POLYMER SCIENCE ADN

ENGINEERING

Chapter 3

Chapter Outline

 3.1 Classification of Polymers

 3.2 Addition Polymerization
 3.3 Condensation Polymerization
 3.4 Degree of Polymerization
 3.5 Typical Thermoplastics
 3.6 Structure–Property Relationships
in Thermoplastics
 3.7 Effect of Temperature on
Thermoplastics

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 Chapter Outline (Continued)

 3.8 Mechanical Properties of

Thermoplastics
 3.9 Elastomers (Rubbers)
 3.10 Thermosetting Polymers
 3.11 Adhesives
 3.12 Additives for Plastics
 3.13 Polymer Processing and Recycling

Section 3.1
Classification of Polymers
 Linear polymer - Any polymer in which molecules
are in the form of spaghetti-like chains.
 Thermoplastics - Linear or branched polymers in
which chains of molecules are not interconnected to
one another.
 Thermosetting polymers - Polymers that are heavily
cross-linked to produce a strong three dimensional
network structure.
 Elastomers - These are polymers (thermoplastics or
lightly cross-linked thermosets) that have an elastic
deformation > 200%.

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Figure 3.1 Schematic showing linear and branched polymers. Note that branching can occur in any type of polymer (e.g.,
thermoplastics, thermosets, and elastomers). (a) Linear unbranched polymer: notice chains are not straight lines and not
connected. Different polymer chains are shown using different shades and design to show clearly that each chain is not
connected to another. (b) Linear branched polymer: chains are not connected, however they have branches. (c)
Thermoset polymer without branching: chains are connected to one another by covalent bonds but they do not have
branches. Joining points are highlighted with solid circles, (d) Thermoset polymer that has branches and chains that are
interconnected via covalent bonds. Different chains and branches are shown in different shades for better contrast.
Places where chains are actually chemically bonded are shown with filled circles.

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 Table 3.1 Comparison of the three polymer categories

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Figure 3.2 Three

ways to represent the
structure of
polyethylene: (a) a
solid three-
dimensional model,
(b) a three-
dimensional “space”
model, and (c) a
simple two-
dimensional model.

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Figure 3.3 Two ways to represent the benzene ring. In this

case, the benzene ring is shown attached to a pair of
carbon atoms, producing styrene.

Example 3.1
Design/Materials Selection for Polymer
Components
Design the type of polymer material you might select for
the following applications: a surgeon’s glove, a beverage
container and a pulley.
Example 3.1 SOLUTION
 The glove must be capable of stretching a great deal
in order to slip onto the surgeon’s hand. This
requirement describes an elastomer.
 A thermoplastic such as polyethylene terephthalate
(PET) will have the necessary formability and ductility
needed for this application.
 A relatively strong, rigid, hard material is required to
prevent wear, so a thermosetting polymer might be
most appropriate.
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 Section 3.2
Addition Polymerization
 Addition polymerization - Process by which polymer
chains are built up by adding monomers together
without creating a byproduct.
 Unsaturated bond - The double- or even triple-
covalent bond joining two atoms together in an
organic molecule.
 Functionality - The number of sites on a monomer
at which polymerization can occur.

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Figure 3.4 The addition reaction for producing

polyethylene from ethylene molecules. The unsaturated
double bond in the monomer is broken to produce active
sites, which then attract additional repeat units to either
end to produce a chain.

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Figure 3.5
Initiation of a
polyethylene
chain by chain-
growth may
involve (a)
producing free
radicals from
initiators such as
benzoyl peroxide,
(b) attachment of
a polyethylene
repeat unit to one
of the initiator
radicals, and (c)
attachment of
additional repeat
units to propagate
the chain.

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Figure 3.6
Termination of
polyethylene chain
growth: (a) the
active ends of two
chains come into
close proximity, (b)
the two chains
undergo combina-
tion and become
one large chain, and
(c) rearrangement
of a hydrogen atom
and creation of a
double covalent
bond by dispropor-
tionation cause
termination of two
chains.

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 Example 3.2
Calculation of Initiator Required
Calculate the amount of benzoyl peroxide initiator required
to produce 1 kg of polyethylene with an average molecular
weight of 200,000 g/mol. What is the degree of
polymerization? Assume that 20% of the initiator is
actually effective and that all termination occurs by the
combination mechanism.
Example 3.2 SOLUTION
The molecular weight of ethylene = (2 C)(12) + (4 H)(1) =
28 g/mol. Therefore, the degree of polymerization is:

200,000 g/mol  7143 ethylene molecules per average chain

28 g/mol
(1000 g polyethylene)(6.021023 monomers/mol)  2151023 monomers
28 g/mol

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Example 3.2 SOLUTION (Continued)

The combination mechanism requires the number of

benzoyl peroxide molecules to be:

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215  10 ethylene molecules
 0.03  10 23
7143 ethylene / chain
The molecular weight of benzoyl peroxide is (14 C)(12)
+ (10 H)(1) + (4 O)(16) = 242 g/mol. Therefore, the
amount of initiator needed to form the ends of the
chains is:

(0.03  10 23 )(242 g/mol)

 1.206 g
6.02  10 23

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 Section 3.3
Condensation Polymerization
 Condensation polymerization - A polymerization
mechanism in which a small molecule (e.g., water,
methanol, etc.) is condensed out as a byproduct.

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Figure 3.7 The condensation reaction for polyethylene

terephthalate (PET), a common polyester. The OCH3 group
and a hydrogen atom are removed from the monomers,
permitting the two monomers to join and producing methyl
alcohol as a byproduct.

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 Example 3.3
Condensation Polymerization of
6,6-Nylon
Nylon was first reported by Wallace Hume Carothers, of du
Pont in about 1934. In 1939, du Pont’s Charles Stine
reported the discovery of this first synthetic fiber to a
group of 3000 women gathered for the New York World’s
Fair. The first application was nylon stockings that were
strong. Today nylon is used in hundreds of applications.
Prior to nylon, Carothers had discovered neoprene (an
elastomer).
The linear polymer 6,6-nylon is to be produced by
combining 1000 g of hexamethylene diamine with adipic
acid. A condensation reaction then produces the polymer.
Show how this reaction occurs and determine the
byproduct that forms. How many grams of adipic acid are
needed, and how much 6,6- nylon is produced, assuming
100% efficiency?

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Example 3.3 SOLUTION

The molecular structures of the monomers are shown

below. The linear nylon chain is produced when a hydrogen
atom from the hexamethylene diamine combines with an
OH group from adipic acid to form a water molecule.

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Example 3.3 SOLUTION (Continued)

Molecular weight of hexamethylene diamine is

116 g/mol, of adipic acid is 146 g/mol, and of water is
18 g/mol. The number of moles of hexamethylene
diamine added (calculated below) is equal to the
number of moles of adipic acid:

1000 g  8 . 621 moles  xg

116 g / mol 146 g / mol
x = 1259 g of adipic acid required

The number of moles of water lost is also 8.621:

y = (8.621 moles) (18 g/mol) = 155.2 g H2O

Total amount of nylon produced is

1000 g + 1259 g – 2(155.2 g) = 1948.6 g.

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Section 3.4
Degree of Polymerization
 Degree of polymerization - The average molecular
weight of the polymer divided by the molecular
weight of the monomer.

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 Example 3.4
Degree of Polymerization for 6,6-Nylon
Calculate the degree of polymerization if 6,6-nylon has a
molecular weight of 120,000 g/mol.

Example 3.4 SOLUTION

The molecular weights are 116 g/mol for hexamethylene

diamine, 146 g/mol for adipic acid, and 18 g/mol for water.
The repeat unit for 6,6-nylon is:

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Example 3.4 SOLUTION (Continued)

The molecular weight of the repeat unit is the sum of the

molecular weights of the monomers, minus that of the
two water molecules that are evolved:

Mrepeat unit = 116 + 146 – 2(18) = 226 g/mol

Degree of polymerization = 120,000/226 = 531

The degree of polymerization refers to the total number

of repeat units in the chain. The chain contains 531
hexamethylene diamine and 531 adipic acid molecules.

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 Example 3.5
Number and Weight Average Molecular
Weights
We have a polyethylene sample containing 4000 chains
with molecular weights between 0 and 5000 g/mol, 8000
chains with molecular weights between 5000 and 10,000
g/mol, 7000 chains with molecular weights between
10,000 and 15,000 g/mol, and 2000 chains with molecular
weights between 15,000 and 20,000 g/mol. Determine
both the number and weight average molecular weights.

Example 3.5 SOLUTION

First we need to determine the number fraction xi and

weight fraction fi for each of the four ranges. We can then
use Equations 3-2 and 3-3 to find the molecular weights.

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Example 3.5 SOLUTION (Continued)

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 Section 3.5
Typical Thermoplastics

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Table 3.3 (Continued)

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Table 3.4 (Continued)

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 Section 3.6
Structure–Property Relationships
in Thermoplastics
 Branched polymer - Any polymer consisting of
chains that consist of a main chain and secondary
chains that branch off from the main chain.
 Crystallinity is important in polymers since it affects
mechanical and optical properties.
 Tacticity - Describes the location in the polymer
chain of atoms or atom groups in nonsymmetrical
monomers.
 Liquid-crystalline polymers - Exceptionally stiff
polymer chains that act as rigid rods, even above
their melting point.

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Figure 3.8 Head-to-tail versus head-to-head arrangement of

repeat units. The head-to-tail arrangement is most typical.

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Figure 3.9 Three

possible
arrangements of
nonsymmetrical
monomers: (a)
isotactic,
(b)syndiotactic,
and (c)atactic.

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Figure 3.10 Four types of copolymers: (a) alternating monomers,

(b) random monomers, (c) block copolymers, and (d) grafted
copolymers. Circles of different colors or sizes represent different
monomers.

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Figure 3.11
Copolymerization
produces the
polymer ABS,
which is really
made up of two
copolymers, SAN
and BS, grafted
together.

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Section 3.7 Effect of Temperature on

Thermoplastics
 Degradation temperature - The temperature above which
a polymer burns, chars, or decomposes.
 Glass temperature - The temperature range below which
the amorphous polymer assumes a rigid glassy structure.

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effect of
of

amorphous
thermoplastic.
the modulus of
elasticity for an
temperature on
Figure 3.13 The

Note that Tg and

Tm are not fixed.
Figure 3.12
The effect of

the structure
and behavior

thermoplastics.
temperature on

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Figure 3.14 The

relationship
between the
density and the
temperature of the
polymer shows the
melting and lass
temperatures.
Note that Tg and Tm
are not fixed;
rather, they are
ranges of
temperatures.

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Figure 3.3 The folded chain ,model for crystallinity in

polymers, shown in (a) two dimensions and (b) three
dimensions.

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Figure 3.16 Photograph of

spherulitic crystals in an amorphous
matrix of nylon ( 200). (From R.
Brick, A. Pense and R. Gordon,
Structure and Properties of
Engineering Materials, 4th Ed.,
McGraw-Hill, 1977.)

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Example 3.6
Design of a Polymer Insulation Material
A storage tank for liquid hydrogen will be made of metal,
but we wish to coat the metal with a 3-mm thickness of a
polymer as an intermediate layer between the metal and
additional insulation layers. The temperature of the
intermediate layer may drop to 80oC. Design a material for
this layer.

Example 3.6 SOLUTION

A material that has good ductility and/or can undergo

large elastic strains is needed. We therefore would prefer
either a thermoplastic that has a glass temperature below
80oC or an elastomer, also with a glass temperature below
80oC. Of the polymers listed in Table 3-2, thermoplastics
such as polyethylene and acetal are satisfactory. Suitable
elastomers include silicone and polybutadiene.

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Example 3.7
Impact-Resistant Polyethylene

A new grade of flexible, impact-resistant polyethylene for

use as a thin film requires a density of 0.88 to 0.915
g/cm3. Design the polyethylene required to produce these
properties. The density of amorphous polyethylene is
about 0.87 g/cm3.

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Example 3.7 SOLUTION

We can use the data in Table 3-3 to calculate this density if

we recognize that there are two polyethylene repeat units
in each unit cell (see Example 3.16):

c  (4C)(12)  (8H )(1)  0.9932 g / cm3

(7.42)(4.95)(2.55)(1024)(6.021023)

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 Example 3.7 SOLUTION (Continued)

We know that ρa = 0.87 g/cm3 and that ρ varies from

0.88 to 0.915 g/cm3. The required crystallinity then
varies from:

% Crystalline  (0.9932)(0.88  0.87)  100  9.2

(0.88)(0.9932  0.87)
% Crystalline  (0.9932)(0.915  0.87)  100  39.6
(0.915)(0.9932  0.87)

Therefore, we must be able to process the polyethylene

to produce a range of crystallinity between 9.2 and
39.6%.

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Section 3.8
Mechanical Properties of
Thermoplastics
 Viscoelasticity - The deformation of a material by elastic
deformation and viscous flow of the material when stress
is applied.
 Relaxation time - A property of a polymer that is related
to the rate at which stress relaxation occurs.

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Figure 3.17 The stress-strain curve for 6,6-nylon, a typical

thermoplastic polymer.

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Figure 3.18 Necks are not stable in amorphous polymers,

because local alignment strengthens the necked region and
reduces its rate of deformation.

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 Example 3.8
Comparing Mechanical Properties of
Thermoplastics
Compare the mechanical properties of LD polyethylene, HD
polyethylene, polyvinyl chloride, polypropylene, and
polystyrene, and explain their differences in terms of their
structures.
Example 3.8 SOLUTION

Let us look at the maximum tensile strength and modulus

of elasticity for each polymer.

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Example 3.8 SOLUTION (Continued)

We can conclude that:

1. Branching, which reduces the density and close packing of
chains, reduces the mechanical properties of polyethylene.
2. Adding atoms or atom groups other than hydrogen to the
chain increases strength and stiffness. The methyl group in
polypropylene provides some improvement, the benzene ring of
styrene provides higher properties, and the chlorine atom in
polyvinyl chloride provides a large increase in properties.
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Figure 3.19 The effect of temperature on the stress-rupture

behavior of high-density polyethylene.

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Figure 3.20 Creep curves for acrylic (PMMA) (colored lines)

and polypropylene (black lines) at 20°C and several applied
stresses.

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 Example 3.9
Design of Initial Stress in a Polymer
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.
Design 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.
Example 3.9 SOLUTION

We can use Equation 3-5 and our initial tests to determine

the relaxation time for the polymer:
   o exp(  t )

6
980  1000 exp(  6 ),    297 weeks
 0.0202
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Example 3.9 SOLUTION (Continued)

Now that we know the relaxation time, we can determine

the stress that must be initially placed onto the band in
order that it still be stressed to 1500 psi after 1 year (52
weeks).

1500  o exp(52 / 297)  o exp(0.175)  0.839o

o  1500  1788 psi
0.839
The polyisoprene band must be made significantly
undersized so it can slip over the materials it is holding
together with a tension of 1788 psi. After one year, the
stress will still be 1500 psi.

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Section 3.9
Elastomers (Rubbers)
 Geometric isomer - A molecule that has the same
composition as, but a structure different from, a second
molecule.
 Diene - A group of monomers that contain two double-
covalent bonds. These monomers are often used in
producing elastomers.
 Cross-linking - Attaching chains of polymers together to
produce a three-dimensional network polymer.
 Vulcanization - Cross-linking elastomer chains by
introducing sulfur or other chemicals.

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Figure 3.21 The cis and trans structures of isoprene. The cis form is
useful for producing the isoprene elastomer.

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Figure 3.22 (a) When the elastomer contains no cross-links, the application of
a force causes both elastic and plastic deformation; after the load is removed,
the elastomer is permanently deformed. (b) When cross-linking occurs, the
elastomer still may undergo large elastic deformation; however, when the
load is removed, the elastomer returns to its original shape.

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Figure 3.23 Cross-linking of polyisoprene chains may occur

introducing strands of sulfur atoms. Sites for attachment of
the sulfur strands occur by rearrangement or loss of a
hydrogen atom and the breaking of an unsaturated bond.

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Figure 3.24 The stress-strain curve for an elastomer. Virtually

all of the deformation is elastic; therefore, the modulus of
elasticity varies as the strain changes.

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Table 3.8 (Continued)

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Figure 3.25 The

structure of the
styrene-butadiene
(SB) copolymer in a
thermoplastic
elastomer. The glassy
nature of the styrene
domains provides
elastic behavior
without cross-linking
of the butadiene.

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 Section 3.10
Thermosetting Polymers

 Phenolics
 Amines
 Urethanes
 Polyesters
 Epoxies
 Polyimides
 Interpenetrating Polymer Networks

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Figure 3.26 Structure of a phenolic. In (a) two phenol rings are

joined by a condensation reaction through a formaldehyde molecule.
Eventually, a linear chain forms. In (b), excess formaldehyde serves
as the cross-linking agent, producing a network, thermosetting
polymer.

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 Section 3.11
Adhesives

 Chemically Reactive Adhesives

 Evaporation or Diffusion Adhesives
 Hot-Melt Adhesives
 Pressure-Sensitive Adhesives
 Conductive Adhesives

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Section 3.12
Additives for Plastics

 Fillers
 Pigments
 Stabilizers
 Antistatic Agents
 Flame Retardants
 Plasticizers
 Reinforcements
 Catalysts

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 Section 3.13
Polymer Processing and Recycling
Forming Processes for Thermoplastics:
 Extrusion
 Blow Molding
 Injection Molding
 Thermoforming

Forming Processes for Thermosetting polymers:

 Calendaring
 Spinning
 Compression Molding
 Transfer Molding

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Figure 3.27 Schematic of an extruder used for polymer processing.

(Source: Adapted from Plastics: Materials and Processing, Second
Edition, by A. Brent Strong, p. 382, Fig. 11-1. Copyright © 2000
Prentice Hall. Adapted with permission of Pearson Education, Inc.,
Upper Saddle River, NJ.)

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Figure 3.28 One technique by which polymer films (used in the manufacture
of garbage bags, for example) can be produced. The film is extruded in the
form of a bag, which is separated by air pressure until the polymer cools.
(Source: Adapted from Plastics: Materials and Processing, Second Edition,
by A. Brent Strong, p. 397, Fig. 11-8. Copyright © 2000 Prentice Hall.
Adapted with permission of Pearson Education, Inc., Upper Saddle River,
NJ.)

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Figure 3.29 Typical forming processes for thermoplastic: (a)

extrusion, (b) blow molding, (c) injection molding, (d)
thermoforming, (e) calendaring, and (f) spinning.
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Figure 3.30 Typical forming processes for thermosetting

polymers: (a) compression molding and (b) transfer
molding.

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Example 3.10
Insulation Boards for Houses
You want to design 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?
Example 3.10 SOLUTION
Glasses tend to be good insulators of heat. However, they will
be heavy, more expensive, and prone to fracture. Polymers
are lightweight, can be produced inexpensively, and they can
be good thermal insulators. We can use foamed polystyrene
since the air contained in the pores adds significantly to their
effectiveness as thermal insulators.
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.

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Figure 3.31 The effect of applied stress on the percent creep

strain for three polymers (for Problem 3.62)

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