FD3046

Plastics and Polymers in Packaging

Prepared by
R.Prakash
Assistant Professor
Department of Food Technology
Dhaanish Ahmed Institute of Technolgy
 UNIT-I

INTRODUCTION TO PLASTICS,
POLYMERS AND DIFFERENT PROCESS
AND PACKAGING
 Syllabus

Polymeric materials – Definitions, Classification

types, properties and applications. Crystalline in
polymers. Polymer degradation Polymer blends,
alloys and composites – Basic concepts Selection
of materials. Additives for plastics – Basic need
for incorporating additives. Classifications of
additives. Types and applications. Incorporation
of additives (Elementary concepts only).
Polymeric materials
 A polymer is any of a class of natural or
synthetic substances composed of very large
molecules, called macromolecules, which are
multiples of simpler chemical units called
monomers.
 Polymers make up many of the materials in
living organisms and are the basis of many
minerals and man-made materials.
Polymeric materials
 Moreover, they constitute the basis of such minerals as
diamond, quartz, and feldspar and such man-made
materials as concrete, glass, paper, plastics, and rubbers.
 The word polymer designates an unspecified number of
monomer units.
 When the number of monomers is very large, the
compound is sometimes called a high polymer.
 Polymers are not restricted to monomers of the same
chemical composition or molecular weight and
structure.
 Classification of Polymers
 Polymers cannot be classified under one
category because of their complex structures,
different behaviours and vast applications.
 We can, therefore, classify polymers based on
the following norms.
 Classification of Polymers
 Classification of Polymers Based on the
Source of Availability
 Classification of Polymers Based on the
Structure of the Monomer Chain
 Classification Based on Polymerization

 Classification Based on Monomers

 Classification Based on Molecular Forces

 Classification of Polymers Based on the Source of
Availability

• Natural Polymers
• Semi-synthetic Polymers
• Synthetic Polymers
 Natural Polymers

• They occur naturally and are found in plants and

animals.
• For example, proteins, starch, cellulose and
rubber.
• To add up, we also have biodegradable polymers
called biopolymers.
 Natural Polymers - Types

• Natural Polymers existing in nature can be grouped into six

main classifications with respect to their sources:
– Proteins,
– Polysaccharides
– polynucleotides,
– polyisoprenes,
– polyesters, and
– and lignin
 Natural Polymers –Proteins

• Proteins are also an integral part of the plant cell wall

serving both structural and functional molecules.
• They determine the functionality and specificity of an
organism
• Proteins are made up of amino acid groups and
sometimes other groups joined together by amide
bonds, also known as peptide bonds.
 Natural Polymers –Proteins
Classification

• Proteins can be classified with regard to

their shape, size, solubility, composition,
and function.
• Proteins – Types – Based on Shape and
Size
– Globular Proteins
– Fibrous Proteins
 Natural Polymers – Proteins – Types
- Globular Proteins

• Globular proteins are water soluble types which are

rather fragile(easily broken) in nature.

• Antibodies, enzymes, and hormones are typical

examples of globular proteins.

 Natural Polymers – Proteins – Types
- Fibrous Proteins

• Fibrous proteins are tougher water insoluble proteins.

• These are usually proteins found in structural tissues

such as hair, nails, and skin.

 Natural Polymers – Proteins – Types
- based on their solubility

• simple,
• compound, and
• derived proteins
 Proteins – Types – Simple Proteins

• Simple proteins are those which when hydrolyzed produce

amino acids only.
• These protein also have subcategories, which are albumins,
globins prolamins, glutelins, histones, prolamins, and
abuminoids.
 Proteins – Types – compound
Proteins
 Compound proteins, also known as conjugate
proteins, are a combination of simple proteins and
prosthetic groups
 Conjugate proteins are of various types depending on
the prosthetic group attached.
 These could be nucleoproteins lipoproteins,
glycoproteins, mucoproteins, phosphoproteins,
metalloproteins, or chromoproteins.
 Proteins – Types – derived Proteins
 Derived proteins are those derived from complete or partial
acidic alkali or enzymatic hydrolysis of simple or conjugate
proteins
 These derived proteins could be either primary or secondary
derived proteins
 Primary derived proteins are proteins, metaproteins, and
coagulated proteins derived from partial hydrolysis of the
protein molecule where very little or no peptide bonds are
broken.
 Secondary proteins are a result of more pronounced cleavage
of the peptide bonds through hydrolysis
 The main types are proteoses, peptones, and peptides.
 Natural Polymers – Proteins – Types
- based on their functions

• Catalytic Functional Protein,

• protective regulatory Protein,
• storage & transport ,
• toxic Protein,
• exotic Protein,
• contractile Protein,
• secretary, and structural proteins.
– Catalytic, regulatory, and protective proteins are enzymes,
hormones, and antibodies respectively
 Natural Polymers Polysaccharides

• Polysaccharides or polycarbohydrates, are the most

abundant carbohydrates found in food.
• They are long-chain polymeric carbohydrates composed
of monosaccharide units bound together by glycosidic
linkages.
• This carbohydrate can react with water (hydrolysis)
using amylase enzymes as catalyst, which produces
constituent sugars (monosaccharides, or oligosaccharides).
• They range in structure from linear to highly branched.
• Examples include storage polysaccharides such
as starch, glycogen and galactogen and structural
polysaccharides such as cellulose and chitin.
 Natural Polymers Polysaccharides -
Applications

• polysaccharides have been extensively used as drug

carriers, building blocks for drug delivery, bioactive
materials, and excipients to enhance drug delivery
 Natural Polymers – Types -
polynucleotides,
• In molecular biology, a polynucleotide is
a biopolymer composed of nucleotide monomers that
are covalently bonded in a chain.
• DNA (deoxyribonucleic acid) and RNA (ribonucleic acid) are
examples of polynucleotides with distinct biological functions.
• DNA consists of two chains of polynucleotides, with each
chain in the form of a helix (like a spiral staircase)..
 Natural Polymers – Types -
polynucleotides, Applications

• Polynucleotides have varied medical

applications but are very sensitive to
environment.
• DNA molecules were explored for the design
of patterned bio sensitive interfaces.
• Polynucleotide-based multilayers are applied
for drug delivery, gene delivery, biosensing,
and barcoding
 Natural Polymers – Types -
polyisoprenes,
• Polyisoprene is strictly speaking a collective name for
polymers that are produced by polymerization of isoprene.
• In practice polyisoprene is commonly used to refer to
synthetic cis-1,4-polyisoprene, made by the industrial
polymerisation of isoprene.
• Natural forms of polyisoprene are also used in substantial
quantities, the most important being "natural rubber" (mostly
cis-1,4-polyisoprene), which is derived from the sap of trees.
 Natural Polymers – Types -
polyisoprenes, - Applications
• Both synthetic polyisoprene and natural rubber are highly
elastic and consequently used to make tires and a variety of
other applications.
• The trans isomer, which is much harder than the cis isomer, has
also seen significant use in the past.
• It too has been synthesized and extracted from plant sap, the
latter resin being known as gutta-percha.
• These were widely used as an electrical insulator and as
components of golf balls.
 Natural Polymers – Types -
polyesters,
• Polyester is a category of polymers that contain the ester functional group in
every repeat unit of their main chain.
• As a specific material, it most commonly refers to a type called polyethylene
terephthalate (PET).
• Polyesters include naturally occurring chemicals, such as
in plants and insects, as well as synthetics such as polybutyrate.
• Polyesters occurring in nature include the cutin component of plant cuticles,
which consists of omega hydroxy acids and their derivatives, interlinked
via ester bonds, forming polyester polymers of indeterminate size.
• Polyesters are also produced by bees in the genus Colletes, which secrete
a cellophane-like polyester lining for their underground brood cells earning
them the nickname "polyester bees"
• Natural polyesters and a few synthetic ones are biodegradable, but most
synthetic polyesters are not.
 Natural Polymers – Types -
polyesters, Applications
• Fabrics woven or knitted from polyester thread or yarn are used
extensively in apparel and home furnishings, from shirts and pants
to jackets and hats, bed sheets, blankets, upholstered furniture and
computer mouse mats.
• Industrial polyester fibers, yarns and ropes are used in car tire
reinforcements, fabrics for conveyor belts, safety belts, coated
fabrics and plastic reinforcements with high-energy absorption.
• Polyester fiber is used as cushioning and insulating material in
pillows, comforters and upholstery padding.
• Polyester fabrics are highly stain-resistant since polyester is a
hydrophobic material, making it hard to absorb liquids.
• Synthetic polyesters are used extensively in clothing industries
 Natural Polymers – Types - lignin,
• Lignin is an aromatic complex polymer of monolignols
(aromatic alcohols) which is found in plant cell walls.
• Later than cellulose, lignin is the most abundant natural
polymer in the planet.
• It is not composed of carbohydrate monomers whereas the rest
of polymers found in plant cell walls are composed of
carbohydrate monomers for example cellulose.
• In wood, it contains about 17-32% of the weight of moisture
free wood depends on the species, age of wood etc; such as in
soft wood average 28%, whereas 24% in hardwood.
• Moreover, it is not equally distributed throughout the same
wood; different parts may content different percentages.
 Natural Polymers – Types - lignin, -
Applications
• It can be utilized in many industries such as pulp & paper,
agriculture and construction.
• Some uses of Lignin are described in below:
• In sulfite pulping process lignosulfonates is an important
byproduct; it contains sulfonate (-SO3-) groups, therefore it is
soluble in water. lignosulfonates can be used as dispersants,
binders, complexing agents and emulsifying agents.
• It can be used as alternative raw materials for plastics.
• Lignin in plants also burns very effectively, It can be used as bio-
based alternative to petroleum.
• The other uses of Lignin are animal feed, coatings, agricultural
chemicals, micronutrients, natural binders, adhesives, resins, and
in the manufacturing of vanillin and textile dyes.
 Semi-synthetic Polymers

• They are derived from naturally occurring

polymers and undergo further chemical
modification.
• For example, cellulose nitrate and cellulose
acetate.
 Semi-synthetic Polymers
• Semi-synthetic polymers are those that occur
naturally, but they are extracted in their
valuable forms through chemical processes.
• Therefore, semi-synthetic polymers are those
that are naturally occurring and also
synthetically made.
• Semi-synthetic polymers are usually derived
from the naturally occurring polymer,
cellulose.
 Semi-synthetic Polymers
• Semi-synthetic polymers are also called thermoplastic
polymers.
• Cellulose is made to go through a process called
acetylation; that is, acetic anhydride is used along with
sulphuric acid, which forms a polymer called cellulose
diacetate.
• This material is usually used to make film glasses that are
thread-like.
• Some of the semi-synthetic polymers examples include
vulcanized rubber which is used in making tyres, and also
gun cotton, which is cellulose nitrate that can be used in the
making of explosives.
 Synthetic Polymers

• These are human-made polymers. Plastic is

the most common and widely used synthetic
polymer.
• It is used in industries and various dairy
products.
• For example, nylon-6, 6, polyether, etc.
Classification of Polymers Based on the Structure of
the Monomer Chain

• Linear Polymers
• Branched-chain Polymers
• Cross-linked Polymers
Linear Polymers

• The structure of polymers containing long and

straight chains falls into this category.
• PVC, i.e., polyvinyl chloride, is largely used
for making pipes, and an electric cable is an
example of a linear polymer.
Branched-chain Polymers

When linear chains of a polymer form branches,

then such polymers are categorised as branched
chain polymers.
For example, low-density polythene.
Cross-linked Polymers

• They are composed of bifunctional and

trifunctional monomers.
• They have a stronger covalent bond in
comparison to other linear polymers.
• Bakelite and melamine are examples of cross-
linked polymers.
Classification Based on Polymerization
Techniques

• Addition Polymerization:
For example, poly ethane, Teflon,
polyvinyl chloride (PVC), etc.
• Condensation Polymerization:
Examples include nylon -6, 6, perylene,
polyesters, etc.
Classification Based on Monomers

• Homomer: In this type, a single type of

monomer unit is present. For example,
polyethene.
• Heteropolymer or co-polymer: It consists of
different types of monomer units. For
example, nylon -6, 6.
Classification Based on Molecular Forces

• Elastomers:
• Fibres:
• Thermoplastics:
• Thermosetting polymers
Classification Based on Molecular Forces

• Elastomers: These are rubber-like solids, and

weak interaction forces are present in them.
For example, rubber.
• Fibres: Strong, tough, high tensile strength
and strong forces of interaction are present.
For example, nylon -6, 6.
• Thermoplastics: These have intermediate
forces of attraction. For example, polyvinyl
chloride.
Classification Based on Molecular Forces

• Thermosetting polymers:
– These polymers greatly improve the
material’s mechanical properties.
– It provides enhanced chemical and heat
resistance. For example, phenolics, epoxies
and silicones.
Crystalline in polymers

• Polymers are like socks. Sometimes they are

arranged in an orderly manner, like the
socks in the drawer of people who need
everything to be ordered. In this case, the
polymer is called crystalline.

• Other times there is no order, and the

polymer chains just form a big tangle like
the socks of those who are messy. When this
happens, the polymer is called amorphous.
Crystalline in polymers
Crystallization of polymers

• Crystallization of polymers is a process

associated with partial alignment of their
molecular chains.
• These chains fold together and form
ordered regions called lamellae, which
compose larger spheroidal structures
named spherulites.
Crystalline in polymers

Schematic model of
a spherulite. Black
arrows indicate
direction of
molecular alignment
Crystalline in polymers

• Crystalline polymers are polymers in

which some parts have crystallized in a
precise order, allowing the formation of
an organized solid unit.
Crystalline Polymers Properties:

Due to their structure and

temperature, crystalline polymers have a
wide range of mechanical and physical
characteristics:

•High density.
•High melting point.
•High resistance to wear and tear.
•Low ductility and impact resistance.
•Opaque to visible light.
Crystalline Polymers Properties:

• The biggest characteristics of crystalline polymers

are: high melting point, rigidity, and resistance to solvent
penetration.
• Although the crystallinity makes polymers robust, it also
lowers their resistance to impacts.
Crystalline Polymers - Example
Amorphous Polymers

• Amorphous polymers have a randomly ordered

molecular structure that lack a sharp melting point.
• The result is that amorphous materials soften
gradually as the temperature increases.
• Amorphous polymers are thermoplastics, as they
can be melted and immediately recast.
• Their lack of ordered structure allows them to bend
and flex more easily than crystalline polymers, and
they also tend to be more transparent.
• Due to their lack of order, amorphous polymers
typically have lower mechanical strength and
stiffness compared to crystalline polymers.
Amorphous Polymers
Amorphous Polymers
Amorphous Polymers

 Polymethyl methacrylate (PMMA / Acrylic)

 Polystyrene (PS)
 Polycarbonate (PC)
 Polysulfone (PSU)
 Polyvinyl chloride (PVC)
 Acrylonitrile butadiene styrene (ABS)
 Polyetherimide (PEI)
Semi Crystalline Polymers

• The degree of crystallinity is estimated by

different analytical methods and it typically
ranges between 10 and 80%, with crystallized
polymers often called "semi-crystalline“.
Semi Crystalline Polymers

• Polyethylene (PE)
• Polypropylene (PP)
• Polybutylene terephthalate (PBT)
• Polyethylene terephthalate (PET)
• Polyetheretherketone (PEEK)
POLYMER DEGRADATION

• Polymer degradation is the reduction in the physical

properties of a polymer, such as strength, caused by
changes in its chemical composition.
• Polymers and particularly plastics are subject to
degradation at all stages of their product life cycle,
including during their initial processing, use, disposal
into the environment and recycling.
• The rate of this degradation varies
significantly; biodegradation can take decades,
whereas some industrial processes can completely
decompose a polymer in hours.
SUSCEPTIBILITY

• The state or fact of being likely or liable to be

influenced or harmed by a particular thing.
POLYMER SUSCEPTIBILITY

• The susceptibility of a polymer to degradation depends

on its structure.
• Epoxies and chains containing aromatic functionalities
are especially susceptible to UV degradation while
polyesters are susceptible to degradation by hydrolysis.
• Polymers containing an unsaturated backbone degrade
via ozone cracking.
• Carbon based polymers are more susceptible to thermal
degradation than inorganic polymers such
as polydimethylsiloxane and are therefore not ideal for
most high-temperature applications.
POLYMER SUSCEPTIBILITY

• The susceptibility of a polymer to degradation depends

on its structure.
• Epoxies and chains containing aromatic functionalities
are especially susceptible to UV degradation while
polyesters are susceptible to degradation by hydrolysis.
• Polymers containing an unsaturated backbone degrade
via ozone cracking.
• Carbon based polymers are more susceptible to thermal
degradation than inorganic polymers such
as polydimethylsiloxane and are therefore not ideal for
most high-temperature applications.
POLYMER DEGRADATION
POLYMER DEGRADATION

• Natural polymers are generally susceptible

to bacterial and fungal attack.
• Polymer degradation of synthetic polymers
can occour under following conditions:
• Degradation during processing
• In-service degradation
• Degradation in the environment
• Degradation during recycling
DEGRADATION DURING PROCESSING

• Thermal oxidation
• Thermal degradation
• Thermo-mechanical degradation
THERMAL OXIDATION

• Although oxygen levels inside processing

equipment are usually low, it cannot be fully
excluded and thermal-oxidation will usually take
place more readily than degradation that is
exclusively thermal (i.e. without air).
• Reactions follow the
general autoxidation mechanism, leading to the
formation of organic peroxides and carbonyls. The
addition of antioxidants may inhibit such
processes.
THERMAL DEGRADATION
• Heating polymers to a sufficiently high
temperature can cause damaging chemical
changes, even in the absence of oxygen.
• This usually starts with chain succession,
generating free radicals, which primarily
engage in dis proportionate and crosslinking.
• PVC is the most thermally sensitive common
polymer, with major degradation occurring
from ~250 °C (480 °F) onwards; other
polymers degrade at higher temperatures.
THERMO-MECHANICAL DEGRADATION

• Molten polymers are non-Newtonian fluids with

high viscosities, and the interaction between their
thermal and mechanical degradation can be complex.
• At low temperatures, the polymer-melt is more
viscous and more prone to mechanical degradation
via shear stress.
• At higher temperatures, the viscosity is reduced, but
thermal degradation is increased.
• Friction at points of high sheer can also cause
localized heating, leading to additional thermal
degradation.
IN-SERVICE DEGRADATION

• Chlorine-induced cracking
• Electronics
• Galvanic action
CHLORINE-INDUCED CRACKING
• Drinking water which has been chlorinated to kill
microbes may contain trace levels of chlorine.
• The World Health Organization recommends an
upper limit of 5 ppm.
• Although low, 5 ppm is enough to slowly attack
certain types of plastic, particularly when the
water is heated, as it is for washing.
• Polyethylene, polybutylene and acetal resin
(polyoxymethylene) pipe work and fittings are all
susceptible. Attack leads to hardening of pipe
work, which can leave it brittle and more
susceptible to mechanical failure.
ELECTRONICS

• Plastics are used extensively in the manufacture of electrical

items, such as circuit boards and electrical cables.
• These applications can be harsh, exposing the plastic to a
mixture of thermal, chemical and electrochemical attack.
• Many electric items like transformers, microprocessors or
high-voltage cables operate at elevated temperatures for years,
or even decades, resulting in low-level but continuous thermal
oxidation.
• This can be exacerbated by direct contact with metals, which
can promote the formation of free-radicals, for instance, by
the action of Fenton reactions on hydro peroxides.
• High voltage loads can also damage insulating materials such
as dielectrics, which degrade via electrical treeing caused by
prolonged electrical field stress.
GALVANIC ACTION

• Polymer degradation by galvanic action was first

described in the technical literature in 1990 by Michael
C. Faudree, an employee at General Dynamics, Fort
Worth Division.
• The phenomenon has been referred to as the "Faudree
Effect", and can possibly be used as a sustainable
process to degrade non-recyclable thermoset plastics,
and also has had implications for preventing corrosion
on aircraft for safety such as changes in design.
• When carbon-fiber-reinforced polymer is attached to a
metal surface, the carbon fiber can act as a cathode if
exposed to water or sufficient humidity, resulting in
galvanic corrosion.
GALVANIC ACTION

• This has been seen in engineering when carbon-

fiber polymers have been used to reinforce
weakened steel structures.
• Reactions have also been seen in aluminium and
magnesium alloys, polymers affected include
bismaleimides (BMI), and polyamides.
• The mechanism of degradation is believed to
involve the electrochemical generation of
hydroxide ions, which then cleave the amide
bonds.
DEGRADATION IN THE ENVIRONMENT

• Photo-oxidation
• Hydrolysis
• Ozonolysis of rubbers
• Biological degradation
Photo-oxidation
Hydrolysis
Ozonolysis of rubbers

• Ozonolysis of the isoprene rubber

was characterised by the formation of methyl
ketone groups which indicated chain rupture.
• Additional absorption bands for ozonide and
peroxide structures were observed and the
intensity of olefinic structure bands decreased
rapidly.
Ozonolysis of rubbers

• In organic chemistry, ozonolysis is an organic

reaction where the unsaturated bonds
are cleaved with ozone (O3).
• Multiple carbon–carbon bond are replaced
by carbonyl (C=O) groups, such as aldehydes, ketones,
and carboxylic acids.
• The reaction is predominantly applied to alkenes, but
alkynes and azo compounds are also susceptible to
cleavage.
• The outcome of the reaction depends on the type of
multiple bond being oxidized and the work-up conditions
Ozonolysis of rubbers

• In organic chemistry, ozonolysis is an organic

reaction where the unsaturated bonds
are cleaved with ozone (O3).
• Multiple carbon–carbon bond are replaced
by carbonyl (C=O) groups, such as aldehydes, ketones,
and carboxylic acids.
• The reaction is predominantly applied to alkenes, but
alkynes and azo compounds are also susceptible to
cleavage.
• The outcome of the reaction depends on the type of
multiple bond being oxidized and the work-up conditions
Ozonolysis of rubbers

• The reaction occurring between double

bonds and ozone is known
as ozonolysis when one molecule of the
gas reacts with the double bond:
Ozonolysis of rubbers

• The use of triphenylphosphine, thiourea, zinc dust,

or dimethyl sulfide produces aldehydes or ketones.
• While the use of sodium borohydride produces
alcohols. (R group can also be hydrogens)
Ozonolysis of rubbers

• The immediate result is formation of an ozonide, which then

decomposes rapidly so that the double bond is cleaved.
• This is the critical step in chain breakage when polymers are
attacked. The strength of polymers depends on the chain molecular
weight or degree of polymerization, the higher the chain length,
the greater the mechanical strength (such as tensile strength).
• By cleaving the chain, the molecular weight drops rapidly and
there comes a point when it has little strength whatsoever, and a
crack forms.
• Further attack occurs in the freshly exposed crack surfaces and the
crack grows steadily until it completes a circuit and the product
separates or fails.
• In the case of a seal or a tube, failure occurs when the wall of the
device is penetrated.
 Ozonolysis of rubbers

Tire showing weather-cracking over Ozone cracking in natural rubber tubing

long-term exposure to the weather.
Biological degradation

• The biodegradation of biodegradable polymers is defined as

chemical decomposition of substances, which is accomplished
through the enzymatic work of microorganisms that lead to a
change in chemical composition, mechanical and structural
properties and forming metabolic products, which are
environmentally friendly materials such as methane, water and
biomass and carbon dioxide.
Biological degradation

• The biodegradation process is affected by various factors

including polymer morphology, structure, chemical treatment and
molecular weight. (1) Polymer structure: biodegradable polymers
have hydrolyzable linkages (capable of undergoing hydrolysis)
along the chain of polymer that are exposed to degradation in the
presence of microorganisms and hydrolytic enzymes.
• Polymers with both hydrophobic and hydrophilic structures are
more degradable than polymers containing either hydrophobic or
hydrophilic structures
Biological degradation
DEGRADATION DURING RECYCLING

• Remelting
• Thermal depolymerisation & pyrolysis
• Chemical depolymerisation
DEGRADATION DURING RECYCLING -
Remelting

• Thermoplastic polymers like polyolefins can be

remelted and reformed into new items.
• This approach is referred to as mechanical recycling
and is usually the simplest and most economical form
of recovery.
• Post-consumer plastic will usually already bare a
degree of degradation.
• Another round of melt-processing will exacerbate this,
with the result being that mechanically recycled plastic
will usually have poorer mechanical properties than
virgin plastic.
DEGRADATION DURING RECYCLING -
Remelting

• Degradation can be enhanced by high concentrations

of hydroperoxides, cross-contamination between
different types of plastic and by additives present
within the plastic.
• Technologies developed to enhance the
biodegradation of plastic can also conflict with its
recycling, with oxo-biodegradable additives, consisting
of metallic salts of iron, magnesium, nickel, and
cobalt, increasing the rate of thermal degradation.
• Depending on the polymer in question, an amount of
virgin material may be added to maintain the quality of
the product
DEGRADATION DURING RECYCLING -
THERMAL DEPOLYMERISATION
• As polymers approach their ceiling temperature,
thermal degradation gives way to complete
decomposition.
• Certain polymers like PTFE, polystyrene
and PMMA undergo depolymerization to give their
starting monomers,
• Where monomers are obtained, they can be converted
back into new plastic (chemical or feedstock
recycling),
DEGRADATION DURING RECYCLING -
PYROLYSIS
• The process of breaking down long polymer chains with the
application of heat is termed as pyrolysis.
• The reaction of pyrolysis is carried out in the absence of oxygen
with or without the presence of a catalyst
• Polyethylene can undergo pyrolysis, with random chain scission
giving a mixture of volatile products.
• pyrolysis products are used as a type of synthetic fuel (energy
recycling).
• In practice, even very efficient depolymerization to monomers tends
to see some competitive pyrolysis.
• Thermoset polymers may also be converted in this way, for
instance, in tyre recycling.
DEGRADATION DURING RECYCLING -
CHEMICAL DEPOLYMERISATION
• The depolymerisation process – often referred to as chemolysis or
solvolysis – uses different combinations of chemistry, solvents and
heat to break down polymers into monomers.
• Monomers are the building blocks of polymers.
• Condensation polymers baring cleavable groups such as esters
and amides can also be completely depolymerised by hydrolysis
or solvolysis.
• This can be a purely chemical process but may also be promoted by
enzymes.
• Such technologies are less well developed than those of thermal
depolymerisation, but have the potential for lower energy costs.
• Thus far, polyethylene terephthalate has been the most heavily
studied polymer.
• Alternatively, waste plastic may be converted into other valuable
chemicals (not necessarily monomers) by microbial action
POLYMER BLENDS

• Polymer blends can be defined as the mixture of at

least two macromolecular compounds, polymers,
or copolymers.
• Polymer-based blends can be classified in to
immiscible or heterogeneous polymer blends,
compatible polymer blends, and miscible or
homogeneous polymer blends.
POLYMER BLENDS
POLYMER BLENDS - various economic and
property advantages accomplished by blending
Polymer Blends
 Types of Polymer Blends - On the basis of miscibility

 Basically there are three different types of blends depending on the miscibility
 Completely miscible blends (Miscible Polymer Blends (pslc.ws)
 In partially miscible blends
 Fully immiscible blends

Completely In partially miscible Fully immiscible

miscible blends blends blends
Polymer Blends - Completely Miscible Blends

Miscible - Meaning
 capableof being mixed; specifically : capable of mixing in any ratio
without separation of two phases. Examples: Oil and water are not
miscible—if you pour oil in a glass of water, it will float to the top.
 Butsalt and water is a miscible mixture which will blend in together to
form a new solution of salt water.

Completely miscible
blends
Polymer Blends - Completely Miscible Blends
 Examples of miscible polymer blends:
 homopolymer–homopolymer:
polyphenylene oxide (PPO) – polystyrene (PS): The miscibility
of the two polymers in l is caused by the presence of an
aromatic ring in the repeat units of both chains
polyethylene terephthalate (PET) – polybutylene
terephthalate (PBT)
poly(methyl methacrylate) (PMMA) – polyvinylidene
fluoride (PVDF)
 homopolymer–copolymer:
polypropylene (PP) – EPDM (Ethylene propylene diene
monomer
polycarbonate (PC) – acrylonitrile butadiene styrene (ABS)
 Polymer Blends -In partially miscible blends
• In partially miscible blends a small part of one of the blend component is
dissolved in the other part.
• This type of blend, which exhibits a fine phase morphology and
satisfactory properties, is referred to as compatible.
• Both blend phases are homogeneous, and have their own Tg.
• An example is the PC/ABS (polycarbonate / acrylonitrile-butadiene-styrene
terpolymer) blends.
• In these blends, PC and the SAN (Styrene-acrylonitrile) phase of ABS
partially dissolve in one another. In this case interface is wide and the
interfacial adhesion is good.

In partially miscible blends

Polymer Blends -Fully immiscible blends

• Immiscible blends have a coarse morphology, sharp interface and poor adhesion
between the blend phases.
• So these blends are of no use without compatibilization
• These blends will exhibit different Tgs corresponding to the Tg of the
component polymers. Examples of fully immiscible blends are PA/ABS
(Polyamide/acrylonitrile-butadiene-styrene copolymer), PA/PPO, PA/EPDM and
 Polymer Blends -Fully immiscible blends

• These blends will exhibit different Tgs corresponding

to the Tg of the component polymers.
• Examples of fully immiscible blends are PA/ABS
(Polyamide/acrylonitrile-butadiene-styrene copolymer),
PA/PPO (polyamide / poly(phenylene oxide), PA/EPDM
(polyamide / Ethylene propylene diene monomer and
PA/PP (polyamide / polypropylene).
 Properties of Polymer Blends

• In general, a miscible blend of two polymers is

going to have properties somewhere between those
of the two unblended polymers.
• Take for example the glass transition temperature,
or Tg for short.
• If we take polymer A and blend it with polymer B,
the Tg will depend on the ratio of polymer A to
polymer B in the blend.
• You can see this in the graph below.
Properties of Polymer Blends

• If polymer B has a higher Tg than polymer A, the Tg of the blend is going

to increase as the relative amount of polymer B in the blend increases.
• The increase is generally linear, like you see in the graph.
• But the plot isn't perfectly linear.
• Sometimes if the two polymers bind more strongly to each other than to
themselves, the Tg will be higher than expected, because the stronger
binding lowers chain mobility.
 Properties of Polymer Blends
• The plot will look like you see in the graph on the right below.

• Of course, in most cases, the two polymers bind less strongly with each other
than with themselves, so the Tgs of the blends are usually a little lower than
expected.
• The Tg plot will look like the one you see above on the left.
• We've been talking about Tgs up until now, but what holds for Tgs generally
holds for other properties.
• Mechanical properties, resistance to chemicals, radiation, or heat; they all
generally plot the same way as the Tg does with respect to the relative amounts
of each polymer in the blend.
 Properties of Polymer Blends

• This makes altering the properties of your blend fairly simple. When you vary
the amount of the two polymers, you vary the properties.
• This can be very useful.
• We shall use the example of poly(phenylene oxide), a.k.a. PPO, to illustrate.
• PPO is a very heat resistant polymer.
• This is wonderful because people need heat resistant materials.
• But it has some drawbacks. It's very hard to process.
• You see, it's too heat resistant.
• Amorphous polymers are usually processed by heating them above their Tgs
so they get soft and gluey.
• But with a Tg of 210 oC, heating PPO enough to make it soft and gluey is not
only difficult, but expensive.
 Properties of Polymer Blends

• Now take polystyrene.

• Remember, polystyrene and PPO blend nicely with each other.
• Since polystyrene has a Tg of only about 100 oC, blending polystyrene

with PPO drops the Tg of the blend down to temperatures which make
the blend much more processable than straight PPO.

For more details on polymers, visit the following website:

The Macrogalleria - a cyberwonderland of polymer fun (pslc.ws)

 ALLOYS OF POLYMERS
• The procedure of mixing polymers with other polymers,
chemical additives, inorganic fillers, and strengthening
fibers has given polymer scientist and engineer an
effective tool to tailor-make materials for attaining
specifically balanced mixtures of physical properties,
with polished characteristics.
• This flexibility of property manipulation is the primary
reason for the variety of applications of polymeric
substances.
• Alloy Polymers form one category of such
multicomponent polymer systems.
 ALLOYS OF POLYMERS
• Polymer alloys are a category of polymer blends where
another polymer’s addition is modified to deliver
controlled morphology, and thus specific performance
traits.
• You can greatly revise the qualities of many plastics by
blending or alloying two or more polymers.
• These phrases are repeatedly exploited interchangeably,
but technically, blends are combinations that are not
entirely compatible, and alloys are fully compatible.
• Polymer alloy comprises a distinct sub-class of polymer
blends; nearly all high-performance engineering blends
are alloys.
ALLOYS OF POLYMERS
ALLOYS OF POLYMERS
Polymer alloys are increasingly being used in engineering applications, such as bearings,
pump impeller, valves, electrical components, gears etc., which traditionally have been
the domain of metals.
ALLOYS OF POLYMERS – Modification in
Properties
• Alloying of AsS with pvc significantly improves the impact strength with
marginal drop in the tensile strength
• The PVC and PMM^ alloy offers an outstanding balance of toughness,
impact resistance and, durability over a broad range of temperatures.
• It can be easily thermoformed, unlike its constituent polymers, and deep
draws can be accomplished without tearing the sheet
 Polymer Composites
• A composite is a material made from at least two or more
materials with significantly different chemical and physical
properties.
• When combined, they form another material that has properties
different from the individual components.
• Components are made of two parts: a fibre and a matrix.
• Fibres can be materials such as polyethylene, glass, carbon fibre,
or Kevlar.
• At the same time, a matrix is what holds the fibres together.
• The matrix is usually a thermoset such as an epoxy resin,
polydicyclopentadiene, or polyimide.
• To make the material of the matrix stronger, the fibres are
embedded into the matrix.
• This is one of the most common types of composite materials,
called fibre-reinforced composites.
Polymer Composites - Properties

• Good corrosion resistance.

• Lightweight
• Good abrasion resistance
• High strength along the direction of their reinforcements
• High stiffness
• faster assembly
• The individual characteristics of the fibre material
• The individual characteristics of the polymer matrix material.
• The ratio to which the fibre and the polymer matrix are combined
(Also known as the fiber volume fraction)
Polymer Composites - Classification

• The first level of classification: This is made according to

the polymer matrix constituents.
• The major component classes under this type of
classification include:
• Metal matrix composites (M.M.C.s)
• Organic matrix composites (O.M.C.’s)– Further
divided into two classes of components: the polymer
matrix composites (P.M.C.s) and the Carbon Matrix
Compos, also known as the carbon-carbon
composites.
• Ceramic matrix composites (C.M.C.s)
Polymer Composites - Classification

The second level of classification: This is made according to

the reinforcement form.
These are further divided into:
• Fibre-reinforced components are further divided into

 fibres containing continuous and

 discontinuous fibres.
• Laminar Composites.
• Particulate Composites.
Polymer Composites - Metal matrix composites
(M.M.C.s)
• Metal matrix composites (M.M.C.’s) are some materials (such as alloys, metallic,
and intermetallic compounds) incorporated with reinforcing phases such as
whiskers, particulates, or continuous fibers.
• According to the matrix material, they are classified into the following metal
matrix configurations:
• Aluminum-based composites; Aluminum is either used as a cast alloy, or it
is used as a wrought alloy (such as AlMgSi, AlZnMgCu, AlCu, AlMg,
AlCuSiMn, AlSiCuMg)
• Super alloy-based composites
• Titanium-based composites
• Magnesium-based composites
• Copper-based composites
Applications of Metal matrix composites
(M.M.C.’s)
 The Aluminum-based matrix composites are widely seen in the aerospace and
automotive industries.
 Fiber-based titanium composites are used in developing the structures of the
aircraft.
 Titanium-based composites are used for manufacturing missile and aircraft
structures, whose operating speeds are very high.
 The main disadvantage of titanium-based composites is that they are highly
reactive.
 Magnesium–matrix composites have lower thermal conductivity and are used
actively in the space industry.
 Superalloys are commonly used for the manufacture of turbine blades as they
operate at higher speeds and temperatures.
Polymer matrix composites (P.M.C.’s)

 These polymer matrix composites are the most produced composite matrix
materials.
 The fibers in Polymer Matrix Composites (P.M.C.’s) are embedded in the organic
polymer matrix.
 This kind of polymer is used to enhance the properties of the materials.
 Its applications range from gadget components to automotive accessories.
 The most common type of polymers that are used as composites is either
elastomers, thermosetting polymers, or thermoplastic polymers.
Polymer matrix composites (P.M.C.’s) -
Advantages
The many added advantages of the Polymer matrix composites (P.M.C.’s) include:
 Attractive optical properties
 Lesser specific weight
 High material stability against corrosion
 Economic mass production
 Ease of shaping
 Good electrical insulation
 Good thermal insulation
Polymer matrix composites (P.M.C.’s) –
Properties
The overall properties of a P.M.C. are affected by its constituents; these are:
 Matrix: This polymer is in the continuous phase. This is the weak link in the
structure of the P.M.C.
 Reinforcement: This part can either be carbon fiber, quartz, basalt, or glass.
This is the main load-bearing element, and it is in the discontinuous phase.
 Interphase: This part is where the load transmission takes place between the
matrix phases and the reinforcement.
 Apart from these factors, the properties of the P.M.C. are affected by the
nature of the interphase, the reinforcement geometry, and the
constituents’ relative proportions.
Polymer matrix composites (P.M.C.’s) –
Properties
The overall properties of a P.M.C. are affected by its constituents; these are:
 Matrix: This polymer is in the continuous phase. This is the weak link in the
structure of the P.M.C.
 Reinforcement: This part can either be carbon fiber, quartz, basalt, or glass.
This is the main load-bearing element, and it is in the discontinuous phase.
 Interphase: This part is where the load transmission takes place between the
matrix phases and the reinforcement.
 Apart from these factors, the properties of the P.M.C. are affected by the
nature of the interphase, the reinforcement geometry, and the
constituents’ relative proportions.
 Polymer composites in simple terms 2024 Kruger Industries
Polymer matrix composites (P.M.C.’s) –
Classifications
The Polymer Matrix Composites (P.M.C.’s) are classified into different categories
based on their stiffness and strength level.
The two distinct types of categories include:
Reinforced plastics:
• These P.M.C.’s have more strength as the embedded
fibrous matter is added to plastics.
Advanced Composites:
• These types of P.M.C.’s contain combinations of matrix and
fibers.
• They facilitate more strength and stiffness.
• These composites contain continuous fibers such as aramid,
graphite, organic fibers, and high-stiffness glass.
Polymer matrix composites (P.M.C.’s) –
Classifications - Glass Fiber Reinforced Plastic
(GFRP) or FRP Composite:

 The Glass Fiber Reinforced polymer composite is produced in the largest

quantities.
 GFRP composite or FRP composite consists of glass fibers in the polymer
matrix.
 The diameter of the glass fiber ranges between 3-20mm. glass is widely used as
reinforcement due to the following reasons:
• One can draw glass easily into fibers from its molten state.
• It is readily available
• Glass is economical to fabricate
• One can use many composite manufacturing techniques.
• The composites produced from glass have high tensile strength.
• When the glass fibers are combined with the polymer matrix, they
possess chemical inertness hence this composite is very useful in
corrosive environments.
 Glass Fiber Reinforced Plastic (GFRP) or FRP
Composite: Applications

Glass Fiber reinforced Plastics – GFRP holds many applications, some of them
include:
 Transportation industries
 Plastic pipes
 Storage container
 Automotive and marine bodies
 Industrial floorings
 Carbon Fiber Reinforced Polymer composites

In Carbon Fiber Reinforced Polymer CFRP composites,

the carbon fibers provide stiffness and strength to the
polymer composites, whereas the polymer matrix holds
the fibers together to provide some toughness.
 Carbon Fiber Reinforced Polymer composites

 Among the other reinforcing fiber materials, Carbon fibers have the highest
specific modulus and specific strength.
 At elevated temperatures, carbon fibers can retain their strength and modulus.
 Carbon fibers are not affected by acids, bases, moisture, etc., at higher
temperatures.
 According to the applications of CFRP, the carbon fibers can be engineered.
 The manufacturing process of Carbon fibers are relatively cost-effective and
inexpensive.
 Non-crystalline and graphite regions are represented by carbon fibers. The matrix
materials include pitch, polyacrylonitrile (P.A.N.), and rayon.
 Usually, the carbon fibers are coated with an epoxy size, which improves the
polymer matrix adhesion.
 Carbon Fiber Reinforced Polymer composites -
Applications

 Both military and commercial, helicopters (wing, body, etc.)

 Extensively used in sports, filament-wound rocket motor,
recreational equipment (fishing rods, golf clubs).
 Cars (aircraft structural components and pressure vessels)
 Aramid fiber reinforced polymer composites
 The first organic fiber used as reinforcement in polymer
composites was an aramid-fiber reinforced polymer.
 When compared to steel and glass fibers, aramid fibers have
better mechanical properties and equal weight.
 This group of materials is known as the poly para phenylene
terephthalamide.
 Kevlar and Nomex are the most common aramid materials.
 Having high strength and moduli, these fibers are weak in
compression.
 These fibers are susceptible to degradation by strong acid
and bases and are stable at high temperatures (-200°C to
 Aramid fiber reinforced polymer composites -
Applications
Applications of Aramid fiber reinforced polymer composites –
AFPC
 Automotive brake
 Missile cases,
 Bulletproof vests,
 Sporting goods, ropes, and clutch lining gaskets, etc.
 Basic concepts Selection of materials.

.
 Basic concepts Selection of materials.

Step 1 - Define key criteria for your part: main task here is to
proper estimate the requirements of the part which can be based
on performance criteria, appearance criteria, and cost targets
(part costs, tooling costs and equipment costs).
 Basic concepts Selection of materials.
Step 2 - Selection of the manufacturing process:
• There are several things to consider when selecting the manufacturing
process of your part.
• On one hand, it is the part size, part complexity, and all over product
volumes.
• On the other hand, you have equipment costs. For example, costs of an
injection moulding machine in case a new one is needed and tooling
costs.
• Production volumes are the driving force here, followed by tooling
costs.
• The material cost can vary from 50% (technical parts) up to 80%
(consumer parts) of your manufacturing costs
 Basic concepts Selection of materials.
Step 2 - Selection of the manufacturing process:
• The economic batch size varies for the different processing
techniques:
 Basic concepts Selection of materials.
Step 3 – Create a short list of materials:
• After we estimated the key criteria and manufacturing process it is
time to create a short list of potential material candidates.
• A grouping into chemical family such as polyolefines, aliphatic
nylons, semi-aromatic nylons, polyesters, polysulfones,
fluoropolymers, polyketones, polyimides, and so on is useful.
• Furthermore, grouping by primary additives such as fiber (glass,
carbon) reinforcement, tougheners, heat stabilizers, flame
retardants is helpful at this stage too.
 Basic concepts Selection of materials.
Step 3 – Create a short list of materials:
• Additionally, you can look for plastic material suppliers in online
databases such as Pro-Plast or you can work with online selection
guides such as these ones: Omnexus.
• Furthermore, CAMPUS material database offers a comparison of
hundreds of grades and their properties in an uniform way (every
resin supplier who contributes to CAMPUS tests their materials in
the same way).
 Basic concepts Selection of materials.
The Step 4 – Evaluation of your data:
• Now the feasibility study can start by evaluating the material data
of the chosen polymers for mechanical, chemical, electrical,
process ability, post-processing capabilities such as laser welding,
painting or metallization.
• Since some load cases of the final part are available, structural
analysis can be done too.
• Cost analysis is crucial for some end markets such as automotive
and it needs to be included at this stage.
• The same is valid for supply chain and global availability of the
suggested materials.
 Basic concepts Selection of materials.
The Step 4 – Evaluation of your data:
• Cost analysis is crucial for some end markets such as automotive
and it needs to be included at this stage.
• The same is valid for supply chain and global availability of the
suggested materials.
• The complexity of the analysis can vary and time wise it can take
days or some months to obtain conclusive results.
 Basic concepts Selection of materials.
Step 5 – Develop your prototypes:
• Now you dive into the product development phase, which has an
iterative character.
• In this phase, the focus is kept on detailed engineering. It is
usually the longest phase and it allows you to create prototypes,
test them, and re-iterate.
• Your material selection list will get more focused and some
materials might fall off the list.
• In corporations, this phase can take place in the Research &
Development (R&D) departments.
 Basic concepts Selection of materials.
Step 5 – Develop your prototypes:
• There, engineers and scientists test and approve the different
materials or they approve a process where the material is
integrated.
• Product development groups have usually the product itself as an
output.
• In some cases, the material needs to be first approved by the
R&D for general design use that it can appear on the selection list
for certain parts in the Product Development group.
 Basic concepts Selection of materials.
Step 6 – Selection of the material:
• In the final step, selection takes place.
• The selection should be already pretty obvious and it should be
not a surprise anymore which material will be used in the product.
• The selected plastic fulfills all the set criteria, including cost
effectiveness.
• Implicit knowledge is turned into explicit results which allow a
fact-based decision.
• If the decision is not yet easy and clear to take, then it is best to
revise some of the steps, especially the starting steps.
 Basic concepts Selection of materials.
Step 6 – Selection of the material:
• It will cause some time delays and is still better to take the extra
loop since a wrong material choice now will lead to potential
higher costs in the future.
• It is always useful to cross-check the results and the suggests with
the resin supplier since they have in-house know-how build up on
their materials including lots of testing and actual applications.
 Additives for plastics -

Step 6 – Selection of the material:

 Basic need for incorporating additives. -

Classifications of additives. Types and applications.

Incorporation of additives (Elementary concepts only).
 Classifications of additives.

Types and applications. Incorporation of additives (Elementary

concepts only).
Additives -Types and Applications .
 Incorporation of additives (Elementary
concepts only).

. fg
 UNIT-II
Syllabus
Injection moulding of thermoplastics materials.
Constructional features of moulding equipment.
Technical specifications of the injection
moulding machine Moulding cycle. Various
process parameters and their influence on the
quality of the moulded products. Trouble
shooting in injection moulding. FRP process -
Ancillaries used in FRP. Processes like hand
layup, spray up & filament winding techniques
 UNIT-III
Syllabus
Extrusion – Constructional features of extruded
equipments, blown film, cast films, multiplayer
films, Biaxially oriented films, Extrusion of
sheets, tapes, box strapping and monofilaments.
Extrusion coating/ lamination Aspects to be
covered are auxillary equipment, plant layouts,
process parameters and their effect on the
quality of the extruded products and trouble
shooting.
 UNIT-IV

CONCEPT AND ADVANCED

PROCESSING OF PLASTICS AND
POLYMER PACKAGING
 UNIT-IV
Syllabus
Blow moulding – Constructional features of a blow
moulding equipment. Materials for blow moulding.
Classification – Extrusion blow moulding ( )
Injection blow moulding & Stretch blow moulding
(injection & extrusion) Comparison of the above
processes Trouble shooting in blow moulding,
Calendering – plant layout – calender roll
construction & configuration. Process parameters
and their influence. Trouble shooting in calendaring
 UNIT-V
Syllabus
Thermoforming - Male mould forming, female
mould forming, plug assist forming &
continuous forming lines. Trimming device and
techniques. Rotational moulding – Materials
used. Principle of biaxial drives & moulding
plants, Foam plastics – Moulding of expandable
polystyrene material. Preparation of expandable
PS beads - Preparation, stabilisation & moulding
stages.