Applications and Processing of Polymers

Polymers play a very important role in human life. In fact, our body
is made of lot of polymers, e.g. Proteins, enzymes, etc. Other naturally
occurring polymers like wood, rubber, leather and silk are serving the
humankind for many centuries now. Modern scientific tools
revolutionized the processing of polymers thus available synthetic
polymers like useful plastics, rubbers and fiber materials. As with other
engineering materials (metals and ceramics), the properties of polymers
are related their constituent structural elements and their arrangement.

Polymer types and Polymer synthesis & processing

Polymers are classified according to their Mechanical and thermal
behavior.

INDUSTRIAL POLYMERS

 PLASTICS
 ELASTOMERS

PLASTICS
 Moldable organic resin
 Either natural or synthetic
 Properties:
 light weight
 wide range of colors
 low thermal and electrical conductivity
 less brittle
 good toughness
 good resistance to acids
 bases and moisture
 high dielectric strength (use in electrical insulation)
 classified in two groups:
o Thermoplasts
 soften when heated and harden when
cooled – processes that are totally
reversible and may be repeated.
 normally fabricated by the simultaneous
application of heat and pressure.
 have the property of increasing plasticity
with increasing temperature which breaks
the secondary bonds between individual
chains.
 Examples: acrylics, PVC, nylons,
polypropylene, polystyrene, polymethyl
methacrylate (plastic lenses or perspex), etc.
o Thermosets
 require heat and pressure to mold them
into shape.
 formed into a permanent shape and cured
or ‘set’ by chemical reactions such as
extensive cross-linking.
  cannot be re-melted or reformed into
another shape but decompose upon being
heated to too high a temperature.
 composed of long chains that are strongly
cross-linked (and/or covalently bonded) to
one another to form 3-D network structures
to form a rigid solid.
 generally stronger, but more brittle than
thermoplasts.
 engineering design applications include one
or more of the following: high thermal
stability, high dimensional stability, high
rigidity, light weight, high electrical and
thermal insulating properties and resistance
to creep and deformation under load.
 Examples: Epoxies, vulcanized rubbers,
phenolics, unsaturated polyester resins, and
amino resins (ureas and melamines).

ELASTOMERS
 known as rubbers
 can undergo large elongations under load, at room
temperature, and return to their original shape when the
load is released.
 There are number of man-made elastomers in addition to
natural rubber. These consist of coil-like polymer chains
those can reversibly stretch by applying a force.
 Raw materials for polymerization are usually derived from coal and
petroleum products. properties of a polymer can be enhanced or
modified with the addition of special materials. This is followed by
forming operation. Addition polymerization and condensation
polymerization are the two main ways of polymerization.

Addition polymerization
 also known as chain reaction polymerization
 process in which multi-functional monomer units are attached
one at a time in chainlike fashion to form linear/3-D macro-
molecules.
 The composition of the macro-molecule is an exact multiple of
for that of the original reactant monomer
 Involves three distinct stages – initiation, propagation and
termination.

Condensation polymerization

 also known as step growth polymerization

 involves more than one monomer species
 there is usually a small molecular weight by-product such as
water, which is eliminated.
 also occur in sol-gel processing of ceramic materials.
 Degree of polymerization

 Polymers, unlike organic/inorganic compounds, do not have a

fixed molecular weight
 Number of repeat units in the chain or ration of average
molecular weight of polymer to molecular weight of repeat unit.

Average molecular weight

 Weight average molecular weight

 is obtained by dividing the chains into size ranges and
determining the fraction of chains having molecular
weights within that range.
 Number average molecular weight
 is based on the number fraction, rather than the
weight fraction, of the chains within each size range.
It is always smaller than the weight average
molecular weight.
Additives

 Foreign substances
 are intentionally introduced to enhance or modify these
properties
 These include – fillers, plasticizers, stabilizers, colorants, and
flame retardants
  Fillers
 used to improve tensile and compressive strength,
abrasion resistance, dimensional stability etc. wood
flour, sand, clay, talc etc are example for fillers.
 Plasticizers aid
 improving flexibility, ductility and toughness of
polymers by lowering glass transition temperature of
a polymer
 generally liquids of low molecular weight
 Stabilizers
 are additives which counteract deteriorative
processes such as oxidation, radiation, and
environmental deterioration.
 Colorants
 impart a specific color to a polymer, added in form of
either dyes (dissolves) or pigments (remains as a
separate phase).
 Flame retardants
 are used to enhance flammability resistance of
combustible polymers
 They serve the purpose by interfering with the
combustion through the gas phase or chemical
reaction

Techniques to Form Polymeric Materials

 (a) whether the material is thermoplast or thermoset

 (b) melting/degradation temperature
  (c) atmospheric stability
 (d) shape and intricacy of the product. Polymers are often
formed at elevated temperatures under pressure

Crystallization, melting and glass transition of Polymers

Crystallization

 an ordered solid phase may be formed having a highly random

molecular structure.
 solidification of metals: involves nucleation and growth.
 measured by volume change as there will be a considerable
change in volume during solidification of a polymer
 rate is dependent on crystallization temperature and also on
the molecular weight of the polymer.
Melting

 occurs when a polymer is heated

 involves transformation of solid polymer to viscous liquid upon
heating at melting temperature, Tm.
 distinctive from that of metals in many respects – melting takes
place over a temperature range; melting behavior depends on
history of the polymer; melting behavior is a function of rate of
heating, where increasing rate results in an elevation of melting
temperature.
 During melting there occurs rearrangement of the molecules
from ordered state to disordered state
  involves breaking of the inter-chain bonds, so the glass- and
melting- temperatures depend on:
o chain stiffness (e.g., single vs. double bonds)
o size, shape of side groups
o size of molecule
o side branches, defects
o cross-linking

Glass transition

 polymer during cooling retains amorphous or non-crystalline

state i.e. disordered molecular structure, rigid solid may be
considered as frozen liquid.
 occurs in amorphous and semi-crystalline polymer
 Upon cooling, this transformation corresponds to gradual
change of liquid to rubbery material, and then rigid solid
 temperature is also influenced by molecular weight, with
increase of which glass transition temperature increases
 temperature is typically 0.5 to 0.75 times the absolute melting
temperature.
 Above the glass transition, non-crystalline polymers show
viscous behavior, and below the glass transition they show
glass-brittle behavior (as chain motion is very restricted), hence
the name glass transition
Mechanical behavior of polymers
 can be specified with many of the same parameters that are
used for metals such as modulus of elasticity,
tensile/impact/fatigue strengths, etc.
 To a much greater extent than either metals or ceramics, both
thermal and mechanical properties of polymers show a marked
dependence on parameters namely temperature, strain rate,
and morphology
 change dramatically with temperature, going from glass-like
brittle behavior at low temperatures to a rubber-like behavior
at high temperatures. Highly crystalline polymers behave in a
brittle manner, whereas amorphous polymers can exhibit
plastic deformation
 . Due to unique structures of cross-linked polymers,
recoverable deformations up to very high strains / point of
rupture are also observed with polymers (elastomers)
 Tensile modulus (modulus) and tensile strengths are orders of
magnitude smaller than those of metals, but elongation can be
up to 1000 % in some cases. The tensile strength is defined at
the fracture point and can be lower than the yield strength.
  As the temperature increases, both the rigidity and the yield
strength decrease, while the elongation increases. Thus, if high
rigidity and toughness are the requirements, the temperature
consideration is important.
 Together molecular weight and crystallinity influence a great
number of mechanical properties of polymers including
hardness, fatigue resistance, elongation at neck, and even
impact strength
 As the degree of crystallinity decreases with temperature close
to melting point, stiffness, hardness and yield strength
decrease
 Elastomers, however, exhibit some unique mechanical behavior
when compared to conventional plastics. The most notable
characteristics are the low modulus and high deformations as
elastomers exhibit large, reversible elongations under small
applied stresses. Elastomers exhibit this behavior due to their
unique, cross-linked structure.
 Elastic modulus of elastomers (resistance to the uncoiling of
randomly orientated chains) increases as with increase in
temperature. Unlike non-cross-linked polymers, elastomers
exhibit an increase inelastic modulus with cross-link density.
Mechanisms of deformation and strengthening of polymers

 An understanding of deformation mechanisms of polymers is

important in order to be able to manage the optimal use of these
materials, a class of materials that continues to grow in terms of use
in structural applications.
 elastic and plastic deformation mechanisms in polymers are quite
different due to
o difference in structure they made of
o size of the entities responsible for deformation
 Plastic
o deformation in metals and ceramics can be described in terms
of dislocations and slip planes, whereas polymer chains must
undergo deformation in polymers leading to different
mechanism of permanent deformation. Unique to most of the
polymers is the viscoelasticity – means when an external force
is applied, both elastic and plastic (viscous) deformation occur.
 viscoelastic materials
o the rate of strain determines whether the deformation in
elastic or viscous.
 viscoelastic behavior of polymeric materials
o dependent on both time and temperature.
 Plastic polymers
o deform elastically by elongation of the chain molecules from
their stable conformations in the direction of the applied stress
by the bending and stretching of the strong covalent bonds.
o there is a possibility for slight displacement of adjacent
molecules, which is resisted by weak secondary / van der Waals
bonds.
 Elastomers
o deform elastically by simple uncoiling, and straightening of
molecular chains that are highly twisted, kinked, and coiled in
unstressed state
 o . The driving force for elastic deformation is change in entropy,
which is a measure of degree of disorder in a system
 Fracture of polymers
o is again dependent on morphology of a polymer
o . As a thumb rule, thermosets fracture in brittle mode
o Covalent bonds are severed during the fracture.
o both ductile and brittle modes are possible mode of fracture for
thermoplasts.
o Many of thermoplasts can exhibit ductile-to-brittle transition
assisted by reduction in temperature, increase in strain rate,
presence of notch, increased specimen thickness and a
modification of the polymer structure.
 deformation of plastic materials
o can be primarily elastic, plastic, or a combination of both types.
o deformation mode and resistance of deformation depends on
many parameters for different plastics.
o factors influence the strength of a thermoplast
 average molecular mass
 degree of crystallization
 presence of side groups
 presence of polar and other specific atoms
 presence of phenyl rings in main chains
 addition of reinforcements
o Thermosets are, however, strengthened by reinforcement
methods.
 Thermoplast
o Strength t is directly dependent on its average molecular mass
since polymerization up to a certain molecular-mass range is
 necessary to produce a stable solid. This method is not used so
often as after a critical mass range, increasing the average
molecular mass does not greatly increase its strength. In
general, as the degree of crystallinity increases, the strength,
modulus and density all increase for a thermoplast. Another
method to increase the strength is to create more resistance to
chain slippage.
Characteristics and typical applications of few plastic materials.
a) Thermo plastics
1. Acrylonitrile-butadiene-styrene (ABS):
Characteristics: Outstanding strength and toughness, resistance
to heat distortion; good electrical properties; flammable and
soluble in some organic solvents. Application: Refrigerator
lining, lawn and garden equipment, toys, highway safety
devices.
2. Acrylics (poly-methyl-methacrylate)
Characteristics: Outstanding light transmission and resistance
to weathering; only fair mechanical properties. Application:
Lenses, transparent aircraft enclosures, drafting equipment,
outdoor signs
3. Fluorocarbons (PTFE or TFE)
Characteristics: Chemically inert in almost all environments,
excellent electrical properties; low coefficient of friction; may
be used to 260o C; relatively weak and poor cold-flow
properties. Application: Anticorrosive seals, chemical pipes and
valves, bearings, anti adhesive coatings, high temperature
electronic parts.
4. Polyamides (nylons)
Characteristics: Good mechanical strength, abrasion resistance,
and toughness; low coefficient of friction; absorbs water and
some other liquids. Application: Bearings, gears, cams, bushings,
handles, and jacketing for wires and cables
5. Polycarbonates
Characteristics: Dimensionally stable: low water absorption;
transparent; very good impact resistance and ductility.
Application: Safety helmets, lenses light globes, base for
photographic film
6. Polyethylene
Characteristics: Chemically resistant and electrically insulating;
tough and relatively low coefficient of friction; low strength and
poor resistance to weathering. Application: Flexible bottles,
toys, tumblers, battery parts, ice trays, film wrapping materials.
7. Polypropylene
Characteristics: Resistant to heat distortion; excellent electrical
properties and fatigue strength; chemically inert; relatively
inexpensive; poor resistance to UV light. Application:
Sterilizable bottles, packaging film, TV cabinets, luggage
 8. Polystyrene
Characteristics: Excellent electrical properties and optical
clarity; good thermal and dimensional stability; relatively
inexpensive Application: Wall tile, battery cases, toys, indoor
lighting panels, appliance housings.
9. Polyester (PET or PETE)
Characteristics: One of the toughest of plastic films; excellent
fatigue and tear strength, and resistance to humidity acids,
greases, oils and solvents Application: Magnetic recording tapes,
clothing, automotive tire cords, beverage containers.
b) Thermo setting polymers
1. Epoxies
Characteristics: Excellent combination of mechanical properties
and corrosion resistance; dimensionally stable; good adhesion;
relatively inexpensive; good electrical properties. Application:
Electrical moldings, sinks, adhesives, protective coatings, used
with fiberglass laminates.
2. Phenolics
Characteristics: Excellent thermal stability to over 150o C; may
be compounded with a large number of resins, fillers, etc.;
inexpensive. Application: Motor housing, telephones, auto
distributors, electrical fixtures.