Dental Biomaterials

Dental Biomaterials
10589_9789813225671_tp.indd 1 21/11/18 3:14 PM

World Scientific Series:
From Biomaterials Towards Medical Devices
ISSN: 2529-816X
Series Editors:
Roger Guilard
Université de Bourgogne
UFR Sciences et Techniques
Faculté des Sciences Mirande
ICMUB – UMR CNRS 6302
9 Avenue Alain Savary, BP 47870
21078 Dijon Cedex, France
Email: roger.guilard@u-bourgogne.fr
Karl M Kadish
Department of Chemistry
University of Houston
Houston, TX 77204-5003, USA
Email: kkadish@uh.edu
Vol. 1 Drug Delivery Systems

edited by Pieter Stroeve (UC Davis) & Morteza Mahmoudi
(Tehran University of Medical Sciences, Iran &
Harvard Medical School, USA)
Vol. 2 Dental Biomaterials

edited by Edward Sacher (École Polytechnique de Montréal, Canada) &
Rodrigo França (University of Manitoba, Canada)
Forthcoming
Biomaterials and Bioengineered Device Research for Ligament Reconstruction

edited by Véronique Migonney ((Université Paris 13, France) &
L’Hocine Yahia (École Polytechnique de Montréal, Canada)
Biomaterials and Bioengineered Device Research for Joint Prostheses

edited by L’Hocine Yahia (École Polytechnique de Montréal, Canada) &
Véronique Migonney (Université Paris 13, France)
Biomaterials and Bioengineered Device Research for

Cardiovascular Applications
edited by Laurence Bordenave (Université de Bordeaux, France)
JQuek - 10589 - Dental Biomaterials.indd 1 26-11-18 10:31:23 AM

World Scientific Series in
From Biomaterials Towards Medical De ices – Vol. 2
Dental Biomaterials
editors
Edward Sacher
École Polytechnique de Montréał, Canada
Rodrigo França
University of Manitoba, Canada
Series Editors
Roger Guilard
Université de Bourgogne, France
Karl M. Kadish
University of Houston, USA
World Scientific
NEW JERSEY • LONDON • SINGAPORE • BEIJING • SHANGHAI • HONG KONG • TAIPEI • CHENNAI • TOKYO
10589_9789813225671_tp.indd 2 21/11/18 3:14 PM

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Library of Congress Cataloging-in-Publication Data

Names: Sacher, Edward, 1934– editor. | França, Rodrigo (Dentist), editor.
Title: Dental biomaterials / edited by Edward Sacher and Rodrigo França.
Other titles: Dental biomaterials (Sacher) | World Scientific series:
from biomaterials towards medical devices ; vol. 2.
Description: New Jersey : World Scientific Publishing, 2018. |
Series: World scientific series : from biomaterials towards medical devices ; volume 2 |
Includes bibliographical references and index.
Identifiers: LCCN 2018033218 | ISBN 9789813225671 (hardcover : alk. paper)
Subjects: | MESH: Dental Materials
Classification: LCC RK652.5 | NLM WU 190 | DDC 617.6/95--dc23
LC record available at https://lccn.loc.gov/2018033218
British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library.
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JQuek - 10589 - Dental Biomaterials.indd 2 26-11-18 10:31:23 AM

“9x6” b3252 Dental Biomaterials
Preface
The development of the science of dental biomaterials has always

been a driving force of dentistry. The first controlled testing of dental
amalgam by Dr. Greene V. Black in 1900, the introduction of the acid
etching technique by Dr. Michael Buonocore in 1955, and the
formulation of polymeric dental filling by Dr. Rafael Bowen in 1962
are just a few examples of the impact of dental biomaterials in restora-
tive dentistry. In the same way, in the 21st century, the flourishing of
nanotechnology and tissue engineering offer opportunities to inno-
vate new biomaterials to promote oral rehabilitation. In dentistry, we
are presently living in a transitional era, where, in dental offices, most
practitioners restore cavities as was done fifty years ago, while, in
dental biomaterials laboratories, new approaches, such as the dental
bioengineering of tissues, are being tested. As a consequence, a trans-
formational wave is forming on the horizon.
The conception and production of dental biomaterials are not
easy tasks. In the past, the evolution of dental materials was based on
an idea, conceived and exploited by a “hero dentist”, while today, this
progress depends on teams of experts in several areas of expertise,
such as biomedical engineering, dentistry, chemistry, biology, and
materials science. The particularity of the oral environment makes
dental biomaterials different from those used in other parts of the
body. As an example, the color and the coefficient of thermal expan-
sion of a ceramic used in a hip prosthesis are not major issues, while
b3252_FM.indd 5 28-11-2018 10:21:26 AM

b3252 Dental Biomaterials “9x6”
vi Preface
they are so for a ceramic used as a dental veneer. Such complexity

requires a new kind of professionals: Dental biomaterials researchers
with broad, deep, and multidisciplinary knowledge.
This book was developed in preparation for this new reality.
We invited experts from universities in Brazil, Canada, Switzerland, and
the United States to present information in advanced recent topics, as
aids to novice researchers in the dental biomaterials field. We have done
this in the following way. Chapters 1–3 provide fundamental informa-
tion on dental biomaterials characterizations. Chapter 4 focuses on
biomaterials aimed at preventing oral diseases, and Chapter 5 discusses
the toxicity of mercury. Chapters 6–8 present comprehensive studies of
ceramic materials and their failure modes. Direct restorative materials
are discussed in Chapters 9–11. Chapter 12 focuses on the important
topic of polymerization contraction stresses occurring in resin-based
composites. Chapters 13 and 14 discuss the use of polymers in pros-
thodontics, and Chapter 15 furnishes information in the new fields of
3D printing and bioprinting in dentistry.
Finally, it is important to recognize that this book was only made
possible thanks to the willingness of all the authors to contribute their
expertises, as well as to the funding agencies that made much of the
work reported in these chapters possible. It is our hope that the
knowledge contained herein will help in furnishing further innova-
tions in the field of dental biomaterials.
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About the Editors
Edward Sacher was born in New York City and

educated in its school system. He received a BS
in chemistry from the City College of New York
and a PhD in physical chemistry from the
Pennsylvania State University. After postdoctoral
fellowships at Ohio State University and the
University of Ottawa, he joined the Film
Department of the DuPont Experimental
Station. This was followed by a position at the
IBM Materials Laboratory. Subsequently, he joined the Department
of Engineering Physics of Montréal’s École Polytechnique, where he
is presently a Professor. He is the Associate Director of the regional
Surface Laboratory, where he carries out research on the physico-
chemical properties of nanoparticles.
vii
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viii About the Editors
Rodrigo França received his DDS degree in

1988 from the University of Itaúna, Brazil, and
his MSc and PhD, in Dental Materials, from the
University of São Paulo, Brazil. Subsequently,
he obtained a second PhD, in Biomedical
Engineering, at Montréal’s École Polytechnique.
He worked as a general practitioner for 18 years.
He has taught dental materials, at both under-
graduate and graduate levels, for the past
20 years. Currently, he is an Associate Professor and Head of the
Dental Materials Division in the College of Dentistry, University of
Manitoba, Canada, and Director of its Dental Biomaterials Research
Laboratory; he also has a cross-appointment in the Department of
Oral Biology. He is a core member of the Biomedical Engineering
graduate program, a member of the Manitoba Institute of Materials,
the Academy of Dental Materials, the Canadian and International
Associations of Dental Research, and the Canadian Biomaterials
Society. His research focuses on physicochemical characterization of
the surface of dental biomaterials, at the nanolevel. The results of his
research team have been presented at several international dental
meetings and published in prestigious peer-reviewed journals.
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Contents
Prefacev
About the Editorsvii
Chapter 1 Surface Analysis Techniques for Dental Materials 1

Edward Sacher and Rodrigo França
1. Introduction 2
1.1. Surface and Interfaces 2
1.2. Surface Energy 3
1.3. Forces at Interfaces 4
1.4. Reactions at Surfaces: Adsorption 4
2. Characterization Techniques 5
2.1. Physicochemical Techniques 7
2.1.1. Contact Angle (CA) 7
2.1.2. X-ray Photoelectron
Spectroscopy (XPS) 8
2.1.3. Auger Electron Spectroscopy (AES) 12
2.1.4. Energy-Dispersive X-ray
Spectroscopy (EDX) 13
2.1.5. Wavelength-Dispersive
Spectrometry (WDS) 14
2.1.6. Time-Of-Flight Secondary Ion
Mass Spectrometry (TOF-SIMS) 15
ix
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x Contents
2.1.7. Laser Ablation Inductively

Coupled Plasma Mass
Spectrometry (LA-ICP-MS) 16
2.1.8. Vibrational Spectroscopies:
Infrared (FTIR) and Raman 18
2.1.9. X-ray Diffraction (XRD) 21
2.2. Morphological Techniques 24
2.2.1. Electron Microscopies 24
2.2.2. Atomic Force Microscopy
(AFM)25
3. Final Recommendations 26
References28
Chapter 2 Nanoindentation Techniques in Dental

Biomaterials33
Mohammad Aramfard and Chuang Deng
1. The Basic Principles of Nanoindentation 34
1.1. Overview 34
1.2. Contact Mechanics 35
1.3. Practical Application of Nanoindentation 39
1.4. The Nanoindentation Probe and Area
Function40
1.5. Operational Modes of Nanoindentation 42
1.5.1. Continuous Stiffness
Measurement42
1.5.2. Scanning Probe Microscopy 42
1.5.3. Nanotribology 43
2. Instrumentation of Nanoindentation 43
2.1. Implementation of Major Commercial
Machines44
2.2. Atomic Force Microscope 44
2.3. State of the Art: In Situ
Nanoindentation45
3. Preliminary Considerations in Dental Materials
Field47
3.1. Human Tooth 47
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Contents xi
3.2. Artificial Dental Materials 49

3.2.1. Ceramics 49
3.2.2. Composites 51
4. Nanoindentation in Dental Materials 52
4.1. Adaptions of Nanoindentation for
Biomaterials52
4.1.1. Probe Selection 52
4.1.2. Creep 53
4.1.3. Viscoelasticity 54
4.1.4. Adhesion54
4.1.5. Hydration 55
4.2. Nanoindentation of Natural Dental
Materials 56
4.2.1. Enamel 56
4.2.2. Dentin 57
4.3. Nanoindentation of Artificial Dental
Materials 59
4.4. Other Types of Tests on Dental
Materials Enabled by Nanoindentation 60
4.4.1. Viscoelastic Properties 60
4.4.2. Creep Behavior 60
4.4.3. Fracture Toughness 61
4.4.4. Nanotribology 62
5. Concluding Remarks and Outlook 62
Acknowledgment63
References63
Chapter 3 Finite Element Analysis in Dentistry 67

Josete B. C. Meira, Alice N. Jikihara,
Pavel Capetillo, Marina G. Roscoe,
Paolo M. Cattaneo, and Rafael Y. Ballester
1. Introduction 68
2. How the Model Geometry is Defined
and Obtained? 68
2.1. Two- or Three-Dimensional Models? 68
2.2. Limitations of 2D Models 69
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xii Contents
2.3. Strategies for Geometry Acquirement 70

2.3.1. Geometry Based on Literature
Data 71
2.3.2. Geometry Based on 3D Scanning 72
2.3.3. Geometry Based on Computed
Tomography 73
2.4. Represented Structures and Model Scale 74
2.4.1. Level A 76
2.4.2. Level B 76
2.4.3. Level C 76
2.4.4. Multiscale 77
3. Mesh Quality and Mesh Convergence 77
3.1. Reducing the Element Size 77
3.2. Increasing Element Order 79
4. Issues Related to Properties of Biological
Materials 80
5. Boundary Conditions and Loading 82
6. Interpretation of FEA Output 82
6.1. The Failure Criteria 83
6.2. The Biological Mechanism 83
6.3. Importance of Results Presentation 84
7. Final Remarks 86
Acknowledgments 87
References 87
Chapter 4 Preventive Dental Material 91

Larissa Bubnowicz and Rodrigo França
1. Introduction 92
2. Preventive Effect of Fluoride on Dentition 92
2.1. Undersaturation versus Supersaturation 93
2.2. Fluoride Physicochemical Reaction
Mechanism Theories 96
2.3. Molecular-Based Structural Model
of Enamel After Fluoridation 99
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Contents xiii
3. Methods of Fluoridation 101

3.1. Community-Based Methods
of Fluoride Use 101
3.1.1. Water Fluoridation 101
3.1.2. Professionally Applied Methods
of Topical Fluoride Use 102
3.1.3. Topical Fluoride Gels 103
3.1.4. Topical Fluoride Foam
and Rinses 104
3.1.5. Topical Fluoride Varnish 104
3.2. Individual Methods of Fluoride Use 105
3.2.1. Fluoridated Dentifrices 105
3.3. Fluoride-Releasing Dental Materials 107
3.3.1. Pit and Fissure Dental
Sealants 107
3.3.2. Glass Ionomer Cements
(GIC) 108
3.3.3. Orthodontic Bonding
Agents 109
3.3.4. Restorative Dental Material 109
3.4. Combination of Methods of
Fluoridation 110
4. Clinical Applications and Recommendations
of Preventive Fluoride 113
References 117
Chapter 5 Mercury Toxicity 125

Gelson Luis Adabo
1. Introduction 126
2. Historical 126
3. Toxicology 128
4. Mercury in Dentistry 131
4.1. Amalgam Safety for Patients 131
4.2. Amalgam Safety for Dentists and
Dental Staff 135
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xiv Contents
4.3. Environmental Issues Related

to Dental Amalgam 139
5. Final Remarks and Recommendations 142
References 142
Chapter 6 Zirconia in Dentistry 147

Paulo Francisco Cesar, Susana
Salazar-Marocho, Erick de Lima,
Lucas Hian da Silva, Karen Fukushima,
and Ranulfo Benedito de Paula Miranda
1. Introduction 148
2. The Bilayer Porcelain/Zirconia 150
2.1. Causes of Porcelain Chipping 150
3. Monolithic Zirconia 153
3.1. Microstructure and Optical Properties 153
3.2. Mechanical Properties 158
4. Fatigue of Dental Ceramics 159
5. Y-TZP for Dental Implants 164
5.1. Tissue/Implant Interfaces 164
5.2. Titanium Implants 164
5.3. Y-TZP Implants 165
References167
Chapter 7 Lithium Disilicate-Based Glass-Ceramics 173

Rodrigo França
1. Introduction 173
1.1. Historical 174
1.2. Classification 176
2. Physicochemical Characterization 178
2.1. Chemical Composition 178
2.2. Mineral Properties 178
3. Fabrication 181
3.1. Nucleation Process 181
3.1.1. Homogeneous Nucleation 182
3.1.2. Heterogeneous Nucleation 183
3.2. Crystallization Process 184
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Contents xv
4. Microstructure 186
4.1. Lithium Disilicate Glass-Ceramics 186
4.2. Zirconia-Reinforced Lithium Silicate
Glass-Ceramics 188
5. Properties of Lithium Disilicate-Based
Glass-Ceramics 191
5.1. Mechanical Properties 191
5.1.1. Fracture Strength 192
5.1.2. Young’s Modulus 193
5.1.3. Fracture Toughness (KIC) 195
5.1.4. Hardness 196
5.1.5. Wear 197
5.2. Other Physical Properties 198
5.2.1. Density 198
5.2.2. Thermal Properties 198
5.2.3. Optical Properties 199
5.3. Chemical Properties 200
5.4. Biocompatibility Issues 201
Acknowledgments 202
References 203
Chapter 8 Fractography of Dental Ceramics 211

Susanne S. Scherrer
1. Introduction 212
2. Qualitative Fractography 213
2.1. Key Fractographic Features 213
2.2. Fractographic Montage of Origins 226
3. Quantitative Fractography and Fracture
Mechanics 227
4. Clinical Failure Analysis 231
4.1. A Systematic Approach 231
4.2. Thin Margin Origins 235
4.3. Contact Wear, Grinding Damage 236
5. Conclusions 239
Acknowledgments 240
References 241
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xvi Contents
Chapter 9 Bioactive Glasses for the Development

of Dental Restorative Materials 245
José Bauer, Ceci Nunes Carvalho,
Edilausson Moreno Carvalho, and
Rodrigo França
1. Introduction 246
2. Bioactive Glasses 247
2.1. Bioglass (45S5) 247
2.2. Biosilicate 250
2.3. Niobium Phosphate Glass 251
3. Restorative Materials Containing Bioactive
Glasses 252
3.1. Glass Ionomer Cements 252
3.2. Composites 256
3.3. Adhesive Systems 261
4. Conclusions and Outlook 265
Acknowledgments 266
References 266
Chapter 10 Dental Adhesives 275

Marcelo Giannini, Patrícia Makishi,
Ronaldo Hirata, and Carolina Bosso André
1. Introduction 276
1.1. Mineralized Dental Tissues 276
1.2. Historic of Bonding Agents 278
2. General Composition 280
2.1. Functional Adhesive Monomers 281
3. Adhesive Systems 282
3.1. Etch-and-Rinse Adhesive Systems 282
3.2. Self-Etching Adhesive Systems 284
4. Advances and Future Perspectives
in Adhesive Dentistry 286
Acknowledgments 289
References 289
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Contents xvii
Chapter 11 Dental Composites — Chemistry and

Composition 295
Carmem S. Pfeifer
1. Introduction 296
2. Current Materials: Methacrylate Chemistry 297
2.1. Polymerization Kinetics of Cross-Linked
Methacrylated Networks 301
2.1.1. Influence of Monomer Choice 301
2.1.2. Implications on Polymerization
Stress Development 302
3. Low-Shrinkage and Low Stress Monomer
Systems 304
3.1. Low-Shrinkage Monomers 304
3.2. Thiol-Ene/Thiol-Methacrylate Systems 307
4. Characterization of Gelation Profiles
in Cross-Linked Networks 311
5. Covalent Adaptable Networks 312
6. Oligomeric Additives 314
7. Monomers with Increased Hydrophobicity 316
8. Water- and Enzyme-Stable Monomers 317
9. Antimicrobial Monomers 320
10. Final Considerations 323
References 324
Chapter 12 Development of Polymerization Contraction

Stresses in Resin-Based Composites 335
Roberto Ruggiero Braga, Marcela
Charantola Rodrigues, and Yvette Alania
1. Introduction 336
2. Experimental Methods for Polymerization
Stress Determination 337
2.1. Mechanical Tests 337
2.1.1. Systems Using Rigid Frames
for Axial Force Detection 337
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xviii Contents
2.1.2. Systems Based on Cantilever

Deflection338
2.1.3. Crack Analysis 338
2.1.4. Ring Slitting Method 339
2.2. Methods used for Assessing Stress
Distribution339
2.2.1. Photoelasticity 339
2.2.2. Finite Element Analysis 340
2.3. Influence of Test Parameters on Stress
Results340
2.3.1. Specimen Dimensions 341
2.3.2. Bonding Substrate 341
2.3.3. Feedback Loop 342
2.4. Relationship Between Polymerization
Stress Tests and In Vitro Tests
for Assessing Quality of the Bonded
Interface342
3. Polymerization Stress Determinants Related
to Composite Formulation 343
3.1. Polymerization Shrinkage 344
3.2. Elastic Modulus 346
3.3. Degree of Conversion 347
3.4. Polymerization Kinetics 348
4. Local Factors Associated to Stress
Development349
4.1. Composite Confinement and Volume 349
4.2. Substrate Compliance 350
5. Strategies for Minimizing Polymerization
Stress Development 351
5.1. Low-Modulus Liners 352
5.2. “Soft-start” Photoactivation 353
5.3. Incremental Technique 356
5.4. Composite Pre-Heating 356
5.5. Low Shrinkage Composites 357
5.5.1 Low-Modulus Fillers 358
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Contents xix
5.5.2 Commercial Low-Shrinkage
Composites358
5.5.3 Experimental Composite
Materials359
6. Composite Water Sorption as a Means
for Polymerization Stress Reduction 361
References362
Chapter 13 Flexible Impression Materials 371

Charlene S. Solomon
1. Introduction 372
1.1. History 372
2. Classification 375
3. Flexible Impression Material Properties 376
3.1. Ease of Manipulation 377
3.2. Accuracy 378
3.2.1. Elastic Recovery 379
3.2.2. Dimensional Stability 379
3.3. Flow Properties/Rheological Properties 379
3.4. Flexibility 380
3.5. Wettability/Hydrophilicity 380
3.6. Biocompatibility 381
3.7. Tear Strength 381
4. Aqueous Hydrocolloid Impression Materials 381
4.1. Agar/Reversible Hydrocolloids 381
4.1.1. Composition 381
4.1.2. Manipulation and Properties 382
4.2. Alginate/Irreversible Hydrocolloids 383
4.3. Hybrids/Alginate Alternatives 385
4.3.3. Clinical Applications 387
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xx Contents
5. Non-Aqueous Elastomeric Impression

Materials387
5.1. Polysulfides 388
5.2. Silicones 389
5.2.1. Condensation-Type Silicones 389
5.2.1.1. Composition 389
5.2.1.2. Manipulation and
properties390
5.2.2. Addition-Type Silicones 390
5.2.2.1. Composition 390
5.2.2.2. Manipulation and
properties391
5.3. Polyethers 393
5.4. Hybrid Vinylpolyether Silicones 394
6. Disinfection Procedures 395
References398
Chapter 14 Resilient Liners for Removable Prosthesis 401

Igor J. Pesun
1. Introduction 402
2. Composition of Resilient Denture Liners 403
3. Physical Properties 404
4. Viscoelastic Properties and Compliance 407
5. Color 412
6. Microbiological Interaction 413
7. Uses of Resilient Denture Liners 414
8. Maintenance of Resilient Denture Liners 416
9. Conclusions and Outlook 416
References 417
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Contents xxi
Chapter 15 3D Printing — Additive

Manufacturing of Dental Biomaterials 421
Rodrigo França, Jeff Winkler, Helen H. Hsu,
Maedeh Rahimnejad, and Zahra Abdali
1. Introduction 422
2. Additive Manufacturing of Dental
Devices 423
2.1. Additive Manufacturing in Restorative
Dentistry 423
2.1.1. Hard Tissue: Bone
Reconstruction 424
2.2. Kinds of Additive Manufacturing
Techniques: Advantages/Disadvantages 426
2.2.1. Solid Free-Form Fabrication
(SFF) 427
2.2.2. Selective Laser Sintering (SLS) 427
2.2.3. Stereolithography (SLA) 428
2.2.4. Inkjet Printing Techniques 429
2.3. Implants Suitable for 3D Printing 430
3. Bioprinting 431
3.1. Hydrogels as Bioinks 433
3.1.1. Hydrogel for Pulp-Regeneration 436
3.1.2. Hydrogels for Periodontal
Regeneration 438
3.2. Importance of Cross-Linking Process
in Bioprinting Constructions 438
3.2.1. Physical Cross-Linking 439
3.2.2. Chemical Cross-Linking 439
3.2.3. Physical and Chemical
Cross-Linking Combination 441
3.3. Properties of Bioink 443
3.3.1. Mechanical Properties 443
3.3.2. Permeability 445
3.3.3. Degradation 446
3.3.4. Viscosity 449
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xxii Contents
3.4. Methods of Bioprinting 451

3.4.1. Bioprinting Parameter: Nozzle
Diameter and Pressure 453
4. Future Perspective 454
5. Conclusion 455
References 456
Index463
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Chapter 1
Surface Analysis Techniques

for Dental Materials
Edward Sacher*,‡ and Rodrigo França†,§

*Regroupement Québecois de Matériaux de Pointe,
Département de Génie Physique, École Polytechnique de Montréal,
C.P. 6079, Montréal, Québec H3C 3A7, Canada
†
Department of Restorative Dentistry, Dental Biomaterials
Research Laboratory, College of Dentistry, University
of Manitoba, 780 Bannatyne Av, Winnipeg,
Manitoba R3E 0W2, Canada
Edward.sacher@polymtl.ca
‡
§
Rodrigo.franca@umanitoba.ca
For many years, dental materials researchers have made significant

efforts to understand the chemical and mechanical behaviors of
restorative materials, implants, etc., to assure positive interaction
with oral tissues. The main focus of these studies has been on bulk
properties. However, all reactions between dental materials and the
host tissues occur at the interface between their two surfaces. Bulk
and surface physicochemical compositions may be quite different.
Consequently, meticulous surface characterizations should be car-
ried out on dental materials to better comprehend their behaviors in
such situations.
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2 Dental Biomaterials
1. Introduction
Information on the chemistry, crystal structure, size, roughness,
etc., of a surface is often needed by the dental researcher. There are
techniques available today that will provide such information.
However, these techniques are often in the domain of chemists and
physicists, whose primary interests lie outside the area of dental
research; dental researchers, who have little background in the phys-
ics, chemistry, or mathematics of such techniques, may be loath to
use them for that reason, despite the potential benefits. It is the
purpose of this chapter to acquaint them with several of the more
common surface characterization techniques, and what they will be
able to achieve by using them.
This chapter is designed to inform the dental researcher what
information any given technique is capable of offering when carried
out by a surface scientist competent in that technique. While it is not
necessary for the dental researcher to have expertise in physics, chem-
istry, and mathematics, they are the major pillars on which biomaterial
surface research is constructed, and there is no reason why the dental
researcher should not avail himself of such aid.
1.1. Surface and Interfaces

A surface is the boundary layer of a solid or liquid; in equilibrium,
when exposed to air or vapor; the surface is generally pictured as hav-
ing length and width, but no depth. In fact, all real surfaces have some
minimal depth. This is because, in the interior, an atom is surrounded
uniformly, with the interaction energy of that atom (A in Figure 1) and
its neighbors uniformly distributed; however, at the surface (B in
Figure 1), the energy distribution is not uniform, due to the lack of
structural uniformity (i.e. neighbors lying below, but not above, the
surface atoms). This generally results in slight structural changes at the
surface. Since structural interactions extend beyond nearest neighbors,
the energy distribution at the surface does not change abruptly over
one monolayer, but over several, creating a surface with some depth,
over which conditions change more gradually.
b3252_Ch-01.indd 2 27-11-2018 02:56:36 PM

Surface Analysis Techniques for Dental Materials 3
Figure 1. Cross-section representation of the atomic arrangement of a bio-

material. Bulk atoms (A) are in equilibrium, while surface atoms (B and C)
have an additional surface free energy
An interface is a boundary between two condensed phases in

equilibrium: solid–solid, solid–liquid, or two immiscible liquids. The
importance of the interface is due to the fact that this is where all
reactions between the biomaterial and the biological environment
occur. In dentistry, phenomena such as osseointegration and dentin
adhesion occur, at the molecular level, at the interface. At this level,
all materials exposed to air adsorb gases, which form a thin superficial
layer. In the same way, dental materials, when immersed in biological
fluids (saliva, blood, etc.), are immediately covered by biomolecules,
such as water, sugars, and proteins. Such adsorption is driven by the
thermodynamic need to reduce the surface free energy.
1.2. Surface Energy

In order to create a surface, energy must be applied to a volume, by
breaking bonds and interrupting interactions; that is, the formation
of a surface is energetically unfavorable. For liquids, the surface
energy density (energy per unit area of surface) is identically equal to
the surface tension (force necessary to open a unit length of crack to
form the surface). For solids, unless there is some drastic chemical
or physical change that occurs on surface development, they are
essentially equal.
b3252_Ch-01.indd 3 27-11-2018 02:56:37 PM

Thermodynamics informs us that, in three dimensions, physical or

chemical reactions will occur spontaneously when the change in Gibbs
free energy is negative. In a similar fashion, in two dimensions (i.e. at
a surface), reactions will occur spontaneously when the change in
Helmholtz free energy, which is directly related to the surface tension,
is negative. This is why, for example, iron rusts: the oxidation that
occurs leads to a surface product having a lower surface tension than
does the unoxidized surface.
1.3. Forces at Interfaces

Interatomic forces within materials, and across their interfaces, can be
both polar and non-polar (dispersive). Also, they can be strong or
weak. Polar interactions involve permanent dipoles (or multipoles)
across an interface, while dispersive interactions involve instantaneous
dipoles (i.e. van der Waals interactions). Polar interactions are by far
the stronger of the two. Both types of interaction are invariably pre-
sent, even in highly polar or highly dispersive materials.
In the case of non-crosslinked polymeric filler materials, polar
groups are often able to reorient to some extent. For the most used
dental adhesive monomers, hydroxyethyl methacrylate (HEMA), this
permits the adhesive surface to exhibit a low surface energy to air
(polar groups oriented to provide a highly dispersive surface) and a
low interfacial energy in water (polar groups oriented to provide a
highly polar surface).
1.4. Reactions at Surfaces: Adsorption

Adsorption is the exposure to, and adhesion of, species from the sur-
rounding medium to the surface. In the formation of rust, water
vapor and oxygen from the surrounding atmosphere adsorb onto the
metal surface within a very short time following exposure, subse-
quently reacting to form a mixed hydrated oxide/hydroxide which,
when enough Fe2O3⋅H2O is formed, becomes red rust.
Two areas of importance to the dental profession, which bear on
adsorption, are adhesion and biocompatibility.1 Common examples of
adsorption in dentistry are the wettability and adsorption of saliva on
b3252_Ch-01.indd 4 27-11-2018 02:56:37 PM

enamel2 or a denture acrylic base3 and the passivation layer formed in

titanium implants4 or basic alloys (NiCr and CoCr).
The adsorption of biomolecules and proteins on surfaces has been
noted as a major factor for understanding the biocompatibility of
biomaterials.5,6 Indeed, what distinguishes a biomaterial from other
materials used in engineering is the fact that the body reacts tolerantly
to them and negatively to the others.7 All of these biochemical reac-
tions take place at the biomaterial surface, and the adsorption of bio-
molecules and proteins leads to a hierarchical bioreaction process that
can result either in the healing or in the necrosis of the tissue.8
To understand protein adsorption, surface characterization meth-
ods have been used to provide quantitative details about the atomistic
level of the interfaces.9 The effects of surface-driven forces, including
hydrophobic and electrostatic interactions, are fundamentals to
protein adsorption and desorption.
In dentistry, protein adsorption has been studied to improve the
osseointegration of dental implants,10 understanding biofilm attach-
ment on tooth structure,11 and remineralization.12
2. Characterization Techniques
These techniques fall into two broad categories, physicochemical and
morphological. Physicochemical techniques elucidate the physical
and chemical properties of a material, such as its crystal structure and
chemical groups, while morphological techniques reveal the size,
roughness, and shape of a material. A schematic representation of the
techniques is given in Table 1.
There are many different characterization techniques; however,
only a few provide insights into the outermost atomic layers. The
techniques we have chosen to discuss are those readily found in
research laboratories, whose use entails reasonable costs and whose
data are readily interpretable by those in the field. Some deal with
elements at the surface, while others offer necessary information on
molecules. They run the gamut from qualitative to quantitative
analyses, wherein qualitative methods give information on only the
presence of elements or compounds, while quantitative methods
measure their amounts. Further, they vary in sensitivity, ranging from
b3252_Ch-01.indd 5 27-11-2018 02:56:37 PM

b3252_Ch-01.indd 6

Table 1. Surface analyses techniques
Vibrational Diffraction
Ion spectroscopies Electron spectroscopies spectroscopies methods
Contact TOF- ATR-FTIR
angle SIMS LA-ICP-MS XPS AES EDX WDS Raman XRDa
Depth probed <1 nm 2–5 nm Bulk 10 nm 1 nm 4 mm 0.5–2 mm 5 nm
Surface energy Yes No No No No No No No No
+++ ++ +++++ ++ +++ +++ ++ +++
b3252 Dental Biomaterials

Composition
Quantitative No No Eb E&M E semi E Mc M
Qualitative No E&M E E&M E E M M
Destructive No Yes Yes No No No No No No
UHV required No Yes No Yes Yes Yes Yes No No
Spatial resolution +++ ++ ++++ + + +++
Trace detection ppb ppt 0.1% 0.1% 1% ppm 0.1% 0.1%
Depth profiling No Yes Yes Yes No Yes
Mapping No Yes Yes Yes Yes Yes Yes Yes Yes
Elements detected All > He < Zr > Be Org Crystalline
Notes: aUsing the in-plane XRD technique.

b
E: Elemental level.
c
M: Molecular level.
“9x6”
27-11-2018 02:56:37 PM
parts per hundred (i.e. percent) to parts per billion (ppb) or parts per
trillion (ppt). Many of the techniques to be described operate under
high vacuum (UHV), whose main purpose is to extend the mean free
path (i.e. the average distance between molecular collisions) of the
information-carrying particles (e.g. electrons), so that they may be
properly treated before detection. However, using UHV can be a
challenge when working with porous materials, such as dentin.
The depth probed varies with the technique. Some techniques can
provide information on the outermost monolayer or two (<1 nm),
while others probe several nanometers. However, methods can some-
times be applied to increase or decrease the probe depth of these
techniques; e.g. changing the XPS take-off angle or progressively
etching the surface. In addition, spatial resolution can vary, from
<1 nm to several micrometers, and this feature is especially important
if chemical mapping is required.
No single technique provides complete answers to surface analy
tical questions, and therefore several complementary techniques must
be used in approaching a problem. Special attention should also be
paid to sample preservation. Some techniques can destroy the sample
by radiation or sputtering. Destructive techniques should always be
preceded by all the non-destructive techniques.
2.1. Physicochemical Techniques

2.1.1. Contact Angle (CA)
The surface energy of a non-distortable solid is determined indirectly,
using liquids whose surface tensions are known. A sessile drop of such
a liquid, placed on a flat, smooth solid surface, forms a contact
angle, θ, with that surface. In the plane of that surface, the Young–
Dupré equation describes the equilibrium at any point along the cir-
cumference of the drop:
γ (at the solid-liquid interface) + [cos θ × γ (at the liquid-vapor interface)]

= γ (at the solid-vapor interface).
b3252_Ch-01.indd 7 27-11-2018 02:56:37 PM

Figure 2. Example of the effect of the light curing source on the surface
energy of self-etch resin cement. Two samples of the same self-etch resin
cement were cured using a Quartz-Tungsten-Halogen light (QTH) or a
Light-Emitting Diode light (LED)
When the surface is wet by the liquid (i.e. θ = 0), γ (at the liquid–
vapor interface) is equal to zero, and γ (at the solid–liquid interface)
is equal to γ (at the solid–vapor interface). That is, in order to wet a
solid surface, the surface tension of the liquid must be equal to, or less
than, that of the surface. Wetting assures extensive contact, and is
desirable for good adhesion.
CA measurement is the least expensive and simplest technique
used to probe the surface. It is also the only one able to directly deter-
mine solid surface thermodynamics, such as surface free energy,
enthalpy, and entropy. However, they do not provide sample surface
composition and are more applicable to low-energy solids, such as
polymers, as seen in Figure 2. It is important to note that the Young–
Dupré equation applies only to smooth, homogeneous surfaces;
rough surfaces require the Wenzel or Cassie–Baxter equations.12,13,14
In dentistry, CA is commonly used for determining the hydrophi-
licity of impression materials15,16 and dental bonding agents.17,18 Some
water-drop CA values of dental materials are shown in Table 2. New
techniques, such as microdroplet approaches, and further detail infor-
mation can be obtained in specialized reviews.19,20
2.1.2. X-ray Photoelectron Spectroscopy (XPS)

This technique, also called Electron Spectroscopy for Chemical
Analysis (ESCA), uses a probe beam of mono-energetic X-rays to
b3252_Ch-01.indd 8 27-11-2018 02:56:38 PM

Table 2. Contact angle of water drop

for some dental biomaterials
Biomaterial CA(q)
Addition silicone a
53
Amalgam a
77
Condensation silicone a
98
Glass Ionomer cementb 65
Polyether b
49
Resin-based composite b
35
Universal bonding agent b
39
Sources: aAdapted from Ref. [3]; bunpublished data.
irradiate a sample. The X-rays interact with electrons in various

orbitals of energy lower than that of the X-rays, causing them to be
emitted. The X-rays are photons; quantum mechanics tells us that
photons cannot be fragmented. That is, on reacting, they are totally
destroyed, with some of their energy overcoming the energy that
binds the electron in its orbital, some of the energy overcoming the
potential energy of the surface (the work function), and the remain-
der is given to the emitted electron as kinetic energy (Figure 3).
The spectrometer measures the kinetic energy of the emitted elec-
tron, which, depending on the magnitude of the energy and the
angle of the detector to the sample, can come from depths between
0.8 and 10 nm. Knowing the energy of the X-ray photon, and cor-
recting the energy scale to account for the work function (a simple
process), gives the binding energy, the energy in which XPS spectra
are presented.
Each element has a specific binding energy range for each elec-
tron orbital (see Table 3 and Figure 4); the electron density around
each emitting atom additionally influences the exact binding energy,
so that the C1s peak for, e.g. an alcohol falls at ~286.5 eV while that
for a carbonyl falls ~1 eV higher (Figure 5). One may, as a result of
these effects, qualitatively distinguish ionic valences, as well as polar
organic structures (e.g. oxidation products, how many halides are
bonded to a single carbon, etc.).
b3252_Ch-01.indd 9 27-11-2018 02:56:38 PM

Figure 3. Photoemission on X-ray irradiation. Eb = binding energy with

which the electron is held in the atom; h = Planck constant (6.62 × 10-34 J s),
v = frequency (Hz) of the radiation; EKE = kinetic energy of the
photoelectron
Table 3. Binding energy of XPS peaks of ele-

ments frequently encountered in dentistry
Elements XPS peak Binding energy (eV)
Calcium Ca2p3/2 347
Carbon C1s 285
Fluorine F1s 684
Oxygen O1s 532
Phosphate P2p3/2 133
Silicon Si2p3/2 102
Titanium Ti2p3/2 458
Zirconium Zr3d5/2 182
Further, because the quantum mechanical effects that govern

photon interactions differ only slightly across any given spectrum, the
component peak areas contributing to that spectrum are in the same
ratios as are the components in the material being tested. That is, the
ratio of the C1s spectral component peaks (e.g. hydroxyl, carbonyl,
b3252_Ch-01.indd 10 27-11-2018 02:56:38 PM

Figure 4. XPS survey spectra of dental enamel, dentin, resin-based compos-
ite (Filtek Supreme, 3M, St. Paul, MN, USA), and a dental implant (Astra,
Dentsply, SW)
carboxylic acid, etc.) in a given spectrum are in the same ratio as the
chemical groups in the material being tested. Moreover, the existence
of peak sensitivity factors for each element permits the evaluation of
the relative ratios of all the peaks in all the spectra being considered.
That is, to within a few percent, an XPS analysis is both qualitative
and quantitative. Newer instruments can be used to chemically map a
surface, using one of these peak components.
b3252_Ch-01.indd 11 27-11-2018 02:56:39 PM

Figure 5. The C1s XPS high-resolution peak deconvolution of a self-etch

bonding agent (iBond Self-etch, Heraeus Kulzer, Gr)
Some limitations of this technique include the impossibility to

detect H and He, the necessity for UHV (that challenges the analysis
of porous surface, such as dentin), and the fact that some spectra
overlap others. There are relatively few examples of surface analyses
using XPS in dentistry. Some studies, in areas such as bonding
agents,21,22 pulp-capping materials,23 fluoride gels,24 and dental
implants4,25 show the potential of this technique. In medicine, XPS is
used largely to characterize biomaterials,26,27 nanoparticles for drug
delivery,28–30 and for infection control.31
2.1.3. Auger Electron Spectroscopy (AES)

As seen in Figure 3, the emitted photoelectron in the XPS process
leaves a hole in its atomic orbital. An electron from the outer layer can
fall into the inner layer to occupy the hole, and the excess energy can
be emitted as an X-ray photon (X-ray fluorescence, XRF) or emitted
as another electron in an outer layer (Auger electron). The detection
b3252_Ch-01.indd 12 27-11-2018 02:56:40 PM

of this electron is called AES. In an AES spectrometer, the initial hole

is formed using an electron beam.
AES is a surface technique, probing ~0.2 to ~1.0 nm. This tech-
nique has infrequently been used to provide limited relevant qualita-
tive and quantitative information on the elemental composition and
chemical environment of the surface, but is plagued by the often
opposing chemical shifts of the three electrons involved in the Auger
process. When possible, the use of XPS is simpler and, involving only
one electron, is easier to interpret. A distinct advantage of AES lies in
the fact that it can be incorporated into a scanning electron micros-
copy (SEM), using the monoenergetic electron beam to cause the
emission of the first electron. Such an electron beam can probe very
small sites, and is useful in the study of grain boundaries in metals and
alloys. Since the electron beam can be rastered, it is possible to study
the surface distribution of elements. AES has been used to probe
dental implants32 and corrosion at dental alloy surfaces,33 and to assess
the interaction of biofilms and restorative material.34
2.1.4. Energy-Dispersive X-ray Spectroscopy (EDX)

EDX is probably the most often used technique for dental biomaterial
chemical characterization. As it is normally installed on an SEM, EDX
can be used during SEM examination, providing qualitative elemental
analysis of a sample in a few minutes. Another convenience is the fact
that it can be used to analyze a broad range of materials and sample
sizes.
As mentioned in the section on AES, an atom can reduce its
energy by emitting secondary X-rays (X-ray fluorescence). These are
detected and displayed, as seen in Figure 6.
Although EDX does not provide quantitative analyses, it may be
used as a semi-quantitative method if a known standard, similar to the
sample, is available.
Because the probe depth is >1 μm, EDX is not a surface tech-
nique. However, it has been used to probe bulk chemical composi-
tion, contrasting it with the surface composition obtained by XPS.23,26
Mapping may be carried out, using the EDS raster mode.
b3252_Ch-01.indd 13 27-11-2018 02:56:40 PM

Figure 6. EDX spectra of dental enamel
Other limitations of EDX include the fact that it cannot detect H,

He, or lithium (an important component of some dental ceramics),
some elements are difficult to be detected due to peak overlap (e.g.
titanium and vanadium), and the EDX beam can decompose polymer
film samples, such as adhesives.
2.1.5. Wavelength-Dispersive Spectrometry (WDS)

This technique, also known as wavelength-dispersive X-ray fluores-
cence spectrometry (WDSXRF) or X-ray microprobe, was primarily
used for X-ray spectral characterization.35 The major difference
between WDS and EDS is that WDS can provide quantitative results
of the elements present at the sample.
As with EDS, WDS is not a surface technique, and it cannot detect
element < Be, but can provide better bulk information than EDS due
to its greater spectral resolution (~5 eV, compared to ~100 eV). Despite
these advantages, WDS is less used than EDS, probably because it is
slower in producing spectra (hours, compared to seconds), and because
the larger size of the equipment (especially for multichannel systems)
does not fit easily into SEM systems, as does EDS.
b3252_Ch-01.indd 14 27-11-2018 02:56:40 PM

Figure 7. WDS mapping of a pulp-capping material (Theracal, Bisco, IL,

USA). Theracal (T) was applied at the pulpal floor of the cavity and restored
with resin-based composite (RC). In a, silicon content is displayed; in b,
calcium; in c, phosphorus, and in d, zircon
In dentistry, WDS has been used for the analyses of ceramics,36

protein attachment,37 and fractographic analyses.38 It has also been
used to map ion release from pulp-capping materials, as seen in
Figure 7.
2.1.6. Time-Of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS)

Mass spectrometry (MS) is a well-know, well-established technique
that measures the masses of charged atoms or molecular fragments,
in atomic mass units (or Daltons, D). The use of a primary ion beam
(e.g. isotopically pure Bi+, Cs+, etc.) to produce the atoms or frag-
ments by an ejection process called sputtering, makes possible the
b3252_Ch-01.indd 15 27-11-2018 02:56:40 PM

measurement of these secondary ions, and is referred to as secondary

ion mass spectrometry (SIMS).
A problem with this technique, for those interested in character-
izing surfaces, is that SIMS instruments use high-energy primary
beams to characterize depth profiles; this is referred to as dynamic
SIMS. Such beams quickly sputter away the surface one may wish to
characterize. A variation of this technique uses much less energetic
beams, in which an exceedingly small fraction of the surface layer is
sputtered away during the length of the experiment; this is referred to
as static SIMS. The sputtered atoms are detected in a drift tube, in
which the time of flight of a fragment is used to establish its mass;
thus, TOF-SIMS. Distinct advantages of the use of a drift tube
include the high mass sensitivity possible (0.001 D), the capability of
detecting trace quantities, and the possibility of chemical mapping.
While only the first few monolayers are sputtered, those fragments
include neutrals, as well as fragments that are both positively and
negatively charged; it is the charged fragments that are detected (see
Figure 8). Although the use of calibration standards gives quantitative
results in fields such as the semiconductor industry, there is a general
lack of knowledge of the efficiency of the sputtering process in pro-
ducing fragments, as well as the fractions of those fragments that are
positively or negatively charged; because of this, TOF-SIMS is gener-
ally used as a qualitative technique. That is, while the technique is
capable of detecting trace ions in the ppb range, the detected intensi-
ties of the various fragments cannot be used to quantify the species
present in the sample. Nonetheless, TOF-SIMS is useful as a con-
firmatory technique, as well as in detecting the onset of a chemical
reaction.
2.1.7. Laser Ablation Inductively Coupled Plasma

Mass Spectrometry (LA-ICP-MS)
This technique is exceptional in detecting trace elements in solid sam-
ples. In fact, the detection limits obtained by LA-ICP-MS can
approach one part per trillion. In this technique, a Nd:YAG laser is
focused at the surface, vaporizing the probed area; these fragments
b3252_Ch-01.indd 16 27-11-2018 02:56:40 PM

Figure 8. TOF-SIMS spectra for a biphasic calcium phosphate bioceramic

(Boneceramic, Straumann, Gr). Part a displays positive ions and part b,
negative ions
are transported into a high-energy plasma of an ICP mass spectrom-

eter, and the detected masses are used to detect the composition of
the sample.39
While this technique is more frequently used for bulk characteri-
zation (laser beam size 10–100 mm), LA-ICP-MS offers the possibility
of making an elemental map during depth profiling, which can help
to understand differences between surface and bulk compositions.
A femtosecond laser pulsing technique is now available, which can
reduce the beam size to <100 nm.40
Being one the most powerful techniques for trace element detec-
tion, LA-ICP-MS is frequently used in toxicological studies. An inter-
esting report used this technique on human enamel and dentin, to
detect an individual’s chronological nutrition record.41 Another paper
assessed the amount of trace titanium in perio-implant oral mucosa.42
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2.1.8. Vibrational Spectroscopies: Infrared (FTIR)

and Raman
Beyond the red region of the visible portion of the electromagnetic
spectrum lies the infrared (IR) region, appearing at frequencies from
~500 to 4,000 cm−1, where cm−1 is referred to as wavenumbers. This
is the region in which molecules vibrate, with each vibrational peak
representing the motions of an irreducible vibration (i.e. a vibration
not composed of a combination of several other vibrations). Further,
because the energy (frequency) of the vibration depends on the
reduced mass of the atoms participating, each vibration appears at a
specific frequency, over a short frequency range; the reason for the
short frequency range is that the rest of the molecule attached to the
chemical group that is vibrating at that particular frequency offers
some slight participation.
The vibrations that are seen include stretching, deformation,
wagging, etc., each at its appropriate frequency. Since, e.g. the

stretching frequency of one group may fall at, or near, the deforma-
tion frequency of another, the group responsible is identified by con-
firming that all its vibrations appear at their appropriate frequencies in
the spectrum. The information gained from a vibrational spectrum
identifies the chemical groups present on the sample. For a pure
material, the existence and positions of the component peaks serve to
identify it, when matched against spectra found in various databases.
For an impure material, one will at least know which chemical groups
are present. As generally used with solids, vibrational spectroscopy is
qualitative, with a sensitivity of ~5%.
Two techniques, based on different physical processes, are used to
obtain vibrational spectra: IR and Raman spectroscopies. Because
they are based on different processes, the selection rules, concerning
which vibrational peaks are seen with that technique, are different.
Thus, some peaks appear in both types of spectra, and others, in one
or the other. Spectral mapping is possible.
Photoacoustic IR is an interesting application of IR spectros-
copy, which is potentially very important to the dental researcher
because opaque materials may be sampled. It uses a special airtight
b3252_Ch-01.indd 18 27-11-2018 02:56:40 PM

photoacoustic cell, generally filled with helium (He) or other inert

gas, at atmospheric pressure; the cell is inserted into the sample
chamber of the spectrometer. A light source (photo-) provides the
energy that provokes the vibration; when the vibration relaxes, a
small fraction of a second later, it heats the trapped He, raising its
pressure slightly, and is detected by a sensitive miniature microphone
(-acoustic) within the cell. A plot of the pressure change as a func-
tion of frequency gives the photoacoustic spectrum, essentially iden-
tical to the IR spectrum. A distinct advantage of photoacoustic IR is
that its probe depth is less than 100 nm, while the probe depth of
its IR competitors are much bigger than that.
The spectrometers presently used are IR interferometers, which
give interferograms. The mathematical Fourier transform (FT) of an
IR interferogram gives the IR spectrum; the process is known as FTIR
spectroscopy, and, in the case of Raman, FT Raman spectroscopy.
Attenuated total reflectance (ATR)-FTIR is very often used in
dentistry. This involves relatively simple sample preparation, since
the sample (film or solid material) can be placed directly on the ATR
crystal and probed by the IR radiation passing through the crystal.
The sampling depth is ~5 mm, which means ATR cannot probe the
surface at nanolevel. However, this type of crystal material can
reduce the absorption at the interface, diminishing the probe depth;
e.g. using a diamond crystal, the penetration depth is reduced to
2 mm, and using a germanium crystal, ~0.6 mm.43 ATR-FTIR (or
Raman) is used in dentistry for assessing the degree of conversion of
polymeric materials, such as resin-based composites and bonding
agents. The correlation of the values of the aliphatic C=C peak at
~1,638 cm−1 and the aromatic C–C peak at ~1,608 cm−1, before and
after curing, makes it possible to estimate the degree of polymeriza-
tion of a polymer.44,45
Figure 9 shows an ATR-FTIR spectrum of a universal dental
adhesive. In this spectrum (as in most of organic materials), we
can define two regions: 4,000–1,500 cm−1, the functional groups
region, and 1,500–400 cm−1, the fingerprint region. Peaks in the first
group are used to confirm the presence of specifics types of bonds,
b3252_Ch-01.indd 19 27-11-2018 02:56:40 PM

Figure 9. FTIR spectrum of a universal bonding agent (All-Bond Universal,

BISCO, IL, USA). The inset shows the range between 1,660 and 1,590
cm−1, with two bands, C=C and C–C, which can be used to determine the
degree of conversion of acrylic-based polymers, when compared before and
after curing
and peaks in the second region indicate a unique pattern from each
organic compound. The interpretation of FTIR spectra can be carried
out by comparison of each peak/band position with the large amount
of information available in the literature. Table 4 provides a selection
of frequently used functional groups of dental materials.
For materials containing many compounds, the spectral interpre-
tation can be a challenge, because peaks may overlap. As an example,
the ATR-FTIR spectra of some pulp-capping materials are shown in
Figure 10.23
b3252_Ch-01.indd 20 27-11-2018 02:56:42 PM

Table 4. FTIR frequencies of some functional group vibrational modes

often found in dental materials
Functional group Vibrational mode Wavelength (cm-1)
Hydrocarbons:
Methyl(–CH3) C–H stretching 2,870 (sym); 2,960 (asym)
Methylene (–CH2–) C–H stretching 2,860 (sym); 2,930 (asym)
Vinyl (C=CH2) Vinyl bending 910, 990
Vinyl (C=C) C=C stretching 1,600–1,680
Aromatic C Monosubstitution 730–770, 680–720
Oxygen groups:
Aliphatic alcohols (CO→H) OH stretch (free) 3,600–3,640
Phenols (C–O↓H) OH stretch (H-bonded) 3,200–3,400
Carboxylic acids (C–C→O) C–O–H bend 1,300–1,400
aliphatic (C=→O) C–C–O stretch (dimer) 1,200–1,320
aromatic (C=→O) C=O stretch (dimer) 1,710
Aldehydes aliphatic C=O stretch 1,690
Esters aliphatic C=O stretch 1,730
C=O stretch 1,745
Amines (aromatic):
Primary Ar-NH2 N→H stretch 3,500
Secondary Ar2NH N→H stretch 3,400
Tertiary Ar3N No NH
Heteroatom compounds:
Halogenated compounds: Aliphatic halide 720–1,400
Phosphorus compounds: C→F 530–800
Silicon compounds: C→Cl
Phosphates esters 1,250–1,290
P=→O 720–850
P→O 800–1,000
Si→F 2,100–2,200
Si→H 700–820
Si→C 1,000–1,100
Si→O→Si 820–920
Si→OH
Source: Adapted from Ref. [43].
2.1.9. X-ray Diffraction (XRD)

XRD is used to establish the identity or phase of a solid material
through the determination of the diffraction pattern of its crystal
b3252_Ch-01.indd 21 27-11-2018 02:56:42 PM

Figure 10. FTIR spectra for four pulp capping materials. Symbols represent
calcium compounds:  CaCO3 (Aragonite),  CaCO3 (Calcite),  Ca3SiO5,
 Ca2SiO4,  Ca10(PO4)6(OH)2,  CaSO4, Ca2Mg5Si8O22(OH)2,  Ca(OH)2.
Adapted from [Ref. 26]
structure. A crystalline sample is rotated with respect to a mono-

energetic X-ray beam, using small steps of angle change over a limited
range of angles. The diffractogram, having diffraction peaks at specific
angles, is normally referred to as a 2θ scan. It is then compared to a
database of spectra; the one that is generally used is still referred to as
the Joint Committee on Powder Diffraction Standards (JCPDS) data
set, despite the fact that the organization renamed itself as the
International Centre for Diffraction Data (ICDD) almost 40 years
ago. It can be used to identify a pure material, a mixture of materials
b3252_Ch-01.indd 22 27-11-2018 02:56:43 PM

and, because different phases have different crystal structures, it can

distinguish one phase from another.
XRD can function as a surface technique when used in in-plane
diffraction. In this technique, the incident and diffracted beams are
nearly parallel to the sample surface.46 In this way, the probed depth
can be as small as 5 nm; further, by changing the incident angle, a
depth profile can be carried out. XRD can be used to measure crystal
size, using the Scherrer formula47:
Kλ
τ= ,
β cos θ
where t is the crystal size (its diameter, if spherical), λ is the wavelength

of the incident wave, θ is the Bragg angle of diffraction, H is the width
at half peak height, and k usually takes the value 0.89. For accuracy, a
known silicon pattern is used, using the XRD peaks near to ~40°.26
XRD is extensively used in dentistry to detect phases of titanium
implants,48 dental ceramics,49 and bioceramics for bone growing26,50
(see Figure 11).
Figure 11. XRD spectra from three bioceramics for bone growing. Adapted
from [Ref. 26]
b3252_Ch-01.indd 23 27-11-2018 02:56:43 PM

2.2. Morphological Techniques

2.2.1. Electron Microscopies
Because electrons have shorter wavelengths than visible light, micro-
scopes using an electron probe beam give images having resolution
several orders of magnitude higher than that by optical microscopes
(~0.1 nm, compared to ~200 nm, all under optimal conditions).
There are two basic electron microscopy variants, transmission elec-
tron microscopy (TEM) and scanning electron microscopy (SEM).
Since the TEM electron beam is transmitted through the sample to
obtain an image, it results in an image of the sample volume; for this
reason, special, very careful thinning (~100 nm) is required to obtain
photomicrographs by this technique, as shown in Figure 12. The use
of biological samples is problematic because special techniques are
needed to avoid sample drying in the high instrument vacuum.
A distinct advantage of the technique, for samples for which drying
is not a concern, is that a diffraction pattern may be obtained at any
point on the scan, permitting the determination of the crystal struc-
ture at that point.
In the case of SEM, the electron beam is rastered across the
sample, and the secondary electrons emitted are used to produce
the photomicrograph, as shown in Figure 13. It is about an order
of magnitude lower in resolution than TEM and, because the
source of the secondary electrons is the sample surface, it gives an
image of that surface, rather than of the volume. While SEM does
not require sample thinning, precautions similar to those for TEM
are required, when sample drying is a problem. A variation of SEM,
environmental SEM (ESEM), uses differential pumping to accom-
modate samples in various working atmospheres. Another varia-
tion, scanning transmission electron microscopy (STEM), rasters
an electron beam that is transmitted through the sample; a distinct
advantage of this variation is its ability to obtain high angle annular
dark field (HAADF) images, which sense differences in atomic
mass, and can distinguish image locations having atoms of different
masses.
b3252_Ch-01.indd 24 27-11-2018 02:56:43 PM

Figure 12. TEM image of a lithium disilicate CAD-CAM ceramic

[Unpublished data]
2.2.2. Atomic Force Microscopy (AFM)

AFM is a variant of surface probe microscopy, in which a sharp tip is
rastered across a surface while a piezoelectric element measures its
height displacement. It gives a topographical image of the surface,
with a height resolution of less than 1 nm. The lateral resolution is
lower, depending on the surface roughness and the curvature of the
microscope tip. Several operational modes can be employed, depend-
ing on the sample and the information requirements. These include
contact mode (where the tip remains in contact with the sample),
non-contact mode (where the repulsive interaction between tip and
b3252_Ch-01.indd 25 27-11-2018 02:56:44 PM

Figure 13. SEM image in backscattering mode of a pulp-capping materials.

Topography, crystallinity, and distinction of phases can be assessed
[Unpublished data]
sample is measured), and tapping mode (where the tip intermittently

contacts the surface at a high frequency).
The information obtainable include roughness, dynamic mechanical
properties, magnetic properties, frictional coefficients, etc. A new AFM
technique, recently commercialized (Anasys NanoIR2), provides IR
data on a 0.1 µm scale. As mentioned before, surface roughness is cru-
cial for understanding adhesion phenomenon, AFM can provide a pro-
file of the surface at nanometric scale. For instance, Figure 15 d isplays
a 2D histogram of depth found in the samples shown in Figure 14.
3. Final Recommendations
Now that the reader is aware of the potential information that can be
obtained from skilled surface analysis, we emphasize the following, as
the order in which such studies should be carried out:
b3252_Ch-01.indd 26 27-11-2018 02:56:44 PM

Figure 14. Tapping-mode AFM images showing the effect of bleaching

treatment on the enamel surface. The bleaching agent used was 7.5% hydro-
gen peroxide (Poladay, SDI, Sydney, Au), 15 min once a day for 2 weeks
[Unpublished data]
(1) The dental researcher should first meet with the surface scientist
to discuss exactly what information is sought, whether the tech-
nique chosen is capable of offering such information, and the
time and cost of the study. The advice of the surface scientist is
extremely important to the success of the study.
(2) The samples should be prepared specifically for the study, in the
surface scientist’s laboratory, under his supervision, immediately
prior to insertion into the instrument.
b3252_Ch-01.indd 27 27-11-2018 02:56:45 PM

Figure 15. 2D histogram (XZ) of the surface roughness of the samples

from Figure 14 [Unpublished data]
(3) The dental researcher should participate in the data acquisition,

in order to assure that the correct data are acquired and that time
is not wasted.
(4) The dental researcher should participate in the data analysis, to
give his views of how the data should be analyzed, and whether
further analysis, in a different direction, is warranted.
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b2530 International Strategic Relations and China’s National Security: World at the Crossroads
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Chapter 2
Nanoindentation Techniques
in Dental Biomaterials
Mohammad Aramfard* and Chuang Deng†

Department of Mechanical Engineering,
University of Manitoba, 15 Gillson Street,
Winnipeg, MB, R3T 5V6, Canada
*aramfarm@myumanitoba.ca
†
chuang.deng@umanitoba.ca
Since tooth tissues and those artificially made to mimic them are
generally small and microscopically heterogeneous, conventional
mechanical characterization methods for testing bulk materials are
usually not applicable. Nanoindentation, which is a technique to
extract various mechanical properties of materials at small volume by
impressing a nanometer-scale probe into the surface, thus becomes
a crucial tool for characterizing dental biomaterials. In this chapter,
the basic principles of nanoindentation, the practical instrumenta-
tion of nanoindentation, the adaptation of nanoindentation tech-
niques for testing biomaterials, and some specific applications of
nanoindentation in dental materials are briefly introduced and
discussed.
33
b3252_Ch-02.indd 33 27-11-2018 02:57:20 PM

1. The Basic Principles of Nanoindentation

1.1. Overview
It has been long recognized by the materials science community that
the surface contacts between materials are highly dependent on their
mechanical properties. The theory of contact mechanics and many
experimental techniques based on surface indentation and impression
have thus been developed to extract the mechanical properties of vari-
ous types of materials. Due to its inexpensive and relatively non-
destructive nature, indentation is perhaps the simplest, most direct,
and most c ommonly applied means of testing the mechanical proper-
ties of materials.
Traditional indentation techniques include Vickers, Rockwell,
Brinell, and Knoop hardness tests, depending on the shape of the
indenter and the range of hardness result. With the rapid develop-
ment of nanoscience and nanotechnology, nanoindentation, an
indentation with sub-micrometer probe and penetration depth, was
developed in the mid-1970s and has now become commonplace for
the measurement of mechanical properties at small volumes. Hardness,
which is an important mechanical property of materials to tell if a
material is “hard” or “soft”, is defined based on the contact mechan-
ics and can be directly measured from nanoindentation. Surprisingly,
the same setup that is used to measure the hardness can be used to
measure the Young modulus based on some assumptions and
calculations which are discussed in Section 1.2.
Although the most common use of nanoindentation is for the
measurement of hardness and elastic modulus since its introduction
in the 1970s, considerable progress has been made in nanoindenta-
tion techniques so that it can be used to perform other mechanical
tests such as wear, creep, scratch, and compressive tests. In the mean-
time, nanoindentation has also been improved in such a way that
various types of materials, including dental biomaterials under in vivo
conditions, can be tested. In the following sections, the basic theory,
principles, and general techniques of nanoindentation will be briefly
introduced.
b3252_Ch-02.indd 34 27-11-2018 02:57:20 PM

Nanoindentation Techniques in Dental Biomaterials 35
1.2. Contact Mechanics

The main assumptions of nanoindentation come from contact
mechanics, which studies bodies in contact. The problem of punching
an elastic semi-infinite medium (the half-space) by an elastic sphere
(the indenter) was first studied by Hertz,1,2 as shown in Figure 1.
The contact radius a can be obtained by Eq. (1) and is strongly
dependent on the elastic properties of the two materials in contact,
the geometry of the indenter, and the load applied:
3 PR
a3 = , (1)
4 E*
where P is the load on the sphere, R is the radius of curvature, and

E * is the sum of the reduced Young moduli of the indenter and the
half-space as defined in Eq. (2):
2 2
1 (1 - v ind ) (1 - v hlf )
= + , (2)
E* E ind E hlf

in which v is the Poisson ratio. The amount of displacement of the
surface under the indenter is computed as
1 3 P  r2 
h= 2 - , r ≤ a. (3)
E * 2 4a  a 2 

Figure 1. The contact between an elastic sphere and an elastic half-space
under the influence of pressure P. Adapted from Ref. [3]
b3252_Ch-02.indd 35 27-11-2018 02:57:21 PM

For the case of contact between two non-rigid spheres of radii R1

and R2, assuming R = (1/R1 + 1/R2)-1, the relationship between the
indentation depth h and the pressure P is given by
4
P= E * Rh 3/2 . (4)
3
The mean contact pressure Pm is defined as the ratio of the applied
load to the contact area, which helps to relate the load to mechanical
stress:
P
Pm = . (5)
pa2
Substituting Eq. (5) into Eq. (1), one can get
 4E *  a (6)
Pm =  .
 3p  R

Equation (6) has a significant physical meaning in that it relates
a stress to a strain ratio of a/R, so it has an understanding similar to
tensile test.
Figure 2 shows a conical indenter with cone angle a penetrating
the half-space. The maximum depth of the penetration depends on
the load, the reduced moduli of the system, and the cone angle as
in Eq. (7):
2 2
P= E * tan a hmax . (7)
p
Figure 2. The contact between an elastic conical indenter and an elastic

half-space under the influence of pressure P. Adapted from Ref. [3]
b3252_Ch-02.indd 36 27-11-2018 02:57:21 PM

Figure 3. Schematic of the loading and unloading of a sharp indenter on

an elastic–plastic half-space. Adapted from Ref. [4]
The basis of nanoindentation to extract material properties is

due to the fact that by indenting an elastic–plastic material, after
the indenter reached the maximum load and penetration upon
unloading, only the elastic part is recovered. In other words, at the
beginning of the unloading step, the load versus displacement
occurs in the elastic deformation regime. Based on this fact, Oliver
and Pharr introduced the method to measure the Young modulus
of materials by nanoindentation.4,5 Figure 3 shows the schematic of
the loading and unloading of a sharp indenter on an elastic–plastic
half-space.
By assuming that the procedure is about the unloading part, in
the aforementioned equations, h is replaced by (h - hf), in which hf is
the final depth remaining due to plastic deformation. As a result,
Eq. (4) becomes
4
P= E* R (h - h f )3/2 . (8)
3
In hardness tests, stiffness S is defined as the derivative of the load

with respect to the depth6–8:
dP
S= = 2E * R (h - h f )1/2 . (9)
dh
By relating the depth to the contact area between the indenter

and the surface, the relationship between the contact area, the
b3252_Ch-02.indd 37 27-11-2018 02:57:21 PM

stiffness, and the reduced modulus is derived, which can be used to

compute the reduced modulus as shown in Eq. (10):
dP 2
S= = E* A . (10)
dh p
Here, A is the projected area of an indent. The hardness H is

computed simply by dividing the load by the area:
P
H = . (11)
A
Figure 4 shows the schematic of the load versus displacement of

an indentation test on an elastic–plastic material, and as it is shown in
the figure, stiffness is measured at the beginning of the unloading
process. The load versus displacement curve is the most important
data to be used for computing the material properties.
Figure 4. Schematic of the load versus displacement curve obtained from
an indentation test. Pmax is the maximum load and S is the stiffness of initial
unloading
b3252_Ch-02.indd 38 27-11-2018 02:57:22 PM

1.3. Practical Application of Nanoindentation

In the previous section, the underlying theory of contact mechanics
and indentation was explained. In this section, the practical applica-
tion of the theory is discussed based on the following assumptions:
· The tested material is half-space.

· There is no flaw, crack, or phase change in the vicinity of the
indentation.
· The surface is smooth enough.
· The material behaves as elastic–plastic.
· The material is homogeneous and isotropic.
The first four assumptions are necessary to have an accurate

result, for example the Young modulus, but the last assumption is
required only if the obtained property is assumed to be pertaining to
the whole material. For example, if the material is not homogeneous,
the Young modulus obtained from indentation test is only valid for
that point and if the material is anisotropic, the Young modulus
obtained is only valid in a specific direction. The application of
nanoindentation to test materials which violate these assumptions will
be discussed later.
To apply the theory of contact mechanics to extract the material
properties, additional studies are needed from experiments. It has
been shown experimentally that the unloading curve obeys the fol-
lowing rule5:
P = a (h - h f )m , (12)

in which a and m are fitting constants which depend on the material.
To find the relationship between depth and contact area, the sink in
depth, hs , is modeled from elastic models as in Eq. (13):
ePmax
hs = , (13)
S
b3252_Ch-02.indd 39 27-11-2018 02:57:22 PM

where w is a constant that depends on the geometry of the indenter.

The contact area is a function of contact depth hc, which can be
deduced from Figure 3:
ePmax
hc = hmax - . (14)
S
Here, it is assumed that the area is a function of contact depth,

i.e. A = F(hc), and is determined from the geometry of the indenter
probe as explained in the next section. By finding the contact area
and substituting it in Eqs. (10) and (11), the reduced modulus and
hardness can be computed. It should be noted that the reduced
modulus obtained from Eq. (10) is a combination of moduli of sam-
ple and the machine, so the machine compliance should be known in
order to compute the sample modulus.
1.4. The Nanoindentation Probe and Area Function

Depending on the types of materials being tested and the properties
being explored, probes with different geometries are needed for
nanoindentation. While load and penetration depth can be easily
controlled and monitored during a nanoindentation test regardless
of the geometry of the probe, the contact area, which is an impor-
tant parameter used in Eqs. (10) and (11) to extract the nanohard-
ness and stiffness of the material, is hard to measure directly and
expected to vary significantly for probes with different geometries.
An area function, which is the projected area of an indent as a poly-
nomial function of the indenter, is thus used and should be deter-
mined carefully based on the geometry of the probe. With this area
function, it is also possible to gain real-time nanohardness values
from a load versus displacement curve. The most commonly used
probes include Berkovich, conical, Vickers, and spherical as shown
in Figure 5.
In Vickers, the half angle is q = 68° and in Berkovich it is q =
68.27°,which has three faces. The ideal area function for different tips
is summarized in Table 1. Table 1 shows the area function of different
b3252_Ch-02.indd 40 27-11-2018 02:57:22 PM

Figure 5. Indentation parameters for (a) spherical, (b) conical, (c) Vickers,
and (d) Berkovich indenters. Adapted from Ref. [3]
Table 1. Area function for dif-

ferent probes
Area function,
Tip A(hc)
Vickers 24.504h 2c
Berkovich 24.5h 2c
Cube corner 2.6h 2c
Knoop 108.21h 2c
Conical ph 2c tan2a
Spherical p(2Rhc - h 2c )
probes used in nanoindentation as a function of hc; however, these

equations are for ideal probes, and for real probes they may deviate
from the ideal equation. To find the real function, a number of tests
at different depths is performed on a material for which Young modu-
lus is known, then the ideal function with some constants is fitted to
satisfy the testing results. In general, this procedure should be done
frequently since the tip wears out and the area function can change.
Generally, the actual area function is closer to the ideal one when the
indentation depth is deeper.3 Another deviation from the ideal func-
tion is the pile-up or sink-in phenomena. In pile-up, the material
comes up due to indentation and causes the contact area to be bigger
than a normal test, and in sink-in the material goes lower so the con-
tact area is less than a normal test, as shown in Figure 6.
b3252_Ch-02.indd 41 27-11-2018 02:57:23 PM

Figure 6. Schematic comparison between contact areas of sink-in and pile-
up (a) cross-section view and (b) plan view. Adapted from Ref. [3]
1.5. Operational Modes of Nanoindentation

1.5.1. Continuous Stiffness Measurement
Besides vertical penetration, nanoindenters have been modified to do
different tests and measure different properties. One feature that is
added to a nanoindenter is called Continuous Stiffness Measurement
(CSM). CSM is a mode in nanoindenation that instead of measuring
only the stiffness from the unloading step of maximum load does
many small loading/unloading steps during the whole loading pro-
cess. It enables to have the desired quantity, for example Young
modulus, at different depths from the near surface until the final
depth.9 Figure 7 shows the schematics of the load–displacement curve
in the CSM mode.9
1.5.2. Scanning Probe Microscopy

Scanning Probe Microscopy (SPM) is a method of probing the sur-
face and measuring the topography using a fine probe. SPM method
can be used by the nanoindenter to give the semi in situ images of the
tested sample surface. SPM imaging is integrated in some commercial
nanoindenters, for example, the Hysitron TriboScope nanoindenters,
by using the same probe for vertical penetration in a horizontal scan-
ning mode. It can be used before and after the conventional indenta-
tion test to produce the topography of the surface and shows the
impression of the indentation.
b3252_Ch-02.indd 42 27-11-2018 02:57:23 PM

Figure 7. Load versus displacement in CSM mode
1.5.3. Nanotribology
Nanoindentation can also be used for scratching and wear tests as
used in nanotribology.10 In these tests, conical tips are kept in contact
with the sample under specific loads and the sample is moved in this
condition. Based on the testing condition, properties of wear or coef-
ficient of friction can be obtained. Figure 8 shows the optical images
of impression of a probe on the surface of ta-C coatings on Si
substrate.11
2. Instrumentation of Nanoindentation

Testing at nanoscales has its own restrictions, and sensing and actuat-
ing up to several nanometers and micronewtons needs special instru-
mentation. The actuation is usually performed by inducing magnetic
forces, electrostatic, spring, or piezo. Each of the above-mentioned
methods have their advantages and disadvantages. For example, piezo
actuators have precise accuracy at lower scales such as several nanon-
ewtons, while m agnetic inducers can exert forces up to several
Newtons. Displacement measurement can be done by different meth-
ods such as optical measuring, differential capacitor, and differential
transducer.
b3252_Ch-02.indd 43 27-11-2018 02:57:23 PM

Figure 8. (a) Optical images of nanoscratch test impressions up to 300 mN

on 20 nm ta-C and (b) SEM images of wear test impressions on 20 nm ta-C
film at 50 mN for 3,000 cycles. Adapted from Ref. [11]
2.1. Implementation of Major Commercial Machines

Major producers of standalone nanoindenters are Hysitron Inc.,
USA, Agilent Technologies Inc., USA, and Micromaterials Ltd., UK.
As one example, Figure 9 shows the Hysitron TI950 TriboIndenter.
This nanoindenter has a special three-plate capacitive transducer to
control the displacement of the probe.
2.2. Atomic Force Microscope

Atomic Force Microscope (AFM) is a device consisting of a cantilever
tip which is being moved on a surface in non-contact mode and
b3252_Ch-02.indd 44 27-11-2018 02:57:23 PM

Figure 9. Hysitron TI950 TriboIndenter. Published with permission of

Hysitron, INC
measures the topography of the surface by measuring the force exerted

on the tip due to the interatomic forces between the tip and the sur-
face.12 The measurement can be done by measuring the deviation of
light reflected from the cantilever or the variation in the length of a
spring attached to the cantilever. AFM can also be used for nanoinden-
tation purposes by impressing the AFM tip into the sample surface.
The advantages of using the AFM as a nanoindenter are the fol-
lowing: (1) the topography can be assessed prior to nanoindentation,
so the indentation location can be very accurate. (2) Since AFM is
very sensitive up to several nanonewtons, it can be used to indent
ultrathin films up to 10 nm.13 To use the AFM as a nanoindenter, it
should comply with the assumptions in nanoindentation, i.e. tip
geometry should be matched with the assumptions in nanoindenta-
tion theory.
2.3. State of the Art: In Situ Nanoindentation

Sometimes, it is necessary for the evolution of the tested material to
be observed in real time during the nanoindentation. By placing the
b3252_Ch-02.indd 45 27-11-2018 02:57:24 PM

Figure 10. (a) In situ SEM nanoindentation of a TiN/SiNx thin film.

Adapted from Ref. [16] and (b) In situ TEM nanoindentation of a silver
nanoparticle. Adapted from Ref. [14]
nano indenter inside a Scanning Electron Microscope (SEM) or

Transmission Electron Microscope (TEM), the nanoindentation pro-
cess can be viewed in great detail.14–16 Figures 10 (a) and 10(b) shows
the in situ SEM nanoindentation of TiN/SiNx thin coating16 and
in situ TEM nanoindentation of a silver nanoparticle.14
Nanoindentation can also be used with other instruments to per-
form tests in different conditions. For example, for materials that
need to be in special environment, tests can be done inside a glovebox
(for example, battery materials) or inside a vacuum chamber. Another
b3252_Ch-02.indd 46 27-11-2018 02:57:25 PM

adoption of nanoindentation is to have a temperature controlling

stage for higher or lower temperature than ambient temperature.
3. Preliminary Considerations in Dental Materials Field

3.1. Human Tooth
The human tooth is made of two main components: a coronal hard
upper part and a vascular pulp lower part, which is the root of the
tooth. The crown consists of an outer enamel, and below it is dentin,
which are hard parts of a human tooth, as shown in Figure 11. The
primary application of human tooth is to cut, crush, and break the
food, so it becomes easier for the digesting system.
Enamel is the hardest and stiffest tissue in body and is made of
96–98% wt. of inorganic minerals, mainly hydroxyapatite, and the rest
is water and organic matrix.18 Figure 12 shows the hierarchical struc-
ture of the enamel consisting of hydroxyapatite rods with inter-rod
enamel surrounding.19
Figure 11. (a) Human tooth anatomy and (b) Zoomed view to show the
different types of dentin. Adapted from Ref. [17]
b3252_Ch-02.indd 47 27-11-2018 02:57:26 PM

Figure 12. (a) Schematic of enamel hierarchy, (b) and (c) SEM images of
different faces. Adapted from Ref. [19]
Since enamel is the outer part of the tooth which is in contact

with other teeth and food and it undergoes both shear stress and
normal stress up to 2.5 GPa which cannot be repaired, it has to be
durable in comparison with other tissues.20 Below the enamel sits
dentin which has the same mineral as enamel but less in weight
percentage (70%). Therefore, it is more elastic than enamel. Dentin
contains cross-sectional tubules which extend from the interface
between pulp and dentin to the interface between dentin and
enamel.18 These tubules increase the permeability of dentin. Dentin
is divided into different sections from pulp to enamel: predentin,
circumpulpal dentin, and mantle dentin, which are shown in
Figure 11(b).
Pulp is a connective tissue which is highly vascularized and inner-
vated and consists of the pulp chamber of the crown and root canals.18
Pulp is made up of different cells immersed in an organic matrix, of
which is 25% is composed of organic materials and the rest is water.
Because of high amount of water, pulp is a soft tissue which dries
when the tooth is dried and leaves a hole in the tooth. Pulp’s roles are
to build dentin, to supply nutrition to it, to serve as a conduit for
nerves which give dentin sensitivity, and to repair dentin if needed,21
as shown Figure 11.
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3.2. Artificial Dental Materials

Since the emergence of dentistry in human history around 3000
B.C.,22 a wide range of materials from gold to ivory have been used.
In modern dentistry, four main categories of dental materials are
being used including metals, ceramics, polymers, and their compos-
ites.23,24 Table 2 shows the general properties of three main categories
of dental materials including their mechanical properties.25
A good dental material should be biocompatible, form proper
bonds with surroundings, be good looking, have properties close to
the natural tooth material, and be capable of repairing tissues if neces-
sary.24 There is no permanent material to be used in dentistry; how-
ever, materials based on their application are divided into temporary
and long term. On the other hand, based on the application of the
materials, they can be divided into three main categories, namely,
preventive, restorative, and auxiliary materials. Table 3 shows the
summary of common types of preventive and restorative dental mate-
rials in terms of their applications.24
In this section, the mechanical properties of each group of artifi-
cial dental materials is briefly presented.
3.2.1. Ceramics
Ceramics are non-metallic inorganic materials which usually exhibit
high hardness and brittleness. In clinical applications, aesthetics is
the most important feature of ceramic materials.27 After ceramics
were first introduced in 1774, it took over 190 years until the intro-
duction of a porcelain-fused-to-metal system which caused the
demand for ceramic systems to increase significantly in the 1960s.27
In general, porcelain-only restoratives have two major problems; one
is the brittle fracture of ceramics which causes the porcelain to break
suddenly, and the second is the abrasive effect of the opposing tooth,
which causes the tooth moving against the porcelain to wear out.
Porcelain fused to metal e nables the system to have both the aesthet-
ics of porcelain, which is the closest material to the natural tooth
crown, and the strength of metal simultaneously.
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b3252_Ch-02.indd 50

Table 2. General properties of metals, ceramics, and polymers
Metals Ceramics Polymers
Intermetallic Inorganic
Properties Alloys compounds salts Crystalline Glasses Rigid Rubbers
Hardness Medium to Hard Medium to Hard Hard Soft Rubbers
hard hard
Strength Medium to Medium Medium High High Low Low

high
Toughness High Low Low Most low, Low Low Medium
some high
Elastic modulus High High High High High Low Very Low
Electric conductivity High High Low Low Low Low Low
Thermal High High Low Low Low Low Low
conductivity
Thermal Expansion Low Low Low Low Low High High
Density High High Medium Medium Medium Low Low
Translucency None None Medium High High High Low
Examples Gold-copper Amalgam Gypsum, zinc SiO2, Al2O3 Dental Poly (methyl Impression
phases phosphate porcelain methacrylate) materials
“9x6”
27-11-2018 02:57:26 PM
Table 3. Applications and durability of preventives and restorative dental

materials
Applications Potential
Material type of products preventive benefits Durability
Resin adhesive A F (certain products) M
Resin sealant S S M
Resin cement L F (certain products) M
Composite B, L, R F M
Hybrid ionomer B, L, R F M
Glass ionomer (GI) A, B, L, R, S F, S L, M
Metal-modified GI R F L, M
Zinc oxide-eugenol B, L, T — L,M
Zinc phosphate B, L — M
Zinc polycarboxylate B, L — M
Zinc silicophosphate B, L F M
Resin composite R F (certain products) H
Dental amalgam R — H
Ceramic R — H
Metal-ceramic R — H
Metal-resin R — M, H
Temporary acrylic resin T — L
Denture acrylic R — H
Cast metal R — H
Wrought metal R — H
Notes: A = Adhesive, B = Base, L = Luting Agent, S = Pit/Fissure Sealant, R = Restorative, T =
Temporary Restorative. Potential Preventive Benefits: F = Fluoride-releasing Material, S =
Sealing Agent. Durability: L = Low, M = Moderate, H = High.
3.2.2. Composites
Resin-based composites were first used mostly as adhesive or direct
restorative in 1960s.28 Due to aesthetic problems of amalgam and by
improving the filler materials, the demand is now for resin-based
b3252_Ch-02.indd 51 27-11-2018 02:57:26 PM

composites which have good appearance and also strong bonding to

tooth.26 However, the high wear rate of composites limits their life-
time, especially in a high stress environment.
4. Nanoindentation in Dental Materials

4.1. Adaptions of Nanoindentation for Biomaterials
Knowing the mechanical properties of biological materials, specifically
dental materials, is crucial in clinical applications.29 Due to the hierar-
chical nature of biological materials and the fact that they are found
in small sizes, it is hard to test them using conventional methods for
testing inorganic materials. This is where alternative tools such as
nanoindentation can be used. Nanoindentation, with its flexibility in
testing small samples and even in situ testing, is an ideal tool to
extract mechanical properties of tissues. Since nanoindentation can be
used to measure local properties, it is useful to map the properties and
examine the influence of changes in tissue on the properties.
Microindentation has been used for many years to measure
mechanical properties of soft tissues such as cartilage.30,31 For exam-
ple, millimeter indentation was used to investigate the healthy and
diseased cartilages.30 One of the first applications of nanoinstruments
in dentistry was to use the nanohardness test to measure mechanical
properties of teeth.32–34 Since the biological materials are usually adhe-
sive and possess time-dependent behavior,35 the conventional method
used in nanoindentation explained in Sections I and II needs to be
altered accordingly.
4.1.1. Probe Selection

For testing biomaterials using nanoindentation, two factors should be
considered regarding the proper probe selection. The indenting probe
should have a reasonable size, which means if the probe is too large
compared to the testing sample, the result is under the influence of
other parts, or if the sample is too big compared with the probe, the
result is local and does not represent the property of the whole sample.
In the same sense, sharp probes such as Berkovich and cube corner are
b3252_Ch-02.indd 52 27-11-2018 02:57:26 PM

usually used when testing small samples such as a cell and larger
probes such as flat punch and spherical tips are used for tissues.
4.1.2. Creep
Creep is the phenomenon related to time-dependent behavior in tis-
sues, especially soft tissues. Creep means that the material shows defor-
mation under constant load.36 In nanoindentation with sharp loading
function, creep causes a so-called “nose” when the indenter is unload-
ing from the maximum depth, as shown in Figure 13(a). The simplest
solution to exclude the effect of creep from unloading part is to use a
trapezoidal load function which causes the viscoelastic material to
deform under constant load due to creep and upon unloading; only
elastic deformation is involved with unloading29,37,38 as shown in
Figure 13(b). Obviously, the holding time depends on the material’s
characteristics and loading rate and can vary between 3 and 120 s.29 In
Figure 13. Schematics of (a) rectangular load function and the load–

displacement curve of viscoelastic material associated with it showing nose
when unloading due to creep and (b) trapezoidal load function and eliminat-
ing the creep effect in load–displacement curve. Adapted from Ref. [29]
b3252_Ch-02.indd 53 27-11-2018 02:57:27 PM

addition to trapezoidal load function, some numerical calculations were

developed to consider viscoelasticity as a more rigorous solution.29
4.1.3. Viscoelasticity
Biological tissues when exhibiting high viscoelastic behavior, espe-
cially for highly hydrated and organic tissues, cannot be fully under-
stood with simple elastic models. A linear viscoelastic material can be
modeled by
E = Estr + iElos,(15)
where E is the complex dynamic modulus, Estr is storage modulus, Elos

is the loss modulus, and i is the imaginary unit. Storage modulus
represents elastic behavior of the material, while loss modulus
describes the viscous behavior, and in perfectly elastic material it is
equal to zero. Using nanoindentation and performing dynamic test,
loss and storage moduli can be determined.37 Using Berkovich tip and
assuming standard Kelvin model to describe linear viscoelastic materi-
als, Sadr et al. studied four adhesive materials.39 They reported creep
compliance functions and showed that the moduli considering viscoe-
lastic behavior is fairly less than the modulus measured and reported
by the nanoindentation device.40
4.1.4. Adhesion
Adhesion is another issue related to nanoindentation of tissue mate-
rials. Adhesion means that the material sticks to the probe without
using force, which causes artificial negative forces during withdrawal
of the probe from the sample, as shown in Figure 14. If the adhe-
sion force is significant, the measured E-modulus is overestimated.35
If the indentation is performed with a spherical tip, Johnson–
Kendall–Roberts method can be used to improve the accuracy.40 In
this method, the load–displacement data is acquired before the
probe touches the surface, so the negative adhesion force is
b3252_Ch-02.indd 54 27-11-2018 02:57:27 PM

Figure 14. Force–displacement curve for indentation of a poly (dimethyl)

siloxane sample. Padh is the maximum adhesive force during unloading rela-
tive to reference zero before tip reaches sample. “A” shows the adhesion
between sample and tip when approaching. “B” shows the unloading of tip
at maximum depth. “C” shows pull-up points where, upon withdrawal of tip
from sample, adhesion between tip and sample causes the nanoindenter to
sense a negative force. Adapted from Ref. [29]
measured. Figure 14 shows the schematic of such a load–displace-

ment curve.
4.1.5. Hydration
Hydration and dehydration also have great influence on the result of
the test. Comparison between hydrated and dehydrated bone sample
tests shows an increase of moduli between 11% and 28% from hydrated
to dehydrated.41,42 A demineralized dentin was tested using AFM
nanoindentation and showed significant increase of one order of mag-
nitude when desiccated. Even after rehydration, the E-modulus was
still bigger than the original hydrated sample.43 So, it should be noted
that sample preparation time and condition can significantly change
the properties of tissues, even hard tissues such as bone and dentin.
b3252_Ch-02.indd 55 27-11-2018 02:57:27 PM

4.2. Nanoindentation of Natural Dental Materials

Knowing the mechanical properties of human teeth helps research-
ers to better understand the functions of different parts in teeth and
to design and build proper artificial materials close to the natural
materials.44 In this section, the mechanical characterization of differ-
ent parts of the human tooth by nanoindentation are briefly
explained.
4.2.1. Enamel
Cuy et al. showed using nanoindentation mapping that enamel is not
homogenous and its properties depend not only on chemical compo-
sition but also position and the orientation of rods.45 They used
Berkovich probe and performed tests on prepared samples of enamel,
and the displacement range of the tests were typically 400 nm or 800
nm. The Poisson’s ratio was selected as 0.25. They kept the samples
in the ambient environment for long enough to avoid changing of
material properties during tests so the results are expected to be
higher than if they were conducted in wet environment. Their results
are shown in Figure 15 as maps of E-modulus and hardness.45 Based
on their results, the hardest and stiffest part of the enamel is the outer
part. Hardness and Young modulus decreases when moving to the
inside of the tooth, and it is directly correlated to the calcium content
of the enamel.44–46
Jeng et al. conducted indentation tests using AFM on enamel rods
and reported that enamel head is harder and stiffer than enamel tail and
the axis.46 Furthermore, it was shown that the enamel rods are aniso-
tropic in their axial section.47 In this work, the effect of rotating the
Berkovich probe on the sample was investigated and SEM images were
taken, which found the asymmetric pile-up of indentation impressions
due to anisotropic behavior of the enamel rod. Measured values of
hardness and E-modulus were different based on the machine which
was used, the probe, the range of load, the strain rate, and the hydra-
tion content of the sample.44,48 For example, higher loads resulted in
lower measured hardness and E-modulus.49
b3252_Ch-02.indd 56 27-11-2018 02:57:27 PM

Figure 15. (a) Hardness and (b) E-modulus map of enamel. Adapted from
Ref. [45]
4.2.2. Dentin
Dentin has a more complex structure in comparison to enamel, and
it was the focus of several works to study its mechanical properties.
Similar to enamel, hierarchical structure of dentin has great influence
on mechanical properties. The orientation and density and mineral
content of tubules and collagen fibers are parameters affecting the
mechanical properties of dentin.44,50
Cohen et al. cut off the coronal dentin and embedded it in epoxy
and used AFM quasi-static indentation with cube corner probe.50
They examined a typical tubule in dentin which consists of a lumen
which is a hole in the middle, PeriTubular Dentin (PTD), which is the
mineralized collar around lumen and surrounding mineralized colla-
gen-rich matrix called InterTubular Dentin (ITD). Cohen et al. also
conducted indentations with same peak load in the radial lines from
lumen outward.50 The inset of Figure 16(b) shows the AFM image of
the sample and the indentation impressions. The hardness increases
from ITD with 1.2 GPa until the highest value of 4.7 GPa is seen in
PTD and then decreases slightly to 4 GPa at the lumen edge, as is
obvious from the size of impressions in Figure 16.50
Ziskind et al.51 used CSM nanoindentation with Berkovich tip to
extract hardness and E-modulus of the same sample as Cohen et al.50
b3252_Ch-02.indd 57 27-11-2018 02:57:28 PM

Figure 16. Averaged (a) E-modulus and (b) hardness spatial results of a

single tubule from lumen edge to ITD from Ref. [51]. E-modulus results are
compared with Ref. [52]. The inset in (b) shows the AFM image of single
tubule and the impressions of indentations. Numbers show the load in
micronewton. Adapted from Ref. [50]
mentioned above. The E-modulus and hardness values decreased

gradually when traveling from lumen edge to ITD, as shown in

Figure 16. As expected, although the trend of results is the same as
mentioned in Ref. [50], due to the change in testing situation, the
b3252_Ch-02.indd 58 27-11-2018 02:57:29 PM

measured E-modulus and hardness from a Berkovich probe are lower

than the results obtained by using a cube corner probe.
The decay in hardness and stiffness of dentin was also shown to
be exponentially correlated to the mineral content of the tissue.53 In
addition, environmental parameters such as hydration level and tem-
perature significantly influence dentin mechanical properties. For
example, by testing different samples that were dehydrated and wet
and previously frozen and not frozen, it was shown that dehydrated
samples have higher hardness and E-modulus. For previously frozen
hydrated samples, the E-modulus and hardness decreased significantly
in comparison with not-frozen wet samples, which is attributed to the
damage caused by water inside the tissue during freezing. However,
since dry samples have less water content, freezing did not change the
properties significantly.54 Using nanoindentation and measuring the
energy dissipation, it was shown that dry dentin exhibits stronger
elastic–inelastic behavior than wet dentin.55 In a comparative work by
using the Berkovich probe, the conventional method of nanoindenta-
tion was compared with the CSM method. It was shown that the
CSM method measures higher values than the conventional method
for both enamel and dentin at different peak loads.56
4.3. Nanoindentation of Artificial Dental Materials

The best materials to be used in clinical dentistry are the ones that are
closer to the characteristics of real tooth materials. This is the motiva-
tion to test the dental materials and to evaluate their performance.
Basically, tests to be done on artificial and natural dental materials are
the same; so in this section, some of the methods used in character-
izing artificial dental materials are only highlighted briefly.
A wide range of nanoindentation tests have been done on restora-
tive materials to extract their mechanical properties.57,58 For example,
nanoindentation with conical probe has been used to extract stress–
strain curve from load–displacement response of some dental restora-
tives based on approximations that relate the maximum displacement
and load to strain and stress, respectively.57 Based on the stress–strain
curves, it was found that Wiron alloy has the closest stress–strain
behavior to enamel, while Mark II and VM9 ceramics have higher
b3252_Ch-02.indd 59 27-11-2018 02:57:29 PM

strength. Ilie and Hickel also used nanoindentation to investigate the

nanomechanical properties of different composite materials.59 They
measured the hardness, elastic modulus, and dynamical properties
such as storage and loss moduli of materials in two different condi-
tions. They concluded that silorane-based composites exhibit good
properties which make them suitable for clinical applications.59
4.4. Other Types of Tests on Dental Materials Enabled

by Nanoindentation
Nanoindentation can be used to extract other properties of tooth tis-
sues such as the tribological26,60–62 and dynamic37,63–65 properties. For
example, using AFM with cube corner tip, Balooch et al.64 measured
the maximum width of the DEJ to be 2–3 µm, which is much less
than the previous reported data, and the storage modulus of enamel
close to the DEJ to be in the range of 51–74 GPa (average 63 GPa).
Other types of mechanical tests on dental materials enabled by
nanoindentation are explained in the following paragraphs.
4.4.1. Viscoelastic Properties

Balooch et al.43 measured the viscoelastic constants of demineralized
dentin under three conditions using a flat punch probe for AFM and
assuming the standard linear solid model. In particular, the relaxed
elastic modulus and relaxation time constants under constant strain
and constant stress have been measured.
4.4.2. Creep Behavior

Creep behavior in enamel has been studied by He and Swain using
nanoindentation with Berkovich probe.66 They applied trapezoidal
load function, held the maximum force for 900 s, and recorded the
displacement at this step as creep. And for back creep, they held the
probe on the sample at the minimum load for 900 s. Figure 17
shows the creep and back creep when this method is used to inves-
tigate the influence of ambient conditions on creep behavior of
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Figure 17. (a) Trapezoidal load function in nanoindentation for creep and
back creep test. (b) Displacement versus time for holding time at maximum
load (creep) and minimum load (back creep). Adapted from Ref. [66]
enamel.66 The results implied that different environmental mediums

may influence both the creep and the back creep behavior of enamel
regardless of the load.
4.4.3. Fracture Toughness

Originally developed for Vickers hardness, fracture toughness from
nanoindentation is estimated based on the following equation50,68:
E P
Kc = a , (16)
H c 3/2
b3252_Ch-02.indd 61 27-11-2018 02:57:29 PM

in which Kc is fracture toughness, P is applied load, H is hardness, E

is E-modulus, c is the length of the crack from the center of the
indentation on surface, and a is an empirical calibration constant. This
procedure has significant uncertainty, and on top of that it only works
for brittle materials. The most brittle part of tooth is enamel, which
has been studied using this method using a cube corner tip.67 The
advantage of using a sharp indenter is to initiate the crack with lower
applied load. As an example, Marshall et al. reported fracture rough-
ness of 0.6–0.9 MPa . m1/2 for DEJ using a cube corner,68 and
Ayatollahi and Karimzadeh reported the maximum value of 1.06
MPa . m1/2 for intact enamel.69
4.4.4. Nanotribology
The nanotribological properties of tooth is another interesting topic
to study using nanoindentation including both scratch and wear tests.
Guidoni et al. used a conical probe and an increasing load function to
perform single scratch tests on dry and wet enamel samples.70 By
comparing results of wet and dry enamels, it is shown that plastic
deformation plays an important role on the abrasive behavior of
enamels. They also performed a wear test by scanning an area with the
probe at certain loads and concluded that the plastic deformation
occurred in the first scan. After that, the probe slid much smoother
over the deformed surface and caused fatigue deformation.70 Rod and
interrod sections in enamel have also been studied under nanoscratch
tests by using a conical probe.62 It was shown that interrod enamel is
less resistant to wear. Furthermore, the wear and scratch tests have
been performed on tooth enamel to investigate the effect of bleaching
on enamel.61 The wear rate, which is the rate of volume of surface
removed during the test, and friction coefficient have been meas-
ured61 from this work by using a Berkovich probe.
5. Concluding Remarks and Outlook

In biology and specifically dentistry, understanding the properties of
tissues is crucial for clinical purposes. Since dental materials are usually
b3252_Ch-02.indd 62 27-11-2018 02:57:29 PM

small and heterogeneous at micrometer or even nanometer scales,

conventional methods for testing bulk materials are generally not
applicable. In this respect, nanoindentation as a powerful non-
destructive tool to extract mechanical properties at small scales has
been widely used in recent years to test dental materials. With proper
adaptations, various nanoindentation techniques have been used to
extract the mechanical properties of both natural and artificial dental
materials, including the elastic modulus, hardness, viscoelastic proper-
ties, and nanotribological properties. It is expected that in the near
future, with the increasing popularity of state-of-the-art nanoindenta-
tion techniques such as in situ nanoindentation, the mechanical prop-
erties of dental materials can be mapped more accurately with their
hierarchical microstructures than currently available, which will have
a profound impact on revealing the wear and decay mechanisms of
dental materials during clinical use.
Acknowledgment
This work was supported by NSERC Discovery Grant under RGPIN
430800-2013, Canada.
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Chapter 3
Finite Element Analysis in Dentistry
Josete B. C. Meira*,§, Alice N. Jikihara*,

Pavel Capetillo*, Marina G. Roscoe†,
Paolo M. Cattaneo‡, and Rafael Y. Ballester*
*Department of Biomaterials and Oral Biology,
University of São Paulo São Paulo, SP, Brazil
†
Department of Orthodontics and Restorative Dentistry,
University of Guarulhos São Paulo, SP, Brazil
‡
Section of Orthodontics, Department of Dentistry, Faculty
of Health Science, Aarhus University, Aarhus, Denmark
§
jo@usp.br
Finite element analysis (FEA) presents a wide range of application in

dentistry. FEA models can precisely calculate the material stress in
conditions of geometry and boundaries that can properly represent
the clinical reality. However, like any research model, the FEA
requires some simplifications to be feasible. The researcher’s chal-
lenge is to distinguish between the necessary simplifications and the
misrepresentative ones. This chapter presents some information to
help FEA users to improve their FEA result interpretation. In addi-
tion, it will help readers who are not familiar with this technique to
understand the power of this tool and enable them to critically ana-
lyze the published FEA studies.
67
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1. Introduction
The experimental tests explored in the previous chapter enable the
mechanical characterization of dental materials and the comparison
between analogous materials in standard conditions. Once the
mechanical characteristics are set, it is possible to go forward in pre-
dicting the material behavior a “quasi-real” scenario by using finite
element analysis (FEA). The real shape of the test object and actual
loading application can be represented in the FEA model.1,2 FEA has
been used to provide a better understanding of experimental tests,3
so, this chapter will focus on the “clinical scenario” studies.
In the last decade, there was a large increase in the number of
FEA papers in dentistry. It is expected that in this large pool of arti-
cles, we can find studies with important errors in model generation
and/or with fundamental flaws in result interpretation. The great
challenge for the readers is to recognize the studies with major faults
and critically evaluate the limitations of the generated conclusions.
Still, it is important to remember that finite element models are
always simplified representations of the reality. Experimental models
are also simplifications of reality. It is possible to say that all models
present some limitations. Therefore, the researcher’s challenge is to
distinguish between the necessary or required simplifications from
the misrepresentative ones, for either the experimental models or the
FEA ones.
2. How the Model Geometry is Defined

and Obtained?
2.1. Two- or Three-Dimensional Models?
A consistent FEA can be developed either with a simple two-dimen-
sional (2D) geometry or with a more complex 3D patient-based
model. Between these two extremes, there is a wide range of geo-
metric complexity that can be used for modeling. Frequently, mod-
els of teeth with 2D geometry are criticized due to errors generated
by limitations inherent to 2D models (see Section 2.2). However,
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Finite Element Analysis in Dentistry 69
planar representations are still well accepted in studies involving the

simulation of complex phenomena, such as crack propagation4 and
fatigue.5 2D models are also recommended in the early stages of a
simulation. The strategy is to start the investigation with simple mod-
els and then gradually increase the degree of complexity throughout
the study.
The construction of a 2D geometry can be easily performed with
the computer-aided design (CAD) features of the finite element
software. In patient-based models, the geometry is obtained using
modern methods of image acquisition (see Section 2.3). These mod-
els have become increasingly common, due to technological advances
in medical imaging technology and computation fields. Equipment
and technology, previously restricted to selected research groups,
have become more widespread in the dental clinics and in dental
academia. However, it is important to notice that the results obtained
in a model based on precise measurements of a single patient might
be more limited with respect to the generalization of their findings
than those obtained in anatomically simplified models with average
measurements of a population. In addition, an excess of anatomical
details can create “noise” that may compromise or conceal the rele-
vant results.
2.2. Limitations of 2D Models

In 2D FEA models, the geometry is drawn in two dimensions, but
the software considers that the real object is in fact a 3D entity. The
plane models (plane stress and plane strain) assume that the object has
the same geometry along the non-represented axis (z-axis), while the
axisymmetric models assume a 360° revolution around the symmetric
axis (Figure 1). Furthermore, the plane stress model considers that
the thickness in z direction is very small when compared to x and y
dimensions, which makes the stress in z insignificant. It justifies the
simplification of sz = 0 used for these models. On the other hand, the
plane strain models consider that the thickness in z is very large,
which makes the strain in z insignificant. Therefore, ez = 0.
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Figure 1. 2D models of a root with an intraradicular post. In plane stress

and plane strain models, no hoop tensile stress is generated due to the inter-
pretation of the software regarding the real object geometry. In axisymmetric
model, the hoop tensile stress is present
Because of these geometric assumptions, both plane models are

not able to represent the tensile hoop stresses generated in the real root
due to the intrusion of an intraradicular post, for example Ref. [6].
However, axisymmetric models can satisfactorily represent this wedge
effect, since they reproduce the real structural stiffness of the root.
The main limitation of this model is its inability to simulate clinically
relevant oblique loading conditions.
2.3. Strategies for Geometry Acquirement

The anatomic geometry can be obtained by different approaches.
In this chapter, we focus in three geometry sources: literature data,
3D scanners, and computer tomography (CT). Regardless of the
image data source, the anatomic model is converted into a
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Figure 2. Overview of different approaches used for FEA models

construction
parameterized model by the CAD software and, finally, to a discre-

tized model by the FEA software (Figure 2).
2.3.1. Geometry Based on Literature Data

The geometric shape and measurement data of the anatomic structure
are collected from the literature. A well-known source for dental
anatomy parameters is available in Wheeler’s Dental Anatomy,
Physiology, and Occlusion.7 The book presents, in a grid of 1 mm2,
accurate figures of tooth external contours from five standard aspects:
labial, lingual (or palatal), mesial, distal, and occlusal (or incisal).
Tables with average values of key measurements of each type of tooth
are also offered: length of crown, length of root, mesiodistal diameter
of crown, mesiodistal diameter of crown at cervix, buccolingual diam-
eter of crown, buccolingual diameter of crown at the cervix, curvature
of cementoenamel junction, and curvature of cementoenamel junc-
tion on distal. The authors also dedicate a chapter to pulp chambers
b3252_Ch-03.indd 71 27-11-2018 02:58:46 PM

and root canal in which the internal anatomy of the tooth is explained
in detail.
Drawing the anatomic model from this data requires the operator
to be highly skilled in CAD software. First, the outer and inner curves
are drawn, then the outer and inner surfaces are created from the
curves, and finally the solids are created, based on the surfaces.
During this process, it is interesting to divide the model in strategic
planes (for example, buccolingual or mesiodistal) to facilitate the
viewing of the details. It is also important to avoid gaps and interpen-
etration of solids. Otherwise, the operator will have problems to mesh
the model after transferring it to the FEA software.
2.3.2. Geometry Based on 3D Scanning

In the last decade, the CAD/CAM technology has become more and
more widespread in dentistry; thus, dentists and prosthetic technicians
had the possibility to familiarize themselves with 3D scanners. There
are three types of 3D scanners: laser, LED light, and contact. In gen-
eral, resolution (number of dots per unit area measured by the device),
trueness (degree of closeness to the true value), precision (deviation
of measurements from the mean value), and accuracy (sum of trueness
and precision) do not depend directly on the type of scanner. Thus,
different types may have the same resolution and accuracy, depending
on specific technical characteristics of the appliance.
The accuracy of contact scanners is dependent on the capacity of
the scanning tip to reach the desired surface. Therefore, it can present
limitations in copying some of the details. Moreover, the object must
necessarily be coupled to a support, so it is restricted to extraoral scan-
ning. A recent study8 evaluated some parameters of different types of
extraoral 3D scanners and found values between 34.3 points/mm2 and
299.8 points/mm2 for the resolution, and 29–46 μm for trueness.
The data are typically recorded in an STL file,a a format taken
from the 3D-printing technology, in which only the 3D-surface
The STL has several after-the-fact backronyms such as “Standard Triangle Language”
a
and “Standard Tessellation Language”.
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geometry is described in a triangular mesh. Generally, the STL mesh

guides the construction of the geometric model, but not the FEA
mesh, since it does not have sufficient quality, and/or is characterized
by triangles with compromised edges.
The acquisition of geometry by 3D scanning is limited to the
external surfaces of the object. In order to obtain the internal geom-
etry of interest for FEA models, it is necessary to use other methods
of image acquisition, such as drawing from literature data, as described
in Section 2.3.1, or in combination with CT data.9
2.3.3. Geometry Based on Computed Tomography

Two types of CT are used for clinical application in dentistry: cone-
beam-CT (CBCT) and fan-beam-CT (FBCT). CBCT is used more as
a complementary diagnostic test for guiding dental treatment, espe-
cially in implantology. It allows a considerable decrease of the radia-
tion dose when compared to FBCT, reducing patient exposure to
ionizing radiation. When details of tooth geometry are important for
the FEA model, the anatomical volume view has to be limited to the
region corresponding to few teeth. FBCT is usually indicated as a
medical complementary test, and it can offer high resolution for a
whole skull model, due to its higher radiation power.
The resolution of CTs is low when compared to that from micro-
CTs (µCT). While the voxel from CT is around 0.3 × 0.3 × 0.3 mm3,
that from µCT is in the range of 1–50 μm. Therefore, µ-tomography
is preferred for low scale-models (see Section 2.4). However, µ-CT is
not feasible for large size models due to dimensional limitation of the
equipment, in which only small objects can be scanned, and by the
fact that the radiation level is much higher, when compared to clinical
tomography. Therefore, these features limit the use of µCT as an
“in vivo” investigation tool, at least for humans. Only geometries of
extracted teeth models or those from human autopsy, excised bone
samples, or small animal models can be scanned with this strategy.
An important feature of CTs is that they can provide not only the
external contours but also the internal geometry of the anatomical
structures in a non-destructive and non-invasive way. The method
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applies a segmentation process, based on differences in pixel gray-

level values in the image, which is dependent on the radiopacity of the
tissue.
Recently, some specific software have been created and improved
to convert medical images of DICOMb files into 3D FEA models.10–12
They offer intuitive tools to provide fast and consistent image seg-
mentation. Furthermore, its finite element mesh preparation work-
flow allows the user to obtain high-quality volumetric meshes that can
easily be converted into finite element mesh by the FEA software.
2.4. Represented Structures and Model Scale

The decision about the structures that should be represented
depends on the purpose of the study. Generally, all essential struc-
tures should be represented and well discretized (see Section 3).
However, sometimes it is not so easy to define which structures are
essential for a specific study. If non-essential structures are repre-
sented (or if the mesh density is exaggerated in regions of less
interest — see Section 3), there will be no gains, but an unneces-
sary computational cost.
Let us give an example: for studying the stress polymerization of
a class II composite restoration, it is not useful to represent the whole
root. Representing just the cervical portion of the root ensures that
the boundary restriction remains sufficiently far away from the region
of interest.13,14
If the researcher is unsure about the extension of the root that
should be represented, some preliminary exploratory analysis is rec-
ommended. The strategy to be used in this process is similar to that
used for obtaining the convergence curve (see Section 3): run a series
of models with different root length representation, and then analyze
the selected result parameter at the region of interest as a function of
DICOM is the abbreviation for Digital Imaging and Communications in Medicine

b
and corresponds to a series of standardization of medical images in order to create a

common language between professionals and between medical imaging devices.
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root extension. The ideal model will be the one in which a minimal
root length is represented for independent results.
Another important aspect related to the discretization process is
that the model must represent only compatible size structure. When
representing a thin structure, the suitable element will be very
small, because the structure should have at least three layers of ele-
ments. Therefore, if a complete large structure is represented in the
same model, the number of elements would be excessively high,
which may make it unfeasible. What is the solution? Avoid repre-
senting structures of very different order of magnitude in a single
model.
For didactic and practical purposes, this chapter divided FEA
models for dentistry into three scale levels, according to the size of
the represented structures (Figure 3). Still, sometimes, it is impossible
or unproductive to represent all the structures of interest in a single
Figure 3. Didactic classification of FEA model scales: Level A — simulation

of a whole maxilla, jaw, or skull represented (example from Ref. [12]);
Level B — simulation of a tooth or few teeth (example from Ref. [15]);
Level C — simulation of micro- or nanostructure of a material. Adapted
from Ref. [16]
b3252_Ch-03.indd 75 27-11-2018 02:58:46 PM

model due to the computational cost. Multiscale modeling represents

a solution for those cases.
2.4.1. Level A
This scale refers to FEA models in which the whole maxilla, jaw, or
skull are represented. This type of model is becoming more frequent
due to the facilities in acquisition of anatomic geometry from
DICOM tomography files (see Section 2.3.3) and increased advances
in computer science. In this scale, the tooth is usually represented as
a single body, as if it was composed of a single material.10,11,17,18 In
some cases, the distinction between cortical and trabecular bone is
not represented.12,19,20 In general, only thick structures like tooth,
bone, and implants are represented in these models. Yet, in some
studies the periodontal ligament (of 0.2–0.3 mm thickness) is also
simulated.10,11,19,20
2.4.2. Level B
This scale refers to FEA models in which a tooth (or part of it) or a
group of teeth are represented. In this scale, the tooth is represented
with more details, including enamel, dentin, and pulp. Depending
on the study focus, restorations,21,22 cavities,23,24 and intraradicular
posts25 are also represented. The bone is sometimes represented
distinguishing cortical from trabecular,26 and sometimes only the
cortical layer is considered. Contrary to level A models, structures
as thin as 0.3 mm, such as periodontal ligament, are generally
represented.26
2.4.3. Level C
This scale refers to FEA models in which the micro- or nanostruc-
ture of a material or a multilayer adhesion is represented. The large
increase of articles using this scale in the last decade can be attrib-
uted to the possibility of obtaining experimentally the mechanical
b3252_Ch-03.indd 76 27-11-2018 02:58:46 PM

properties of the materials in micro- or nanoscales from tests like

nanoindentation, atomic force microscopy, or micropillar compres-
sion experiments.
This scale has been well explored in studies of adhesive interfaces
in which microscopic structures, such as intertubular dentin, hybrid
layer, adhesive layer, adhesive tags, and smear plugs are represented.16,27
Parameters such as thickness of the layer of dentin infiltrated by adhe-
sive, thickness of the adhesive layer, etc., are based on images achieved
from scanning electron microscopy. Yet, the structures have been rep-
resented by primitive geometries (such as rectangles, triangles, paral-
lelepipeds, cylinders cones, spheres), ignoring the precise irregular
shapes disclosed by microscopy.
2.4.4. Multiscale
In a multiscale analysis, two or more models, with different scale lev-
els, are related. The results of the first one are used as an input for the
next scale level in two ways: upscaling or downscaling. The upscaling
approach has been used in studies of mechanical characterization of
enamel28–31 and bone,32 while the downscaling approach has been
used in studies of adhesion and dental trauma.33
3. Mesh Quality and Mesh Convergence

It is well known that a finer mesh results in a more accurate solution.
However, using the finest mesh in the whole model is usually a bad
strategy because unnecessary calculation will be performed, produc-
ing a useless computational cost. The mesh convergence study ena-
bles the acquisition of a mesh that satisfactorily balances accuracy and
rationalization of computing resources.
3.1. Reducing the Element Size

Generally, the mesh is refined by reducing the element size. A good
approach in FEA simulation is to start the study with a coarse mesh.
b3252_Ch-03.indd 77 27-11-2018 02:58:46 PM

Although this mesh gives an inaccurate solution, it is very useful in

the early stages of the analysis, when some model verifications are
required (e.g. check of the applied loads and constraints). After these
verifications, the mesh is systematically refined and the convergence
curve is created.
In order to obtain the convergence curve, a selected result param-
eter at the region of interest is plotted as a function of a measure of
“mesh density” (Figure 4), such as the number of elements in the
whole model or in the region of interest. Although the decrease of
element size is somehow an indicator of increase in mesh density, the
element size should not be used in the x-axis of the convergence
curve. The convergence is achieved at the ideal mesh density point, in
which the result does not change significantly with the increase of the
refinement. This is also a guarantee that unnecessary calculation will
not be performed.
In some cases, each increase of mesh density in the convergence
curve is achieved by splitting all the elements in the model. However,
the local mesh refinement is preferable instead of refining the whole
mesh model (Figure 5). In that case, it is important to create transition
regions to gradate the element size from coarse to fine meshes. The
elements away from regions of interest can be considerably larger than
those in regions of interest, without jeopardizing the analysis accuracy.
Figure 4. Mesh convergence curve
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Figure 5. Mesh convergence by reducing element size: generalized and

localized refinement
3.2. Increasing Element Order

The mesh can also be refined by increasing the element order. In this
case, the geometry and the number of elements in the mesh are not
modified. It continues the same, but with a higher-order element. For
example, if a first-order element (like a linear triangular one, which
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Figure. 6. (a) Comparison between the results of first-order element

(tria 3) with a second-order element (tria 6). (b) Mesh convergence curve of
different refinement technique
has three nodes) has been used in the coarse model, a second-order
element (like a parabolic triangular element, which has six nodes) can
be chosen for the refined model. This is an easy and fast way to refine,
because no remeshing is needed. However, as every element and
region of the model receives the same increase in calculating power,
the computational costs increase faster than with the local refinement
previously presented. This technique is interesting for a quick evalua-
tion of a “final model” in which the convergence test has not been
performed (Figure 6).
4. Issues Related to Properties of Biological Materials

Usually, the material properties data used in FEA models are obtained
from published experimental studies. Researchers are faced with the
problem of a large dispersion of data recorded for the biological
structures. There are two main reasons for this dispersion: (1) bio-
logical materials are not homogeneous and standardized, since they
vary as a function of individual aspects (genetic, age, gender, etc.);
and (2) the methods used to obtain the mechanical properties of
biological materials are not as standardized as those of materials for
engineering analysis.
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Dispersion motivates some researchers to perform their own

experimental tests in order to obtain the required material proper-
ties inputs for FEA models.34 This approach does not solve the dis-
persion problem, as the new result will be one more in the spectrum
of the available data. Nevertheless, it is interesting because the
authors are not limited to published data and more specific and
accurate input for the particular conditions of the study can be
obtained. On the other hand, an approach that is usually not
encouraged by journal reviewers is to use properties from other FEA
studies. Although that would be not critical for some cases, it can
propagate inaccuracies.
Many FEA studies represent biological materials as isotropic, lin-
ear, and elastic. In these cases, only two parameters are necessary: the
modulus of elasticity and the Poisson’s ratio. However, biological
materials are usually more complex, and do not behave as an iso-
tropic, linear and elastic material.35 On the other hand, the more
complex the material properties to be modeled, the higher the risk for
inaccuracy or misinterpretation of the results.
Nonlinear elastic and viscoelastic models are frequently used for
periodontal ligament. This thin soft connective tissue that links tooth
to bone is composed of two basic components: the collagen fibers
(which are arranged in different directions along the root contour)
and the fluid interstitial matrix. This histologic arrangement allows
the PDL to perform as both a shock absorber and a load transmitter
from tooth to bone.
Experimental studies have shown that periodontal ligament acts as
a viscoelastic, anisotropic, and heterogeneous material.36 Therefore,
the way it behaves during loading and unloading conditions varies
depending both on the velocity of force application as well as from its
duration. In FEA studies, the PDL has been simulated using distinct
constitutive models, which have been organized into two groups:
(1) models for instantaneous or short-term loading cases; and
(2) models for delayed or long-term loading cases. The first group
contains different elastic constitutive laws, like linear-elastic, hiperelas-
tic, or nonlinear.37 The second group includes viscoelastic, poro-
elastic,38 and multiphase models.
b3252_Ch-03.indd 81 27-11-2018 02:58:48 PM

5. Boundary Conditions and Loading

The boundary conditions define the loading and the constraints
applied to the model (usually to the nodes), and therefore deter-
mine the FEA output. In general, in a 2D model, each free node has
4 degrees of freedom (2 translations and 2 rotations), while in a 3D
model each free node has 6 degrees of freedom (3 translations and
3 rotations).
Constraints represent imposition of displacements on a finite ele-
ment model, which might be null to enable the software to reach a
numerical solution in the analysis. These restrictions of displace-
ments concern rotations and translations around X, Y, and, for the
3D models, Z-axes.
Loadings can be applied using different methods, such as point
loads, pressure, distributed loads across a specific area, as well as loads
simulated by the contact of the antagonist tooth. Regardless of the
loading method, high magnitude of stresses is always expected around
the loaded nodes. Still, these are not realistic stress concentrations,
thus in all finite element models, loading and constraints should
remain sufficiently far from the region of interest to ensure accuracy
of the results.
6. Interpretation of FEA Output

Interpretation of the results is a very critical stage of biomechanics
FEA simulation. It requires a thorough knowledge of the FEA meth-
odology, of the related mechanical concepts, and of the biological
phenomenon under study. Integrating all these forms of knowledge is
not an easy task. It usually requires time, practice, reflection, and
patience. Therefore, the learning curve in this step is usually more
prolonged than that of the previous steps. It takes longer for the
beginner to acquire autonomy to choose the sound failure criterion
and to describe the generated data.
An additional difficulty appears because the failure, while usually
evident in experimental tests, in FEA is mostly not directly discerna-
ble. For example, in an FEA simulation of a tooth restored with a post
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and a metal-ceramic crown, the stress distribution map obtained by

the FEA is not enough for determining the risk of root fracture. It is
necessary to compare the stress values generated in each structure
with the correspondent strength of its material.
6.1. The Failure Criteria

In a simplified approach, we can say that the fracture of brittle materi-
als is governed by the magnitude of tensile stresses. Therefore, the
maximum principal stress (s1) is frequently used as the failure criteria
for these materials, since it represents the maximum tensile stress.
In addition, one important measure that needs be taken care of when
analyzing these cases is checking the compressive stresses, especially
the maximum compressive stresses, given by the minimum principal
stress criteria (s3). The compressive stress promotes a protective effect
in the brittle material because it hinders the propagation of cracks that
grow in the perpendicular direction to the compression. With regard
to ductile materials, they usually fail before the fracture, because the
plastic deformation that appears beyond the yield strength tends to
jeopardize the object function. As the plastic deformation is mainly
governed by the shear stress, Tresca or Von Mises criterion is gener-
ally used to assess the risk of failure of ductile materials.
In biomechanical simulations, the choice of the failure criterion is
based not only on the nature of the material under study (brittle or
ductile), but also on the biological mechanisms involved in the failure
process. Furthermore, the chosen failure criteria result must be con-
sistent with clinical outcome of published randomized controlled tri-
als (RCT). Therefore, specified failure criteria have been created in
the FEA studies in Dentistry and Medicine, such as algorithms for
bone remodeling.39,40
6.2. The Biological Mechanism

The orthodontically induced inflammatory root resorption (OIIRR)
treatment is a very didactic example to demonstrate the importance
of integrating the theoretical concepts of failure criteria with the
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Figure 7. Compressive stresses that have been used to predict the obstruc-
tion of PDL vessels: minimum principal stress, hydrostatic stress, and radial
stress. The coordinate system in the radial stress image exhibits the orienta-
tion of radial (rr), tangential (tt), and hoop (qq) stresses
biological mechanisms involved in the phenomenon under study.

Although the resorption occurs in the root, it is not linked with the
stress supported by dentin or cement, as suggested in some studies.41–43
It is well described in the literature that the biological mechanisms
associated with OIIRR is the obstruction of PDL vessels in over-
compressed areas,44–49 Therefore, the failure criteria need to take into
account what happens in PDL that favors the blood stasis. The mini-
mal principal stress or the compressive values of hydrostatic or radial
stresses have been used to predict OIIRR by FEA50–53 (Figure 7). It
seems coherent that if these compressive stresses exceed the capillary
hydrostatic pressure (4.7 kPa), the risk of obstruction and resorption
is high.50–52
6.3. Importance of Results Presentation

FEA software usually present results as a map of the distribution of
the response of interest (pressure, strain, displacement, etc.), in which
each color represents a range of values. Although the programs
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automatically set the scale, it is interesting to the user to make some

manual adjustments to improve the viewing and interpretation of the
outcomes. For example, when displaying the map of the maximum
principal stress (s1), it is interesting to set the minimum value to zero,
to easily differentiate the regions with positive s1 values from those
with negative values. Likewise, for the minimum principal stress (s3)
the maximum value should be set in zero (Figure 8). While positive
values of s1 refer to the maximum tensile stress, negative values indi-
cate tension-free region. While negative values of s3 refer to the maxi-
mum compressive stress, positive values indicate compression-free
region. The simple adjustment on the scale already helps to visualize
these different areas. In addition, the distribution map of the figure
can be complemented with a figure of the orientation of s1 or s3.54
In many cases, the presentation in maps may not be enlightening
to the phenomenon under study. The researcher can then use other
reports provided by the software to build, in an intelligent but labori-
ous way, other modes of most enlightening presentation. For instance,
results on interfaces are better represented using graphs instead of the
Figure 8. Map distribution of maximum principal stress
b3252_Ch-03.indd 85 27-11-2018 02:58:49 PM

habitual map-distributed figure. The response is usually plotted as a

function of cumulative selected nodes distance.55 It is important to
define which side of the interface will be explored. For example, in a
cement–post interface, the user can chose to plot the stress in the
cement or the stress in the post. The two curves should also be plot-
ted, but the presentation of average stress (of cement and post) is not
recommended because it lacks a physical sense.
Another important issue is that the statistical analysis is usually
dispensable in FEA studies for comparing results among different
models. It is not well acknowledged among researchers habituated
with clinical or experimental study design, in which the variability is
inherent. Therefore, it is a common (but unsuitable) criticism from
some journals reviewers. The absence of statistic is explained due to
absence of experimental error. It is useless to run a certain FEA model
more than once, waiting for random variation in the response. The
response will be exactly the same in different runs (if the model is the
same regarding input data and mesh). The judgment as to whether
the differences are significant or not will be aided only by the good
sense of the researcher in recognizing that the discrepancy signifi-
cantly interferes in practice. For instance, a stress difference about
only 1% should be considered irrelevant for studies on specimen shape
subjected to resistance test if the real tests vary by more than 10%. In
some specific FEA study designs, the statistical analysis is used, but it
is the exception, not the rule.
7. Final Remarks
· FEA presents a wide range of application in dentistry. Some stress
studies can only be performed using this methodology, since
stresses are not visible experimentally.
· Simplifications are inherent to any model (even experimental mod-
els) and impose specific limitations that do not necessarily invali-
date the study. FEA is no different. The researcher’s challenge is to
distinguish the necessary simplifications from the misrepresentative
ones.
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· Meticulousness and thoroughness in organizing and displaying the

FEA results facilitate the interpretation of the authors and the
understanding of the reader.
Acknowledgments
We would like to thank CNPq for Alice Jikihara’s PhD scholarship
of Capes and also for Pavel Capetillo’s PhD scholarship, which
were essential for the writing of this chapter. We would also want
to thank FAPESP for the constant financial support in our FEA
studies.
References
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1913.
2. Liao, Z. et al. J. Biomech. 2015, 48 (16), 4214–4220.
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(Amsterdam: Elsevier, 2010), p. 401.
8. Gonzalez de Villaumbrosia, P.; Martinez-Rus, F.; Garcia-Orejas, A.;
Salido, M. P.; Pradies, G. J. Prosthet. Dent. 2016, 116, 543–550.e1.
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15. Benazzi, S. et al. PLoS One 2013, 8 (7), e69990.
16. Junior, M. M. et al. Int. J. Adhes. Adhes. 2012, 35, 114–119.
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17. Ludwig, B. et al. Am. J. Orthod. Dentofacial Orthop. 2013, 143 (3),
426–435.
18. Lee, N. K.; Baek, S. H. Am. J. Orthod. Dentofacial Orthop. 2012, 141
(3), 345–351.
19. Tominaga, J. Y. et al. Am. J. Orthod. Dentofacial Orthop. 2014, 146 (2),
166–174.
20. Yu, I. J. et al. Eur. J. Orthod. 2014, 36 (4), 394–402.
21. Dejak, B.; Mlotkowski, A. Dent. Mater. 2013, 29 (12), e309–e317.
22. Ichim, I. P. et al. Dent. Mater. 2007, 23 (12), 1562–1569.
23. Rodrigues, F. P. et al. Dent. Mater. 2012, 28 (2), 123–132.
24. Cuddihy, M. et al. Dent. Mater. 2013, 29 (6), 626–634.
25. Ausiello, P. et al. Dent. Mater. 2011, 27 (12), 1285–1294.
26. Mattos, C. M. et al. J. Dent. 2012, 40 (5), 423–432.
27. Anchieta, R. B. et al. Dent. Mater. 2015, 31 (2), 141–153.
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30. Ma, S; Scheider, I.; Bargmann, S. J. Mech. Behav. Biomed. Mater. 2016,
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32. Podshivalov, L.; Fischer, A.; Bar-Yoseph, P. Z. J. Mech. Behav. Biomed.
Mater. 2011, 4 (6), 888–899.
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41. Oyama, K. et al. Eur. J. Orthod. 2007, 29 (2), 113–117.
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71 (2), 127–131.
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Orthop. 2015, 147 (5), 610–626.
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45. Schwarz, A. M. Int. J. Orhodontia. 1932, 18, 331–352.

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129 (4), 504–510.
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218–227.
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492 e1–e9; discussion 492–493.
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51. Hohmann, A. et al. Comput. Methods Programs Biomed. 2009, 93 (2),
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52. Field, C. et al. Am. J. Orthod. Dentofacial Orthop. 2009, 135 (2),
174–181.
53. Viecilli, R. F. et al. Am. J. Orthod. Dentofacial Orthop. 2008, 133 (6), 791
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b2530_FM.indd 6 01-Sep-16 11:03:06 AM

Chapter 4
Preventive Dental Material
Larissa Bubnowicz and Rodrigo França*

Department of Restorative Dentistry University
of Manitoba, 780 Bannatyne Ave., Winnipeg, Canada
*Rodrigo.franca@umanitoba.ca
Fluoride is routinely used within the preventive clinical practice of

the oral healthcare profession, as it is the only therapeutic agent to
effectively control dental caries. It is therefore expected that dental
materials with the ability to release fluoride may control the recur-
rence of caries to the surrounding dental surfaces and reduce caries
incidence in the entire dentition. This chapter begins with an over-
view of dental caries as a multifactorial disease; its causes and deter-
minant factors, the limitations of the anti-caries effect of fluoride, and
how former theoretical concepts are no longer deemed acceptable
are subsequently discussed. The preventive effect of fluoride on den-
tition details the processes of undersaturation versus supersatura-
tion, the fluoride physicochemical reaction mechanism theories, and
the newly proposed structure model of enamel fluoridation. Overall,
this provides a comprehensive understanding of the mode of action
of topical fluorides and aids in the development of new caries treat-
ment strategies. As an oral healthcare practitioner, it can be chal-
lenging to decide which combinations of methods of fluoride
delivery should be recommended, and the treatment decisions for
91
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disease management vary among practicing professionals. In spite

of considerable evidence that supports modern management of car-
ies and a minimally invasive treatment approach, “traditional den-
tistry” is still widely practiced. In conclusion, for caries prevention
and therapeutic fluoride regimens, the movement of evidence-
based research to the practicing oral healthcare team is crucially
important.
1. Introduction
It is firmly established that fluoride is the only therapeutic agent
known for effective caries control1 and has been attributed to the
decline of the prevalence, and severity, of dental caries in most devel-
oped countries.2–5 The routine application of topical fluoride, a well-
known preventive clinical practice within the oral healthcare profession,
reduces demineralization of tooth enamel from acid production, a
main contributing factor to tooth decay and dental caries.6 It is
expected that dental materials with the ability to release fluoride may
control the recurrence of caries to the surrounding dental surfaces,
even contributing to the reduction of caries incidence in the entire
dentition.1
2. Preventive Effect of Fluoride on Dentition

Dental caries is a multifactorial disease, caused by a complex and
dynamic interplay among bacterial pathogenic activity, nutritional
diet, and the host itself.8 More simply stated, caries is a biofilm-
sugar-dependent disease, each of which is a negative determinant
factor in caries progression in any dental surface, be it intact, sealed,
or restored.1,6
The presence of fermentable sugar carbohydrates1,7 with that of
biofilm adhesion and accumulation on the tooth surface results in
the production of acid.8 Specifically, the presence of dietary sugars
aids in this, specially sucrose which is the most cariogenic. Besides
being easily fermented into acids, sucrose is the only carbohydrate
that changes the biofilm matrix, enabling the bacteria to synthesize
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Preventive Dental Material 93
extracellular polysaccharides that enhances the overall cariogenicity

of the biofilm.1,8–11
At the molecular level, this induces mineral loss from the underly-
ing tooth structure and eventually the dissolution of the enamels’
mineral hydroxyapatite (HAp, Ca10(PO4)6(OH)2).12
Saliva and fluoride are two other determinant factors in the devel-
opment of the disease. Both function to have substantial, positive
effects on the reduction of enamel mineral loss.
Saliva acts to clear the fermentable substrates and/or buffer the
acids produced, and fluoride acts to enhance mineral precipitation
back on the teeth. Fluoride frequently available to the aqueous oral
environment (fluid phase of biofilm or saliva) as a free soluble is ideal;
it interferes with the caries process by effectively reducing deminerali-
zation and enhancing remineralization of tooth enamel and dentin.
The limitations of the anti-caries effect of fluoride need to be
acknowledged. It is important to clarify that neither are able to pre-
vent the development of carious lesions, as they do not impede the
formation of biofilm on any dental surface, inhibit acid production
from sugars, or affect bacterial metabolism.8,13
Therefore, concepts that were once deemed to be theoretically
reasonable, such as “fluoride strengthens teeth”, “increases the resist-
ance of teeth to acids”, and “reduces the acid produced by bacteria”,
are no longer deemed acceptable theories with regard to caries reduc-
tion associated with fluoride use.8,13,14 The effect of fluoride in the oral
cavity is its presence in a soluble, ionic form to reduce mineral loss,
through the precipitation of fluorapatite on the tooth structure.8,15,16
2.1. Undersaturation versus Supersaturation

In its stable state, at a neutral pH of 7, dental enamel hard tissue has
sufficient calcium (Ca2+), phosphate ((PO4)3-), hydroxyl (OH-), and
fluoride (F-) ions in the immediate vicinity of its crystal lattice to
maintain equilibrium with the surrounding oral fluid. When not in
equilibrium, one of two results: undersaturation, where hydroxyapa-
tite dissolves, or supersaturation, where minerals from the oral envi-
ronment are deposited in the enamel, occurs (Figure 1).
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Figure 1. Ions of a cariogenic acid attack. Adapted from Ref. [17]
During a cariogenic acid attack, pathogenic bacteria Streptococcus

mutans existing in the plaque biofilm form organic acids from any
available carbohydrates.1,8 This production of acid lowers the pH
value of the oral environment, and thus the process of undersatura-
tion begins.
As the acids dissociate, proton ions (H+) are released, increasing
the H+ concentration in the plaque surrounding the tooth. As a result,
the concentration of hydroxyl ions decreases, protonating phosphate
ions. In order to maintain equilibrium between the oral environmen-
tal fluid and the vicinity of the tooth surface, both phosphate and
hydroxyl ions dissolve out of the tooth. This process eventually leads
to the dissolution of calcium from hard tooth structure, causing tooth
demineralization (Figure 2(a)).
When the ingestion of sugar ceases and as the pH increases, the
process of supersaturation commences, initiated with the precipita-
tion of minerals back into the tooth structure. Remineralization
(Figure 2(b)) begins specifically when calcium and phosphate ions
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Figure 2. The processes of enamel demineralization and remineralization.

(a) During a cariogenic attack, acid production lowers the pH value of the
oral environment, initiating undersaturation. This process leads to the dis-
solution and demineralization of tooth mineral (hydroxyapatite) from an
intact surface, or adjacent to a dental restoration. (b) As saliva clears out
sugar and buffers the produced acid, the pH increases and the process of
supersaturation commences. Remineralization occurs in the surfaces previ-
ously demineralized. Adapted from Ref. [1]
b3252_Ch-04.indd 95 27-11-2018 02:59:29 PM

are redeposited into the crystal voids of demineralized enamel,

re-forming the hydroxyapatite crystalline enamel structure.
The natural phenomenon of remineralization is enhanced if fluo-
ride is present in the oral environment, as the mineral ion accelerates
and promotes the overall process, even at very low concentrations
(Figure 3).8 As long as fluoride is present in the oral cavity at this
time, fluorapatite will form first and more rapidly, over that of
hydroxyapatite.1
In contrast, fluorapatite has a lower solubility product, which
means it remains stable even at low pH values and is more acid-
resistant than the original hydroxyapatite (demineralization starts as
pH~5.5 for HAp and ~4.6 for FAp).19 Therefore, fewer minerals are
lost, and at a slower rate, to dissolution during cariogenic acid attacks,
ultimately slowing the progression of caries development1 and clinical
observation.3
But even in its presence, if there is significant mineral loss, fluoride
is unable to replenish the porous area inside the enamel and the clini-
cal signs become visible in the form of a white spot lesion. However,
fluoride will help to impair this process by arresting the caries lesion
progression. Remineralization in the presence of fluoride results in the
white spot eventually having a shiny surface, but its white aspect, from
the porous areas underneath, will always partially remain.8,14
These processes, as described above, occur every single time sugar
is ingested, resulting in an acidogenic challenge. Their complexity
depends on a multitude of dynamic and influential factors, all of
which play an important role in caries activity and vary from individ-
ual to individual based on enamel composition, pathogenic bacteria
present in the plaque biofilm surrounding the tooth, saliva mineral
content, frequency of sugar consumption, daily oral hygiene habits,
and access to routine oral healthcare.
2.2. Fluoride Physicochemical Reaction

Mechanism Theories
Even though fluoride has been known as a caries preventive agent
for decades,20 controversy nevertheless remains on the exact
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Figure 3. The mode of action of fluoride on the enamel tooth structure.
(a) The mechanism of fluoride on the inhibition of enamel demineralization.
If fluoride is delivered to the biofilm or saliva from a fluoride reservoir, the
event described in Figure 2(a) is lessened; fewer minerals are lost as a slower
rate to dissolution. Fluoride reservoirs, as depicted, are fluoridated dentifrice
(left) or fluoride-releasing restorative dental materials (right). (b) The effect
of fluoride on the process of enamel remineralization, described in Figure
2(b), is enhanced by fluoride sources made available to the plaque biofilm
and saliva, precipitating the formation of the more stable and acid-resistant
fluorapatite mineral. Adapted from Ref. [1]
b3252_Ch-04.indd 97 27-11-2018 02:59:29 PM

physicochemical reaction mechanism and products after teeth fluor-

idation. Pure, direct substitution to form fluorapatite (FAp), or
incomplete substituted products creating calcium fluoride (CaF2),
are discussed as two of the major fluoride reactivity theories.
One of the two major fluoride reactivity theories describes how ele-
mental fluoride reacts with hydroxyapatite crystals, (Ca5(PO4)3OH),
of dental enamel to become isostructural fluorapatite, (Ca5(PO4)3F),
thus creating firmly bound fluoride within the enamel crystal rod
structure. It is the lower solubility of fluorapatite, (FAp), which more
strongly resists demineralization, and therefore carious lesion forma-
tion, in an acidic oral environment.21
The second theory suggests that free fluoride ions chemically
react with calcium, released from hydroxyapatite dissolution, to create
calcium fluoride, (CaF2), an alternative loosely bound form of fluo-
ride on the enamel crystallite surface.
Forms of fluoride reactivity can be described in the following
equations22:
Iso-ionic exchange of F− for OH− in apatite:
Ca10(PO4)6OH2 + 2 F- à Ca10(PO4)6F2 + 2 OH-(1)
Apatite dissolution with CaF2 formation:
Ca10(PO4)6OH2 + 20 F− à 10 CaF2 + 6 PO43− + 2 OH−(2)
Equations (1) and (2) describe the current theorized forms of

fluoride reactivity mechanisms Eq. (1) demonstrates the pure substi-
tution of the hydroxyl groups, OH−, with that of free solution fluo-
ride ions to form FAp. Equation (2) shows how the free solution
fluoride ions chemically react with released calcium from demineral-
ized hydroxyapatite to create CaF2.
Currently, it remains rather inconclusive which reaction mecha-
nism theory is responsible for the caries-preventive effect of fluoride.6
Regardless, in healthy human enamel, it is apparent that fluorapatite
is indeed present in addition to hydroxyapatite, ultimately resulting in
increased stabilization of the overall apatite structure.23
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2.3. Molecular-Based Structural Model

of Enamel After Fluoridation
After fluoridation by an acidic agent, the surface of enamel can be
described by a three-layer model, containing calcium fluoride (CaF2),
calcium hydroxide (Ca(OH)2), fluorapatite (FAp, Ca5(PO4)3F), and
hydroxyapatite (HAp, Ca5(PO4)3OH).18,24 This newly proposed struc-
ture model of fluoridated enamel helps with the comprehension of
the influence of topical fluoride application in the pathogenic mecha-
nism of dental caries and tooth decay.
Topical fluoridation of enamel results in changes in the surface
structure of HAp by the formation of other compounds. Many stud-
ies18,24 have shown that FAp is found in highest concentration within
a thin layer next to the original bulk enamel, which agrees with previ-
ously published results.21 It is well known that its acid-resistant prop-
erties protect the enamels’ HAp from dissolution and demineralization,
as previously discussed.
Previously published research18,25,26 has consistently found that an
atomic layer of CaF2 exists on the enamel surface. It is theorized that
when fluoride is present in greater quantities than is necessary for the
crystallization of FAp, precipitation of CaF2 occurs.27 That this super-
ficial layer is both acid soluble and accumulates on the surface enamel
suggests that it acts as a fluoride reservoir, releasing fluoride ions for
further FAp formation or enzyme induction.
Ca2+ + 2F− à CaF2. (3)
Equation (3) describes large, residual quantities of free soluble

fluoride ions (F−) precipitate CaF2. As adapted from Gerth et al.,
2007.18
Between the layer of FAp and CaF2, a layer of antimicrobial
effective calcium hydroxide, Ca(OH)2, has been identified and is
thought to be the product of the reaction of immediately formed
CaF2 and unreacted HAp.18 The efficiency of calcium hydroxide is
based on its antimicrobial effect and potential for inducing minerali-
zation.28,29 Because of its basic pH value, it acts as a neutralizing
b3252_Ch-04.indd 99 27-11-2018 02:59:29 PM

agent and stops the dissolution of teeth by the acidic milieu of bac-
teria causing caries.30
Even though calcium hydroxide has various practices in dentistry,
such as its use as medication during root canal treatment, until
recently, it has not been described as a product of enamel fluoridation.
Based on the current findings of recent evidence and research studies,
there is strong support to identify this compound as part of the sug-
gested structure model (Figure 4).18
Therefore, this discovery and more detailed understanding may
provide deeper insight into the mode of action of topical fluorides and
for the development of new caries treatment strategies.
2 HAp + CaF2 à 2 FAp + Ca(OH)2. (4)
Equation (4) describes Calcium hydroxide (Ca(OH)2) as the

product of the reaction mechanism between immediately formed
calcium fluoride (CaF2) and unreacted hydroxyapatite (HAp). As
adapted from Gerth et al., 2007.18
Figure 4. Three-layer molecular-based structural model of fluoridated

enamel and its relationship to the pathogenic mechanisms of caries.
Adapted from Ref. [18]
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3. Methods of Fluoridation
Fluoride is known to elicit an anti-cariogenic effect when available
continuously at very low concentrations in the oral cavity, by the same
mode of action irrespective of the means of fluoride delivery. The
methods of fluoride delivery that will be discussed here are meant to
continuously supply the oral cavity and environment with this ion,
thus reducing the development and progression of caries lesions.8
3.1. Community-Based Methods of Fluoride Use

3.1.1. Water Fluoridation
Almost all water contains some low levels of naturally occurring fluo-
ride. Many communities adjust the fluoride level of the water supply
to an optimal concentration known to reduce tooth decay and pro-
mote good oral health. This practice is known as community water
fluoridation. Because of the drastic decline in tooth decay since its
initiation, the Centers for Disease Control and Prevention (CDC)
named “fluoridation of drinking water to prevent dental caries as one
of 10 great public health interventions of the 20th century”.3 Years of
research attest to its effectiveness and safety,31 and support commu-
nity water fluoridation as the most successful and cost-effective mode
of delivering fluoride on a population basis to all people.
In the 1930s, scientists studied the epidemiology of fluorine and
dental caries, and found that children who drank water with naturally
high levels of fluoride had less tooth decay.32 After much research, in
1945, the city of Grand Rapids, Michigan, was the first to add fluo-
ride to its city water system in order to provide residents with its
benefits.
When fluoride is systemically ingested, it returns to the oral cavity
through salivary secretions. For this mechanism of action to be effec-
tive, fluoridated water must be ingested continuously. There is a
measurable effect of having the dentition continuously bathed by
fluoride-enriched saliva; a previous study33 has demonstrated that
even a micromolar increase, from 0.01 to 0.02 ppm, in fluoride
b3252_Ch-04.indd 101 27-11-2018 02:59:30 PM

concentration in saliva has a tremendous and significant effect to

caries control.
When fluoridated water is used for food preparation and/or for
cooking meals, fluoride is made available to the oral environment
upon consumption. The benefits of cooking with fluoridated water
are discussed in a recent paper34; while foods cooked with fluoridated
water are being chewed, an increase in fluoride concentration in saliva
is observed prior to swallowing. This supports the concept that a
prolonged fluoride effect is accomplished by low concentrations
returning to the oral cavity via saliva.
In 2001, the CDC3 published recommendations on the use of fluo-
ride to prevent and control dental caries.35 Based on the evidence that
frequent exposure to low concentrations of fluoride daily will effec-
tively reduce dental caries risk in all age groups, the CDC recommends
all dentate individuals drink water with an optimal level of fluoride.
3.1.2. Professionally Applied Methods of Topical Fluoride Use

It was the acknowledgment of the role of fluoridated water in caries
reduction that initiated the development of other modes of fluoride
delivery, specifically professional topical fluoride application of high-
concentration gels (from 9,000 to 12,300 ppm F) and varnishes
(22,500 ppm F).17
The main mechanism is a reaction between the soluble fluoride,
of the manufactured topical product, and the enamel tooth mineral,
precipitating calcium fluoride-like deposits (CaF2). These deposits act
as a fluoride reservoir, slowly dissolving and releasing fluoride into the
oral environment.36 These fluoridated products must be reapplied to
maintain their caries-preventive effect.17
There is a clear evidence37–39 of the anti-caries effect of profes-
sional applications of topical fluoride.40 The evidence supports that
individuals with moderate and high risk of dental caries may benefit
most from professionally applied fluoride adjuncts41; however, they
are also used in those with additional needs.17 The level of evidence-
based documentation differs by method of topical fluoride use and
among age groups.17
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Table 1. The American Dental Association’s Council on scientific affairs

published recommendations on the use of professionally applied topical
fluorides for individuals of moderate and high caries risk for all age
groups
Moderate risk High risk
Under age 6 Fluoride varnish at Fluoride varnish; 2–4 times per year
6-month intervals (6- or 3 month intervals)
6–18 years of Fluoride varnish or gel at Fluoride varnish or gel; 2–4 times
age 6 month intervals per year (6 or 3 month intervals)
Over 18 years Fluoride varnish or gel at Fluoride varnish or gel; 2–4 times
of age 6 month intervals per year (6 or 3 month intervals)
Note: Low-risk patients may not benefit from professional topical fluoride applications.
Source: Adapted from Refs. [17, 42].
Based on clinical trials and evidence-based studies, the American

Dental Association’s Council of Scientific Affairs recently published
recommendations on the use of fluoride gel and varnish for profes-
sional topical fluoride treatments, with the choice dependent on age
and risk category (Table 1).42 Evidence-based clinical practice requires
that the oral healthcare practitioner assess caries risk level prior to
recommendation and implementation of treatment.17,42
3.1.3. Topical Fluoride Gels

Traditionally, the administration of high-concentration topical fluo-
ride gel in trays was the standard of professionally applied fluoride
treatments. Common fluoride gel products include acidulated phos-
phate fluoride (APF) and sodium fluoride (NaF).41 It is still the
method most frequently used clinically by oral healthcare practition-
ers as specific caries-preventive agents in adult clients.2
Miller and Vann43 expanded on the above recommendations of
the ADA Council of Scientific Affairs (Table 1), addressing topical
fluoride use in children under the age of 6, with special healthcare
needs, and attention span or cooperation concerns.17
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3.1.4. Topical Fluoride Foam and Rinses

Topical fluoride foam was introduced into dental practices in the
1990s and since has been commonly used. However, topical foam is
not clinically recommended,17 as evidence shows that its clinical effi-
cacy is not as strong as that for fluoride gel and varnish.17,41 There is
no evidence to support rinses.17
3.1.5. Topical Fluoride Varnish

Topical fluoride varnish is a resin-based, 5% sodium fluoride treat-
ment material for the prevention of enamel and root surface caries.
This dental material facilitates prolonged adherence to the tooth
surface structures, is able to deposit large amounts of fluoride on
enamel, and acts as a sustained fluoride source.17,44–47
Additional attractions are that administration takes less time, cre-
ates less discomfort, and is widely accepted amongst patients. Sodium
fluoride varnish was first introduced as a desensitizing agent, for den-
tinal hypersensitivity associated with exposed root surfaces and as a
cavity liner.17
Prior to fluoride varnish, there was no safe way to administer topi-
cal fluoride to children under the age of 3. Their limited ability to
control swallowing and spit effectively eliminates gels, foams, and
rinses as viable treatment options.
For children 6 years or younger, there is strong evidence from
systematic reviews of randomized controlled trials48,49 to support fluo-
ride varnish applications at 6-month intervals, for moderate- and
high-risk patients, and every 3 months in high-risk patients.50,17
For children between the ages of 6 and 18 years, with moderate
and high risk of caries, systematic reviews support fluoride varnish
application every 6 months, and every 3 months in high-risk chil-
dren. Marinho et al.50 conducted an evidence-based review of rand-
omized, and quasi-randomized, controlled trials with blind outcome
assessment in children up to 16 years for the duration of at least
1 year.35 This review indicates a substantial caries-inhibiting effect of
fluoride varnish in both deciduous and permanent dentition.
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This age range is when orthodontic treatment typically com-

mences, and the appliances involved increase the risk for enamel dem-
ineralization. Investigations51–53 have demonstrated that fluoride
varnish has the capability to reduce or minimize enamel demineraliza-
tion adjacent to orthodontic brackets.17
The main uses of fluoride varnish in adults are for remineraliza-
tion and control of root caries, caries prevention for those at high risk,
and treatment of dentinal sensitivity. For individuals over 18 years of
age, there is some evidence to support administration at 6-month
intervals for those at moderate and high risk, and every 3 months for
patients at high risk.50 However, this level of evidence is low as it is
centered on expert committee reports and opinions, rather than pro-
spective, randomized clinical trials.17
Petersson et al.54 conducted a systematic search of the literature
published between 1966 and August 2003 to evaluate the caries-
preventive effect of professional fluoride varnish treatments.35 Of the
24 reports included from randomized and controlled clinical trials,
the results suggest limited evidence for permanent dentition.
3.2. Individual Methods of Fluoride Use

3.2.1. Fluoridated Dentifrices
Among individual methods of fluoride delivery, the use of fluoridated
dentifrices is by far the most important and shall be the basis of our
discussion.
Daily use of fluoride dentifrices forms the foundation of caries
prophylaxis in all age groups,55 as it combines the caries-protective
processes of fluoride with the mechanical removal of plaque biofilm.
Its practice is strongly supported by unequivocal evidence-based
research37,56 and has been a main contributing factor in the caries
decline observed in both developed57 and developing countries.58,59
Fluoride dentifrices can control caries incidence in originally
intact dental surfaces, interfere with caries lesion progression adjacent
to dental restorations, and can be spread throughout the mouth
enriching the oral environment, saliva,60,61 and even biofilm not
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perfectly removed.55,62,63 The effectiveness and efficacy of this mode of

fluoride delivery is based largely on client compliance; the effect
increases with frequent toothbrushing.23,55
Many high-quality, randomized, and controlled studies con-
ducted in the previous decade have proven conventional fluoride
toothpastes, those containing 1,000–1,500 ppm F, as highly effective
for caries control.55
Marinho et al.64 conducted a search of the Cochrane Oral Health
Group’s Trial Register and supplementary databases on randomized,
or quasi-randomized, controlled trials with blind outcomes assess-
ment for analysis of comparative caries-prevention data for fluoridated
dentifrice.35 The search firmly established the benefits of fluoride
toothpaste.
Twetman et al.65 systematically reviewed and evaluated the scien-
tific literature between 1966 and 2003 on the caries-preventive
effect of fluoride toothpastes in various age groups.35 The results
suggest that toothpastes containing 1,500 ppm F have a superior
caries-preventive effect, than those of 1,000 ppm F, and that there is
a strong evidence for the daily use of fluoride toothpaste to prevent
carious lesions.
Based on the evidence that frequent exposure to low concentra-
tions of fluoride daily will effectively reduce dental caries risk in all age
groups, in 2001, the CDC3 recommended that all dentate individuals
should brush their teeth twice a day with fluoride toothpaste.35
Toothpastes of increased fluoride concentration of 5,000 ppm F
have been recently introduced with the purpose of controlling root
caries. There is some evidence66 on the effectiveness of these tooth-
pastes, when compared to the conventional, but a literature review is
still non-existent.
Recently in the last few years, a quantity of clinical studies67 and
systematic reviews68,69 of the literature have been published on low
fluoride concentration dentifrices, 250–500 ppm F.
In summary, low-concentration fluoridated toothpastes are not
able to control caries under a high cariogenic challenge,67 are not as
effective as the conventional fluoridated pastes,68 and are effective to
control caries only in caries-inactive, but not caries-active, children.70
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The following studies and reviews also validated the effectiveness

of fluoride in conventional strength dentifrice formulations,69 its abil-
ity to manage caries in caries inactive children,70 and control the
appearance of new lesions.70
3.3. Fluoride-Releasing Dental Materials

Increasing evidence suggest that decay around dental restorations is
due to the occurrence of a new carious lesion adjacent to pre-existing
one.71 It is expected that dental materials with the ability to release
fluoride may control this recurrence of caries to surrounding dental
surfaces, even contributing to the reduction of caries incidence in the
entire dentition.1
Fluoride-releasing dental materials may be considered the ideal as
they supply the oral cavity with a constant source of slow-release fluo-
ride and the effects are not dependent on client compliance.1 At this
time, these materials still lack clinical basis to confirm an anti-caries
effect.1
3.3.1. Pit and Fissure Dental Sealants

In the late 1960s, sealing anatomical pit and fissures of occlusal sur-
faces with a thin layer of resin dental material was introduced as a
caries-preventive method,2,72 and this has now evolved to incorporate
fluoride into the newest materials.73 Guidelines recently developed
by the American Dental Association Council on Scientific Affairs74
recommend dental sealants for all age groups.2
When compared to no sealants, the evidence suggests sealing the
occlusal surfaces of permanent molars with resin-based sealants to
prevent caries,1 even over existing bacteria.2,75 The conclusion of a
Cochrane Review, by Ahovuo-Saloranta et al.76 of sealants in the
permanent dentition of 5–10-year-old children, supports this
recommendation.35
The potential of glass ionomer cements (GIC) to release fluoride
is a strong incentive for their use as pit and fissure sealing materials,
especially in deciduous and partially erupted posterior permanent
b3252_Ch-04.indd 107 27-11-2018 02:59:30 PM

dentition.77 However, the evidence presently available remains incon-

clusive as to the effectiveness of materials, other than resin-based
ones.78,79
Mejare et al.66,73 performed a systematic review and concluded
there is limited evidence to substantiate that fissure sealing with resin-
based materials has a caries-preventive effect and that evidence is
incomplete for glass ionomers used as pit and fissure dental sealants.
Current findings suggest, among oral healthcare practitioners,
that dental sealants are an infrequent caries-prevention choice for
adults, and therefore potential candidates may not be receiving treat-
ment.2 Studies80,81 found that sealants are placed more frequently by
dentists with knowledge of the benefits and cost-effectiveness, those
who recently attended continuing education about prevention for
children, by recent graduates, and independent of the insurance
variable.2
3.3.2. Glass Ionomer Cements (GIC)

As non-metallic restorative dental materials, with ease of use, good
retention, reduced post-operative sensitivity, and anti-cariogenic
properties, GIC are an excellent therapeutic alternative.
Along with the ability to release fluoride, these cements can be
recharged with the ion from an alternative source, such as fluoridated
dentifrices. In fact, Benelli et al.82 established that plaque biofilms
which adhesively form on glass ionomer restorations become enriched
with GIC-released fluoride, leading to confirmed inhibition of dem-
ineralization around these restorations.
This anti-cariogenic ability is just one motivation for their current
use for restorations, common use as an orthodontic bracket adhesive,
and potential future use as pit and fissure sealing materials.
At this time, systematic literature reviews fail to confirm the
greater benefit of glass ionomers to reduce caries around restora-
tions,83 when compared to composite resin, and the available scien-
tific evidence is unconfirmed as to whether glass ionomer or
resin-modified glass ionomer are equally effective to those of resin-
based dental sealants.1
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These indeterminate outcomes were also observed8,63,84 when res-

torations of glass ionomer and composite resin were tested against the
use of fluoridated and non-fluoridated dentifrice. The concomitant
use of fluoride toothpaste may explain why studies fail to demonstrate
clinical effectiveness,8,83 as the caries-preventive effect can be substi-
tuted by fluoride delivered from dentifrice.
3.3.3. Orthodontic Bonding Agents

During the stages of orthodontic treatment, the presence of ortho-
dontic appliances increases retentive sites in the dentition and may
cause pain and discomfort.85 As a result, there is often increased
biofilm accumulation and risk of carious lesion development, as it
more difficult for individuals to properly perform daily oral hygiene
routines.
Initial enamel lesions have the potential to develop as early as
6 months after the bonding of orthodontic appliances.86,87 Enhancing
fluoride bioavailability during the course of the duration of ortho-
dontic treatment compensates for this increased caries risk and is
achieved by using fluoride-releasing orthodontic bonding, adhesives
and/or cements. These materials act as fluoride reservoirs reducing
the incidence of white spot lesions.1
Because of the absence of studies meeting inclusion criteria, a
Cochrane systematic review85 could not reach a conclusion of whether
the usage of these bonding materials, during orthodontic treatment,
decreases the occurrence and severity of white spot lesions. Additional
systematic reviews85,88–91 were unable to deduce evidence-based rec-
ommendations for their effectiveness to adhere orthodontic appli-
ances on these developing lesions.
3.3.4. Restorative Dental Material

Fluoride-releasing restorative dental materials are highly favored by
the clinician as multipurposed; besides restoring the dentition,
they help to prevent the development of new decay and carious
lesions.1
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Very few clinical trials and systematic reviews have been conducted
that consider anti-caries effect as the outcome measure. Therefore,
it remains unknown whether fluoride-releasing restoratives signifi-
cantly reduce caries risk in comparison to non-fluoride-releasing
restoratives.
Based on in vitro and in situ experimental studies, fluoride-releasing
dental materials present the necessary properties to be clinically effec-
tive on caries control; however, this effectiveness is not still proven.1
In summary (Table 2),1 there is a clear need for further investigation
of well-designed, randomized controlled clinical trials to investigate
the anti-caries benefit of fluoride-releasing dental materials.
3.4. Combination of Methods of Fluoridation

As an oral healthcare practitioner, it can be challenging to decide
which combinations of methods of fluoride delivery should be recom-
mended. Most doubt stems from the clinician’s difficulty in compre-
hending the mechanism of action of each method of fluoride and how
fluoride is supplied to the oral cavity, as previously discussed in the
preceding sections.
Universal consideration is that both drinking water with an
optimal fluoride concentration and fluoridated dentifrice be recom-
mended for all individuals.8 Data and evidence-based studies91,92
support their effectiveness to control caries and that the current
low caries prevalence is as a result of their continuous use by many
populations.8
Additional fluoride sources and measures might require recom-
mendation for individuals at moderate and high risk for dental caries
(Table 3).8,46,92,93 These may include professional topical fluoride
application and the use of fluoride-releasing dental materials. The
study of Splieth et al.94 found that, over the past two decades, fluo-
ride application routinely administered in a dental office plus the
use of fluoride toothpaste achieved significant caries reductions
(Figure 5).35 The investigators suggest that in high caries risk groups,
topical fluoride applications six or more times per year in combination
with effective plaque removal can successfully prevent caries. And
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b3252_Ch-04.indd 111
“9x6”
Table 2. Summary of the conclusions of presently available evidence-based research on fluoride-releasing dental
materials
Type of dental
material Systematic reviews RCT Conclusions
Pit and fissure Ref. [73] Fissure sealing with resin-based materials has a caries preventive effect. It
sealants Ref. [79] is still not known whether F-releasing resin-based sealants provide any
additional benefit. There is still uncertainty concerning the

Ref. [78]
effectiveness of fissure sealing with other materials
Ref. [73]
Bonding Ref. [90] None The evidence on the effectiveness of using F-releasing material to bond
orthodontic Ref. [88] or cement orthodontic appliances on white lesion spots development is
materials Ref. [91] still inconclusive

Ref. [89]
Ref. [85]
Restorative Ref. [90] It is still not known whether F-releasing restoratives reduce caries risk in
materials comparison to non F-releasing restoratives, There is weak evidence that
GIC confers greater caries protection than amalgam in single-surface
restoration in permanent teeth
27-11-2018 02:59:30 PM
Table 3. Recommendations on methods of fluoride delivery at a

community-based, individual, and professionally applied level of approach
Method of Community- Professionally
delivery based Individual applied Recommendations
Fluoridated X Recommended to
water all individuals; no
restrictions
Fluoridated X Daily use
dentifrice recommended to
(1,000–1,500 all individuals;
ppm F) young children
should use a
small amount
Topical fluoride X According to caries
application risk or activity, at
(gel, varnish) the community
or individual
levels
Combinations According to caries risk or activity, at the community or
of methods individual levels
Source: Adapted from Refs. [8, 91–92].
80
70
Prevented Facon (%)
60
50
40
30
20
10
0
Gel Toothpaste Varnish All Varnish Varnish Pit and
Primary Applicaons Permanent Fissure
Teeth Teeth Sealant
Figure 5. Prevented fraction (%) of decayed, missing, and filled tooth surfaces
(ΔDMFS) for various fluoride prevention methods. Adapted from Ref. [35]
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Table 4. Different levels of approach for fluoride use and mode for its
delivery in the oral environment
Approach for fluoride use Mode (examples)
Community level Water fluoridation
Individual level Fluoridated dentifrice
Professionally applied Fluoride-releasing dental materials, topical fluoride
application (gel, varnish)
Combinations Fluoridated dentifrice + fluoride-releasing dental
materials
Marinho et al.95 concluded that topical fluorides used in addition to

fluoridated toothpaste achieved a modest caries reduction compared
to toothpaste alone.35
However, there also is evidence55 that regular use, 3 times per
day, of fluoridated toothpaste is able to achieve a level of enamel
demineralization inhibition that cannot be improved with the asso-
ciation of a professional fluoride application; no significant improve-
ment of the combined effect is observed.8 This is confirmed by a
literature review by Marinho et al.96 on the combination of methods
of fluoride versus fluoride toothpaste alone.8 The same was
observed63 when restorations of glass ionomer and composite resin
were tested.
Ultimately when considering the evidence, though contradictory,
when fluoridated dentifrice is used on a regular basis and caries activ-
ity is under control, no additional method of fluoride use is recom-
mended. For persons at moderate to high risk of caries, professional
topical fluoride application and fluoride-releasing dental materials
may be considered complementary methods of fluoride delivery.8
4. Clinical Applications and Recommendations

of Preventive Fluoride
Although it has been known for many years that dental caries is an
infectious disease, the management of the disease and treatment
b3252_Ch-04.indd 113 27-11-2018 02:59:31 PM

decisions for caries management vary considerably among practicing

oral healthcare professionals.35,97–105 Current surveys indicate that
“traditional drill, fill and bill dentistry” is still widely practiced in spite
of considerable evidence that supports modern management of caries
and a minimally invasive treatment approach.35
Certain clinicians lack confidence in their ability to detect early
lesions,35 to arrest the disease, and to remineralize enamel106; there-
fore, restorations are often placed early and unwarrantedly. Others
practice minimally invasive dentistry, monitoring early lesions and
providing preventive therapeutic treatment aimed to arrest caries and
remineralize enamel.35,99,107–115 Thus, there is extensive variability in
caries risk assessment, caries lesion detection, decisions on when and
how to treat carious lesions, the best treatment options for high-risk
patients, and the best method for monitoring disease.
There is some evidence2 to support this variability and the notion
that dentists use prevention based on caries treatment philosophy
learned in dental training,35 uncertainty of overall caries activity,35 pay-
ment method and insurance coverage,35 patient understanding of car-
ies as a disease,35 patient recall interval,35 economic status,116 and/or
community expectations for standards of care.35
A profound demonstration of this is that Riley et al.2 confirms
patients with dental insurance were significantly associated with
greater use of in-office preventive modalities (Figure 6).
Minimally invasive dentistry is based on the principles of modern
caries management. Its focus is to that of traditional prevention,
prophylaxis and fluoride, and minimal intervention of caries risk and
prevention assessment, carious lesion monitoring and delayed inter-
vention.35 More specifically, these include accurate lesion detection,
classification of lesion severity, assessment of caries risk, matching of
treatment to the risk level, monitoring of non-cavitated carious tooth
surfaces, remineralization therapies, and appropriate recall intervals
according to treatment outcomes and current risk levels.
From a survey of Yorty and Brown,117 and among Dental Practice-
Based Research Networks (DPBRN) practices,2,118–119 it is clear that
concepts of minimal intervention dentistry are becoming more widely
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Figure 6. Frequency of use of preventive fluoride methods by dentists

among Dental Practice-Based Research Networks. OTC, over-the-counter;
Rx, prescription. Adapted from Ref. [2]
accepted, as emphasized by an obvious shift in dental schools toward

modern management of the disease, assessment of caries risk, and
delayed cavitation restoration.35
Evidence2,120 show that dentists who report more conservative
decisions in clinical treatment scenarios were more likely to use caries
preventive agents, and oral healthcare practitioners who most fre-
quently use caries prevention were also those who regularly perform
caries risk assessment and individualized caries prevention. These
findings are validated by the case scenarios of Riley et al.2; dentists
who delay restoration until a more-advanced lesion depth use pre-
vention with a higher frequency in their practices, and frequency of
fluoride and sealant use are highly associated with the conservative–
aggressive caries management continuum.
It is encouraged that oral healthcare professionals clinically prac-
tice caries risk assessment strategies on a routine basis. It is only after
the identification of caries risk status that appropriate preventive
regimens and treatment may be determined, recommended, and
implemented. Risk of developing dental caries exists on a continuum
and changes over time as the risk factors change. Therefore, it is
b3252_Ch-04.indd 115 27-11-2018 02:59:32 PM

imperative that for modern management of caries to be successful,

lesion severity be monitored during any active treatment method105,121
and caries risk status be re-evaluated on a continual, recurrent basis
(Figure 7).35,50
Conscientious use of conventional prevention methods is suffi-
cient for most low-risk patients; if additional fluoride treatment is
indicated, a low-dose/high-frequency application is recommended.
For moderate- and high caries risk individuals, fluoride prevention
therapy alone is not the solution. For each client, the health inter-
vention of caries control measures should be determined by a com-
bination of considerations and risk factors: practical, based on
individual client-centered needs and patient preference; scientific,
that which demonstrates the greatest effect in preventing caries
based on evidence-based research, daily oral hygiene habits, nutri-
tion and diet, high levels of S. mutans in saliva (>106 CFU/mL
saliva), access to routine oral healthcare and fluoride exposure, exist-
ence of exposed root surfaces, and multisurface restorations; and
other socio-economic factors.8,17
It is suggested that some oral healthcare practitioners currently
lack what is considered to be the best evidence-based clinical practice.
Cooperation and communicating recent research findings between
Practice-Based Research Networks, organized oral healthcare, and
educational institutes is important in advancing scientific evidence
Figure 7. Minimally invasive dentistry treatment approach and modern

caries management plan of dental caries as an infectious disease. Adapted
from Ref. [35]
b3252_Ch-04.indd 116 27-11-2018 02:59:32 PM

into the daily clinical practice of all oral healthcare providers. For car-
ies prevention and therapeutic fluoride regimens in particular, this
movement of evidence-based research to the practicing oral health-
care team is crucially important.
References
1. Cury, J. A.; de Oliveira, B. H. ; dos Santos, A. P. P.; Tenuta, L. M. A.
Dent. Mater. 2016, 32, 323–333.
2. Riley, J. L. III; Gordan, V. V.; Rindal, D. B.; Fellows, J. L.; Ajmo, C. T.;
Amundson, C.; Anderson, G. A. Community Dent. Oral. Epidemiol.
2010, 38, 360–370.
3. Centers for Disease Control and Prevention. Recommendations for
using fluoride to prevent and control dental caries in the United States,
MMWR, 2001, 50, 1–42.
4. Burt, B. A. Acta Odontol. Scand. 1998, 56, 3.
5. Featherstone, J. D. J. Am. Dent. Assoc. 2000, 131, 887–899.
6. Arends. J.; Christoffersen, J. J. Dent. Res. 1990, 69 (Special Issue),
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b3252_Ch-04.indd 124 27-11-2018 02:59:32 PM

Chapter 5
Mercury Toxicity
Gelson Luis Adabo

Department of Dental Materials and Prosthodontics,
Faculty of Dentistry of Araraquara, UNESP. R. Humaitá,
1680, Araraquara — SP, 14801-385, Brazil
Mercury is a highly toxic heavy metal that is in liquid state at

ambient temperature. It exists naturally, and is released from the
earth’s crust, by rock outgassing, or volcanic activity. Mercury resi-
dues are also produced by anthropogenic activities, such as mercury
extraction, petroleum industry, coal-burning power stations, residen-
tial heating systems, waste incinerators, and gold mining. Mercury
vapor remains in the atmosphere for months and can be found in
the metallic or elemental form (Hg0), inorganic form (Hg1+ and
Hg2+), and organic form (carbon-containing compounds). Mercury
is hazardous to human health. It may affect mainly the respiratory,
nervous, renal, and immune system, and is considered by the World
Health Organization (WHO) as one of the 10 chemicals that are a
major public health concern.1 It spreads globally by atmospheric
transport and can impair human health directly or by bioaccumula-
tion via ecosystems.
125
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1. Introduction
Dental amalgam is the most popular material for direct restoration
in posterior teeth. Silver–tin–copper–zinc alloy particles are mixed
together with elemental mercury (typically 1:1 by weight) producing
an amalgam that is inserted into a tooth cavity, and carved into the
tooth’s form. The crystallized amalgam acquires mechanical proper-
ties to resist the chewing force, and it may last in the mouth for more
than 20 years. It was introduced in 1830, and at the beginning of the
1900s, the first approved formulation was developed. Since its intro-
duction, it has been used because of its suitable physical properties,
high longevity, low cost, low technical sensitivity, and efficient sealing
at the interface to dental tissues. These characteristics make dental
amalgam highly relevant to use in large dental care programs for poor
populations. Regardless of the efficacy of this biomaterial, the lack of
esthetics and concerns about the effect of the mercury on the health
of patients and professionals, as well as environmental issues, place
dental amalgam at the center of a great debate.
2. Historical
The controversy is as old as dental amalgam. In 1848, the American
Society of Dental Surgeons stated that using mercury-based resto-
rations constituted malpractice.2 The toxicity of mercury is fairly
known, but some dentists and dental professional organizations,
such as the Fédération Dentaire Internationale (FDI),3 the European
Union agency “Scientific Committee on Emerging and Newly
Identified Health Risks (SCENIHR),4 and the American Dental
Association (ADA),5 have considered amalgam safe for patients
because they believe that amalgam has a minimal amount of unre-
acted mercury after setting. On the other hand, these agencies recog-
nize the risks for dental staff because of mercury vapor produced
during manipulation to insert a new restoration or for removal of an
old one. In addition, mercury vapor can be released into the dental
office from spread mercury and solid fresh amalgam residue. However,
those agencies have considered that the occupational risks can be
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Mercury Toxicity 127
managed if simple hygiene precautions and technical procedures to

minimize the exposition to mercury are followed.
The Minamata Bay disaster, in Japan, highlighted how hazard-
ous mercury can be. In 1956, an unknown disease affected about
3,000 people, characterized by severe neurologic signs and symp-
toms. Minamata was a poor fishing village, where in the 1930s a plant
was built for manufacturing acetaldehyde and polyvinyl chloride using
mercury. The company began to discharge mercury residues into the
bay, and after decades, the ecosystem reached a critical pollution level.
The metallic mercury was converted into methylmercury by water
organisms, and this lead to the contamination of the entire food
chain — especially shellfish and predator fish — which is a typical food
for that population. Eventually, “Minamata Disease”, as it was known
at that time, was diagnosed as result of poisoning by methylmercury.
Approximately 700 people who developed the disease, died. In 1971,
another famous mercury poisoning occurred in Iraq, known as the
“Basra poison grain disaster”, when the population made flour to cook
bread using grain for planting that had been treated with a methylmer-
cury fungicide. This caused mercury poisoning in more than 6,000
people and lead to 500 deaths. These tragedies brought into question
the safety of mercury for all applications, including dentistry.
Beginning in the 1990s, several non-expert newspaper and maga-
zines published news articles, and there were television programs
showing the dangers of amalgam restoration. It spread the contro-
versy to the public, and patients became anxious about the effects of
mercury from amalgam restorations on their general health, asking
for amalgam fillings in tooth-colored restorations to be replaced. One
of the most striking pieces of news was presented on the “60 Minutes”
news program (CBS television). An interview with Dr. Murray Vimy
(University of Calgary) who performed an experiment adding radio-
active marker in amalgam fillings in sheep’s teeth showed how quickly
mercury could be identified in the organs, especially in the kidney.
Since then, replacement of amalgam restorations with mercury-free
materials has been indicated by some orthomolecular medicine prac-
titioners, claiming that the mercury is responsible for several systemic
diseases or chronic illness.6
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3. Toxicology
Mercury toxicity depends on its form (elemental, mercury salts,
organic), time of exposure, and dose, which may have different target
organs. Organomercury, as ethylmercury that was widely used as a
preservative in some vaccines and especially methylmercury (MeHg)
found in seafood, is the most hazardous for human health. Elemental
mercury (Hg0) from the atmosphere or wastewater accumulates in
water and is converted into organic mercury by microorganisms,
which contaminate the food chain of aquatic organisms, particularly
fish. Even though acute poisoning is rare, chronic consumption of
contaminated fish remains relevant, especially for pregnant women
and infants. MeHg from mercury-rich food enters the human body
via intestinal absorption, and when it reaches the bloodstream, it
adheres mainly to cysteine that is delivered to the whole body. The
maximum level in the blood occurs at about 2 days after exposure.
After 4 days, MeHg is distributed throughout the body and can be
found in the brain, peripheral nerves, bone marrow, liver, and kid-
neys.7 MeHg can cross the placenta and the blood–brain barrier
(BBB), and depending on the intensity and individual susceptibility,
it may impair the growth and migration of neurons in fetal brain.8
Mercury salts may be found in cosmetics and can be absorbed
through the skin. Chronic poisoning is difficult to diagnose because
the symptoms may be confused with other diseases. In addition, acute
poisoning does not impair the neural system, but a high dose affects
the gastrointestinal tract, causing severe symptoms such as vomiting,
hematemesis, intestinal perforation, proctitis, and may evolve to car-
diovascular collapse and renal failure.9
Chronic poisoning by mercuric mercury may occur associated
with mercury vapor poisoning in workers who are occupationally
exposed. The target organs are the kidneys, which lead to renal tubu-
lar necrosis and/or autoimmune glomerulonephritis. However, mer-
curous mercury is less dangerous. It was used as a laxative and is
poorly absorbed by the intestine, but a part of it is transformed into
mercuric mercury that can be absorbed and cause some toxicity.
Acute poisoning with mercury salts can also lead to death.9
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Elemental mercury (Hg0) is a liquid and vaporizes at room

temperature, but the vapor will not be perceived because it does not
have an odor or a color. Hg0 is highly lipid soluble — 80% of the
inhaled mercury vapor is retained in the body. It is absorbed by
the lungs and enters in the alveolar membranes, where it is quickly
distributed to the whole body. When it reaches the bloodstream, part
of the H0, which is a significant neural toxin, will remain in plasma
and part will be rapidly converted into its inorganic form (Hg2+) by
the red blood cells, but this reaction is not quick enough to prevent
a small portion from crossing the BBB. In the central nervous system
(CNS), the oxidized form is unable to cross the BBB because of its
low lipophilicity; the inorganic mercury will be attached to the
sulfidryl groups in proteins to be immobilized in brain for years to
decades as mercuric selenide, especially in the cerebellum. The half-
life of the oxidized mercury in blood is quite short (1–4 days), and it
is slowly excreted in urine, feces, and breast milk for up to 90 days.
However, part of the mercury remains mainly in the kidney, brain,
and in lower amounts in the lung, breast, thyroid, adrenals, pancreas,
liver, gastrointestinal tract, testes, prostate, muscles, exocrine glands,
and immune system cells.
Chronic poisoning produces mainly neurological dysfunction,
which varies according to the severity. Acute elemental mercury poi-
soning is rare, and signs and symptoms include weakness, myalgia,
chills, fever, nausea, vomiting, diarrhea, dyspnea, cough, and chest
pain. Lungs are more severely affected, and the pulmonary toxicity
may lead to necrotizing bronchitis and pneumonitis, compromising
respiratory function. There is risk of death, but recovery may be com-
plete or partial with subsequent residual interstitial fibrosis.10
Symptoms of chronic poisoning resulting from a low dose include
subtle neurological effects impairing psychomotor and cognitive
functions. People poisoned with a low dose describe fatigue, weak-
ness, anorexia, and gastrointestinal disturbance, which are non-spe-
cific, and low-dose poisoning is difficult to diagnose. However, high
levels of chronic poisoning produce tremor, depression, loss of
memory, severe behavior and personality changes, emotional excit-
ability, fatigue, psychotic reactions (delirium, hallucinations, and
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suicidal tendency) and gingivitis, which characterize the erethism

syndromes. In the kidneys, mercury produces reactive oxygen species,
which have nephrotoxic effect even in subcytotoxic doses.
The kidney is composed of tubular segments with different func-
tions, and is an excretion route for waste products from metabolic
process, drugs, and xenobiotics, which can potentially lead to kidney
injury. Because of injury to tubular cells, cytoplasmic proteins are
released into the urine, which can indicate renal tubular damage, and
which might indicate a potential toxicant based on the eliminated
protein. Theoretically, mercury accumulates in the proximal tubules,
and the presence of glutathione-S-transferases-α in urine suggests
proximal tubule damage and possible kidney injury. Albumin is
another biomarker of interest, if this protein is almost totally filtered
by the proximal tubules. When the albumin concentration is high,
it can indicate a reduction in glomerular filtration and tubular
absorptive capacity. It may predict a renal disease or nephrotoxicant
exposure.11
Mercury concentration in blood and urine are commonly used to
measure the risk of poisoning, but these tests are not able to indicate
the mercury load in the organs. Considering that the half-life of mer-
cury in bloodstream is short (up to 4 days), it is not feasible to quan-
tify the amount of mercury accumulated in the body once the blood
exam reports a picture of that short period. The mercury concentra-
tion in urine represents a better measure because it shows an estima-
tive of mercury intake, but it does not indicate mercury in the target
tissues.12 Moreover, interpersonal variations should be considered.
Taking into account that CNS is one of mercury’s main target
organs, neurological tests are proposed to aid in diagnosing mercury
poisoning. Neuropsychologic and neurophysiologic status may
include tests of attention, short-term memory, verbal memory, visual
memory, manual dexterity, verbal fluency, visuomotor ability, depres-
sion and anxiety inventories, and electromyography and nerve con-
duction testing. The objective of the neurological tests is to correlate
their results with a high concentration of mercury in the air, blood,
and urine, as well as examinations to measure biomarkers of renal
damage.
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4. Mercury in Dentistry

Since the 1990s, the concerns about the effects of mercury from
dental amalgam have started a major debate that pitted the US Food
and Drug Administration (FDA),13 FDI3 and ADA,1 which have
defended the continued use of dental amalgam, against the recom-
mendation of the WHO,1 US Environmental Protection Agency
(EPA), and other organizations, which propose banning amalgam.
Eventually, in 2013, the Minamata Convention on Mercury, an inter-
national treaty signed by 140 countries, agreed to phase out produc-
tion and trade of products containing mercury until 2020. However,
even after the use of amalgam is phased out, it is not known how
many teeth have been restored with amalgam. Therefore, the concern
will remain for decades, because existing amalgam restorations may be
negatively affecting patients’ health, and removal of old amalgam
restorations will produce mercury vapor and amalgam particles, put-
ting dentists at an occupational risk and also having a negative effect
on the environment.
4.1. Amalgam Safety for Patients

According to the WHO, dental amalgam is the primary intake source
of mercury for the general population, which is higher than that
found in food, water, and air.1 Patients are exposed to some amalgam
vapor for up to 2 weeks when the restorations are placed or removed
for replacement. After placement, small quantities of mercury vapor
leach continuously from the restoration, which is absorbed by inhala-
tion (80%), for the lifetime of the restoration.
The actual mercury level in the body tissues may be directly veri-
fied only via autopsy. Guzzi et al.14 reported on amalgam restorations
and their relationship to mercury retained in brain, thyroid, and kid-
ney in 18 cadavers. Cadavers with 12 or more restored teeth showed
more mercury accumulated in the tissues than cadavers that had three
or less restored teeth. Brain tissues (frontal lobe cortex and pituitary
glands) showed significantly higher mercury level compared to thy-
roid and kidney tissues. Bjorkman et al.15 found a strong correlation
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between the number of amalgam restorations and mercury in the

occipital cortex and pituitary and thyroid glands. Additionally, the
kidneys are recognized as an important target organ, but autopsies
have not found a large amount of mercury in these organs. Alcohol
abuse may reduce the mercury load, but it is unclear how alcohol
interferes with the metabolism of mercury.16
The maximum value of urinary mercury concentration (HgU)
that is considered safe for most people in the general population is
less than 10 μg Hg/L. There is a positive correlation between HgU
and the number of amalgam surfaces. Each amalgam restoration
surface will add approximately 0.1 μg Hg/L to the HgU.16 However,
mercury concentration in blood and urine seems not to be corre-
lated with disease symptoms that are associated with amalgam
restorations.
Based on the number of restorations, the patient’s eating habits,
and chewing gum and bruxism, daily mercury uptake may reach
22 μg/d, but for most people the dose is below to 5 μg/d.18 If the
limit exposure to mercury vapor (0.3 mg/m3) is taken, then the expo-
sure is estimated to be equivalent to 4.9 μg/d intake.19 In other
words, people who have large amount of amalgam restorations would
have exposure to mercury as if they were in an environment with the
maximum of mercury vapor acceptable as safe. In 2011, Richardson
et al.16 estimated that 67.2 million Americans exceeded those condi-
tions. However, while most people are resistant to long-term, low-
level mercury exposure, part of the population is sensitive to its toxic
effects, even those who have normal blood and urine mercury
levels.10
“Amalgam-disease”, which has symptoms that include buccal
discomfort, diffuse body pain, weakness, fatigue, and dizziness, and
some diseases such as thyroid dysfunction, anemia, cardiopathy, and
renal disease, has been self-reported by patients who suspect being
chronically poisoned by amalgam restorations. However, this “dis-
ease” might be related to psychological factors, and it has been found
in patients who have a tendency toward somatization.20 Björkman
et al.21 studied the concentrations of immune mediators (cytokines,
chemokines, and growth factors) in serum in patients with health
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complaints attributed to amalgam after removal of all dental amalgam

restorations and compared with a healthy group. At baseline, patients
with health complaints had slightly higher value in immune media-
tors in serum, but 12 months after amalgam removal, the concentra-
tions of Th1-type proinflammatory marker decreased to the same
extent as what was reported for the reference group. Gottwald et al.22
studied the relationship between toxicological, allergological, and
psychological aspects in patients with amalgam-associated complaints
with a group with similar numbers of amalgam fillings. There was
higher atopic predisposition, psychic strain, and depression scores in
the group of patients with complaints, but toxic exposure to mercury
was not different from the control group.22 Sjursen et al.23 compared
a group of patients who attributed health complaints to amalgam fill-
ing to a control group with no intervention. Amalgam restorations
were replaced with mercury-free material, and the subjective health
complaints were measured after 3 months, and at 1 and 3 years after
intervention. The results showed a reduction in the symptoms, but it
was not possible to conclude if the subjective improvement in health
was a result of a psychological effect of the elimination of the “amal-
gam anxiety”.23 Melchart et al.24 treated patients with subjective
complaints, which could not be explained by a medical or psycho-
logical disorder, using three different strategies, removal of dental
amalgam, removal in combination with high-dose vitamin, and trace
element therapy, with a non-removal group whose patients partici-
pated in a health promotion program only. The authors observed
similar reduction in the subjective complaints, for both the group
with amalgam removal and the non-removal group that was treated
by therapy of health promotion program.24 In a complementary
study, Weidenhammer et al.25 investigated the effect of amalgam
removal on women using a questionnaire comprising affective symp-
toms, neuropsychological symptoms, general somatic complaints,
and some intraoral symptoms at baseline and after 12 months. There
was no statistical difference between the group that had an amalgam
restoration removed and the control group that was treated based on
a psychological model as a strategy to enhance general health.
Irrespective of amalgam removal, patients’ symptoms decreased.25
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However, the psychological role in “amalgam disease” may not com-

pletely explain the symptoms. Sensitive people who have certain
genetic polymorphisms may exhibit different effects of mercury cyto-
toxicity. Thus, amalgam filling removal can effectively induce health
improvement.26
The major concern is to estimate the actual risk for pregnant
women and children. Considering that children are more susceptible
to poisoning, the association of exposure from amalgam fillings in
pregnant women or lactating mothers with neurodevelopmental dis-
abilities in children has been investigated. There is evidence that ele-
mental mercury can be found in amniotic fluid, placenta, and umbilical
cord blood, as well as in fetal liver, kidney, and brain. Inhaled mercury
vapor enters into the placenta and can cross the fetal BBB, leading to
a concern about potential neurological damage. Moreover, lactating
women may excrete mercury in colostrum and breast milk.9,27–30
Regardless of the knowledge that breast milk can contain mercury, the
WHO1 recognizes the minimal risks of breastfeeding.
The impact of amalgam restorations on children has been studied
by several authors. Bellinger et al.31 is one of the most-cited studies.
The authors compared the neuropsychological outcome of full-scale
IQ scores, tests of memory and visuomotor ability, and renal glo-
merular function in 534 children who had teeth restored using amal-
gam (n = 267) or mercury-free materials (n = 267) during a 5-year
follow-up period. No statistically significant differences were found
between children in the two groups, either with regard to neuropsy-
chological aspects or renal integrity; there was, however, a higher
mean urinary mercury level in children with amalgam fillings.31
DeRouen et al.32 reported the results of a 7-year follow-up study after
restorative procedures in children with amalgam restorations or com-
posite restorations. Urinary mercury concentrations increased in chil-
dren after placement of amalgam restorations, but there were no
statistically significant differences in neurobehavioral and neurological
tests between the groups.32 A similar conclusion was drawn by Ye
et al.33 who measured the effect of mercury from amalgam fillings in
children, aged 7–11 years, on renal function and neurobehavioral
and neuropsychological performance, and concluded that HgU was
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slightly elevated in children with amalgam fillings, but there were no

evidence of adverse effects on children’s health.
However, genetic aspects and predispositions should be consid-
ered. Elimination of Hg involves glutathione-s-transferase (GST), and
depends on enzymes related to glutathione synthesis and degradation.
Selenium is structurally incorporated into selenoproteins, and it acts
as an antioxidant, protecting against mercury toxicity. However, many
glutathione-related enzymes are highly polymorphic, and the poly-
morphism may be related to disturbances in antioxidant action and to
modulation of the detoxification system.34,35 Woods et al. (2008)11
evaluated urinary concentrations of biomarkers of renal proximal
and distal tubular integrity in subjects (8–18 years old) who were
treated with amalgam or composite. Biomarkers were annually meas-
ured for 7 years after the dental treatment. GST-π is the biomarker
for distal tubular integrity, and its levels increased, especially in
females.11 Genetics vary for the heme pathway enzymes copropor-
phyrinogen oxidase (CPOX), metallothionein (MT), and catechol-O-
methyltransferase (COMT), which have important roles in mercury
metabolism and elimination, as well as in regulating dopamine and
other neurotransmitter availability. In addition, polymorphism in the
serotonin transporter may interfere with the limbic system that is
associated with mood and behavior, as well as neuromotor function
and visual perception.36–40
4.2. Amalgam Safety for Dentists and Dental Staff

The “mad-hatter syndrome” is the earliest occupational risk that was
associated with using mercury, and it is characterized by symptoms
such as tremors, irritability, and mental instability. In the 19th cen-
tury, felt for hats was obtained from small animals’ furs that was sepa-
rated from the skin using mercuric nitrate. The felt was repeatedly
immersed in boiling water to shape the hat, followed by drying. In
this process, the room was saturated with mercury vapor causing a
high level of chronic poisoning. The disease was generally represented
as the eccentric “Mad Hatter” character seen in the book Alice’s
Adventures in Wonderland, written by Lewis Carroll in 1865.
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Currently, those who work in chloralkali plants, with fluorescent

lamps, switches, sphygmomanometers, and in the thermometer
industry, as well as dentists, who work on placing or replacing amal-
gam restorations, are daily occupationally exposed. These people can
be exposed to long-term low-dose mercury poisoning for years.
Neuropsychological impairment is the main symptom seen in those
workers, but psychological disorders encompass a wide array of social,
behavioral, and physiological conditions with different etiologies,
thus making it difficult to diagnose the condition earlier. Thus, work-
ers exposed to a potentially hazardous environment must be exam-
ined periodically to monitor the chronic occupational mercury
exposure risk or to diagnose the syndrome as early as possible.
The chloralkali industry is the main industrial activity that uses
mercury for the production of sodium hydroxide and chlorine gas
from sodium chloride, and this process involves electrolysis in which
liquid mercury is used as cathode. Electrolysis separates the sodium
and chlorine gas, but it results in the escape of high amounts of mer-
cury vapor and chlorine gas into the air. Because of the intense mer-
cury vapor generated during that activity, the parameters for
occupational risk were usually based on the chloralkali plant working
conditions. Fortunately, mercury vapor action is reduced in an envi-
ronment where chlorine gas exists concomitantly, once mercury vapor
(Hg0) converts to Hg+2Cl2−1. Hg+2 is not able to cross the BBB.
Therefore, the mercury concentration limit that is acceptable for
chloralkali workers may not be safe for other occupations.16
The maximum amount of mercury vapor suspended in the air at
an ambient temperature of 24°C is 18 mg/m3 before condensing.
Regulatory agencies establish limits for mercury vapor in the air to
which a worker can be exposed at any time. According to the
Occupational Safety and Health Administration (OSHA), United
States, the air concentration permissible exposure limit (PEL) is
0.1 mg/m3. Canadian law determines that 0.15 mg/m3 is an occupa-
tional exposure limit (ceiling exposure value). Other agencies estab-
lished the time-weighted for hour/workday or hour/workweek. For
the National Institute for Occupational Safety and Health (NIOSH),
United States, the recommend exposure limit (REL) is 0.05 mg/m3
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for a 10-hour workday and a 40-hour work week. On the other hand,
the European Scientific Committee on Occupational Exposure Limit
Value determined 0.02 mg/m3 for an eight-hour workday.
The concern about the impact of mercury vapor on dental staff is
an important part of the mercury debate because dentists and dental
assistants are exposed to mercury vapor during manipulation, inser-
tion, carving, finishing, and polishing procedures to make an amal-
gam restoration, as well as exposure during removal of an old
restoration. When amalgam is cut with dental burs, small particles are
produced increasing the surface area and facilitating mercury vapori-
zation. In addition to the immediate vapor generated to restore teeth
or remove amalgam restorations, the rest of the liquid mercury and
amalgam residue may increase the mercury vapor concentration in the
dental office. Warwick et al.41 measured mercury vapor levels released
in the air during amalgam removal, using simultaneous water spray
and suction, using suction only, and using neither suction nor water
spray. The authors concluded that when water spray and suction were
used, the arithmetic mean of mercury vapor was 0.008 mg/m3, which
is below the Occupational Health and Safety threshold limit value for
an eight-hour time-weighted period (0.025 mg/m3).41 However,
amalgam removal can produce particles in the range of 1–3 µm to
submicron size that are fully respirable, and may be lodged in the
lungs or ingested.42 Therefore, the use of masks to block particles and
to reduce vapor inhalation must be used during all procedures.
However, the usual masks are not able to filter these particles and
vapor. To be effective, a “half-mask” respirator with a pre-filter that is
capable of removing particles as small as 0.3 microns is advisable.
In addition to the mercury vapor in air measurements, the urinary
mercury levels should be tested periodically to identify occupational
risks. The threshold limit of the biological exposure index (BEI) has
been set to 35 µg Hg/g creatinine. Values above this limit reflect low
mercury exposure, but impairments in neurological functions have
been related to concentrations below 25 µg Hg/g creatinine.43
Studies have shown that the HgU level is not directly related to health
impairment of dental professionals. Symptoms of diseases that are
typical of long-term chronic mercury poisoning have been reported,
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even for dentists and dental assistants who have HgU levels close to
the general population.
Ritche et al.44 compared health and cognitive function of dentists
to a control group with a similar university education. The mercury
vapor in the air at different places in the dental office related to the
clinical procedure (amalgam insertion or removal) was also measured,
and 68% of dental offices were shown to have mercury levels higher
than the OES stated by the Health and Safety Executive (0.025 mg/m3
for an eight-hour day). Among the psychological evaluation, there is
significant difference in memory disturbance only, but it was not pos-
sible to correlate this result to mercury exposure. Dentists showed
HgU levels over four times higher than that for the control group,
but the average of HgU of dentists was below the biological exposure
index (BEI).44 In other study, Moen et al.45 compared neurological
symptoms of dental assistants to assistant nurses and concluded that,
in the dental assistants group, the occurrence of neurological symp-
toms, psychosomatic symptoms, memory, concentration, fatigue, and
sleep disturbance were significantly higher than the reference group,
particularly with regard to memory deficit. No difference was found
concerning mood, anxiety, and perception of health status.
For removing old amalgam restorations, dentists and dental assis-
tants must use personal protective equipment (EEP). It is advisable to
use a rubber dam to help contain the amalgam grinding debris. The
restoration has to be cut by slicing with an efficient dental bur under
a constant water spray and a high volume evacuation. To overcome
uncertainty about dental staff safety regarding dental amalgam, the
FDI46 (2007) published a Mercury Hygiene Guidance, with the fol-
lowing recommendations: avoid direct skin contact with mercury or
freshly mixed dental amalgam and exposure to potential sources of
mercury vapor; train all personnel evolved with amalgam manipula-
tion; install impervious, easy-to-clean surfaces including continuous
seamless-sheet flooring extending up the walls; and work in well-
ventilated areas, with fresh air exchanges and outside exhaust. If the
work areas are air-conditioned, replace the air-conditioning filter
periodically; use pre-capsulated amalgam; use an amalgamator with a
completely enclosed arm that complies with international standard
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ISO 7488; and recap single-use capsules after use, if feasible. Store
them in a closed container and dispose of them through a mercury
reclamation company that handles amalgam waste; use high-volume
evacuation systems (fitted with traps or filters) when finishing or
removing amalgam; clean amalgam contaminants from instruments
before heat sterilization or heat disinfection; avoid heating mercury or
amalgam or any equipment used with amalgam; and follow best man-
agement practices for amalgam waste.
Other dangerous sources of mercury vapor exposure are related
to improper clean-up of the dental office, lack of ventilation and air-
conditioner cleaning; porous and/or floors with cracks, such as carpet
or wood, making it difficult to remove the mercury. Moreover, even
an apparently insignificant amount of spilled mercury can produce
high concentration of mercury vapor indoors.1 In case of a mercury
spill, the FDI recommends the following protocol: pick up the drop-
lets using adhesive tape or a hypodermic syringe; mix small mercury
spills (less than 10-g) with an alloy powder to form amalgam and add
the resultant scrap to the scrap container; use a commercial mercury
spill clean-up kit to manage larger spills (10-g or more); never use a
vacuum cleaner of any type; do not use household cleaning products;
do not pour or allow mercury to go down the drain; do not use a
broom or a paintbrush to clean up mercury; and prevent people
whose shoes may be contaminated with mercury from walking around
or leaving the spill area until the mercury-contaminated items have
been removed. Handling and use of bulk mercury is to be strongly
discouraged. Check the dental surgical area for mercury vapor, prefer-
ably annually or after a spill clean-up.46
4.3. Environmental Issues Related to Dental Amalgam

Mercury into the atmosphere comes back to the surface via wet and
dry atmospheric deposition. When mercury reaches the surface, its
vapor may return to the atmosphere in a reemission cycle between the
air, soil, and water, which gradually increases the accumulation,
mainly in aquatic ecosystems. Elemental or inorganic mercury can
convert to the organic form by anaerobic bacteria in natural settings.
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Water with high mercury levels is the main environmental concern

because it can potentially affect crops, drinking water, and particularly
the aquatic food chain, causing bioaccumulation.
There is much uncertainty about estimating new emission and
reemission of mercury into the atmosphere from natural and
anthropogenic sources. In 2013, the United Nations Environment
Programme (UNEP)47 published a report on global mercury assess-
ment, where the current annual mercury release from natural sources
was estimated to be up to 600 t/y, from anthropogenic emissions, it
was approximately 2,000 t/y, and from reemission, it was more than
4,000 t/y. Mercury emission from natural and anthropogenic sources
has increased after the industrial age, and in the last 100 years, emis-
sion increased 300–500%, while reemission increased 200%. The data
suggest that human activities are mainly responsible for the global
increase of mercury in the environment.48
Approximately 84% of the mercury load related to anthropogenic
activities is from combustion of fossil fuels. Among the other anthro-
pogenic sources, dental amalgam has an important role in the envi-
ronmental accumulation, but the real impact of dental amalgam is not
known. A European Commission report estimated that dentistry
accounts for approximately 75 t/y, of which about 45 t/y is attrib-
uted to dental office effluent. This waste reached the impressive mark
of up to 13% of the overall European emissions into surface water.
A concern about the effect of dental amalgam on the environment
is the mercury released as result of human cremation; it is estimated
that each human body has an average 2.5 g of mercury from dental
restoration, amounting at 3.6 t/y globally. Regardless of pollution
control devices, cremation remains an important source of mercury
vapor.47
The main source of mercury in dentistry is from restorative pro-
cedures and removal of old amalgam restorations. To make an amal-
gam restoration 15–50% of the prepared amalgam is lost as amalgam
scrap — a non-contact waste from surplus of trituration and carving,
and the remaining amount in used capsules. If this solid waste, as well
as the extracted teeth with amalgam restoration and waste that has
contact with human fluids such as rubber dams, cotton rolls, and
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particles retained in the filters, is sent for incineration, it will produce

mercury vapor emission.49 On the other hand, if those residues are
sent to landfill sites, the mercury may become volatile by leaching
from the landfill.50
During an old amalgam restoration removal, a sludge constituted
by a heterogeneous mixture of liquids and particles of amalgam and
dental tissues is trapped into the drain. This sludge has a wide range
of macroscopic to submicron size particles, which may reach the
sewerage systems. Inorganic mercury from amalgam waste can be
converted to MeHg by a biochemical mechanism resulting from sul-
fate-reducing bacteria, which are common in the patient’s mouth.
MeHg has been found in dental wastewater in significantly higher
concentrations than in natural settings. Even taking into account the
mercury removal efficiency by wastewater treatment facilities, 4% of
mercury is released into the environment.51 As a complicating factor,
oxidizing substances that are usually applied as a vacuum disinfectant
may release mercury from amalgam waste.49
Amalgam separators were developed to reduce emission of amal-
gam particles into the waste water. This equipment can be based on
centrifugation, sedimentation, and filtration principles. A 95% efficacy
in preventing amalgam particles is expected, according to the interna-
tional standard organization (ISO 11143), but there is a large varia-
tion in removal efficiency among the working methods in the
separators. Despite the recommendation, installing amalgam separa-
tors is not mandatory in most countries, even though there is increas-
ing environmental concern.
General procedures to be followed by dental clinics can be sum-
marized according to the amalgam waste management adopted by the
FDI: “Dental offices should collect, store safely and forward for recy-
cling as much of the amalgam waste as possible, regardless of whether
or not it has been in contact with a patient. Such waste includes used
amalgam capsules, excess amalgam and amalgam waste retained in
chair side traps, vacuum pump filters and amalgam separators.
Extracted teeth restored with amalgam can also be recycled with
other types of amalgam waste. If amalgam separators are to be
installed in the dental clinic, they should comply with ISO 11143.”
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The Minamata Convention on Mercury, a multilateral environ-

ment agreement to help reduce global mercury pollution by
anthroponogenic activities, was signed in 2013, and this agree-
ment expects to reduce or eliminate the use of mercury where it is
feasible. For dental amalgam, it was agreed to phase-down and
create initiatives to reduce its use, focusing rather on the caries
prevention and health promotion, on research for developing new
and effective dental restorative materials, and on sound lifecycle
waste management.52,53
5. Final Remarks and Recommendations

(1) Dental amalgam is considered safe for most patients, including
children, but sensitive people who have genetic polymorphisms
may be at higher toxicological risk. It is recommended that deci-
sions for amalgam placement or replacement of any other restora-
tive material be made on an individual basis.
(2) Dentists and dental assistants may be subject to long-term, low-
level chronic mercury exposure, and although most professionals
are minimally affected, the mercury concentration in the air,
urine, and biological markers must be monitored in workers, in
case some are sensitive to the mercury toxicity.
(3) Dental amalgam is an important source of wastewater mercury
pollution, and best practices of waste management are required
to protect the environment.
References
1. WHO. Exposure to Mercury: A Major Public Health Concern. Preventing
Disease through Healthy Environments, 2006, 4. Available at: http://
www.who.int/phe/news/Mercury-flyer.pdf (Accessed 29 May 2018).
2. Heyer, N. J.; Echeverria, D.; Martin, M. D.; Farin, F. M., Woods, S.
J. Toxicol. Environ. Health 2010, 72 (9), 599–609.
3. FDI. World Dental Federation. Statement on Dental Amalgam, 1999.
Available at: https://www.fdiworlddental.org/sites/default/files/media/
documents/WHO-consensus-statement-on-dental-amalgam-1997.pdf
(Accessed 29 May 2018).
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4. Scientific Committee on Emerging and Newly Identified Health Risks

(SCENIHR). The Safety of Dental Amalgam and Alternative Dental
Restoration Materials for Patients and Users (San Francisco:
May 2008).
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DentalProducts/DentalAmalgam/ucm171120.htm#ifu.
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et al. Am. J. Forensic Med. Pathol. Off. Publ. Natl. Assoc. Med. Exam.
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Sykes, L. K. et al. BioMetals. 2014, 27 (1), 19–24.
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b2530_FM.indd 6 01-Sep-16 11:03:06 AM

Chapter 6
Zirconia in Dentistry
Paulo Francisco Cesar*, Susana Salazar-Marocho,

Erick de Lima, Lucas Hian da Silva, Karen Fukushima,
and Ranulfo Benedito de Paula Miranda
Department of Biomaterials and Oral Biology,
University of Sao Paulo, Av. Prof. Lineu Prestes,
2227 — Cidade Universitária, São Paulo, Brazil
*paulofc@usp.br
This chapter intends to present information regarding many aspects

of the use of zirconia in dentistry. First, the composition, micro-
structure, and mechanical properties are discussed. The second part
deals with the problem of chipping of dental porcelains applied over
Y-TZP structures, its causes, and possible solutions for the problem.
The third part presents the innovations related to translucent zirco-
nia, explaining how manufacturers managed to increase light trans-
mittance by means of tailoring the microstructure. The fourth part
explains how zirconia reacts to the aging phenomenon that occurs
in the oral cavity. The fatigue mechanisms and laboratory chewing
simulation works are discussed. Finally, the fifth and last part pre-
sents the advantages and disadvantages of zirconia implants in
comparison to titanium implants.
147
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1. Introduction
Zirconium dioxide (ZrO2) or zirconia is used in dentistry to fabricate
frameworks for anterior and posterior fixed dental prostheses (FDP)
and abutments for dental implants because of its excellent properties
such as high strength, high biocompatibility, and high chemical
stability.
The 3 mol% yttria-stabilized tetragonal zirconia polycrystal
(3Y-TZP) material was first applied in restorative dentistry in 1995.1
From this year on, 3Y-TZP ceramics stood out among all other types
of dental ceramics due to the superiority of its mechanical properties
such as high fracture toughness (from 4.4 to 15.0 MPa · m1/2) and
flexural strength (1,100 MPa) compared with feldspathic porcelains,
glass ceramics, alumina, and glass-infiltrated ceramics.2–4 The superior
mechanical properties of Y-TZP result from the toughening mecha-
nism (phase transformation); however, its almost purely crystalline
composition also improved its mechanical properties as opposed to
materials with amorphous phases in their composition.
Zirconia is a material with polymorphic crystal structure that
has three crystalline forms: monoclinic (m), tetragonal (t), and
cubic (c). At room temperature, the material is stable in the mono-
clinic form until 1170°C. When heated at higher temperatures,
the transformation to the tetragonal phase occurs, and subse-
quently to cubic phase at about 2370°C, which exists up to the
melting temperature of 2680°C. During cooling, at temperatures
below 1070°C, the transformation from the tetragonal to the
monoclinic phase (t → m) takes place accompanied by a volumetric
expansion of 3–4.5%.
The addition of dopant oxides or stabilizers to the zirconia, such
as calcium oxide (CaO), magnesium oxide (MgO), yttrium oxide
(Y2O3), aluminum oxide (Al2O3), or ceria (CeO2). promote the
formation of
(i) fully stabilized zirconia (FSZ) in the cubic form by adding suf-
ficient amounts of stabilizing oxides (16 mol% MgO, 16 mol%
CaO, or 8 mol% Y2O3);
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Zirconia in Dentistry 149
(ii) partially stabilized zirconia (PSZ) formed by nanoscale particles

in the monoclinic or tetragonal phase immersed in the cubic zir-
conia matrix. The stabilizers added are CaO, MgO, or also Y2O3
(in smaller proportion than that used for TZP);
(iii) tetragonal zirconia polycrystals (TZP) consist predominantly of
the tetragonal phase stabilized at room temperature with Y2O3
(usually 3 mol%), leading to the Y-TZP (stabilized tetragonal
zirconia polycrystals). Small amounts of secondary cubic phase
have also been reported in TZP.5,6
As stated before, the Y-TZP is the most commonly used zirconia-

based dental material. The transformation from tetragonal to mono-
clinic phase in Y-TZP restorations can be induced by usual procedures
such as the adjustment with diamond burs and sandblasting, which
incorporate surface defects as scratches and grinding flaws. The phase
transformation results in volume expansion with the generation of
compressive stresses with an approximate depth of 30 µm,7 which
hinders crack propagation,8 thus increasing the fracture toughness of
the material.
Highly crystalline ceramic materials such as Y-TZP have no vitre-
ous phase in the microstructure, and therefore their translucency is
lower than that observed for materials with high glass content, such
as feldsphatic ceramics. Therefore, restorations built with Y-TZP need
to be veneered with a more aesthetic and compatible ceramic mate-
rial. Feldspathic porcelains and glass ceramics are the most used
veneering materials for this purpose.9 Recently, more translucent
Y-TZPs have been developed to fabricate monolithic fixed partial
dentures.
The basic microstructure of 3Y-TZP consists of equiaxed grains
with an average diameter ranging from 0.2 to 0.5 µm. The sintering
temperature has a great influence on the final grain size as sintering
the material at lower temperatures results in smaller grains.
Restorations obtained from 3Y-TZP can be machined in the par-
tially sintered (soft machining) or fully sintered (hard machining)
states. The latter processing method is more time consuming, involves
high wear of the milling instruments, and can cause unwanted phase
b3252_Ch-06.indd 149 27-11-2018 02:59:59 PM

transformation and irreversible damage to the ceramic surface. Thus,

soft machining is the preferred processing method for dental Y-TZPs
due to its higher efficiency in producing dental prostheses. On the
other hand, the fully sintered zirconia has a smaller fraction of pores,
higher hardness, and better resistance to hydrothermal aging. Y-TZP
is presented commercially in the form of plates, cylinders, or partially
sintered discs that are milled in a computer-aided design/computer-
aided machining (CAD/CAM system) to achieve the final shape of
the dental restoration.
2. The Bilayer Porcelain/Zirconia

Due to aesthetic limitations, Y-TZP restoration need to be veneered
with a porcelain layer with relatively low mechanical properties.
Although clinical follow-ups have shown low failure rates for single
crowns produced with Y-TZP frameworks, a high failure probability
of the veneering porcelain has been reported in these studies.10 This
type of failure is called chipping of the porcelain veneer layer and var-
ies according to the size of the chipped area, from small porcelain
fractures (which can be repaired by polishing the restoration) to more
extensive fractures that require remaking the FPD entirely.11
2.1. Causes of Porcelain Chipping

One of the causes of chipping of the veneering ceramic applied to
Y-TZP frameworks is the association between thermal residual
stresses existing within the restoration and the mechanical stresses
generated by masticatory cycles. Thermal residual stresses are gener-
ated during rapid cooling of the restoration in the furnace for porce-
lain sintering.
During the preparation of an all-ceramic restoration using the
traditional method for porcelain application, both materials (infra-
structure and veneering layer) are submitted to a series of thermal
cycles to apply the different porcelain layer and reproduce the anat-
omy of a particular tooth. At the end of each cycle, the restoration is
cooled to room temperature.12
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Studies showed that the thermal residual stresses are developed

during the cooling stage of the ceramic restoration,13 and two main
factors are described as being responsible for the development of
these thermal stresses: the differences in the coefficient of thermal
expansion (CTE) between the porcelain and Y-TZP and the tempera-
ture gradient created during cooling.14,15 The last sintering cycle per-
formed is the most important since it determines the final residual
stress profile in the ceramic restoration.
The coefficient of thermal expansion (CTE) mismatch between
the Y-TZP framework (αinfrastructure) and the veneering porcelain
(αporcelain) results in different contraction rates for these two materials
during cooling of the ceramic piece. The resulting thermal residual
stress profile in the restoration will depend on the porcelain layer
exhibiting a higher or lower CETL than that of the Y-TZP used as
framework.
When the porcelain veneering layer has a much higher CTE com-
pared to that of the infrastructure (αinfrastructure < αporcelain), pre-existing
cracks in the porcelain layer will propagate more easily during the
application of chewing mechanical loads due to the accumulation of
tensile residual stresses in the porcelain. On the other hand, an oppo-
site situation (αinfrastructure > αporcelain) will result in the development of
compressive stresses in the porcelain. These compressive stresses will
make it more difficult for small flaws or defects present in the material
to propagate during the clinical performance of the restoration, thus
reducing the risk of material failure.
The thermal gradient generated along the ceramic restoration
occurs because both the Y-TZP and the veneering porcelain have
very low thermal diffusivity when compared to metal alloys. During
fast cooling of the ceramic restoration, low thermal diffusivity gen-
erates a temperature difference between deeper regions (near the
Y-TZP infrastructure) and the outer surface of the veneering por-
celain layer. This fact is critical because the outer surface solidifies
first, while the inner layers remain liquid (above the glass transition
temperature, Tg). This thermal gradient between the deeper layers
and the outer surface of the veneering porcelain influences the
appearance of thermal residual stresses along the restoration.
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A solution found by researchers during the production of an

all-ceramic restoration to reduce the formation of thermal residual
stresses resulting from the thermal gradient was to perform a porce-
lain sintering cycle associated with a slow cooling protocol in order to
ensure a temperature homogenization in the various thicknesses of
the porcelain veneering layer.16,17
In addition to the thermal residual stresses, studies also pointed
out the design of the Y-TZP framework, the mechanical properties,
and processing method of the porcelain layer as possible factors
related to the occurrence of porcelain chipping. The zirconia frame-
work design is considered a risk factor for chipping in situations in
which the porcelain is left without the framework support.17 The
cusps and interproximal regions are the areas with highest chipping
rates due to the larger volume of porcelain applied in these places to
reproduce the dental anatomy. It is recommended to individualize the
design of the infrastructure according to each clinical case, in order to
ensure the greatest support possible for the porcelain layer that is
applied on the Y-TZP framework.
The fact that dental porcelains have the lowest mechanical proper-
ties compared to all dental ceramic materials also influences the chip-
ping rate of the porcelain layer. In addition to this, the presence of
defects in the veneering layer related to the processing method may
favor the porcelain chipping.18,19
The application of porcelain by the traditional or stratification
technique, in which a porcelain slurry is applied to the Y-TZP infra-
structure with the aid of a brush, generates a veneering layer with
high porosity, which reduces the mechanical properties of the struc-
ture. Thus, new processing techniques have been developed in order
to obtain a coating layer with improved mechanical properties.
One of these techniques is the so-called press-on technique, in
which porcelain pellets are pressed over a Y-TZP framework (previ-
ously milled and sintered). The process is conducted in a special fur-
nace under high temperature, resulting in a porcelain layer with lower
porosity and better mechanical resistance compared to porcelain lay-
ers built by the traditional method.20
Two techniques have been recently introduced in the market
with the objective of reducing the risk of chipping of the veneering
b3252_Ch-06.indd 152 27-11-2018 02:59:59 PM

porcelain layer. In one of these systems, a layer of Y-TZP (infrastructure)

and a veneering porcelain layer are produced via CAD-CAM and
then bonded together by means of a cementation step. This system
aims to avoid the appearance of thermal residual stresses generated
during the cooling of the restoration. The porcelain used in the
veneering layer is produced in ideal industrial conditions that
ensure a material with less defects, resulting in a more homogene-
ous and mechanically resistant porcelain layer. The other system
uses CAD-CAM blocks of a lithium disilicate glass-ceramic to pro-
duce the veneering layer. This material has a higher crystalline
content and better mechanical properties when compared to felds-
pathic porcelain. The bond of the veneering layer with Y-TZP
infrastructure is made by means of a low fusion temperature glass-
ceramic, using a sintering cycle that promotes fusion of the two
layers (veneering and framework) and final crystallization of the
veneering layer.
3. Monolithic Zirconia

In 2011,21–22 dentistry started using monolithic restorations of Y-TZP,
and consequently the chipping problem presented by veneering
ceramics was eliminated. However, in the beginning, these mono-
lithic restorations offered only a satisfactory aesthetic result due to
lower translucency of Y-TZP and its use was restricted to molars.21,23
With the development of novel processing methods, more translucent
Y-TZPs were developed for monolithic restorations in the anterior
area.23,24
3.1. Microstructure and Optical Properties

Currently, the microstructure and the composition of monolithic
zirconia are significantly different from those of conventional Y-TZP.
The first attempt to reduce the opacity of the Y-TZP involved a
decrease in the amount of sintering additives in its composition.25
Sintering additives have different refractive indexes compared to
zirconia (ZrO2) and therefore increase the opacity of the Y-TZP due
to high light scattering.
b3252_Ch-06.indd 153 27-11-2018 02:59:59 PM

Figure 1. Photomicrograph by scanning electron microscopy of the con-

ventional Y-TZP microstructure. Red ellipses show the presence of crystalline
grains of alumina previously identified by energy dispersive spectroscopy
An additive frequently used in Y-TZP is aluminum oxide (alumina;

Figure 1), which inhibits the growth of zirconia grains during sinter-
ing and increases the ceramic resistance to low-temperature degrada-
tion (LTD). A smaller alumina content (0.1 mass%) is present in the
microstructure of the Y-TZP for monolithic restorations in compari-
son to the conventional Y-TZP (0.43 mass%),26 resulting in higher
translucency for the first.
The increase in translucency observed for monolithic Y-TZP res-
torations is also related to smaller crystalline grain sizes, which are
associated to higher density and a reduced number of impurities, flaws,
and porosities. Among these, the factor that contributes the most for
the increased translucency of Y-TZP is the crystalline grain size.
Grain size is the microstructural property that is more directly
related to the control of translucency and opacity of polycrystalline
ceramics. Initially, the creation of ceramic materials with high translu-
cency was possible by promoting the increase of the crystalline grain
b3252_Ch-06.indd 154 27-11-2018 03:00:00 PM

Figure 2. Image representing the interaction of light with the Y-TZP

microstructure. The light path is represented by the blue arrows, and red
ellipses show the regions of grain boundaries where refraction and scattering
of light occur. The final light intensity is lower due to reflections and scatter-
ings suffered during transmission
size during sintering.27 Larger grains lead to a reduction in the num-

ber of grain boundaries, and consequently less scattering (Figure 2).
However, for Y-TZP, it is known that a larger crystal grain size
directly reflects a decrease of its mechanical properties and loss of the
stability of the tetragonal phase. Therefore, increasing the grain size
of Y-TZP is not a viable option to improve its translucency.
An alternative to increase the translucency of Y-TZP is to decrease
the grain size down to a level that can mitigate the influence of the
birefringence phenomenon and thus generate a less opaque mate-
rial.28 Birefringence occurs in Y-TZP due to the large amount of
tetragonal crystal phase (>90%), which is a crystal that has different
refractive indexes according to space orientation in the microstruc-
ture. This anisotropic behavior of the refractive index causes signifi-
cant scattering of the light when it is transmitted through the
material.
Studies have shown that decreasing the grain size also decreases
the birefringence influence of anisotropic structures, thus increasing
b3252_Ch-06.indd 155 27-11-2018 03:00:01 PM

the translucency.23,24 This technique is still under development, since

there is no ideal mathematical model for Y-TZP to define the correct
grain size that eliminates the large birefringence of the tetragonal
crystals of zirconia. However, it is believed that to achieve a translu-
cency close to the one presented by feldspathic porcelain, the grain
size should be around 120 nm.29 Currently, it is not possible to obtain
a Y-TZP piece with such a small grain size using conventional fur-
naces. Nevertheless, by reducing as much as possible the grain size of
the Y-TZP for monolithic restorations (Table 1) and decreasing the
amount of sintering additives, it is possible to achieve a significant
improvement in the translucency. Figure 3 shows photomicrographs
obtained by scanning electron microscopy of the microstructures of
monolithic restorations by Y-TZP and conventional Y-TZP, showing
the size of the crystalline grain of each material.
One of the most accepted ways to measure the translucency of a
material is by means of the translucency parameter.30 The translucency
parameter is the color difference measured for one material when it is
placed first on a white background and then on a black background;
to calculate this difference, the color of the material is measured based
on reflected light (reflectance). Hence, the translucency parameter
indicates the influence of a background color (black or white) on the
final color of a material. A material that is highly opaque will show
small values of color difference in the above-mentioned condition,
Table 1. Mean diameter (Feret) of the crystalline

grains of conventional and monolithic restorations
Y-TZPa
Mean ± Standard
Material deviation (nm)
Conventional Y-TZP 700 ± 270
(Cercon Zircônia, Dentsply)
Y-TZP for monolithic restoration 550 ± 210
(Lava Plus, 3M ESPE)
Note: aValues obtained based on 800 crystalline grains measured
on three specimens of each material.
b3252_Ch-06.indd 156 27-11-2018 03:00:01 PM

(a) (b)
Figure 3. Photomicrographs obtained by scanning electron microscopy of

the microstructure of Y-TZP suitable for monolithic restorations (a) and
conventional Y-TZP (b), showing the size of the crystal grain at a magnifica-
tion of 20,000×
i.e. the material has a high masking ability. When the material is very
translucent, the color difference will be large, indicating that the back-
ground color has greater influence on the final color of the material.
Knowing this concept, it is expected that higher values of translucency
parameter will be observed for monolithic Y-TZPs than for conven-
tional Y-TZPs. In pieces with thicknesses close to that used in mono-
lithic prosthetic restoration (1 mm), the translucency parameter values
measure in conventional Y-TZPs are approximately three units higher
than those measured for monolithic Y-TZPs.31 This difference of three
units may seem insignificant on a scale from 0 (fully opaque material)
to 18.1 (translucency parameter of human tooth enamel).32 However,
scientific studies on optical properties showed that the human eye can
see variations of translucency (i.e. color differences) in dental ceramics
restorations when differences in the range of two units are obtained.33
Table 2 shows approximate values of translucency parameter measured
for thicknesses of 1 mm of dentin and enamel, a Y-TZP brand suitable
for monolithic restorations, and two Y-TZP brands indicated for fab-
rication of fixed dental prostheses infrastructure.31
In addition to Y-TZP for monolithic restorations, other materials
are emerging in the market as a result of the association of tetragonal
b3252_Ch-06.indd 157 27-11-2018 03:00:03 PM

Table 2. Translucency parameters of human

teeth structures in comparison with different types
of Y-TZPs31,32
Translucency
Material parameters
Dental enamel 18.1
Dentin 16.4
Y-TZP for infrastructures 5.5
(Cercon Base, DeguDent GmbH)
Y-TZP for infrastructures 10.5
(Lava Standard, 3M ESPE)
Y-TZP for monolithic restorations 13.5
(Lava Plus, 3M ESPE)
zirconia with cubic zirconia crystalline phase. Such material cannot be

called yttria-stabilized tetragonal zirconia polycrystals (Y-TZP),
because a most of its microstructure is composed of cubic zirconia
(>25%).34 Cubic zirconia provides aesthetic advantages for monolithic
restorations because it has an isotropic refractive index. In other
words, its cubic crystal shape keeps the same refractive index regard-
less of its spatial orientation in the structure. However, if on one hand
the cubic zirconia promotes an aesthetic advantage to the m aterial, on
the other hand it promotes a decrease in mechanical properties.
3.2. Mechanical Properties

As mentioned earlier, Y-TZP has excellent mechanical properties
when compared to other ceramics. The most clinically relevant prop-
erties to be considered are: flexural strength, fracture toughness, and
hardness. The flexural strength of conventional Y-TZP is one of the
highest amongst all dental ceramics.35 The Y-TZP for monolithic res-
torations also has a good flexural strength, which is similar to that of
conventional Y-TZP.36 Table 3 shows the main mechanical properties
for the two kinds of Y-TZP.
As shown above, the Y-TZP has high hardness compared to
enamel (~3.2 GPa)38 or feldspathic porcelain (~4.5 GPa),39 and this
b3252_Ch-06.indd 158 27-11-2018 03:00:03 PM

Table 3. Main mechanical properties of conventional and suitable–for-

monolithic restorations Y-TZPa,37
Flexural Fracture toughness Hardness
Material strength (MPa) (MPa·m1/2) (GPa)
Y-TZP for infrastructures 990 3.63 12.88
Y-TZP for monolithic 1,416 3.24 13.11
restorations
Note: aValues obtained for pieces manufactured using ceramic powders from Tosoh Corporation.
Large variations in these properties can occur between among the brands available.
property along with others is directly related to the potential of the

material to wear the opposing tooth. In general, all ceramic prosthe-
ses are not indicated for patients with parafunctional habits, such as
bruxism, because these restorations have a high potential for antago-
nist tooth wear.40 An exacerbated antagonist tooth wear can com-
promise the entire occlusion balance of a person and cause serious
future complications.41 Nevertheless, despite the high wear potential
of Y-TZP, the scientific literature shows that monolithic restorations
with good surface finishing do not cause significant wear of the
antagonist dentition.
Other factors that have direct influence on the wear process are:
the type of food being processed, the individual chewing pattern, the
salivary properties (e.g. acidity), and the surface roughness of the
restorative material. The property that proved to be more directly
linked to antagonist wear was the restoration surface roughness.37,38
A monolithic Y-TZP restoration has good surface finishing and prob-
ably will not wear significantly the antagonist element. However, fol-
lowing up these Y-TZP restorations is important because if there is a
surface quality loss their wear potential will increase due to its high
hardness.
4. Fatigue of Dental Ceramics

Despite the excellent mechanical properties of Y-TZP, there were
many doubts regarding the possibility of achieving success with this
material in dentistry, as it showed a high failure rate in the medical
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field. A literature review published in 2006 showed that, in 2001,

approximately 400 femoral head prostheses (hip joint implant) frac-
tured in a short period of time, causing a drop of more than 90% in
Y-TZP implants sales for a specific brand (Prozyr) between 2001 and
2002.42
When zirconia is applied in an organism, i.e. exposed to tempera-
tures near to 37°C and to moisture, aging occurs by slow transforma-
tion of the tetragonal superficial grains to monoclinic phase due the
presence of water or water vapor and this phenomenon is called low
temperature degradation (LTD). The transformation starts on iso-
lated grains at the surface by a stress corrosion mechanism, and this
initial transformation of a specific grain may be related to its lower
yttria content, a specific surface orientation, the presence of residual
stresses, or the presence of cubic phase. This transformation is
induced by the reaction of water molecules with zirconium oxide,
leading to the formation of hydroxides on the crack surface. The T-M
grain transformation leads to an increase in volume, inducing stresses
around it and resulting in the microcrack formation. These cracks
allow more water to penetrate into the material structure, leading to
additional grain transformation, and generating more cracks with
subsequent increase in surface roughness and degradation of the
mechanical properties.42
An important aspect to be considered when studying the fracture
phenomenon in dental ceramics is the fact that clinical failures are
usually related to a fatigue process. The fatigue failure occurs after the
material has been subjected to stresses of lower magnitude than those
related to the static fracture strength of the material. Fatigue is a pro-
cess involving nucleation, propagation, and coalescence of cracks.43,44
An important phenomenon that is observed in ceramic materials
subjected to fatigue is the subcritical or slow crack growth (SCG).
This phenomenon is caused by the interaction of water with the
ceramic material on the tip of cracks that are under stress. In the pres-
ence of stresses below a critical level, the water causes hydrolysis of the
metal oxide of the material, resulting in a stable growth of these
cracks.45 SGC is extremely sensitive to the load applied to the struc-
ture and also depends on the ambient humidity, temperature, and
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other external variables, which means that under suitable conditions,

defects can grow for some time until they reach a critical size, leading
to catastrophic failure.46,47 The oral environment presents many ele-
ments that favor SGC in ceramic restorations, such as water present
in saliva, mastication forces that generate subcritical stresses, tempera-
ture around 37°C, and pH variations. SCG can be characterized by
the stress corrosion coefficient (n), which is dimensionless and indi-
cates the susceptibility of the material to the growth of defects that
lead to failure. Once the value of n is known, it is possible to predict
the degradation in strength of the materials subjected to SCG.
Therefore, high values of n indicate less susceptibility to SCG.43
The fatigue behavior of ceramic material can be characterized
using direct or indirect laboratorial tests. Direct methods are not very
popular for testing dental materials due to their complexity and the
necessity of using large specimens. For these reasons, the indirect
methods are the most used, and they are based on classic flexural
strength tests.43 The most used techniques are the dynamic fatigue,
static fatigue, and cyclic fatigue tests.48
A widely used method to determine SCG parameters in ceramic
materials, without performing direct measurement of crack growth is
the dynamic fatigue test. This is the preferred test method because it
allows an estimation of lifetime in a less subjective way than those
obtained by the measurement of the crack; in addition, the defects
and fractures simulated by this method are more clinically relevant.43
Using the dynamic fatigue test, it is possible to determine the SGC
parameters. The cyclic fatigue test allow the determination of SCG
parameters, the fatigue resistance, the lifetime, and the fatigue limit of
the material.
In general, in cyclic fatigue tests, stresses are applied repeatedly and
regularly. The generated stresses can be axial (tension-compression),
flexural, or torsional. There are three types of cyclic stresses. The
reverse cycle is represented schematically by a regular sinusoidal time-
dependent curve, which has a symmetric amplitude, i.e. the alterna-
tion of maximum tensile stress values to the minimum compression is
of equal magnitude. When repeated stress cycles are applied, maxi-
mum and the minimum stresses are asymmetric in relation to zero.44
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Another way to study the dental ceramic fatigue behavior is using

chewing simulators to assess the strength degradation of these materi-
als after mechanical cycling. During simulation of mastication, the
application of low loads in a 100% humidity environment may trigger
subcritical growth of defects similar to what occurs in the restoration
function in the oral cavity.
Reproducing the factors involved in the chewing process is rela-
tively difficult, and the first simulators had as main objective to
reproduce the chewing dynamics, but they were not designed to test
dental materials under fatigue. In 1968, a device comprising a num-
ber of steel wires was developed, in which the load was applied to
simulate the muscular strength generated during mastication. The
machine was activated by an electric engine that moved two antago-
nistic stone models. In this device, the direction of force application
was a major concern, as the objective was to recreate the jaw open-
ing and closing dynamic.49 Another study used a dry human skull
instead of stone models to analyze the influence of stresses gener-
ated during chewing on bone growth.50 The introduction of com-
puterized finite element models represented an evolution in this
field, as it allowed the simulation of the dynamics involved in chew-
ing for various purposes, such as analysis of the influence of muscle
stresses caused by chewing on the bone surface growth, distribution
of masticatory forces on the jaw and muscle movements during
mastication.51–53
With the evolution of chewing simulators, scientists developed
machines that allowed the mechanical cycling of dental restorations
in vitro with the ultimate goal of aging dental materials. These devices
were seeking to recreate the oral environment by using parameters
such as masticatory loads, direction of applied forces, cycles frequency,
presence of moisture, and temperature around 37°C. An example of
such a simulator is the ACTA equipment, developed at the Dental
College of Amsterdam (ACTA Academisch Tandheelkunde Centrum
Amsterdam), which is composed of two wheels that rotate in oppos-
ing directions, one that contains the specimens and the other acts as
the antagonist.54
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There are more sophisticated simulators that allow both wear, due
to sliding between two surfaces, and the application of loads in the
vertical axis. Thus, antagonist pistons will apply the load, while a
lower support, which contains the specimen, performs horizontal
movements, compatible with sliding surfaces during mastication.55–57
These simulators also allow adjustments in its structure in order to
make the most accurate simulation of the elements present in the oral
cavity, such as use of natural teeth as antagonists and use of materials
that simulate the periodontal tissue during loading.
The “Alabama machine” (University of Alabama, USA) can gen-
erate localized or generalized wear. This machine uses springs for load
application (maximum 200 kg). The Munich Artificial Mouth devel-
oped in the Ludwig Maximilians University Munich, is a machine
driven by pneumatic cylinders that apply sliding force (linear distance
of 8 mm) between specimens and antagonists. The OHSU machine,
developed at Oregon Health and Science University in Portland
(USA), uses human molars cusps that are processed to acquire the
shape of spheres with 10 mm diameter. These cusps are pressed
against the specimens with a slurry composed of a mixture of poppy
seeds with PMMA beads (polymethyl methacrylate). First, a 50 N
load is applied on the specimen, with a linear sliding of 8 mm, yield-
ing an abrasive wear and after a static load of 80 N is applied to cause
localized wear. Another machine developed by Zurich University also
uses cusps of maxillary molars as antagonists and applies loads of 50
N with a frequency of 1.7 Hz. In this case, the cusps are pressed
against the specimen surfaces, which are mounted over a rubber base,
with an angulation of 45°, allowing sliding between the surfaces.
Some chewing simulators models do not promote sliding of
antagonists or samples, and therefore were not initially designed for
wear tests. In these machines, the specimens are attached to a base and
the load is applied by pistons that perform vertical movement by
pneumatic system. These devices allow adjustments for cycling with or
without load impact between the piston and the specimen.58 The use
of chewing simulators may be considered a great resource to evaluate
the strength degradation of ceramic materials after in vitro aging.
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5. Y-TZP for Dental Implants

5.1. Tissue/Implant Interfaces
Biomaterials used as implants should interact with the human body,
and this interaction will promote a response from the body. The
interaction depends on factors associated with tissue (type, age,
health, blood circulation) and factors associated with the implant
(composition, surface morphology, porosity). Thus, there are four
different types of response to the interaction/interface/reaction
implant tissue59:
 Toxic: cells that are nearby and touch the implant die.
 Biologically inert: a fibrous capsule is developed around the
implant. The fibrous tissue formed has the objective of isolating
the implant from the rest of the body. Metals, ceramics, and poly-
mers can produce this type of response.
 Bioactive: a bond occurs at the interface between the implant and
the tissue. This type of interaction prevents the implant from mov-
ing and mimics the type of interface that is formed when natural
tissues are repaired.59
Another important concept is the biocompatibility. A biocompat-

ible biomaterial is one that has the ability to obtain an appropriate
host response in a specific application. This definition emphasizes that
biocompatibility is not only the lack of toxicity, but is also related to
the fact that the biomaterial should perform its function properly.
Depending on the application, the same biomaterial may or may not
be considered biocompatible.59,60 For example, feldspathic porcelain is
biocompatible when applied as a laminate veneer. But if it is used as a
dental implant material, it would not be considered biocompatible,
since its mechanical properties are not sufficient for this function.
5.2. Titanium Implants

Dental treatments involving implants have brought many solu-
tions for the oral rehabilitation of edentulous patients and also a
b3252_Ch-06.indd 164 27-11-2018 03:00:03 PM

considerable improvement in their psychosocial characteristics.61

The success of an implant can be influenced by several factors, such
as its diameter, length, surgical technique, patient health, and
biomaterial.62
In implantology, the biomaterial most commonly used to replace
the lost tooth root is titanium (commercially pure titanium or tita-
nium alloy, Ti‑6Al‑4V), which has excellent biocompatibility and high
mechanical properties.61,63 There is a very large number of clinical
studies that followed this biomaterial for periods that exceed 10 years
and showed a success rate higher than 90%.61,64,65
Despite the good results in these clinical trials, in some clinical
situations titanium implants cannot yet fully satisfy the patients’ aes-
thetic expectations. This is due to an inherent characteristic of tita-
nium, which is its grayish color. The dentist must evaluate each
clinical case carefully, and during planning of the oral rehabilitation he
should discuss with the patient about this topic. The grayish color of
titanium implants may compromise the final aesthetic result in two
ways: (a) with time, due to gingival recessions, the implant can be
exposed and dark areas start to appear, and (b) change of gingival
color, since the darkened color of the implant may appear by transpar-
ency through the peri-implant tissues in patients with thin gingival
biotype. This problem is more serious in treatments involving ante-
rior teeth and in patients who show a large area of the gum in their
smiles.66–68
Another disadvantage of using titanium is related to allergic
responses reported in the literature. The descriptions of these cases
show that hypersensitivity to titanium is a possible reason for the fail-
ures observed in some rehabilitations. However, there is a lack of
epidemiological data on the incidence of hypersensitivity to titanium,
and it is known that millions of patients have been rehabilitated with
titanium implants and had no allergic reaction.69,70
5.3. Y-TZP Implants

Yttria-stabilized tetragonal zirconia polycrystals (Y-TZP) have white
coloration, and is one of the main alternatives to titanium for
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treatments involving implants with great aesthetic requirement. The

feature that allows the application of Y-TZP in implantology is its
relatively high fracture toughness (KIc), which is greater than those of
all other dental ceramics and is associated with the toughening mech-
anism known as martensitic transformation.
Companies that produce Y-TZP implants try to convince clini-
cians of the fact that patients are increasingly demanding more aes-
thetic treatments, and that this growing demand would be fulfilled by
ceramic implants. Research carried out in Europe shows that more
than half of the patients (53%), when asked what biomaterial they
would prefer for rehabilitation with dental implants, responded that
they do not know which biomaterial is the best. But among those
who have a preference for a biomaterial, the number that prefer a
ceramic implant (35%) is 3.5 times higher than the number of patients
who prefer metallic implants (10%).
Studies in vitro and in vivo showed that the surface of the Y-TZP
is less susceptible to adhesion of bacteria from the oral flora when
compared with titanium.71–73 However, some studies have recently
shown that Y-TZP and titanium have similar responses in relation to
bacteria colonization.74–75
It should be emphasized that the Y-TZP is classified as a bioin-
ert material. A bioinert material has a weak interaction with the
surrounding living tissues.76 In implantology, low bioactivity
adversely affects the osseointegration process and can lead to
implant failure. Surface modifications are used to overcome this
feature and may be performed in different ways, such as acid etch-
ing, lasers, coating with calcium phosphate ceramics, or micropat-
terned silica thin films. The goal is to promote better and faster
osseointegration.77–80 In fact, Y-TZP implants with different surface
treatments showed similar levels of osseointegration compared to
titanium implants.81
There are few studies in the literature using the Y-TZP implants,
and they did not follow-up patients for more than 5 years. One
study followed 831 Y-TZP implants for a period of 5 years,
observing a success rate of 95%.8 Another study followed 170

Y-TZP implants for 3 years and showed a success rate of 82%.83
b3252_Ch-06.indd 166 27-11-2018 03:00:03 PM

One work followed 20 implants in aesthetic areas for a period of

4 years and had a success rate of 100%.67 There is clearly a lack of
long-term scientific evidence to justify the use of ceramic oral
implants. The existing studies show that Y-TZP has a great poten-
tial to be a very interesting alternative to titanium for selected
clinical cases. Therefore, clinicians must wait for additional clinical
trials that can bring more long-term results regarding Y-TZP
implants.84
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Re, D. Int. J. Dent. 2014, 2015, 415029.
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Ferencz, J. L.; Silva, N. R. 2012, 7, 396–417.
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100 (5), 344–347.
70. Siddiqi, A.; Payne, A. G.; De Silva, R. K.; Duncan, W. J. Clin. Oral
Implants Res. 2011, 22 (7), 673–680.
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Periodont. 2004, 75 (2), 292–296.
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de Albuquerque Junior, R. F.; Ribeiro, R. F. Clin. Oral Implants Res.
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b2530_FM.indd 6 01-Sep-16 11:03:06 AM

Chapter 7
Lithium Disilicate-Based Glass-Ceramics
Rodrigo França
Department of Restorative Dentistry, University of Manitoba,
780 Bannatyne Ave., Winnipeg, Canada
Rodrigo.franca@umanitoba.ca
Among dental ceramic restorations, the glass-ceramics group has

been improving the quality of the services provided by dentists.
Within this group, lithium disilicate-based glass ceramic has gained
much popularity in recent years. The focus of this chapter is to dis-
cuss the contribution of lithium disilicate-based glass-ceramics for
dental applications. The goal is to provide fundamental information
to dental researchers about chemical composition, nucleation and
crystallization mechanisms, and microstructure. In addition, physical
and chemical properties and biocompatibility issues are reviewed.
1. Introduction
The development of glass-ceramics in the second half of the 20th
century brought a great benefit to several areas of the ceramics field,
dentistry included. Different from a normal glass, which has an amor-
phous structure, or conventional sintered ceramics, which undergo
spontaneous crystal growth, glass-ceramics display a glassy matrix
173
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where a controlled crystallization process can convert about 99.5% of

the glassy phase into crystalline phase.1–3 This crystallization process
provides several properties that explain the success of glass-ceramics,
such as a very low amount of porosity (sometimes 0% porosity), work-
ability (they can be molded as glass, pressed, milled, or sintered), and
their final physical structure can be fully engineered for a particular
application.3
1.1. Historical
This elegant class of materials was discovered accidentally by
Dr. Stanley. D. Stookey, in 1953, when he worked in the field of pho-
tosensitive glasses at Corning Glass, Inc.4 According to him, his inten-
tion was to produce a lithium silicate glass able to carry a photographic
image. By accident, he permitted the oven temperature to reach
850°C instead of 450°C. To his surprise, inside the oven he saw a
solid white material that had not melted, as expected. When this
sample was removed from the furnace, it fell on the ground. The
sample not only did not break like glass, but produced a “metallic
sound”. He called this new material Fotoceram and latter Pyroceram.
Since then, more than 2,000 patents were granted on glass-ceramics
only in the USA, and many products were produced using glass-
ceramics, such as cookware, telescope mirrors, and missile’s
noisecones.3,5
In dentistry, several glass-ceramics compositions have been used
for dental restorations, as shown in Table 1. The first glass-ceramics
were leucite-based sintering ceramics, used for veneering metallic
structures, and mica used for inlays and crowns. Both materials
brought advances to the restorative technique. First, the leucite
crystal formation (KAlSi2O6) permitted feldspathic porcelains to
achieve a coefficient of thermal expansion (CTE) compatible to the
metal core, and also improved optical and mechanical properties.
Second, mica-based ceramics (KMg2.5Si4O10F2), like the Dicor
systems, launched new concepts to produce monolithic all-ceramic
restorations using either centrifugal casting technique or machining
technologies (CAD/CAM).5,6
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Lithium Disilicate-Based Glass-Ceramics 175
Table 1. Some glass-ceramics materials used in dentistry

Crystalline phase Chemical formula Commercial brand
Mica KMg2.5Si4O10F2 Dicor*
Leucite KAlSi2O6
Lithium Disilicate Li2Si2O5 IPS e.max Press, Celtra Press
Lithium Meta/Disilicate Li2SiO3 / Li2Si2O5 IPS-e.max CAD, Suprnity
Note: *No longer available in the dental market.
Subsequently, lithium disilicate systems have provoked the interest

of many researchers. Dr. George V. Beall, a leader in this field, con-
ducted several projects at Corning Inc.7–9 In the early 1990s, his team
developed a lightweight and strong lithium disilicate glass-ceramic,
using compositions in the SiO2–Li2O–Al2O3–K2O–P2O5 system. At
about the same time, Dr. Wolfram Höland and collaborators,10 from
Ivoclar Vivadent AG, developed a similar composition, now called IPS
e.max Press,11 a glass-ceramics with blade-like crystals, which could
produce dental restorations by molding process.5,9 Subsequently
Dr. Höland’s team12 produced an improved lithium disilicate glass-
ceramic with rod-like crystals and excellent mechanical properties.
This product, called IPS e.max® CAD, can be easily machinable (using
CAD/CAM techniques) when it is in the lithium metasilicate phase,
and subsequently transformed to lithium disilicate on additional heat
treatment. More recently, other companies have launched their glass-
ceramics using: a) Zirconia-reinforced lithium silicate systems: Celtra®
Duo and Celtra® Press from Dentsply Sirona,13–14 and Vita Suprinity®
from Vita Zahnfabrik.15; b) Lithium aluminosilicate ceramic rein-
forced with lithium disilicate: Straumann n!ceTM, from Straumann.
Figure 1 displays fracture toughness values (SEVNB) from the
groups of glass-ceramics in Table 1. Lithium disilicate-based glass-
ceramics appear to satisfy most of the requirements for a metal-free
dental crown or small bridge, with more than 90% of success rate.
This fact may explain, for example, the success of lithium disilicate
glass-ceramics (Empress® 2/ IPS e.max® systems), which produced
more than 45 million dental restorations since 1991.3,6,9,16
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Figure 1. Fracture toughness values (SEVNB) for dental glass-ceramics

listed in Table 1. Values according to the manufacturer
1.2. Classification
ISO 6872:2015 classify dental ceramics into two types17:
Type I: Ceramic products that are provided as powders, pastes, or

aerosols.
Type II: All other forms of ceramic products.
This standard furnishes a classification according to the clinical

use and the minimal flexural strength needed. Class 3 contains the
monolithic ceramic for single-unit anterior or posterior prostheses
and three-unit prostheses not involving molar restoration adhesive or
non-adhesive restorations.
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According to this norm, all lithium disilicate-based glass-ceramics

available on the dental market fit in Type II, because they are mono-
lithic, and Class 3, because their flexural strength reaches more than
300 MPa but not 500 MPa (as Class 4).
Lithium disilicate-based glass-ceramics can also be categorized
according to the processing to create dental restorations.
(a) Pressing: In this technique, a ceramic ingot is put into an oven,

where it reaches a viscous stage at ~850–920°C, and then is
forced to flow into a cavity in a refractory mold.5,18 Normally, the
ingot is composed of highly crystalline LS2 glass-ceramics, and
this procedure occurs in a dental technician’s lab, using the well-
known lost-wax technique.
(b) CAD/CAM: In this process, a ceramic ingot (partially or fully
sintered) is ground to shape the desired dental structure. The
computer-aided design (CAD) method is used to create a digi-
tal model of the restoration, and a computer-aided milling
(CAM) machine transforms the ingot into the final dental res-
toration. This procedure simplifies the work of the dentist and
the dental technician, and saves time for patients. Normally, the
procedure takes place chairside, and just one appointment is
needed. Restorations from partially sintered ingots (lithium
metasilicate) must be annealed to achieve the final crystalline
stage (LS2).
Lithium disilicate-based glass-ceramics can be ranked by their

compositions. The manufacturer and some authors have pointed out
that high percentage of zirconia (ZrO2) and or alumina (Al2O3) have
a major impact on the microstructure and, consequently, on the
properties of dental restorations. Currently, there are the conven-
tional lithium disilicate glass-ceramics, with ~2% ZrO2, the so-called
zirconia-reinforced lithium silicate ceramics, with ~10% ZrO2, and
the alumina-reinforced lithium silicate ceramics, with ~11% Al2O3.
Table 2 displays the commercial brand names, according to the pro-
cessing and the chemical composition.
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Table 2. Classification of commercial products a ccording

to processing and the chemical composition
Composition Pressing CAD/CAM
Low Zr and Al (%) e.Max Press e.Max CAD
High Zr (%) Celtra Press Celtra Duo
Suprinity
High Al (%) n!ce
2. Physicochemical Characterization
2.1. Chemical Composition
The chemical compositions of lithium disilicate-based glass-
ceramics can vary according to technical processing and manufac-
ture formulation. In Table 3, an approximate composition (Wt.%),
from manufacturer’s scientific reports are given for some
products.
These amounts provide little information on the chemical compo-
sition. To obtain a more accurate analysis, our research group has
analyzed those materials, using X-ray photoelectron spectroscopy
(XPS) for the surface atomic composition, and laser ablation ion cou-
pled plasma mass spectroscopy (LA-ICP-MS) for bulk atomic compo-
sition. The XPS results (%) are displayed in Table 4.
2.2. Mineral Properties

It is important to notice that, in the composition provided by
manufacturers, oxygen appears combined with other atoms, mean-
ing that silicon is the major component of glass-ceramics. Silicon
has been known to humans since pre-historical times, probably
because it is the second most abundant element on earth (indeed,
with oxygen, it represents 4 out of every 5 atoms present on earth’s
crust). Silicon, in the pure state, is very rare, and silicate is its more
frequent compound (~95%). Important crystalline silicates include
nesosilicates, sorosilicates, cyclosilicates, inosilicates, phyllosilicates,
b3252_Ch-07.indd 178 27-11-2018 03:02:14 PM

Table 3. Chemical composition (Wt.%) according to the manufacturer

IPS e.max® Vita Celtra Straumann
CAD suprinity® DUO n!ce®
SiO2 57–80 56–64 58 64–70
Li2O 11–19 5–21 18.5 10.5–12.5
K2O 0–13 1–4 — 0–3
P2O5 0–11 3–8 5 3–8
ZrO 0–8 8–12 10.1 0–0.5
Al2O3 0–8 1–4 1.9 10.5–11.5
MgO 0–5 — — —
CaO — — — 0–0.5
CeO2 — 0–4 2 —
Tb4O7 — — 1 —
Pigments — 0–6 — 0–9
Table 4. Atomic composition by XPS for CAD/CAM ceramics

e.Max CAD Celtra Duo Suprinity CAD Straumann n!ce
O 1s 51.5 44.4 45.1 49.1
Si 2p 26.4 17.8 19.7 25.5
Li 1s 11.8 27.4 24.1 11.6
C 1s 2.5 0.6 1.5 5.6
Al 2p 1.4 1.2 1.3 5.0
P 2p 2.1 0.5 0.7 0
Ca 2p 0.3 1.6 1.7 0.2
K 2p 0.7 0.3 0.3 —
Zn 2p 0.2 — — —
Y 3p 0.3 — — 0.2
Zr 3p 0.1 1.6 1.7 —
Sr 3p 0.3 0.2 — —
Ce 3d 0.1 0.3 0.2 0.3
Yb 4d — 1.5 1.5 —
N 1s — — — 2.2
F 1s — — — 0.2
b3252_Ch-07.indd 179 27-11-2018 03:02:14 PM

and tectosilicates. In lithium disilicate-based glass-ceramics, the

main silicate forms are:
(1) Lithium disilicate (Li2Si2O5 or LS2), a phyllosilicate form, a

layered silicate where Si shares three oxygen atoms with its neigh-
bors (Figure 2).19,20
(2) Lithium metasilicate (Li2SiO3 or LM), an inosilicate, single-chain
silicate (also called pyroxene). In this form, Si shares only 2 oxy-
gen atoms. It is a metastable phase present at a temperature
between 500°C and 800°C (Figure 2).
(3) Cristobalite (SiO2), a stable form of silica that is a tectosilicate,
also known as framework silicates. In this form, Si shares all
4 oxygen atoms.5,21
Lithium was first isolated from the sheet silicate mineral petalite,
LiAlSi4O10, and afterward, from spodumene, LiAlSi2O6.19 This alkali
metal was originally used as a flux in porcelain formulations and in
toughened glass production, as a Na ion exchange-strengthening
agent. Besides the types already mentioned, other lithium compounds
found on lithium disilicate-based glass-ceramics include lithia (LiO2),
present in the initial glass, and lithium orthophosphate (Li3PO4), an
inductor for LM and LS2 growth.22
Aluminum is frequently found in natural silicates (e.g. kyanite,
andalusite, mullite, sillimanite, and kaolinite). Kaolinite rocks produce
the well-known china clay or kaolin (Al2Si2O5(OH)4). Sillimanite and
mullite are also found in porcelain, as a refractory material, due to
their high melting points and chemical stability.5 Lithium aluminosili-
cates (LAS) can have two crystalline phases, b-spodumene and
b-eucryptite, and these phases have a low coefficient of thermal
expansion.9
Another compound that plays an important role includes phos-
phorus pentoxide (P2O5), which is added as the main nucleating
agent.21,22 Other nucleating agents include ZrO2, CaO2, and ZnO2.23
Ceria (CeO2) can work as a nucleation agent, and also produces fluo-
rescence, a desirable feature to mimic natural tooth.5
b3252_Ch-07.indd 180 27-11-2018 03:02:14 PM

Figure 2. Molecular representation of Li2SiO3 and Li2Si2O5
3. Fabrication
3.1. Nucleation Process
The control of the crystallization mechanism permits manufacturers
to design and produce glass-ceramics with desirable properties. The
main factor that rules crystal formation and growth is the nuclea-
tion process. Figure 3 schematizes the procedure (temperature/
time cycle) to obtain a glass-ceramic body.1
In the first step, a base glass is produced at high temperature by
melting the components. Then, the material is cooled to room tem-
perature. At this point, normally, the base glass is very homogeneous;
it can be completely amorphous or can contain very small crystals.
In the next step, the material is heated to a holding temperature, at
which the nucleation phase occurs. This phase can last 2 or 5 h. In the
final step, the nucleated glass is heated even more, to permit crystal
growth. The maximum temperature and the duration of this phase are
controlled by the manufacturer to increase the kinetics of growth of
all crystalline phases. This process can crystallize more than 90% of
the original glass. For instance, in dentistry, manufacturers provide
LS2 glass-ceramics for the pressing procedure, with approximate 70%
crystallinity.1,7,24,25
b3252_Ch-07.indd 181 27-11-2018 03:02:15 PM

Figure 3. Schematic temperature–time for the controlled crystallization of

a glass ceramic body. Adapted from Ref. [1]
Nucleation and crystallization processes are complex and have

been studied for several decades. Nevertheless, a mathematical model
able to describe the nucleation process is not yet available. Very often,
this process can result in various kinds of crystals and glasses instead
of only one kind of each. For that reason, it is very important to
understand the thermodynamics of the first nuclei, also called critical
nuclei, to determine how crystals are formed and how they were
grown. The mechanism of nucleation is often divided into two kinds:
homogeneous or heterogeneous. Nucleation can be initiated either at
the surface or into the volume of the glass. In the next sections, a
synthesis of all of these concepts is provided for dental researchers.
For further information, see Refs. [6–7, 25–33].
3.1.1. Homogeneous Nucleation

The formation of the critical nuclei in the base glass depends on the
formation of an interface between the two phases. Glasses are nor-
mally thermodynamically unstable. When the base glass is heated, and
the temperature reaches the glass transition range, the devitrification
b3252_Ch-07.indd 182 27-11-2018 03:02:16 PM

process starts. The kinetics are very complex, but the thermodynamic
driving force involves the increase of the Gibbs free energy of a very
small region (including its surface energy) for interface boundary
formation. In this mechanism, critical nuclei can be formed on the
surface or in the volume of the glass.1,5,8
3.1.2. Heterogeneous Nucleation

This kind of nucleation can be associated to foreign substrates, cata-
lytic agents, or grain boundaries different from the base glass.5 It is
the most frequent technique used for controlling crystal growing in
glass-ceramics, especially LS2 systems. Basically, it is expected that the
foreign nucleation agent produces a high interfacial energy with the
base glass. This can be obtained in different ways as detailed below:
(1) When the nucleating agent is a metallic substance with a different

coefficient of thermal expansion, a mechanical stress is produced
in the interphase, during the hitting process, with the base glass
increasing its Gibbs free energy. Ag, Au, Ce, and Pt have been
used as metallic nuclei in Li–Si systems.5,8
(2) Another technique for heterogeneous nucleation is the microim-
miscilibity approach, where oxides from Ti, Zr, P, Ta, W, and Fe
can form a microphase inside the base glass, promoting phase
separation. The increasing temperature provides the kinetic
energy for a primary crystal phase formation, which will lead to
the formation of additional crystal phases, including the main
crystalline phase.4–8,22,26
An example of using microimmiscility to achieve crystal growing

in lithium disilicate glass-ceramics is that described by Iqbal et al.30:
6(Si-O- +Li) + P2O5 = 2Li3PO4 + 3(Si–O–Si). (1)
When a lithium disilicate glass, containing > 2 mol% of P2O5,

reaches 500–560°C, the reaction described in Eq. (1) takes place,
forming lithium orthophosphate (Li3PO4) and cristobalite. Li3PO4
b3252_Ch-07.indd 183 27-11-2018 03:02:16 PM

Figure 4. The phase diagram of the Li2O–SiO2 system according to Ref.
[35]. Reprinted with the permission of Elsevier Science Publishers B.V
acts as heterogeneous nuclei and LM (metastable α’) and LS2 (b’)

start to form on its surface. These primary and intermediary phases
will subsequently contribute to the transformation of a stable crystal-
line phase of LS2 (Figure 4). Further, the addition of P2O5 provides
a volume nucleation process, which permits controlling of the crystal-
lization mechanism.22,30,34
3.2. Crystallization Process

Crystal growth process: Controlling the crystal growth of a multicom-
positional glass-ceramic such as lithium disilicate system is not sim-
ple. Indeed, all steps must be well managed by the manufacturer to
produce a glass-ceramic with intended properties. The mechanism
b3252_Ch-07.indd 184 27-11-2018 03:02:16 PM

depends on the temperature and the degree of supersaturation. The

thermodynamics of the nuclei/glass matrix interface will control the
kinetic and morphological development of the process.
There are different models to describe crystal growth. Lithium
disilicate glass-ceramic has a volume crystallization model, different
from the surface crystallization used in leucite glass-ceramics.34,36 As
shown in Figure 5, the volume model provides not only a high level
of lithium disilicate glass-ceramic crystallization but also a highly
interlocked crystal network. This crystalline pattern results in great
toughness and other desirable mechanical properties of the lithium
disilicate-based glass-ceramics systems.
Crystal growth with the deposition of crystalline overlayers on
foreign nucleation agents, called epitaxy, depends on several factors.
The most important of them is the close relations between the lattices
of the foreign nuclei and the forming crystal. The mismatch should
not be more the 15%.5,25 It also explains the fast LS2 crystallization
process, since Li3PO4 and Li2SiO3 are both orthorhombic crystals
with very similar lattice parameters.20
Figure 5. SEM image of e.Max press after etching with 5% HF
b3252_Ch-07.indd 185 27-11-2018 03:02:17 PM

The epitaxy of glass-ceramics with composition SiO2–Li2O–K2O–

Al2O3–ZrO2–P2O5 (IPS e.Max CAD) was well explained by Holand
et al.34 and other researchers.29,37–39 After the heterogeneous nuclei
formation described in Eq. (1), nanophases of Li2SiO3 and Li2Si2O5
begin to precipitate on the Li3PO4 crystal surface. Between 530°C
and 590°C, lithium metasilicate crystals grow with a dendritic shape,
but LS2 nanophase sites do not show any crystallization in this tem-
perature range. Li2SiO3 has maximum crystal growth above 750°C.
Above 780°C and until 820°C, the Li2SiO3 phase completely decom-
poses, and Li2Si2O5, the main phase, undergoes a rapid growth.
Furthermore, cristobalite undergoes a decomposition process below
820°C, as described in Eq. (2).
SiO2 (crystal) + Li2SiO3 (metastable phase)

= Li2Si2O5 (main crystal phase). (2)
4. Microstructure
4.1. Lithium Disilicate Glass-Ceramics
Lithium metasilicate (Li2SiO3), as an inosilicate, have a single chain
structure. In addition, Li2SiO3 epitaxial growth produces a dendritic
structure, with an orthorhombic crystal shape.5,22 Figure 6 displays a
SEM image from an IPS e.Max CAD ingot sample (blue block) after
etching with 5% HF.
In this intermediary stage, the Li2SiO3 ingot can be easily milled
by a CAD/CAM machine because its mechanical strength is lower
than the final LS2 phase.
After thermal treatment at 820°C, Li2SiO3 undergoes a transfor-
mation to Li2Si2O5 (Eq. (2)), which provokes a structural modifica-
tion of the crystalline phase. This transformation was well explained
by Zhang et al.39 and the mechanism is illustrated in Figure 7.
According to these authors, after the temperature reaches 820°C, the
dendritic structure of LM decomposes to rod-like crystals. As the Li/Si
molar ratio becomes lower than the base glass, Li+ ions migrate from
LM crystal to the glassy matrix and react with the silicate frame-
work, forming LS2. In addition, the LM structure probably tends to
b3252_Ch-07.indd 186 27-11-2018 03:02:17 PM

Figure 6. SEM image of e.Max CAD (blue stage) after etching with 5% HF
Figure 7. Mechanism transformation of LM to LS2 according to Ref. [39].

Reprinted with the permission of Elsevier Science Publishers B.V
b3252_Ch-07.indd 187 27-11-2018 03:02:18 PM

Figure 8. Phyllosilicate structure of the lithium disilicate crystal
reorient from the single chain structure to a phyllosilicate structure,

to become electrically neutral.
Figure 8 shows the final phyllosilicate structure of the lithium
disilicate crystal. It has a sheet structure, as in 2 monoclinic cell, with
a mass of 105.05 Da.5,20,40
Our research group found that, at the nanolevel, after the thermal
transformation, the LS2 crystal presents a “corn-like” shaped struc-
ture, as shown in Figure 9. The presence of rod-like LS2 crystals,
about 60 nm in diameter, confirms the formation of two kinds of LS2
crystals, as hypothesized by Zhang et al.39
4.2. Zirconia-Reinforced Lithium Silicate

Glass-Ceramics
Zirconia dental ceramic (Y-TZP) is known for its high toughness and
flexural strength. However, the formation and the cementation pro-
cesses of YTZP are not simple as glass-ceramics-based dental restora-
tions. In 2016, a new monolithic glass-ceramic was released onto the
dental market, claiming to be zirconia-reinforced lithium silicate (ZLS).
These products were developed by Degudent GmbH and the
Fraunhofer Institute for Silicate Research ISC, and they go by the
brand names Suprinity (Vita) and Celtra (Dentsply).13–15,41,42 Suprinity
is a CAD/CAM monolithic glass-ceramics with a fabrication process
similar to IPS e.Max CAD. Celtra presents two different products;
b3252_Ch-07.indd 188 27-11-2018 03:02:18 PM

Figure 9. SEM image, high magnification of e.Max press after etching with
HF 5%. (100,000×). “Corn-like” structure of LS2 crystals
one can produce dental restorations by a molding process (Celtra

Press) and another, a machinable one (Celtra Duo). Different from
Suprinity and e.Max CAD, Celtra Duo does not need an additional
thermal treatment after being milled in a CAD/CAM machine.14,37
There are few data available on the physicochemical characteriza-
tion, nucleation process, and microstructure of these new products.
However, manufacturers advertise that ZLS glass-ceramics contain
approximately 10% ZnO2 by weight. According to them, zirconia
works as a nucleating agent to produce four to eight times smaller
crystals than LS2.13 These small crystals would create an “ultra-fine”
microstructure, responsible for optimal mechanical and optical prop-
erties.13–15,42 Figures 10 and 11 present SEM images of Celtra Duo
and Suprinity, respectively.
Belli et al.37 using Raman spectrometry and XRD, reported the
presence of Li3PO4, Li2SiO3, and Li2Si2O5 in Celtra DUO and
Suprinity. They suggested that ZrO2 is present only dissolved in the
glass matrix and is not present in the crystal structure.37 Another
b3252_Ch-07.indd 189 27-11-2018 03:02:18 PM

Figure 10. SEM image of Celtra DUO after etching with 5% HF
Figure 11. SEM image of Suprinity after etching with 5% HF
b3252_Ch-07.indd 190 27-11-2018 03:02:19 PM

study,43 using XRD, showed Suprinity also has aluminum silicate and
tetragonal zirconia.
Related to the crystallization process of ZLD glass-ceramics, Belli
et al.37 noticed an increase of peak intensity for Li3PO4 and Li2SiO3
after thermal treatment at 840°C for Suprinity. This finding may indi-
cate a crystal growth of these phases that would contrast with the
process of conventional lithium disilicate glass-ceramics (IPS e.Max
CAD). They also detected a decreased intensity of the Li2Si2O5 peak
for Suprinity and Celtra Duo, compared with IPS e.Max CAD.
SEM images showed that after etching with 5% HF acid, Suprinity
and Celtra Duo display rod-like crystals, different from the needle-
like crystals found in LS2 samples.37,43 Apel et al.44 demonstrated that
a content of about 4% wt ZrO2 can prevent Li2Si2O5 crystal growth.
Our XPS and LA-ICP-MS results (Table 4) confirm a high content of
ZrO2 in both ZLS glass ceramics but no crystalline zirconia structure
was found by XRD.37
5. Properties of Lithium Disilicate-Based

Glass-Ceramics
In this section physical, chemical, and biological properties will be
discussed. The mechanical properties of lithium disilicate-based glass-
ceramics have been very well investigated. However, relatively few
data are available related to other important physical properties, such
as thermal, electrical, and optical. Even in some manufacturers’
scientific documentation, essential information is not available, which
underlines the importance of having independent dental scientists do
research on these issues.
5.1. Mechanical Properties

In Dentistry, the analysis of mechanical properties plays a major role
in selecting restorative materials.45 From the general practitioner’s
standpoint, having high fracture strength is considered fundamental
in dental ceramics. One reason for that is because a catastrophic
b3252_Ch-07.indd 191 27-11-2018 03:02:20 PM

failure of a ceramic restoration, under masticatory loading, could be

interpreted as malpractice by the lay patient. However, for a dental
material researcher, there are many other important mechanical prop-
erties which should be investigated, such as Young’s modulus, a
Weibull modulus, fracture toughness, hardness, tribological features,
and others.45,46 Only an analysis of the complete set of these properties
will bring a deeper understanding of the behavior of a dental ceramic.
The 6872:2015 ISO standard brings recommendations for
mechanical testing. For flexural test methods, only three-point bend-
ing, four-point bending, and biaxial flexure (piston-on-three-balls)
are accepted. According to this norm, the preferable number of
30 samples, with the requirement that all samples must be from the
same lot, should be observed.17
5.1.1. Fracture Strength

As brittle materials, glass-ceramics exhibit little or no plastic deforma-
tion before fracture. Different from ductile materials such as metals,
this ceramic never experiences necking or fatigue fracture by cold
working. A fracture of a glass-ceramics dental restoration is always a
result of the production and the propagation of a crack. The origin of
a crack can be explained according to Griffith47: “flaws in the materi-
als can act as stress concentrators and that the separation of surfaces
in fracture takes place sequentially rather than simultaneously across
the cross section”.1,48 In consequence of this theory, the fracture fail-
ure of a glass-ceramic depends on the probability of a Griffith flaw
initiating the crack under the specific stress. This probability could
explain why the spread range of fracture strength results from lithium
disilicate-based glass-ceramics found in the literature.16,45,49–57
Figure 12 displays the flexural strength of lithium disilicate-based
glass-ceramics from different research groups.
Static load-bearing test results are not easily correlated with the
clinical performance of ceramic restorations. The particularity of oral
environmental conditions is a major factor to contribute for the mis-
match between in vitro and clinical results. The effect of water, tem-
perature pH fluctuations, and cyclic loading can have a negative
impact in the mechanical behavior of glass-ceramics.
b3252_Ch-07.indd 192 27-11-2018 03:02:20 PM

Figure 12. Flexural strength of e.Max press using different testing meth-
ods. Adapted from Ref. [11]
In vitro cyclic fatigue tests have been introduced to fill this gap
because they try to reproduce intraoral conditions. However, the
lack of standards for cyclic fatigue testing and the different setups
preclude the possibility of comparing results from different articles.
Nawafleh et al.57 reviewing several studies on the fatigue resistance
of LS2 dental restorations, concluded that the range of loadings
(30–1400 N), the frequency of cycles (10.000–3.6 million), and
thermocycling (4–60ºC) do not reproduce the normal mastication
or the thermo-fluctuations inside the mouth. For more details about
cyclic fatigue tests, consult the following references.53,57–61
5.1.2. Young’s Modulus

The elastic modulus of a ceramic material connotes the force capable
of resisting the variations in the interatomic spacing when the struc-
ture is under loading. For one-phase ceramics, the elastic modulus can
also be correlated with the lattice energy.1 However, for two-phase
b3252_Ch-07.indd 193 27-11-2018 03:02:20 PM

ceramics, such as glass-ceramics, the elastic modulus reflects the inter-

relationship of the elastic moduli of both phases.62 The following
equations may be used to calculate the upper and the lower bounds
on the elastic moduli:
Eu = V2E2 + (1 − V2)E1,(3)
1/El = V2/E2 − (1 − V2)/E1,(4)
where Eu is the upper bond, and El is the lower bond, V2 is the volume
fraction of the phase with modulus E2, and E1 is the modulus of the
other phase. The first model, Eu, assumes that the strain is the same
in each phase, and the second model, El, assumes that the stress is the
same in each phase.1
Several studies have assessed Young’s modulus of lithium
disilicate-based glass-ceramics.37,38,43,54,58,63,64 As shown in Table 5, the
mean can fluctuate from 95 to 107 GPa. Some of these articles pre-
sent standard deviation values, such as those of Ivoclar Vivadent for
e.Max systems.11 Nevertheless, more studies are needed to determine
the elastic moduli accurately for multiphase ceramics, such as the LS2
and ZLS systems.
Table 5. Mechanical properties of lithium disilicate-based glass-ceramics

e.Max Celtra
e.Max Press CAD Duo Suprinity
Young’s modulus (GPa) 95 (± 5) 95 (± 5) 107.9¥ 104.9¥
Weibull modulus (MPa 2.64* 1.9* 5.5¥ 5.5¥
m1/2)
Fracture toughness 2.5–3 2.0–2.5 2.65 2.0
(SEVNB) (MPa m1/2)
Hardness (GPa) 5.5 7
Flexural strength (MPa) 400 (± 40)
Sources: Adapted From *Ref. [49] and ¥Ref. [37].
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5.1.3. Fracture Toughness (KIC)

The fracture toughness of a material indicates the ability of its struc-
ture to resist crack propagation. A dental ceramic with high fracture
toughness envisages good clinical performance.38,49,50,65 ISO 6872:
2015 and ASTM E1820-16 describe the standard test methods for
measuring fracture toughness. Diverse approaches have been used to
assess fracture toughness, among them the most common methods
are indentation strength, indentation fracture, single-edge V-notched
beam (SEVNB), compact tension, and chevron-notched short rod
(CNSR).50,65–67 Each method has advantages and limitations, and
some are technique-sensitive. Probably for that reason, the literature
reports different KIC values for the same lithium disilicate-based glass-
ceramics, as shown in Figure 13. (For further information about crack
propagation, fracture toughness, and Weibull modulus consult the
chapter on Fractography.)
Figure 13. Fracture toughness of CAD/CAM glass-ceramics from differ-

ent research groups
b3252_Ch-07.indd 195 27-11-2018 03:02:21 PM

5.1.4. Hardness
In lithium disilicate-based glass-ceramics, hardness testing is fre-
quently used to determine the resistance to deformation, densifica-
tion, and fracture.68 The measurement techniques commonly employed
in the dental literature are those of Vickers52,58,66,69 and Knoop.70,71
These hardness tests can have many pitfalls, especially when testing
polycrystalline materials, such as like glass-ceramics. Factors such as
crystal size, grain boundaries, the hardness of the glassy phase, and the
hardness of the crystalline phase may be responsible for the large scat-
ter of results.68,72 Nanoindentation testing has been introduced, in the
ceramic research field, as a powerful tool for providing more accurate
results.73,74 The small indentations used in this technique may be on
the order of 10 nm to 1 mm, and the loads may be 10–100 mN. The
nanoindentation technique can provide the Young’s modulus and the
hardness values continuously, along different crystalline phases of
lithium disilicate-based glass-ceramics.38,63,74 Figure 14 shows nanoin-
dentation results for some commercial products. For more informa-
tion, please consult the chapter on Nanoindentation.
Figure 14. Hardness values from nanoindentation tests
b3252_Ch-07.indd 196 27-11-2018 03:02:22 PM

5.1.5. Wear
Wear and other tribological properties are directly related to hardness.
Ideally, it is expected that restorative ceramic materials have wear rates
as low as that of natural enamel. Further, it is not suitable that they
cause attrition and abrasion of opposing teeth.58,75,76 In one study,75
the results of which are found in Figure 15, the wear rates of LS2 and
ZLS glass-ceramics showed no statistical difference from that of den-
tal enamel after 120,000 cycles. However, the author called attention
to a detectable reduction in the wear rates when Celtra DUO under-
goes the optional glaze step. Another in vitro study76 showed that
LS2 glass-ceramics increased the wear rate 1.7 times when the pH of
the solution decreased from pH 7 to pH 3. In another study, the
abrasion of LS2 glass-ceramic by toothbrushing was studied.77 The
authors pointed out that all the glass-ceramics studied had a reduction
of the superficial gloss by the high abrasivity of the toothpaste slurry.
Figure 15. Wear rate of lithium disilicate-based glass-ceramics compared

with enamel. Adapted from Ref. [75]
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5.2. Other Physical Properties

5.2.1. Density
The density of a glass-ceramic is mainly determined by the atomic
packing of the crystalline structure. A close-packed structure with
oxygen ions has a high density of atomic packing, and thus more
atoms per volume. In contrast, structures with simple cubic packing
of the oxygen atoms, e.g. SiO2, have low densities.1,5 Density of LS2
and ZLS glass-ceramics are ~2.6 g/cm3, and these values are less than
half, compared with 3Y-TZP materials (6 g/cm3).37 The Ultrasonic
Pulse Echo method or Density Functional Theory are normally used
for density characterization.37,64 However, the Archimedes method is
still used. This method consists of obtaining the mass the sample and
then dividing by the volume of water displaced. One study showed
lower density values for LS2 and ZLS when the Archimedes method
was used.43
5.2.2. Thermal Properties

Heat capacity, thermal conductivity, and the coefficient of thermal
expansion (CTE) are crucial properties of a dental ceramic. Heat
capacity, or thermal capacity, measures the amount of thermal energy
necessary to raise the temperature of the material by 1°C.78 ASTM
E1269-11 details the standard test method for determining specific
heat capacity, using differential scanning calorimetry. The measure-
ment of this property permits examining the difference between vitre-
ous and crystalline phases of glass-ceramics.78,79
Thermal conductivity is the amount of heat conducted through
the body per unit temperature gradient.1,5,8 It can be measured by
several techniques; one method that has gained popularity is the Laser
Flash Technique, which can also provide heat capacity and thermal
diffusivity data.80 The LiO2–SiO2 glass system (21–79 wt.%) has a
thermal conductivity ~0.901 Wm−1 k−1 at 30°C.81 More research is
needed to characterize the heat capacity and thermal conductivity of
the LS2 and ZLS dental glass ceramics, because these properties are
important in understanding thermal stresses in materials that need to
be annealed to obtain high mechanical strength.
b3252_Ch-07.indd 198 27-11-2018 03:02:23 PM

Table 6. Physicochemical properties of lithium disilicate-based

glass-ceramics
e.Max Press e.Max CAD Celtra DUO Suprinity
CTE (100–500°C) 10.55 ± 0.35 10.45 ± 0.4 12.3
(10−6 K−1)
Density (g/cm3) 2.5 ± 0.1 2.5 ± 0.1 2.62 ± 0.01¥ 2.58 ± 0.06¥
Linear shrinkage 0.2
during tempering
(%)
Chemical solubility 40 ±10 40 ±10 40
(mg/cm2)
Poisson’s ration 2.3 0.215¥ 0.222¥ 0.208¥
Notes: Data from manufacturer’s reports.

¥
Ref. [37].
The CTE expresses the amount of dimensional changing (volume

or linear) per degree of temperature change. It is expressed in the fol-
low equation:
∆l
α = (5)
l ∆T
In a ceramic structure, the specific volume of any given crystal

increases with temperature. As the vibrations of atoms increase,
the lattice energy increases, corresponding to a lattice expansion.
Thermodynamically, the internal energy in the ceramic lattice
increases but the entropy decreases.1,5,7 Lithium disilicate glass-
ceramics may have very different CTE values; depending on their
composition, the CTE can be near zero for cookware tools or near
10 × 10−6 k−1 for dental applications, as shown in Table 6.3,5,8,9
5.2.3. Optical Properties

Ceramic dental restorations were introduced in dentistry mainly
because they mimic the aesthetic features of natural teeth. Nowadays,
cosmetic properties are as important as mechanical properties, and
they are the principal demand and the first feature remarked on by
patients. On this issue, glass-ceramics for all ceramic restorations
b3252_Ch-07.indd 199 27-11-2018 03:02:24 PM

Figure 16. Clinical case showing six anterior laminates using lithium

disilicate-based glass-ceramics (Courtesy Dr. Carlos Francci, University of
Sao Paulo.)
were able to copy or even “outperform natural tooth structure”

(Figure 16).5 Nevertheless, optical properties, such as opacity, trans-
lucence, absorption, refractive index, dispersion, surface gloss, and
color have been barely studied for LS2 systems82–90 and minimally for
ZLS systems.91
5.3. Chemical Properties

Dental ceramics are considered more chemically stable than other
dental materials. However, they are not insoluble in oral fluids.92–94
The broad range of pH values (e.g. fruit juices at pH 2.0, soy beans
at pH 12) to which a dental ceramic is exposed can result in surface
corrosion.93 This chemical corrosion can increase surface roughness,
staining and biofilm attachment, and affect fracture strength.95
ISO 6872:2015 recommends a chemical solubility test in 4%
acetic acid at 80 ± 3°C for 16 h.17 The maximal chemical solubility
b3252_Ch-07.indd 200 27-11-2018 03:02:24 PM

permitted for a class 3 ceramic is < 100 mg/cm2. Table 6 shows that
the chemical solubility of the lithium disilicate-based glass-ceramic
assessed is < 50 mg/cm2, far below the standard limit. However,
clinical reports have mentioned patients’ complaints due to overglaze
degradation.93,96–98
5.4. Biocompatibility Issues

Nowadays, lithium has been used in several applications in engineer-
ing (e.g. glass-ceramics for cooking utensils, battery systems, etc.) and
medicine (e.g. as a drug for neurological disorders) besides dental
restorations. Issues related to the biosafety of these lithium-based
products have been raised in the literature.99–101 Further, the number
of cases of lithium-related diseases has increased over the last decades.
In Dentistry, some researchers have pointed out the potential release
of lithium ions from all ceramic restorations.93,102–105
The recommended daily intake of lithium is between 0.1 and
3.4 mg, but levels up 10 mg/day have shown no adverse effect on
human health.106 In medicine, drugs containing lithium salts have
been used since the 1940s for psychiatric treatment, notably for cases
involving bipolar disorder and depression.107 For patients with mild
bipolar disorder, the prescribed lithium dosage normally is between
200 and 400 mg/day but, in severe cases, it can reach 2000 mg/
day.108 Extensive research has been carried out on the collateral effects
of lithium-based drugs in medicine; due to the narrow therapeutic
index (0.6–1.5 meq/L), there is little space between therapeutic and
toxic levels.99,107,109 Neurological dysfunction is the most important
potential sequela of lithium intoxication; however, in these cases, the
lethal rate is lower than 1%.99 Table 7 displays some of these systemic
side effects for acute and chronic intoxication with lithium, according
to Ref. [106, 109].
Probably due to the excellent biocompatible results obtained
from feldspathic porcelains, dental researchers have presumed that the
new ceramics are not hazardous.102 Only a few studies have been pub-
lished on ion release from lithium disilicate-based glass-ceramics, and
in vitro cytotoxicity tests are even rarer.102,110,111 Reports have detected
b3252_Ch-07.indd 201 27-11-2018 03:02:24 PM

Table 7. Systemic effect of lithium intoxication according to Ref. [106, 109]
Symptoms of lithium intoxication
System Acute Chronic

Nervous Tremor, weakness, hyperreflexia, muscle twitching, may lead to
seizures or coma
Renal Urine concentrating defect Nephritis, nephrogenic diabetes
insipidus, renal failure
Digestive Nausea, vomiting, diarrhea
Cardiovascular Prolonged QT interval and Myocarditis
T-wave changes
the following ions from LS2 glass-ceramics on acid immersion tests:

potassium, silicon, aluminum, and lithium.92,103,105 Messer et al.
assessed the mitochondrial activity of fibroblasts in contact with den-
tal ceramics; they reported severe cytotoxicity for LS2 pressable glass-
ceramics.102 However, the authors recognized that their results could
not be extrapolated to clinical performance. Anusavice and Zang,103
studying glass-ceramics from the Li2O–Al2O3–CaO–SiO2 system,
detected a very low amount of lithium ion released, even under
lengthy storage conditions (pH 11 and 80ºC). They calculated that,
even assuming that someone has all his teeth crowned, the amount of
lithium ion released would be 1.2 mg/day.
Manufacturers recognized that dental technicians are those with
highest biological risk potential.11 Often, ceramic restorations need to
be ground and polished in dental labs; as a consequence, the dental
technician is exposed to the inhalation of fine dust that can contain
lithium and other minerals. Using protective masks and suction
equipment are a source of additional protection, which must be car-
ried out to avoid health issues.
Acknowledgments
The author acknowledges Dr. Edgar D. Zanotto and Dr. Edward
Sacher for reviewing this chapter. Also, thanks are due to the students
b3252_Ch-07.indd 202 27-11-2018 03:02:24 PM

Muna Bebsh, Ana Carla Carvalho Fernades, and Miguel França for
performing some of the experiments and for doing some of the art-
work. Thanks to Elsevier Science Publishers B.V. for allowing to the
use of some figures. This chapter was made possible due to the fund-
ing received from College of Dentistry Research Grant from the
University of Manitoba.
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b2530_FM.indd 6 01-Sep-16 11:03:06 AM

Chapter 8
Fractography of Dental Ceramics
Susanne S. Scherrer
Division of Fixed Prosthodontics-Biomaterials,
University Clinic of Dental Medicine, University of Geneva,
1, rue Michel-Servet, 1204 Geneva, Switzerland
susanne.scherrer@unige.ch
Fractography has a tremendous potential in providing to the clinical

and scientific community key information regarding failure analysis
of dental ceramic materials with respect to design issues, processing,
and handling. This chapter provides an overview of applied qualita-
tive (descriptive) and quantitative fractography to dental ceramics.
The most common fractographic features found in dental ceramics
have been illustrated and described. Qualitative fractography is
mainly shown for clinical fractured ceramic restorations, for which
key fractographic features have been identified for determination of
the crack propagation direction and the origin of failure. A system-
atic approach on how to analyze such clinical failures is further
described, including the use of in vivo replicas for securing valuable
fracture surface information of in situ remaining broken parts.
Quantitative fractography is applied on in vitro strength-tested
specimens, for which the critical crack is measured on the fractured
surface providing useful information regarding processing issues and
correlating with toughness estimates.
211
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1. Introduction
Fractography is described by the ASTM C1322 as the means and
methods for characterizing fractured specimens or components.1
It involves a meticulous surface failure analysis, searching on its frac-
tured surface specific crack features, indicating the overall crack
propagation direction, the final breakthrough zone, and pointing
back to the crack origin (flaw) or area in which fracture started.
It is applied to laboratory specimens with controlled fractured
conditions as well as to in-service failures. Fractography is part of
fracture mechanics and failure analysis to locate and characterize frac-
ture origins, crack sizes, and surface crack pattern and has been docu-
mented in several key standards1–3 and reference books.4–8 The ability
to read cracks and understand fractured surface are routinely used in
the field of mechanical engineering and R&D laboratories. It however
created an impact on the dental ceramic field only in the 1990 with
the very first papers published using fractography for clinically failed
ceramic parts.9–11 The major breakthrough of using fractography in
Dentistry occurred with the free e-book NIST Recommended Practice
Guide: Fractography of Ceramics and Glasses by George Quinn,5 for
which a second edition is now available and downloadable from
http://dx.doi.org/10.6028/NIST.SP.960-16e2. This book has pro-
vided the needed practical tools and guidance with a wealth of infor-
mation (over 500 illustrations) to perform good fractographic failure
analysis and includes many examples of dental ceramics.
Currently, a large variety of dental ceramic materials is available
with different chemical compositions (K, Na alumina-silicates, lithium
disilicates, alumina, zirconia), reinforcing microstructures (leucite,
sanidine, mica, fluorapatite, lithium disilicate, alumina, zirconia), and
fabrication process (i.e. porcelain-fused-to-metal, heat-pressing, glass-
infiltration, polymer-infiltration, layering and sintering, CAD-CAM of
ceramic blocs). Due to their chemical and microstructural differences,
fracture surface analysis can be quite challenging, and thus a good
knowledge of fracture surface features is needed. The type of ceramic,
mode of failure, processing in the laboratory, sintering schedules, coef-
ficients of thermal expansion (CTE), and ceramic surface treatments
b3252_Ch-08.indd 212 27-11-2018 03:02:37 PM

Fractography of Dental Ceramics 213
such as grinding or sandblasting, are important information when

analyzing a fractured surface. Most clinical fractures are often due to a
combination of negatively affecting factors which include ceramic pro-
cessing flaws, grinding damage, inadequate design, thermal residual
stresses in conjunction with mechanical loading, and localized exces-
sive contact wear. The careful analysis of fracture surface using micros-
copy will reveal a topography which contains characteristic fracture
surface features or patterns in relation to the fracture process helping
in tracing back to a fracture origin, usually a critical flaw.
This chapter will provide an overview of qualitative fractography
which identifies and describes fracture surface crack features tracing
back to the fracture origin site, as well as quantitative fractography,
based on critical flaw size measurements and fracture mechanics rela-
tionships for dental ceramics.
2. Qualitative Fractography
2.1. Key Fractographic Features
Qualitative fractography, also called descriptive fractography, is per-
formed on the fracture surface of broken parts to identify all charac-
teristic features regarding crack propagation and crack origin. There
are many fractographic markings that have been described for ceram-
ics and glasses.1,5 A selection of the most common fracture surface
features in dental ceramics is shown in Figures 1–11. The nomencla-
ture and definitions of fracture surface features (or markings) used
and described below are reproduced from the NIST Recommended
Practice Guide: Fractography of Ceramics and Glasses.5 Typical surface
crack features seen in ceramic parts that failed clinically such as hackle,
wake hackle, and twist hackle are radiating outward from an origin
(usually a critical flaw), indicating the crack propagation direction
(dcp). These features when closely monitored on the entire fractured
part will trace back to the fracture origin.
By definition, Hackle is a line on the surface running in the local
direction of cracking (dcp), separating parallel but non-coplanar por-
tions of the crack surface (Figure 1).
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Figure 1. Hackle (h) in a 3Y-TZP ceramic. The direction of crack propaga-
tion (dcp) is indicated by arrows. A couple of arrest lines are temporarily
stopping the crack front
Figure 2. Wake hackle in a veneering ceramic. The direction of crack

propagation (dcp) is indicated by an arrow
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Figure 3. Twist hackle (th) and dcp on a 3Y-TZP
Figure 4. Arrest lines and dcp on a 3Y-TZP
b3252_Ch-08.indd 215 27-11-2018 03:02:40 PM

Figure 5. Wallner lines (wl) and Gull wings (gw) shown in two fractured
surfaces of veneering ceramics. Figure (a) is a lower magnification of
Figure 3 showing Wallner lines (wl) twist hackle and an arrest line above
the Wallner lines. Figure (b) has many sequentially following ripples which
are Wallner lines (wl) and a few gull wings, emanating from pores and
often combined with a wake hackle
Figure 6. Fracture mirror centered around a surface flaw (origin) in a bro-
ken zirconia bend bar. Hackle are radiating from the mirror region outward
toward the compression zone. The direction of crack propagation (dcp) is
indicated by the black arrows
Wake hackle is a hackle mark extending from a singularity

(i.e. a pore, an inclusion) at the crack front in the direction of crack
propagation (Figure 2).
Twist hackle is a hackle that separates portions of the crack sur-
face, each of which has rotated from the original crack plane in
b3252_Ch-08.indd 216 27-11-2018 03:02:42 PM

Figure 7. Gold-coated specimen. Fracture mirror (m) centered around an

origin (o) which is a surface flaw in a broken zirconia bend bar. Hackle are
radiating from the mirror region
Figure 8. Load-to-fracture test and schematic of a zirconia bend bar bro-
ken in 3-point bending. A compression curl is easily recognizable as the crack
path deviates from its direction of crack propagation (dcp) while entering the
compression zone of the ceramic bend bar specimen
b3252_Ch-08.indd 217 27-11-2018 03:02:43 PM

Figure 9. Schematic of a fracture surface in a zirconia bend bar broken in

3-point bending. A compression curl together with a few arrest lines is recog-
nizable at the top. The direction of crack propagation (dcp) is indicated by
the black arrows. The failure origin is located on the opposite side which is
under tension
Figure 10. Compression curl in a clinically broken dental zirconia implant.

The direction of crack propagation (dcp) goes from right to left
response to a lateral rotation or twist in the axis of principal tension

(Figure 3). An arrest line is a sharp line on the fracture surface
defining the crack front shape of an arrested or momentarily hesi-
tated crack prior to resumption of crack propagation under a more
or less altered stress configuration (Figure 4). Wallner line, which
is a form of arrest line, is a rib-shaped mark with a wave-like con-
tour caused by a temporary excursion of the crack front out of plane
in response to a tilt in the axis of principal tension. It may also form
from passage of the crack front through a region with a locally
b3252_Ch-08.indd 218 27-11-2018 03:02:43 PM

Figure 11. Compression curl in a chip fracture of a feldspar-based veneering

ceramic in a porcelain-fused-to-metal crown. The compression curl is present
around the periphery of fractured surface as indicated by the dotted line. The
dcp goes from top to bottom, exiting at the compression curl. Excessive
occlusal contact pressure visible on the worn surface was responsible for
initiating and propagating the crack within the veneering ceramic
shifted stress field, as an inclusion, pore, or surface discontinuity

(Figure 5 (a,b)). Among the most common Wallner lines seen in
dental ceramics are Gull wings within glassy veneering ceramics
(Figure 5(b)). An arrest line is very sharp, whereas a Wallner line is
rather rounded in its contour. The crack origin is always located on
the concave side of an arrest line. It may however not be the critical
crack origin, which should be identified by mapping the crack
propagation direction over the entire piece based on the recogni-
tion of key crack features as will be shown in clinical examples of
fractured ceramic restorations.
A fracture mirror is a relatively smooth region surrounding
and centered on the fracture origin (Figure 6). Although mirrors
have been extensively documented for soda lime glass, they are
more difficult to see in polycrystalline ceramics,12 especially with
coarser microstructure, and dental feldspar-based porcelains.13 The
inherent roughness of the microstructure is dictating the smooth-
ness and light reflectivity of the mirror region surrounding the
origin. Figure 6 illustrates a mirror region surrounding a surface
b3252_Ch-08.indd 219 27-11-2018 03:02:44 PM

flaw in a 3Y-TZP dental zirconia bend bar which has an average

microstructure of 500 nm grain size. Both images are taken with a
stereomicroscope and lateral illumination to bring out the surface
roughness and the mirror smoothness. Gold-coated specimens may
help in the identification of a mirror using lateral illumination3,5
and optical microscopy. In Figure 7, an example of a broken bend
bar after gold coating is given when viewed under a stereomicro-
scope. The mirror is centered around the origin, which is a surface
flaw of the tensile side. Except for zirconia dental implants and
round-shaped connectors in bridge frameworks, mirrors will how-
ever rarely be seen in broken clinical dental ceramic restorations.
This is due to the 3D complex multilayered shape of the ceramic
restoration and often thin margins, which implies that the size of a
mirror would usually exceed the ceramic thickness at the fracture
origin site.
If bending is involved in the fracture process, then a compression
curl (also called cantilever curl) will be present in the form of a curl
(curved surface) just prior to the breaking through of the ceramic
component. An example is given in Figure 8 of a zirconia bend bar
undergoing flexural testing. The crack moves from the origin on the
tensile side to the compressive loaded surface, where it is slowed
down and changes direction (curve) before breaking through the
specimen. On the fracture surface (Figure 9), the compression curl is
easily recognizable by a curvature and arrest lines, which are often
visible next to a compression curl as the crack is slowed down when
entering the compression zone.
Compression curls are rather frequently seen in clinical failures
as a flexure component and is often part of the fracture process.
Figure 10 illustrates the fracture of a zirconia implant reconstructed
by a ceramic crown. The fracture surface as viewed under the SEM
shows a bend just before final breakage.
Figure 11 shows a veneering ceramic chip fracture with the
occlusal chewing side on top and a compression curl all the way
around the periphery. The schematic indicates the direction of crack
propagation based on an initial crack at the occlusal contact wear
b3252_Ch-08.indd 220 27-11-2018 03:02:44 PM

surface and the presence of the compression curl. Localized contact

pressure was responsible for this premature ceramic fracture in a
porcelain-fused-to-metal crown.
A fracture origin is the critical flaw from which fracture started.
It may be an inherent population of defects (also called flaws) due to
the processing parameters which include quality of the starting pow-
der (impurities), chemical composition, phase composition, particle
size distribution, state of agglomeration, granule forming (binders),
powder compaction (pressing parameters), homogeneity of particle
packing, granule friction (binders), sintering, green state machining,
partially sintered state machining, hard (sintered) machining and han-
dling (22). These defects vary in size, shape, distribution and orienta-
tion. They are either volume distributed from the fabrication process
(pores, large grains, microstructure heterogeneity, inclusions) or sur-
face distributed from surface treatment (precracks, edge chips,
machining scratches or grooves) (22). The material will fail when the
nominal strength is overcome by a defect concentrated stress peak.
Volume flaw origins are usually introduced during the processing
steps of powder compaction and sintering. The most documented
ceramic material in Dentistry is zirconia, as the fabrication route is
quite sensitive. The choice of the powder (purity, granules size),
pressing (compaction) procedure (static, isostatic in 2D or 3D, pres-
sure), sintering (debinding, sinter schedule, temperature, and time),
grinding steps in the partially sintered ceramic, and grinding post-
sintering are all critical steps in the processing that may create defects
that are more critical than the inherent material flaws. Examples of
flaw origins encountered in dental zirconia bend bars after strength
testing14–15 are shown in Figures 12–17 and illustrate problems
encountered in the processing steps. Such a flaw population has to be
thoroughly documented and described before condemning a specific
ceramic material. If these processing defects are also encountered in
clinically failed parts, then the fabrication methods and quality control
need to be improved.
Figure 12 shows volume defects which are the origin of failure in
zirconia bend bars. Both volume flaws are pores resulting from green
b3252_Ch-08.indd 221 27-11-2018 03:02:44 PM

Figure 12. Critical volume flaws in 3Y-TZP bend bars tested in 4-point

bending. The origin in (a) and (b) is a big void (35 µm) between agglomer-
ates created during green compaction. The direction of crack propagation is
indicated by the black arrows. The origin in (c) and (d) is a 70 µm elongated
volume flaw 300 µm below the tensile surface and was more critical than its
neighbor defect located near the surface
powder compaction problems. Inside the pore (Figure 12(b)), zirco-

nia agglomerates are visible and the zirconia grains round in shape
indicating free air sintering. In Figure 12 (c,d), the critical volume
pore origin is rather elongated in shape and located 300 µm subsur-
face. Hackle is radiating outward from both volume pore origins as
indicated by the arrows.
It is helpful to have within the SEM an option for EDAX to verify
elemental composition of failure origins. For zirconia, sinter aids such
as CaO are part of the chemical composition in very small mol%.
If the distribution is not well controlled some localized concentration
may lead to excessive grain growth. Figure 13 shows the failure
b3252_Ch-08.indd 222 27-11-2018 03:02:45 PM

Figure 13. Fracture origin in 3Y-TZP. Volume pore surrounded by exces-

sive grain growth due to a localized concentration of CaO used as sinter aid
in the powder composition
origin, a volume pore surrounded by a smooth surface corresponding

to localized excessive grain growth. Hackle and wake hackle are visi-
ble, emanating from the tiny pores on the fracture surface. Inside the
pore, very large zirconia grains (~10 µm) are visible. EDAX measured
7.6 mol% of CaO, which exceeds by far the usual <1 mol%.
b3252_Ch-08.indd 223 27-11-2018 03:02:45 PM

Figure 14. Failure origins are microporous regions located 10–20 µm

below the tensile surface in two dental 3Y-TZP bend bars provided by dif-
ferent manufacturers
Figure 15. Critical surface flaws produced by machining during specimen

preparation. Deep (coarse) grinding grooves at an angle to the tensile stress
have created critical crack sizes from which the fracture started, as seen by
fine hackle emanating from the origin and propagating along the black
arrows toward the compression surface
b3252_Ch-08.indd 224 27-11-2018 03:02:47 PM

Figure 16. Critical surface flaws (pores) in 3Y-TZP bend bars introduced
during the powder compaction step and reaching the surface after specimen
shaping to the requested dimensions
Figure 17. Surface flaw origins from compositional inhomogeneity in

3Y-TZP bend bars. The critical crack sizes for both semi-elliptical crack
origins are delineated by the black arrows. Compositional inhomogeneity
of CaO led to localized grain growth and micropores as seen by the differ-
ence in microstructure. A mirror region is surrounding the fracture origins
(o) followed by hackle indicating the direction of crack propagation (dcp)
and a compression curl (cc) before final breakthrough
b3252_Ch-08.indd 225 27-11-2018 03:02:48 PM

Volume flaws may also be located very close to the tensile

surface and are then described as near the surface (or subsurface)
volume flaws.1 Examples are given in Figure 14 which shows two
fracture origins corresponding to microporous regions of respec-
tively 50 × 40 µm (Figure 14 (a,b)) and 15 × 5 µm (Figure 14 (c,d))
located 10–20 µm below the tensile surface. Hackle is radiating
outward from the origins. Fracture and tensile surfaces are viewed at
an angle in Figure 14 (a,c), which helps in distinguishing it from
origins located on the tensile surface. The zirconia bend bars were
provided by different manufacturers for research purposes14–15
demonstrating similar problems arising from processing.
Surface origins are often related not only to machining or grind-
ing of specimens (Figure 15) but can also result from critical pores
(Figure 16) or compositional inhomogeneity (Figure 17). In bend
bars, the grinding should be smooth (below the critical flaw size of the
material) and parallel to the stress direction which corresponds to the
long axis in a bend specimen in order to avoid machining defects to be
activated during mode I loading rather than the material’s inherent
flaws. Examples of specimen preparation machining defects activated
during flexural strength testing are shown in Figure 15 for zirconia.
Deep (coarse) grinding grooves at an angle to the tensile stress have
created critical crack sizes from which the fracture started, as seen by
fine hackle emanating from the origin and propagating along the black
arrows toward the compression surface.14 Figure 16 shows the origin
to be a large pore at the tensile surface from which twist hackle is ema-
nating, whereas in Figure 16(b) the origin is a porous region in direct
contact with the ground surface. Figure 17 is an example of a surface
flaw origin resulting from compositional inhomogeneity in 3Y-TZP
bend bars. EDAX confirmed the presence of CaO which was respon-
sible for an excessive grain growth, thus weakening the zirconia locally
where the stress concentrated.
2.2. Fractographic Montage of Origins

With ceramic testing, a probability function such as the two-parameter
Weibull distribution is often used to describe the strength data.
b3252_Ch-08.indd 226 27-11-2018 03:02:48 PM

Figure 18. Fractographic montage or labeling of fracture origins on a

Weibull plot
A fractographic montage is helpful to better understand the data dis-

tribution in correlation with the type of critical flaws as recommended
in the ASTM C1322.1 If no images are shown, the Weibull graph can
also be labeled describing the flaw population with letters and/or
colors.13 Figure 18 is a schematic illustration of such a Weibull fracto-
graphic montage. The drawings are replaced by SEM or stereomicro-
scopic images. A minimum of the three weakest and three best
specimens should be analyzed using fractography.
3. Quantitative Fractography and Fracture Mechanics

Dental ceramics are brittle materials following the principle of linear
elastic fracture mechanics (LEFM). Several fracture toughness tests
have been developed and described in the ASTM C1421 standard
among which the surface crack in flexure (SCF) test is one2 which
uses fractographic analysis for crack size determination. In this test,
b3252_Ch-08.indd 227 27-11-2018 03:02:48 PM

Figure 19. Pre-crack in an SCF broken bend bar. The critical crack depth
a and width 2c are measured for determination of the maximum Y stress
intensity shape factor (either Y depth or Y surface) based on Newman and
Raju equations
a small but sharp pre-crack is introduced with a Knoop indenter

with a slight tilt of 0.5° (to make the pre-crack easier to discern and
measure after fracture), the indentation zone and associated residual
stress field is further removed by polishing, and the bend bar is frac-
tured in 4 point bending (σf flexural strength). The fracture tough-
ness (KIc) is calculated using fractographic techniques for the crack
size measurement (depth a and width 2c), and Newman and Raju
equations2,16 for the Y-stress intensity shape factor coefficient for both
the deepest point of the pre-crack periphery (Yd) and the point at the
surface (Ys) (Figure 19), with the maximum Y (Yd or Ys) being finally
used in the fracture toughness Eq. (1):
KIc = Y σf√a,(1)
where a is the crack depth, σf the flexural strength, and Y the stress
intensity shape factor (based on Newman and Raju).
This SCF standard has been applied to several dental ceramics
including mica glass-ceramic17 and leucite-based porcelains with vary-
ing composition and leucite crystal content.18,19 The identification of
the critical crack boundary by fractographic means is dependent on
the microstructure of the ceramic and the final fracture surface rough-
ness. Coarser microstructures increase the difficulty to correctly inter-
pret the crack size as reported for mica glass-ceramic.17 An example of
such crack size identification after SCF testing in liquid nitrogen is
shown in Figure 20 for a feldspathic dental porcelain.18
Quantitative fractography is also used to obtain fracture tough-
ness estimates from strength-tested specimens by determining the
b3252_Ch-08.indd 228 27-11-2018 03:02:48 PM

Figure 20. Dental porcelain fracture surfaces in an SCF test.18 The critical
pre-crack size (width and depth) from a Knoop indentation is marked with
arrows
Figure 21. Fracture surface of a 3Y-TZP specimen broken in 4-point

bending. The critical flaw (origin) is a localized excessive grain growth flaw
of 13 × 37 µm. The flexure strength was 680 MPa
size and location of the critical crack and correlating these flaws with
ceramic processing issues. Examples of such application to strength-
tested ceramic specimens is provided in Figure 21 on zirconia bend
bars in which the critical flaws on the surface responsible for failure
is related to excessive grain growth at the surface due to a localized
concentration of CaO as a sinter additive.15 Fracture toughness
estimates can be calculated from critical crack size measurements
(width and depth). In Figure 21, the flexure strength was 680 MPa.
The critical flaw size is 37 µm wide and 13 µm deep. Based on
Raju–Newman equations, the Y factor is 1.4 for this specimen,
b3252_Ch-08.indd 229 27-11-2018 03:02:49 PM

which gives a KIc estimate of 3.4 MPa√m. This is far lower than clas-
sic dense 3Y-TZP which has a fracture toughness around 4.5–5.0
MPa√m. Other work using fracture mechanics relationships and
Newman and Raju Y calculations have been successfully applied to
moisture-assisted subcritical crack growth effects on alumina glass-
infiltrated ceramic and alumina porcelain.20
Fracture toughness estimates were also calculated based on quan-
titative fractography for other dental ceramics such as lithium disili-
cate and amorphous glass,21 and 3Y-TZP22 using calculations of the Y
factor based on Randall’s23 interpretation of Irwin’s work.24
Alternatively, the researcher can use approximations of stress
intensity shape factors (Y) as provided in the ASTM-C13221 for
surface flaws that are semi-circular (c = a) or semi-elliptical cracks
depending on the c length with respect to a. Figure 22 is adapted
from the ASTM C1322,1 reproducing examples of Y factor values
for small surface crack shapes in flexure test bars. Such rapid
Figure 22. Stress intensity factor Y for semi-circular or semi-elliptical sur-

face cracks in tension stress fields. Adapted from Ref. [1]
b3252_Ch-08.indd 230 27-11-2018 03:02:50 PM

approximations are useful to determine fracture toughness estimates

based on crack size measurements and flexural strength values for
bend bars or, alternatively, estimate the strength from known KIc and
critical crack size.
4. Clinical Failure Analysis

4.1. A Systematic Approach
Dental ceramics have been developed for specific restorative needs
such as inlays, onlays, crowns, bridges, implant abutments, and
implants. Clinical and mechanical considerations will dictate the
choice of the ceramic material to restore or replace a tooth and are
part of the daily work in every dental office or medical institution
treating patients. Although ceramic restorations in Dentistry overall
have a very good long-term outcome, 1–5% may fracture prema-
turely within the first 5 years of service (Figure 23). These sudden
fractures occur without any warning during chewing and are often
due to a combination of negatively affecting factors such as ceramic
processing flaws in the dental laboratory, grinding damage, design
deficiencies, thermal residual stresses in conjunction with
Figure 23. Premolar clinical fracture of a Procera® alumina crown made of

an alumina framework layered with a veneering ceramic (Nobel Rondo™).
(a) and (b) show the recovered broken part before cleaning on which frac-
tographic analysis will be performed. Adapted from Ref. [25].
b3252_Ch-08.indd 231 27-11-2018 03:02:50 PM

mechanical loading, chewing impacts, and localized excessive pres-

sure visible from contact wear. The possibility of recovering a bro-
ken part (Figure 22(b)) and analyzing it fractographically helps in
understanding the premature failure and forwarding the needed
feedback to all the actors involved (dentist, dental laboratory tech-
nician, manufacturer, and patient).
Fractography has been applied to assess clinical ceramic broken
parts mainly as a descriptive approach11,25–31 as fracture origins are
rarely well-defined flaws as encountered in strength-tested specimens
for crack size measurements. Few papers have applied with success
fracture mechanic principles based on determination of critical flaw
sizes on broken ceramic restorations for stress estimates.9,10,32–34
Descriptive fractography can be successfully performed, providing
that key fractographic features are identified on the ceramic broken
surface using a microscope and the methods described earlier.
Before starting with the fractographic analysis, relevant informa-
tion connected to the failure event and the material need to be col-
lected. Hence, knowledge of the ceramic material, time to failure,
circumstances of the fracture event, intraoral location of the broken
part, and possibly an intraoral photograph (Figure 23) are very use-
ful in the overall investigation. A systematic approach of every failure
case is recommended and is described in the following example
(Figures 23–25), which has been published in greater detail.25 The
first step is to document the broken part with an overall image under
a stereomicroscope (Figures 23 and 24). Areas of interest labeled with
numbers (Figure 24) are selected based on the presence of some easy-
to-spot surface crack features (compression curl, arrest lines, larger
hackle). Lateral illumination will help in making these features stick-
ing out at low magnifications under the stereomicroscope. Gold coat-
ing (Figure 24) can enhance some fractographic features such as a
compression curl, hackle, and arrest lines, and will provide a good
opinion as to the direction of the cracking and aid in simplifying the
search for the origin before starting SEM. An overall drawing while
viewing under the optical stereomicroscope helps to quickly secure
topographic information (Figure 24).
b3252_Ch-08.indd 232 27-11-2018 03:02:50 PM

Figure 24. Gold coating and viewing under the stereomicroscope of the

fractured part of Figure 23. A quick drawing is performed of the key features
seen at low magnification and the zones of interest labeled 1–4 for further
analysis under the SEM. Adapted from Ref. [25]
A higher depth of field and power of SEM (Figure 25) are needed
to visualize in greater detail smaller crack features such as hackle, wake
hackle, and twist hackle. Each zone of interest (1–4) is viewed at
higher magnification, and key features indicate the direction of crack
propagation (dcp), which is then mapped locally.
In zone 4 of Figure 25(a) is the compression curl which was
already identified as such in the stereomicroscope. Several wake
hackles (Figure 25(b)) confirm the dcp exiting on that distal crown
side. The glassy veneering ceramic of zone 3 (Figure 25(d)) shows
again wake hackle, indicating that the crack moved toward the com-
pression curl. Zone 2 (Figure 25(c)) may confuse a beginner frac-
tographer as it shows cracking of the crown from the occluding
surface downward to the alumina framework as shown by the mul-
tiple arrest lines and wake and twist hackles. However, a big arrest
line stops the crack and no further hackles are entering from there
inside the alumina framework. This is a secondary event and should
not be confused as the fracture origin. Zone 1 (Figure 25(e)) is of
key interest. It shows a series of hackles and wake hackles within the
veneering ceramic (Figure 25(f)), with the crack path going straight
up toward the occlusal side. The origin is to be searched at the
b3252_Ch-08.indd 233 27-11-2018 03:02:51 PM

Figure 25. SEM of the broken part following a systematic approach. Zones
of interest (1–4) illustrate key features for the dcp. Zone 4: Compression curl
(cc) (a) and wake hackle (b). Zone 3 (d): Hackle in the veneering ceramic.
Zone 2 (c): Surface crack arrested at the border with the alumina framework.
Zone 1: Wake hackle (e, f). Margin ceramic chip and fracture origin (g). (h):
Summary of the overall dcp and crack origin (circle) located at the mesial
margin
b3252_Ch-08.indd 234 27-11-2018 03:02:52 PM

mesial margin in zone 1 (Figure 25(g)). A veneering ceramic chip of

approximately 2 × 1 mm is visible containing several arrest lines,
hackle, and wake hackles. No clear origin was identified, but the
black arrows at the margin indicate the area where the crack started
(Figure 25(g)). The overall crack path is marked on the fracture sur-
face of the broken part (Figure 25(h)) as well as the origin site
(ellipse) indicating a failure from the mesial margin. This is not sur-
prising as margins in dental restorations are areas subjected to Hoop
stress. This mesial margin, possibly weakened by the ceramic chip,
was the starting point of the catastrophic fracture which occurred
4 years after intraoral service during a chewing episode.25 From the
margin, the crack propagated upward, toward the occlusal surface,
then rotated over the corner of the alumina framework to exit at the
distal side of the crown. The cement used was a glass-ionomer cement
which has a weak adhesion to tooth substrates (dentin, enamel) and
no chemical bond to alumina or metal. Resin-based cements nowa-
days provide a better adhesion to the tooth substrate and to ceramics.
It could have added a few MPas in the fracture strength by bonding
the ceramic crown to the tooth substrate, but the problem of clinical
failure is far more complex than narrowing it down to a cement issue.
Publications of clinical failures can use fractographic montages11,31
based on an initial overview and adding detailed views of selected
zones of interest which allows to follow the search and identification
of key fractographic features.
4.2. Thin Margin Origins

Thin ceramic margins are problematic as the machining and labora-
tory processing of the ceramic may be complex even for high-strength
materials such as alumina or zirconia. Cervical margin origins have
been identified in 22 fractured alumina crowns recovered for fracto-
graphic analysis.30 Dominant Hoop stresses combined with thin mar-
gin design, machining, and complex laboratory handling were
responsible for premature fracture. An example of such thin margin
finishing is shown in Figure 26 of cervical margin fracture origins.
b3252_Ch-08.indd 235 27-11-2018 03:02:52 PM

Figure 26. Fracture origins starting at the inner side (intaglio) of the alu-
mina crown framework at the cervical margin
4.3. Contact Wear, Grinding Damage

Occlusal contact wear is often connected to the fracture event
when a partial chip-type fracture of the veneering ceramic is
involved. The veneering ceramics are mainly silica-based with low
fracture toughness around 0.7–0.9 MPa√m and fracture strengths
around 70–100 MPa. These esthetic but weak ceramics are layered
over an existing high-strength framework (alumina, zirconia, metal)
for the final crown shape and will undergo cyclic loading with variable
loads from the antagonist tooth or restorative material having differ-
ent hardness and state of surface roughness. It is therefore not surpris-
ing to see on the occluding surface, with time, a wear pattern. What
is critical is the localized loading magnitude and frequency, the sur-
face roughness state, and surface damage. A rough ceramic surface will
lower the fracture strength of the ceramic as well as any grinding dam-
age introduced from adjusting the occlusion. Examples of fracture
origins related to contact wear and grinding damage are shown in
Figures 27 and 28. The first case (Figure 27) shows a clinical ceramic
chip fracture in which contact wear and occlusion played a role.
A silicon impression was taken intraorally of the fractured sur-
face, poured in epoxy resin and gold coated for SEM analysis. This
technique is called the replica technique35 and is helpful in clinical
fractures when the broken part cannot be retrieved without damage
b3252_Ch-08.indd 236 27-11-2018 03:02:52 PM

Figure 27. Gold-coated epoxy replica of a veneering ceramic chip of a

premolar crown viewed under stereo and SEM. Low magnification under the
SEM shows multiple origins at the incisal edge arrested by multiple arrest
lines. The fracture propagated toward the gingival margin as seen from
hackle, wake hackle, and twist hackle. The presence of incisal wear indicates
pressure and friction during chewing and lateral excursions, exceeding the
resistance of the weak veneering ceramic
b3252_Ch-08.indd 237 27-11-2018 03:02:53 PM

or made available for failure analysis. The reproduction of details is

excellent providing that no biofilm is adherent on its surface. On
the gold-coated epoxy replica, features such as hackle, wake hackle,
twist hackle, and arrest lines can be seen on the fracture surface of
the veneering ceramic. A quick drawing helps to capture the surface
morphology and characteristic features. Further analysis with the
SEM shows a jagged incisal edge with multiple starter cracks (black
arrows) followed by arrest lines. The fracture propagated to the
gingival side of the crown as seen by the hackle, wake and twist
hackles. The incisal ridge shows some wear indicating friction dur-
ing chewing and lateral excursions, exceeding the resistance of the
weak veneering ceramic. This early fracture most probably occurred
due to a slightly too long incisal cusp which underwent shearing
during lateral chewing movements, resulting in microchipping over
time until a bigger fracture chipped off portions of the veneering
ceramic. More information regarding this case can be found in the
literature.36
Figure 28 illustrates more contact wear chip fractures origins
(a–d) as well as grinding damage from occlusal adjustment (e,f).
Figures (a) and (b) are porcelain fractures in a porcelain-fused-to-
metal crown after 1 year, starting at the occlusal contact wear surface
and moving downward, toward the gingiva. This case was already
seen in Figure 11 for documentation of a compression curl. Figures
(c) and (d) show a veneering ceramic chip fracture starting from a
localized contact wear zone at the occluding surface. Figures (e) and
(f) illustrate a chip fracture of a veneering ceramic in conjunction with
diamond grinding damage. Higher magnification of the ground sur-
face shows brittle cracking of the ceramic (f). These cases all illustrate
the technical challenges in Dentistry, which are well-distributed
occluding contacts on ceramic restorations, recognizing excessive
wear, and smoothening by polishing these worn surfaces as well as
those adjusted for occlusion purposes with diamond burs. Longitudinal
clinical studies are still lacking with regard to the use of fractography
when reporting survival and success data, but a recent report has
provided some classification suggestions based on fractographic
analysis of clinical fractures.37 Further clinical retrospective evaluation
b3252_Ch-08.indd 238 27-11-2018 03:02:53 PM

Figure 28. Chip fractures of veneering ceramics. Contact wear origins are
illustrated in Figures (a–d). Diamond grinding damage origin associated
with brittle fracture failure mode is shown in Figures (e,f)
of chippings of veneering ceramics over zirconia framework have con-

firmed occlusal contact wear as failure origins.38
5. Conclusions
The purpose of this chapter is to familiarize the fractographer with
dental ceramic issues regarding fracture analyses. The most powerful
b3252_Ch-08.indd 239 27-11-2018 03:02:54 PM

tool for clinical failure analysis is a descriptive (qualitative) fractog-

raphy, consisting of a thorough search on the fracture surface of
characteristic crack feature indicators of the overall crack propaga-
tion direction and thus pinpointing back to the area of crack origin.
A systematic approach should however be applied covering the
entire fracture surface with zones of interest for more detailed
microscopy including SEM. The hunt for information regarding the
circumstances of failure and the processing details in the laboratory
remain difficult to get as these may be biased by the issue of free
replacement. Design, processing, handling, choice of the ceramic
for restorative purposes, biting habits, and the oral environment are
parameters to consider when analyzing clinical failures. Quantitative
and qualitative fractography should be part of every strength test
and follow the guidelines provided in existing standards and books.
The knowledge of critical flaw and type of flaw population existing
within a tested ceramic is of outmost importance if improvement in
the ceramic material and processing are to be expected. There is
enough information within the dental literature which can guide
the reader for more in-depth applications of fractography to dental
ceramics.
Acknowledgments
This work is a result of years of invaluable personal teaching received
by Janet and George Quinn with respect to the application of fractog-
raphy to ceramic fractures of dental restorative materials. Janet was a
leader within the dental materials community, working at the
American Dental Association — former Paffenbarger Research Center
focusing on failure analysis of dental materials. Very sadly, she passed
away in 1998.39 George Quinn, her husband, has worked most of his
life for the National Institute of Standards and Technology develop-
ing standards related to strength testing, fracture mechanics, and
fractography. His NIST recommended practice guide on fractography
of ceramics and glasses5 was the kick off for the dental materials
community to get more involved in using fractography on in vitro
and in vivo ceramic dental materials.
b3252_Ch-08.indd 240 27-11-2018 03:02:54 PM

References
1. ASTM-C1322-15, Standard Practice for Fractography and Char
acterization of Fracture Origins in Advanced Ceramics (ASTM
International, 2015).
2. ASTM-C1421-16, Standard Test Methods for Determination of Fracture
Toughness of Advanced Ceramics at Ambient Temperature (ASTM
International, 2016).
3. ASTM-C1678-10, Practice for Fractographic Analysis of Fracture
Mirror Sizes in Ceramics and Glasses (ASTM International, 2010).
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The American Ceramic Society, 1990).
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Ceramics and Glasses. Special Publication 960-16e2. (Washington, D.C.:
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http://dx.doi.org/10.6028/NIST.SP.960-16e2: 2016.
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b2530_FM.indd 6 01-Sep-16 11:03:06 AM

Chapter 9
Bioactive Glasses for the Development

of Dental Restorative Materials
José Bauer*,§, Ceci Nunes Carvalho†,¶,

Edilausson Moreno Carvalho*, and Rodrigo França‡,
*Discipline of Dental Materials, Federal
University of Maranhão (UFMA)
Rua dos Portugueses, 1966,
65080-805, São Luís, Brazil
†
Department of Endodontic, Dental School
of UNICEUMA — Universidade Ceuma,
Rua Josué Montello Nº 1, Renascena II,
65075-120, São Luis, MA, Brazil
‡
Dental Biomaterials Research Laboratory,
University of Manitoba,
780 Bannatyne Avenue,
Winnipeg, Manitoba R3E 0W2, Canada
§
bauer@ufma.br
ceci.carvalho@ceuma.br
¶

Rodrigo.Franca@umanitoba.ca
The use of bioactive glasses in developing materials for use in den-

tistry is rising every day. Numerous researchers have published
enlightening articles on the development and characterization of
new biomaterials containing bioactive glass. This chapter will discuss
245
b3252_Ch-09.indd 245 27-11-2018 03:04:09 PM

the types of bioactive glass and how these materials have been
applied to the development of new dental restorative materials.
1. Introduction
The development of bioactive materials in dentistry has been a domi-
nant topic in recent publications in the field of dental materials. At
present, there are different groups of researchers in the world in quest
of an objective: to include bioactive glasses in restorative materials
with the intention of developing “smart materials”. We searched the
PubMed database using the keywords “glass + bioactive + dental +
materials”. This figure definitely shows an increasing trend toward
research related to bioactive materials, indicating that the use of bio-
active materials in Dentistry has been a “big” research topic in the
past two decades.
Figure 1 shows that in the last 20 years, scientific publications
involving bioactive restorative materials have increased considerably.
Basically, bioactive particles are included in restorative materials with
a view to bringing about benefits such as neutralization of acid pH,
bacterial inhibition, action against metalloproteinases enzymes, and,
particularly, stimulation of enamel and dentin remineralization.
Today, there are innumerable bioactive glasses available to
researchers. The first bioactive glass was invented by Larry Hench at
Figure 1. Number of scientific publications involving bioactive restorative

materials from 1995 to 2015
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Bioactive Glasses for the Development of Dental Restorative Materials 247
the University of Florida in 1969. The main discovery was that a glass
with the composition 46.1 mol.% SiO2, 24.4 mol.% Na2O, 26.9 mol.%
CaO, and 2.6 mol.% P2O5, later termed 45S5 and Bioglass, exhibited
notable properties of interaction with live tissues. The name ‘‘Bioglass’’
was trademarked by the University of Florida as a name for the origi-
nal 45S5 composition. It should therefore only be used in reference
to the 45S5 composition and not as a general term for bioactive
glasses.1 This glass exhibits the highest bioactivity index and is still
considered the gold standard of bioactive materials.
Recently, a new bioactive glass, denominated Biosilicate, was
developed by a group of researchers at the University of São Carlos,
under the guidance of Prof. Edgar D. Zanotto who worked in col-
laboration with Prof. Larry L. Hench. The purpose of developing this
biosilicate was to find a glass that would have a high bioactivity index,
and simultaneously present superior mechanical properties that would
favor better obtainment of particles.2
Bioactive glasses containing niobium have also drawn attention.
Researchers at the Nuclear and Energy Research Institute (“Instituto de
Pesquisas Energéticas e Nucleares — IPEN”), under the guidance of
Prof. José Roberto Martinelli, have developed a bioactive niobium
phosphate glass with high mechanical strength and great chemical stabil-
ity for use in bone grafting. The precursor of the bioactive glass devel-
oped by Martinelli was the vitreous system P2O5–PbO–Nb2O5–K2O,
also called niobium phosphate, containing lead, developed by Prof.
Oswaldo Luiz Alves of the State University of Campinas.3
In spite of the large number of bioactive glasses on the market,
this chapter will be devoted to these three bioactive glasses only:
(i) 45S5, (ii) Biosilicate, and (iii) niobium phosphate.
2. Bioactive Glasses
2.1. Bioglass (45S5)
There are diverse glasses and glass-ceramics containing silica in their
composition used in biomedical applications. The chemical composi-
tions, morphological characteristics, and mechanical properties of
these glasses may be adjusted according to the interest of the research.
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The first bioactive glass was developed by Larry Hench, who in

1971, developed an Na2O–CaO–P2O5–SiO2 system with a high bioac-
tivity index.
The majority of bioactive glasses are silicate based, and to present
high bioactivity, the concentrations of SiO2 must be around 60% in
mol, have high relative contents of Na2O and CaO, and maintain a
high CaO/P2O5 ratio.
For this material to be bioactive, a chemical action must occur on
the material surface after its insertion in the body. A carbonated
hydroxyapatite layer is formed on the material surface, which pro-
motes the bond interface with the tissue.4–9 Three fundamental factors
are necessary for a silicate glass to present bioactivity: (1) its composi-
tion must contain an SiO2 content lower than 60% in mol; (2) high
relative Na2O and CaO contents; and (3) a high Ca/P ratio. These
factors allow the glass surface to become reactive when in contact
with an aqueous medium. The physicochemical mechanisms involved
in the formation of the bioactive bond with tissue and the sequence
of cellular events are presented in Table 1.
Table 2 lists the stages of reactions on bioactive material surfaces.
The mechanisms involved in Stage 1 (ionic exchange) and Stage 2
Table 1. Sequence of interfacial events involved in bond

formation between bone tissue and bioactive materials
Stages Events
1 Bioactive glass in contact with body fluids
2 Formation of SiOH bonds
3 Transformation of SiOH + SiOH → Si–O–Si + H2O
4 Adsorption of Ca + PO4 + CO3
5 Carbonated hydroxyapatite formation
6 Action of macrophages
7 Approximation of mesenchymal cells
8 Differentiation of mesenchymal cells
9 Bone matrix formation
10 Bone matrix crystallization
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Table 2. Stage of reactions in bioactive implants

Stages of
superficial
reactions Events
1 Rapid exchange of Na+ and K+ ions with H+ and H3O+ ions of the
Si–O–Na+ + H+ + OH− solution → Si–OH+ + Na+ (solution) + OH+.
This stage is frequently controlled by the process of diffusion.
2 Loss of soluble silica in the form of Si(OH)4 into the solution,
resulting in the breakage of the Si–O–Si bonds and formation of
Si–OH at the interface of the vitreous solution. This stage is
frequently controlled by the interfacial reactions.
3 Condensation and repolymerization of the layer rich in SiO2 on the
surface, depleting alkaline cations and alkaline earth elements.
4 Migration of Ca+2 e PO4−3 groups to the surface by means of the
layer rich in SiO2 forming a film rich in CaO–P2O5 on the surface
of the layer rich in SiO2, followed by the growth of an amorphous
film rich in CaO–P2O5 by incorporating soluble calcium and
phosphate from the solution.
5 Crystallization of the amorphous film of CaO–P2O5 by incorporating
OH, CO3−2 anions, or F− from the solution to form a layer of
hydroxyl, carbonate, and fluorapatite.
(silica network dissolution) are described precisely; however, the

mechanisms that act in Stage 3 (condensation and repolymerization
of silica) are not well known. The superficial reactions involved in
Stages 1–4 are being determined for a large number of vitreous
compositions.4–9
The ratio of carbonated hydroxyapatite formation (Stage 4) and
time of onset of crystallization (Stage 5) vary considerably. When the
ratio of formation becomes excessively slow, no formation of bond
between the implant material and bone tissue occurs, and the material
presents no bioactivity.
This entire bioactivity mechanism has led to 45S5 being a suc-
cess among the bioactive glasses. The 45S5 bioglass has been used
in over a million patients to repair bone defects in the jaw and in
orthopedics.1,4 Hench, in 2006,6 wrote, “After 30 years, as a result
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of satisfactory contracts and commercial relationships, Bioglasses are

sold in 35 countries. A wide variety of other bioactive materials are
also now in use worldwide”. In the field of Dentistry, in 2009,
40 years after the discovery of 45S5, the one millionth tube of tooth
paste containing 45S5 was sold. This material occludes dentinal
tubules and remineralizes the surface of teeth, thereby eliminating the
cause of dentinal hypersensitivity.7
However, the bioactive glass 45S5 has shown disadvantages such
as low mechanical strength and low fracture toughness. On the other
hand, innumerable researchers have incorporated 45S5 glass into the
development of dental restorative materials with excellent results.10–15
2.2. Biosilicate
Today, we know that other materials may also be bioactive, such as for
example, new compositions of glasses, glass ceramics, and the family
of calcium phosphate ceramics.16 Thus, a new bioactive glass, called
Biosilicate, was developed. The inventors had in mind the develop-
ment of a material that would preserve the high bioactivity index
shown by bioactive glasses and would simultaneously have superior
biomechanical properties. Its composition is very close to that used in
45S5, with a microstructure controlled to prevent crystallization dur-
ing the production of the glass ceramic. Thus, in 1997, after promis-
ing results, a patent was deposited about the obtainment of highly
bioactive glass ceramics.17 An important characteristic of Biosilicate is
the possibility of obtaining more regular and less abrasive particles
without cutting surfaces, therefore, less aggressive to gingival and
mucosal tissues. Some researchers have shown that this material is a
high-strength, high-toughness glass-ceramics with bioactivity equiva-
lent to that of the grandfather 45S5 bioactive glass.18–20
In a recent review of studies developed with Biosilicate, this
product was shown to present a high potential for use in restorative
material. The authors described, “Biosilicate has been evaluated in
28 theses and dissertations and in more than 30 scientific papers over
the last 20 years. These studies have demonstrated its efficiency
for regenerating bone tissue and treating dental hypersensitivity.
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Biosilicate presents some important features for bone tissue regenera-

tion: it is highly bioactive, osteoconductive, osteoinductive, non-
cytotoxic, non-genotoxic and has antibacterial properties”.2,21–25 On
the other hand, few studies in the field of restorative materials have
been developed with this bioactive material.
2.3. Niobium Phosphate Glass

One of the disadvantages of some bioactive glasses is their poor
chemical durability in aqueous media; however, this durability may be
modified with the addition of niobium oxide. The addition of nio-
bium (Nb) creates a vitreous structure made up of chains (–O–P–O-
Nb–O–P–O–) or in some cases, predominantly bonds of the
(–O–Nb–O–Nb–O–) type, making the glass more chemically stable as
the niobium oxide content is increased.26 This modification may con-
tribute to increasing the bioactivity26–29 and biocompatibility.28 Small
concentrations of Nb2O5 added to bioactive glasses may also increase
the velocity of binding and formation of bone tissue to glass.30,31
This gain in performance may be explained in the following man-
ner: in simulated body fluid (SBF), the Nb–OH functional groups
acquire a negative charge and induce apatite formation with the depo-
sition of an amorphous calcium compound. Afterward, an amorphous
form of calcium phosphate is transformed into hydroxyapatite.32
Moreover, niobium pentoxide alone is capable of promoting crystal-
lization and mineralization of the surrounding tissues.33 As opposed
to silica, Nb actively participates in the osseointegration reaction due
to its elevated biocompatibility.34 The incorporation of Nb pentoxide
(Nb2O5) may also increase the radiopacity and hardness of experimen-
tal adhesive materials.35,36
In spite of the 45S5 bioglasses having elevated bioactivity, its use
is restricted to applications in which high mechanical strength is not
required.
Whereas, a niobium phosphate glass has demonstrated high
mechanical strength, high chemical stability, biocompatibility, bioac-
tivity, and its flexural strength values were higher than those of 45S5
glass37 and close to those of Biosilicate.38
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This study gave origin to a patent under the title “Bioactive

niobium phosphate glasses for osseointegrated applications” (WO
2004026781 A1) deposited in 2003. Because of these promising
results, researches have been developed with niobium phosphate with
the purpose of developing intelligent restorative materials in diverse
fields of Dentistry.39–41
3. Restorative Materials Containing Bioactive Glasses

Initially, bioactive glasses in Dentistry were mainly used for coating
titanium implants42 or for the treatment of dentin hypersensitivity.7
Bioactive particles have been incorporated into glass ionomer
cements, composites and, ultimately, in adhesive systems. Therefore,
we are going to discuss each of these materials separately.
3.1. Glass Ionomer Cements

Glass ionomer cements are exceptional restorative materials, mainly
used in primary teeth. The antimicrobial properties of glass ionomer
cements are directly related to the quantity of fluoride released by
these materials.43 The fluoride ion (F−) is capable of diminishing dem-
ineralization and increasing remineralization of a carious tissue, and in
low concentration, modifying the metabolism of the bacteria that
cause caries. F− may also interfere in the adhesion of the biofilm pel-
licle to the tooth and inhibition of microbial growth.43,44
In spite of all these positive characteristics, this material also has
clinical and mechanical limitations, such as unfavorable esthetics due
to is low translucence, sensitivity of manipulation technique, sensitiv-
ity to water during setting, short working time, low fracture strength,
low resistance to hardness and wear, and low bond strength.44–48
To improve these limitations of conventional glass ionomer
cement, resin monomers were added to its composition. Thereby,
in addition to fluoroaluminosilicate glass, there is also bisphenol
glycidyl methacrylate (BisGMA), triethylene glycol dimethacrylate
(TEGDMA), urethane dimethacrylate (UDMA), and 2-hydroxy ethyl
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methacrylate, (HEMA) in the composition of the powder, thus giving

rise to the resin-modified glass ionomer cements (RMGICs). In spite
of the addition of these resin monomers to the conventional glass
ionomer cements having improved the clinical and mechanical prop-
erties of these materials, the RMGICs do not present bioactivity as
yet.44,46,49,50 The powder composition of the glass ionomer cement was
designed so that the glass can react with the weak acid, polycarboxylic
acid, and even if it contains both calcium and phosphate, it does not
show any bioactivity.51
On the other hand, the incorporation of 45S5 into glass ionomer
cements may favor the formation of an Si-rich layer capable of stimu-
lating the deposition of carbonated hydroxyapatite [Ca10(PO4)6(OH)2],
which is responsible for the induction of osseointegration and remin-
eralization of the hard tissues of teeth.
One study evaluated the release of Si, Ca, and P ions from con-
ventional glass ionomer cement and resin-modified glass ionomer
cement doped with 45S5 (10 and 30 wt.%). The authors demon-
strated that the addition of 45S5 to these materials provided the
precipitation of Ca-P on the surface, capable of mineralizing human
dentin in vitro. This modification may also provide the materials with
antimicrobial properties.52 These same authors evaluated the mechan-
ical strength (compressive strength, modulus, and Vickers hardness)
of glass ionomers doped with 45S5 (10% and 30%). Their results
demonstrated that the addition of 45S5 particles to the GICs
decreased the compressive strength and modulus of elasticity. This
suggests that the 45S5 particles might be only loosely attached to the
GIC matrix. Thus, 45S5 particles probably acted as fillers that had not
been adhered into the matrix of GIC leading to decreased mechanical
properties. This could also be seen with resin-modified GICs, espe-
cially when a higher weight fraction (30%) of 45S5 particles was used.
Another explanation is that 45S5 is less reactive for poly acrylic acid,
and therefore less surface reaction of BAG occurs. The addition of
45S5 to GIC may increase the microhardness of the material surface
after 180 days of storage in water due to the deposition of Si- and
Ca-based precipitates. The increase in microhardness may also be
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linked to the Ca2+ released from the bioactive glass to form carboxy-
late salt leading to an increase in the degree of polymerization in the
silicate network.53
However, innumerable studies have shown that the incorpora-
tion of bioactive glasses could reduce the mechanical properties of
GICs.51,54,55 But, their clinical use ought to be restricted to applica-
tions where their bioactivity can be beneficial, such as root surface
fillings and liners in dentistry, and where high compressive strength is
not necessarily needed.54
The addition of bioactive glasses to GIC may not compromise the
mechanical performance of the material, but provide a bioactive
potential. Matsuya et al.53 evaluated the bioactivity of the new GIC in
the SBF and found no apatite formation on the surface of the newly
set cement at least within 4 weeks. This may perhaps have been due
to the presence of polyacrylic acid that inhibited the apatite forma-
tion, and concluded it might be difficult to obtain a bioactive glass
ionomer cement. These results indicated that polyacrylic acid sup-
presses the apatite forming ability of bioactive glass.56
Choi et al.57 found that an addition of sol–gel derived glass with
a bioactive composition (70SiO2·25CaO·5P2O5) added to the com-
mercial GIC did not significantly alter the diametral tensile strength
and induced the precipitation of an apatite bone-mineral phase
on the surface after immersion in a SBF, showing in vitro bone
bioactivity.
With the purpose of evaluating the impact on the mechanical
properties of demineralized dentin in contact with modified-
GIC+45S5, Khoroushi et al.58 demonstrated that resin-modified glass
ionomer (RMGI) containing bioactive could compensate for this loss
of strength of demineralized dentin. They found the mean FS of dem-
ineralized dentin increased by almost 20% after contact of modified-
GIC with 45S5.
These characteristics make it possible to use GICs with the addi-
tion of bioactive glass on carious dentin, or with partial removal of the
carious tissue, which would make it possible for dentin remineraliza-
tion to occur. These results are very encouraging for the use of this
potential combination for the mineralization of dentin capping.59
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A large step forward in recent studies published was the obtainment

of nanoparticles of bioactive glasses for overcoming the problem of the
reduction in mechanical properties of GIC when bioactive glass was
added. In 2016, Valenezhad et al.44 showed that the addition of 10%
of bioactive glass nanoparticles was an optimal concentration for cell
adherence and acceptable mechanical properties.
Encouraging results were also found with the addition of Biosilicate
to two modified GICs. The addition of 2% biosilicate did not harm the
compressive strength of the materials tested, and increased the bond
strength to dentin.60 However, ion release and bioactive compound
formation tests with this mixture need to be evaluated.
Another interesting point of view adopted recently was the
development of bioactive glasses containing fluoride. This may lead
to the development of a material with the capacity for increasing
bone mass and mineral density, improving the resistance of the
apatite structure to acid attack, and better antibacterial properties.
This new bioactive material is an interesting candidates for various
clinical applications, such as dentinal tubule occlusion in the treat-
ment of dentin hypersensitivity.61 In SBF, this new bioactive glass
can form fluorapatite, which is more acid resistant than carbonated
hydroxyapatite.62
In the meantime, there are no published studies with the inclu-
sion of NbG glass in modified GIC; however, there are some studies
in progress. The preliminary results have indicated that the inclusion
of NbG glass did not reduce the flexural strength of two modified-
GICs, when added in the concentrations of 5%, 10%, and 20% by
weight (Table 3).
Table 3. Results of the flexural strength (MPa) test of RMGICs with the
addition of niobium phosphate (NbG) bioactive glass in different
concentrations*
Materials Control 5% 10% 20%
Vitro Fil LC 28.41 ± 7.95 33.06 ± 8.4 25.70 ± 4.4 29.16 ± 7.82
Resiglass 45.67 ± 9.31 46.77 ± 9.95 46.73 ± 9.95 52.49 ± 8.98
Note: *Unpublished data.
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Table 4. pH values of two RMGI with 20% NbG over 7 days*
Mixture pH 24 h 48 h 72 h 96 h 120 h 144 h 168 h
Resiglass pH 7 5.2 6.0 6.7 6.7 6.7 6.7 6.8
pH 4 4.8 5.0 4.9 5.0 4.7 4.8 4.8
Vitro Fil LC pH 7 6.0 6.9 7.4 7.5 7.4 7.4 7.3
pH 4 5.7 5.9 6.0 6.1 5.8 5.9 5.9
Note: *Unpublished data.
This result may be related to the greater chemical stability of the

NbG glass that would work as filler, as opposed to 45S5 glass that
undergoes solubility, exposing the material to degradation. The pH
monitoring data over the course of 7 days in two conditions of pH
(4 and 7) with 20% NbG are described in Table 4.
These data demonstrated that the NbG glass in the concentration
of 20% tended to neutralize the acid pH in the medium and of the
GIC. The increase in the initial pH is important to inhibit bacterial
growth and paralyze the demineralization process. Another important
finding obtained with the inclusion of NbG particles in modified GIC
was the possibility of deposition of precipitates responsible for bioac-
tivity (Figure 2).
3.2. Composites
Some studies have been published, with the inclusion of bioactive
glasses in composites, and some fields of Dentistry, such as restora-
tive dentistry, Orthodontics and Endodontics. These researches have
reported success with the inclusion of bioactive glasses in resin com-
posites, orthodontic bracket bonding materials and endodontic fill-
ing materials.
The bioactive glass incorporated into an endodontic sealer con-
tributed to an increase in ion release, promoting an alkaline pH in the
medium.63
Although the antimicrobial effect of bioactive glasses has not yet
been completely understood, it may be related to the elevation of pH
in aqueous suspensions. It has been reported the bioactive glass
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Figure 2. Precipitation (black arrow) in a sample of RMGI (Resiglass) with

20% NbG after 14 days immersion in a phosphate-buffered saline solution.
(Unpublished data — Further analysis is required to determine the composi-
tion of precipitates)
S53P4 had a greater antiseptic effect than that observed for calcium
hydroxide, and apparently this effects would not be related to pH
only.64,65
Another important finding was that the addition of 45S5 particles
to resin cements for endodontic filling made this material a powerful
inhibitor of MMP and collagen degradation.66 The reduction of
MMPs has been shown to have a positive effect on bone formation.67
On the market, it is possible to find an endodontic filling material
called BC Sealer (calcium silicates, monobasic calcium phosphate,
zirconium oxide, tantalum oxide), which the manufacturer suggests
has bioactivity, anti-inflammatory, and anti-bacterial capacity, without
post-operative complications. Zhang et al.68 demonstrated that this
material has a high pH, close to 12, and that this contributed to the
elimination of bacteria such as Enterococcus faecalis.
In the same study, the authors demonstrated that the small parti-
cle size and hydrophilic nature of the BC Sealer allows it to flow into
all aspects of the canal anatomy, and this favors a high bond strength
to root dentin.69 Shokouhinejad et al.70 compared the bond strength
of the EndoSequence cement, BC Sealer, and AH Plus either in the
presence or absence of a smear layer. In conclusion, the bond strength
of this new bioceramic cement was equal to that of AH Plus with or
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without the smear layer. This good performance of bond strength to

root dentin of bioactive cements may also be linked to the formation
and deposition of by-products at the cement/dentin interface.
The BC Sealer cement shows high calcium ion release.71 However,
this does not mean that this material presents the capacity for bioac-
tivity, in spite of the presence of precipitates (Figure 3) on the root
dentin surface, which suggested a possible bioactivity. Readouts made
by X-ray diffraction (XRD) did not confirm the presence of
hydroxyapatite (Unpublished data).
Bioactive glasses have also been used in an attempt to develop a
bioactive gutta-percha capable of filling the root canal system in a
humid environment, without the use of any filling cement.72 New
composites containing phosphated glasses, capable of releasing ions
to form a precipitate and promote sealing have been evaluated.10,12,72,73
These experimental materials showed desirable properties for an
endodontic filling material, such as alkaline capacity, adhesion to root
dentin,12,72 radiopacity, and bioactivity.10,73 A group of researchers
have developed a commercial product (BioGuta) with the addition of
45S5 glass to the polymer matrix of gutta-percha that showed promis-
ing results as a single root canal filling material. This material (under
investigation) made the resulting composite materials bioactive and
improved their immediate sealing ability.
Figure 3. Precipitation in root dentin surface (black arrows) stimulated by

BC sealer. (C — Cement BC sealer. D — Root dentin)
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Recently, Carvalho et al.39,40 developed and patented a gutta-

percha with a high concentration of NbG glass. Preliminary results
showed that this material is self-adhesive, bioactive, has antimicrobial
properties, and has a bond strength similar to that obtained with the
well-established filling cement AH Plus.
In an small scale, studies have also been conducted in the field
of Orthodontics for the development of materials containing bioac-
tive particles used for bracket bonding. Up to now, there are only
three studies that have evaluated the inclusion of bioactive glasses
in bonding materials.74–76
The function of this incorporation of bioactive glasses is to pre-
vent bacterial colonization around brackets. The presence of bacteria
around brackets may lead to demineralization of the enamel surface
and formation of incipient caries, denominated white spot (WSL).
The high prevalence of WSL still causes concern as they could lead to
carious lesions and esthetic alterations that would compromise the
orthodontic treatment. According to Tufekci et al.77 the prevalence of
WSL during orthodontic treatment (nearly 50% of patients after
12 months) is due to many factors: (1) fixed orthodontic appliances
make oral hygiene more difficult;78 (2) increase bacterial flora around
the bracket;79 and (3) reduce the pH at the enamel interface, resulting
in mineral loss.80
As has been described in different points of this chapter, the
incorporation of bioactive glasses may solve this problem, due to their
bactericidal and pH neutralizing action. Brown et al.74 suggested that
the incorporation of 45S5 glass into bracket bonding materials could
lead to the development of smart materials that provide a reservoir of
ions crucial to remineralization or to protect enamel against demin-
eralization. In same way, another study showed that smart materials
had the best preventive effect against WSL formation and helped to
reduce superficial enamel softening surrounding orthodontic brackets
when compared with a conventional resin adhesive.75 Altmann et al.76
developed a material for bracket bonding, containing an antibacterial
monomer (1,3,5-tri acryloyl hexahydro-1,3,5-triazine) and bioactive
glass (phosphate invert glass/niobium pentoxide). The authors found
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very promising results, such as a significant reduction in bacterial

growth, deposition of phosphate content, high degree of conversion,
and acceptable bond strength values. These authors have evaluated
these materials in both in situ and in vivo studies.
Bioactive fillers have also been added to resin composites with the
purpose of reducing biofilm aggregation on the restorative material
surface, and thereby reducing leakage at the restoration interface.
Thus, the researchers have attempted to reduce the high clinical fail-
ure rate of resin-composite restorations in posterior teeth. Exploration
into bioactive filler potential for use in resin-based dental restorative
composites has only very recently begun.81 It is of the utmost impor-
tance for the restorative material to inhibit bacterial growth, and if it
is not capable of preventing this growth, it should be capable of pro-
viding ions so that remineralization of the demineralized dental sub-
strate may occur. Xu et al.82 showed that a plaque pH of 6.0–5.5 is
potentially cariogenic, and pH of 5.5–4 is cariogenic or of danger to
cavity formation. So, it is desirable for Ca/PO4 composite to be
“smart”, to increase the release of caries-inhibiting ions at a lower pH,
when the Ca and PO4 ions are most needed.
On the other hand, the addition of bioactive glass to the com-
posite must not compromise its mechanical properties and clinical
performance. An excellent performance as regards the properties was
obtained with the incorporation of 5, 10, and 15 (wt.%) of bioactive
glass (45S5) into resin composite. Resins containing bioactive glass
(BAG composite) showed comparable or better properties than
commercial resins (Heliomolar, Filtek Z250 and Filtek Supreme
Plus) that were attributed to: (1) a higher filler content; and (2) a
microstructure morphology with better promotion of the toughen-
ing mechanisms of crack deflection and bridging.81 The same group
of researchers succeeded in proving that a resin composite containing
15 (wt.%) of bioactive glass inhibited biofilm formation and penetra-
tion into marginal gaps of restorations.83,84 Some studies have success-
fully added bioactive glasses to composites containing silver (Ag) to
combine regenerative and antibacterial properties in one and the same
material.85,86
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3.3. Adhesive Systems

Adhesive systems must penetrate into the entire demineralized colla-
gen network, so that after polymerization, the collagen fibers will be
protected against degradation caused by the MMPs.87,88
However, different studies have shown that adhesive systems
contain hydrophilic monomers that may be cleaved by the action of
H2O, leaving the collagen fibers unprotected.89–91 Some studies have
demonstrated that the interface with dentin produced by the con-
ventional adhesives deteriorates within a short period.35,88,92,93 This
behavior may compromise the clinical performance of the material
and favor the appearance of secondary caries, marginal staining, and
sensitivity.93,94
Various alternatives have been observed for improving the behav-
ior of the bond interface.95 Application of chlorhexidine solutions in
different concentrations,96 multiple layers of adhesives,97,98 electrical
currents,99 appliances that improve the infiltration of adhesives into
the collagen layer,100 longer time of application/agitation, and longer
light activation time98,101 are changes in the application protocol
which lead to an increase in the number of steps, and consequently in
clinical time.
Some authors have suggested the addition of inorganic particles
to the resin matrix to improve the mechanical behavior of the mate-
rial.93,102 Particles differing in nature have been used colloidal silica,102
zirconium,103 Ytterbium trifluoride,104 and barium borosilicate.93 On
the other hand, the addition of inorganic particles to the resin matrix
must not function only as a reinforcement to improve the mechanical
properties. An alternative found in the literature was the incorpora-
tion of particles to inhibit the action of MMPs and bacteria, and to
stimulate remineralization of the collagen matrix.105
At present, growing interest in new restorative materials has been
observed, associated with bioactive glasses (45S5) that induce remin-
eralization of the bond interface by means of phosphate and calcium
ion release,15,88,106–113 favoring the elevation of pH at the interface,
acting as an antimicrobial agent,112,114–116 and inhibiting MMPs.105
b3252_Ch-09.indd 261 27-11-2018 03:04:13 PM

In the field of development of bioactive adhesive systems, a group

led by Salvatore Sauro has obtained excellent results with the addition
of bioglass (45S5). Their studies have pointed toward a bioactive
adhesive system that remineralizes the collagen fibers, recovers the
mechanical properties of dentin, stabilizes the bond strength values,
and reduces nanoleakage.107
The incorporation of bioactive particles into dental adhesives
can also act as a filler to improve the mechanical properties of the
material. Some manufactures have reinforced adhesives systems by
adding fillers as a component.117 This material could therefore act as
a stress absorbing layer, because of its lower elastic modulus, by
allowing deflection between composite/dentine and improving
marginal seal.118 Furthermore, adhesives with fillers may have radi-
opacity, and prevent clinicians from being misled into interpreting
adhesive radiotransparency as gap formation or recurrent caries at
the restoration margin.119
On the other hand, there is no etch-and-rinse and self-etch adhe-
sive capable of completely replacing water in the extrafibrillar and
intrafibrillar collagen compartments with resin monomers.120,121 The
objective of adding bioactive particles is to stimulate remineralization
in areas where the collagen is unprotected and to compensate degra-
dation of the polymer matrix.
Taubock et al.112 incorporated 20 wt.% of ultrafine particles (SiO2–
Na2O–CaO–P2O5–Bi2O3) into the Bis-GMA/TEGDMA matrix.
A material with bioactive properties and capacity to raise the pH in
aqueous suspensions, as a result of the release of alkali ions, mainly
Na+, and the incorporation of protons (H+) into the corroding mate-
rial, gave these particles their anti-microbial activity.122,123 This author
added Bi2O3 with the purpose of making the adhesive system
radiopaque.
Recently, a study demonstrated that the incorporation of nio-
bium phosphate glass (40 wt.%) alone was capable of providing the
adhesive system with radiopacity (Figure 4). The addition of this
bioactive glass also provided an increase in the degree of conver-
sion, hardness, and stabilized the bond strength after 6 months of
storage in water.41
b3252_Ch-09.indd 262 27-11-2018 03:04:14 PM

Figure 4. Radiopacity of human tooth and two adhesive systems: control
(no addition of glass particles) and an experimental adhesive containing 40%
NbG
Along the same lines, the addition of the same NbG glass did not
change the degree of conversion, increased the hardness, and pro-
vided the commercial adhesive systems (Prime Bond, Dentsply) with
radiopacity, but it was not capable of preventing the reduction in
bond strength after 6 months of storage. However, it was possible to
observe particles of NbG glass obliterating the entrance of dentinal
tubules and within the adhesive layer (Figure 5) (Unpublished data).
The use of an adhesive system doped with bioactive glasses would
be of greater use in deep cavities and/or under carious tissue. Up to
now, new studies have been found in the literature with bioactive
adhesive systems under carious dentin.
A bioactive glass impregnated in carious dentin could interrupt
the process of demineralization,124 bacterial growth,125 and the
enzymatic action of metalloproteinases.11,50,106,126–128 The application
of bioactive glass in caries-affected dentin creates a smear layer rich
in minerals,129 which could remineralize dentin and recover the
b3252_Ch-09.indd 263 27-11-2018 03:04:14 PM

Figure 5. Presence of NbG particles at the entrance of the dentinal tubules
(white arrow) and within the adhesive layer
mechanical properties of this tissue. Moreover, the presence of bioac-

tive glass microparticles acts as a link for binding with functional
monomers (MDP) of adhesive materials.50,130
Studies in progress have presented interesting results, showing
that the bioactive NbG glass was capable of increasing the bond
strength values only to dentin from which carious tissue had been
completely removed. Airborne particle abrasion with microparticles
of NbG in deep dentin may have sealed the entrance to the dentinal
tubules (Figure 6), making it difficult for the passage of water to
occur or serving as a link with the restorative material, and thus
increasing the bond strength values. Other studies with a “bioactive
adhesive” and bioactive glass need be conducted to evaluate their
b3252_Ch-09.indd 264 27-11-2018 03:04:16 PM

Figure 6. NbG microparticles in dentinal tubules (white arrows) after air-
borne particle abrasion with bioactive glass
ability to remineralize hybrid layers or affected dentin and to restore

the mechanical properties of structures. At this time, many research-
ers are looking for adhesive materials capable of remineralizing hybrid
layers and completely restoring the mechanical properties of mineral-
depleted dental collagen structures within resin-bonded interfaces
through biomimetic apatite formation.131
4. Conclusions and Outlook

The first bioactive glass formulations were developed over 40 years
ago. However, some mechanisms by which these materials interact
with body tissues remain not fully elucidated. The use of bioactive
b3252_Ch-09.indd 265 27-11-2018 03:04:18 PM

particles in dentistry generated a lot of research that enabled the

development of biomaterials with the most varied applications.
Although various formulations of bioactive glasses have been reported
in the literature, this chapter has focused on only three of them, as
well as their inclusion in restorative materials commonly used.
However, most of the literature on the application of bioactive
glass in restorative materials consists of laboratory research. Given the
promising results found in this work, further studies are necessary in
order to prove the clinical application for these biomaterials.
Acknowledgments
The authors are grateful to Foundation for the Support of Scientific
and Technological Research of Maranhão (FAPEMA–BEPP 6527/
2014).
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124. Banerjee, A. Br. Dent. J. 2013, 214, 107.
125. Waltimo, T.; Brunner, T. J.; Vollenweider, M.; Stark, W. J.; Zehnder, M.
J. Dent. Res. 2007, 86, 754.
126. Sauro, S.; Watson, T. F.; Thompson, I.; Banerjee, A. J. Dent. 2012,
40, 896.
127. Sauro, S.; Watson, T. F.; Thompson, I. J. Dent. 2010, 38, 411.
128. Wang, Z.; Jiang, T.; Sauro, S.; Wang, Y.; Thompson, I.; Watson, T. F.;
Sa, Y.; Xing, W.; Shen, Y.; Haapsalo, M. J. Dent. 2011, 39, 746.
129. Bakry, A. S.; Takahashi, H.; Otsuki, M.; Tagami, J. Dent. Mater. 2013,
29, 357.
130. Carvalho, E. M.; Lima, D. M.; Carvalho, C. N.; Loguercio, A. D.;
Martinelli, J. R.; Bauer, J. J. Prosthodont. Res. 2015, 59, 129.
131. Sauro, S.; Pashley, D. H. Int. J. Adhes. Adhes. 2016, 69, 39.
b3252_Ch-09.indd 273 27-11-2018 03:04:18 PM

b2530_FM.indd 6 01-Sep-16 11:03:06 AM

Chapter 10
Dental Adhesives
Marcelo Giannini*,‡, Patrícia Makishi*,§,

Ronaldo Hirata†,¶, and Carolina Bosso André*,
*Department of Restorative Dentistry,
Piracicaba Dental School, State University
of Campinas-SP, Brazil
†
Department of Biomaterials and Biomimetics,
New York University, College of Dentistry
New York, USA
‡
giannini@fop.unicamp.br
§
pmakishi@hotmail.com
¶
rh1694@nyu.edu
carolina.bosso@gmail.com

Adhesive dentistry is among the fastest growing fields in dental

science. The treatment methods are a continuous learning process
for practitioners and require adaptation to new technologies, mate-
rials, clinical techniques, and research findings. A realistic prediction
about the success of a dental restoration requires a deep understand-
ing of the bonding mechanism, including mechanical, chemical, and
biological viewpoints, as well as the consideration of the risks and
contributing factors that may affect the durability of dental restora-
tions. In vitro bonding evaluations as marginal adaptation, bond
strength, and interaction of the bond with the tooth substrate are
275
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well recognized as comparative tools of the restorative materials

bonding performance in vivo.
1. Introduction
1.1. Mineralized Dental Tissues
Human teeth contain two mineralized tissues called enamel and dentin.
Enamel is the hardest tissue of the human body and is composed of
minerals, which make up 96% of its composition.1 The remainder of its
composition is water and some proteins, such as amelogenins and
enamelins. The main mineral component is the hydroxyapatite, which
is formed by calcium phosphate crystals. The enamel has high Young’s
modulus (approximately 83 GPa) and high tensile strength (approxi-
mately 42 MPa) because of its high mineralization level. However,
when enamel is stressed transversally to its prismatic orientation, the
strength is significantly weaker (approximately 11 MPa).2,3 Enamel rod
or prims are the basic units of dental enamel (Figure 1), which is formed
by ameloblast cells during the early stage of enamel formation.1
The amelo–dentinal junction is the interfacial area between
enamel and underlying dentin (Figure 2) which has biomechanical
Figure 1. SEM images showing the human dental enamel (R: rods; Arrows:
interrod area) from a transversal cut (a) and from a longitudinal cut (b)
(5,000× magnification)
b3252_Ch-10.indd 276 27-11-2018 03:04:36 PM

Dental Adhesives 277
Figure 2. SEM image showing the amelo-dentinal junction (between

arrows), that is the interfacial region between the dentin (D) and enamel (E)
properties that avoid catastrophic tooth fractures from the cracks

formed in outer enamel.3,4 Unlike enamel, the dentin is a complex
dental tissue in terms of morphology, composition, and physiology.
The composition depends on the analysis location, and the main
components are minerals (70–45% by weight), organic content
(33–18%), and water (22–12%). The inorganic phase is basically
hydroxyapatite, which is deposited around collagen fibrils during the
dentinogenesis. Besides collagen, other organic components are pre-
sent, such as glycoproteins and proteoglycans. The dentin structural
units are the dentinal tubules and intertubular and peritubular
(or intratubular) dentin (Figure 3).1
b3252_Ch-10.indd 277 27-11-2018 03:04:37 PM

Figure 3. SEM images showing the structural units of dentin (Arrow: den-
tinal tubule, IT: Intertubular dentin and Intratubular dentin: whitish aspect
around the tubules) for occlusal superficial dentin close to enamel (a) and
deep dentin close to pulp chamber (b) (2,000× magnification)
1.2. Historic of Bonding Agents

The improvement of bonding agents had run parallel with the mor-
phological and physiological mineralized hard dental tissues studies.
Adhesion to enamel began with Buonocore et al., 1955, in which the
phosphoric acid altered, morphologically and chemically, the enamel
surface.5 For dentin, the starting point was when Nakabayashi et al.,
1982, infiltrated adhesive monomers into conditioned dentin, which
has been called as hybrid layer or resin–dentin interdiffusion zone.6
The first dentin bonding agents contained glycerophosphoric acid
dimethacrylate,7,8 n-phenylglycine glycidyl methacrylate (NPG-
GMA),9 polyurethane resin10 orcyanoacrylate.11
The second generation of adhesives contained halophospho-
rous esters of unfilled resins such as Bis-GMA, and poor clinical
results were obtained with these adhesives.12,13 At the beginning of
the 1990s, some commercial dental adhesive brands became avail-
able for use with composite resin in direct restorations. This third
generation introduced the concept of a “primer” for dentin bond-
ing and was combined with etched enamel with phosphoric acid.
Primers were hydrophilic solutions of organic or mineral acids that
b3252_Ch-10.indd 278 27-11-2018 03:04:38 PM

were able to modify or partially remove the smear layer, allowing

the monomer resins to penetrate into dentinal tubules resulting in
resin tags formation. Also, these adhesives were able to chemically
bond with calcium from hydroxyapatite; however, the early micro-
leakage in dentin margins of composite restorations was not com-
pletely avoided.14,15
The application of phosphoric acid to etch the dentin was sug-
gested by Fusayama et al., 1979,16 but was clinically accepted only
during the nineties. The “total-etch” (enamel and dentin etching) or
the etch-and-rinse adhesives combined with wet-bonding technique
have been used until now (Figures 4 and 5). Hydrophilic monomers
infiltrate into the wet demineralized dentin forming the hybrid layer
or resin–dentin interdiffusion zone.17 The first acidic hydrophilic
monomer used in a commercial self-etching adhesive was the phenyl-
P. This category of bonding agent was also introduced during the
1990s.18,19 Many acidic resin monomers for self-etching systems have
been developed; however, the methacryloyloxi-decyl-dihydrogen-
phosphate (10-MDP) functional monomer seems to be the most
effective in bonding resin-based materials to dentin.20,21
Figure 4. SEM images showing the resin–enamel interfaces with etch-and-
rinse (a) and self-etching adhesive systems (b). Arrows show the enamel–
adhesive interfaces (E: enamel; AL: adhesive layer; CR: composite resin)
b3252_Ch-10.indd 279 27-11-2018 03:04:38 PM

Figure 5. TEM image (a) showing the resin–dentin interface of an etch-
and-rinse adhesive. The hybrid layer (HL) corresponds to the infiltration of
adhesive resin monomers into dentin with exposed collagen by acid etching
(1,100× magnification) (Vermelho PM and Giannini M, 2011). Confocal
laser microscopy image (b) showing the resin–dentin interface of an etch-
and-rinse adhesive. The rhodamine dye (red) was incorporated to the bond-
ing agent (25× objective lens). (*: resin tags; AL: adhesive layer; D: dentin;
CR: composite resin)
2. General Composition
Contemporary bonding agents contain resin monomers (hydropho-
bic and hydrophilic ones), organic solvents (such as acetone, alcohol,
and/or water), chemical initiator system, inhibitor, fillers (such as
colloidal silica, pyrogenic silica, and silicate glasses), and other com-
pounds (such as copolymers, desensitizing agents, sources of fluoride,
and antibacterial agents). Alcohol and acetone are monomers sol-
vents, indispensable for a good penetration of the monomers, while
water is important for the hydrolysis of functional monomers and to
re-expand the collapsed collagen network for the etched dentin tech-
nique. The fillers increase the polymer’s intrinsic strength and also
promote fluoride release depending on its composition. Initiators are
responsible for polymerizing the monomers, while inhibitors increase
the shelf life of the adhesive systems.22
Regarding hydrophilic resin monomers, they can be wetting
agents, responsible for penetrating into etched tooth surface and
b3252_Ch-10.indd 280 27-11-2018 03:04:39 PM

bond to calcium from hydroxyapatite and to collagen fibrils, which

are called adhesion-promoting functional monomers. The wetting
agents have small molecular dimensions and in uncured state they are
present as a fluid resin that is solvable in water, alcohol, and/or ace-
tone. The most popular wetting agent is the 2-hydroxyethyl meth-
acrylate (HEMA).22
2.1. Functional Adhesive Monomers

Functional monomers are acidic, have hydrophilic properties, and
can bond to calcium of the hydroxyapatite via chelate or ionic bond.
Their etching aggressiveness depends on the acidity of adhesive
monomeric composition. In general, dihydrogen acids are more
acidic that monohydrogenic ones because dihydrogen acids form
more protons following the dissociation reaction. Sulfonic acid,
phosphate, phosphonate, and carboxyl groups have been used in
commercial products. They act as wetting agents, demineralize the
dentin surface by causing proton release from functional groups, and
function as adhesion promoters by chemical reaction.22–24
NPG-GMA and N-tolylglycine glycidyl methacrylate (NTG-
GMA) have also been used as adhesion promoting monomers and are
co-initiators as is dimethylaminoethyl methacrylate (DMAEMA).23,25
The 4-methacryloyloxyethyl trimellitate anhydride (4-META) and
4-methacryloyloxyethyl trimellitic acid (4-MET) present two carbox-
ylic groups which are responsible for the demineralizing properties
and enhancing the wetting. These functional monomers are indicated
for adhesion to enamel, dentin, amalgam, metals alloys, or gold. The
4-META functional monomer is an organic acid anhydride derived
from carboxylic acid and is able to chelate to calcium from hydroxyapa-
tite. The salicylic group of N-methacryloyl-5-aminosalicylic acid
(5-NMSA) also chelates with calcium.20,22,27,28
The dihydrogenphosphate group of 10-MDP dissolves partially
the smear layer and etches the dentin surface, reacting chemically with
calcium from hydroxyapatite of enamel or dentin and forming cal-
cium salt. Studies have shown that 10-MDP forms stronger and more
stable ionic bonds with calcium than with other functional
b3252_Ch-10.indd 281 27-11-2018 03:04:39 PM

monomers.20,22,28 10-MDP has also been shown to bond alloy metals,

composites, and zirconia ceramics, and for this reason is used in the
new multimodes and single-step adhesives.
Other functional monomers such as 11-methacryloyloxy-1,10-
undecanedicarboxylic acid (MAC-10), 4-acryloyloxyethyl trimellitate
anhydride (4-AETA), Di-HEMA-phosphate, and HEMA-phosphate
are the main ingredients of some commercial adhesives. The amide
monomers bonds to collagen via a hydrogen bridge bond between
the carboxyl and amide groups of the monomer with the carboxyl
groups of collagen.24,29
The methacryloyloxy dodecylpyridinium bromide (MDPB) is a
hydrophobic monomer compound with antibacterial agent (dode-
cylpyridinium bromide).30,31 The hydrophilicity of the spacer group of
functional monomers determine their hydrophilic behavior and sus-
ceptibility to hydrolysis in aqueous solutions by water uptake. The
ester group of acrylates, phosphate, and carboxyl groups used in func-
tional monomers can hydrolyze in water.22
The main less-hydrophilic adhesive resin monomers are the
UDMA, Bis-GMA, TEG-DMA, other dimethacrylates, and mono-
mers. They are responsible for the formation of a densely cross-linked
polymer film following the polymerization reaction. They also keep
the surface hydrophobic against water uptake.32,33
3. Adhesive Systems
3.1. Etch-and-Rinse Adhesive Systems
This category of adhesives involves a previous etching with phos-
phoric acid, rinsing with water, and applying the adhesive on a wet
demineralized dentin. Etch-and-rinse adhesives can be used following
two or three steps; the first step being the acid etching for both types
of these adhesives. After etching for 15 s, the dentin is rinsed with
water to remove the acid gel and the mineral dissolved. The deminer-
alized dentin must be wet, and water occupies the spaces of the
removed mineral by the acid etching step.34,35
The acid etching removes the smear layer and smear plugs, dem-
ineralizing the dentin 5–10 mm in depth. In this demineralized area,
b3252_Ch-10.indd 282 27-11-2018 03:04:39 PM

the resin monomers are able to infiltrate forming the “hybrid layer”
or “resin–dentin interdiffusion zone”,6 which represents the replace-
ment of mineral with adhesive resin monomers (Figure 6). When a
three-step etch-and-rinse adhesive is used, an adhesive solution
known as primer is applied before hydrophobic bonding resin (third
step), while for two-step etch-and-rinse adhesives, a single combined
solution of hydrophilic and hydrophobic monomers is used. The
primer is a solution containing basically HEMA and a solvent such as
water or ethanol. The bonding resin is less hydrophilic and contains
Bis-GMA, TEG-DMA, UDMA, other hydrophobic resins, and other
components. The two-step etch-and-rinse adhesives are often used in
Restorative Dentistry and represent a combination of primer and
bonding resin in a single but complex mixture.17,21
If the demineralized dentin is poorly infiltrated with resin mono-
mer or if it slowly hydrolyses and leaches resin monomers from the
hybrid layer due to poor polymerization, the intrinsic matrix metalo-
proteinases (MMP) activity of dentin matrix can be expressed, leading
to an attack on the denuded collagen. This behavior could weaken the
hybrid layer, accelerating the loss of resin and collagen degradation.
Studies have demonstrated that the hydrophilic characteristic of the
adhesive monomers could compromise the long-term bonding effec-
tiveness and that insufficient resin infiltration or an incompletely
Figure 6. SEM images showing the resin–dentin interfaces with two-steps
(a) and three-steps (b) etch-and-rinse adhesives (HL: hybrid layer; *; resin
tags: D: dentin; AL: adhesive layer; CR: composite resin) (1,000× magnifica-
tion) (Carvalho et al., 2013)
b3252_Ch-10.indd 283 27-11-2018 03:04:39 PM

cured hydrophilic monomer could remain at the bottom of the hybrid

layer, leading to leakage. Consequently, both factors may expose the
collagen matrix, which may be degraded by proteolytic enzymes.36–38
In an attempt to enhance the mechanical properties and reduce
biodegradation rates, studies have focused on the incorporation of
MMP inhibitors in the bonding procedure, such as chlorhexidine,
galardin, and flavonols.39,40 Studies have reported the use of chlorhex-
idine, which exhibits an inhibitory effect against MMPs and cysteine
cathepsins (another class of collagenolytic enzymes).41,42 However,
controversial results regarding the pre-treatment of dentin with chlo-
rhexidine before bonding have been reported. While some studies
have shown long-term preservation of integrity of the hybrid layers
and bonding efficacy, other studies indicated no detrimental effect on
the bond strength or the sealing ability.37,43–46
Another approach would be to inactivate the endogenous MMPs
via biomodification of the dentin matrix with collagen cross-linkers.
Glutaraldehyde has been used as a cross-linking agent for years.31,38
Other cross-linkers agents, such as proanthocyanidin extract and car-
bodiimide have been used to inactivate the proteolytic activity of
MMPs and increase the bond strength of adhesives to dentin.47–49
3.2. Self-Etching Adhesive Systems

The main characteristic of self-etching systems is the use of non-rinse
acidic monomers, i.e. no phosphoric acid etching and water rinsing
steps are required. The acidic monomers are present on formulation,
which are responsible for micromechanical and chemical bonding.
These two bonding mechanism have provided good results in the
laboratory and the clinic, especially for the self-etching primers. The
three-steps etch-and-rinse adhesives have also been described as effec-
tive bonding agents when compared to self-etching primers.21,50,51
The self-etching primers are applied in two steps: primer and
bonding. The acidic primers are aqueous solution containing organic
solvents, wetting agent (such as HEMA), and a functional monomer
with carboxyl or phosphate groups. The fluid bonding resin is less
hydrophilic and is mixed with primer to reduce the hydrophilicity of
b3252_Ch-10.indd 284 27-11-2018 03:04:40 PM

the resin monomers, which are in contact with dentin, giving a more
hydrophobic outer surface to bond with the restorative composite.22
The all-in-one or single-step self-etching adhesives are the most
simplified bonding agents. They are a complex aqueous solution
containing hydrophilic and hydrophobic resin monomers, organic
solvents, initiators, and other components, depending on the com-
mercial product. Studies have indicated that this category of self-
etching system, as well as two-steps etch-and-rinse adhesives produced
less durable composite restorations, according to clinical and labora-
tory investigations.21,50,51
Based on the acidic aggressiveness of self-etching adhesives, they
are classified as “mild” (pH around 2) and “strong” (pH < 1). For
mild pH self-etching adhesives, the collagen fibrils are only partially
exposed, with residual hydroxyapatite still attached to the collagen
fibrils and available for chemical interaction with functional mono-
mers (Figure 7). For strong self-etching adhesive solutions, the dentin
etching is similar to the effects found with 37% phosphoric acid
etching.21,23
In order to reduce the hydrophilicity and increase the bonding
durability, some single-step self-etching adhesives are free of HEMA
Figure 7. TEM image showing the resin–dentin interface with two-step

self-etching adhesive (a) (3,000× magnification) (Vermelho PM, master
thesis — 2011). SEM image showing the resin–dentin interfaces with single-
step self-etching adhesive (b) (HL: hybrid layer; *: resin tags; D: dentin; AL:
adhesive layer; CR: composite resin) (1,000× magnification)
b3252_Ch-10.indd 285 27-11-2018 03:04:40 PM

monomer. These HEMA-free self-etching adhesives also contain a

functional monomer, such as carboxylic acid monomers, which also
play the role of wetting agents.52–54 However, some concerns have
been raised for the clinical use of simplified all-in-one adhesives,
because the degree of conversion seems to be low when compared to
two-step self-etching and etch-and-rinse adhesives. The low conver-
sion rate can compromise the mechanical strength and form an adhe-
sive film that behaves as a semi-permeable membrane, with high
permeability through polymerized adhesive layer.55–59
4. Advances and Future Perspectives

in Adhesive Dentistry
A trend in adhesive dentistry is to provide simple and time-effective
chairside solutions. One of these examples is the multimode adhe-
sives, or so-called universal adhesives. The multimode adhesives con-
tain 10-MDP and are self-etch adhesives designed using the same
concept as that used for all-in-one adhesives; however, they incorpo-
rate the versatility of being adaptable to different clinical situations
such as the use on enamel, dentin, alloy, ceramic, or composite sub-
strates. A long-term investigation indicated that current universal
adhesives may perform equally well on an etched enamel substrate as
a conventional adhesive system, without leakage; however, they may
have a bonding performance that is equal to or inferior than a con-
ventional self-etching adhesive when using dentin as a substrate, with
similar degradation patterns at the tooth–dentin interface.60 In addi-
tion, this new category of adhesive system exhibited good long-term
bonding performance to sandblasted indirect resin composite.
However, the use of separate bottles of silane and bonding resin
resulted in superior bond strength for etched-glass-based ceramic.61
Thus, it can be speculated that the bonding performance of universal
adhesives are manufacturer- and substrate-specific.
Another issue that should be addressed is that the bond forma-
tion between the resin composite and tooth structure can be chal-
lenging because two different interfaces must be considered: that
between the dentin/enamel substrate and adhesive system, and that
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between the adhesive system and resin composite. Polymerization

shrinkage of methacrylate-based resin composites during curing may
result in contraction stress and a loss of marginal adaptation, which
may lead to early failures. Current resin composite technology is
focused on the polymeric matrix, developing systems with reduced
polymerization shrinkage stress to reduce the contraction stress dur-
ing the polymerization.62 For posterior restorations, a new category
of resin composites have been examined to reduce the polymeriza-
tion shrinkage and stress with a single increment, known as bulk-fill.
Due to the differences in filler loading and resin matrix characteris-
tics of this new category of resin composites, the mechanical proper-
ties can be expected to be material dependent. Studies have
demonstrated that bulk-fill composites have higher volumetric
shrinkage than conventional composites, even when their polymeri-
zation shrinkage values are lower.63 However, in a Class I cavity, less
volumetric polymerization contraction than that in a conventional
composite was observed when a bonding agent was applied.64
Therefore, it can be assumed that current adhesives and resin com-
posites play a major role in the long-term success of restorations and
that their mechanical and chemical properties should be considered
as a combined set.65,66
The ultimate goal in dental materials science is the development
of self-adhesive restorative materials, without the need for an adhe-
sive to bond to the tooth substrate. Ideally, these materials should
also provide aesthetic characteristics, with great functionality and
durable bonding at affordable costs. Attempts have been made
regarding the development of self-adhesive resin composites with the
incorporation of functional monomers that serve as adhesion pro-
moters to hydroxyapatite67; however, the separate use of adhesive and
resin composite components still results in superior bonding perfor-
mance.68 Once the limitations related to the mechanical and chemical
properties of these restorative materials are properly addressed, it will
be possible to have even simpler and faster procedures with durable
bonding in the future.
Restorative techniques and dental materials have evolved signifi-
cantly over the years, expanding our clinical options. It appears
b3252_Ch-10.indd 287 27-11-2018 03:04:40 PM

reasonable to assume that much of this evolution was based on in

vitro and in vivo evaluation tests. Although the current evaluation
methods provide good information on the biomechanical properties
of restorative materials, it is of crucial importance for researchers to
investigate the materials from different aspects, developing even
more sophisticated yet clinically relevant methods to evaluate the per-
formance of restorative materials.
The introduction of digital technologies is reshaping the model
for research and clinical care in three dimensions. One example is
the use of optical coherence tomography (OCT) to follow-up on
adhesive restorations over time and to non-invasively predict the
bond durability.69 This field is a very revolutionary and exciting
field for diagnostic and treatment in Dentistry. Within the range of
non-invasive imaging techniques, OCT has been reported to be a
promising high-resolution biomedical optical method to examine
the microstructural details of hard and soft oral tissues over a small
distance. This technology implements high-resolution, volumetric,
and cross-sectional tomographic imaging of the internal micro-
structure of materials and biological tissues on the micron-scale
based on depth-resolved optical reflectivity.70 This technique has
been applied in Dentistry to characterize caries,71 assess gaps
between the resin–tooth interface in two-dimensional (2D) and
three-dimensional (3D) images,68,69 and evaluate voids and internal
defects in restorations.72 More recently, studies have investigated
the association between real-time OCT findings related to the mar-
ginal adaptation of restorative materials and the bond strength,69
gap formation and the bond strength,73 and the effect of marginal
sealing ability on demineralization progress.74 It has thus been pos-
sible to better understand and mimic the degradation process in
vitro using different factors in the same sample, which is clearly
clinical relevant. Chairside diagnosis will also open new horizons
into non-invasive procedures, and OCT can be a helpful tool in the
selection of the most appropriate treatments and preventive meas-
ures. It is assumed that Dentistry will continue to advance and that
new, better, smarter technologies will continue to emerge and affect
both research and clinical practice.
b3252_Ch-10.indd 288 27-11-2018 03:04:40 PM

Acknowledgments
This book chapter was partially supported by the São Paulo Research
Foundation (FAPESP #2013/22823-9 and #2009/51674-6), the
Coordination for the Improvement of Higher Education Personnel
(CAPES #1777-2014 and #1778-2014) and The National Council
for Scientific and Technological Development (CNPq #307217-
2014-0). The authors are grateful to Dr. Adriana Oliveira Carvalho
and Dr. Paulo Moreira Vermelho for providing SEM and TEM
images.
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28. Hanabusa, M.; Yoshihara, K.; Yoshida, Y.; Okihara, T.; Yamamoto, T.;
Momoi, Y.;Van Meerbeek, B. Eur. J. Oral Sci. 2016, 124, 204.
29. Nishiyama, N.; Suzuki, K.; Asakura, T.; Komatsu, K.; Nemoto, K.
J. Dent. Res. 2001, 80, 855.
30. Imazato, S.; Russell, R. R.; McCabe, J. F. J. Dent. 1995, 23, 177.
31. André, C. B.; Gomes, B. P.; Duque, T. M.; Stipp, R. N.; Chan, D. C.;
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32. Asmussen, E.; Peutzfeldt, A. Dent. Mater. 1998, 14, 51.
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34. Bertolotti, R. L. J. Esthet. Dent. 1991, 3, 1.
35. Kanca, J. 3rd. Quintessence Int. 1992, 23, 625.
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Caries Res. 2003, 37, 58.
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37. Pashley, D. H.; Tay, F. R.; Yiu, C.; Hashimoto, M.; Breschi, L.;
Carvalho, R. M.; Ito, S. J. Dent. Res. 2004, 83, 216.
38. Pashley, D. H.; Tay, F. R.; Breschi, L.; Tjaderhane, L.; Carvalho, R. M.;
Carrilho, M.; Tezvergil-Mutluay, A. Dent. Mater. 2011, 27, 1.
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J. Dent. 2012, 40, 1052.
40. Perdigao, J.; Reis, A.; Loguercio, A. D. J. Esthet. Restor. Dent. 2013, 25,
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41. Tersariol, I. L.; Geraldeli S.; Minciotti, C. L.; Nascimento, F. D.;
Paakkonen, V.; Martins, M. T.; Carrilho, M. R.; Pashley, D. H.; Tay, F. R.;
Salo, T.; Tjaderhane, L. J. Endod. 2010, 36, 475.
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Geraldeli, S.; Tezvergil-Mutluay, A.; Carrilho, M. R.; Carvalho, R. M.;
Tay, F. R.; Pashley, D. H. Dent. Mater. 2013, 29, 116.
43. Gurgan, S.; Bolay, S.; Kiremitci, A. J. Oral Rehabil. 1999, 26, 836.
44. de Castro, F. L.; de Andrade, M. F.; Duarte Junior, S. L.; Vaz, L. G.;
Ahid, F. J. J. Adhes. Dent. 2003, 5, 129.
45. Turkun, M.; Turkun, L. S.; Kalender, A. Quintessence Int. 2004, 35,
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46. Carrilho, M. R.; Geraldeli, S.; Tay, F.; de Goes, M. F.; Carvalho, R. M.;
Tjaderhane, L.; Reis, A. F.; Hebling, J.; Mazzoni, A.; Breschi, L.;
Pashley, D. J. Dent. Res. 2007, 86, 529.
47. Bedran-Russo, A. K.; Pereira, P. N.; Duarte, W. R.; Drummond, J. L.;
Yamauchi, M. J. Biomed. Mater. Res. B. Appl. Biomater. 2007, 80, 268.
48. dos Santos, P. H.; Karol, S.; Bedran-Russo, A. K. J. Biomech. 2011, 44,
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Tay, F. R.; Pashley, D. H.; Arola D. Dent. Mater. 2016, 32, 211.
50. Reis, A. F.; Arrais, C. A.; Novaes, P. D.; Carvalho, R. M.; De Goes,
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51. Reis, A. F.; Giannini, M.; Pereira, P. N. Dent. Mater. 2007, 23, 1164.
52. Cantanhede de Sa, R. B.; Carvalho, A. O.; Puppin-Rontani, R. M.;
Ambrosano, G. M. B.; Nikaido, T.; Tagami, J.; Giannini, M. J. Adhes.
Dent. 2012, 14, 543.
53. Mahdan, M. H. A.; Nakajima, M.; Foxton, R. M.; Tagami, J. J. Dent.
2013, 41, 861.
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54. Van Landuyt, K. L.; De Munck, J.; Ermis, R. B.; Peumans, M.; Van
Meerbeek, B. Clin. Oral Investig. 2014, 18, 1045.
55. Ferracane, J. L.; Greener, E. H. J. Biomed. Mater. Res. 1986, 20, 121.
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J. Dent. 2002, 30, 371.
57. Bae, J. H.; Cho, B. H.; Kim, J. S.; Kim, M. S.; Lee, I. B.; Son, H. H.;
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58. Cadenaro, M.; Antoniolli, F.; Sauro, S.; Tay, F. R.; Di Lenarda, R.; Prati,
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525.
59. Nunes, T. G.; Garcia, F. C.; Osorio, R.; Carvalho, R.; Toledano, M.
Dent. Mater. 2006, 22, 963.
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61. Makishi, P.; Andre, C. B.; Lyra, e Silva, J. P.; Bacelar-Sa, R.; Correr-
Sobrinho, L.; Giannini, M. Oper. Dent. 2016, 41, 541.
62. Ferracane, J. L. Dent. Mater. 2011, 27, 29.
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Soares, L. E.; Martin, A. A.; Ambrosano, G.; Giannini, M. Dent. Mater.
2015, 31, 1542.
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39, 441.
66. Hirata, R.; Clozza, E.; Giannini, M.; Farrokhmanesh, E.; Janal, M.;
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Biomater. 2015, 103, 798.
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Vulicevic, Z. R.; Ferrari, M. Am. J. Dent. 2012, 25, 239.
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2013, 41, 80.
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Res. 2015, 94, 1070.
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b2530_FM.indd 6 01-Sep-16 11:03:06 AM

Chapter 11
Dental Composites — Chemistry

and Composition
Carmem S. Pfeifer
Department of Restorative Dentistry, Oregon Health
and Science University,
2730 SW Moody Ave., Portland, OR, 97201, USA
pfeiferc@ohsu.edu
Dental composites have significantly evolved since their introduction

on the market in the early 1960s. Most of the innovations have
focused on the inorganic phase, with the basic chemistry for the
organic phase still based on methacrylate polymerizations. The rea-
son for that is the very robust polymerization mechanism, which
progresses at faster rates at room temperature, and also the conveni-
ence of on demand cure via photoinitiation. The materials are rela-
tively stable and present acceptable mechanical properties. However,
the average lifetime of restorations is still only about 10 years in ser-
vice, with replacements being costly both financially and in terms of
tooth structure. The main causes for replacement are secondary caries
and fracture. This chapter examines the progress made so far in
updating the organic matrix of commercially available systems, as well
as perspectives for future developments. Strategies to reduce interfa-
cial and bulk stress development, water sorption and solubility, and
295
b3252_Ch-11.indd 295 27-11-2018 03:06:09 PM

overall degradation by hydrolysis and esterase attack are reviewed.

Basic concepts in polymerization mechanisms are also summarized.
1. Introduction
Dental composites have become the most popular choice for direct
esthetic restorations and are ubiquitously used in dental offices across
the globe. Their basic composition consists of an inorganic phase
(mostly glass fillers) and an organic matrix. Most of the developments
that translated into commercial products since the introduction of
the first iteration of direct restorative composites have involved the
filler phase. The organic matrix remains mostly based on meth-
acrylate chemistry, since BisGMA was patented by Rafael Bowen in
the late 1950s. Even though new monomers have been introduced
in the market, more notably in the last 15 years, the basic polymeriz-
able functionality still relies on methacrylates, for a number of dif-
ferent reasons. The main advantage of this chemistry is the fast
polymerization rate under mild conditions, usually at room tempera-
ture and using photoinitiation. This allows dentists to polymerize the
materials on demand, and allows for pigmentation and other types of
characterization, making it an excellent choice for highly esthetic res-
torations. However, in the current state, composite restorations only
last an average of 10 years in service, with the main reason for failure
being secondary decay, post-operative sensitivity, and fracture.1
Secondary decay is usually brought about by failure of the adhesive
interface. This can be caused by polymerization stress generation that
leads to separation of the material from the substrate, in a phenome-
non analogous to the delamination due to stress generation in the
coatings industry.2–4 In addition, the adhesive and composite materials
are prone to degradation by hydrolysis or enzymatic action via the
ester bonds present in the methacrylate.5,6 This leads not only to the
breakdown of the material over time but also acts as the source for
potentially toxic leachates.
In spite of the many efforts to replace or aggressively modify
methacrylate monomers, very few examples have come to commercial
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Dental Composites — Chemistry and Composition 297
fruition. One notable example is the use of epoxide ring-opening

polymerization, which aimed at reducing the inherent stress genera-
tion, due to the lower molar shrinkage coefficient of those materials
compared to methacrylates. Other efforts have focused on producing
more hydrophobic materials to reduce water/salivary degradation, or
higher molecular weight monomers to reduce polymerization shrink-
age. These examples of novel monomers will be discussed in this
chapter, along with an overview of methacrylate polymerization.
2. Current Materials: Methacrylate Chemistry

Methacrylate monomers have the general chemical structure repre-
sented in Figure 1. They polymerize via a free-radical mechanism,
through chain-growth reactions. Monofunctional methacrylates were
the first monomers to be used to produce restorative composites.7
Due to their high shrinkage values, as well as all the issues involved
with linear polymers (high water sorption and solubility, for example),
these monomers tended to produce materials with very poor clinical
performance.8–10 Those primitive compositions also used large quartz
particles as fillers, leading to unacceptable clinical wear.11,12 In addi-
tion, in those early days, no adhesive was used prior to the application
of the composite, which all combined, ultimately gave dental com-
posites a bad reputation. In the late 1950s, Rafael Bowen synthesized
the monomer that is still being used today as the main component
for many commercial formulations: bisphenol A diglycidyl ether
dimethacrylate, widely known as BisGMA (Figure 1). This molecule
has a few desirable features: (1) It presents two methacrylate func-
tionalities, one on each end of the molecule, and therefore, is capable
of forming a cross-linked network; (2) it has a very stiff backbone,
responsible for forming rigid cross-links; (3) it presents two hydroxyl
groups, capable of strong secondary intermolecular interactions
(these two items combined confer good mechanical properties to the
monomer); (4) it presents a relatively high molecular weight (512 g/
mol), and therefore, a lot less shrinkage than the first monometh-
acrylates used.
b3252_Ch-11.indd 297 27-11-2018 03:06:09 PM

Figure 1. General structure of dimethacrylate monomers and common

examples of dimethacrylates used in dental composites
The disadvantage with BisGMA is that the same hydroxyl

groups that promote toughening of the network also cause this
monomer to present high viscosity, which prohibits the addition of
adequate amounts of filler particles — those present as a powder,
and are responsible for about 60% of the volume of the material
and most of the mechanical properties. For that reason, a low vis-
cosity, di-functional diluent is usually employed. Triethylene glycol
b3252_Ch-11.indd 298 27-11-2018 03:06:09 PM

dimethacrylate (TEGDMA) is the most common (Figure 1), but its

lower molecular weight (286 g/mol) significantly increases the
shrinkage of the final material.13 Therefore, in more modern com-
mercial materials, TEGDMA has been totally or partially replaced
by other diluent monomers, such as urethane dimethacrylate and
ethoxylate bisphenol A dimethacrylate (UDMA and BisEMA,
respectively), which present higher molecular weights (470 and
540 g/mol, respectively — Figure 1). The addition of diluents also
has an implication on reaction kinetics, as will be explored in the
following sections.
The combination of these high molecular weight di-methacrylate
monomers significantly reduced the polymerization shrinkage and
improved the mechanical properties compared to the primitive mono-
methacrylate versions.
In addition, the use of modern adhesives prior to composite
placement, especially with the advent of dentin bonding, has greatly
improved interfacial stability. However, the polymerization shrink-
age for a typical methacrylate-based composite is still around 4%.14
Although that does not seem like a significant amount, the fact that
the polymerization of these materials takes place confined by the
adhesion to the cavity preparation walls leads to the development of
interfacial stresses during polymerization, which can lead to the de-
bonding of the restoration and formation of interfacial gaps. In the-
ory, the presence of such gaps may facilitate the colonization of
cariogenic bacteria, and it has been proposed that this is the mecha-
nism for the development of secondary decay.15–17 It has been demon-
strated that S. mutans can indeed colonize the bottom of such gaps.18
However, with the current clinical evidence, researchers have still not
been able to establish a definitive correlation between stress genera-
tion and secondary decay. In fact, many of the low-shrinkage/low-
stress materials that present improved performance in vitro have failed
to show improved performance clinically.19,20 This is due to the com-
plex, multifactorial nature of dental caries development. Nevertheless,
a lot of effort has been placed in developing low-shrinkage/low-stress
materials, starting in the 1990s and persisting until today. Those will
be addressed in the subsequent sections.
b3252_Ch-11.indd 299 27-11-2018 03:06:09 PM

Another facet of methacrylates is the presence of ester bonds in

the network. Those bonds have been shown to be labile in aqueous
environment and through the action of esterases present in saliva and
dentinal tissue.21–24 A number of studies have demonstrated that
methacrylate monomers are prone to degradation by cholinesterase,
leading to the formation of products such methacrylic acid, triethyl-
ene glycol methacrylate (TEGMA), and bis-hydroxy-propoxy-phenyl-
propane (Bis-HPPP), all markers of resin-matrix breakdown, and all
of those with potential cytotoxicity effects.22–24 This effect has been
demonstrated to be time- and enzyme-concentration dependent.22,25–26
However, some controversy still exists as to whether the enzymes
present in saliva or dentinal tissues have enough specificity to degrade
methacrylate esters, as well as whether the esters are accessible to
these enzymes, particularly in the bulk of the material. In any event,
it is undeniable that water molecules are definitely small enough and
non-specific enough to attack those ester bonds, and simple hydroly-
sis by water molecules indeed results in the same degradation prod-
ucts. Apart from the potential biocompatibility concerns, the water
uptake and degradation of the organic matrix also contributes to the
breakdown of the material itself, facilitating crack propagation, espe-
cially under fatigue, and ultimately bulk fracture.27–29 In addition,
when used in the more hydrophilic compositions of dental adhesives,
the breakdown of esters in methacrylates can be potentiated.30 Several
authors have demonstrated an effect known as “water treeing”, which
consists of water seeping through the adhesive layer over time, caus-
ing degradation on the margins of the restorations.31 This has moti-
vated some companies to introduce compositions that are more
hydrophobic and/or with alternative chemistries, to improve the
resistance to water and enzymatic degradation. In 2012, the National
Institute of Dental and Craniofacial Research in the United States has
spearheaded an initiative to develop new dental composite monomers
departing from methacrylate chemistry (http://grants.nih.gov/
grants/guide/rfa-files/RFA-DE-13-001.html). The main goal of
this initiative was to double the service life of dental composites.
Those new proposed chemistries, along with others available in the
literature, will be discussed later in this chapter.
b3252_Ch-11.indd 300 27-11-2018 03:06:09 PM

2.1. Polymerization Kinetics of Cross-Linked

Methacrylated Networks
2.1.1. Influence of Monomer Choice
The free-radical, chain growth polymerization reaction of meth-
acrylates can be divided in three non-consecutive phases: initiation,
propagation, and termination. Methacrylates are relatively stable in
ambient conditions, and therefore, for the reaction to commence,
some form of activation needs to take place to generate enough radi-
cals to overcome the energy of activation of methacrylate conversion.
This activation can be achieved via thermal, redox, or photochemical
mechanisms, or a combination of those, provided that the correct
pairing of appropriate initiators and energy source is employed. The
concentration of vinyl double bonds can be followed in real time
using an infrared spectrometer, and the degree of conversion of
monomer to polymer can be calculated.32,33 Once the first radical is
generated, it can attack the first vinyl double bond, and start propaga-
tion. At this stage, the reaction is chemically controlled, as the molec-
ular weight of the polymerizing species has not yet increased to the
point of significantly increasing viscosity, and molecular mobility
remains high. Therefore, the only limiting factor is the availability of
initiators/source of energy and monomers. At this stage, propagation
and termination reactions occur concomitantly and at similar rates. As
the reaction progresses, viscosity starts to increase, and the reaction
becomes diffusion-controlled, hindering the mobility of larger mole-
cules and by consequence, termination by bi-molecular interaction.
This leads to a significant decrease in the rate of termination. At the
same time, small molecule monomers are still relatively free to
move, so the rate of propagation increases in relation to termina-
tion, leading to auto-acceleration of the reaction (Tromsdorff
effect), up until the point when the maximum rate of polymeriza-
tion is recorded. This effect can be observed in the reaction kinetics
curve depicting rate of polymerization as a function of degree of
conversion (Figure 2). The gelation of the forming network is an
important landmark because it influences the limiting conversion
achieved by a monomer system, as well as polymerization stress
b3252_Ch-11.indd 301 27-11-2018 03:06:09 PM

Figure 2. Polymerization kinetics of a dimethacrylate monomers. The

graph depicts the rate of polymerization as a function of degree of double
bond conversion. Important landmarks are highlighted
relaxation opportunities (Figure 3). The exact gel point is very dif-
ficult to determine solely from the reaction kinetics curve, so other
tools, such as an oscillating rheometer coupled with an infra-red spec-
trometer, are often used to determine the conversion at the onset of
gelation.34 As the reaction further progresses, the decrease in mobility
affects even small molecule movement, and therefore the rate of
propagation also starts to decrease, in a phenomenon known as auto-
deceleration, observed after the maximum rate of polymerization is
recorded (Figure 2). That point marks the onset of vitrification of the
network.34
2.1.2. Implications on Polymerization Stress Development

At the bottom of the auto-deceleration slope, the network is com-
pletely vitrified, and any further conversion results in significant stress
build up (Figure 3). This is explained by the fact that the limited
amount of conversion that takes place in this phase is a result of the
reaction of either trapped monomers or of increased cross-linking.
The additional conversion leads to shrinkage, which develops within
a non-compliant network, which cannot deform to accommodate the
additional dimensional changes.34 It has long been accepted that any
mechanism that can delay the onset of gelation and vitrification as a
b3252_Ch-11.indd 302 27-11-2018 03:06:10 PM

Figure 3. Diagram showing a schematic representation of the different

phases of a methacrylate polymerization reaction. The system presents a lot of
mobility in the monomeric state (M), until the onset of the gel phase. As the
polymerization progresses, it becomes diffusion-controlled, and autoaccelera-
tion is a result of decreased rate of termination. The onset of vitrification (V)
correlates with the maximum rate of polymerization (the peak of the rate of
polymerization versus degree of conversion curve), where the rate of propaga-
tion also becomes diffusion-controlled. The reaction decelerates from that
point into the vitrified stage, and results in incomplete conversion. The polym-
erization stress as a function of conversion (left graph) highlights the fact that
most of the stress development takes place after the network is vitrified, when
small increments in conversion result in significant increases in stress
function of conversion (not time) has a significant impact on polym-

erization stress development, as stresses can be more easily relaxed in
the pre-gel and pre-vitrification stages.35,36 Those strategies will be
explored in the subsequent sections.
In the specific case of photopolymerizations, the rate of polymeri-
zation (Rp) can be related to the irradiance (Ia) on the light source by
the following equation:
1/ 2
 ϕI 
Rp = kp [M ]  a 
 k 
t
b3252_Ch-11.indd 303 27-11-2018 03:06:11 PM

where kp is the rate of propagation, kt is the rate of termination, ϕ is

the quantum yield of initiation (the number of propagating chains per
photon absorbed), and [M] is the monomer concentration at any
given time.
The important conclusion from this equation is that the rate of
polymerization is dependent on the square root of the irradiance.34
This means that, for an appreciable reduction in rate of polymeriza-
tion to take place, the irradiance of the light needs to drop by a factor
of 2 orders of magnitude. Many photoactivation protocols proposed
in the early 2000s have relied on this principle in an attempt to delay
gelation and consequently reduce polymerization stress.37,38 However,
the irradiances proposed were still too high compared to the conven-
tional protocols, and ultimately, the instances where stress reduction
was indeed observed could be related to decreased overall degrees of
conversion, rather than appreciable changes in reaction kinetics.39
The development of tools that allowed the measurement of stress
simultaneously with conversion in real-time have made possible the
demonstration that the final stress development achieved with the
photoactivation methods generally known as “soft-start” was actually
comparable to continuous methods.39
3. Low-Shrinkage and Low Stress Monomer Systems

3.1. Low-Shrinkage Monomers
With the aim of reducing shrinkage and ultimately reducing bulk and
interfacial stress, researchers and manufacturers have focused on syn-
thesizing new monomers with either higher molecular weight or with
intrinsically lower molar shrinkage coefficient. The molar shrinkage
coefficient can be calculated with the following equation:
VS = [C = C] × DC × k,
where [C = C]0 is the initial carbon–carbon double-bond concentra-

tion (in mol/mL); DC is the fractional degree of conversion, and k is
the molar shrinkage coefficient for methacrylates (20.4 mL/mol).40
b3252_Ch-11.indd 304 27-11-2018 03:06:11 PM

The coefficient defines the amount of volume loss taking place from
the reaction of each polymerizable functionality.
From this equation, it becomes clear that higher molecular weight
monomers lead to less shrinkage for the same amount of conversion.
This can be easily visualized in Figure 4.
A few examples of monomers with higher molecular weights have
made it into commercial products, with notable examples being the
dimer acid dimethacrylate (800 g/mol, used in N’Durance®,
Septodont-Confidental) and the DX-511, originally a patent from
Dupont (895 g/mol, used in Kalore, GC). These monomers’ molec-
ular structures are shown in Figure 4. The shrinkage of these com-
mercial materials has been compared to conventional methacrylates,
and it has been shown that they indeed produce values 10–30% lower
than the controls.41,42 The resulting stress, however, follows a differ-
ent ranking, as it depends not only on the nominal shrinkage, but also
on the final conversion and stiffness of the resulting network.41
Figure 4. The effect of monomer size on overall polymerization shrinkage

is shown in this diagram. The situation depicted on the top shows low
molecular weight monomers resulting in greater overall volumetric shrinkage
than the polymerization depicted on the bottom. Courtesy of Dr. Josete
Meira
b3252_Ch-11.indd 305 27-11-2018 03:06:11 PM

Also from the theoretical shrinkage equation, one can predict that
some monomers with intrinsically lower molar shrinkage coefficients
also lead to less shrinkage. That is the case of ring-opening mono-
mers, such as SOC’s and epoxides,43–45 for which a few examples are
shown in Figures 5 and 6. In the case of epoxides, the opening of the
ring results in a much lower molar shrinkage coefficient.46 In other
words, even though it is a ring-opening polymerization, there is still
net shrinkage, albeit smaller than for methacrylates.
For SOCs monomers, there is actually net expansion of the
network. In the case of the only commercial example using epoxide
chemistry (Filtek Silorane or Filtek P90, 3M-ESPE), in vitro stud-
ies have shown that the shrinkage and stress values are indeed lower
than for conventional methacrylates (including examples from the
same manufacturer), with comparable mechanical properties.41
SOCs monomers have also shown great promise, with signifi-
cantly reduced shrinkage values, on the order of 30% lower than
Figure 5. Molecular structure of alternative monomers currently used in

commercial products. (a) Oxirane (Filtek LS, 3M-ESPE); (b) TCD-
urethane (Venus Diamond, Heraeus Kulzer); (c) Dimeracid cimethacrylate
(N’Durance, ConfiDental-Septodont); and (d) DuPont DX-511 (Kalore,
GC America)
b3252_Ch-11.indd 306 27-11-2018 03:06:12 PM

Figure 6. Molecular structure of a few examples of monomers based on

spiro-orthocarbonate chemistry43,44
methacrylate controls.44,45 There are not commercial examples for den-

tal products using this chemistry, which can be at least in part attrib-
uted to the fact that ring-opening polymerizations do not progress
through a free-radical mechanism, but rely on cationic polymeriza-
tions, which are far more sensitive to the conditions in the environ-
ment, such as moisture.47 As already mentioned, in clinical testing of
the commercially available products, the high molecular weight as
well as the ring-opening monomer-based materials were not statisti-
cally different from conventional methacrylates in terms of restoration
longevity or margin quality.19,48–50
3.2. Thiol-Ene/Thiol-Methacrylate Systems

Shrinkage reduction has been proposed as a viable strategy to reduce
stress at the bonded interface, with some commercial success as
already pointed out. Other strategies have focused on reducing stress
per se, mainly resorting to modifications on the vinyl polymerization
reaction directly. One such approach is the use of chain-transfer reac-
tions, which are capable of delaying the point in conversion when
gelation and vitrification take place, as is the case with thiol-ene
systems, which polymerize through step-growth reactions.51 These
materials present a variety of features that makes them attractive for
dental material applications. The chain-transfer reactions of thiol to
ene affords delayed network formation, and that, allied to the fact
b3252_Ch-11.indd 307 27-11-2018 03:06:12 PM

that thiol-ene reactions show much lower molar shrinkage (since

the carbon–carbon double bond in this case is only monofunc-
tional), results in stress reduction compared to methacrylate polym-
erizations.52,53 Moreover, these are virtually insensitive to oxygen
inhibition.54,55 The major drawback is that the presence of flexible
sulfur bonds in the polymer backbone decreases Tg and jeopardizes
mechanical properties in general.54
In contrast with chain-growth polymerizations, in step-growth
reactions the molecular weight of the forming chains does not rise
significantly until much later in conversion (Figure 7). In cross-linked
networks, this means that the limitation to molecular diffusion and
stiffness build up only occurs at the later stages in conversion,34 which
in practice means that the overall stress build up is significantly
reduced.56 For typical thiol-ene systems, the stoichiometric ratio of
thiol to ene is kept at 1:1, and the ene monomer structure is carefully
selected so that it will not preferentially undergo homopolymerization
Figure 7. Schematic representation of the molecular weight evolution in

chain-growth polymerizations compared with step-growth polymerizations.
From: http://polymerdatabase.com/polymer%20chemistry/Chain%20versus%
20Step%20Growth.html
b3252_Ch-11.indd 308 27-11-2018 03:06:12 PM

through chain growth.57 With the aim of delaying gelation and reduc-
ing stress while still maintaining good mechanical properties, ternary
thiol-ene/methacrylates compositions have been proposed.58,59 In
this case, there is competition between chain and step growth mecha-
nisms as the methacrylate can undergo both homopolymerization and
chain transfer with the thiol, in addition to the thiol-ene reaction,60,61
which disturbs the stoichiometric balance and may result in incomplete
consumption of the thiol62 and/or ene.63 For a series of thiol-ene/
methacrylate systems, it has been demonstrated that the ene con-
sumption is delayed until the methacrylate-thiol reaction is largely
complete.64 In turn, methacrylate conversion still progresses at a
slower rate, indicating that the chain transfer reactions to thiol are
determinant in delaying gelation.
Interestingly, the stress reduction obtained in the ternary system
is also achieved with thiol-methacrylates.65 In those instances, thiols
are capable of reducing the kinetic chain length by introducing chain-
breaking events.66 Chain transfer is a chain-breaking mechanism in
which the new radical formed through the transfer is considered to be
a new initiation site.34 The addition of chain-transfer agents (thiols
being very efficient in this role) in amounts as low as 0.1 wt.% signifi-
cantly reduces the rate of polymerization and the radical chain
length.66,67 As the thiol concentration increases, the reaction with the
methacrylate monomer becomes a more important factor in network
development.62,63 Previously reported data shows, for thiol-meth-
acrylate systems with high thiol concentrations, that the transfer rate
constant (ktr) is significantly higher than the propagation rate con-
stant (kp).62 This was accompanied by a delay in the auto-acceleration,
which in turn was optimized for methacrylate functional groups
molar fractions of 60% and 80%.62 The mechanism through which
methacrylate gelation is delayed by chain-transfer to thiol has also
been described in studies on thiol-acrylate systems intended for sur-
face functionalization.68–70 In these cases, amine catalysts were effi-
ciently applied to avoid polymerization through addition to the vinyl,
which leads to the advantageous predominance of chain-transfer from
carbon-thiol radicals. However, this can also be achieved without
resorting to the addition of catalysts by tailoring the reactivity,
b3252_Ch-11.indd 309 27-11-2018 03:06:12 PM

functionality, and concentration of both the thiol and the acrylate/

methacrylate, opening a new avenue to gelation control.
The modification of the kinetic profiles is expected to affect net-
work characteristics and mechanical properties. Thiol monomers
added to a methacrylate network will also very likely produce lower
Tg values due to the flexibility of the thio-ether bonds incorporated
in the polymer backbone through chain-transfer reactions to the
methacrylate, but with the benefit of producing more homogeneous
networks. By decreasing the breadth of tan delta relative to the cure
temperature (meaning narrower Tgs), higher conversion is achieved
before gelation, giving opportunity for viscous flow to accommodate
the stress generation, which has been demonstrated in ternary
thiol-ene/acrylate systems.54,71 Moreover, because of the chain trans-
fer itself, higher conversion and shorter chains are likely to result34
and, especially for multifunctional thiols, this is expected to contrib-
ute to a tighter network and improved mechanical properties.64 In the
same fashion, backbone structure features, like the presence of cyclic
substitutions, may reinforce the resulting polymer network and
enhance overall mechanical properties.54,71
Specifically for use as dental materials, thiol-ene networks have
been investigated in conjunction with methacrylates in ternary sys-
tems, to ensure the formation of strong networks.53,58 The reduc-
tion in polymerization stress in those ternary systems reaches 55%,
with similar or only modestly diminished mechanical properties.53
High Tg materials have been designed, resorting to the use of func-
tionalities such as norbornenes,53 and/or to the synthesis of pre-
polymerized oligomers.72,73 The materials can be photoactivated, as
already mentioned, but there are concerns with the long-term
stability and shelf-life of these materials in base-containing formu-
lations, such as is the case in camphorquinone-amine-initiated com-
posites.74 The malodor concern is mitigated by the use of high
molecular weight thiol species and disappears with polymerization.
Even if they are not currently used in commercial formulations,
thiol-based materials provide a very versatile platform for stress
reduction and water-stable materials, as will be explored further
in this chapter.
b3252_Ch-11.indd 310 27-11-2018 03:06:12 PM

4. Characterization of Gelation Profiles

in Cross-Linked Networks
Rheometry has been classically used to follow mechanical property
development during polymerization, and it provides useful informa-
tion on the gelation behavior.75 The gel point is defined as the stage
of network formation in which one single macromolecule is formed,
and that spans the entire sample.76 There are several experimental
routes to determine the onset of gelation. In practice, the rheometer
subjects the material to a sinusoidal shear force, at a given strain rate
and frequency, and measures the generated stress. From the stress–
strain curve, the complex modulus (G*) is calculated (as the slope of
that curve over time). Through a Fourier transform applied to G*, the
elastic and viscous components (storage and loss moduli, G′ and G ″,
respectively) can be determined. When the material is in the unpolym-
erized state, the viscous component predominates, and the magnitude
of G* was shown to be dependent on the applied frequency.77 As the
material polymerizes and transitions from a viscous liquid (pre-gel)
to a visco-elastic solid (post-gel), two phenomena can be observed.
First, the magnitude of modulus is no longer frequency-dependent.
That way, in multi-frequency experiments, the Winter–Chambon
criterion defines the gel point as the stage in conversion where the
measured modulus is the same regardless of the frequency applied to
the material (Figure 8(a)). Second, the elastic component becomes
predominant in the complex modulus determination. Another param-
eter to determine the onset of gelation then derives: that is the point
in conversion where a cross-over between loss and storage moduli
development curves is observed (Figure 8(b)).
The practical determination of the cross-over point, however, is
somewhat complicated in methacrylates not only because polymeriza-
tions are very fast but also because the increase in modulus for some
materials exceeds 5 orders of magnitude at full conversion,78 close to
the range limit the rheological apparatus can accommodate. As a con-
sequence, the measurement is conducted with partial cures, generally
keeping polymerization rate very slow. For photoactivated systems, it
develops that the irradiance used for the testing is much lower than
b3252_Ch-11.indd 311 27-11-2018 03:06:12 PM

Figure 8. (a) Loss tangent, tan d, of a trifunctional thiol system plotted as
a function of UV exposure time for different frequencies (as labeled in the
figure). The intersection of tan d at a single point (t = 1,480 s) determines
the gel point. (b) Evolution of the elastic (G ′) and viscous (G ″) moduli as
a function of exposure time for a trifunctional thiol system. The frequency
of oscillation is 10 rad/s. G ″ is initially larger than G ′, but as the photo-
cross-linking progresses, G ′ supercedes G ″. From Chiou et al., 1996,
Macromolecules
what is practically employed. More meaningful data can be obtained

through the simultaneous measurement of modulus and conversion,
as shown in the literature.65,79
5. Covalent Adaptable Networks

As explained for thiol-ene and thiol-methacrylate networks, the pres-
ence of thiols during network formation leads to gelation at much
higher conversions compared to traditional chain-growth polymeriza-
tions, which ultimately leads to increased conversion and reduced
stress. While these polymerizations are advantageous from those
standpoints, drawbacks include thiol malodor and the relatively low
Tg achieved. Importantly, as with most cross-linked networks used in
materials for structural applications, thiol-enes and thio-methacrylates
are thermosets, which means once the polymerization reaction is
complete, the networks are not amenable to any further rearrange-
ment. More recently, networks capable of undergoing stress relaxa-
tion via photo-induced bond rearrangement, also known as “covalent
b3252_Ch-11.indd 312 27-11-2018 03:06:13 PM

adaptable networks”, have been proposed.80 By definition, these net-

works contain some type of reversible covalent bond or cross-link that
enables the cross-linked structure to respond chemically to an applied
stimulus, via breakage and reformation of such bonds.80 The adapta-
bility of the network can occur via different pathways, including
reversible addition and condensation and reversible bond exchange
processes.81 In the bond exchange type, as the reaction progresses and
as the external stimulus is applied, the bond density is maintained
without chemical degradation, nor compromise to physical proper-
ties.81 These networks find applications as self-healing materials, as
well as in high stress/strain situations, such as for restorative dental
materials.
Of particular interest for use as dental materials is the addition
fragmentation chain-transfer through allyl sulfide functionalities, as
proposed recently.82 As shown in Figure 9, the concentration of radi-
cals and double bonds available to react is kept throughout the reac-
tion, which effectively leads to stress relaxation without impairing
Figure 9. Covalent adaptable network structure based on crosslink units

with allyl sulfide groups capable of radical addition-fragmentation to relieve
stress during the polymerization. The presence of additional thiol termi-
nated polymer chains allows for the reversible random replacement of exist-
ing carbon–sulfur linkages leading to the dissipation of stress throughout the
cross-linked polymer network. From http://sigmaaldrich.com/technical-
documents/articles/materal-matters/the-progress-in-development.printerview.
html (Stansbury and Bowman, Material Matters 2010, 5.3, 73)
b3252_Ch-11.indd 313 27-11-2018 03:06:14 PM

final network properties.82 When incorporated into thiol/meth-

acrylate networks, this was shown to reduce final stress by as much as
75%, with stress relaxation behavior being denoted by decreased val-
ues from a maximum.82,83 Those systems presented final glass transi-
tion temperature above ambient temperature, albeit slightly below
that of the unmodified methacrylate network.82 To alleviate the
potential for decreased mechanical properties expected in thiol-con-
taining networks, subsequent studies have used norbornene-function-
alized monomers, which were able to keep the stress reduction and
alleviate the concern of reduced Tg.83 Several structure–property
relationship studies conducted for applications in different fields have
demonstrated the ability of these networks to allow maximum stress
relaxation without prejudice to mechanical properties.83 A variation of
this technology is currently being used in one commercial material
(Filtek Bulk Fill Posterior, 3M ESPE).
There are other commercial materials based on stress-relaxing
monomers, such as what is claimed by DENTSPLY-Caulk, but the
formulation is proprietary.84
6. Oligomeric Additives

Pre-polymerized compounds have been used in dental composite
materials for quite some time, with notable examples in microfilled
materials, in which pre-polymerized composite particles are added
back into the unpolymerized matrix. In that case, this allows for the
incorporation of relatively large amounts of micrometer-sized silica
particles, as well as reduces the polymerization shrinkage, via the
reduction on the concentration of monomers available to react in the
material as being used by the dentist.85 More recently, the use of
loosely cross-linked polymerized particles has been proposed and,
given the nanometer size scale of such particles, the term nanogel was
coined. Nanogels have been proposed for use in industrial coatings to
reduce shrinkage and stress, as well as nanocarriers for drug deliv-
ery.86–88 Recently, they have been proposed for dental applications. To
that end, the nanogels are synthesized in solution using a relatively
low concentration of cross-linker monomers and chain-transfer
b3252_Ch-11.indd 314 27-11-2018 03:06:14 PM

agents, to control molecular weight and form networks that can be

dispersed into a secondary monomer matrix.89,90 The addition of the
pre-polymerized particle leads to a reduction in shrinkage, and cor-
responding reduction in stress in resins and highly filled systems,
with no prejudice to mechanical properties.89,90 The nanogel network
can be tailored to encompass a wide range of glass transition tem-
peratures via, for example, varying the degree of branching,91 as well
as can be used as a very versatile platform for tethering different
functionalities, such as methacrylates (for co-polymerization with the
secondary network) and thiols (for further stress reduction via chain-
transfer reactions).92
Another example of pre-polymerized compounds are thioure-
thane oligomers.93–96 The main advantages of thiourethane networks
are the sharp glass transition temperature, which denotes a very
homogeneous network, and the toughness reported for some formu-
lations.97–99 Thiourethane networks can also be applied as pre-polym-
erized additives.93–96 In these cases, oligomeric particles with molecular
weights around 5 kDa are synthesized in solution using multifunc-
tional thiols and isocyanates, in such a way that pendant thiol moieties
are left for subsequent reactions and functionalization.95 The pendant
thiol concentration and the ultimate glass transition temperature of
the oligomers can be tailored by judicious selection of the starting
thiol and isocyanate materials. It has been demonstrated that the
addition of thiourethane oligomers to dimethacrylate networks is able
to increase the toughness and fracture toughness by at least two-
fold,96 which has been attributed to the introduction of thiocarbamate
bonds.97 In fact, thiol-isocyanate networks have been previously
employed in applications where high impact resistance is desirable.98,99
In addition, the presence of pendant thiol functionalities renders
them capable of chain-transfer reactions with the surrounding meth-
acrylate matrix. In addition to the intrinsic reduction in shrinkage
achieved with the addition of pre-polymerized particles (as is the case
with the aforementioned nanogels), those chain-transfer reactions are
able to delay gelation and vitrification.93 Both these factors contribute
to reductions in polymerization stress of up to 60% observed with
these materials,96 as seen in Figure 10.
b3252_Ch-11.indd 315 27-11-2018 03:06:14 PM

Figure 10. (a) Polymerization stress and (b) Fracture toughness values for
the 25wt% filler BisGMA/UDMA/TEGDMA cement and for the commer-
cial cement (RelyX Ultimate) with 0 (control), 10% and 20 wt% of thio-
urethane oligomer added. Adapted from Ref. [95]
7. Monomers with Increased Hydrophobicity

Dental restorations reside in a relatively harsh environment, where
variations in pH, biofilm development, and the presence of moisture
and organic solvents are a constant challenge. For that reason, the
use of hydrophobic compositions has been proposed as a way to
reduce the effects of water aging. Fluorine chemistry has been pro-
posed, with several monomers being synthesized with potential den-
tal applications.100 Fluorine-derivatives of BisGMA have been shown
to produce much lower water sorption and increase the contact
angle of resin composites, but with somewhat reduced mechanical
properties for some examples.100 Potential miscibility issues with
other co-monomers partly explains the reduced properties, and the
addition of moderate amounts of solvents (aldehydes and ketones)
has been successful in overcoming the issue.101,102 More recent work
on this chemistry has shown improved mechanical properties in rela-
tion to a BisGMA control using monomers derived from ure-
thanes.103–105 In addition, a few examples of monofunctional
fluorinated methacrylates have been proposed for use as adhesive
monomers.106,107 In this case, the rationale is to decrease water per-
colation through the adhesive barrier, a phenomenon demonstrated
with dentin adhesives (“water-treeing”31).
b3252_Ch-11.indd 316 27-11-2018 03:06:14 PM

Figure 11. Molecular structure of a few examples of fluorinated mono-

mers proposed for dental applications. Adapted from Refs. [100, 101, 105]
Other examples of increased hydrophobicity include the monomers

shown in Figure 11. Those specific examples were designed to reduce
stress, respectively, via ring-opening polymerization (silorane, A) and
polymerization-induced phase-separation (dimer-acid derivatives, B),
as already mentioned. The hydrophobicity of commercial materials
containing those monomers has been tested in terms of water sorp-
tion and solubility.42,108,109 Siloranes have demonstrated significantly
lower water sorption/solubility values compared to conventional
methacrylate controls. 42,108,109 Dimer-acid derivative-containing
materials presented water sorption/solubility values comparable
with the methacrylate controls.42 Clinical studies, however, have
failed to demonstrate the potential to extend the lifetime of restora-
tions constructed with these materials compared to conventional
methacrylates.49,50
8. Water- and Enzyme-Stable Monomers

For fluorinated monomers, the rationale for use is to inhibit material
interaction with the aqueous environment while still relying on ester-
containing methacrylate monomers. Other approaches have focused
b3252_Ch-11.indd 317 27-11-2018 03:06:14 PM

on replacing methacrylates with other polymerizable functionalities to

avoid the presence of the hydrolysable ester bond. One noteworthy
example, with commercial application in adhesive systems so far, is the
methacrylamide chemistry.110 Methacrylamides have the general
chemical structure shown in Figure 12. In general, they also polymer-
ize via a chain-growth radical mechanism, with reactivity varying
according to the substitutions in R1 and R2. In general, acrylamides
are more reactive than methacrylamides, and secondary acryl/meth-
acryl-amides are more reactive than tertiary counterparts.111,112 The
latter has been reported to require the use of chain-transfer agents to
allow for ambient temperature polymerization via radical-assisted
mechanisms.113 These monomers are attractive for use in dentistry
because they have been shown to have enhanced stability in aqueous
environments and, for select examples, enhanced stability when sub-
jected to enzymatic challenges.114 For those reasons, the use of meth-
acrylamides has been proposed for dental composites.115 One study
has demonstrated that composite formulated with a multifunctional
methacrylamide presented mechanical properties comparable to the
methacrylate counterpart, while presenting much greater stability
after storage in aqueous ethanol solutions containing 20 wt.% phos-
phoric acid at 37°C for 4 months.116 Under those harsher conditions,
the carbamate present in the methacrylamide has shown, as expected,
Figure 12. Molecular structure of ester-free monomers.
b3252_Ch-11.indd 318 27-11-2018 03:06:15 PM

to be much better able to resist degradation than the methacrylate. In

addition, methacrylamide phosphonic acids (Figure 12) have been
proposed for dental adhesives. While the phosphonic acid moiety
keeps the molecule hydrophilic and imparts self-etching character, the
polymerization via the methacrylamide or acrylamide moieties makes
the resulting network less prone to degradation.117 At least one com-
mercial example exists (AdheSE, Ivoclar-Vivadent) that contains
methacrylamides in the composition.
Other ester-free monomers include vinyl ethers and vinyl sulfones,
whose general chemical structure is shown in Figure 12. Vinyl ethers
have demonstrated resistance to hydrolysis in aqueous environments
and to degradation by cholinesterase.118 However, they usually require
super-ambient temperatures or cationic initiation mechanisms to
homopolymerize to any appreciable extents,118,119 which can be diffi-
cult to impossible to achieve in the oral environment. Viable co-
polymerization pairs at room temperature include methacrylates,120,121
though that option re-incorporates ester bonds into the network, or
thiol-ene co-polymerizations,122 with the disadvantage of low Tgs,123
or homopolymerization via RAFT initiation mechanisms.124 Vinyl
sulfones have recently been proposed for use as restorative dental
materials, mainly because of their expected hydrolytic stability, in
turn conveyed by the absence of ester functionalities.125 Vinyl sul-
fones were shown to have much greater reactivity toward thiol
monomers compared to acrylates due to the greater electron defi-
ciency of the former,126 and also to form networks presenting much
higher glass transition temperature compared to classic thiol-ene
networks.127–128 The good mechanical properties, namely toughness
and fracture toughness, have been attributed to strong intermolecu-
lar interactions of dipole nature.125 All of those features make these
networks very attractive for use as dental materials. Initiator systems
based on photo-base generators allow for the temporal control of
polymerization reactions.129 Combined, these two technologies
might make the translation of thiol-vinyl sulfone materials to clinical
use more of a reality.
Recently, azide-alkyne networks have been proposed as biomateri-
als.130,131 The copper-catalyzed azide-alkyne reaction has first been
b3252_Ch-11.indd 319 27-11-2018 03:06:15 PM

Figure 13. General reaction scheme for alkyne-azides, catalyzed by copper

I. Copper I is reduced copper II either by reaction with sodium ascorbate or
in the presence of a photoinitiator. Adapted from Refs. [133, 135]
described by Sharpless and collaborators,132,133 and progresses accord-

ing to the schematic shown in Figure 13.
These materials have been suggested for potential use in dental
composite formulations because they are ester-free, not prone to
hydrolysis or enzymatic degradation, and can be photoactivated on
demand to produce glassy materials at room temperature.134 The
photochemical reduction of the copper catalyst was a milestone
responsible for allowing spatial–temporal control of the polymeriza-
tion reactions.135 So far, these materials have shown significant
polymerization stress reduction in relation to methacrylate networks,
with only modest decrease in flexural strength and modulus.134 As far
as resistance to degradation, at least for use as fluorescent nano-
spheres for live cell imaging, these materials present good stability in
solution.136 Potential pitfalls include toxicity concerns with the use of
the copper catalyst, as well as a blue tint as a result of incomplete
copper reduction.
9. Antimicrobial Monomers

The interaction between restorative materials and the oral biofilm
has been investigated in great detail. As already mentioned, the
action of salivary and dentinal enzymes can lead to degradation of
methacrylate monomers and the formation of products such as
methacrylic acid and BisHPP. These products may have stimulating
or inhibitory effects on caries-forming bacteria, especially at low
pH.137,138 Upregulation of virulence genes in S. mutans as a result of
exposure to such products also has been shown.137 Enzymes and
acidic hydrolysis originating from the biofilm, however, have also
b3252_Ch-11.indd 320 27-11-2018 03:06:15 PM

been suggested to accelerate the degradation of dental materials.6,22

Acquired pellicle formation on the surface of dental materials occurs
virtually instantaneously, and mature biofilm can be observed roughly
on the same time-scale as in pristine enamel.16 The presence of the
biofilm can potentially accelerate not only the degradation of
the composite restoration but also of the bonded interface,21 and
the presence of cariogenic bacteria on stress-induced marginal gaps
in vitro has also been demonstrated.18 Even though clinical studies
have failed to demonstrate a definitive correlation between stress-
induced marginal gaps and secondary decay, the fact that bacteria can
penetrate those spaces is definitely a matter of concern. With that in
mind, materials based on antimicrobial and antifouling monomers
have been developed.139,140 The largest body of literature for antibac-
terial monomers for dental applications is on the group of quaternary
ammonium methacrylates, or QAMs.141–151 Examples of QAM mono-
mers proposed for use in dental composites are shown in Figure 14.
The quaternization of the tertiary amine moiety renders the molecule
positively charged, which promotes interaction with the bacterial cell
wall.152 Several iterations of these monomers have been synthesized,
and the charge density and size of the side chain have been correlated
with the efficiency of such monomers/polymers to disrupt the integ-
rity of the bacterial wall.146,151,153 At least for the materials reported so
far, however, the action mechanism seems to be contact kill, which
means the bactericidal effect is not marked in the bulk of the biofilm
layer, unless unreacted monomers or degradation by-products leach
into the biofilm.146 In this case two concerns arise: the sustainability
Figure 14. Molecular structure of examples of antibacterial monomers

proposed for use in dental materials. Adapted from Refs. [146, 157]
b3252_Ch-11.indd 321 27-11-2018 03:06:15 PM

of the bactericidal effect and toxicity to pulpal or epithelial cells. For

those reasons, the combination of QAMs with protein-repellent
monomers, which would avoid the formation of the acquired pellicle
on the surface of the restoration, thus rendering the material antifoul-
ing and potentiating the action of QAMs.154 QAMs have also been
included in self-healing material formulations, loaded into vesicles
containing healing liquid, which are activated upon crack propagation
through a composite material.155 Potential problems that may arise
with this method, however, include decreased mechanical properties
with the inclusion of vesicles and incomplete reaction of the healing
liquid, posing cytotoxicity concerns.155 Overall, the use of quaternary
ammonium methacrylates in commercial materials is still limited to
one product, and long-term clinical studies with this material are still
scarce.156
Figure 15. Illustration of nanodiamond powder and the influence of

annealing conditions on the bactericidal effect of said particles. Negatively
charged ND and NDraw/NDraw n.u were shown to exhibit strong antibac-
terial properties under aqueous conditions, while NDp caused bacterial death
only at high ND concentrations. NDpure, independent of their charge, did
not show any bactericidal effects. Adapted from Ref. [159]
b3252_Ch-11.indd 322 27-11-2018 03:06:16 PM

More recently, non-quaternary ammonium alternatives have been

proposed, such as the use of thiazoles.157 At least in one study, this
system has shown the advantages of increased conversion and
decreased water sorption and solubility in relation to un-modified
methacrylate, without prejudice to mechanical properties.157 Biofilm
and cytotoxicity studies for thiazole-based dental materials are not
available to date.
Finally, the use of oxidized nanodiamond particles has been pro-
posed as an antibacterial alternative in dental materials.158,159 Surface
properties seem to play a key role on the efficacy of the antibacterial
effect of these particles, with partially oxidized particles rendering the
most potent results against gram positive and gram negative bacte-
ria.159 Mechanical properties of composites containing these nanopar-
ticles were shown to increase with the concentration of nanodiamonds
up to 20 wt.%, concentration at which a two-fold increase in fracture
toughness is observed.158,160 The use of nanodiamonds is yet to be
investigated for use in dentistry.
10. Final Considerations
In spite of the effervescent research on alternative chemistries for
restorative dental materials, most monomers and organic matrices in
commercial products are still based on methacrylates. As previously
mentioned, they polymerize under mild conditions to relatively high
degrees of conversion and produce glassy materials, with a reasonable
lifetime. Compared to amalgams and other metal-based restorations,
nevertheless, esthetic composite restorations still fall short. New and
improved materials are necessary to avoid costly re-treatments and to
preserve natural tooth structure. The future seems to lie with materi-
als that interact well with the environment surrounding them, which
means that, besides presenting low polymerization stress and good
mechanical properties and chemical stability, the search is for a com-
position that will simultaneously be able to resist biofilm formation,
be antibacterial, and be bioactive, both in terms of mineralization and
in terms of epithelial cell attachment (in the case of class II and V
b3252_Ch-11.indd 323 27-11-2018 03:06:16 PM

restorations, for example). This is an extremely tall order, but pro-

gress is underway.
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b2530_FM.indd 6 01-Sep-16 11:03:06 AM

Chapter 12
Development of Polymerization
Contraction Stresses in Resin-Based
Composites
Roberto Ruggiero Braga*, Marcela

Charantola Rodrigues, and Yvette Alania
Department of Biomaterials and Oral Biology,
School of Dentistry, University of São Paulo,
Av. Prof. Lineu Prestes, 2227 — São Paulo, Brazil
*rrbraga@usp.br
Photoactivated dimethacrylate-based composites have become the

material of choice for direct tooth restorations due to their
aesthetics, virtually unlimited working time, cure on command, and
adhesiveness to tooth structure, which requires minimal cavity
preparation. During polymerization, the transition from a viscous
paste to a glassy polymer is accompanied by substantial shrinkage.
As volumetric change is restrained by the composite adhesion to the
walls of the cavity preparation and cannot be compensated by plastic
deformation due to the material’s increasing stiffness, stresses build
up at the tooth–restoration interface. Furthermore, being a localized
state and not a material-intrinsic property, stress magnitude depends
on how compliant the bonding substrate is to shrinkage forces.
Polymerization stress can potentially be related to several clinically
335
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undesirable outcomes, such as post-operative sensitivity, develop-

ment of white lines around the restoration margins, tooth crack-
ing, and, ultimately, new caries lesions. Several strategies were
proposed to reduce polymerization stress magnitude, with limited
success. They include the development of “low-shrinkage” com-
posites, light-curing protocols with modulated irradiance, low
modulus liners, incremental placement techniques, and composite
pre-heating.
1. Introduction
Resin-based composites have become the material of choice for direct
restorations, both in anterior and posterior teeth. Besides being aes-
thetically appealing, it presents the advantage of “cure on command”.
Moreover, despite the lack of sound scientific evidence on health-
related issues caused by dental amalgams, resin composites have virtu-
ally replaced them in posterior restorations. However, the use of resin
composites is not without its limitations. Its placement technique is
more time consuming and technique sensitive, and longitudinal clini-
cal studies report higher annual failure rates compared to amalgam.1
One of the main causes of composite restoration failure is the recur-
rence of caries lesions at the tooth–restoration interface.2 Though
caries development has multiple causes, there is some scientific
evidence linking this occurrence to the presence of gaps at the tooth–
restoration interface.3 Interfacial debonding may occur due to defi-
ciency in the adhesive system application, degradation of the adhesive
layer, or as a consequence of polymerization stress development.
During polymerization, stresses arise as a result of composite
shrinkage and elastic modulus development.4 Though its occurrence
has been reported by Bowen, the inventor of dimethacrylate-based
composites, in 1967,5 it was not until the late 1980s with the studies
by Feilzer et al. that this topic gained wider attention.6 To date, there
is no definite evidence linking polymerization stress with the clinical
performance of resin composite restorations. However, the abun-
dance of laboratory studies relating polymerization stress with failure
of the bonded interface makes it almost impossible to deny its
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Development of Polymerization Contraction Stresses in Resin-Based Composites 337
importance in this process.7 In this chapter, the factors involved in

polymerization stress development are described, as well as the testing
methods and the approaches proposed to reduce stress magnitude.
2. Experimental Methods for Polymerization

Stress Determination
Stress is a vectorial entity, and therefore cannot be directly measured.
Stresses are calculated, for example, using recorded force values, as
well as the geometry and dimensions of the specimen. Specimen
boundary conditions are also important, as they affect its behavior
during the test. Polymerization stress can be assessed by different
methods, the most ubiquitous being those using load cells mounted
on rigid frames to record the axial shrinkage force. Other mechanical
tests use more complex mathematical solutions to calculate stress
from variables affected by composite shrinkage forces, such as the
ring-slitting method and the crack analysis method. Finite element
analysis (FEA) and photoelasticity are useful tools to observe stress
distribution within the composite and support experimental findings.
Other methods, such as the use of strain gauges to determine cuspal
deflection caused by shrinkage forces, are used as an indirect assess-
ment of polymerization stress magnitude. Obviously, every method
has advantages and limitations. Unfortunately, due to the lack of
standardization, the comparison of data from different studies must
be conducted very judiciously.
2.1. Mechanical Tests

2.1.1. Systems Using Rigid Frames for Axial Force Detection
Load cells connected to rigid frames can be used to record the axial
force generated by composite shrinkage. In the basic setup, the com-
posite is applied between two rods, one of them connected to the
load cell of a universal testing machine or custom-built rigid frame-
work. When the composite shrinks, it pulls both rods toward each
other and the load cell records the force development over time.
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A feedback loop is normally used to monitor the approximation of the

rods and command the crosshead to re-establish the initial distance
between the rods. Force values are divided by the cross-sectional area
of the specimen to obtain the nominal (average) shrinkage stress.
With photoactivated composites, specimen thickness is usually lower
than 1 mm to ensure a homogeneous curing. The choice of rod mate-
rial has a definite effect on stress magnitude. Stiffer rods (e.g. steel or
glass) reduce the compliance of the testing system, resulting in higher
stress values. On the other hand, with less stiff substrates, such as
acrylic, the recorded values are lower because a fraction of the shrink-
age force causes elongation of the rod and, consequently, is not
detected by the load cell.8 When testing a series of materials, their
relative rankings may change according to the compliance of the
testing system,9 meaning that one must be aware of its influence on
composite behavior.
2.1.2. Systems Based on Cantilever Deflection

Testing methods using single cantilever devices rely on its length,
elastic modulus, and deflection to calculate shrinkage stress.10
Alternatively, a cantilever load cell can be used to record the force
directly.11 In both cases, a disc-shaped specimen is made by inserting
the composite between two opposing rods close to the free extremity
of the beam. The compliance of the system can be modulated by
changing the cantilever beam length (i.e. the shorter the beam, the
lower is the compliance).
2.1.3. Crack Analysis

In this method, Vickers indentations are made on soda-lime glass
discs (approximately 1 mm in thickness) with a central perforation,
at a predefined distance from the hole margin. The corner cracks
developed from the indentation are measured under a light micro-
scope and the perforation is filled with the tested composite. After
polymerization, the corner cracks are remeasured and stress at the
glass substrate around the indentation is calculated based on crack
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growth and glass fracture toughness.12 Stress at various distances

from the glass/composite interface can be calculated by changing the
indentation site.13
2.1.4. Ring Slitting Method

Different from the previous methods, where it is possible to monitor
stress development, the ring slitting method is used to determine
residual stresses in the composite. Composite rings (internal diameter:
15 mm, external diameter: 18 mm, thickness: 1 mm) are made using
a metallic mold. After curing, two reference marks 3 mm apart are
made in the specimen. Digital images of the ring are obtained before
and after sectioning between the reference marks with a rotating dia-
mond blade. The residual stress in the composite ring is calculated
based on the change in distance between the marks, ring dimensions,
and composite elastic modulus. The elapsed time between curing and
sectioning is critical because of post-cure polymerization. Likewise,
the interval between sectioning and imaging also affects the stress
values obtained due to stress relaxation.14
2.2. Methods used for Assessing Stress Distribution

2.2.1. Photoelasticity
Mechanical testing provides an average stress value for the entire
specimen. However, polymerization stresses are not uniformly distrib-
uted along the composite/substrate interface or within the bulk of
the material, and knowing how stresses are distributed in a compos-
ite-filled cavity is important to understand some of the failure mecha-
nisms found with adhesive restorations. Photoelastic analysis uses a
transparent resin material that when stressed shows what is called
“interference fringes” under polarized light.15 A higher number of
fringes at a particular site indicates the photoelastic resin is under
higher stress. Stress levels can also be quantified if the photoelastic
resin’s stress optical coefficient is previously determined. The pho-
toelastic resin can be used as the substrate where a box or cylindrical
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cavity is prepared and filled with composite. Therefore, what is

actually being measured is the stress at the bonding substrate result-
ing from composite polymerization.16
2.2.2. Finite Element Analysis

The FEA uses computer-generated models to evaluate polymerization
stress magnitude and distribution. A mesh is applied to the model
(using, for example, tetrahedral elements) and the magnitude of the
stress vector on each node is calculated. Results are expressed based
upon “failure criteria”. For brittle materials, such as resin composites
and the tooth structure, the maximum principal stress criteria (i.e.
maximum tensile stress) is more appropriate.9 Another frequently
found failure criteria is Von Mises. However, it seems less appropriate
for the problem in question, since it is based on the distortion energy
theory, more suitable for ductile materials. The accuracy of the
method is highly dependent on the parameters used in modeling,
such as elastic modulus and Poisson’s coefficient (both of the com-
posite and the substrate), composite shrinkage, and boundary condi-
tions. Usually, simplified representations such as two-dimensional
axisymmetric models are preferred to reduce computational costs.8
Ideally, FEA results should be validated by data obtained experimen-
tally. In fact, the association of both methods allows for a much more
consistent interpretation of the results of either test alone.17
2.3. Influence of Test Parameters on Stress Results

The previous section represents an overview of the most frequently used
testing methods according to the literature. Due to the lack of a stand-
ardized method, stress values from different studies are not comparable.
In fact, even among seemingly similar methods direct comparisons may
be problematic due to variations in the compliance of the testing sys-
tem. Compliance is the reciprocal of stiffness (unit: mm/N). As a gen-
eral rule, testing systems with high compliance result in low recorded
forces because part of the force generated by composite shrinkage
causes elongation of the system components and, consequently, is not
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detected by the load cell.8 There has been some debate on which
compliance level provides the most clinically meaningful results. While
low-compliance systems represent the most critical situation in terms of
stress generation — in other words, the composite “full stress-generat-
ing potential” — the biological substrates on which composites are
applied (enamel, dentin, cement) are relatively compliant. Therefore, in
theory, data gathered from high-compliance systems would be more
representative. In any scenario, the elements of the testing system with
a direct effect on compliance and, consequently, on stress magnitude
must be taken into consideration when comparing data from different
studies. They are described in the following sections.
2.3.1. Specimen Dimensions

Testing methods based on load cells mounted on stiff frames use disc-
shaped specimens, with the diameter following the perimeter of the
rods used as bonding substrate (usually between 3 mm and 5 mm).
Specimen height is around 1 mm, which is important to ensure a
homogeneous curing of the composite in cases where the rod material
is transparent (glass or acrylic) and photoactivation is accomplished
with the tip of the curing unit at the opposite end of one of the rods.
When metal rods are used as substrate, keeping the thickness low is
less of an issue, as photoactivation must be conducted with the light
tip perpendicularly to the long axis of the specimen. In case of self-
cure composites, specimen height is limited by the possibility of shap-
ing the cylinder between the rods without slumping.
Specimen radius and height define its level of confinement, usually
expressed as the ratio between both dimensions (see C-factor, below).
In low compliance systems, there is a direct relationship between
radius-to-height and nominal stress.18 On the other hand, in high com-
pliance systems, stress is directly related to the specimen’s volume.19
2.3.2. Bonding Substrate

The bonding substrate for the composite is the most influential vari-
able defining polymerization stress magnitude. The first reports of
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mechanical tests for stress determination used steel rods.6 However,

bonding composite to metal relies solely on the irregularities created
on the metal surface by sandblasting. As a consequence, debonding is
a likely event under relatively high shrinkage forces, and if it happens,
the specimen is lost. Glass can be sandblasted and coated with a silane
primer to improve the bond strength to composite. An additional
advantage of using glass rods is the possibility of light curing through
one of the rods, which allows for a more homogeneous curing com-
pared to positioning the light guide perpendicularly to the specimen
long axis.20 However, debonding or even glass fracture may occur
under high shrinkage forces. The use of acrylic (polymethyl meth-
acrylate, PMMA) rods increases the compliance of the testing system
considerably. That, along with a strong bonding to the composite and
the possibility of light curing through the rod, makes this substrate the
most convenient of the three.21 Depending on the properties of the
composites tested, their relative rankings may differ according to
the bonding substrate (i.e. compliance level) of the testing system.22
2.3.3. Feedback Loop

The longitudinal compliance of a testing system can also be modu-
lated by the use of a transducer to monitor the relative distance
between both upper and lower rods. When the transducer registers an
approximation between its fixation points caused by shrinkage forces,
the software controlling the testing machine can command the actua-
tor to return the transducer reading to zero (with a resolution as low
as 0.1 µm). This continuous elongation of the specimen restricts the
compliance of the testing system to the elongation taking place
between the transducer fixation points. Therefore, the use of a trans-
ducer significantly lowers the system’s compliance.
2.4. Relationship Between Polymerization Stress Tests

and In Vitro Tests for Assessing Quality
of the Bonded Interface
Significant correlations were observed between polymerization stress
values obtained in low compliance testing systems and in vitro
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microleakage, suggesting that higher interfacial stresses were respon-

sible for the debonding of the interface.23,24 However, when a series
of commercial composites were tested for polymerization stress in
both low and high compliance systems and the results were com-
pared with bond strength to dentin, microleakage, and marginal
gaps, stronger correlations were observed with data obtained in the
high compliance system. Also, no relationship was observed between
stress determined in the low compliance system and bond strength
to dentin.25 Therefore, the use of high compliance testing systems
for polymerization stress determination seems to be more repre-
sentative of the possible effects on the quality of tooth–composite
interfaces.
3. Polymerization Stress Determinants Related

to Composite Formulation
Resin composites are composed of an organic matrix, constituted by
the combination of different monomers, and an inorganic fraction,
usually constituted by silanated glass fillers. Also, photoinitiators
such as camphorquinone and a tertiary amine are also present. Its
polymerization reaction can be described as having two different
phases: the pre-gel phase, when the material still presents a low
elastic limit, allowing for plastic deformation of the growing poly-
mer chains under relatively low stress values,26 and the post-gel
phase, when the establishment of a polymer network impedes the
mobility of free radicals and other reactive species. In the post-gel
phase, the reaction rate decreases and the material develops a glassy
character.27
Polymerization reaction of resin-based composites occurs by
chain growth, where monomers are successively added to the reactive
site (free radical polymerization). During the reaction, the addition of
monomers to the growing chain results in a volumetric shrinkage.
The fraction of shrinkage occurring prior to gelification (pre-gel or
non-rigid shrinkage) does not have any clinical consequences.28
The post-gel shrinkage, on the other hand, is clinically relevant, as at
this stage the material cannot compensate the reduction in shrinkage
by viscous flow, and stress starts to build.29,30
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At this point, it is important to point out that polymerization

stress development is not determined only by volumetric shrinkage.
Composite elastic modulus is also an important determinant of stress
magnitude. Is possible to state that, as a rule of thumb, the higher the
composite shrinkage and the elastic modulus, the higher its polymeri-
zation stress will be. However, these two characteristics are not neces-
sarily related in a direct manner. For example, if two composites with
different filler fractions are compared, the material with higher filler
content will present lower shrinkage and higher modulus than the
other. Moreover, as will be discussed in this chapter, there are several
other modulating factors in polymerization stress development. These
factors can be intrinsic (i.e. related to composite formulation) or
extrinsic (related to the substrate on which the composite is applied).
Among the intrinsic factors, those related to the organic and inor-
ganic components of the material will be discussed in the following
sections.
3.1. Polymerization Shrinkage

Polymerization shrinkage is a time-dependent phenomenon that takes
place throughout the entire polymerization reaction.31 During the
pre-gel phase, the stress generated due to shrinkage is relieved by
plastic deformation. At the onset of gelation (gel point), there is a
sudden increase in viscosity and the polymer transitions from a liquid
to a gel. The polymer network is established, and polymer cross-
linking density keeps increasing concomitantly to the increase in stiff-
ness. During this phase, the material already presents some stiffness
and is not capable of plastic deformation. Therefore, the shrinkage
that takes place during this phase is responsible for the development
of polymerization stress.29,32
Post-gel shrinkage represents a percentage varying between 17%
and 32% of the total shrinkage, indicating that for the most part
volumetric shrinkage occurs during the pre-gel phase. Moreover,
when different materials are compared for pre-gel shrinkage (using
the strain gauge method) and total shrinkage (using a mercury
dilatometer), no linear correlation between both variables are
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observed, meaning that the characteristics of polymer network for-

mation vary as a function of material composition and reaction
kinetics. The strong correlation observed between polymerization
stress and post-gel shrinkage and the lack of correlation between
stress and total shrinkage confirm that volumetric shrinkage occur-
ring prior to vitrification has very little effect on polymerization
stress development.33
Composite shrinkage is determined by its inorganic fraction and
the composition of its organic matrix. Commercially available materi-
als present filler fractions between 46% and 74% by volume.34 Barium,
strontium, zirconia, and silica glasses are the inorganic fillers most
often found in commercial composites, and are added to the material
with the purpose of reducing shrinkage, improving mechanical prop-
erties, and to make them radiopaque.35
In general, polymerization shrinkage of commercial composites
vary between 1% and 4%,34 and the volumetric filler fraction is
inversely related to the magnitude of shrinkage.36 That occurs because
the increase in filler fraction reduces the concentration of carbon dou-
ble bond per unit volume in the material.37 However, incorporating
high percentages of particles with the purpose of reducing the volume
of organic matrix does not seem an effective approach to reduce post-
gel shrinkage and polymerization stress,33 since the increase in inor-
ganic content, besides promoting an increase in elastic modulus, also
reduces monomer mobility during polymerization.38
Organic matrix formulation also influences the polymerization
shrinkage of resin-based composites. Dental composites usually pre-
sent in their formulation the monomers BisGMA (bisfenol-A glycidyl
methacrylate or 2,2-bis[4-(2-hydroxy-3-methylacryloxypropoxy)-
phenyl]propane) and TEGDMA (triethylene glycol dimethacrylate or
2-methyl-2-propenoic acid). Other monomers, such as BisEMA (eth-
oxylated bisphenol-A dimethacrylate) and UDMA (urethane dimeth-
acrylate) can also be found in several commercial composite
formulations. These monomers are combined in different ways and
proportions with the objective of optimizing mechanical properties
and reducing composite shrinkage, warranting a high degree of
conversion and suitable handling characteristics for the material.
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BisGMA is a high molecular weight and high viscosity monomer

(512 g/mol). Its viscosity is due to the presence of two hydroxyl
groups that favor the establishment of intermolecular hydrogen
bonds. It also presents two aromatic rings that reduce molecular rota-
tion. Such characteristics preclude Bis-GMA as a homopolymer to
reach high degrees of conversion. TEGDMA (286 g/mol) is a highly
flexible molecule due to the presence of ether groups which, associ-
ated with its low molecular weight and absence of intermolecular
interactions, allows for a high degree of conversion. However, these
characteristics are associated with a high volumetric shrinkage of poly-
mers containing high amounts of this monomer,27,39 which also
increases polymerization stress development.8 For example, in unfilled
resins, a 20 wt.% increase in TEGDMA concentration doubled
polymerization stress values.40
TEGDMA can be partially or totally replaced by BisEMA or
UDMA to reduce shrinkage.41 However, the lower viscosity of
TEGDMA is responsible for a higher degree of conversion of BisGMA/
TEGDMA copolymers, in comparison to BisGMA/BisEMA.36
3.2. Elastic Modulus

Elastic modulus shows a direct relationship with the inorganic
content of resin composites. This property is defined by the stiffness
of the particles and the way these particles interact among themselves
within the material.42 In experimental materials with similar organic
contents, the elastic modulus increased by approximately four times
between 25 wt.% and 60 wt.% of fillers.36
The composition of the organic phase may also influence the elas-
tic modulus of resin composites. High BisGMA concentrations
reduce polymer stiffness by lowering its degree of conversion and
cross-linking density. On the other hand, its rigid molecular structure
and the establishment of intermolecular hydrogen bonds contribute
to the stiffness of the formed polymer.39,43,44 Low-viscosity monomers
are usually employed to reduce the material’s viscosity and increase
the molecular mobility of the organic matrix, therefore increasing its
degree of conversion.45
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The elastic modulus has an important role in the development of

composite polymerization stress.31,33,36,38 According to Hooke’s law,
stress is determined by the stiffness of the material when subjected to
a given strain. Therefore, assuming the resin composite as a perfectly
elastic material, the higher its elastic modulus and polymerization
shrinkage, the higher the contraction stress will be. In fact, during
polymerization the composite changes from a viscous paste to a vis-
coelastic (albeit predominantly elastic) material, and therefore stress
cannot be calculated simply as the product of both variables.
However, the relationship between elastic modulus and stress devel-
opment can differ depending on the testing system used.22,36 An inverse
relationship between elastic modulus and polymerization stress was
observed when high-compliance testing systems were used; however, a
direct relationship between both variables is found in low compliance
systems, for example, using glass or metal as bonding substrates.8,22
3.3. Degree of Conversion

Degree of conversion is defined as the percentage of carbon double
bonds present in the uncured material that were consumed in the
polymerization reaction. Therefore, it indicates the quality of the
formed polymer. A high degree of conversion is necessary to optimize
mechanical properties and reduce degradation of resin-based compos-
ites.46 However, the relationship between degree of conversion and
mechanical properties is not linear and above a certain threshold
increases in conversion are not followed by improvements in mechan-
ical behavior.47
In the polymerization of linear dimethacrylate monomers, the
establishment of a covalent single bond between the carbon atom with
an unpaired electron (i.e. the free radical) and a monomer with a car-
bon double bond results in a reduction in the distance between them.
For this reason, degree of conversion is linearly related to volumetric
shrinkage.48 Degree of conversion is directly related to the viscosity of
the initial monomer mixture. This is explained by the fact that conver-
sion stops when the glass transition temperature (Tg) of the forming
polymer reaches the temperature of the reaction. The Tg of the initial
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monomer mixture is related with their viscosity in a way that less

viscous mixtures have low glass-transition temperature.49 High filler
contents may reduce degree of conversion, probably due to an
increase in light attenuation and a reduction in monomer mobility.37
Though a linear, direct relationship between degree of conversion
and total volumetric shrinkage exists, the same is not true for the
relationship between polymerization stress and shrinkage. As previ-
ously mentioned, not all shrinkage causes stress. Moreover, stress is
also determined by the development of elastic properties by the poly-
mer, restricting stress relief by viscous flow. Therefore, initially, stress
levels do not raise considerably with conversion, until approximately
a degree of conversion of approximately 40% is reached. Beyond that
conversion level, polymerization stress increases dramatically with
small increments in conversion.30
3.4. Polymerization Kinetics

The free-radical polymerization of dimethacrylate composites is diffu-
sion-controlled, meaning its progress (in terms of reaction rate and
ultimate conversion) is defined by the mobility of the reacting species in
the developing network. Initially, propagation and termination are
chemically controlled, meaning that the availability of monomers and
free radicals make both events equally likely to occur. At this stage,
polymerization proceeds at relatively low rates. As the reaction contin-
ues, the viscosity of the reaction medium increases and propagation
becomes more prevalent, which leads to a sudden increase in reaction
rate (known as “auto-acceleration”, or “gel effect”). Further increases
in viscosity hinders the mobility of the reactive species and reduces the
availability of monomers close to the reactive end of the free radical,
causing the reaction to proceed at progressively lowers rates (auto-
deceleration) until the material reaches vitrification.27 The occurrence of
gelation is very important in terms of stress development because it is
after the so-called “gel point” (i.e. the degree of conversion correspond-
ing to the onset of auto-acceleration) that stresses start to build up.
Reaction rate does not seem to have a strong influence on polym-
erization stress development. Significant reductions in stress of
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photoactivated composites were observed only in cases where reac-

tion rate was reduced below a certain threshold value.30 Clinically, it
is unlikely that reaction rate of light-cured materials can be reduced
to the appropriate values without compromising the degree of con-
version. On the other hand, the lower reaction rate displayed by self-
cured composites seem to favor lower polymerization stress values.50
4. Local Factors Associated to Stress Development

As mentioned before, stress is not a basic material property, but a local
physical state.51 Therefore, its magnitude and distribution are not
defined only by the composite intrinsic characteristics (e.g. volumetric
shrinkage, elastic modulus, and reaction rate). The geometry and
dimensions of the tooth cavity, as well as the stiffness (or its reci
procal, compliance) of the bonding substrate are extremely influen-
tial. In fact, depending on the local conditions, composite properties
may have opposite effects on stress development, as explained in the
following sections.
4.1. Composite Confinement and Volume

One of the first variables identified as having a definite influence on
stress magnitude was the confinement conditions imposed on the
composite during polymerization. If a mass of composite had total
freedom to shrink, no stress would be generated. However, polymeri-
zation always take place with the composite bonded to a substrate, for
example, the tooth cavity walls. It has been demonstrated that in a
typical load cell testing setup, polymerization stress is directly related
to the composite bonded-to-unbonded surface ratio, termed “cavity
configuration factor” or C-factor.6,18 This relationship was confirmed
by microleakage23,24 and bond strength studies.52 Due to its simplicity,
the C-factor was rapidly assimilated by researchers and clinicians. For
example, restorations with a high C-factor were “doomed to failure”
due to the high interfacial stresses. The reduction of C-factor was the
justification for inserting the composite into the cavity in small incre-
ments.53 However, this idea was challenged by in vitro investigations
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showing that interfacial integrity was associated with cavity volume,

and not its C-factor.54,55 Moreover, the efficacy of the incremental
placement technique was shown to increase final tooth deflection.56 In
fact, a 12-year longitudinal study did not find a particularly high
annual failure rate for class I restorations with high C-factor.57 This
contradiction was explained by the fact that the effect of composite
volume and C-factor on stress development depends upon the compli-
ance of the surrounding structures. The relationship between nominal
stress and C-factor was observed in low compliance testing systems,
using either steel (elastic modulus: 207 GPa) or glass (elastic modulus:
64 GPa) as bonding substrate. However, when PMMA (elastic modu-
lus: 3 GPa) rods were used instead of glass, the increase in compliance
resulted in a linear direct relationship between the normalized nomi-
nal stress (i.e. nominal stress divided by the system’s longitudinal
compliance) and specimen volume. Interestingly, by varying specimen
height and diameter it was possible to compare conditions with similar
volumes and different C-factors. In such cases, experimental groups
corresponding to higher confinement displayed higher stress values.19
4.2. Substrate Compliance

The compliance of the structures surrounding the composite, either
represented by the bonding substrate in the testing system or the cavity
preparation in a tooth, is determined by the elastic modulus of the
substrate and amount of deformation presented by the structure when
subjected to shrinkage forces (cuspal deflection, for example). The
influence of compliance on polymerization stress development cannot
be underestimated. In fact, it is the reason why results from different
studies can lead to quite divergent conclusions. FEA revealed that
depending on the level of compliance, stress may be directly related to
composite shrinkage or its elastic modulus. For example, if a group of
composites with different filler concentrations (and, therefore, oppo-
site characteristics in terms of shrinkage and modulus) are tested in a
low compliance scenario, those with the highest elastic modulus, but
not necessarily the highest shrinkage will develop the highest stress.
On the other hand, if the same group of materials is tested in a high
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compliance system, the highest stress levels will be displayed by the

composites also with the highest shrinkage, but with the lowest elastic
modulus. This happens because even though only the shrinkage forces
manifesting in the longitudinal direction are actually recorded by the
load cell, radial stresses also build up at the composite/rod interface.
If the composite has a high elastic modulus, the ratio between the
elastic modulus of the rod and the composite (Erod/Ecomposites) dimin-
ishes, and radial shrinkage stress causes bending of the rod interface
away from the composite center, counteracting the axial shrinkage
forces and reducing the load cell reading. With less stiff composites,
this phenomenon does not occur and, consequently, load cell reading
is not reduced.9 It is important to point out that if variations in shrink-
age and modulus occur in tandem (for example, if one composite is
tested at different conversion levels), stress will be directly related to
both shrinkage and modulus, regardless of the testing system compli-
ance. In testing systems using rigid frames and a feedback loop (see
Section 2.3.3), longitudinal compliance due to rod elongation is
directly related to the rod initial length (i.e. from the bonding surface
to the point where the transducer sensor is attached) and inversely
related to the rod’s cross-sectional area and elastic modulus.18 Radial
(transversal) compliance cannot be analytically calculated. However,
rod deformation due to radial forces can be estimated by FEA.
In vitro studies revealed that the amount of remaining tooth
structure affects residual stress distribution in restored teeth. In small
cavities, due to the larger volume of tooth structure, the compliance
is reduced and higher stresses are developed at the tooth/restoration
interface. Conversely, in large cavities, the relatively thin cavity walls
yield to the shrinkage forces and, as a consequence, higher stresses are
predicted in the tooth structure.51
5. Strategies for Minimizing Polymerization

Stress Development
Over the last decades, several attempts were made to reduce the stress
developed in composite restorations. Variations in the restorative
technique, as well as the development of low-shrinkage composites
b3252_Ch-12.indd 351 27-11-2018 03:06:53 PM

have been proposed to reduce the magnitude and effects of contrac-

tion stress. These methods include the use of low-modulus interme-
diate layers, light irradiation protocols, and incremental layering
technique. The development of new low-shrinkage materials through
modifications of current formulations or by the introduction of new
filler technologies and monomer chemistries have also been the subject
of several studies.
5.1. Low-Modulus Liners

The application of an intermediate low-modulus liner between the
tooth structure and the resin composite is the basis for the technique
known as the “elastic wall concept”.58,59 Theoretically, a low modulus
liner could contribute to reduce the shrinkage stress generated by the
subsequent layer of high-modulus material by increasing the compli-
ance of the bonding substrate where the restorative composite will be
applied. The shrinkage force generated by the restorative composite
would cause the elongation of the low-modulus liner and, conse-
quently, reduce the stress developed at the bonded interface.60
Flowable composites are one example of intermediate material
used in this technique. These low-viscosity resin-based restorative
materials differ from conventional resin composites in their lower
filler load and/or higher content of low viscosity monomers. They
were developed to simplify the placement procedure and improve the
adaptation to the cavity. Their low elastic modulus (granted by the
relatively low filler content) would make them suitable to be applied
as an intermediate “stress relieving” layer.61 However, the results in
the literature are contradictory. While there are reports stating the use
of flowable as a liner improves marginal seal,62 other studies reported
no improvement in marginal integrity.63–66
Undoubtedly, there is a wide spectrum of products with a broad
range of physical characteristics.66,67 Besides, despite having a lower
elastic modulus than non-flowable (high viscosity) composites, it may
not be low enough to counteract the effects of their high volumetric
shrinkage. Actually, flowable composites presented higher polymeri-
zation shrinkage68 when compared with non-flowable composites,
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and both type of materials presented similar contraction stress

values.21,67,69 Furthermore, significant stress relief was only observed
when an unfilled resin was used as intermediate layer.69,70
The thickness of the liner is also an important parameter, with
thicker layers providing a higher stress reduction.61 Reductions in
contraction stress between 24% and 37% have been verified for com-
posites tested in a low-compliance rigid frame system with multiple
adhesive layers (up to 276 mm) in comparison with the stress regis-
tered when only one layer of unfilled resin was applied (maximum
thickness: 68 mm). These results were also confirmed by the reduced
microleakage along the tooth/restoration interface when adhesive
thickness was increased.71 A disadvantage of this technique is that an
adhesive layer too thick usually shows an increased porosity,72 it is
more susceptible to wear and hydrolytic degradation, and if the adhe-
sive is radiolucent, a thick layer can provide a false diagnosis on future
examinations.71
The use of glass ionomer or resin-modified glass ionomer as an
intermediate layer, called “sandwich technique”, was proposed with
the intention of achieving a better dentinal surface sealing.73 The use
of resin-modified glass-ionomer cements underneath the composite
was shown to improve marginal adaptation when compared to com-
posite-only restoration, built either by layering or by bulk insertion.74
Also, cuspal deflection due to composite shrinkage was significantly
reduced when glass ionomer was used as liner (approximately 1 mm
of thickness).75 This can be attributed to the glass ionomer’s slow
curing rate, which allows for stress relaxation when subjected to
shrinkage forces from the subsequent composite layer.76 Indeed,
stress reduction ranging from 18% to 50% was verified when a
0.15–0.30 mm layer of glass ionomer was applied to the bonding
substrate in a low-compliance testing system.70
5.2. “Soft-start” Photoactivation

Alternative curing routines were developed with the intent of reduc-
ing composite curing rate at early stages of photoactivation, increas-
ing its flow capacity before gelation and, consequently, reducing the
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shrinkage forces exerted by the hardening material on the bonded

interface.77 Low curing rates are attained either by using low irradi-
ances (i.e. light power per unit area, mW/cm2) during the first few
seconds of photoactivation or by applying an initially low energy dose
to the composite (i.e. irradiance over a period of time, mJ/cm2) using
a short pulse, followed by an interval “in the dark”. By doing so, less
free radicals are generated and the reaction proceeds at lower rates,
allowing more time for the curing composite to flow (i.e. undergo
plastic deformation) under shrinkage forces and postponing stress
build-up before the gel point conversion is reached. The recom-
mended energy dose is delivered by complementing the irradiation
using a high irradiance for the necessary time period. In order to be
effective, soft-start curing protocols should be able to reduce contrac-
tion stress without compromising the degree of conversion or
mechanical properties.32,78,79
There are different soft-start curing protocols described in the
literature. The “ramped” protocol consists of initial light exposure
with reduced irradiance for a certain period of time, gradually increas-
ing to a maximum irradiance value.80 “Step-curing” uses an initially
low irradiance for a few seconds, immediately increasing to the maxi-
mum irradiance,81 and the “pulse-delay” curing protocol consists of
initial light exposure at very low irradiance, a subsequent delay (of
seconds or even minutes) without irradiance followed by a second
exposure at full irradiance.60 When a two-step curing routine is
adopted, three aspects should be observed: the initial light intensity,
the exposure duration of the initial low-intensity irradiation, and the
time interval between the two irradiations.32 Previous studies agree
that an initial pulse with exposures up to 1 J/cm2 and less than
100 mW/cm2 for a period no longer than 7 s seems to be the most
efficient curing setting for reducing shrinkage stress.82 However, the
benefit of using lower initial light intensity to relieve the shrinkage
stress prior to the vitrification stage has a limited action,40,83,84 and yet
the irradiance of the initial pulse remains a controversial matter
among authors.82
Photopolymerization protocols often show a variable effect on
polymerization stress, because it is dependent on material composition
b3252_Ch-12.indd 354 27-11-2018 03:06:53 PM

and the energy densities applied to the samples.85,86 Those observations

may lead to the misinterpretation of positive results in investigations
on polymerization stress.21 Indeed, the literature is inconsistent regard-
ing the reduction of shrinkage stress when different soft-start curing
methods are used. Some results have shown that the exponential ramp
polymerization model reduced the maximum shrinkage stress (up to
20%) when compared to stepped and continuous curing model.21,80
Reductions in shrinkage stress between 19% and 33% were observed
using pulse-delay (up to 5 min delay) when compared to continuous
light-curing methods.77 Nonetheless, some clinical and in vitro studies
refer to a lack of benefit from soft-start methods regarding polymeriza-
tion shrinkage, evaluated through marginal seal and the modified
Ryge/USPHS criteria.87–89 Notwithstanding, it seems consensual
among researchers that longer delay periods between pulses would
increase possibility for chain relaxation. Indeed, dark periods ranging
from 1 to 5 min have demonstrated significant reductions in shrinkage
stress.77,82,83 Those findings reveal that longer delay times are needed in
order to achieve a reasonable amount of shrinkage stress, which is
unrealistic in the clinical practice.83
A major concern when using soft-start irradiation protocols is
related to a possible reduction in degree of conversion. Also, there is
evidence showing that the pulse-delay protocol resulted in lower poly-
mer cross-linking density compared to the continuous, high irradiance
curing method.90 Low degrees of conversion are associated with poor
mechanical properties and higher degradation. Therefore, is very
important to deliver the recommended energy dose to the composite,
regardless of the curing protocol.91,92 In fact, one must not assume that
a preset energy application sequence for photopolymerization is
optimal for all composites, since chemical composition varies and may
strongly influence degree of conversion and shrinkage stress
values.21,80,83,85 Polymerization kinetics is also material dependent.
Finally, it must be considered that the viscous flow of the material dur-
ing an extended pre-vitrification stage may have minimal consequences
because most shrinkage stress is developed during and after the vitrifi-
cation stage.83 Therefore, opportunities for polymer relaxation would
be restricted during a very short period during light activation.21
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5.3. Incremental Technique

Composite incremental layering was first suggested by Lutz.53 The
rationale is to direct the polymerization vectors favorably to reduce
the risk of interfacial debonding93 and decrease the C-factor, allowing
a larger surface for the composite of flow and partially dissipate the
shrinkage stress.59 Incremental techniques may vary according to layer
orientation, i.e. the horizontal, oblique, facio-lingual, U-oriented, or
the cusp-oriented layering technique.93 Among those, oblique incre-
ments were shown to improve the marginal integrity because the
occlusal-most layer would never be tied simultaneously to both facial
and lingual enamel margins. The use of an incremental technique
resulted in significantly less microleakage than the use of a bulk tech-
nique,94 and cuspal deflection.95
As usual, literature on this topic is controversial, as other studies
did not find any difference between filling techniques.96,97 Moreover,
through FEA it has been reported that incremental composite resto-
ration actually results in higher polymerization shrinkage stresses than
bulk fillings, contrary to the widely accepted evidence. The criticism
is based on the finding that the contraction of each individual layer
would cause the deformation of the cavity and the displacement of the
cusps, decreasing the cavity volume, which result in a higher stress
state.56,98 Cavity depth is a possible reason why incongruent results are
reported. As the depth of the cavity increases, bulk insertion may
prevent the resin composite from been appropriately cured at the bot-
tom surface as the irradiance decreases. This gradient in conversion
may favor some stress relief.99
5.4. Composite Pre-Heating

Composite pre-heating was introduced as an alternative to lower its
viscosity and, consequently, improve adaptation to cavity walls.100 An
additional benefit is that the higher temperatures allow for increased
mobility of the reactive species with consequent increase of degree of
conversion27,101–104 and hardness of the resin composite.105 This is
explained by the fact that the increased molecular vibration forces the
b3252_Ch-12.indd 356 27-11-2018 03:06:53 PM

monomers further apart, allowing them to slide by each other more

readily106 leading to the delay of auto-deceleration and postponing
vitrification, allowing the reaction to continue for longer times.27,100
Indeed, if preheated, it is possible to reduce the energy dose without
compromising the degree of conversion.102,103,107 However, increased
polymerization rate also associated with curing at high temperatures
may lead to an increased polymerization stress, unless the low viscos-
ity (induced by preheating the composite) permits chain relaxation
and, therefore, lower shrinkage stress.103
Although some studies have not demonstrated relevant bene-
fits, since no significant reduction on shrinkage stress nor reduced
microleakage was observed when compared with non-heated resin
composite,100,108,109 another study reported a significant relaxation
percentage and a 55% reduction on final stress when composite is
heated up to 40°C or 60°C.103 A commercially available heating
device has shown limited efficacy in terms of stress reduction,
explained by the fact that the temperature of the pre-heated com-
posite drops rapidly once it is removed from the heating
device.103,110 Another important factor to consider is the composite
heat that will be transferred to the dentin–pulp complex and its
consequence on pulpal response. Literature shows a 15% risk of
induced necrosis when the intra-pulpal temperature is increased by
5.5°C and a 60% chance when there is an increase of 11°C.111
Preheating the composite as well as the heat generated by the
curing light may increase heat buildup, which was shown to reach
8°C at the pulpal floor.112
5.5. Low Shrinkage Composites

Over the years, several modifications in resin composites formulations
have been proposed in order to reduce polymerization shrinkage.
Marketed as “low shrinkage” materials, most of them are dimeth-
acrylate-based with modifications in the filler phase. Changes in the
photoinitiator systems and polymerization inhibitors have also been
reported.113 Manufacturers and researchers are continuously investi-
gating new alternative monomers with reduced shrinkage.
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5.5.1 Low-Modulus Fillers

The use of silica particles without any surface treatment (non-bonded)
or functionalized with non-functional silane was proposed aiming to
minimize the interaction between the filler surface and the forming
polymer, therefore providing sites for stress relief. Stress reductions
between 30% and 50% were obtained compared to a composite with
silane-treated microfillers. Unfortunately, the handling characteristics
were negatively affected by increasing its viscosity.20
The addition of high-density polyethylene (HDPE) spheres in
composites was another approach attempting to reduce contraction
stress with minimal effect on mechanical properties. The incorpora-
tion of porosity or microvoids between the spheres and the polymer
matrix is expected to produce areas for stress relief.114 A 23–29% stress
reduction was achieved by adding 20% of HDPE spheres on both
hybrid and nanofilled composites. The less-rigid nature of the spheres
helped reduce the contraction stress but negatively affected the
mechanical properties. Fracture toughness, flexural strength, and flex-
ural modulus were reduced with the incorporation of HDPE spheres,
limiting the efficacy of this approach.115
High molecular weight polymeric nanoparticles, or nanogels, were
tested as additives to reduce the reactive group concentration and,
therefore, the polymerization shrinkage. When a high nanogel content
is incorporated on a resin matrix, viscosity changes dramatically.116.
Polymeric fibers produced by electrospinning processes represent
another way to add pre-polymer particles into resin composites.117
5.5.2 Commercial Low-Shrinkage Composites

A new monomer system, named silorane, was made commercially avail-
able in the last decade. Silorane is a cationic ring-opening monomer
synthesized from the combination of a hydrophobic siloxane backbone
and an oxirane ring. It is characterized by its biocompatibility, hydro-
phobicity, insensitivity to oxygen, high reactivity, and low shrinkage.
Silorane pre-gel time is 7.6 s, which is significantly higher when com-
pared with dimethacrylate-based composites.118 Its volumetric
b3252_Ch-12.indd 358 27-11-2018 03:06:53 PM

shrinkage stress was reported as being as low as 1.34%, and significant

stress reductions (from 82% to 95%) were observed when compared
with other low-shrinkage commercial products.94,119,120 Part of its low
shrinkage can be attributed to its low degree of conversion, which is
expected because of the tetrafunctionality of the silorane molecules.19
Other attempts to reduce shrinkage include modifications in a
urethane-based methacrylate resin that led to a reduction of 60–70%
in shrinkage stress, explained by a reduction in polymerization rate.
In this material, shrinkage stress was reduced by plastic flow occurring
during the pre-gelation phase.121 Also, the use of a high molecular
weight (MW = 895) reactive oligomer (DX-511, DuPont) with a stiff
structural core and flexible arms,122 a high molecular weight mono-
mer was derived from dimer acid methacrylates (dimer dicarbamate
dimethacrylate — DADMA) with high reactivity with BisEMA and
UDMA.123 A highly filled, BisGMA-based composite containing
74 vol% of glass fillers was also developed, However, its contraction
stress was not significantly reduced due to the high elastic modulus
granted by the filler fraction.34 Overall, these new formulations
exhibited polymerization shrinkage similar to those of traditional

composites,34 except by the silorane-based material which showed half
of the total shrinkage developed by a nanohybrid composite.34
However, a severe reduction (75%) in elastic modulus was seen for the
silorane composite after 4-month storage in ethanol.34
Recently, materials with improved photoinitiator dynamics, con-
trolled polymerization contraction stress, and increased translucency
were developed for insertion in bulk. In fact, the use of bulk-fill mate-
rials on extensive cavities has demonstrated lower cuspal deflection
and contraction stress.121,124 However, other studies found that bulk-
fill composites presented a much higher shrinkage when compared
with conventional resin composites.125–127
5.5.3 Experimental Composite Materials

Much interest has been focused on the development of low-shrinkage
materials, either by introducing new filler technologies or chang-
ing monomer chemistry. Several alternatives to conventional
b3252_Ch-12.indd 359 27-11-2018 03:06:53 PM

dimethacrylate monomers have been proposed. The first approach

was the use of spiro orthocarbonates (SOCs), an ester of orthocar-
boxylic acid, characterized by the presence of bicyclic compounds in
a ring opening polymerization. In such monomers, for every van der
Waals bond converted to a covalent bond, at least two rings are
opened during polymerization, inducing a local volumetric expansion
in order to compensate for volumetric shrinkage.128 Initially, reduc-
tions in polymerization shrinkage (38% reduction with copolymer
containing 33 wt.% SOCs) were minimal, probably due to insufficient
ring opening rate.41 However, when SOCs were mixed with epoxy
resin, a considerably higher reduction in polymerization shrinkage
was obtained.129 Nonetheless, several drawbacks were observed:
the polymerization reaction did not occur with visible light,
SOCs-containing composites exhibited poor mechanical strength,

and volumetric expansion was insufficient to counteract for the
polymerization shrinkage.130
Developmental silicon-containing tetraoxaspiroundecane mono-
mer (TOSU) belongs to the spiroorthocarbonates-type monomers
reported to undergo polymerization with expansion in volume due to
double ring opening. A 10% mol addition of TOSU monomer to a
silorane gives a dramatic reduction in polymerization stress with only
a modest reduction in physical properties. It had 90% less shrinkage
stress than silorane.119 Experimental monomer FIT-852 is a nonlinear
difunctional methacrylate with molecular weight of 1200. Based on a
modification of UDMA and very similar to the DuPont monomer
structure, this FIT-852 monomer is expected to achieve higher con-
version, lower shrinkage values, and also improve the toxicity
observed with Bis-GMA. Despite its lower shrinkage, its mechanical
performance still needs to be improved.131
The thiol-ene photopolymerization has also gained much atten-
tion as a different approach to formulate novel materials. Due to the
step growth evolution of the network, the thiol and ene monomers
are quickly consumed, while low molecular weight species participate
in early stages of polymerization. Thus, this mechanism causes a delay
on gel point conversion lowering induced shrinkage and shrinkage
stress.132
b3252_Ch-12.indd 360 27-11-2018 03:06:53 PM

Despite continuous improvements on techniques and develop-

ment of new materials, no method has been shown to be totally effec-
tive in abating the effects of polymerization shrinkage.95 Although
little or no clinical evidence sustains the hypothesis that composite
materials with greater polymerization shrinkage have poorer clinical
performance, laboratory data from several studies support this belief;
however, effectiveness must come from clinical outcomes,78 and such
data rarely come to light. In the meantime, as a better understanding
emerges regarding the complex process of network formation and the
relationships between materials and its properties, further advances
are certain to follow.113 Surely, it is likely that new materials with
proved low polymerization shrinkage will dominate the market before
a complete understanding of this clinically important phenomenon is
achieved.78
6. Composite Water Sorption as a Means

for Polymerization Stress Reduction
Water uptake by dimethacrylate-based composites is considered a
clinical problem because it is associated with chemical degradation,
loss in mechanical properties, staining, and hydrolysis of the tooth/
restoration interface.133 Notwithstanding, hygroscopic expansion of
resin composites may reverse tooth deformation caused by polymeri-
zation shrinkage stress, as verified after immersion periods varying
from 4 weeks to 6 months.134–136 Such a finding seems contradictory
based on the fact that polymerization shrinkage is not completely
offset by hygroscopic expansion.137 However, only the post-gel
shrinkage is responsible for stress development, and therefore it is this
fraction of the total shrinkage that must be compensated.134 This
reduction in cuspal deflection overtime cannot be ascribed to com-
posite stress relaxation by viscoelastic deformation because no reduc-
tion in tooth deformation was recorded when the restored teeth were
kept in silicone oil instead of water.138 The relaxation of residual
stresses by water uptake was also verified using the ring-slitting
method. The calculated residual stress in composite rings kept in
water for seven days was approximately 30% lower compared to those
b3252_Ch-12.indd 361 27-11-2018 03:06:53 PM

kept dry.139 It is important to remember that water uptake cannot

avoid clinical problems usually related to polymerization stress devel-
opment such as post-operative sensitivity, enamel cracking, and inter-
facial debonding but, still, it seems to compensate for the residual
stresses responsible for cuspal deflection.
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b2530_FM.indd 6 01-Sep-16 11:03:06 AM

Chapter 13
Flexible Impression Materials
Charlene S. Solomon
Department Restorative Dentistry, University of Manitoba,
780 Bannatyne Avenue, Winnipeg, MB, R3E 0W2, Canada
charlene.solomon@umanitoba.ca
Flexible dental impression materials form an integral part of daily

clinical practice. It allows for the making of accurate impressions or
a negative replica of the mouth and oral structures. These flexible
impression materials are mostly selected based on their physico-
chemical properties and applications. A thorough knowledge of
impression material classifications and their respective properties
allows for an educated and evidenced-based decision for impression
materials selection. The various classes of flexible impression
materials commercially available allow for a wide range of clinical
practice applications from routine diagnostic impressions to preci-
sion impression for intricate fixed restorative procedures. Although
the desirable physicochemical properties of flexible impression mate-
rials are well researched and documented, impression materials
continue to evolve to meet the demands of improved and advanced
dental and clinical practice technologies. Newer contemporary
hybrid impression materials emerged in the early 2000s combining
the best properties of an economical alginate impression material
with the accuracy of an elastomeric impression material. This chapter
371
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focuses on the history and development of the different flexible

impression materials, elaborating on specific physicochemical
properties for each class of flexible impression material.
1. Introduction
Flexible impression material forms a foundational and integral
component of everyday clinical dental practice. Dental practitioners use
flexible impression materials to make accurate impressions of the oral
tissues to make a gypsum stone model, which serves as a positive replica
of the oral structures. The gypsum stone models can be easily and con-
veniently manipulated on a bench top to evaluate, modify, and be used
to fabricate an indirect oral prosthesis. Indirect prostheses can be fixed,
meaning crowns or bridges that are permanently fixated to the natural
teeth or implants or it can be removable referring to complete or partial
dentures, mouth guards, bruxism splints, and orthodontic appliances.
Impression materials have evolved over time as the esthetic and
implant realm of dentistry saw new technologies and techniques
emerge for the fabrication of intricate and often complex indirect
prostheses. More specifically, dental impressions evolved from labor-
intensive, technique-sensitive procedures to simplified-impression
techniques with user-friendly and accurate impression materials.
Clinical practice demands impression materials with high accuracy,
dimensional stability, and hydrophilicity. In addition, the clinical prac-
tice setting benefits from materials that can be manipulated and han-
dled with efficiency. This relates to the dispensing technique, patient
acceptance, and ease of cleanup of the materials.
Research on flexible impression materials has focused mainly on
in vitro material properties testing as a function of its clinical require-
ments.1–4 This chapter provides a broad overview of flexible impres-
sion materials, its classification, history, and its physical properties as
it relates to impression making in clinical dental practice.
1.1. History
The history and development of flexible dental impressions started in
the 20th century, known as the era of innovations and technology.
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Flexible Impression Materials 373
This era in the dental realm started with the introduction of the
porcelain jacket crown by Charles Land in 1903, and the introduction
of the lost wax technique by William Taggart in 1907. This was
the start of fabrication of direct and indirect fixed restorations. The
historical development of impression materials was founded in the
development of impression materials for mostly complete dentures.5
The first successful flexible impression materials introduced to
dentistry were the aqueous reversible agar hydrocolloids in the 1930s.
The agar material sets in a flexible gel form and allowed for accurate
recording of undercuts. The agar hydrocolloids were an improvement
to the waxes, plaster, and compound materials that were available at the
time.6–8 Sears introduced agar hydrocolloids into fixed prosthodontics
in 1937,9,10 and it became the standard of excellence for impression
making. The agar material was the same material that bacteriologists
used in their petri dishes.6 The making of an agar hydrocolloid impres-
sion requires equipment such as a conditioning unit9 to convert the agar
gel form to a liquid state and special water cooling impression trays.6
Its clinical application was initially limited to removable partial dentures
until Sears introduced a different technique whereby reversible hydro-
colloids can be used for inlays, crown, and bridges.7
A second aqueous, but irreversible alginate hydrocolloid flexible
impression material was introduced during World War II, at a time
when agar hydrocolloids were scarce. This was due to the fact that
most of the processing of the algae used for the manufacturing of
agar-agar at the time was done in Japan.5–7 The processing of a native
brown algae yielded a new flexible aqueous impression material with
an alginate base. The introduction of alginate impression materials
became a desirable and convenient alternative impression material.
In contrast to agar hydrocolloids, the making of an alginate impres-
sion requires no special equipment or special impressions trays, and it
involves a simple mixing of powder and liquid components. Its physi-
cal properties allowed a controlled setting process with the material
exhibiting toughness and resiliency.7
The first non-aqueous flexible material introduced was the poly-
sulfides in 1953.11 It provided greater strength and stability than the
hydrocolloids and was popular in its application for completed
denture impressions. The 1960s saw the introduction of two more
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non-aqueous impression materials in fixed prosthodontics, namely the

condensation silicones and polyethers. These non-aqueous materials
had a rubber-like consistency, were user-friendly, and easier to mani
pulate and clean up than the polysulfides. The polyethers provided a
significant improvement in dimensional stability and accuracy by means
of its improved mechanical properties. The significance of this material
is that it maintained its high accuracy and competitiveness with other
elastomers well into the 21st century with improvement in delivery
mechanisms. The condensation silicones were less stable than polyethers
as it polymerized by means of a condensation reaction, forming a by-
product affecting the accuracy of the final set material (see Table 1).
The next significant development in the history of flexible impres-
sion materials was the development of addition type silicones (vinyl-
polysiloxanes or VPS) as part of the Apollo space program7 in the
1970s. The VPS impression materials became the impression material
of choice for fabrication of high-precision prosthesis such as crowns
and bridges. It has superior dimensional stability compared to its
predecessors, but comparative to polyethers.
The 21st century saw the introduction of flexible hybrid impres-
sion materials, specifically alginate–silicone and VPS–polyether
combinations. These hybrid materials provide unique impression

properties that combine the benefits of a low-cost impression material
with the high-dimensional accuracy of another.
Currently, the alginate hydrocolloids, addition-type silicone, and
polyethers are the most common flexible materials used for advanced
restorative procedures in clinical dental practice.
Table 1. History timeline for flexible dental

impression materials
1937 Reversible hydrocolloids, agar
1943 Irreversible hydrocolloids, alginates
1953 Polysulfides
1960s Condensation Silicone
1965 Polyether
1970 Addition Silicone
2000s Hybrid Impression materials
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2. Classification
Flexible dental impression materials can be classified according to its
chemistry, mechanical properties, viscosity, or applications. Dentists
learn and identify dental materials mainly by their chemical composi-
tion. Different chemistries bring about a specific set of characteristics
that may be suitable for a specific dental application. Figure 1 catego-
rizes flexible materials by chemistry, broadly classified into aqueous
and non-aqueous impression materials including the newer hybrid
impression material varieties.
The aqueous impression materials are natural polymers and
consist of two main groups, the reversible and irreversible hydro
colloids. The non-aqueous impression materials are synthetic p olymers
and also referred to as elastomers. The term elastomer refers to a
polymer that has viscoelastic properties. Both aqueous and non-

aqueous impression materials groups are elastic and flexible, but only
the synthetic polymers are referred to as elastomers.
Agar
Reversible
Hydrocolloids
Aqueous/
Alginate
Hydrocolloids
Irreversible
Hydrocolloids
Alginate-Elastomer
Flexible Impression Hybrids
Materials Elastomer-Elastomer
Polysulphides
Condensation
Non-Aqueous/
Silicones
Elastomers
Addition
Polyethers
Figure 1. Classification of flexible impression materials
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Hybrid impression materials are grouped into two main chemistries.

One hybrid group consists of an alginate–elastomer combination, and a
second hybrid group consists of exclusively elastomer combinations.
3. Flexible Impression Material Properties

The most important characteristics for flexible impression materials
are its accuracy and elasticity. The accurate recording of the contours
of teeth and supporting structures demands a material that flows into
cervices and over contours, capturing intricate tooth preparation
details and sets without distortion. Similarly, the material should
flow and engage to the full depth of tooth and soft tissues undercuts
and withdraw from those undercuts without distortion or tearing.
It should also be capable of being disinfected without affecting its set
properties and must maintain its dimensional accuracy.
A thorough knowledge and understanding of impression material
properties at every stage of the clinical and laboratory processes is key
for an accurate final outcome of the clinical procedure. The life of a
flexible dental impression involves the following sequenced clinical
and laboratory steps:
(1) mixing of impression material,

(2) loading of impression material into an impression tray,
(3) positioning and seating of the loaded impression tray inside the
mouth,
(4) setting of the impression material,
(5) removal of the set impression material,
(6) disinfection,
(7) transportation to a dental laboratory,
(8) pouring of a gypsum stone into dental impression,
(9) separation of gypsum stone cast from dental impression.
At each of the aforementioned stages in the life of a dental

impression, specific material characteristics and qualities are desired
to achieve an overarching goal of making an exceptionally accurate
final prosthesis on the final gypsum stone model. Table 2 summarizes
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Table 2. Desirable impression material properties at

impression making
Stages of impression making Desired material properties
Mixing Ease of manipulation
Biocompatibility
Loading of impression tray Suitable viscosity
Flow & Flexibility
Flow and flexibility
Intraoral positioning and seating of Hydrophilicity/Wettability
the loaded impression tray Accuracy
Biocompatible
Accuracy
Setting
Dimensional stability
Elastic recovery
Flexibility
Removal of the set material
Tear strength
Biocompatibility
Disinfection
Transportation/Delayed pouring Dimensional stability
Wettability
Accuracy
Pouring of a stone model
Biocompatibility
Elastic recovery
Flexibility
Removal of set stone model
Tear strength
the desired properties of the impression material at every stage in the

clinical and laboratory processes.
3.1. Ease of Manipulation

The ease by which flexible impression materials can be handled
and manipulated plays a crucial role in the everyday dynamics of a
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busy dental office. Manufacturers continue to improve formula-

tions and dispensing methods for maximum efficiency at the
chairside.
Irreversible hydrocolloids are powder and liquid systems that are
mainly hand mixed, but semi-automatic mixing techniques are avail-
able to enhance mixing and provide a smoother material consistency.
These powder formulations may be color-coded; the material changes
color during mixing to indicate timing of tray loading and prevents
the overspatulation of material.
Most elastomeric impression materials are dispensed with auto-
mated systems and mixing tips for efficiency and void-free mixes.12 Its
benefits include reduced contamination, and it eliminates voids,12–14
and produces less wastage15 as is often seen with spatulation methods.
The auto-mixing allow ease of dispensing by injecting material
directly around critical tooth preparations and into the custom tray.
Auto-mixing saves time by eliminating the need for cleaning of
mixing bowls and spatulas. Auto-mixing is the preferred mixing
technique for dentists, dental students, and dental assistants16
allowing an improved workability compared to hand mixing.
3.2. Accuracy
Accuracy of dental impressions is measured in two ways. First, it has
to meet a specific standard as determined by the American Dental
Association (ADA) and the International Standards Organization
(ISO). The ADA specification #19 for elastomeric materials states
that this materials should be able to record fine details of up to
25 μm.17 The International Standards Organization (ISO) for dental
elastomeric materials classifies a Type III impression material as one
that can produce a line of 0.020 mm in width.18
Second, accuracy is measured as a function of dimensional stabil-
ity by measuring tooth-to-tooth dimensions within the same arch and
in the cross-arch.17 This is a function of how accurate the material can
produce a copy of the oral structures. The majority of impression
materials today provide excellent accuracy when used correctly.
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3.2.1. Elastic Recovery

Dental impressions are typically subjected to compressive and tensile
forces upon seating and removal of the impression. This is inevitable
as impression material often engages into soft or hard tissue under-
cuts. The maximum tensile strain tend to be greater than the maxi-
mum compressive force.19 The ISO 4823 standard for elastomeric
material specifies elastic recovery from a 30% compressive strain,
although the validity of using compressive strain rather than tensile
strain has been questioned.19 This is termed as elastic recovery, and no
impression material has absolute 100% elastic recovery.17
3.2.2. Dimensional Stability

The ability of a dental impression to be accurate and maintain its form
and dimension over a period of time is critical to provide an accurate
and predictable final impression. Dental practitioners who discern-
ingly embrace contemporary dental manufacturing technology and
materials may need to courier their dental impressions to out of prov-
ince or out of state locations to access specific technologies. Courier
services could involve more than a 24 h delay in pouring of the
impression. This clinical reality demands an impression material with
high dimensional stability.
Dimensional change can be affected by: (1) polymerization
shrinkage, (2) loss of a condensation reaction by-product such as
water or alcohol, (3) thermal contraction from oral temperature to
room temperature, (4) absorption of water or disinfectant over time,
(5) incomplete recovery of deformation.20 Vinyl polysiloxane impres-
sion material possesses ideal dimensional stability as it forms no by-
product upon setting, and pouring of impressions can be delayed for
hours, days, and even weeks after making the final impression.17
3.3. Flow Properties/Rheological Properties

The ability of an impression material to flow is referred to as its rheo-
logical properties. Flow properties allow impression materials to move
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into microspaces in the oral cavity and record minute details such as
grooves, tooth–gingiva interfaces, and beveled tooth margins. A low
viscosity impression material flows readily to accurately capture intri-
cate details. A medium body or heavy viscosity impression materials
flows less, but accurately captures macrostructures such as tooth con-
tour and arch form. When used in combination, the medium or heavy
viscosity materials provide the overall support for the impression,
while the light body records finer details.
3.4. Flexibility
Flexibility refers to the stiffness or rigidity of a material. Ideal flexibil-
ity allows the dental impression material to be easily removed from
undercuts in the mouth without any discomfort. It should also have
sufficient rigidity to withstand any tearing or distortion. At the same
time, it should support the ease of removal of the gypsum stone cast
when separated from the impression.
3.5. Wettability/Hydrophilicity
The mouth is a moist environment, and the properties of wettability
and hydrophilicity are important for accurate impressions.
Hydrophilicity is the affinity for water, and the wettability of an
impression material is the ability to flow and adhere onto solid sur-
faces. Wettability allows for ease of flow and an intimate contact
between tooth structures and the impression material.21 At the same
time, also allow ease of wettability by water-containing gypsum mate-
rial when pouring a stone cast. Inadequate wetting of an impression
is characterized by the incorporation of voids and bubbles in stone
casts.22,23 Voids are typically seen on critical areas of stone cast such as
preparation margins and grooves.
Wettability of an impression material is a function of the contact
angle formed between the surface of the wetted solid and tangential
to the curved drop at the point of contact. A small angle (less than
90°C) indicates good wettability22 and large angles indicate a poor
affinity24 or low wettability.
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3.6. Biocompatibility
Biocompatibility refers to a material’s ability to maintain accuracy and
dimensional stability when coming into contact with other materials.
This would include operator gloves, disinfection products, gypsum
stone, and clinical medicaments.
3.7. Tear Strength

For dental impression making, the material that engages in interden-
tal and subgingival areas are often thin and of a low viscosity variety.
This makes it particularly prone to tearing upon removal. The amount
of force needed to tear a specific material divided by the thickness of
the material is termed tear strength.20
4. Aqueous Hydrocolloid Impression Materials

The two main groups of aqueous materials are the reversible agar
hydrocolloids and the irreversible alginate hydrocolloids. The revers-
ible agar impression material has largely been replaced with irreversible
alginate materials today, but is included here for completeness.
4.1. Agar/Reversible Hydrocolloids

When Sears introduced reversible hydrocolloids in 1937,9,10 it soon
became the standard of care for impressions for indirect restorations.6
At that time, it was regarded as the best impression material for
detailed and precision impressions. Its applications were for full arch
or quadrant impressions without deep undercuts.25
4.1.1. Composition
Agar hydrocolloids are complex polysaccharides that are extracted
from seaweed. The agar hydrocolloid materials exist in two forms; a
gel and a sol form. The sol form comprises a random arrangement of
polysaccharide chains, and the gel form represents organized and
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aligned polysaccharide chains. Agar impression materials are supplied

in tubes in a gel form, which is viscous and flexible. The sol state is
fluid with a low viscosity. Its main ingredients are agar as a gelling
agent, borax to improve strength, potassium sulfate for dental stone
compatibility, and alkylbenzoates as preservatives.25 The water con-
tent is as high as 80%, and the agar content on average may be 15%.6
4.1.2. Manipulation and Properties

Heat applied to agar hydrocolloid converts its gel form to a sol state
with a consistency suitable for dental impressions. Cooling of the
sol state reverts the material back to a viscous gel state. Special
temperature-controlled water baths are needed for the liquefaction
of the gel state, and special water-cooling impression trays are needed
to solidify the sol agar intraorally. The water baths have three sections
that accommodate three different temperatures for liquefaction, stor-
age, and tempering of the agar. The water cooling metal stock trays
consist of narrow-diameter metal tubing attached to the outside of
the tray, which in turn can be attached to a water supply inlet. The gel
is converted to a liquid state by boiling it at 100°C for about 10 min.
The agar is then placed in the storage unit of the water bath at
65–68°C for a ready-to-use consistency. At impression making, the
material is tempered at 46°C for two minutes and loaded into the
impression cooling trays. The flow of cold water (18–21°C) around
the periphery of the tray cools the material and supports the conver-
sion from sol to gel state. Bear in mind that this water-cooling effect
takes place while the impression tray is seated intraorally, making this
a more complex impression technique.
Agar hydrocolloid impressions exhibit a high degree of accuracy
and detail, producing a high quality and precise indirect dental
casting. This can be attributed to its fluid sol state and true hydro-
philic property,17 allowing it to flow better and record fine details
more accurately.
Agar impressions should be poured immediately to avoid the loss
of water during storage (syneresis) or absorption of water (imbibi-
tion). The minimum storage time for agar impressions is 1 h in 100%
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relative humidity. It has poor mechanical properties and low tear

resistance. It is an inexpensive material with no unpleasant taste or
odor. The main drawbacks of agar impression materials are that they
need specialized equipment, are dimensionally unstable, and the den-
tal impression can only be used for single casts.25 In addition, the
water cooling trays are fairly bulky to place due to the additional
metal water channels attached.
4.2. Alginate/Irreversible Hydrocolloids

Alginate hydrocolloids are the workhorse impression material for
routine diagnostic impressions in most dental practices. It is gener-
ally well tolerated by patients and economical.26 It is mostly supplied
as a powdered alginate material mixed with water to produce a
creamy consistency for dental impressions. It is supplied in a two-
paste system too,26 also known as modified alginates.20 Based on its
composition, the consistency, setting time, color, and taste may vary
between manufacturers. It is available in both regular and fast
setting times.
4.2.1. Composition
Alginates are extracted from seaweed and supplied in a powder form.
The alginate powder is the sodium or potassium salt of alginic acid
that is easily soluble in water. It has calcium sulfate as a reacting
agent and sodium phosphate as a retarder. The bulk of the powder
contains inorganic fillers (zinc, talc, diatomaceous earth), which
determines the flow properties and strength of the set alginate. The
diatomaceous earth contains silica particles that can become air-
borne during fluffing of the powder, risking inhalation of fine silica
particles.20 A dustless alginate is available with additional glycol
components that make the alginate powder denser and less able to
become airborne.
The final alginate impressions consist of approximately 80% of
water, which makes it susceptible to distortion if water is lost
(by syneresis) or water is absorbed (by imbibition).27 The time delay
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between making the impression and pouring a gypsum cast and the
manner of storage is critical to avoid these two phenomena of
syneresis or imbibition from occurring.

The alginate powder tends to settle with storage and may affect the
final water:powder ratios at the time of mixing. It is recommended
that stored alginate powder be shaken or fluffed before mixing to
aerate and allow for an even distribution of its constituents. Special
powder scoops and water measuring cups are used to ensure accurate
powder:water ratios. Mixing of the powder and water is done at
room temperature, with the wet alginate mixture being pressed
against the side of a rubber mixing bowl to eliminate any air entrap-
ment during mixing. Automated rotating mixing bowls can provide
an automated mixing technique producing less air bubbles in the set
material.28 Automated mixing techniques also produce a more
homogenous mix with a reduced working time.28 Slower or faster
setting times can also be manipulated by using either cooler or
warmer water, respectively.29
Alginate impression material demonstrate maximum accuracy
when it has a cross-sectional thickness of 4–6 mm.17 The use of appro-
priate sized stock trays allows for this bulk of thickness for alginate
impression material. A perforated impression tray further secures the
impression material to avoid separation of the set material from the
tray during impression removal. Alginate tray adhesive is recom-
mended for non-perforated trays.20
Setting of alginate impression material occurs within two minutes,
and upon removal, the saliva is rinsed off under running water and
then disinfected by means of a spray technique. Traditionally, these
impressions are to be poured immediately or within 30 min of making
the impression. The extended-time alginates were shown to exhibit
dimensional stability for up to 100 h.27
The dimensional stability of alginate impression materials is a key
function of its chemical composition. Aqueous impression materials
contain 80% water and are particularly sensitive to distortion by either
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evaporation of its water content (syneresis) or the absorption of water

(imbibition). Therefore, the general recommendation is that alginate
impression material be poured immediately to avoid the phenomena
of syneresis or imbibition to occur. There is no clear evidence on the
dimensional stability of alginate impression materials as a function of
the pouring time30 and storage time for that matter. However, casts
produced from alginate impressions stored in 100% relative humidity
at different storage times for up to 5 days showed no difference in
surface detail production and dimensional accuracy.31
4.3. Hybrids/Alginate Alternatives

Alginate impression material has been modified by the incorporation
of silicone polymers32 to function as alginate alternatives (AA) with
comparable function and applications of alginates, but with improved
stability and ease of mixing and dispensing of silicones. These materi-
als have been referred to as alginate alternatives, alginate substitutes,
or a hybrid impression material.
There appear to be conflicting terminologies based on properties
of the AA, with some describing it as a superior alginate alternative
and others describing it as a low-cost VPS alternative. Although
described as an AA, it is classified as a Type II addition silicone.34 It is
available in one viscosity only, a medium-body addition-type polyvinyl
siloxane-based material.35
Its cost is considerably more than that of conventional alginates35
and less than that of vinyl polysiloxanes. A probable explanation for
its lower cost is explained by the omission of palladium in the chemi-
cal formula.33 Palladium is an expensive component in conventional
vinyl polysiloxanes impression materials that acts as a scavenger for
excess hydrogen gas during the setting process.
4.3.1. Composition
The term hybrid denotes the combination of alginate and silicone
elastomers, providing the ease and economics of alginates but with
the quality and stability of an elastomer. Due to the presence of vinyl
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polysiloxane in alginate alternatives, the testing of the physical

properties of AA is measured and assessed in accordance with

American National Standards Institute and American Dental
Association (ANSI/ADA) No. 19 for elastomeric impression
materials.33 It has shown to reproduce detail (25 μm line) as required
by specification No.19 for elastomeric materials, but demonstrating
deformation properties of alginates.36 Although referred to as an
alginate alternative, its properties are closely aligned to that of elasto-
meric materials.

Alginate alternatives are dispensed with auto-mixing technologies
that provide a predictable and even consistency with a precise setting
time. The additional features of ease of impression making with
reduced mixing times, reduced intraoral setting times, and less clean-
ing-up time compared to traditional alginates are added benefits.
In vitro investigation on the physical properties of AA shows
superior performance as regards detail reproduction, gypsum com-
patibility, and linear dimensional change.33,34 The improved rheo-
logical properties of this material allow it to better capture surface
detail when compared to conventional alginates.34 This property is
suggested to be a function of the flow properties of the VPS
constituent.33
The earlier reports on the first alginate alternatives available
showed a material with improved tear and compressive strength but
with no improvement in dimensional stability.37 Subsequent tear
strength testing showed AA to reproduce thin intrasulcular and
interproximal areas, suggesting higher tear strengths than traditional
alginates.33
Impressions made with AA exhibit excellent dimensional stability
with a 4 h delayed pour when compared to conventional alginate
impression material.35 Some manufactures suggest pouring can be
delayed for up to 14 days without loss of accuracy (Alginot by Kerr).
The stability of AA impressions not only allows for a delayed pour of
the impression but also allows for the making of multiple, accurate
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diagnostic casts from one impression.20 The recommendation is that

AA be poured 60 min after mixing as the material shows more outgas-
sing with cast porosity when poured immediately.33
4.3.3. Clinical Applications

Alginate alternative impression material has similar but more wide-
spread clinical applications to the traditional alginate materials. This
is mainly due to its properties of increased accuracy and prolonged
dimensional stability. It is often marketed as a stable and reliable
preliminary impression material for improved productivity. Other
applications include opposing dentition models for full arch crown-
and-bridge cases, case study models, orthodontic models, retainers
and splints, sports guards, and whitening trays. In particular, its
function as an accurate template for crown-and-bridge provisional
crowns are highlighted.38
Due to its stiffness, it may not be suitable for making impression
in areas of severe soft tissue undercuts, such as maxillofacial impres-
sions or for teeth that show signs of mobility.
5. Non-Aqueous Elastomeric Impression Materials

Where the aqueous hydrocolloid groups of flexible impression materi-
als are natural polymers, the non-aqueous elastomers are synthetic
polymers. Both are elastic and flexible, though the non-aqueous
groups are referred to as elastomeric impression materials or elasto-
mers. The elastomers are rubber-like impression materials produced
by cross-linked polymers of silicone and oxygen and addition of long
chains. This gives it a unique chemistry with superior properties to
the aqueous impression materials. It is supplied as two components, a
base and catalyst system, that are mixed for impression taking. They
are formulated in various consistencies and setting times giving them
a wide range of clinical applications. The elastomers attempt to
address two main shortcomings associated with hydrocolloid impres-
sion materials, namely poor tear resistance and poor dimensional
stability. In addition to being easily handled, mostly odorless, and
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tasteless, elastomers gained quick acceptance within the dental com-

munity and became the gold standard for precision impressions.
Chemically, there are three main groups of polymer-based elasto-
meric impression materials namely (1) Polysulfides (PS), (2) Silicones/
Vinylpolysiloxanes (VPS), both condensation and addition type, and
(3) Polyethers (PE). Elastomeric hybrid impression materials are
available too, namely vinylpolyether silicone (VPES).
5.1. Polysulfides
Polysulfide impression material was the first elastomeric impression
material to be introduced in the 1950s and was also referred to as
mercaptan or thymol.
5.1.1. Composition
The base of this two-paste system contains a polysulfide polymer that
contains a multifunctional mercaptan (–SH) polymer, a suitable filler
to provide strength, a plasticizer to provide appropriate viscosity, and
a small quantity of sulfur (0.5%) to accelerate the reaction. The cata-
lyst paste contains an inert oil to form the paste, sulfur as a catalyst,
and lead dioxide that allows for cross-linking and polymerization
reaction.20

Its clinical advantages include long working time, accuracy, high tear
strength, economical, less hydrophobicity, and a longer shelf life.
It records details of 25 μm and less, meeting the standard of accuracy
as set by the American Dental Association. Polysulfide impression
materials have the highest resistance to tearing; however, it is more
susceptible to permanent distortion.20 It exhibits significant radi-
opacity due to its lead dioxide content.18,39 This also makes poly-
sulfide one of the most radiopaque impression materials in the
market. The radiopacity may be beneficial for the radiographic iden-
tification of a ccidentally swallowed or aspirated impression material.
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Polysulfide impression material is a reasonably accurate impres-

sion material that provides excellent detail when used with a custom-
ized impression tray. However, it needs to be poured within 24 h as
there is a significant potential for shrinkage and distortion. Multiple
pours are not recommended. A significant drawback is its unpleasant
odor due to the lead dioxide content. The base and catalyst pastes are
hand mixed, and so it is often described as being messy. It tends to
stain clothes due to the presence of the lead dioxide.
5.2. Silicones
Silicones are the vinyl polysiloxanes (VPS) of the elastomeric impres-
sion materials group. Silicones are generally hydrophobic by nature,
and its chemical structure exhibits hydrophobic aliphatic hydrocarbon
groups surrounding the siloxane bonds. The addition of surfactants
to the elastomeric impression materials changed it from a hydropho-
bic to a hydrophilic material.23,40 There are two main types of silicone
materials; a condensation-type silicone referred to as C-silicones and
an addition-type silicone also referred to as A-silicones.
5.2.1. Condensation-Type Silicones

The most important difference between condensation and addition
silicones is their dimensional stability. Condensation silicones
exhibit dimensional changes after setting due to the formation of
by-products. Although not meeting the standard for accurate
impression making, C-silicones nonetheless are widely used in other
clinical and laboratory procedures.
5.2.1.1. Composition
The formation of condensation silicones (C-silicones) occurs
through cross-linking between terminal groups of silicone polymers
and an alkyl silicate to form a three-dimensional network.20 The
polymerization process of C-silicones produces ethyl alcohol as a
by-product of the condensation setting reaction. The evaporation of
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the ethyl alcohol is responsible for most of the contraction that

occurs during the setting reaction.
5.2.1.2. Manipulation and properties

Condensation silicones are available in a base and catalyst system,
which involves a viscous base and a catalyst paste. Accurate dispensing
of the base and catalyst components together with vigorous hand
mixing by means of folding in of the two components and finger
molding produces a smooth rubberlike consistency. Upon setting
polymerization, there is some contraction that occurs as a result of the
formation of by-products. This make the C-silicones less accurate
than its A-silicone counterpart. In addition, C-silicones are hydropho-
bic in nature, making it less wettable and not advocated for precision
impressions in a moist oral environment. Its clinical applications
include duplication procedures, the making of customized matrices to
make provisional restorations, and its use in a variety of dental labora-
tory procedures.
5.2.2. Addition-Type Silicones

Addition or A-silicones are the most common elastomeric impres-
sion material used for precision impressions in dental practice. Its
superior properties of accuracy and dimensional stability have signifi-
cantly increased its use and demand, with it now constituting a sig-
nificant component of the dental impression material market.
Addition silicones are also termed as polyvinyl siloxanes (PVS) or
vinyl polysiloxanes (VPS).
5.2.2.1. Composition
Addition silicones (A-silicones) set by means of an addition reaction
with no by-product formation. The base paste contains a polymethyl-
hydrosiloxane and a divinylpolysiloxane. The catalyst paste contains
divinylpolysiloxane and a platinum salt. The addition reaction occurs
between a siloxane with a terminal hydrogen and a siloxane with a
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terminal vinyl group, forming a cross-linked silicone rubber. Therefore,

based on its chemical composition, the commonly used alternative
term polyvinylsiloxanes (or VPS) is incorrect.29
Hydrogen gas forms during the addition reaction, but does not
affects its dimensional stability.20 This hydrogen gas can produce min-
ute voids in the gypsum model, especially if the impression is poured
immediately. Manufacturers add a noble metal such as palladium that
acts as a scavenger for the hydrogen gas. A delayed pour of 30 min
will allow sufficient time for the hydrogen gas to escape and reduce
the risks of potential voids in the gypsum model.
Silicones generally are hydrophobic in nature. To improve its
clinical performance, manufactures add a non-ionic surfactant to
provide hydrophilic-like properties to the A-silicones. This allows
improved wettability of the impression material.
5.2.2.2. Manipulation and properties

The A-silicones are considered to be the most accurate impression
material, and apart from the putty viscosity, all other A-silicone vis-
cosities can reproduce fine detail of 0.020 mm in width.18 The addi-
tion silicone impression material is a more dimensional stable
material when compared to polysulfide, condensation silicones, and
polyether.
Addition silicones are manufactured and available in four different
consistencies namely:
(1) Low viscosity

(2) Medium viscosity
(3) High viscosity
(4) Very high viscosity/Putty
The viscosity of an impression material increases with the propor-

tion of filler content,18,41 meaning low viscosity silicone materials will
have a higher flow property.41 Less filler content and higher flow
records fine detail more accurately, but has greater polymerization
shrinkage.17 Higher viscosity impression materials are therefore used
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in combination with low-viscosity varieties to provide the best out-

come for the final impressions. The higher viscosity material is
injected into an impression tray and forms the bulk of the impression
and provides support for low viscosity material. The low viscosity and
higher flow impression material is injected around the intricate tooth
preparations and forms the wash that records fine detail. The impres-
sion tray with higher viscosity material is then seated intraorally over
the preparations covered with low viscosity material and is allowed to
set. The high viscosity impression material also pushes the lower vis-
cosity material into the sulcular area and due to its higher filler con-
tent, has less polymerization shrinkage.17 A combination of medium
and low viscosity impression material is more accurate than a putty
and low viscosity combination.18
Silicones are available in regular and fast setting times. Fast set
materials have less retarder and results in a shorter setting time.41
Silicone materials are mainly hydrophobic in nature. However, their
wettability has been improved by the incorporation of a non-ionic
surfactant.17,29
Like any other dental impression material, VPS undergoes small
amounts of contraction upon setting due to polymerization shrink-
age. This occurs as the impression cools from mouth to room tem-
perature.29 An appropriate VPS-matched adhesive painted on the
custom tray will support impression material shrinkage toward the
tray17 and potentially reduce the polymerization shrinkage. A-silicone
impression materials typically undergo a 0.15–0.2% polymerization
shrinkage42 that is compensated by an equal compensatory setting
expansion of the high-strength gypsum material used for the stone
model.
Addition silicones exhibit similar radiopaque characteristics to
polysulfides. The radiopacity of a material can be expressed as a func-
tion of the radiopacity of a certain thickness of aluminum. It is esti-
mated that a minimum radiographic value equal to 1.5 mm thickness
of aluminum is needed for a material to be detected radiographically.39
Addition silicone exhibit falls within this category. Used in combina-
tion with selected radiographic stents, it can assist with implant treat-
ment planning.
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Of all the elastomeric impression materials, vinyl polysiloxanes

exhibit the most elastic recovery, with the possibility of distortion
being almost non-existent.20
Sulfur-containing clinical latex gloves can inhibit the setting of
A-silicones, and so alternative glove varieties are recommended for
use during A-silicone usage.
5.3. Polyethers
Polyether impression material is another popular elastomeric impres-
sion material for precision impressions. It terms of accuracy and
dimensional stability, it is often compared to VPS in many research
papers. Polyethers and A-silicones are the only two elastomeric
impression materials recommended for implant impressions.43
Polyether impression material is a single consistency impression-
ing system. It is available as a two-paste base and catalyst system that
can be hand mixed or it can be delivered by means of a cartridge
system or automixing devices for consistent results.
5.3.1. Composition
The baste paste contains liquid polyether and fillers with inert oils.
The activator paste contains a sulfonate ester in hydrocarbons.

Polyether has been developed and evolved over the years with
improved flow properties, wettability, better taste, and improved elas-
ticity.44 Unlike VPS impression materials, polyethers are truly hydro-
philic17 and allow for void-free impressions in moist conditions.
Its hydrophilicity is due to the presence of functional groups such as
carbonyl and ether groups that enable the water molecule to interact
through hydrogen bonding.21
Although a single-consistency impression material, it has excellent
flow properties allowing for the capture of fine detail for precision
impressions. It is also known for its low tear strength and rigidity.
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The rigidity of PE is twice that of VPS, and greater force is needed to

remove the PE impression from the mouth.44 It has a snap-set behavior,
meaning the material sets quickly as soon as the working time has
passed. Removal may be especially difficult in dentate patients with
larger interdental embrasures or undercuts around pontics. It is benefi-
cial to rather block out any potential undercuts with soft dental wax to
facilitate ease of removal of the impression. Its high rigidity is a com-
mon cause for gypsum stone fractures when the impression and stone
cast is separated.17 In contrast, handling properties of PE demonstrates
superior accuracy and predictable in implant impressions.
Drawbacks with polyethers are its poor taste, relatively low tear
strength, and rigidity upon removal. Unlike VPS materials, polyether
should be poured within an hour17 or at least 25 h. The recommenda-
tion is that polyether be stored in a dry and cool environment (rela-
tive humidity below 50%) and not be left in disinfectant solution for
extended periods of time.20 This will reduce the risk of potential water
absorption and leaching of its water-soluble plasticizer.
5.4. Hybrid Vinylpolyether Silicones

Vinylpolyether silicone (VPES) is a hybrid impression material intro-
duced in 2008 with the intent to combine the best properties of poly-
ether and polyvinylsiloxane impression materials. Another term used
for this hybrid combination is vinylsiloxanether.45
5.4.1. Composition
The exact formulations of this impression material is proprietary, but
it is suggested to consist of 5–20% of PE content.46 As both compo-
nent materials are elastomers, this hybrid material allows for a chemi-
cal bond between VPES and VPS.45

This hybrid impression material were introduced to exhibit the high
tear strength and dimensional stability of VPS and the intrinsic
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hydrophilic nature and improved flow of polyether.19 The end result

is a predictable impression with high accuracy and dimensional stabil-
ity and improved wettability. It is available in multiple viscosities and
different setting times for different clinical applications.
Current evidence-based information on the properties of this
material is not readily available. One study compared the dimensional
stability of a conventional heavy-body VPS to that of the hybrid VPES
material.46 VPES were found to function within the limits of ADA
Specification No.19 for VPS materials, and showed stability after dis-
infection and a 2-week storage time. The VPES demonstrated less
dimensional change after 2 weeks, and this finding is thought to be a
function of its rigidity. The casts produced from monophasic VPES
impressions after a 2-week storage period showed excellent and com-
parable dimensional stability to monophasic VPS and PE.47
This material shows promise as it combines the best properties of
VPS and PE impression materials. It is suggested to be a good alter-
native to PE for implant impressions45 based on its accuracy and rigid-
ity. Of note is that the PVES material was reported to have a better
taste rating than PE.45
6. Disinfection Procedures

Disinfection of impression materials forms a critical component in the
clinical and laboratory use of flexible impression materials. Disinfection
of impression material received a more urgent focus more so in the
late 20th century with the outbreak of AIDS48 and the realities of
cross-contamination. Contaminated dental impressions can produce
contaminated casts by means of cross-infections.49,50 Disinfection of
dental impressions therefore prevents cross-contamination between
the dental clinic and laboratory, and between dental professionals and
any staff who may be handling or transporting the impression. It is
the responsibility of the dental healthcare provider to disinfect
impressions prior to sending it to the laboratory.
The disinfection process typically involves an immersion in
a chemical disinfectant solution for a specific period of time.
Some impression materials are sensitive to immersion, and a spray
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technique for disinfection is then recommended. Spraying is not as

effective as immersion as complete contact of the disinfectant on all
the impression surfaces is not always possible. In addition, spray dis-
infection can create aerosols and increase the risk of staff exposure.51
An immersion technique is therefore the preferred choice of disinfec-
tion. Disinfection of a dental impression most appropriately starts
with rinsing under running water to remove all saliva and possible
blood contaminants. This initial rinse removes a significant amount
of the microorganisms.17 This is followed by exposure to a chemical
disinfectant for a known period of time, by means of an immersion
or a spray.
Most impression materials can be disinfected with Environmental
Protected Agency (EPA)-registered solutions. Table 3 summarizes
appropriate chemical solutions and disinfection techniques for
flexible impression materials. Glutaraldehyde is the preferred solu-
tion for disinfection, but chlorine compounds and iodophors are
suitable too.
Alginate impressions harbor three times more microorganisms
than silicone impression materials.52 Suitable disinfectant solutions
include glutaraldehyde, chlorine-based, and iodophor solutions.
Immersion disinfection of alginates were shown to produce dimen-
sional changes.53 Others believed that a 10-min imbibition may be
beneficial to alginates to counteract the syneresis-associated
shrinkage.48 Contrary to the belief that alginates tend to expand on
immersion with water, alginates generally shrink after a short
period of expansion.54 Immersion demonstrates more shrinkage
for alginates54 and potential distortion. The recommended disin-
fection technique for alginate impression materials are spraying
rather than immersion to avoid potential imbibition, the absorp-
tion of water.53 Spray disinfection has no effect on the surface
detail and the accuracy of stone models made from alginate
impressions.31,52
The elastomeric impression materials, particularly vinyl polysi-
loxanes and polyethers can be immersed in chemical solutions with-
out affecting its surface properties or accuracy.20 Disinfectant
solutions typically do not affect the accuracy or dimensional stability
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Table 3. Recommended disinfection protocols

Material Method Disinfectant
Agar Short exposure <10 min Chlorine compounds or
idodophors
Alginates Spray Chlorine compounds or
Immerse with caution idodophors
Gluteraldehyde
Hybrid Alginate-VPS Gluteraldehyde, idodophors,
phenolics
Polysulfide Immersion Gluteraldehyde, chlorine
compounds, idodophors,
phenolics
Condensation VPS Immersion Gluteraldehyde, chlorine
phenolics
Addition VPS Immersion Gluteraldehyde, chlorine
phenolics
Polyether Immerse with caution Chlorine compounds or
idodophors
Hybrid VPES Immersion Gluteraldehyde
of impression materials.55,56 The recommended disinfectants for VPS

and PE include sodium hypochlorite, gluteraldehyde-, and alcohol-
based solutions. Both sodium hypochlorite and gluteraldehyde disin-
fectant solutions do not affect the wettability VPS and PE impressions.57
The new VPES impression material demonstrated stability after
immersion in a 2.5% gluteraldehyde solution for 20–30 min.46,47 Casts
produced from VPES show excellent dimensional stability and are
comparable to VPS and PE.47
Polyether is the one impression material that is susceptible to
extended immersion times (>10 min). This is due to its true hydro-
philic nature, which causes it to absorb moisture from the
environment.20
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References
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S213–S215.
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N. C. J. Prosthet. Dent. 2015, 114 (4), 536–542.
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66 (2), 261–265.
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(Massachusetts: Kluwer Academic Publishers, 1999), p. 476.
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Sinhoreti, M. A. Braz. Dent. J. 2012, 23 (4), 417–421.
32. McCabe, J. F. W. A. W. G. Applied Dental Materials, 9th ed. (Hoboken:
Wiley-Blackwell, 2008), p. 312.
33. Baxter, R. T.; Lawson, N. C.; Cakir, D.; Beck, P.; Ramp, L. C.; Burgess,
J. O. Operative Dent. 2012, 37 (5), 540–547.
34. Patel, R. D.; Kattadiyil, M. T.; Goodacre, C. J.; Winer, M. S. J. Prosthet.
Dent. 2010, 104 (5), 325–332.
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(1939) 1984, 108 (2), 210–211.
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38. Shannon, A. AlgiNot: A Stable, Reliable Preliminary Impression Material
for Improved Productivity Inside Dentistry [Online], 2006. Available at:
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preliminary-impression-material-for-improved-productivity.
39. Parissis, N.; Iakovidis, D.; Chirakis, S.; Tsirlis, A. Aust. Dent. J. 1994,
39 (3), 184–187.
40. Re, D.; De Angelis, F.; Augusti, G.; Augusti, D.; Caputi, S.; D’Amario, M.;
D’Arcangelo, C. Int. J. Dent. 2015, 2015, 428286.
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41. Lawson, N. C.; Cakir, D.; Ramp, L.; Burgess, J. O. J. Esthet. Restor.
Dentist. 2011, 23 (3), 171–176.
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100 (4), 285–291.
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2004, 24 (2), 109–117.
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Dent. Relat. Res. 2012, 14 (1), 144–151.
46. Nassar, U.; Chow, A. K. J. Prosthodont. 2015, 24 (6), 494–498.
47. Nassar, U.; Oko, A.; Adeeb, S.; El-Rich, M.; Flores-Mir, C. J. Prosthet.
Dent. 2013, 109 (3), 172–178.
48. Kotsiomiti, E.; Tzialla, A.; Hatjivasiliou, K. J. Oral Rehabil. 2008,
35 (4), 291–299.
49. Connor, C. Int. J. Prosthodont. 1991, 4 (4), 337–344.
50. Owen, C. P.; Goolam, R. Int. J. Prosthodont. 1993, 6 (5), 480–494.
51. Miller, C. H, Infection Control and Management of Hazardous Material
for the Dental Team, 5th ed. (Amsterdam: Elsevier Mosby: St. Louis,
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52. Demajo, J. K.; Cassar, V.; Farrugia, C.; Millan-Sango, D.; Sammut, C.;
Valdramidis, V.; Camilleri, J. Int. J. Prosthodont. 2016, 29 (1), 63–67.
53. Hamedi Rad, F.; Ghaffari, T.; Safavi, S. H. J. Dent. Res. 2010, 4 (4),
130–135.
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28 (7), 749–755.
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2014, 72 (8), 618–622.
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Health: JIOH 2015, 7 (6), 80–83.
b3252_Ch-13.indd 400 27-11-2018 03:07:10 PM

Chapter 14
Resilient Liners
for Removable Prosthesis
Igor J. Pesun
Division of Prosthodontics, Department
of Restorative Dentistry,
College of Dentistry, University of Manitoba,
780 Bannatyne, Winnipeg, MB, R2E1J6, Canada
Igor.Pesun@umanitoba.ca
Resilient or soft liners for removable prosthesis are used to improve

the comfort of the existing denture, treat denture stomatitis, and
allow for the functional impressioning of the soft tissues to reline
dentures. The resilient denture liners are made up of silicone elasto-
mer materials or plasticized acrylic resin. These materials are modi-
fied in such a way to achieve the desired elastic properties and
resilience when they are bonded to the removable prosthesis. It is
also important that resilient liners have properties that allow for
their use in the harsh oral environment. The resilient material needs
to have adequate elastic properties and have adequate resilience that
can be maintained over time. Patients who have difficulty adapting
to their prosthesis due to thin mucosa, sharp bony ridges, persistent
sore mouth, or significant oral defect benefit from the use of resil-
ient liners.
401
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1. Introduction
In the United States, one out of every five person in the age group of
18–74 years wears some type of removable prosthetic appliance. The
population of the United States has a complete edentulism rate of
10.5%. Current demographics indicate that nearly 61 million people
in the United States will wear some sort of removable appliance by
the year 2020.1 The dental profession has advanced in restoring the
function and esthetics of the completely edentulous, but 60% of
the patients who wear dentures have some problem with them.2–5
Statistically, there is no difference between males and females when
comparing satisfaction of their prosthesis.2
The use of resilient denture liners started as early as 1943, but
only since the 1960s have resilient liners been effective.6 Resilient
denture liners are often used in the hope of minimizing pressure and
reducing trauma to denture-supporting mucosa.7 These patients
have difficulty in adapting to the hard surface of the denture material
due to: (1) bony ridges with thin, non-resilient soft tissue coverage,
(2) persistent denture-sore mouth, (3) knife-edge ridges resulting
from advanced resorption of the residual alveolar ridges, (4) ridges
with tissue undercuts where surgical intervention is contraindicated
due to medical history, (5) relief for maxillary tori or other heavy
bony prominences, and (6) prosthetic restorations for congenital or
acquired oral defects.
As such, these materials should exhibit a low level of plastic
deformation and elasticity, and their level of rigidity should be
such as to enable them to act as and energy-absorbing layer during
usage. The ideal resilient liner should have the following properties:
(1) ease of processing, (2) cushioning effect upon the mucosa,
(3) no adverse effects on the denture base, (4) inhibit mycotic
growth, and (5) ridge adaptability. The physical properties should
include, (1) permanent resilience, (2) dimensional stability during
and after processing, (3) low water sorption and solubility, (4) ade-
quate bond strength to the polymethyl methacrylate, (5) high abra-
sion resistance, (6) color stability, and (7) no changes over different
temperatures.
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Resilient Liners for Removable Prosthesis 403
The processing of resilient denture liners should have the criteria

suggested by Lewis and Castleberry.8
Certain biological requirements are also desirable: (1) no burning
or irritation of the oral tissues, (2) no bad taste or odor, (3) inhibitory
action on fungal growth (mycotic), (4) non-toxic, (5) durability in
the oral environment, and (6) stability in the oral environment.
Ideal mechanical properties for resilient denture liners includes
(1) ease of processing, (2) ease of finishing, (3) ease of polishing, and
(4) adhesion to, but without an effect on, denture resin properties.
Clinical properties include (1) no staining or discoloration, (2)
adequate thickness of the resilient liner without weakening of the
denture base, and (3) ease of finishing and polishing.6,9–11
Quality Desired outcome

Viscosity The material reproduces the details of the mold, and color-
ants remain suspended
Bubbles There are no bubbles in the cured material
Shrinkage There is no shrinkage, or any shrinkage that occurs is
subclinical
Working time The working time is long enough to carefully fill the mold
Curing temperature The curing temperature is low enough so that the mold is
not damaged
Recovery The material is easily removed from the mold without dam-
aging either
Trimability The material is capable of being trimmed
2. Composition of Resilient Denture Liners

The earliest resilient liners were natural rubbers. The first synthetic
materials were plasticized polyvinyl chlorides. Currently, there are two
types of materials that are used as resilient denture liners; plasticized
acrylic resins and silicone elastomers. Plasticized acrylic resin-based
materials are higher methacrylate homologs and hydrophilic acrylics
that were developed with plasticizers to allow for these materials to be
resilient. The plasticizers are found in the liquid and may contain ethyl
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alcohol, ethyl acetate, and an aromatic plasticizer (e.g. butyl phthalyl

butyl glycolate). When the polymethyl methacrylate cures, the plasti-
cizers situate themselves between the polymer chains. They are not
chemically attached to the polymer chains but behave like molecular
lubricants. The polymer chains do not cross over each other with the
plasticizer, they slide over each other more easily. The type and vol-
ume of plasticizer incorporated into the material determines the prop-
erties of the material. All of these plasticizers can dissolve or evaporate
over time. The loss of the various plasticizers in the oral environment
results in the material hardening over time. By controlling the chem-
istry of the resilient liner, the useful life can range from as little as
several days or weeks to several years. The biggest clinical advantage
of these materials is their excellent adhesion to the polymethyl meth-
acrylate denture bases.
Silicone elastomers are materials available in two forms; a two-
component base/catalyst that is a cold cure material or as a one-
component heat-cured material. Silicone elastomer materials stay
resilient longer than the plasticized acrylic resin materials. The silicone
elastomers molecule is very resilient and stable overtime. As silicone
elastomers are chemically different from the polymethyl meth-
acrylates, they have poor adhesion. Silicone elastomers require the
use of an adhesive bonding agent to prevent delamination of the
material over time.
3. Physical Properties
Ideal physical properties are achieved by having a polymer that has an
appropriate glass transition temperature (Tg). Temperature plays a
significant role in the observed physical properties of a polymer used
in the formation of a resilient denture liner. Glass transition tempera-
ture is defined as: a range of temperature for each individual polymer
where the behavior of the material changes from hard and brittle to
soft and flexible. A glass transition temperature needs to be lower
than mouth temperature. Mouth temperature is approximately 32°C
(range 0–55°C). Acrylic-based polymers have a glass transition
b3252_Ch-14.indd 404 27-11-2018 03:07:49 PM

temperature that can be modified by the addition of plasticizers to the

polymer’s molecule.
Dependant on the plasticizers added to the polymer’s molecule,
the desired properties of resilient are modified to provide higher
elasticity during mastication and then behave viscously to accommo-
date functional and non-functional forces. This resilient material is
then able to minimize and relieve pain during function for denture
wearers.
An ideal resilient denture liner does not permanently deform and
lose resilience over time. If a material does not permanently deform
and it returns to its pre-deformation state, it is said to be elastic.
Elasticity is an evaluation of a materials’ ability to recover and return
to its original form after having a strain applied to it. The ability of a
material to absorb energy without undergoing permanent deforma-
tion is known as resilience.
There are several examples of successful use of mandibular denture-
resilient liner materials to reduce the symptoms of discomfort beneath
acrylic dentures.12 Resilient denture liners have the ability to adapt to
the patient’s ridge, which can only be attained if the material’s behav-
ior has a time-dependent component. Unfortunately, a material that
returns to its original shape almost instantly after the load has been
removed does not comply as well as a more viscous material.13 This
indicates the difficulty in attaining all the requirements of a good
resilient liner from one type of material. The ideal characteristics of a
resilient liner material are higher elasticity during mastication and
then behaving viscously to accommodate functional and non-func-
tional forces to relieve pain, in addition to durability and stability in
the oral environment over long periods of time.
Although these prostheses go a long way toward helping these
individuals cope with the discomfort of wearing dentures, the pros-
theses are not perfect. The life expectancy of the liner is 4–6 years, but
can be as little as 1 year, although some have shown to be serviceable
even after the denture needs to be replaced due to wear on the acrylic
teeth.14–18 Most of the material on the market today are acrylic resin
polymers or copolymers of the powder liquid type that when
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processed have some resiliency to them. These remain soft by the use
of ethyl or butyl methacrylate in combination with methyl meth-
acrylate to produce the soft copolymer. Another technique involves
the addition of external plasticizers to the monomer. These materials
did have the disadvantage of the plasticizer leaching out, especially in
the presence of alcohol, thus resulting in hardening of the resilient
liner.9,19
Silicone elastomers materials are also available for lining denture
prosthesis. They have been found to be significantly more stable and
are currently the material of choice for a permanent soft lining mate-
rial. Silicone elastomer resilient denture liners are more elastic than
liners made of soft acrylics. Tests on the wear of silicone elastomer-
based materials showed that elastic materials, especially heat-cured
single-component materials are less likely to deform and lose resil-
ience over time, with no changes over different temperatures, or after
prolonged soaking.20–22 Heat-cured single-component materials have
long-lasting serviceability for their physical and mechanical proper-
ties. Molloplast-B is a methacryloxy propyl trimethoxy silane heat
polymerized silicone elastomers rubber. The curing agent reacts with
reactive groups of the polymer, leaving methacrylate groups available
to bond with the PMMA denture base material, (e.g. Lucitone199).23
The chemical properties of heat-cured silicone elastomer rubbers
account for compatibility with oral tissues, dimensional stability, resil-
iency, and compliance. However, there are still problems reported
with the clinical use of silicone elastomer rubber resilient liners. For
instance, Molloplast-B has shown some loss of compliance with long
periods of use in the oral environment.24
The resilient liners fail because of the degradation of the material,
which leads to both hardening and color changes, sorption of odors,
bacterial growth, and breakdown of the bond between the resilient
liner and the polymethyl methacrylate.15,25 Considering the cost
involved in replacing these materials and the harm that a degraded
material inflicts on the soft tissue, there is a compelling need for
improved soft lining material.
Researchers have concentrated on improving the tensile strength;
tear strength, percent elongation, and Shore-A hardness of the
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resilient liners.6,12,26,27 The process of accelerated aging is used to

measure the physical properties and color of soft denture liners. This
process exposes the materials to an environment with controlled heat,
humidity, and periodic spraying with distilled water. Accelerated aging
dramatically affected the physical and mechanical properties of the
resilient liners.21,28 Other environmental factors that can affect the
physical properties of soft denture liners include functional wear,
time, exposure to adhesives, and cleaning agents. Food stains can also
cause significant changes in the color of the elastomers.
4. Viscoelastic Properties and Compliance

Masticatory forces are mainly compressive and delivered cyclically.
The force for a mastication cycle is characterized by a rapid closure of
the mandible, followed by a deceleration just before tooth contact.
In the case of denture wearers, the mastication load is believed to be
close to 2.17 N mm−2. These factors are responsible for the shortened
life expectancy of the prosthesis. Reproducing all of these factors in a
laboratory is very difficult, if not impossible, therefore, full evaluation
of the performance of resilient liners requires that it be evaluated
in situ. One problem with in situ evaluation of resilient lined dentures
is that there are no standard tests for measuring the physical proper-
ties of the resilient liner. The tests for tensile strength, tear strength,
and percent elongation require standardized samples that are destroyed
during testing. The Shore-A hardness test requires a 6 mm minimum
thickness for material. The amount of resilient liner that can be placed
within a denture is limited to 2−3 mm; therefore, the Shore-A hard-
ness cannot be used.
The general consensus is that the resilient liner material should
undergo minimal changes during use. A balance must exist between
the underlying mucosa and the denture-resilient liner. According to
previous studies, the resilient liner will not act as a shock absorber
based solely on its viscoelastic properties; instead, it functions as a
spring in series with the oral mucosa.29 The resilient liner will absorb
the energy applied to the denture only if its elastic modulus is lower
than the soft tissue,23 meaning a softer, more compliant resilient liner
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would be appropriate for a patient whose ridge is extremely thin and

sore. On the other hand, if the case requires improvement of mastica-
tory function, or relief during parafunctional habits, a stiffer resilient
liner would be preferable due to its effectiveness in distributing stress
more uniformly.30
An essential requirement for a soft lining material is its ability to
recover elastically following compression during mastication and to
retain its elasticity over fairly long periods of time. A good resilient
liner material must also be characterized by a relative degree of viscoe-
lasticity. The viscoelastic properties of a material have been effective
in determining the serviceability of permanent soft lining materials
and their apparent softness when comparing acrylic resins and silicone
elastomers materials.31 An elastic behavior has been attributed to sili-
cone elastomer-based resilient denture liners; whereas acrylic-based
liners behave more viscously.32 Of the physical properties of resilient
liner materials investigated, resiliency can best predict the effective-
ness of a material. An effective resilient liner material can absorb the
impact forces during mastication with minimal deformation and dete-
rioration over time. The definition of resiliency cannot be literally
applied to the materials used as resilient denture liners, but only to
perfectly elastic materials. A material that is perfectly elastic is not
very compliant. Compliance is a measurement of the softness or flex-
ibility of a material. A more general definition of compliance is the
strain of an elastic body expressed as a function of the force produc-
ing the strain.
Compliance is a physical property which defines a solid material
that deforms as easily as it recovers.23 Resilient materials are used to
give dentures a cushioning effect upon the oral mucosa of patients
with chronic alveolar ridge and tissue soreness, pathological changes,
and bone loss. A viscoelastic material behaves elastically while having
a dissipating component of deformation. The efficiency of a resilient
liner is dependent on the viscoelastic properties and durability of the
material. The silicone elastomers rubbers are the best materials for
maintaining their resiliency over time and resisting initial water
absorption. Resilient liners are viscoelastic materials and as they age
and absorb water they may become more elastic and less viscous,
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which can lead to failure of strength.33 This reduction in compliance

is inversely related to a material’s baseline softness, i.e. the higher the
baseline compliance is, the more the reduction in compliance with
use.34 This behavior is more commonly found in acrylic-based resil-
ient liners, and the research is less constant in reference to the silicone
elastomers-based resilient liners.
Evaluation of resilient lined denture prostheses in situ requires
non-destructive tests. If resilient liner materials are to protect the
soft mucosal tissues, then the dynamic nature of these tissues must
be considered. Force displacement plots for human tissues are gener-
ally nonlinear, indicating that these tissues behave like viscoelastic
material.35 The force displacement curves for elastomers are also
non-linear.27 This non-linear relationship implies that the physical
properties are time dependent. The viscoelastic nature of these mate-
rials occurs under low loads on the order of those experienced during
function. The applied stress associated with this load has not been
quantified, though an average stress of 1.5 Nmm−2 used with the load
cell seems close to the stress observed clinically.36 The maximum stress
seen by these materials occurs during eating or parafunctional habits.
The magnitude of the stress on the appliance depends on the oral
habits of the patient. One method for testing time dependent physical
properties of viscoelastic materials is to produce a force displacement
curve with a low maximum force. This is a non-destructive test that
can be done by applying the force at a specific rate then measuring the
displacement of the material with time.12,22
Investigators have used direct and non-destructive techniques to
determine compliance.20,27,32,34,36 Many of the methods described
apply static loads to the material.20,34,36 Several studies do accurately
reproduce the cyclical force experience during mastication.27,32
Another common method for measuring softness of resilient liner
materials is Shore-A testing. The Shore-A durometer’s operating
instructions recommend a minimum specimen thickness of 6 mm.
Measurements of thinner samples tend to reveal characteristics of the
surface beneath the resilient denture liners.37 This is not clinically
applicable because resilient liner material thickness in dentures rarely
exceeds 3 mm.
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Very few clinical studies have quantified and characterized the

viscoelastic properties of resilient liner materials using a dynamic tech-
nique. Dynamic mechanical analysis (DMA) measures the shear stor-
age modulus G’, the shear loss modulus G’’, and the phase angle (ë).
G’ defines the material’s stiffness and is the ratio of the applied stress
to strain.27 Another technique tests materials with a modified Instron
1185 Tensile-testing machine. This machine measures strain
semi‑continuously during cyclic loading, and a linear voltage dis-
placement transducer (LVDT) obtains displacement.22 Both of these
studies used extensive mathematical calculations to conclude, from
the deformation behavior of the tested materials that silicone elasto-
mers resilient denture liners behave nearly elastically, while acrylic
resins are more compressible and better in absorbing energy.
The force–displacement curves for silicone elastomers and
mucosa are non-linear with time, thus dynamic testing should be
used to evaluate the physical properties of these materials.38 Because
of this time-dependent nature and the need for a non-destructive
test, a preliminary investigation was done to determine if the force–
displacement curves measured by applying a cyclic square wave force
to a sample could measure changes in the physical properties of the
elastomer. This is the square wave compliance test. Compliance test-
ing with the closed-loop servo hydraulic system dynamically repro-
duces the stresses a resilient liner experiences in vivo during rapidly
applied forces due to mastication, swallowing, and speech. The MTS
closed-loop servo hydraulic testing system of the MDRCBB (MTS
Systems, Eden Prairie, MN) was used for the compliance test.39
A sample is mounted on the moveable base of the hydraulic actuator,
Figure 1. The actuator was moved up until the sample contacted the
5 mm diameter steel ball bearing mounted on the 100 lb. load cell
attached to the rigid cross-member of the MTS system. Contact was
indicated by an increase in force measured by the load cell. The actua-
tor is run in a load control mode and programmed to apply a com-
pressive force to the test sample following a square wave pattern
(force on–force off, etc.). The load cell measures the force transferred
through the sample. The displacement is measured using the internal
LVDT (Linearly Variable Displacement Transducer) mounted on the
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servo hydraulic actuator. The force–displacement curve is recorded

using a Nicolet 310 Storage Oscilloscope (Nicolet Instrument
Corporation, Madison, WI), then saved for future analysis. Force and
displacements are given in volts. Preliminary results indicated that for
strains below 20% this method could non-destructively measure the
stiffness of an elastomer sample.39
An important consideration for a proper resilient liner is its thick-
ness. Excessively thick resilient denture liners result in a denture with
an increased risk of fracturing, while if the resilient liner is too thin it
is ineffective. In a clinical situation, a resilient liner cannot exceed
3.0 mm and it is rarely made to a constant thickness throughout the
denture. The thickness of the resilient denture liner should then be
kept between 2.5 and 3.5 mm. If it is thinner than this, it will bottom
out and result in the denture feeling just as hard on the soft tissue as
if there was no soft liner. This thickness restricts the use of the liners
to the mandibular dentures as if the maxillary denture was to be 4 mm
thick it would impede the patients overall function. As such, most
liners are only used to improve the comfort of mandibular dentures.
Resilient liner materials are used to reduce impact forces on
denture-bearing mucosa. Studies have found silicone elastomers-base
liners behave well during impact absorption and display good ser-
viceability. One of the problems of silicone elastomer resilient liner
materials is their apparent hardness upon initial insertion of the lined
denture. The instantaneous pressure tissues experience during masti-
cation is better withstood and less damaging when the resilient liner
is highly resilient or almost perfectly elastic. A more viscous material
may be desirable in response to slowly applied forces like those dur-
ing parafunctional habits and speech.
Durability of permanent resilient lined dentures is relevant to
their clinical success. Longitudinal studies have reported the service-
ability of heat-cured single component materials-lined dentures as
being as long as 9 years. Heat-cured single component materials, the
gold standard of permanent resilient liners has some drawbacks, in
particular, ease of processing has been indicated to be low due to its
more viscous state before curing. MPDS-SL is a more fluid material,
thus making its distribution over the denture base easier and more
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even. Heat-cured single-component materials like most other resilient

liners tend to change in color and display fungal growth after rela-
tively short periods of use.
Data indicated a slight decreased or unchanged compliance value
of silicone elastomer-based liner materials, in particular heat-cured
single-component materials.7,12,22 In the cases where no change was
observed, the duration of the study was less than 6–12 months and
the methods used the Shore-A hardness test.24
The increase in compliance of heat-cured single-component
materials could be due to the cleaning regimen used by the patients.40
A parallel study found that patients’ dentures cleaned with denture
paste tended to have a more positive compliance change, while those
cleaned by soak tablets tended to have more negative compliance
change.40
5. Color
Color stability is a required characteristic of denture soft lining mate-
rials, with national and international standards specified by the ADA
as Specification No. 12 (American Dental Association 1975). The
ADA recommends the use of the CIE Lab color differential system.
In this system, all colors are obtained from the blend of three basic
colors; red, blue, and green at varying proportions. Patients are more
satisfied when their denture resilient liners are indistinguishable from
the acrylic base, and the motivation to maintain the dentures is
dependent on the ease of cleaning of the materials and the design of
the denture. Maintaining color stability of the resilient liner is not
often a problem with silicone elastomer-based liners, yet a displeasing
liner color may constitute a reason for its replacement.23 Unlike most
other soft lining materials, the silicone elastomers-based liners are not
easily discolored, though they can incorporate colorants from ingested
foods, drinks, or tobacco products.
Color analysis is normally done using a reflectance spectropho-
tometer; however, because of the size of most dental prostheses, this
technique is not practical. A second method of color analysis was
reported by Haug et al.41 The Minolta Chromameter (Minolta
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Camera Co. Ltd., Osaka, Japan) was used to measure the color of
elastomer samples. It used the CIE Lab tristimulus values: L*, a*, and
b*. In the L*a*b* color system L* is the Value of the sample, a* is the
red–green axis, and b* is the yellow–blue axis. Color change (DE) is
calculated with the formula DE = (DL*2 + Da*2 + Db*2)1/2. A value for
DE = 1 or larger is considered visually detectable. This method is non-
destructive and can measure time dependent change color.
Silicone elastomer rubber materials are composed of polymers
of dimethyl siloxane, which is a viscous liquid cross-linked with
good elastic properties. Silicone elastomer rubbers, in particular
Molloplast-B, are especially resistant to initial water absorption.
Clinically, the material became darker, possibly due to the addition
of ingested colorants by water diffusion.42
6. Microbiological Interaction

The genus Candida contains approximately 200 species found in
many environments, ranging from plants to the human gastrointesti-
nal tract. Candida is a commensal yeast but under certain circum-
stances may become an opportunistic pathogen, where it can invade
human tissues causing severe to life threatening pathologies.
Denture stomatitis is caused by fungal growth on dentures and is
the most common form of Candida infection in humans, with
roughly 50% of denture wearers being infected.10,43–45 Several other
factors promote oropharyngeal candidiasis, many associated with den-
ture patients, including malignancies, diabetes, immunodeficiency,
and malnutrition. Candida albicans is the main etiological agent of
oropharyngeal candidiasis and denture stomatitis.
Candida glabrata is another common species present in the oral
cavity, gastrointestinal tract, and respiratory tract. C. glabrata infec-
tions have been associated with endocarditis, meningitis, and multifo-
cal disseminated disease.46 Quantifying Candida type and prevalence
on denture products is essential for the safety of denture-wearing
patients. Due to the infectious tendencies of Candida, other species
such as C. tropicalis, Issatchenkia oreintalis (formerly C. krusei), and
C. parapsilosis could also be present.
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Numerous clinical tests are used to identify Candida species

such as carbohydrate assimilation, germ tube, and an assortment of
media. These tests are specific to one species, labor intensive, and
expensive. CHROMagarÔ Candida is a medium designed for isolat-
ing and identifying Candida species. CHROMagarÔ Candida iden-
tifies Candida species by colony characteristics, such as color and
texture and can accurately identify C. albicans, C. glabrata, C. tropi-
calis, Issatchenkia oreintalis, C. dubliniensis, C. neoformans, and usu-
ally C. parapsilosis, and C. guillermondii.47 The effectiveness of
CHROMagarÔ specificity is 100% for C. albicans, C. tropicalis, and
Issatchenkia oreintalis and 97% for C. glabrata.48 The presence of
fungal growth on Molloplast-B samples ranges from 65% to 85% of
silicone elastomers liner samples.10,43,49 Newer materials are being
developed that only allow fungal growth on 45% of samples.49
The most abundant species found on silicone elastomeric resilient
liners include C. albicans and C. glabrata.10,43,49 Makila and Hopsu-
Havu found C. tropicalis as the third most abundant Candida species
on silicone elastomers liners,10 while Wright et al. found C. samata
and C. parapsolosis to be the next two most abundant species.43
7. Uses of Resilient Denture Liners

Resilient denture liners have multiple uses and come in various forms
depending on the purpose for which they are intended.
Over-the-counter (OTC) dentures liners are temporary liners that
also provide adhesive properties to aid in retention of the patients’
dentures. They are sold in the form of preformed thermoplastic pads
usually made of wax-impregnated gauze, resin gels, or strips. They
only last a day or so and should not be used or recommended. As they
are not customized to fit the patient’s soft tissue contour, they tend
to hide the ill-fitting dentures and result in damaged ridges and soft
tissues. When patients use OTC denture liners over time, they also
present with mucositis and Candida albicans infection.
Tissue conditioners are generally plasticized acrylic resin-based
powder and liquid-based materials. The polymers have plasticizers
that provide for the softest material with good elastic recovery
b3252_Ch-14.indd 414 27-11-2018 03:07:49 PM

properties. Although they do not undergo permanent deformation,

they generally lose softness in days and must be replaced. The hard-
ening of the material is due to the leaching and evaporation of
the plasticizers. Tissue conditioners flow for hours during use mak-
ing them ideal for use after surgical procedures or in cases where
patients has sore ridges due to poorly fitting dentures. Patients with
mucositis related to Candida albicans infection can be treated with
a tissue conditioner with an antifungal medication incorporated
into the material.
Functional impression materials are used in cases where there is
difficulty in fitting the denture due to changes in the soft tissue sup-
porting the denture. In situations where the dentures teeth are ade-
quate and the vertical dimension of occlusion is at the desired height
and the denture is to be relined, a functional impression can be made.
The denture does not need to be remade, and polymers with plasti-
cizers are used to obtain an impression under functional stresses.
Functional impression material should have good flow with minimal
elastic recovery. The flow allows for continual adaption of the material
to the soft tissues in response to functional stresses. To allow for the
functional impression and relining of the denture, the undercuts are
removed from the denture and the functional impression material is
added to the denture. The patient wears the denture for a week,
removing the denture nightly. The denture is then sent to the labora-
tory for processing. As these materials deform plastically to record
tissue, the functional impression results in a very well-fitting denture
for the patient.
Short-term resilient denture liners are silicone elastomers or plas-
ticized acrylic resin with plasticizers. These are most often fabricated
in the patient’s mouth. Silicone elastomers set is similar in principle
to VPS impression materials. They are used in case where the patient
is having issues with their current dentures and they are being
assessed for future dentures or treatment of denture stomatitis. The
denture relieved in areas that are causing trauma to the tissues and
the periphery is trimmed to allow for at least a 2 mm bulk of material
at the junction with the hard denture base. These will often last
several months.
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Long-term resilient denture liners are mostly silicone elastomer-

based materials although there are few plasticized acrylic resin-based
ones available. Long-term resilient denture liners are generally heat-
cured laboratory-processed materials. The denture is fabricated using
standard protocol with a modification to the processing procedure to
allow for the processed resilient liner. A spacer is placed to allow for
3 mm of resilient denture material and the hard acrylic is initially
processed to initiate the curing. The hard material is partially cured as
the free ends of the polymer chains are needed to allow for the bond-
ing of the silicone elastomers or the plasticized acrylic resin to the
polymethyl methacrylate. The spacer is removed and the resilient
denture liner is placed and the denture is fully cured. Denture is
recovered, finished, and processed. A sealer is often placed over the
resilient liner before the denture is delivered.
8. Maintenance of Resilient Denture Liners

All acrylics have porosities and micro-roughness that allow for the
adhesion of a biofilm that results in the growth. Candida albicans is
common to 50% of patients who wear removable prostheses. Due to
the softness of resilient denture liners, cleaning must be done care-
fully. It is best to soak the dentures in a cleaning solution that does
not contain alcohol or chlorine cleaners.49
9. Conclusions and Outlook

A good resilient liner is essential to reduce the impact of mastication
on the supporting tissue of removable prosthesis. The thickness of the
resilient denture liner should then be kept between 2.5 and 3.5 mm.
Delamination is an issue with resilient denture materials. It is impor-
tant to have a bulk of material at the junction of the materials and a
chemical bond. Resilient denture liners change in all the color variables
measured from baseline to the 6-month period of wear by the patients.
Candida has the potential to become an opportunistic pathogen and
should be investigated in the development of new denture materials.
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Microbiol. Immunol. 1999, 14 (3), 183–189.
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b2530_FM.indd 6 01-Sep-16 11:03:06 AM

Chapter 15
3D Printing — Additive
Manufacturing of Dental Biomaterials
Rodrigo França*, Jeff Winkler, Helen H. Hsu,

Maedeh Rahimnejad, and Zahra Abdali
Department of Restorative Dentistry and
Department of Biomedical Engineering,
University of Manitoba, 780 Bannatyne Avenue, Winnipeg,
MB, R3E 0W2, Canada
*Rodrigo.franca@umanitoba.ca
3D printing of dental devices is a new-age method of manufacturing

using an additive process, which contrasts with the normal subtrac-
tive or molding processes used in traditional restorative dentistry.
This chapter will serve as a review of the technology available as of
present, and it is divided into two sections. In the first section,
aspects such as the biostability and biocompatibility of 3D-printed
dental devices will be examined, and this section will serve to pro-
vide an overview of the types of implants commonly produced via
3D printing. In addition, this first section describes the inherent
risks and advantages for devices realized utilizing this methodology.
The second section will be focused on the topic of bioprinting/3D
printing of cells for organic tissue reconstruction. Fundamental con-
cepts of bioprinting, common methods, biomaterials used, and
421
b3252_Ch-15.indd 421 27-11-2018 03:09:49 PM

other factors for a successful bioprintable structure will be discussed.

Lastly, the properties of final bioprintable constructs (mechanical
variations, permeability, and degradability) will be considered.
1. Introduction
3D biomaterial printing is considered as one of the foremost revo-
lutionary technologies to date. As famously quoted by the previous
President of the United States of America, Barack Obama, 3D
printing technology has “the potential to revolutionize the way we
make almost everything”.1 It is a methodology using 3D tooling
for producing 3D models. Called Additive Manufacturing, it is
also referred to as rapid prototyping, solid free-form, computer
automated, or layered manufacturing depending on the kind of
production method used.2–4 In the recent years, the medical com-
munity has just begun to explore the many benefits of employing
3D printing technology to realize human bodily implants never
before possible.
The process of generating a 3D-printed device for a patient begins
with a patient’s visit to a doctor. Computer-aided design software is
utilized to generate a virtual model of the dental device that matches
the patient’s internal anatomy exactly. In collaboration with the
design engineer, the doctor specifies the type of manufacturing tech-
nology, that is, the type of material and the structure that is to be
desired for the end product. Once agreed upon, the device is printed
and a physical dental appliance is produced in rough shape and form.
Most devices require additional finishing, such as cleaning, coating,
and most certainly always sterilization prior to being delivered to the
operating room.
The most outstanding advantage of 3D-printed biomaterials is
the ability to produce patient-specific devices that can be engineered
to exactly match the requirements set forth by the patient’s anatomy.
Although a giant leap for the production of medical devices, 3D
printing suffers from the major limitation arising from the printability
of materials, in particular the lack of advancements relating to print-
ability of a larger variety of biomaterials.5,6
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3D Printing — Additive Manufacturing of Dental Biomaterials 423
2. Additive Manufacturing of Dental Devices

In Dentistry, additive manufacturing was introduced as a manufactur-
ing technique early in the 1990s.7 However, in that time, it was used
mostly for prototyping study models, and for producing guides used
in surgical procedures.4 Recently, with the introduction of modern
radiological tools in the dental field (i.e. computed tomography,
cone-beam computed tomography, and optical surface scans), this has
allowed for the use of additive manufacturing to be utilized in a larger
variety of dental applications and implants.
2.1. Additive Manufacturing in Restorative Dentistry

Literature regarding indirect dental restorations manufactured by
3D-printing techniques is, as of now, rare. However, it is only a ques-
tion of time before the technology of 3D printing becomes an every-
day device at dental technician labs and at clinical offices around the
globe. First, because the advantages of the digital impression would
be from the computer-aided design computer-aided manufacturing
(CAD-CAM) technique:8
• Patient comfort: eliminates the claustrophobic feeling that some

patients have when the impression material is in their mouths.
• It is a clean procedure, avoiding the usual “chaos” of a typical
dental impression.
• No risk of cross-infection.
Secondly, different from the CAD-CAM technique, additive

manufacturing offers the possibility to design complex indirect res-
torations layer by layer. Parameters such as surface roughness,
mechanical properties, and optical properties can be engineered to
generate a dental prosthesis with high performance. Some examples
of interim crowns, metallic crown and bridge copings, implants and
abutments, chirurgical plates, and partial removable denture frame-
works (Figure 1) are currently manufacturable.4,7,9–12
The limitations of rapid prototyping of indirect restorations at
present are: the cost of the printing device, the time of learning a
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Figure 1. Partial removable denture framework manufactured by SLS tech-

nique. Adapted from Ref. [12]. Reprinted with the permission of Elsevier
Science Publishers B.V
complex technology, and the lack of dental materials available for dif-
ferent 3D-printing techniques.
2.1.1. Hard Tissue: Bone Reconstruction

The principle of rapid prototyping is to use 3D computer models for
the reconstruction of a 3D physical model by the addition of material
layers.13 Customized implants and prosthetics are one of the other
widely explored areas for application of rapid prototyping.14,15 Efforts
have been made on the development of artificial organs and tissues
using additive manufacturing.14–16 Tissue engineering, particularly
bone tissue, is rapidly expanding to become the most common type
of application for 3D-printed medical/dental implants. Human bones
are present in two different forms: cancellous, typically sponge-like in
structure with a large degree of porosity (50–90%); or cortical, com-
pact in structure having less than 10% porosity.16 In developing a bone
tissue implant, the porosity much match as closely as possible to the
surrounding bone; too porous and the implant will easily collapse, too
compact and the surrounding (human) bone tissue will be resorbed
by the body leading to the eventual loss of attachment of the implant.
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In the past, porous bone structures have been mimicked via tech-
niques such as chemical/gas foaming, solvent casting, particle/salt
leaching, freeze drying, foam gels, etc.; however, these techniques did
not allow for the selection or control of pore size, shape, or scaffold
interconnectivity.16 3D printing allows for the direct control of pore
size, shape, or scaffold interconnectivity because it is an additive
manufacturing technique, and extremely thin layers are printed one
atop another, layer after layer, until an overall complete structure is
formed. By this method, it is possible to design, slice by slice, the
exact internal composition of each and every aspect of a bone tissue
implant so as to match precisely with the surrounding tissues present
in the individual’s body. Internal channels or hanging features that
often cause difficulty with traditional manufacturing techniques are
realized with ease utilizing 3D printing since surrounding unbound
powder material acts to support the structure until fabrication is
complete.2 Common techniques for 3D printing of bone tissue
include extrusion (deformation and solidification), polymerization,
laser-assisted sintering, and direct writing processes.16
3D printing of bone tissue can be done with a variety of differ-
ent ceramic, metallic, polymeric, and other natural or synthetic com-
posite materials. Powdered forms of tricalcium-phosphate (TCP),
hydroxyapatite (HA), alumina (Al2O3), zirconia, polylactic acid
(PLA), polypropylene (PP), and countless other types of high-
strength, man-made synthetic substrates,2,16 and any mixture of
them can be used as a substrate for the 3D printing process, each
of which has a long list of advantages and disadvantages relative to
one another. Calcium phosphate-based ceramic materials stand out
among the crowd and are widely used as substrate for bone-tissue
implant production via 3D printing as these materials possess excel-
lent bioactivity, osteoconductivity, and generally are very similar in
composition to human bone structure.16 Other tests have shown
HA-printed materials to support the formation of capillaries and
blood vessels within.17
As an aside from substrate selection, binder selection, that is,
the choice of material used to bind and hence solidify powder mate-
rial, is incredibly critical for successful implant fabrication as well.
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Starch-based binders have shown good candidacy for producing bone

tissue structures closely matching the properties of human trabecular
bone.16 Bone tissue implants printed with polyethylene using a starch-
based binder have been shown to produce a porosity of 22.3–49.7%,
resulting in a tensile strength of 4 MPa, and have not shown any
toxicity to osteoblast cells, the primary bone extracellular matrix-
producing cells of the human body.16
2.2. Kinds of Additive Manufacturing Techniques:

Advantages/Disadvantages
Several different types of 3D-printing techniques have become popu-
lar in recent times, solid free-form fabrication (SFF), stereolithogra-
phy (SLA), selective laser sintering (SLS), and 3D plotting/direct-write
bioprinting are just to name a few.3,5,6 Each of these techniques has its
own inherent advantages/disadvantages, and most techniques specify
the type of biomaterial that must be used to facilitate the fabrication
process. The major disadvantage thus is the lack of selection of bio-
materials available for each type of manufacturing/printing process.
Commercially available devices are suitable for most patients. However,
applications are generally very limited so far, and the issue is still in an
early stage of research.
Rapid prototyping in general can only be applied to structures not
exceeding certain dimensions as 3D printers are not able to produce
extremely large products; this, however, is not a major concern for
dental applications.5 Even still, this limitation is currently overcome
by producing a miniature version of a large structure by post-process-
ing or by dividing the whole model into smaller parts which can be
combined after printing. The major limitation of rapid prototyping
lies within time and cost spent in generation of 3D objects.18 For
some authors, a widespread use of rapid prototyping for surgical
planning or individual implant design does not seem to be justified
because standard planning procedures or standard implants are suf-
ficient.18 However, in complicated cases, additional costs of rapid
prototyping may be compensated by reduced operating times and
higher success rates of the surgical procedure. The time needed for
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producing a 3D object also limits its use in surgery to elective cases

and makes it unsuitable for emergency cases.18,19
2.2.1. Solid Free-Form Fabrication (SFF)

SFF is a type of rapid prototyping, which offers a method to control
both the micro- and macroarchitecture to create complex biomedical
devices. This technique allows for the design and fabrication of com-
plex 3D structures which can be patient specific.19 Some fabrication
techniques use two materials in the course of constructing parts. The
first material is the part material and the second is the support mate-
rial, which is used to support overhanging features during construc-
tion.19 The support material is later removed by heating or is dissolved
with a solvent, commonly water. Depending on the fabrication tech-
nique, it is also possible to combine materials of different elasticity or
color in one model. This can be useful to create more realistic models
for educational or research purposes, or for naturally looking pros-
thetics. In addition, patient-specific imaging can be used to customize
builds for individuals.20,21 While conventional material processing
techniques can be highly effective in scaffold engineering, SFF tech-
nologies offer exciting opportunities for tissue engineering of highly
complex maxillofacial tissues. The selection of the fabrication tech-
nique depends upon the materials of interest, machine limitations,
and the specific requirements of the final scaffold.19,20
2.2.2. Selective Laser Sintering (SLS)

SLS is based on small particles of thermoplastic, metal, ceramic, or
glass powders that are fused by a high-power, focused laser.6,22,23
Materials include polymers such as nylon, glass-filled nylon or poly-
styrene, or metals such as steel, stainless steel alloys, bronze alloys, or
titanium. The key advantage of this technique is the ability to directly
make metallic devices such as dental implants that promote bone
ingrowth and regeneration for load-bearing applications in which
high fracture toughness and mechanical strength are needed.22,23 Even
for non-load-bearing applications, polymers can be processed without
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Figure 2. Raw stage of a 3D printed dental implant surface. Laser heat

causes unwanted fusion of the neighboring powder particles
the use of an organic solvent. It is slightly easier to achieve composi-

tional gradients in SLS than SLA by spreading different powder
between different vertical layers, but compositional gradients in the
horizontal plane is very limited. The main disadvantages are limited
materials which fuse but do not decompose under the laser beam
(high temperatures) and the post-processing needed to remove
trapped powder.22,23 Another limitation is the conduction and diffu-
sion of laser heat that causes unwanted fusion of neighboring pow-
der particles, thus limiting the resolution of final features (Figure 2).
Lastly, smaller pore sizes are limited since the created pores depend
on the particle size of the powder used. Powder particles that are
too small cannot be used due to poor spreading from powder
clumping.22,23
2.2.3. Stereolithography (SLA)

The advantages of SLA are the ability to create complex shapes with
internal architecture, ease of removal of unpolymerized resin, and
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extremely high feature resolution.5,6 The main disadvantage of SLA

is the scarcity of biocompatible resins with proper SLA processing
properties. Additional challenges are the use of photointiators and
radicals which may prove cytotoxic with long processing times,
entrapment of unreacted monomer and residual photoinitiator,
and the inability to create compositional gradients along horizontal
planes.6,13 Photopolymerized resin also has poor mechanical proper-
ties that are needed for hard tissue engineering.5,6 For these reasons,
in dentistry SLA has a main role producing chairside devices like
anatomic models for maxillofacial framework manufacturing.4
2.2.4. Inkjet Printing Techniques

Inkjet printing techniques are based on different kinds of fine pow-
ders such as plaster or starch.3 After a layer of the powder has been
dispensed by a piston, the parts of this layer belonging to the 3D
object are bonded by an adhesive liquid, the binder, deposited by
another piston.20 Inkjet printing techniques can also be used to gener-
ate a 3D scaffold with different types of tissue by printing living cells
and biomaterials simultaneously.24 The first hurdle associated with
these techniques is expanding upon the limited variety of available 3D
printable biomaterials (biomaterial inks), which currently do not
adequately represent the physical, chemical, and biological complexity
and diversity of tissues and organs within the human body.3 Newly
developed biomaterial inks, and the resulting 3D-printed con-
structs, must meet numerous interdependent requirements, includ-
ing those that lead to optimal printing, structural, and biological
outcomes. The second challenge is developing and implementing
comprehensive biomaterial ink and printed structure characteriza-
tion combined with in vitro and in vivo tissue- and organ-specific
evaluation.3,24 This perspective outlines considerations for address-
ing these technical hurdles that, once overcome, will facilitate rapid
advancement of 3D biomaterial printing as an indispensable tool
for both investigating complex tissue and organ morphogenesis and
for developing functional devices for a variety of diagnostic and
regenerative medicine/dental applications.20,24
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2.3. Implants Suitable for 3D Printing

Medical implants generated via the process of 3D printing are most
often used in applications relating to the restoration of anatomic
defects, the reconstruction of structural-based complex tissues (e.g.
bone) with intricate 3D microarchitecture, and also for producing
scaffolds atop which stem cells are typically deposited via traditional
techniques. In the latter, designed surface properties and scaffold
nanoarchitecture play roles in cell adhesion, proliferation, as well as
differentiation.2
Examples with high success rates for 3D biomaterial printing
applications are the cases involving large cranial defects. It has posed
a significant challenge for neurosurgeons in the past, particularly
owing to the high infection rate in the areas of the brain (33% by
one study)25 and significant bone resorption often seen around the
graft region even when utilizing autologous bone for the graft.
In the past, both titanium plates and mesh have been utilized to
cover the cranial defect as titanium possesses the strength and bio-
compatibility properties desirable. However, such titanium grafts do
not allow for the integration of human tissue and remain visible for
the duration of the patient’s life, sometimes causing severe psycho-
logical impacts.25 Also, another common consequence arising from
titanium graft is an increased sensitivity to temperature changes in
the area around the graft, or foreign body sensation. A recent study
presented the conclusions from the utilization of a 3D-printed
bioceramic porous hydroxyapatite (HA) graft applied to the cranial
defect. The study reports the results of 60 individuals, aged 17–75
years, who underwent complex cranial reconstructive surgery using
customized 3D-printed grafts.25 Cranial defects were located in the
frontal–parietal–temporal, and frontal–occipital areas, respectively,
and were greater that 25 cm2 in size. Within the entire population,
no incidence of infection was observed through the entire recovery
time for the 51 patients who complied with attending all follow-up
examinations within 2 years after the initial surgery. At the 2-year
mark, the entire population also did not report any signs of rejection
of the implant, neither were there any signs of foreign body reaction
observed. Osteointegration of the implant was noted as normal for
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the majority of the patients, with 49 of the 51 patients reporting they

were “very satisfied” with the implant, with the remaining 2 patients
reporting as “moderately satisfied”. One particular downside of the
3D-printed bioceramic porous hydroxyapatite (HA) implant is that,
much like human bone, it is susceptible to fracture. Three patients
reported implant fractures during their recovery periods, and each
fracture was determined due to unrelated traumatic events sustained
to the area of the graft.
Another case study involves a 3D-printed dental implant whereby
the implant was realized by a form of SLS, namely direct-laser metal
forming (DLMF). This study focused on a 50-year old female patient
with a non-restorable second maxillary premolar.26 In the past, sur-
rounding bone resorption, infection, and implant fracture were com-
mon pitfalls of dental implants produced with traditional manufacturing
techniques. With the use of DLMF-generated dental implants, the
ability to design a porous surface with the desired control of pore size
can be obtained. This allows for the highly desirable variability of
density throughout the premolar implant. Put simply, it is desired that
the implant has high density at the core for large load absorption, yet
conversely it is desired that the outer surface be highly porous to
promote anchorage via osteointegration. As a result, the implant pro-
duced is capable of lasting almost a life-time due to the high strength
and favorable osteointegration properties resulting from the design of
specific pore size. In addition, the healing timeframe is accelerated
substantially from such a design. The patient returned for examina-
tion 1 year following implant of the premolar device. The implant was
noted as stable, with no signs of infection, pain, or suppuration.
Radiographic imaging displayed desirable osteointegration, and the
crown complex was noted as “very similar to that of natural tooth”.
The implant showed exceptional aesthetic integration and had no
associated prosthetic complications.26
3. Bioprinting
The shortage of replacement organs is still an ongoing issue in the
medical and biomedical fields, and researchers are constantly
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investigating new methods to create new organs or replicate bodily

organs. Bioprinting organs and tissues is one of the promising solu-
tions that scientists have come out with in recent years. Its objective
is to restore, support, or increase the human tissue functionality while
maintaining the biocompatibility with and conformity of the tissues.
However, many more studies are needed to first develop a successful
technique for generating bioprinted organs with complex geometry
and second to assess their biocompatibility in different patients. Thus,
this leads to the rise of biological 3D printing which manufactures
cell-encapsulated scaffolds.27,28
From a biomedical point of view, creating a cultured tissue and
mimicking the surrounding environment which contains the extracel-
lular matrix (ECM), various cells, and growth factors is admirable to
replicate tissues functions in vitro. But, providing the cell and ECM
interactions complexity and also multicellular construction proper-
ties with appropriate vascular systems is challenging in biomedical
engineering.29
Bioprinting is a developing technology in the field of tissue engi-
neering and regenerative medicine. This process includes simultane-
ous cell, biomaterial, and/or growth factor deposition under pressure
via microscaled nozzles. 3D bioprinting is a procedure of controlling
and managing the cell proliferation, attachment, and migration within
3D constructs. Moreover, as compared to solid scaffolds, the highly
porous micro-/macroenvironment of bioprinted scaffolds is extremely
beneficial for cell survival and differentiation, as metabolite, nutrient,
and oxygen diffusion can be accomplished.30,31
The primary definition for biocompatibility is the compatibility
with living tissues or biological systems without causing toxicity and
immunological rejection. More generally, performance with a suita-
ble host response in a particular condition and time could be a defi-
nition for biocompatibility.32 Specifically, the artificial matrix must
not only provide acceptable cell viability and growth but also provide
suitable mechanical strength, ECM-like chemical and biological
properties, signal transduction, and facilitate the exchange of nutri-
ents, gases, and metabolic waste throughout the matrix. In the most
recent years, organ transplantation or drug delivery systems have seen
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tremendous improvements due to bioprinted scaffolds in the form of

hydrogels.30,33,34
To construct a bioprinted organ, many different factors that are
interrelated and must be considered; their ability to work together
affects their performance and subsequently the cell viability. The first
consideration in the bioprinting process is the selection of an appro-
priate bioink; natural or synthetic, viscosity, printability, cross-linking
and synthesis method, as well as degradability are just a few of the key
factors to consider.
3.1. Hydrogels as Bioinks

Hydrogels are polymeric materials that are used as bioinks with the
consistency similar to that of water-swollen gels. According to Peppas
and Hoffman,35 several mechanisms are used to form hydrogels:
(1) primary covalent cross-links;

(2) ionic forces;
(3) hydrogen bonds;
(4) affinity or “biorecognition” interactions;
(5) physical entanglements of individual polymer chains;
(6) a combination of two or more of the above interactions.35
Porosity and natural tissue resemblance are two main features of

hydrogels that have made these 3D networks an amenable environ-
ment for cell survival and differentiation. Moreover, the hydrogel
diffusivity enhances the exchange of nutrients and the elimination of
cell metabolites.36
A wide range of natural and synthetic polymers have been used to
construct hydrogels with different properties. The most commonly
used natural polymers for biological 3D printing are based on colla-
gen,37–39 hyaluronic acid,40 gelatin,33,41 chondroitin sulfate,42 fibrin,43
alginate,44 chitin,33 and silk.45 Among all these natural polymers, col-
lagen and gelatin have been the most widely investigated since they
are biocompatible, biodegradable, and are plentiful in nature. In some
cases, natural polymers have presented issues that have lead to
b3252_Ch-15.indd 433 27-11-2018 03:09:51 PM

research involving a combination of natural polymers with other poly-

mers or use with some modifications (Figure 3).39
For instance, pure gelatin solution has a low viscosity at physio-
logical temperatures, which makes it tedious to be printed alone.
Mixing gelatin with other viscous polymers, for example, alginate,45
hyaluronic acid,46,47 fibrin,43 and silk,45 is an approach to increase the
viscosity for bioprinting. Another solution to enhance viscosity is par-
tial cross-linking of polyethylene glycol polymer derivatives and gela-
tin blends before bioprinting.48 Poor bioprinting resolution is another
of the significant drawbacks associated with using gelatin as a bioink.
To improve bioprinting resolution, gelatin should be mixed or
blended with other polymers. It has been reported that blending gela-
tin methacrylamide with PEG to provide partial cross-linking
improved the resolution significantly, as shown by the reduction of
strut size from 1,100–1,300 µm to 350–450 µm, during bioprinting
with a 200 µm diameter nozzle.48
Figure 3. Types of chemically cross-linked hydrogels. According to Ref. [39].

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Klotz et al. focused on gelatin-based bioprinted hydrogels as

injectable hydrogels for cell encapsulation in bioprinting. They
mentioned that gelatin can cross-link with different types of poly-
mers such as acrylamide, ferulic acid, furfurylamine, methacryloyl,
etc., for cell encapsulation. So, the properties of gelatin could be
easily manipulated in a cost-effective way, which also improves bio-
compatibility and biodegradability.41 Wei Long Ng et al. developed
a gelatin-based bioink for skin bioprinting consisting of chitosan
and gelatin, in which polyelectrolyte complex was prepared for
desirable wound healing properties. This bioprinted hydrogel
showed constant mechanical properties under physiological condi-
tion in a week.33,49
Similar to gelatin, pure collagen has a low viscosity which makes
it a difficult material to be printed. Many efforts have been focused
on improving the viscosity using other polymers,50 such as agarose,51
chitosan,52 fibrin,53 as well as hyaluronic acid.54 Blending with other
polymers not only enhances the viscosity of collagen but also improves
the shape fidelity. For instance, a collagen-based printed cylinder
could be made 2 mm higher by adding 3% agarose and allowed to
keep its shape for a day.51 Also, collagen swelling capability has been
improved (up to 85%) by combining collagen with phospholipid for
cornea tissue repair application.38 Furthermore, collagen-based bio-
materials have the potential to provide cells with protection during
bioprinting. Investigations demonstrated 86% viability of collagen-
laden bovine aortic endothelial cells in which a 25 gauge nozzle was
used. The scaffolds kept their viability and maintained their original
spatial organization after 35 days of maintenance in culture.55 In addi-
tion to cellular protection, collagen bioinks are able to preserve cell
functionality and viability in printed cell-laden structures. Studies
have shown that encapsulated human mesenchymal stromal cells in
bioprintable type I collagen were induced to differentiate toward
osteoblasts and adipocytes.51
Despite all the positive aspects of natural polymers, these prod-
ucts suffer from low mechanical properties and purity. Synthetic
biodegradable polymers could solve this problem and have been
b3252_Ch-15.indd 435 27-11-2018 03:09:52 PM

utilized in scaffold construction, and these include common syn-

thetic polymers including polyethylene glycol,56 polylactic acid,57
polyglycolic acid,58 and their copolymers.57 To achieve a broad range
of suitable properties (biological, biophysical, and mechanical) for
bioprinting, a combination of natural and synthetic hydrogels is a
reasonable method. For instance, due to low viscosity, pure PEG is
not appropriate for microextrusion bio 3D printing. However, inte-
gration of PEG derivatives into other bioinks as cross-linkers
increases both mechanical properties of hydrogels and bioprinting
resolution.56
3.1.1. Hydrogel for Pulp-Regeneration

Examples of a 3D-bioprinted dentin/pulp complex are not yet
available in the literature. However, it will merely be a question of
time because “the fundamental building blocks of this tissue” are
already accessible.59 Potential sites of stem cell for dentin/pulp
regeneration are: postnatal dental pulp or exfoliated deciduous stem
cells, as well as periodontal ligament stem cells among others.60–62
Collagen, PEGylated fibrin, gelatin, and synthetic self-assembled
nanofibrous peptide are some types of hydrogels already tested for
injectable scaffolds for dentin/pulp regeneration.61,63–65 In an interest-
ing report,66 heparin-conjugated gelatin was used to develop an
injectable nanosphere system, which was in the form of nanofibrous
biodegradable poly-L-lactic acid microsphere scaffold (Figure 4).
Dental pulp stem cells were seeded on these microspheres; the
system was injected in a full-length human root canal (11 mm). Then
the roots were implanted in an animal model (back of nude mice), for
9 weeks. The in vitro results showed complete regeneration of pulp
tissue in the lower two-thirds of the root canal (Figure 5).66
Revascularization of the new tissue has been the major hitch for
pulp regeneration techniques. Hydrogels with the controlled release
of angiogenic growth factors have been proposed.59,61 However, issues
such as the duration of the angiogenic growth factor release and the
place where this drug is delivered are still objectives to be
accomplished.61
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Figure 4. Overview of an SEM image that shows the dental pulp stem cells
adhering to the surfaces of the hierarchical microspheres, expanding their
processes and grasping the microspheres to form cell/microsphere aggre-
gates. Adapted from Ref. [66]. Reprinted with the permission of Elsevier
Science Publishers B.V
Figure 5. Regenerated pulp-like tissue filled both the apical and middle third
regions and reached the coronal third of the canal. Adapted from Ref. [66].
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3.1.2. Hydrogels for Periodontal Regeneration

The periodontal system has a complex interaction among its anatomic
features: cementum, periodontal ligament, and alveolar bone. This
triphasic interphase brings an extra challenge for developing 3D bio-
printable solutions for periodontal regeneration.67 Multiphasic scaf-
folds with various compartments have been proposed for mimicking
the architectural configuration of the periodontium.59,67,68 Literature
suggests several kinds of hydrogels as bioinks: N-(2-hydroxy) propyl-
3-trimethyl ammonium chitosan chloride, quaternized chitosan with
a-b glycerophosphate, poly(lactic-co-glycolic acid) (PLGA), and
polycaprolactone.61,67–69
Hydrogels work as a scaffold for pluripotent cells, and they are
frequently combined with calcium phosphate cements, hydroxyapa-
tite, and beta-tricalcium phosphate to enhance periodontal heal-
ing.67 Also, recombinant human bone morphogenetic proteins
(rhBMP) are often added to the mix to promote periodontal regen-
eration. However, literature suggests that recombinant human
growth/differentiation factor-5 (rhGDF-5) can have better perfor-
mance in alveolar bone regeneration than rhBMP2 and rhBMP7.70
Also, high doses of rhBMP2 and rhBMP7 were found to be associ-
ated with root resorption and ankylosis in an animal model.61,70
3.2. Importance of Cross-Linking Process

in Bioprinting Constructions
The type of polymer selected for bioprinting mainly depends on the
type of cross-linking technique employed to generate 3D networks.
Various cross-linking mechanisms to obtain a structurally stable poly-
meric network include photo,- ion-, electrostatic, pH-, and tempera-
ture-based cross-linking mechanisms. Care must be taken when
choosing the cross-linking method, as the viability of the encapsulated
cells will be significantly affected by environmental conditions such as
heat or pH. Similarly, the cross-linking technique influences construct
outcomes with considerations of gelation via reversible or irreversible
processes. To preserve the shape of hydrogels in bioprinting, gelation
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is an important and necessary factor which can be introduced physi-

cally, chemically, or via both procedures. The mentioned cross-linking
methods modify the hydrogels mechanical properties, biocompatibil-
ity, and gelling time.
3.2.1. Physical Cross-Linking

Hydrogels that are cross-linked physically are the most popular cate-
gory of hydrogels utilized in bioprinting. This mechanism of cross-
linking involves polymer chain entanglements, hydrogen bonding,
and hydrophobic as well as ionic interactions. Significant biocompat-
ibility and good interaction with delicate molecules are the main
properties of physically cross-linked hydrogels. Thermogelation and
self-assembly are attractive as physical cross-linking systems due to
their low cytotoxicity, for example, copolymers consisting of hydro-
phobic polylactic acid (PLA) and hydrophilic PEO moieties are com-
monly used for this reason.36,71
3.2.2. Chemical Cross-Linking

Low mechanical strength is the main weakness for physically cross-
linked hydrogels. This flaw affects the bioprinted structure’s stability
significantly. Therefore, the chemical cross-linking method opens new
horizons toward improvement of hydrogel stability, printability, and
mechanical properties in order to be used in bioprinting constructs.
Generally, gel precursors and a mixture of two solutions with low
viscosity enable the chemical cross-linking process to achieve a hydro-
gel with higher viscosity. The reaction is initiated using radical polym-
erization and functional groups.
Free radical polymerization is a common way to achieve appropri-
ate hydrogels for biomedical applications.56,72 Hydrogels which are
polymerized through vinyl functional groups are generated by redox,
thermal, and photo initiators.73,74 Among the natural and synthetic
polymers, chitosan,75,76 hyaluronic acid,54 dextran,44 PVA, and PEG,77,78
respectively, are the most popular hydrogels in bioprinting. Photo-
polymerization provides a rapid rate of cross-linking; however, long
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exposure of cells to UV affects cell viability.73,74 Furthermore, the heat

released during the cross-linking procedure may lead to cellular
necrosis. So, it is important to keep UV light intensity between 5 and
10 mW/cm2 to prevent cell loss. Polymerization utilizing UV light
in vivo is not efficient since the skin has low UV light penetration and
absorption (>99%).79 Polymerization through redox and thermal
initiators like ammonium peroxydisulfate and N,N,N’N’-tetramethyl
ethylene diamine (TEMED) are other alternatives. Enhancement of
initiator concentration provides higher mechanical strength and lower
gelation time. While increasing initiator concentration can be useful,
it can incur negative effects as well, e.g. 10 mM may increase cytotox-
icity and decrease cell viability to less than 30% after 4 days in cell
culture.80 Hence, free radical polymerization in hydrogels preparation
needs further development to be used as a robust and suitable
method.
The other type of chemically cross-linked hydrogels are those
which are synthesized by reaction of their monomer functional
groups. Schiff-based formation, peptide ligation, Michael-type addi-
tions, and “click” chemistry are the most common reactions in this
category (Figure 3). In Schiff-based formation, an amine functional
group reacts with an aldehyde group.75 Glutaraldehyde is a frequent
cross-linker which in spite of its high efficiency, results in toxicity, cell
matrix degradation, and, consequently, prevents cell growth even if at
low concentration. So, to remove unreacted reagents, hydrogels
cross-linked by glutaraldehyde need to be extracted extensively. To
reduce the toxicity effect of aldehyde groups, they can combined with
other biocompatible polymers like hyaluronic acid.81 Also, reactive
aldehyde functional groups can be generated through oxidation of
polysaccharides including alginate,82 dextran,44 and hyaluronic acid.54
Aldehyde groups and PEG derivatives that create thiazolidine rings
could be used to synthesize hydrogels through a peptide ligation
method.83,84 The reactions occur at moderate experimental conditions
with a high rate of gelling (few minutes). Michael addition is the
other method to prepare hydrogels via reaction of electrophilic func-
tional groups such as vinyl, acrylate, or maleimide with nucleophiles
like an amine or thiol group. So, polymers including dextran,85
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hyaluronic acid,78 and PEG78 are suitable for this kind of reaction.
Peptides containing thiol groups have been used to create hydrogels
with biofunctionality, which have improved cell adhesion and extra-
cellular matrix production.86 Generally, these types of hydrogels dem-
onstrate good mechanical strength and mild gelling time between 0.5
and 60 min. The hydrogel’s properties can be changed by alteration
in functional group reactivity and cross-linker concentration which
affects cross-linking density. Because of moderate circumstances in
the Michael addition method, cells are not affected notably in hydro-
gel preparation and can normally sustain their viability for days to
months.87 However, excess concentration of thiol functional groups
could lead to cell damage, which acts as restricting factor in their
utilization.
Another strategy for chemical cross-linking is the reaction of
azides and terminal alkynes using a copper catalyst.88,89 Modified hya-
luronic acid and gelatin have been used to synthesize biological
hydrogels via click chemistry, mimicking the natural cartilage extracel-
lular matrix.90 Faster gelation, no by-products, and stability under
physiological conditions are the most important advantages of this
method. However, due to copper toxicity for mammalian cells, click
chemistry catalyzed by copper may put end users in danger of death.88
As removing the copper catalyst from the hydrogel is difficult and
complicated, copper-free click polymerization methods have attracted
researchers’ attention as a new method in hydrogel preparation for
biomedical applications. Table 1 summarizes the advantages and
drawbacks of different cross-linking methods through the reaction of
functional groups.
3.2.3. Physical and Chemical Cross-Linking Combination

Due to reversible interactions in physically cross-linked hydrogels,
they have lower mechanical strength than chemically cross-linked
hydrogels. On the other hand, biofavorable components in chemically
cross-linked hydrogels could influence their biocompatibility.
Although mechanical properties could be enhanced by increasing the
molecular weight of polymers and cross-linkers concentration, it will
b3252_Ch-15.indd 441 27-11-2018 03:09:53 PM

Table 1. Chemical cross-linking methods through functional groups

Functional
Chemical groups
reaction involved Advantages Drawbacks
Schiff-based Amine and  Applicable for  Possible side
formation aldehyde incorporating and reaction by
cross-linking aldehyde
proteins and amine-  Unstable Schiff-
bearing peptides based linkages in
acidic conditions
Peptide N-terminal  Mild reaction  Complicated
ligation cysteine and conditions protection and
aldehyde  High substrate de-protection steps
specificity in synthesis of
 High efficiency of peptides
cross-linking
Michael-type Acrylate, vinyl,  Moderate reaction  Cell toxicity by
additions thiol, and condition unreacted thiol
amine  Adjustable groups
properties
appropriate for cell
encapsulation
Click Azide and  Fast gelation  Toxic copper from
chemistry alkyne  High reaction catalyst
efficiency
 Stability
be difficult then to control hydrogel viscosity. Mixing techniques of

cross-linking both physically and chemically generate hydrogels with
suitable biocompatibility and improved mechanical performance. For
example, hydrogel development via the combination of photopolym-
erization and stereo complexation, an 8-arm PEG–PDLLA, and an
8-arm PEG–PLLA, stereo-complexed hydrogels functionalized with
methacrylate groups (40%) are produced.91 These hydrogels can be
post-cross-linked using the application of UV light. The risk of cell
damage and death from heat decreases because of the lower amount
of initiator used for photopolymerization, which is approximately
b3252_Ch-15.indd 442 27-11-2018 03:09:53 PM

0.003 wt.% in comparison with conventional photopolymerization

and cross-linking methods that use 0.05 wt.%. The other combined
systems consist of mixing different cross-linking methods involving
inclusive complexation, stereo complexation, thermo-gelation,
Michael addition reactions, and photopolymerization.92,93 The combi-
nations result in rapid gelling time, improved biocompatibility, and
easier control of hydrogel properties.
3.3. Properties of Bioink

An appropriate bioink should fulfill biological requirements that
include compatibility with cells and the ability to provide appropriate
mechanical and physical features during the bioprinting process.
From the physical perspective, the bioink should show gel-like behav-
ior, having enough viscosity to stand freely. But, if the gel has higher
stiffness with an associated high modulus, it will require a great shear
force to inject the ink influencing cell viability and gel strength (frac-
ture). From the mechanical perspective, the single-printed filaments
need enough high strength and stiffness to keep the post-printing
integrity of the structure.94,95
3.3.1. Mechanical Properties

Recently, there have been several studies undertaken on the initial
mechanical properties of soft tissue structures and material charac-
terization after printing.96–98 To improve the mechanical strength
of bioprinted structures, researchers have used a variety of different
approaches: polymer concentration, cross-linking density, and the dif-
ferent methods for establishing cross-link structures can all act to
improve the mechanical properties of final products.99 For instance, a
multi-cross-linking approach was used by Skardal et al. to produce
extrudable bioinks and then a secondary cross-linking stabilized and
increased the stiffness of the end products in order to match the
desired tissue type. To modulate mechanical properties of hydrogel
bioinks, they used combinations of polyethylene glycol cross-linkers
with different molecular weights, geometries (linear, 4-arm, and 8-arm),
b3252_Ch-15.indd 443 27-11-2018 03:09:53 PM

and functional groups. This method enabled them to produce hydro-

gels with shear stiffness values ranging from approximately 100 Pa to
20 kPa and provided control over mechanical properties to mimic
tissue stiffness.53 In addition, hydrogels can be formed using natural
or synthesized materials by chemical, physical, or biological cross-
linking methods. For example, collagen can be chemically cross-
linked by covalent bonding agents, which bind either free amine or
carboxyl groups of collagen. Binding can occur via dehydrothermal
treatment, UV radiation, or biologically by transglutaminase. Each of
these methods have demonstrated different degrees of mechanical
strength that depend on the mechanism, concentration, and exposure
time.95
Mechanical properties of in vitro bioprinted hydrogels play an
important role to mimic the in vivo mechanochemical microenviron-
ment. In a study by Zhang et al., a 3D in vitro soft tissue model with
changing structures and porosity based on the 3D cell-assembly tech-
nique was constructed. Cells were embedded in a matrix of gelatin/
alginate to examine mechanical characteristics and structural integ-
rity, especially during the first 7 days of culture.100 Based on the 3D
soft tissue model results, it was seen that mechanical properties were
affected by structural configuration. More importantly, it was
observed that after 3 days of cell culture, the structural integrity and
mechanical properties reduced drastically. This initial reduction could
be due to the gelatin degradation during the first day under culture
conditions as temperature changed. In addition, they observed the
degradation of alginate in the 3D in vitro tissue models at the later
stage, a possible explanation could be because of the effects of cellular
activities and exposure to the culture conditions. Therefore, stability
under both in vitro and in vivo conditions needs to be carefully con-
sidered before selecting an appropriate hydrogel.100
In an effort by Hunt et al., rheological analysis was used to
study the change in mechanical properties of alginate hydrogel dur-
ing 28 days of in vitro culture. The results confirmed that despite the
fact that at early-stage cellular activities influenced negatively encap-
sulating alginate mechanical characteristics, over a longer culture
period, the hydrogels maintain acceptable mechanical integrity to
b3252_Ch-15.indd 444 27-11-2018 03:09:53 PM

show gel-like properties. In fact, as alginate degraded, encapsulated

cells were released and started to proliferate and secrete extracellular
matrix to facilitate tissue regeneration.101
3.3.2. Permeability
In 3D bioprinting, hydrogels not only serve as bioinks to deliver cells
or support cell growth, but also provide cells with access to oxygen
and nutrients which are essential for differentiation and proliferation.
Therefore, hydrogels used in 3D printing should possess another
important characteristic: a porous structure that allows filtration of
oxygen and other such nutrients.102 Besides, an interconnected pore
network is essential for the effective mass transfer of gas, nutrients,
and waste to achieve satisfactory cell viability.103 When the engineered
constructs are thicker than 1 mm, oxygen and nutrients perfuse with
difficulty into the constructs, which may result in cell death.36,104
Additionally, it is undeniable that structures with enough porosity
are proper to be used for functional tissues and organs with high
thickness and metabolic activities because they have the ability to
provide an integrated vascular network.99 In fact, the internal archi-
tecture of tissue constructs plays a crucial role as it provides a porous
environment for media exchange, vascularization, tissue growth, and
engraftment. Recently, researchers have taken advantage of an innova-
tion to prepare gel-like structure with hollow channel embedded
arrays and utilized the resulting structure as a potential substitute for
blood vessel networks. To fabricate several kinds of hollow nanofila-
ments, researchers have used a core–shell electrospinning technique.
In this innovation, two immiscible solutions were electrospun
through a coaxial, two-capillary spinneret.105,106 Inspired by this con-
cept, some researchers used a coaxial nozzle, which plays a key part in
electrospinning equipment to fabricate microfluidic channels.107–108 A
commercially available, affordable, open-source 3D bioprinter modi-
fied with a microfluidic print-head was used by Attalla et al.108 to
create a system for generating a perfusable vascular network inte-
grated with the cell. The print-head consisted of an integrated coaxial
nozzle that provided the ability to fabricate hollow tubes based on
b3252_Ch-15.indd 445 27-11-2018 03:09:53 PM

calcium-polymerized alginate. By changing the flow rates or print-

head speed, hollow channel diameter could be accurately controlled
and varied. Hollow channel samples showed good cell viability after
24 h and 72 h, with about 81% and 70% viability, respectively. But,
non-vascularized samples exhibited a significant decline in cell main-
tenance during this time period, from around 61% to 20%.108
3.3.3. Degradation
The main objective of bioprinted constructs is to allow the body’s
own cells, over time, to produce their own extracellular matrix and
eventually replace the implanted scaffold. So, the first criterion for
selecting an appropriate material for the bioprinted structure is their
biodegradability, either by enzymes or hydrolysis.109 Most synthetic
biodegradable polymers are degraded by hydrolysis, which will lead
to accumulation of acids in the local area, therefore altering the
environment’s pH and causing toxicity. Secondly, due to the body’s
immune response by macrophages, some hydrogels are destroyed
by enzymes, which results in an inflammatory reaction around the
implanted scaffold.110
The degradation properties of a hydrogel play a crucial role in
the success of a bioprinted implant. Though, most of the by-prod-
ucts of polymers that are biodegradable are known to be non-toxic;
there is limited data that shows acidic by-products depend on the
rate of hydrogel degradation.110 Kang et al. reported that the acidic
by-product of PLGA can cause the degeneration of neocartilage
tissue.111
Natural polymers are mostly biodegradable, and the degradation
products are non-toxic. For example, metalloproteases normally
degrade collagen, and hence cells in bioprinted hydrogels can control
the procedure of degradation.112 Gelatin has been modified to pro-
duce a photopolymerizable hydrogel via methylacrylate group addi-
tion to create methylacrylated gelatin (GelMA) for bioprinting
applications.46 Fibrin has been recently utilized within injectable
hydrogels and cell delivery vehicles. Due to autologous cells derived
from plasma, the degradation products of fibrin are biocompatible
b3252_Ch-15.indd 446 27-11-2018 03:09:53 PM

and the risk of inducing a foreign body reaction is low.112 Alginate has
low toxicity, and gels formed as a result of divalent cations such as Ba+
or Ca+ cooperatively interact with alginate to produce ionic links
between chains of polymers. Studies show that the alginate hydrogel
cross-linked by means of ions represents uncontrolled and slow dis-
solving behavior instead of demonstrating a particular trend of degra-
dation.113 Cao et al. studied the effect of Ca+ concentration on cell
viability and alginate hydrogel biocompatibility. Calcium ions can be
used for cross-linking and improving printability; however, it has been
demonstrated that higher Ca+ concentrations have a higher probabil-
ity of inducing cell death.114 Chitosan can be degraded by human
bodily enzymes and its structure is similar to glycosaminoglycan,
hence it has good biocompatibility and non-toxic behavior. Chitosan
is able to dissolve easily in diluted acids and form a gel like structure
by pH enhancement, which are good features for chitosan. Lysozyme
facilitates the degradation of chitosan, and the degradation kinetics
proportionally depend on the degree of its crystallinity. Hyaluronic
acid is a glycosaminoglycan and is present in most of the mammalian
tissues. Its degradation process naturally takes place due to the pres-
ence of hyaluronidase, and it has been extensively applied for wound
healing and skin regeneration and in various joint disorders such as
osteoarthritis. Different methods like covalent cross-linking with
hydrazide derivatives, annealing, and esterification have been used to
prepare hyaluronic acid hydrogels. In addition, hyaluronic acid can be
incorporated with other polymers like alginate, collagen, and gelatin
to create composite hydrogels.115,116
Polyethylene glycol (PEG), a hydrophilic polymer, has a high
water content, which can be incorporated into other polymer net-
works by cross-linking. By not eliciting a host immune response and
being an easily modifiable polymer, PEG is a suitable polymer for
biomedical applications. To achieve hydrogels which are able to
degrade hydrolytically with physiologically acceptable degradation
time scales, PEG is conjugated and functionalized with ester func-
tional groups utilizing lactide or glycolide groups. As PEG chains
have hydroxyl functional groups, they can be modified to form differ-
ent PEG derivatives. PEG is not able to be adsorbed by the human
b3252_Ch-15.indd 447 27-11-2018 03:09:53 PM

body because of the lack of protein binding sites. These synthetic

hydrogels successfully attract scientists for their use in bio 3D print-
ing. For instance, photocurable PEG hydrogels are widely utilized in
encapsulation of cells due to their naturally inert structure. Moreover,
owing to its well structure, PEG can be employed as a mediator to
immobilize the RGD sequence, a segment of protein which provides
cell adhesion.107,117
Polylactic acid (PLA) is one of the popular synthetic polymers
which has been used in bioprinting. Slow degradation rate, high ten-
sile strength and modulus (~4.8 GPa), and low extension potentially
make PLA an appropriate load-bearing alternative. However, the
degradation rate is based on crystallinity degree and porosity of the
construct. PLA is able to produce high-strength fibers that introduces
the field of scaffold fabrication for replacement of ligaments.
Polyglycolic acid (PGA) is highly crystalline and insoluble in most of
the organic solvents. Although the degradation properties may
change by utilizing different types of processing methods, PGA deg-
radation products are natural metabolites. PGA degradation includes
random hydrolysis of the ester bonds. In addition to hydrolysis, some
enzymes, particularly those which have esterase activity, can decom-
pose PGA structure. Various factors such as crystallinity, configuration
of structure, molecular weight, and implantation site affect the degra-
dation rate of PGA. Although desirable biocompatibility of PGA has
been demonstrated by different in vitro and in vivo analyses118; two
main problematic issues have been detected. One of them is related
to orthopedic applications in which normally large size implants are
required that leads to by-product release from PGA degradation pro-
ducing a highly acidic environment. It was determined that toxic
products can be produced by PGA acidic degradation.118 The inflam-
matory response is the other concern, triggered via small released
particles during degradation. Copolymer polylactic-glycolic acid
(PLGA) shows high resistance behavior to be degraded hydrolyti-
cally.58 Bulk erosion occurs in PLGA by hydrolyzing ester bonds.
Different parameters affect the rate of degradation including molecu-
lar weight, the lactic acid/glycolic acid proportion, and matrix
b3252_Ch-15.indd 448 27-11-2018 03:09:53 PM

structure. Ease of processing makes PLGA a common copolymer, as

it facilitates fabrication to develop several constructs.58
It is undeniable that cells must be subject to pressure and mechan-
ical forces that occur through the bioprinting process. Therefore,
there is an important question that must be answered. If cells are
being compulsorily influenced by or subjected to external forces
brought on by the bioink and biofabrication process, what will be the
cell’s fate? Investigations show that proliferation, motion, and differ-
entiation of living cells, as dynamic compounds, will change under
external forces and stimuli. Changes in cell geometry cause changes
in mechanical signals, which consequently result in alteration of
chemical signals and cellular regulations. The characteristics of the
bioink are determined through its formalization and crucially affect
the formed structure’s delivery and integrity. More importantly, the
bioink should possess some properties similar to the biological
requirements that are essential for the cell system.94,119
3.3.4. Viscosity
Viscosity plays a key role in the properties of bioinks, and the ability
of a hydrogel to be printed is partially controlled by its viscosity.
Printability, or the hydrogel printing effectiveness, was studied by
means of using compressed oxygen in order to drive hydrogels
through a tube which delivered the bioink to print-head nozzles.119
The software controlled the deposition by opening the print-head
nozzles with precise timing while simultaneously configuring their
movement over the printing surface. Bioinks in this system needed to
have similar viscosity to be effectively steered via the tube and ejected
from the nozzles.110
The viscosity of bioink is primarily influenced by the bioink con-
centration and is easily controllable. In addition, cross-linking pro-
cesses can affect the viscosity of the bioink. It is important to control
the extent of cross-linking within the biomaterials to obtain a suitable
printing viscosity. Pre-cross-linked polymers could be too viscous to be
used in the bioprinter. This issue has been addressed in the study by
b3252_Ch-15.indd 449 27-11-2018 03:09:53 PM

Murphy et al., who compared specific properties such as biocompati-

bility and printability of different hydrogels.110 It was reported in this
study that pre-cross-linked chitosan-based hydrogels showed highest
cell death most likely because of the ammonium hydroxide vapor treat-
ment utilized to pre-cross-link the hydrogel. Due to the high viscosity
of certain hydrogels, they were not able to print the hydrogel using the
bioprinting hardware. Therefore, these hydrogel solutions were printed
utilizing a syringe deposition technique instead.
Long Ng et al.,33 used a modification in the cross-linking method
of chitosan-based hydrogels to increase the printability. The authors
took advantage of the interaction between polyelectrolyte complexes,
like positively charged chitosan and negatively charged gelatin to
improve its printability. The positively charged ammonium ions from
chitosan react with carboxylate groups from the ampholytic gelatin to
form a polyelectrolyte complex. This method was much better than
pre-cross-linking of the bioink, which increased the bioink viscosity
undesirably.
The other strategy to control bioink viscosity and printability is to
combine the ink with another component to modify the properties
and form a gel that possesses proper biological features and satisfies
the desired physical extrusion criteria. In the work done by Chung
et al., rheological properties of alginate–gelatin hydrogels were com-
pared with pre-cross-linked alginate and alginate hydrogel to describe
their printability.120 Easy gelation, cell compatibility, and appropriate
stability of alginate were presented as the convincing reasons to
choose this polymer in the abovementioned study. By changing the
concentration of alginate or by hydrogel pre-cross-linking prior to
printing, rheological requirements for extrusion printing were
obtained. The viscosity and storage modulus of alginate-based bioinks
could be enhanced by employing the gelling characteristics at low
temperatures, without the need for Ca2+ addition. Besides, this
method made these gels more cell-friendly. According to live and
dead cells assays, primary myoblasts maintained viability within the
alginate–gelatin hydrogel, even after being printed at two or three
times higher pressures than pressures that would normally provide
good filament size and resolution.
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3.4. Methods of Bioprinting

To assess the biocompatibility of bioprinting in microenvironment
engineering, cell viability and functionality after the bioprinting pro-
cess must be affirmed for different printing systems.27,28,30 To exem-
plify, for the hamster ovary cells and rat primary embryonic motor
neurons printing, a thermal inkjet printer was employed. During the
cell suspension preparation, due to osmotic effects of phosphate-
buffered saline, 15% of cells were lysed. During bioink printing, due
to temperature enhancement in the ejector reservoir, 3% of cells were
lysed. Furthermore, 74% viability was reported in primary rat embry-
onic hippocampal and cortical neuron printing.30 Recently, various
bio 3D-printing systems have gained 90% cell viability in comparison
to control groups of non-printed cell cultures, which illustrate the
explicit application of bio 3D-printing in future for several cell types
ranging from neurons to stem cells. Additionally, for high-throughput
single-cell isolation and pattering, valve-based bioprinting technology
has been employed. Stem cell viabilities were stated around 97% and
94% in pre- and post-bioprinting procedures, respectively. Also,
results demonstrated that functional genomic information of stem
cells were maintained during bioprinting.30
Applications of tissue engineering and 3D bioprinting technol-
ogy could involve various methods. The most common methods
include the stereolithography apparatus (SLA) and digital light pro-
cessing (DLP) techniques in which a vat of liquid photopolymer
resin and a UV laser are used to provide the 3D structures. fused
filament fabrication (FFF) utilizes material extrusion and creates a
structure layer by layer. Selective laser sintering (SLS) fuses powder
of a polymer by applying heat from a high-power laser, and the last
is inkjet 3D printing, which consists of powder bed and binder jet-
ting. Among the abovementioned common 3D bioprinting meth-
ods, FFF is not suitable for cell printing since it does not utilize any
solvent. Inkjet 3D printing has been used for printing of cells and
cell-encapsulated hydrogels, though it does not provide appropriate
mechanical properties and may damage cell membrane and their
functionalities during solution injection. Besides, SLA and DLP
b3252_Ch-15.indd 451 27-11-2018 03:09:53 PM

printing technologies increase cytotoxicity due to uncured photoini-

tiator in photopolymerization.121
From the laser power perspective, there is another category in 3D
bioprinting, classified into the laser-assisted and laser-free bioprinting
methods. In laser-assisted bioprinters, a laser beam, a focusing system,
and a substrate are the main components. Living cells lead to deter-
mined positions on a substrate through a light trap created by the
laser beam and focusing system. Excessive thermal energy exposure
by the laser light onto the cell biolayer which overheats living cells
can be one of the challenges in this method. Long exposure time
and direct contact of the cell with the laser light causes low rates of
cell survival. If the laser does not contact directly with living cells,
the cells’ survival rate will improve up to 95% cell viability. To over-
come this important challenge, lights with near infrared wavelength
(700–1,000 nm) have been utilized. However, DNA is not able to
absorb near infrared photons, and free radical generation will be
retarded too. Therefore, laser-guided direct bioprinting is defined as
a system that does not cause mutation or trigger apoptosis, although
optimization of wavelengths continues to exist as an open and
unsolved issue. Laser-free bioprinters have been inspired by inkjet
desktop printers. In these methods, printing pressure plays a pivotal
role in cell viability. In this regard, some other factors such as needle
shape and printing pressure affect cell viability and thus the biocom-
patibility of the bioink.28
Cell encapsulation technology that is based on picoliter droplet
using an acoustic apparatus has been developed in recent times.
Acoustic droplet formation rate can achieve up to 100,000 droplets
per second with high cell viability. Droplets are formed from an open
liquid reservoir and no nozzle is needed for the generation of a drop-
let. Complications regarding shear clogging will be avoided. In addi-
tion to these advantages, acoustic waves do not put living cells in
danger because of low power droplet generation within only a few
pulses, occurring within microseconds. In addition, acoustic ejectors
can be combined in an adjustable array format as multiple ejectors,
which would increase the printing rate and allow the deposition of
several types of cells and ECM. Various biomaterials could be printed
b3252_Ch-15.indd 452 27-11-2018 03:09:53 PM

through the ejectors such as living cells, ECM proteins, nutrients,

therapeutic drugs, and growth factors simultaneously from the same
platform via integration of microfluidic systems into the ejectors.
To gain reproducible outcomes for the cell-encapsulating droplet
deposition, bioprinting spatial precision should be comparable to
the cell size, for instance, around 10–20 µm in hydrogel or bioink.
Acoustic techniques have been introduced as a method that can
eject droplets in a broad size range from 3 µm in diameter to several
hundred micrometers.28
3.4.1. Bioprinting Parameter: Nozzle Diameter and Pressure

Bioprinting methods which dispense the living cells by syringe affect
various parameters with varied effects on living cells and the overall
quality of the bioprinted construct. For example, nozzle diameter and
the movement speed of nozzle head are parameters which could influ-
ence cell viability. Reduction in diameter of the dispensing nozzle will
enhance the dispensing shear forces that living cells inside the nozzle
experience. Also, changing the movement speed of the nozzle head
could induce additional compressive or tensile forces on the dispensed
strands.122 For instance, at high speeds dispensed strands will be
stretched and lead to higher tensile forces on the encapsulated cells,
while, at lower speeds, the dispensing forces are lower and living cells
experience less compression.123
The results obtained by Chang et al.98 showed that cell recovery
was dependent on procedure parameters. All dispensing pressures,
5, 10, 20, and 40 psi, demonstrated notable cell recovery of control
values at the 7-day time endpoint with 94.67%, 91.07%, 90.02%,
and 87.06% recovery values, respectively. Based on the calculation
of the percentage of cell recovery, the smallest nozzle diameter
group (i.e. 150 mm) represented meaningfully reduced cell viability
and the larger nozzle diameter experimental groups between 250
and 400 mm exhibiting relatively higher cell recovery. From the
information presented in abovementioned study, it can be concluded
that cell recovery shows sensitivity to the parameters of the printing
procedure. At higher pressures, cell recovery was higher and less for
b3252_Ch-15.indd 453 27-11-2018 03:09:54 PM

small nozzle tip diameter. A similar result was obtained by Nair et al.,
which showed a more significant effect of dispensing pressure than
the nozzle diameter on cell viability.122
Aside from the fact that viscosity affects the printability, it can
influence other parameters like dispensing pressure within the noz-
zle.124 A more viscous hydrogel would require a higher dispensing
pressure, and this increment in dispensing pressure was shown to
induce a significant decrease in cell viability. It is obvious that at
higher dispensing pressure highly viscous bioinks can eject easily.
However, the shear stress could be increased by higher viscosity, lead-
ing to reduced cell viability and increased cell damage. Referring to
Yu et al., the cell-laden conduits direct the fabrication ability utilizing
an extrusion-based bioprinting technique.100 They reported that
due to variation in dispensing pressure, quantifiable cell death could
be induced by the bioprinting procedure. In their study, most of the
dead cells were distributed along the edge of the printed structure
walls, where shear stresses were at the highest level. In another rele-
vant effort by Tirella et al., the shear stress influence on cell viability
and functionality endured during the process of deposition were sys-
tematically investigated.125 They employed a method that provided
low shear stress extrusion of viscous hydrogel solutions consisting of
cells. By process parameter optimization, like modifying the bioink
concentration, nozzle diameter, pressure, and speed, they could over-
come limitations created by viscous bioink.
4. Future Perspective
Additional progress for 3D printing technologies is needed for the
ability to increase the resolution without sacrificing shape and
the strength of the device. For both SLS and 3DP, there is a chal-
lenge with creating stronger structures without increasing dimen-
sions.126 To create small features which survive the fabrication
process, powder particles must be bound together tightly. Additional
work is needed to move to SLS and 3DP with smaller resolu-
tions.126,127 Advances of SLA have been made to synthesize new bio-
degradable moieties; however, these materials have not been FDA
b3252_Ch-15.indd 454 27-11-2018 03:09:54 PM

approved. Although macro- and microarchitecture has made great

strides in the past 5 years, additional work should focus on the nano-
architecture (e.g. biochemical molecules).126,127
Due to harsh processing conditions of SFF methods (e.g. heat,
organic solvent), biochemical molecules are not generally incorpo-
rated directly into the scaffold. While biochemical molecules can be
coated onto structures in post-processing, there is a need for sus-
tained growth factor release over time.23,126 Therefore, strategies to
incorporate biochemical molecules directly into scaffolds for pro-
longed release will be needed. These systems unfortunately are not
optimized for biomaterials of interest for in vitro and in vivo stud-
ies, and advances are still being made to improve the methods for
biomaterials.
5. Conclusion
Although there has been recent progress in the field, medical
research has already benefited from rapid prototyping providing a
new vision into physiological and pathological processes. Several
technical challenges have yet to be overcome. In cases where materi-
als can be printed, 3D printing is particularly advantageous for one-
of-a-kind, customized complex devices that are not cost-effective in
conventional manufacturing methods. However, current biomaterial
availability does not adequately represent the physical, chemical, and
biological complexity and diversity of tissues and organs within the
human body. The invention of a greater variety and complexity of
printable materials is a key aspect that requires large developments
for the more widespread acceptance and use of 3D printing to take
place. Still, for the materials currently available for bioprinting appli-
cations, biocompatibility is an essential factor that poses many chal-
lenges yet to be overcome. The dream of printing a complete living
tissue that can be readily implanted into the body and can replace
damaged bodily organs with complex functions, sadly, is still a dis-
tant dream. Nevertheless, at least some of the limitations presented
within this chapter might be overcome by future technological
developments.
b3252_Ch-15.indd 455 27-11-2018 03:09:54 PM

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Index
A B
acetone, 280 3D biomaterial printing, 422
acidulated phosphate fluoride, base glass, 181
103 biocompatibility, 5, 381
ACTA equipment, 162 biocompatibility issues, 201
addition type silicones bioglass (45S5), 247
(vinylpolysiloxanes), 374 bioinks, 438
additive manufacturing, 422 bioprinting, 426
adsorption, 4 biosilicate, 250
agar, 373 BisGMA, 296
alabama machine, 163 bisphenol A diglycidyl ether
alcohol, 280 dimethacrylate, 297
alginate, 373, 433 boundary conditions, 82
alginate alternatives, 385 Bragg angle of diffraction, 23
alginate–silicone, 374 Brinell, 34
all-in-one, 285 Buonocore, 278
alumina, 177, 425
aluminum silicate, 191 C
amalgam safety, 131 3D computer models, 424
antimicrobial monomers, 320 calcium fluoride, 98
arrest line, 218 calcium hydroxide, 100
attenuated total reflectance, 19 Candida albicans, 413
Auger electron spectroscopy, 12 Candida glabrata, 413
auto-mixing, 378 carbonated hydroxyapatite,
azide-alkyne, 319 249
463
b3252_Index.indd 463 27-11-2018 03:10:23 PM

464 Index
cavity configuration factor, 349 degree of conversion, 347

ceria, 148 density, 198
C-factor, 349 dental amalgam, 126
chain-growth reactions, 297 dental composites, 295
chain-transfer reactions, 307 dentifrices, 105
chipping, 150 dentin, 57
chitin, 433 dextran, 439
chitosan, 447 DICOM, 74
chondroitin sulfate, 433 digital light processing (DLP), 451
chronic poisoning, 128 dihydrogenphosphate group, 281
closed-loop servo hydraulic testing dimethacrylate, 315
system, 410 dimethacrylate-based composites,
collagen, 433 336
color stability, 412 dimethylaminoethyl methacrylate
compound materials, 373 (DMAEMA), 281
compression curl, 220 dipoles, 4
compressive tests, 34 direct-laser metal forming (DLMF),
computer-aided design/ 431
computer-aided machining disinfection, 376, 395
(CAD/CAM), 150, 177 dodecylpyridinium bromide, 282
condensation silicones, 374 dustless alginate, 383
cone-beam-CT, 73 dynamic mechanical analysis, 410
contact angle, 7 dynamic SIMS, 16
contact wear, 236
continuous stiffness measurement, E
42
elastic modulus, 346
crack analysis, 338
elastic recovery, 379
creep, 34, 53
elastic wall concept, 352
cristobalite, 186
electron spectroscopy for chemical
cross-linked methacrylated
analysis (ESCA), 8
networks, 301
elemental mercury, 129
crystal growth process, 184
enamel, 56
crystallization processes, 182
endodontic sealer, 256
cubic zirconia, 158
energy-dispersive X-ray
spectroscopy (EDX), 13
D environmental issues, 126
degradation, 446 environmental issues related
degradation by hydrolysis, 296 to dental amalgam, 139
b3252_Index.indd 464 27-11-2018 03:10:23 PM

Index 465
epitaxy, 185 H
ester bonds, 300 2-hydroxyethyl methacrylate
ester functionalities, 319 (HEMA), 281
esthetic restorations, 296 hackle, 213
etch-and-rinse, 282 hardness, 196
extracellular matrix (ECM), 432 Helmholtz free energy, 4
heterogeneous nucleation, 182–183
F high angle annular dark field
failure criteria, 83 (HAADF), 24
fan-beam-CT, 73 Hooke’s law, 347
fatigue, 159 hoop stresses, 235
fibrin, 433 hyaluronic acid, 433
finite element analysis, 337, 340 hydration, 55
flexibility, 380 hydrocolloids, 373
flowable composites, 352 hydrogels, 433
fluorapatite, 98 hydrogen gas, 391
fluoride, 92 hydrophilic monomers, 279
fluoride varnish, 104 hydroxyapatite, 425
fluorinated monomers, 317 hydroxyethyl methacrylate, 4
fracture mirror, 219
fracture strength, 192 I
fracture toughness, 195 incremental layering, 356
free-radical mechanism, 297 initiator systems, 319
fused filament fabrication (FFF), 451 interface, 3
interfacial gaps, 299
G
2D geometry, 68 K
gelatin, 433 Knoop hardness tests, 34
gel effect, 348
gel point, 348 L
Gibbs free energy, 4, 183 laser ablation inductively coupled
glass fillers, 296 plasma mass spectrometry, 16
glass ionomer cements, 108, 252 leucite, 174
glass transition temperature, 404 linearly variable displacement
glutaraldehyde, 284 transducer, 410
griffith, 192 linear voltage displacement
grinding damage, 236 transducer, 410
gull wings, 219 lithium aluminosilicates, 180
b3252_Index.indd 465 27-11-2018 03:10:23 PM

466 Index
lithium metasilicate, 186 nanogels, 314

loadings, 82 nanoindentation probe, 40
low shrinkage, 357 nanotribology, 43, 62
low-shrinkage monomers, 304 neurological dysfunction, 129
low temperature degradation, 160 niobium phosphate glass, 251
N-methacryloyl-5-aminosalicylic
M acid (5-NMSA), 281
10-MDP, 281 nozzle diameter, 453
4-methacryloyloxyethyl trimellitate nucleation process, 181
anhydride (4-META), 281
4-methacryloyloxyethyl trimellitic O
acid (4-MET), 281 occupational health, 137
11-methacryloyloxy-1,10- oligomeric additives, 314
undecanedicarboxylic acid optical properties, 199
(MAC-10), 282 organic matrix, 295
magnesium, 148 orthodontic bonding agents, 109
mass spectrometry, 15 over-the-counter, 414
matrix metaloproteinases (MMP),
283 P
mercury, 125 3D patient-based model, 68
mercury concentration, 130 3D plotting/direct-write, 426
mercury toxicity, 128 PEGylated, 436
mesh convergence, 77 permeability, 445
mesh quality, 77 petalite, 180
methacrylamides, 318 phosphorus pentoxide, 180
methacrylate chemistry, 296 photoacoustic IR, 18
methacryloxy propyl trimethoxy photo-base generators, 319
silane, 406 photoelasticity, 339
methacryloyloxy dodecylpyridinium photoinitiation, 295
bromide (MDPB), 282 phyllosilicate structure, 188
microbiological interaction, 413 physical cross-linking, 439
monolithic zirconia, 153 physicochemical techniques, 5
monomers, 297 pit and fissure, 107
plastizised polyvinyl chlorides, 403
N polar interactions, 4
N-(2-hydroxy) propyl-3-trimethyl polycaprolactone, 438
ammonium chitosan chloride, polyethers, 374
438 polylactic acid, 425
b3252_Index.indd 466 27-11-2018 03:10:23 PM

Index 467
poly(lactic-co-glycolic acid) rockwell, 34

(PLGA), 438 root caries, 106
poly-L-lactic acid, 436
polymerization, 295, 336 S
polymerization kinetics, 301 3D scanners, 72
polymerization shrinkage, 299 sandwich technique, 353
polymerization stress, 296, 336 scanning electron microscopy, 24
polypropylene, 425 scanning probe microscopy, 42
polysaccharides, 381 scherrer formula, 23
polysulfides, 373 scratch, 34
post-cure polymerization, 339 selective laser sintering, 426
pre-heating, 356 self-etching adhesive systems, 284
pressing, 177 shear loss modulus G, 410
probe selection, 52 silicate glass, 248
properties of bioink, 443 silicon-containing tetraox-
pulse-delay, 354 aspiroundecane monomer, 360
silicone elastomers, 404
Q silk, 433
quaternary ammonium silorane, 358
methacrylates, 321 single-step self-etching adhesives,
quaternized chitosan with a-b 285
glycerophosphate, 438 slow crack growth, 160
sodium fluoride, 103
R soft copolymer, 406
Raman spectroscopies, 18 soft-start photoactivation, 353
ramped, 354 solid free-form fabrication, 426
recombinant human bone spiro orthocarbonates, 360
morphogenetic proteins, 438 spodumene, 180
recover elastically, 408 static SIMS, 16
removing old amalgam step-curing, 354
restorations, 138 step-growth reactions, 307
renal disease, 130 stereolithography, 426
residual stresses, 339 stereolithography apparatus, 451
resilient denture liners, 402 stiffness, 38
resin-modified glass ionomer stress relieving, 352
cements, 253 surface, 2
restorative composites, 297 surface energy, 3
reversible hydrocolloids, 373 surface origins, 226
b3252_Index.indd 467 27-11-2018 03:10:23 PM

468 Index
surface tension, 3 viscoelastic properties, 60

systematic approach, 232 viscosity, 449
volume flaw origins, 221
T volume flaws, 226
techniques, 451 VPS–polyether combinations,
tetragonal zirconia, 149, 191 374
thiol-ene, 307
thiol-ene photopolymerization, 360 W
thiourethane oligomers, 315 wake hackle, 216
time-of-flight secondary ion mass wallner line, 218
spectrometry, 15 water fluoridation, 101
topical fluoride, 92 wear, 34, 197
topical fluoride foam and rinses, wettability, 380
104
topical fluoride gels, 103 X
total-etch, 279 X-ray diffraction, 21
transmission electron microscopy X-ray photoelectron spectroscopy,
(TEM), 24 8
tricalcium-phosphate, 425
twist hackle, 216 Y
Young modulus, 34, 37
U yttria, 148
under high vacuum (UHV), 7 yttria-stabilized tetragonal zirconia
urinary mercury concentration, 132 polycrystals, 158
yttrium, 148
V Y-TZP for dental implants, 164
Vickers, 34
vinyl ethers, 319 Z
vinylpolyether silicone, 388 zirconia, 177, 425
vinyl sulfones, 319 zirconia-reinforced lithium silicate,
viscoelasticity, 54 188
b3252_Index.indd 468 27-11-2018 03:10:23 PM

Dental Biomaterials

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What are some of the different types of dental biomaterials discussed in the text?

What are some of the different types of dental biomaterials discussed in the text?

What are some techniques mentioned for analyzing dental biomaterials?

What are some techniques mentioned for analyzing dental biomaterials?

Dental Biomaterials

10589_9789813225671_tp.indd 1 21/11/18 3:14 PM

Vol. 1 Drug Delivery Systems

Vol. 2 Dental Biomaterials

Biomaterials and Bioengineered Device Research for Ligament Reconstruction

Biomaterials and Bioengineered Device Research for Joint Prostheses

Biomaterials and Bioengineered Device Research for

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Library of Congress Cataloging-in-Publication Data

British Library Cataloguing-in-Publication Data

Copyright © 2019 by World Scientific Publishing Co. Pte. Ltd.

For any available supplementary material, please visit

Typeset by Stallion Press

JQuek - 10589 - Dental Biomaterials.indd 2 26-11-18 10:31:23 AM

The development of the science of dental biomaterials has always

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they are so for a ceramic used as a dental veneer. Such complexity

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About the Editors

Edward Sacher was born in New York City and

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viii About the Editors

Rodrigo França received his DDS degree in

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Chapter 1 Surface Analysis Techniques for Dental Materials 1

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2.1.7. Laser Ablation Inductively

Chapter 2 Nanoindentation Techniques in Dental

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3.2. Artificial Dental Materials 49

Chapter 3 Finite Element Analysis in Dentistry  67

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2.3. Strategies for Geometry Acquirement  70

Chapter 4 Preventive Dental Material 91

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3. Methods of Fluoridation  101

Chapter 5 Mercury Toxicity 125

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4.3. Environmental Issues Related

Chapter 6 Zirconia in Dentistry 147

Chapter 7 Lithium Disilicate-Based Glass-Ceramics  173

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Chapter 8 Fractography of Dental Ceramics  211

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Chapter 9 Bioactive Glasses for the Development

Chapter 10 Dental Adhesives  275

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Chapter 11 Dental Composites — Chemistry and

Chapter 12 Development of Polymerization Contraction

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2.1.2. Systems Based on Cantilever

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Chapter 13 Flexible Impression Materials 371

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5. Non-Aqueous Elastomeric Impression

Chapter 1 Surface Analysis Techniques for Dental Materials 1

2.1.7. Laser Ablation Inductively

Chapter 2 Nanoindentation Techniques in Dental

3.2. Artificial Dental Materials 49

Chapter 3 Finite Element Analysis in Dentistry 67

2.3. Strategies for Geometry Acquirement 70

Chapter 4 Preventive Dental Material 91

3. Methods of Fluoridation 101

Chapter 5 Mercury Toxicity 125

4.3. Environmental Issues Related

Chapter 6 Zirconia in Dentistry 147

Chapter 7 Lithium Disilicate-Based Glass-Ceramics 173

Chapter 8 Fractography of Dental Ceramics 211

Chapter 9 Bioactive Glasses for the Development

Chapter 10 Dental Adhesives 275

Chapter 11 Dental Composites — Chemistry and

Chapter 12 Development of Polymerization Contraction

2.1.2. Systems Based on Cantilever

Chapter 13 Flexible Impression Materials 371

5. Non-Aqueous Elastomeric Impression

Chapter 14 Resilient Liners for Removable Prosthesis 401

Chapter 15 3D Printing — Additive

3.4. Methods of Bioprinting 451

1.1. Surface and Interfaces

1.2. Surface Energy

1.3. Forces at Interfaces

1.4. Reactions at Surfaces: Adsorption

2.1. Physicochemical Techniques

2.1.2. X-ray Photoelectron Spectroscopy (XPS)

2.1.3. Auger Electron Spectroscopy (AES)

2.1.4. Energy-Dispersive X-ray Spectroscopy (EDX)

2.1.5. Wavelength-Dispersive Spectrometry (WDS)

2.1.6. Time-Of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS)

2.1.7. Laser Ablation Inductively Coupled Plasma