; Precision Woven Polyolefins, 1991; Portnoy, 1994a,b; Precision
Screening Media, 1997). Woven Screening Media, 1997).
Polypropylene is also used in health-care-related Useful properties for medical applications
applications such as packaging for health and include an excellent resistance to solvents and auto-
beauty aids, cosmetics, and nutritional products. It clave heat, good tensile strength and stiffness, a
100 PLASTIC FILMS IN FOOD PACKAGING

long flex life, a high heat distortion temperature, or polyamide are 13
20% more dense, resulting in
and a low density and moisture vapor transmission increased resin cost. In Japan, filled grades are
rate (MVTR). Polypropylene is easily processed substituted for ABS in rice cookers and are also
into complex shapes and is generally nontoxic, being used in coffee makers and large thermos
chemically inert, and tolerant to sterilization. flasks. Processors use barium sulfate fillers to
The low to moderate level of additives used for obtain surface finishes similar to those obtained
stabilization do not usually interfere with medical with ABS. Other useful properties for small appli-
use. Polypropylene waste forms noncorrosive incin- ances include abrasion resistance and resistance to
eration products, and the material is easier to recy- fruit juices, bleach, and cleaning liquids; in addi-
cle than many other polymers. Most polypropylene tion, high-flow grades allow easier coloring and
grades easily pass USP Class VI and Tripartite processing of unique shapes than metal (Colvin,
testing protocols (From Rexene Technology, 1987; 1996; O’Neill, 1996).
Performance Polyolefins, 1991; Portnoy, 1994a). Glass-reinforced polypropylene is used in the
The use of polypropylene in medical products is base of the Bosch-Siemens hand mixer. High rigid-
cost-effective. Chemical inertness results in a lon- ity, toughness, and heat resistance enable the resin
ger shelf life, and handling costs and costs per unit to withstand the severe loads encountered in uses
volume are reduced due to polypropylene’s light- such as kneading dough. The use of polypropylene
weight. The cost-effectiveness of polypropylene has has resulted in lower material costs compared to
led to its substitution for other materials such as polyamide, the original material used in the mixer
glass and other plastics, a trend that is expected to (Hostacom, 1993).
continue with the current emphasis on cost contain- The excellent stress cracking resistance of poly-
ment in health care (Precision Woven Screening propylene makes it useful in commercial hair
Media, 1997; Performance Polyolefins, 1991; dryers, which undergo many heating and cooling
Portnoy, 1994b). cycles per day. Polypropylene in the Wella M36
Several medical applications of polypropylene Sensortronic drying hood provides dimensional sta-
are shown in Figure 6.10. bility and accuracy, even at high temperatures, and
allows snapfit hooks and cable cleats to be inte-
grally molded into the chassis, eliminating addi-
tional assembly operations. The resin used (Hoechst
6.3 Appliances Hostacom) is flame retardant, with a UL
94 V
0
rating (Hostacom, 1993).
Appliance applications of polypropylene include Polypropylene is used in various models of the
ductwork for dryers, door liners for dishwashers, Rowenta steam irons. In the Dolphino, natural
wash racks and lids for clothes washers, hand color, stabilized polypropylene replaced PC.
mixers, and hair dryers. Mineral-filled polypropyl- Although changing materials usually requires
ene is used in refrigerator liners, replacing ABS changing molds, no major mold changes were nec-
(DeBoest, 1988). essary—only adjustments that took 2 days to com-
plete. The tank was molded with in-line coloring
using a 2% masterbatch. In the Surfline DE41, the
6.3.1 Small Appliances upper and lower housing parts and the tank base
The use of polypropylene in small appliances is are made from 10% mineral-reinforced polypropyl-
growing, as producers strive to lower production ene; advantages include lightweight, heat resis-
costs; the use of polypropylene is growing faster tance, and a balanced rigidity/toughness ratio. The
than any other resin. In kitchen appliances, polypro- surface finish is not affected by long-term exposure
pylene is being substituted for engineering plastics to steam, and snap-fits can be molded in, allowing
such as ABS, PC, and polyamide. Although ABS, for lower cost assembly and easier servicing
an amorphous polymer, provides better scratch (Colvin, 1996; Hostacom, 1993).
resistance and a higher surface finish than homo- The Rowenta deep fat fryer uses a high-gloss,
polymer polypropylene (65
80% Gardner gloss temperature- and scratch-resistant grade of polypro-
scale compared to 95% for ABS), resins like ABS pylene. Improved processing and a reduction in the
6: APPLICATIONS OF POLYPROPYLENE FILMS 101

(a) (b)

(c) (d)

(e)

Figure 6.10 Various medical applications of polypropylene. (a) Centrifuge tubes, (b) connectors, (c) syringes
and drug containers, (d) trays, syringes, connectors, and woven fabrics, and (e) containers and IV supplies
(Amoco Polypropylene Homopolymers, 1992; Boschert, 1997; From Rexene Technology, 1987; Mitsui Sekka;
Performance Polyolefins, 1991).
102 PLASTIC FILMS IN FOOD PACKAGING

number of different plastics used in the part dishwashers, primarily for cost reduction; how-
resulted in high cost savings (Barnetson, 1997). ever, the use of polypropylene also eliminates
In the juice centrifuge of the multifunctional MK3 corrosion and allows structures and supports to be
kitchen appliance from Bosch-Siemens Hausgeräte, built in for functional integration (Barnetson,
10% mineral-reinforced polypropylene withstands 1997; O’Neill, 1996).
very high mechanical stress due to the high-speed Substitution of polypropylene for established
centrifuge (2400 rpm). The easy-flowing, hard and resins such as ABS requires changes in processing,
rigid grade can withstand the centrifugal force including minimizing the length of the parting line
over the long term and can be injection molded in due to the higher flow rate of polypropylene com-
a filigree part with 2304 openings (Figure 6.11) pared to ABS, and the necessity of designing rein-
(Future—The Hoechst Magazine, 1992). forcements such as ribs into housings to
The pump housing and the flange between compensate for the lower structural strength. Newer
the motor and housing in the BADU “90” swim- grades designed for large appliances have increased
ming pool pump are made from 30% glass- stiffness, higher temperature and deformation resis-
reinforced polypropylene. Material damage due tance, and improved surface hardness, and they are
to heat from the pump is eliminated because of easier to process. The sound-deadening properties
the high heat-deflection temperature (HDT/B of of polypropylene compared to metal are useful
155 C; 311 F); other useful properties are chemi- when appliances in smaller dwellings are placed in
cal resistance, rigidity, toughness, and dimen- the kitchen instead of the basement or laundry
sional stability. The pump is thick walled but room, and the recyclability of polypropylene aids in
lightweight, due to the low density of polypropyl- meeting consumer demands for recyclable compo-
ene (Hostacom, 1993). nents and in adhering to environmental regulations
Several applications of polypropylene in small (O’Neill, 1996).
appliances are shown in Figure 6.11. Whirlpool uses polypropylene reinforced with
30% chemically coupled glass fibers for a washing
machine drum; the spin speed of the machine is
6.3.2 Large Appliances 1200 rpm. The geometry of the drum was opti-
Use of polypropylene in large appliances is mized using a CAD study that simulated the defor-
increasing, due to its low cost and the enhanced prop- mation of the washing machine drum at high spin
erties of newer grades. Polypropylene is competing speeds, in order to offset high-speed stresses.
with thermosets, metals, and other thermoplastics To improve the connection between the motor
such as styrenics. The weight of polypropylene used and the container, belt pre-tensioning was used
in washing machines was estimated as 22 lb/unit to compensate for material creep. Use of polypro-
in 1995; use is expected to rise to 44 lb/unit in 2000 pylene led to a lower cost production process, bet-
as it replaces engineering polymers (O’Neill, 1996). ter integration of functions, and a water- and
Polypropylene is used in washing machine energy-saving part design (Future—The Hoechst
drums (typically 30% glass-reinforced, 40% talc- Magazine, 1992).
filled, and homopolymer). Unfilled polypropylene A 40% mineral-reinforced grade is used in the dis-
is used in drums for top-loading machines at spin penser dish of a Miele washing machine. The most
speeds of B600 rpm; a glass-reinforced grade is important requirement of a dispenser dish is deter-
now used in a front-loading drum with a spin gent resistance; a second requirement is the ability to
speed of 1200 rpm, replacing metal. In 1995, withstand a reasonable amount of stress due to vibra-
General Electric began using an injection-molded tions of the motor. The rigidity of polypropylene and
glass-reinforced polypropylene drum to eliminate its excellent chemical resistance make it useful for
the need for metal stamping. Other applications this application, and the dish design, with three com-
include pump housings; 90% of all West partments, allows for water penetration throughout
European washing machines have plastic pump the dish and for efficient detergent removal
housings, with a 60:40 ratio between talc-filled (Future—The Hoechst Magazine, 1992).
and glass-reinforced grades. Talc-filled bases are Polypropylene (30% mineral-reinforced) is used
used for washing machines, washer-dryers, and in the inner door of a Bosch-Siemens Hausgeräte
6: APPLICATIONS OF POLYPROPYLENE FILMS 103

(a1) (a2)

(b) (c)

(d) (e)

Figure 6.11 Applications of polypropylene in small appliances ((a)
(e) made of Hostacom from Hoechst
and (f) from Amoco). (a) Parts for a commercial hair dryer, (b) steam iron, body is made from polypropylene,
(c) juice centrifuge, (d) swimming pool pump, (e) hand mixer, and (f) coffee maker (Amoco Polypropylene
Homopolymers, 1992; Future—The Hoechst Magazine, 1992; Hostacom, 1993).
104 PLASTIC FILMS IN FOOD PACKAGING

(f) 6.4.1 Floor Coverings and Home

Furnishings
Polypropylene floor coverings are used in homes,
offices, and automobiles. Polypropylene fibers are
also used in upholstery fabric, wall coverings, and
bedding. Polypropylene is economical—its low den-
sity provides more fiber per pound of polymer—and
durable, able to withstand years of traffic with no
change in appearance. Due to its low weight com-
pared to other fibers, carpets can be produced with
more volume but with the same surface weight.
Floor coverings are stain resistant, colorfast, static
resistant, and nonallergenic—polypropylene is not
affected by moisture, mold, or mildew and does
not support fungi or bacteria (Polyolefin: Because
It Works).

Figure 6.11 (Continued)

6.4.2 Automotive
Needle-punched polypropylene carpeting has
been developed for automotive use. It is lightfast
GmbH tumbler dryer that has the largest loading and aging resistant and is used in floor coverings,
porthole of all tumble dryers on the market. The rear parcel shelves, and in the boot. The use of
inner door with integral fluff filter holder ensures polypropylene in automotive textiles, in addition to
perfect closure of the porthole opening and serves the diversity of other automotive applications
as a carrier for the outer door. The good rigidity, of polypropylene, aids in the goal of achieving a
high dimensional accuracy, and high HDT/B single-material system for easy recycling (Inform—
(of .120 C; .240 F) of polypropylene ensure Hostalen PP, 1995).
tight door closure and reliable dryer operation.
High gloss provides a pleasant appearance, and
very good flow properties are useful for large parts 6.4.3 Apparel
(Hostacom, 1993). The wicking action of polypropylene makes it
Several applications of polypropylene in large useful in clothing for outdoor sports, such as hik-
appliances are shown in Figure 6.12. ing, skiing, biking, and swimming. Polypropylene
does not absorb moisture, so polypropylene cloth-
ing worn next to the skin does not get wet from
6.4 Textiles and Nonwovens perspiration; the moisture passes through the mate-
rial into the air or to an outer absorbent material,
Polypropylene fibers are used in carpeting, auto- such as cotton. Clothing also dries faster. The low
mobile interiors, apparel, geotextiles, and nonwo- density of polypropylene makes it lightweight (the
ven applications. Polypropylene is versatile, only fiber lighter than water) and useful in swim-
colorfast, chemically resistant, economical, light- wear, biking shorts, and other apparel. Gases, such
weight, and environmentally friendly. It has good as oxygen, pass through the material; this “breath-
insulating properties and a soft textile feel, and ability” ensures that the wearer remains cool and
fibers are insensitive to moisture and dirt. Use of comfortable, even in warm weather (Polyolefin:
polypropylene in textiles has grown since the mid- Because It Works).
1970s; textile applications now account for 25% of Polypropylene apparel resists fading, odors,
the total polypropylene market in western Europe, stains, mold, mildew, and bacteria. It is easy
comprising 20% of western Europe’s synthetic fiber to care for; it is colorfast, even in chlorinated
production. environments, and light and dark colors can be
6: APPLICATIONS OF POLYPROPYLENE FILMS 105

(a1) (a2)

(b) (c)

(d) (e)

Figure 6.12 Polypropylene applications in large appliances. (a) Inner door of a washing machine, (b) washing
machine drum, (c) dispenser unit for a washing machine, (d) washing machine pump, and (e) dispenser unit for
dishwashers. All are made of Hostacom from Hoechst (Future—The Hoechst Magazine, 1992).
106 PLASTIC FILMS IN FOOD PACKAGING

washed together. Most apparel can be dried in 6.4.5 Nonwovens

home dryers at low temperatures (Polyolefin:
Because It Works). Nonwoven fabrics are used in sanitary products,
surgical garments, geotextiles, and other applica-
tions. In sanitary products—disposable diapers,
feminine hygiene products, and adult incontinence
6.4.4 Industrial Applications and aids—a soft nonwoven cover stock maintains dry-
Geotextiles ness and comfort. Fibers have high tear strength,
Polypropylene is used in filters and filaments, as even when wet, and moisture is transported through
cordage for rope, fish netting, and other applica- the material. Disposable surgical nonwovens,
tions. Cordage is lighter than water, so nautical including shoe covers, gowns, caps, and bedding,
ropes float, and the strength-to-weight ratio is up to are economical and ensure proper sanitation.
10 times that of steel. The nonwettable fibers are Nonwoven bouffant caps, wipes, and cleaning pads
useful in oil-absorbing booms, soaking up oil, fuel, are used in restaurants and food service areas to
hazardous wastes, inks, and solvents. Other uses are keep food preparation areas free of contamination.
in woven packing bags (Big Bags), strapping tape, Other uses include carpet backing, mattress pads,
binder twine, tarpaulins, artificial grass, tow ropes cushions, vacuum cleaner bags, overnight courier
for motor vehicles, and brushes (Elber, 1993; envelopes, and automotive car covers.
Inform—Hostalen PP, 1995; Polyolefin: Because Protective garments prevent contamination of
It Works). sensitive appliances in ultraclean rooms by workers.
Filtration products are used in the medical, elec- Agricultural nonwovens provide air, light, and water
tronics, chemical, mining, and food processing permeability to seeds and plants and protect against
industries. They are used in biotechnology and med- cold, bad weather, and insect pests. As a result, early
ical research for cell separation, tissue cultures, sowing is possible, and plants grow well, with a
fluids filtration, water purification, drug preparation, high yield (Future—The Hoechst Magazine, 1992;
and blood treatment. Filters are used in clothes Inform—Hostalen PP, 1995; Polyolefin: Because
dryers, power tools, coffee machines, and water fil- It Works).
ters. The woven mesh structure filters out water, oil, Several applications of textiles and nonwoven
fuel, lint, debris, food, and other impurities. Filters fabrics are shown in Figure 6.13.
are available that meet Food and Drug
Administration (FDA) requirements for food contact 6.5 Packaging
applications (CFR Title 21) and can be obtained in a
variety of forms—bags, tubes, pouches (Polyolefin: Packaging is used to contain, protect, and iden-
Because It Works; Precision Woven Screening tify the products within the package. Packaging
Media, 1997). protects the product from mechanical damage and
Geotextiles can be woven or nonwoven. They biological attack and informs the customer about
are used in building and construction sites and in such topics as the product’s size, ingredients, and
landfills. In concrete and asphalt paving installa- instructions for use. It provides convenience
tions, geotextiles reduce crack formation and throughout the life of the product—during shipping,
increase pavement strength and durability. At con- retail, and final use—and can help preserve fresh-
struction and landscaping sites, they stabilize soil ness of food products that are likely to spoil.
against erosion, prevent sediment runoff, and pro- The most important application for plastic packag-
mote rapid revegetation. Open-mesh fences reduce ing is in food packaging (Barnetson, 1996, 1997;
wind, sand, and snow damage; provide crowd con- Goddard, 1993; Polymers in Contact with Food, 1991).
trol at concerts and sporting events; and protect
hazardous work sites and utility areas. All geotex- 6.5.1 Plastics Versus Other
tiles have high tear strength; other properties
can be tailored to the particular application by Packaging Materials
the choice of grade and processing parameters Common packaging materials include wood,
(Inform—Hostalen PP, 1995; Polyolefin: Because glass, metal, paper, and plastic. Advantages of plas-
It Works). tics as packaging materials include easy processing,
6: APPLICATIONS OF POLYPROPYLENE FILMS 107

(a) (b)

(c) (d)

(e) (f)

Figure 6.13 Polypropylene applications in textiles and nonwoven fabrics. (a) Rope, (b) outdoor apparel,
(c) geotextiles, (d) and (e) woven filters, (f) disposable diapers, (g) packing bags (Big Bag), (h) surgical
garments, and (i) automotive upholstery and automotive interior cladding part with trim (Amoco
Polypropylene Homopolymers, 1992; Inform—Hostalen PP, 1995; Polyolefin: Because It Works;
Precision Woven Screening Media, 1997).

low cost, and lower weight due to a lower density than glass; for the same strength as plastic, glass
than other packaging materials. Plastic packages packaging requires a higher volume and weight.
can be optimized for a particular application, and For example, a plastic drink bottle with a wall
they are more impact resistant than glass, which thickness of ,1 mm (0.04 in.) is equivalent in
breaks when dropped and requires more careful strength to a glass bottle with a wall thickness of
handling. Plastics have a lower volume occupancy 2
3 mm (0.08
0.1 in.) (Barnetson, 1996).
108 PLASTIC FILMS IN FOOD PACKAGING

(g) (h)

(i)

Figure 6.13 (Continued)

Disadvantages of plastics include environmental games, hardware, frozen foods, and cigarette wrap.
stress cracking, poor stacking strength compared to Use of polypropylene in packaging is growing,
other packaging materials, and problems with steril- especially in blow-molded containers, sheet, profile
ization when used in medical applications. Due to and film extrusion, and injection-molded packag-
their similar molecular structure, polyolefins such ing. New grades with high stiffness, high clarity,
as polypropylene can absorb paraffins and solvents, and good elastomeric properties have enabled poly-
which can cause deformation. Unlike glass and propylene to replace both plastic and nonplastic
metals, plastics do not provide a complete barrier packaging materials. The trend in packaging toward
to gases and moisture. However, new techniques thinner walls, lighter weight, and greater stiffness
such as lamination or coextrusion, or a combination (in order to conserve resources) fits well with poly-
of plastics with other packaging materials (paper, propylene’s balanced combination of properties:
aluminum foil), can provide good product protec- toughness, stiffness, hardness, excellent chemical
tion (Barnetson, 1996). resistance, and low density (Bailey and Brauer,
1994; Barnetson, 1997).
6.5.2 Use of Polypropylene in Some estimates indicate that up to two-thirds of
polypropylene’s growth is due to replacement of
Packaging other thermoplastics. Polypropylene has replaced
One-third of all polypropylene applications is in the more expensive polystyrene in many food pack-
packaging. Polypropylene is used in packaging bis- aging applications due to a lower cost and proper-
cuits, crisps, sweets, bread, pasta, dairy products, ties such as toughness, resistance to stress cracking,
convenience foods, dried fruits, snacks, syringes, and favorable organoleptic properties. It is being
and medicine bottles. Polypropylene films are used considered as a substitute for PETP (polyethylene
in flexible packaging, for shirts, hosiery, bread, and terephthalate polyester) in applications such as
produce, and in shrink-wrap applications for toys, dairy containers and peanut butter jars due to the
6: APPLICATIONS OF POLYPROPYLENE FILMS 109

increased clarity of new resins, and oriented, coex- generally sensitive to processing conditions. The
truded films are used as a replacement for cello- addition of clarifying agents to random copolymers
phane in the snack food industry (Barnetson, 1997; provides see-through clarity to polypropylene pack-
Polymers in Contact with Food, 1991). aging, important in many packaging applications
Polypropylene is preferred over polyethylene such as rigid containers. Combined with the other
terephthalate (PET) for use in hot-filled products favorable properties of polypropylene (heat distor-
such as juice drinks due to its resistance to high tion temperature, stiffness, impact strength, cost,
temperatures (heat distortion temperature at 66 psi recyclability, etc.), clarified resins compare favor-
of 99
127 C (210
260 F) compared to 38
129 C ably to other materials used in rigid packaging,
(100
264 F) for PET). Although its oxygen barrier such as PET, styrene acrylonitrile (SAN), polysty-
properties are poor, polypropylene provides five rene, and PVC. Clarified polypropylene is clearer
times the moisture vapor transmission (MVT) per- than high-density polyethylene (HDPE) and has
formance of PET and at least ten times the MVT superior organoleptic properties and heat resis-
of polystyrene, making it useful in packaging dry tance—it can be hot-filled at temperatures up to
foods and moisture-sensitive products such as 100 C (212 F) compared to 91 C (196 F) for
coated analgesics and vitamins. The use of polypro- HDPE (Milliken Chemical, 1996; Polymers in
pylene packaging in these applications extends Contact with Food, 1991).
shelf life and can eliminate the necessity of adding Clarified polypropylene sheet is used in thermo-
dessicants to the container to prevent moisture formed cups for Brisa purified water as a replace-
accumulation (Milliken Chemical, 1996). ment for the more costly polystyrene. The 8-oz.
foil-sealed cups are equal in clarity to polystyrene
and provide an 8-week shelf life, compared to 3
4
6.5.3 High-Crystallinity and High- weeks for polystyrene. The polypropylene cups are
Melt-Strength Grades resistant to ozone and have better organoleptic
High-melt-strength grades of polypropylene allow properties. They are more rigid and tougher than
it to be processed on high-speed, wide-web (up to polystyrene cups, and are ozone resistant. They can
142-cm, 56-in.-wide sheet) packaging equipment be easily crushed after use without breaking into a
commonly used in the food industry. Conventional number of shards (Milliken Chemical, 1996).
low-melt-strength polypropylene cannot be pro-
cessed on wide-web equipment due to a tendency
to sag during sheet extrusion. Low-melt strength
6.5.5 Metallocene Polypropylene
also causes a rapid wall thinning, so that thicker The development of metallocene catalysts has
walls are necessary to account for nonuniform wall resulted in improved properties for packaging appli-
thicknesses. Heterophasic copolymers, such as cations, including greater puncture resistance, high-
polypropylene polymerized with ethylene
propyl- er impact strength, greater low-temperature impact
ene rubber, are also used on wide-web equipment strength, and better organoleptic and optical proper-
and are commonly used in such melt-phase thermo- ties than Ziegler
Natta polypropylene. Metallocene
formed products as microwaveable food packaging resins for packaging applications also have good
due to low odor and taste transmission properties flow resistance, high stiffness, high transparency,
(Bailey and Brauer, 1994; Himont, 1992). and high heat resistance. High gas permeation rates
Highly crystalline grades are used in producing of metallocene resins make them useful in packag-
highly rigid film (film for labels), very thin-walled ing vegetables, which continue to respire after
flexible packaging (twist film, stand bags), and packing (Barnetson, 1996, 1997).
thermoformed articles. They are used in disposable The enhanced clarity of mPP makes it useful in
packaging for microwave foods due to improved thin-walled, transparent-molded packaging such as
heat resistance and low creep (Barnetson, 1997). frozen food packaging. Transparency of one grade
of mPP homopolymer (M Novolen NX 50081,
BASF AG) in supplier trial runs was 93%, com-
6.5.4 Clarified Polypropylene pared to 47% for high-crystallinity polypropylene
Polypropylene random copolymers have moder- and 89% for new clarified, nucleated resins.
ate clarity, although the clarity of polyolefins is Random copolymer mPP was even more
110 PLASTIC FILMS IN FOOD PACKAGING

transparent (95% transparency) and was only closures, due to the resin’s stiffness, resistance to
slightly lower than that of PET (100% transpar- stress cracking, and living hinge properties, and it
ency). Trials of mPPs with melt flow rates from 4 is used in tamper-evident closures for medicines,
to 120 indicate that nucleators, used to increase the liquor, and food products. Polypropylene is repla-
crystallinity, stiffness, and clarity of conventional cing HDPE in applications such as crates and paint
polypropylene, also benefit mPP (Metallocene containers (Barnetson, 1997; Future—The Hoechst
Grades, 1997). Magazine, 1992; Milliken Chemical, 1996; Oertel,
The high melt flow rate of mPP reduces cycle 1996; Polymers in Contact with Food, 1991;
times when molding thin-walled containers while Thompson et al., 1987).
still providing toughness and stiffness. Cycle time Biaxially oriented, clear polypropylene bottles
of a 60 MFR (melt flow rate) mPP was 10% faster and jars produced by a single-stage injection blow-
than a nucleated grade, with comparable clarity and molding process may compete with PET containers
gloss. Cycle times of 60 MFR mPP and a high- as a substitute for glass containers. Oriented poly-
crystallinity grade were equal, but the mPP pro- propylene is one-third less expensive than PET,
vided significantly higher clarity and gloss even when allowing for extra wall thicknesses to
(Metallocene Grades, 1997). compensate for higher flexibility. It performs better
New free-flowing mPP grades for injection in hot-fill applications and has good water barrier
molding are suitable in applications such as tubs properties; however, polypropylene is a poor barrier
for dairy products, ice cream, cosmetics containers to gases, and methods to coat the material with a
and for thin-walled nonfood packaging and high- better barrier polymer such as polyvinylidene chlo-
volume transport containers and crates (Barnetson, ride or ethylene vinyl alcohol (EVOH) are currently
1996, 1997). under development. Possible applications for these
containers include pasteurized products, pickles,
sauces, creams, instant coffee, and powdered milk
6.5.6 Rigid Packaging (Roberts, 1989).
Polypropylene is widely used for rigid packag- Polypropylene is suitable for containers used in
ing, such as margarine tubs, yogurt containers, microwave cooking, as long as the food product
trays, milk jugs, and bottles. Thermoformed poly- does not have a high fat content and the container
propylene margarine tubs have replaced most PS is designated as “microwave use only”. In these
and PVC tubs. Random copolymers are frequently cases, the moisture in the food ensures that the
used in products such as food storage containers food temperature does not exceed 100 C (212 F),
due to their excellent clarity and good balance of which is near the hot-fill temperature limit of poly-
impact strength and stiffness. In thin-walled parts, propylene. Blends of materials are used in contain-
such as injection-molded delicatessen containers or ers designed for dual oven use. For example, a
yogurt cups with a length-to-thickness ratio of up blend of polypropylene, molded pulp, fillers, and
to 400:1, use of polypropylene copolymers with additives can withstand temperatures from 240 C
high melt flow rates (35 g/10 min) can reduce con- (240 F) to 200 C (392 F), similar to CPET.
tainer weights by 30% over containers produced The containers have a pearlescent finish and lack
with other materials. Containers are tough, rigid, the wrinkled corners common on paperboard trays.
and recyclable. They provide a moisture barrier and Many microwaveable products contain several
top-load strength, and the low-temperature resis- layers of different materials for shelf-stable packag-
tance protects the product at refrigerator tempera- ing (see Section 6.5.8). Shelf-stable products may
tures (Barnetson, 1997; Future—The Hoechst be stored at ambient temperatures and do not require
Magazine, 1992; Milliken Chemical, 1996; Oertel, refrigeration (Polymers in Contact with Food, 1991;
1996; Polymers in Contact with Food, 1991; Roberts, 1989).
Thompson et al., 1987). Examples of polypropylene in rigid packaging
Polyethylene is the material most used in rigid include a coffee cream jug (Figure 6.14) made of a
packaging; however, due to its lower flexural mod- single material for easy recycling. The design incor-
ulus compared to polypropylene, it requires a porates a tear-off ring that can be pulled with the lid
greater wall thickness in thin-walled containers. strip. The high-impact strength and low-temperature
Polypropylene is used in screw-on caps and resistance of polypropylene provides product
6: APPLICATIONS OF POLYPROPYLENE FILMS 111

(a) (b)

(c) (d)

Figure 6.14 Applications of polypropylene in rigid packaging. (a) A VCR case with a living hinge, (b) drug
packaging, (c) blow-molded container for household cleaner (Pro-fax, Himont), (d) container for purified water,
similar in clarity to PET, (e) candy containers, (f) dairy containers (Amoco), (g) packaging for compact discs,
(h) clear color packaging for household products, (i) Brisa single-serve bottled water containers, (j) a coffee
cream jug made of a single material for easy recycling (Hostalen, Hoechst), and (k) ketchup bottles (Advancing
Resin and Equipment Technology, 1995; Amoco Polypropylene Homopolymers, 1992; Future—The Hoechst
Magazine, 1992; Milliken Chemical, 1996).
112 PLASTIC FILMS IN FOOD PACKAGING

(e) (f)

(g) (h)

Figure 6.14 (Continued)

protection during transport, on the supermarket shelf, reduced in weight, have 25% post-consumer
and in the refrigerator. A high-clarity polypropylene recycled content, or be recycled at a particular rate.
is used as the container for Pledge Household Polypropylene is more easily recycled than other
Cleaner (Figure 6.14), due to its combination of clar- resins and can be recycled in small amounts
ity, impact strength, and economy. The bottle, with a (B10%) as a component of the HDPE waste stream.
linerless polypropylene closure, is produced using a Also, its low density reduces the weight of the pack-
single material for easier recycling (Future—The age (Milliken Chemical, 1996; Oertel, 1996).
Hoechst Magazine, 1992; Himont, 1992).
Recent environmental regulations concerning the
use of packaging material has led to increased use 6.5.7 Film
of polypropylene in rigid packaging. To reduce the Polypropylene is used in flexible packaging in
amount of packaging that ends up in landfills, applications such as shrink-wrap films, snack food
many US states require that packaging materials be packaging, textile bags, and cigarette packaging.
6: APPLICATIONS OF POLYPROPYLENE FILMS 113

(i) (j)

(k)

Figure 6.14 (Continued)

Oriented polypropylene is the second most domi- magazines; in office stationery films; in industrial
nant material used in packaging, surpassed only by laminates and supports for adhesive tapes; and in
polyethylene, and the use of polypropylene in films films for metallization used in applications such as
is increasing. gift wrapping and snack food packaging. It is com-
Although three types of materials are used in flexi- monly used for packaging products that must be
ble packaging—paper, thin gauge aluminum, and protected against moisture absorption or loss.
plastics—plastic films are more in demand than both Coextruded OPP films are used in the snack food
of the other materials combined (Graves, 1995). industry as a replacement for cellophane (Polymers
Biaxially oriented polypropylene (BOPP) film is in Contact with Food, 1991; Polypropylene, 1993).
used in packaging for biscuits, crisps, baked goods, Opaque, coextruded, oriented polypropylene film
sweets, bread, pasta; in cigarette wrap, shrink wrap, (pearlized or cavitated) is formed from coextrusion
and shrink labels; in lamination of books and of three layers; the outer layers are homopolymers
114 PLASTIC FILMS IN FOOD PACKAGING

or copolymers, and the middle layer is a homopoly- barrier packaging methods has reduced food spoil-
mer containing small particles. The particles are age to 2
3%, compared to 30
50% in Third
usually calcium carbonate, although polyamides or World countries where packaging techniques are
polyesters are also used. Copolymers are preferred less developed (Barnetson, 1996; Polymers in
for the outer layers due to good cold seal adhesion, Contact with Food, 1991; Roberts, 1989).
good heat sealability, and ease of conversion. Polyvinylidene chloride, polyamide, and EVOH
During the orientation process, voids are formed are commonly used as barrier polymers in coatings
within the core layer, which lowers the density to and coextrusions. A typical multilayer structure
0.62
0.72 g/cm3 (from 0.91 g/cm3 for uncavitated consists of two layers of polypropylene separated
OPP). The voids also cause light to be scattered, by a layer of EVOH, with adhesive layers (tie
resulting in an opaque film useful for packaging layers) to hold the polypropylene and EVOH layers
fat-containing products such as chocolate and high- together. The plastic ketchup bottle is composed of
fat biscuits. With cavitated film, the high-fat foods this multilayer structure, with polypropylene for
do not create the appearance of an oily deposit on rigidity and water vapor resistance and EVOH for
the outside of the product when they come in con- oxygen resistance. “Lamipac” trays, made of a six-
tact with the packaging (Polymers in Contact with layer structure based on polypropylene/PVC/poly-
Food, 1991). propylene, are used in General Foods’ “Today’s
Polypropylene film provides excellent UV resis- Choice” ready-meals and “Sheba” cat food. The
tance and transparency, and additives can be used “Lamipac” containers are closed by a vacuum heat
to increase performance properties. It can be seal process and are shelf stable (shelf life of up to
printed, laminated, and metallized and is easy to 24 months), retortable, and microwaveable. “Top
handle on automatic packaging machines. Several Shelf” entrees from Hormel are vacuum packed in
applications of polypropylene packaging are shown a four-layer polypropylene tray using PVC as the
in Figure 6.15 (Polymers in Contact with Food, barrier layer; product shelf life is up to 18 months.
1991). The easy-open lid is also a multilayer structure
(Oertel, 1996; Polymers in Contact with Food,
1991; Roberts, 1989).
6.5.8 Barrier Packaging MAP is used for fresh products such as meat,
Different materials vary in their ability to limit fish, pasta, poultry, salads, and vegetables, in order
passage of gases, liquids, and solids. Metals and to satisfy an increasing demand for fresh, additive-
glass (without any pinholes) are impermeable to and preservative-free foods. In these packages, the
everything, while paper is permeable to almost composition of the natural air atmosphere inside
everything. Due to their nonpolar molecular struc- the container is replaced by a gaseous mixture. The
ture, polyolefins have a very low water permeabil- gases used depend on the product but generally
ity but are readily permeable to gases such as include nitrogen (an inert gas used to replace oxy-
oxygen and carbon dioxide and to hydrocarbons gen) and carbon dioxide (to retard the growth of
(Barnetson, 1996). mold and aerobic bacteria). High barrier materials,
Barrier materials are coatings or multilayer com- such as a laminate of PVC rigid foil and polyethyl-
binations of plastics designed to reduce water and ene film, are generally used for the container; how-
gas diffusion into and/or out of the rigid or flexible ever, laminated materials such as PVC
coated
package. Barriers to oxygen are necessary to pre- oriented polypropylene are used in the lids of ther-
serve food freshness; oxygen can cause a chemical moformed MAP trays (Polymers in Contact with
change in the product and rancidity in fat products. Food, 1991; Roberts, 1989).
Water vapor can change the physical appearance of
a product by either caking a dry material (i.e. flour)
or by causing it to become soggy. Carbon dioxide 6.6 Consumer Products
does not cause food spoilage and is used to protect
some foods against spoilage. Barriers to other gases Polypropylene is used in other applications such
such as nitrogen are used in modified atmosphere as housewares, recreational equipment, toys, office
packaging (MAP) to extend the shelf life of fresh equipment, and lawn furniture. In housewares,
foods without the use of preservatives. The use of polypropylene is used in large and small containers
6: APPLICATIONS OF POLYPROPYLENE FILMS 115

(a) (b)

(c) (e)

Figure 6.15 Applications of polypropylene films in packaging. (a) Snack food packaging using metallized film
(Amoco), (b) snack food packaging using clear film (Amoco), (c) floral packaging (Escorene, Exxon), and (d)
apparel packaging (Escorene, Exxon) (Amoco Polypropylene Homopolymers, 1992; Polypropylene, 1993).

for food and other uses (Figure 6.16). Random molding of oversized, high-performance house-
block copolymers, which combine a random copol- wares such as the deep, 33-gallon (125 l)
ymer matrix with a dispersed rubber phase, and ToteLocker and 50-gallon (190 l) RoughTote by
improved random copolymers provide high clarity Rubbermaid, the under-the-bed and hangable closet
and low-temperature impact strength, important in clothing bins by Sterlite, and the 10-quart (9 l)
housewares used in freezer storage. New, high-flow “fresh-food keepers” by Culver (Leaversuch, 1996;
grades of random and impact copolymers allow the Thompson et al., 1987).
116 PLASTIC FILMS IN FOOD PACKAGING

(a) (b)

(c) (d)

Figure 6.16 Polypropylene applications in housewares. (a) Stackable laundry baskets (Rubbermaid),
(b) 33-gallon ToteLocker (Rubbermaid), (c) clear food containers, and (d) various household products (Amoco
Polypropylene Homopolymers, 1992; Leaversuch, 1996).

Polypropylene’s low density makes it useful in (Figure 6.17). Polypropylene (UV stabilized, 20%
recreational items such as bicycle helmets, ice cool- calcium-filled) provides durability and safety in
ers, surfboards, and flotation devices, and its tough- the mower deck, and a proprietary grade in the
ness is useful in luggage and lawn mower parts. cowling cover and discharge chute provides good
Polypropylene is used as a substitute for ABS in long-term weathering resistance and a high-gloss
“hard”, injection-molded luggage, although most Class A finish (Barnetson, 1997; High-Impact PP,
“hard” luggage (66%) is still made from ABS. New 1997; Neopolen).
grades of enhanced polypropylene are being used in Wheels on the Ryobi self-propelled, battery-
lawn furniture, providing higher stiffness and warp operated lawn mower are made from a long glass-
resistance and lighter weight than the commonly fiber-reinforced, chemically coupled polypropyl-
used 20% and 40% talc-filled grades. High-impact ene composite. The material provides strength,
polypropylene is used in the deck, cowling cover, chemical resistance, lubricity, and moisture resis-
and discharge chute of a new cordless lawn mower tance. High strength is required in the two front
6: APPLICATIONS OF POLYPROPYLENE FILMS 117

Figure 6.17 A cordless lawn mower. The mower

deck, cowling cover, and discharge chute are made
Figure 6.18 Drive wheel on the Ryobi self-
from high-impact polypropylene (Ferro Corp.) (High-
propelled, battery-operated lawn mower, made
Impact PP, 1997).
from a long glass-reinforced, chemically coupled
polypropylene composite (Verton MFX, LNP
Engineering Plastics). Gear teeth are molded
drive wheels, where final gear reduction takes
into the wheel (Verton Structural Composites,
place through molded-in gear teeth (Figure 6.18),
1996).
and the fertilizers and pesticides sprayed on the
lawn require that the wheels be resistant to chem-
ical attack. The low moisture absorption of poly-
propylene provides good dimensional stability Polypropylene pipes have a long service life,
for the gear teeth, even when the mower is run good impact strength, and good chemical resis-
in damp grass and stored outside. Also, the natu- tance. They are nontoxic, with a neutral taste
ral lubricity of the material allows the gears and odor, and are easily welded. Pipes provide
to run in a dry state, eliminating the need for long-term pressure resistance, and heat stabilized
grease, which would collect dirt and cause greater pipes can withstand high service temperatures.
wear. Other materials considered were mineral- Pipes do not corrode and do not attract lime
filled polypropylene, which lacked the required deposits. Polypropylene block copolymer was
strength, and PC, which was not as chemically used as the material for pressurized pipes by
resistant (Verton, 1995). Hoffman-LaRoche AG to carry waste water from
chemical production to a treatment plant, a dis-
tance of 3.6 km (2.2 mi). Two pipelines for alter-
6.7 Building and Construction nating operation were laid in an underground
tunnel large enough to walk through. The material
In the building and construction industries, poly- had to withstand pH values of from 1.5 to 15, an
propylene is used in walls and partitions, as insula- operating pressure of 2.3 bar (33.3 psi), and tem-
tion for power cables and telephone wires, and in peratures up to 35 C (95 F); the block copolymer
pipes. Pipe applications include underfloor heating, exhibited better creep strength at higher tempera-
hot and cold water, sanitary engineering, and pipe tures than other pipe materials and performed
fittings (Figure 6.19) (Future—The Hoechst better in heat aging tests (Borealis Press Release,
Magazine, 1992; Oertel, 1996; Techniques, 1986; 1995; Future—The Hoechst Magazine, 1992;
Vestolen P, 1995). Vestolen P, 1995).
118 PLASTIC FILMS IN FOOD PACKAGING

(a) (b)

Figure 6.19 Pipe applications of polypropylene. (a) Hot and cold water pipes (Vestolen PP, Vestolen GMBH)
and (b) underfloor heating pipes (Vestolen PP, Vestolen GMBH) (Hostalen, Hoechst) (Future—The Hoechst
Magazine 1992; Vestolen P, 1995).

References Czerski, J., 1992. Polypropylene in Automotive

Applications, Conference Proceedings (ISBN
Advancing resin and equipment technology makes 0-9023-48-87-6), Rapra Technology Limited.
clarified polypropylene viable for clear, Thin- DeBoest, J.F., 1988. Reinforced Polypropylenes (PP),
wall rigid packaging, 1995. Supplier marketing Engineered Materials Handbook, vol. 2, Engineering
literature. Milliken Chemicals. Plastics, Reference Book. ASM International.
Amoco polypropylene homopolymers, 1992. Supplier Dufton, P., 1992. Use of Polypropylene in the
technical report (PP-8m). Amoco Chemical Company. Automobile Industry, Polypropylene in Automotive
Bailey, M.S., Brauer, D., 1994. Polypropylene: Applications, Conference Proceedings (ISBN
New Array of Polymer Variations Expand End- 0-9023-48-87-6). Rapra Technology Limited.
Use Applications, Modern Plastics Encyclopedia Elber, G., 1993. Back to Basics: Polypropylene,
1995, Reference Book (M603.1.5). McGraw-Hill. Plastics Design Forum, Trade Journal 18 (5)
New York, NY. Advanstar Communications.
Barnetson, A., 1996. Plastic Materials for Packaging. Ewen, J.A., 1997. New Chemical Tools to Create
Rapra Technology Limited, monograph (ISBN Plastics, Scientific American, general circulation
1-85957-068-2). magazine.
Barnetson, A., 1997. Advances in Polymers: From Rexene Technology: Radiation Resistant
Market and Technical Trends. Rapra Technology Polypropylenes, 1987. Supplier technical report (EPP
Limited, monograph (ISBN 1-85957-098-04). 7037 10/87 4M JP). Rexene Products Company.
Borealis press release, 1995. Supplier marketing Future—The Hoechst Magazine, 1992. Supplier
literature. Borealis A/S. newsletter (HB920EBR/014). Hoechst.
Boschert, N.L., 1997. Thermoplastic vulcanizates Goddard, R., 1993. Packaging Materials, Reference
in medical applications. Medical Plastics and Book (ISBN 0-902799-34-7). Pira—The Research
Biomaterials, Trade Journal 4 (1) Canon Association.
Communications. Graves, V., 1995. Polypropylene: A Commodity
Colvin, R., 1996. Performance PPs make gains in Plastic Reaches Record Highs in 1994
kitchen appliances. Modern Plastics, Trade Production, Modern Plastics Encyclopedia 1996,
Journal 73 (13) McGraw-Hill. Reference Book (M603.1.6). McGraw-Hill.
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High-Impact PP Provides Durability in Lawnmower, Polypropylene, 1993. Supplier technical report

1997. Advanced Materials and Processes, Trade (11112-5). Exxon Chemical.
Journal 151 (3) ASM International. Portnoy, R.C., 1994a. Polypropylene for Medical
Himont—Seize the Opportunity to Open New Device Applications, Medical Plastics and
Markets and Reduce Costs, 1992. Supplier mar- Biomaterials, Trade Journal 1 (1) Canon
keting literature (PL-007). Himont. Communications.
Hostacom Journal 1, 1993. Supplier newsletter Portnoy, R.C., 1994b. Polypropylene for Medical
(BW HJ 01 E 9073/022). Hoechst UK Limited. Device Applications, Medical Design and
Inform—Automotive Industry, 1995. Supplier Manufacturing Proceedings, Conference
newsletter (2). Hoechst. Proceedings. Canon Communications.
Inform—Hostalen PP for Textile Applications, Precision Woven Screening Media for Healthcare
1995. Supplier newsletter (4). Hoechst. and Specialty Applications, 1997. Supplier tech-
Inform—Hostalen PP, 1996. Supplier marketing lit- nical report (P/C #450-0052000.000). Tetko.
erature (H 801 PR D/E 0197/035 DW4). Hoechst Roberts, R., 1989. Monograph (ISSN: 0889-3144).
Aktiengesellschaft. Recent Developments in Materials for Food
Leaversuch, R.D., 1996. Houseware Molders Seek Packaging. Rapra Technology Limited
Out New PP Technologies, Modern Plastics, Royle, K., 1992. Polypropylene in Automotive
Trade Journal 73 (13) McGraw-Hill. Applications—Introduction, Polypropylene in
Libert, D., Rosenthal, D.J., 1992. Versatility of Automotive Applications, Conference
Polypropylene Block Copolymers for Automotive Proceedings (ISBN 0-9023-48-87-6). Rapra
Applications, Polypropylene in Automotive Technology Limited.
Applications, Conference Proceedings (ISBN Smock, D., 1997. New Plastic Designs, Plastics
0-9023-48-87-6). Rapra Technology Limited. World, Trade Journal 55 (4) PTN Publishing.
Metallocene Grades Offer Improved Clarity, Techniques: Fastening Thermoplastics with Screws
Toughness, 1997. Modern Plastics, Trade Journal. and Inserts, 1986. Supplier technical report
McGraw-Hill. (BPC-8723). Borg-Warner Chemicals.
Milliken Chemical: Quality Leadership Through The Hostalen PP and Hostacom Ranges for the
Research, 1996. Supplier marketing literature Automotive Industry: Properties and Applications,
(LF-482-01). Milliken Chemicals. 1996. Supplier technical report (H 801/1 e PR
Mitsui Sekka. Supplier marketing literature. Mitsui 0397/035 DW 4). Hoechst.
Petrochemical Industries. Thompson, W.R., Bortolini, W., Young, D.R.,
Neopolen P., Expanded Polypropylene Beads, sup- Davies, J.K., 1987. Polypropylene, Modern
plier technical report—BASF Corporation. Plastics Encyclopedia 1988, Reference Book
O’Neill, M., 1996. Polypropylene Makes Inroads in (M603.1). McGraw-Hill.
Large Applicances, Modern Plastics, Trade Verton is the Strength Behind the Wheel of New
Journal 73 (5) McGraw-Hill. Ryobi Lawnmowers, 1995. Supplier marketing
Oertel, C.G., 1996. Applications, Polypropylene literature. LNP Engineering Plastics.
Handbook, Reference Book (ISBN 3-446-18176- Verton Structural Composites, 1996. Supplier tech-
8). Carl Hanser Verlag. nical report (270-196). LNP Engineering Plastics.
Performance Polyolefins for the Healthcare Market, Vestolen P—Underfloor Heating Pipes and Water
1991. Supplier marketing literature (6615/591). Service Pipes made of Vestolen P 9421, 1995.
Quantum Chemical Corporation. Supplier technical report (7.95/KL). Vestolen
Polymers in Contact with Food, 1991. Conference GMBH.
Proceedings (ISBN 0-90-2348-66-3). Rapra Williams, G.J., 1992. Polypropylene in the
Technology Limited. Automotive Industry, Polypropylene in Automotive
Polyolefin: Because It Works. Supplier marketing Applications, Conference Proceedings (ISBN
literature. American Polyolefin Association. 0-9023-48-87-6). Rapra Technology Limited.
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 7 Emerging Technologies in Food Packaging: Overview
Jung H. Han
PepsiCo Corporate Research, PepsiCo Inc., Plano, TX, USA

7.1 Introduction as an important parameter in packaging

development.
Food packaging is a process to establish a pack- Food industry uses a lot of packaging materials,
age for food. Package in US Federal Food, Drug and and thus even a small reduction in the consumption
Cosmetics Act is defined as “An act for preventing of materials for each package would result in a sig-
the manufacture, sale, or transportation of adulter- nificant cost and material reduction, and may
ated or misbranded or poisonous deleterious foods, improve solid waste problems. Various new pack-
drugs, medicines, and liquors, and for regulating aging technologies have attempted to reduce the
traffic therein, and for other purposes” (Title 21, volume and/or weight of materials in efforts to
Chapter 9, Subchapter II, Section 321b). Packaging minimize resources and costs. Several trends in the
is one of the most important processes to maintain food packaging evolution have been remarkable
the quality of food products during storage, transpor- (Testin and Vergano, 1990), including source
tation, and end use (Kelsey, 1985). It prevents qual- reduction, design improvement for convenience and
ity deterioration, and facilitates distribution and handling, and environmental concerns regarding
marketing efficiencies. The basic functions of pack- packaging materials and processes. Food packaging
aging are protection, containment, information, and has evolved from simple preservation methods to
convenience (Kelsey, 1985). A good package can convenience, point-of-purchase marketing, material
not only preserve food quality but also significantly reduction, safety, tamper-proofing, and environ-
contribute to a business profit. Beyond the functions mental issues (Stilwell et al., 1991). Since the
of preservation, packaging also has secondary World Trade Center tragedy in 2001, food technol-
functions—such as selling and sales promotion. ogists have focused their attention on revising pack-
However, the main function of food packaging is to aging systems and package designs to increase food
achieve preservation and the safe delivery of safety and security. The level of concern regarding
food products until consumption. During distribu- the use of food and water supplies as the possibility
tion, the quality of the food product can deteriorate of bioterrorism has increased (Nestle, 2003).
biologically and chemically as well as physically. Therefore, many applications of active packaging
Therefore, food packaging contributes to extending will be commercially developed for the security
the shelf life and maintaining the original quality and safety enhancement of food products.
and the safety of the food products. Although food packaging has evolved in its vari-
Yokoyama (1985) suggested the conditions nec- ous functions, every package still has to meet the
essary to produce appropriate packaging, which are basic functions. Food packaging reduces food waste
mass production, reasonable and efficient packag- and spoilage during distribution and decreases the
ing material, suitable structure and form, conve- cost of preservation facilities. It extends the shelf
nience, and consideration of disposal. Therefore, life of foods and provides safe foods to consumers.
according to these conditions, packaging designing A good package has to maintain the safety and
and development requires not only an industrial quality of foods as well as being convenient, allow-
design capability, creativity, and marketing tools ing sales promotion, and addressing environmental
but also advanced knowledge of engineering and issues.
environmental science. Preservation, convenience, The quality of the packaged food is directly
and the other basic functions of packaging are cer- related to the food and packaging material attri-
tainly important, but its disposal should be treated butes. Most food products deteriorate in quality

Ebnesajjad: Plastic Films in Food Packaging. DOI: http://dx.doi.org/10.1016/B978-1-4557-3112-1.00007-7

© 2013 Elsevier Inc. All rights reserved. Adapted from a chapter in: Han, Innovations in Food Packaging (2005). 121
122 PLASTIC FILMS IN FOOD PACKAGING

due to mass transfer phenomena. These phenom- New software and part installations in unit
ena can occur between the food product and the operations have been introduced, and high-speed
atmospheric environment, between the food and automation has been achieved by using new
the packaging materials, or among the heteroge- servomotors, subsystem parts, and software technol-
neous ingredients in the food product itself ogies such as the machine vision system (Tucker,
(Krochta, 1997). Therefore, mass transfer studies 2003). The processing and packaging equipment
of the migration of package components and food has new functions that feature increased safety,
ingredients; of the absorption and desorption of quality, and productivity, and therefore it seems
volatile ingredients, flavors, and moisture; of gas that the development of new packaging functions
permeation; and of the reaction kinetics of oxida- may go hand in hand with the development of new
tion and ingredient degradation are essential for processes, materials, and equipments. Packages
food packaging system designs. may have new purposes if new functional packag-
ing materials and/or materials containing functional
inserts/parts are used. Developing new packaging
technologies implies not only new material devel-
7.2 Innovations in Food opment but also new packaging design systems.
Processing and Packaging Yam and Lee (2012) listed some socioeconomic
reasons that drive packaging innovations, such
Year after year, technology becomes better. as consumer lifestyle, value of products, profits,
Most developments in the field of food technology safety/biosecurity, regulations, and environmental
have been oriented toward improving food proces- concerns.
sing and products more conveniently, more effi-
ciently, at less cost, and with higher quality and
safety levels. Traditional thermal processes have
7.3 Food Packaging Technologies
offered innovative developments in the food pro-
cessing industry; these include commercial sterili- 7.3.1 Extra Active Functions of
zation, quality preservation, shelf-life extension,
and safety enhancement. Extended shelf-stable pro- Packaging Systems
ducts manufactured by retorting or aseptic proces- Active packaging has been defined differently by
sing are available in any grocery store and do not many researchers. Among them Robertson (2006)
require refrigeration. These types of products are defined it as “packaging in which subsidiary consti-
very convenient at any place or time and are easy tuents have been deliberately included in or on
to handle, therefore benefiting producers, proces- either the packaging material or the package head-
sors, distributors, retailers, and consumers. The space to enhance the performance of the packaging
major function of extended shelf-stable food pack- system”. Many new “extra” functions have been
aging is to construct a protective barrier against the introduced in active packaging technologies,
invasion of microorganisms. including oxygen-scavenging and intelligent func-
Beyond this simple barrier function, there has tions, antimicrobial activity, atmosphere control,
been more research and development introducing edibility, biodegradability, etc. Food packaging per-
new purposes for food packaging systems. Among forms beyond its conventional protective barrier
these, significant new functional packaging systems function. The new active packaging systems
which have been successfully commercialized are increase product security, safety, protection, conve-
active packaging, modified atmosphere packaging nience, and information delivery. Active packaging
(MAP), and edible films/coatings. systems extend the shelf life of food products by
The development of new packaging functionali- maintaining their quality longer, increase their
ties has been possible because of technological safety by securing foods from pathogens and bioter-
advances in food processing, packaging material rorism, and enhance the convenience of food pro-
science, and machinery. Among the many new cessing, distribution, retailing, and consumption.
technologies, the development in processing and There are many applications of active packaging
packaging machinery is notable, leading to higher technologies, several of which have been commer-
standards of regulation, hygiene, health, and safety. cialized and are used in the food industry; these
7: EMERGING TECHNOLOGIES IN FOOD PACKAGING: OVERVIEW 123

include oxygen-scavenging, carbon dioxide
absorb- depending on different viewpoints. It contains intelli-

ing, moisture-scavenging (desiccation), and antimi- gent functions that have been studied to enhance
crobial systems. Most researchers report that the shelf convenience for food manufacturing and distribution
life of packaged foods has been extended by using and, increasingly, to improve food security and
these active packaging systems, but the combinations safety verification (Rodrigues and Han, 2003).
of multiple active packaging technologies have been
suggested to improve the quality and safety of foods,
and present a future trend in promising new research
7.3.2 Modified Atmosphere
and development project (Cooksey, 2010). Oxygen- Packaging
scavenging systems have been commercialized in the MAP is traditionally used to preserve the fresh-
form of a sachet that removes oxygen from within ness of fresh produce, meats, and fish by control-
packages. An oxygen-free environment can prevent ling their biochemical metabolism, such as
food oxidation and rancidity, and the growth of aero- respiration or fermentation. Nitrogen flushing, vac-
bic bacteria and molds. Carbon dioxide-scavenging uum packaging, and carbon dioxide injection have
packaging systems can prevent packages from inflat- been used commercially for many years. However,
ing due to the carbon dioxide formed after the pack- current research and development has introduced
aging process—for example, packaged coffee beans new modified atmosphere technologies such as
may produce carbon dioxide during storage as a result inert gas (e.g. argon) flushing for fruits and vegeta-
of nonenzymatic browning reactions. Fermented pro- bles, SO2 or ClO2 gas releasing for fruits, carbon
ducts such as pickles, sauces, kimchi (lactic acid fer- monoxide injection for red meats, and high oxygen
mented vegetables), and some dairy products can flushing for red meats. For a MAP system to work
produce carbon dioxide after the packaging process. effectively, optimal packaging material with proper
Carbon dioxide-scavenging systems are also quite gas permeability properties must be selected. The
useful for products that require fermentation and use of MAP systems is attractive to the food indus-
undergo aging processes after they have been packed. try because there is a fast-growing market for
Moisture-scavenging systems have been used for a fresh-cut processed fruits and vegetables, nonfrozen
very long time for packaging dried foods, moisture- chilled meats/fish/poultry, ready-to-eat meals, and
sensitive foods, pharmaceuticals, and electronic semiprocessed bulk foods.
devices; in these systems, desiccant materials are MAP dramatically extends the shelf life of pack-
included in the package in the form of a sachet. aged food products, and in some cases food does
Recently, the sachets have contained humectants as not require any further treatments or any special
well as desiccants to control the humidity inside the care during distribution. However, in most cases,
package more specifically. Moisture-scavenging sys- extending shelf life and maintaining quality require
tems that are based on desiccation are evolving to a multiple hurdle technology system—for example,
control the moisture by maintaining a specific relative temperature control in addition to MAP is generally
humidity inside the package by absorbing or releasing essential to maintain the quality of packaged foods.
moisture. The hurdle technology concept is therefore impor-
Antimicrobial packaging applications are directly tant for MAP applications, since the modified
related to an improved level of food microbial atmosphere provides an unnatural gas environment
safety and bioterrorism as well as to extended shelf that can create unexpected and serious microbial
life by preventing the growth of spoilage and/or problems such as the growth of anaerobic bacteria
pathogenic microorganisms. The growth of spoilage and the production of microbial toxins. Therefore,
microorganisms shortens the food’s shelf life, while the inclusion of a temperature control system is
the growth of pathogenic microorganisms endan- very important for quality preservation and micro-
gers public health. Antimicrobial packaging sys- bial control together with the maximum effective-
tems consist of packaging materials, in-package ness of MAP.
atmospheres, and packaged foods, and is designed
to kill or inhibit the microorganisms that cause
food-borne illnesses (Han, 2000, 2003a,b). 7.3.3 Edible Films and Coatings
Intelligent packaging has been categorized both as The use of edible films and coatings is an appli-
a part of active packaging and as a separate entity, cation of active food packaging, since the edibility
124 PLASTIC FILMS IN FOOD PACKAGING

and biodegradability of the films are functions pouches should resist pressure changes and maintain
beyond those of conventional packaging (Han, seal strength. Since these new technologies each pos-
2002). Edible films and coatings are useful materi- sess unique process characteristics, packaging materi-
als produced mainly from edible biopolymers and als should be selected with these characteristics in
food-grade additives. Most biopolymers are natu- mind.
rally existing polymers, including proteins, polysac- These new packaging materials and/or systems
charides (carbohydrates and gums), and lipids not only need to work technically but they should
(Gennadios et al., 1997). Plasticizers and other also be examined scientifically to ensure their
additives are included with the film-forming biopo- safety and lack of toxicity, and be approved by reg-
lymers in order to modify the film’s physical prop- ulatory agencies. In some cases, countries may
erties or to create extra functionalities. require new regulations and legislation for the use
Edible films and coatings enhance the quality of of these new processing and packaging technolo-
food products by protecting them from natural dete- gies. The globalization of the food industry
rioration processes. The application of edible films enforces international standards and compliance
and coatings is an easy way to improve the physical with multiple regulations. New technologies should
strength of the food products, reduce particle clus- also be examined for their effect on product quality
tering, and enhance the visual and tactile features and public health, and the results of these tests
of food product surfaces (Cuq et al., 1995). They should be disclosed to the public, government agen-
can also protect food products from oxidation, cies, processors, and consumer groups. However,
moisture absorption/desorption, microbial growth, some criteria (such as threshold levels, allowable
and other chemical reactions. The most common limits, and generally acceptable levels) are decided
functions of edible films and coatings are that they politically, as are rulings on how to practice and
are barriers against oils, gas, or vapors, and that review the policy. Scientific intervention is limited,
they are carriers of active substances such as anti- but it is important that scientific research results
oxidants, antimicrobials, colors, and flavors and suggestions be sought and respected during
(Guilbert and Gontard, 1995; Krochta and De political decision making. Consumers buy and
Mulder-Johnston, 1997). Thus edible films and decide what they want. It is also very important to
coatings enhance the quality of food products, develop new packaging innovations that consumers
which results in an extended shelf life and want, choose, and adapt their life style to accept
improved safety. the benefits (Spencer and Junkus, 2007).

7.4 New Food Processing 7.5 Future Trends in Food

Technologies Packaging
Besides the traditional heat processes for food A continuing trend in food packaging technology
preservation, many other new thermal and nonther- is the research and development of new materials
mal treatment technologies have been developed that possess very high-barrier properties. High-
recently. These include irradiation, high-pressure pro- barrier materials can reduce the total amount of
cesses, pulsed electric fields, UV treatments, antimi- packaging materials required, since they are made
crobial packaging, etc. Some of these processes have of thin or lightweight materials with high-barrier
been commercially approved by regulatory agencies. properties. The use of high-barrier packaging mate-
These new technologies generally require new rials reduces the costs in material handling, distri-
packaging materials and new package design in order bution/transportation, and waste reduction.
to achieve optimum processing efficiency—for Convenience is also a “hot” trend in food packag-
example, packages that undergo an irradiation pro- ing development. Convenience at the manufacturing,
cess are required to be resistant to high energy to distribution, transportation, sales, marketing, con-
prevent polymer degradation, those that undergo sumption, and waste disposal level is very important
UV treatments of packaged foods require UV and competitive. Convenience parameters may be
light transmittable packaging materials, and retortable related to productivity, processibility, warehousing,
7: EMERGING TECHNOLOGIES IN FOOD PACKAGING: OVERVIEW 125

traceability, display qualities, tamper resistance, easy Guilbert, S., Gontard, N., 1995. Edible and biode-
opening, and cooking preparation. gradable food packaging. In: Ackermann, P.,
A third important trend is safety, which is related Jägerstad, M., Ohlsson, T. (Eds.), Foods and
to public health and to security against bioterrorism. Packaging Materials—Chemical Interactions. The
It is particularly important because of the increase in Royal Society of Chemistry, Cambridge, UK,
the consumption of ready-to-eat products, minimally pp. 159
168.
processed foods, and precut fruits and vegetables. Han, J.H., 2000. Antimicrobial food packaging.
Food-borne illnesses and malicious alteration of Food Technol. 54 (3), 56
65.
foods must be eliminated from the food chain. Han, J.H., 2002. Protein-based edible films and
Another significant issue in food packaging is coatings carrying antimicrobial agents.
that it should be natural and environmentally In: Gennadios, A. (Ed.), Protein-Based Films and
friendly. The substitution of artificial chemical Coatings. CRC Press, Boca Raton, FL,
ingredients in foods and in packaging materials pp. 485
499.
with natural ingredients is always attractive to con- Han, J.H., 2003a. Antimicrobial packaging materi-
sumers. Many ingredients have been substituted als and films. In: Ahvenainen, R. (Ed.), Novel
with natural components or naturally degradable Food Packaging Techniques. Woodhead
materials. This trend will also continue in food Publishing Ltd, Cambridge, UK, pp. 50
70.
packaging system design areas. To design environ- Han, J.H., 2003b. Design of antimicrobial packag-
mentally friendly packaging systems that are more ing systems. Int. Rev. Food Sci. Technol. 11,
natural requires, for example, the partial replace- 106
109.
ment of synthetic packaging materials with biode- Kelsey, R.J., 1985. Packaging in Today’s Society,
gradable or edible materials, a consequent decrease third ed. Technomic Publishing Co., Lancaster,
in the use of total amount of materials, and an PA.
increase in the amount of recyclable and reusable Krochta, J.M., 1997. Edible protein films and coat-
(refillable) materials. ings. In: Damodaran, S., Paraf, A. (Eds.), Food
Food science and packaging technologies are Proteins and Their Applications. Marcel Dekker,
linked to engineering developments and consumer New York, NY, pp. 529
549.
studies. Consumers tend to continuously want new Krochta, J.M., De Mulder-Johnston, C., 1997.
materials with new functions. New food packaging Edible and biodegradable polymer films: chal-
systems are therefore related to the development of lenges and opportunities. Food Technol. 51 (2),
food processing technology, lifestyle changes, and 61
74.
political decision-making processes as well as sci- Nestle, M., 2003. Safe Food: Bacteria,
entific confirmation. Biotechnology, and Bioterrorism. University of
California Press, Berkeley, CA, p. 1.
Robertson, G.L., 2006. Food Packaging Principles
References and Practice, second ed. CRC Press, Boca Raton,
FL, p. 291.
Cooksey, K., 2010. Active packaging and the shelf Rodrigues, E.T., Han, J.H., 2003. Intelligent pack-
life of foods. In: Robertson, G.L. (Ed.), Food aging. In: Heldman, D.R. (Ed.), Encyclopedia of
Packaging and Shelf Life—A Practical Agricultural and Food Engineering. Marcel
Guideline. CRC Press, Boca Raton, FL, Dekker, New York, NY, pp. 528
535.
pp. 367
381. Spencer, K., Junkus, J.C., 2007. Consumer choice:
Cuq, B., Gontard, N., Guilbert, S., 1995. Edible responses to new packaging technologies.
films and coatings as active layers. In: Rooney, In: Han, J.H. (Ed.), Packaging for Nonthermal
M. (Ed.), Active Food Packaging. Blackie Processing of Food. Blackwell Publishing, Ames,
Academic & Professional, Glasgow, UK, IA, pp. 139
185.
pp. 111
142. Stilwell, E.J., Canty, R.C., Kopf, P.W., Montrone,
Gennadios, A., Hanna, M.A., Kurth, L.B., 1997. A.M., Arthur D. Little, Inc., 1991. Packaging for
Application of edible coatings on meats, poultry the Environment, A Partnership for Progress.
and seafoods: a review. Lebensm. Wiss. Technol. AMACOM, American Management Association,
30 (4), 337
350. New York, NY.
126 PLASTIC FILMS IN FOOD PACKAGING

Testin, R.F., Vergano, P.J., 1990. Food Packaging, Yam, K.L., Lee, D.S., 2012. Emerging food pack-
Food Protection and the Environment. A aging technologies: an overview. In: Yam, K.L.,
Workshop Report. IFT Food Packaging Lee, D.S. (Eds.), Emerging Food Packaging
Division. The Institute of Food Technologists, Technologies. Woodhead Publishing Ltd.,
Chicago, IL. Oxford, UK, pp. 1
9.
Tucker, B.J.O., 2003. A view on the trends affect- Yokoyama, Y., 1985. Materials in packaging.
ing the current development of food processing In: Hashimoto, S. (Ed.), Package Design in
and packaging machinery. Int. Rev. Food Sci. Japan, vol. 1. Rikuyo-Sha Publishing, Tokyo,
Technol. 11, 102
103. Japan, pp. 113
115.
 8 Introduction to Active Food Packaging Technologies
Michael L. Rooney
Formerly Food Science Australia, CSIRO

8.1 Introduction quality retention and the convenience of packaged

goods was not utilized.
The field of active packaging has been the sub- The processes by which food quality is lost often
ject of substantial research and development for involve interaction with substances taken up from
only the past two decades. It remains largely at that their environment. This may mean a loss or gain of
stage of development at the time of writing. The water, ethylene, or oxygen, and contamination with
term “active packaging” was first applied by microorganisms. There are also some substances
Labuza (1987) and may be defined as packaging that build up in the packaged food on storage,
that performs some desired function other than including the containment and cooking odors result-
merely providing a barrier to the external environ- ing from the oxidation of fats and oils. Some of
ment (Hotchkiss, 1994; Rooney, 1995a). Active these compounds are normally lost when foods are
packaging should not be confused with “intelligent cooked shortly before serving. The utility of foods
packaging”, which informs or communicates with can be enhanced significantly if the package contri-
the consumer regarding the present properties of butes to the processes of heating or cooling. These
the food, or records aspects of its history. effects are summarized in Tables 8.1 and 8.2.
There are also more expansive definitions in use The principles upon which packaging acts are
to elaborate the effects achieved by packaging, but not limited to any one scientific discipline.
there is the potential for blurring the distinctions Chemical reactions have been used to remove
between activity and intelligence. A more helpful atmospheric gases such as oxygen, carbon dioxide,
approach is to use the term “active and intelligent and ethylene. Water is merely absorbed by sub-
packaging”, as used in the literature that resulted stances with high affinity, such as silica gel, dehy-
from the Actipack Project funded by the European drated lime, or polyol humectants. Volatile organic
Commission (de Jong, 2003). compounds are largely adsorbed by porous solids
The scope of active packaging research and such as zeolites. In some cases, the strong adsorp-
development was consolidated by Rooney (1995a), tion of ethylene onto inorganic solids has been
and its development has been described and evalu- used to retain the vapor in equilibrium with the
ated (Brody et al., 2001; Gontard, 2000). Several surrounding environment. Self-heating packages
reviews have discussed the field from differing normally involve exothermic or endothermic chem-
points of view (Labuza and Breene, 1989; Meroni, ical reactions in a second compartment of the
2001; Rooney, 2000). package.
Traditionally, packaging is desired to assist in Active packaging is normally designed to
the maintenance of the quality of the food at the address one property or requirement of the food or
level achieved at the final stage of its processing. beverage. The property normally chosen is that
In practice, the quality decreases in packaged stor- most critical as the first limiter of quality or shelf
age because, in part, the combination of packaging life. To this extent, active packaging is provided to
process and packaging material availability does fine-tune the properties of the packaging to meet
not exactly match the specific requirements of each the requirements of the food. This is not different
food or beverage. Packaging has normally been from the normal aim of the packaging technologist
expected to be inert toward the packaged product, to match the requirements of the food with the
but the potential for packaging to contribute to the properties of the packaging.

Ebnesajjad: Plastic Films in Food Packaging. DOI: http://dx.doi.org/10.1016/B978-1-4557-3112-1.00008-9

© 2005 Elsevier Inc. All rights reserved. Reproduced from a chapter in: Han, Innovations in Food Packaging (2005). 127
128 PLASTIC FILMS IN FOOD PACKAGING

Table 8.1 Mechanisms of Food Quality Loss

Quality Attribute Result of Presence Packaging Activity

Mold Microbial spoilage Antimicrobial surface
Antimicrobial release
Oxygen scavenging
Oxidation Rancidity Oxygen scavenging
Odor absorption
Antioxidant release
Color change Oxygen scavenging
Nutrient loss Oxygen scavenging
Food chemistry Odor/flavor formation Absorption
Water movement Texture change Dessication
Microbial spoilage Humidity buffering
Absorption of condensate
Senescence (produce) Premature ripening Ethylene scavenging
1-MCP release
Atmosphere modification

Table 8.2 Convenience Attributes

Effect Opportunity Activity

Heating Convenience meals Microwave susceptors
Vending machines Self-heating cans and cups
Military rations
Cooling Vending machines Self-cooling cans and cups
Summer outdoor events
Gas generation Gasification of beer Widgets

8.2 Drivers for Choice of Active the processing, packaging, and distribution of foods
and beverages are shown in Figure 8.1.
Packaging
The decision to consider active packaging for a
food or beverage is commonly based on factors typi- 8.2.1 Economic Advantage
cally involved in any package selection. These con- The optimal passive packaging solution for a
siderations include economic advantage, process particular product sometimes results in an initial
engineering limitations, convenience in use, envi- quality or shelf life that is at a level below that con-
ronmental impacts, and secondary effects resulting sidered desirable. The packaging may be coupled
from some other change in the processing or packag- with a packaging process that introduces costs in
ing. The latter effects may result from new product terms of line-speed limitation or use of additional
introduction due to lifestyle changes or the availabil- processes. Packages of oxygen-sensitive foods can
ity of technologies that remove a limitation formerly require evacuation followed by inert-gas flushing
experienced. Some of the constraints on optimizing and evacuation a second time. Introduction of an
8: INTRODUCTION TO ACTIVE FOOD PACKAGING TECHNOLOGIES 129

Engineering limitations
Occluded gases
Frothing on degassing
Small package evacuation

Environmental impacts
Direct economies Changes in packaging
Cost reduction material
Reduced capital Use of recycled materials

Food processing
Packaging properties
Marketing

Side effects Time-dependent processes

MAP packages retaining Occluded gases
water vapor Slow formation of odors
Centralized packaging Permeation of gases
reducing portion sizes Leakage of gases

Figure 8.1 Current constraints on food processing, packaging, and marketing.

oxygen scavenger provides the opportunity for characteristic of powders, when spray dried, is the
removal of two or more of these steps. The general occlusion of air within food particles. The release
case has been considered by Rooney (1995b). of this gas occurs slowly and is not achieved by
Removal of the bitter principle, limonin, from means of evacuation on the processing line (King,
orange juice can be achieved by means of a batch 1955). The gas may be desorbed by equilibration
adsorption step during processing, but use of an active with nitrogen over a period of days, but this is read-
packaging material may achieve an acceptable effect ily achieved by means of active packaging rather
(Chandler and Johnson, 1973; Chandler et al., 1968). than by employing nitrogen-flushed holding tanks
Naringin is a bitter principle in grapefruit juice, and it within the production line.
has been shown that large concentrations of this com-
pound can be removed from the juice by contact with
an active packaging material (Soares and Hotchkiss, 8.2.3 Time-Dependent Processes
1998). Such an approach allows the potential for the The slow release of gases occluded in food pro-
time taken to distribute the product to be used to ducts may also be viewed as a time-dependent
advantage. This may result in avoidance of capital for process best addressed by the package during
equipment to remove the naringin in-line. storage and distribution. Two forms of active pack-
aging have been used to address the particular case
8.2.2 Process Engineering of release of carbon dioxide from roasted coffee
beans. The incorporation of one-way valves into
Limitations flexible, gas-flushed coffee packs applies a physical
Oxygen dissolved in beverages can be removed remedy, whereas inclusion of a sachet containing
by vacuum treatments or nitrogen flushing. These absorbents for both carbon dioxide and oxygen has
processes do not always fit well with existing pro- been utilized for cans (Russo, 1986).
cessing equipment due to frothing, so removal of There are other time-dependent chemical pro-
oxygen by means of active packaging is an attrac- cesses that are readily addressed by the use of
tive option. Similar considerations apply to the active packaging. These include the scavenging
flushing of small sachets containing low-density of traces of aldehydes formed during the oxidation
powders that are readily made airborne, thus inter- of fats and oils in foods, which give the product a
fering with sealing of the package. An additional rancid odor long before any nutritional damage has
130 PLASTIC FILMS IN FOOD PACKAGING

been done (Brodie and Visioli, 1994). Other odor- concentrations of oxygen and carbon dioxide
ous compounds are also formed in foods during involved in the respiration of the produce (Kader
storage, and the range of commercial active pack- et al., 1989; Varoquaux, 2000). Concurrently, the free
aging approaches has been reviewed (Brody et al., movement of transpired water vapor is substantially
2001; Rooney, 1995a). It is important to avoid odor reduced compared with that found in an unsealed
removal if this could remove indicators of micro- bag. Consequently the relative humidity rises and
bial growth in foods. there may be condensation of some of this water due
Besides processes occurring in foods during stor- to cycling in the cold chain. There is therefore a need
age, there is also a time-dependent impact of the for this condensate to be kept away from the produce,
permeability of some packaging materials to atmo- for example, by means of superabsorbent pads or,
spheric gases. Oxygen and water vapor are of most possibly, by inclusion of a humidity buffer in the bag
concern, and substantial research has been directed to raise the dew point (Louis and de Leiris, 1991).
to the development of plastics with an enhanced Centralized processing of foods can result in
barrier to oxygen (Rooney, 1995a). The greatest changes in the surface-to-volume ratio of foods, as
development resources have been applied to reduc- evidenced by cut salads, diced fruit, and single cuts
ing the oxygen transmission rate of PET bottles, of steak. When each of these is packaged, there are
especially for use with beer and fruit juices. The challenges for the package engineer that are different
related problem of oxygen leaking under beer clo- from those posed by the unprocessed product.
sures has been addressed by oxygen-scavenging Removal of fruit skin introduces more concerns about
closure liners (Teumac, 1995). microbial growth, and so there are opportunities for
edible coatings containing approved antimicrobials to
be used to advantage. Similar considerations may
8.2.4 Secondary Effects apply to sliced meat.
Although marketing considerations are a recog-
nized driver leading to technical changes in the
packaging of foods, changes in processing methods 8.2.5 Environmental Impacts
commonly lead to changed requirements for the The application of the “three Rs” (reduce, recycle,
packaging. The beer industry has sought to intro- or reuse) to food package selection introduces the
duce PET bottles in place of some or all glass opportunity to question whether the food’s require-
bottles for several years (Anonymous, 2000). The ments are being met by passive packaging alone. The
flavor of beer is seriously degraded by atmospheric desire to replace glass packaging with PET is driven
oxidation of some components (Teumac, 1995). in part by a requirement to reduce weight during
PET has an oxygen permeability that is six times distribution and to reduce the incidence of broken
too high to provide the required shelf life, so its glass. Although PET cannot match all of the desirable
barrier needs to be increased. The most economic properties of glass, some of its properties relevant to
PET-based approach at present appears to be to specific packaging uses can be upgraded by active
include an oxygen scavenger in the middle of three packaging. The barrier to oxygen is being raised by
layers in a multilayer bottle structure. An added several companies using oxygen scavengers within
advantage of such a structure is the scavenging of the bottle walls (Anonymous, 2000). Such scavengers
oxygen dissolved in the PET, which is capable of bring the added benefit of removing oxygen dissolved
diffusing into the beer. Bottles containing an active in the PET, which is capable of diffusion into the
barrier can also, to some extent, scavenge some of packaged beverage over time.
the oxygen dissolved in the beer. Thus, the intro- The introduction of recycled PET has the poten-
duction of the PET bottle has resulted in oxygen tial to introduce odors into lightly flavored liquids,
removal from the beer—something not achievable and there is potential for development of taint
by use of glass. absorbers for use in such packaging.
Possibly a more important side effect is found
when fresh produce is sealed in polyolefin bags,
either as carton liners or as retail packs, both of which 8.2.6 Enhanced Convenience
help generate modified atmospheres. The seal allows Consumption of convenience foods, both within
the permeability of the plastic to regulate the and outside the home, has resulted in the
8: INTRODUCTION TO ACTIVE FOOD PACKAGING TECHNOLOGIES 131

development of a range of easy-to-use packages, of packaging activity are favorable when compared
such as “clamshells”, pizza boxes, and lidded with those of mold growth, oxidation, and accumu-
disposable cups. Temperature retention in such lation of odors.
foods and beverages has proved not to be easy, The decision as to whether the source of activity
since the insulation characteristics of such conven- should be localized or spread throughout the packag-
tional passive packaging appear to be at its eco- ing material may be limited by the form of the pack-
nomic limit. The perceived need for active age as well as the requirement of the food/beverage.
packaging in temperature control is found in the Commercial active packaging for gas atmosphere
event market, for military use, and for vending modification is available as a variety of inserts, and
machine sales. Self-heating cups and cans and in some cases is incorporated into the package
self-cooling cans are examples of developments structure.
designed to overcome this limitation.
The use of microwave susceptors in packaging
for pastries and crisp convenience products seems 8.3.1 Localized Effects
to be limited to few products other than microwave Inserts such as sachets, cards, and self-adhesive
popcorn. This form of active packaging appeared to labels are used to achieve a range of atmospheric-
have substantial potential when introduced. modification effects. The range available commer-
cially in the early days of active packaging has
been tabulated and discussed by Abe (1990). Since
8.3 Forms of Active Packaging that time, the nature of the inserts has changed in
terms of both their content and materials of con-
The choice of the form to be taken by the active struction. This has been a significant advance, par-
packaging is made on the basis of three broad con- ticularly where finely powdered ingredients have
siderations. Most important is the requirement of been replaced with the equivalent substances incor-
the food, followed by the packaging format, and porated into plastic strips.
the requirements of the active agent. Rigid packs that are sealed with a lid or similar
The demands of the food can be visualized by closure offer the opportunity for incorporation of
considering the potential application of gas activity into either the body of the pack or the
exchange in a retail pack of ground beef. Removal closure. A variety of closure liners have been
of oxygen or addition of carbon dioxide may be the developed for the market, commencing with
chosen method of reducing spoilage by aerobic oxygen-scavenging closure liners for use on beer
microorganisms. bottles (Teumac, 1995). The use of closure liners as
This application appears too demanding, as air the carrier allows both the container and the basic
pockets remain within the product. However, pro- closure to be unchanged despite the introduction of
ducts like shredded cheese or fresh pasta, which are the active function.
packaged in low-oxygen/high-carbon dioxide atmo-
spheres, would be more amenable to successful
atmospheric modification involving package activ- 8.3.2 Whole-Package Activity
ity. In this case, the removal of oxygen could be Increasingly, research and development atten-
achieved either by including oxygen-absorbing tion has moved from localized effects to the
sachets in the package or by chemically active plas- achievement of whole-package activity. This is
tic packaging. driven by the needs of beverages in particular and
The relative rates of food degradation and gas to gain specific benefits with some foods.
exchange between the food and its environment Beverages sensitive to oxygen are largely pack-
determine whether or not turbulent mixing is neces- aged in glass. The recent trend toward replacement
sary. If turbulence is needed, it can be provided of glass with polyester in bottles and jars has
only with evacuation or gas flushing, as occurs dur- necessitated an increase in the barrier of the latter
ing pack filling. In other cases, the lower energy to oxygen (and carbon dioxide in the case of
exchange generated by active packaging occurs beer). The oxygen-barrier enhancement may be
only in response to a concentration gradient. This achieved by oxygen scavenging within the bottle
approach is particularly suitable where the kinetics wall (Brody et al., 2001).
132 PLASTIC FILMS IN FOOD PACKAGING

Both beverages and foods may benefit from providing an outer surface with antimicrobial prop-
active packaging that is antimicrobial. Unless the erties. The latter is potentially important when used
antimicrobial agent is volatile, it is necessary for with finger foods such as hors d’oeuvres.
the packaged product to contact the package The requirements of foods that involve edible
surface. The latter may be active because of its coatings can be very complex, so the active contri-
antimicrobial surface chemistry or due to migration bution provided by the additive may not be a major
of an agent onto the contact layer of the food or consideration in the formulation of the coating.
beverage (Han, 2000).
Migration of an active agent from a package onto
a food can occur by diffusion from one phase to the
other. In the case of solid or semisolid foods, inti- 8.4 History of Active Packaging
mate contact may require evacuation (or package The recognition of active packaging as a generic
collapse due to gas absorption, as occurs with approach is a relatively new occurrence, as evi-
cheeses). If the active agent is required to act on the denced by the earliest reviews bringing together the
surface of the food, migration into the latter will concepts, even if using different descriptors—such
impose some conditions of relative diffusivities as “smart” (Anonymous, 2000; Labuza and Breene,
from the packaging and into the food. This will also 1989; Sacharow, 1988). The field has been devel-
apply to pastes and other high-viscosity liquids. In oping largely as a series of niche markets, owing to
the case of beverages, some agitation of the package the current approach of the package converting and
contents may be required to achieve the intended resin industries of viewing it in terms of a series of
effect sufficiently and rapidly. The reverse require- market opportunities. The user industries, typified
ments apply when a migrating species is removed by the food industry, have presented these opportu-
from the food/beverage, although diffusion to the nities in isolation, and this situation may continue
package surface may well be the faster process. for some years. The approach of considering a
Meroni (2001) has proposed that the functional- range of packaging options (both passive and
ity of packaging be categorized in order that all active) as a whole is not yet common practice.
involved can understand the level of packaging Many of the developments have been logical
design required. She defines a basic level of active consequences of earlier commercial products or of
packaging as one that has little or no intelligence noncommercial research publications. There are,
added. An intermediate level may, for instance, however, some concepts that appear to have estab-
include sensors that might determine the heating lished new lines of investigation or commercial
time the package with a susceptor might require in development. Any choice of this type is necessarily
a microwave oven. The superior level of complex- subjective, but some of these are shown in
ity might involve more combinations of effects, Table 8.3, and the discussion that follows indicates
such as releasing color and flavor into the product. their significance.
Developments in nomenclature of this kind will
probably be necessary since such concepts are find-
ing their way into definitions of active packaging, 8.4.1 Active Packaging for
such as in Brody et al. (2001). Processed Foods and Beverages
Oxygen Scavenging
8.3.3 Edible Coatings The earliest approaches to the removal of oxygen
When an edible coating contributes to the packag- from canned milk powder involved the use of oxi-
ing of a food, the coating performs first as a food dizable metal powders (Tallgren, 1938). A system
component. However, because it is normally made with some control over the commencement of oxy-
from one or more food constituents, it may need pro- gen uptake was introduced by Kuhn et al. (1970),
tection against microbial activity. Hence if a mobile who used palladium catalyst attached to the inside
antimicrobial agent is incorporated therein, the coat- of the can lids to catalyze the oxidation of hydrogen
ing can serve several additional functions. These gas mixed with the nitrogen flush in the canning of
include providing some self-preservation, helping to milk powder. The process was incorporated into
reduce the microbial load on the food surface, and foil laminate pouches by the American National
8: INTRODUCTION TO ACTIVE FOOD PACKAGING TECHNOLOGIES 133

Table 8.3 Some Seminal Technology Adaptations in Active Packaging

Technology Significance References

Pd catalysis of hydrogen Triggering of oxygen scavenging King (1955)
oxidation
Ethylene oxidation by Reactive removal of ethylene in produce packs Scott et al. (1970)
permanganate
Singlet oxygen reactions in Light as a trigger in oxygen scavenging Rooney and Holland
plastics (1979)
Side-chain crystallizable Gas permeability adjustment with temperature Stewart et al. (1994)
polymers in cold chain

Can Company (Warmbier and Wolf, 1976). This be undesirable when present in excess—as in natu-
work represented the beginning of the research ral cheeses, coffee, or kimchi. Approaches to its
activity that led to the introduction of flexible removal have continued to involve the incorpo-
oxygen-scavenging packs in 1996 by BP Amoco ration of lime into sachets, or of one-way valves, as
Chemicals and the Cryovac Division of Sealed Air in retail coffee packs (Abe, 1990; Gaglio, 1986). In
Corporation. Since that time, refinement of the contrast, release of the gas has been achieved by
chemistry used has continued at a steady pace. use of sodium bicarbonate and food acids in
Concurrent research designed to meet the needs sachets. When the combined antimicrobial effects
of the beer industry for trapping oxygen diffusing of oxygen scavenging and carbon dioxide release
under closures resulted in a range of polymeric are required, both effects can be achieved if ferrous
closure-liner modifications. These involved several carbonate is used as the active ingredient.
chemistries, but those used most successfully incor-
porate sulfites, iron powder, and ascorbic acid
Removal of Odors and Flavors
(Teumac, 1995).
The approach of including oxidizable com- The development of unpleasant flavors as a con-
pounds in porous sachets was concurrently con- sequence of food processing can be the result of
ducted in Japan, resulting in the introduction of thermal degradation of components, such as pro-
Agelesss by Mitsubishi Gas Chemical Co. in 1977 teins, or of reactions such as the Maillard reaction.
(Smith et al., 1995). Recent developments of these Oxidation of fats and oils is also accelerated at pro-
porous sachets have led to a variety of self- cessing temperatures. Besides these reactions, there
adhesive labels and cards for insertion into food can be a slow generation of unpleasant flavors
packages (Sakakibara, 2000). when fruit components are disturbed from their
Parallel developments for the polyester industry structural components in the fruit. The bitter princi-
have resulted in a range of approaches to oxygen ple, limonin, builds up in orange juice after pasteur-
scavenging by polymeric and low-molecular- ization and renders juice from some cultivars
weight compounds within polyester bottle walls undrinkable. Chandler and Johnson (1979) showed
(Anonymous, 2000). The first approach was the that substantial quantities of limonin could be
oxidation of MXD-6 polyamide by the permeating removed by acetylated paper, following earlier
oxygen in the presence of a transition metal cata- work involving cellulose acetate gel beads
lyst (Cochran et al., 1991). These developments (Chandler et al., 1968).
include multilayer systems as well as blends with The concept of odor removal using chemical
PET in monolayer bottles. affinity was further developed by Brodie and
Visioli (1994), who used the reaction of aldehydes
with amino polymers. The approach of focusing on
Carbon Dioxide Scavenging or Release more specific reactions has been taken a step fur-
Carbon dioxide serves as an antimicrobial gas in ther by Soares and Hotchkiss (1998), who showed
modified atmosphere packaging (MAP), but it can that the naringin content of grapefruit juice could
134 PLASTIC FILMS IN FOOD PACKAGING

be reduced to acceptable levels by using naringi- inorganic adsorbents into plastic liner bags, but
nase immobilized within cellulose triacetate film. subsequent research involved sachets of porous
This increasing use of specific effects highlights solids containing potassium permanganate. Recent
the aim of active packaging to achieve a specific research by Chamara et al. (2000) demonstrated
effect without necessarily impacting on other prop- that the shelf life of Kolikuttu bananas could be
erties of packaging. extended from 24 days to 54 days at 14 C and 94%
relative humidity by incorporation of a potassium
permanganate scavenger into polyethylene bags of
Active Packaging for Produce the fruit. Ripening after storage in this way was
MAP of produce has been practiced to varying found not to differ from that found in the absence
degrees for several decades, following the success- of the scavenger. Research from the same laborato-
ful controlled atmosphere storage of pome fruits. ries showed that a similar effect could be achieved
Although some contribution to modification of the with Pollock avocados (Chamara et al., 2002). The
package atmosphere by choice of the permeability latter are used commercially, but recent advances
of the package is regularly achieved, research have included a metal complex and cyclic com-
toward better atmospheres has been conducted for pounds that react with ethylene. The latter are tetra-
at least two decades. The use of hydration of zenes, which react very rapidly and quantitatively,
patches over holes in the packaging was the initial with a concurrent change in color (Holland, 1992).
approach, and this was followed by the develop- The condensation of water in produce packs
ment of Intellipacks by the Landec Corporation noted above has also been found to inhibit the
(Stewart et al., 1994). The latter material has a ethylene-adsorbing capacity of a natural zeolite,
sharp change in gas permeability at specific molecular sieve 5A, and activated carbon
selected temperatures, allowing compensation for (Yamashita, 2000). The condensation of water was
temperature changes during distribution. found to lead to the release of ethylene already
Besides the respirational gases, the movement of adsorbed. An alternative approach found useful was
water transpired by produce in a lined carton or a to utilize palladized carbon, a common catalyst
retail pouch is also a cause of quality loss or at used in organic chemistry. This allowed storage of
least buildup of fog on the plastic. Antifog coatings broccoli for a week at 10 C, whereas the product
were introduced and are still used. Proposals for the was unsaleable after this time when no ethylene
removal of water vapor by a form of humidity buff- scavenger was used.
ering initially involved porous bags of sodium More recently, 1-methylcyclopropene (1-MCP)
chloride (Shirazi and Cameron, 1992). This was vapor has been found to inhibit the hormonal effect
followed by the introduction of thin pouches of ethylene on the senescence of produce. Inserts that
containing humectants such as glycols and carbohy- release 1-MCP into packages have become available
drates (Labuza and Breene, 1989). At present, commercially and have some regulatory approval for
humidity is still largely uncontrolled in wholesale produce application in the United States.
packs for produce. This topic provides a challenge,
particularly for desiccant manufacturers, to mini-
mize losses due to buildup of condensate on fruits Active Packaging for Fresh Meat
during distribution. Packaged unprocessed meats are supplied in sev-
The aging of produce and flowers can be delayed eral forms, including fresh retail cuts, MAP cuts,
by the use of MAP but accelerated by exposure to and chilled vacuum-packed primals. These
ethylene. This plant hormone is generated endoge- packages often exhibit ambient, increased, and
nously, especially when a particular item has been decreased levels of oxygen, respectively. The MAP
injured or is at an advanced stage of ripening. The and vacuum-packaged cuts feature raised carbon
ethylene generated by one fruit can also trigger the dioxide levels. The major chemical route to quality
senescence of many others, and so packages require loss involves the formation of brown metmyoglobin
an ethylene-scavenging capability rather than just a at oxygen levels that are approximately between
high permeability that reduces buildup of the gas 0.1% and 2.0%. Inclusion of oxygen-scavenging
generated within the pack but dissipates it else- sachets that also have the capacity to release some
where. Early developments involved incorporating carbon dioxide enables further enhancement of the
8: INTRODUCTION TO ACTIVE FOOD PACKAGING TECHNOLOGIES 135

maintenance of ideal packaging conditions. Earlier change to the active polymer. Such chemical
forms of active packaging involved the inclusion of changes may lead to changed compatibility or degra-
a bicarbonate and an organic acid in pads that dation (or cross-linking) of the host polymer if the
absorb weep from cut meat. More recent oxygen activity involves free-radical reaction mechanisms.
scavenging has involved the addition of water to When silicone oxygen-scavenging films based on
sachets to trigger more rapid oxygen scavenging singlet oxygen reactions were being developed in
because the metmyoglobin formation is rapid and the author’s laboratory, exudation of an insoluble
irreversible in retail packs. Oxygen-scavenging oxidation product was observed within a few hours
plastics have the potential to contribute substan- when an otherwise soluble substrate was oxidized.
tially to the removal of oxygen originating from Such an occurrence is particularly noticeable in
occlusion and permeation of the film material. silicones that are often poor solvents for organic
The quality of fresh meat is also limited by the compounds. In some forms of active packaging,
growth of slime-forming bacteria, and recent sustained migration of substances in or out of a
research aimed at providing packaging films that packaging plastic is necessary to achieve the desired
release organic acids offers potential for reducing effect. Such systems include, for instance, the
this effect. Films that release lactic acid are particu- release of antimicrobials, flavors, or antioxidants,
larly attractive, as this acid is normally present in and uptake of water vapor, oxygen, ethylene, or
the meat and can be effective when applied at the taints (Floros et al., 1997). The polymer required to
cut surface. support these effects may therefore differ from that
used in a plastic with an otherwise similar passive
role. The latter roles include that of a heat-seal or
8.5 Impact on Packaging Materials barrier layer in a pouch, or a closure liner in bottles.
Restrictions imposed by the diffusion of selected
and Processes species in polymers normally result in the active
Creation of activity in packaging materials fre- layer being as close as practicable to the food.
quently involves the introduction of additional
components into otherwise inactive materials, typi- Premature Activity
cally plastics. Besides the intended effect, there
may be unintended consequences that must be Some active components are unaffected by the
addressed in order to bring the package to market. presence of air in the distribution environment. Such
These additional considerations impact on material components include ethylene absorbers, odor absor-
properties and the manner in which they must be bers, and the like. However, when the air contacts a
used either in order to achieve their desired effect packaging material containing a compound reactive
or to be processable in the expected manner. with oxygen or water vapor, there is the opportunity
for premature commencement of activity, resulting
in a lower effectiveness when the package is used.
8.5.1 Material Properties For this reason, the concept of activation (or trigger-
Active components may form homogeneous ing) has been the subject of much patenting.
mixtures with the existing plastic or may occur in a Oxygen-scavenging plastics are now commonly
separate phase. The range of options available has triggered by exposure to ultraviolet (UV) light
been described in detail (Rooney, 2000). Some (Ching et al., 1994; Rooney and Holland, 1979;
active polymers may be used as polyblends whereas Speer et al., 1993). Active systems consisting of
low-molecular-weight additives may dissolve in the sachets containing desiccants or reduced iron
base polymer. Components that must be used as powder are normally kept free from air in barrier
powders may interfere with the optical properties laminate pouches, as they become active when
of the plastic as well as its propensity for tearing. exposed to the relevant air components.
Some hard particles can lead to reduced sharpness
of slitter blades and possibly increase the wear in
extruder barrels. 8.5.2 Process Adaptation
Chemical effects may impact on material proper- Active packaging may require some level of
ties where the activity involves substantial chemical adaptation at the stages of plastic extrusion,
136 PLASTIC FILMS IN FOOD PACKAGING

package fabrication, or when the pack is filled and Aim Stage Contribution
sealed. If the chemistry causing activity is inhibited
by the presence of antioxidants, it may be necessary Retain
Grower
quality
to control their addition to a greater extent during
Preservation
extrusion. Some additives would be unstable at
Retain
extrusion temperatures (200
370 C), and so it is quality
Transporter
likely that they will be applied to the packaging as Plant
operation
internal coatings. It has been reported recently that a Unique
Processor
flavor additive manufacturer in the United States, properties Package
cost
ScentSational, has developed encapsulated food
aromas in a form that does not degrade under normal Reduce
Distributor Preservation
loss
plastics extrusion conditions (Ver-Bruggen, 2003a).
It is more likely that adaptation will be required
Retain Ease of
in the package converting or shortly before filling. freshness
Consumer
use
This occurs with the insertion of sachets or the
application of self-adhesive labels to lidding film Figure 8.2 The distribution chain: targets and
for thermoformed trays. Triggering of oxygen- opportunities for active packaging.
scavenging systems by means of brief exposure to
UV light may occur at the film stage, with empty
packs as with PET bottles, or after package filling. active packaging. Cost savings on packaging opera-
Various irradiation systems have been described in tions, such as reduced vacuum use, and packaging
patents (Ching et al., 1994; Rooney, 1993; Speer material cost would be other inputs.
et al., 1993). The potential for benefits to be generated along
the distribution chain can be visualized using the
topics in Figure 8.2 or from other considerations.
Space limitations prevent showing the possible
8.6 Active Packaging and the benefits, such as being able to market a difficult
Distribution Chain fish-oil product because of the oxygen scavenging
possible with redesigned packaging. Another bene-
The direct effects of active packaging systems fit not shown is the possibility of better conformity
discussed above can be used to differing extents by with regulations, as with removal of aluminum foil
the participants in the food and beverage distribution from aseptic brick packs and replacement with a
chain. The wide range of technologies, either avail- barrier plastic with an enhanced barrier due to oxy-
able or in the process of development, will deliver gen scavenging.
benefits that depend upon both the aim of the partic-
ipant and the drivers that participant sees in the par-
ticular business. This distribution of desired outputs 8.7 Regulatory Environment
and the prospects for active packaging inputs are
shown diagrammatically in Figure 8.2. Integration of active and passive technologies
The food chain may be followed from the will be assisted when the actions of regulators have
grower to the consumer. The grower and distributor been clearly understood by potential petitioners. The
need primarily to retain harvested quality until the European Commission took a step in this direction
product reaches (for instance) the processor. by funding the Actipack Project (de Jong, 2003).
Optimum quality retention may be achieved by the This project involved the coordinated work of six
selection of packaging with some activity, such as research institutes and three commercial enterprises
humidity buffering or ethylene scavenging. in evaluating existing active technologies and classi-
Processors need to differentiate their products from fying them in terms of their regulatory features. The
those made by others from the same raw materials, migration of ingredients from some active packag-
and so will be expecting contribution from simplifi- ing materials was investigated, and results for two
cation of plant operations—such as by eliminating iron-based oxygen absorbers have been reported
juice debittering operations and replacing this with (Lopez-Cervantes et al., 2003). The outcome of the
8: INTRODUCTION TO ACTIVE FOOD PACKAGING TECHNOLOGIES 137

research project was a series of proposals forming Ching, T.Y., Katsumoto, K., Current, S., Theard,
a new Framework Directive to replace 89/109/EEC L., 1994. Ethylenic oxygen scavenging composi-
(Ver-Bruggen, 2003b). These amendments, if imple- tions and processes for making same by transes-
mented, will provide clear mechanisms for introduc- terification in a reactive extruder. International
tion of further commercial developments in the Patent Application PCT/US94/07854.
field. Consideration of these proposed amendments Cochran, M.A., Folland, R., Nicholas, J.W.,
is not expected before late 2004 (Ver-Bruggen, Robinson, M.E., 1991. Packaging. US Patent
2003a). 5021515.
Several packaging technologies based on active de Jong, A., 2003. Food Packag. Bull. 12 (3
4),
concepts have been approved by the US Food and 2
5.
Drug Administration (FDA) without change to the Floros, J.D., Dock, L.L., Han, J.H., 1997. Food
normal Premarket Notification process. Brody et al. Cosmetics and Drug Packaging, 10
17.
(2001) have noted the benefit of the earlier FDA Gaglio, L., 1986. In: Bakker, M. (Ed.), Wiley
approval of sandwiching postconsumer PET recy- Encyclopedia of Packaging Technology. John
clate between virgin PET in their later approval of Wiley & Sons, New York, NY, pp. 691
692.
some oxygen-scavenging compositions. Some zeo- Gontard, N., 2000. Les Emballages Actifs. Paris,
lites containing silver ions have been approved for France, Editions TEC & DOC.
use in plastics packaging for food in Japan and, by Han, J.H., 2000. Food Technol. 54 (3), 54
65.
the FDA, in the United States. The requirements of Holland, R.V., 1992. Absorbent material and uses
the EPA must be considered in the United States, thereof. Australian Patent Application No. PJ6333.
and the position of antimicrobial compositions may Hotchkiss, J.H., 1994. Abstracts of the 27th Annual
be less clear there at present. Additives to packag- Convention. Australian Institute of Food Science
ing plastics may have implications for the environ- and Technology, North Sydney, Australia.
ment when the package is returned to the earth via Kader, A., Zagory, D., Kerbel, E.L., 1989. Crit.
landfill or incineration, so regulations of the EPAs Rev. Food. Sci. Nutr. 28, 1
30.
are a consideration in formulating packaging. King, J., 1955. Food Manuf. 30, 441.
Kuhn, P.E., Weinke, K.F., Zimmerman, P.L., 1970.
In: Proceedings of the Ninth Milk Concentrates
Conference, Pennsylvania State University, 15
References September.
Labuza, T.P., 1987. In: Proceedings of the
Abe, A., 1990. In: Proceedings of the International Icelandic Conference on Nutritional Impact of
Conference on Modified Atmosphere Packaging, Food Processing, Reykjavik, Iceland.
Part 1. Stratford-on-Avon, UK. Labuza, T.P., Breene, W.M., 1989. J. Food Proc.
Anonymous, 2000. Verpackungs Rundschau 51 (2), Preserv. 13, 1
69.
6
7. Lopez-Cervantes, J., Sanchez-Machado, D.I.,
Brodie, V., Visioli, D., 1994. Aldehyde scavenging Pastorelli, S., Rijk, R., Paseiro Louis, P.J., de
compositions and methods relating thereto. US Leiris, J.-P., 1991. Active Packaging. Etude
Patent 5284892. Technologique, International Packaging Club,
Brody, A.L., Strupinsky, E.R., Kline, L.R., 2001. Paris, France.
Active Packaging for Food Applications. Meroni, A., 2001. Food Packag. Bull. 10 (4
5), 2
7.
Technomic, Lancaster, PA. Rooney, M.L., 1993. Oxygen scavengers indepen-
Chamara, D., Illeperuma, K., Galapatty, P.T., dent of transition metal catalysts. International
Sarananda, K.H., 2000. J. Hort. Sci. Biotechnol. Patent Application PCT/AU93/00598.
75, 92
96. Rooney, M.L., 1995a. In: Rooney, M.L. (Ed.),
Chamara, D., Illeperuma, K., Nikapitiya, C., 2002. Active Food Packaging. Blackie, Glasgow, UK,
Fruits 57, 287
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172.
Chandler, B.V., Johnson, R.L., 1979. J. Sci. Food Rooney, M.L., 1995b. In: Rooney, M.L. (Ed.), Active
Agric. 30, 825
832. Food Packaging. Blackie, Glasgow, UK, p. 76.
Chandler, B.V., Kefford, J.F., Ziemelis, G., 1968. Rooney, M.L., 2000. In: Giles, G.A., Bain, D.R.
J. Sci. Food Agric. 19, 83
86. (Eds.), Materials and Development of Plastics
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Packaging for the Consumer Market. Sheffield properties and applications. In: El-Nokaly, M.A.,
Academic Press, Sheffield, UK, pp. 105
129. Pratt, D.M., Charpentie, B.A. (Eds.), ACS
Rooney, M.L., Holland, R.V., 1979. Chem. Ind. Symposium Series No. 520. American Chemical
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Russo, J.R., 1986. Packaging (Chicago) 31 (8), Tallgren, H., 1938. Keeping food in closed contain-
26
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Sacharow, S., 1988. Prepared Foods, 121
122. as zinc dust, Fe powder, Mn dust etc. British
Sakakibara, Y., 2000. In: Proceedings of the Patent 496935.
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Soares, N.F.F., Hotchkiss, J.H., 1998. J. Food Sci. Ver-Bruggen, S., 2003b. Active and Intelligent
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Speer, D.V., Roberts, W.P., Morgan, C.R., 1993. Warmbier, H.C., Wolf, M.J., 1976. Mod. Packag.
Methods and compositions for oxygen scaveng- 49, 38.
ing. US Patent 5211875. Yamashita, I., 2000. In: Gontard, N. (Ed.), Les
Stewart, R.F., Mohr, J.M., Budd, E.A., Lok, X.P., Emballages Actifs. Editions TEC & DOC, Paris,
Anul, J., 1994. Polymeric delivery systems— France, pp. 219
227.
 9 Oxygen-Scavenging Packaging
Michael L. Rooney
Formerly Food Science Australia, CSIRO

9.1 Introduction weight of the food. Removal of oxygen to these

small amounts by conventional means is not gener-
Traditionally, oxygen-sensitive foods and bev- ally achievable if the food or beverage has compo-
erages have been packaged in such a way as to nents that react rapidly. Beer is one of the most
minimize their exposure to oxygen. This oxygen studied beverages, and it has been found that an
may be in the package at the time of sealing, or uptake of around 1 ppm (or a little more) results in
may enter the pack by permeation or leakage over the beer reaching its shelf life. A conventional bot-
the storage life. The first source of oxygen has fre- tle closed with a crown seal allows an uptake or
quently been addressed by the use of evacuation around 750 ppb of oxygen over 3 months and
and inert-gas flushing, while the ingress has been 2000 ppb over 8 months (Teumac, 1995).
minimized by optimal sealing and the use of high-
barrier packaging materials. The approaches used
to solve both oxygen problems are now recognized 9.2 Reviews
as providing only partial solutions, leaving options
for improvements in food quality, production and The various aspects of oxygen-scavenging pack-
distribution economics, reduction in environmental aging systems have been reviewed as part of
impacts, and increased convenience of use. general reviews of active packaging, but most of
The impact of oxygen on food quality, and ulti- the reviews of the subject itself are found in the
mately shelf life, is dependent not only upon the proceedings of conferences (Brody et al., 2001;
quantity of oxygen available for chemical oxidation Kline, 1999). This field is commercially the most
or support of growth of organisms but also upon developed in active packaging, but most of the
the rate of the reactions which consume the oxygen. papers at conferences still consist of presentations
This, in turn, will be influenced by the solubility of by developers or vendors of systems. There is still
the gas in the medium provided by the food or bev- a lack of detailed investigation of the comparative
erage. The oxidation of fat in, for example, potato performance of the systems on offer to the food
chips has been shown to be highly dependent upon industry. Brody et al. (2001) have described most
water activity, with a minimum rate at aw 0.3
0.4, of the commercial plastics-based systems and have
and the increase in reaction rate above this value is given examples of their potential use. Smith et al.
interpreted in terms of the formation of an aqueous (1995) have dealt in depth with the applications of
multilayer on the food with consequent dissolution oxygen-absorber sachets, but there have been sub-
of oxygen and enhancement of the oxidation stantial developments in the area of adhesive
(Taoukis et al., 1988). Much of the trade literature oxygen-absorber “labels” since that time.
on oxygen-scavenging packaging presents a focus
on the quantity of oxygen in a package without
consideration of the widely different rates at which 9.3 History
food quality can be degraded.
The quantity of oxygen which must be taken up The development of oxygen-scavenging systems
by a food to limit its shelf life to 1 year has been has followed two lines, depending upon whether
estimated for a range of foods (Koros, 1990). The the oxidizable substance was designed to be a part
quantities lie in a range of a few parts per million of the package or to be inserted into it with the
to a few hundred parts per million based on the food. The insert approach includes self-adhesive

Ebnesajjad: Plastic Films in Food Packaging. DOI: http://dx.doi.org/10.1016/B978-1-4557-3112-1.00009-0

© 2005 Elsevier Inc. All rights reserved. Reproduced from a chapter in: Han, Innovations in Food Packaging (2005). 139
140 PLASTIC FILMS IN FOOD PACKAGING

labels, adhesive devices, or free sachets included insertion into cans. This patent was assigned to the
with the food. Modification of packaging materials US government. He saw the need for prevention of
to confer oxygen-scavenging capability includes oxidation of dehydrated products in particular, and
monolayer and multilayer materials and reactive noted the capability of a variety of sulfite forms to
closure liners for bottles and jars. be useful in the presence of an acid such as lactic
acid. The reactions required the presence of water
and this could be added, even though some might
9.3.1 Package Inserts
be available as water of crystallization in one or
Oxidation of Metals more of the salts. It is clear that the use of oxidase
Brody et al. (2001) refer to early attempts to scav- enzymes was already being discussed, and Bloch
enge oxygen using ferrous sulfate in the 1920s. An noted the reactivity of bisulfites at refrigerator tem-
early patent was authored by Tallgren (1938), who peratures when enzymes were inefficient. It is inter-
proposed the use of iron, zinc, or manganese to esting to note that he recognized the need for
remove oxygen from canned foods. This approach intimate mixing of the bisulfite with an activator
was developed further, but research focused on the such as an iron salt, particularly in the presence of
use of iron powder in sachets of porous material. a porous support such as carbon or silica gel.
Since the oxidation of iron is not inherently rapid, Another useful feature was his recommendation of
the approach of adding accelerators or adsorbents the inclusion of a carbonate salt to release carbon
became popular. Addition of sodium carbonate was dioxide to maintain pressure in flexible packs as
patented by Buchner (1968), and the use of alkali the oxygen is removed. Most of these considera-
metal halides was patented by the Mitsubishi Gas tions are emphasized in the more recent literature
Chemical Company in 1977, leading to the range of of oxygen absorbers. Perhaps, most important was
Agelesst sachets, cards, labels, and closure liners. his recognition that the relative rates of bisulfite
The development of these concepts into commercial oxidation and food degradation might be different.
products was accompanied by a progressive move- The reaction of sodium metabisulfite in the pres-
ment of the innovation from Europe to Japan, in ence of lime was patented by Yoshikawa et al.
which the bulk of the current market is found. (1977). These workers showed that the uptake of
Dainelli (2003) reported that around 12 billion oxygen could be triggered by the presence of water
oxygen-absorber units were sold in Japan in 1999, in the food. This concept was concurrently being
versus 300,000 in the European Union. applied in the development of iron-based systems
Iron-based compositions in the form of self- and marks the key concept in providing a useful
adhesive labels are manufactured by Multisorb commercial oxygen-absorber system that could be
Technologies under the trade names FreshMaxt stored and handled before use.
and FreshCardt in the United States of America. Oxygen absorbers based on sulfur compounds
These adjuncts are applied to the inner wall or have been replaced by iron-based compositions,
lidding film of packages as part of the filling opera- although the former are still used in combination with
tion. This allows placement of the absorber in a ascorbic acid in oxygen-scavenging closure liners.
preselected position, such as behind the print on the The use of oxidase enzymes for the removal of
lidding film in packs of smoked and sliced meats in oxygen from food packages has been discussed by
the United Kingdom. Thus the esthetic property of Brody and Budny (1995) and Brody et al. (2001).
the system is enhanced while retaining the func- The earliest known application of an oxygen
tionality. An added benefit is that the absorber is absorber in a sachet was reported to be that of
prevented from moving to a position where its Scott (1958). This system involved the oxidation of
access to the headspace would be inhibited by inti- glucose catalyzed by glucose oxidase in the pres-
mate contact with a piece of food. ence of water. The hydrogen peroxide formed was
removed by the action of catalase. The concept was
commercialized by Scott’s company, Fermco
Other Oxidation Reactions Laboratories, using the trade name “Oxyban”. A
Patents for the oxidation of sulfites began commercial enzymic oxygen scavenger in a sachet
appearing as early as 1965, when Bloch proposed is marketed internationally by Bioka, a Finnish
the use of bisulfite salts in cloth or paper bags for company.
9: OXYGEN-SCAVENGING PACKAGING 141

The oxidation of hydrogen to form water may 9.3.2 Packaging Materials as

appear to be a very attractive mechanism for oxy-
Oxygen Scavengers
gen scavenging. This process has been used by
microbiologists for deoxygenating anaerobic jars Although the performance of oxygen-absorbing
for cultivation of anaerobes for many years. The sachets was quite satisfactory for a wide range of
process was proposed for the packaging of milk food storage conditions, a number of limitations to
powder in cans by King (1955) and subsequently their use in practice were recognized. The esthetics
by Abbott et al. (1961). The process involved flush- of inserts, coupled with a concern about possible
ing cans of milk powder with a mixture of hydro- ingestion or rupture, as well as their unsuitability
gen (7%) in nitrogen. The hydrogen reacts with for use with beverages, drove researchers to seek
oxygen on the surface of palladium-coated steel package-based solutions. The approach of using the
attached by means of adhesive tape to the inside of packaging material as the medium for the oxygen-
the lid. The particular benefit of this process was scavenging chemistry was developed independently
the removal of oxygen released from pores in the in several laboratories and countries. Not surpris-
spray-dried powder over several days following ingly, the reactions were initially the same as used
closure. in the sachet technologies, but eventually it was
A variety of other systems, such as catechols, recognized that the restrictions applying to package
glycols, and boron compounds, have been the sub- inserts need not apply to the package. This has
ject of patents or have been released for commercial allowed a multiplicity of oxygen access problems,
sale. Both the Toppan Printing Company and the arising from quite disparate packaging factors, to
Mitsubishi Gas Chemical Company have developed be addressed, thus permitting targeting of problems
ascorbic acid-based sachet systems for use where at their source rather than waiting for the oxygen to
fast oxygen absorption is required in the presence of enter the package to be absorbed by an insert, such
carbon dioxide. Generally, these compositions are as a sachet. Some of the chemistries and reaction
nonmetallic and do not place restrictions on the use media used in packaging-material-based systems
of metal detectors on packaging lines. are summarized in Table 9.1.

Table 9.1 Oxygen Scavengers with Different Chemistries

Substrate Medium Structure Application Commercial

Hydrogen Pd/alumina Sandwich Foil laminates Briefly
Singlet oxygen Plastics Homogeneous Plastics No
acceptors plastic packaging
Sulfites Salt blend Sandwich Laminates No
Sulfites Solution Sandwich Bag-in-box No
Sulfites/ascorbate Plastics Compound Closure liner Yes
Aromatic polyamide Polymer/ Mono/multilayer PET bottles Yes
blend
Iron powder Plastics Compound Plastics Yes
packaging
Reducible compounds Plastics Blend/polymer Plastics No
packaging
Polymer-bound olefins Plastics Coextrusions Flexibles Yes
Polydiene block Plastics Blend/multilayer PET bottles Yes
copolymers
142 PLASTIC FILMS IN FOOD PACKAGING

The use of palladium on alumina as a catalyst Cook (1969) described the use of an all-organic
is common in organic chemistry. Its use in a system involving a plastic bilayer separated by a
sandwich of the powder in a laminate containing solution of common antioxidants in a minimum
a polyvinyl alcohol barrier layer and the polyole- quantity of a high-boiling organic solvent.
fin heat-seal layer offered a number of advan- Antioxidants are normally designed to trap free
tages as a headspace scavenger (Kuhn et al., radicals originating from the first step of autoxida-
1970). The packages of intermediate moisture tion, so the claimed reduction in oxygen permeabil-
foods or milk powder were flushed with a mix- ity is a surprising discovery. This system was
ture of hydrogen, 5%, in nitrogen and sealed. The designed to reduce the oxygen permeability of the
hydrogen and nitrogen both diffuse through the bilayer primarily for meat packaging, with one
sealant to the powdered palladized alumina. The example being a sandwich between two layers of
water formed on the catalyst surface is absorbed PVDC.
by the alumina. The packaging is expensive to Plastics with blended sulfites have also been
fabricate, and the use of hydrogen mixtures is not used to remove oxygen diffusing under bottle clo-
popular in the industry. None of this detracts sures. Teumac (1995) has summarized commercial
from the inherent high efficiency of the process, developments since 1989, and describes the compo-
which demonstrated quite early that high perme- sitions as including up to 7% sodium sulfite and up
ability of the sealant layer is beneficial in oxygen to 4% sodium ascorbate. In some patents, the use
scavenging. of isoascorbic acid has been proposed. In the
Farrell and Tsai (1985) introduced the concept of sulfite-free compositions, the quantity of ascorbate
dealing with the enhancement of oxygen permeabil- determines the scavenging capacity while the
ity of plastic packages during and after retorting. amount of catalyst determines the rate. A parallel
They noted that the quantity of water permeating development in Japan by Toyo Seikan Ltd involved
the package was enough to hydrate the sulfite or the use of iron in the closure liner.
another hygroscopic salt mixed with it. They took The success of iron in package inserts gave
advantage of this fact to provide a concentrated momentum to research into the potential use of iron
aqueous solution of the oxidizable sulfite between in plastic-based compositions. In the early 1990s,
two layers of the packaging material to achieve a several companies launched products based on
high rate of oxygen removal at retort temperature. compounds of iron with polyolefin polymers. These
The problem of enhanced permeability of EVOH were launched in Japan (Toyo Seikan’s Oxyguard)
barrier layers to oxygen during retorting has been and in the United States of America (Amoco
approached by Tsai and Wachtel (1990) by Chemicals’ Amosorb 1000 and 2000). The latter
attempting to keep the EVOH dry or by Bissot became Shelfplus when bought by Ciba Specialty
(1990) by including microscopic inorganic platelets Chemicals. These resins are extrudable under nor-
in the polymer to introduce a longer diffusion path. mal conditions of temperature, and are used in
It appears that a combination of the oxygen- oxygen-barrier laminations to packages, particularly
scavenging packaging coupled with the use of a for foods subjected to conditions of high tempera-
desiccant might reduce the access of oxygen to the ture and humidity and especially in thermoformed
packaged food during the postretorting period when trays. Toyo Seikan produced pouches for blood-
the EVOH slowly loses water, thereby increasing product bags with one transparent side and one
its barrier action. white-pigmented Oxyguard side. These develop-
Scholle (1977) advanced the concept of using an ments were accompanied by several similar pro-
aqueous solution of the sulfite trapped between the posed compositions, which did not reach
layers of a multiwall package, such as bag-in-box. commercialization.
This concept was directed at the rapid removal of Incorporation of iron into resin strips placed in
headspace and dissolved oxygen from liquid foods sachets has been utilized by the Mitsubishi Gas
and beverages such as wine. This is a particular Chemical Company as an alternative to filling the
problem associated with bag-in-box, where it is dif- sachets loosely with reduced iron powder. The
ficult to avoid air headspaces due to both filling, sachets contain polyolefin strips, which are micro-
and that already between the webs used to make up porous, and the pores allow the oxygen and water
the bag. vapor increased access to the iron particles
9: OXYGEN-SCAVENGING PACKAGING 143

compared with the same composition in a continu- 0.4

ous film strip. This innovation addresses the need
0.35
for sachets that do not interfere with microwave

Volume O2 (ml)
reheating of the food, such as semiaseptic rice. 0.3
Another welcome benefit is removal of the
danger of accidental release of iron powder if the 0.25
sachet is ruptured when the package is opened, for
0.2
example with a knife. Brody et al. (2001) describe
a patent by Kawatiki et al. (1992) involving a 0.15
seemingly related concept involving microvoids 0 2 4 6 8 10
generated by stretching an iron-loaded strip of Time (days)
plastic. Figure 9.1 Effect of illumination (solid line) and
darkness (dashed line) on the cumulative volume of
Homogeneous Plastic Structures oxygen permeating a scavenger film laminate.

The progress from package insert to reactive

polymers, via various blends of solids (or inclusion
of trapped liquid scavenger solutions), also scavenger side. In darkness the laminate displayed
included homogeneous solutions of reagents in its normal permeability characteristics, but when
polymers. This provided the opportunity for illuminated it not only prevented permeation but
increased clarity of flexible and rigid packaging also scavenged oxygen that had permeated during
and reduced interference with the inherent proper- the previous dark period. This process continued
ties of the polymers used. This also had the poten- until the concentration of scavenger was reduced to
tial to reduce limitations on the component a point at which scavenging was now incomplete
polymers, which might be desired in particular and some oxygen permeation occurred. This
packaging structures. research demonstrated, for the first time, activation
There was the first multilayer plastic structure in by light as well as the finite oxygen-scavenging
which antioxidants were claimed to function as capacity of film-based scavengers—a topic that has
oxygen “getters”. According to Brody et al. (2001), subsequently become commercially important.
the process involved dispersing very minor portions Plastics compositions with a higher scavenging
of conventional antioxidants in or between layers in capacity for oxygen were subsequently investigated
a multilayer. The process appears not to have by the same research team (Rooney and Holland,
advanced from that point. 1979), and the factors affecting the rate of oxygen
The first plastic to incorporate dissolved reagents scavenging by solutions of singlet oxygen acceptors
with known oxidation chemistry involved the light- in polymers were elucidated. During the 1980s,
energized excitation of oxygen diffusing into the there appears to have been no reported research
plastic (Rooney and Holland, 1979). The substrate other than this academic work focusing on the poly-
for oxidation does not react with ground-state oxy- mer as a reaction medium for diffusing oxygen
gen, so the oxygen to be scavenged had to be molecules (Rooney et al., 1981). It was shown that
excited to the singlet state. This was achieved by ascorbic acid could perform as a singlet oxygen
including a photosensitizing dye and exposing the acceptor and that the photochemistry imposed lim-
scavenger film to visible light. The process occurs its on the scavenging rate (Rooney et al., 1982).
only while the scavenger film is exposed to the The use of one polymer as both the reagent and the
light, as shown in Figure 9.1. reaction medium was investigated using natural
The laminate consisting of polyethylene/polyam- rubber (Rooney, 1982). This work was extended to
ide 6/cellulose acetate contained a singlet oxygen other rubbers which display different inherent reac-
acceptor, 1,3-diphenylisobenzofuran, 8 3 1022 M, tivities with singlet oxygen while having similar
and methylene blue dye, 102 M. The laminate sepa- values of oxygen permeability. The process was
rated the two compartments of a permeability cell, applied in a poly(furyloxirane) designed to have an
air was placed on the polyamide side, and nitrogen even higher reactivity toward singlet oxygen
with a small oxygen residue was placed on the (Maloba et al., 1994).
144 PLASTIC FILMS IN FOOD PACKAGING

A more practical approach to creating a poly- from the food and the sachets were not prematurely
meric total barrier to oxygen permeation based on activated unless exposed to the air for too long.
the transition-metal-catalyzed oxidation of aromatic The concept of triggering an otherwise unreactive
polyamides was developed by the Carnaud Metal plastic system was also demonstrated in the 1970s
Box Company under the trade name Oxbart in the singlet oxygen approach to oxygen scaveng-
(Cochran et al., 1991). The key advantage initially ing (Rooney and Holland, 1979). Around the same
seen for such a process was the ability to blend the time, Rabek and Ranby (1975) showed that the
polymer plus catalyst with polyethylene terephtalate oxidative degradation of a plastic in sunlight was
(PET) in the manufacture of bottles for wine and substantial if a photosensitizer and a transition
beer. Few polymers are compatible with PET, so metal salt were dispersed therein. Against this
this approach constituted a breakthrough in the background, the breakthrough concept of single-
development of PET bottles for oxygen-sensitive dose triggering has been developed and introduced
beverages in general. It was shown that around commercially. Speer et al. (1993) were the first to
200 ppm of cobalt is necessary in a 7% blend of claim that films of unsaturated polymers, such as
MXD-6 polyamide in PET in order to generate a poly(1,2-butadiene), could very effectively scav-
total barrier to oxygen permeation (Folland, 1990). enge ground-state oxygen provided they contained
Several developments by competing companies a transition metal catalyst and a photosensitizer.
have resulted in approaches that use this chemistry The use of pendant CQC double bonds was
either in a PET matrix or in a separate MXD-6 designed to minimize rupture of the polymer back-
polyamide layer coinjected with two layers of PET. bone during oxidation. This overcame one of the
One such patent involves use of a blend of MXD-6 significant drawbacks of the process of Rooney
polyamide, polyester, and a cobalt salt in the core (1982). Speer’s process has been developed with a
layer of bottles (Collette, 1991). Other commercial large number of patents and has been marketed by
approaches have been to incorporate the cobalt into the Cryovac division of Sealed Air Corporation
a thin (10 μm) layer of MXD-6 sandwiched under the trade name OS 1000t.
between PET layers in bottles. The approach of using autoxidation of unsatu-
An alternative approach to dealing with the PET rated groups on a polymer as a basis for oxygen
compatibility issue was devised in Amoco scavenging has been taken up by Chevron
Chemicals (Cahill and Chen, 1997). This approach Chemical Company, in a further development of
involved making a block copolymer of a polybuta- the Cryovac concept. In this case, the oxidizable
diene with PET with the trade name Amosorbt moiety is a cyclohexene side group bound to the
3000, sold by BP Amoco. The PET caused the backbone, for instance by transesterification (Ching
compatibilization while the polybutadiene was the et al., 1994). The novelty of this process lies in its
oxidizable polymer. The process is catalyzed by apparent “tasteless” achievement of oxygen
means of a transition metal salt. This polymer lent removal. The earlier approaches involving autoxi-
itself to use in PET bottle manufacture, since the dation of noncyclic side groups are claimed to have
catalyst can be added at a late stage in the imparted some taste to the food.
injection-molding process, and premature oxidation The chemistries employed in the oxidation of
can be minimized. Even though the injection- aromatic polyamides and of hydrocarbon polymers
molded preforms have been heated while contain- with various side groups have the common theme
ing the catalyst, they have a substantial shelf life of using light-triggering to produce enough free
due to the low permeability of the thick layers of radicals to remove the antioxidants remaining after
PET, especially when the Amosorbt 3000 is in a extrusion. The transition metal catalysts then facili-
buried layer. Perhaps, an improvement would be to tate the rupture of the hydroperoxides formed and
include some form of triggering or activation closer accelerate the ongoing chain reactions.
to the time of filling the bottle. A radically different process also triggered by
Triggering of oxygen-absorbing sachets was an light has been developed without the use of photoi-
essential feature present from the time they were nitiation. This process involves the light excitation
initially introduced commercially. In that case the of a photoreducible component, such as a quinone,
trigger was the water necessary for the rusting of followed by its photoreduction. This new photore-
iron by the oxygen. In general, this water came duced species is then oxidized by the oxygen that it
9: OXYGEN-SCAVENGING PACKAGING 145

scavenges. In this case, the polymer was inactive thin barrier layer. The latter limitation may be a
until exposure to, for example, ultraviolet light— requirement of the package for other reasons, such
something that might not be applied until immedi- as in aseptic brick packs or with close-fitting ther-
ately before package filling (Rooney, 1993). The moformed films used for vacuum packaging. The
species reactive toward oxygen is therefore not most recent need for barrier enhancement is found
present during thermal processes such as extrusion in PET bottles for beer, where beer is packaged
and blow molding. with a very low oxygen concentration but is
There have been other approaches to scavenging degraded by oxygen permeating the PET.
oxygen from food packs or to enhancing the barrier Headspace scavenging is beneficial when, even
of packs such as bottles. These have generally been though the package may provide a high barrier, the
variants on those mentioned here, and some have residual oxygen is not readily removed to the nec-
been reviewed elsewhere (Brody et al., 2001; essary level by conventional means. This is typi-
Rooney, 1995). The processes that have progressed cally the case with beverages and products with a
to the market or which are undergoing commercial porous structure not economically deoxygenated by
development are described in ever-increasing detail evacuation or gas flushing. Such products include
in the forest of patent applications that have been bakery items and spray-dried and freeze-dried
published. Despite the density of this forest, it is foods. Beverages that are not readily deoxygenated
clear that several different food distribution pro- include those that froth readily yet contain air bub-
blems can be solved by using these scavengers. bles due to the presence of fruit pulp.
These problems have their genesis in the nature of
the newer packages as well as the requirements of
high-speed filling and the use of distribution tem-
peratures that impose demands upon the packaging.
9.4 Application to Food and
Perhaps the greatest demand has been made by the Beverage Packaging
shift from glass and metal cans to substantially
The interest in, and adoption of, oxygen-
plastic packs.
scavenging systems has been driven by the wide
The requirements of foods that impact on pack-
range of mechanisms by which oxygen can contrib-
age selection involving oxygen scavenging can
ute to loss of food quality. These mechanisms
basically be subdivided into enhancement of barrier
include:
and headspace scavenging (Figure 9.2). Frequently
both requirements are present, but the most eco-
• nutrient loss,
nomical approach to package selection may be
made by using oxygen scavenging to address one • discoloration,
problem or the other. • microbial spoilage,
Barrier enhancement is commonly needed where • rancidity,
the product is packaged in an impermeable package
with a closure allowing oxygen entry, or when the • organoleptic deterioration,
product has a very low headspace and the oxygen • infestation by insects and vermin.
ingress needs to be prevented while maintaining a
Pathogen growth is not included in the above
list, as measures to prevent their growth should
Packaging problem already be in place. Each one of these mechanisms
has its own kinetics and level of sensitivity at
which the effect on the food becomes unacceptable.
Barrier enhancement Headspace scavenging
Table 9.2 shows a selection of foods that benefit
from oxygen scavenging and indicates the impor-
Thin films Gaseous tance of the speed at which quality deterioration
bottles dissolved
closures trapped occurs. Hence, although a pack of full-cream milk
powder which has been nitrogen flushed may have
Figure 9.2 Roles for oxygen-scavenging packaging an oxygen content of around 5% after desorption
plastics. from the pores, the oxidation occurs sufficiently
146 PLASTIC FILMS IN FOOD PACKAGING

Table 9.2 Oxygen Sensitivity of Some Foods flavor and color degradation of Havarti cheese is
strongly enhanced by fluorescent display lights
Food/ Substrate Rate (Randell et al., 1995). These authors showed that
Beverage
by reducing the headspace oxygen in these packs to
Milk powder Fat Slow 0.1%, the formation of pentanol (the indicator of
Cheese Mold Slow quality loss) could be essentially eliminated,
Beer Flavors Moderate
regardless of the illumination conditions tested. The
benefit demonstrated by such work is that oxygen
Wine Preservatives Moderate scavenging can contribute not just to the package
Juice Vitamin C Fast properties but also to the conditions under which a
Fish Oil Fast food might be distributed.
The oxidation of vitamin C in orange juice occurs
rapidly, and this reaction usually results in substan-
tial deoxygenation of the juice in ambient barrier
packaging in aseptic brick packs. The result is the
slowly to present only a minor problem. Beer, on loss of the vitamin, coupled with the consequent
the other hand, is similarly sensitive to oxidation of generation of browning products several months
oils which cause off-flavor development. However, later. Beverages do not lend themselves to protec-
the damage done by the initial oxygen uptake tion by oxygen-absorber sachets or labels, so over-
results in flattening of the flavor and can take some coming this problem has been delayed pending the
months off the potential shelf life. This is crucial to development of plastics with scavenging capability.
the introduction of PET packaging for this The development of these plastics has been
beverage. described largely in patents, so there are very few
The choice of packaging for preserved fish pro- peer-reviewed research results published. One such
ducts is severely limited by the rapid oxidation of investigation, from the author’s laboratory, involved
the polyunsaturated oils present. Indeed, a variety the measurement of dissolved oxygen concentra-
of fish-oil products cannot be packaged in glass tions, ascorbic acid, and total vitamin C assays, and
jars because the residual oxygen present is browning of the juice when stored in an oxygen-
sufficient to cause unacceptable levels of both scavenging laminate under refrigerated and ambient
discoloration and rancid odor. Packaging that sca- conditions (Zerdin et al., 2003). The laminate (OS)
venges oxygen at a rate much greater than the pouches consisted of EVOH/oxygen-scavenger film/
food oxidation calls for rapid scavenging coupled EVA, and the pouches contained orange juice from
with package design that maximizes the area of freshly packed aseptic brick packs. The juice was
scavenger available. resterilized with dimethyldicarbonate on repacking
Prevention of mold growth is a major role for in the pouches in order to avoid microbial oxygen
oxygen scavenging (Smith et al., 1995). Although uptake. The scavenger film was an improved version
mold is one of the major causes of food quality of one that involved photoreduction of a polymer-
loss, the slow rate of growth in many foods pro- bound reducible compound that had been described
vides an opportunity for oxygen scavenging to previously (Rooney and Horsham, 1998). It was
reduce oxygen levels to around 0.1%, which inhi- found that the oxygen was scavenged in less than 3
bits such growth. The capacity of oxygen scaveng- days at ambient temperature, and that the quantity of
ing to prevent mold growth on processed meat was ascorbic acid lost during that time was reduced com-
addressed by Randell et al. (1995). They demon- pared with that in the control pouches. The loss of
strated that even in the presence of a pinhole in the ascorbic acid from the juice packed in the scavenger
seal of packages, an oxygen-absorber sachet could pouch was consistently less than that in the reference
suppress growth for useful periods. They found that over a period of 1 year (Figure 9.3). The extent of
the concurrent degradation of the meat color by the browning of the juice was reduced by around 33%
action of the fluorescent display lights on the oxi- when the juice was packaged with the scavenger
dation reaction was also prevented. laminate. Results broadly similar to these were
Color loss due to photo-oxidation is not limited reported by Rodgers (2000), whose results were
to processed meats. It has also been shown that the obtained by an independent laboratory and used the
9: OXYGEN-SCAVENGING PACKAGING 147

400
Reference
350
OS
300

Ascorbic acid (mg/ l)

250

200

150

100

50

0
0 50 100 150 200 250 300 350 400
Storage time (days)

Figure 9.3 Concentration of ascorbic acid in orange juice packed in oxygen scavenging and reference
pouches stored at 25 C.

metal catalyzed and photoinitiated polymer-bearing The application of oxygen scavenging has not
cyclohexenyl groups. been limited to plastic packages. The shelf life of
The results obtained at refrigerator temperature cracker biscuits in metal cans, as measured by hex-
by Zerdin et al. (2003) were similar to those anal formation and peroxide value development,
obtained under ambient conditions. The oxygen was almost doubled at 25 C (Berenzon and Saguy,
concentration was similar after 3 days. The brown- 1998). It was found that with the addition of
ing was suppressed at low temperature in both the oxygen-absorber sachets, no oxidative odors were
control and test pouches. Thus, oxygen scavenging observed after 44 weeks at 25 C and 35 C. Results
may be significantly more necessary where aseptic such as these support the view that the method of
packs are distributed under ambient conditions oxygen scavenging will vary with the food/package
than where short shelf-life juices are distributed combination, and that no one approach is likely to
chilled. satisfy the varying demands of food and beverage
Besides the direct effects of suppressing oxida- packaging.
tion or microbial growth on the food, there are
other aspects of food quality that can be influenced
by use of oxygen scavengers. Chilled beef is 9.5 Future Opportunities
conventionally distributed at the wholesale level as
primal cuts weighing several kilograms, vacuum- The field of oxygen scavenging using plastics is
packaged in shrink bags with low oxygen perme- still largely under development, even though the
ability, at 0 C. The drip, or liquid exudate lost use of sachets, labels, and closure liners is well
under these circumstances has been minimized, but established. The introduction of new technologies
recent research into the use of nonvacuum packag- will depend upon the drivers revealed in the food
ing with the presence of an oxygen-scavenger and packaging industries. The major driver should
sachet has revealed a further improvement (Payne be the curiosity of food technologists interested in
et al., 1998). These investigators found that drip seeking better outcomes when they introduce new
loss could be substantially reduced by avoiding the or modified products. This in turn may be expected
compression effect of evacuation and removing the to be a result of the education process. Another
residual oxygen by using an oxygen-absorber driver of importance will be the need to achieve
sachet (Agelesst Z50). Results like these are indic- current (or better) quality levels as packaging is
ative of the potential for oxygen scavenging to con- changed, especially when newer materials are used.
tribute to quality and logistic parameters associated This is being observed already with the introduction
with food distribution in the wider sense. of PET bottles and jars in place of rigid metals and
148 PLASTIC FILMS IN FOOD PACKAGING

glass. Even in the latter packaging, there are ample Cochran, M.A., Folland, R., Nicholas, J.W.,
opportunities to enhance the product quality for the Robinson, M.E.R., 1991. Packaging. US Patent
consumer by scavenging of the headspace already 5021515.
present therein. The potential impact on canned Collette, W., 1991. Recyclable multilayer plastic
foods can only be guessed at currently. preform and container blown therefrom. US
Regulation by both food authorities and those Patent 5077111.
caring for the environment will also have major Cook, J.M., 1969. Flexible film wrapper. US Patent
impacts. A variety of scavenging systems have 3429717.
already been approved in Japan, the United States Dainelli, D., 2003. Active packaging materials: the
of America, and European countries, among others. CRYOVACs OS1000 oxygen scavenging film.
The expected amendment of the Food Packaging In: Paper presented at Active and Intelligent
Directive by the European Commission in late Packaging: Ideas for Tomorrow and Solutions for
2004/2005 to address active packaging will make Today (on CD). TNO, Amsterdam, The
the future paths to introduction clearer, even though Netherlands.
oxygen removal is not really the main thrust of the Farrell, C.J., Tsai, B.C., 1985. Oxygen scavenger.
expected changes. The potential for reduction in the US Patent 4536409.
complexity of multilayer plastics structures and the Folland, R., 1990. In: Proceedings of the Pack
reduction in rigid packaging use following the use Alimentaire ‘90. Innovative Expositions Inc.,
of oxygen scavenging may be expected to have Princeton, NJ, Session B-2.
favorable outcomes for the environment, as long as Kawatiki, T.T., Kume, K., Nakag, K., Sugiyama,
there are no adverse impacts in the manufacturing M., 1992. Oxygen absorbing sheet: molded,
process. stretched low density ethylene copolymer con-
taining iron powder with electrolyte on surface.
US Patent 5089323.
King, J., 1955. Food Manuf. 30, 441.
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 10 Antimicrobial Packaging Systems
Jung H. Han
PepsiCo Corporate Research, PepsiCo Inc., Plano, TX 75024 USA

10.1 Introduction food packaging, logistics, trade, and consumer

studies.
The quality of foods has been defined as their
degree of excellence and includes factors such as
taste, appearance, and nutritional content. Quality is
a composite of characteristics that have significance 10.2 Food Safety
and make for acceptability. However, acceptability
can be highly subjective. Based on deterioration fac-
10.2.1 Spoilage of Food Products
tors and determination procedures, quality may Most foods are perishable. Food spoilage is
include various aspects such as sensory quality, caused both biologically and chemically. In addi-
microbial quality, and toxicological quality. These tion to the chemical degradation of food ingredients
aspects are not separate from one another—for through oxidation processes, most spoilage pro-
example, microbial contamination damages sensory cesses are due to biological mechanisms such as
quality and safety. Microbial food quality relates to auto-degradation of tissues by enzymes, viral con-
all three groups of factors, since the growth of bacte- tamination, protozoa and parasite contamination,
ria generates undesirable odors and life-threatening microbial contamination, and attack by rodents and
toxins; it changes the color, taste, and texture of insects. The growth of microorganisms is the major
food; and also reduces the shelf life of the product. route for food spoilage, leading to degraded quality,
Microbial growth in packaged foods significantly shortened shelf life, and changes in natural micro-
decreases its safety and the security of public health. flora that could induce pathogenic problems.
In our society, fast foods, convenience foods, and Microbial spoilage of food products is caused by
fresh foods are essential elements. Many food indus- many bacteria, yeast, and molds; however, their
tries produce minimally processed foods, precut growth is dependent on nutrients, pH, water activ-
fruits/vegetables, and ready-to-eat foods for the ity, and presence of oxygen. Therefore, the many
purpose of maximum convenience and freshness. different potential microorganisms that could con-
In food manufacturing on a mass-production taminate food products and the various growth
scale, food safety is a top priority for producers, the environments present difficult problems in prevent-
food industry, governments, and public consumers. ing the spoilage.
Improper treatment and accidental cross- For the food industries, the prevention of food
contamination of foods can cause major problems of spoilage is a very important issue in determining
recall and serious food-borne illnesses. Furthermore, profit. Furthermore, reducing food spoilage can
the safety of food and related public health issues prolong the shelf life of food products and accord-
can be jeopardized by malicious tampering, extor- ingly extend market boundary, resulting in
tion for benefits, trials to obtain public attention for increased profit.
any reasons, and terrorism (Kelly et al., 2003). Since
the 2001 tragedy of the World Trade Center,
consideration of food and water safety has assumed
10.2.2 Food-Borne Illness
major importance, and protecting food chains Food-borne illness is caused by contamination of
against bioterrorism is regarded as a significant food products by microorganisms or microbial tox-
aspect of public safety (Nestle, 2003). Food ins. Many food processing technologies have been
safety has become a significant subject of trends in developed to prevent such contamination by the

Ebnesajjad: Plastic Films in Food Packaging. DOI: http://dx.doi.org/10.1016/B978-1-4557-3112-1.00010-7

© 2013 Elsevier Inc. All rights reserved. Adapted from a chapter in: Han, Innovations in Food Packaging (2005). 151
152 PLASTIC FILMS IN FOOD PACKAGING

inactivation of pathogens. Traditionally, thermal and safety enhancement involve technical develop-
processes such as blanching, pasteur, and commer- ment, such as a database for tracking products,
cial sterilization have been used for the elimination intelligent packaging for monitoring foreign matters
of pathogens from food products. Currently, various in products, robotic automation for warehousing,
new nonthermal technologies are being studied to and new security seals on distribution packages.
assess their effectiveness and mechanisms. Such The protective function of food packaging has
new processes include irradiation, pulsed electric become more significant with respect to safety
fields, high-pressure processes, and the use of new enhancement. Among all of the potential technolo-
antimicrobial agents. However, these new technolo- gies, practical approaches to enhance the safety of
gies cannot completely prevent the contamination food products include the use of advanced tamper-
and/or growth of pathogens. Some of these methods evident or tamper-resistant packaging, and intelli-
still require regulatory permission for their com- gent packaging that indicates any tampering and
mercial use. It is also very hard to control patho- contamination and has a high-barrier design
gens because of the wide variety of microbial (Rodrigues and Han, 2003). The use of tamper-
physiology, pathogenic mechanisms, and passage evident packaging and intelligent packaging is
of contamination; the complexity of food composi- highly desirable to minimize the risk of the mali-
tion; their sensitivity to antimicrobial agents; the cious activities of terrorists endangering public
mass-production nature of food processing; and dif- safety through the food product chain. In addition
ficulties in early detection. to the visual indication of disintegration and con-
There are many prevention systems that are used tamination of packages, antimicrobial packaging
by the food industry, such as hazard analysis and systems can kill or inhibit the growth of pathogenic
critical control points (HACCP), sanitation standard microorganisms that may be injected into packaged
operating procedures (SSOP), good manufacturing foods without any visual evidence of tampering.
practice (GMP), and various inspections. The good With the positive contribution to food safety of the
practice of these quality systems is much more new smart design of food packaging, antimicrobial
important and effective in eliminating pathogen packaging systems can also protect food products
problems from food system than is the use of reli- more actively.
able new technologies. Tamper-evident packaging and intelligent pack-
aging are considered to be passive monitoring sys-
10.2.3 Malicious Tampering and tems. Antimicrobial packaging can reduce the risk
of tampering and bioterrorism by eliminating con-
Bioterrorism taminating microorganisms as well as maintaining
One of the primary functions of food packaging the quality of packaged food products by reducing
is to protect food from unintentional contamination the potential for cross-contamination of food pro-
and undesirable chemical reactions as well as to ducts with spoilage and pathogenic
provide physical protection. However, recently, the microorganisms.
need has arisen for packaging systems to be capable
of protecting food from intentional contamina-
tion—that is, malicious tampering (Kelly et al., 10.3 Antimicrobial Packaging
2003). To secure food safety from tampering and
bioterrorism, many systematic protocols are Antimicrobial packaging is a system that can kill
required—such as new food and drug regulation, or inhibit the growth of microorganisms and thus
and new security acts (e.g., bioterrorism acts and extend the shelf life of perishable products and
Homeland Security guidelines for imported goods). enhance the safety of packaged products (Han,
Enhanced traceability is also required so that any 2000). Antimicrobial packaging can kill or inhibit
potentially tampered goods can be removed from target microorganisms (Han, 2000, 2003a).
the food chain. Security against tampering and ter- Antimicrobial functions of packaging materials/sys-
rorism can be improved by systematic preparation, tems can be achieved by creating unfavorable
practical regulation, inspection, emergency environments to target microorganisms by eliminat-
response training, and other systematic protocols. ing their essential growth requirements and render-
However, issues such as traceability, food security, ing contact of antimicrobials to the target
10: ANTIMICROBIAL PACKAGING SYSTEMS 153

microorganisms (Cho et al., 2009). These systems very important issue in maintaining the quality and
are constructed either by containing antimicrobial safety of the products.
agents in an independent device (e.g., sachet or
pad) or in the packaging materials (Lopez-Carballo
et al., 2012). Among many applications such as 10.4 Antimicrobial Agents
oxygen-scavenging packaging and moisture-
control packaging, antimicrobial packaging is one Various antimicrobial agents could be incorpo-
of the most promising innovations of active rated into conventional food packaging systems
packaging technologies (Floros et al., 1997). It and materials to create new antimicrobial packag-
either uses antimicrobial packaging materials and/ ing systems. The food-grade condition of an anti-
or antimicrobial agents inside the package space microbial agent is the most essential requirement
or inside foods. Most food packaging systems for constructing antimicrobial packaging system
consist of the food products, the headspace (Lopez-Carballo et al., 2012). Table 10.1 shows
atmosphere, and the packaging materials. Any one potential antimicrobial agents and food-grade pre-
of these three components could incorporate an servatives. They can generally be classified into
antimicrobial element to increase antimicrobial three groups: chemical agents, natural agents, and
efficiency. probiotics.
Antimicrobial packaging research generally
started with the development of antimicrobial pack- 10.4.1 Chemical Antimicrobial
aging materials that contain antimicrobial chemi-
cals in their macromolecular structures. However, Agents
without the use of alternative packaging materials, For the purpose of food preservation, all packag-
common packaging materials can be utilized for ing ingredients must be food grade. Chemical
antimicrobial packaging systems when there is anti- agents can be mixed with food ingredients, incorpo-
microbial activity in packaged foods or in the in- rated into packaging additives, or inserted into the
package atmosphere. Edible antimicrobial agents headspace atmosphere. The antimicrobial agents
can be incorporated into food ingredients, while will be in contact with and consumed alongside the
antimicrobial resources can be interleaved in the in- food products in these applications. Therefore, the
package headspace in the form of sachets, films, chemical antimicrobial agents should be controlled
sheets, or any in-package supplements to generate as food ingredients regardless of where the chemi-
antimicrobial atmospheres. cal antimicrobial agents were positioned initially—
Besides the use of antimicrobial packaging mate- in the food products, in the packaging materials,
rials or antimicrobial inserts in the package head- or in the package headspace atmosphere. In the
space, gaseous agents have been used to inhibit the case of nonfood-grade chemicals, the only way to
growth of microorganisms. Common applications incorporate the chemical into the food packaging
include carbon dioxide for modified atmosphere system is to bind it chemically to the polymers of
packaging, sulfur dioxide for berries, and ethanol the packaging material (immobilization). In this
vapor for confections. These gases are injected into case, the migration of residual amounts of
the package headspace or into palletized cases after the nonfood-grade chemical into the food products
shrink-wrapping of a unit load on a pallet. Vacuum, is prohibited by regulation. Therefore, it is neces-
nitrogen-flushing, and oxygen-scavenging packag- sary to verify that there is no migration of the
ing, which were originally designed for preventing chemical from packaging material to food, and
the oxidation of packaged foods, also possess anti- there is no residual free chemical after the immobi-
fungal and antimicrobial properties which act lization reaction. There will be detailed explanation
against aerobic bacteria, since these microorgan- of immobilization systems later in this chapter.
isms are restrictively aerobic (Han, 2003b; Smith The most common chemical antimicrobials used
et al., 1990). However, these technologies, which by researchers are the various organic acids.
control the low oxygen concentration to inhibit the Organic acids are widely used as chemical antimi-
growth of aerobic microorganisms, could cause crobial agents because their efficacy is generally
anaerobic microbial growth. Controlling anaerobic well understood and they are cost effective. Many
bacteria in modified atmosphere packaging is a organic acids, including fatty acids, are naturally
154 PLASTIC FILMS IN FOOD PACKAGING

Table 10.1 Examples of Potential Antimicrobial Agents for Antimicrobial Food Packaging Systems

Classification Antimicrobial Agents

Organic acids Acetic acid, benzoic acid, lactic acid, citric acid, malic acid, propionic acid, sorbic acid,
succinic acid, tartaric acid, mixture of organic acids
Acid salts Potassium sorbate, sodium benzoate
Acid Sorbic anhydride, benzoic anhydride
anhydrides
Para-benzoic Propyl paraben, methyl paraben, ethyl paraben
acids
Alcohol Ethanol
Bacteriocins Nisin, pediocin, subtilin, lacticin
Fatty acids Lauric acid, palmitoleic acid
Fatty acid Glycerol monolaurate
esters
Chelating EDTA, citrate, lactoferrin
agents
Enzymes Lysozyme, glucose oxidase, lactoperoxidase
Metals Silver, copper, zirconium
Antioxidants BHA (butylated hydroxyanisole), BHT (butylated hydroxytoluene),
TBHQ (tert-butylhydroquinone), iron salts
Antibiotic Natamycin
Fungicides Benomyl, Imazalil, sulfur dioxide
Sanitizing gas Ozone, chlorine dioxide, carbon monoxide, carbon dioxide
Sanitizers Cetyl pyridinium chloride, acidified NaCl, triclosan
Polysaccharide Chitosan
Phenolics Catechin, cresol, hydroquinone
Plant volatiles Allyl isothiocyanate, cinnam-aldehyde, eugenol, linalool, terpineol, thymol, carvacrol,
pinene
Plant/spice Grape seed extract, grapefruit seed extract, hop beta acid, Brassica erucic acid oil,
extracts rosemary oil, oregano oil, basil oil, other herb/spice extracts, and their oils
Probiotics Lactic acid bacteria
Source: Modified from Han (2000, 2003a,b) and Suppakul et al. (2003a).

existing chemicals and have been used historically. acids have a wider antimicrobial spectrum and
Currently, most are produced by chemical synthesis stronger activity than a single organic acid.
or are chemically modified natural acids. Organic Fungicides are also common antimicrobial
acids have characteristic sensitivities to micro- agents. Imazalil has been incorporated into the wax
organisms. For example, sorbic acid and sorbates coating of oranges and other citrus fruits. Since
are very strong antifungal agents, while their anti- fungicides are not permitted as a direct food preser-
bacterial activities are limited—they have various vatives, they cannot be mixed into food ingredients
antimicrobial mechanisms. Therefore, the correct or added to food-contact packaging materials as
selection of organic acids is essential to produce food-contact substances. Therefore, it is necessary
effective antimicrobial agents. Mixtures of organic to design antimicrobial food packaging systems
10: ANTIMICROBIAL PACKAGING SYSTEMS 155

when nonfood-grade antimicrobial agents, such as natural compounds and are known to have a wide
fungicides, are used. Food sanitizers and another antimicrobial spectrum of activity against various
chemical antimicrobial groups are included in microorganisms. Major components of these
Table 10.1. They are food cleansing agents, food- extracts and essential oils are phenolics,
contact substances, or food-contact surface saniti- terpenes, and aliphatic alcohols whereas compounds
zers. Residual food sanitizers on foods are permit- such as ketones and aldehydes are minor compo-
ted, with specific control limits. Thus, the use of nents (Tiwari et al., 2009). Apart from antimicro-
food sanitizers has many advantages over the use bial activity, they offer other advantages including
of other nonfood-grade antimicrobial agents such as antioxidative activity and their effect as alternative
fungicides. medicines. However, their mode of action and
Various inorganic compounds are also used as kinetics are generally unknown, and their chemical
active antimicrobial agents when incorporated in stability is also of concern. In addition, they create
packaging materials. Silver, and its complexes with some problems with respect to flavors.
porous materials such as zeolite are used as antimi- Specificity of enzymes should be considered
crobial particles in addition to polymeric films or carefully, since antimicrobial activity is very sensi-
surface coating (Pehlivan et al., 2005). Silver, tive to environment and substrate. As an example,
especially in nanoparticle form, shows strong anti- the activity of lysozyme can be significantly
microbial activity against bacteria, molds, and affected by temperature and pH. In most cases,
yeasts. It acts by disturbing cell-wall permeability, lysozyme is not effective against gram-negative
respiration, and cellular replication (Feng et al., bacteria. This is due to the complex cell-wall struc-
2000; Li et al., 2010; Saulou et al., 2010). Titanium ture of gram-negative bacteria and the specificity of
oxide (TiO2) is a nontoxic Food and Drug lysozyme for peptidoglycan. Many research results
Administration (FDA) approved (as GRAS) food- demonstrate the efficient antimicrobial activities
contact material exhibiting strong antimicrobial against spoilage and pathogenic microorganisms,
activity with a similar mode of action to silver after including gram negatives in combination with lyso-
UV excitement (Chawengkijwanich and Hayata, zyme and other bacteriocins such as nisin, and che-
2008; Cho et al., 2007; Kikuchi et al., 1997). lating agents such as EDTA after incorporating into
Some gases act as effective antimicrobial agents edible biopolymer coatings or plastic films (Coma,
when vaporized in the package headspace and 2008; Conte et al., 2007; Güçbilmez et al., 2007;
dissolution onto the food surface (Han, 2000). Han, 2005).
Gases commonly used for this purpose are Various bacteriocins, such as nisin, pediocin, lac-
carbon dioxide, sulfur dioxide, chlorine dioxide, ticin, propionicin, etc., can be incorporated into
ethanol, and ozone (Han, 2005; Suppakul et al., foods and/or food packaging systems to inhibit the
2003a). growth of spoilage and pathogenic microorganisms
Chitosan, a deacetylated chitin, possesses antimi- (Daeschul, 1989). Bacteriocins are peptidic toxins
crobial and film-forming ability (Dutta et al., 2009; produced by bacteria to inhibit the growth of simi-
Joerger, 2007). In spite of the popularity of chitin lar bacterial strains (Lopez-Carballo, 2012). The
as a raw material in antimicrobial polymer research, extracted bacteriocins, which are generally small
it is still not listed as a GRAS status material by molecular weight peptides, can be utilized in vari-
FDA. ous ways; however, it is very important to charac-
terize their resistance to thermal treatment and pH.
10.4.2 Natural Antimicrobial In the case of fermented food products, live bacte-
ria that produce bacteriocins can be intentionally
Agents added as probiotics in the packaged food system to
Table 10.1 includes herb extracts, spices, obtain antimicrobial effectiveness.
enzymes, and bacteriocins as naturally occurring
antimicrobial agents. Due to consumer demand for
chemical-preservative-free foods, food manufac- 10.4.3 Probiotics
turers are now using naturally occurring antimicro- Table 10.1 also shows the possible use of probio-
bials to sterilize and/or extend the shelf life of tics (Lactobacillus reuteri) to control Escherichia
foods. Herb and spice extracts contain multiple coli O157:H7 (Muthukumarasamy et al., 2003).
156 PLASTIC FILMS IN FOOD PACKAGING

Various microorganisms, for example, lactic acid systems. This clearly shows the interactive effects
bacteria, produce bacteriocins and nonpeptide of food ingredients, microorganisms, and antimicro-
growth-inhibiting chemicals such as reuterin. These bial agents. All of these are complex systems that
naturally produced antimicrobials can inhibit the cannot be explained by a single chemical mecha-
growth of other bacteria. Probiotics can therefore nism. Therefore, it is strongly recommended that
effectively control the competitive undesirable experiments examining the efficiency of an antimi-
microorganisms. Many traditional fermented food crobial packaging system should be conducted
products contain antimicrobial probiotics. There using a real food instead of culture broth or agar
has been much research and development regarding media. Table 10.2 lists examples of antimicrobial
the function of antimicrobial probiotics for the food packaging systems that have been tried,
preservation of fermented foods. Currently there is mostly by university researchers, over the past two
only limited research into the use of probiotics for decades.
the purpose antimicrobial of packaging design.
With the of development new technology for the
delivery of live probiotics, their use as an antimi- 10.5.1 Antimicrobial Mechanisms
crobial source for antimicrobial food packaging An antimicrobial agent has specific inhibitory
will increase in future due to its safety and activity and mechanisms against each microorgan-
effectiveness. ism. Therefore, the selection of antimicrobial
agents is dependent on their efficacy against a tar-
get microorganism. There is no “magic bullet” anti-
10.5 System Design microbial agent that will work effectively against
all spoilage and pathogenic microorganisms
There are various factors to be considered in because all antimicrobial agents have different
designing antimicrobial systems. Antimicrobial sys- activities that affect microorganisms differently.
tems can be constructed by using antimicrobial This is due to the characteristic antimicrobial
packaging materials, antimicrobial inserts (such as mechanisms and the differences in physiology of
sachets) to generate antimicrobial atmosphere con- the microorganisms. Simple categorization of
ditions inside packages, or antimicrobial edible microorganisms may be very helpful to select spe-
food ingredients in the formulation of foods. Since cific antimicrobial agents, which may be catego-
antimicrobial packaging systems are designed to rized by oxygen requirement (aerobes or
control the growth of microorganisms in packaged anaerobes), cell-wall composition (gram-positive
foods, the systems essentially consist of packaging and gram-negative), growth stage (spores or vegeta-
materials (or packages), foods, the in-package tive cells), optimal growth temperature (thermo-
atmosphere, target microorganisms, and antimicro- philic, mesophilic, or psychrotrophic), or acid/
bial agents. These five elements are related to one osmosis resistance. In addition to the microbial
another and to the final system design features. characteristics, the antimicrobial characteristics of
To study the effectiveness of antimicrobial food the agent are also important in understanding the
packaging systems with respect to the relative efficacy as well as its limits. For example, some
effects of these elements, many choices of combi- antimicrobial agents inhibit essential metabolic (or
nations should be examined using real food sys- reproductive genetic) pathways of microorganisms,
tems. The majority of research has been conducted while others alter cell membrane/wall structure.
using culture media, which provides the richest Two major mechanisms of microbial inhibition are
nutritional quality and the most favorable environ- microbiocidal and microbiostatic effects, which are
ment for microbial growth, and antimicrobial pack- discussed below.
aging materials. Most microorganisms in culture
media are not stressed compared to microorganisms
under normal conditions in foods. Many antimicro- 10.5.2 Microbiocidal
bial systems that show strong antimicrobial activity It is expected that antimicrobial packaging sys-
against target microorganisms in culture media do tems would kill target spoilage and pathogenic bac-
not demonstrate the same antimicrobial activity teria, since the system could eliminate any
when they are actually incorporated into food microorganisms from the food/packaging system.
10: ANTIMICROBIAL PACKAGING SYSTEMS 157

Table 10.2 Antimicrobial Food Packaging Systems Constructed by Researchers

Antimicrobial Agents Packaging Foods Microorganisms Researchers

Materials
Organic acids
Benzoic acids PE Tilapia Total bacteria Huang et al. (1997)
fillets
Ionomer Culture Penicillium spp., Weng et al. (1997)
media Aspergillus niger
Para-benzoate LDPE Simulants Migration test Dobias et al. (2000)
PE coating Simulants Migration test Chung et al.
(2001a)
Styrene- Culture Saccharomyces Chung et al.
acrylate media cerevisiae (2001b)
Benzoic and sorbic PE-co-met- Culture Asp. niger, Weng et al. (1999)
acids acrylate media Penicillium spp.
Sorbates LDPE Culture S. cerevisiae Han and Floros
media (1997)
Pastry Total bacteria Silveira et al.
dough (2007)
PE, BOPP, Water, Migration test Han and Floros
PET cheese (1998a,b)
LDPE Cheese Yeast, mold Devlieghere et al.
(2000a)
MC (methyl Water Migration test Rico-Pena and
cellulose)/ Torres (1991)
palmitic acid
MC/HPMC/ Water Migration test Vojdani and Torres
fatty acid (1990)
MC/chitosan Culture Chen et al. (1996)
media
Starch/ Chicken Baron and Sumner
glycerol breast (1993)
WPI (whey Culture S. cerevisiae, Ozdermir (1999)
protein media Asp. niger,
isolate) Penicillium
roqueforti
CMC/paper Cheese Ghosh et al. (1973,
1977)
PE Culture S. cerevisiae, Weng and Chen
media molds (1997); Weng and
Hotchkiss (1993)
Cellulose Pastry Staphylococcus Silveira et al.
dough spp., (2007)
mesophilics,
psychrotrophs
Sorbate and propionates PE/foil Apples Firmness test
(Continued )
158 PLASTIC FILMS IN FOOD PACKAGING

Table 10.2 (Continued)

Antimicrobial Agents Packaging Foods Microorganisms Researchers

Materials
Yakovleva
et al. (1999)

Acetic and propionic Chitosan Water Migration test Ouattara et al.

acids (2000a)
Na-lactate, K-sorbate, Chitosan Smoked Listeria Neetoo et al.
Na-diacetate salmon monocytogenes (2008b); Ye et al.
(2008a)
Enzymes
Lysozyme PVOH Water Migration test Buonocore et al.
(2003)
Lysozyme, nisin Ca-alginate Smoked Lis. Datta et al. (2008)
salmon monocytogenes,
Salmonella
anatum
Lysozyme, nisin, EDTA SPI, zein Culture Escherichia coli, Padgett et al.
media Lactobacillus (1998)
plantarum
Lysozyme, nisin, propyl WPI Culture Lis. Rodrigues and Han
paraben, EDTA media monocytogenes, (2000)
Salmonella
typhimurium,
E. coli O157:H7,
Brochothrix
thermosphacta,
Staphylococcus
aureus
Immobilized lysozyme PVOH, Culture Lysozyme Appendini and
polyamide, media activity test Hotchkiss (1996,
cellulose 1997)
acetate
Glucose oxidase Fish Fields et al. (1986)
Bacteriocins
Nisin PE Beef B. Siragusa et al.
thermosphacta (1999)
LDPE Smoked Lis. Neetoo et al.
salmon monocytogenes (2008a)
HPMC Culture Lis. Coma et al. (2001)
media monocytogenes,
S. aureus
Hot dog Lis. Franklin et al.
monocytogenes (2004)
HPMC/ Culture Sebti et al. (2002)
stearic acid media
(Continued )
10: ANTIMICROBIAL PACKAGING SYSTEMS 159

Table 10.2 (Continued)

Antimicrobial Agents Packaging Foods Microorganisms Researchers

Materials
Lis.

Corn zein Shredded Total aerobes Cooksey et al.

cheese (2000)
Corn zein, Culture L. plantarum Dawson et al.
wheat gluten media (2003)
Ethylene-co- Culture Lactobacillus Leung et al. (2003)
acrylic media leichmannii
PVC Chicken Sal. typhimurium Natrajan and
Sheldon (2000)
Chitosan Milk, Yeast, total Lee et al. (2004)
orange bacteria
juice
Nisin, lacticins LDPE, Culture Aspergillus An et al. (2000)
polyamide media flavus, Lis.
monocytogenes
LDPE, Oyster, Total aerobes, Kim et al. (2002a,b)
polyamide beef coliform bacteria
Nisin, EDTA PE, PE
PE Beef B. Cutter et al. (2001)
oxide thermosphacta
Nisin, citrate, EDTA PVC, Chicken Sal. typhimurium Natrajan and
polyamide, Sheldon (2000)
LLDPE
Nisin, organic acids Acrylics, Water Migration test Choi et al. (2001)
mixture PVA-co-PE
Nisin, lactate PP Cooked Lis. Jofre et al. (2008)
ham monocytogenes
Nisin, enterocin, sakacin PP Cooked Lis. Jofre et al., 2007
ham monocytogenes
Nisin, lauric acid Zein Simulants Migration test Hoffman et al.
(2001)
Soy protein Turkey Lis. Dawson et al.
bologna monocytogenes (2002)
Nisin, pediocin Cellulose Turkey Lis. Ming et al. (1997)
casing breast, monocytogenes
ham, beef
Pediocin WPI Culture Listeria innocua Quintero-Salazar
media et al. (2003)
Polymers
Chitosan Cheese Lis. Coma et al. (2002)
monocytogenes,
Lis. innocua
Pork Total bacteria Yingyuad et al.
(2006)
(Continued )
160 PLASTIC FILMS IN FOOD PACKAGING

Table 10.2 (Continued)

Antimicrobial Agents Packaging Foods Microorganisms Researchers

Materials
Chitosan/ Strawberry E. coli Yi et al. (1998)
paper
Chitosan/PE Turkey Lis. Joerger et al.
breast monocytogenes (2009)
Chitosan/ Ham Lis. Ye et al. (2008b)
Surlin monocytogenes
Chitosan, herb extracts LDPE Culture L. plantarum, Hong et al. (2000)
media E. coli,
S. cerevisiae,
Fusarium
oxysporum
Chitosan acetate Culture E. coli, Vibrio Park et al. (2003)
media vulnificus, Sal.
typhimurium,
Salmonella
enteritidis,
Shigella sonnei
UV irradiation, excimer Polyamide Culture Pseudomonas Paik and Kelly
laser media fluorescens, (1995); Paik et al.
Enterococcus (1998)
faecalis,
S. aureus
Natural extracts
Grapefruit seed extract LDPE, Ground Total aerobes, Ha et al. (2001)
polyamide beef coliform bacteria
LDPE Lettuce, E. coli, S. aureus Lee et al. (1998)
soy
sprouts
Grapefruit seed extract, Na-alginate, Culture Cha et al. (2002)
lysozyme, nisin kappa- media
carrageenan
Clove extract LDPE Culture L. plantarum, Hong et al. (2000)
media F. oxysporum,
E. coli,
S. cerevisiae
Herb extract, Ag- LDPE Lettuce, E. coli, An et al. (1998)
zirconium cucumber S. aureus,
Leuconostoc
mesenteroides,
S. cerevisiae,
Asp. niger,
Aspergillus
oryzae,
(Continued )
10: ANTIMICROBIAL PACKAGING SYSTEMS 161

Table 10.2 (Continued)

Antimicrobial Agents Packaging Foods Microorganisms Researchers

Materials
Penicillium
chrysogenum
LDPE Strawberry Firmness test Chung et al. (1998)
Cinnam-aldehyde, Chitosan Bologna, Enterobacter, Ouattara et al.
eugenol, organic acid ham lactic acid (2000a,b)
bacteria,
Lactobacillus
sakei, Serratia
spp.
Cinnam-aldehyde, Algae film Sausage E. coli O157:H7, Ku et al. (2008)
catechin Lis.
monocytogenes
Horseradish oil Paper in Ground E. coli O157:H7 Nadarajah et al.
pouch beef (2002, 2003)
Horseradish extract and PE/EVOH/ Ground E. coli O157:H7 Muthukumarasamy
Lactobacillus reuteri PET pouch beef et al. (2003)
(probiotics)
Lemon extract Agar Mozzarella Total bacteria Conte et al. (2007)
cheese
Allyl isothiocyanate PE film/pad Chicken, E. coli, Sal. Takeuchi and Yuan
meats, enteritidis, Lis. (2002)
smoked monocytogenes
salmon
Paper pad Cheese Penicillium, Winter and Nielsen
Geotrichum, (2006)
Aspergillus spp.
Green tea extract PVA/starch Culture E. coli Chen et al. (2003)
(catechins) media
Carvacrol EVOH Culture Lis. innocua, Cerisuelo et al.
media E. coli, (2010a,b)
Salmonella spp.
Basil extract LDPE Culture E. coli Suppakul et al.
media (2003b)
Cheese Total bacteria Suppakul et al.
(2008)
Others
Benomyl Ionomer Culture Halek and Garg
media (1989)
Imazalil LDPE Bell pepper Miller et al. (1984)
LDPE Cheese Weng and
Hotchkiss (1992)
Ageless Sachet Bread Molds Smith et al. (1989)
(Continued )
162 PLASTIC FILMS IN FOOD PACKAGING

Table 10.2 (Continued)

Antimicrobial Agents Packaging Foods Microorganisms Researchers

Materials
O2 absorber Sachet Sponge Molds Guynot et al.
cake (2003)
BHT HDPE Breakfast Hoojjatt et al.
cereal (1987)
Ethanol Silica gel Culture Shapero et al.
sachet media (1978)
Silicon oxide Bakery Smith et al. (1987)
sachet
Hinokithiol Cyclodextrin Bakery Gontard (1997)
sachet
Chlorine dioxide Plastic films Migration test Ozen and Floros
(2001)
Sachet Chicken Total bacteria Cooksey (2005)
Sulfur dioxide Paper, Grapes Botyris cenerea Scully and
sachet Horsham (2007)
Titanium oxide PP Lettuce E. coli Chawengkijwanich
and Hayata (2008)
Hexanal, hexenal, hexyl Modified Sliced E. coli, Sal. Lanciotti et al.
acetate atmosphere apple enteritidis, Lis. (2003)
packaging monocytogenes
Carbon monoxide Modified Pork chops Total bacteria, Krause et al.
atmosphere lactic acid (2003)
packaging bacteria
Carbon dioxide Sachet Fresh Pseudomonas Coma (2008)
meats spp.
Triclosan Styrene-co- Culture Enterococcus Chung et al. (2003)
acetate media faecalis
LDPE Chicken Lis. Vermeiren et al.
breast monocytogenes, (2002)
S. aureus, Sal.
enteritidis, E. coli
O157:H7
Hexamethylenetetramine LDPE Orange Yeast, lactic acid Devlieghere et al.
juice bacteria (2000b)
Silver zeolite LDPE Cucumber Total bacteria An et al. (1998)
Oolong tea E. coli An et al. (1998)
Silver zeolite, silver LDPE Culture S. cerevisiae, Ishitani (1995)
nitrate media E. coli,
S. aureus, Sal.
typhimurium,
Vibrio
parahaemolyticus
Natamycin Cellulose Cheese P. roqueforti
(Continued )
10: ANTIMICROBIAL PACKAGING SYSTEMS 163

Table 10.2 (Continued)

Antimicrobial Agents Packaging Foods Microorganisms Researchers

Materials
Oliveira et al.
(2007)

Total bacteria, Pires et al. (2008)

molds
Antibiotics PE Culture Sal. typhimurium, Han and Moon
media Klebsiella (2002)
pneumoniae, E.
coli, S. aureus
BOPP, biaxially oriented polypropylene; CMC, carboxyl methyl cellulose; EVOH, ethylene vinyl alcohol; HPMC, hydroxypropyl methyl
cellulose; LDPE, low-density polyethylene; LLDPE, linear low-density polyethylene; MC, methyl cellulose; PE, polyethylene; PVA, polyvinyl
acetate; PVOH, polyvinyl alcohol; PET, polyethylene terephthalate; PP, polypropylene; SPI, soy protein isolate; WPI, whey protein isolate.

Though in practise it is very hard to remove all through a seal defect, leakage, opening, or any
microorganisms, microbiocidal antimicrobial sys- other means, the suppressed microorganisms can
tem may kill the target microorganisms when the grow or their spores can germinate. Therefore, it is
antimicrobial concentration goes above the mini- critical to maintain the concentration of the antimi-
mum inhibitory concentration (MIC) for a while. crobial agent above the MIC during the entire shelf
With other treatment to encourage the antimicrobial life of the packaged foods. Chemical indicators that
activity of the packaging system, such as refrigera- show the concentration or microbial growth would
tion, the antimicrobial effectiveness will be be very beneficial in microstatic antimicrobial
increased; however, generally refrigeration is not packaging systems, and this is one concept of intel-
necessary when all of the system factors satisfy the ligent packaging (Rodrigues and Han, 2003).
requirements. Refrigeration may be very effective
in inhibiting the growth of untargeted (unexpected)
10.5.4 Functioning Modes and
microorganisms. If the initial concentration of
microbiocidal antimicrobial systems is lower than Volatility
the MIC of the target microorganisms, and the con- Microorganisms grow primarily on the surfaces
centration has never been above the MIC, the agent of most packaged solid or semisolid foods (Brody
may show a microbiostatic instead of a microbioci- et al., 2001). Therefore, antimicrobial activity
dal effect. Therefore, it is very important to main- should take effect on these surfaces. The antimicro-
tain the antimicrobial concentration above the MIC bial activity may be located in the packaging mate-
for certain critical periods to eliminate the target rials, in the in-package atmosphere, or in the
microorganisms. If the package has been hermeti- headspace, varying by incorporation method. The
cally sealed, the packaged foods may not contain antimicrobial activity should be transferred to the
any live microorganisms even when the concentra- surface of the food to suppress the microbial
tion decreases to below the MIC due to the migra- growth. Therefore, incorporation methods and
tion or loss of the agent after the critical period. transfer techniques are critical in designing effec-
tive antimicrobial packaging systems. As examples
of incorporation methods, antimicrobial agents
10.5.3 Microbiostatic have been impregnated into packaging materials
Microbiostatic agents can inhibit the growth of before final extrusion (Han and Floros, 1997; Nam
microorganisms above a certain critical concentra- et al., 2002), dissolved into coating solvents (An
tion (i.e., MIC). However, when the concentration et al., 2000), added in edible coating materials
is lower than the critical concentration, or when the (Rodrigues and Han, 2000; Rodrigues et al., 2002),
agent is removed from the packaging systems and mixed into sizing/filling materials such as
164 PLASTIC FILMS IN FOOD PACKAGING

paper and cardboard (Nadarajah et al., 2002). solubility (or partition coefficient) as well as diffu-
Gaseous antimicrobial agents can also be added to sivity of the agent in the food are very important
the package atmosphere (Krause et al., 2003; characteristics to maintain the surface concentra-
Lanciotti et al., 2003). tion above the effective MIC during the expected
The edible coating system has various benefits shelf life. If the agent is incorporated into packag-
due to its edibility and biodegradability (Krochta ing material initially, it should escape from the
and De Mulder-Johnston, 1997). The edible coating packaging material and dissolve into the food
may be either a dry coating or a wet battered coat- before diffusing into the food core. Therefore, the
ing. Dry coatings can incorporate chemical and nat- significant characteristic constants of the mass
ural antimicrobials, and play the role of a physical transfer profile are the diffusivity of the agent in
and chemical barrier as well as a microbial barrier the packaging material, the solubility (or partition
(Han, 2001, 2002). Wet coating systems may need coefficient) of the agent in the food at the surface,
another wrapper. However, the wet system can and the diffusivity of the agent in the food. It is
carry many different types of functional agents as important for the food/packaging/antimicrobial
well as probiotics and antimicrobials (Gill, 2000). agent system to have mass transfer kinetics appro-
Lactic acid bacteria can be incorporated into the priate to the microbial growth kinetics in order to
wet coating system to control the competing unde- provide efficient antimicrobial activity. To under-
sirable bacteria. Such a system may be very benefi- stand the concentration distribution profile, it is
cial to the fresh produce, meats, and poultry necessary to use mass transfer models that have
industries. For edible coating purposes, various bio- more than two-layer diffusion and interface parti-
polymers are used as an antimicrobial hosting tioning (or dissolution). Since the migrating agent
matrix, including chitosan, soy protein, whey pro- is nonvolatile, this system requires intact contact-
tein, corn zein, methyl cellulose, hydroxypropyl ing between the packaging materials and the food
methyl cellulose, starch, and other gums (Han, surface. The food should be a continuous matrix
2005; Min and Krochta, 2007). form without significant pores, holes, air gaps, or
Chemical immobilization covalently binds the heterogeneous particles, due to the interference of
agents into the chemical structures of packaging the latter with diffusion. One-piece, solid, semi-
materials when regulations do not permit the migra- solid (soft solid) foods and liquid products are
tion of agents into foods (Appendini and Hotchkiss, good examples of products that could use this non-
1996, 1997; Halek and Garg, 1989; Miller et al., volatile migrating antimicrobial packaging system.
1984). The immobilized antimicrobial agents will Practical examples of this system may include
inhibit the growth of microorganisms on the contact cured or fermented meats and sausages battered
surfaces of packaged products. with antimicrobial agents, natural cheeses sprayed
with potassium sorbate before packaging, antimi-
crobial plastic films for deli products, antimicrobial
10.5.5 Nonvolatile Migration wax coatings on fruits, and antimicrobial cleansing
The mass transfer of nonvolatile antimicrobials of fruits/vegetables before packaging. The advan-
is dominated by diffusional migration. Nonvolatile tages of this nonvolatile migrating system are the
agents will be positioned initially in the packaging simplicity of the design, which could be installed
materials or between the package and the surface ahead of the current packaging process without
of the food. If nonvolatile antimicrobial agents are high investment, and the easy maintenance required
incorporated into packaging material matrix, diffu- to control its effectiveness.
sivity of the agents is a primary kinetic constant of
the transfer in the matrix to the surface of the
matrix that governs the overall migration profile 10.5.6 Volatile Migration
from the matrix to contacted food surface (Choi Many researchers have claimed that it is neces-
et al., 2005; Han, 2000). If the agent is sprayed sary to have intact contact of the antimicrobial
onto the surface of food, the initial surface con- material with the food surface to facilitate the
centration will be very high and then start to migration of the active agent for maximal effective-
decrease due to dissolution and diffusion of the ness (Suppakul et al., 2003a; Vermeiren et al.,
agent toward the center of the food. Therefore, the 2002). However, this is not necessary when using
10: ANTIMICROBIAL PACKAGING SYSTEMS 165

volatile antimicrobial agents. To maintain the sur- can be attached to the polymer through covalent
face concentration above a certain MIC, it is very cross-linkers. Since the agents are not mobile, their
important to control the headspace gas concentra- activity is limited to the contact surface only. This
tion, since the volatile agent’s concentration in the limitation is more critical in solid or semisolid
headspace has been equilibrated with the concentra- foods. However, in liquid foods, the disadvantages
tion on the food surface and in the packaging mate- of this nonmigration characteristic may be minimal.
rials. Initially the volatile agent is placed in the This system could be designed for large-size mem-
packaging material, whether it is a film, container, brane reactors or processing units to convert any
sachet, or tray. After packaging the food, the vola- preexisting substrates into valuable compounds
tile agent vaporizes into the headspace, reaches the using immobilized enzymes. For the future, it is
surface of the food, and is absorbed by the food. important that this packaging system be evaluated
The mass transfer of a volatile agent in the packag- to assess whether it can be used effectively as a
ing system is more dynamically balanced. The unit operation substituting reaction process during
release rate of the volatile agent from the packaging any necessary timed processes such as aging, chill-
system is highly dependent on its volatility, which ing, tank-holding, etc.
relates to the chemical interaction between the vol- As a food packaging system, this nonmigration
atile agent and the packaging materials. There are system has unique advantages in marketing and reg-
ways to control the volatility of the agent in the ulation. Since the active agents cannot migrate, this
packaging system, including the use of oil, cyclo- system requires a very small amount of attached
dextrin, or microencapsulation. These techniques agents. This may reduce the overall cost of packag-
can control the volatility of the agent and, eventu- ing systems that use very expensive antimicrobial
ally, the headspace concentration. The absorption agents. A nonmigrating system can include agents
rate of headspace volatiles into the food surface is that are not permitted as food ingredients or food
related to the composition of the foods, as the additives. With the verification of nonmigration, the
ingredients undergo chemical interactions with the packaging material may contain any food-contact
gaseous agents. Since most volatile agents are gen- substances. From the marketing point of view, this
erally lipophilic, the lipid content of the food is an system is attractive because the food does not con-
important factor in determining the headspace tain any chemical antimicrobial agents throughout
concentration. its shelf life. However, in contrast to the benefits,
Volatile antimicrobial agents have many advan- this system may use only a very limited selection of
tages. They can be used effectively for highly antimicrobial agents and may also be limited in
porous, powdered, shredded, irregularly shaped, application to certain types of foods.
and particulate foods, such as ground beef, shred-
ded cheese, small fruits, mixed vegetables, etc. 10.5.8 Shapes and Compositions
Because the majority of volatile antimicrobial
agents are natural herb and spice extracts are this of Systems
system is linked to the nutraceutical research and Packaging is a system used to contain and pro-
development area as well as being easily accepted tect enclosed products, which consists of a product,
by consumers and governmental regulatory a package, and the in-package atmosphere.
agencies. Antimicrobial agents may be incorporated in the
nonfood parts of the packaging system, which are
10.5.7 Nonmigration and the package or the in-package atmosphere.
Antimicrobial agents can be incorporated directly
Absorption in packaging materials in the form of films, over-
The nonmigration system uses nonmigratory coating on films, sheets, trays, and containers, or in
antimicrobial polymers, in which the antimicrobial the in-package space in the form of inserts, sachets,
agent does not migrate out of the polymer because or pads. Edible coatings also can contain edible
it is covalently attached to the polymer backbone antimicrobial agents, protecting the coated foods
(Steven and Hotchkiss, 2003). Besides the antimi- from microbial degradation (Han, 2001).
crobial agents, other bioactive agents (such as Figure 10.1 illustrates some possible forms of anti-
enzymes, proteins, and other organic compounds) microbial packaging systems (Han, 2003a).
166 PLASTIC FILMS IN FOOD PACKAGING

Food Food Food

(a) (b) (c)

Food Food
Food

(d) (e) (f)

Figure 10.1 Possible ways to construct antimicrobial food packaging systems. (A) The use of antimicrobial
packaging materials, (B) antimicrobial coating on conventional packaging materials, (C) immobilization of
antimicrobial agents in polymeric packaging materials, (D) the use of antimicrobial trays or pads, (E) the use of
sachet/insert containing volatile antimicrobial agents, and (F) antimicrobial edible coating on foods. Source:
Adapted from Han (2003b).

10.6 Commercialization mechanical energy input. The extrusion temperature

is related to the thermal degradation of the antimi-
Some commercial antimicrobial packaging sys- crobial agent, and the specific mechanical energy
tems are listed in Table 10.3. Most systems consist indicates the severity of the process conditions that
of silver-containing active agents. Table 10.4 lists also induce the degradation of the agents. Nam
potential applications of antimicrobial packaging et al. (2002) showed a severe decrease in the activ-
and food groups. Since foods are complex systems, ity of lysozyme in an extruded starch container as
there are many factors to be considered in commer- the extrusion temperature increased. In many cases,
cializing antimicrobial packaging systems. this thermal degradation is the reason for selecting
solvent compounding (i.e., wet casting/coating)
10.6.1 Technical Factors methods (Cho et al., 2009; Han et al., 2007). In the
case of wet casting (i.e., using solvent to cast films
Compatibility of Process Conditions and and containers such as cellulose films and collagen
Material Characteristics casing), the solubility and reactivity of the antimi-
There are three methods for manufacturing com- crobial agents and polymers to the solvents are the
mercial antimicrobial packaging materials other critical factors. The solubility relates to the homo-
than independent antimicrobial inserts such as geneous distribution of the agents in the polymeric
sachets, labels, or pads: (1) coating of antimicrobial materials, while the reactivity relates to the activity
packaging material mix on films or paper surfaces, loss of the reactive antimicrobial agents.
(2) blending antimicrobials with plastic resins for The physical properties of the antimicrobial agent,
extrusion film processes, and (3) immobilization of such as its solubility, are also important. For exam-
antimicrobials on film surfaces (Han, 2000). Film/ ple, when water-soluble agents are mixed into plastic
container casting methods, that is, extrusion coating resins to produce antimicrobial films, the extrusion
or wet casting, are important to maintain antimicro- process may be beset with various problems, includ-
bial effectiveness. In the case of extrusion, the criti- ing crevice hole creation in the films, powder-
cal variables related to the residual antimicrobial blooming, the loss of physical integrity, and/or the
activity are extrusion temperature and specific loss of transparency due to the heterogeneous
10: ANTIMICROBIAL PACKAGING SYSTEMS 167

Table 10.3 Examples of Commercial Antimicrobial Packaging Products and Manufacturers

Trade Name Active Manufacturer References

Compounds
Piatech Ag oxide Daikoku Kasei Co. (Japan) Brody et al. (2001)
Silvi Film Ag oxide Nimiko Co. (Japan) Brody et al. (2001)
Okamoto Super Okamoto Industries, Inc. (Japan) Brody et al. (2001)
Wrap
Apacider Ag zeolite and Sangi Co. (Japan) Brody et al. (2001)
others
Zeomix Ag zeolite Shinanen New Ceramics Co. Brody et al. (2001)
(Japan)
Bactekiller Kanebo Co. (Japan) Brody et al. (2001)
Cleanaid Gyunghyang Ind. Co. (Korea) Cho et al. (2009)
AgION AgION Technologies LLC (USA) Suppakul et al.
(2003a); www.agion-
tech.com
MicroFree Ag, copper DuPont (USA) Brody et al. (2001);
oxide, zinc Vermeiren et al.
silicate (2002)
Novaron Ag-zirconium Milliken Co. (USA) Vermeiren et al.
phosphate (2002)
Surfacine Ag-halide Surfacine Development Co. (USA) Vermeiren et al.
(2002)
Ionpure Ag/glass Ishizuka Glass Co. (Japan) Vermeiren et al.
(2002)
Microban Triclosan Microban Products Co. (USA) Brody et al. (2001)
Sanitized, Triclosan and Sanitized AG/Clariant (Switzerland) Suppakul et al.
Actigard, others (2003a); Vermeiren
Saniprot et al. (2002)
Ultra-Fresh Triclosan and Thomson Research Associates Vermeiren et al.
others (Canada) (2002)
WasaOuro Allyl Green Cross Co. (Japan) Brody et al. (2001)
isothiocyanate
Wasa Power Sekisui Plastic Co. (Japan) Cho et al. (2009)
MicroGarde Clove and Rhone-Poulenc (USA) Brody et al. (2001)
others
Take Guard Bamboo Takex Co. (Japan) Brody et al. (2001)
extract
Acticap Ethanol Freund Industrial Co. (Japan) Smith et al. (1987)
Ageless SE Mitsubishi Gas Chemical (Japan) Cho et al. (2009)
Biocleanact Antibiotics Micro Science Tech Co. (Korea) Han and Moon
(2002)
Microatmosphere Chlorine Southwest Research Institute (USA), Brody et al. (2001)
dioxide Bernard Technologies Inc. (USA)
(Continued )
168 PLASTIC FILMS IN FOOD PACKAGING

Table 10.3 (Continued)

Trade Name Active Manufacturer References

Compounds
Microsphere MicroActive Corp. (USA) Scully and Horsham
(Microgarde) (2007)
Knick’n Clean Helrik Bobke (Germany) Cho and Han (2009)
Grape Guard Sulfur dioxide Quimica Osku S.A. (Chile) Scully and Horsham
(2007)
Uvasy Grapetek (S. Africa) Scully and Horsham
(2007)

blending of the hydrophilic agents with the hydro- Physical Properties of Packaging
phobic plastics. Therefore, the compatibility of anti- Materials
microbial agent and packaging material is an
The physical and mechanical properties of pack-
important factor. Various spice extracts and essential
aging materials are affected by the incorporated
oils could be blended with plastic resins such as
antimicrobial agents. If the antimicrobial agent is
polyethylene or ethylene vinyl alcohol due to their
compatible with the packaging materials, a signifi-
compatible hydrophobicity to form plastic coating
cant amount of the agent may be impregnated into
layers or free-standing films (Cerisuelo et al., 2010a,
the packaging material without any deterioration of
b; Farris et al., 2010; Hernandez-Muñoz, 2005). The
its physical and mechanical integrity (Han and
pH of the system is also important. The activity of
Floros, 1997). However, excess antimicrobial agent
most antimicrobial chemicals changes with pH. The
that is not capable of being blended with packaging
pH of the packaging system mostly depends on the
materials will decrease physical strength and
pH of the packaged foods, and therefore consider-
mechanical integrity (Cooksey, 2000). Polymer
ation of the food composition along with the chemi-
morphology studies are very helpful in predicting
cal nature of the antimicrobial agent is important as
possible loss of physical integrity when the antimi-
well as consideration of the packaging material reac-
crobial agent is added to the packaging material.
tion with the chemical nature of the agents (Han,
Small-sized antimicrobial agents can be blended
2003b).
with polymers and may be positioned in the amor-
Storage and distribution conditions are also signif-
phous regions of the polymeric structure without
icant factors, including storage temperature and
significantly interfering with polymer
polymer
time. This time
temperature integration affects the
interactions. If a high level of antimicrobial agent
microbial growth profile, chemical reaction kinetics,
is mixed into the packaging materials, the space
and the distribution profile of antimicrobial agents in
provided by the amorphous region will be filled
the food. To prevent microbial growth, storage at a
and the mixed agent will start to interfere with the
temperature range favorable for microbial growth
crystalline region. Although there is no damage to
should be avoided or minimized for the whole
the physical integrity at low levels of antimicrobial
period of storage and distribution.
agent addition, optical properties can be changed—
In the case of modified atmosphere packaging
for example, there may be a loss of transparency or
with antimicrobial gas, the active gas permeation
a change in the color of the packaging materials
through the packaging materials may change with
(Han and Floros, 1997).
temperature and time during the whole period of
storage and distribution. When the gas composition
is altered through active gas permeation, unex- Controlled Release Technology
pected gas invasion, or a seal defect, microorgan- The design of an antimicrobial packaging system
isms that are not considered as target requires a balanced consideration of controlled
microorganisms may spoil the packaged foods. release technology and microbial growth kinetics.
 10: ANTIMICROBIAL PACKAGING SYSTEMS
Table 10.4 Potential Applications of Antimicrobial Food Packaging

Antimicrobials Meat/Poultry Dairy Seafood Produce Bakery Beverage Minimally Processed

Organic acids Fresh meat, Cheese Fruits, Fruit Precut salad, noodle,
and their salts sausage, ham, vegetables, juice, pasta, steamed rice,
chicken jam/jelly wine sauce/dressing
Ethanol Nuts Bread, Noodles, pasta,
cakes, sandwiches
cookies
Bacteriocins Fresh meat, Cheese Fish, Ham/egg sandwiches
sausage, ham, shellfish
chicken
Enzymes Fresh meat, Cheese Fish, Ham/egg sandwiches,
sausage, ham, shellfish meatball pasta
chicken
Chelating Fresh meat, Cheese Fish, Fruits, jam/ Fruit juice Precut fruits, sauce/
agents sausage, ham, shellfish jelly dressing
chicken
Fungicides Citrus,
berries,
nuts
Sanitizers Fresh meat, Fish, Fruits, Precut salad
chicken shellfish vegetables
Volatile Fresh and Shredded Fish, Berries, Bread, Fruit juice Noodles, pasta,
essential oils processed cheese shellfish, nuts, jam/ cakes, steamed rice,
meats, ground dried fish jelly cookies sandwiches,
beef, chicken hamburgers, precut
nuggets salad, sauce/dressing
Spices Fresh and Cheese Fruit juice Noodles, pasta,
processed steamed rice,
(Continued )

169
 170
Table 10.4 (Continued)

Antimicrobials Meat/Poultry Dairy Seafood Produce Bakery Beverage Minimally Processed

meats, fresh and Fish, sandwiches, sauce/
cooked chicken dressing
Probiotics Fresh and Cheese, Fermented Deli mix
processed yogurt vegetables
meats, cured
meats
Oxygen Fresh and Shredded Dried Nuts, jam/ Bread, Fruit Noodles, pasta,
scavengers processed cheese fish jelly cakes, juice, steamed rice,
meats, ground cookies wine sandwiches,
beef, dried hamburgers, sauce/
meats, chicken dressing

PLASTIC FILMS
IN
FOOD PACKAGING
10: ANTIMICROBIAL PACKAGING SYSTEMS 171

When the mass transfer rate of an antimicrobial diffused into the food. Rapid diffusion of the anti-
agent is faster than the growth rate of the target microbial agents in the food decreased the surface
microorganism, loaded antimicrobial agent will be concentration rapidly. The surface concentration is
diluted to less than the effective critical concentra- highly dependent on the release rate from the pack-
tion (i.e., MIC) before the expected storage period aging materials (diffusivity of packaging materials)
is complete, and the packaging system will lose its and the migration rate through the foods (diffusivity
antimicrobial activity because the packaged food of the foods). Since the flux of the release from the
has almost infinite volume compared to the volume packaging materials decreases as the amount of
of packaging material and the amount of antimicro- antimicrobials in the packaging materials decreases
bial agent. Consequently, the microorganism will with release time, the period in which the surface
start to grow following depletion of the antimicro- concentration is maintained above the MIC needs
bial agent. On the other hand, when the migration to be carefully estimated, considering its rapid
rate is too slow to maintain the concentration above decay profile (Figure 10.2A).
the MIC, the microorganism can grow instantly, When the solubility of antimicrobial agents in
before the antimicrobial agent is released. the packaged food is very low, the antimicrobial
Therefore, the release rate of the antimicrobial concentration on the contact food surface is the
agent from the packaging material to the food must maximum that its solubility will allow. Since the
be controlled specifically to match its mass transfer release rate is slower than unconstrained free diffu-
rate with the growth kinetics of the target microor- sion, the period at which the concentration can be
ganism. Controversially, in the case of antimicro- maintained above the MIC in slow-release systems
bial edible coating systems, the mass transfer of is generally longer than in free diffusion systems. If
antimicrobial agents is not desirable, since the the antimicrobial agents are impregnated into the
migration of the incorporated antimicrobial agents polymeric packaging materials, the diffusivity of
from the coating layer into the food product dilutes the agent through the polymeric matrix will control
the concentration in the coating layer. Compared to the release rate. This system, shown in
the volume of the coating layer, the coated food Figure 10.2B, may include, for example, sorbic
has almost infinitive volume. Therefore, the migra- acid anhydride or propyl-para-benzoic acid in plas-
tion will deplete the antimicrobial agent in the coat- tic films that wrap high-moisture foods such as fruit
ing layer, decrease the concentration below the jelly or soft cheese. Since the antimicrobial agents
MIC, and thus reduce the antimicrobial activity of are less soluble in water, the release of these agents
the coating system. The migration of incorporated from hydrophobic plastic will be very slow. It takes
antimicrobial agents contributes to antimicrobial more time to reach the maximum peak concentra-
effectiveness in the case of packaging systems; on tion, and there will be a longer period above the
the contrary, no migration is beneficial in the coat- MIC than in the system shown in Figure 10.2A.
ing system. After the agents initially located on the surface of
The solubility of the antimicrobial agents in the plastic films have migrated into the food, the
foods is a critical factor in its release. If the antimi- release flux will decrease because the agents posi-
crobial agent is highly soluble in the food, the tioned inside the plastic film should diffuse to the
migration profile will follow unconstrained free surface of the plastic film. Because of this internal
diffusion, while very low solubility creates a diffusion, the release kinetics do not show a zero-
dissolution-dependent monolithic system. For order profile with a constant release flux. The con-
example, when highly soluble potassium sorbate centration on the food surface will decrease due to
was incorporated in packaging materials (e.g., plas- the migration of the agent into the contained food
tic films or papers) and the antimicrobial packaging products as well as the reduction of release flux.
materials were used for semisolid or high-moisture Figure 10.2C illustrates the longer period of con-
foods, such as paste, yogurt, fruit jelly, soft cheese, centration above the MIC given by membrane sys-
and sliced ham, the potassium sorbate dissolved in tems, which consist of a permeable membrane that
the food immediately after packaging. The potas- controls the release rate. In the case of liquid phar-
sium sorbate concentration increased very rapidly maceuticals, the release rate will be controlled by
on the surface of the foods and the surface concen- the permeability of the liquid agents through the
tration decreased slowly as the potassium sorbate control layer. Until the liquid agent is depleted, the
172 PLASTIC FILMS IN FOOD PACKAGING

Surface concentration

Storage time Storage time Storage time

(a) (b) (c)

Figure 10.2 Release profiles of antimicrobial agents from various systems. (A) Unconstrained free diffusion
from packaging materials or fast dissolution from antimicrobial tablets, (B) slow diffusion of very low solubility
agents from monolithic packaging materials, and (C) membrane (reservoir) system with constant flux of
permeation, slow dissolution from antimicrobial powder/tablets, or gaseous agent release from concentrated
antimicrobial sachets/tablets with constant volatility in a closed packaging system. Dashed lines and arrows
indicate the minimum inhibitory concentration (MIC) of a target microorganism and the period of shelf life
maintaining the surface concentration over the MIC, respectively.

system maintains a zero order of release with a protective functions of providing moisture and oxy-
constant permeation flux. This system may include gen barriers as well as physical protection. The
volatile agent concentrates, such as horseradish oil. effectiveness of antimicrobial packaging is generally
Horseradish oil contains allyl isothiocyanate, which enhanced by combination with other preservation
is a strong, volatile flavoring and antimicrobial hurdles, such as modified atmosphere packaging,
agent. The volatile agent will partition between the low pH, high pressure, or low water activity
oil and the headspace of packages. If there is (Cooksey, 2005; Jofre, 2008; Vartiainen et al.,
enough oil in the package, the headspace concentra- 2003). The microbial hurdle provides the extra func-
tion will equilibrate and stay above the MIC until tion of protection against microorganisms, which has
the oil has disappeared. Such equilibrated partition- never been achieved by conventional moisture- and
ing is an important factor in controlling the release oxygen-barrier packaging materials. Therefore, anti-
rate as well as the headspace concentration. microbial packaging is an active packaging and hur-
dle technology application. The hurdle technology
concept of antimicrobial packaging systems can
Extra Advantages enhance the efficiency of other sterilization pro-
Traditional preservation methods sometimes cesses, such as aseptic processes, nonthermal pro-
include antimicrobial packaging concepts—for cesses, and the conventional thermal process, where
example, the sausage casings of cured/salted/smoked the sterile foods are packaged in the antimicrobial
meats, smoked pottery/oak barrels for fermentation, packaging systems.
and brine-filled pickle jars. The basic principle of Since such systems can incorporate natural anti-
these traditional preservation methods and antimicro- microbial agents such as plant and herb extracts or
bial packaging is one of hurdle technology applica- probiotics, it is considered that natural antimicro-
tions. The extra antimicrobial function of the bial packaging design development has a connec-
packaging system is another hurdle to prevent the tion to nutraceutical research and pharmacognosy.
degradation of quality and improve the safety of This relationship may be helpful in transferring
packaged foods, in addition to the conventional food packaging knowledge to the area of
10: ANTIMICROBIAL PACKAGING SYSTEMS 173

Table 10.5 Factors to Be Considered for Marketing of New Antimicrobial Packaging Systems

Advantages Disadvantages
Safety enhancement Changes in culinary culture
Security achievement Lifestyle changes of consumers
Shelf-life extension Cost of new materials and systems
Health promoting effect Regulation conflict
Market attention Market conflict with conventional packaging, political decision making

nutraceutical and pharmaceutical research because the new system with their culture and lifestyles, and
of the studies on the barrier properties of materials other various reasons.
against volatile active ingredients and the studies Table 10.5 summarizes the pros and cons of the
on the clinical effectiveness of natural active new antimicrobial packaging systems in terms of
agents. marketing. From the consumer’s standpoint, other
than increased cost, the broad utilization of antimi-
10.6.2 Regulatory, Marketing, and crobial packaging should not require any significant
changes in the organoleptic properties of foods
Political Factors (Gutierrez et al., 2009) or their lifestyle.
The use of antimicrobials should follow the Since the antimicrobial agent is in contact with or
guidelines of regulatory agencies (Brody et al., migrating into food, the organoleptic properties and
2001; Han, 2003a,b; Meroni, 2000; Vermeiren toxicity of the antimicrobial agent should be ade-
et al., 2002). Antimicrobial agents are additives of quate to avoid quality deterioration and to maintain
packaging material, not food ingredients; however, the safety of the packaged foods. The antimicrobial
when the antimicrobial agents migrate into foods, agents may possess a strong taste or flavor, such as
they also require food ingredient approval—as for a bitter or sour taste, as well as an undesirable aroma
food-contact substances and packaging additives. that can affect sensory qualities adversely. In the
Therefore, the use of natural antimicrobial agents case of antimicrobial edible protein film/coating
included in plant extracts or spices is a very prom- applications, the allergenicity or chronic disease
ising alternative because of their appeal as natural caused by the edible protein materials, such as pea-
products, consumers’ preference, and because they nut protein, soy protein, and wheat gluten, should be
do not conflict with regulations. considered before use (Han, 2001).
For the commercialization of antimicrobial pack- The legality of antimicrobial activity in new
aging systems, various marketing factors are packaging systems has many critical controversial
involved—for example, logistics, cost, and consumer aspects. For example, research and development
acceptance (Meroni, 2000). The use of antimicrobial departments would not like to claim “antimicrobial
packaging systems should not create any conflict activity” on their products for commercial use,
with the current logistic systems of the food indus- since there is no antimicrobial agent that can elimi-
try. If new packaging systems require totally new nate all types of microbial growth. The potential
transportation, distribution, and warehousing sys- growth of microorganisms in their new antimicro-
tems, it would not be feasible to commercialize bial packaging systems could therefore reduce the
them. The antimicrobial packaging systems should company’s creditability as well as being a possible
be manageable within current packaging-related cause for a serious law suit. However, for market-
logistic systems. Reasonable cost recovery should be ing purposes, there is no point in using a new anti-
promised for the commercialization of new packag- microbial packaging system, as far as profits are
ing systems. Consumers’ acceptance of the use of concerned, if the company cannot claim “antimicro-
new antimicrobial packaging systems is critical. This bial activity”. This example shows that the use of
acceptance may be related to the convenience and antimicrobial packaging systems possesses a politi-
easiness of the use of a new system, any conflict of cal aspect.
174 PLASTIC FILMS IN FOOD PACKAGING

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 11 Damage Reduction to Food Products During
Transportation and Handling
Jay Singha and S. Paul Singhb
a b
California Polytechnic State University, San Luis Obispo, CA, USA; Michigan State University, East Lansing, MI, USA

11.1 Introduction packaging is to protect the goods purchased by the

consumer from wastage and damage. Without pack-
Packaging plays a key role in protecting the aging, handling many products would be messy,
product from contamination by external sources, inefficient, costly, and in some cases impossible.
and reducing damage during its transportation and The United Kingdom Institute of Packaging pro-
handling in the supply chain from the producer and vides the following definitions of packaging
manufacturer to the consumer. In the United States (Gawith and Robertson):
alone, estimated annual losses due to damaged pro-
ducts exceed $10 billion. This covers processed • a coordinated system of preparing goods for
foods, perishables, consumer products, and elec- transport, storage, retailing, and end use;
tronic and hardware products sold in retail stores. A • a means of ensuring safe delivery to the ulti-
major portion of this loss is in the fresh and pro- mate consumer in a sound condition at mini-
cessed food category. The use of proper packaging mum cost; and
materials and methods to minimize food losses and
to provide safe and wholesome food products has • a techno-economic function aimed at minimiz-
always been a primary focus of food packaging. ing costs of reusing, recycling, or disposing
New packaging technologies are constantly being while maximizing sales (and hence profit).
challenged to provide better quality, wholesome,
and safe foods with extended shelf life, while limit- According to Abbott (1989), the term “packag-
ing the environmental pollutions and disposal pro- ing,” as defined by the Packaging Institute, USA,
blems. Packaging is also designed to play a and used in both teaching and practice, is the enclo-
significant marketing role with strong appeal sure of products in a container to perform one or
through the use of logos and company brands to several of the major functions described in the fol-
display food products in an attractive form. lowing sections.
Packaging shapes and forms have been widely
adopted for brand recognition. This is evident when
considering shaped packages by Coca Cola 11.2.1 Containment
Company in the beverage sector. The choice of This function refers to the containment of the
packaging materials and forms is dictated primarily product for handling, transportation, and use and is
by economic, technical, and legislative factors. often considered to be the “original” package func-
tion required to move products in various forms and
shapes. The different product forms, such as solids,
11.2 Functions of Packaging liquids, and gases, can make this function a critical
factor in the selection process for the type of mate-
Packaging has been defined as all products made rial and package system. A package must be able to
of any materials of any nature to be used for the con- contain a product in order to protect it from various
tainment, protection, handling, delivery, and presen- environments. For example, fresh produce (fruits
tation of goods, from raw materials to processed and vegetables) needs to be able to fit well inside
goods, and from the producer to the user or the con- the container with little wasted space (Boyett et al.,
sumer (Packaging Regulations, 2004). The aim of 1996). Delicate and irregularly shaped produce

Ebnesajjad: Plastic Films in Food Packaging. DOI: http://dx.doi.org/10.1016/B978-1-4557-3112-1.00011-9

© 2008 Elsevier Inc. All rights reserved. Reproduced from a chapter in: Kutz, Handbook of Farm, Dairy, and Food Machinery (2008). 181
182 PLASTIC FILMS IN FOOD PACKAGING

Figure 11.1 Layers of packaging.

such as asparagus, berries, or soft fruit may • Quaternary: Unitized shipping package (an
require specially designed containers to accommo- example of this is a pallet load of stretch
date them. From a distribution system approach, wrapped, corrugated fiberboard shipping cases
packaging may be broken down by layers filled with cereal cartons).
(Figure 11.1):
11.2.2 Protection
• Primary: The primary package has direct con-
tact with the product (an example of this is a The second function, protection, relates to pro-
pouch for cereals). It provides the initial and tecting the contents from deterioration due to physi-
the major protective barrier from moisture. cal and climatic changes during normal
The materials and printing inks used are regu- transportation and storage. This could mean pro-
lated by government agencies to ensure that tecting the product from shock (drops) and vibra-
any toxic chemicals do not migrate and trans- tion (transportation) by using cushioning. It could
fer to the product. also mean using a high-barrier film to prevent oxy-
gen and moisture from entering a package and
• Secondary: The secondary package contains causing spoilage to a food product. The protection
and/or unitizes primary package(s) (an exam- function also relates to protecting the outside envi-
ple of this is the paperboard carton containing ronment from contamination by the contents, espe-
the cereal). They contain and protect the cially if they are hazardous materials (HazMat).
primary units placed inside throughout the Examples of these protection functions are seals
handling, transportation, and warehousing and valves specifically designed to contain contents
environments. Sometimes secondary packag- in HazMat packages.
ing may be specially designed and printed to Sometimes the element of protection also aids in
display primary packages on the sales floor. food preservation. For example, produce containers
• Tertiary: Refers to the shipping package (an need to be designed to provide an optimum envi-
example of this is a corrugated fiberboard ronment for the longest shelf life possible. These
shipping case containing several cereal containers may include special materials to deliber-
boxes). This is used predominately for ship- ate water loss, insulate from heat and cold, or pro-
ment and warehousing purposes. vide a favorable mix of oxygen and carbon dioxide.
11: DAMAGE REDUCTION TO FOOD PRODUCTS DURING TRANSPORTATION AND HANDLING 183

Aseptically packaged dairy products will only nutritional label, health claims, and reduced-calorie
remain shelf stable for as long as the integrity of statements (The Clemson University Cooperative
the package is not compromised. As a rule, once Extension Service, 2002). These fall under the Fair
the integrity of the package is breached, the food Packaging and Labeling Act and the Nutrition Label
product will no longer stay preserved. and Education Act. Emotional/motivational/selling
Proper packaging is an important component in information is intended to gain interest and help sell
both food production and related industries. the product such as purchase incentives, recipes,
Products must be adequately protected to ensure contests, logos, color, overall design, photographic
integrity and safety at all destinations in the supply images, and illustrations (The Clemson University
chain. Many damaging hazards exist between har- Cooperative Extension Service, 2002).
vest and the time when products reach consumers’
hands. A properly designed package can ensure
adequate protection from the most adverse of con- 11.2.4 Utility
ditions, whether initially caused by human, Lastly, utility relates to the ease of use or perfor-
machine, or environmental issues, or a combination mance of the package system. This includes the
of all three. Products need protection during trans- ease of opening and closing (if required), reuse,
port and distribution, from climatic effects such as application, dispensing, and especially a provision
heat, cold, moisture, drying, hazardous substances, for instructions and directions Singh and Singh,
contamination, and infestation. 2005. One of the main reasons for the dramatic rise
A majority of groceries are subject to biological in food packaging is convenience. Consumers are
spoilage caused by the normal enzyme-induced demanding convenience and quick food prepara-
maturation and by microbiological putrefaction tion. Packaging that allows bagged salads, fresh-cut
caused by molds, bacteria, and yeasts. Packaging vegetables for stir-fry, case-ready meat, and bag
can decrease or retard this spoilage. Synthetic pack- and boil pasta or rice are all examples of food
aging can also contaminate the product, for exam- packaging that allow convenience to the consumer
ple, plastic packaging can contaminate some foods to prepare good-quality and multi-ingredient
with toxic petrochemical-based chemicals, addi- healthy meals in a short time. Additional examples
tives, inks, or sealants. of convenience packaging include easy-open bever-
age and food cans, frozen food packs, microwav-
able containers, wine cardboard casks, individually
11.2.3 Communication wrapped butter and stock cubes, and controlled dis-
The third function, communication, is often used pensing with spouts, squeeze bottles, spray cans,
to identify the contents, quality, quantity, and man- aerosols, etc. for sauces, cooking oils, jellies,
ufacturer, etc. There are also various federal and pastes, and sauces (Reduce Packaging, 2005).
state requirements that may be required as part of Figure 11.2 shows examples of various convenience
this function, depending on the product to be pack- packages for soups. Among notable trends in soup
aged and the choice of packaging materials used. packaging are easy-open tops on metal cans and
An example of this is the nutrient information label microwavable primary packaging in the form of
requirement on all food packages. Additional fea- plastic single-serve cups and stand-up pouches.
tures, such as precautionary labeling, helps provide Most specialty packaging today often has several
information for safe use, handling, and storage of features that address the utility function of a pack-
the container. Flavors, alcohols, preservatives, and age and is often the driving force for the sales of
cooking wines are examples of food products that the product. An example would be a tamper-evi-
may require HazMat packaging, depending on dent, child-resistant closure used for a pharmaceuti-
quantity and shipping method. Pictorial markings cal product that provides an easy-to-open feature
are used to mark and identify a package and are for the elderly. Various research studies are being
often used both for domestic and international conducted as the pool of elderly with limiting dex-
labels to identify the safe handling, storage, and terity pose a greater challenge for easy access to
human interaction with the container. packaged contents for foods and pharmaceuticals.
Legal/regulated information on the package label One or more of these primary functions are
includes net quantity declaration, ingredients listing, essential in characterizing a container or system to
184 PLASTIC FILMS IN FOOD PACKAGING

Figure 11.2 Examples of convenience packaging Figure 11.3 Examples of single-serve cereal
for soups. packaging.

be termed as a package. Packaging comes in many

forms, such as convenience foods, individually
packed serves, microwaveable meals, easy-opening
packaging, secure packaging for hazardous chemi-
cals and pharmaceutical drugs, and packaging of
fresh food for transport and display (Reduce
Packaging, 2005). The form of the package is deter-
mined to some extent by the functions of the pack-
aging to contain, preserve, protect, and
communicate information. Figure 11.3 shows the
trends in the breakfast cereal products. Note the
single-serve packages. Figure 11.4 Meat trays using prepacked case-
The growth in the packaging industry has led to ready meat using Sealed Air modified packaging.
greater specialization and sophistication based on
the health and environmental friendliness of the
packaging material. So to meet the goal of packag- contamination is inevitable (Sacharow, 1980). The
ing it is necessary to develop the right type of pack- principal role of packaging meats is to prevent mois-
aging materials, form, machinery, and process. ture loss, exclude foreign odors and flavors, and to
reduce the effects of oxidation. To ensure these tar-
gets are met, the packaging used needs to have good
tear and puncture resistance, while providing a
11.3 Food Product Categories pleasing appearance for the purchaser in a retail
store temperature-controlled display environment
11.3.1 Meats (Sacharow, 1980). Figure 11.4 shows meat trays
Meats pose special problems for the packaging using prepacked case-ready meat using Sealed Airs
industry, due to the highly perishable and biologically modified packaging.
active nature of the product (Sacharow, 1980). On In supermarkets, fresh meat is placed in rigid
average, they have a maximum 2
3 day shelf life thermoformed plastic trays and overwrapped with a
in tray packs. Color changes due to oxidation will transparent or heat-shrink film. The tray is usually
also reduce consumer acceptance and potential sales expanded polystyrene (EPS) of a contrasting color
(Sacharow, 1980). Traditional meat packaging meth- to promote the freshness and quality look of the
ods are not intended to prevent bacterial contamina- meat it contains. Blotters or absorbent pads are
tion. Meat is handled so frequently for retail sale that placed underneath the meat to absorb excess juices.
11: DAMAGE REDUCTION TO FOOD PRODUCTS DURING TRANSPORTATION AND HANDLING 185

New retailing methods such as case-ready meat for

beef, ground beef, pork, chicken, turkey, lamb, and
veal strive to reduce handling and contamination
(Salvage, 2005). This practice streamlines distribu-
tion and reduces time for products to move through
the supply chain from manufacturer to customer.
Case-ready meat is prepared in a central location
and shipped to individual supermarkets already
packaged and ready for immediate sale. Most pro-
ducts prepared this way are identical in packaging
as meat cut and packaged by a butcher in a store
(Salvage, 2005). This centralized system is common
in Europe, but has only recently been introduced
into the United States by leading retailer WalMart
Stores Inc. using packaging innovation developed Figure 11.5 Seafood (shrimp) in display ready from
by companies such as Sealed Air Corporation and Thailand for Kroger Inc. in vacuum packaging.
Pactiv Inc. Case-ready red meat is still growing, but
benefits include extended shelf life, hermetically
sealed and leak-free packs, and better food safety
because of reduced human contact (Salvage, 2005).
Stores that have adopted this program now include
Albertsons, Kroger, Safeway, Target, and WalMart,
among others (Salvage, 2005).

11.3.2 Seafood
Retail fresh seafood sales are growing, up by
13% each year, thanks to innovative methods for
commercially raising fish and advancements in
packaging materials. These factors help bulk
retailer Costco sell approximately 30,000 tons of
salmon fillets and shrimp per year. New packaging
Figure 11.6 Seafood (scallops) in display ready
materials are important because they prolong shelf
from China for Kroger Inc. in vacuum packaging.
life while maintaining freshness of the product.
This is possible because the packaging prevents
damage during transportation and addresses temper-
ature concerns (Barry, 2003). Examples of seafood every 5.5 of increase in temperature (Sacharow,
packaging for an imported product are shown in 1980).
Figures 11.5 and 11.6. Once seafood is harvested and packaged, tem-
Fresh seafood has an extremely limited shelf peratures need to be quickly reduced to prevent
life. This timeframe may be reduced to a few hours microbial growth, and flavor and texture loss. The
if proper packaging methods are not followed to potential for botulism reproduction is also a reason
prevent spoilage, such as dehydration, natural juice why the Food and Drug Administration (FDA)
loss, odor permeation, bacterial growth, and incor- maintains strict guidelines for seafood packaging.
rect temperature control (Sacharow, 1980). Fish Seafood must be in contact with a limited oxygen
must be immediately gutted and cleaned prior to flow to prevent deadly anaerobe microbial growth
packaging, and refrigerated transportation is neces- (Barry, 2003). Also, too much contact with oxygen
sary to prevent enzymatic and bacterial contamina- and improper temperatures will allow the natural
tion (Sacharow, 1980). Temperature control is fish oils and fats to rapidly oxidize and go rancid.
extremely critical to maintain a high quality and Fresh seafood is transported by air to reach mar-
unspoiled product. The rate of spoilage doubles for kets faster. Lightweight protective containers are
186 PLASTIC FILMS IN FOOD PACKAGING

necessary for distribution. Bulk containers are usu- corrugated’s 98% dominance of the produce market
ally wax-coated corrugated boxes that help promote (Major, 2003). The Corrugated Packaging Alliance
insulation and efficiently reduce the amount of responded to this threat by developing the CCF.
required refrigeration. Corrugated containers offer superior protection
because the fluted material provide built-in air
cushioning and minimize damage from abrasion
11.3.3 Vegetables and Fruits and bruising. In the near future, CCFs are expected
Fruits and vegetables purchased at supermarkets to have a 5:1 market share over RPCs (Fibre Box
are living plant organs which, when growing, Association, 2005).
exhibit features such as respiration, transpiration, The Fibre Box Association (FBA) and the
synthesis, and degradation of chemical constituents. European Federation of Corrugated Board
When harvested, the produce is removed from a Manufactures (FEFCO) have outlined standards to
source of water and mineral and organic nutrients, ensure compatibility between different manufac-
but remains living. Greening and sprouting of turers in the United States and Europe. According
stored onions and root tubers and the sweating of to these associations, a full stack of containers
produce in polythene bags as a result of transpira- will be 597 mm 3 398 mm, while a half-stack
tion and water loss are just a few examples of this will be 398 mm by 298 mm. Footprint configura-
retention of living processes. As soon as produce is tions may not overhang any European or
harvested, the processes leading to breakdown American standard pallets, which are 1200 mm 3
begin and cannot be stopped. However, the rate at 1000 mm or 40 in. 3 48 in., respectively. Also,
which breakdown occurs can be slowed and losses these containers must be able to stack in mixed
minimized by employing the correct handling loads with other FBA- and FEFCO-approved con-
methods after harvest. tainers, regardless of manufacturer, without
Major retailers, such as WalMart and Sam’s sacrificing load stability or container integrity
Club, have pushed the produce industry to adopt a (Paperboard Packaging, 2000).
modular and interlocking common footprint con- Reasons to choose CCFs include savings on
tainer solution for use in transportation, storage, shipping costs, and these versatile containers dou-
and floor displays. Common footprints require stan- ble as point-of-purchase displays. Corrugated
dardized dimensions and stacking features to ensure weight is much lighter than plastic and can fit
compatibility between differing container manufac- 7.5
22% more products per truckload (Fibre Box
turers and materials (Major, 2003). These contain- Association, 2005). Once the displays reach stores,
ers are packed in the fields with the desired crop they can be sent directly to the floor. High-quality
then distributed to stores without repackaging printing will attract customer attention. Paperboard
(Fibre Box Association, 2005). Citing improve- Packaging (2000) reports that the FBA and the
ments in product integrity, reduced shrinkage, bet- FEFCO standards allow significant design flexibil-
ter space efficiency, and reduction in labor costs, ity. Containers from different manufactures may
the supermarket and bulk club industries have vary in style, depths, venting features, graphics,
found container standardization to be an important colors, and self-locking mechanisms, while still
development (Paperboard Packaging, 2000, 2002). conforming to the common footprint design
No longer will boxes and cartons of varying size be (Figure 11.7). This provides the flexibility to create
transported, warehoused, and produce repackaged. a container that offers maximum protection and mar-
There are two competing systems on the market; ketability for specific fruits and vegetables (Fibre
returnable plastic containers (RPCs) and the corru- Box Association, 2005).
gated common footprint (CCF). However, CCFs are limited to one-time use. This
is an environmental waste concern. The corrugated
industry is quick to point out that approximately
Corrugated Common Footprints 74% of all box material manufactured today is
Recyclable CCFs were introduced in 2000 as a recycled (Fibre Box Association, 2005). Grocery
response to the emergence of common footprint retailers recycle at even higher rates because they
RPCs. RPC display-ready bins promised to improve earn money when used boxes are recovered (Fibre
efficiency, durability, airflow, and to attack Box Association, 2005).
11: DAMAGE REDUCTION TO FOOD PRODUCTS DURING TRANSPORTATION AND HANDLING 187

Figure 11.8 A returnable plastic container.

Figure 11.7 A corrugated common footprint tray.

nutrition. Widely used methods for food proces-
sing include canning, freezing, refrigeration,
Returnable Plastic Containers dehydration, and aseptic processes. Processing
technologies are designed to rid foods of harmful
RPCs share common footprint, tab, and recepta- organisms and make products shelf
cle locations with CCFs. A joint study by the stable (Hormel, 2005). The United States
Corrugated Packaging Alliance and the Reusable Department of Agriculture (USDA) even has a
Pallet and Container Coalition (RPCC) indicates special Processed Foods Unit. According to the
that when mixed together on a pallet, both offer USDA, the idea of this specialized research team
similar performance (Harper, 2004). In other is to enhance the marketability and healthfulness
words, the mixed loads containing RPCs and of agricultural commodities and processed pro-
CCFs performed as well as loads of either 100% ducts to better benefit consumers.
CCFs or RPCs (Harper, 2004). This allows super- Nonprocessed foods are the raw materials and
markets flexibility regarding how fruits and agricultural commodities that are turned into pro-
vegetables are shipped on the same pallet. cessed foods ready for consumer use.
The California Strawberry Commission financed
a study to determine which material provided a fas-
ter cool-down rate, an important factor with perish-
able produce. Initial results indicated that CCFs 11.4 Food Product Distribution
beat RPCs. However, revised findings found “no Environment
measurable difference in cooling. . .” between cor-
rugated and plastic containers (Zind, 2003). 11.4.1 Harvesting
According to the RPCC, plastic is less detrimen-
Harvesting is the initial stage in supply chain
tal to the environment than the one-time use corru-
distribution (Figure 11.9). This is a critical time for
gated system. The study showed that plastic
growers, as overall integrity cannot improve after
required 39% less total energy, produced 95% less
this point (FAO, 1989). Therefore, items will need
total solid waste, and generated 29% less total
to be packed and shipped with care to avoid addi-
greenhouse gases (Figure 11.8) (RPCC, 2005).
tional and preventable damage. Produce prices are
dependent on physical condition (FAO, 1989).
11.3.4 Processed Versus Fruits and vegetables are still considered to be
living organisms after harvest. However, posthar-
Nonprocessed vest longevity is limited. The rate of deterioration
Food processing is a $500 billion industry in depends on how fast water and nutrient reserves are
the United States (Hormel, 2005). Processors depleted (FAO, 1989). If harvested crops sustain
offer an almost limitless supply of foods. These damage, the rate of deterioration increases.
items come packaged in various ways to meet Therefore, careful harvesting is the first step for a
consumer demand for safety, convenience, and successful and safe journey to retail outlets.
188 PLASTIC FILMS IN FOOD PACKAGING

Figure 11.9 Harvesting of grapes. Figure 11.10 Empty CCF trays.

11.4.2 Packing
Fruits and vegetables are especially sensitive Throughout the shipping stage, food products
foods. Large produce quantities need proper pack- need to be carefully loaded and protected to prevent
aging to minimize losses in the most cost-effective damage from a wide assortment of potential
way. Each time crops are handled or repackaged, hazards. Loads need to be positioned accordingly to
the chance of irreversible damage increases. fit inside transportation containers efficiently and
To protect crops during this stage, certain pre- remain stable. For example, proper stacking is nec-
cautions need to be taken. Wooden crates may have essary to prevent shifting or collapsing. In other
rough surfaces, sharp nails, and staples. If contain- cases, foods need to be protected from vibrations
ers are overpacked, compression damage will occur and jolts. This may be achieved by special packag-
when they are stacked. Dropping and/or throwing ing materials or if being shipped by truck, equip-
containers, as well as any additional rough han- ping the trailer with shock absorbers and low-
dling, will cause further damage. pressure tires (FAO, 1989).
Container sizes used should be easy to handle
and maneuver. A standardized system such as
RPCs and CCFs is one example (Figure 11.10). 11.4.4 Storage and Shelf Life
These containers are of a uniform size that reduce Storage for most meats, seafood, and produce
excess handling and provide better stacking and involves some sort of refrigeration. Their storage
loading qualities (FAO, 1989). and shelf lives are dependent upon biological and
environmental conditions (FAO, 1989). Warm tem-
peratures will increase the natural enzymatic break-
11.4.3 Shipping down rate in foods. Since produce is considered a
Food is transported from producers to packing living organism after harvest, food and water
houses or processing plants and from processors to reserves will become depleted causing spoilage.
retail markets. It is important that fresh foods are Microbiological organisms may also penetrate natu-
shipped quickly and efficiently since they are per- ral openings or broken surfaces causing decay.
ishable and susceptible to injury. Refrigerated Cool storage temperatures slow down natural bio-
trucks, railroad cars, and cargo ships are all modes logical processes and decay in the foods we eat.
of transportation used, sometimes in conjunction Many fresh seasonal and highly perishable food
with each other on long journeys. Airplane use is crops are processed to preserve nutrients and avoid
typically reserved for highly perishable items, such wastage. Processing expands consumer choices and
as fish, or expensive foods, such as live lobsters. allows for greater flexibility (FAO, 1989).
11: DAMAGE REDUCTION TO FOOD PRODUCTS DURING TRANSPORTATION AND HANDLING 189

11.5 Major Causes of Food water activity levels, and maintain appropriate oxy-
gen flow will help keep foods fresher longer.
Spoilage/Damage in Supply Chain
United Nation statistics indicate that half of the 11.5.3 Chemical
third-world population does not have access to ade-
Oxidation is the major chemical reaction that
quate food supplies. In addition, 25% of food that
leads to spoilage. Certain components and charac-
is successfully produced will be lost after harvest
teristics contained in foods, such as fats and vita-
due to mishandling, spoilage, or pest infestation
mins, are susceptible to atmospheric oxygen. It also
(FAO, 1989). Even food with small amounts of
promotes mold growth. Other sources of chemical
damage may have properties such as taste, visual
changes are caused by light and components in the
blemishes, and the rate of deterioration adversely
packaging material. These reactions cause flavor
affected (FAO, 1989). Proper packaging helps alle-
alteration, discoloration, surface damage, and decay
viate some of these issues. Developed countries,
(FAO, 1989).
such as those in Europe and in North America,
have access to better packaging methods and tech-
nology. As a result, these countries experience sub- 11.5.4 Macrobiological Spoilage
stantially lower rates of spoilage and wastage. Macrobiological spoilage is caused by insects,
Most packaged food deterioration and spoilage rodents, birds, and pilfering by humans (FAO,
occurs when the container is opened or compro- 1989). Initial damage incurred by these factors may
mised to the external environment (Robertson, be minor and could be overlooked. However, even
1993). Knowledge of the various types of spoilages the most minor tissue wounds will make food more
and contaminants allows packing and processing susceptible to microbial damage, causing the food
firms to choose the correct materials for their to be inedible and leading to sickness or death.
products.
11.5.5 Physical
11.5.1 Microbiological Spoilage Physical injuries can be classified as either
This is a major factor in food spoilage. A host of mechanical or physiological. Mechanical damage
microorganisms may flourish in foods. They multi- leads to spoilage because it may cause bruising or
ply rapidly within the food and produce by- deep punctures that cause water loss and rapid
products that cause chemical changes to affect decay in fruits and vegetables or other undesirable
color, texture, flavor, or nutritional value. These effects in other food products. Mechanical effects
containments may also release toxins, which lead to may result from impact or shock associated with
illness or even death. dropping, throwing, or sudden starting and stopping
of a vehicle. Vibration damage also may result
from various transportation methods including
11.5.2 Biochemical truck, train, airplane, and boats. Compression and
Biochemical refers to enzymatic deterioration. crushing are caused by flimsy or oversized contain-
Enzymes are naturally found in plant and animal ers, overfilled containers, or containers stacked too
tissue that control digestion and respiration. Upon high and unable to support heavy loads.
harvest, these enzymes begin to destroy the tissue Physiological deterioration may increase natural
and cause spoilage. Some enzymes come in contact deterioration because of high temperatures, low
with the food as a consequence of microbial humidity, or other physical injuries.
growth. They have several main functions of which
food processors and packaging professionals should 11.6 Packaging Materials
be aware. First, enzymes act as catalysts and accel-
erate the rate of chemical reactions that occur. Packaging is essential. It is designed to surround,
Second, specific enzymes may be modified to pro- enhance, and protect. Packaging perishable food
duce desired longevity effects. Proper packaging products is particularly cumbersome. The supply
methods and materials can slow enzymatic activity. chain, which starts at the grower, ultimately ends up
Containers that maintain low temperatures, protect at the supermarket and the consumer. Bags, crates,
190 PLASTIC FILMS IN FOOD PACKAGING

hampers, baskets, cartons, bulk bins, and palletized The following is a brief overview of the packag-
containers are all examples of the various types of ing materials commonly used for packing as stand-
containers that may be used in different parts of the alone packaging or in conjunction with each other.
journey. There are approximately 1500 different
types of packages that may be used, sometimes in
conjunction with each other (Boyette et al., 1996). 11.6.1 Paper
According to one study, a significant percentage of Cardboard and pasteboard are both terms used
produce buyer and consumer complaints may be for corrugated fiberboard, a material commonly
traced to container failure because of poor design or used for boxes. This paper-based product is avail-
inappropriate selection and use (Boyette et al., able in many different styles and weights made to
1996). accommodate a wide variety of food products.
A World Health Organization study has indi- Demand for corrugate has been growing steadily at
cated that in developed countries with sophisti- an average of 2
3% per year in Europe, where it
cated storage, packaging, and distribution systems, dominates with a 63% market share over other
wastage of food is estimated at only 2
3%. In packaging material alternatives such as plastics
developing countries without these systems, wast- (FEFCO 2011).
age is estimated at between 30% and 50% (Soroka, According to the Corrugated Packaging Council,
2002). the product is easy to identify. Corrugated, in its
According to the United Nations (1969), food is most basic design, has two main components, an
packaged for two main reasons; to preserve it and arched, wavy, layer called “fluting”, which is glued
to present it in an attractive form to the buyer. In in between two smooth sheets called “liners” (The
order to successfully satisfy these requirements, Corrugated Packaging Allowance, 2005). Together
various materials are used. The factors involved in they form a double face. The fluted liner can be
selecting these materials include: made in varying sizes, each size denoted by a letter,
A to E. Size A has the largest flutes and E the
• the composition of the food product and its smallest. The grades are assigned according to
physical state; paper weight and thickness.
• nature of deteriorative reactions that may occur; The flutes are the essential component in corru-
gated material. They give containers strength and
• modes of transportation used to bring the
add protection. When the flutes are anchored to the
product to market;
linerboard with adhesive, they resist bending and
• time before consumption; pressure from all directions (fibrebox.org). When a
• who the target consumer will be; and piece of corrugated fiberboard is placed on its end,
• overall budget for the product. the flutes form rigid columns, capable of supporting
weight without compressing. This allows many
Ideally all food containers should exhibit the fol- boxes to be stacked on top of each other. When
lowing properties: pressure is applied to the side of the board, the
space in between the flutes serves as a cushion to
• Sanitary protect the container’s contents, thus providing
shock protection. The flutes also provide insulation
• Nontoxic
against sudden temperature changes. The liners
• Transparent placed on the outer sides protect the flutes from
• Tamperproof damage and increase the container’s overall
strength.
• Easily disposable
For produce transportation, double-faced corru-
• Protective against light gate is commonly used. The materials used on the
• Easily opened or closed inner and the outer layers are determined by the
• Impermeable to gases or odors product it will hold. For example, the inner layer
may be coated to resist moisture while the outer
• Resistant to chemical or mechanical damage layer will usually be printed to identify the contents
• Easily printed or labeled. and for display inside retail outlets (FEFCO, 2011).
11: DAMAGE REDUCTION TO FOOD PRODUCTS DURING TRANSPORTATION AND HANDLING 191

Corrugated materials have standards to ensure and touch it without causing bruising or other dam-
boxes shipped by rail or truck do not fail during age (APME, 2001). The shatterproof material keeps
transportation. The first rules established in the the package intact, and prevents chips or shards
United States were in 1906. Corrugated fiberboard from contaminating the food. Polyethylene (PE)
must protect from bursting to withstand forces dur- films are the dominant material for fruit and
ing rough handling, be able to withstand weight vegetable packaging in retail stores. Produce
placed on top of the box, and allow for a maximum remains fresh during transportation and handling
weight of contents that can be safely placed in the because the material is breathable, allowing the cor-
box. These measurements are usually printed on the rect ratio of oxygen, carbon dioxide, and water
outside of the container. vapor to fill the bag. Some produce varieties can be
protected by rigid clamshells (Figures 11.11 and
11.12). This inexpensive package encloses high-
11.6.2 Plastic value items such as fruit, berries, precut salads, and
Plastics are a versatile medium used to protect mushrooms and prevents delicate items from crush-
and prevent damage to a variety of food products. ing (The Clemson University Cooperative
They are available in a variety of thick, thin, rigid, Extension Service, 2002).
or flexible forms, ranging from bottles to liners, to PE is the dominant plastic material in use today,
accommodate almost any food product. with a 56% market share. Other types of plastic
Traditionally, this material is only considered for used are polypropylene (PP), polyethylene tere-
primary or secondary packaging. This is changing phthalate (PET), polystyrene (PS), polyvinyl chlo-
as manufacturers and distributors have adopted ride (PVC), EPS, low-density polyethylene
RPCs for tertiary packaging use with fresh produce. (LDPE), and high-density polyethylene (HDPE).
Now plastics use may be considered at all levels in Material descriptions according to the American
the supply chain (APME, 2001). According to the Plastics Council (2005) are as follows:
American Plastics Council, each pound of plastic
can prevent up to 1.7 lb of food from being wasted • PET: Clear and tough material. Has good gas
due to spoilage, contamination from foreign sub- and moisture barrier properties. Commonly
stances and organisms, or packaging failure (APC, used for beverage containers, food containers,
2005). boil-in food pouches, and processed meat
Since plastic is light in weight, it also saves costs packages.
in transportation and is therefore a cost-effective • HDPE: Used for milk, juice, and water bot-
material. Plastic also extends the life of perishable tles, as well as cereal box liners. Translucent
produce to eliminate waste and preservatives. The material is well suited for products with a
transparent nature allows people to look at food short shelf life. Has good strength, stiffness,

Figures 11.11 and 11.12 Bunches of grapes being packed in plastic clamshell trays.
192 PLASTIC FILMS IN FOOD PACKAGING

toughness, and chemical resistance. Gases are packaging due to its excellent ductility and
permeable. drawability.
• PVC: Widely used for construction applica- Tin-free steel comprises of low carbon steel and
tions because of stable properties. This rigid a thin coating of chromium, aluminum, or enamel.
plastic is commonly used for clear food pack- Cans made from this material can no longer be sol-
aging such as food wrap, vegetable oil bottles, dered and must be welded or cemented.
and blister packaging. It has great strength Tinplate and tin-free steel are commonly used to
and toughness and resistance to chemicals, manufacture three-piece cans. These cans can be
oils, and grease. mechanically seamed, bonded with adhesive,
welded, or soldered (Soroka, 2002). Soldered food
• LDPE: This plastic is predominant for film cans are no longer permitted in North America.
applications. It is tough and flexible, while Three-piece cans are the most popular worldwide
still maintaining transparency. It makes seal- because they are cheap to produce, and since all
ing easy and is a good barrier to moisture. pieces are made from flat sheets with no stretching
Common applications include shrink-wrap, required.
plastic bags, and squeezable food bottles. Aluminum is the most abundant metallic constit-
• PP: This strong material has a high melting uent used for packaging. Often referred to as the
point, making it a good candidate for hot-fill transportation metal, aluminum alloys with magne-
liquids. Resistant to other chemicals, grease, sium for strength provides one-third the strength
oil, and moisture. Commonly used for marga- of steel at one-third the weight. Among its
rine and yogurt containers, caps for contain- notable properties, aluminum is light, weaker than
ers, wrapping to replace cellophane, and steel, easy to work with, inexpensive, nontoxic, a
medicine bottles. good barrier down to 1 ml thickness, nonmagnetic,
• PS: Can come in two different forms, either does not rust, no “taste”, and has an excellent recy-
rigid or foamed. Usually, it is clear, hard, brit- cle record.
tle, and has a low melting point. Typically Aluminum cans are often two piece in construc-
used for protective packaging such as egg car- tion with a seamless body plus a top cap. They are
tons, containers, lids, fast-food trays, dispos- very popular in the US beverage industry. The
able plastic cutlery, and cups. machinery used to manufacture these cans is costly
compared to three-piece cans because the process
stretches metal. The two most commonly used pro-
cesses in manufacture of two-piece cans are draw
11.6.3 Metal and iron, and draw and redraw.
In the 1790s, Nicolas Appert became the first
person to conserve food in a metal container.
Today, commercial canning is made possible by 11.6.4 Glass
materials such as steel, aluminum, tin, and chro- Glass refers to an inorganic material fused at
mium. Each material offers food processors differ- high temperature and cooled quickly so that it soli-
ent properties and preservation methods. Producers difies in a vitreous or noncrystalline state. The
choose metal for food and beverages for reasons main constituent of glass, silica, is an abundantly
including mechanical strength, low toxicity, super- available element because it exists in the form of
ior barrier properties to gases, moisture and light, sand. Lime and soda are the other two major com-
and ability to withstand a wide extreme of tempera- ponents of glass. Cullet or recycled glass is often
tures. These qualities help ensure the integrity and desired as one of the primary constituents because
safety of a wide variety of food products. it provides excellent energy efficiency and saves
The most commonly used metals for packaging time for the manufacturers. Large-scale glass
are tinplate, tin-free steel, and aluminum. Tinplate manufacturing for food products was introduced in
comprises of low carbon steel with a thin layer of the late 1800s. Today’s glass containers are lighter
tin. The tin layer may be as thin as 0.38 μm and stronger than their predecessors. Amber and
(Soroka, 2002). Tinplate is nontoxic and corrosion green glass provides light protection for sensitive
resistant and is well suited for conversion into foods.
11: DAMAGE REDUCTION TO FOOD PRODUCTS DURING TRANSPORTATION AND HANDLING 193

Glass is impermeable to gases, moisture, odors, consistently improved upon to play an “active” role
and microorganisms and is probably the most inert by slowing down quality-impairing processes
packaging material available today. Glass also pro- within the packaging itself, due to the advances in
vides other benefits such as it can be molded into a polymer chemistry. Examples of active packaging
variety of shapes and sizes, is ideal for high-speed systems include use of oxygen scavengers, ethylene
filling lines, is made from abundant raw materials, absorbers, moisture regulators, taint removal sys-
and is reusable, recyclable, and resealable. Among tems, ethanol and carbon dioxide emitters, and
its greatest drawbacks are the facts that glass is antimicrobial-releasing systems.
brittle and usually breaks under an applied tensile In active packaging, a substance or substances
strength and has the least ability to withstand sud- are incorporated into the packaging to fulfill an
den temperature change, unlike other packaging active role in protecting the foodstuff against con-
materials. tamination, such as aroma components of microor-
The manufacture of glass containers involves ganism growth. Until recently, carbonated
either blow-and-blow process used in manufactur- beverages in plastic bottles tended to have limited
ing narrow mouth containers, press-and-blow pro- durability compared with conventional glass bot-
cess used for wide mouth applications, and the tles. With recent developments, the shelf life of
most recent one, narrow-neck-press-and-blow pro- beer in 0.33 l PET bottles has been increased from
cess gaining favor for manufacture of narrow 6 to 9 months (Beverage Machines Magazine,
mouth containers, due to its ability to distribute the 2006).
material more evenly thereby requiring less As a majority of food products are light sensi-
material. tive, ultraviolet light barriers, which preserve the
transparency of the bottles or containers, are being
incorporated into the substrates of the packages. As
11.7 “Smart” Packaging related to informative packaging, external or inter-
nal indicators that document quality alterations dur-
With modern development and enhancements in ing the storage period, such as temperature changes
packaging technology, today’s packaging is provid- or interruptions in the cold chain, are rapidly com-
ing more than just the basic functions. Smart pack- ing into use. Active packaging is also being used as
aging is a term coming into use more frequently security features in the form of labels that track
and covers a number of functionalities, depending manipulation or misuse of the product prior to its
on the product being packaged, which includes sale.
food, beverage, pharmaceutical, and household pro-
ducts (Butler, 2001). Examples of current and 11.7.2 Modified Atmosphere
future functional “smartness” include the following
points: Packaging
Food preservation technology accounts for two
• packages that retain integrity and improve the main factors of ever-increasing importance, extend-
shelf life; ing product life and reducing the amount of addi-
• enhances the product attributes such as its fla- tives used. Modified atmosphere packaging (MAP)
vor, aroma, and taste; allows for these demands to be met. MAP involves
modifying the atmosphere surrounding the product
• assists with product access and indicates seal inside the package. This in turn allows chemical,
integrity; enzymatic, or microbiological reactions to be con-
• responds actively to changes in product or trolled and therefore reduces or eliminates the main
package environment; and processes of deterioration in the product. The pack-
• confirms product authenticity. age usually has a low permeability to gas, so that
the initial concentrations of the added gases remain
unchanged after the package is sealed.
11.7.1 Active Packaging MAP can be used to extend the shelf life of
Traditional “passive” packaging techniques that many fruit and vegetables. Most fruit and
only allow for a short shelf life are being vegetables age less rapidly when the level of
194 PLASTIC FILMS IN FOOD PACKAGING

oxygen in the atmosphere surrounding them is With mandated use of this technology by major
reduced. This is because the reduced oxygen slows suppliers to industry giants such as WalMart,
down the respiration and metabolic rate of the pro- Albertsons, and Tesco, this technology is already
ducts and therefore slows down the natural aging being adopted in the consumer goods supply
process. Elevating the level of carbon dioxide to chains. With standardization and reduced costs, this
levels of 2% or more can also be beneficial. noncontact technology is set to be as commonplace
Elevated CO2 levels can reduce the product’s sensi- as barcodes.
tivity to ethylene and can also slow the loss of
chlorophyll. High CO2 levels can also slow the
growth of many of the postharvest fungi that cause
rot. All these effects can help to extend the storage 11.8 Trends in Protective Food
and shelf life of fresh produce (Joblin, 2001). Packaging of 2000 and Beyond
The following sections discuss some of the food
11.7.3 Controlled Atmosphere packaging trends and damage reduction trends in
Packaging food packaging (Figures 11.13
11.15).
The major difference between controlled atmo-
sphere packaging (CAP) and MAP is that the con-
centrations of the gases in a MAP package may 11.8.1 Food Packaging Trends
change after sealing, due to use of oxygen and the This is a broad overview of major packaging
expelling of carbon dioxide by microbes and changes that have occurred in recent years and are
because of the slightly permeable nature of the playing a dominant role in food packaging. While
package. In a CAP package, the gas concentrations the general transition to plastics rather than glass
do not change during storage. To achieve this, the and metal as primary packaging materials con-
use of a gas-impermeable package, such as metal tinues, the more recent and revolutionary introduc-
or glass is preferred, and also provides a way of tion of biobased and biodegradable plastic materials
controlling the atmosphere inside the package. continues to lead. Innovations are going on every
day, leading the effort in specialty coatings directly
11.7.4 Intelligent Packaging on food products to enhance shelf life and quality
aspects such as texture, aroma, and flavor. In addi-
The stakes in food cold chains are high and the tion, the US market continues to develop more
loss of a trailer of food due to improper handling or cost-effective packaging methods for palletized
transport is measured in hundreds of thousands of quantities led by club stores such as Costco Inc.
dollars. Because of the financial pressure and
increasing regulatory demands for better record-
keeping resulting from the Bioterrorism Act, sup-
pliers and logistics service providers are turning to
systems that combine radio-frequency identification
(RFID) with temperature and humidity sensors.
RFID is an age-old technology that has recently
realized its potential in supply chain systems.
Traditional supply chain management systems pro-
duce information regarding “transactions” (orders,
shipments, and payments) and “location” (ware-
housing, traffic, and inventory). However, perish-
able goods also require information regarding their
“condition” (time and temperature) as they change
in value while in the supply chain. RFID promises
to provide real-time tracking of goods while in
transit, thereby providing a clearer picture of the Figure 11.13 A packed CCF tray with four
distribution environment. clamshell containers.
11: DAMAGE REDUCTION TO FOOD PRODUCTS DURING TRANSPORTATION AND HANDLING 195

Figure 11.14 A pallet load of grapes being Figure 11.17 Flexible pouch and metal can
protected until shipment. packaging for seafood.

and Sam’s Club (WalMart Stores Inc.). These con-

cepts significantly reduce the amount of secondary
and tertiary packaging compared to retailers that
display merchandise on store shelves. Some key
primary packaging evolutions of recent times are as
follows:

1. Stand-up pouches replacing metal cans:

High-barrier foil laminated or metalized flexi-
ble packaging continues to replace metal
cans. Multilayer plastics in flexible pouches
are replacing traditional paperboard juice
boxes. Examples include CapriSun fruit juice
for young children and tuna fish introductions
Figure 11.15 Palletized loads of grapes being
by Star Kist (Figures 11.16 and 11.17).
prepared for shipment.
2. Plastic bottles replacing glass bottles: There
is a continuous shift in the beverage industry
from glass to plastic bottles. Most blow-
molded plastic bottles can be made in-house
which reduces dependency on external sup-
pliers and shrinks the supply chain. Also, by
using shrink-sleeve labels, multiple product
lines can be filled in the same blow-molded
bottle without major changeovers. Glass bot-
tles are still holding their competition for
high value and premium beverage launches.
Shaped primary packages are easy to produce
with plastic, provide new product launches
with shorter lead times and provide market
share in a competitive environment. Heinz
used this to launch specialty ketchups and
Figure 11.16 Stand-up pouch and juice box. sauces for children (Figure 11.18).
196 PLASTIC FILMS IN FOOD PACKAGING

3. Convenience for on-the-go food packages: visibility plays a key role from bagged salads,
The US customer continues accepting pack- to fresh produce in thermoformed containers,
aging launches that provide convenience to spices. However, the gas transmission
while driving and placing in cup holders in requirements for these plastics vary from
automobiles (Figure 11.19). Products range extremely high barrier in the case of spices to
from snack foods, cereal with milk, and sal- low barrier for salads. The customer wants
ads. An examples range is Frito Lays Inc., more visibility of the actual product being
who offer a range of snack foods in blow- purchased (Figures 11.20 and 11.21).
molded plastic bottles with shrink labels that
fit automotive cup holders and allow con-
sumption while driving. These replace the tra- 11.8.2 Damage Reduction Trends
ditional bag and pouch. The various innovations and trends discussed in
4. Clear plastics packaging: The consumer con- the previous section all lead to a reduction of dam-
tinues to demand more esthetically pleasing age in shipment. Protection (physical and chemical)
containers for food packaging. Product is an underlying function of a package, and gener-
ally all package improvement and changes will usu-
ally result in reduction of damage as protection is
increased. In addition, there are some key changes
that clearly can help reduce damage beyond the pri-
mary package change.
Use of good-quality pallets is the key to reducing
damage to both rigid and flexible primary
packages. The most widely used pallets to distrib-
ute food products, both fresh and processed, are
made of wood. Low-quality lumber, protruding
nails, insufficient deck or base coverage, moisture
content, and infestation are all factors that can lead
to damage of food products and packages when
shipped on wooden pallets. For this reason, most
retailers use reusable plastic pallets in downstream
shipping between distribution centers to stores. An
Figure 11.18 Some plastic ketchup bottle forms. alternate to a single-use wooden pallet are high-
quality wooden pallets that can be leased and
reused. These are often an economically better
choice but also offer additional benefits due to the
high-quality construction.

Figure 11.19 Convenience-driven snack food Figure 11.20 Vine ripe tomatoes in a biodegradable
packaging. PLA plastic thermoformed container.
11: DAMAGE REDUCTION TO FOOD PRODUCTS DURING TRANSPORTATION AND HANDLING 197

reduction solutions than launch a massive new

product in a retail distribution and be subject to a
major recall or loss.

References
Abbott, D.A., 1989. ISBN 0-8403-5273-5.
Packaging Perspectives. Kendall/Hunt Publishing
Co., Dubuque, IA.
American Plastics Council (APC), n.d. The Many
Uses of Plastics. Retrieved 17 May 2005 from
,http://www.americanplasticscouncil.org..
Association of Plastics Manufacturers in Europe
Figure 11.21 Bagged salads with brand identity in (APME), 2001. Insight into consumption and
see-through packaging. recovery in Western Europe. Publication ref.
2002/GB/04/02, Brussels, Belgium.
Barry, C., 2003. Seafood packaging nets innova-
Today, most companies leasing wooden pallets tion: a swelling tide of progressive packaging is
to the food industry (CHEP USA Inc.) offer a setting the stage for a seafood revolution. Food
picture-frame bottom section and a large percentage Drug Pack 67 (9), Retrieved 28 August 2005
of the top deck covered with deck-boards to reduce from Factiva database.
damage from stacked products and packages. Also Beverage Machines Magazine, 2006. Active and
these are true four-way entry block-style pallets Intelligent Packaging. Retrieved 6 March 2006 from
that can be easily handled with fork trucks and pal- ,http://www.trpackaging.com/packaging/news.nsf/0/
let jacks. Reduced handling results in lower damage ACF6FFB8FC5118BAC1256BBF0050FE1C?
as compared to products on conventional stringer OpenDocument ..
pallets. In addition to the quality of pallets, the Boyette M.D., Sanders D.C., Rutledge G.A., 1996.
placement of products on pallets is critical. Both Packaging Requirements for Fresh Fruits and
underhang and overhang can greatly affect the load Vegetables. Published by the North Carolina
transfer in stacked loads and thereby result in dam- Agricultural Extension Service. Retrieved 2
age. Use of slip sheets to distribute load among March 2005 from ,http://www.bae.ncsu.edu/
layers and the pallet surface is a common way to programs/extension/publicat/postharv/ag-414-8..
address these issues. Butler, P., 2001. Smart packaging—intelligent
The unitization method of loads on a pallet is packaging for food, beverages, pharmaceuticals
also critical. Choice of appropriate shrink-wrap, and household products. Mat. World 9 (3),
stretch wrap, banding, netting, gluing, and strapping 11
13.
are all choices that need to be examined for specific EUFIC 2010. The greatest thing since sliced bread?
product and packaging needs. Use of corner posts A review of the benefits of processed foods.
and top caps can reduce damage in caseless pallet- Retrieved 12 October 2012 from http://www.
ized loads designed for club store shipments. eufic.org/article/en/food-technology/food-processing/
Most of these issues and potential solutions expid/benefits-processed-food-review/
should be addressed by using lab-based accelerated FEFCO 2011. Annual Statistics 2011. Retrieved 12
test evaluations. The use of test methods developed October 2012 from http://www.fefco.org/sites/default/
by American Society of Testing and Materials and files/documents/Fefco_AnnualEvaluation_2011.pdf.
the International Safe Transit Association allow Fibre Box Association, n.d. Informational Brochure.
users to conduct preshipment tests on palletized Retrieved 10 March 2005 from ,http://www.
configurations to simulate different distribution fibrebox.org/Info/docs/CCF_Brochure.pdf..
methods from truckload to less than truckload to Food and Agriculture Organization of the United
single parcel shipments. It is important to test a Nations (FAO), 1989. Prevention of Post-Harvest
few pallets of the product and identify damage Food Losses Fruits, Vegetables and Root Crops:
198 PLASTIC FILMS IN FOOD PACKAGING

A Training Manual. FAO code: 17 AGRIS: Burdens. Retrieved 10 March 2005 from ,http://
J11ISBN 92-5-102766-8. Rome, Italy. Available www.pneuma.enea.it/cm/web/jsp/utils/news.jsp?
at http://www.fao.org/docrep/T0073E/T0073E00. item=62&mode=1&l=IT..
htm Robertson, G.I., 1993. Food Packaging Principles
Gawith, J.A., Robertson, T.R., 2000. Wrapping and Practice. Marcel Dekker, New York, NY.
up packaging technology. J. Home Econ. Inst. Sacharow, S., 1980. Principles of Food Packaging,
Aust. Macquarie, ACT: Telecom Technology second ed. AVI Publishing Company, Inc.,
Education Conference, 7, 6
14. Westport, CT.
Harper R., 2004. Test Proves Compatibility of Salvage, B., 2005. Case-ready penetration: although
Unlike Containers. Supermarket News. Retrieved not at volume proponents predicted years ago,
9 March 2005 from Factiva database. case-ready red meat continues growth expansion.
Jobling, J., 2001. Modified atmosphere packaging: Nat. Prov. 8 (6), 13.
not as simple as it seems. Good Fruit Veg. Mag. Singh, S.P., Singh, J., 2005. Pictorial markings and
11 (5). labels for safe transport and handling of pack-
Kutz, M., 2007. Handbook of Farm, Dairy, and aged goods. Pack. Tech. Sci. 18 (3), 133
140.
Food Machinery. William Andrew, Inc. Norwich, Soroka, W., 2002. Fundamentals of Packaging
NY, pp. 665
693. Technology, third ed. Institute of Packaging
Major, M., 2003. Supermarket Fresh Food Professionals. Naperville, Illinois.
Business: Plastic and Corrugated Find a Fit, The Clemson University Cooperative Extension
Progressive Grocer. Retrieved 9 March 2005 Service, 2002. Starting a food business: product,
from Factiva database. process, and packaging analysis and develop-
Packaging (Essential Requirements) Regulations, 2004. ment. White Paper. Retrieved 12 October 2012
Government Guidance Notes (S.I. 2003 No. 1941). from http://www.clemson.edu/extension/hgic/
Department of Trade and Industry. Printed and pub- food/pdf/hgic3869.pdf
lished in the UK by the Stationery Office Ltd. The Corrugated Packaging Alliance, n.d.
Paperboard Packaging, 2000. Europe, US Share Corrugated Basics. Retrieved 22 March 2005
Compatible Footprint Standards. Retrieved 9 from ,http://cpc.corrugated.org/Basics..
March 2005 from Factiva database. United Nations, 1969. Packaging and Packaging
Paperboard Packaging, 2002. Sam’s Club Adopts Materials with Special Reference to the Packaging
Footprint Standard. Retrieved 9 March 2005 of Food. Food Industry Studies Number 5.
from Factiva database. Zind T., 2003. RPCs and Corrugated Vie for Favor
Reusable Pallet and Container Coalition (RPCC), n. of Produce Shippers and Supermarkets. Retrieved
d. Study Shows RPCs Reduce Environmental 9 March 2005 from Factiva database.
 12 Food Packaging Machinery
Harold A. Hughes
Michigan State University, East Lansing, MI, USA

12.1 Introduction 12.1.3 Communication

Packaging is an essential activity in the food Every package communicates information. The
industry. Virtually every food product is packaged communication may be simple and straightforward,
one or more times before it reaches the ultimate such as a label listing the contents and showing the
consumer. Packages are used at each stage in the source and destination. However, most retail food
process of production and distribution of food pro- packages include expensive and elaborate multicolored
ducts: from farms to processing plants, between labels, bar codes, and radio-frequency tags. Every
processing plants, from processing plants to ware- retail food package must include a nutritional label.
houses to retail outlets, and from retail outlets to
consumers. A package can hold a food product, 12.1.4 Utility
several food products, or packages of food pro-
ducts. There are many package forms including Some packages and package components are
wraps, pouches, bags, boxes, cups, trays, cans, designed to add value to the packaged product.
tubes, and bottles. Spout shakers and similar fitments enable consumer
Packages perform one or more of the following to apply spices, salt, and similar materials more
four basic functions: containment, protection, com- easily and accurately. Printed directions add conve-
munication, and utility. Each function is discussed nience. Handles enable small children to handle
briefly in the following sections. large packages conveniently and safely.
The modern food production and distribution
system could not function without packaging. Even
12.1.1 Containment fresh food, such as bananas, oranges, tomatoes, or
lettuce, is packaged for transport from the store to
Many food products, especially liquids and free the consumer’s residence. The packages may be
flowing solids, are contained in packages to facili- made of corrugated board, mesh bags, paper bags,
tate convenient handling and to avoid spillage and or plastic containers. A large percentage of the
loss of the product. Table salt and granulated sugar fresh products are packaged by hand.
are examples of free flowing solids. Liquid food However, unlike the fresh products mentioned
products include water, milk, fruit juices, and a above, most modern food products are prepared or
wide assortment of other products. processed in factories and then packaged for distri-
bution to warehouses and stores and ultimately to
consumer’s residences. Most of the packaging is
12.1.2 Protection done by machines set up into systems. The packag-
Food products must be protected against contam- ing equipment often receives the prepared product
ination by microorganisms and a wide array of from an adjacent preparation area. Four example
other hazards. Depending on the characteristics of production and packaging systems are described in
the product and other factors, it may be necessary Table 12.1.
to provide protection against gain or loss of mois- The descriptions illustrate two important princi-
ture, oxygen, CO2, and other constituents, from ples about packaging machines. The first is that
crushing and other distribution damage, from packaging machines are generally set up as a sys-
improper temperature, from light, from tampering tem. It is unusual for a packaging operation to have
and theft, and against numerous other hazards. only one machine. Rather, there is nearly always a

Ebnesajjad: Plastic Films in Food Packaging. DOI: http://dx.doi.org/10.1016/B978-1-4557-3112-1.00012-0

© 2013 Elsevier Inc. All rights reserved. Adapted from a chapter in: Kutz, Handbook of Farm, Dairy, and Food Machinery (2008). 199
200 PLASTIC FILMS IN FOOD PACKAGING

Table 12.1 Description of Some Typical Food Packaging Systems

Product Steps in the Preparation/Packaging System

Milk in one gallon plastic 1. Milk is received at the plant, filtered, processed as necessary, and
jugs stored in large stainless steel tanks
2. Plastic jugs are manufactured on site by blow molders and placed into
temporary storage
3. The jugs and the milk are conveyed to a filling machine, which meters
one gallon of milk into each container
4. The filled jugs are capped, washed, and labeled
5. The completed gallon packages of milk are placed into plastic crates
for handling
6. The crates are stacked and conveyed to a refrigerated temporary
holding area
Soup in metal cans 1. The constituents for the soup are delivered to the plant
2. The metal cans, labels, and other packaging components are
delivered to the plant
3. The soup is prepared and conveyed to the packaging line
4. The cans are depalletized and conveyed into the packaging line
5. The cans are cleaned as necessary
6. Empty cans and the soup are conveyed to a filling machine and the
soup is metered into the cans
7. The can end is applied
8. The filled cans are retorted
9. Labels are applied to the cans
10. Completed cans are packed into corrugated trays
11. The filled trays are wrapped with shrink-wrap and palletized
Granulated sugar in multiwall 1. Sugar is extracted from sugar cane or sugar beets and transported to
paper bags a temporary holding area
2. Preprinted, multiwall paper bags and rolls of heavy Kraft paper are
delivered to the plant
3. Empty bags are held open by the filling machine and the specified
weight of sugar is metered into the bag
4. The top of the bag is rolled over, crimped, and glued shut
5. Bags of sugar are bundled together and wrapped in Kraft paper
6. The bundles of sugar are palletized and moved to a warehouse
Assorted chocolates in 1. Decorated paperboard cartons, plastic trays, plastic overwrap,
paperboard cartons corrugated shipping containers, labels, and other packaging
components are delivered to the plant
2. Chocolates are manufactured and placed into temporary holding
locations in the packaging area
3. Empty cartons are conveyed past the filling station where a robot
picks up individual pieces of chocolate and places them into particular
locations in a thermoformed plastic tray
4. Filled trays are placed into cartons
5. A lid is placed on the cartons
6. Completed cartons are wrapped in plastic film
7. Wrapped cartons are placed into the shipping containers, which are
closed, taped, labeled, and palletized
8. The loaded pallets are moved to a warehouse for temporary storage
12: FOOD PACKAGING MACHINERY 201

series of machines. For example, the milk system 1 qt of motor oil into different plastic bottles or
generally includes a filler, a capper, a labeler, and 2 qt of milk into paperboard or gable-topped car-
other machines. The packages go down the packag- tons. However, since this chapter addresses only
ing line, moving from machine to machine as dif- food products, motor oil and other nonfood pro-
ferent operations are performed. ducts will be ignored. Filling machines used in
The second principle is that there are almost food systems measure out a quantity of product by
always options in the way that a particular opera- volume or weight.
tion can be performed. The options may be pro-
vided by different machines. Alternatively, there
may be a choice to not use a machine. For example,
in the candy packaging system, the individual 12.3 Volumetric Fillers
pieces of candy could be placed into the carton by Volumetric fillers deliver a measured volume of
a robot or by people working with their hands. product into each container. Volumetric systems
The next portion of this chapter will discuss are flexible and can be adapted to a wide variety of
some of the different types of packaging machines products, ranging from water to thick pastes or
that are available, including machine capacity, powders, and other dry products.
operating principles, and other characteristics. The Most fillers can be adjusted to deliver a desired
discussion will start with filling machines. quantity of product. A typical unit can be adjusted
over a 10-fold range. For example, a particular
machine might be adjusted to deliver any volume
12.2 Filling Machines from 2 fluid ounces to 20 fluid ounces.

The filling machine is usually the most important

machine in a food packaging line. The filler per- 12.3.1 Piston Fillers
forms two critical functions. It measures out a spe- Piston fillers (Figure 12.1) are the most common
cific quantity of a food product and places that type of volumetric fillers. Piston fillers measure
metered quantity of food into a package. The and deliver the product by the action of a single
machine may also perform other functions, such as piston. On the intake stroke, the piston draws prod-
making and closing the package. Most fillers can uct out of a supply tank, through a directional
be set up to work on many different products. For valve, and into the measuring chamber which
example, a machine that is used to meter water into houses the piston. Then, on the following delivery
12 oz. plastic bottles could also be used to meter stroke, the valve leading to the container is opened

(a) (b)
Piston moving up Piston moving down

Valve Valve
open closed

Valve Valve
closed open

Empty Filling
container container

Charging piston Filling container

Figure 12.1 Piston filler operation.

202 PLASTIC FILMS IN FOOD PACKAGING

(a) (b)
Air pressure in Supply
Air pressure in
Supply tank
Air off tank Air in

Plunger Plunger
Diaphragm Diaphragm

Measuring Measuring
chamber chamber

Valve Valve
Valve Valve
closed open
open closed

Empty container Filling container

Figure 12.2 Diaphragm filler operation.

and the valve leading to the supply chamber is top of the plunger, forcing the product out of the
closed causing the product to flow out of the cham- chamber and into the container. The filled container
ber and into the container. The filled container is is then conveyed away and replaced by another
then conveyed away and replaced by another empty empty container and the process cycle repeats.
container and the process repeats.
The length of the stroke and the diameter of the
chamber determine the volume of product that is 12.3.3 Timed Flow Fillers
metered out. To alter the quantity of product, either If a liquid product flows through a tube of spe-
the stroke length or the chamber diameter (or both) cific size at a constant rate, the total quantity of
must be changed. On most machines, the stroke product delivered depends on the length of time that
length can be adjusted easily. However, to change the product flows. For example, if one cup flows
chamber diameter, the entire chamber must be through the tube in 1 s, two cups will flow through
removed and replaced, a relatively complex and the tube in 2 s, 3 cups in 3 s, etc. The accuracy of
time-consuming operation on most machines and the metering process depends on smoothness of flow
not possible on some machines. and the precision of the timing mechanism
(Figure 12.3). The equipment set includes a supply
tank and a pump, along with a timer and various
12.3.2 Diaphragm Fillers pipes (Figure 12.4). To fill larger containers, the
Diaphragm fillers (Figure 12.2) are similar in prin- timer setting is increased. To adjust the filling speed
ciple to piston fillers. Instead of a rigid piston and (volume/unit of time) is increased or decreased.
cylinder, a diaphragm filler has a flexible diaphragm The fillers that have been discussed so far are
which can be distorted to adjust its volume. The oper- mostly intended for use with liquids, such as milk,
ation of a diaphragm filler is straightforward. When water, pancake syrup, cooking oil, alcoholic bev-
the cycle starts, the valve at the bottom of the supply erages, and other thin liquids. There are equipment
tank is opened and the valve to the empty container is variations that enable the machines to be used with
closed. Air pressure in the supply tank forces the thicker products.
product out of the tank and into the measuring cham-
ber. The top of the chamber is formed by the dia-
phragm with the plunger above. As product flows 12.3.4 Auger Fillers
into the chamber, the diaphragm and plunger are Auger fillers are a widely used type of volumetric
lifted. When the plunger reaches a preset position, the filling equipment used for many types of dry products
valves are reversed and air pressure is applied to the and thick pastes (Figure 12.5). The product is held
12: FOOD PACKAGING MACHINERY 203

Quantity of product delivered in

a particular length of time
9

Quantity of product (1000 cm3)

7

6 5400cm3 in 6 s

3
1800cm3 in 2s
2

1 2 3 4 5 6 7 8
Time (s)

Figure 12.3 Delivery of product from a timed flow filler.

Supply tank
Timer

Tank
Agitator
Pump
Auger

Figure 12.4 Timed flow equipment arrangement.

temporarily in a conical shaped bin and metered and

Container
conveyed out through an opening at the bottom by an
auger. The auger must be specially designed and
manufactured to suit the product. The filler manufac- Figure 12.5 Auger filler.
turer or a specialty manufacturer should be contacted
to make the augers. The volume of product to be
delivered is directly related to the number of degrees If the density of the product is constant, metering
that the auger rotates. The control can be based on a specific volume of product also defines a particu-
time, which requires that the speed of rotation be con- lar weight of product. Volumetric filling is a good
stant, or it can be based on the degrees of rotation. choice for products of this type.
To change the volume of product delivered, the time
that the auger rotates can be increased or decreased. 12.4 Weight Filling
Some powders tend to bridge in the hopper and
not flow into the auger. To prevent bridging, manu- Weight filling is used to meter products that do
facturers make various types of agitators that rotate not have uniform density and for products that
together with the auger. The agitator breaks up the require more accurate metering than is possible
bridged product and keeps the product flowing using volumetric fillers. There are two types of
smoothly to the auger. weight filling: gross weight and net weight.
204 PLASTIC FILMS IN FOOD PACKAGING

Product
hopper

Feeder

Product
Weighing
hopper

Hopper
Scale Valve
Filled
containers

Figure 12.6 Net weight filler.

Scale
12.4.1 Net Weight Fillers
Figure 12.7 In-line filler.
Net weight fillers (Figure 12.6) measure out the
desired weight of product and convey the measured
product to the container. The metering step is done
inside the machine, before the product is introduced container will be overfilled. One approach is to set
into the container. The scale measures only the the scale to “underweight” the container. Another
weight of the product. When the weight of the prod- approach is to change the machine design. Simply
uct in the hopper reaches the preset value, the feeder locating the cutoff valve closer to the container will
stops and the hopper opens to discharge the product reduce the amount of product in the fill tube when
into a funnel which guides the product into the con- the valve closes, so the container is filled more
tainer. After the product has been placed into the accurately.
container, the filled container is moved away and an Gross weight fillers are less complicated and less
empty container is moved into position to be filled. costly than net weight units. In addition, because
the weight of the containers is preset into the scale
rather than being weighed, as is done by the net
12.4.2 Gross Weight Fillers weight units, gross weight fillers tend to be less
A gross weight filler (Figure 12.7) measures the accurate than net weight fillers. Therefore, gross
combined weight of the product and the package. weight equipment tends to be selected for lower
Before the filling operation begins, a sample of value products. In addition, net weight fillers han-
packages are weighed individually and the average dle the product more times than gross weight fil-
is calculated. The metering scale is then preset with lers. Therefore, gross weight fillers tend to be the
the sum of the desired product weight and the aver- more popular choice when brittle or fragile pro-
age weight of a container. The product is metered ducts, such as potato chips, are being packaged.
directly into a container until the scale determines
that the proper (combined) weight has been
reached. At that time, the product flow is termi- 12.5 In-Line or Rotary Fillers
nated, the filled container is moved out and an
empty container is moved into position to be filled. There are two basic arrangements of fillers: in-
There are several machine arrangements that can line and rotary. Each will be described and dis-
be used to improve the accuracy of weight filling cussed here.
equipment. From Figure 12.7, it can be seen that
there is some product in the fill tube when the
valve closes. This product, of course, still falls into 12.5.1 In-Line Fillers
the container after the valve closes. A method of In-line fillers (Figure 12.8) are widely used for
compensating for this product is required or every filling liquid and paste food products, such as
12: FOOD PACKAGING MACHINERY 205

Rotary
Time-delay Supply
Filler Filler turret
sensor tank
heads heads

Overhead
Empty Filled Star
supply tank
bottles bottles wheel
Star
wheel

Rear Front
block block
Empty Bottle Filled
Figure 12.8 Gross weight filler. bottles movement bottles

water, beverages, fruit juices, ketchup, mayonnaise, Figure 12.9 Rotary filler.
and many other products, into metal cans, glass bot-
tles, and other containers. Obviously, an in-line
filler must have at least one filling head but most Rotary units range in size from as few as 4 heads
have six or more heads. An in-line filler, including to as large as 140 heads or even more. The large
a short section of conveyor belt, is usually posi- units are used on high-speed beverage lines of the
tioned in a packaging line between an in-feed con- type used for filling metal cans with beer or soft
veyor and an out-feed conveyor. Typically, the drinks. Lines for these products can operate as fast
conveyors are a little wider than the diameter or as 2500 cans per minute or 1600 glass bottles per
width of the containers. minute. Slower lines are used for milk, pancake
The following description of the operation of an syrup, juices, and many other products. The rota-
in-line filler refers to the four head unit shown in tional speed of the in-feed star wheel and the rotat-
Figure 12.8. The filling procedure starts when empty ing turret must be synchronized so that each empty
containers are conveyed into the filler in single file container is placed in the proper position below a
by the in-feed conveyor. The containers are held in filler head on the turret. Similarly, the star wheel
position by the rear block as shown in Figure 12.8 on the out-feed side must align with the filled con-
until the four containers have been filled properly. tainers as they are taken off the turret and placed
Then, the filler heads are raised and moved back out back on the conveyor.
of the way, allowing the four newly filled containers Any of the volumetric or weight filler heads can
to start moving down the line toward the out-feed be used on either in-line or rotary fillers. Filler
conveyor. After a time delay (set on the time-delay heads are usually a major portion of the cost of a
sensor), the rear block is moved back and out of the large rotary filler.
way, allowing empty containers to start moving into
position for filling. After the four filled containers
have moved past the front block, it is repositioned to 12.6 Cap Application Machines
prevent the next set of containers from simply pass-
ing through the machine unfilled. After four contain- After a container has been filled, it continues
ers pass the rear block, the rear block is downstream to the next machine which is usually
repositioned, the filler heads move into position and the capper. Like fillers, cappers can be set up in
the cycle repeats. either an in-line or rotary arrangement.
Simultaneously, caps are fed down a chute from
a cap orienting machine which puts all caps into
12.5.2 Rotary Fillers the same orientation. Like fillers, cappers can be
Rotary fillers (Figure 12.9) remove empty con- set up in either an on-line or rotary arrangement.
tainers from the in-feed conveyor and place them When an in-line capper is being used, the contain-
on the rotating turret of the filler. As the containers ers pass under the end of the cap chute which is
travel around the periphery of the filler, they are adjusted so that the upper portion of the leading
filled and then placed onto the out-feed conveyor. edge of the container catches the lower edge of the
206 PLASTIC FILMS IN FOOD PACKAGING

Figure 12.10 Cap chute and spinning disk tightener.

(a) (b)

Intermittent Intermittent
rotation rotation
Gripping ring Gripping ring
deflated inflated
Air out Air in

Chuck moves down Chuck moves up

Figure 12.11 Operation of pneumatic chuck.

cap, pulling it out of the chute and setting it in relative motion that would cause the containers to
place on top of the container. Then the container, pass between the disks. Instead, a spindle capping
with the cap, passes through a set of spinning disks setup is used. A spindle (Figure 12.11) is mounted
which tighten the cap to the desired application tor- on a vertical shaft that rotates as the spindle travels
que (Figure 12.10). around the periphery of the machine. The spindle
The in-line arrangement shown in Figure 12.10 has a “chuck” at the lower end with a torque-
is very popular, but like in-line fillers, there is an limiting clutch above.
upper limit on capping speed. For lines that exceed The operating cycle described here is for a
the capacity of in-line equipment, rotary cappers machine applying screw caps. The cycle of steps is
can be used. The arrangement of capping heads essentially the same whether metal or plastic screw
around the periphery of a rotary capper is similar to caps, metal lug caps, or some other type of cap is
the arrangement of rotary filler. The filled contain- being applied.
ers are removed from the line by the entrance star The operating cycle begins when a cap is deliv-
wheel and placed on the capper. As the capper ered to the capping machine. In one system, as the
rotates, the caps are applied and tightened. Then, capper rotates, a peg on the outside of the frame of
the filled and capped containers are set back onto the capper pulls a cap out of the chute in a fashion
the line to be moved to the next station. The spin- similar to the way that a container pulls a cap out
ning disk arrangement used on in-line cappers can- the end of the chute in an in-line setup. In another
not be used on rotary cappers because the filled system, the empty chuck passes over a swinging
containers move with the turret, and there is no arm holding a cap. The chuck is lowered over the
12: FOOD PACKAGING MACHINERY 207

cap and picks it up. The arm then moves back to Mechanical chucks operate in a similar fashion
pull another cap from the chute. except that the jaws are held closed by a spring
When the cap is in the correct position, the spin- linkage. The linkage opens when the preset applica-
dle moves down and the chuck opens to fit over the tion torque is reached while the cap is being
cap. Then, the chuck closes to grip the cap and the applied.
spindle moves away, carrying the cap with it.
While the spindle is picking up the cap, the con- 12.6.2 Chuck-Type Press-On
tainer is moved into position. Then, the spindle
begins to turn and simultaneously moves downward Cappers
screwing the cap onto the container. When the The operation of a chuck-type press-on capper is
required (preset) application torque is reached, (i) similar to the operation of screw-type cappers,
the clutch opens and stops driving the chuck or (ii) except that the twisting motion used to screw the
the chuck opens and starts to slip around the cap. cap down is not required. Instead, the cap is held in
In either case, the spindle lifts away, releasing the the chuck while it is positioned and pressed straight
container to be discharged through the exit star down onto the top of the bottle. The application
wheel and back onto the conveyor to travel to the force can be controlled in several ways. The spring-
next machine. operated capper head application pressure can be
Only one spindle is involved in capping each regulated by adjusting the collar that sets the spring
container. Capping speed can be increased by using tension. Similarly, the movement of the capper
a machine with more spindles. Each spindle and head can be controlled by air pressure in a pneu-
container goes through the same sequence of opera- matic unit. Chuck-type press-on cappers can be
tions. While a peg is picking up a cap at one designed to suit caps and bottles of almost any size
spindle, another spindle is moving into position, and shape.
another spindle is applying a cap, another spindle is
releasing the container, and a container is leaving 12.6.3 Roller-Type Press-On
the machine through the exit star wheel. Depending
on the number of spindles on the capper, the
Cappers
sequence may be divided into even more steps. A In roller-type press-on cappers (Figure 12.12),
rotary capper typically has 3
12 or even more the cap is dropped or otherwise placed on the top
spindles, depending on the filling speed that is of the bottle. It is then passed under rollers that
required. press the tap tightly onto the containers. A shallow
cap may be pressed on by a single roller. Deeper
caps may require two or even three rollers to push
12.6.1 Chucks and Clutches them on completely. Roller cappers are generally
Screw caps can be applied by rotary capping used to apply caps with flat tops. The first roller
machines that have spindles with pneumatic levels and seats the cap. The remaining rollers press
chucks, mechanical chucks, or roller mechanisms the cap further onto the bottle. Irregular shapes
(Figure 12.11) The pneumatic type is illustrated in often cause problems when they pass under the
Figure 12.11. The doughnut-shaped gripping ring is rollers.
relaxed or deflated when the chuck is lowered to
pick up a cap. The ring is made of soft, pliable
material that will not scratch or mar the surface of 12.7 Induction Cap Sealing
the cap. When the ring is inflated, it grips the cap,
enabling it to be picked up. Different sized rings Today, increasing numbers of rigid and semirigid
can be installed in the chuck to provide gripping food packages are fitted with induction-welded
characteristics that are suitable for a particular bot- inner seals. The Food and Drug Administration
tle and cap combination. Also, variations exist in requires this type of technology for many pharma-
the method for applying the force. One variation ceutical products. The rules were instituted follow-
has a solid gripping ring with an area above where ing a famous product tampering incident. Inner
pressure can be applied, causing the ring to expand seals are not required for food products. However,
in the horizontal direction to grip the cap. manufacturers are adopting the technology to
208 PLASTIC FILMS IN FOOD PACKAGING

Figure 12.12 Roller-type press-on capper.

Cap

Pulpboard Cap

Wax Paper or foam

Aluminum Aluminum
Polymer Polymer

Four-layer seal Three-layer seal

Cap

Polymer
Aluminum foil
Wax
Pulpboard

Cross-section of
cap with inner seal

Figure 12.13 Induction inner seals and cap with seal included.

prevent spills and for product protection. Food pro- coil mount supports the coil over a conveyor. An
ducts that are packaged with inner seals include alternating magnetic field is produced around the
peanut butter, edible oils, ketchup, honey, spices, coil. Several thousand times a second, the field
jellies, and syrups. expands and contracts and then expands and con-
There are two primary types of inner seals tracts in the opposite direction. The water cooling
(Figure 12.13). The four-layer seal shown on the system removes excess heat from the cables and
left was originally developed when induction inner the coil. Modern systems are more efficient, so the
seals were first applied to packaging. The three- water cooling system is often not required.
layer inner seal was a later development. Seals are provided by the cap supplier. Each of
An induction sealing system may consist of a the four layers of the seal has a specific function,
power supply, a sealing coil, a sealing coil mount, as described here. A seal is held inside a cap by
a water recirculating system, and necessary electri- friction or a small glue spot (Figure 12.13). Caps
cal cables to connect the power supply and the seal- are applied to bottles and tightened in the usual
ing coil. The power supply converts regular line fashion, as discussed previously. The capped bottles
electrical current into the necessary power and fre- leave the capper and are carried down a conveyor
quency needed to seal bottles. The output energy is to the induction sealing coil. As the bottles pass
transmitted to the sealing coil by the cables. The under the sealing coil, the lines of magnetic force
12: FOOD PACKAGING MACHINERY 209

in the alternating magnetic field cut through the 12.9.1 Vffs Equipment
aluminum layer in the inner seal inducing a current
to flow the surface of the aluminum layer. The alu- Vffs machines are popular and widely used to
minum is not a perfect conductor, so it has some package a vast array of food products, including dry
electrical resistance. As a result, heat is produced in cereals, granular sugar, cake mixes, flour, and many
the aluminum. The heat causes the wax layer to others. The operation of an ffs machine is easy to
melt and be adsorbed into the pulp board layer. It understand. As the name indicates the material
also softens the polymer which seals the aluminum being packaged flows vertically down the machine
to the top of the bottle as it cools. The heating pro- as the various package forming, filling and sealing
cess often loosens the cap. Retorqueing, using a operations are performed.
unit similar to an in-line disk-type cap lightener, is The web of material (usually plastic or a lami-
generally used. nate) that will be formed into packages is fed into
the machine from a roll (Figure 12.14). The web is
usually printed with the manufacturer’s logo, prod-
uct illustrations, nutritional labels, and other
12.8 Flexible Packaging information.
The web is threaded through a series of rollers,
The discussions above have primarily addressed guides, and tensioning devices. Even movement of
glass and plastic bottles, jugs, and similar rigid or the material is critical for smooth machine opera-
semirigid containers. However, many food products tion. The web is then fed over a specially shaped
are packaged in pouches, bags, wraps, and other former (Figure 12.14). As the web travels over the
forms of flexible packaging. Flexible packaging is wings of the former, it is automatically wrapped
probably the oldest form of packaging. Ancient around the outside of the filler tube and the edges
hunter gatherers used available natural materials, are brought together and positioned for sealing the
such as leaves, and animal parts to form flexible back seam that will form a tube of the flexible
containers to wrap food products for protection and material.
for carrying and storing convenience. Of course, all The package material passes down the outside of
of their packaging was done by hand. the filler tube. As it moves, the edges are heat

12.9 Form-Fill-Seal Equipment

A form-fill-seal (ffs) machine performs three dis- Filling tube
Former
tinct operations:

1. form the package,

2. close and seal the package. Side seal bar
Web

Form-fill-seal equipment is popular because it

Seal bar
can be used on a wide variety of products ranging
from dry powders, such as cake mixes, to liquids,
such as salad dressings or pizza sauce. There are
Seal bar
three types of ffs equipment:

1. vertical form-fill-seal (vffs) machines, Cut-off knife

2. horizontal form-fill-seal (hffs) machines,
3. thermo form-fill-seal (tffs) machines. Figure 12.14 Operation of a vffs machine.
210 PLASTIC FILMS IN FOOD PACKAGING

sealed together, forming a tube. At the bottom of starts when a flat web of material, usually plastic
the filler tube, a pair of heat seal jaws closes on the film or a laminate with a heat sealable surface, is
tube, flattening it and simultaneously sealing the unwound from a roll (Figure 12.15). The web is
top of a filled pouch and then forming the bottom threaded through a series of rollers, guides, and ten-
of the next pouch. Then a heated knife cuts off the sioning devices. Uniform tension on the material is
bottom pouch which is conveyed away. critical for smooth machine operation.
At the same time, the product is loaded into the Packaging material from a preprinted supply roll
pouch through the filler tube. As the tube of mate- is folded in half. Side and bottom seals are applied.
rial continues moving downward, the heat sealing A cutoff device separates the individual pouches
mechanism forms the top of a filled pouch and the which are transferred to clamps on a conveyor
bottom of the next pouch. chain which, in turn, moves them past the stations
The sealing jaws are often triggered by an elec- for other operations. Just ahead of the filling posi-
tric eye mechanism which reads a black registration tion, the clamps are moved closer together, causing
spot printed in the web. In this way, the preprinted the pouch tops to open. Filling can be done in one
graphics will appear correctly on the completed or two steps. A two-step filling setup is illustrated
package. The pouch length can be adjusted easily. in Figure 12.15. The first filler head utilizes rapid
However, the filler tube must be replaced to change flow and the second filler “tops off” the filling
the diameter of the package. operation. After filling has been completed, the
clamps are pulled apart, causing the top of each
Aseptic Packaging pouch to close. The pouches are then heat sealed.
In the final step, the pouches are picked off the
A specialty form of vffs machinery is used to
conveyor chain and placed directly into a shipping
make aseptic packaging of the type often called
container or onto a belt conveyor.
“Brick-Pack” or “drink box”. Aseptic packaging is
sterilized in a hydrogen peroxide dip and formed
into a package. Then the product which has also 12.9.3 Tffs Equipment
been sterilized is piped into the newly formed box
Tffs equipment uses two films to make packages.
by double-wall pipe which has sterile air in the
In the most common arrangement, one plastic web
outer layer. Aseptic technology is also used to
is thermoformed into a tray and the other is heat
package products into premade containers. The sys-
sealed onto the tray to form the cover
tem is essentially the same, except that the con-
(Figure 12.16). The bottom material unrolls from
tainer forming step is skipped.
the supply roll and passes initially into a section of
the tffs machine equipped with heaters to soften the
12.9.2 Hffs Equipment plastic web. As the material moves forward, it
The flow of material in a hffs machine is essen- passes next into the forming section where a combi-
tially horizontal. The package forming process nation of pressure and vacuum pulls the plastic into

Plow assembly
Draw rollers
First fill
Sealing station Second fill
Cut off

Top closed
Top sealed
Bottom seal
Side seal
Pouch opened
Web roll

Pick off

Figure 12.15 Operation of a hffs machine.

12: FOOD PACKAGING MACHINERY 211

Upper web Plastisol

(heat sealable) Can end

Heater Flange
Loading Heating bar
Cut-off
knife Can body

Thermoforming Can end with Can body with

ring of plastsol end placed on top
prepared for seaming
Bottom web
(thermoformable) Can end

Figure 12.16 Operation of a tffs machine.

Can body

the shape of a tray to be used as the bottom of the

package. The thermoformed plastic then moves into First-operation Second-operation
the loading section where the food product is seam seam

placed into the tray cavities. The loading operation Figure 12.17 Can seaming.
can be done by hand, by robots, or by various
metering devices similar to the dry products and
liquid products discussed previously. After the trays At the food or beverage plant, the cans are taken
are loaded, the second plastic web (often transpar- off the pallets by depalletizing machines. They
ent) is fed in from the top and heat sealed onto the travel down a conveyor to the can washer and onto
edges of the trays. the filler. Except in very small systems, cans are
The final operation is to cut the individual trays filled by a rotary filler of the type discussed earlier.
apart and send them on down the line for any fur- After the cans have been filled, the can end is
ther packaging steps. placed on the top of the can cylinder. The projec-
Tffs machines are used to package sandwich tion of the can end and the flange on the can are
meat, pasta products, cut meat, medical products, then folded tightly together around the periphery,
and many other products, even nails, bolts, saw forming a tight seal (Figure 12.17) known as a dou-
blades, and other hardware. The machines are avail- ble seam.
able in a variety of sizes, both in length and width. The folding and sealing operation, which
Such machines are used in food plants and in the attaches can ends and closes the cans, is done by a
meat departments of grocery stores. Depending on can seamer or can closer. When used at a can
the kind of product, the filled packages can be shelf manufacturing plant, the machine is known as a
stable, refrigerated, or frozen. double seamer. Can seamers can be used on metal
cans, either two-piece or three-piece cans and on
12.10 Canning Machinery cans made of other materials, particularly plastic.
The operation is essentially identical for all can
Two types of cans are available: three-piece and types.
two-piece. Cans are made by can manufacturers A double seam consists of a “first operation”
and delivered to the user’s location in pallet load which curls the outside of the can end around the
lots. The three-piece cans leave the can company can flange and a “second operation” which forms
with one can end attached to the sidewall of the and irons out a tight hermetic seal between the can
can, forming what is essentially a deep cup. Two- and the can end. Hermetic seals are secure against
piece cans are formed into a single-piece deep cup the entry of microorganisms and maintain the steril-
and leave the can company in that form. Cans are ity of the food or beverage that has been packaged
palletized in layers separated by sheets of corru- in the can.
gated board, heavy paperboard, plastic sheeting, or There are two general types of seamers: head-
similar material. spin and can-spin. On a head-spin seamer, the can
212 PLASTIC FILMS IN FOOD PACKAGING

Mounting and designs. Tube and tray-type cartons are made from
dirve shaft single paperboard blanks that are scored, folded,
and glued to form the carton. Cartons are economi-
Seam profile cal. The material is inexpensive compared to other
packaging materials. Cartons can be collapsed to
Seam profile take up minimal space in shipment to the user. A
carton provides protection for a product, makes it
easier to handle, supplies a surface that can be
printed and attractively decorated to add sales
Figure 12.18 Roller for can seamer.
appeal to the product, and makes it possible to mar-
ket several items in a single package. Cartons can
is held while the seaming head, which has first- be creased and folded into shapes which are semi-
operation and second-operation seaming rolls rigid or rigid. However, while cartons are used as
(Figure 12.18), rotates around the can and gradually containers for many products, they are not gener-
forms the can end and the can flange into a tight ally rigid enough to be used as shipping containers.
seam. On a can-spin seamer, the can is rotated Cartons are used to package candy, pasta, dry
around its center axis. The seaming rolls, mounted cereal, beans, and other dry products, as well as liq-
on levers, are moved into position in a sequence to uid products, such as milk and orange juice. In
engage the can and form the seam. A variation of addition, several packages of other products can be
the can-spin process uses a seaming rail which has packed into a carton. An example is a pizza kit in a
been machined to the desired final shape of the carton which contains a paper pouch of a dry crust
seam. The top of the rotating can is forced against mixture, a second pouch containing powdered
the rail to form the seam. cheese, and a metal can of tomato sauce.
Seamers used in the food industry can be semi-
automatic or automatic. Semiautomatic seamers are 12.11.1 Carton Filling
motor-driven single station units used on low-speed
lines and for making test packages in laboratories. The following brief description of the operation
Automatic seamers are single or multiple head of a typical cartoner will demonstrate the features
machines used to close cans of vegetables, soups, and capabilities required by users. There is a great
beverages, and other food products, mostly for variety of machines for setting up and closing car-
commercial trade. On food or beverage packaging tons. Some are high speed and automatic and some
lines, the can closing speed can range from as low are semiautomatic and of lower capacity. The most
as 100 cans per minute to as high as 2500 cans per common is the horizontal cartoner for tuck end car-
minute. tons (Figure 12.19).
Can seamers are designed for a particular can- The collapsed cartons are taken from the ship-
diameter range, can height range, and speed range. ping container, loaded into the magazine on the
Canning speed is expressed in cans per minute or cartoner, and held in place by spring pressure or a
hour. A seamer which is in service can be modified weight. A single carton is pulled off the front or
to run any can and end within the designated diam- bottom of the stack by a swinging or rotating arm
eter and height range by fitting the proper can and with vacuum cups attached. The flat carton is then
end change parts. held in place by a pocket on a conveyor chain. At
the same time, a pusher bar applies pressure to the
trailing edge, forcing it to open and holding it
against the front corner of the chain pocket. The
12.11 Carton Filling and Closing combination of vacuum cups pulling and the pres-
Machinery sure from the pusher bar holds the carton securely
in position as it opens.
Cartons are paperboard containers that are manu- As the carton moves along with the chain, the
factured by converters and then filled and closed in product is pushed into the carton by hand, by pneu-
a food packaging plant. Cartons are made in a wide matic cylinder, or by a cam-operated mechanism
variety of sizes and shapes, and in numerous that travels along next to the chain. Then, the
12: FOOD PACKAGING MACHINERY 213

12°
0.188

5.000
3.500 15°
10° 0.125

5.000

0.563 12.000

10.000 4.969

10.000

Figure 12.19 Reverse tuck carton.

carton is closed. The dust flaps on the leading edge make it more difficult for the cartoner to perform
are wiped into position by stationary bars as the the folding and tucking actions involved in closing
carton moves along. Trailing flaps are folded for- a carton. As a consequence, jams become more
ward by mechanical fingers that move faster than common. One solution is to store the unused car-
the carton travel speed. Then, the tucks are folded tons in an environmentally controlled space or at
in by curved bars that bend the score lines and least give the stored cartons time to equalize
guide the tuck flaps into the proper slots. moisture before attempting to run them on the
Since cartons move rapidly into, through, and machine.
out of the cartoner, the carton design must be pre-
cise and the manufacturing must be workmanlike.
If not, carton jams will occur. 12.12 Metal Detectors
Other factors that will influence the machinabil-
ity of the cartons are the weather and storage condi- Metal is a potential hazard in all types of food
tions. In the winter, the air is cold and holds products. The hazard can be reduced greatly by
less moisture. As a result, the cartons are usually using proper equipment and an effective program
dryer, flatter, and easier to run. However, as the to manage the so-called “tramp metal”. Metal
season progresses and the temperature rises, the air detection is also an issue in pet food systems, but
takes up more water. The cartons absorb moisture this discussion will focus on human foods and
from the air and often take on a twisted or curved beverages.
shape because the absorption is not uniform in all Metal in food can cause injury to people, pets,
areas of the carton blank. The twists and curves and other animals. It often leads to a loss of good
214 PLASTIC FILMS IN FOOD PACKAGING

will. Incidents of product contamination routinely metal detector has three coils. The front and rear
receive attention from the media, both local and coils are connected to the same AC power supply,
national. A contamination incident can damage a but the rear coil is the reverse of the front coil
company’s reputation. Metal in the food can cause (Figure 12.20). The center, detector, coil is con-
damage to machinery. Finally, the contamination nected to the control unit. The front and rear coils
could lead to an expensive product recall. produce alternating magnetic fields which are bal-
The consequences are serious enough to warrant anced and out of phase with each other. Each of the
a carefully planned program to find and remove end coils induces a voltage in the middle coil.
unwanted metal contamination, including the use of When the detector is empty, the voltages cancel
metal detection equipment. There are many sources each other out so that there is no output signal in
of metal in a typical food plant. Broken machinery the detector coil. This situation will remain
is an obvious source. Most food products are pro- unchanged as packages pass through the unit unless
cessed in metal equipment and packaged by metal there is metal in the package.
equipment. Moving parts wear and eventually small When a piece of metal is moved through the
pieces of metal fall from a machine. Some of the aperture into the detector unit, the metal will inter-
small pieces fall into the food product. Dropped act with the front coil and cause a voltage to be
tools are another source of metal as are items which induced in the piece of metal. This voltage, in turn,
fall from workers’ clothes. Items that could cause will cause a current to flow on the piece of metal.
contamination in this way include nuts and bolts, That current on the piece of metal causes an unbal-
screws, nails, pens, rulers, etc. Jewelry worn by anced condition on the middle (detector) coil which
workers can fall off and get into the food. can be sensed and used to trigger an automatic
Examples include rings, watches, and earrings. And rejection device.
sometimes the contamination is not an accident. Nonconducting objects can pass by the sensor
Systems may be sabotaged by individuals who wish without causing a disturbance of the balance on the
to damage the company or make a legal claim for sensor coil, but the metal detector will pick up both
monetary damages. ferrous and nonferrous metals since the detection
The metal detection process that will be dis- process depends on the electrical conducting prop-
cussed is based on the magnetic induction process, erties of the metals.
the same process that is used to heat the caps in an For this reason, food packaged in aluminum
induction cap sealing system and which makes trays, cups with aluminum foil covers, and similar
most electric motors spin.
In simple terms, the metal detector produces an
oscillating electromagnetic field. The food products Rear coil
Detector
and packages pass through the field. The presence
of metal causes a disturbance in the field which can
be detected and used to trigger an action to reject Front coil
the contaminated product, whether or not it is in a
package.

12.12.1 Typical Metal Detectors

Aperture
A common type of metal detector (Figure 12.20)
consists of a heavy metal case and a control unit.
The case has an aperture (opening) large enough
for a conveyor carrying packages and/or products
to pass through. However, there are other arrange-
ments that may be advantageous in certain circum-
stances. For example, a metal detector can be AC power supply
mounted around the filler tube on a vffs machine. It
Case removed to show coils
detects metal in the free-falling stream of product
passing through the tube as the pouch is filled. A Figure 12.20 Metal detector.
12: FOOD PACKAGING MACHINERY 215

packages cannot be inspected by a metal detector. A metal detector, by itself, will not provide
There is an alternate design, using a static electro- assurance that all metal has been detected and
magnetic field that can be used on aluminum removed. For best results, the metal detector should
packages because it will only detect ferrous be a part of a quality assurance program specifi-
metals. cally designed for each product.
This page intentionally left blank
 13 Compostable Polymer Properties and Packaging
Applications
Ewa Rudnik
Scientific and Research Centre for Fire Protection – National Research Institute,
Józefów, Poland

13.1 Introduction useful life they will biodegrade in a composting

process. The idea of compostable polymers is in
Compostable polymers have been designed to agreement with life cycle thinking.
be disposed of after their useful life by means of To summarize, the requirements a material must
organic recycling, that is, composting, and are one satisfy to be termed “compostable” include miner-
of the strategic options available for the manage- alization (i.e., biodegradation to carbon dioxide,
ment of plastic waste. Composting is an attractive water, and biomass), disintegration into a compost-
alternative for reducing solid waste and is espe- ing system, and completion of its biodegradation
cially suitable for those segments of conventional during the end-use of the compost, which, more-
plastics for which recycling is difficult or econom- over, must meet relevant quality criteria, for exam-
ically not feasible. Use of compostable polymers ple, no ecotoxicity. The satisfaction of requirements
for packaging applications, especially in food should be proved by standardized test methods.
packaging is still growing (Mahalik et al., 2010; Compostable polymers can be classified accord-
Mensitieri et al., 2011; Siracusa et al., 2008). ing to their source of origin or method of their
Growing environmental awareness and new rules preparation (Figure 13.1).
and regulations, as well as new trends in solid waste On the basis of origin, compostable polymers
management have led scientists to increase their are derived from renewable or petrochemical
investigations into the design of compostable poly- resources.
mer materials that easily degrade under well-defined The potential uses for biodegradable packaging
environmental conditions. materials include (Tharanathan, 2003):
ASTM (ASTM D, 6400-04) and ISO (ISO,
17088) Standards define “compostable plastic” as:
1. use and throw, disposable packaging materials,
“a plastic that undergoes biological degradation dur-
ing composting to yield carbon dioxide, water, inor- 2. routine consumer goods for day-to-day use,
ganic compounds and biomass at a rate consistent such as plates, cups, containers, and egg
with other known compostable materials and leaves boxes,
no visually distinguishable or toxic residues.” 3. disposable personal care napkins/sanitary
The difference between biodegradable and pads, diapers, etc.,
compostable polymers lies in additional require- 4. lamination coating,
ments related to the latter. Besides biodegradation
into carbon dioxide, water, inorganic compounds, 5. bags for agricultural mulching (nursery).
and biomass, compostable polymers must fulfill
other criteria such as compatibility with the com- The field of applications of compostable poly-
posting process, no negative effect on quality of mer in food-contact articles includes disposable
compost, and a degradation rate consistent with cutlery, drinking cups, salad cups, plates,
other known composting materials. overwrap and lamination film, straws, stirrers, lids
It is noteworthy that compostable plastics are a and cups, plates, and containers for food dispensed
priori designed for a given method of safe disposal, at delicatessen and fast-food establishments
that is, composting. This means that after their (Siracusa et al., 2008).

Ebnesajjad: Plastic Films in Food Packaging. DOI: http://dx.doi.org/10.1016/B978-1-4557-3112-1.00013-2

© 2013 Elsevier Inc. All rights reserved. Adapted from a chapter in: Rudnik, Compostable Polymer Materials (2008). 217
218 PLASTIC FILMS IN FOOD PACKAGING

Compostable polymer materials

temperature (Tg) of about 55 C and melting point
(Tm) of about 180 C (Lunt, 1998; PROBIP, 2004;
Södergård and Stolt, 2002). Introduction of stereo-
Origin Petrochemical Renewable chemical defects into poly(L-lactide) (i.e., mesolac-
tide or D-lactide incorporation) reduces the melting
Conventional synthesis point, rate of crystallization, and extent of crystalli-
zation of the resulting polymer but has little effect
Biotechnology
on glass transition temperature (Drumright et al.,
2000). After roughly 15% incorporation of meso-
Methods of lactide, the result is no longer crystallizable. For
preparation Modification of
biomass products example, introduction of mesolactide depresses the
crystalline melting point to 130 C (Lunt, 1998).
Blending The molecular weight, macromolecular structure,
and the degree of crystallization of PLA vary sub-
Figure 13.1 Classification of compostable stantially depending on the reaction conditions in
polymers. the polymerization process (Gupta and Vimal
Kumar, 2007).
Of the three possible isomeric forms, PLLA and
poly(D-lactic acid) are both semicrystalline in
13.2 Biodegradable Polymers nature, and poly(mesolactic acid) or PDLLA is
from Renewable Resources amorphous. Racemic PLA—synthesized from pet-
rochemicals—is atactic, that is, it exhibits no ste-
13.2.1 Poly(lactic acid) reochemical regularity of structure, is highly
amorphous, and has a low glass transition tempera-
Properties ture. Amorphous grades of PLA are transparent
Poly(lactic acid) (PLA) exhibits a balance of per- (Table 13.1).
formance properties that are comparable to those of PLA has good mechanical properties, thermal
traditional thermoplastics (Vink et al., 2004). PLA plasticity and biocompatibility, is readily fabricated,
can be fabricated in a variety of familiar processes and is thus a promising polymer for various end-use
and brings a new combination of attributes to pack- applications. From a physical property standpoint, it
aging, including stiffness, clarity, dead fold and is often loosely compared to polystyrene (PS)
twist retention, low-temperature heat sealability, as (Drumright et al., 2000). Like PS, standard-grade
well as an interesting combination of barrier proper- PLA has high modulus and strength and is lacking
ties including flavor, aroma, and grease resistance in toughness. The toughness of PLA can be dramati-
(Table 13.1). cally improved through orientation, blending, or
PLA polymers range from amorphous glassy copolymerization (Drumright et al., 2000).
polymers with a glass transition temperature of PLA possesses high transparency and is an excel-
about 50
60 C to semicrystalline products with lent material for packaging (Gupta and Vimal
melting points ranging from 130 C to 180 C, Kumar, 2007). PLA is an inherently polar material
depending on the sequence of enantiomeric repeat- due to its basic repeated unit of lactic acid. This
ing units (L and D) in the polymer backbone high polarity leads to a number of unique attributes
(Jamshidi et al., 1988). such as high critical surface energy that yields excel-
Generally, commercial PLA grades are copoly- lent printability. Another benefit of this polar polyes-
mers of poly(L-lactic acid) (PLLA) and poly(D,L- ter polymer is its resistance to aliphatic molecules
lactic acid) (PDLLA), which are produced from L- such as oils and terpenes (Gupta and Vimal Kumar,
lactides and D,L-lactides, respectively (Martin and 2007; Hartmann and Whiteman, 2000). Apart from
Avérous, 2001). The ratio of L- to D,L-enantiomers this, PLA possesses stiffness, clarity and twist reten-
is known to affect the properties of PLA, such as tion, low-temperature heat sealability, as well as an
melting temperature and degree of crystallinity. excellent combination of barrier properties including
Enantiomerically pure PLA, poly(L-lactide) is a flavor and aroma barrier characteristics. Possible
semicrystalline polymer with a glass transition application of PLA in liquid and juice packaging
Table 13.1 Properties of Some Commercially Available PLA

Nature Nature Workss PLA Biomers Hycail

Workss PLA Resin General purpose L9000 HM 1011
(PROBIP, (NatureWorks) (PROBIP, (Hycail)
2004) 2004)
Physical properties
Melt-flow rate (MFR) 10
30 3
6 2
4
(g/10 min)
Density (g/cm3) 1.25 1.24 1.25 1.24
Haze 2.2
Yellowness index 20
60
Clarity Transparent
Mechanical properties
Tensile strength at 53 48 70 62
yield (MPa)
Elongation at yield 10
100 2.5 2.4 3
5
(%)
Flexural modulus 3828 3600
(MPa)
Flexural strength 83
(MPa)
Notched Izod impact 0.16
(J/m)
Thermal properties
HDT ( C) 40
45, 135
Vicat softening point Not 56
( C) determineda
Glass transition 55
65 60
63
temperature ( C)
Melting point ( C) 120
170b 150
175
c
Barrier properties
Transmission rate: 550
oxygen (cm3-mil/m2/
24 h atm)
Transmission rate: 3000
carbon dioxide (cm3-
mil/m2/24 h atm)
Transmission rate: 325
water vapor (g-mil/m2/
24 h atm)
Optical propertiesc
Haze (%) 2.1

Gloss, 20 90
a
Close to glass transition temperature.
b
Amorphous and crystalline, respectively.
c
NatureWorkss PLA Polymer 4042D (Technical Data Sheet); All properties measured on 1.0 mil film; O2 and CO2 at 23 C; 50% RH; H2O
at 38 C; 90% RH.
220 PLASTIC FILMS IN FOOD PACKAGING

was suggested based on permeability studies of a The first products were aimed at packaging film
variety of polymers to D-limonene, a major compo- and fibers for textiles and nonwovens. For packag-
nent of orange juice flavor (Hartmann and ing, clear films with good barrier properties but low
Whiteman, 2000). Upon testing, no D-limonene heat-seal properties can be produced. For fibers it
could be detected passing through the PLA film. could mean apparel with better drape and moisture
An overview of polylactides as packaging mate- management and industrial clothing with better UV
rials, summarizing the main properties of PLA, was resistance, reduced flammability, and good resistance
given by Auras et al. (2004). PLA films have better to soiling and staining (Additives for Polymers,
UV light barrier properties than low-density poly- 2000). Cargill Dow’s PLA has been designated as a
ethylene (LDPE), but they are slightly worse than new generic fiber type by the US Federal Trade
those of cellophane, PS and poly(ethylene tere- Commission. PLA now joins other classifications
phthalate) (PET) (Auras et al., 2004). PLA films including cotton, wool, silk, nylon, and polyesters as
have mechanical properties comparable to those of a recognized fiber category. Examples of main appli-
PET and better than those of PS. The CO2, O2, and cations of PLA are given in Table 13.2.
water permeability coefficients of PLA are lower Business segment opportunities and examples of
than those of PS and higher than those of PET. commercially available products are listed below
(Vink et al., 2004).
Processing
1. Rigid thermoforms (clear fresh fruits and
PLA resin can be tailor-made for different fabri-
vegetable clamshells, deli meat trays, opaque
cation processes, including injection molding, sheet
dairy (yogurt) containers, bakery, fresh herb
extrusion, blow molding, thermoforming, film form-
and candy containers, consumer displays and
ing, or fiber spinning (Drumright et al., 2000). The
electronics packaging, disposable articles, and
key is controlling certain molecular parameters in
cold drink cups),
the process, such as branching, D-isomer content,
and molecular weight distribution. Injection molding 2. Biaxially oriented films (candy twist and
of heat-resistant PLA products requires rapid crystal- flow wrap, envelope and display carton win-
lization rates, which can be achieved by using PLA dows, lamination films, product (gift basket)
that contains less than 1% D-isomer and often by the overwrap, lidding stock, die cut labels, floral
addition of nucleating agents (Drumright et al., wrap, tapes, shrink sleeves, stand-up pouches,
2000). Extrusion-thermoforming is optimized at a D- cake mix, cereal, and bread bags),
isomer content that does not allow crystallization to 3. Bottles (short shelf-life milk, edible oils, and
occur during the melt processing steps, with 4
8% bottled water).
D-isomer content being the effective range.
The recommended process temperature for Hycail In addition to traditional food packaging applica-
PLA is 190
240 C (Hartmann and Whiteman, 2000). tions, several companies are exploring nonfood
The processing temperature profile of Nature packaging applications for PLA, including (Vink
Works PLA 3001 D-polymer, designed for et al., 2004):
injection-molding applications, comprises melt tem-
perature 200 C, feed throat 25 C, feed temperature • Mitsui-Chemical telephone cards,
(crystalline pellets) 165 C, feed temperature (amor- • Sanyo compact disk,
phous pellets) 150 C, compression section 195 C,
metering section 205 C, nozzle 205 C, and mold • Matsushita (Panasonic) battery packaging,
25 C (Gupta and Vimal Kumar, 2007). For extru- • Fujitsu PC body components.
sion grades the processing temperature profile
ranges from 180 C to 210 C.
13.2.2 Polyhydroxyalkanoates
Applications Properties
PLA products are finding uses in many applica- The family of polyhydroxyalkanoates (PHAs)
tions, including packaging, paper coating, fibers, exhibits a wide variety of mechanical properties
films, and a host of molded articles. from hard crystalline to elastic, depending on the
13: COMPOSTABLE POLYMER PROPERTIES AND PACKAGING APPLICATIONS 221

Table 13.2 Main Applications for PLA

Sector Examples
Packaging Food packaging, films, rigid thermoformed food, and beverage containers,
carrier bags and labels, coated papers and boards, battery packaging,
windows for envelopes
Agriculture Sheet or molded forms for time-release fertilizers, plant clips
Transportation Parts of automobile interiors (head liners, upholstery, spare tire covers)
Electric appliances and CD, computer keys, cases for Walkmans, wrappers for CDs
electronics
Houseware Carpets
Other (fibers and fabrics) Textiles and nonwovens

composition of monomer units (Khanna and comonomer to reduce the crystallinity and presum-
Srivastava, 2005). Solid-state poly(3-hydroxybuty- ably increase the flexibility of the resulting copoly-
rate) (P(3HB)) is a compact, right-handed helix mer. The copolymerization with 3-hydroxyvalerate
with a two-fold screw axis (i.e., two monomer units (3HV) was the first attempt performed by ICI
complete one turn of the helix) and a fiber repeat (Imperial Chemical Industries) in the early 1980s.
of 0.596 nm (Braunegg et al., 1998). The stereoreg- However, the crystallinity of poly(3-hydroxybuty-
ularity of P(3HB) makes it a highly crystalline rate-co-3-hydroxyvalerate) (P(3HB-co-HV)) never
material. Its melting point is around 177 C, close to falls below 50% due to the isodimorphism of the P
that of polypropylene (PP), with which it shares (HB-co-HV) copolymer. It has been reported that
other similar properties, although the biopolymer is poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P
stiffer and more brittle. (HB-co-HHx)) shows a greater Tm, at a given mol%
The densities of crystalline and amorphous PHB comonomer, in comparison to P(HB-co-HV).
are 1.26 and 1.18 g/cm3, respectively (Khanna and Interestingly, hexanoate and larger comonomers
Srivastava, 2005). depress Tm in the same manner regardless of their
P(3HB) is water insoluble and relatively resistant molecular sizes. This feature indicates the break-
to hydrolytic degradation. This differentiates P(3HB) down of the isodimorphism occurring in the P(HB-
from most other currently available bio-based plas- co-HV) copolymer by the incorporation of comono-
tics which are either moisture or water soluble. mer units with three or more carbon units
Mechanical properties like Young’s modulus and (Padermshoke et al., 2005).
tensile strength of PHB are close to that of PP Incorporation of other hydroxy acid units to
though extension to break is markedly lower than form PHA copolymers can improve properties such
that of PP (Table 13.3) (Khanna and Srivastava, as crystallinity, melting point, stiffness, and tough-
2005; Lee, 1996). However, due to the high stereo- ness (Khanna and Srivastava, 2005). As the fraction
regularity of biologically produced macromolecules, of 3HV increases, the copolymer becomes tougher
PHB is a highly crystalline polymer that is stiff and (increase in impact strength) and more flexible
brittle. It is also thermally unstable during processing (decrease in Young’s modulus). The increase in
(Padermshoke et al., 2005). The molecular weight of melting temperature with increasing 3HV fraction
PHB degrades significantly at temperatures just without affecting degradation temperature allows
above the Tm. This unfortunate aspect poses a limita- thermal processing of copolymer melts without
tion of, for example, the application to a flexible thermal degradation. The melting temperature (Tm)
film, which is one of the largest uses of biodegrad- of P(3HB) homopolymer was 178 C, and the copol-
able polymers. As a consequence, many attempts to ymer P(3HB-co-3HV) with a 95 mol% of 3HV was
copolymerize a different comonomer with PHB 108 C (Kunioka et al., 1989). A minimum value
monomer to improve its mechanical properties have (around 75 C) of melting temperature was
been made. One idea is to include a more bulky observed at approximately 40 mol% 3HV, where
222 PLASTIC FILMS IN FOOD PACKAGING

Table 13.3 Comparison of Mechanical Properties of PHAs and PP (Khanna and Srivastava, 2005; Lee, 1996)

Melting Young’s Tensile

Copolymer Temperature Modulus Strength Elongation
Polymer Content ( C) (GPa) (MPa) at Break (%)
PP 2 170 1.7 34.5 400
P(3HB) 2 179 3.5 40 5
P(3HB-co- 3 mol% 170 2.9 38 2
3HV) 3HV
P(3HB-co- 9 mol% 162 1.9 37 2
3HV) 3HV
P(3HB-co- 14 mol% 150 1.5 35 2
3HV) 3HV
P(3HB-co- 20 mol% 145 1.2 32 2
3HV) 3HV
P(3HB-co- 25 mol% 137 0.7 30 2
3HV) 3HV
P(3HB-co- 3 mol% 166 2 28 45
4HB) 4HB
P(3HB-co- 10 mol% 159 2 24 242
4HB) 4HB
P(3HB-co- 16 mol% 2 2 26 444
4HB) 4HB
P(3HB-co- 64 mol% 50 30 17 591
4HB) 4HB
P(3HB-co- 90 mol% 50 100 65 1080
4HB) 4HB
P(4HB) 2 53 149 104 1000
P(3HHx-co- 61 2 10 300
3HO)
P(3HB-co- 133 0.2 17 680
6 mol%
3HA)
P(3HB-co- 52 2 20 850
3HHx)

the crystal lattice transition took place. For copo- copolymers composed of primarily HB with a frac-
lymers poly(3-hydroxybutyrate-co-4-hydroxybuty- tion of longer chain monomers, such as HV, HH or
rate)s (P(3HB-co-4HB)), the Tm value decreases HO, are more flexible and tougher plastics.
from 178 C to 150 C as the 4HB content increases The copolymer P(3HB-co-3HV) has lower crys-
from 0 to 18 mol%, then is almost constant in the tallinity and improved mechanical properties
composition range from 18 to 49 mol% 4HB. (decreased stiffness and brittleness, increased tensile
PHAs made of longer monomers, such as strength and toughness) compared to P(3HB), while
medium chain length mcl-PHAs, that is, with still being readily biodegradable. It also has a higher
C6 2 C14 monomers, are typically elastomeric, melt viscosity, which is a desirable property for
sticky materials, which can also be modified to extrusion blowing (PROBIP, 2004). Copolymers
make rubbers (Suriyamongkol et al., 2007). PHA polyhydroxybutyrate-co-valerate (PHBV) and Poly
13: COMPOSTABLE POLYMER PROPERTIES AND PACKAGING APPLICATIONS 223

Table 13.4 Properties of P(HB-co-HHx)s (Narasimhan, 2004)

% C6 (hexanoate) Melting Point, Tm ( C) Applications

0 (PHB) 180 Hard, brittle, crystalline
4 150 Hard, some elasticity Molded articles
6 145 Hard, elastic, flexible Fibers
10 125 Soft, elastic, flexible Films
18 95 Soft, rubbery Coatings

(3-hydroxybutyrate-co-3-hydroxyhexanoate)s have a Processing

range of properties depending on composition
Homopolymer P(3HB) has good thermoplastic
(Table 13.4).
properties (melting point 180 C) and can be pro-
P(HB-co-HHx) combines the thermomechanical
cessed as classic thermoplast and melt-spun into
properties of PE (strength, flexibility, ductility,
fibers. It has a wide in-use temperature range (arti-
toughness, and elasticity) with the physicochemical
cles retain their original shape) from
30 C to
properties (compatibility) of polyesters (printability,
120 C. Articles made of P(3HB) can be autoclaved.
dyeability, and barrier performance). It forms
However, it is fairly stiff and brittle, and it has
blends with PLA and thermoplastic starch (TPS).
somewhat limited applications. PHB has a small
The oxygen permeability of commercial PHA
tendency to creep and exhibits shrinkage of 1.3%.
was investigated and compared to oil-based poly-
A comparison of injection-molding conditions
mers conventionally used in the food packaging
between homopolymer PHB and PP is given in
domain (Corre et al., 2012). PHAs show intermedi-
Table 13.6 (Rabetafika et al., 2006).
ate to high oxygen barrier properties depending on
PHBV is thermoplastic and can be processed by
the considered grade and compared to PA6 MXD6
injection molding, extrusion, blow molding, film
which has very high oxygen barrier properties and
and fiber forming, and lamination techniques.
PS 1560 which presents low ones.
The Nodax family of PHAs is suitable for differ-
Properties of some commercial PHAs are given in
ent conversion processes, including injection mold-
Table 13.5.
ing, cast film, cast sheet for thermoforming, melt-
The possibility for using PHB or P(3HB) in food
extruded paper, and board coatings (www.nodax.
packaging was investigated (Bucci et al., 2005). It
com/).
was found that PHB can be used in injection-molding
processes for the manufacture of packaging for food
products with the same equipment used for PP pack- Applications
age injection. However, the process conditions must Cups based on polylactate (PLA) and PHB were
be adjusted to the characteristics of the polymer and a found to be as effective as high-density polyethyl-
specific mold must be used. ene (HDPE) cups in protecting an orange juice
The performance of the PHB packaging (500 ml simulant and a dressing from quality changes dur-
packaging (jar-cap set)) was evaluated through ing storage (Haugaard et al., 2003). The orange
physical tests (visual analysis and light transmis- juice simulant and the dressing were stored in PLA,
sion), comparing it with PP packaging, migration PHB, and HDPE for 10 weeks at 4 C under fluores-
tests of packaging components, and biodegradation cent light or in darkness. The suitability of PLA
assays (Bucci et al., 2007). The evaluated PHB was and PHB compared to HDPE was investigated by
shown to be promising for use in food packaging, determination of color changes and loss of ascorbic
since it acts as a good barrier to light incidence in acid of the juice simulant, and by determination of
the UV range. In relation to the migration of com- color changes, primary (peroxide value) and sec-
ponents, pigmented PHB packaging can be recom- ondary lipid oxidation (volatiles determined by
mended for different foods under conservation static headspace) products and reduction of α-toco-
conditions in the long and short terms. pherols of the dressing.
224 PLASTIC FILMS IN FOOD PACKAGING

Table 13.5 Properties of Commercial PHAs (PROBIP, 2004)

P(3HB) P(3HB) P(3HB-co- P(3HB-co-3HHx)

Biomer P240 Biomer P226 3HV) Biopol Kaneka, Nodax
Physical properties
MFR (g/10 min) 5
7 9
13 0.1
100
3
Density (g/cm ) 1.17 1.25 1.23
1.26 1.07
1.25
Transparency (%) 0.7 White powder/
translucent film
Mechanical properties
Tensile strength at 18
20 24
27 10
20
yield (MPa)
Elongation at yield 10
17 6
9 10
25
(%)
Flexural modulus 1000
1200 1700
2000 40 Several orders of
(MPa) magnitude
Thermal properties
HDT ( C) 2
60
100
Vicat softening 53 96 60
120
point ( C)

Table 13.6 Injection Molding Conditions of PHB and PP (Rabetafika et al., 2006)

Parameters PHB PP

Melt temperature ( C) 160 180
Hopper temperature ( C) 25 25
Fill temperature ( C) 130 230

Clamp zone ( C) 140 250

Mixture zone ( C) 150 250

Nozzle ( C) 160 250

Mold ( C) 10
15 10
15

Initially, PHAs were used in packaging films formed products, binding materials, and films.
mainly in bags, containers, and paper coatings Markets for the Nodax family of PHAs (www.
(Khanna and Srivastava, 2005; Lee, 1996; Reddy nodax.com/) include:
et al., 2003). Similar applications in conventional
commodity plastics include disposable items such as • Packaging
razors, utensils, nappies, feminine hygiene products, • Single use and disposable items
cosmetic containers, shampoo bottles, and cups • Housewares
(Kunioka et al., 1989). P(3HB-co-3HHx) (Nodax)
has applications in flushable materials (e.g., feminine • Appliances
hygiene products), coatings, synthetic papers, heat- • Electrical and electronics
13: COMPOSTABLE POLYMER PROPERTIES AND PACKAGING APPLICATIONS 225

Table 13.7 Glass Transition Temperatures of TPS Using Different Plastification Levels (Avérous and Fringant,
2001)

% Plasticizer Level Glycerol Content Water Content Glass Transition

Starch (wt%) (wt%) (wt%) ( C)
74 26 10 16 43
70 30 18 12 8
67 33 24 9 27
65 35 35 0 220

• Consumer durables Rodriguez-Gonzalez et al., 2004; Van Soest et al.,

• Agriculture and soil stabilization 1996a,b,c). Plasticizers containing amide groups
such as urea, formamide, and acetamide or a mix-
• Adhesive and soil stabilization ture of plasticizers have been also studied (Ma and
• Adhesives, paints, and coatings Yu, 2004; Ma et al., 2005, 2006; Shogren et al.,
• Automotive 1992; Thunwall et al., 2006).
The mechanical properties of a low- and a high-
molecular mass TPS were monitored at water
13.2.3 Thermoplastic Starch contents in the range of 5
30% (w/w). The stress-
strain properties of the materials were dependent on
Properties the water content. Materials containing less than
The glass transition temperature (Tg) of dry 9% water were glassy with an elastic modulus
amorphous starch is experimentally inaccessible between 400 and 1000 MPa (Avérous and Fringant,
owing to the thermal degradation of starch poly- 2001). Different starch sources were extruded with
mers at elevated temperatures (Poutanen and the plasticizer glycerol, and glass transition tem-
Forsell, 1996). It is estimated that the Tg of the dry peratures and mechanical properties were evaluated
starch is in the range of 240
250 C (Poutanen and (Avérous and Fringant, 2001). Above certain glyc-
Forsell, 1996). Native starch is a nonplasticized erol contents, dependent on the starch source, a
material because of the intra- and intermolecular lower glass transition temperature Tg resulted in
hydrogen bonds between hydroxyl groups of starch decreased modulus and tensile strengths and
molecules. During the thermoplastic process, in the increased elongations. For pea, wheat, potato, and
presence of a plasticizer, a semicrystalline granule waxy maize starch, the Tg was 75 C,143 C, 152 C,
of starch is transformed into a homogeneous mate- and 158 C, respectively. Properties of potato and
rial with hydrogen-bond cleavage between starch wheat and TPS are given in Table 13.8.
molecules, leading to loss of crystallinity. The effect of the type and amount of plasticizer
The physical properties of the TPS are greatly on the mechanical, thermal, and water-absorption
influenced by the amount of plasticizer present. In properties of melt-processed starch was investigated
most literature covering TPS, polyols were usually (Huang et al., 2005). It was reported that, in gen-
used as plasticizers, of which glycerol is the most eral, monohydroxyl alcohols and high-molecular
common. The effect of plastification level on glass weight glycols failed to plasticize starch, whereas
transition of TPS is presented in Table 13.7. shorter glycols were effective.
According to the plasticizer/starch, TPS presents The mechanical properties of starch-based plas-
a large range of properties. A number of studies on tics of native corn, potato, waxy corn, and wheat
the effects of plasticizers on the properties of TPS starch, produced by compression molding of native
have been carried out. Plasticizers used include starch and glycerol in the weight ratio 0
3, were
polyols such as glycerol, glycol, xylitol, sorbitol, strongly dependent on the water content and starch
and sugars, and ethanolamine (Avérous and source (Yang et al., 2006).
Fringant, 2001; Da Roz et al., 2006; De Graaf The mechanical and melt-flow properties of two
et al., 2003; Forsell et al., 1997; Huang et al., 2005; thermoplastic potato starch materials with different
226 PLASTIC FILMS IN FOOD PACKAGING

Table 13.8 Properties of TPSs

Potato TPS (Hulleman et al., Wheat TPS (Avérous,

1998) 2004)a
MFR (g/10 min)
Density (g/cm3) 1.34
1.39
Transparency (%)
Mechanical properties
Tensile strength at yield (MPa) 22 1.4
21.4
Elongation at yield (%) 3 3
104
Tensile modulus (MPa) 1020 11
1144
Thermal properties
Glass transition temperature ( C) (2)20
43
α-transition (DMTA) ( C) 1
63
Properties after equilibrium at 23 C and 50%, 6 weeks; glycerol to starch ratio: 0.135
0.538; water content: 9
13 wt%.
a

amylose contents were evaluated (Da Roz et al., polymers such as starch depend on their water con-
2006). After conditioning at 53% relative humidity tent (Stepto, 2006). If precise dimensions are
(RH) and 23 C, the glycerol-plasticized sheets with required, processing should be carried out so that
a high amylose content (HAP) were stronger and products are formed at approximately the equilib-
stiffer than the normal TPS with an amylose con- rium in-use water content. For potato starch, for
tent typical for common potato starch. The tensile example, this means water contents of around 14%
modulus at 53% RH was about 160 MPa for the for use under ambient conditions (50% RH,
HAP and about 120 MPa for the plasticized native 20
25 C) (Stepto, 2006). If higher water contents
potato starch (NPS). The strain at break was about are used in processing, distortion and shrinkage
50% for both materials. will occur as the equilibrium water content is natu-
rally achieved after processing. In addition, higher
water content can induce more hydrolytic degrada-
Processing
tion of the starch chains during processing and also
Various industrial processing techniques have gelatinization rather than melt formation. If lower
been used to prepare starch plastics, including water contents are used, thermal degradation can
kneading, extrusion, compression molding, and occur during processing, as well as swelling after
injection molding (Van Soest and Kortleve, 1999). processing.
Processing temperatures are in the range of
100
200 C, although care has to be taken at tem-
peratures above 175 C because of starch molecular Applications
breakdown (Van Soest, 1997; Van Soest and The first commercial product made of injection-
Kortleve, 1999; Van Soest and Vliegenthart, 1997). molded TPS was the drug-delivery capsule Capill,
Most research has been focused on water and glyc- and further products are gradually appearing, for
erol as the most important additives. As melt-flow example, golf tees, cutlery, plates, and food con-
accelerators lectin, glycerin monostearate, and cal- tainers (Stepto, 2006). In addition, extrusion has
cium stearate have been studied. Several native been applied to produce rigid foams, suitable for
starches have been processed, such as wheat, rice, loose-fill packaging. Starch can be transformed into
corn, waxy maize starch, high amylose corn starch, a foamed materials using water steam, replacing the
and NPS (Van Soest and Kortleve, 1999). The PS foam as packaging material (Siracusa et al.,
dimensions of molded objects from hydrophilic 2008). Packaging is the dominant application area
13: COMPOSTABLE POLYMER PROPERTIES AND PACKAGING APPLICATIONS 227

for starch-based polymers (PROBIP, 2004). Main commercial applications, plasticizers are used in
application areas include: conjunction with cellulose esters. Triethyl citrate is
usually used for CA and dioctyl adipate for CAP.
• foams (for the loose-fill foam market), Through plasticization of CA by an environmen-
• films (for agriculture, e.g., mulch films), tally friendly triethyl citrate plasticizer, the CAs
are processable at 170
180 C, much below the
• shopping bags, melting point of CA (233 C) (Mohanty et al.,
• moldable products (pots, cutlery, fast-food 2003). Materials processed by extrusion followed
packaging). by injection molding exhibited better properties
compared to those processed by extrusion followed
13.2.4 Other by compression molding, as additional shear
forces applied during injection molding resulted in
Compostable Polymers from a stiffer product. Cellulosic plastics fabricated
Renewable Resources through injection molding at a higher temperature
Cellulose (190 C) exhibited better tensile properties than
their counterparts injected molded at a compara-
Properties
tively lower temperature (180 C) (Mohanty et al.,
Cellulose esters, besides cellulose esters of inor-
2003).
ganic esters and cellulose ethers, were pioneer com-
pounds of cellulose chemistry, and they remain the Applications
most important technical derivatives of cellulose Materials such as metal, plastic, wood, paper,
(Klemm et al., 2005). Unlike commodity plastics and leather are coated with polymers primarily
such as polyolefins, cellulose cannot be processed for protection and for improving their properties.
thermoplastically. However, derivatization, that is, For this purpose, CA, CAP, and CAB are the most
esterification, can yield materials suited for thermo- important classical and solvent-based cellulose
plastic processing. Cellulose esters, such as cellu- esters of the coating industry (Klemm et al., 2005).
lose acetate (CA), cellulose acetate propionate Cellulose esters are widely used in composites and
(CAP), and cellulose acetate butyrate (CAB), are laminates as binder, filler, and laminate layers. In
thermoplastic materials produced through the esteri- combination with natural fibers, they can be used
fication of cellulose (Mohanty et al., 2003). A vari- to some extent as composites from sustainable raw
ety of raw materials such as cotton, recycled paper, materials with good biodegradability. An additional
wood cellulose, and sugarcane are used in making domain of cellulose esters is their use in controlled-
cellulose ester biopolymers in powder form. Such release systems, as well as membranes and other
powders combined with plasticizers and additives separation media (Edgar et al., 2001; Klemm et al.,
are extruded to produce various grades of commer- 2005). In the field of controlled-release systems,
cial cellulosic plastics in pelletized form. Of great cellulose esters are used as enteric coatings, hydro-
interest as potential biodegradable plastics are also phobic matrices, and semipermeable membranes
long-chain aliphatic acid esters of cellulose (Edgar for applications in pharmacy, agriculture, and
et al., 2001; Joly et al., 2005). cosmetics.
Cellulose esters are characterized by their stiffness, CA is widely used in food packaging (baked
moderate heat resistance, high moisture vapor trans- goods and fresh produce; Weber, 2000). CA pos-
mission, grease resistance, clarity and appearance, sesses relatively low gas and moisture barrier prop-
and moderate impact resistance (Edgar et al., 2001). erties and has to be plasticized for film production.
Some properties of commercial cellulose esters Other applications of cellulose esters include:
are given in Table 13.9.
Processing • thin films,
Cellulose esters are easy materials to extrude and • containers,
injection mold (Edgar et al., 2001). Some of their • handles,
innate properties include a relatively narrow win-
dow between the melt-flow temperature and the • optical applications,
decomposition temperature. Therefore, in most • automotive applications,
228 PLASTIC FILMS IN FOOD PACKAGING

Table 13.9 Properties of Cellulose Esters (www.ides.com/)

CAP Albis CAP CP800 (10% CAB Albis CAB B900 (10%
Plasticizer) Plasticizer)
Physical properties
MFR (g/10 min)
Density (g/cm3) 1.21 1.19
Water absorption at 24 h 1.6 1.4
Mechanical properties
Tensile strength at yield 31.7 28.3
(MPa)
Elongation at break (%) 30 30
Flexural modulus (MPa) 1240 1170
Flexural strength (MPa) 41.4 37.2
Thermal properties
HDT ( C)
Vicat softening point ( C) 102 104

GTT ( C)
Melting point ( C)

• toys, 2005; Srinivasa and Tharanathan, 2007; www.ides.

• writing instruments, com/). Chitin and chitosan degrade before melting,
which is typical of polysaccharides with extensive
• electric insulation films, lights, and casings. hydrogen bonding (www.ides.com/).
Chitosan can form transparent films, which may
Chitosan find application in a variety of packaging applica-
Properties tions (Kumar, 2000; www.ides.com/). In 1936,
Chitin and chitosan are examples of highly basic Rigby was granted a patent for making film from
polysaccharides. Chitin is highly hydrophobic and is chitosan and a second patent on making fibers from
insoluble in water and most organic solvents. It is a chitosan (www.ides.com/). The films were
hard, white, inelastic, nitrogenous polysaccharide described as flexible, tough, transparent, and color-
(www.ides.com/). An important parameter, which less with a tensile strength of about 6210 kPa.
influences its physicochemical and biomedical char- Plasticizing agents are essential generally to
acteristics, is the degree of N-acetylation, especially overcome the brittleness of the biopolymeric films.
in chitosan. Converting chitin into chitosan lowers Chitosan films were prepared by blending with
the molecular weight, changes the degree of N-acet- polyols (glycerol, sorbitol, and polyethylene glycol
ylation, and thereby alters the net charge distribu- (PEG)) and fatty acids (stearic and palmitic acids),
tion, which in turn influences the degree of and their mechanical and barrier properties were
agglomeration (Srinivasa and Tharanathan, 2007). studied (Kumar, 2000). The tensile strength of the
The average molecular weight of chitin is blended films decreased with the addition of poly-
1.03
2.5 3 106 Da, but upon N-deacetylation, this ols and fatty acids, whereas the percent elongation
reduces to 1.0
5 3 105 Da. Chitosan is soluble in was increased in polyol blend film, but fatty acid
dilute acids such as acetic acid and formic acid. blend films showed no significant differences.
Chitosan has many useful characteristics such as Glycerol blend film showed a decrease, whereas
hydrophilicity, biocompatibility, biodegradability, sorbitol and PEG blend film showed an increase in
and antibacterial characteristics (Di Martino et al., water vapor permeability values.
13: COMPOSTABLE POLYMER PROPERTIES AND PACKAGING APPLICATIONS 229

The effect on the quality of mango fruits engineering. It is also known as an adsorptive mate-
(Mangifera indica) during modified atmosphere rial, for example, sorbent for heavy metal ions. It
packaging was investigated (Srinivasa et al., 2002). has been used for the production of edible coatings.
The fruits were kept in carton boxes whose top sur- Chitosan films were used in extending the shelf life
face was covered with either chitosan film or with of vegetables (Srinivasa and Tharanathan, 2007).
LDPE (positive control) or kept as such (control)
and stored at room temperature (27 6 1 C at 65%
RH). The CO2 and O2 levels measured on day 3 Proteins
were 23
26% and 3
6%, and at the end of the Properties
storage period they were 19
21% and 5
6%, Until recently, the only uses and applications for
respectively. The fruits stored as such had a shelf proteins were in food sciences (Swain et al., 2004).
life of 9 6 1 days, whereas those stored in LDPE The development of studies on nonfood uses of agri-
showed off-flavor due to fermentation and fungal cultural raw materials initiated an interest in protein-
growth on the stalk and around the fruits, and they based plastics. A number of proteins of plant origin
were partially spoiled. On the other hand, fruits have received attention for the production of biode-
stored in chitosan-covered boxes showed an exten- gradable polymers. These proteins are corn zein,
sion of shelf life of up to 18 days and without any wheat gluten, soy protein, and sunflower protein.
microbial growth or off-flavor. The major drawback of protein-based plastics,
The antimicrobial activity of chitosan and its apart from keratin, is their sensitivity to RH. For
derivatives against different groups of microorgan- example, it was reported that after being submerged
isms such as bacteria, yeast, and fungi are used in water for 20 h, soy protein sheets absorbed up to
in food packaging applications (Honarkar and 180% water (Zheng et al., 2003).
Barikani, 2009). Soy protein plastics are rigid, but tend to be brit-
tle and water sensitive (Mo and Sun, 2003; Zheng
Processing
et al., 2003). The water resistance of soybean
Chitosan possesses an excellent ability to form
protein-based plastics can be improved by chemical
porous structures (Di Martino et al., 2005). It can
modification or blending, for example, with polye-
be molded in various forms as porous membranes,
sters (Mo and Sun, 2003). The flexibility of soy-
blocks, tubes, and beads. Chitosan also readily
bean protein-based plastics can be improved by
forms films and produces material with very high
adding various plasticizers (Mo and Sun, 2003;
gas barrier. Chitosan films are prepared by dissol-
Zheng et al., 2003). It was reported that depending
ving chitosan in dilute acid and spreading on a
on the moisture and glycerol contents, soy protein
leveled surface and air-drying at room temperature
plastic sheets displayed properties from rigid to soft
(Srinivasa and Tharanathan, 2007). Films are also
(Zheng et al., 2003). The glass transition tempera-
prepared by drying at 60 C in an oven by spreading
ture of the sheets varied from approximately 27 C
the solution on plexiglass.
to 50 C with moisture contents ranging from 26%
Applications to 2.8% and 30 parts of glycerol.
Chitosan has prospective applications in many Among proteins, wheat gluten with its unique
fields such as biomedicine, waste water treatment, viscoelastic properties and its water insolubility is
functional membranes, and flocculation (Kurita, of particular interest for the preparation of biode-
2001; Rinaudo, 2006; Srinivasa and Tharanathan, gradable polymer materials. To control the brittle-
2007). Chitosan has been used in the purification of ness of protein-based materials and to lower their
drinking water and in cosmetics and personal care shaping temperature, the addition of plasticizer is
products. They have excellent biological properties generally required (Pommet et al., 2005). Water
such as biodegradation in the human body, biocom- and glycerol are common plasticizers of wheat glu-
patibility, and immunological, antibacterial, and ten. Other compounds including polyols, sugars,
wound-healing activities and also a variety of medi- ethylene glycol and its derivatives, lipids, and
cal uses such as wound dressings, drug delivery, emulsifiers have been tested as gluten plasticizers.
and encapsulation (Kurita, 2001). Chitosan has Various compounds, differing in their chemical
found a potential application as a support material functions, number of functional group and degree
for gene delivery, cell culture, and tissue of hydrophobicity, including water, glycerol,
230 PLASTIC FILMS IN FOOD PACKAGING

1,4-butanediol, lactic and octanoic acids, have been plasticized with glycerol, and wheat gluten materi-
tested as wheat gluten plasticizers in a thermoplas- als plasticized with water are given in Table 13.11
tic process (Pommet et al., 2005). and Table 13.12, respectively.
The glass transition temperature (Tg) of hydro- The influence of a set of hydrophilic plasticizers
phobized and native wheat gluten and its protein varying in their chain length (ethylene glycol and
fractions, with water mass fraction from 0 to 0.2, longer molecules) on the tensile strength and elon-
was studied using modulated differential scanning gation at break of cast gluten films was studied
calorimetry (DSC) (Mo and Sun, 2003). The Tg (Mangavel et al., 2003). Properties of deamidated
values of unplasticized products were approxi- gluten films enzymatically cross-linked were stud-
mately 175 C whatever the treatment (hydrophobi- ied (Larré et al., 2000). The action of transglutami-
zation) or the fraction tested, except for the gliadin- nase with or without the addition of external
rich fraction (162 C) (Micard and Guilbert, 2000). diamines induced a simultaneous increase in tensile
Thermal properties of corn gluten meal and its pro- strength and elongation at break but tended to
teic components were investigated by Di Gioia decrease the contact angle between the film surface
et al. (1999) (Table 13.10). and a water droplet.
Processing and modification routes to produce The effect of various cross-linked or hydropho-
and improve properties of biodegradable plastics bic additives (aldehydes, plant tannins, alcohols,
from soy isolate have been studied (Vaz et al., and fatty acids) on the mechanical properties and
2005). Soy isolate, acid-treated soy, and cross- water resistance of thermomolded films made from
linked soy were subsequently compounded, a sunflower protein isolate plasticized with glycerol
extruded, and injection molded. The obtained plas- have been studied (Larré et al., 2000). The use of
tics were rigid and brittle with stiffness ranging octanoic acid resulted in high tensile strength
from 1436 MPa for soy, to 1229 MPa for glyoxal (7 MPa), whereas the use of octanol resulted in a
cross-linked soy, up to 2698 MPa for heat-treated great increase in tensile elongation (54%). Several
soy. Mechanical properties of soy protein materials polyalcohols (glycerol, ethylene glycol, diethylene

Table 13.10 Glass Transitions Temperatures of Protein Materials (Di Gioia et al., 1999)

Glass Transition Conditions Technique

Material Temperature ( C)
Corn gluten material 176 0% DMTA;
moisture MDSC
Extracted proteic component of corn 164 0% DMTA;
gluten (zein) moisture MDSC
Extracted proteic component of corn 209 0% DMTA;
gluten (glutelin) moisture MDSC

Table 13.11 Mechanical Properties of Soy Protein Sheets (Zhang et al., 2001)

Glycerol Stress at Elongation at Tensile Young’s Toughness

(Parts) Yield Point Yield Point (%) Strength Modulus (MPa)
(MPa) (MPa) (MPa)
10 40.6 2.4 40.6 1226 0.4
20 33.9 7.9 34.0 1119 21.2
30 15.0 8.8 15.6 374 18.8
40 1.6 2.5 9.1 176 13.0
50 1.5 4.3 7.1 144 11.1
13: COMPOSTABLE POLYMER PROPERTIES AND PACKAGING APPLICATIONS 231

Table 13.12 Mechanical Properties of Wheat Gluten Materials Plasticized with Different Amounts of Water
(Zhang et al., 2006)

Water Content Tensile Strength Elongation at Young’s Modulus

Sample (%) (MPa) Break (%) (MPa)
W1 13.8 13.6 19.2 219.3
W2 15.7 7.5 57.4 143.0
W3 18.8 4.9 79.2 104.8
W4 21.2 3.0 91.4 67.5
W5 24.2 2.3 84.3 77.8

glycol, triethylene glycol, and propylene glycol) were and 10% glycerol (w/w relative to the protein
tested as sunflower protein plasticizers (Honarkar and amount) (Vaz et al., 2005). The extrusion was
Barikani, 2009). The additives produced soft, brown, carried out at temperatures ranging from 70 C to
and smooth films with good mechanical properties 80 C (temperature necessary for the splitting of the
(σmax 5 6.2
9.6 MPa; εmax 5 23
140%) with a disulfide bridges and loss of the tertiary structure of
high level of impermeability to water vapor the protein). Glycerol-plasticized wheat gluten
(1.9
9.9 3 1022 g m21 s21 Pa21). However, these sheet was produced by extrusion at the barrel and
films were only moderately resistant to water. die set temperature of 130 C (Hochstetter et al.,
Glycerol and triethylene glycol were proposed as the 2006).
most suitable plasticizers for sunflower proteins.
With a worldwide production estimated at about Applications
33 million metric tons, cottonseed is the most Protein-based plastics have been used, alone or
important source of plant proteins after soybeans in mixtures, to obtain edible films and coatings.
(Orliac et al., 2002). The viscoelastic behavior of They have been used to protect pharmaceuticals
cottonseed protein isolate, plasticized with glycerol, and to improve the shelf life of food products.
was characterized in order to determine the temper- Some commercialization of protein films has been
ature range within which cottonseed protein-based realized in collagen sausage casing, gelatin pharma-
materials can be formed by extrusion or thermo- ceutical capsules, and corn zein protective coatings
molding (Orliac et al., 2002). The results indicated for nutmeats and candies (Irissin-Mangata et al.,
that cottonseed proteins are thermoplastics with a 2001).
Tg ranging from 80 C to 200 C when the glycerol Soybean protein can be used to produce a wide
content varies from 0% to 40% (w/w, dry basis). variety of nonfood products, including plastic films,
building composites, insulating foams, plywood
Processing adhesives, and other wood bonding agents (Kumar
Two important processes are used to make et al., 2002).
protein-based films: a wet process based on disper- The thermoplasticity and good film forming
sion or solubilization of proteins, and a dry process properties of wheat gluten may be used to produce
based on thermoplastic properties of proteins under natural adhesives (Day et al., 2006). Gluten’s adhe-
low water conditions (Rinaudo, 2006). sive properties make it useful in pressure-sensitive
Effects of molding temperature and pressure on medical bandages and adhesive tapes. Gluten has
properties on soy protein polymers were evaluated the ability to provide edible protection for food or
(Mo et al., 1999). The maximum stress of food components against interactions with the envi-
42.9 MPa and maximum strain of 4.61% of the ronment as they can serve as barriers to mass trans-
specimen were obtained when soy protein isolate fer (e.g., oxygen, water vapor, moisture, aroma,
was molded at 150 C. Native soy protein was con- lipids) (Day et al., 2006).
verted into a thermoplastic material in a corotating Some example applications of proteins from var-
twin-screw extruder in the presence of 35% water ious sources are given in Table 13.13.
232 PLASTIC FILMS IN FOOD PACKAGING

Table 13.13 Examples of Proteins Technical Applications (IENICA, 1996
2000)

Protein Technical Application

Soybean protein Paper coatings, plywood adhesives
Maize zein Printing inks, floor coatings, grease-proof paper
Keratin Textiles, cosmetics
Rapeseed meal protein Adhesives, plastics
Wheat gluten Adhesives, coatings, cosmetics

13.3 Biodegradable Polymers and modulus. The influence of polyester composi-

tion on the thermal and mechanical properties of a
from Petrochemical Sources
series of aliphatic homopolyesters and copolyesters
13.3.1 Aliphatic Polyesters and prepared from 1,4-butanediol and dimethyl esters
of succinic and adipic acids was studied by Tserki
Copolyesters et al. (2006a,b). The homopolymer PBS is a highly
Properties crystalline polymer exhibiting a melting point (Tm)
of 114.1 C and heat of fusion (ΔHf) of 68.4 J/g,
Poly(butylene succinate) (PBS) is a commercially
while for poly(ethylene adipate), which is a less
available, aliphatic polyester with many interesting
crystalline polymer, the corresponding values are
properties, including biodegradability, melt pro-
60.5 C and 52.8 J/g, respectively. Copolyesters
cessability, and thermal and chemical resistance
exhibited an intermediate behavior depending on
(Fujimaki, 1998; Sinha Ray and Bousmina, 2005;
their composition. Glass transition temperature Tg
Uesaka et al., 2000). PBS has excellent processability,
decreased with increasing adipate unit content
so can be processed in the field of textiles into melt
from 231.3 C to 260.7 C. The homopolymer PBS
blow, multifilament, monofilament, flat, and split yarn
exhibited the highest tensile strength, which
and also in the field of plastics into injection-molded
decreased with increasing adipate unit content,
products, thus being a promising polymer for various
passed through a minimum at copolyester close to
potential applications (Fujimaki, 1998).
equimolarity and then increased toward the value
Commercial aliphatic polyesters and copolyesters
of poly(ethylene adipate). It was observed that in
under the trade name Bionolle (Showa Highpolymer,
contrast to tensile strength, the elongation at break
Japan) are white crystalline thermoplastics, have
increased for adipate unit content of 20
40 mol%.
melting points ranging from about 90 C to 120 C,
Chain extension reaction resulted in increase of
glass transition temperatures ranging from about
polyester molecular weight leading to increased
245 C to 210 C, and a density of about 1.25 g/cm3.
tensile strength (Tserki et al., 2006). Polyester crys-
The main physical and mechanical properties of
tallinity and melting temperature decreased upon
various Bionolle grades, including 1000 series
chain extension, while glass transition temperature
(PBS), 2000 and 3000 series (poly(butylene succi-
increased.
nate adipate), PBSA), and 6000 series (poly(ethyl-
Crystallization and melting behavior of polye-
ene succinate)) are given in Table 13.14.
sters based on succinic acid and respective aliphatic
The effects of ethyl and n-octyl branches on the
diols, with 2
4 methylene groups were studied by
properties of PBS and poly(ethylene adipate)
(Papageorgiou and Bikiaris, 2005). The equilibrium
(PEAd) were investigated (Jin et al., 2000). Glass
melting points were found to be 114 C, 133.5 C,
transition and melting temperature, crystallinity,
and 58 C for poly(ethylene succinate), PBS, and
melt viscosity, and spherulite growth rate decreased
poly(propylene succinate), respectively. The corre-
with an increase in the degree of chain branching.
sponding values for enthalpy of fusion were 180,
The addition of n-octyl branches improved the
210, and 140 J/g. Poly(propylene succinate) exhib-
elongation and tear strength of PBS considerably
ited the slowest crystallinization rates and lowest
without a noticeable decrease of tensile strength
degree of crystallinity among these polyesters.
13: COMPOSTABLE POLYMER PROPERTIES AND PACKAGING APPLICATIONS 233

Table 13.14 Properties of Typical Grades of Bionolle (Fujimaki, 1998)

PBSU PBSU PBSU PESU LDPE HDPE

Property #1000 #2000 #3000 #6000 F082 5110 PP 210
l90 C
MFR (g/ 1.5 4.0 28 3.5 0.8 11 3.0a
10 min)
Density (g/cm3) 1.26 1.25 1.23 1.32 0.92 0.95 0.90
Melting point 114 104 96 104 110 129 163
( C)
Glass transition 232 239 245 210 2120 2120 25
temperature
( C)
Yield strength 336 270 192 209 100 285 330
(kg/cm2)
Elongation (%) 560 710 807 200 700 300 415
3
Stiffness 10 5.6 4.2 3.3 5.9 1.8 12.0 13.5
(kg/cm3)
Izod impact 30 36 .40 10 .40 4 2
strengthb (Kg-
cm/cm) 20 C
Combustion 5550 5640 5720 4490 .11,000 .11,000 .11,000
heat (cal/g)
MFR was measured at 230 C.
a
b
Izod impact strength was measured with notched samples.

Processing PTT is crystalline, hard, strong, and extremely

tough. The density of PTT is slightly lower than
PBS may be processed using conventional polyole-
PET and similar to PBT. The tensile strength and
fin equipment in the range 160
200 C (Fujimaki,
flexural modulus decrease between PET, PTT, and
1998). Injection, extrusion, or blow molding is
PBT, respectively (Table 13.15). The thermal and
suitable for processing PBS.
relaxation characteristics of PTT are intermediate
to the properties of PET and PBT, and are typical
Applications of those encountered with semiflexible polymers of
Applications include mulch film, cutlery, con- low to medium crystallinity (Kalakkunnath and
tainers, packaging film, bags, and “flushable” Kalika, 2006). The reported equilibrium melting
hygiene products (Fujimaki, 1998). temperature for PTT is approximately 237 C, with
a corresponding 100% crystalline heat of fusion
estimated to be 30 kJ/mol (Pyda et al., 1998).
13.3.2 Aromatic Polyesters and To improve the thermal and mechanical proper-
Copolyesters ties of biodegradable aliphatic polyesters, introduc-
ing aromatic terephthalate units into the main chain
Properties of aliphatic polyesters has been considered to pro-
As an engineering thermoplastic, poly(trimethy- duce aliphatic
aromatic copolyesters with better
lene terephthalate) (PTT) has a very desirable prop- physical properties as well as still having biode-
erty set, combining the rigidity, strength, and heat gradability (Gan et al., 2004).
resistance of PET with the good processability of The solid-state microstructures and thermal prop-
poly(butylene terephthalate) (PBT) (PROBIP, 2004). erties of aliphatic
aromatic copolyesters of poly
234 PLASTIC FILMS IN FOOD PACKAGING

Table 13.15 Properties of PTT (PROBIP, 2004; www.ides.com/)

PTT PTT RTP 4700 PET PBT Celanex 1300 A

(PROBIP, (www.ides.com/) (PROBIP, (www.ides.com/)
2004) 2004)
Physical properties
MFR (g/10 min) 90
3
Density (g/cm ) 1.35 1.33 1.40 1.31
Haze (%) 2
3
Mechanical properties
Tensile strength 67.6 61 72.5 55.2
at yield (MPa)
Elongation at .10%
yield (%)
Tensile modulus 2551
(MPa)
Flexural strength 98 82.7
(MPa)
Flexural modulus 2760 2758 3110 2200
(MPa)
Thermal properties
HDT ( C) 59 65
Vicat softening 265
point ( C)
GTT ( C) 45
75 80 60

Melting point ( C) 225 225

(butylene adipate-co-butylene terephthalate) were melting temperature (approximately 121 C) was

investigated by wide-angle X-ray, solid-state 13C over 100 C lower than that of PBT.
nuclear magnetic resonance, DSC, and atomic force Ecoflex (PBAT), a commercialized alipha-
microscopy (Gan et al., 2004). Both the melting tic
aromatic copolyester from BASF, was character-
temperature and crystallinity of copolyesters ized to be an ideal random copolymer with 44 mol%
showed minimum values at around 25 mol% butyl- of BT units. The glass transition occurs at 230 C, and
ene terephthalate content, which is the transition the melting point is 110
115 C (Mecking, 2004). The
point from PBA crystal structure to PBT crystal physical and mechanical properties of this soft thermo-
structure. It was reported that introducing 40 mol% plastic are similar to those of LDPE, and it can be pro-
or more butylene adipate units could reduce the cessed on conventional equipment for LDPE. Ecoflex
glass transition temperature (Tg) of the copolyesters complies with food safety requirements, is water- and
from 66 C to below 210 C, and reduce the melt- tear-resistant, elastic, printable, and weldable (BASF).
ing temperature Tm from above 200 C to about Properties of Ecoflex are given in Table 13.16.
100 C (Gan et al., 2004). Biodegradable ideal ran-
dom copolymer poly(butylene adipate-co-tere-
phthalate) (PBAT) was melt-spun into fibers with a Processing
take-up velocity up to 5 km/min (Shi et al., 2005). For injection-molding processing of PTT melt
Despite the ideal randomness and composition (1:1) and mold temperatures were suggested to be
of PBAT copolymers, the PBAT fiber showed a between 232
260 C and 88
121 C, respectively
well-developed PBT-like crystal structure, while its (www.ides.com/). PTT can be spun and drawn at
13: COMPOSTABLE POLYMER PROPERTIES AND PACKAGING APPLICATIONS 235

Table 13.16 Properties of Aliphatic
Aromatic Copolyesters (www.ides.com/)

Ecoflexs F a
(www.ides.com/)
Physical properties
Melt volume flow rate (cm3/10 min) 3.5
3
Density (g/cm ) 1.26
Transmittance (%) 82
Mechanical properties
Tensile strength at yield (MPa) 35
44
Tensile strength at break (%) 560
710
Tensile modulus (MPa)
Flexural strength (MPa)
Flexural modulus (MPa)
Shore D hardness 332
Thermal properties
HDT ( C)
Vicat softening point ( C) 80

GTT ( C)
Melting point ( C) 112
b
Barrier properties
Permeation rate: oxygen (ml/(m2 d bar)) 1400
2
Permeation rate: water vapor (g/(m d)) 170
a
A copolyester mainly based on 1,4-butanediol, adipic acid, and terephthalic acid.
b
Ecoflex F BX 7011 (BASF).

high speeds, resulting in a fiber suitable for applica- PTT may be used to produce fibers for carpets
tions such as sportswear, active wear, and other spe- and industrial textiles where it has good resilience
cialty textiles (PROBIP, 2004). PTT has been melt- and the wearability of nylon, combined with the
spun at various take-up velocities from 0.5 to 8 km/ dyeability, static resistance, and chemical resistance
min to prepare fiber samples (Wu et al., 2002). The of PET (PROBIP, 2004). As a spunbond fiber for
effect of take-up velocity on the structure and prop- apparel, its property set includes good stretch
erties of as-spun fibers has been characterized recovery, softness, and dyeability.
through measurements of fiber fringence, density, Main applications include:
wide-angle X-ray scattering, DSC melting behavior,
tensile properties, and boiling water shrinkage. • Fibers (textile, carpet, apparel),
The processing temperature of Ecoflex copolymer • Packaging (films).
is 140
170 C (melt temperature) (www.ides.com/).
According to the manufacturer (BASF), Ecoflex
Applications has been developed for the flexible films sector.
PTT is an opaque rigid thermoplastic useful for Typical applications include agricultural films, carrier
many structural applications, for example, in carpet, bags, and compost bags. The material is marketed as
textile, film and packing, and other engineering a compostable packaging film, as a hydrophobic pro-
thermoplastic markets, where rigidity, strength, and tective coating for food containers, and as a blend
toughness are required (Shafee, 2003). component (Mecking, 2004). Ecoflex is suitable for
236 PLASTIC FILMS IN FOOD PACKAGING

food packaging as a protective film or as component makes PCL a promising candidate for biomedical
of laminated paper (BASF). Example of application applications, such as controlled drug delivery
include: wrapping paper, drink cartons, fast-food (Edlund and Albertsson, 2002). PCL is used mainly
packaging, and drink cups. Copolyesters with a higher in thermoplastic polyurethanes, resins for surface
terephthalic acid unit have been reported to be suited coatings, adhesives, and synthetic leather and fabrics
for fiber applications. (Funabashi et al., 2007). It also serves to make stif-
feners for shoes and orthopedic splints, and fully
13.3.3 Poly(caprolactone) biodegradable bags, sutures, and fibers (Funabashi
et al., 2007). PCL is often mixed with starch to
Properties obtain a good, biodegradable, low-cost material.
Polycaprolactone (PCL) was developed as a bio- The main applications of PCL comprise (Solvay):
degradable plastic of aliphatic polyester type derived
from the chemical synthesis of crude petroleum • biodegradable bottles,
(Funabashi et al., 2007). It has a low-melting point • biodegradable films,
(approximately 60 C), low melt viscosity, and is • controlled release of drugs, pesticides, and
easy to process (Funabashi et al., 2007). PCL has fertilizers,
good water, oil, and chlorine resistance.
The PCL chain is flexible and exhibits high elon- • polymer processing,
gation at break and low modulus. The elongation at • adhesives,
break and tensile strength of PCL films have been • nonwoven fabrics,
reported to be between 450% and 1100% and 25
and 33 MPa, respectively (Koening and Huang, • synthetic wound dressings,
1995; Matzinos et al., 2002). These values are quite • orthopedic casts.
high as compared with the elongation at break,
500
725%, and tensile strength, 9.7
17.2 MPa, of
LDPE (Matzinos et al., 2002). The main drawback 13.3.4 Poly(esteramide)s
of PCL is its low melting point, which can be over-
come by blending it with other polymers or by radi-
Properties
ation cross-linking processes, which result in Poly(esteramide)s (PEA) constitute a new series
enhanced properties suitable for a wide range of of thermoplastic polymers that can combine high
applications (Sinha Ray and Bousmina, 2005). technical performance with good biodegradability
Properties of commercially available CAPA and (Botines et al., 2002; Ferré et al., 2003; Grigat
Tone PCLs are given in Tables 13.17 and 13.18 et al., 1998; Lips et al., 2005; Lozano et al., 2004).
(Solvay; Union Carbide). BAK 1095 is an example of a poly(esteramide)
commercialized by Bayer but its production
Processing stopped in 2001. This is a statistical polymer with
an amide/ester ratio of 6/4 based on 1,4-butanediol,
PCL can be processed by the usual thermoplastic
adipic acid and 1,6 aminohexanoic acid. BAK poly
processing techniques, including blow and slot cast
(esteramide)s differing in the amide/ester ratio have
film extrusion, sheet extrusion, and injection mold-
been synthesized and characterized (Ferré et al.,
ing. The low melting point of PCL polymers
2003). Spectroscopic analyses of BAK poly(estera-
requires lower temperatures than polyethylene and
mide)s with 50/50, 60/40, and 70/30 amide/ester
other polyolefins.
ratios showed a random distribution of monomers,
According to the manufacturer’s information, the
which was in agreement with their low crystallinity
extrusion parameters for PCLs are: 70
120 C (CAPA
(12
14%). BAK polymers showed a decrease in
6500) and 130
165 C (CAPA 6800) (Solvay).
the melting and glass transition temperatures when
the ester/amide ratio was increased. In the same
Applications way, Young’s modulus decreased (Table 13.19).
PCL is recognized as a biodegradable and non- The influence of substituting adipic acid by
toxic material. Its high permeability to low molecu- terephthalic acid units on the thermal and mechanical
lar species at body temperature and biocompatibility properties of poly(esteramide)s has been investigated
13: COMPOSTABLE POLYMER PROPERTIES AND PACKAGING APPLICATIONS 237

Table 13.17 Properties of CAPA PCLs (Avérous et al., 2000b)

Property CAPA 6500 CAPA 6800

Molecular weight (Mn) 4750 6 2000 69,000 6 1500

Melting point ( C) 60
62 60
62
Heat of fusion (J/g) 76.9 76.6
Crystallinity (%) 56 56

Crystallization temperature ( C) 25.2 27.4

Glass transition ( C) 260 260

MFR (g/10 min) (190 C/2.16 kg) 28 7.29
Tensile yield stress (MPa) 17.2 14
Tensile modulus (MPa) 430 500
Strain at break (%) .700 920
Flexural modulus (MPa) 411 nd
Hardness (Shore D) 51 50

Viscosity (Pa  s) (70 C, 10.1/s) 2890 12,650

Viscosity (Pa  s) (100 C, 10.1/s) 1353 5780

Viscosity (Pa  s) (150 C, 10.1/s) 443 1925

Table 13.18 Properties of Tone PCLs (Wang et al., 2003)

Property P-767 P-787

3
Density (g/cm ) 1.145 1.145

MFR (g/10 min) (190 C) 30 4
Tensile strength (MPa) 21.3 39.7
Tensile modulus (MPa) 435 386
Ultimate elongation (%) 600
800 750
900
Flexural modulus (MPa) 575 514
Flexural stress at 5% strain (MPa) 23.4 21.0
Izod impact (J/m) (notched) 82 350
Izod impact (J/m) (unnotched) No break No break
Water absorption 0.3508 0.3295
Hardness (Shore D) 55 55

(Lozano et al., 2004). A regular increase in glass preformed bisamide-diol, 1,4-butanediol, and
transition and melting temperatures with the aro- dimethyl adipate (Lips et al., 2005). The polymers
matic content was observed. Moreover, the mechani- had a low and a high melt transition, corresponding
cal properties showed an increase in chain stiffness with the melting of crystals comprising single ester-
with the aromatic content. amide sequences and two or more esteramide
High molecular weight segmented poly(estera- sequences, respectively. The low melt transition is
mide)s comprising different ester to amide ratios between 58 C and 70 C and is independent of poly-
have been prepared by melt polycondensation of a mer composition. By increasing the hard segment
238 PLASTIC FILMS IN FOOD PACKAGING

content from 10 to 85 mol%, the high melt transi- antielectrostatic properties, chemical resistance, and
tion increased from 83 C to 140 C while the glass toughness (Gohil et al., 2006). It has also good gas
transition temperature increased from 245 C to barrier properties and good printability. The final
25 C. Likewise, the elastic modulus increased properties of PVA depend on the properties of its
from 70 to 524 MPa, the stress at break increased parent polymer, that is, poly(vinyl acetate), its poly-
from 8 to 28 MPa, while the strain at break merization conditions, and degree of hydrolysis.
decreased from 820% to 370%. Basic properties of PVA and PVA-based systems
also depend upon the degree of polymerization, dis-
Processing tribution of hydroxyl groups, stereoregularity, and
crystallinity (Chiellini et al., 1999). For example,
The processing conditions of BAK poly(estera- the degrees of hydrolysis and polymerization affect
mide) are similar to those of polyolefins (Grigat the solubility of PVA in water (Hassan and Peppas,
et al., 1998). BAK 1095 resin can be processed into 2000). PVA grades with high degrees of hydrolysis
film and also into extruded or blow-molded parts have low solubility in water. The presence of ace-
on conventional machinery used for processing tate groups affects the ability of PVA to crystallize
thermoplastics. Processing conditions are given in upon heat treatment (Hassan and Peppas, 2000).
Table 13.20. PVA grades containing high degrees of hydrolysis
are more difficult to crystallize.
Applications Commercial PVA grades are available with vari-
Potential applications for BAK 1095 resin include ous degrees of hydrolysis and polymerization.
uses in the horticulture, agriculture, and food sec-
tors. Specific examples are biowaste bags, agricul- Processing
tural films, plant pots, plant clips, cemetery Two technologies are used for PVA film produc-
decoration, and one-way dishes (Grigat et al., 1998). tion—casting from viscous water solution or blown
extrusion from melt. Plastic items based on PVA
13.3.5 Poly(vinyl alcohol) film are mainly obtained using casting techniques
(Chiellini et al., 2003). However, due to interest in
Properties biodegradable PVA-based film, melt-processing
Poly(vinyl alcohol) (PVA) is a water-soluble technology has been developed. The main difficulty
polymer based on petroleum resources with inter- in PVA thermal extrusion processing is the close
esting properties such as good transparency, luster, proximity of its melting point and decomposition

Table 13.19 Properties of PEAs (Ratto et al., 1999; Wang et al., 2001)

BAK 70/30
BAK 1095 (Wang BAK 70/30 (Ratto BAK 60/40 (Ratto (Ratto et al.,
Property et al., 2001) et al., 1999) et al., 1999) 1999)
Density (g/
cm3)
MFR (g/
10 min)
(190 C)
Tensile 27 29 27 11
strength
(MPa)
Tensile 250 285 250 128
modulus
(MPa)
Elongation at 570 432 570 24
break (%)
13: COMPOSTABLE POLYMER PROPERTIES AND PACKAGING APPLICATIONS 239

temperature (Chiellini et al., 2003). The thermal • Binders for pigmented paper coatings, ceramic
degradation of PVA usually starts at about 150 C materials, and nonwoven fabrics.
or above, depending upon the PVA grade (degree
of hydrolysis and pH). In order to improve the ther-
mal stability and processing properties of PVA, the 13.4 Blends
use of plasticizers is required. Various plasticizers In order to obtain compostable polymer materials
such as water, glycerol, ethylene glycol, and its with the best compromise between mechanical and
dimer and trimer, amine alcohols, and polyvalent processing properties and cost, as well as compost-
hydroxyl compounds have been applied. ability, various blends of biodegradable polymers
have been studied. For example, blends such as
PLA/PHA, and PLA/starch have improved perfor-
Applications mance with respect to degradation rate, permeabil-
PVA is largely used as fiber, film, in the paper ity characteristics, and thermal and mechanical
industry, in textile sizing, as a modifier of thermo- properties. Overall processability is thus improved
setting resins, in plywood manufacture, as pressure- and the range of possible applications for PLA is
sensitive adhesives, and as an emulsifier (Chiellini broadened. Blends of PLA and natural fibers have
et al., 1999; Gohil et al., 2006). It is mainly used as increased durability and heat resistance and resulted
a sizing agent or stabilizer of dispersion systems. In in a lower cost to weight ratio compared to
particular, the four major segments of PVA con- unblended PLA (PROBIP, 2004).
sumption comprise warp sizing, paper coating, All possible systems, including blends of polymers
coatings, and films (Chiellini et al., 1999). based on renewable and petrochemical resources
PVA applications include textile-sizing agents, have been developed. However, most attention is
paper processing agents, emulsification dispersants, given to starch-based blends (Avérous, 2004;
films and general industrial use, in particular: Avérous et al., 2000b; Bastioli, 1998; Wang et al.,
2003). Starch is one of the most inexpensive and
• Textile sizing and finishing, most readily available of compostable polymers. The
• Laminating adhesives, renewability of starch is another of its advantages.
The major drawback of TPS is its sensitivity to water
• Size in paper and paperboard manufacture, and poor mechanical properties. TPS is a hydrophilic
• Water-soluble films for packaging and release material. To overcome moisture sensitivity and
applications, changes in mechanical properties of TPS in relation
• Protective colloid in emulsion polymerization to the crystallinity and the contents of plasticizer and
processes, water, during aging, blending TPS with other biopo-
lymers has been commonly performed (Avérous
• Photosensitive coatings, et al., 2000b). Associations between TPS and other
• Binders for building products such as ceramics, biopolymers include aliphatic polyesters such as
ceiling tiles, floor coatings, and paper board, PCL, PLA, PHBV, and polyesteramide (PEA). Some

Table 13.20 Processing Conditions for BAK (Wang et al., 2001)

BAK 2195 BAK 1095


Melting point 175 C 125 C
Mass temperature 180
200 C 140
220 C
Mold temperature 50 C 30
40 C
Deforming Good Reasonable
Fogging No No
Corrosion No No

Drying conditions 2 h at 70 C 2 h at 90 C
240 PLASTIC FILMS IN FOOD PACKAGING

starch-based blends have been commercialized such compatibilizer containing an anhydride functional
as Mater-Bi (Novamont) or Bioplast (Biotec). group incorporated into the polyester backbone was
The properties of commercially available starch- used. The addition of a small amount of compatibi-
based blends are summarized in Table 13.21. lizer increased the strength significantly over the
Different compositions of wheat TPS and PCL uncompatibilized blend. For the compatibilized
were melt blended by extrusion and injected blend, the tensile strength was invariant with starch
(Avérous et al., 2000b). It was noticed that the content when compared to the original polyester,
addition of PCL to the TPS matrix allowed the while it decreased with increase in starch content
weakness of pure TPS to be overcome: low resil- for the uncompatibilized blend.
ience, high moisture sensitivity, and high shrinkage, The interfacial interaction between PLA and
even at low PCL concentrations, for example, starch was improved, and mechanical properties
10 wt%. However, a fairly low compatibility of PLA blends with starch were enhanced by add-
between both polymeric systems was reported. For ing methylene diisocyanate (Wang et al., 2001,
PCL-based blends, the resulting mechanical proper- 2003).
ties depend both on plasticization level and PCL Blending TPS with other biodegradable polye-
content (Table 13.22). sters such as PEA could be an interesting way to
PCL, due to its low melting point (B65 C), is produce new biodegradable starch-based materials
difficult to process by the conventional techniques (Avérous et al., 2000a). A range of blends was
used for thermoplastic materials. Blending of starch studied with glycerol (plasticizer)/starch contents
with PCL improves its processability and further- ratios varying from 0.14 to 0.54 (Avérous et al.,
more promotes its biodegradation. Poly(ε-caprolac- 2000a). BAK PEA concentrations were up to 40 wt
tone)/plasticized starch blends varying in starch %, TPS remaining as the major phase in the blend.
content were processed by conventional extrusion, It was reported that the addition of BAK to the
injection molding, and film blowing techniques TPS matrix allowed the weaknesses of pure TPS to
(Matzinos et al., 2002). Blending plasticized starch be overcome: low mechanical properties, high
with PCL increased the modulus and decreased the moisture sensitivity, and high shrinkage in injec-
other mechanical properties (i.e., strength and elon- tion, even at 10 wt% BAK. The tensile yield prop-
gation at yield and break) of both injection-molded erties of PEA blended with granular corn starch or
specimens and films. potato starch over a range of strain rates were
The processability, mechanical and thermal prop- investigated (Willett and Felker, 2005). Yield stress
erties, and biodegradability of PBSA/starch films increased relative to unfilled PEA with starch vol-
containing up to 30 wt% corn starch were studied ume fraction and stress rate when corn starch was
(Ratto et al., 1999). Increasing the starch content the filler. When potato starch was used, the yield
led to an increase in modulus and decrease in ten- stress decreased with starch volume fraction at low
sile strength, elongation to break and toughness. strain rates, and increased at high strain rates.
Mechanical properties of TPS blended with poly
(hydroxy butyrate) (PHB) confer higher perfor-
Applications
mance than those of pristine TPS (Lai et al., 2006).
In particular, a significant increase in tensile Commercially available starch-based blends
strength and tear strength is observed for TPS (Novamont Mater-Bi) depending on the grade are
(potato starch) blended with PHB at low- used in the following areas (Bastioli, 1998):
gelatinization degree. For example, for TPS
Mater-Bi Z Class
blended with 7% PHB, the tear strength reaches
44.1 kJ/m2, a 12-fold increase over unfilled TPS at Mainly for films and sheets.
25% glycerol content. Technology: film blowing (ZF03U/A).
The properties of blends of starch and aliphatic Use: bags, nets, paper lamination, mulch films,
biodegradable polyesters, including poly(ε-capro- twines, wrapping film.
lactone), PBS, and a butanediol-adipate-
terephthalate copolymer were studied (Mani and Mater-Bi Y Class
Bhattacharya, 2001). To improve the compatibility For rigid and dimensionally stable injection
between the starch and the synthetic polyester, a molded items.
13: COMPOSTABLE POLYMER PROPERTIES AND PACKAGING APPLICATIONS 241

Table 13.21 Properties of Commercially Available Starch-Based Blends (Grevellec et al., 2001; PROBIP, 2004)

Starch
( . 85%)/ Starch/PCL Starch/CA Starch/CA Modified
Copolyester Mater-Bi Mater-Bi Bioplast Starch
Mater-Bi ZF03U/A Y1010U GF105/30 Cornpol
NF01U (PROBIP, (Grevellec (PROBIP, (PROBIP,
(PROBIP, 2004) 2004) et al., 2001) 2004) 2004)
Physical properties
MFR (g/ 2
8 10
15 5
9 5
6
10 min)
Density (g/ 1.3 1.23 1.35 1.21 1.2
cm3)
Transparency
(%)
Mechanical properties
Tensile 25 31 25
30 44,38 30
strength at
yield (MPa)
Elongation at 600 900 2
6 400, 500 600
900
yield (%)
Tensile 120 180 2100
2500 10
30
modulus
(MPa)
Thermal properties
HDT ( C) 85
105
Vicat 65 105
125
softening
point ( C)
GTT ( C)
Melting point 110 64
( C)
Samples aged 2 weeks at 23 C and 50% RH.

Technology: injection molding. In general, the main applications of starch-based

Use: cutlery, boxes, flowers pots, seedling plant materials include (PROBIP, 2004):
trays, golf tees, vending cups, and pens.
• Packaging: leaf collection compost bags,
Mater-Bi V Class packaging films, shopping bags, strings,
For rigid and expanded items. straws, tableware, tapes, technical films, trays,
and wrap film.
Technology: foaming.
• Agricultural sector: mulch film, planters,
Use: loose fillers and packaging foams as a
planting pots, encapsulation and slow release
replacement for PS.
of active agents such as agrochemicals.
Technology: injection molding.
• Transportation: fillers in tires.
Use: soluble cotton swabs, soluble items.
242 PLASTIC FILMS IN FOOD PACKAGING

Table 13.22 Mechanical Properties of TPS/PCL Blends (Srinivasa et al., 2007)

PCL TPS Formula Modulus Maximum Elongation Impact

(wt (Components in (Mpa) Tensile Strength at Break (%) Strength
%) wt%) (Mpa) (kJ/m2)
100 190 14.2 .550 No break
0 Starch 74/glycerol 997 21.4 3.8 0.63
10/water 16
25 Starch 74/glycerol 747 10.5 2.0 1.57
10/water 16
40 Starch 74/glycerol 585 9.0 2.4 2.99
10/water 16
0 Starch 70/glycerol 52 3.3 126.0 No break
18/water 12
25 Starch 70/glycerol 93 5.9 62.6 No break
18/water 12
0 Starch 67/glycerol 26 2.6 110.0 No break
24/water 9
25 Starch 67/glycerol 80 5.3 42.2 No break
24/water 9
0 Starch 65/glycerol 2 0.61 90.7 No break
35
10 Starch 65/glycerol 8 1.05 61.9 No break
35
25 Starch 65/glycerol 36 2.87 43.1 No break
35
40 Starch 65/glycerol 71 5.19 50.4 No break
35

• Miscellaneous: nappy back sheets, soluble packaging of batteries with removable printed
cotton swabs, soluble loose fillers, cups, cut- film on back side, trays and bowls for fast-
lery, edge protectors, golf tees, mantling for food, envelopes with transparent window,
candles and nets. paper bags for bread with transparent window
• Agriculture and horticulture: mulching films,
13.5 Summary tomato clips
• Short-life consumer goods: hygiene products
Physical and mechanical properties of the main
such as nappies, cotton swabs, stationary, and
compostable polymers are summarized in
prepaid cards.
Tables 13.23 and 13.24.
Applications of compostable polymer materials • Long-life consumer goods: apparel, for exam-
which have been commercialized or are in the devel- ple, T-shirts, socks, blankets, mattresses, cas-
opment/demonstration stage include (Bastioli, 1998): ings for Walkmans, CDs (compact disks),
computer keys, small components of laptop
• Packaging: films and trays for biscuits, fruit, housing, spare wheel covers, automobile inter-
vegetables and meat, yoghurt cup, nets for iors including head liners and upholstery and
fruit, grocery bags, rigid transparent possibly for trimmings.
13: COMPOSTABLE POLYMER PROPERTIES AND PACKAGING APPLICATIONS 243

Table 13.23 Summary of Properties of Compostable Polymer Materials Derived from Renewable Resources
(Van de Velde and Kiekens, 2002)

Property PLA L-PLA DL-PLA PHB

3
Density (g/cm ) 1.21
1.25 1.24
1.30 1.25
1.27 1.18
1.262
Glass transition ( C) 45
60 55
65 50
60 5
15

Melting temperature ( C) 150
162 170
200 Amorphous 168
182
Tensile strength (MPa) 21
60 15.5
150 27.6
50 40
Tensile modulus (GPa) 0.35
3.5 2.7
1.14 1
3.45 3.5
4
Ultimate tensile strain (%) 2.5
6 3
10 2
10 5
8

Table 13.24 Summary of Properties of Compostable Polymer Materials Derived from Petrochemical
Resources (Averous and Fringant, 2001)

Property PCL PEA PBSA PBAT

3
Density (g/cm ) 1.11 1.05 1.23 1.21
Glass transition ( C) 260 230 245 230
Melting temperature ( C) 60
62 125 92
94 110
115
Tensile strength (Mpa) 20.7
42
Tensile modulus (Gpa) 0.21
0.44
Ultimate tensile strain (%) 300
1000

13.5.1 Major Markets of 245 million kilograms (541 million pounds) in 2007
(Plastics Additives, 2008). This was expected to
Compostable Polymer Materials
increase to over 545 million kilograms (1203 million
• Agricultural and fishery (mulch films, pots for pounds) by 2012, a compound average annual
transplanting, fishing lines and nets), growth rate of 17.3%. This report breaks the market
• Civil engineering and construction (sand bags, down into applications of compost bags, loose-fill
flora sheets, curing sheets), packaging, and other packaging, including medical/
hygiene products, agricultural and paper coatings,
• Leisure goods (golf tees, marine sports, and
and miscellaneous. Of these, compost bags have the
mountain climbing),
largest share of the market. At nearly 110 million
• Food packaging (trays for perishable food, kilograms (242 million pounds) in 2007, this seg-
fast-food containers), ment was expected to reach 266 million kilograms
• Packaging (kitchen garbage, composting bags, (586 million pounds) by 2012. Loose-filled packag-
bin liner bags, shopping bags), ing has the second largest share of the market.
• Textile goods (clothes, mats), At an estimated 73 million kilograms (162 million
pounds) in 2007, this segment was expected to reach
• Daily use (pen cases, disposal shavers), 97 million kilograms (214 million pounds) by 2012.
• Electronic (electronic equipment cases),
• Automotive industry (car parts). References
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 14 Waste Management for Polymers in Food
Packaging Industries
Ioannis S. Arvanitoyannis
University of Thessaly, Department of Agriculture Crop Production and Rural Environment Nea Ionia, Magnesia, Greece

14.1 Biodegradable Synthetic 14.1.1 Novel Biodegradable

Copolymers and Composites Copolyamides Based on Diacids,
The continuously increasing extent of pollution of
Diamines, and α-Amino Acids
the environment has recently given rise to demands The novel copolyamides, based on adipic acid
for novel biodegradable polymers, mainly for appli- (AA), 1.6-hexane diamine (1.6-HD), isophorone
cations related to food packaging and agriculture diamine (IPD), bis(para-aminocyclohexyl)-methane
(Huang, 1985; Kumar, 1987; Schnabel, 1981). The (PACM-20), and various α-amino acids (L-tyrosine,
main emphasis was initially focused on the synthesis proline, alanine, glycine, glutamic acid), were syn-
of novel aliphatic polyesters (Chiellini and Solaro, thesized by a two-stage melt polycondensation
1992; Schnabel, 1981; Vert et al., 1992) due to their (100 C and 250 C for 1 and 2 h, respectively). The
higher susceptibility to biodegradation with regard to semicrystalline and, occasionally, amorphous nature
other polymers such as polyamides (PAs) and poly- of the copolyamides based on the salt of 1.6-
anhydrides (Satyanarayana and Chaterji, 1993; HD/AA (1:1 mol/mol)/α-amino acids was shown
Zhang et al., 1993). Among the aliphatic polyesters, by wide-angle X-ray diffraction (WAXD). Several
poly(ε-caprolactone) (PCL) (Tokiwa et al., 1983, biodegradability experiments (burial in soil, alkali
1988), poly(β-methyl-δ-valerolactone) (Nakayama and enzymatic hydrolysis) were carried out to test
et al., 1993, 1995a,b), polylactide (Kim et al., 1992, the susceptibility of these polymers to degradation.
1993; Satyanarayana and Chaterji, 1993; Vert et al., The physical properties of the copolymers were
1992), and their copolymers (Den Dunnen et al., investigated before and after biodegradability test-
1993; Gaymans and de Haan, 1993; Shiaw et al., ing. The observed gradual increase in Xc of the
1994) have been suggested as the most promising in NaOH-insoluble fraction of the copolyamides was
terms of potential applications. The low glass transi- proportional to their exposure to alkali hydrolysis.
tions and low melting points of most polyesters have It is thought that the initial gradual dissolution of
oriented several researchers toward exploring other the amorphous parts results in higher crystallinity
potential avenues, such as the direct polymerization values, similar to what has been reported for the early
of α-amino acids (Kiyotsukuri et al., 1992; Wu, stages of in vivo and in vitro degradation of poly-(L-
1992; Yang et al., 1993) or copolymerization of lac- lactide) (PLLC poly(L-lactide-co-caprolactone)), poly-
tams with lactones (Goodman, 1984; Goodman and glycolide (Chu, 1981), and PCL (Pitt et al., 1981).
Vachon, 1984a,b,c; Goodman and Valavanidis, The degradation process of biodegradable polymers
1984) in an attempt to synthesize novel polymers occurs in two steps. In the first stage, chain scission
with higher thermal resistance. The biodegradability occurs preferentially in the amorphous regions of
tests conducted on the copolyesteramides were highly the semicrystalline polymer. The initial random
promising and favored potential applications (Huang, chain scissions result in a decrease of the degree of
1985; Kumar, 1987). However, the difficulties entanglement, thus facilitating and even consider-
encountered in producing high molar mass and ably promoting the mobility of nondegradable chain
environmentally degradable copolyamides have been segments in these regions. This mobility promotes
restrictive factors, in terms of applications, for the crystallization, as reflected by the high Xc values.
copolyamides (Bera and Jedlinski, 1993; Chen et al., However, following the dissolution of the amorphous
1993; Yang et al., 1993). regions, the degradation proceeds to the crystalline

Ebnesajjad: Plastic Films in Food Packaging. DOI: http://dx.doi.org/10.1016/B978-1-4557-3112-1.00014-4

© 2013 Elsevier Inc. All rights reserved. Adapted from a chapter in: Arvanitoyannis, Waste Management for the Food Industries (2008). 249
250 PLASTIC FILMS IN FOOD PACKAGING

regions. A substantial decrease in the molar masses and susceptibility to degradation (Arvanitoyannis
of the copolymers was recorded when the copoly- et al., 1994a,b,c,d, 1995a,b,c,d,e,f,g; Goodman and
mers were exposed to NaOH (10% wt/vol NaOH, Sheahan, 1990a,b). Synthesis of copolyesteramides
80 C) (Arvanitoyannis et al., 1993, 1994a,b,c,d, has been carried out in a three-stage process: 1.6-
1995a,b,c,d,e,f,g). The effect of alkali hydrolysis HD was mixed with a diacid (AA, sebacic acid
was very pronounced for the copolymers rich in (SA), or octadecanedioic acid (ODA)) and ε-capro-
α-amino acids because they underwent a significant lactone (ε-CL) and was kept at 120 C, 180 C, and
reduction in the molar mass of polymeric chains, 250 C for 2 h, 2 h, and 0.5 h, respectively
thus resulting in number average molecular weights (Arvanitoyannis et al., 1994a,b,c,d, 1995a,b,c,d,e,f,
Mn as low as 2100. The tensile strength (TS) and g). Although the melting points Tm versus ε-CL con-
tensile modulus of copolyamides were shown to tent showed eutectic curves (minimum at 20/20/60
undergo a sharp decrease after the copolymer sam- for SA, ODA, or AA/1.6-HD/ε-CL), similar to other
ples were treated with alkali solutions for more copolymers (Kehayoglou and Arvanitoyannis,
than 20 h. In fact, a linear dependence of TS on the 1990), the melting points versus the ε-CL content
Mn with regard to the exposure time of alkali were found to give straight lines (Arvanitoyannis
hydrolysis was established. The molar mass of et al., 1994a,b,c,d, 1995a,b,c,d,e,f,g). The substantial
copolyamides was not substantially affected when difference in the heat of fusion between the ester-
the copolyamides were buried in soil. Overall, when rich and the amide-rich copolymers possibly could
the content of α-amino acids was higher than 15%, be attributed to the incompatibility of crystal struc-
they turned from semicrystalline to amorphous tures (monoclinic or triclinic for PAs in contrast to
according to DTA (differential thermal analysis) and the orthorombic for PCL) (Arvanitoyannis et al.,
WAXD measurements. The potential degradability 1994a,b,c,d). An increase in ε-CL content resulted
of the synthesized copolyamides was confirmed by in broadening of peaks and in decreases in the Tm
various biodegradability experiments, such as alkali and Tg values due to the higher flexibility of the
hydrolysis, microbial-bacterial attack (burial in soil), polymeric chain imparted by the incorporation of
and enzymatic hydrolysis. It is envisaged that these ε-CL. The total organic carbon (TOC) measure-
copolyamides may find various applications because ments indicated that only the ester-rich copolyester-
of their enhanced susceptibility to biodegradation. amides ( . 50% ester content) could be considered
biodegradable because the TOC values for the
amide-rich copolyesteramides were very low
14.1.2 Novel Biodegradable (Arvanitoyannis et al., 1994a,b,c,d, 1995a,b,c,d,e,f,
Copolyesteramides from g). It was also found that the weight loss percentages
ε-Caprolactone and Various PA of the copolyesteramides after their immersion in
alkali solution increased with an increase in ε-CL
Salts content. The weight loss rate was greatly enhanced
The biodegradation of synthetic polymers is of after the first 10 h, reaching up to about 50% (after
considerable interest to environmentalists, industri- 30-h exposure) and was accompanied by a substan-
alists, and academic researchers as well (Chen tial decrease in Mn, as determined by GPC (gel per-
et al., 1993). Aliphatic polyesters have been long meation chromatography). Enzymatic hydrolysis
considered as the most promising polymers for was also conducted in order to study the degradation
applications in which biodegradability is a prerequi- products. Nuclear magnetic resonance (NMR) anal-
site (Kim et al., 1992, 1993; Satyanarayana and ysis of the degradation products showed that cleav-
Chaterji, 1993; Vert et al., 1992). However, syn- age primarily occurs at ε-CL
ε-CL labile bonds in
thetic poly(amino acids) and PAs, though regarded the polymer backbone, whereas the amide bonds
as the analogs of proteins and natural peptides, (OQCaNHa) are characterized by low suscepti-
have not yet found the extent of expected applica- bility to degradation. The thermal properties (Tg,
tion, mainly because of preparation difficulties Tm) showed a linear decrease against the CL content,
(Huang, 1985; Yang et al., 1993). The aliphatic while the TOC increased considerably. Enzymatic
copolyesteramides recently have been suggested and alkali hydrolysis, as well as burial in soil experi-
and partially investigated as a polymer family with ments, all showed that an increase in CL content
much potential concerning functional performance reflected an increase in the susceptibility of
14: WASTE MANAGEMENT FOR POLYMERS IN FOOD PACKAGING INDUSTRIES 251

copolyesteramides to biodegradation. Chen and his because they can combine high-molecular weight
colleagues’ (2012) study presented the successful with lower melt viscosities than the linear PLLA
synthesis of amphiphilic mPEG-b-PCL-based (N- (Aragade and Peppas, 1993; Gijpa and Pennings,
phthaloylchitosan-grafted poly (ethylene glycol) 1994a,b). The polymerization of L-lactide (LLA)
methyl ether) block copolymers bearing benzyloxy with polyol (i.e., pentaerythritol, glycerol, or sorbi-
and hydroxyl side groups on the PCL block by ring- tol) was carried out in the presence of two catalysts
opening polymerization of 4-benzyloxy-ε-caprolac- (stannous octoate (Sn(Oct)2) and tetraphenyl tin
tone (4-BOCL) and ε-CL with methoxy PEG (TPhT)) at 130 C for 4 days (Arvanitoyannis et al.,
(550 g mol21) as the initiator and Tin(II) 2- 1995a,b,c,d,e,f,g, 1996a,b). The GPC traces of the
ethylhexanoate (SnOct2) as the catalyst. These copo- LLA/GL or LLA/pentaerythritol copolyesters (syn-
lymers were differentiated by scanning calorimetry, thesized with (Sn(Oct)2)) gave monodisperse
1 H NMR, and gel permeation chromatography. The curves, thus indicating the occurrence of only one
thermal properties (Tg and Tms) of the block copoly- mechanism. In contrast, the biomodal GPC traces,
mers depend on the polymer composition. Adding a recorded when TPhT was used as the catalyst, sup-
larger amount of 4-BOCL and/or ε-CL to the macro- port the previously expressed suggestion that two
molecular backbone causes a decrease in Tg and an mechanisms are in action, one initiated by the poly-
increase in Tms. The micellar characteristics in the ol and the other via the catalyst. The DSC (differ-
aqueous phase were investigated by fluorescence ential scanning calorimetry) results (bimodal traces)
spectroscopy, transmission electron microscopy further support the existence of two mechanisms.
(TEM), and dynamic light scattering (DLS). The degradation rates of these polyesters were stud-
ied by enzymatic and alkali hydrolysis, primarily in
terms of changes in weight, Mn, and TOC. NMR
14.1.3 Novel Star-Shaped analysis of degraded products confirmed the sug-
gested cleavage of hydrolyzable bonds of star-
Copolylactides shaped PLLA. High polyol contents strongly favored
Strong interest in the eventual, and preferably extensive cleavage of polymeric chains, thus result-
rapid, biodegradation of synthetic polymers has ing in an increase of crystallinity. It is noteworthy
developed only in past years, primarily in response that the theoretical capability of polyols to act as
to the growing problem of waste disposal of plas- cross-linking agents was not confirmed by solubil-
tics (Lenz, 1993). Polyesters attracted much ity experiments on the synthesized copolyesters
research interest in view of their satisfactory perfor- (Arvanitoyannis et al., 1995a,b,c,d,e,f,g, 1996a,b).
mance property wise and their inherent biodegrad-
ability. PCL and PLLA (poly(L-lactide)) were the 14.1.4 Biodegradable Composite
most responsive to biodegradation both in vitro and
in vivo (Nishida and Tokiwa, 1992, 1993a,b; Reeve Materials
et al., 1994). Apart from these two homopolymers The development of novel polymeric materials
(PCL and PLLA), several copolymers, based on that degrade slowly is considered a very important
these two components, have been synthesized in an research area, especially in view of their various cur-
attempt to “tailor” the properties of the homopoly- rent and potential applications as environmentally
mers for special applications (Kricheldorf et al., degradable materials (Albertsson et al., 1994; Storey
1988; Mikos et al., 1993; Zhang et al., 1993). An and Shoemake, 1993). Although D-, or L-lactide and
effective in situ process has been the main incen- ε-CL seem to be the most popular monomers, espe-
tive for the introduction of a soft segment such as cially in the field of polymeric composite materials
poly(ethylene glycol) in PLLA (Cerrai and Tricoli, (Li et al., 1990a,b,c) mainly related to medical appli-
1993; Kobayashi et al., 1991). The difficulties cations, PAs are another promising class of polymer
encountered in processing PLLA remained the that appeals to a wider range of applications
major limiting factor in applications despite the (Gonsalves et al., 1993). It is anticipated that these
well-accepted biocompatibility and biodegradability novel thermoplastic materials have a lot of potential
of PLLA (Kim et al., 1992, 1993; Leenslag, 1984). because of their inherent advantages over the major-
Novel branched star-shaped polymers are envisaged ity of thermoset materials (Arvanitoyannis and
as a potential solution to the processing problem Psomiadou, 1994), namely, control of their
252 PLASTIC FILMS IN FOOD PACKAGING

percentage crystallinity (physicochemical proper- Fanta, 1994; Shogen, 1993). The main advantages
ties), ease of processing, and “friendliness” to of these blends can be summarized as follows
the environment (Arvanitoyannis et al., 1995a,b,c, (Scott and Gilead, 1995):
d,e,f,g). Composites, consisting of AA/1.6-HD/
L-proline or L-glycine and short E-glass fibers, 1. property tailoring by proper selection of com-
were prepared by the hand lay-up method ponents and their ratios,
(Srivastava and Lal, 1991). The crystallinity of the 2. lower cost by using blending (i.e., extrusion,
copolyamide matrix was determined from WAXD casting) instead of synthetic,
following the generally accepted procedure for
constructing the diffraction pattern of a composite 3. routes for production of novel materials,
material. Determination of percentage of crystal- 4. ecological factors (environmentally friendly
linity in composite materials with DTA is compli- and usage of plastic wastes).
cated by the occurrence of nucleation fronts on
the glass fibers, in addition to the statistical nucle- Mixtures of low-density polyethylene (LDPE)
ation from the melt, known as transcrystallinity. with gelatinized potato, rice, wheat, and soluble
Therefore, occurrence of multiple melting peaks starch, with or without ethylene acrylic acid
should be attributed to different spherulite (EAA) as a compatibilizer, were extruded in the
morphologies (Arvanitoyannis and Psomiadou, presence of 15
20% water. As long as the starch
1994). Detection of void content is very critical in content in the blends does not exceed 20%, the
terms of determining the shelf life and perfor- mechanical properties of the LDPE/starch blends
mance of the composite material. The main rea- still lie within acceptable operational limits.
sons for the occurrence of voids in the degradable Typical scanning electron microscopy (SEM)
composite materials are the following: entrapment microgaphs taken after fracture clearly showed the
of air within pelletized material, residual moisture, blend morphology and the distribution of each
and shrinkage volume of the core region. component (Psomiadou et al., 1998). The wheat
starch particles are deformed and interspersed
within the LDPE matrix. Although in several pre-
14.1.5 Natural
Synthetic Polymer vious publications the failure modes of polyethyl-
Blends ene (PE) were investigated and analyzed, a
tentative failure mechanism of PE/starch blends
It has been estimated that approximately 2% of was only recently put forward (Arvanitoyannis
all plastics (mostly nondegradable) eventually end et al., 1997, 1998). Brittleness and ductility are the
up in the environment, thus contributing consider- two main failure modes. Whichever of these two
ably to the currently acute ecological problem. The prevails depends not only on the deformation fea-
current trend toward protection of the environment tures and fast or slow crack growth (Chudnovsky
is expressed by using degradable polymers and com- et al., 1995; Stojmirovic et al., 1992) but also on
posting or recycling the “recalcitrant” polymers. conditioning of the sample over certain relative
Blends of natural and synthetic polymers have been humidity environments. Therefore, the ensuing
considered a promising avenue for preparing poly- plasticization of the LDPE/starch blends could be
mers with “tailor-made” properties (functional phys- due to penetration of water and filling of voids.
ical properties and biodegradability). Constructing a tentative micromechanical model to
depict the geometries, arrangements, and interac-
tions of components within a composite material
14.1.6 Partially Degradable Blends has always been a challenging task (Christensen,
Starch-based plastics initially attracted some 1979). The main difficulties arise from inherent
research interest, but their development was not strength variations within the mass of the compos-
as expected, mainly because of their inadequacy ite systems and the need for long-term predictions
with regard to mechanical properties and water concerning the performance of the composite in
transmission (Giffin, 1994; Otey et al., 1974). In an terms of the mechanical properties. Although a
attempt to overcome this problem, synthetic poly- previously described system (Reifsnider, 1994)
mers/starch blends were investigated (Lawton and was initially suggested for fiber-matrix composite
14: WASTE MANAGEMENT FOR POLYMERS IN FOOD PACKAGING INDUSTRIES 253

materials, it could possibly be applied in the case

O2
of LDPE/EAA/wheat starch composites as well.
k
According to this model, deformed starch particles
High MW-low MW-organic fragments-CO2
constitute the core material, and this is surrounded
1 O2 1 energy-energy biomass-endogenous
by an LDPE/EAA continuous matrix. Depending
respiration; growth; and cell division
on the relative distribution of the EAA, regions of
LDPE/starch/EAA vary in their plasticity; a high
EAA content promotes greater plasticity in the Both soil burial and bioreactor exposure experi-
matrix, while in regions of lower EAA content, ments showed a decrease in percentage elongation
debonding and slipping may occur at the matrix/ and considerable weight loss, which could be
starch particle interface. described as a two-stage process (Krupp and Jewell,
Both LDPE and high-density polyethylene 1992). The first stage consists of partial starch
(HDPE) were thoroughly investigated with regard removal, and only at a later stage does a slow rate
to their gas permeability (GP) (Van Krevelen, of degradation of LDPE occur. Most investigations
1990; Yasuda and Stannett, 1962) because of their consider enzymatic oxidation, dehydrogenation, and
extensive use in food packaging applications. carbon
carbon breaking processes to be the pre-
LDPE is a semicrystalline polymer of both amor- dominant degradation mechanisms of LDPE
phous (intralamellar, interlamellar, and interspheru- (Albertsson and Karlsson, 1994; Albertsson and
litic) and crystalline (ribbon-like lamellae) areas Ranby, 1979; Albertsson et al., 1994). However, the
(Michaels and Bixler, 1961). The presence of starch biodegradation rate of LDPE/starch blends can be
particulates as fillers within the LDPE matrix, apart effectively accelerated only if the starch content is
from disturbing the continuity of the LDPE network higher than 10%. Similar conclusions were also
and contributing to the inhomogeneity of the sys- reached by other researchers (Goheen and Wool,
tem, substantially enhances the GP of the LDPE/ 1991; Gould et al., 1990; Narayan, 1991; Wool,
starch composite structure because of their strongly 1995) who, in addition, applied the percolation the-
hydrophilic character. The water is either strongly ory (Stauffer, 1985) assisted by computer simulation
bound (0
12%) or is capillary moisture (12
30%). (Peanasky et al., 1991). In general, the higher the
The temperature dependence of GP and gas diffu- starch content, the worse the performance of the
sion (GD) of the blends is described by the well- composite materials will be (lower TS and modulus,
known Arrhenius equations. higher GP and water vapor transmission rate), but
At this point, it is worth emphasizing the impor- the higher their biodegradability. An increase in
tance of the activation energy of diffusion because moisture or EAA (whenever used) content of these
of its involvement in chain separation, which is composite materials induced plasticization of the
necessary for the eventual “loosening” of the struc- samples. The degradability of LDPE/starch blends
ture. Certainly, the incorporation of starch particles was confirmed by weight loss measurements and
disrupts the LDPE network by imparting some flex- changes in mechanical properties.
ibility and mobility and thus reducing the required
energy per unit chain separation. An increase in
temperature enhances the cavity and channel forma- 14.2 Chitosan
Poly(Vinyl
tion even more, thereby facilitating the diffusivity Alcohol) Blends
and permeability. The diffusion and the permeation
activation energies were found to fall in the follow- Poly(vinyl alcohol) (PVA) can be prepared by
ing order with regard to the permeating gas: ED hydrolysis of a variety of poly(vinyl esters) and poly
(N2) , ED(O2) , ED(CO2). This order is in agree- (vinyl ethers) and has many applications in pharma-
ment with other reports, assuming that there is no ceuticals, cosmetics, and the paper and food indus-
interaction between the permeant gas and the tries, either alone or in blends with other polymers,
matrix (LDPE/starch). LDPE/starch blends have such as poly(3-hydroxy butyrate) (Azuma et al.,
been used commercially for the past 15
20 years. 1992), polyacrylic acid (Daniliuc and David, 1996),
The generally accepted degradation scheme of a β-chitin (Lee et al., 1996), cellulose (Hasegawa
high molar mass polymer consists of the following et al., 1992a,b, 1994), among others. Chitosan is the
stages: deacetylated product of chitin. Next to cellulose,
254 PLASTIC FILMS IN FOOD PACKAGING

chitin is the second most abundant polysaccharide in adsorption and cell activity on blends is still
nature (Rathke and Hudson, 1994). Chitin is associ- unknown. The objective is to investigate the correla-
ated with other polysaccharides in fungal cell walls, tion between protein adsorption behaviors and cell
while in animal forms, chitin is associated with pro- activities in chitosan/PCL blend films. Chitosan/
teins (Muzzarelli, 1977). The production of chitin is PCL films with different mass ratios were prepared
possible primarily as a secondary activity related to by spin coating with chitosan/PCL mixture solution.
the marine food industry (Zikakis, 1984). Chitosan Atomic force microscopy (AFM), drop shape analy-
has been used in a very wide range of applications, sis (DSA), quartz crystal microbalance (QCM), and
such as prevention of water pollution by chelating MTT (microwave thermal treatment) methods were
heavy metals or radioactive isotopes, in membrane used to analyze the surface morphology, hydrophi-
separation (Aiba et al., 1986), in medicine and bio- licity, protein adsorption, and cell metabolic activity
technology, and in the food areas, either as a food of films. These properties are largely related to the
packaging material because of its antimicrobial mass ratio of chitosan and PCL. The cell metabolic
action, or as dietary fiber and a potential medicine activity observed on hydrophobic PCL films is
against hypertension thanks to its scavenging action superior, and cell adhesion level on hydrophilic
for chloride ions (Furda and Brine, 1990; Ishikura, chitosan films is excellent (Min et al., 2011).
1993; Muzzarelli, 1996; Okuda, 1995). The prepara-
tion of chitosan/PVA blends was carried out as fol-
lows. The PVA solution was added, under vigorous 14.3 Landfill
stirring and heating, to the chitosan solution and
then the plasticizer was added and mixed into the Landfill has served mankind for much longer than
solution for 10
15 min until dispersed. Then the any alternative disposal option. Landfilling is defined
solution was cast over plexiglass plates. Low- as the disposal, compression, and embankment fill of
molecular weight compounds added to chitosan/ waste at appropriate sites. Landfill for the moment
PVA blends are shown to lower the melting point is easy, adjustable with lower cost than other disposal
and the glass transition Tg. Wide-angle X-ray dif- methods, and stands alone as the only all waste mate-
fraction patterns (WAXDP) showed that PVA has a rial disposal method (Clarke et al., 1999; Karakasidis,
high percentage crystallinity (Xc 5 54%). The 1997). Although landfill was traditionally selected by
observed reduction in percentage crystallinity in many communities because of its low cost, it has
chitosan/PVA blends should be due to “crystalliza- become prohibitively expensive. The costs of landfill
tion disturbance” of chitosan in the blend state. rose due to the decreasing number of landfill sites
Novel chitosan/PVA composite packaging films and the more sophisticated techniques and operating
were prepared by the casting method, and the effects practices (Adams et al., 1996; Von Schoenberg,
of chitosan concentration on the structures, mechani- 1995). Important factors that need to be taken into
cal properties, permeability for oxygen, and water account for the correct function of disposal sites are
vapor were presented in the Li et al.’s (2011) study. the selection of the site, its design and organization,
Mechanical properties of these films, which were operating performance and life cycle, and biodegrad-
evaluated by the tensile test and the barrier proper- ability of the wastes (Karakasidis, 1997). The envi-
ties, showed that the elongation at break (E) of the ronmental impact of waste landfilling depends on the
composite films decreased rapidly with the addition design and operational mode of the landfill facility
of chitosan, whereas the TS presented an almost and the nature of the waste deposited (Dascalopoulos
opposite trend. Both the water vapor and oxygen et al., 1998). The landfill gas generated at landfill
transmission rate values were increased with the sites was considered barely controllable and one of
increasing amount of the chitosan in the composite the main disadvantages of this method. However, the
films. Based on the obtained results, the optimum production of such gas has recently been perceived as
property of the composite films were chitosan/PVA a promising source of highly combustible fuel since
blends at a weight ratio of 3:5, in which the TS and it is a clean source of fuel (Clarke et al., 1999; Von
elongation at break of the packaging films were Schoenberg, 1995).
34.12 MPa and 40.24%, respectively. In order to comply with the EU ELV (End-of-
Chitosan/PCL blend has a perspective in bioma- Life Vehicles) Directive, an increase in the recy-
terials. However, the correlation between protein cling rate of automobiles to 80% by 2006 and 85%
14: WASTE MANAGEMENT FOR POLYMERS IN FOOD PACKAGING INDUSTRIES 255

by 2015 must be met (EC, 2000). On average, the legislative regulations for emissions and environmen-
plastic content of a car was 9% and the average tal standards, would be an important process contrib-
thermoplastic content is about 45% polyolefin uting to the economy and environment, both now
(40% PP, 4
6% PE). The properties of a blow- and in the future (Bastian et al., 1995). Waste com-
molded bottle prepared from 100% postconsumer bustion with energy recovery is usually cost-effective
HDPE showed that this recycled polymer exceeded only in large, heavily populated metropolitan areas.
the material specifications for virgin plastic This approach becomes less appealing with low fossil
designs. Similarly, a sample of thermoplastic poly- fuel cost, strong markets for paper, and the necessity
olefin (TPO, 100% polypropylene (PP)) obtained for disposing of a substantial volume of residue, a
entirely from shredder residue (SR) displayed suffi- part of which may be hazardous (Mark, 1995).
cient material strength for future separation and However, the main problems to be addressed prior to
reprocessing (Ambrose et al., 2002). extensive utilization of this method are the finite risk
of contamination, noise, odor, fire and explosion
hazards, vegetation damage, ground water pollution,
14.4 Incineration and air pollution (El-Fadel et al., 1997). The con-
sumption of crude oil, natural gas, and pit coal, nor-
An alternative method of waste disposal to land- mally used in district heating plants, can be
fill is waste incineration. Waste incinerators use the substantially lowered by the incineration of plastic
process of combustion to convert the waste materi- waste. Assuming that the efficiency of an incinera-
als into carbon dioxide and water. Incineration resi- tion plant and a district heating plant is the same
dues usually consist of small quantities of HCl, S, (80%), the incineration of 1-kg LDPE releases
and other volatile compounds and ash (Waite, 43.3 MJ, which corresponds to 0.08-kg crude oil,
1995). However, it is obvious that not all household 0.07-kg natural gas, and 0.25-kg pit coal (Molgaard,
waste materials are combustible. Reduction of 1995). The cost of landfill or incineration varies in
waste volume by 80
90% is achieved with inciner- different countries, as do the treatment routes
ation. Therefore, it should be considered as a means employed by different European nations (Morris
of reducing the amount of waste to be disposed of et al., 1998; Palin and Whiting, 1998; Simons et al.,
by landfill rather than a method of ultimate disposal 1995).
on its own (Von Schoenberg, 1995).
Combustion can be regarded either as a pretreat-
ment method for the waste prior to its final disposal 14.5 Pyrolysis
or as a means for increasing value to waste by energy
recovery (Dascalopoulos et al., 1998). Incineration High-molecular weight substances cannot be
became an increasingly popular method of waste dis- purified by physical processes like distillation,
posal by the beginning of the 1970s when many extraction, or crystallization. They can only be
incinerators were constructed (Waite, 1995). The recycled by pyrolysis of their macromolecules into
effect of polymers on the combustion of municipal smaller fragments. Pyrolysis can be used to convert
solid waste (MSW) has not been satisfactorily mixed plastic wastes to oil products, combustible
assessed in the past. The Association of Polymer gas and heavy residues. The pyrolysis products may
Manufacturers in Europe (APME), in conjunction then be suitable for common petrochemical separa-
with academia, launched an in-depth program aimed tion processes. Pyrolysis is the thermal degradation
at understanding the role of polymers in MSW com- of macromolecules in the absence of air, and it gen-
bustors. The APME program on energy recovery erates oils and gases, which are suitable for chemi-
from used plastics is focused on exploring all techni- cal utilization or generation of energy. In fact, the
cally different means (Mark, 1995). Co-combustion pyrolysis products consist of 34% ethylene, 9% pro-
is regarded as one of the most promising means for pane, 39.7% oil (mainly aromatic compounds), and
economic and safety reasons. As a result, conversion 1.7% residue (Faaij et al., 1998; Kaminsky, 1995).
of polyurethanes together with other materials such The Constantinople composting and recycling
as textiles, wood, paper, and other plastics into plant, constructed in 2001, is one of the few com-
energy in “state of art” incinerators, which meet all posting plants in Turkey. During test operations of
health and safety requirements and the respective the plant, it was reported that the weight of the
256 PLASTIC FILMS IN FOOD PACKAGING

oversize materials (OM) above an 80-mm sieve also studied. The formation of coke during copyro-
was about 40% of the total incoming waste. They lysis of LDPE wax with naphtha was comparable
mainly consist of plastic bags that were full of gar- to the coking of pure naphtha. Slightly higher for-
bage, which resulted in operational problems in the mation of coke was obtained at PP wax solution at
plant. In a study, the composition of OM was deter- the beginning of the measurements, on the clean
mined and evaluated, particularly to find the eco- surface of the reactor. After a thin layer of coke
nomic losses in the plant. It was determined that covered the walls, the production was the same as
approximately 58% of the OM transferred to the that from naphtha. The results confirmed the possi-
landfill area due to operational failures and inter- bility of polyalkene recycling via the copyrolysis of
ruptions could be used at the plant with improved polyalkene oils and waxes with conventional liquid
operational conditions. Otherwise, the plant would steam cracking feedstocks in already existing indus-
realize an annual economic loss of about 640
800 trial ethylene units (Hajekova and Bajus, 2005).
million US$. Compost quality in the plant has been The results obtained proved that the oil/wax frac-
satisfactory, but source-separated collection, at least tions obtained from the thermal decomposition of
the separation of the wet from the dry fraction, is polyalkenes under mild conditions can be added to
needed to increase the amount of compost and liquid charges for steam cracking in the amount of
recovered materials. To increase the amount of 10 mass%. It is not necessary to separate the oil
compost and captured recyclable materials in the and wax fractions from each other at this level.
Constantinople plant, all plastic garbage bags Such a separation would unnecessarily increase the
should be torn in the first step of the process. costs for preparing these raw materials. The gases
However, appropriate waste collection (higher formed by the decomposition of polyalkenes can be
organic and recyclable content) from potential dis- burnt, but in the case of fluid cracking of polyalk-
tricts of the city is still an important factor for the enes, they can also be returned to the process as
plant. The best way to improve the situation would fluidizing gas. They can also be added to the
be source-separated collection, at least the separa- streams of gases that are formed at the steam crack-
tion of the wet from dry fractions. In Turkey and ing unit, and thus the already existing equipment
some other developing countries, it is difficult to for separation of gases from steam cracking can be
operate plants optimally, especially publicly owned utilized. A 10 mass% concentration of oil/waxes
plants, due to investment and administrative pro- does not cause any problems on spreading. Slightly
blems. The most important inadequacy in any envi- warming up the raw material in the tank is
ronmental management activity in those countries sufficient.
is the operating problems and the lack of research
during operation of the plants (Kanat et al., 2006).
The thermal decomposition of polyalkenes was 14.6 Reuse and Recovery
investigated as a recycling route for the production
of a petrochemical feedstock. LDPE and PP were One of the priorities set in most countries around
thermally decomposed individually in a batch reac- the world is drastic waste reduction. Where waste
tor at 450 C, thus forming oil/wax products. Then cannot be avoided, it must be recovered, preferably
these products were dissolved in primary heavy in an environmentally friendly way. This simply
naphtha to obtain steam cracking feedstock. The means recover and reuse something after its initial
selectivity and kinetics of copyrolysis for 10 mass function has expired. The ways that the recovered
% solutions of oil/waxes from LDPE or PP with material can be used may be similar or dissimilar
naphtha in the temperature range from 740 C to to their original function (Lemann, 1995). The
820 C at residence times from 0.09 s to 0.54 s were strategies identified to help waste prevention
studied. The decomposition of polyalkene oil/waxes include material life extension, process manage-
during copyrolysis was confirmed. It was shown ment, and reduction of material used (Bergner,
that the yields of the desired alkenes (ethene, pro- 1995). The term “reuse” expresses the identification
pene), according to polymer type, increased or only of the most cost-effective avenue in reusing goods,
slightly decreased compared to the yields from components, and materials. When a product is
naphtha. In addition to the primary reactions, the designed, the requirements of reuse and collection
secondary reactions leading to coke formation were processes need to be taken into account (Stahel,
14: WASTE MANAGEMENT FOR POLYMERS IN FOOD PACKAGING INDUSTRIES 257

1995). Moreover, the recovery and reuse of waste States and Europe. A study on composting in the
must not result in an enrichment of hazardous sub- United States lists 15 facilities that are currently oper-
stances within the substance life cycle. All plastic ational and an additional 23 that are under construc-
materials interact with “products” to a certain tion or at planning or designing stages. In Europe,
extent. This interaction can either be superficial or composting facilities are operational or under con-
more extensive, followed by absorption into the body struction in France, Holland, Switzerland, Italy,
of the plastic. Contamination of refillable containers Greece, and Spain (Renkow and Rubin, 1998).
through migration of substances (i.e., dyes, flavors) Composting has been officially recognized as a form
into the plastic could occur at various times during of recycling and is expected to play an even more
the material’s shelf life. Although these substances important role in future waste management opera-
may not be affected by the washing process, they tions. Although composting has been rapidly gaining
might subsequently be released into the food on their importance, the development of suitable technology
reuse, with serious implications regarding both con- still relies on practical experience. Composting still
sumer safety and sensory characteristics of food. has to grow from an art to a well-established technol-
A plastic container is suitable for refilling when it ogy. Composting refers to a self-heating, aerobic pro-
is resistant to the uptake of chemical and microbio- cess of organic wastes and other industrial organic
logical (toxicological) hazards and taints. Exposure compounds in order to convert them to a mature plant
to chronic toxins is statistically unlikely to occur compatible substrate. If a material is considered
with contaminated containers, but a single exposure compostable, biodeterioration/biodegradation should
at a high level could be a major issue (Castle, 1994). transform it into compost (Blanc et al., 1995; Narayan
and Snook, 1994; Raschle et al., 1995; Tokiwa et al.,
1989). Under optimal degradative conditions, a con-
14.7 Composting trolled composting process can be completed within 3
MSW composting is an alternative to the disposal months, while under normal conditions this takes 1 to
of wastes that has attracted interest in the United 2 years (Kaiser et al., 1995). The final product of

Energy content of
Process EAP: LCA of goods
materials, transport,
analysis and services
and waste

Energy
data

Input–output Energy intensities Energy intensities of

Prices
energy analysis of sectors goods and services

Economic
Final Expenditure
input–output Energy requirements
demand survey
data of households

IO-EA–process IO-EA–expenditure IO-EA–basic

Figure 14.1 Data and operations needed for the three different energy analysis methods. Source: Adapted
from Kok et al. (2006).
258 PLASTIC FILMS IN FOOD PACKAGING

Basic Residual Capital

goods goods goods

Manufacturing

Transport

Trade

Transport Transport

Consumption

Transport

Recycling Transport Waste

Figure 14.2 Life cycle of a product as used in the IO-EA-process method. Source: Adapted from Kok et al. (2006).

composting is rich in organic matter but its concentra- and water by employing thermophilic microorgan-
tion of key nutrients, usually too low to compete with isms. Under normal temperature conditions (i.e., room
commercial fertilizers, improves the soil structure temperature), chemical oxidation plays a minor role.
through its enrichment with humic substances At the same time, there is a release of heat resulting in
(Marilley et al., 1995; Masters, 1998). Besides the a temperature increase within the composting matter.
microflora required for composting, composts can The process requires a blend of materials with appro-
also harbor potentially pathogenic and/or allergenic priate physical and chemical properties and pertinent
bacteria and molds like Aspergillus fumigatus (Lott management to ensure that suitable process conditions
Fischer et al., 1995). The aim of the composting oper- are maintained. The process takes place at tempera-
ation is to obtain, preferably in the short term with tures high enough to destroy pathogens. MSW com-
limited cost, compost with of desired quality. All com- posting treats all readily degradable components of
posting operations should take place under controlled, the waste stream such as paper, food, and wood,
environmentally safe conditions. During the process, which account for 55
70% (by weight) of a commu-
gas and heat may be released that can be used for nity’s residential solid waste. The two basic processes
energy recovery while, at the same time, volume applied in large-scale composting are classified as
reduction of the original material by up to 40% can be windrow-based and in-vessel technologies. In wind-
achieved. Furthermore, the process is considered to be row systems, waste is conveyed to a central open-air
“environmentally friendly” and financially viable, but facility and formed into windrows that are 3- to 5-ft
only under proper guidance and management. The (1- to 1.5-m) high. The windrows are turned periodi-
basic reaction of the composting process is the oxida- cally to maintain a stable temperature and decomposi-
tion of organic matter with oxygen to carbon dioxide tion rate, and water is periodically added to maintain
14: WASTE MANAGEMENT FOR POLYMERS IN FOOD PACKAGING INDUSTRIES 259

product by plugging the screen or reducing the degra-

Laser dation of biodegradable materials by blocking the
oxygen flow. The composting process is further
affected by temperature, moisture, pH, nutrient sup-
ply, and oxygen availability, while temperature also
plays an important role in hygiene (Beffa et al.,
Light mixer 1995; Gajdos, 1995; Guneklee and Kubocz, 1995;
Hamelers, 1994; Hanna, 1994; Neumann, 1995;
Peringer et al., 1995; Schaub and Leonard, 1996;
Siegenthaler, 1995; Vos, 1994). The composting
process is shown in Figure 14.14.
Light distributor

14.8 Recycling
According to Waite (1995), “recycling is a very
broad term referring to the conversion of waste into
Color separation filter
a useful material”. While recycling is second in the
priority of waste management options, it has gained
ground in many European and American countries
as an essential ingredient for the reduction of wastes
Light converter that would otherwise be landfilled. Over the past
decade, the emphasis on the part of MSW manage-
ment has been on recycling due to the introduction
of waste management hierarchy. Recycling is a rela-
Processor tively old method with a well-recorded history.
(100x) Metals have been recycled since their discovery
because of their high value, rarity, and properties
Figure 14.3 Glass laser sorting system. Source: that allow near indefinite reprocessing. The recy-
Adapted from Arvanitoyannis and Bosnea (2001a,b). cling of old textiles is equally old since historically
they were used for the production of paper. Among
the factors which have contributed to improving the
an appropriate moisture content. After the targeted recycling process are the decrease in available land-
decomposition level has been attained, the composted fill and the urgent need for raw materials recovery
product is ready for assembly and distribution to end that could be used by reducing the amount of natural
users. Vessel systems employ considerably more resources consumed. Moreover, the increasing pub-
sophisticated technologies that offer a highly con- lic interest in environmental protection has enhanced
trolled enclosed environment for effecting the biologi- the importance of recycling as an alternative solu-
cal decomposition, thus leading to a high-quality tion to the constantly escalating waste problem
product. This system is more capital intensive than (Alter, 1997; Vogas, 1995).
windrow technologies, and the sophisticated techni- According to NSWA (National Solid Waste
ques require highly trained facility operating person- Management Association), recycling consists of six
nel. Therefore, the composting process is anticipated basic steps:
to play an important ecological role in the promotion
of the biological carbon cycle. Similarly to the recy- 1. Collection and sorting of recyclable materials
cling of other materials, composting requires high- from the waste stream,
quality raw materials, thereby ensuring that no toxic 2. Raw material reclamation by special treat-
and hazardous residues are included in the product. In ment, so that they could replace virgin mate-
addition to compromising product quality, materials rials in manufacturing operations,
that are resistant to biodegradation may severely affect
compost processing. Nondegradable plastic films may 3. Marketing of the recycling materials,
interfere with the film screening of the composted 4. Market establishment for recycled materials,
 260
Magnet
extractors

Waste Metal and paper

Color-sorted collection Pre–sorting Crushing
glass removal

Paper
extractors

Glass
bottles

Removal of wrong
Glass
Molding/shaping Melting colors and Sieving
fragments
other impurities

Jars, jugs,
etc.

PLASTIC FILMS
Figure 14.4 Glass recycling process. Source: Adapted from Arvanitoyannis and Bosnea (2001a,b).

IN
FOOD PACKAGING
14: WASTE MANAGEMENT FOR POLYMERS IN FOOD PACKAGING INDUSTRIES 261

1. the packaging or product design: since the

Aluminum
product should be designed for recycling,
can mixed plastic materials which complicate the
recycling operations should be avoided,
2. the raw materials: it is essential that the prod-
uct does not contain any nonrecyclable raw
materials,
Shredding 3. management operations: that is, identifying
Paint
removal
distribution channels,
4. legislation: inspection of legislation for packag-
ing and taxes involved to verify that it does not
Delaquering oven Labels
interfere with recycling management options,
5. consumer education concerning recycling:
increasing the percentage of informed and edu-
Dirt Residual
cated consumers concerning recycling further
moisture promotes the recycling management scheme,
Screening
6. technological advances and their applications:
Contami- this plays an important role in improving the
nants recycling processes (Vogas, 1995).

As far as the economic viability of recycling is

Rotary furnace
concerned, it needs to be measured against the
alternative waste management operations. The cost
of recycling is mainly governed by three elements
(Pearson, 1996):
Can melting
1. the cost to collect and to sort,
2. minus the cost of landfill avoided,
3. minus the revenue from the recyclable sold
by the material recovery facility.
Blending
with molten
metal Industrial recycling is so well established that under
ordinary commercial practices many secondary mate-
rials are destined only for recovery or reclamation
Figure 14.5 Flow diagram for metal recycling. and not for discard and final disposal (Alter, 1997).
Source: Adapted from Onusseit (2006). The percentage of recycling of glass, aluminum, and
polyethylene terephthalate (PET) in the European
5. Public involvement in the recycling programs Union and the United States is given in Figure 14.15.
operations,
6. Collection recycling programs target the use-
less materials from the waste stream and treat 14.8.1 Plastic Recycling
them in such a way so that they could return The number of recyclable materials collected
to the industries as raw materials for packag- through the waste stream is quite large and consists
ing applications (Vogas, 1995). of glass, plastic, scrap metal, tins, paper and board,
fabrics, oils, construction materials, ash, and
Any responsible recycling operation has to meet organic substances (Waite, 1995). Plastic makes up
market, economic, and environmental requirements. around 8% of the total waste weight out of which
The viability of recycling depends on the following nearly 85% are thermoplastics: these are mainly
factors: PET, HDPE/LDPE, polyvinyl chloride (PVC), and
262 PLASTIC FILMS IN FOOD PACKAGING

100
90

Percentage (%)
80
70
60
50
40
30
1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 2004
Year

Figure 14.6 Recycling rate for aluminum cans in Sweden and the United States (1984
2004) (V Sweden and
’ the United States). Source: Adapted from http://container-recycling.org/alumrate/gaphs.htm.

PP. The recycling rate for all plastic bottles dropped management operations. The United States has his-
from 24.5% in 1996 to 23.7% in 1997. PET soda bot- torically relied on landfilling as its principal dis-
tles represent 26% of total plastic bottle production posal technique. In 1972, approximately 20,000
and 40% of total plastic bottles recycled. PET bever- landfills were operational, while in 1990 this was
age and soda bottles combined represent 44% of total reduced to 6300 landfills in which over 80% of US
plastic bottle production and 48% of total plastic bot- MSW was disposed. The number of landfills is
tles recycled. The recycling rates for PET soda bot- expected to decrease even further to 2100 by
tles and for all PET bottles have been in decline for the end of 2000, while recycling and other waste
several years in the United States. PET soda bottle management techniques would handle the main
recycling rate (36%) was 8% lower than in 1996 and bulk of wastes (Anonymous, 1990; Jenkins, 1991;
25% lower than in 1994. Total PET bottle recycling Liesemer, 1992). In contrast to the United States,
rate (25%) was 9% lower than in 1996 and 18% Japan, with a much higher population density, in
lower than in 1994. One reason for the drop in the 1990 employed landfill for only 52% of its solid
PET bottle recycling rate is the fact that PET resin waste and Western Europe about 60%. Incineration,
production increased by 45% between 1994 and combined with energy recovery, was widely used in
1997. Another is the fact that 60% of the PET soda Japan (47% of MSW) as an important method of
bottle market is made up of single-serve bottles, and solid waste disposal in 1990 (Jenkins, 1991).
most of those soda bottles are consumed away from Currently, in Western Europe, about 75% of plastics
home and away from curbside recycling bins. If the are landfilled, while 25% are recovered in the form
major soft drink companies were to use 25% recycled of either new material or useful energy. In 1993,
content in their PET soda bottles, they could boost just over 50% of MSW generated in Sweden was
the PET bottle recycling rate from the current rate of incinerated, and the energy recovered was used for
36% to 61%, the total PET bottle recycling rate from district heating (94%) and for electricity (6%)
25% to 40%, and the total plastic bottle recycling (Tamaddon et al., 1995). Finally, only 8% of MSW
rate from 24% to 30% (Anonymous, 1994, 1998). in Canada is incinerated, one of the lowest propor-
Statistics show that plastic waste is set to become tions among developed countries. Canada is the
one of the largest categories in MSW. Although leading country in terms of the amount of waste per
only representing around 4% of total oil consump- capita sent to landfill and has below-average rates of
tion, plastics represent a valuable resource. The 4% diversion to recycling or composting (Gilbert, 1998).
of the world’s oil consumption used in plastic pro- Even though recycling is becoming increasingly
ducts actually helps users of oil (transport, heating, important, not many comparative figures are avail-
etc.) to become more energy efficient. Therefore, able, and there are large differences in performance
plastic recycling is important to the plastic industry, in recycling rates between countries (APME, 1999).
energy savings, and the environment. The European community generally recycled by
In the United States, plastics account for 13% by mechanical recycling about 7% of the total plastics
weight of waste and are handled by MSW consumed in 1995.
14: WASTE MANAGEMENT FOR POLYMERS IN FOOD PACKAGING INDUSTRIES 263

Recycling of
aluminum

Conventional method Direct convention method

Scrap Scrap

Precompacting
Comminution

Metal losses
Remelting
by burning

Fe particle
Liquid separation
Dross
aluminum

Casting Casting scrap

Cleaning

Homogenizing

Annealing
Scrap and
Sawing
trimmings

Delivery to Blending
extrusion plant

Preheating
Cold pre
compacting

Extrusion
Hot extrusion
butts

Sintering
Cutting to Scrap and
final size trimmings

Total
Extruded Extruded
new
product product
scrap

Figure 14.7 Flow charts of recycling aluminum scrap by conventional and direct convention method. Source:
Adapted from Gonostajski et al. (2000), Lazzaro and Atzori (1992), and Samuel (2003).
264 PLASTIC FILMS IN FOOD PACKAGING

Coils,
ingots
HCI:HNO3  3:1;
Dissolve 6.67%
concentration

Cold rolling 1
Heat up 80°C
Single foil Double rolled
production foil production

Final cutting Interphase cutting

and trimming and dueling Filter

Deionized
Wash residue
water

Cold rolling 2

Dilute

Final cutting,
trimming,
and separation
AAS Perkin-Elmer
analysis AAS

Final
annealing Figure 14.9 Metal assay approach for float and
sink products. Source: Adapted from Zhang and
Forssberg (1997).

251,000 t in 1996 to 334,000 t in 1997, but this

method is used only in Germany. Europe, in 1997,
Packing recycled 14
15% of plastic packaging waste, of
which 25 million tons was turned into energy (http://
www.apme.org/press/htm/PR030299.htm). In 1995,
Figure 14.8 Scheme of aluminum foil production Germany recycled 60% of consumed plastic of
unit. Source: Adapted from Logozar et al. (2006). which 20.56% was recycled mechanically, 27.85%
was sent abroad, and 9.56% by feedstock recycling.
In Western Europe, 25% of the plastics consumed In 1996, the total recycling rate rose by 7.6%. After
during the period 1996
1997 were recovered 1991, when the packaging ordinance was set in
(4,364,000 t) while, at the same time, there was an Germany, there was an enormous increase in its
8% increase in total plastics consumption and a 12% national recycling rates. In 1991, Germany began a
increase of recycling volume in 1996. In total, 8% of very ambitious plastics recycling plan, the aim of
plastics recovered from Europe’s waste stream was which was to separate and recycle 80% of plastic
mechanically recycled, with agriculture (31%) and components in packaging waste (Plinke and Kaempf,
distribution sectors (23%) remaining the two sectors 1995). In 1994, it was estimated that 460,000 t was
with the largest proportions of mechanically recycled collected, although there was a recycling capacity of
plastics. Feedstock recycling rose by 33% from only 250,000 t. Unfortunately, this surplus was
14: WASTE MANAGEMENT FOR POLYMERS IN FOOD PACKAGING INDUSTRIES 265

Bauxite

Bayer process

Red mud Alumina

Hall-Heroult
Waste process
basin

AI° White dross

Dross/recycled
AI°

Salt flux smelter

furnace

Landfill
Black dross/
AI° salt cake

Leaching
process

Recycled
AI° NMP

Figure 14.10 Aluminum schematic recycling process in Brazil. Source: Adapted from Shinzato and
Hypolito (2005).

dumped in other countries, undermining their own remaining urban solid waste was successfully
recycling industries (Ball and Unsworth, 1995). Italy recycled in 1993, which accounts for a total of
is the second country in Europe in terms of recycling 1,370,000 t of waste. Out of this waste, 6100 t of
plastic industries. In 1992, the number of recycling PET (72% of beverage containers) were recycled
industries that imported recyclable materials from (Fahrni, 1995). Moreover, according to the latest
the international market reached a rate of 66.5% figures from PET Container Recycling Europe, PET
(Pinetti, 1995). In 1995, Austria and Switzerland recycling had risen by 66% in 1996 throughout
mechanically recycled 15% and 11.9% of plastic Europe. In Switzerland, plastics were collected early
waste, respectively (Hertzog, 1995; Mader, 1992). In on and also used as regranulate, but the recycling
Switzerland, 80% of household waste was inciner- rate in Switzerland and neighboring countries is dis-
ated and 20% landfilled in 1990, while 49% of the appointingly low at about 5
6%. It is estimated that
266 PLASTIC FILMS IN FOOD PACKAGING

Collection
of municipal
waste

Waste
incineration

Slag
treatment

Sieve

Magnetic
extractor

Sieve 1st

No Is particle size
5mm?

Yes
Slag
Slag
Sieve 2nd product
product

No

No Is particle size Eddy current

12mm? Yes separator
Shredder

Magnetic Ferrous Nonferrous

extractor fraction fraction

Sieve

Yes Nonferrous
Is particle size Magnet
12mm? fraction

Figure 14.11 Process chain of slag processing with additional steps of metal recovery. Source: Adapted from
Quinkertz et al. (2001).

more than 700,000 t was consumed in Switzerland, Liesemer, 1992). The official recycling rate for the
of which only 400,000 t was collected and returned year 1997 increased to 27% of total municipal dis-
for recycling and only 35,000 t of regranulate was cards, twice the rate of a decade ago, while 9.5% is
used for further manufacture. The United States mechanically recycled. Nearly 1.4 billion pounds of
recycled about 2% in 1985, less than 5% of total postconsumer plastic bottles were recycled in 1997,
plastic waste in 1994, while there was an increase of a 4% increase from 1.32 billion in 1996. Even
about 4% in recycling plastic in 1996 (Jenkins, 1991; though more plastic bottles were recycled in 1997
14: WASTE MANAGEMENT FOR POLYMERS IN FOOD PACKAGING INDUSTRIES 267

Pulping
waste
paper

Coarse
screening

High-density
cleaning

Fine
screening

Low-density
cleaning

Thickening

Dispersing

Freshwater
Deflaking and
defining

Sheet
formation

DAF Pressing Effluent

Drying

Paper

Figure 14.12 Process water usage and wastewater discharged from the board paper mill. Source: Adapted
from Sohair et al. (2006).

than ever before, the recycling rate for plastic bottles plastics for 2004 were 22, 26, and 3.2 for PET,
decreased from 24.5% in 1996 to 23.7% in 1997. HDPE, and PP, respectively. As regards the United
Recycling of PET soft drink and beverage bottles States, the postconsumer bottles recycle rate in 2005
reached an all-time high of 649 million pounds for was 24.3% (www.plasticsresource.com) (Tables 14.4
1997. The recycling rate for PET bottles was the and 14.5).
highest overall bottle recycling rate of any resin type In Australia, recycling comprised about 11% of
at 25.4%. HDPE bottle recycling increased 7% in the semirigid and rigid plastics disposal operations
1997 to 704 million pounds. Both natural and pig- in 1992 and it involved about 42% of HDPE, 29%
mented bottle rates saw significant gains in 1997. In of PET, and 6% of vinyl polymers in 1996. As far
the United States, the percentages of recycled as Japan is concerned, in 1995, 28% of total plastic
268 PLASTIC FILMS IN FOOD PACKAGING

Polymer
Solvent (LDPE, Paper
(xylene) HDPE, PP)

Size
Dissolution
reduction

Polymer Paper
solution impregnation

Mixing Pulping

Cooling
co-precipitation Washing

Filtration De-inking
Solvent
(xylene)
Vacuum
Paper fibers
drying

Composite

Sample
molding
(190–270°C)

Figure 14.13 Polyolefin/newspaper fiber composites preparation and characterization flow sheet. Source:
Adapted from Baroulaki et al. (2006).

waste was recycled: 11% mechanically and 17% by 100% recovered, only small amounts of consumed
thermal recycling, 35% of plastic went for incinera- plastics and paper are recycled (Barron and Ng,
tion, and 37% was dumped on reclaimed land with- 1996; Okawa, 1995). In the EEC (European
out any prior recycling. Furthermore, it was Economic Community), it is expected that 50
65%
expected that by the beginning of 2000, more than of packaging materials would be recovered, and
90% of plastics would be recycled in Japan (20% 25
45% would be recycled by a minimum for
mechanically and 70% by thermal recycling), while each material of 15% by weight. In developing
landfilling would account for less than 10% in countries such as India, the problem of waste
waste management operations. Hong Kong recycles becomes a major issue since its collection, transpor-
much of its industrial and commercial paper and tation, and disposal are unscientific and chaotic.
plastics, with this taking place entirely on the basis Since formal investment on infrastructure is not
of existing market prices. However, in the case of increasing, most of these countries have to rely on
domestic solid wastes, the level of recycling is gen- private-sector initiatives for waste disposal
erally low. Although aluminum cans are nearly (Dasgupta and Sharma, 1995; Gupta et al., 1998).
14: WASTE MANAGEMENT FOR POLYMERS IN FOOD PACKAGING INDUSTRIES 269

Micro
Oxygen/air Moisture
organisms

Nutrients Organic/compostable waste CO2

N, P, K Utilizable carbon source

Breakdown
Energy Humus/compost
products

New micro
organisms Heat

Death Polymerization

Figure 14.14 Composting process. Source: Adapted from Arvanitoyannis (1999).

Collection of Recyclable Materials volume of hospital waste. Many pilot plants have
been set in various hospitals because it was proven
In most countries, the collection of MSW falls
that packaging waste is more easily collected and
under the jurisdiction and direction of local authori-
recycled in hospitals than private households pro-
ties. Such authorities could be district councils,
vided that the required infrastructure and manage-
municipalities, or county councils. Each waste col-
ment are in place. Research and commercial
lection authority is responsible for organizing the
experience clearly show that the more complicated
collection of MSW for a particular area and deliv-
the job becomes for the householder, the less recy-
ering the waste to a point of disposal as directed by
clable materials are likely to be obtained. Since
each country’s ministry or responsible nationwide
the capital cost for equipment to collect material
authority. This is an enormous task for the authori-
at the curb and the labor associated with getting
ties because communities have to learn how to
the material into the truck represent about 70% of
transform the collection to an economically viable
total collection costs, which equals to 50% of total
enterprise. Traditionally, trash has been collected at
handling cost, it is essential for the authorities to
the curbside of the homeowner. In such cases, it is
design a highly efficient collection system (Beattie
possible to obtain 70% or more of the recyclables
and Kerell, 1995; Gellenbeck, 1995; Gordon,
from the household wastes. In contrast, voluntary
1991; Organisation for Economic Co-operation
drop-off and payback approaches to gathering the
and Development (OECD), 1987; Young and
recyclables from household wastes amount to only
Gordon, 1991).
20% and 10%, respectively. In several cases, a
mixed system of collection has been endorsed
(Chang et al., 1995; Chiellini, 1994). As far as haz- Drop-Off Centers
ardous household waste is concerned, several coun- This is the simplest method for collection of recy-
tries have already introduced national legislation clable materials. The system operates by placing spe-
for centralized collection schemes. It has been esti- cially designed buckets of large capacity at strategic
mated that plastics constitute about 40% of the total spots in the municipality. The public is asked to
270 PLASTIC FILMS IN FOOD PACKAGING

Table 14.1 Recycling Data for Metals (kg/ton)

Parameter Aluminum Ferrous Metal

Virgin Recycled Virgin Recycled
Energy (GJ) 140.00 11.70 25.20 9.43
Air emissions
CO2 2900.00 4.36 1820.00 595.00
PFC (perfluorocarbons) (CO2 eq.) 2226.00 0.00 0.00 0.00
CH4 6.53 2.71 0.0097 1.29
NOx 17.30 0.62 2.76 1.77
VOCs (volatile organic compounds) 24.50 0.30 0.23 0.02
SOx 47.60 2.88 5.11 2.98
PM (particulate matter) 10.00 0.00 1.31 7.22
Pb 1.93 3 1023 0.38 7.60 3 1024 6.59 3 1024
Hg n/a n/a n/a n/a
25
Cd n/a 4.37 3 10 n/a n/a
22 22
HCl 0.81 5.81 3 10 8.57 3 10 0.10
Water emissions
Pb water 1.47 3 1027 0.00 2.92 3 1022 2.90 3 1022
Hg water 0.00 0.00 n/a n/a
25
Cd water 0.24 0.06 9.75 3 10 9.38 3 1025
TCDD (tetrachlorodibenzo-p-dioxin) 1.20 3 1026 4.42 3 1028 n/a n/a
eq. water
Source: Adapted from Haight (2004).

collect the recyclable materials and transfer them by 3. It is essential to maintain sites and to manage
their own means to the drop-off centers. Then the the littering problem, thus avoiding any
local authorities are responsible for delivering the health implications (NSWA, 1990).
materials to the waste operation facilities. Basic
advantages are the low capital cost necessary and the Payback Centers
possibility for a 24-h operation. Usually, lack of pub- These are centers where the consumer deposits
lic cooperation in this collection scheme is its main the recyclable materials and receives a compensa-
disadvantage. It is quite inconvenient for the public to tion to ensure that cooperation will be maintained.
collect and dispose the materials at the drop-off cen- The basic advantage is the high quality of obtained
ters, while there is also the contamination problem of material and high public involvement rates. Long
the recyclable materials. It is difficult for the collec- distances between consumers and these centers
tion scheme to result, by itself, in high recycling rates. make the operation of this method rather difficult
Many local authorities who operate such drop-off cen- (Pearson, 1996; Vogas, 1995).
ters have concluded the following:
Combination of Systems
1. Sites must be selected to provide maximum There are numerous examples of how an appropri-
access but minimum nuisance to neighbors. ate combination of the above-mentioned methods
2. All centers should be frequently emptied to results in viable and successful results (Brandrup,
ensure that there is always capacity to deposit 1992). The method that each local authority will use
delivered materials. depends on waste collection operations, experience
14: WASTE MANAGEMENT FOR POLYMERS IN FOOD PACKAGING INDUSTRIES 271

Table 14.2 Recycling Data for Glass (kg/ton) raw materials. Plastic and glass can first be separated
from each other by mechanical or manual means and
Parameter Glass then once more according to their type. Sorting is
Virgin Recycled carried out in specially designed sorting plants that
Energy (GJ) 14.10 9.23 employ semi- or fully automatic processes, depend-
ing on the type, size, and technical standards of the
Air emissions
plant. The introduction and use of automated plastic
CO2 632.00 278.00 sorting systems have lowered processing cost and
PFC (CO2 0.00 0.00 improved the purity of the separated plastics over the
eq.) past few years, thereby increasing the quantity of
CH4 1.11 0.83 recycled plastics.
Various separation systems are used in different
NOx 2.73 1.69
countries, each having different capacity and sensor
VOCs 0.24 0.17 types, such as the OTTO system (Germany), PET
SOx 4.37 3.11 recycling Schweiz (Switzerland), P & R environ-
PM 0.89 0.43 mental (United States), and Ipia (Novate Milanese,
26 Italy). The technologies for separating postcon-
Pb 5.01 3 10 1.15 3 1026
sumer plastics into their appropriate components
Hg 1.30 3 1026 3.00 3 1027 fall into two categories: macro-separation and
Cd 1.35 3 1025 2.95 3 1026 micro-separation.
HCl 5.96 3 1022 0.98 Macro-separation involves removing discarded
materials from waste and separating them into dif-
Water emissions ferent components by handling the individual items
Pb water 3.60 3 1028 1.90 3 1028 manually or automatically. Macro-separation allows
Hg water 2.55 3 1028 1.95 3 1028 separation of a wide range of materials from each
other. The following techniques and methods fall
Cd water 2.20 3 1024 2.55 3 1024
under these categories:
TCDD eq. W n/a n/a
23
BOD 6.9 3 10 5.1 3 1023 1. Gravity/centrifugation
(biochemical
2. Methods based on the shape of the individual
oxygen
demand) fragments (manual, 3-D measuring devices)
3. Optical (X-ray, infrared (IR), near infrared
Source: Adapted from Haight (2004).
(NIR), fluorescence, etc.)
obtained by other municipalities, possibilities pro- 4. Metal detectors
vided by the particular site, population characteris- 5. Sonic techniques (ultrasonic technique)
tics, convenience to the consumer, recycling goals,
number of individual materials, contamination issues, Micro-separation involves separating polymers
capital and operational costs, raw materials market, by type after they have been shredded and chopped
public behavior, current working positions, available into small pieces of approximately 1/8 to 1/4 in.
technology, legislation, weather conditions, hygiene (0.3
0.6 cm) in diameter. This category comprises
issues, and political factors. It is important to realize techniques based on the following:
that recycling is not only a collection and recovery
method of waste but is also the last part of the life 1. Geometry (air classification, micronization)
cycle of the materials in which the consumer/recycler 2. Density (hydrocyclone, swim/sink)
is a key factor (Vogas, 1995).
3. Melting point (heated rolls)
14.8.2 Sorting 4. Electrostatic
After collection, the recyclables are conveyed to a 5. Mechanical (peeling)
facility for processing into a form suitable for sale as 6. Solving behavior (temperature gradient)
Table 14.3 Recycling Data for Paper Products (kg/ton)

Parameter Newspaper Fine Paper Corrugated Board Mixed Paper

Virgin Recycled Virgin Recycled Virgin Recycled Virgin Recycled
Energy 46.43 25.57 43.05 23.40 29.23 13.64 36.85 26.21
(GJ)
Air emissions
CO2 2400.00 1385.00 1100.00 1507.00 896.00 1019.00 1304.00 1752.00
PFC (CO2 0.00 2 3060.00 0.00 2 4580.00 0.00 2 4580.00 0.00 2 4580.00
eq.)
CH4 0.03 0.02 0.02 0.02 0.01 0.01 0.02 0.01
NOx 10.40 5.26 8.74 5.38 6.25 5.56 7.94 5.44
VOCs 11.20 7.19 8.27 18.47 3.87 35.40 6.86 23.89
SOx 16.30 9.40 12.88 9.80 7.74 10.40 11.23 9.99
PM 4.63 2.80 4.81 3.10 5.07 3.56 4.89 3.25
24 24 24 24 24 24 24
Pb 4.52 3 10 2.63 3 10 3.52 3 10 2.67 3 10 2.03 3 10 2.73 3 10 3.05 3 10 2.69 3 1026
Hg n/a n/a n/a n/a n/a n/a n/a n/a
Cd n/a n/a n/a n/a n/a n/a n/a n/a
26 26 26 26 26 26
HCl n/a 3.87 3 10 3.57 3 10 4.51 3 10 8.93 3 10 5.46 3 10 5.29 3 10 4.81 3 1026
Water emissions
Pb water 1.63 3 1027 6.35 3 1028 1.46 3 1027 6.59 3 1028 1.20 3 1027 6.95 3 1028 1.38 3 1027 6.71 3 1028
Hg water 3.82 3 1028 2.33 3 1028 2.69 3 1028 1.40 3 1028 9.92 3 1029 0.00 2.15 3 1028 9.51 3 1029
Cd water 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BOD 3.51 3.09 2.71 3.29 1.52 3.58 2.33 3.38
Source: Adapted from EPA (2002) and Haight (2004).
 14: WASTE MANAGEMENT
Table 14.4 Recycling Parameters for Plastics (kg/ton)

FOR
Parameter PET PE PP PS PVC

POLYMERS
Virgin Recycled Virgin Recycled Virgin Recycled Virgin Recycled Virgin Recycled
Energy (GJ) 107.15 46.07 79.76 19.94 76.42 19.87 84.8 11.63 59.8 9.13
Air emissions

IN
CO2 2363 163 2400 163 2100 942 2200 942 2000 942

FOOD PACKAGING INDUSTRIES

PFC (CO2 25 0.016 28 0.016 28 0.016 24 0.016 22 0.016
eq.)
CH4 9.5 0.081 6.5 0.081 6.4 0.081 6.9 0.081 6.3 0.081
NOx 7.2 6.95 7.8 6.95 7.7 6.95 5.9 6.95 5.8 6.95
VOCs 14 n/a 4.9 n/a 5.4 n/a 5.2 n/a 5.3 n/a
SOx 4.6 n/a 1.5 n/a 1.7 n/a 2.4 n/a 1.4 n/a
PM n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a
Pb n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a
Hg n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a
Cd 0.058 n/a 0.011 n/a 0.014 n/a 0.014 n/a 0.016 n/a
HCl n/a n/a n/a n/a n/a n/a n/a n/a n/a n/a
Source: Adapted from Molgaard (1995), Eulalio et al. (2000), EPA (2002), and Haight (2004).

273
274 PLASTIC FILMS IN FOOD PACKAGING

Table 14.5 Treatment Routes Employed by European and Other Nations (%MSW)

Nation Recycled and Composted Incineration Landfill

Switzerland 29 59 12
Denmark 23 48 29
Sweden 19 47 34
France 13 42 45
The Netherlands 19 35 45
Germany 18 36 46
Austria 24 11 65
Norway 11 22 67
Finland 15 2 83
Belgium 3 54 43
Italy 10 16 74
Spain 30 6 65
Ireland 3 0 97
Luxembourg 3 75 22
Portugal 15 0 85
United Kingdom 2 10 88
Canada 12 8 80
United States 17 16 67
Greece 0 0 100
Source: Adapted from Onusselt (1997).

Table 14.6 Glass Container Recycling Rates in Europe (%)

Country 2006 2007 2008 2009 2010 2011

Germany 18.04 18.19 18.70 18.81 18.17 18.72
France 17.77 16.69 16.16 15.70 15.12 15.24
Italy 16.47 16.14 16.59 16.59 16.82 16.43
Poland 5.19 5.48 3.94 4.52 4.73 4.56
United Kingdom 10.02 10.00 10.97 10.53 11.11 10.64
Spain 9.97 9.90 9.68 9.60 9.50 9.51
Portugal 5.08 5.48 5.65 6.41 6.29 6.22
Austria, Belgium, Denmark, Estonia, 9.31 9.58 9.36 9.45 9.35 9.40
Sweden, Switzerland, The Netherlands
Bulgaria, Czech Republic, Greece, 5.33 5.36 5.44 5.30 5.12 5.64
Hungary, Romania, Slovakia
Turkey 2.77 3.14 3.56 3.05 3.74 3.78
Source: Adapted from FEVE (2012).
14: WASTE MANAGEMENT FOR POLYMERS IN FOOD PACKAGING INDUSTRIES 275

Table 14.7 Energy and Emissions from Recycled and Virgin Glass Production

Recycled Glass Virgin Savings/Tons Savings/Tons

(100%)/Tons Glass/Tons Recycled Glass Recovered
Source Produced Produced Produced Glass Used
Energy 5.8 9.6 3.8 3.7
consumption (GJ)
Air emission (g) 428 17,780 17,352 16,831
particles
CO 57 105 48 47
NOx 1586 2270 684 663
N2O 12 106 94 91
SOx 2652 3927 975 946
HCl 6 75 69 67
HF 2.4 1 2 23 2 22
Ammonia 2 4 2 1.9
Lead 16 0 2 16 2 15.5
Water emissions (g)
BOD 1 1 0 0
COD (chemical 2 4 2 1.9
oxygen demand)
Total organic 20 26 6 5.8
compounds
Solid waste (kg) 29.3 4.0 2 25.3 2 24.5
Source: Adapted from Arvanitoyannis and Bosnea (2001a,b).

70

60

50
Percentage (%)

40

30

20

10

0
1997 1998 1999 2000 2001 2002 2003
Year

Figure 14.15 The percentage recycling of glass, aluminum, and PET in the European Union and the United
States (V PET in European Union, ¢ aluminum in European Union,  glass in European Union, ’ PET in the
United States, X aluminum in the United States, and K glass in the United States). Source: Adapted from
http://container-recycling.org/aluminrate/gaphs.thm and http://europa.eu.int/lib/.
276 PLASTIC FILMS IN FOOD PACKAGING

Gravity and centrifugal techniques make use of the for identification. The main systems available need
different densities (specific gravity) of the materials. a relatively smooth-surfaced plastic to be effective.
Such a system is employed by Duales System, MIR systems are accurate, but the polymer to be
where the mixed plastics, after being cleaned, are sus- identified needs to be close to the sensor for at least
pended in water and enter the centrifuge as a suspen- a second and identification takes a few seconds
sion. Particles with a higher density than water more. Systems that use UV and visible spectros-
precipitate down to the centrifuge bowl while the copy are also used for polymer identification.
lighter particles float on the surface and are extracted. Electrical charges vaporize the plastic’s surface,
Sorting out specific types of plastic is feasible but the and the analysis of the emissions gives an accurate
process has to be repeated with several centrifuges. identification regardless of the color or coating.
Other methods employ rotating disks and inclined Computer software is essential in these devices.
belts. The principles of plastic flotation show that it Another technique is based on laser-induced plasma
is more flexible than other techniques and could spectroscopy where lasers are used to vaporize the
prove useful in separating mixtures of plastics, but plastic’s surface and the emissions are analyzed by
more research needs to be carried out for its success- a spectrometer. The device is highly accurate, addi-
ful implementation in industry. Separation according tives can also be identified, and the method is quite
to shape can be conducted manually. Optical methods rapid. Raman spectroscopy is a method under
are based on IR, UV, and visible spectroscopy; laser- development that is expected to become one of the
induced plasma spectroscopy; X-ray spectroscopy; most reliable identification technologies. This sys-
and fluorescence and NIR detectors. IR spectroscopy tem uses lasers to generate light from the sample
uses the way different materials respond to IR light that provides identification upon analysis. Laser
for identification. Although IR spectroscopy is very impulse thermography is another identification
selective and rapid, it is rather expensive and technique that uses laser beams. A carbon dioxide
unsuitable for industrial applications, apart from spe- laser generates two “spots” of energy onto a sam-
cial sorting installations, because only thin-film speci- ple. The rise in temperature is measured, as is the
mens can be scanned. The X-ray spectroscopic cooling rate, which both differ based on materials.
processes that are commonly used are fast, and reli- Although fast, it is still under development because
able, but are appropriate only for PVC detection since of current limitations. Mass spectroscopy may also
they depend heavily on the layer thickness while be used in identification. Finally, color images can
sources of radiation are objective, comparatively be identified with special digital cameras to recog-
expensive, and of limited applicability. This process nize different colors for sorting mixed plastics or
is usually combined with IR spectroscopy. Some of removing contaminants. In addition, another system
the latest methods employ NIR systems, which have uses people to identify and sort items passing on a
proved to be more advanced than IR because of its conveyor belt simply by their touching the image of
fast response and higher detectability. In this area, a selected items on a video screen.
tremendous amount of research has been carried out Electrostatic techniques are based on the electri-
over the past few years. A system using NIR was cal properties of plastics. Plastics have a range of
developed by Buhler and launched in late 1993. The electrical properties and any differences can be
system, named NIRIKS, enormously increased the used both to identify and separate them. The exist-
measuring speed and was designed as a pure indus- ing devices are portable and cheaper than many
trial unit. other systems. Unfortunately, they are only really
The system was flexible, rapid, and quite accu- effective at differentiating plastics with distinctly
rate. Another system using NIR was developed by different characteristics, which is a limitation factor
Bayer and employs fluorescence spectroscopy regarding their applicability. Any water in the sys-
(XFS, X-ray fluorescence spectroscopy) for identi- tem can also cause problems. A project funded in
fying halogens and heavy metals. Short-wave NIR Germany called “optical recycling” aimed at devel-
spectroscopy uses low-wavelength IR light for oping a reasonably priced process in which a
polymer identification. The technology is quite lim- single compact device would detect the type of
ited but the equipment is easy to use, compact, and plastic by using NIR, the color with color cameras,
portable. Fourier transform mid-infrared spectros- the shape by using a 3-D measuring device, and
copy (MIR) uses the light reflected from a plastic any impurities and residues present in the package
14: WASTE MANAGEMENT FOR POLYMERS IN FOOD PACKAGING INDUSTRIES 277

with an X-ray module. Strongly charged particles desired properties. Finally, molded-in codes can be
of plastics are deflected in free fall in a high- used for identification and sorting of plastic waste.
voltage field (120,000 V) toward the electrode and Molded bar codes appear to be the simplest, most
are separated. This method of sorting is based on cost-effective approach, but their main disadvan-
electrostatic differences between polymers, and it is tage resides in the possibility that any damage
independent of density, size, or shape. The advan- occurring to the label, which is likely to happen,
tages of this technique are its effectiveness and the would render the code illegible. The analysis on the
low energy required, but it is still on the pilot scale composition and properties of plastic waste and the
and the presence of additives makes the separation physical properties of plastics demonstrates that,
difficult. although several separation technologies can be
Another technique is the use of tracers (i.e., fluo- applied to separate mixed plastics, their applicabil-
rescent) for identification and sorting of plastics. A ity is still very limited (Brown, 1993; Eisenreich
European project, set for the implementation of tra- et al., 1995; Hull et al., 1994; Kenny, 1995;
cers on an industrial scale, concluded that it is a fast Lambert, 1995; Riess, 1995; Saetti and Peroni,
and reliable identification technique. Furthermore, 1995; Schudel and Koller, 1995; Soler, 1992).
marking by tracers can differentiate between grades The techniques used for separation of different
of generic type plastics and also by destination, for kinds of plastics are based on differences in den-
example, one specific tracer used for plastics not to sity, shape, color, physicochemical properties, and
be recycled. The ultrasonic technique is based on solubility. The solubility-based processes (SDP)
the use of ultrasound attenuation measurements, include stages of dissolving a series of incompatible
which were developed for medical diagnostic ana- polymers in a common solvent at various tempera-
lyzes by Langton. A specialized computer was tures or in different solvents, so that one polymer is
designed for this specific application and patented separated each time. The method employed to
by Hull and Langton in order to assist the classifica- recover the polymer after the dissolution stage varies.
tion and identification of polymer waste. The ultra- So far, the SDP have been successfully applied in a
sonic analysis offers a cheap, reliable technique able laboratory scale for the recycling of PP pipes, rigid
to be used both on- and off-line. PVC bottles, polystyrene (PS) waste foam, LDPE
By air classification, it is quite easy to distin- film from greenhouses, and HDPE bottles from agro-
guish a thick-walled from a thin-walled polymer chemical packaging (Pappa et al., 2001; Poulakis and
such as LDPE and HDPE. Any small and big frag- Papaspyrides, 1995). The technique involves the fol-
ments can be effectively identified by microniza- lowing steps, shown graphically in Figure 14.16:
tion. This method is usually applied to separate
PET and PVC. The different specific densities of 1. Cutting the waste into smaller pieces and, if
plastic are used in some sorting plants for develop- necessary, washing with water.
ing automatic sorting techniques as long as the 2. Preliminary separation of the initial mixture
mixed plastics to be sorted are not too heavily con- to two or more mixtures by flotation in water
taminated. The hydrocyclone is an old technique or another liquid.
using this property. In a hydrocyclone, the shredded
3. Addition of a solvent (S) that selectively dis-
and washed plastic fragments are separated in a
solves only one of the polymers under certain
centrifugal field according to their density, resulting
conditions.
in purity of more than 99%. Another device demon-
strated recently is based on solubility of polymers. 4. Filtration to remove the nondissolved polymers.
Using this technique, it is possible to separate six 5. Addition of an antisolvent (AS) to precipitate
or more polymer categories by dissolving them all the dissolved polymer.
in a solvent system and taking advantage of the dif- 6. Filtration and drying of the precipitated
ferent temperature dissolving points (each polymer polymer.
dissolves at a different temperature). This method
has proved to be effective both in laboratory analy- 7. Separation of the S/AS mixture by distillation
sis and industrial applications. This is a very prom- for reuse.
ising technique since modern packages usually 8. Application of the same procedure for each
employ several polymers in order to achieve the polymer of the mixture.
278 PLASTIC FILMS IN FOOD PACKAGING

Precipitation

polymer

polymer
vessel

Dryer
Filter

Pure
Wet
S/AS mixture
Polymer
solution

Distillation

Solvent
column
Filter
Transfer

Antisolvent
Dissolution
Flotation

vessel
Solvent
Washing
Cutting
Polymer
waste

Figure 14.16 Flow diagram of the selective dissolution/precipitation method for the separation of polymer
mixtures. Source: Adapted from Pappa et al. (2001).
14: WASTE MANAGEMENT FOR POLYMERS IN FOOD PACKAGING INDUSTRIES 279

In this study, the SDP method was applied to sep- plastics by froth flotation. In principle, selective
arate mixtures consisting of polyolefins—LDPE, flotation separation of plastics can be achieved by
HDPE, PP—at both laboratory and pilot scale. the following methods:
Excellent recoveries were achieved and the quality
of the recycled polymers remained practically intact. 1. gamma flotation using a liquid medium with
The feasibility study of the method for a high- a specific value of the surface tension,
capacity unit, based on the scale up of the pilot one, 2. chemical conditioning using adsorption of
showed that the cost of the recycled polymer is com- wetting agents,
parable to the commercial price of the virgin one.
Dodbiba et al. (2002) studied the separation of 3. physical conditioning, for example, plasma
PET
PE and PET
PP mixtures in order to improve treatment or wet oxidation,
the grade of the raw input used in PET bottle recy- 4. hydrophobic modification using a chemical
cling. First, PET bottles and their caps (made of PE conditioning agent such as a plasticizer, for
or PP) were shredded and the floatability of each example, diisodecylphthalate on PVC.
polymer was tested. Even with the addition of the
wetting reagents, dodecylamine acetate (DAA) or In general, all these methods emphasize the
PVA, the results did not suggest that the required modification of the plastic surface or the flotation
99.995% purity of PET plastic could not be medium, and in many cases, this can be success
achieved by flotation. Second, the mixtures were with different plastics leading to high selectivity in
separated with a sink
float process using a drum separating mixtures. From the results, it was shown
separator. Finally, as the required purity of PET that plastics flotation is affected not only by surface
could not be obtained by either technique alone, a chemical factors but also by gravity factors. It is
system utilizing a combination of the two processes suggested that plastics flotation should be carried
was developed. This system easily achieved the out by a combination of froth flotation and gravity
desired PET grade. Finally, some sink
float experi- separation. According to this relation, the idea of
ments were performed in a magnesium sulfate particle control was first applied for the separation
medium (dense medium separation). of plastics mixtures. From the separation results, it
Shen and coworkers (2002) found that the float- was deduced that this method can greatly increase
ability of all the plastics decreased with the addition the separation efficiency for flotation separation of
of surfactant, but they are different in floatability plastics mixtures. The particles in cutting products
and follow the order POM (polyoxymethylene) , are not uniform in size and shape. Cutting products
PVC , poly(methyl methacrylate) (PMMA) , of PMMA and POM have a relatively wide size
PET , polycarbonate (PC) , acrylonitrile butadiene distribution and contain a considerable number of
styrene (ABS) , PS. From the separation test results particles of less than 1 mm in diameter, which are
of several plastic mixtures, it was shown that the difficult to depress by wetting agents. PVC and PS
Gamma flotation method not only can be used to give an intermediate size distribution with an inter-
separate plastics mixture with different densities, mediate left tail but a small right tail. Finally, ABS,
such as separation of POM and PVC from PC, POM PC, and PET gave a relatively narrow particle size
and PVC from PS and ABS, PET and PMMA from distribution. Particle shape tends to be more irregu-
PS and ABS, but also can be used to separate plas- lar in the fine size fractions. The equation and the
tics mixtures with similar density, such as separation experimental results showed that particle size and
of PMMA from PC. Products with grade higher than shape control are important for plastics flotation. It
99% and recovery higher than 97% can be obtained is an effective way to improve the separation effi-
for the separation of some plastic mixtures. It was ciency for plastics flotation (Shen et al., 2001).
found that the depressing effect of surfactant 15-S-7 The dry separation of a mixture of three plastics
on the plastics is mainly due to the reduced liquid by combining air tabling and triboelectric separa-
surface tension, and flotation selectivity for the plas- tion has been described (Dodbiba et al., 2005).
tics with identical particle size is dominated by con- While air tabling is effective for particles of differ-
tact angle, particle density, and shape. ent density, the triboelectric separation can be used
Over recent years, several experimental studies for separation of particles of similar density. Before
have been reported describing the separation of commencing the separation tests, the effectiveness
280 PLASTIC FILMS IN FOOD PACKAGING

of the separating devices was evaluated by analyz- cleaning processes of these plastics (Santos et al.,
ing the effects of the particle size and the difference 2005). Since polyolefins and PET have different
in density between components of the mixture. A characteristics, the conditions used during the wash-
two-stage process has been proposed for separating ing process also differed from each other.
mixed plastics prior to recycling. PP, PET, and Specifically for PET, a step that carries out the sepa-
PVC were selected for investigation as they are ration of labels and caps residue by differences in
widely used in the manufacture of everyday pro- density is necessary. Furthermore, the susceptibility
ducts. An air table was employed for the first stage of PET to adhesive residues during processing also
of the process to collect a PP-rich low-density frac- requires more aggressive conditions in the washing
tion and a PET/PVC high-density fraction. In the step in order to maximize the adhesive removal
second stage, the PET/PVC fraction was separated (Sanko, 1999). Care was taken not to use high alka-
by means of a triboelectric separator utilizing dif- linity content. As an alternative, increments in bath
ferences in surface charge. A mixture of PP, PET, temperature are recommended. Ordinary tap water
and PVC was selected for investigation. Each com- without addition of any chemical was used for the
ponent amounted to one-third of the total mass of prewashing step. Caustic soda was then used in the
the mixture. Thus, high-density plastics (i.e., PET washing step for both plastics, though surfactant was
and PVC) amounted to approximately 67% of the used only for PET. No significant differences in the
total. Before commencing the separation tests, the effluent characteristics were found between the two
effectiveness of the techniques was evaluated by types of plastic studied and between the prewashing
investigating the effects of the particle size and the and washing steps, except those differences intrinsic
difference in density between components of the to the cleaning processes (temperature, surfactant,
mixture. The triboelectric separation was effective caustic soda concentration). Some specific unit dif-
for separating materials of similar density. ferences are necessary depending on the type of
However, an upper limit of particle size was set plastic used due to extrapolation of emission limits
after considering the magnitude of the surface of oil and grease in the polyolefins prewashing step
potential attained by plastics and the maximum and Pb excess in the PET washing step.
electric field strength that the triboelectric separator Cryo-comminution of plastic waste was recently
could create without causing electric breakdown. introduced by Gente and coworkers (2004).
The air tabling was effective if the density differ- Laboratory comminution tests were carried out
ence between particles was at least 450 kg/m3 and under different conditions of temperature and sample
the feed was properly sized. A general schematic preconditioning adopting CO2 and liquid nitrogen as
flow sheet of the dry process for separating mix- refrigerant agents. The temperature was monitored
tures of three plastics is shown in Figure 14.17. by thermocouples placed in the milling chamber.
The plastic waste samples (PET, HDPE, and PP) Moreover, different internal mill screens have been
were taken from an MSW separating and compost- adopted. A proper procedure has been set up in order
ing plant (Araraquara, SP, Brazil). The PET con- to obtain a selective comminution and a size reduc-
sisted predominantly of carbonated soft drink tion suitable for further separation treatment. Tests
bottles, plus a few water and vegetable oil bottles. have been performed on plastics coming from medi-
The HDPE and PP were mainly packaging materials cal plastic waste and from a plant for recycling spent
from cleaning, personal hygiene, utensils, food, and lead batteries. Results coming from different mill
automotive mineral oil products. The polyolefins devices have been compared taking into consider-
were mixed in a proportion 9:1 (HDPE:PP) accord- ation different indexes for representative size distri-
ing to a recent study on MSW composition (Mancini butions. The results of the performed tests showed
et al., 2000). Owing to the heterogeneity of contami- cryo-comminution improves the effectiveness of size
nation of these wastes, one lot (ca. 40 kg) for each reduction of plastics, promotes liberation of constitu-
of these materials (PET and polyolefins) was ground ents, and increases specific surface size of commi-
in a knife mill and then mixed and homogenized in nuted particles in comparison to a comminution
an appropriate bag. Afterwards, three samples of process carried out at room temperature.
about 3 kg each were taken from these lots and Flame treatment was effectively used to modify
cleaned independently in order to achieve three typi- the surface of plastics to allow water-based coatings
cal samples of wastewater generated during the to be attached. The effect of the treatment was to
14: WASTE MANAGEMENT FOR POLYMERS IN FOOD PACKAGING INDUSTRIES 281

PP, PET,
PVC

Shredding

Screening I

No

Is screening I
appropriate?
Screening II
Yes
No
Screening II
Is screening II
appropriate?
Product
Air table
1
Yes

Air table
Triboelectric
cyclone separator

Product Product
2 3

Figure 14.17 A general scheme flow sheet of the dry process for separating mixtures of three plastics.
Source: Adapted from Dodbiba et al. (2005).

produce hydrophilic species on the surface of the Separation of the treated virgin plastic by froth flo-
plastic. The process is therefore potentially useful tation was found to be possible, by careful control
for the separation of plastics by froth flotation, pro- of added frother. The technique was then consid-
vided that the production of the hydrophilic surface ered for the treatment of postconsumer plastic bot-
can be achieved selectively. PVC and PET were tles. It was demonstrated that flame treatment was
selected for investigation as they were found as a effective in rendering the surface of both plastics
comingled product in the recovery of beverage con- hydrophilic, although the process alone was not
tainers (Pascoe and O’Connell, 2003). A simple, sufficiently selective. Hydrophobic recovery of the
but effective, flame treatment method for flaked PVC, but not the PET, was achieved by raising the
plastics was developed. The treatment involved the temperature of the material to 140 C for a period
use of an acceleration chute that delivers the flakes of 10 min. A two-stage flotation process was tested
through the flame of an angled burner. In experi- for the separation of the plastics. In the first stage,
ments with virgin plastics, the PVC was found to PET was floated away from the PVC capitalizing
be less susceptible to surface modification than on differences in particle thickness and surface con-
PET, as indicated by contact-angle measurement. tamination. The float product was then subjected to
282 PLASTIC FILMS IN FOOD PACKAGING

flame treatment and hydrophobic recovery prior to process is followed by the shredding and separating
the second stage of flotation. In this stage, the PVC steps, thus reducing the mixed plastics to a grain
was conveyed to the float product leaving a PET- size of less than 50 mm and producing a more or
rich sinks fraction. less homogeneous material. The target of agglomer-
Hearn and Ballard (2005) developed two sorting ation is to convert mixed plastics into a product
techniques using the electrostatic properties of with specific properties suitable for recycling. The
materials to produce separate material streams for final product should be pure and easily processable.
the purposes of recycling. Trials were undertaken In this process, the preshredded mixed plastics
using typical common items of waste packaging, were fed into rotating blades and heated to
giving encouraging results. Early results indicate 135
140 C. As a result, small pieces of film sheet-
reliable operation under a range of environmental ing cake together and can then be processed into
conditions; however, the effects on sorting effi- compact plastic granules. Moreover, inpelletizers
ciency of extremes of surface contamination, mois- are also employed so that plastics compacted by
ture, temperature, and humidity have yet to be means of pressure are cut off by cutters and subse-
quantified. It is recognized that the presence of quently pelletized. However, agglomeration is con-
high levels of surface contamination on the waste sidered a “young” technology requiring further
items to be streamed may cause problems, particu- research and development work (Pearson, 1996).
larly for the triboelectric sensor probe. Preliminary
examination of material from an MRF (materials
recycling facility), however, suggests that these 14.8.4 Mechanical Recycling
materials are generally not heavily contaminated The purpose of mechanical recycling is to pro-
with anything other than moisture. The presence of cess postconsumer plastics and recover a secondary
surface water does significantly influence both raw material for the production of new items
charge generation and triboelectrification. MRFs (Pearson, 1996). Packaging material sorted into
and plants where these techniques are likely to be individual fractions is either melted down directly
applied lend themselves to the application of driers and molded into a new shape or melted after being
or air curtains that could be installed upstream of shredded into flakes and processed into granules
the electrostatic sorting area. It is also recognized called regranulate. There are several mechanical
that this technique may not be appropriate for all recycling processes: extrusion and intrusion, injec-
polymer types but can be used in conjunction with tion molding, transfer molding process, and regra-
other techniques. Such techniques may include an nulation (http://www.eps.co.uk/mechanical.html). In
optical sensor to separate PVC from HDPE and the extrusion process, the regranulate is heated and
Fourier transform IR spectroscopy (Hearn, 2003) to melted into a plastic mass, which is then transferred
sort the stream containing PET/PETE and PS. to molds for simple products such as profile section
Difficulties may be encountered with certain pack- or sheets. The only difference between extrusion
aging geometries and the presence of labels and and intrusion processes is that, in the latter, impuri-
coatings with respect to all of these issues, the use ties such as glass fragments, sand, and wooden
of the small triboelectric probe is an advantage as it pieces can remain in the plastic melt. The extruder
can be directed at an area of packaging that is most is designed in a way so that impurities are embed-
likely to constitute exposed polymer. ded in the plastic melt. The molten mass is pressed
directly into molds such as honeycomb-type paving
stones. Circulation of cold water speeds up the
14.8.3 Preparation for Recycling hardening process of the paving stones, which can
After the materials have been collected and be removed from the molds after a short time. The
sorted, they must be converted into a homogeneous molten plastic mass, during the injection molding
pourable bulk material that is easy to transport and process, is injected into a mold under high pressure.
store and is suitable for recycling. The quality crite- Similar to the intrusion process, the machines are
ria are high bulk density, defined grain size, low designed for processing mixed plastics containing
chlorine content, and low dust content. These prop- impurities. The molten plastic is pushed by the pis-
erties can usually be achieved within the frame of ton into the mold for the article to be produced.
the agglomeration process. The agglomeration The pressure on the piston remains constant until
14: WASTE MANAGEMENT FOR POLYMERS IN FOOD PACKAGING INDUSTRIES 283

the tray has cooled down and can safely be into individual materials. Recent predictions for the
removed from the mold (Pearson, 1996). During packaging film market suggest the replacement of
the molding process, mixed plastics are shaped into PS and PVC with PP.
finished products by means of direct melting and Therefore, the use of compatibilizers—chemical
molding, either without or after only coarse pre- additives that assist the blending of various polymer
shredding. Finally, in the regranulation process, the types—helps to alleviate some of the problems of
postconsumer plastics are sorted into different frac- blended polymers. The addition of 5% of an
tions, heated, and regranulated. The plastic pro- ethylene-vinyl acetate (EVA) film grade polymer of
duced in this way can be used in various sectors 28% VA content substantially improved the proper-
such as construction (frame sections, cable insula- ties of 85/15 LLDPE/PP mixtures (Teh et al.,
tion, piping, insulating materials, etc.), packaging 1994). Furthermore, several new linear ethylene
and logistics (film sheeting, hollow containers, polymers have been successfully used to increase
transport containers, pallets), and industry (shaped the recyclable content of postconsumer recycled
parts for the car industry). Recycled films can be polyolefins to high levels, while maintaining good
manufactured from used PE films. Films of film properties (Begley and Hollifield, 1993).
recycled materials and virgin material can be perma- Safety and contamination considerations and cur-
nently joined to produce frame sections of film sheet- rent legislative standards are the main obstacles for
ing by co-extrusion (http://www.environment97.org/). an extensive use of mechanically recycled polymers
It is estimated that the recycling rate for foamed PS by the food packaging industry. Nevertheless, pack
can reach 100%. The material is broken down to its designers and polymer scientists can facilitate the
components and either added to new foamed PS recyclability of food packs so they can be easily
packaging or regranulated to produce the starting used for other applications. The obvious dominance
material PS that is utilized for the manufacture of of the food sector within the overall packaging
injection-molded parts. In Germany, a recycling market suggests that a response of this kind by the
rate of 40% has already been achieved. However, it food packaging industry is expected to have a key
should be mentioned that current standards and reg- influence on the future of plastic recycling.
ulations prevent secondary plastics from being used The increasing consumption of polymeric
to an even greater extent. For instance, packaging blends results in a great environmental impact
for foodstuff may only be manufactured from virgin because the used plastics are discarded in nature in
polymers. Similarly, the production of certain types a nonrational form. As a solution to all these pro-
of piping prohibits the use of regranulate. In princi- blems, recycling becomes a powerful strategy
ple, most of the 9.1 million tons of plastic utilized regarding the reduction of the environmental
in packaging in Western Europe could be recycled impact caused by plastic waste. Polymeric blends
by remelting and extrusion or molding into films. were prepared with mechanical recycling and char-
Actually, in 1996, 53% of the plastic sales for acterized. LDPE/Al residues from cartoned pack-
packaging were recycled mechanically, and more aging were blended with recycled HDPE/LDPE
than 90% has been recycled in Germany since and virgin PE resins. It was observed that pro-
1997. Therefore, the mechanical recycling process cessability, mechanical properties, chemical resis-
is an important technique despite the problems that tance, and water absorption are dependent on the
have been encountered in practice (Halle, 1994), blend compositions. Also, an aluminum film was
including the high cost of collection and separation found to remain as isolated particles in the poly-
equipment, the lack of a substantial and reliable meric matrix, and the mechanical behavior of the
market for the recycled material, and limited appli- blend depends on the aluminum dispersion.
cations (i.e., exemption of food packaging materi- Moreover, the blend water absorption depends on
als) for the recycled materials. The implications of recycled material contamination, mainly PAs.
mechanical recycling have partially influenced Finally, the amount of recycled material added to
packaging design. The three predominant trends the blends determines both chemical stability and
can be summarized as follows: an increased need thermal characteristics (Paula et al., 2005).
for simple structures consisting of a single polymer Recycling of mixed plastic wastes composed of
or at least a single polymer type instead of complex LDPE matrix and PP was carried out by compound-
multilayer structures, which are difficult to separate ing using single-screw or twin-screw extruders.
284 PLASTIC FILMS IN FOOD PACKAGING

Blends of virgin polymers were prepared to com- wastes and elastomers is a cost-effective process to
pare mechanical properties of both virgin and recover feedstocks for the petrochemical industry.
regenerated materials. First, a model composition The Hamburg process, using an indirectly heated
of virgin LDPE/PP blend was prepared to study the fluidized bed, can be varied to produce mainly
effect of process parameters and that of different monomers, aliphatic hydrocarbons, or aromatics. At
types of compatibilizers. Second, the results were temperatures of 450 C, PMMA is depolymerized to
applied to industrial postconsumer plastic waste. more than 98% of the monomer. However, the
The mixture of plastic wastes was purified in a influence of fillers on the monomer yield has been
pilot plant by grinding, washing, and separating. studied. PS as feed gives up to 75% of styrene and
The detailed treatment is shown in Figure 14.18. 10% of oligomers. First demonstration plants are
By adding compatibilizing agents such as ethylene- running for feedstock recycling of PMMA in a flu-
propylene-diene monomer, ethylene-propylene idized bed.
monomer, or PE-g-(2-methyl-1,3-butadiene) graft Schemes such as the Duales System Deutschland
copolymer, elongation at break and impact strength in Germany (“green dot”) have addressed feed recy-
were improved for all blends. The effect of these cling, but there remains the high energy and process
various copolymers was quite different and was in costs of the feedstock recycling technology. Thermal
relation to their chemical structure. The recycled and catalytic cracking, although effective, require
blends exhibited suitable properties leading to significant operating temperatures and are strongly
applications that require good mechanical proper- endothermic, leading to large adiabatic temperature
ties (Bertin and Robin, 2002). falls across reactors. Oxidation methods, energeti-
cally more favorable, are carried out at high tempera-
ture and have associated difficulties such as
14.8.5 Feedstock Recycling dangerous emissions, product quality, and expensive
The main purpose of feedstock recycling is to materials of construction. Hydro-cracking studies
convert prepared postconsumer plastics into their have been limited to date and merit further study
basic components, such as oil, gas, naphtha, and to since the process is exothermic and can be carried
use them as secondary feedstocks in refineries or out at significantly lower temperatures (Garforth
petrochemical industries for the production of new et al., 2004). Total plastic waste generated and recov-
plastics, paints, or adhesives. Post-consumer plastics ered in Western Europe is given in Figure 14.19.
may also be utilized as a substitute for valuable raw Feedstock recycling by catalytic cracking of a
materials like oil. Plastics can be effectively applied real plastic film waste from Almeria greenhouses
in the production of steel. Currently, the carbon and (Spain) toward valuable hydrocarbon mixtures was
hydrogen molecules bound in plastics are used for studied over several acid catalysts (Serrano et al.,
the reduction of iron oxide. A single industrial-scale 2004). The plastic film waste was mostly made up
plant for feedstock recycling has a capacity of of ambient degraded LDPE and EVA copolymer,
100,000 t of postconsumer plastic per year. The the vinyl acetate content being around 4 wt%.
techniques employed consist of hydrogenation, Nanocrystalline HZSM-5 zeolite (crystal size
BASF (Badische Anilin und Soda Fabrik) process, B60 nm) was the only catalyst capable of degrad-
etc. and are of crucial importance in the recycling ing completely the refuse at 420 C despite using a
of plastics (Caluori, 1995). very small amount of catalyst (plastic/catalyst mass
Steel and iron have been overtaken after a period ratio of 50). However, mesoporous catalysts (Al-
of 3000 years as the most used and most versatile SBA-15 and Al-MCM-41), unlike as occurred with
materials by the different kinds of plastics, and this virgin LDPE, showed fairly close conversions to
in a period of only 50 years. Feedstock recycling is that of thermal cracking. Nanocrystalline HZSM-5
one of the greatest challenges for the recycling of zeolite led to 60 wt% selectivity toward C1
C5
plastics, and various technologies have been suc- hydrocarbons, mostly valuable C3aC5 olefins, that
cessfully demonstrated and continue to be devel- would improve the profitability of a future indus-
oped. Kaminsky and coworkers (2004) investigated trial recycling process. The remarkable perfor-
different processes such as degradation of plastics mance of nanocrystalline HZSM-5 zeolite was
to monomers, pyrolysis into monomers and oil, gas- ascribed to its high content of strong external acid
ification into syngas. Pyrolysis of mixed plastic sites due to its nanometer dimension, which are
 14: WASTE MANAGEMENT
Water
Slugs

FOR
fibers

POLYMERS
Plastics Metal Wet
Conveying Filtration
waste detection grinding

Hydrocloning I
Filtrate
(D  2)

IN
FOOD PACKAGING INDUSTRIES
Hydrocloning II Pure Metals
(D  1) materials Stones
Glasses

Light Heavy
Polyolefins Drying Filtration
fraction fraction

PVC
PET
PS

Figure 14.18 Flow sheet of the recycling pilot plant. Source: Adapted from Bertin and Robin (2002).

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