INTRODUCTION: POLYMERIC MATERIALS

POLYMERS
Polymers are very large molecular structures made by reacting together small and comparatively
simple molecules (monomers). The reactions are termed polymerisation processes and may be of
simple addition type, addition polymerisation or condensation polymerisation. The structure of the
final compound and to a large extent, its properties will be determined by the structure of the
original reactants and the type of polymerisation process.

Polymers are “Organic compounds, natural or synthetic, with high molecular weight made of
repetitive structural units ”, Large size chains formed from the covalent union of various
monomer units (macromolecule).
They are very large molecular structures made by reacting together small and comparatively
simple molecules (monomers). The reactions are termed as polymerisation processes and may be
of simple addition type, addition polymerisation or condensation polymerisation. The structure
of the final compound and to a large extent, its properties will be determined by the structure of
the original reactants and the type of polymerisation process.
PLASTIC
1. Polymer whose fundamental property is plasticity (thermoplastic). It is deformed plastically
under the action of pressure and or heat .
2. Mixture (of a polymer with additives) that can be transformed by flowing or moulding in
liquid or molten state.
A plastic material is any of a wide range of synthetic or semi-synthetic organic solids that are
moldable. Plastics are typically organic polymers of high molecular mass, but they often contain
other substances. They are usually synthetic, most commonly derived from petrochemicals, but
many are partially natural.
The materials, which are derivatives of carbon, chemically combined with hydrogen, oxygen or
any other non-metallic substance, and their structures, in most cases, fairly complex are known
as organic materials.
Organic materials may be natural or synthetic, i.e. prepared or manufactured artificially. The
naturally available organic materials include wood, natural rubber, coal, petroleum and food
products, etc. The synthetic organic materials include, plastics, lubricants, rubber, soap oils,
synthetic fibres, etc
GENERAL CHARACTERISTICS OF POLYMERIC MATERIALS

Advantages Applications
Easy processing Products of elevated consumption
High ductility Plastics for packaging
Light products Automobiles, aeronautics and aerospace
Thermal insulators Construction
Electric insulators Coatings for wires
High resistance to corrosion Tubes, bins, boxes, coatings

HISTORIC INTRODUCTION OF POLYMERS

Polymers: synthetic and natural materials: they include; Cellulose, starch, proteins, leather ,
wool , cotton , synthetic fibres of polyesters and polyamides, plastics, rubbers, adhesives etc
HISTORICAL BACKGROUND

Origins of Humanity ⇒ natural products: leather , wool, cellulose….

1838: Vulcanizing of natural rubber

1846 Cellulose nitrate
1870 Celluloid
1907 Bakelite
1920 Macromolecular Hypothesis (Staudinger)
1926 Polyvinyl chloride (PVC)
1933 Poly ethylene (PE)
1938-39 Nylon (fibers) y Polystyrene (PS)
1954 Polypropylene (PP)
1960 Applications of Epoxy Resins
198- Polymers of high specifications
Examples

CLASSIFICATION OF POLYMMERIC MATERIALS

2. CLASSIFICATION
According to applications
Elastomers. Are materials with very low modulus of elasticity and high extensibility
Plastics. Are the polymers in which, when a sufficiently intense force is applied, they
irreversibly deform
Fibres. Present a high modulus of elasticity and low extensibility
Coatings. Are substances, normally liquid, that adhere to the surface of other materials
Adhesives. Are substances that combine a high adhesion and a high cohesion,
According to their behaviour with temperature
Thermoplastic. Flow on heating and they become hard on cooling. Their molecular structure
presents few (or none) crosslinks.
Thermosetting. They chemically decompose when heated, instead of flowing. This behaviour is
due to a crosslinked structure

KEY TERMS WITH REGARD TO POLYMERS

The following terms are encountered when studying polymer structures.

Monomer: this refers to the small molecule from which a polymer is synthesized.

Polymerisation: this is the term for chemical reactions in which comparatively simple substances
react together to give, complex molecular forms with very high molecular weights. There are two
types of polymerisation reactions, namely addition and condensation polymerisation. The reactants
in polymerisation reactions are known as monomer (meaning single unit) and the product of the
reaction is a polymer (many units).

Homopolymer: this refers to a polymer made by polymerisation of the same type/ specie of
monomer.

Copolymer: this refers to a polymer made by the polymerisation of two different species of
monomer.

Linear polymer: this is a polymer composed of long fibrous molecular chains and may be a
homopolymer or copolymer.

Branched polymer: this where the molecules in a branched polymer consist of linear chains with
a series of side chains grafted on.
Cross-linked polymer: in this polymer, there are short links joining adjacent polymer chains to
one another at various points. The hardness and rigidity of the material increases as the number of
cross-links increases.

Network polymer: this is one whose molecular structure is in the form of a large three-
dimensional net. This is the typical structure of a thermoset material.

Glass transition temperature (Tg): the glass transition occurs in amorphous (or glassy) and
semicrystalline polymers, and is due to a reduction in motion of large segments of molecular
chains with decreasing temperature. Upon cooling, the glass transition corresponds to the gradual
transformation from a liquid to a rubbery material, and finally, to a rigid solid. The temperature
at which the polymer experiences the transformation from rubbery to rigid states is termed the
glass transition temperature, Tg.

Degradation temperature (Td): when heated to high temperatures, the covalent bonds between
the atoms in the linear chain may be destroyed, and the polymer may burn or char. It is also called
decomposition temperature.

Addition Polymerisation

Chain reaction or addition polymerization reaction is a polymerization process in which two

species, i.e., a monomer and a free radical catalyst are involved. The monomer unit contains at
least one double bond.

During the polymerization process, the free radical reacts with the double bond carbon monomer,
breaking it apart. The monomer then bonds to the free radical and the free electron is transferred
to the outside carbon atom in the reaction. The reaction propagates by the reaction of the free
electron monomer unit with the double bond of successive monomer units.

Termination occurs when another free radical (R─O•), left over from the original splitting of the
organic peroxide, meets the end of the growing chain. This free-radical terminates the chain by
linking with the last CH2 -component of the polymer chain. This reaction produces a complete
polymer chain. Termination can also occur when two unfinished chains bond together.

Illustration

Formation of free radical from an organic peroxide.

R—O—O—R → R—O• +R—O•, With (•) representing the free electron

Reaction of free radical with monomer unit

Propagation of polymerisation reaction

Termination of reaction

Stepwise reaction (condensation polymerization)

Step-wise reactions involve two different types of di-functional monomers or end groups that react
with one another, forming a chain. Condensation polymerization also produces a small molecular
by-product (water, HCl, etc.). E.g. The formation of Nylon 66, a common polymeric clothing
material, involving one each of two monomers, hexamethylenediamine and adipic acid, reacting
to form a dimer of Nylon66.
At this point, the polymer could grow in either direction by bonding to another molecule of
hexamethylenediamine or adipic acid, or to another dimer. This reaction process can, theoretically,
continue until no further monomers and reactive end groups are available. This reaction is slower
than addition polymerization. Typically, this process breeds linear chains that are strung out
without any cross-linking or branching, unless a tri-functional monomer is added.

On the basis of structure, polymers are subdivided into linear and non-linear types as shown in the
following figure.

Figure: schematic representations of (a) linear,(b) branched,(c) cross linked, and (d) network (three
dimensional) molecular structures. Circles designated individual repeat units.

Polymers can be broadly classified as thermoplastics, elastomers and thermosets.

Thermoplastic materials soften when heated and regain their rigidity when cooled. These are
polymers with linear, branched or lightly cross-linked structures.
Thermosets soften or melt when first heated but then cure to become permanently hard rigid
materials with networked structures.

Elastomers (natural and synthetic rubbers) are lightly cross-linked materials with very low elastic
moduli which can accommodate large amounts of strain but return to their original dimensions
when the load is removed.

Structure and Properties of Thermoplastic Polymers (in brief)

In general, thermoplastic polymers are linear polymers, made up of long covalently bonded
carbon chains, but some thermoplastics materials may be of the branched

type or be lightly cross-linked. A thermoplastic material softens when heated and sets into a rigid
form again on cooling, the changes during heating and cooling being reversible. The properties of
thermoplastics are sensitive to temperature, structure and strain rate. Below a certain temperature,
the glass transition temperature Tg, a thermoplastic is a brittle elastic solid but above this
temperature the value of modulus of elasticity (E) reduces greatly and the material becomes visco-
elastic. The value of Tg is dependent on the complexity of the molecular structure and is -120⁰C
for polyethylene and 95⁰C for the more complex structured polystyrene.

Structure and Properties of Thermosets (in brief)

Thermosets are materials which, on first heating, melt and then set or cure into a hard rigid shape
. During this curing or setting process a full network molecular structure is developed producing a
material which is a hard elastic solid. This is a non-reversible process. Cold setting plastics are of
this type but in this case the curing reactions forming a network structure take place at room
temperature once resin and a hardener have been mixed together.

Structure and Properties of Elastomers (in brief)

Elastomers are a group of thermoplastic materials which have low elastic moduli giving large
deformations under relatively low loads and which return to their original dimensions after the
loads have been released. They possess linear polymer structures with a small number of cross-
links between molecules and, in many cases, the molecules form into coils behaving as minute
helical springs. It is the presence of cross-links which cause the materials to return to their original
dimensions after load removal.

Isomerism
This is the phenomenon whereby two or more polymer molecules or repeat units have the same
composition but different structural arrangements and properties (e.g. boiling temperature of
normal butane is -0.5⁰C, and that of isobutene is -12.3⁰C).

Two types of isomerism in polymers are possible: stereoisomerism and geometrical isomerism.

Stereoisomerism denotes the situation in which atoms are linked together in the same order (head-
to-tail) but differ in their special arrangement to form isotactic, syndiotactic and atactic
configurations as follows.

(a) Isotactic: all the R groups are (b) Syndiotactic: the R groups
situated on the same side of alternate sides of the chain.
the chain.

Geometrical isomerism
(c) Atactic: the R groups are
Consider two carbon atoms bonded by a double
randomly bond in a chain. H atom or radial R bonded to
positioned.
these two atoms can be on the same side of the chain (cis structure) or on opposite sides of the
chain (trans structure).

Cis-polyisoprene Trans-polyisoprene
POLYMER CRYSTALLINITY AND DEGREE OF CRAYSTALLINITY

Atomic arrangement in polymer crystals is more complex than in metals or ceramics. Unit cells
are typically large and complex.

Polymer molecules are often partially crystalline (semi-crystalline), with crystalline regions
dispersed within an amorphous material.

The degree of crystallinity may range from completely amorphous to almost entirely crystalline
(up to about 95%). In contrast, metal specimens are almost always entirely crystalline, whereas
many ceramics are either totally crystalline or totally noncrystalline. Semicrystalline polymers are,
in a sense, analogous to two-phase metal alloys.

The density of a crystalline polymer will be greater than an amorphous one of the same material
and molecular weight, since the chains are more closely packed together for the crystalline
structure. The degree of crystallinity by weight may be determined from accurate density
measurements, using:

 c ( s −  a )
% crystallin ity =  100
 s ( c −  a )

where  s is the density of a specimen for which the percentage crystallinity is to be determined,

 a is the density of the totally amorphous polymer, and  c is the density of the perfectly crystalline
polymer. The values of  a and  c must be measured by other experimental means.

Example: The density of totally crystalline polyethylene has been determined to be 0.998 g/cm3.
Calculate the percentage crystallinity of a branched polyethylene that has a density of 0.925 g/cm3.
The density for the totally amorphous material is 0.870 g/cm3. (Ans: 46.4%).

Several factors influence the ability of a polymer to crystallise:

• Complexity. Crystallinity is easiest for simple addition polymers, such as polyethylene, in

which no bulky molecules or atom groups that might interfere with the close packing of
the chains are attached to the carbon chain.

• Rate of cooling during solidification: slow cooling, which permits more time for the
chains to become aligned, encourages crystallisation.

• Annealing. Heating an amorphous structure just below the melting temperature provides
the thermal activation that permits crystals to nucleate and grow.

• Degree of polymerisation. Polymers containing long chains are more difficult to

crystallise.

• Deformation. Slow deformation of the polymer between the melting and glass transition
temperatures may promote crystallisation by straightening the chains, thus permitting them
to move closer together.

CRYSTALLIZATION, MELTING AND GLASS TRANSITION

Polymers are known by their highly sensitive mechanical and/or thermal properties. This section
explains their thermal behavior. During processing of polymers, they are cooled from liquid state
to form final product. During cooling, an ordered solid phase may be formed having a highly
random molecular structure. This process is called crystallization. The melting occurs when a
polymer is heated. If the polymer during cooling retains amorphous or non-crystalline state i.e.
disordered molecular structure, the rigid solid may be considered as frozen liquid resulting from
glass transition. Thus, enhancement of either mechanical and/or thermal properties needs to
consider crystallization, melting, and the glass transition.

Crystallization

Crystallization and the mechanisms involved play an important role as it influences the properties
of plastics. As in solidification of metals, polymer crystallization involves nucleation and growth.
Near to solidification temperature at favorable places, nuclei forms, and then nuclei grow by the
continued ordering and alignment of additional molecular segments. Extent of crystallization is
measured by volume change as there will be a considerable change in volume during solidification
of a polymer. Crystallization rate is dependent on crystallization temperature and also on the
molecular weight of the polymer. Crystallization rate decreases with increasing molecular weight.

Melting

Melting of polymer involves transformation of solid polymer into viscous liquid upon heating at
melting temperature, Tm. Polymer melting is 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.
This is influenced by molecular chemistry and structure (degree of branching) along with chain
stiffness and molecular weight.

Glass transition

Glass transition occurs in amorphous and semi-crystalline polymers. Upon cooling, this
transformation corresponds to gradual change of liquid to rubbery material, and then rigid solid.
The temperature range at which the transition from rubbery to rigid state occurs is termed as glass
transition temperature, Tg. Glass transition temperature is also influenced by molecular weight,
with increase of which glass transition temperature increases. Degree of cross-linking also
influences the glass transition such that polymers with very high degree of cross-linking do not
experience a glass transition. The glass transition 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.
Melting involves breaking of the inter-chain bonds, so the glass- and melting- temperatures depend
on:

✓ chain stiffness (e.g., single vs. double bonds)

✓ size, shape of side groups

✓ size of molecule

✓ side branches, defects

✓ cross-linking

MECHANICAL BEHAVIOUR OF POLYMERS

Polymer mechanical properties can be specified with many of the same parameters that are used
for metals such as modulus of elasticity, tensile/impact/fatigue strengths, etc. However, polymers
are, in many respects, mechanically dissimilar to metals. To a much greater extent than either
metals or ceramics, both thermal and mechanical properties of polymers show a marked
dependence on temperature, strain rate, and morphology. In addition, molecular weight and
temperature relative to the glass transition play an important role.

A simple stress- strain curve can describe different mechanical behavior of various polymers. As
shown in the figure below, the stress-strain behavior can be brittle, plastic and highly elastic
(elastomeric or rubber-like). Mechanical properties of polymers 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. These phenomena are highly temperature dependent,
even more so with polymers than they are with metals and ceramics. 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 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. In general, decreasing the strain rate has the same influence on the strain-strength
characteristics as increasing the temperature: the material becomes softer and more ductile.

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. The
chance of brittle failure is reduced by raising molecular weight, which increases brittle strength,
and by reducing crystallinity. As the degree of crystallinity decreases with temperature close to
melting point, stiffness, hardness and yield strength decrease. These factors often set limits on the
temperature at which a polymer is useful for mechanical purposes.

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
with increase in temperature. Unlike non-cross-linked polymers, elastomers exhibit an increase in
elastic modulus with cross-link density.

Characteristics and Typical Applications of Few Plastic Materials

a) Thermo plastics

1. Fluorocarbons (PTFE- Polytetrafluoroethylene or TFE-tetrafluoroethylene)

 Characteristics: Chemically inert in almost all environments, excellent electrical
properties; low coefficient of friction; may be used to 260ºC; relatively weak and poor
cold-flow properties.
Application: Anticorrosive seals, chemical pipes and valves, bearings, anti-adhesive
coatings, high temperature electronic parts.
2. 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
3. Polycarbonates
Characteristics: Dimensionally stable: low water absorption; transparent; very good impact
resistance and ductility.
Application: Safety helmets, lenses, light globes, base for photographic film
4. 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.
5. 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.
6. Polyester (PET or PETE-Polyethylene terephthalate)
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 150ºC; may be compounded with a large
number of resins, fillers, etc.; inexpensive.
Application: Motor housing, telephones, auto distributors, electrical fixtures.