Understanding Polymers
Understanding Polymers
Understanding Polymers
POLYMER BASICS
1.1. Introduction
Polymeric materials have been used since early times, even though their exact nature
was unknown. In the 1400s, Christopher Columbus found natives of Haiti playing with
balls made from material obtained from a tree. This was natural rubber, which became
an important product after Charles Goodyear discovered that the addition of sulfur
dramatically improved the properties; however, the use of polymeric materials was still
limited to natural-based materials. The first true synthetic polymers were prepared in the
early 1900s using phenol and formaldehyde to form resins-Baekelands Bakelite. Even
with the development of synthetic polymers, scientists were still unaware of the true
nature of the materials they have prepared. For many years, scientists believed they
were colloids - a substance that is an aggregate of molecules. It was not until the 1920s
that Herman Staudinger showed that polymers were giant molecules or
macromolecules. In 1928, Carothers developed linear polyesters and then polyamides,
now known as nylon. In the 1950s, Ziegler and Nattas work on anionic coordination
reactions catalyzed to the development of polypropylene; high-density, linear
polyethylene; and other stereospecific polymers.
Materials are often classified as metals, ceramics, or polymers. Polymers differ from the
other materials in a variety of ways but generally exhibit lower densities, thermal
conductivities and moduli. A comparative study of the properties of polymers has been
made against metals and ceramics with the findings as shown in the table below:
Table: 1.1.
1
MgO 3.6 - 105 205000
(2000oC)
High density 0.96 0.0052 1014-1018 350-1250
polyethylene
Plastics Polystyrene 1.05 0.0008 1018 2800
Polymethyl 1.2 0.002 1016 3500
methacrylate
Nylon 1.15 0.0025 1014 2800
Polymeric materials are used in a vast array of products. In the automotive area, they
are used for interior parts and in under-the-hood applications. Packaging applications
are a large area for thermoplastics, from carbonated beverage bottles to plastic wrap.
Application requirements vary widely, but, luckily, plastic materials can be synthesized
to meet these varied conditions.
1.2. Definitions
What is a "Polymer"?
The word Polymer finds its origin from the Greek "poly" meaning many, and "meros",
parts or units. A polymer is a group of many units. You combine many monomers (one
unit) to create a polymer.
The term degree of polymerization gives us the number of monomer units consumed to
form a polymer molecule. Hence it is a measure of the molecular weight of the polymer.
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Simulation of Polymerization Process
POLYMERIZATION
Polymer
D.P. = 8
Depolymerization
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1.3. Classification of Polymers
Polymers
Bulk Emulsion
Homopolymer Copolymer
Suspension Solution
Polymers are broadly classified based upon their availability to mankind. Thus two
different types of polymers are classified as Natural polymers and Synthetic polymers.
However man has been able to modify the properties of some naturally occurring
polymers by virtue of certain chemical treatments. They have gradually emerged as a
new class of polymers called the semi-synthetic polymers.
a) Natural polymers
b) Synthetic polymers
c) Semi-synthetic polymers
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1.3.1. Natural Polymers
Years ago, before there were plastics and synthetic polymers, in fact, all the way back
to the beginning of the earth, nature was using natural polymers to make life possible.
Natural polymers include the RNA and DNA that are so important in genes and life
processes. In fact, messenger RNA is what makes possible proteins, peptides, and
enzymes. Enzymes help do the chemistry inside living organisms and peptides make up
some of the more interesting structural components of skin, hair, and even the horns of
rhinos. Other natural polymers include polysaccharides (sugar polymers) and
polypeptides like silk, keratin, and hair. Natural rubber is, naturally a natural polymer
also, made from just carbon and hydrogen. Let's look at each of the main families of
natural polymers closely.
1) Polysaccharides
1a) DNA and RNA - They contain polymer backbones which are based on sugar units.
This makes them polysaccharides, although in the case of RNA and DNA, there are well
ordered groups attached to the sugar units that give these polymers their unique
capabilities.
1b) Wood and potatoes - Another family of polysaccharides includes starch and
cellulose. Starch is a high molecular weight polysaccharide. Foods like bread, corn, and
potatoes are full of starch. Starch may have as many as 10,000 sugar units all linked
together. Another very important member of the polysaccharide family is cellulose. This
is the main polymer that makes up plants and trees. Wood is primarily cellulose. This
polymer is different than starch. Starch is soluble in hot water and can easily be made
into useful objects. Cellulose, on the other hand, is highly crystalline and almost totally
insoluble in anything. Cotton is a form of cellulose that is used in most of our clothes.
1c) Chitin - Another member of the polysaccharides is chitin. It makes up the shells of
crawfish, shrimp, crabs, lobsters, and other crustaceans. It is hard, insoluble and yet
somehow flexible. Chemically, chitin is poly (N-acetylglucosamine).
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2) Proteins and Polypeptides
2a) Proteins - These were the first examples of polyamides. Both share many common
traits but they are very different in how they are made and in their physical properties.
They are alike in that the both contain amide linkages in the backbone.
2b) Enzymes These are one of the key types of polypeptides and are crucial to life on
earth. Enzymes are the catalysts that do specific jobs. In fact, oftentimes each enzyme
does only one type of job or makes only one kind of molecule. This means that there
have to be lots of different enzymes, all made of different combinations of amino acids
joined in unique ways in polypeptides, to do all the jobs that any living organism needs
done.
2c) Silk - One of the unique polypeptides that we used very early for its superb
properties was silk. Silk is made by tiny caterpillars trying to spin cocoons for their
transformation into moths. The silk is spun into fibers. The structure of silk molecules is
unusual for a polypeptide. It possesses lots of the unsubstituted amino acid, glycine.
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3) Polyisoprene (Natural rubber)
a) Thermoplastics These are polymers having the property of softening or fusing when
heated and of hardening and becoming rigid again when cooled. Thermoplastic
materials can be remelted and cooled time after time without undergoing any
appreciable chemical change. Examples are:
i. Polyethylene (PE)
ii. Polypropylene (PP)
iii. Polystyrene (PS)
iv. Polyethylene terephthalate (PET)
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Table: 1.3.1. Physical properties of some common Thermoplastics
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Table: 1.3.2. Physical properties of some Filled Thermosets
Phenolic
Wood Flour
filled 1.34-1.45 5-9 0.2-0.6 260-400 300-350 150-177
Polyester
Glass filled
SMC 1.7-2.1 8-20 8-22 320-400 300-350 150-177
Glass filled
BMC 1.7-2.3 4-10 15-16 300-420 300-350 150-177
Melamine
Cellulose
filled 1.45-1.52 5-9 0.2-0.4 350-400 250 120
Urea,
Cellulose
Filled 1.47-1.52 5.5-13 0.2-0.4 300-400 170 77
Alkyd
Mineral
Filled 1.60-2.30 3-9 0.3-0.5 350-450 300-450 150-230
Epoxy (bis A)
Mineral
Filled 1.6-2.0 5-15 0.3-0.4 300-400 300-500 150-260
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Common examples include the following:
Examples:
i. Polyethylene (PE)
b) Copolymers They consist more than one type of repeating unit (monomer).
i. Alternate Copolymers
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The different monomer units place themselves in an alternative sequence
in the polymer chain thereby maintaining a typical order.
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iv. Graft Copolymers
Based upon the chemical nature of monomers the polymers can be classified
accordingly. Some examples are:
i. Addition Polymers
e.g. Polyolefins
ii. Condensation polymers
e.g. Polyamides
i. Bulk Polymers
ii. Solution Polymers
iii. Suspension /Slurry Polymers
iv. Emulsion Polymers
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1.3.2.6. Type of Structure
The structure of the polymer chain can play a pivotal role in determining its various
physical and mechanical properties like density, strength and toughness, etc. Thus
another way of classifying polymers is by its structure, which can be of the following
types:
i. Linear Polymers
Polymers in which the individual chains are covalently bonded to each other thereby
leading to the formation of a three dimensional network fall under this category.
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Examples of crosslinked polymers are:
a) Vulcanized rubber
b) Bakelite
c) Polyimides
Crystalline Polymers
Highly crystalline polymers are rigid, high melting, and less affected by solvent
penetration. Crystallinity makes a polymer strong, but also lowers their impact
resistance. As an example, samples of polyethylene prepared under high pressure
(5000 atm) have high crystallinities (95 - 99%) but are extremely brittle.
Polymer molecules are very large so it might seem that they could not pack together
regularly and form a crystal. It now is known that regular polymers may form lamellar
(plate-like) crystals with a thickness of 10 to 20 nm in which the parallel chains (shown
in different colors in the simulated structure at the right) are perpendicular to the face of
the crystals.
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Amorphous Polymers
Polymer chains with branches or irregular pendant groups cannot pack together
regularly enough to form crystals. These polymers are said to be amorphous. A two-
dimensional schematic of an amorphous polymer is shown below.
Amorphous regions of a polymer are made up of randomly coiled and entangled chains.
They have been compared to a bucket containing a large number of entangled worms -
each one 20-foot long and of 1/4-inch thickness. The worms are so tangled that an
entire worm cannot slide past the others, but small portions of the worms can twist
around within the mass. Amorphous polymers are softer, have lower melting points, and
are penetrated more by solvents than are their crystalline counterparts.
i. Molding grades
This class includes plastics for blow molding, roto molding, injection molding, etc.
ii. Extrusion grades
Plastics for film application, stretch tapes, pipes, profiles, sheets, etc. fall under
this class.
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1.4. Polymer Properties
Types of polymer 'properties' can be broadly divided into several categories based upon
scale. At the nano-micro scale are properties that directly describe the chain itself.
These can be thought of as polymer structure. At an intermediate mesoscopic level are
properties that describe the morphology of the polymer matrix in space. At the
macroscopic level are properties that describe the bulk behavior of the polymer.
The identity of the monomers comprising the polymer is generally the first and most
important attribute of a polymer. Polymer nomenclature is generally based upon the
type of monomers comprising the polymer. Polymers that contain only a single type of
monomer are known as homopolymers, while polymers containing a mixture of
monomers are known as copolymers. Poly (styrene), for example, is composed only of
styrene monomers, and is therefore is classified as a homopolymer. Ethylene-vinyl
acetate, on the other hand, contains more than one variety of monomer and is thus a
copolymer. Some biological polymers are composed of a variety of different but
structurally related monomers, such as polynucleotides composed of nucleotide
subunits.
A polymer molecule containing ionizable subunits is known as a polyelectrolyte. An
ionomer is a subclass of polyelectrolyte with a low fraction of ionizable subunits.
The simplest form of polymer molecule is a straight chain or linear polymer, composed
of a single main chain. The flexibility of an unbranched chain polymer is characterized
by its persistence length. A branched polymer molecule is composed of a main chain
with one or more substituent side chains or branches. Special types of branched
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polymers include star polymers, comb polymers, and brush polymers. If the polymer
contains a side chain that has a different composition or configuration than the main
chain, the polymer is called a graft or grafted polymer. A cross-link suggests a branch
point from which four or more distinct chains emanate. A polymer molecule with a high
degree of crosslinking is referred to as a polymer network. Sufficiently high crosslink
concentrations may lead to the formation of an 'infinite network', also known as a 'gel', in
which networks of chains are of unlimited extend - there is essentially all chains have
linked into one molecule.
H H
| |
-(- C - C -)-
| |
H R
Tacticity has to do with which side of the chain the R group is placed. Fischer
projections can be used to show the three different types of tacticity:
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Isotactic
Syndiotactic
Atactic
Head-tail placement has to do with which carbon the R group is placed on (rather than
which side the R group is on as in tacticity).
H H
| |
C-C
| |
H R
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The carbon with the R on it can be called the "head", and then to maintain consistency,
the carbon, and the carbon without the R should be called the tail. It has been observed
that polystyrene connection with two benzene groups on adjacent carbons is called a
"head-to-head" placement, so from this it follows that the presence of an R group on a
carbon makes that carbon a "head" carbon.
H H H H
| | | |
C-C-C-C Head to Tail placement
| | | |
H R H R
H H H H
| | | |
C-C-C-C Head to Head placement
| | | |
H R R H
H H H H
| | | |
C-C-C-C Tail-to-Tail placement
| | | |
R H H R
1.4.2.1 Crystallinity
When applied to polymers, the term crystalline has a somewhat ambiguous usage. In
some cases, the term crystalline finds identical usage to that used in conventional
crystallography. For example, the structure of a crystalline protein or polynucleotide,
such as a sample prepared for x-ray crystallography, may be defined in terms of a
conventional unit cell composed of one or more polymer molecules with cell dimensions
of hundreds of angstroms or more.
A synthetic polymer may be described as crystalline if it contains regions of three-
dimensional ordering on atomic (rather than macromolecular) length scales, usually
arising from intramolecular folding and/or stacking of adjacent chains. Synthetic
polymers may consist of both crystalline and amorphous regions; the degree of
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crystallinity may be expressed in terms of a weight fraction or volume fraction of
crystalline material. Few synthetic polymers are entirely crystalline.
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Young's Modulus quantifies the elasticity of the polymer. It is defined, for small strains,
as the ratio of rate of change of stress to strain. Like tensile strength this is highly
relevant in polymer applications involving the physical properties of polymers, such as
rubber bands.
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1.4.3.4. Compressive Strength & Modulus
The compressive strength of a material is the compressive force per unit area that it
can withstand.
ABS 65 2.5
Acrylic 110 3
Nylon 6 50 2.3
Polyamide-Imide 130 5
Polycarbonate 70 2.0
Polyethylene 80 1
Terephthalate (PET)
Polypropylene 40 1.5
Polystyrene 70 2.5
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1.4.3.5. Flexural Strength & Modulus
The flexural strength of a material is defined as its ability to resist deformation under
load. For materials that deform significantly but do not break, the load at yield, typically
measured at 5% deformation/strain of the outer surface, is reported as the flexural
strength or flexural yield strength. The test beam is under compressive stress at the
concave surface and tensile stress at the convex surface.
ABS 65 2.5
Acrylic 110 3
Nylon 6 50 2.3
Polyamide-Imide 130 5
Polycarbonate 70 2.0
Polyethylene 80 1
Terephthalate (PET)
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Polyimide 150 2.5
Polypropylene 40 1.5
Polystyrene 70 2.5
This property determines the ability of the material under consideration to withstand
instant shock loading. There may various impact strength of a plastic material can be
expressed by various terms depending upon the test procedure namely:
a) Izod impact
Specimen is held as a vertical cantilevered beam and is broken by a pendulum.
Impact occurs on the notched side of the specimen.
b) Charpy impact
Specimen is held as a simply supported beam and is impacted on the side opposite
the notch.
c) Tensile Impact
The tensile impact test measures the amount of force needed to break a specimen
under a high speed tensile load introduced through a swinging pendulum. The
thickness and width of the test specimen is recorded. The specimen is then
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clamped to the crosshead and placed into the pendulum. The pendulum is released
and allowed to strike the anvil breaking the specimen. The tensile impact energy is
recorded and then corrected impact energy is calculated.
Stress relaxation describes how polymers relieve stress under constant strain. Polymers
exhibit stress relaxation owing to the fact that they are viscoelastic in nature, i.e. they
have both the properties of an elastic solid material as well as a viscous liquid material.
1.4.3.8. Creep
Creep is the term used to describe the tendency of a solid material to slowly move or
deforms permanently to relieve stresses. It occurs as a result of long term exposure to
levels of stress that are below the yield strength or ultimate strength of the material.
Creep is more severe in materials that are subjected to heat for long periods, and near
the melting point. Creep deformation is "time-dependent" deformation.
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1.4.5.2. Boiling point
The boiling point of a polymer substance is never defined due to the fact that polymers
will decompose before reaching theoretical boiling temperatures.
The following physical properties undergo a drastic change at the glass transition
temperature of any polymer:
a) Hardness
b) Volume
c) Modulus (Youngs module)
d) Percent elongation-to-break
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Table : 1.4.3. Glass transition temperatures & melting points of some common
polymers
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insulator in heat-generating applications and in structures in which heat dissipation is
important.
1.4.5.7. Flammability
For many plastic applications, the consequences of exposure to an actual flame must
be considered. This is important not only in electrical applications, but also in any
applications where the plastic constitutes a significant percentage of the exposed area
of a defined enclosed space.
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1.4.6.5. Dissipation Factor
When an electrical field is applied across a material, it becomes polarized. Upon
reversal of the potential, the polarization of the material also reverses. This is generally
witnessed with an alternating current and energy is dissipated as heat due to the rapid
change in polarization. The dissipation factor is a measure of that heat dissipation. A
low dissipation factor becomes important when plastics are used as insulators in high-
frequency applications such as radar & microwave equipments.
Table : 1.4.4. Typical values of dielectric constant, dissipation factor and volume
resistivity of various thermoplastics at room temperature
Material Description Dielectric Constant Dissipation Factor Volume Resistivity
(cm-ohm)
Chain length
Increasing chain length tends to decrease chain mobility, increase strength and
toughness, and increase the glass transition temperature (Tag). This is a result of the
increase in chain interactions such as Van deer Waals attractions and entanglements
that come with increased chain length. These interactions tend to fix the individual
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chains more strongly in position and resist deformations and matrix breakup, both at
higher stresses and higher temperatures. Chain length is related to melt viscosity
roughly as 1:103.2, so that a tenfold increase in polymer chain length results in a
viscosity increase of over 1000 times.
Branching
Branching of polymer chains also affect the bulk properties of polymers. Long chain
branches may increase polymer strength, toughness, and Tag due to an increase in the
number of entanglements per chain. Random length and atactic short chains, on the
other hand, may reduce polymer strength due to disruption of organization. Short side
chains may likewise reduce crystalline due to disruption of the crystal structure.
Reduced crystalline may also be associated with increased transparency due to light
scattering by small crystalline regions. A good example of this effect is related to the
range of physical attributes of polyethylene. High density polyethylene (HDPE) has a
very low degree of branching, is quite stiff, and is used in applications such as milk jugs.
Low density polyethylene (LDPE), on the other hand, has significant numbers of short
branches, is quite flexible, and is used in applications such as plastic films. The
branching index of the polymer is a parameter that characterizes the effect of long-chain
branches on the size of a branched macromolecule in solution. Dendrites are a special
case of polymer where every monomer unit is branched. This tends to reduce
intermolecular chain entanglement and crystallization. Alternatively, dendrite polymers
are not perfectly branched, but share similar properties to dendrites due to their high
degree of branching.
Chemical cross-linking
Cross linking tends to increase Tag and increase strength and toughness. Cross linking
consists of the formation of chemical bonds between chains. Among other applications,
this process is used to strengthen rubbers in a process known as vulcanization, which is
based on cross linking by sulfur. Car tires, for example, are highly cross linked in order
to reduce the leaking of air out of the tire and to toughen their durability. Eraser rubber,
on the other hand, is not cross linked to allow flaking of the rubber and prevent damage
to the paper.
Degree of crystalline
Increasing degree of crystalline tends to make a polymer more rigid. It can also lead to
greater brittleness. Polymers with degree of crystalline approaching zero or one will
tend to be transparent, while polymers with intermediate degrees of crystalline will tend
to be opaque due to light scattering by crystalline / glassy regions.
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2.0 Polymerization Reactions
There are two fundamental polymerization mechanisms. Classically, they have been
differentiated as addition polymerization & condensation polymerization.
In addition polymerization new monomer adds on the growing polymer chain via the
reactive active centre which can be a
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2.1.1. Free Radical Polymerization
One of the most common and useful reactions for making polymers is free radical
polymerization. It is used to make polymers from vinyl monomers, that is, from small
molecules containing carbon-carbon double bonds. A free radical is simply a molecule
with an unpaired electron. The tendency of this free radical to gain an additional
electron in order to form a pair makes it highly reactive so that it breaks the bond on
another molecule by stealing an electron, leaving that molecule with an unpaired
election (which is another free radical). Free radicals are often created by the division of
a molecule (known as an initiator) into two fragments along a single bond. Polymers
made by free radical polymerization include polystyrene, (poly methyl methacrylate),
poly (vinyl acetate) and branched polyethylene.
This process is often used to make polyolefins: addition polymers of olefins (what are
now known as alkenes).
During the formation of a polymer chain of subsequent kinetic events take place:
1. Radical formation
2. Initiation
3. Propagation
4. Termination
Free Radical Formation: The formation of free radicals can take place in a number of
ways. Radicals can be produced by photo-initiation, radiation (gamma-radiation or
electron beam), and electrochemical reaction or by thermal initiation. They are
commonly generated by breaking chemical bonds in such a way that the two electrons
involved in the bond end up on the two separate fragments of the original molecule.
This is called 'homolytic cleavage. The stability of a radical refers to the molecule's
tendency to react with other compounds. An unstable radical will readily combine with
many different molecules. However a stable radical will not easily interact with other
chemical substances. The stability of free radicals can vary widely depending on the
properties of the molecule.
The following diagram shows the formation of a radical from its initiator benzoyl
peroxide & 2, 2-azo-bis- isobutyrylnitrile (AIBN).
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Initiation: The first step in producing polymers by free radical polymerization is
initiation. This step begins when an initiator decomposes into free radicals in the
presence of monomers. The instability of carbon-carbon double bonds in the monomer
makes them susceptible to reaction with the unpaired electrons in the radical. In this
reaction, the active center of the radical "grabs" one of the electrons from the double
bond of the monomer, leaving an unpaired electron to appear as a new active center at
the end of the chain. Addition can occur at either end of the monomer. This is the
addition of the first monomer unit to the initially formed free radical.
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The whole process including the breakdown of the initiator molecule to form radicals
followed by the radicals reaction with a monomer molecules is called the initiation step
of the polymerization.
Propagation: This is the process for the growth of the chains. In the propagation stage,
the process of electron transfer and consequent motion of the active center down the
chain proceeds.
The radical derived from the initiator will grab another electron from the nearest
convenient source - if a carbon-carbon double bond is present, this will result in the
formation of a new single bond and the regeneration of the radical centre.
This process, the adding of more & more monomer molecules to the growing chains is
called the propagation.
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Another, less common method of termination is chain disproportionation where two
radicals meet, but instead of coupling, they exchange a proton, which gives two
terminated chains, one saturated and the other with a terminal double bond.
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2.1.2. Cationic Polymerization
Cationic polymerization is the one of the three major types of chain polymerization
involving positively charged or electrophilic active centers at the growing chain end.
Both alkenes & heterocyclic monomers can be polymerized catatonically.
Cationic polymerization is not only important commercial processes, but in some cases
are attractive laboratory techniques for preparing well-defined polymers & copolymers.
Polyacetal, poly (tetramethylene glycol), poly (e-caprolactam), polyaziridine,
polysiloxanes as well as butyl rubber, poly (N-vinyl carbazol), polyindenes &
poly(vinylether)s are synthesized commercially by cationic polymerization.
Electron donating groups are needed as the R groups because these can stabilize the
propagating species by resonance. Examples:
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Propagation is usually very fast. Therefore, cationic vinyl polymerizations must often be
run at low temperatures. Unfortunately, cooling large reactors is difficult and expensive.
Also, the reaction can be inhibited by water if present in more than trace amounts; so
careful drying of ingredients is necessary (another expense).
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Drawback of cationic polymerization:
The biggest drawback of cationic polymerization is its high reactivity & instability
of the growing carbonations leading to uncontrollable polymerization
characterized by incomplete initiation, important chain transfer & irreversible
termination reaction.
Cationic polymerization is less efficient than free-radical polymerization due
to the caustic nature of cation-producing reagents. An example of a cation-
initiated polymerization is the reaction of ethene with sulfuric acid.
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The mechanism of anionic polymerization is a kind of repetitive conjugate addition
reaction
Electrons withdrawing groups (ester, cyano) or groups with double bonds (phenyl, vinyl)
are needed as the R groups because these can stabilize the propagating species by
resonance. Examples:
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Formation of polyether from a methoxide & 1, 2 epoxy ethane
The beauty of anionic polymerization lies in the lack of termination reactions when
carried out under the appropriate conditions (living polymerization). This means that the
propagating species remains unchanged at the chain end when the monomer is
consumed, so subsequent chemical reactions can be carried out.
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Here Mt represents transition metals such as Ti, Mo, Cr, V, Ni or Rh. In the formation of
this monomer-catalyst complex, a coordination bond is involved between a carbon atom
of the monomer & the metal of the catalyst. The coordinated metal-carbon formed in
the monomer catalyst complex acts as the active centre from where propagation starts.
The incoming monomer is incorporated at the active centre of the metal carbon bond,
from where the chain growth starts.
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Life cycles of catalysts for olefin coordination polymerization:
1. Early generation Ziegler- Natta catalysts for ethylene & propylene polymerization
2. Philips catalyst for ethylene polymerization
3. Forth generation Ziegler-Natta catalyst for ethylene polymerization
4. Forth generation Ziegler-Natta catalyst for propylene polymerization
5. Metallocene based catalyst for olefin polymerization leading to polymers of
various stereoregularity.
The best-known Ziegler- Natta catalysts are those derived from TiCl4 or TiCl3 and an
aluminium alkyl. The catalyst system appears to function by formation of coordination
complex between the catalyst, growing chain & the incoming monomer. Hence the
process is referred to as coordination addition polymerization & the catalyst as
coordination catalyst.
The catalyst complex of the TiCl3/AlR3 system essentially acts as template for the
successive orientation & isotactic placement of the incoming monomer units. Though a
number of structures have been proposed for the active species, they fall into either of
two general categories: monometallic & bimetallic.
Structure (I), represent a bimetallic species, is the coordination complex that arises from
the interaction of the original catalyst components (titanium & aluminium compounds)
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with exchange of R & Cl group. Structure (II) represent a monometallic species
constitutes an active titanium site at the surface of a TiCl3 crystal. Besides the four
chloride ligands that the central Ti atom shares with its neighbouring Ti atoms, it has an
alkyl ligand a vacant orbital. Chain propagation by the bimetallic mechanism occurs at
metal centers of the bridge complex. With the chain growth taking place always from the
metal end, the incoming monomer is oriented, for stearic reason, with the =CH2 group
pointing the lattice & the CH3 group to one side, with the result that the process leads to
the formation of an isotactic polymer.
It is generally accepted that the d-orbital in the transition element are the main source of
catalytic activity & that it is the Ti-alkyl bond that acts as the polymerization centre
where chain growth occurs. For -TiCl3 catalyst the active centre is formed by the
interaction of aluminium alkyl with an octahedral vacancy around Ti. To elaborate the
five coordinated Ti3+ on the surface has a vacant d-orbital, which facilitates
chemisorption of the aluminium alkyl & this is followed by alkylation of the Ti3+ ion by an
exchange mechanism to form the active centre TiRCl4. The vacant site at the active
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centre can accommodate the incoming monomer unit, which forms a complex with
the titanium at the vacant d-orbital & is then inserted into the Ti-alkyl bond. After the
monomer is inserted into the Ti-alkyl bond, the polymer chain migrates back to the initial
state, while the vacant site migrates to its original position to accept another monomer
molecule. This migration is necessary, as otherwise an alternating position would be
offered to the monomer leading to the formation of a syndiotactic polymer instead of an
isotactic polymer.
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Ziegler-Natta polymerization is a great way to make polymers from hydrocarbon
monomers like ethylene and propylene. But it doesn't work of for some other kinds of
monomers. For example, we can't make poly (vinyl chloride) by Ziegler-Natta
polymerization. When the catalyst and co catalyst come together to form the initiating
complex, radicals are produced during intermediate steps of the reaction. These can
initiate free radical polymerization of the vinyl chloride monomer. Acrylates are out, too,
because Ziegler-Natta catalysts often initiate anionic vinyl polymerization in those
monomers.
For a long time, Ziegler-Natta polymerization was the most useful and versatile reaction
for producing polymers of a specific desired tacticity. But recently a new type of
polymerization, also using metal complexes as initiators, has been developed, called
metallocene catalysis polymerization.
This catalyst system boosted the activity of metallocene-based catalyst & produced
uniform polyethylene with the narrow molar mass distribution typical of single site
catalyst. This metallocene catalyst system provides a unique opportunity for new tailor
made polymers increased the range of co-monomers that could be used. An interesting
peculiarity of metallocene system is that the difference in the reactivities of ethane,
propene & higher - olefins is markedly less compared to the conventional Ziegler-Natta
catalyst. This opens many possibilities for the synthesis of copolymers.
ARDC/CS/Internal 45
Cross-linking often involves joining monomers with an -OH (hydroxyl) group and a freely
ionized -H on either end (such as a hydrogen from the -NH2 in nylon or proteins).
Normally, two or more different monomers are used in the reaction. The bonds between
the hydroxyl group, the hydrogen atom and their respective atoms break forming water
from the hydroxyl and hydrogen, and the polymer.
Polyester is created through ester linkages between monomers, which involve the
functional groups carboxyl and hydroxyl (an organic acid and an alcohol monomer).
Nylon is another common condensation polymer. It can be manufactured by reacting di-
amines with carboxyl derivatives. In this example the derivative is a di-carboxylic acid,
but di-acyl chlorides are also used. Another approach used is the reaction of di-
functional monomers, with one amine and one carboxylic acid group on the same
molecule:
The carboxylic acids and amines link to form peptide bonds, also known as amide
groups. Proteins are condensation polymers made from amino acid monomers.
Carbohydrates are also condensation polymers made from sugar monomers such as
glucose and galactose.
Condensation polymerization is occasionally used to form simple hydrocarbons. This
method, however, is expensive and inefficient, so the addition polymer of ethene
(polyethylene) is generally used.
Condensation polymers, unlike addition polymers may be biodegradable.
The most commonly known condensation polymers are proteins, fabrics such as nylon,
silk, or polyester.
The monomers that are joined by condensation polymerization have two functional
groups. A carboxylic acid and an amine can form an amide linkage, and a carboxylic
acid and an alcohol can form an ester linkage. Since each monomer has two reactive
sites, they can form long-chain polymers by making many amide or ester links. Let's
look at two examples of common polymers made from the monomers.
Example 1.
A carboxylic acid monomer and an amine monomer can join in an amide linkage.
As before, a water molecule is removed, and an amide linkage is formed. An acid group
remains on one end of the chain, which can react with another amine monomer.
ARDC/CS/Internal 46
Similarly, an amine group remains on the other end of the chain, which can react with
another acid monomer.
Thus, monomers can continue to join by amide linkages to form a long chain. Because
of the type of bond that links the monomers, this polymer is called a polyamide. The
polymer made from these two six-carbon monomers is known as nylon-6, 6. (Nylon
products include hosiery, parachutes, and ropes.)
Example 2:
A carboxylic acid monomer and an alcohol monomer can join in an ester linkage.
ARDC/CS/Internal 47
3.0 Polymerization Processes
Polymerization is the process of bonding repeating single units (monomers) into long
chains polymers. It is a very common chemical process, which involves numerous
different variables. The functionality of a polymer is related to its physical structure and
shape, so being able to create different families of size distribution can create different
functional products.
Different process parameters can affect the physical structure of the polymer, so being
able to precisely control the critical parameters of paramount importance.
The technologies that have been developed for the production of polyolefins, olefin
homopolymer & copolymers are:
Polyethylene Polypropylene
(LDPE)
ARDC/CS/Internal 48
The fundamental differences in the various olefin polymerization processes reflect the
different approaches that have been devised to remove the substantial heat of
polymerization.
There could be two possibilities if the resulting polymer is soluble in a monomer the
viscosity of the medium increases gradually in the course of polymerization & the net
result is a monolithic block of polymer .The other is, if the polymer is insoluble in a
monomer the polymer obtained is in the form of powder or a porous body. The latter
process is more preferred.
ARDC/CS/Internal 49
Since polymerization process takes place at very high temperature & high
pressure, as a result of which major processing parameters heat transfer &
viscosity are difficult to achieve.
Polymerization temperature & rate of reaction can only be controlled by vigorous
agitation.
Due to vigorous agitation control over degree of polymerization & growth of
polymer chain also becomes difficult resulting in poor control over molecular
weight & density.
Bulk polymerization result in a very low conversion of ~ 30%. The conversion
doesnt increase with longer reaction time.
Because of these disadvantages, it is used in few cases, which are produced in large
scale.
High pressure LDPE has certain properties, which are difficult to obtain by low-pressure
technologies. Typical features for LDPE are long branching of the polymer chains & a
wide variation in molecular weight distribution, which may be reasonably narrow,
medium or broad as well as symmetrical or asymmetrical. The molecular structure is
usually tailored according to the specific application.
LDPE has been commercially produced in high-pressure reactors for more than four
decades. The polymerization of branched polyethylene was discovered by ICI in 1933,
when chemical reactions under very high pressure were studied. Development of
commercial free-radical-initiated, high pressure PE process technology by the end of
1930s was the foundation of the polyolefin industry. Two-reactor technology i.e. tubular
& autoclave are employed in the high-pressure polymerization of ethylene.
LDPE: Free radical Extreme operating condition (150 -3000C & 2500-3000 atm)
ARDC/CS/Internal 50
Polymerization Condition:
Temperature: 250 C
ARDC/CS/Internal 51
High degree of back mixing.
ARDC/CS/Internal 52
Polymerization Condition:
Temperature: 150-300 C
ARDC/CS/Internal 53
Proprietary designs baffle or partition the reactor into discreet zones enabling
control of molecular species & amount of long chain branching of polymer in
these zones.
Back mixing does take place in the autoclave reactor.
Walls of the autoclave unit are thick to accommodate high pressure- heat of
reaction is removed by the introduction of fresh feed.
Upon exiting the reactor the material passes through medium pressure & low-
pressure separators (separate ethylene from LDPE polymer).
Polymer enters the pelletization process to be pelletised.
All the new world scale LDPE plants are tubular process technology. This technology is
widely licensed by a number of companies, including Sabic Euro Petrochemicals
/Stamicarbon, Basell (Lupotech T), ExxonMobil, EniChem & Atofina. Autoclave
technology is available from Equistar, Enichem, Exxon Mobil & Simon-Carves (ICI
process.
The main advantages of this process (in which monomer, polymer & solvent
coexist) are that the solvent can absorb a great part of the heat of reaction.
Consequently polymer structure, molecular weight & molecular weight
distribution can be controlled resulting in a good product homogeneity & uniform
quality.
The benefits of this type of polymerization, over the conventional bulk
polymerization, are that it reduces the viscosity of the reaction not allowing auto-
acceleration at high monomer concentrations.
ARDC/CS/Internal 54
If the temperatures required to melt the monomer are too high, or if bulk
polymerization would be so exothermic as to be hazardous, one may wish to use
solution polymerization process.
Change penalties i.e no production loss during the grade change.
This process produces polymer resin of narrow MWD (i.e. injection molding
grades).
Disadvantages:
Reaction temperature is limited by the boiling point of the solvent used, which in
turn restricts the rate of reaction that may be achieved
The solubility of a polymer decreases with increasing molecular weight and it is
necessary to select a good solvent to dissolve the polymer. To select a good
solvent, one has to compare the solubility parameter of the polymer to the
solubility parameters of the available solvents
It is difficult to free the solvent, which means that there is almost always chain
transfer to the solvent & hence a restriction on the molar mass of the product
ARDC/CS/Internal 55
1. Stirred Autoclave Reactor
2. Separator
3. Separator
4. Pelletiser
5. Compressor
1. All raw ingredients including ethylene feed, hydrogen, etc are dissolved into a
solvent resulting in a solution composed of the raw ingredient required.
2. Catalyst s required in the reactor.
3. Solution is introduced into one or more stirred autoclave reactors-temperature,
residence time & mixing are controlled.
4. Polymer solution exits the reactors solvent is flashed off in a separator & returns
to distillation.
5. Polymer passes through a low-pressure separator into an extruder.
6. A devolatization extruder is used in some cases to remove residual hydrocarbons
while stripping vessels (post extrusion) may also be used in some processes to
accomplish this task.
Three main types of solution processes have been developed by DOW (Dowlex), DSM
(Compact, now owned by Sabic Euro Petrochemicals) & Dupont (Sclaritech, now owned
by Nova Chemicals). The strength of a solution process are short product transition
times, ability to produce polyethylene of very low density (e.g. VLDPE, PE elastomers &
elastomer) and the ability incorporate higher alpha olefins co-monomers such as 1-
octene. LLDPE & other low-density polyethylene with higher alpha olefins show good
strength, toughness & sealing properties.
ARDC/CS/Internal 56
in monomer, which is dispersed in water. A dispersing agent is incorporated to stabilize
the suspension. For any nonpolar monomer this process offers a method of eliminating
many of the problems, which are encountered in bulk & solution polymerization, heat
removal in the former case & solvent reactivity & solvent removal in the latter.
Advantages:
Disadvantages:
For the polymers (synthetic elastomer) that are very soluble in their monomer,
stirring has to be extremely vigorous otherwise the partially reacted droplets
undergo agglomeration. For tacky polymers (such as synthetic elastomer) are
very prone to undergo agglomeration, so that suspension polymerization cannot
be used for the polymers.
The monomer recovery is very difficult.
Despite these disadvantages the suspension technique is used industrially, poly (vinyl
chloride) being produced by this method. In this process vinyl chloride monomer is
suspended in demineralised water to which gelatin has been added as suspending
agent & caproyl peroxide added as initiator. Polymerization takes place under an
atmosphere of nitrogen at 50 C, taking 12 hours to reach 85-90 % completion, at which
point reaction is stopped. Pure PVC is obtained from the suspension by centrifugation.
The primary product in the slurry units is HDPE with MDPE as a secondary product.
Chevron Philips, BP Solvay, Basell, Borealis & Sumitomo Mitsui have their own slurry
technology. Currently, long jacketed loop reactors & continuous stirred tank reactors
are mostly used for slurry polymerization.
ARDC/CS/Internal 57
A systematic loop reactors used for ethylene polymerization by solution polymerization
is shown below:
ARDC/CS/Internal 58
3.4. Emulsion polymerization
Emulsion polymerization is a complex heterogeneous polymerization that at present is
most widely used & important route to synthetic polymer colloid. This process is also
carried out in a water medium. An emulsifier either anionic or cationic soap, is added to
break the monomer into very small particles. The initiator is in solution in the water.
After polymerization, the polymer can be precipitated, washed & dried or the mixture
can be used directly. The major difference suspension with that of emulsion
polymerization is that in the latter case the monomer droplets are approximately 0.1 to
1mm in size & the particles in the former are 10-7 to 10-6 mm in size & second the
catalyst is dissolved in the aqueous phase in the latter but is incorporated directly into
the droplets in the former.
ARDC/CS/Internal 59
The continuous water phase is an excellent conductor of heat and allows the
heat to be removed from the system, allowing many reaction methods to
increase their rate.
Since polymer molecules are contained within the particles, viscosity remains
close to that of water and is not dependent on molecular weight.
The final product can be used as is and does not generally need to be altered or
processed.
The very small particles formed resist agglomeration thus allowing the
preparation of tacky polymers.
Inverse phase (water in oil) emulsion is possible.
The polymer is obtained in a convenient, easily handled, & often directly useful
form.
The first successful theory to explain the distinct features of emulsion polymerization
was largely developed by Smith and Ewart, and Hawkins1 in the 1940s, based on their
studies of polystyrene.
The following steps2 summarize the Smith-Ewart-Harkins theory for the mechanism of
free-radical emulsion polymerization:
A monomer is dispersed or emulsified in a solution of surfactant and water
forming relatively large droplets of monomer in water.
Excess surfactant creates micelles in the water.
Small amounts of monomer diffuse through the water to the micelle.
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A water-soluble initiator is introduced into the water phase where it reacts with
monomer in the micelles. (This characteristic differs from suspension
polymerization where an oil-soluble initiator dissolves in the monomer, followed
by polymer formation in the monomer droplets themselves.) The total surface
area of the micelles is much greater than the total surface area of the fewer,
larger monomer droplets; therefore the initiator typically reacts in the micelle and
not the monomer droplet.
Monomer in the micelle quickly polymerizes and the growing chain terminates. At
this point the monomer-swollen micelle has turned into a polymer particle. When
both monomer droplets and polymer particles are present in the system. More
monomer from the droplets diffuses to the growing particle, where more initiators
will eventually react.
Eventually the free monomer droplets disappear and all remaining monomer is
located in the particles. Depending on the particular product and monomer,
additional monomer and initiator may be continuously and slowly added to
maintain their levels in the system as the particles grow.
The final product is a dispersion of polymer particles in water. It can also be
known as polymer colloid, latex, or commonly and inaccurately as emulsion.
High molecular weights are developed in emulsion polymerization because the
concentration of growing chains within each polymer particle is very low.
ARDC/CS/Internal 61
3.5. Gas Phase Fluidized Bed Polymerization
Gas phase polymerization is the newest technology introduced for the manufacture of
polyolefins. It was developed for the production of polyethylene with the third
generation Ziegler Natta catalyst in the late 1960s. A gas fluidized bed reactor is widely
used in polymer industry for production of polyethylene due to the ability of operation at
lower pressure & temperature, no need of solvent using better solid mixing & heat
removal. In a gas phase reactor the polymerization takes place in a fluidized bed of
polymer particles. Inert gas or gas mixture is used for fluidization. The gas flow is
circulated through the polymer bed & a heat exchanger in order to remove the
polymerization heat.
The development of the gas phase technology represents a major advance for the
commercial production of polyolefins. A gas phase process avoids the problem of the
high cost remaining in the high mileage slurry & solution processes (associated with
recycling of diluents or solvent and drying of the polymer)
The first commercial gas phase HDPE plant using a fluidized bed reactor was
constructed by Union carbide in 1968 other gas phase polymerization processes using
different types of reactors have also been developed by BASF, Naphthachimie &
Amoco.
The gas phase polymerization of ethylene is typically carried out at 85-100 C under a
pressure of 20-25 atm. The ethylene monomer circulates, thus removing the heat of
polymerization & fluidizing the catalyst bed. In order to keep the temperature of the
process at values below 100 C, gas conversion is maintained at 2-3 per pass. In the
production of polypropylene by the gas-phase process usually the polymerization
temperature is lower & ranges from above 50 to 85 C& the pressure ranges from 15 to
40 atm.
ARDC/CS/Internal 62
Steps Involved in Polymerization:
1. Feed gases such as ethylene, butene or hexene, hydrogen etc are introduced to
the fluidized bed in the base of the gas phase reactor.
2. Catalyst is introduced to the reactor.
3. The exothermic heat of reactions controlled by the fresh feed gas circulation.
4. High reaction throughput rates & low conversion rates per pass typically
achieved- fed gases recycle through the reactor entering the base & exiting at
the top.
5. Granular PE product is produced in the reactor & intermittently discharged out of
the reactor into a purge bin, hydrocarbons are removed, granular materials
conveyed to pelletisation followed by pellet conveying to finishing area.
Although an innovative technology, the process for high-density polyethylene did not
offer clear economic advantages over the established slurry process. In the case of
linear low-density polyethylene, the fluidized bed process is competitive with the
solution & high-pressure processes, with lower capital & operative costs. In the case
of polypropylene industry uses two different methods for carrying out propylene
ARDC/CS/Internal 63
polymerization depending on the chosen method of heat removal. Use is made of
fluidized bed, as in the case of polyethylene manufacture, & of mechanically agitated
dry powder beds with evaporative cooling in vertical & horizontal autoclaves;
propylene is recycled by removal as condensed vapour & reintroduction into the
monomer feed. This has the effect of removing the majority of the heat of
polymerization.
In all these & other polymerization techniques, the ultimate properties of the
polymer such as molecular weight, molecular weight distribution, molecular structure
& chemical homogeneity are very much dependent on factors such as effective
removal of heat of polymerization, provision of proper residence time & effective
mixing to ensure uniform temperature profile & reactant distribution throughout the
system.
ARDC/CS/Internal 64
Comparison between the Different Polymerization Processes
Viscosity of the medium Viscosity of medium Viscosity of the medium does Viscosity of the medium
increases very rapidly & increases slowly but not not increases appreciably increases throughout the
at high conversion proper difficult to maintain proper polymerization.
mass transfer becomes mass transfer even at
difficult high conversion
Require longer duration Require longer duration Require longer duration for High conversion achieved
for high conversion for high conversion high conversion in shorter duration
Suitable for producing Suitable for producing low Suitable for producing Suitable for producing
medium to high molecular molecular weight medium to high molecular very molecular weight
weight products. products. weight products. products.
Most widely used in Suitable for free-radical, Suitable for free radical & Suitable for free radical &
industrial processes cationic, anionic & co- polycondensation polycondensation
involving free radical ordination polymerization polymerization. polymerization.
polycondensation &
polyaddition
polymerization.
Products is minimum Isolation becomes Isolation is easy as the Emulsion can be directly
contaminated, easy to difficult, products product is obtained as used for paints,
isolate & can be directly contaminated with solvent powder/beads & can be used adhesives & so on. Solid
used for molding products & solvent related for direct molding purposes. products can be isolated
impurities. by breaking the emulsion.
Product contaminated
with emulsifier, stabilizer
& so on.
ARDC/CS/Internal 65
Comparison of Different Polyethylene Processes
% Conversion per 17 - 20 5 97 95
Pass
Comonomers
4-Methylpent-1-ene
b) % Max
8 - 10 9 - 10 8 - 10 8 - 10
(gm/10 min)
ARDC/CS/Internal 66
4.0 Polyolefin Manufacturing Technologies
Global demand for polyethylene (PE) has grown quickly since its early days. The
primary reasons for this sustained growth are:
a) PE is a well-established plastic resin with a broad application range. Its use has
grown faster than overall economic growth worldwide.
b) PE continues to have the potential to replace traditional materials like glass,
wood, paper and metal. Today, the family of polyethylene resins represents the
largest single group of plastic materials produced and consumed in the world.
Not all organizations have the capabilities or want to invest in acquiring the capabilities
to develop process technologies. Instead, licensing third party technology enables many
organizations to utilize state-of-the-art process know-how to fulfill their resin needs or to
ARDC/CS/Internal 67
enter a particular market, without having to invest heavily in developing proprietary
process technologies.
High pressure LDPE production was first started in the 1950s and, while this technology
has been overshadowed in recent years by its LLDPE rival, processors still appreciate
LDPE's good optical and processing qualities.
Two basic processes are available for the production of low density polyethylene:
stirred autoclave or tubular routes. The tubular reactor has been gaining preference
over the autoclave route due to its higher ethylene conversion rates. The reaction is
carried out using a free radical initiator consisting of one or two peroxides with or
without oxygen. The processes can generally be used to make copolymers with polar
comonomers, such as EVA polymer.
ARDC/CS/Internal 68
termination. Another free radical step, which has an immense importance as far as
polymerization of LDPE is concerned, is the chain transfer reactions. In this step the
active free radical sites at the ends of growing chains jump to another site on the same
polymer molecule, another polymer molecule, or a solvent, monomer, or a modifier.
Chain transfer affects the size, structure, and end groups of the polymers. The chain
transfer agents are those that can donate hydrogen atoms during the reaction.
Peroxide type and concentration, as well as reactor temperature, control the initiation
rate. The propagation rate increases with pressure and temperature. The rate of chain
termination is controlled by free radical concentration and by the amount of chain
transfer agent present in the reaction mixture.
ARDC/CS/Internal 69
In the high-pressure LDPE process, the molecular weight of the individual polymer
chains is not uniform. The breadth of this molecular weight distribution depends on the
reactor process (tubular or autoclave) and can be further influenced by the reaction
conditions.
Process Overview
The overall processes for the tubular reactor and the autoclave reactor systems are
very similar except for the design of the reactor system itself. The two reactor
technologies have the capabilities of producing different products for different end-use
markets.
The main steps occurring during the process include the following:
ARDC/CS/Internal 70
Tubular Reactor Features
The tubular reactor is essentially a plug flow reactor. Multiple peroxide injection points
are used along the length of the reactor to maximize conversion of ethylene to LDPE
and optimize product properties.
ARDC/CS/Internal 71
Since the autoclave is an adiabatic CSTR, addition of the cooler, fresh feeds of ethylene
balances the heat of polymerization.
ARDC/CS/Internal 72
Homopolymer LDPE ranging from 0.915 to 0.935 g/cm3 density
EVA copolymers up to greater than 30 wt % vinyl acetate content
Very-high-clarity grades for specialty film applications
Process overview
The Lupotech T process is the leading high pressure tubular reactor process for the
production of low density polyethylene (LDPE) and Ethylene Vinyl acetate copolymers
(EVA). Worldwide over 50 licenses for this technology with a total capacity of over six
million tones per year have been granted with single line capacities of up to 400kt/a.
Products from the Lupotech T process cover the whole range of melt flows and
densities, and can be used for all LDPE applications including the wide range of EVA
grades.
High pressure tubular reactors are offered in two generally different forms, shown in the
figures. In a TS reactor the total ethylene flow from the hyper-compressor is preheated
to 150-180C and fed to the inlet of the first reaction zone. Reaction is initiated by
injection of organic peroxides. As the reaction mixture cools after the first reaction peak,
additional peroxide initiator is added to start a second reaction zone. There can be
further peroxide injection points giving a total of three to five reaction zones.
In a TM reactor (multiple cold gas injection) the compressed ethylene is split into
several streams and fed into the reactor at a number of positions. 40 to 70% of the total
ethylene is preheated to 150-180C before addition of peroxide that, together with the
oxygen, sets off the first reaction zone. The other 30-60% of the ethylene is cooled and
further split into more or less equal quantities that are injected at different locations
along the reactor. Together with addition of initiator this results in the desired number of
reaction zones.
ARDC/CS/Internal 73
ARDC/CS/Internal 74
Products and Applications
LDPE
Film
Wide range of film applications include shrink and heavy-duty packing films, films
for laminates, carrier bags, composite and crack films, deep freeze bags and
agricultural films. Injection molding & blow molding
Enhanced technical properties include flowability, rigidity and stress cracking
resistance
Full range of grades includes specialty products for high purity pharmaceutical
applications and good organoleptic properties.
Pipe Coating
Corrosion protection properties with a well-balanced property profile for long term
durability, excellent processing, high mechanical strength and chemical resistance
Broad applications including power cables, insulation for coaxial cables and
telephone cable cores and sheathing materialInsulation for 1kV overhead cables and
conductive compounds
Very high resistance to environmental stress cracking
ARDC/CS/Internal 75
Linear Low Density and High density Polyethylene
Production Technology
4.1.3. Spherilene Technology from Basell
Basells Spherilene technology is an advanced gas phase process platform for the
production of polyethylene. The process can be used to produce the entire range of
linear polyethylene grades using a single catalyst system with true swing capability. The
product range includes linear low density polyethylene (LLDPE), medium density
polyethylene (MDPE) and high density polyethylene (HDPE). Premium bimodal grades
for demanding applications such as pressure pipes and high strength film are the
highlights of the Spherilene process.
ARDC/CS/Internal 76
Process Parameters Features
Process Advantages:
a) Versatility
Continuous operation, swing capability between LLDPE and HDPE using a single
family of Avant Z Ziegler catalysts
Spherilene S configuration with a single fluidized bed gas phase reactor provides
a low investment and operating cost option for production of a focused range of
polymers with monomodal molecular weight distributions
Spherilene C configuration with two fluidised bed gas phase reactors in cascade
provides the broadest range of ethylene polymers, including premium bimodal grades
c) Reliability
ARDC/CS/Internal 77
d) Quality
Complete low pressure PE product portfolio with a density range from 0.915
to 0.962 g/cm3
Excellent process stability
Superior quality with minimum property variation
High first pass prime with low off-spec production
MDPE
HDPE
Injection molding
Raffia, fiber and filament
Blow molding
Bimodal Film
PE80 and PE100 pipe
ARDC/CS/Internal 78
4.1.4. Hostalen Technology from Basell
Process overview:
ARDC/CS/Internal 79
Process Parameters Features
Process advantages
No undesired by-products
Reduced resource consumption and lower emissions through closed-loop
hexane system during polymerization
c) Production costs
d) Design Flexibility
e) Process Versatility
f) Product Quality
g) Economical
ARDC/CS/Internal 80
Cash cost advantages over other processes for bimodal HDPE production
Outstanding HDPE resins can be sold at higher business margins
Monomer purification unit not required if monomer is delivered from a state of-
the-art cracker
ARDC/CS/Internal 81
4.1.4. Sclairtech LLDPE/HDPE Swing Technology
from Nova Chemicals
Process overview:
Sclairtech technology offers polyethylene producers a unique and flexible way to grow
with their emerging market needs. The versatile solution process technology allows
resin manufacturers to participate in all market segments by economically producing, on
a single line, LLDPE and HDPE grades across a very wide range of melt indices, by
utilizing butene or octene comonomer. Resins can also be designed with a molecular
weight distribution from narrow to broad, according to the needs of the processor and
the application. The unique tailoring capability of the technology provides the ability to
produce high performance resins to meet the customer needs in diverse market
segments.
ARDC/CS/Internal 82
Product Capability:
VLDPE Specialties
LLDPE Film
Extrusion Coating
Wire and Cable Jacketing
Rotomolding
Injection Molding
Pipe/Pipe coating
MMWHDPE Film
Blow Molding
Nonwovens
ARDC/CS/Internal 83
4.1.5. Mitsui CX Process
Process Overview:
It is a bimodal slurry phase process to produce high quality HMW-HDPE for Ultra-thin
film, Small & Large blow molding and Gas/Water pipes.
A Mitsui plant generally consists of the following sections:
Catalyst/Co-catalyst handling & metering
Product homogenization
ARDC/CS/Internal 84
The presence of two CSTR in a Mitsui line creates two possible routes of
polymerization:
a) Parallel Polymerization Route where the two reactors are connected in parallel
with respect to each other as shown below:
Reactor - 1 Second
Flash Centrifuge For Drying /Extrusion
Drum
Reactor - 2
Under parallel polymerization route again there are two different modes of operation:
b) Series Polymerization Route where the two reactors are connected in series with
respect to each other as shown below:
Second Flash
For Drying / Centrifuge
Drum
Extrusion
ARDC/CS/Internal 85
Operating Conditions are different in both reactors
MFR/Density different in both reactors
Used for Broad MWD
Co-monomers: C4, C6
Product Capabilities
The CX Process can provide resins t6o suit a wide variety of applications by simply
changing the operating conditions of the reactor system without a catalyst change. CX
products cover all important applications of CX products as mentioned below:
Ultrathin film
Heavy-duty bags
Bleach and detergent bottles
Automobile fuel tanks
Large Industrial containers
Telecom cable insulation
Gas pipes
High Pressure water pipes
Beer crates & vegetable containers
Rope & nets
Tape
ARDC/CS/Internal 86
4.1.6. Slurry-Loop-Reactor Technology from Chevron
Phillips
Process Overview:
Since the PE particles do not reach temperatures high enough to go into solution, they
form discrete white particles the size of sand that form a slurry in the liquid isobutane.
The separation of the polymer particles from the slurry is done by allowing a slipstream
of reactor slurry to leave the process and drop from 40 kg/cm2 pressure to almost
atmospheric pressure. This pressure drop vaporizes the isobutane diluent, whereas the
remaining polymer particles drop by gravity into a fluidized bed of polymer particles,
where most of the remaining hydrocarbons are removed by a countercurrent flow of
nitrogen.
After drying the polymer particles are pneumatically conveyed to the extruder,
additivated with small amount of special chemicals and pelletized.
ARDC/CS/Internal 87
Process Parameters Features
Unimodal Product
Ease of Operation - Loop Structure Ideal for
Pressure:~ 39bar, Temp. : 100 150C Removal of Heat
Solvent: Isobutane Product Strengths HDPE Pipe & HDPE Blow
(Marlex Grades)
Catalyst: Chromium oxide based catalyst
Single Reactor Process Tailoring of MWD
Co-monomers: C4,C6 difficult
ARDC/CS/Internal 88
4.1.7. Borstar Loop-Gas Technology from Borealis
Process Overview:
The process starts when catalyst is fed into the loop reactor. With Borstar, no further
addition of catalyst is required for the gas-phase reactor.
The loop reactor can be run in a stable manner due to the use of supercritical propane
as the polymerization medium. The special conditions also significantly reduce reactor
fouling. This key advantage comes from reduced polymer solubility above the critical
point.
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Process Parameters Features
Bimodal Product
Pressure: ~ 65,20bar, Temp. : 80C Tailored MWD possible
Solvent : Propane Pdt. Strengths Broad MWD Frac. MFI
LLDPE Film, HDPE BM
Catalyst: Ziegler Natta
Weakness High Haze in LLDPE Film
Co-monomers: C4
With Isobutane, as used in other processes, Polymer solubility is higher. This increases
the risk of reactor fouling and limits the density range that can be achieved.
Separate control of the two reactors is at the very heart of Borstar benefits. The resin's
modality is easily controlled, whether unimodal or bimodal.
For bimodal polymers, low molecular weights are formed in the loop, while high
molecular weights are formed in the gas-phase reactor. And the same high production
rates are possible with unimodal resins.
It's also possible to manipulate the comonomer content between the two reactors for
bimodal polymers. Increasing this content in the gas phase reactor - where the high
molecular weight fraction is produced - provides softness, higher impact resistance and
improved sealability.
a) Borstar yields a number of special property and structural benefits. These include
high environmental stress-cracking resistance (ESCR), low shrinkage and long-term
creep/burst resistance.
Borstar PE Products
Film
Pipe
Extrusion coating
Injection Molding
Wire and cables
Blow Molding
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4.1.8. Unipol PE Gas Phase Process
Process overview
The process requires high degree of purity of the raw materials and polymer grade
ethylene. Raw material purification steps involve the use of molecular sieves, guard
beds, etc.
The reaction system can be subdivided into several sections: reaction loop, catalyst
feeding, and product discharge and separation.
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4.2. Polypropylene Technologies
The first commercial production of polypropylene was in the 1950s following the
discovery of Ziegler-Natta catalysts. Since then, the process technology for PP
manufacture has kept pace with catalyst advances and the development of new product
applications and markets. In particular, the relationship between process and catalyst
technology was clearly symbiotic and that of a partnership. Advances in one technology
had always exerted a strong push-pull effect on the other to improve its performance.
The progress in process technology has resulted in process simplification, investment
cost and manufacturing cost reductions, improvement in plant constructability,
operability, and broader process capabilities to produce a wider product mix.
The PP industry is exciting and will continue to grow globally at a rate attractive to
making new investments. This is at par with the growing global demand of PP resin as
shown in the graph below:
Obviously the industry is highly competitive and the resin customers have high
expectations. To favorably compete and to satisfy customers, PP producers must have
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access to world-scale technology when new investment is being considered. The
criteria for world-scale technology are the following:
Today, more companies use Spheripol technology than the technologies of the three
closest competitors combined. More than 20 million tonnes of Spheripol process
capacity have been licensed worldwide. The capabilities of the Spheripol process have
been further enhanced using the latest-generation catalyst technology, which has the
ability to produce new families of reactor-based products with improved properties.
Process Overview:
The Spheripol process is a modular technology. In its most widely adopted configuration
the polymerization section involves the following main units:
Catalyst feeding
Polymerization
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- Gas-phase polymerization (heterophasic impact and specialty copolymer) - option
(gas-phase copolymer unit can be added at a later stage without affecting initial plant
configuration or involving significant implementation costs)
Finishing
The catalyst system used in this process is Ziegler Natta type. It is composed of three
basic parts: (1) a solid catalyst, generally TiCl4 supported on MgCl2; (2) stereoregulating
agents, an internal and external Lewis base; and (3) an aluminium alkyl.
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Spheripol Process
Process Advantages
c) Versatility
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d) Quality
e) Design flexibility
Proven, single line capacities, from 40 to 550 kTA/a are available for
homopolymer, random copolymer or heterophasic impact copolymer
production
Tailored design for chemical or polymer grade monomer feedstock
f) Modular installation
50% average expansion of the initial capacity of existing plants that are
in operation for more than 10 years
Expansion achievable through minor adjustments
Extension of product range by introducing Metallocene PP technology
as an add-on technology
Flexible modular design has very low impact on investment costs
Random copolymers can be produced with excellent optical properties and seal
initiation temperatures in compliance with the U.S. Food and Drug Administration (FDA)
regulations for food contact.
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Thermoformed containers
Blow-molded bottles and parts
With its ability to drive products to new extremes in properties and performance, the
technology continues to emerge as the new benchmark for polypropylene production.
Spherizone technology-based resins have the potential to enlarge the market for
polypropylene into entirely new application areas.
Process Overview:
Polymerization
Finishing
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The catalyst system used in this process is Ziegler Natta type. It is composed of three
basic parts: (1) a solid catalyst, generally TiCl4 supported on MgCl2; (2) stereoregulating
agents, an internal and external Lewis base; and (3) an aluminium alkyl.
Process Advantages:
Basells process technologies have a safety record among the best in the
industry
Structurally identical to the Spheripol process, Spherizone has shown high
reliability
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b) Reducing resource intensity
c) Versatility
d) Quality
e) Design flexibility
f) Modular installation
Flexible modular design, allowing low cost addition of a fluidized bed gas-phase
reactor for heterophasic impact copolymers
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Products and applications
Typical customers manufacturing processes and end uses include:
Film extrusion
MuItifilaments
Nonwovens (meltblown and spunbonded)
Injection molding
Blow molding
Profile extrusion
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4.3.3. Chisso Gas Phase PP Process
Press Overview:
Chisso Gas Phase Polypropylene Process features the use of a horizontal agitated
reactor and the high performance JPP Catalyst. This process provides high
performance and wide-ranging products with competitive investment and operation
costs. The right of license was given to Japan Polypropylene Corporation (JPP),
which is a PP joint venture between Chisso and Mitubishi Chemical Corporation.
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Comparison between CSTR and Chisso Horizontal Reactor
Special features:
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Importance of Plug Flow Characteristics for Impact Copolymer
High Activity
High & Tailored Stereo-Regularity
Excellent Morphology, Less Fines
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Integration of Catalyst, Polymerization & Manufacturing Technologies of JPP bring
Superior Product
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Product Attributes
Homopolymers
Injection molding
Blow molding
Thermoforming
Sheet
Tape (raffia)
Fiber
Cast and BOPP films
Profile extrusion
Random copolymers
Impact Copolymers
Automotive parts
Appliances
House wares
Rigid packaging
Injection molding Thermoforming
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4.3.4. Unipol PP Technology from Dow
Process Overview:
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Catalyst system available from Dow is high-activity Ziegler-Natta-based catalysts
supported on MgCl2. An aluminium-alkyl is used as a co-catalyst. Internal and external
donors are used to vary isotacticity and molecular weight distribution.
The UNIPOL PP Process offers a broad and competitive product capability, including
homopolymer, random copolymers using ethylene or butene, and impact copolymers.
The advanced technology of the UNIPOL PP process is easy to operate, highly reliable,
and provides high product consistency.
Random Copolymers
Impact Copolymers
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5.0. Polyolefin Processing & End-Use Products
A large part of polymer processing technology can be summed up in the statement: get
the shape then set the shape. The general techniques, which are followed for shaping
polymers, include:
The term polymer includes elastomers, plastics & fibers. Here different plastic
processing techniques & plastic end use products would be discussed.
Out of the six polymer processing techniques, the first one, which involves the
deformation of polymer melts, is the most widely used technique in plastic industry.
The reason for this may be as follows:
a) Easier processability of polymer melts in terms of mixing with additives & the final
shaping operation.
b) Simplicity in designing the melt processing equipments as compared to the other
techniques.
c) Lower energy consumption during polymer melts processing.
Deformation of a polymer melt can be done conveniently through extrusion, various
molding operations & sometimes a combination of both the technologies.
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be sized, drawn down, corrugated, etc., to modify & control the shape & dimension
of the section & in some cases the properties (mechanical, optical, etc.). The
process of extrusion is carried out in equipment called extruder.
The screw is the most important component of the extruder. There are five possible
zones in a thermoplastic screw. Since terminology is not standardized in the industry,
different names may refer to these zones. Different types of polymer will have differing
screw designs, some not incorporating all of the possible zones.
a) Feed zone - Also called solids conveying zone. This zone feeds the resin into
the extruder.
b) Melt zone - Also called the transition zone. The resin is melted in this section.
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c) Pressurizing zone - Also called metering or melt conveying. This zone gives
the plastic uniform pressure and flow characteristics.
d) Devolatization zone - In this zone, the melt is unpressurized, allowing trapped
gases to escape and be vented out.
e) Mixing zone -There are two types of mixing zone. They either distribute small
particles evenly, or break large particles into small ones, which can then be
mixed.
The material enters through the feed throat (an opening near the rear of the barrel) and
comes into contact with the screw. The rotating screw (normally turning at up to 120
rpm) forces the plastic beads forward into the barrel, which is heated to the desired,
melt temperature of the molten plastic (usually around 200 C/400 F). In most
processes, a heating profile is set for the barrel in which three or more independently
controlled heaters gradually increase the temperature of the barrel from the rear (where
the plastic enters) to the front. This allows the plastic beads to melt gradually as they
are pushed through the barrel and lowers the risk of overheating which may cause
degradation in the polymer. Extra heat is contributed by the intense pressure and
friction-taking place inside the barrel. In fact, if an extrusion line is running a certain
material fast enough, the heaters can be shut off and the melt temperature maintained
by pressure and friction alone inside the barrel. In most extruders, cooling fans are
present to keep the temperature below a set value if too much heat is generated.
At the front of the barrel, the molten plastic leaves the screw and travels through a
screen pack to remove any contaminants in the melt. The screens are reinforced by a
breaker plate (a thick metal puck with many holes drilled through it) since the pressure
at this point can exceed 5000 psi (34 MPa). The screen pack/breaker plate assembly
also serves to create backpressure in the barrel. Backpressure is required for uniform
melting and proper mixing of the polymer. This breaker plate also does the function of
converting "rotational memory" of the molten plastic into "longitudinal memory"
After passing through the breaker plate, the molten plastic enters the die. The die is
what gives the final product its profile and must be designed so that the molten plastic
evenly flows from a cylindrical profile, to the product's profile shape. Uneven flow at this
stage would produce a product with unwanted stresses at certain points in the profile.
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These stresses can cause warping upon cooling. Almost any shape imaginable can be
created so long as it is a continuous profile.
The product must now be cooled and this is usually achieved by pulling the extrudate
through a water bath. Plastics are very good thermal insulators and are therefore
difficult to cool quickly. Compared with steel, plastic conducts its heat away 2000 times
more slowly. In a tube or pipe extrusion line, a sealed water bath is acted upon by a
carefully controlled vacuum to keep the newly formed and still molten tube or pipe from
collapsing. For products such as plastic sheeting, the cooling is achieved by pulling
through a set of cooling rolls.
2. The extrusion process is well suited to short production runs. The tooling costs are
low and the production change over down time between different sections is very short.
Therefore either long or short production runs are both practical and economical using
the extrusion process.
3. The tooling charges for a set of extrusion dies are very modest when compared to the
set up costs for rolling, casting and forging. Extrusion production lead times can be
relatively short. Overall production times and costs can be significantly reduced,
compared to other methods of manufacture by reducing or even eliminating machining
and finishing operations
A. Films
Film
1. Blown Film
One of the most common methods of film manufacture is Blown Film (also referred to as
the Tubular Film) Extrusion. The process involves extrusion of a plastic through a
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circular die, followed by "bubble-like" expansion. The principal advantages of
manufacturing film by this process include the ability to:
Produce tubing (both flat and gussetted) in a single operation
Regulation of film width and thickness by control of the volume of air in the
bubble, the output of the extruder and the speed of the haul-off.
Eliminate end effects such as edge bead trim and non uniform temperature that
can result from flat die film extrusion.
Capability of biaxial orientation (allowing uniformity of mechanical properties)
Blown Film Extrusion can be used for the manufacture of co-extruded, multi-layer films
for high barrier applications such as food packaging.
Polyethylenes (HDPE, LDPE and LLDPE) are the most common resins in use, but a
wide variety of other materials can be used as blends with these resins or as single
layers in a multi-layer film structure. These include PP, PA, EVOH. In some cases,
these materials do not gel together, so a multi-layer film would delaminate. To
overcome this, small layers of special adhesive resins are used in between. These are
known as tie layers.
Blown film can be used either in tube form (e.g. for plastic bags and sacks) or the tube
can be slit to form a sheet.
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Industrial Packaging
Consumer Packaging
These include the packaging film for frozen products, shrink film for transport
packaging, food wrap film, packaging bags, or form, fill and seal packaging film and
carry bags.
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Laminating film
Polyolefin films are used for laminating aluminium or paper used for packaging
condensed milk or coffee.
Barrier film
These films, made of raw materials such as polyamides and EVOH acting as an aroma
or oxygen barrier, are used for packaging food, e.g. cold meats and cheese.
Agricultural film
Films such as greenhouse film, crop forcing film, silage film, and silage stretch films are
used in agricultural applications.
2. Cast Film
The cast film process involves the extrusion of polymers melted through a slot or flat
dies to form a thin, molten sheet or film. This film is "pinned" to the surface of a chill roll
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(typically water-cooled and chrome-plated) by a blast of air from an air knife or vacuum
box. The film quenches immediately and then has its edges slit prior to winding.
Because of the fast quench capabilities, a cast film generally has much better optics
than a blown film and can be produced at higher line speeds. However, it has the
disadvantage of higher scrap due to edge-trim, and very little film orientation in the
cross-direction.
Cast films are used in a variety of markets and applications, including stretch/cling films,
personal care films, bakery films, and high clarity films.
The most common manufacturing BOPP film is produced by the tubular process, in
which a tubular bubble is inflated or a tentor frame process, in which a thick extruded
sheet is heated to the softening point & is mechanically stretched by 300-400%.
Stretching in the tentor frame produced is usually 4.5:1 in the machine direction & 8:1
in the transverse direction.
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BOPP tenter line production
A. Extruder
B. Melt pump
C. Chill roll
D. Stretching in machine direction
E. Stretching in cross direction
F. To winding euipment
In the double bubble process, a cast tube is blown into a large bubble with
simultaneous stretching in both directions to produce a balance film. This processs is
used to make heat-shrink films as well as standard BOPP films.
Biaxially oriented films are used in food packaging & are replacing cellophane in
application such as snack & tobacco packaging due to favorable properties & low cost.
Oriented films are used as heat shrinkable films in shrink-wrap application.
The tubular water quench process combines the airblown process with chill roll or
conventional water bath and includes drawing a bubble of molten film to a desired
diameter.
Among the different techniques commercially available is shell Tubular Quench (TQ)
process, which involves downward extrusion from an annular die followed by rapid
cooling on water-covered converging boards. At the same time the tubular molten film is
inflated with air in the normal way to give it the required layflat width and thickness.
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Another process known is the Dow-Taga process. In this process, the blown film goes
Through a hollow ring where it is coated with a film of water, which flows from the ring
and on to the film before it, is collapsed. The water film that runs down the converging
boards shock cools the film and causes rapid crystallites formation and hence the
formation of small spherulites with a consequent increase in clarity.
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Among the advantages of the water-cooled tubular process mentioned above are
(1) Low cost,
(2) Ease of conversion into bags and
(3) Flexibility of operation.
These factors have been largely responsible for the large-scale penetration of low-
density PP films into packaging markets. Techniques of water-cooling tubular PP film,
however, have opened up ways of producing clear films, with greater toughness and at
no greater cost than cast PP (CPP) films.
Application: General purpose packaging films such as for garments bags, food
packaging, and other transparent packaging bags.
Pipes
Polyethylene pipes account for a large number of applications and are slowly but
steadily replacing PVC pipes from their application domains. The common applications
of polyethylene pipes include pressure pipes, sprinkler irrigation, gas pipes, drip lateral
pipes and PLB ducts.
Sprinkler Irrigation
Gas Pipes
Pressure pipes
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Drip Laterals
PLB Ducts
The pipe extrusion process involves forcing the polymer melt through a circular die. The
general steps of pipe extrusion can be summarized as below:
Polymer granules are fed into the hopper & conveyed by a rotating screw through a
long cylindrical barrel.
This is then subjected simultaneously to high temperature and pressure, forcing the
melt through the die at a predetermined rate.
The extrudate from the die is sized, cooled and the formed pipe is pulled to the winder
or a cut off device with the aid of haul off device.
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Profiles
To manufacture plastic pipe, industry uses a process known as Profile Extrusion.
This process is used to manufacture plastic products with a continuous cross-
section such as; drinking straws, decorative molding, window trimming and a wide
variety of other products polymer melt into the hollow mold cavity under high
pressure.
The plastic is fed in pellet form into the machines hopper (this machine is known as
an Extruder), the material is conveyed continuously forward by a rotating screw
inside a heated barrel being softened by both friction and heat. The softened plastic
is then forced out through a die and directly into cool water where the product
solidifies. From here it is conveyed onwards into the take-off rollers, which actually
do the pulling of the softened plastic from the die.
The die is a metal plate placed at the end of the extruder with a section cut out of its
interior, this cutout, and the speed of the take-off rollers, determines the cross-
section of the product being manufactured. A simple way to understand this
concept is to consider squeezing a toothpaste tube, the product comes out in a
solid rod because of the opening at the end of the tube, if that opening had a
different cross-section than the product produced would take on that new cross-
section.
Typical Materials for Plastic Profiles: HDPE (High Density Polyethylene), LDPE (Low
Density Polyethylene), LLDPE (Linear Low Density Polyethylene), PETG, Flexible PVC,
Butyrate, Polypropylene Polystyrene ABS
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Advantages
Disadvantages
Sheet Extrusion
Sheet extrusion is a technique for making flat plastic sheets from a variety of resins. The
thinner gauges are thermoformed into packaging applications such as drink cups, deli
containers, produce trays, baby wipe containers and margarine tubs. Another market
segment uses thick sheet for industrial and recreational applications like truck bed
liners, pallets, playground equipment and boats. The third primary use for extruded
sheet is in geomembranes, where flat sheet is welded into large containment systems
for mining applications and municipal waste disposal.
Solid sheet extrusion units consist of at least one extruder and one sheet extrusion die.
They are followed by the polishing stack, in general comprising 3 calenders, calibrating
and cooling the sheet with their surfaces or calender nips. Behind this the roller
conveyor and the draw-off rolls for air cooling are located. The sheet is finally cut and
stored.
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Materials: Polystyrene continues to be the most common polymer for use in sheet
extrusion. It is the dominant material for thermoformed packaging and competes with
ABS and PP in technical markets. End use applications include tubs and pots for yogurt,
margarine, and desserts. Thermoformed packaging is also used in many other
applications in the food industry.
Applications
Within the building and construction industries, sheet extrusion is used for a variety of
applications. One of the main uses of extruded PS sheet is for thermal insulation
materials for walls, roofs, and under floors.
In the automotive industry, sheet is currently used to produce interior trim, panels, and
dashboards. Foamed polyolefin sheet, both cross-linked and non-cross-linked, is also
used in automotive applications.
There are a number of other applications where thermoformed sheet plays a significant
role. These include the manufacturing of luggage, refrigerator liners, and shower units
The figure shows a block diagram of a crosshead extrusion operation with typical
equipment in the line
Unwind station or other wire or cable source to feed the line
Pretensioning station to set the tension through out the process
Preheat station to prepare the wire for coating
Crosshead die
Cooling trough to solidify the polymeric coating
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Test station to assure the wire is properly coated
Puller to provide constant tension through the process
Winder to collect the product
Typical polymers used in wire coating application are Polyethylene, PVC, Polyamide,
Polybutylene terepthlate, Thermoplastic elastomers, ethylene propylene, and
fluropolymers.
These polymers are chosen because of their electrical properties, flexibility, & durability.
Cross linked polyethylene is used in wire coating operation.
Stretch tapes:
Slit film tapes made of polyolefin's such as polypropylene (PP), high density
polyethylene (HDPE) and linear low density polyethylene (LLDPE) and other similar
polymeric materials ate well known and have several applications. The major area of
application includes woven sacks, large industrial sacks and packaging fabrics, geo-
textiles, ropes and twines and miscellaneous industrial woven fabrics.
Slit film tapes can be produced from extruded cast flat or tubular (blown) film. . The
majority of slit film tapes are made from cast films. In this method desired orientation in
slit film tape is accomplished through a series of rollers with increasing speeds and
increasing temperature. After the slit film tapes have been stretched in the machine
direction, they may be reheated on a set of heated rollers and cooled on a set of cooled
rollers to reduce residual shrinkage.
The molten polyolefin is extruded through a suitable extrusion die to form sheet of
required thickness that is suitably cooled by a device like water- quench or chilled
roll(s). Then the substantially amorphous sheet is transported under tension to a
suitable slitting device to be slit into film tapes. The slit film tapes are mono-axially
oriented by drawing in a longitudinal direction, under heated conditions, to arrive at slit
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film tapes which can be defined in terms of an orientation ratio, sometimes also referred
to as the draw or stretch ratio. The unstretched slit film tapes are heated by means of
hot air oven to a temperature just below softening temperature during the drawing or
stretching process & then winding the slit film tapes; characterized in that before the
stretching step, it has a stage of pre-stretching made by passing the slit film tapes
through one set of heated holding rollers turning at a given speed and one set of cooled
pre-stretch rollers turning faster than the heated holding rollers, wherein at least one of
the rollers of the set of holding rollers is heated and at least one of the rollers of the set
of pre-stretch rollers is cooled.
Extruded flat film Slit to flat tapes Stretched hot oven/bed Wound In
Bobbins Woven in circular /Flat looms Coated / Stitched / Printed for
bags
Applications :
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Monofilaments
Monofilament fabrics are constructed from monofilament yarns, recognized by most
people for their use in fishing or weed-wacker line. Monofilament yarn size range, in
nominal diameter, from0.001 (25 microns) up to 0.040 (1,000 microns) and very
consistent in diameter, with the exception of polypropylene which is difficult, to spin
(extrude) without diameter variation.
However the manufacturing process is similar to that of stretch tapes except with a
difference of die type & the processing parameters. The die, which is used in the
monofilament, is a circular die with large number of holes of specified dimension.
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Yarn from the die
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5.2 Plastic Molding Process
Molding is the process of rendering shape to materials by the allowing the plastic melt
to flow, mostly under pressure, into a solid and confined framework called mold.
It is a fast process and is used to produce large numbers of identical items from high
precision engineering components to disposable consumer goods.
Equipments design
The injection system consists of a hopper, a reciprocating screw and barrel assembly,
and an injection nozzle the plasticizing screw, a barrel, band heaters to heat the barrel,
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a stationary platen, and a movable platen. This system confines and transports the
plastic as it progresses through the feeding, compressing, degassing, melting, injection,
and packing stages
The process of injection molding can be reduced to four simple individual steps:
Plasticizing, Injection, Chilling, and Ejection. Each of those steps is distinct from the
others and correct control of each is essential to the success of the total process.
Plasticizing - describes the conversion of the polymer material from its normal
hard granular form at room temperatures, to the liquid consistency necessary for
injection at its correct melt temperature.
Injection - is the stage during which this melt is introduced into a mold to
completely fill a cavity or cavities.
Chilling - is the action of removing heat from the melt to convert it from a liquid
consistency back to its original rigid state. As the material cools, it also shrinks.
Ejection - is the removal of the cooled, molded part from the mold cavity and from
any cores or inserts.
Process Parameters
Advantages
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Highly repeatable process
Almost all thermoplastic & some thermoset can be used
Highly automated, little post-molding finishing required
Direct route from raw material to finished parts.
Disadvantages
Large Crates: Jumbo Crates for Agriculture, Industrial & Retail sectors
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Caps & Closures
It is best suited for basically hollow parts (such as plastic bottles) with uniform wall
thicknesses, where the outside shape is a major consideration.
Polypropylene PP
Polyethylene PE
Polyethylene - Terephthalate PET
Polyvinyl chloride PVC
HDPE
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Equipments design:
There are basically three types of blow molding used in the production of plastic bottles,
jugs and jars. These three types are:
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1. Extrusion blow molding
In extrusion blow molding the parison is formed by forcing molten plastic through
an annular orifice in a die that is part of the die head assembly. The orifice is
formed by the space between the mandrel and the die. Extrusion may be directly
from an extruder, or for large parts for which more material is needed than the
extruder can continuously provide an accumulator is used.
The parison is extruded and drops to between the mold halves and when the
mold closes the parison is sealed. Air injected into the parison inflates it to the
shape of the mold cavity. After cooling and solidification the mold is opened and
the part removed.
Process steps
Step 4. Mold halves open, Blow molding part ready for ejection
After a cooling period the mould is opened and the final article is
ejected. To speed production several identical moulds may be fed in
cycle by the same extruder unit.
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Advantages of Extrusion Blow Molding:
Process Steps
Step 1. Injection
The injection blow molding machine is based on an
extruder barrel and screw assembly which melts the
polymer. The molten polymer is fed into a manifold
where it is injected through nozzles into a hollow,
heated preform mould. The preform mould forms the
external shape and is clamped around a mandrel (the
core rod), which forms the internal shape of the
preform. The preform consists of a fully formed
bottle/jar neck with a thick tube of polymer attached,
which will form the body.
Step 2. Blowing
The preform mould opens and the core rod is rotated
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and clamped into the hollow, chilled blow mould. The
core rod opens and allows compressed air into the
preform, which inflates it to the finished article shape.
Step 3. Ejection
After a cooling period the blow mould opens and the
core rod is rotated to the ejection position. The finished
article is stripped off the core rod and leak-tested prior
to packing. The preform and blow mould can have
many cavities, typically three to sixteen depending on
the article size and the required output. There are three
sets of core rods, which allow concurrent preform
injection, blow molding and ejection
Stretch blow molding produces a part with biaxial molecular alignment. In the
process a preform, or parison, elongated mechanically in the mold and than
expanded radially in a blowing process. A desirable resulting molecular
orientation yields a material with increased strength. This means that products
that are strength-based designs can be produced using less material than if they
were to be produced using simpler blow molding techniques.
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A goal in stretch blow molding is a designed work material developed by
producing desirable molecular orientation. In order to produce and retain desired
structure and specified properties the stretching and blowing processes need to
be carried out at temperature lower than in other blow molding processes and the
allowable temperature range will be smaller and so more difficult to control. A
temperature conditioning station in-line is required, or a re-heating operation
needed for preforms allowed to cool before use or for purchased preforms. This
increased the difficulty of process design and operation and material specification
since polymer properties depend on temperature history, e.g., on temperature,
time at temperature and number of temperature cycles
Process parameters
The main process parameters for extrusion blow molding are those that affect parison
geometry and mechanical properties. Parison geometry is determined by material flow
during extrusion and as the forming parison drops between the mold plates. The
machine parameters that affect material flow and so control parison formation are
Melt temperature
Extrusion ram speed or extrusion pressure
Mandrel and die bushing diameters, orifice size
o Change in orifice during extrusion - parison programming
Mandrel-die shape - exit angle
Mandrel tapered area surface area
Mandrel-die alignment
o Parison wall thickness can be altered slightly by offsetting
To account for part asymmetry
May result in parison curvature
Disadvantages:
Blow molding is used to make many plastic containers, including soft-drink bottles, jars,
detergent bottles, and storage drums.
ARDC/CS/Internal 135
5.2.3 Roto Molding
Rotational molding is a process by which hollow objects can be manufactured from
thermoplastics and occasionally thermosets.
Roto molding is a cost-effective way to produce large parts. With roto-molding process it
is possible to create one piece, seamless and stress free plastic products with superior
surface finish of any size gigantic or small, in every possible shape and even exotic
nature.
Equipments design:
ARDC/CS/Internal 136
Rock & roll machine
Process Steps. The Rotational Molding process is essentially split into four operations:
Step #1. Loading resin into the mold
The rotomolding process is begun by placing a pre-measured
amount of plastic material (in either liquid or powder form) in a
cavity. The mold is then closed and indexed into an oven where it
and its contents are brought up to the molding temperature. As the
mold is heated, it is rotated continuously about its vertical and
ARDC/CS/Internal 137
horizontal axes. This biaxial rotation brings all surfaces of the mold
in contact with the plastic material.
Step 4. Unloading/Demolding
When the polymer has cooled sufficiently to retain its shape and be
easily handled, the mould is opened and the product removed. At
this point powder can once again be placed in the mould and the
cycle repeated.
More than 80% of all the material used is from the polyethylene family. Cross-linked
polyethylene (PE); linear low density polyethylene (LLDPE); high density polyethylene
(HDPE). Other compounds are PVC plastisols, Nylons, and polypropylene
Process parameters:
Mold pressure: A drawback of the rotational molding process has always been the
surface pinholes and internal bubbles that occur in the molded part. These occur
because, as the powder particles melt and coalesce, they trap pockets of air and it
takes a considerable time for these to disappear. It is known that factors such as the
viscosity of the polymer melt, the shape of the powder particles, the particle size and
size distribution, the mould release agent and the metal used for the mould all affect the
pin holing problem. However, the major factor that influences pinhole removal is mould
pressure.
ARDC/CS/Internal 138
Advantages:
Disadvantages
Low shear during processing leading to less compactness & hence inferior
mechanical properties compare to other blow molded products.
Specialty tanks and containers for fuel, water, and chemical processing
Livestock feeders
Drainage systems
Food service containers
Instrument housings
Vending machines
Highway barriers and road markers
ARDC/CS/Internal 139
Light globes
Tool carts
Planter pots
Playing balls
Playground equipment
Headrests
Truck/cart liners
Air ducts
5.3 Thermoforming
Thermoforming is a generic term for the process of producing plastic parts from a flat
sheet of plastic under temperature and pressure. In the highest expression of the
technology, thermoforming offers close tolerances, tight specifications, and sharp detail.
When combined with advanced finishing techniques, high-technology thermoforming
results in products comparable to those formed by injection molding. All of us are
exposed to many thermoformed plastics in our daily lives. They have replaced many
parts previously manufactured from wood, paper, glass, and metal.
ARDC/CS/Internal 140
Thermoforming is a manufacturing process for thermoplastic sheet or film. The sheet or
film is heated between infrared, natural gas, or other heaters to its forming temperature.
Then it is stretched over or into a temperature-controlled, single-surface mold. Cast or
machined aluminum is the most common mold material, although epoxy, wood and
structural foam tooling are sometime used for low volume production. The sheet is held
against the mold surface unit until cooled. The formed part is then trimmed from the
sheet. The trimmed material is usually reground, mixed with virgin plastic, and
reprocessed into usable sheet . There are several categories of thermoforming,
including vacuum forming, pressure forming, twin-sheet forming, drape forming, free
blowing, and simple sheet bending.
Vacuum Forming
Pressure Forming
ARDC/CS/Internal 141
Pressure forming is a variation of vacuum forming that utilizes both vacuum and
compressed air to force the plastic sheet against the mold
The process creates 3 dimensional parts with formed features on both sides. The parts
are typically very strong, stiff, and quite light-weight.
ARDC/CS/Internal 142
Step 4: ... and the hollow body, without solvent, molding
additives and adhesives,
is finished. Furthermore, there are no inner strains.
Drape Forming
Drape forming is similar to straight vacuum forming except that after the sheet is framed
and heated, it is mechanically stretched, and a pressure differential is then applied to
form the sheet over a male mould.
Applications: The largest application for thermoformed articles is for Food Packaging.
Other industries include Toiletries, Pharmaceuticals and Electronics.The modern food
supply chain uses many forms of thermoformed articles. Meat Trays, Microwave &
ARDC/CS/Internal 143
Deep Freeze Containers, Ice Cream and Margarine Tubs, Delicatessen Tubs, Snack
Tubs, Bakery and Patisserie packaging, Sandwich Packs and Vending Drink Cups are
just a few of the food related applications. Other non-food applications include
Manufacturing Collation trays, Blister packaging and Point of Sale display trays.
ARDC/CS/Internal 144
5.4 Trouble Shooting
Blown Film Extrusion Trouble Shooting
High Haze, Low Increase Blow up ratio and Reduce Frost line Height
clarity and gloss
Improve the fusion of the melt by increasing barrel and die temperature
Gels If process temperature has been increased to improve some other performance
wait till the line gels clear
Check with a reportedly cleaner Product to ensure that the Gels are a product
problem and not machine induced
Gauge Variation Check and ensure Die Gap uniformity and accurate Die Centering
and Bubble
Instability Reduce processing Temperature
Create a Air Bag by allowing some of the Blow Up air within the film Lay Flat at
ARDC/CS/Internal 145
the winder Nip
Lower Output For a Fixed RPM Screw, temperature modification (negative profile) may help
Increase the Screw RPM (for a variable rpm screw) and to keep the motor load
constant, increase the Barrel temperature to reduce the melt viscosity
Gels and Increase the processing temperature and if possible change the screen pack and
Unmelts clean the die
Blocking and Reduce the nip roll pressure and Create a air gap in the lay flat before the winder
Openability
If possible, mix Antiblock masterbatches
Haze, Lower Ensure good fusion and melt homogenization by adjusting the processing
Clarity and temperature
Gloss
Increase the die temperature
Low Tenacity Increase stretch ratio. To maintain tape width, the spacer width may be increased.
Tape Breakage Ensure uniform fusion and smooth film surface. Increase processing temperature if
required to achieve this.
ARDC/CS/Internal 146
Reduce Stretch Ratio and Line speed
Check and if Possible Change the Screen pack and clean the die
Increase the nip roll pressure to squeeze out the carried over water and ensure correct
positioning of the knife
Improve the Cast Film surface if the same is rough (replace screen pack, clean die,
increase processing temperature)
Low Output For a fixed (maximum) RPM extruder, temperature modification may be tried
Increase the screw RPM (for a variable rpm screw) and modify the temperature to adjust
the extruder motor load to normal
ARDC/CS/Internal 147
Extrusion Coating
Unmelts and Delamination Increase the melt temperature to achieve a clean curtain.
Surging and Thickness Ensure uniform mixing if a Blend is being used. Avoid a multiple (3 or
Variation more) component blend.
If the thickness variation is localized then check and ensure the die gap
uniformity
Pipe Extrusion
Problems Possible Remedies
Low Throughput Increase the Screw RPM and Modify the Temperature Profile to avoid
increase in the Motor Load
Surface Finish Reduce the processing temperature in case outer surface has a pitted
appearance
ARDC/CS/Internal 148
without the lubricating layer
Injection Molding
Problems Possible Remedies
Silver Streaking Reduce Processing Temperature and eliminate non uniform Processing
Temperature
Reduce Shot size and eliminate erratic feed and erratic cycle time
Sink Marks Avoid Insufficient Material in the mold - Increase shot weight, injection
pressure, plunger forward time, injection speed
Mold Sticking / Difficult Reduce Process Temperature, Shot weight, Plunger forward time
Demolding
Eliminate undercuts or rough surface Polish Mold Surface
ARDC/CS/Internal 149
Improve flow paths in the mold
Fractures, Cracks Eliminate internal Stresses in the molded article arising out of
unbalanced mold design
Blow Molding
Rough Surface, Black Remove local Air Pockets with adequate venting
Specks
Avoid thermal degradation Reduce processing temperature
Melt Fracture and Rough Increase processing temperature to reduce shear and melt fracture
Parison
Reduce Extrusion speed
Check the die shaping profile. Reduce Shaping depth and shaping land
Warping and Distortion Avoid shrinkage difference arising from varying wall thickness
Non Uniform Wall Improve melt strength to avoid sagging parison from the die
Thickness
Reduce Melt temperature
Review the length of the blown part and its suitability for molding in the
ARDC/CS/Internal 150
given processing constraints
Weld Line Problem / Redesign pinch-off to prevent low material content at the weld
Thinning at Parting Line
Increase blowing pressure Avoid any constriction in the Blow air line
Avoid keeping the knife too far away from the die
Part Blow Out Avoid very high Blow up ratio If possible use a wider die
Avoid very sharp pinch off and ensure mold is not over heated
Roto Molding
Mold Release Problem Incorporate a mold release agent (Calcium Stearate, GMS etc)
Warped Molding Avoid Sagging of Hot Plastics Reduce the oven temperature
Avoid any vacuum formation in the molded part Vent off before
ARDC/CS/Internal 151
demolding
Use accurate Roto Molding Grade and Avoid excess of mold release
agent
Bubble/Pin Holes / Rough Avoid Inadequate melting / Fusion of the powder in the mold Increase
Exterior Interior Surface oven/furnace temperature or heating cycle time
Check the welded corners and joints of the mold to avoid any
bubbles/defects in such areas
Long Molding Cycles Check the heating capacity of the heating oven Avoid any loss of heat
due to any shield
Thermoforming
Adjust sheet gauge and polish roll openings to just provide enough material to fill nips
Lines and
Improve cooling.
bands in the
a. Reduce polish-roll temperature.
transverse
b. Eliminate thin spots in sheet.
direction of
c. Improve sheet contact with polish rolls by increasing line tension.
extrusion
d. Ensure nip gaps are the same on both sides of the sheet.
e. Reduce melt temperature
ARDC/CS/Internal 152
Reduce oven temperature or cycle time.
Excessive
sheet sag
Reduce melt flow of GPPS for blend or run on a narrower thermoformer
ARDC/CS/Internal 153
6.0 Polyolefin Grades of HPL
Haldia Petrochemicals Limited is one of the largest integrated Greenfield
Petrochemical Complex in India. Situated in the eastern region of the port town of
Midnapur, Haldia, it is one of the biggest Petrochemical plants that make use of the
latest technologies round the world.
The HPL complex is primarily engaged in the production of polyethylene (High Density
and Linear Low Density) and Polypropylene. The basic feedstock for producing
Ethylene and Propylene is low aromatic Naphtha, which is mostly imported. Along with
these polymer products, the complex also produces chemicals like Benzene, Butadiene,
Cyclopentane, Carbon black feed stock, Hydrogenated paralysis gasoline and C6
Raffinate. The different technology licensors and contractors along with the nameplate
capacity for the three polymer manufacturing units of HPL are tabulated below:
NAME
PLANT / PLATE
S.No. TECHNOLOGY CAPACITY LICENSOR CONTARCTOR
PRODUCT
Spheripol II Technimont,
3. Polypropylene 245KTA Basell, Italy
Technology Italy
ARDC/CS/Internal 154
6.1 Grade Nomenclature
The brand name for the polymer products of HPL is HALENE- derived from the
combination of HALdia and polyethylENE or polypropylENE. The polyethylene products
are marketed as HALENE H and HALENE L for High Density Polyethylene and Linear
Low Density polyethylene respectively whereas for polypropylene it is HALENE P.
HALENE H nomenclature:
The high density PE grades from Mitsui plant have five to six characters for
nomenclature. The first one is a letter indicating the probable area of application,
followed by four numbers in which the first two digits indicate the density while the last
two digits represents the melt flow index of the polymer. For example the grade R5801
represents
P: Pipe grade
F: Film grade
The high density PE from the Spherilene plant has six characters. The first five have the
same meaning as those of the Mitsui products followed by an extra letter L
representing HDPE from the swing (Spherilene) plant. Sometimes U is used after L to
indicate UV stabilized grades.
HALENE L nomenclature:
Linear low density PE grades are produced only from the Spherilene plant. They are
designated by six characters starting with the number 7. The following three numbers
denote their density. MFI is indicated by the fifth number. The nomenclature ends with a
letter indicating the specialty additivation or application. For example:
ARDC/CS/Internal 155
72307E indicates LLDPE of 0.923 g/cc density and 7 g/10 min MFI meant for Extrusion
coating applications.
HALENE P nomenclature:
Polypropylene produced in the Spheripol II plant has three varieties: PP Homopolymer,
PP Impact Copolymer and PP Random Copolymer. They have four to five characters
for nomenclature. The first letter indicates the application followed by a number
indicating the type of PP. The last two digits imply the MFI of the grade. Examples are
as follows:
R- Raffia Grade
1: PP Homopolymer,
3: PP Impact Copolymer
10 - MFI of 10 g/cc
ARDC/CS/Internal 156
6.2. Different Grades
6.2.1 Polyethylene Grades
6.2.1.1. HDPE Grades - Halene H
ARDC/CS/Internal 157
M5018L General purpose injection molded applications
Halene H
Film Grades
F5400
ARDC/CS/Internal 158
F5001
ARDC/CS/Internal 159
Raffia Grades
R5801
Property Value Target Attributes
HD T6
Property Value Target Attributes
ARDC/CS/Internal 160
HD T9
Property Value Target Attributes
ARDC/CS/Internal 161
E5201S
Property Value Target Attributes
B6401
Property Value Target Attributes
ARDC/CS/Internal 162
B5500
Processability
ARDC/CS/Internal 163
Monofilament Grades
HD T10
Property Value Target Attributes
HD T10S
ARDC/CS/Internal 164
Injection Molding Grades
M5018L
Property Value Target Attributes
M5002L
Property Vaue Target Attributes
ARDC/CS/Internal 165
M5005L
Property Value Target Attributes
M5025L
Property Value Target Attributes
ARDC/CS/Internal 166
M6007L/LU
Property Value Target Attributes
ARDC/CS/Internal 167
LL T12 Wire & Cable Application
73204T Rotomolded tanks for industrial water storage, sanitation & agriculture
ARDC/CS/Internal 168
Halene L
Film Grades
71601S
Property Value Target Attributes
71501S
Property Value Target Attributes
ARDC/CS/Internal 169
71601W
Property Value Target Attributes
71602S
ARDC/CS/Internal 170
71602W
ARDC/CS/Internal 171
Rotomolding Grades
73005T/U
Property Value Target Attributes
73204T
Property Value Target Attributes
ARDC/CS/Internal 172
Extrusion Coating Grade
72307E
Property Value Target Attributes
ARDC/CS/Internal 173
6.2.2. Polypropylene Grades Halene P
PP Homopolymer Grades
ARDC/CS/Internal 174
PP Impact Copolymer
PP Random Copolymer
ARDC/CS/Internal 175
Halene P
PP Homopolymer Extrusion Grade
F103
R103
Property Value Target Attributes
ARDC/CS/Internal 176
T103
Property Value Target Attributes
F110
Property Value Target Attributes
E116
Property Value Target Attributes
ARDC/CS/Internal 177
E125
Property Value Target Attributes
M 106
Property Value Target Attributes
ARDC/CS/Internal 178
M108
Property Value Target Attributes
M110
Property Value Target Attributes
ARDC/CS/Internal 179
M310
Property Value Target Attributes
M310S
Property Value Target Attributes
ARDC/CS/Internal 180
M312
Property Vaue Target Attributes
M311T
Property Value Target Attributes
M325
Property Value Target Attributes
ARDC/CS/Internal 181
PP- Random Copolymer
B202S
Property Value Target Attributes
B200
Property Value Target Attributes
ARDC/CS/Internal 182
7.0 Plastic Material Testing & Identification
The advent of modern science and technology has lead to the inclusion of testing as an
integral part of research and development activities. With time, the manners in which
things are done today are quite different from what it used to be. The emphasis is on
automation, high production, and cost reduction. There is also a growing demand for
intricately shaped, high tolerance parts. These coupled with consumer awareness has
made testing of materials extremely necessary and compulsory for each and every
production house. The following are some of the major reasons for testing:
In the last two decades, just about every manufacture has turned to plastics to achieve
cost reduction, automation, and high yield. The lack of history along with the explosive
growth and diversity of polymeric materials has forced the plastics industry into placing
extra emphasis on testing and on developing a wide variety of testing procedures.
Testing of plastics can be segregated under the different type of properties that can be
tested. Mechanical Property testing
The mechanical properties, among all the properties of plastic materials, are often the
most important properties because virtually all service conditions and the majority of
end-use applications involve some degree of mechanical loading.
ARDC/CS/Internal 183
7.1. Mechanical Property Testing
Tensile test is a measurement of the ability of a material to withstand forces that tend to
pull it apart and to determine to what extent the material stretches before breaking.
Tensile modulus, an indication of the relative stiffness of a material, can be determined
from a stress-strain diagram. Different types of plastic materials are often compared on
the basis of tensile strength, elongation and tensile modulus data.
Flexural strength is the ability of the material to withstand bending forces applied
perpendicular to its longitudinal axis. The stress induced by the flexural load is a
combination of compressive and tensile stresses. The flexural modulus is a measure of
the stiffness during the first or initial part of the bending process. This value of the
flexural modulus is, in many cases, equal to the tensile modulus.
Factors affecting the test results:
Specimen Preparation
Temperature
ARDC/CS/Internal 184
Test Conditions
With more and more metals being replaced from their conventional field of application
by plastics, it has become highly important to thoroughly understand the behavior of
plastics under long-term load and varying temperatures. Such behavior is described in
terms of creep properties.
When a plastic material is subjected to a constant load, it deforms quickly to a strain
roughly predicted by its stress- strain modulus, and then continues to deform slowly with
time indefinitely or until rupture. This phenomenon of deformation under load with load
with time is called creep. All plastics creep to certain extent. The degree of creep
depends upon several factors, such as type of plastic, amount of load, temperature and
load.
The creep measurement technique involves the application of a fixed amount of load to
a specimen and then the measurement of the resulting deformation as a function of
time.
The creep values can be obtained by applying constant load to the test specimen in
tension, compression, or flexure and measuring the deformation as a function of time.
The values are most commonly referred to as tensile creep, compressive creep, and
flexural creep.
Stress relaxation is defined as a gradual decrease in stress with time, under a constant
deformation (strain). This characteristic behavior of the polymers is studied by applying
a fixed amount of deformation to a specimen and measuring the load required to
maintain it as a function of time.
f) Impact Testing
The impact properties of the polymeric materials are directly related to the overall
toughness of the material. Toughness is defined as the ability of the polymer to absorb
applied energy. The area under the stress-strain curve is directly proportional to the
toughness of a material. Impact energy is a measure of toughness. The higher the
impact energy of a material, the higher the toughness and vice versa. Impact resistance
is the ability of the material to resist breaking under a shock loading or the ability to
resist the fracture under stress applied at high speed.
Factors affecting the impact strength are as follows:
Rate of loading
ARDC/CS/Internal 185
Notch Sensitivity
Temperature
Orientation
Processing conditions and types
Degree of crystallinity, Molecular Weight
Method of loading
g) Hardness Tests
ARDC/CS/Internal 186
Rockwell Hardness (ASTM D 785)
This measures the net increase in depth impression as the load on the indenter is
increased from a fixed minor load to a major load and then returned to a manor load.
This is used for measuring the relative hardness of soft materials and is based on the
penetration of a specified indentor forced into the material under specified conditions.
Two types of durometers are most commonly used - Type A (for softer materials) and
Type D (for slightly harder materials).
This test is devised for measuring hardness of both reinforced and non-reinforced rigid
plastics.
ARDC/CS/Internal 187
7.2. Thermal Property Testing
HDT Fixtures
Significance
Heat Deflection Temperature (HDT) distinguishes between the materials, which lose
their rigidity over a narrow temperature range, and those, which are able to sustain light
loads at high temperatures.
ARDC/CS/Internal 188
Application
In screening and ranking the plastic materials for short term heat
resistance
For evaluating plastic profiles or sheets which are rigid at room
temperature
Objective
To determine the temperature at which a specified needle of 1 mm2 flat circular cross
section will penetrate to a depth of 1 mm in a plastic specimen subjected to controlled
rate of heating under fixed load.
ARDC/CS/Internal 189
Significance
The Vicat Softening Point of a plastic gives an indication that polymeric materials soften
or lose their rigidity when heated.
Application
Objective
To determine the temperature at which plastic and elastomers exhibit brittle failure
under specified impact condition.
Apparatus A
Apparatus B
ARDC/CS/Internal 190
Significance
It gives an indication that at low temperatures all plastics tend to become rigid and
brittle. This happens because at low temperatures the mobility of polymer chains is
greatly reduced.
Application
Objective
This test method covers procedure for comparing the relative rate of burning and/or
extent of burning of self-supporting plastics in the form of bars, molded or cut sheets.
Significance
This test gives an idea about the expected fire hazards from a particular plastic item
depending upon its form an application.
Application
ARDC/CS/Internal 191
Ignition Behavior of Some Typical Plastics
ARDC/CS/Internal 192
7.3. Optical Property Testing
a) Refractive Index (ASTM D 542)
Objective
The test method aims in measuring the refractive index of a plastic material. Refractive
index of a sample may be defined as the ratio of the velocity of light in a vacuum (or air)
to its velocity in a transparent medium.
Significance
Refractive index values are important to design engineers involved in designing lenses
for cameras, microscopes, and other optical equipments.
Application
ARDC/CS/Internal 193
b) Luminous Transmittance & Haze (ASTM D 1003)
Objective
To determine the capability of a given test specimen to allow the incident light rays to
pass through it.
Significance
Luminous transmittance is defined as the ratio of transmitted light to the incident light.
Haze is defined as the percentage of transmitted light, which in passing through a
specimen deviates from the incident beam, by forward scattering.
Application
ARDC/CS/Internal 194
c) Color (ASTM E313)
Objective
Significance
This test is most commonly used to evaluate color changes in a material caused by real
or simulated outdoor exposure.
Application
Objective
ARDC/CS/Internal 195
Significance
Gloss can be inherent in the material, a result of the molding process, or a result of
surface texture. Gloss can also be affected by environmental factors such as
weathering or surface abrasion.
Application
Objective
ARDC/CS/Internal 196
Significance
Application
Objective
ARDC/CS/Internal 197
Significance
Application
This test helps is determining the suitability of plastics containers for liquid storage,
handling and transportation.
ESCR Specimen
ESCR testing is performed by slowly bending the test specimens and placing them in a
holding clamp. The clamp and specimens are then placed in a test tube and immersed
in a specified reagent. The test tube is sealed and placed in a constant-temperature
bath. Multiple test specimens are tested at one time.
ARDC/CS/Internal 198
ESCR Specimens in Holder
Specimens are inspected periodically for failure. Cracks generally develop at the notch,
perpendicular to the notch, and run to the edge of the specimen. Any cracks constitute
failure, not just cracks that reach the edge of the specimen. Cracks sometimes appear
beneath the surface and are visible as surface depressions. If a depression develops
into a surface crack the time at which the depression was noted is taken as the time of
failure.
ESCR Test
Three test conditions are specified. Condition A is generally used for polyethylene with
densities between 0.910 and 0.925 g/cm. Condition B is used for polyethylene with
densities greater than 0.925 g/cm. Condition C is used for accelerated testing of
materials with extremely high ESCR values.
A summary of the differences in the different test conditions is listed below.
ARDC/CS/Internal 199
ESCR Test Conditions
A min 3 0.5 50
Objective
This method is based on observing the level to which a test specimen sinks in a liquid
column exhibiting a density gradient.
Significance
All plastics are sold on a cost per weight basis not on a cost per unit volume basis. Such
a practice increases the significance of the density.
Application
ARDC/CS/Internal 200
b) Apparent (Bulk) Density (ASTM D 1895)
Objective
Bulk density is defined as the weight per unit volume of material. Bulk density is
primarily used for powders or pellets.
Significance
The test can provide a gross measure of particle size and dispersion, which can affect
material flow consistency and reflect packaging quantity. It is the measure of fluffiness
of a material.
Application
Objective
To measure the rate of extrusion of molten resin through a capillary of a specified length
and diameter under prescribed conditions of temperature and load.
Significance
ARDC/CS/Internal 201
A Melt Flow Tester
Application
d) Viscosity Tests
Dilute Solution Viscosity of Polymers (ASTM D 2857)
Objective
ARDC/CS/Internal 202
Ubbelohde calibrated viscometer tube in a constant temperature water bath
Significance
It is basically a measure of the average size or extension in space of polymer
molecules. It is empirically related to the average molecular weight of linear polymer.
The presence of additives has a significant influence on the viscosity of the polymer.
Application
ARDC/CS/Internal 203
7.7. Thermal Analysis Techniques
Thermal analysis consists of a family of analytical techniques in which a property of the
sample is monitored against time or temperature while the temperature of the sample is
programmed.
Objective
The basic principle underlying this technique is that, when the sample undergoes a
physical transformation such as phase transitions, more (or less) heat will need to flow
to it than the reference to maintain both at the same temperature. Whether more or less
heat must flow to the sample depends on whether the process is exothermic or
endothermic. For example, as a solid sample melts to a liquid it will require more heat
flowing to the sample to increase its temperature at the same rate as the reference. This
is due to the absorption of heat by the sample as it undergoes the endothermic phase
transition from solid to liquid. Likewise, as the sample undergoes exothermic processes
ARDC/CS/Internal 204
(such as crystallization) less heat is required to raise the sample temperature. By
observing the difference in heat flow between the sample and reference, differential
scanning calorimeters are able to measure the amount of heat absorbed or released
during such transitions. DSC may also be used to observe more subtle phase changes,
such as glass transitions
Application
Crystallization temperature
Fusion temperature (Melting point/range)
Oxidation Induction Time (Degradation study)
Cross linking of polymer molecules
ARDC/CS/Internal 205
b) Thermogravimertic Analysis (TGA)
Objective
Significance
A TGA derivative weight loss curve can be used to tell the point at which weight loss is
most apparent such as thermal or oxidative degradation. Hence it provides us the data
on thermal and oxidative stability, composition analysis, reaction kinetics, aging stability,
degradation profile, percentage of volatiles, etc.
Application
ARDC/CS/Internal 206
c) Thermomechanical Analysis (TMA)
Objective
TMA Instrument
ARDC/CS/Internal 207
Significance
Transition temperature
Expansion coefficient
Softening point
Heat Deflection Temperature
Thermal reorientation
Mold Shrinkage, etc.
ARDC/CS/Internal 208
7.8. Spectroscopy
Spectroscopy is the most significant tool to identify the polymer materials. It identifies
the functional groups, chemical linkage and geometrical isomerism. Widely used
spectroscopic techniques are Infra-Red spectroscopy and UV Visible Spectroscopy.
Infra red spectroscopy studies vibrational modes of molecules. An infra red spectrum
arises when molecules undergo transition between different internal energy levels. The
energy difference between the states represents the frequency of the radiation emitted
or absorbed. The IR wavenumber range is 350 to 5000 cm-1.
Features:
Samples can be tested in the form of film, solution or solid/pellet. Samples should be
preferably transparent or semi-transparent. Moreover, the sample thickness should be
as minimum as possible.
Application
ARDC/CS/Internal 209
Typical IR Spectra
ARDC/CS/Internal 210
b) UV Visible Spectroscopy
When an atom or molecule absorbs energy, electrons are promoted from their ground
state to an excited state. In a molecule, the atoms can rotate and vibrate with respect to
each other. These vibrations and rotations also have discrete energy levels, which can
be considered as being packed on top of each electronic level.
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Possible electronic transitions of , , and n electrons are shown below:
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Significance
Here the spectral peaks are corresponding to the energy difference between two
transition levels and since each transition level has its own internal energy levels, the
UV visible spectra is shallow as compared to the infra red spectrum.
Application
Sl
End Product Distinguishing Characteristics Plastics
no.
PP (BO)
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6 Housewares- Rigid, good impact, opaque, HDPE
buckets, mugs, medium scratch resistance
drums, etc.
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high impact, smaller sizes can be HDPE
coiled
18 Water storage tanks, Rigid, high impact, non-corrosive LLDPEW, MLDPE, HDPE
Chemical tanks
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References
1. Polymer Handbook by J. Brandrup, Edmund H. Immergut, Eric A. Grulke
23. http://en.wikipedia.org/wiki
24. http://pslc.ws/macrogcss
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