CAGAYAN STATE UNIVERSITY

Carig Campus
College of Engineering

CHEMISTRY FOR ENGINEERS

CHEM111
UNIT III
CHEMISTRY OF ENGINEERING
MATERIALS: POLYMERS
Learning Objectives:
At the end of this unit, the students will be able to:
1. Describe the composition, properties and manufacturing methods of the three groups of
polymers: thermoplastics, thermosets, and elastomers.
2. Compare the physical and mechanical properties of polymers with those of metals.
CONTENTS:
I. Plastics
II. Important Thermoplastics
III. Important Thermosetting Resins
IV. Elastomers

INTRODUCTION
This chapter discusses the composition, properties and the manufacturing of polymers. The
word polymer is derived from the Greek words poly (many) and mer (parts). Polymers are
substances whose very large molecules are made up of many repeating subunits or sections. These
sections, often referred to as polymer chains, have average molecular weights ranging from 10,000
to more than 1 million g/mol which are created by chemically bonding several “mers” together to
form massive molecules known as macromolecules.
Polymerization is the mechanism by which small molecules composed of one unit (known as a
monomer) or a few units (known as oligomers) are chemically bonded together to form these giant
macromolecules. Polymerization usually starts with the development of long chains in which the
atoms are tightly bound by covalent bonding.
Synthetic and naturally occurring polymers exhibit a diverse range of properties (different
toughness, elasticity, melting points, flexibility, etc.) and have been developed for a wide range of
uses in our daily lives as will be shown in the module.

I. PLASTICS
Plastics are materials consisting mostly of polymers (either naturally occurring and improved or
chemically manufactured) often containing additives such as fibers, fillers, pigments, and the like,
which further enhance their properties. Plastics are classified as thermoplastics, thermoset resins
and elastomers.
Plastics are high-polymer materials which can be formed or shaped into various shapes by the
controlled application of heat and strain. Resins are simply the binders used in plastics and these
two terms are sometimes used synonymously.
Plastics are mostly made from the processing of chemicals derived from fossil fuels although
several plastics are now being derived from biodegradable materials such as corn, cotton, and
Module 15_Polymers: Page 1 of 12
biochemically synthesized plastics from bacteria. Compared with most metals and ceramics, plastics
have low strength, stiffness, and low melting temperatures. However, they also have lower densities
and good chemical resistance (they do not react with a number of chemicals/solvents).

CLASSES OF PLASTICS/RESINS:
1. Thermoplastic resins or thermoplastics soften upon heating and harden when cooled. These
transformations are NOT chemical but physical in nature which means that repeated heating
and cooling does not alter the main chemical structure and properties of the polymer chain.
They are composed of long chains of monomers and typically behave in a plastic, ductile
manner. The chains may or may not have branches and individual chains are intertwined.
Thermoplastics can be amorphous (their polymer chains are tangled together without apparent
structure) or crystalline (the polymer chains are arranged with some semblance of structure).
2. Thermoset resins or thermosets are plastics that have been heated during the molding process
until the structure has been ‘set’ (i.e. fixed and hardened). This hardened material cannot be
softened again, hence the setting is permanent and irreversible.
Unlike thermoplastics, thermosets DO NOT MELT upon heating; instead, they begin to
decompose or change chemically. The material cannot easily be reprocessed after the cross-
linking reaction has occurred, and hence, recycling thermoset plastics is extremely difficult.
They are composed of long chains (linear or branched) of molecules that are strongly cross-
linked to one another forming complex three-dimensional network structures. Thermosets are
generally stronger, but are more brittle, than thermoplastics.
3. Elastomers are plastics that maintain their original structure despite elastic deformations of
more than 200 per cent. They may either be thermoplastics or lightly interlinked thermosets.
The polymer chains of elastomers consist of coil-like molecules that can be extended reversibly
by applying force. Elastomers are more commonly referred to as rubber.

A. COMPOUNDING
The process of mixing additives to virgin plastics is called compounding.
Additives and their functions:
a. Resin is the binding substance; it binds all the additives together.
b. Filler/s are added to modify the properties of plastics. They can give the plastic better
hardness, tensile strength, finish and workability.
- Fibrous fillers such as wood flour, cotton fiber, chopped rags impart improved
mechanical strength to plastics;
- Asbestos increases heat resistance;
- Mica or slate powder improves electrical properties;
- Examples: Plastics embedded with glass mats are known as fiber reinforced plastics
(FRP) which are very strong and can be used to make the gates of dams, corrosion
resistant pipes and tanks, safety helmets, jeep bodies; PVC laminated to steel or
aluminum are used in some kitchen appliances and surfaces as they are waterproof and
easy to clean.
c. Plasticizers are small molecules and act as internal lubricants and help improve the
plasticity and flexibility of the polymer.
d. Waxes, oils, stearates and soaps are used to improve the finish and reduce the sticking
tendency of the plastic to the molds used to shape them.
e. Coloring materials are used to impart beauty/increase appeal and to give UV protection to
the finished material.

Module 15_Polymers: Page 2 of 12

B. PROCESSING OF PLASTIC
1. Calendering is a method commonly used in the production of continuous films or sheets. The
compounding material is run between two highly polished metallic rollers rotating in an
opposite direction. While passing through the gap between the rollers, the sheet is formed.
Sheet thickness varies with the size of the gap between the rollers.

https://www.ecomolding.com/wp-content/uploads/2018/09/Calendering-Animation-1.gif

Figure 3b.1.1. A typical calendering process

2. Die Casting. This relatively cheap technique is use for acrylics, polyesters, phenols and
urethans. Compounded material is fed into die cavities or casts (essentially the molds which
shape the plastic) made up of metals or plaster of paris and it is heated until crosslinking
takes place.
3. Film Casting. A compounded solution (compound diluted in the appropriate solvent) is
continuously dropped or poured on a moving belt. The solvent evaporates quickly and films
are obtained. Cellophane papers and photographic films are produced using this process.

Figure 3b.1.2. A schematic representation of the film casting process.

4. Compression Moulding. This method can be used to manufacture both thermosetting and
thermoplastic materials. Thermoset moldings are most commonly done by inserting the solid
material in a heated die (or cast) prior to cross-linking. The application of high pressure and
high temperature allows the polymer to melt and fill the die. The polymer is then allowed
to continue to harden. This process can be used to manufacture small electrical housings as
well as fenders, hoods, and side panels for vehicles.

Module 15_Polymers: Page 3 of 12

 Figure 3b.1.3. The compression molding process

5. Injection Molding. Thermosetting polymers in the form of liquid resins are first inserted into
a blender and are then fed directly into a heated mold to create a shape. Shape formation
and curing take place concurrently within the mold.

Figure 3b.1.4. The injection molding process

6. Blow Molding. The hollow preform of a thermoplastic called a parison is inserted into a die
is ‘blown’ or stretched towards the walls of a die using gas pressure. This method is used to
manufacture plastic bottles, cans, vehicle fuel tanks and other hollow forms and containers.

Figure 3b.1.5. The blow molding process

7. Extrusion. This is the most commonly used thermoplastic manufacturing technique. A screw
mechanism composed of one or two screws (twin screws) drives thermoplastic heaters and
additives into a die opening to create solid designs, film, covers, tubes and pipes.
Extrusion can serve two purposes. First, it offers a means to create basic forms (Figures
3b.1.6 and 3b.1.7) consistently and continuously. Second, the extrusion process provides an
ideal setup to mix in additives in the manufacturing of polymers, which can then eventually
be shaped using some other tool.

Figure 3b.1.6. A very basic layout of an extruder.

The arrows show the flow of material.

Module 15_Polymers: Page 4 of 12

 (Fundamentals of Modern Manufacturing: Materials, Processes, and Systems, 3rd Ed.)
Figure 3b.1.7. Schematic of an extruder with labeled parts.

Extrusion also can be used to coat wires and cables with either thermoplastics or elastomers. It
can also be used to manufacture plastic bags and tubes thru a process called blown-film extrusion.

Figure 3b.1.8. The method of blown-film extrusion.

The thermoplastic polymer is extruded upwards in
the shape of a tube. Air is blown onto the vent,
allowing it to expand and cool off. These tubes can
then be processed further: they can be cut/sealed,
etc.

C. MECHANICAL PROPERTIES OF THERMOPLASTICS

When load is applied to a material, polymers will respond differently to metals, due to
differences in their chemical structures and arrangements. Polymers behave like a cross between
an elastic solid and a viscous liquid. There is no set relationship between stress and strain and
the behavior of the material can be significantly impacted by temperatures. However, certain
formulas can be applied to approximate certain behaviors.
𝝈 = 𝝈𝟎 𝒆𝒙𝒑(− 𝒕⁄ ) 𝑬𝒒. (𝟑𝒃. 𝟏. 𝟏)
𝛌
Where 𝜎 values represent stresses at two different time periods (𝜎0 = 𝑠𝑡𝑟𝑒𝑠𝑠 𝑎𝑡 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑡𝑖𝑚𝑒,
𝜎 = 𝑠𝑡𝑟𝑒𝑠𝑠 𝑎𝑡 𝑡𝑖𝑚𝑒 𝑡) and λ = relaxation time.

Note that 𝜎0 is not equal to 𝜎. This is due to a phenomenon called stress relaxation. Stress
relaxation is a behavior of polymers and is defined as the decrease in stress over time under
constant strain. Stress is the amount of force being experienced by the material whereas strain
is the change in the shape of the material or the deformation when stress is applied. Stress
relaxation occurs because viscoelastic materials, such as polymers, experience some plastic
strain when it has been kept in a strained condition for some time (e.g. a rubber band which has
been stretched for a long time will remain somewhat stretched even when you remove the
stresses that have caused it to stretch).

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 Example 3.1
A band of polyisoprene is to hold together a bundle of steel rods for up to one year. If the
stress on the band is less than 1500 psi, the band will not hold the rods tightly. Determine the
initial stress that must be applied to a polyisoprene band when it is slipped over the steel. A
series of tests showed that an initial stress of 1000 psi decreased to 980 psi after six weeks.
Strategy and Solution:
Although the strain on the elastomer band may be constant, the stress will decrease over
time due to stress relaxation.
6 𝑤𝑒𝑒𝑘𝑠
980𝑝𝑠𝑖 = (1000 𝑝𝑠𝑖)𝑒𝑥𝑝(− )
λ
6 𝑤𝑒𝑒𝑘𝑠 980
− = ln ( ) = ln(0.98) = −0.0202
λ 1000
6 𝑤𝑒𝑒𝑘𝑠
λ= = 297 𝑤𝑒𝑒𝑘𝑠
0.0202
Now that we know the relaxation time, we can determine the initial stress that should be
placed on the band at the start time such that the band will still be stressed to 1500 psi after
1 year.
1 𝑦𝑒𝑎𝑟 52 𝑤𝑒𝑒𝑘𝑠
1500 𝑝𝑠𝑖 = 𝜎0 𝑒𝑥𝑝 (− ) = 𝜎0 𝑒𝑥𝑝 (− )
297 𝑤𝑒𝑒𝑘𝑠 297 𝑤𝑒𝑒𝑘𝑠
1500 𝑝𝑠𝑖 = 𝜎0 𝑒𝑥𝑝(−0.1751) = 0.8394𝜎0
1500 𝑝𝑠𝑖
𝜎0 = = 1,787 𝑝𝑠𝑖 𝑜𝑟 1.79 × 103 𝑝𝑠𝑖
0.8394
In order for the stress to still be at 1500 psi after a year (enough to keep the bundle
together), the initial stress that should be applied to the polyisoprene (perhaps through
tightening) should be 1787 psi AT THE MINIMUM.
.

II. IMPORTANT THERMOPLASTICS

1. POLYETHYLENE (PE)
▪ Polymerized ethylene; also called polythene.
▪ Rigid, waxy, white, translucent non–polar material. It has good chemical resistance against
acids, alkali, and salt solutions. It has good insulating properties but is susceptible to organic
solvents, particularly kerosene.
▪ There are two types:
a) Low Density Polyethylene (LDPE) – has a branched structure and is flexible and tough
b) High Density Polyethylene (HDPE) – is a completely linear polymer (no branching) and
compared to LDPE it has a better chemical resistance, higher softening point, greater
rigidity but lower impact strength.
▪ Polythene is used to make thin sheets, tubes, or bags for domestic use. It is also used in
manufacturing toys, coated wires and cables, bags for packing, bottles, caps and insulator
parts.
2. POLYPROPYLENE (PP)
▪ Obtained by polymerizing propylene in the presence of a Ziegler-Natta Catalyst as shown in
the following reaction

Module 15_Polymers: Page 6 of 12

 ▪ Superior to polyethylene in terms of resistance to chemicals, hardness, strength, and moisture
proofing quality.
▪ Fibers of polypropylene are very strong. They are used to make ropes, carpets, blankets, bags,
apparels, etc. PP is also used as a packaging material for pharmaceutical and cosmetic
products, for making sterilizable hospital equipment, appliance parts, molded luggage,
colorful furniture, etc.

Figure 3b.2.1. Yogurt tubs are

just one of the everyday materials
we see that are made of
polypropylene.

3. POLY VINYL CHLORIDE (PVC)

▪ Vinyl chloride is the monomer for PVC and the monomer is produced by the direct addition
of HCl to acetylene at 60-80°C. It is then polymerized to create PVC.

▪ PVC is a colorless, odorless, non-flammable, chemically inert powder. It contains 53–55% Cl2
by mass and softens at around 80°C.
▪ It is resistant to water, light, O2, inorganic acids and alkaline substances, oil, and petrol.
However, it is soluble in hot chlorinated hydrocarbons.
▪ It is a widely used plastic. It has high rigidity and chemical resistance but is brittle, so its use
is mainly in making cables, water hoses, toys, rain coats, rexin, pipes of petroleum industry,
floor covering, refrigerator components, tires, cycles, motor cycles, mudguards, etc.
4. POLYTETRAFLUOROETHYLENE (TEFLON)
▪ Obtained by the polymerization of a water–emulsion of tetrafluoro ethylene, under pressure
and in the presence of benzoyl peroxide as a catalyst.

▪ TEFLON has strong inter chain forces due to the presence of highly electronegative elements
in the regular polymer structure. This gives the material unique properties such as extreme
toughness, high softening point, high chemical resistance, low coefficient of friction and a
waxy touch, good mechanical and electrical properties.
▪ It is used for insulating motor, transformers, cables, wires, etc. Non-stick cookware is made
of TEFLON. It can also be used in manufacturing gaskets, pump parts, tank linings, pipes and
tubes for the chemical industry, non-lubricating bearings and to make non-reactive coatings.
5. POLYURETHANE
▪ These are a varied range of crosslinked polymers made from two liquids - isocyante and a
polyol (a hydrocarbon with multiple hydroxyl groups)– joined together by urethane
(carbamate: −NH−(C=O)−O−) links.

Module 15_Polymers: Page 7 of 12

 ▪ It can be foamed like polystyrene but unlike thermicoal, it is soft and spongy.
▪ It has low thermal conductivity and is used as an insulating material in refrigerators. It is also
use in making pillows and mattresses. A coating of polyurethane can also be applied over
leather, which improves the appearance and quality of the leather: bags coated with
polyurethan look attractive and the shoes feel comfortable.
6. POLYAMIDES (NYLON-66)
▪ Polyamides are synthetic polymers having recurring amide groups, which have a structure
similar to that of polypeptides.
▪ Nylon which belongs to this class is used for making fibers. Nylon is strong, tough, elastic, and
can be dyed easily. Nylon also possesses high abrasion resistance and is chemically stable.
▪ Used primarily for fibers which can be used in making socks, undergarments, dresses and
carpets.

https://www.bluelinelabels.com/wordpress/wp-content/uploads/2016/09/Plastics-Image1.jpg

Figure 3b.2.2. Plastic Resin Identification Codes

III. IMPORTANT THERMOSETTING RESINS

1. PHENOLIC RESINS
▪ Phenolic resins are rigid, hard and water resistant.
▪ They are also resistant to non-oxidizing acids and organic solvents but are susceptible to alkali
solutions.
▪ It is widely used as a metal substitute where high tensile strength is not necessary. An inert
material, it can be substituted for glass. It can also be used in making insulator parts like
switches, plugs, heater handles. It can be moulded to cabinets for TVs and radio and telephone
parts. It may be used as adhesives in paints and varnishes, cation exchanger resin for water
softening.
2. EPOXY RESIN
▪ Epoxy Resins possess outstanding properties which makes it the major constituent of adhesives
in paint industry and as insulator in electrical industry. These properties are:

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 a. Adhesion to various metals
b. Chemical inertness
c. Stability at high temperatures
d. Flexibility
e. Toughness
f. Low shrinkage during cure.
3. POLYESTER
▪ Fibers of Polyester have high tensile strength, resiliency and is stable to hydrolysis. Thus, the
fabric made from this material is crease resistant.
▪ It is mostly used in manufacturing of synthetic fibers like terylene, Dacron, etc. which are
finally used for making garments for men, women, and children.
▪ It can be blended with wool and used for making carpets, blankets, upholsteries, quilts, etc.
▪ It can also be reinforced with glass to form safety helmets, airplane parts, paratroop, wire
insulators, fighter parachute.

IV. ELASTOMERS
A variety of natural and synthetic polymers called elastomers show a significant volume (>200
per cent) of elastic deformation as stress is applied. Rubber bands, car tires, O-rings, hoses and
electrical wire insulation are typical uses for these materials. Elastomers are sometimes referred to
as "rubbers" because raw natural rubber is an elastomer.
1. NATURAL RUBBER
▪ It is the thermoplastic latex which is inert, resilient, electrically non-conductive produced
from the sap of various trees.
▪ Made up of polymerized isoprene (natural rubber is made primarily of cis-isoprene aka
isoprene rubber; gutta-percha, a type of rubber, is made mostly of trans-isoprene)

▪ The molecular weight of raw rubber is about 100,000–150,000 g/mol.

▪ It is an amorphous solid, transparent, impervious to gases, elastic in nature.
▪ Rubber slowly oxides when exposed to air and it softens and liquifies upon heating.
▪ Vulcanization of Rubber
- Discovered in 1839 by Charles Goodyear, this is a process which improves the quality of
rubber by compounding it with sulfur. It introduces sulfur to the double bond of rubber at
100-140°C. When the sulfur enters into the double bond, it forms crosslinks between the
polymer chains and gives the structure more toughness.
▪ Chewing gum contains a base that is made from natural rubber, styrene butadiene, or
polyvinyl acetate (PVA).

2. SYNTHETIC RUBBERS
Synthetic rubbers are artificially manufactured elastomers which can be stretched to twice
its length and still retain its original shape. Like natural rubbers, synthetic rubbers are
compounded with additives to improve certain characteristics of the finished material. These
additives may be plasticizers, antioxidants, fillers, vulcanizing agents like sulfur, colors, etc.

Module 15_Polymers: Page 9 of 12

 A. POLYBUTADIENE (butadiene rubber or Buna-S)
▪ This is a relatively low-cost rubber, but the resistance to solvents is poor. As a result, it is
used as a toughening material to make other elastomers.
▪ Similar to polyisoprene in structure, but the repeat unit has four carbon atoms consisting
of one double bond (poly isoprene has 5 carbon atoms in its repeat unit).

▪ It is mainly used for the manufacturing of tires, soles of shoes, insulating wires and cables,
adhesive and lining for wheels.
B. BUTADIENE-STYRENE RUBBER (BSR OR BS)
▪ Used for automobile tires.
C. BUTYL RUBBER
▪ Butyl rubber, or polyisobutadiene, is used to make the inner tubes for tires, vibration
mounts, and weather-stripping material.
D. POLYCHLOROPRENE or NEOPRENE (GR-M)

▪ Is a common material for hoses and electrical insulation.

▪ It is used in the making of conveyor belts, adhesives, gaskets, and as linings for reaction
vessels, and for making pipes that carry corrosive gases and oils.

E. Other synthetic rubbers such as: Styrene rubber (GR-S), nitrile rubber (GR-A), thiocol (GR-P),
Hypalon, polyurethane, etc.

Example 3.2 HOW TO CHOOSE THE RIGHT TYPE OF MATERIAL

You want to use a material that can be used for making insulation boards that are
approximately 4 ft wide and 8 ft tall. The material must provide good thermal insulation. What
material would you choose?
Solution:
Glass is likely to be good insulators of heat; however, they are heavy, expensive, and
fragile. Polymers on the other hand are lightweight and can be produced cheaply, and they can
also be good thermal insulators. We can use foamed polystyrene since the air contained in the
beads adds significantly to their effectiveness as thermal insulators. For better mechanical
properties, we may want to produce foams that have relatively high density (compared to foams
that are used to make coffee cups). Finally, from a safety viewpoint, we want to be sure that
some fire and flame retardants are added to the foams. Such panels are made using expanded
polystyrene beads containing pentane.
If this material is not present in the market, it can be synthesized or custom made since
polymers can be compounded with other additives with relative ease. A molding process can be
used to make the foams. The sheets can be cut into the required sizes using a heated metal
wire.
.

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Self-Learning Evaluation 3.17
1. What are linear and branched polymers? Can thermoplastics be branched?
2. Briefly describe the possible applications of plastic in engineering and in the industry.
3. Distinguish between Thermoplastic and Thermosetting plastic.
4. What are the major advantages of plastics compared to ceramics, glasses, and metals?
5. A band of a polymer is to hold together a bundle of steel rods for up to one year. If the stress on
the band is less than 1300 psi, the band will not hold the rods tightly. Determine the initial stress
that must be applied to the polymer band when it is slipped over the steel. A series of tests
showed that an initial stress of 1500 psi decreased to 980 psi after two months.
SUMMARY
Classes of plastics or resins:
1. Thermoplastic resins/thermoplastics soften upon heating and harden when cooled.
2. Thermoset resins/thermosets are plastics that have been heated during the molding process
until the structure has been ‘set’. This hardened material cannot be softened again.
3. Elastomers (or rubber) are plastics that maintain their original structure despite elastic
deformations of more than 200 per cent.

• COMPOUNDING - the process of mixing additives to virgin plastics.

PLASTIC PROCESSING:
1. Calendering – used in producing films/sheets by having the polymer ‘squeezed’ between
rollers.
2. Die Casting – compounded material is fed into die cavities/casts and it is heated until
crosslinking takes place.
3. Film Casting - compounded solution is continuously poured on a moving belt; the solvent will
evaporate leaving the films behind.
4. Compression Molding - done by inserting the solid material in a heated die (or cast) prior to
cross-linking; solid is then heated and pressure is applied until it melts and fills the mold.
5. Injection Molding - polymers in the form of liquid resins are first inserted into a blender and are
then fed directly into a heated mold to create a shape.
6. Blow Molding – a hollow preform of a thermoplastic (parison) is inserted into a die and is ‘blown’
or stretched towards the walls of a die using gas pressure.
7. Extrusion - a screw mechanism drives thermoplastic heaters and additives into a die opening to
create solid designs, film, covers, tubes and pipes

𝑷𝑶𝑳𝒀𝑴𝑬𝑹 𝑩𝑬𝑯𝑨𝑽𝑰𝑶𝑹 𝑻𝑶 𝑺𝑻𝑹𝑬𝑺𝑺: 𝝈 = 𝝈𝟎 𝒆𝒙𝒑(− 𝒕⁄ )

𝛌

Module 15_Polymers: Page 11 of 12

 ELASTOMERS can either be natural or synthetic. They are chemically inert, resilient, and do
not conduct electricity. Like thermoplastics and thermosets, elastomers can also be
compounded to improve or to add to its natural characteristics.
.

References:
1. Askeland, D., Wright, W. (2016). The Science and Engineering of Materials (7th Ed). Cengage
Learning, Inc. 20 Channel Center Street Boston, MA 02210 USA. ISBN: 978-1-305-07676-1
2. Datta, S., Mukhopadhyay, R. (2007). Engineering Chemistry. New Age International (P) Ltd.,
Publishers, New Delhi-110002. ISBN (13):978-81-224-2872-8
3. Groover, M. (2007). Fundamentals of Modern Manufacturing: Materials, Proceses, and Sysyems
(3rd Ed.). John Wiley & Sons, Inc.

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