C.

Molecular forces or Thermal behavior

 based on intermolecular forces or thermal (thermomechanical) response

Fibers

Rubbers:-have long range elasticity

low molecular cohesion
tensile strength 300-1000 psi (lbs/sq inch)

Plastics:- stronger than rubbers

tensile strength 4000-13000 psi (lbs/sq inch)
types -hard and stiff or soft and flexible

Fibres: Strongest of the three types of polymer

tensile strength 20000-150000 psi (lbs/sq inch) 24
Thermoplastics (Plastics) : linear or branched polymers with no cross-linking; flexible
(deform elastically); can be melted & reformed on heating i.e. recyclable
 can be melted into a liquid by heating and molded/re-shaped into any desired shape
upon cooling (can be melted repeatedly and casted into various shapes and structures)
 can be soften & flow upon heating and hardened when cooled several times without
any change in their chemistry or properties i.e. no permanent change on heating
 soluble in organic solvents and fusible under many cycles and thus recyclable (waste
thermoplastics can be recovered/refabricated by application of heat and pressure).
 freeze to a glassy state when cooled below their glass transition temperature.
 largest proportion of polymers used in industry like bottles, grocery bags, water piping,
rope, fishing line, car parts, electronic accessories
EX: PE, PP, PVC, polystyrene, polyethylenetheraphthalate, polycarbonate, nylon etc
Advantages:
 Flexible and recyclable
 Fast processing and easy rework
 No chemical reactions occur during application processing
 No curing required
 Thermoplastic binders remain re-workable
 Resists humidity and other harsh environments
Disadvantages:
 Limited service temperature performance
25
 It tend to form weaker adhesive bonds
Thermosetting or Thermosets (resins) : non-linear (3-D) network polymers with
massively cross-linked, very rigid; difficult to mold once formed i.e. not recyclable
 Reacts or degrade rather than melt upon heating and permanently hardened due to
formation of irreversible chemical bond during curing process
 cannot re-shaped after it is cured and thus cannot be recycled (burn/scorch by heat)
 insoluble in solvents and infusible i.e. do not soften & flow upon heating because chain
motion is greatly restricted by a high degree of crosslinking (3D network)
 used as adhesives, super glue, molding compound in semiconductors, integrated
circuits, high temperature applications, counter top laminates, tires (vulcanized rubber)
EX: epoxy resin, phenolic resin (Bakelite), polyester resin, urea formaldehyde resin

Advantages:
 higher melting point and excellent chemical stability
 extremely stronger than thermoplastic materials due to 3D network of bonds with
high cross-linking density (resists deformation and is much more mechanically stable)
 Can react with various surfaces/substrates to form strong chemical bonds
 better suited to high-temperature applications up to high decomposition temperature
Disadvantages:
 less flexible and brittle (heavy crosslinking)
 non-recyclable (non-postformable once get cured)
 Increasing handling inconvenience (required greater control)
 Curing required which can cause mechanical stresses 26
Thermoplastic Thermosetting

27
Thermoplastic Thermosetting

28
Elastomer (rubbers) : rubbery polymers with a low degree of cross-linking that can be
easily stretched to high extensions by applying small stress (high degree of elasticity)
and rapidly recover their original dimension when the applied stress is released
 has low cross-link density (moderately crosslinked) and viscoelasticity (viscosity +
elasticity)
 has very weak intermolecular forces (low Young's modulus E ≈ 3 Mpa) – very flexible
 has low stiffness i.e. can accommodate a large amount of recoverable deformation at
room temp. and high failure strain compared with other materials
 amorphous above their glass transition temperature, so that considerable molecular
reconformation, without breaking of covalent bonds, is feasible
 not recyclable - degrades (burns/scorches) when heat is added
 used for seals (Gasket/Car doors ), adhesives, molded flexible parts, examination
gloves, rubber bands, bouncing balls
Ex: Natural rubber, latex, polyurethane, neoprene/silicone/nitryl/butyl rubber e.g. buna-
s (SBR), buna-n, silicones,

Thermoplastic elastomers: can be melted (soles of tennis shoes)

Thermoset elastomers: flexible and rigid due to network structure (SBR tyres) 29
 Vulcanization
 Network structure is generated or “set” to improve natural rubber’s properties by
thermally induced chemical cross-linking reactions, called Vulcanization.
 Vulcanisation of rubber accidentally discovered in 1839 by reacting with sulphur
 cross-links are added to rubber (soft & sticky) by heating it with sulphur
 stiffness of rubber (elastomer) increased by this adopted cross-linking

Flexible rubber

Rigid vulcanized
rubber
30
Fibers : significantly longer than it is wide (at least 100:1 length-to-diameter ratio) with
high degree of cross-linking that can not be stretched by elastic/plastic deformation
 has very strong intermolecular forces (H-bonding) - strongest engineering materials
 has high stiffness i.e. minimum amount of recoverable/elastic deformation
 has high mechanical strength such as tensile strength, rigidity, thermal stability and
chemical resistance, abrasion resistance (widely used in textile industry – fabric/cloth)
 Natural Fibers: produced by plants, animals, and geological processes
Ex: Vegetable fibers, Wood fibers, Animal fibers, Mineral fibers etc
 Man-made Fibres: regenerated fibers or synthetic fibers with modified chemical
composition, structure, and properties by the manufacturing process
Ex: Nylon 6,6, Carbon fiber, Cellulose fiber, Silicon carbide fiber, fibers made from
polyamide nylon, PET or PBT polyester etc

Nylon 6,6
(polyamide)

31
D. Reaction Kinetics or Polymerization mechanism
Polymer growth mechanism Chain growth Step growth

Chemical reaction kinetics Addition polymers Condensation polymers

 Most condensation polymers are step growth and most addition polymers
are chain growth.
 However there are several exceptions and that is why the two different
systems of classification are needed.
 All polymers can be assigned to either processing characteristics/polymer
structure (Wallace Carothers, 1928-1937, a pioneer of the polymer industry) or
type of polymerization mechanism.

32
1. Polymerization Mechanism
Step-growth polymerization
Bi-/multi-functional monomers react to form first dimers, then trimers, longer oligomers
and eventually long chain polymers by elimination of small molecules (biproduct)
 Proceed by stepwise reaction between functional groups of the reactants/monomers,
so no initiator is required and thus involve more than one monomer species
 Reaction proceeds from monomer to dimer, trimer, tetramer, pentamer, hexamer,
octamer………….. Polymer (i.e. growth of short chains to longer chains)
 Reaction takes place with any sized monomer and process is terminated when all
available monomers are used up
Ex: thermosetting polyesters, phenol fomaldehyde, polyamides, polyurethanes, nylon.

Consumption of monomers
through formation of dimers,
Monomers trimers,….

Oligomer formation

High molecular weight growth

33
 Cl Cl
R H O
H2N
O + H2N
O
H2N
N
Cl
R R
O R
monomer + monomer dimer
R H O Cl R H O R
N
H2N Cl + H2N
O H2N
N
N
O
O R
R O R H Cl
dimer + monomer trimer
R H O R H O R H O R H O
H2N
N
Cl + H2N
N
Cl H2N
N
N
N
Cl
O R O R O R H O R
dimer + dimer tetramer
R H O R Cl
R H O R H
H2N
N
N
O + H2N
O N N
O

O R H H2N N Cl
Cl R
O R H O R
trimer + monomer tetramer

trimer + dimer pentamer

tetramer + monomer pentamer
trimer + trimer hexamer
and so on

R H O R H O
N N
N N
Cl
H O R H O R n
polymer 34
Chain-growth polymerization (Free-radical/Cationic/Anionic)
An Initiator is used to produce a reactive center (free radical or ion), and large number of
monomers joined together to form a linear macromolecule in a short period of time (very
fast process)
 Initiator decompose to produce species R* with reactive centre to start the reaction
 Propagation of the reactive centre by addition of large numbers of monomer
molecules in a chain reaction (nearby monomers are joined onto an initiated chain)
 Each monomer that adds to the reactive centre generates a new reactive centre
 Only initial monomer reacts with the reactive centre (i.e. monomers units are
attached one at a time in a chain like fashion) unlike in step polymerization
 Yield (percentage of monomer conversion into polymer) gradually increases with
time and then chain is terminated when no more monomers are available or when
the chain reacts with another chain.
Ex: thermoplastic polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC),
polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate.

35
Initiation

Propagation

Termination

36
 Main difference between step and chain polymerization
• Chain growth polymerisation usually
occurs by an addition reaction, and step
growth polymerisation usually occurs by a
condensation reaction.
• Step growth is slower than chain growth
• At any %-conversion, high molecular
weight polymer formation in chain growth
• There are no intermediate sized molecules
in step growth

• High-molecular-weight
polymer is formed only
near the end of the In
step-growth
polymerization (i.e., at
high monomer
conversion, typically
>98%).

37