Polymers

Natural and Applied Sciences Department, College of Arts and Sciences,

NEUST

JAN KENNEY D. GONZALES

(Chemistry Instructor)
 Introduction

• Naturally occurring polymers—those derived from plants and animals—have been

used for many centuries; these materials include wood, rubber, cotton, wool, leather,
and silk.

• Other natural polymers such as proteins, enzymes, starches, and cellulose are
important in biological and physiological processes in plants and animals.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Introduction

• Hydrocarbon Molecules

• Most polymers are organic in origin, and a lot of organic materials are hydrocarbons;
(composed of hydrogen and carbon). Furthermore, the intramolecular bonds are
covalent.

• Molecules that have double and triple covalent bonds are termed unsaturated, for a saturated hydrocarbon, all
bonds are single ones.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Introduction

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Polymer Molecules
• The molecules in polymers are gigantic in comparison to the hydrocarbon molecules
already discussed; because of their size they are often referred to as macromolecules.

• These long molecules are composed of structural entities called repeat units.

• The term monomer refers to the small molecule from which a polymer is synthesized.

• A repeat unit is also sometimes called a mer. “Mer” originates from the Greek word
polymer meros, which means part; the term polymer was coined to mean “many mers.”

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Polymer Molecules

Polymers can be classified as organic and inorganic polymers:

• Inorganic polymers – cement, glass, sand, clays
• Organic polymer can be synthetic or natural:
➢ Synthetic polymers – adhesives, fibers, coatings, rubbers
➢ Natural polymers – polysaccharides, proteins, DNA, polyisoprene rubber

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 The Chemistry of Polymer Molecules
Consider again the hydrocarbon ethylene (C2H4), which is a gas at ambient temperature and
pressure, and has the following molecular structure:

If the ethylene gas is reacted under appropriate conditions, it will transform to polyethylene (PE),
which is a solid polymeric material. This process begins when an active center is formed by the
reaction between an initiator or catalyst species (R∙) and the ethylene monomer, as follows:

or

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 The Chemistry of Polymer Molecules
A Listing of Repeat Units for 10 of the
More Common Polymeric Materials

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 The Chemistry of Polymer Molecules
A Listing of Repeat Units for 10 of the
More Common Polymeric Materials

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Type of Molecular Structure

The physical characteristics of a polymer depend not only on its molecular weight and shape but
also on differences in the structure of the molecular chains. Several molecular structures including
linear, branched, crosslinked, and network, in addition to various isomeric configurations.
1. Linear Polymers
• are those in which the repeat units are joined together end to
end in single chains. These long chains are flexible, where each
circle represents a repeat unit. For linear polymers, there may
be extensive van der Waals and hydrogen bonding between
the chains.

• Some of the common polymers that form with linear

structures are polyethylene, poly(vinyl chloride), polystyrene,
poly(methyl methacrylate), nylon, and the fluorocarbons.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
Type of Molecular Structure

2. Branched Polymers
• Polymers may be synthesized in which side-branch chains are
connected to the main ones,; these are fittingly called
branched polymers. The branches, considered to be part of
the main-chain molecule, may result from side reactions that
occur during the synthesis of the polymer.

• The chain packing efficiency is reduced with the formation of

side branches, which results in a lowering of the polymer
density.

• Those polymers that form linear structures may also be

branched. For example, high density polyethylene (HDPE) is
primarily a linear polymer, while low density polyethylene
(LDPE) contains short chain branches.
Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Type of Molecular Structure

3. Crosslinked Polymers
• In crosslinked polymers, adjacent linear chains are joined
one to another at various positions by covalent bonds. The
process of crosslinking is achieved either during synthesis
or by a nonreversible chemical reaction.

• Often, this crosslinking is accomplished by additive atoms

or molecules that are covalently bonded to the chains.
Many of the rubber elastic materials are crosslinked; in
rubbers, this is called vulcanization.

• Examples of cross-linked polymers include: Polyester

fiberglass, polyurethanes used as coatings, adhesives,
vulcanized rubber, epoxy resins and many more.
Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Type of Molecular Structure

4. Network Polymers

• Multifunctional monomers forming three or more active

covalent bonds, make three-dimensional networks, and
are termed network polymers.

• Actually, a polymer that is highly crosslinked may also be

classified as a network polymer. These materials have
distinctive mechanical and thermal properties; the
epoxies, polyurethanes, and phenol-formaldehyde belong
to this group.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Molecular Configuration of Polymers

Stereoisomerism denotes the situation in which atoms are linked together in the same order
(head-to-tail) but differ in their spatial arrangement.

• For one stereoisomer, all the R groups are situated on the same side of the chain as follows:

• This is called an isotactic configuration. This diagram shows the zigzag pattern of the carbon
chain atoms. Furthermore, representation of the structural geometry in three dimensions is
important, as indicated by the wedge-shaped bonds; solid wedges represent bonds that project
out of the plane of the page, dashed ones represent bonds that project into the page.
Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Molecular Configuration of Polymers

• In a syndiotactic configuration, the R groups alternate sides of the chain:

• And for random positioning, the term atactic configuration is used.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Molecular Configuration of Polymers

• Geometrical stereoisomerism • For the alternative isomer the trans

structure, the CH3 and H reside on opposite
Cis and Trans sides of the double bond. Trans-
polyisoprene, sometimes called gutta
• In which the CH3 group and the H atom percha, has properties that are distinctly
are positioned on the same side of the different from natural rubber as a result of
double bond. This is termed a cis this configurational alteration. Conversion
structure, and the resulting polymer, cis- of trans to cis, or vice versa, is not possible
polyisoprene, is natural rubber. by a simple chain bond rotation because
the chain double bond is extremely rigid.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Copolymers

When all the repeating units along a chain are of the same type, the resulting polymer is called a
homopolymer. Chains may be composed of two or more different repeat units, in what are termed
copolymers.

1. Random copolymers - two different units are randomly dispersed along the chain.

2. Alternating copolymer - two repeat units alternate chain positions.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Copolymers

3. Block copolymer: identical repeat units are clustered in blocks along the chain.

4. Graft copolymer of molecular chains to produce an ordered atomic array: homopolymer side
branches of one type may be grafted to homopolymer main chains that are composed of a
different repeat unit.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Thermoplastic and Thermosetting Polymers

• Thermoplastics soften when heated (and eventually liquefy) and harden when cooled—
processes that are totally reversible and may be repeated. Irreversible degradation results when
a molten thermoplastic polymer is raised to too high of a temperature.

• In addition, thermoplastics are relatively soft. Most linear polymers and those having some
branched structures with flexible chains are thermoplastic. These materials are normally
fabricated by the simultaneous application of heat and pressure.

• Most linear polymers are thermoplastics. Examples of common thermoplastic polymers include
polyethylene, polystyrene, poly (ethylene terephthalate), and poly (vinyl chloride).

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Thermoplastic and Thermosetting Polymers

• Thermosetting polymers are network polymers. They become permanently hard during their
formation, and do not soften upon heating. Thermoset polymers are generally harder and
stronger than thermoplastics and have better dimensional stability.

• Network polymers have covalent crosslinks between adjacent molecular chains. During heat
treatments, these bonds anchor the chains together to resist the vibrational and rotational chain
motions at high temperatures. Thus, the materials do not soften when heated. Crosslinking is
usually extensive, in that 10 to 50% of the chain repeat units are crosslinked.

• Only heating to excessive temperatures will cause severance of these crosslink bonds and
polymer degradation. Most of the crosslinked and network polymers, which include vulcanized
rubbers, epoxies, and phenolics and some polyester resins, are thermosetting.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Mechanical Properties of Polymers

Stress-Strain Curve
Three typically different types of stress–strain behavior was found for polymeric materials
• Curve A illustrates the stress–strain character for a brittle
polymer, in as much as it fractures while deforming
elastically.
• The behavior for a plastic material, curve B, is similar to
that for many metallic materials; the initial deformation is
elastic, which is followed by yielding and a region of plastic
deformation.
• Finally, the deformation displayed by curve C is totally
elastic; this rubber-like elasticity (large recoverable strains
produced at low stress levels) is displayed by a class of
polymers termed the elastomers

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Mechanical Properties of Polymers

Viscoelastic deformation
An amorphous polymer may behave like a glass at low
temperatures, a rubbery solid at intermediate
temperatures, and a viscous liquid as the temperature
is further raised. For relatively small deformations, the
mechanical behavior at low temperatures may be
elastic; that is, in conformity to Hooke’s law. At the
highest temperatures, viscous or liquid like behavior
prevails. For intermediate temperatures the polymer is
a rubbery solid that exhibits the combined mechanical
characteristics of these two extremes; the condition is
termed viscoelasticity.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Mechanical Properties of Polymers

Miscellaneous Mechanical Properties

1. Impact strength - the degree of resistance of a polymeric material to impact loading may be
of concern in some applications. As with metals, polymers may exhibit ductile or brittle
fracture under impact loading conditions, depending on the temperature, specimen size,
strain rate, and mode of loading.

2. Fatigue - Polymers may experience fatigue failure under conditions of cyclic loading. As with
metals, fatigue occurs at stress levels that are low relative to the yield strength. Fatigue testing
in polymers has not been nearly as extensive as with metals.

3. Tear strength and hardness - Tear strength, the mechanical parameter that is measured, is the
energy required to tear apart a cut specimen that has a standard geometry. The magnitude of
tensile and tear strengths are related. As with metals, hardness represents a material’s
resistance to scratching, penetration, marring, and so on.
Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Type of Polymeric Materials

1. Plastics - are materials that have some structural rigidity under

load, and are used in general-purpose applications. Polyethylene,
polypropylene, poly(vinyl chloride), polystyrene, and the
fluorocarbons, epoxies, phenolics, and polyesters may all be
classified as plastics.

2. Elastomers – Natural rubber is still utilized to a large degree

because it has an outstanding combination of desirable properties.
However, the most important synthetic elastomer is styrene-
butadiene copolymer (SBR), which is used predominantly in
automobile tires, reinforced with carbon black. Acrylonitrile-
butadiene copolymer (NBR), which is highly resistant to
degradation and swelling, is another common synthetic elastomer.

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Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Type of Polymeric Materials

3. Fibers – Most commercial fiber polymers are utilized

in the textile industry, being woven or knit into cloth or
fabric.
• While in use, fibers may be subjected to a variety of
mechanical deformations—stretching, twisting,
shearing, and abrasion.
• Consequently, they must have a high tensile strength
(over a relatively wide temperature range) and a high
modulus of elasticity, as well as abrasion resistance.
These properties are governed by the chemistry of the
polymer chains and also by the fiber drawing process.

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Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Type of Polymeric Materials

4. Coatings – are frequently applied to the surface

of materials to serve one or more of the following
functions:
• (1) to protect the item from the environment that
may produce corrosive or deteriorative reactions;
• (2) to improve the item’s appearance; and
• (3) to provide electrical insulation.

• Many of the ingredients in coating materials are

polymers, the majority of which are organic in origin.
These organic coatings fall into several different
classifications, as follows: paint, varnish, enamel,
lacquer, and shellac.

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Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Type of Polymeric Materials

5. Adhesives – An adhesive is a substance used to

bond together the surfaces of two solid materials
termed “adherends”.
• There are two types of bonding mechanisms:
mechanical and chemical.

• For mechanical there is actual penetration of the

adhesive into surface pores and crevices. Chemical
bonding involves intermolecular forces between the
adhesive and adherend, which forces may be
covalent and/or van der Waals; degree of van der
Waals bonding is enhanced when the adhesive
material contains polar groups.

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Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Type of Polymeric Materials

6. Films – are materials have found widespread use in the form

of thin films.
• Films having thicknesses between 0.025 and 0.125 mm (0.001
and 0.005 in.) are fabricated.

• Important characteristics of the materials produced and used

as films include low density, a high degree of flexibility, high
tensile and tear strengths, resistance to attack by moisture and
other chemicals, and low permeability to some gases,
especially water vapor.

• Some of the polymers that meet these criteria and are

manufactured in film form are polyethylene, polypropylene,
cellophane, and cellulose acetate
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Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Type of Polymeric Materials

7. Foams – Foams are plastic materials that contain a relatively high

volume percentage of small pores and trapped gas bubbles.
• Both thermoplastic and thermosetting materials are used as foams; these
include polyurethane, rubber, polystyrene, and poly(vinyl chloride).

• Foams are commonly used as cushions in automobiles and furniture as

well as in packaging and thermal insulation. The foaming process is often
carried out by incorporating into the batch of material a blowing agent
that, upon heating, decomposes with the liberation of a gas.

• Gas bubbles are generated throughout the now-fluid mass, which remain
in the solid upon cooling and give rise to a spongelike structure. The same
effect is produced by dissolving an inert gas into a molten polymer under
high pressure. When the pressure is rapidly reduced, the gas comes out of
solution and forms bubbles and pores that remain in the solid as it cools.
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Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Polymers Synthesis and Processing

The large macromolecules of the commercially useful polymers must be synthesized from substances
having smaller molecules in a process termed polymerization.

1. Addition polymerization - (sometimes called chain reaction polymerization) is a process

by which monomer units are attached one at a time in chainlike fashion to form a linear
macromolecule. The composition of the resultant product molecule is an exact multiple for that
of the original reactant monomer.
• Three distinct stages—initiation, propagation, and termination—are involved in addition
polymerization.
• During the initiation step, an active center capable of propagation is formed by a reaction
between an initiator (or catalyst) species and the monomer unit.
• Propagation involves the linear growth of the polymer chain by the sequential addition of
monomer units to this active growing chain molecule.
• Propagation may end or terminate in different ways. First, the active ends of two propagating
chains may link together to form one molecule according to the following reaction.
Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Polymers Synthesis and Processing

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Polymers Synthesis and Processing

2. Condensation polymerization – Condensation (or step reaction) polymerization is the

formation of polymers by stepwise intermolecular chemical reactions that may involve more
than one species.
• There is usually a small molecular weight byproduct such as water that is eliminated (or
condensed). No reactant species has the chemical formula of the repeat unit, and the
intermolecular reaction occurs every time a repeat unit is formed.
• For example, consider the formation of the polyester, poly(ethylene terephthalate) (PET), from
the reaction between ethylene glycol and terephthalic acid; the intermolecular reaction is as
follows:

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Polymer Additives

The properties of a polymer may be modified and enhanced by the inclusion of additive materials.
A finished piece having a desired shape must be fashioned during a forming operation.

1. Fillers – Fillers are materials are most often added to polymers to improve tensile and
compressive strengths, abrasion resistance, toughness, dimensional and thermal stability,
and other properties.

• Materials used as particulate fillers include wood flour (finely powdered sawdust), silica flour
and sand, glass, clay, talc, limestone, and even some synthetic polymers. Often the fillers are
inexpensive materials that replace some volume of the more expensive polymer, reducing
the cost of the final product.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Polymer Additives

2. Plasticizers – The flexibility, ductility, and toughness of polymers may be improved with
the aid of additives called plasticizers.

• Their presence also produces reductions in hardness and stiffness. Plasticizers are generally
liquids having low vapor pressures and low molecular weights. The small plasticizer
molecules occupy positions between the large polymer chains, effectively increasing the
interchain distance with a reduction in the secondary intermolecular bonding.

• Plasticizers are commonly used in polymers that are intrinsically brittle at room temperature,
such as poly(vinyl chloride) and some of the acetate copolymers. The plasticizer lowers the
glass transition temperature, so that at ambient conditions the polymers may be used in
applications requiring some degree of pliability and ductility. These applications include thin
sheets or films, tubing, raincoats, and curtains.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Polymer Additives

3. Stabilizers – Some polymeric materials, under normal environmental conditions, are

subject to rapid deterioration, generally in terms of mechanical integrity. Additives that
counteract deteriorative processes are called stabilizers.

4. Colorants – Colorants impart a specific color to a polymer; they may be added in the
form of dyes or pigments.

• The molecules in a dye actually dissolve in the polymer. Pigments are filler materials that do
not dissolve, but remain as a separate phase; normally they have a small particle size and a
refractive index near to that of the parent polymer. Others may impart opacity as well as
color to the polymer.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Polymer Additives

3. Stabilizers – Some polymeric materials, under normal environmental conditions, are

subject to rapid deterioration, generally in terms of mechanical integrity. Additives that
counteract deteriorative processes are called stabilizers.

4. Colorants – Colorants impart a specific color to a polymer; they may be added in the
form of dyes or pigments.

• The molecules in a dye actually dissolve in the polymer. Pigments are filler materials that do
not dissolve, but remain as a separate phase; normally they have a small particle size and a
refractive index near to that of the parent polymer. Others may impart opacity as well as
color to the polymer.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Polymer Additives

5. Flame retardants – The flammability of polymeric materials is a major concern,

especially in the manufacture of textiles and children’s toys.

• Most polymers are flammable in their pure form; exceptions include those containing
significant contents of chlorine and/or fluorine, such as poly(vinyl chloride) and
polytetrafluoroethylene. The flammability resistance of the remaining combustible polymers
may be enhanced by additives called flame retardants. These retardants may function by
interfering with the combustion process through the gas phase, or by initiating a different
combustion reaction that generates less heat, thereby reducing the temperature; this causes
a slowing or cessation of burning.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Forming Techniques of Polymers

Molding is the most common method for forming plastic polymers. The several molding
techniques used include compression, transfer, blow, injection, and extrusion molding.

1. Compression Molding
For compression molding, the appropriate amounts of
thoroughly mixed polymer and necessary additives are placed
between male and female mold members. The mold is closed,
and heat and pressure are applied, causing the plastic to
become viscous and flow to conform to the mold shape. Before
molding, raw materials may be mixed and cold pressed into a
disc, which is called a preform. Preheating of the preform
reduces molding time and pressure, extends the die lifetime,
and produces a more uniform finished piece.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Forming Techniques of Polymers

2. Injection Molding
• Injection molding, the polymer analogue of die casting
for metals, is the most widely used technique for
fabricating thermoplastic materials.
• The correct amount of pelletized material is fed from a
feed hopper into a cylinder by the motion of a plunger
or ram. This charge is pushed forward into a heating
chamber where it is forced around a spreader so as to
make better contact with the heated wall. As a result,
the thermoplastic material melts to form a viscous
liquid. Next, the molten plastic is impelled, again by ram
motion, through a nozzle into the enclosed mold cavity;
pressure is maintained until the molding has solidified.
Finally, the mold is opened, the piece is ejected, the
mold is closed, and the entire cycle is repeated.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Forming Techniques of Polymers

3. Extrusion - is the molding of a viscous thermoplastic under pressure through an open-

ended die, similar to the extrusion of metals.
• A mechanical screw or auger propels through a chamber the pelletized material, which is
successively compacted, melted, and formed into a continuous charge of viscous fluid. Extrusion
takes place as this molten mass is forced through a die orifice. Solidification of the extruded
length is expedited by blowers, a water spray, or bath. The technique is especially adapted to
producing continuous lengths having constant cross-sectional geometries—for example, rods,
tubes, hose channels, sheets, and filaments.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Forming Techniques of Polymers

4. Blow Molding

• The blow-molding process for the fabrication of

plastic containers is similar to that used for
blowing glass bottles. First, a parison, or length
of polymer tubing, is extruded. While still in a
semi-molten state, the parison is placed in a
two-piece mold having the desired container
configuration. The hollow piece is formed by
blowing air or steam under pressure into the
parison, forcing the tube walls to conform to
the contours of the mold. Of course the
temperature and viscosity of the parison must
be carefully regulated.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
 Forming Techniques of Polymers

5. Casting

• Like metals, polymeric materials may be cast, as when a molten plastic material is poured into
a mold and allowed to solidify. Both thermoplastic and thermosetting plastics may be cast.

• For thermoplastics, solidification occurs upon cooling from the molten state;

• However, for thermosets, hardening is a consequence of the actual polymerization or curing

process, which is usually carried out at an elevated temperature.

Callister Jr, W. D., (2007). Callister's Materials Science and Engineering. John Wiley & Sons.
End of Presentation