ADVANCED POLYMER

CHEMISTRY
IOFS Course-2015

Dr. Chetan Bhongale

Department of Applied Chemistry
 Polymer

A compound consisting of long-chain molecules, each

molecule made up of repeating units connected together

• There may be thousands, even millions of units in a

single polymer molecule

• The word polymer is derived from the Greek words poly,

meaning many, and meros (reduced to mer), meaning
part

• Most polymers are based on carbon and are therefore

considered organic chemicals

©2002 John Wiley & Sons, Inc. M. P. Groover, “Fundamentals of Modern Manufacturing 2/e”
 POLYMERS

A large molecule composed of many

repeated subunits, known as monomers
via chemical bond
Polymer chains

Polypropylene

DNA structure of a biopolymer

 Hydrocarbons Ex: Alkanes

• 1 – Meth-
• 2 – Eth-
• 3 – Prop-
• 4 – But-
• 5 – Pent-
• 6 – Hex-
• 7 – Hept-
• 8 – Oct-
• 9 – Non-
• 10 – Dec-
• 11 – Undec-
• 12 – Dodec-
 Hydrocarbons at Room Temperature

• Gas  Liquid  Waxy • Plastic

 Methane 20 to 40 40 or more
 Ethane 5 to 19 Carbons Carbons
 Propane Carbons
 Butane
 Melting Point

As the length of hydrocarbons get longer, the Melting

Point grows Higher

Melting and Boiling Temperatures of Alkanes

600

500

400
Boiling Point (˚C)
Tempurature (˚C)

300

200
Melting Point(˚C)
100

-100

-200

-300
0 5 10 15 20 25 30 35 40 45
Number of Carbons
 What other material properties change?

 Viscosity

 Hardness

 Toughness

 Flammability
 Bonding

• Covalent

• Ionic (NaCl)

• Polar (H2O)

• Van der Waals

 Rubber Tree

• Sap:
 Sticky
 Viscous
Vulcanization
 Molecular Structure of Polymers

a. Linear
 High Density Polyethylene (HDPE), PVC,
Nylon, Cotton

b. Branched
 Low Density Polyethylene (LDPE)

c. Cross-linked
 Rubber

d. Network
 Kevlar, Epoxy
 Synthesis of Polymers

• Nearly all polymers used in engineering are synthetic

 They are made by chemical processing

• Polymers are synthesized by joining many small

molecules together into very large molecules, called
macromolecules, that possess a chain-like structure

• The small units, called monomers, are generally

simple unsaturated organic molecules such as
ethylene C2H4

©2002 John Wiley & Sons, Inc. M. P. Groover, “Fundamentals of Modern Manufacturing 2/e”
 Addition (chain)
Polymerization

• In this process, exemplified by polyethylene, the

double bonds between carbon atoms in the ethylene
monomers are induced to open up so that they join
with other monomer molecules

• The connections occur on both ends of the

expanding macromolecule, developing long chains of
repeating mers

• It is initiated using a chemical catalyst (called an

initiator) to open the carbon double bond in some of
the monomers
Model of addition (chain) polymerization: (1) initiation, (2) rapid
addition of monomers, and (3) resulting long chain polymer
molecule with ‘n’ mers at termination of reaction
 Step (condensation)
Polymerization
• In this form of polymerization, two reacting monomers
are brought together to form a new molecule of the
desired compound

• As reaction continues, more reactant molecules

combine with the molecules first synthesized to form
polymers of length n = 2, then polymers of length n =
3, and so on

• In addition, polymers of length n1 and n2 also

combine to form molecules of length n = n1 + n2, so
that two types of reactions are proceeding
simultaneously
 Some Examples

• Polymers produced by addition polymerization:

 Polyethylene,
 polypropylene,
 polyvinylchloride,
 polyisoprene

• Polymers produced by condensation polymerization:

 Nylon,
 polycarbonate,
 phenol formaldehyde
Model of step polymerization showing the two types of reactions
occuring:
(a) n-mer attaching a single monomer to form a (n+1)-mer; and
(b) n1-mer combining with n2-mer to form a (n1+n2)-mer

Sequence is shown by (1) and (2)

 Types of Polymers

• Polymers can be separated into plastics and rubbers

• As engineering materials, it is appropriate to divide

them into the following three categories:

1. Thermoplastic polymers
2. Thermosetting polymers
3. Elastomers

where (1) and (2) are plastics and (3) are rubbers
Thermoplastic Polymers - Thermoplastics (TP)

• Solid materials at room temperature but viscous

liquids when heated to temperatures of only a few
hundred degrees

• This characteristic allows them to be easily and

economically shaped into products

• They can be subjected to heating and cooling cycles

repeatedly without significant degradation
 Thermosetting Polymers - Thermosets (TS)

• TS cannot tolerate repeated heating cycles as

thermoplastics can

 When initially heated, they soften and flow for molding

 But elevated temperatures also produce a chemical

reaction that hardens the material into an infusible solid

 If reheated, thermosets degrade and char rather than

soften

©2002 John Wiley & Sons, Inc. M. P. Groover, “Fundamentals of Modern Manufacturing 2/e”
 Elastomers

Polymers that exhibit extreme elastic extensibility

when subjected to relatively low mechanical stress

• Also known as rubber

• Some elastomers can be stretched by a factor of 10

and yet completely recover to their original shape

• Although their properties are quite different from

thermosets, they share a similar molecular structure
that is different from the thermoplastics
 Examples of Polymers

• Thermoplastics:
 Polyethylene, polyvinylchloride, polypropylene,
polystyrene, and nylon

• Thermosets:
 Phenolics, epoxies, and certain polyesters

• Elastomers:
 Natural rubber (vulcanized)
 Synthetic rubbers, which exceed the tonnage of
natural rubber

©2002 John Wiley & Sons, Inc. M. P. Groover, “Fundamentals of Modern Manufacturing 2/e”
 Thermoplastic and thermosetting polymers

Thermoplastic/Thermosoftening Thermosetting Polymers

Polymers

Generally formed by monomers Generally formed by the monomers

containing C=C by addition reaction. having functional groups such as –
NH2, -COOH, -COOR, etc. by
condensation reaction.
These contain linear chain with These are three-dimensional due to
negligible cross-linking. highly cross-linking.

These are reversible to action against These do not soften on heating, but if
heat i.e. they become soft on heating they are heated excessively, they
and hard on cooling, repeatedly. decompose or burn or char.
Molecular weights are relatively lower. Molecular weights range from
moderate to higher.

Soluble in some organic solvents. Insoluble due to high degree of

cross-linkage.
They can be recycled. They can not be recycled.

Shapes can be changed number of Once shape given in the mould,

times by heat/pressure application. reshaping not possible.

Soft, weak, less brittle. Hard, strong and more brittle.

Examples: Polyethylene, PS, PVC, Examples: Phenol formaldehyde,

polycarbonates, nylon, PMMA. urea-formaldehyde, silicones,
unsaturated polyesters.
 Market Shares

• Thermoplastics are commercially the most important

of the three types, constituting around 70% of the
tonnage of all synthetic polymers produced

• Thermosets and elastomers share the remaining

30% about evenly, with a slight edge for the former

• On a volumetric basis, current annual usage of

polymers exceeds that of metals
 Low-Density Polyethylene (LDPE)

Chain Length: 1000-2000

 High-Density Polyethylene (HDPE)

Chain Length: 10,000 – 100,000

 Ultra-high-molecular-weight polyethylene
(UHMWPE)

Chain Length: 2-6 million

Joint
Replacement
Helmet

Gears
 Endless Possibilities

• New
Functional
Groups

• Different
Polymer
Backbones
 Functional Groups

In Monomer In Polymer
• Carboxyl : -COOH -COOR-
• Hydroxyl : -OH -R--O—R-
• Amine : -NH2 -CONH-R-
• Anhydride: -(CO)2O -CO-N-CO-
• Chloride : -Cl -R--O—R-
• Epoxy : -H2C--CH2- -H2C-CH2-O
O
• Isocyanate : -NCO -NH-CO-O-R-
 PVC – (polyvinyl chloride)

Chain Length: 4,000 – 5,000

More Polar  Stronger Bonding (Low Cost)

 Polyethylene Terephthalate (PETE)
“Polyester”

Chain Length: 4,000 – 8,000

Nylon
 Cotton
Chain length: 2000-3500

Long Strands of Cellulose

+ Hydrogen Bonds

Cellulose is the most common organic material on

earth! It is also a primary constituent of wood and paper.
 Polymers in Biology

Starch

DNA

Sugar Proteins
 Kevlar

Strong Network of
Covalent Bonds
And Polar Hydrogen
Bonds
Inorganic Polymers

• Silicon (Si)
Inorganic Polymers

• Silicon (Si)
• Germanium (Ge)
Inorganic Polymers

• Silicon (Si)
• Germanium (Ge)
• Boron-Nitrogen (B – N)
Inorganic Polymers

• Silicon (Si)
• Germanium (Ge)
• Boron-Nitrogen (B – N)
• Aluminum – Nitrogen (Al – N)
• …
• …
• On and so on
 Reasons Why Polymers are Important:

• Plastics can be formed by moulding into intricate part

shapes, usually with no further processing required
 Very compatible with net shape processing

• On a volumetric basis, polymers:

 Cost competitive with metals
 Generally require less energy to produce than
metals

• Certain plastics are transluscent and/or transparent,

which makes them competitive with glass in some
applications
 General Properties of Polymers

• Low density relative to metals and ceramics

• Good strength-to-weight ratios for certain (but not all)

polymers

• High corrosion resistance

• Low electrical and thermal conductivity

 Tm and Tg

• Melting Temperature (Tm): If a polymer is heated, it absorbs heat and

becomes thick and highly viscous liquid. Viscous polymers are generally
elastic in nature. This state of polymer is called ‘viscoelastic state’.

“The temperature above which the viscoelastic state of polymer is achieved is

called Melting Temperature (Tm)”.

• Glass Transition Temperature (Tg): If polymers are cooled below certain

temperature, the polymer chain gets entangled in each other and it is very
difficult to separate them. Polymer becomes hard and brittle and behaves like
a glass. This hard and brittle state of the polymer is called as “glassy state”.

“The temperature below which the polymer becomes hard, brittle and glassy
and above which it is softer and flexible, is called as glass transition
temperature (Tg)”.
 Factors affecting Tg

1. Crystallinity:

2. Molecular weight:

3. Cross-linking and coiling:

4. Intermolecular forces of attraction between polymer chains:

5. Side-groups on chain:

6. Addition of plasticizers:
 Compounding of plastics

Compounding is a process that converts powdery, gummy polymer into soft,

homogenous and modulable mixture with the help of various additives.

“Conversion of raw polymers/plastics into more usable form can be done by

adding many external agents such as plasticizers, vulcanizing agents, stabilizers,
fillers, coloring agents, flame retardants and lubricants is called as “Compounding
of Plastic”.

Compounding Devices:

1. Two-roll mill
2. Kneaders
3. Masticators
4. Paddle blenders
5. Tumblers and blenders, etc.
• Plasticizers: Some polymers have horny texture and cannot be moulded easily.
Plasticizers are added to such plastics and they are converted to soft and
remouldable form. Reduces ‘Tg’ of plastic.
Example: Dibutyl phthalate, dioctyl sabacate are used as plasticizers for
polyvinyl chloride (PVC).

• Vulcanizing agents: Linear and natural rubber is converted into highly cross-
linked and usable rubber by adding vulcanizing agent by a process called
vulcanization. Vulcanized rubber is strong and durable.
Example: Sulphur is a vulcanizing agent for natural rubber.

• Stabilizers: Some thermosoftening plastics/polymers decompose and

decolorize at the moulding temp. In order to make them thermally stable,
stabilizers are added to plastic.
Example: Alkaline earth metals (Pb, Ba, Cd) salts, epoxy compounds are added
in small proportions to PVC to make it stable polymer.

• Fillers: The polymers in their pure form are not mechanically strong. Fillers are
added to polymers during processing in order to make them mechanically strong.
Example: Carbon black, CaCO3, sand (quartz) are added to natural rubber.
• Coloring agents (Pigments): Polymers in their pure form are
colorless/transluscent/dull to look. In order to impart beautiful color to plastic
articles, coloring agents are added during processing.
Example: Paints and salts of transition metals, organic dyes.

• Lubricants: Lubricants like wax, metal stearates, oleates, soaps, etc. are
applied to inner side of a mould before a plastic is moulded. This helps in easier
moulding and glassy finish to the product.
Example: wax, oleates.

• Accelerators: These are catalysts added to thermostat resins to speed up curing

reactions.
Example: ZnO, CaO, oxalic acid, etc.

• Anti-oxidants: Plastics being organic compounds, they are prone to oxidative

degradation, so anti-oxidants are added to prevent slow oxidative degradation or
rapid oxidative degradation at high temp during the processing.
Example: Phosphite, thioesters, etc.
Limitations of Polymers as Engineering Materials

• Low strength relative to metals and ceramics

• Low modulus of elasticity (stiffness)

• Service temperatures are limited to only a few

hundred degrees

• Viscoelastic properties, which can be a distinct

limitation in load bearing applications

• Some polymers degrade when subjected to sunlight

and other forms of radiation
Synthesis of polyethylene from ethylene monomers:
(1) ‘n’ ethylene monomers yields (2a) polyethylene of chain length
‘n’ (2b) concise notation for depicting the polymer structure of chain
length ‘n’
 Polymerization

• As a chemical process, the synthesis of polymers

can occur by either of two methods:
1. Addition polymerization
2. Step polymerization

• Production of a given polymer is generally

associated with one method or the other
 Degree of Polymerization

• Since molecules in a given batch of polymerized

material vary in length, n for the batch is an average;
its statistical distribution is normal

• The mean value of n is called the degree of

polymerization (DP) for the batch

• DP affects properties of the polymer: higher DP

increases mechanical strength but also increases
viscosity in the fluid state, which makes processing
more difficult
 Molecular Weight

• The molecular weight (MW) of a polymer is the sum

of the molecular weights of the mers in the molecule;

 MW = n times the molecular weight of each

repeating unit

 Since n varies for different molecules in a batch,

the molecule weight must be interpreted as an
average
Typical Values of DP and MW for Selected Polymers

Polymer DP (n) MW

Polyethylene 10,000 300,000

Polyvinylchloride 1,500 100,000
Nylon 120 15,000
Polycarbonate 200 40,000
 Glass Transition Temperature of copolymers
Copolymers:

 Two component
 Multicomponent

Glass transition temperature (Tg): It is the

temperature below which it behaves like glass (brittle)
and above which is rubbery

 For every polymer there is one Tg

 For copolymer it is one which is determined by Fox equation

1/Tg = w1/Tg1 + w2/Tg2

Tg : Glass transition temp. of copolymer in Kelvin

Tg1 & Tg2 : Glass transition of constituent homopolymers in Kelvin
 Linear, Branched, and Cross-linked Polymers

• Linear structure– chain-like structure

 Characteristic of thermoplastic polymers

• Branched structure– chain-like but with side branches

 Also found in thermoplastic polymers

• Cross-linked structure
 Loosely cross-linked, as in an elastomer
 Tightly cross-linked, as in a thermoset
Linear structure of a thermoplastic polymer

(a) linear, characteristic of thermoplastics

Branched structure that includes side branches
along the chain

(b) branched
Loosely cross-linked, in which primary bonding
occurs between branches and other molecules at
certain connection points

(c) loosely cross-linked as in an elastomer

Tightly cross-linked or network structure - in effect,
the entire mass is one gigantic macromolecule

(d) tightly cross- linked or networked structure as in a thermoset

 Effect of Branching on Properties

• Thermoplastic polymers always possess linear or

branched structures, or a mixture of the two

• Branches increase entanglement among the

molecules, which makes the polymer:
 stronger in the solid state
 more viscous at a given temperature in the plastic
or liquid state
 Effect of Cross-Linking on Properties

• Thermosets possess a high degree of cross-linking,

while elastomers possess a low degree of
cross-linking

• Thermosets are hard and brittle, while elastomers are

elastic and resilient

• Cross-linking causes the polymer to become

chemically set
 The reaction cannot be reversed
 The polymer structure is permanently changed; if
heated, it degrades or burns rather than melt
 Crystallinity in Polymers

• Both amorphous and crystalline structures are

possible, although the tendency to crystallize is much
less than that for metals or non-glass ceramics

• Not all polymers can form crystals

• For those that can, the degree of crystallinity (the

proportion of crystallized material in the mass) is
always less than 100%
Crystallized regions in a polymer:
(a) long molecules forming crystals randomly mixed with the
amorphous material; and
(b) folded chain lamella, the typical form of a crystallized region
 Crystallinity and Properties

• As crystallinity is increased in a polymer:

 Density increases

 Stiffness, strength, and toughness increases

 Heat resistance increases

 If the polymer is transparent in the amorphous

state, it becomes opaque when partially
crystallized
 Low Density vs. High Density
Polyethylene

Polyethylene type Low density High density

Degree of crystallinity 55% 92%

Specific gravity 0.92 0.96

Modulus of elasticity 140 MPa 700 MPa

(20,000 lb/in2) (100,000 lb/in2)

Melting temperature 115C 135C

(239F) (275F)
 Some Observations About Crystallization

• Linear polymers consist of long molecules with

thousands of repeated mers
 Crystallization involves folding back and forth of
the long chains upon themselves to achieve a very
regular arrangement

• The crystallized regions are called crystallites

• Crystallites take the form of lamellae randomly mixed

in amorphous material
 A polymer that crystallizes is a two-phase
system - crystallites interspersed throughout an
amorphous matrix
 Factors affecting Crystallization

• Slower cooling promotes crystal formation and

growth

• Mechanical deformation, as in the stretching of a

heated thermoplastic, tends to align the structure and
increase crystallization

• Plasticizers (chemicals added to a polymer to soften

it) reduce the degree of crystallinity
 Additives

• Properties of a polymer can often be beneficially

changed by combining it with additives

• Additives either alter the molecular structure or

• Add a second phase, in effect transforming the

polymer into a composite material
 Types of Additives by Function

• Fillers – to strengthen polymer or reduce cost

• Plasticizers – to soften polymer and improve flow
• Colorants – pigments or dyes
• Lubricants – to reduce friction and improve flow
• Flame retardents – to reduce flammability of polymer
• Cross-linking agents – for thermosets and elastomers
• Ultraviolet light absorbers – to reduce degradation
from sunlight
• Antioxidants – to reduce oxidation damage
 Thermoplastic Polymers (TP)

• A thermoplastic polymer can be heated from a solid

state to a viscous liquid state and then cooled back
down to solid
 This heating and cooling cycle can be repeated
multiple times without degrading the polymer

• The reason is that TP polymers consist of linear

(and/or branched) macromolecules that do not
cross-link upon heating

• By contrast, thermosets and elastomers change

chemically when heated, which cross-links their
molecules and permanently sets these polymers
 Mechanical Properties of Thermoplastics

• Low modulus of elasticity (E) (stiffness)

 E is two or three orders of magnitude lower than
metals and ceramics

• Low tensile strength (TS)

 TS is about 10% of the metal

• Much lower hardness than metals or ceramics

• Greater ductility on average

 Tremendous range of values, from 1% elongation
for polystyrene to 500% or more for polypropylene
Relationship of mechanical properties, portrayed as deformation
resistance, as a function of temperature for an amorphous
thermoplastic, a 100% crystalline (theoretical) thermoplastic,
and a partially crystallized thermoplastic
 Physical Properties of Thermoplastics

• Lower densities than metals or ceramics

 Typical specific gravity for polymers are  1.2
 Ceramics specific gravity =  2.5
 Metals specific gravity =  7.0

• Much higher coefficient of thermal expansion

 Roughly five times the value for metals and 10
times the value for ceramics

• Much lower melting temperatures

 More Physical Properties of Thermoplastics

• Specific heats two to four times those of metals and

ceramics

• Thermal conductivities about three orders of

magnitude lower than those of metals

• Insulating electrical properties

 Commercial Thermoplastic
Products and Raw Materials

• Thermoplastic products include moulded and

extruded items, fibers, films and sheets, packaging
materials, and paints and varnishes

• The starting plastic materials are normally supplied to

the fabricator in the form of
powders or pellets
in bags, drums, or larger loads by truck or rail car
 Thermosetting Polymers (TS)

• TS polymers are distinguished by their highly

cross-linked three-dimensional, covalently-bonded
structure within the molecule

• Chemical reactions associated with cross-linking are

called curing or setting

• In effect, the formed part (e.g. pot handle, electrical

switch cover, etc.) becomes one large
macromolecule

• Always amorphous
General Properties and Characteristics
of Thermosets

• Rigid - modulus of elasticity is two to three times

greater than TP

• Brittle, virtually no ductility

• Less soluble than TP in common solvents

• Capable of higher service temperatures than TP

• Cannot be remelted - instead they degrade or burn

 How Cross-Linking is Done in
Thermosetting Polymers

• Three categories:
1. Temperature-activated systems
2. Catalyst-activated systems
3. Mixing-activated systems

• Curing is accomplished at the fabrication plants that

make the parts rather than at the chemical plants
that supply the starting materials to the fabricator
 Temperature-Activated Systems

Curing is caused by heat supplied during part

shaping operation (e.g. moulding)

• Starting material is a linear polymer in granular form

supplied by the chemical plant
 As heat is added, the material softens for
moulding, but continued heating results in
cross-linking

• Most common TS systems

• The term “thermoset" applies best to these polymers

 Catalyst-Activated Systems

• Cross-linking in these systems occurs when small

amounts of a catalyst are added to the polymer which
is in liquid form

• Without the catalyst, the polymer remains stable

• Once combined with the catalyst it changes into solid

form
 Mixing-Activated Systems

• The mixing of two chemicals results in a reaction that

forms a cross-linked solid polymer

• Elevated temperatures are sometimes used to

accelerate the reactions

• Most epoxies are examples of these systems

 Thermosetting vs. Thermoplastic Polymers

• Thermosetting plastics are not as widely used as the

Thermoplastics
 One reason is the added processing costs and
complications involved in curing

• Largest market share TS = phenolic resins with  6%

of the total plastics market
 Compare polyethylene with  35% market share

• Thermosetting Products: countertops, plywood

adhesives, paints, moulded parts, printed circuit
boards and other fiber reinforced plastics
 Elastomers

Polymers capable of large elastic deformation when

subjected to relatively low stresses

• Some polymers can be extended 500% or more and

still return to their original shape

• Two categories:

1. Natural rubber - derived from biological plants

2. Synthetic polymers - produced by polymerization
processes similar to those used for thermoplastic
and thermosetting polymers
 Characteristics of Elastomers

• Elastomers consist of long-chain molecules that are

cross-linked (like thermosetting polymers)

• They owe their impressive elastic properties to two

features:

1. Molecules are tightly linked when unstretched

2. Degree of cross-linking is substantially less than

thermosets
Model of long elastomer molecules, with low degree of
cross-linking: (a) unstretched, and (b) under tensile stress
 Elastic Behavior of Elastomer Molecule

• When stretched, the molecules are forced to uncoil

and straighten

• Natural resistance to uncoiling provides the initial

elastic modulus of the aggregate material

• Under further strain, the covalent bonds of the

cross-linked molecules begin to play an increasing
role in the modulus, and stiffness increases

• With greater cross-linking, the elastomer becomes

stiffer and its modulus of elasticity is more linear
Increase in stiffness as a function of strain for three grades of rubber:
Natural rubber,
Vulcanized rubber and
Hard rubber
 Vulcanization

Curing to cross-link most elastomers:

• Vulcanization = the term for curing in the context of

natural rubber (and certain synthetic rubbers)

• Typical cross-linking in rubber is one to ten links per

hundred carbon atoms in the linear polymer chain,
depending on degree of stiffness desired
 Considerably less than cross-linking in thermosets
 Natural Rubber (NR)

• Natural Rubber consists primarily of polyisoprene, a

high molecular-weight polymer of isoprene (C5H8)

• It is derived from latex, a milky substance produced

by various plants, most important of which is the
rubber tree that grows in tropical climates

• Latex is a water emulsion of polyisoprene (about 1/3

by weight), plus various other ingredients

• Rubber is extracted from latex by various methods

that remove the water
Structure of Polyisoprene
 Vulcanized Natural Rubber

• Properties: noted among elastomers for high tensile

strength, tear strength, resilience (capacity to recover
shape), and resistance to wear

• Weaknesses: degrades when subjected to heat,

sunlight, oxygen, ozone, and oil
 Some of these limitations can be reduced through
the use of additives

• Market share of Natural Rubber  22% of total annual

rubber volume (natural plus synthetic)
 Rubber volume  15% of total polymer market
 Natural Rubber Products

• Largest single market for Natural Rubber is

automotive tires

• Other products: shoe soles, seals, and shock-

absorbing components

• In tires, carbon black is an important additive; it

reinforces the rubber, serving to increase tensile
strength and resistance to tear and abrasion

• Other additives: clay, kaolin, silica, talc, and calcium

carbonate, as well as chemicals that accelerate and
promote vulcanization
 Synthetic Rubbers

• Today, the tonnage of synthetic rubbers is more than

three times that of natural rubber

• Development of synthetic rubbers was motivated

largely by world wars when natural rubber was
difficult to obtain

• The most important synthetic rubber is

styrene-butadiene rubber (SBR), a copolymer of
butadiene (C4H6) and styrene (C8H8)

• As with most other polymers, the main raw material

for synthetic rubbers is petroleum
 Thermoplastic Elastomers (TPE)

A thermoplastic that behaves like an elastomer

• Elastomeric properties not from chemical cross-links,

but from physical connections between soft and hard
phases in material

• Cannot match conventional elastomers in elevated

temperature strength and creep resistance

• Products: footwear; rubber bands; extruded tubing,

wire coating; moulded automotive parts, but no tires
 Processing of Polymers
• Polymers are nearly always shaped in a heated, highly
plastic state

• Common operations are extrusion and moulding

• Moulding of thermosets is more complicated because of

cross-linking

• Thermoplastics are easier to mould and a greater variety

of molding operations are available

• Rubber processing has a longer history than plastics, and

rubber industries are traditionally separated from plastics
industry, even though processing is similar
Fiber Reinforced Plastic
 What are they?

Fibre-reinforced plastic (FRP) (also fibre-reinforced polymer)

is a composite material made of a polymer matrix reinforced
with fibres.

The fibres are usually glass, carbon, or aramid, although other

fibres such as paper or wood or asbestos have been sometimes
used.

The polymers used epoxy, vinylester or polyester thermosetting

plastic, and phenol formaldehyde resins
 Advanced Composites
• Long (continuous) fibers
• Very high performance reinforcements
 Carbon and aramid
• Resins are also very high performance polymers
• Typically aerospace applications
 Engineering Composites

• Shorter fibers/fiberglass
• Lower mechanical properties (stiffness)
• Lower performance resins
 Reinforcements

• Three main types of fibers

 Fiberglass
 Carbon fiber or Graphite
 Organic fibers, aramids (kevlar)
 Fiber Glass

• Spin molten glass

• Different types of glass can be made

 E-glass (improved electrical resistance)
 S-glass (high strength)
 C-glass (high chemical resistance)
 Glass Fiber
The types of glass used are as follows:

• E-Glass – the most popular and inexpensive glass fibers.

The designation letter “E” means “electrical” (E-Glass is
excellent insulator).

• S-Glass – stronger than E-Glass fibers (the letter “S”

means strength). High-strength glass is generally known
as S-type glass in the United States, R-glass in Europe
and T-glass in Japan.

• C-Glass – corrosion and chemical resistant glass

fibers. To protect against water erosion, a moisture-
resistant coating such as a silane compound is coated
onto the fibers during manufacturing. Adding resin during
composite formation provides additional protection. C-
Glass fibers are used for manufacturing storage tanks,
pipes and other chemical resistant equipment.
 Carbon Fiber
• The types of carbon fibers are as follows:

• UHM (ultra high modulus). Modulus of elasticity > 65400

ksi (450GPa).

• HM (high modulus). Modulus of elasticity is in the range

51000-65400 ksi (350-450GPa).

• IM (intermediate modulus). Modulus of elasticity is in the

range 29000-51000 ksi (200-350GPa).

• HT (high tensile, low modulus). Tensile strength > 436 ksi

(3 GPa), modulus of elasticity < 14500 ksi (100 GPa).

• SHT (super high tensile). Tensile strength > 650 ksi

(4.5GPa).
 Kevlar Fiber

• Kevlar is the trade name (registered by DuPont Co.) of

aramid (poly-para-phenylene terephthalamide) fibers.

• Kevlar fibers were originally developed as a replacement

of steel in automotive tires.

• Kevlar filaments are produced by extrusion of the

precursor through a spinnert. Extrusion imparts
anisotropy (increased strength in the lengthwise
direction) to the filaments.

• Kevlar may protect carbon fibers and improve their

properties: hybrid fabric (Kevlar + Carbon fibers)
combines very high tensile strength with high impact and
abrasion resistance.
 Kevlar Fiber
• There are several modifications of Kevlar, developed for
various applications:

• Kevlar 29 – high strength (520000 psi/3600 MPa), low

density (90 lb/ft³/1440 kg/m³) fibers used for
manufacturing bullet-proof vests, composite armor
reinforcement, helmets, ropes, cables, asbestos replacing
parts.

• Kevlar 49 – high modulus (19000 ksi/131 GPa), high

strength (550000 psi/3800 MPa), low density (90
lb/ft³/1440 kg/m³) fibers used in aerospace, automotive
and marine applications.

• Kevlar 149 – ultra high modulus (27000 ksi/186 GPa),

high strength (490000 psi/3400 MPa), low density (92
lb/ft³/1470 kg/m³) highly crystalline fibers used as
reinforcing dispersed phase for composite aircraft
components.
 Reasons for use of polymeric materials as
matrices in composites

• The mechanical properties of polymers are inadequate for

structural purposes, hence benefits are gained by
reinforcing the polymers

• Processing of PMCs need not involve high pressure and

high temperature

• The equipment required for PMCs are much simpler

 Disadvantages of PMC

 Low maximum working temperature

 High coefficient of thermal expansion-

dimensional instability

 Sensitivity to radiation and moisture

 Carbon or Graphite Fiber

• Originally some distinction was made—now the two

refer to the same material

• Made from PAN fibers, pitch or rayon fibers

• Through heating, raw material looses most non-

carbon atoms in the chain

• Processing also aligns carbon chains

• Carbon fibers have very high modulus (stiffness)

 Organic Reinforcement Fibers

• Aramid fibers have greatest strength and modulus

properties of organic fibers

• Kevlar is the most commonly used aramid fiber

• Aramids are strong and stiff but their greatest value is

in impact applications
 Front of airplane wings
 Armor applications
 Reinforcement Forms

• Fiber manufacturers package the fibers on spools

called tows

• Fibers are generally converted to other forms after

manufacturing
 Chopped fibers (including whiskers)
 Mat (random)
 Woven fibers
 Tapes
 Prepregs
 Manufacturing Methods

• Thermoplastic processes using short fibers

 Injection molding
 Extrusion
 Minor changes are made to accommodate the
fiber reinforcements
 All gaps in flow path should be increased
 A resin viscosity decrease may be necessary
 Manufacturing Methods

• Matched die or Compression molding

 Reduced flow path over injection or extrusion

 SMC compression molding allows for continuous
fibers, mats or weaves
 These processes offer parts that are finished on
both sides where most other composite processes
do not
 Manufacturing Methods

• Resin transfer molding

 Fiber preform is placed in the mold cavity
 Preform doesn’t move—resin is pulled/pushed in
 Manufacturing Methods

• Spray-up
 Fibers are chopped, coated with resin and
sprayed onto the mold
 Manufacturing Methods

• Hand Lay-up (wet and prepreg)

Wet
Prepreg
 Manufacturing Methods

• Filament winding and fiber placement

 Fiber placement has greater accuracy
 Fiber placement can wind on less symmetrical and
even partially concave mandrels
• Tubes, tanks, wind turbine blades and rockets
 Manufacturing Methods

• Roll wrapping
 Faster than filament winding
 Limited to symmetrical mandrels
 Manufacturing Methods

• Pultrusion
 High volume production
 Comparable to extrusion but the main processing
force is tension
 Profile is pulled from the machine
Thank you