Lesson 6

Polymer Structures
Outline
1. The Chemistry of Polymer Molecules
2. Molecular Weight & Degree of Polymerization
3. Molecular Structures and Copolymers
4. Thermoplastic and Thermosetting Behavior of Polymers
5. Polymer Crystallinity
6. Diffusion in Polymeric Materials

Polymer Structures
Many of the useful materials like plastics, rubbers and fiber materials are made of synthetic polymers. Synthetic
polymers are produced inexpensively and their properties may be managed to a degree that are superior to their
natural counterparts. Like for example, metals and wood parts are replaced by plastics in some applications,
which have satisfactory properties and produced at lesser cost.

The properties and behaviors of polymeric materials depends on a number of chemical and structural
characteristics. Some of these influences are: 1) degree of crystallinity; it influences on the density, stiffness,
strength and ductility, 2) degree of crosslinking; it influences on the stiffness of rubber like materials, and 3)
polymer chemistry; it influences on melting and glass-transition temperatures.

This lesson discusses basic concepts on polymer structures.

1. The Chemistry of Polymer Molecules

Most polymers are organic in origin like proteins, sugars, carbohydrates and many other organic materials.
Organic materials are compounds containing carbon, most of which are hydrocarbons; that is, they are
composed of hydrogen and carbon. Some of these hydrocarbons are synthesized to produce synthetic polymers
by the process called polymerization. Polymers are bigger molecules compared to hydrocarbons and are often
called macromolecules.

The backbone of carbon chain polymers is a string of carbon atoms. The long molecules are composed of
structural entities called repeat units which are successively repeated along the chain. A repeat unit is called
“Mer” from the Greek word “meros” which means part. Polymer means “many mers” or “many parts”. Examples
of polymers are polyethylene (PE), polyvinyl chloride (PVC), and polytetrafluoroethylene (PTFE). Their
structures and chemistry are discussed below:

1.1 Polyethylene (PE)

The repeat unit of polyethylene contains 2 carbon atoms and 4 hydrogen atoms. Polyethylene is synthesized
from the hydrocarbon ethylene (CH2 = CH2), which is a gas at ambient temperature and pressure. The molecular
structure of ethylene is:
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 H H
C=C
H H

Ethylene gas is reacted under appropriate conditions to transform it to polyethylene, a solid polymeric material.
This process begins when an active center is formed by the reaction between an initiator or catalyst (R) and the
ethylene monomer.

H H H H
R + C=C R–C–C–
H H H H

The polymer chain is formed by the sequential addition of monomer units to the active site. After adding many
ethylene monomer units, the polyethylene molecule is formed.

H H H H H H H H H H H H
R–C–C– + C=C R–C–C–C–C– + n C=C R – (C – C )n–
H H H H H H H H H H H H

1.2 Polyvinyl chloride (PVC)

The repeat unit of polyvinyl chloride contains 2 carbon atoms, 1 chlorine atom and 3 hydrogen atoms. Polyvinyl
chloride is synthesized from vinyl chloride (CH2= CHCl). Similar with polyethylene, the polymerization of
polyvinyl chloride starts with the reaction of catalyst (R) with the vinyl chloride monomer; and sequential
addition of the monomer in the active site results to the formation of polyvinyl chloride.

H H H H H H H H
R+ C=C R–C–C– + n C=C R– (C – C )n –
H Cl H Cl H Cl H Cl

1.3 Polytetraflouroethylene (PTFE)

The repeat unit of polytetrafluoroethylene contains 2 carbon atoms and 4 flourine atoms. The starting material
in the polymerization of polytetrafluoroethylene is tetraflouroethylene (CF2 = CF2). Tetraflouroethylene
monomer reacts with catalyst (R) to form an active site, then sequential addition of the monomer in the active
site forms polytetrafluoroethylene.

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 F F F F F F F F
R+ C=C R–C–C– + n C=C R– (C – C )n –
F F F F F F F F

When all the repeating units along a chain are of the same type, the resulting polymer is called homopolymer.
If the chain is composed of two or more different repeat units, this is termed as copolymers. Repeat units of
common polymeric materials are shown in Table 6.1.

Table 6.1 Repeat units of common polymeric materials

(Source: Callister Jr, W.D. (2007). Materials Science and Engineering: An Introduction)

2. Molecular Weight & Degree of Polymerization

Polymers have extremely large molecular weights. During the polymerization process not all chains will grow
to the same length, resulting to distribution of chain lengths or molecular weights. Ordinarily, an average
molecular weight is specified which may be determined by the measurement of various physical properties. But,
since there is distribution of chain lengths and molecular weights during polymerization, the average molecular
weight of polymers is defined in terms of number average molecular weight (Mn) and weight average molecular
weight (Mw).

2.1 Number Average Molecular Weight (Mn)

The number average molecular weight (Mn) is obtained by dividing the chains into a series of size ranges and
then determining the number fraction of chains within each size range (Figure 6.1a). The number average
molecular weight is expressed as: Mn = ∑ xi Mi

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 where: xi = is the fraction of the total number of chains within the corresponding size range
Mi = represents the mean (middle) molecular weight of the size range i

2.2 Weight Average Molecular Weight (Mw)

The weight average molecular weight (Mw) is calculated based on the weight fraction of molecules within the
various size ranges (Figure 6.1b). It is calculated as: Mw = ∑ w i M i

where: wi = denotes the weight fraction of molecules within the size interval
Mi = the mean molecular weight within the size range

Figure 6.1 Size distributions of number and weight fractions

(Source: Callister Jr, W.D. (2007). Materials Science and Engineering: An Introduction)

Example 1. Compute the number average molecular weight (Mn) for polyvinyl chloride (PVC).

Given:
Molecular Weight Range(g/mole) Mean (Mi) (g/mole) xi Mi*xi
5,000-10,000 7,500 0.05 375
10,000-15,000 12,500 0.16 2,000
15,000-20,000 17,500 0.22 3,850
20,000-25,000 22,500 0.27 6,075
25,000-30,000 27,500 0.20 5,500
30,000-35,000 32,500 0.08 2,600
35,000-40,000 37,500 0.02 750

Required: Mn

Solution:
Mn = ∑ xi Mi
Mn = 375 + 2,000 + 3,850 + 6,075 + 5,500 + 2,600 + 750
Mn = 21,150 g/mol

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Example 2. Compute the weight average molecular weight (Mw) for polyvinyl chloride (PVC).

Given:
Molecular Weight Range(g/mole) Mean (Mi) (g/mole) wi Mi*wi
5,000-10,000 7,500 0.02 150
10,000-15,000 12,500 0.10 1,250
15,000-20,000 17,500 0.18 3,150
20,000-25,000 22,500 0.29 6,525
25,000-30,000 27,500 0.26 7,150
30,000-35,000 32,500 0.13 4,225
35,000-40,000 37,500 0.02 750

Required: Mw

Solution:
Mw = ∑ wi Mi
Mw = 150 + 1,250 + 3,150 + 6,525 + 7,150 + 4,225 + 750
Mw = 23,200 g/mol

2.3 Degree of Polymerization

The degree of polymerization (DP) is an alternate way of expressing average chain size of a polymer; this
represents the average number of repeat units in a chain. The degree of polymerization is related to the number
average molecular weight (Mn) by the equation: DP = Mn/m

where: Mn = is the number average molecular weight

m = is the repeat unit molecular weight

Example 3. Compute the degree of polymerization for example 1.

Given: Mn = 21,150 g/mol (from example 1)

Required: DP

Solution:
a. Solve for m (repeat unit of PVC has 2 carbon atoms, 3 Hydrogen atoms and 1 Chlorine atom)
Find in the periodic table the atomic weight of each element.
C = 2 * 12 g/mol = 24 g/mol
H = 3 * 1 g/mol = 3 g/mol
Cl = 1 * 35.45 g/mole= 35.45 g/mol

m= 24 g/mol + 3 g/mol + 35.45 g/mol

m = 62.45 g/mol

b. Solve for degree of polymerization using: DP = Mn/m

DP = Mn/m
DP = 21,150 g/ mol / 62.45 g/mol = 339

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Clicker Exercise 1
1. Tabulated below is the molecular weight data for polytetrafluoroethylene material. Compute a) the number
average molecular weight, b) the weight average molecular weight, and c) the degree of polymerization.

Molecular Weight range (g/mol) xi wi

10,000-20,000 0.03 0.01
20,000-30,000 0.09 0.04
30,000-40,000 0.15 0.11
40,000-50,000 0.25 0.23
50,000-60,000 0.22 0.24
60,000-70,000 0.14 0.18
70,000-80,000 0.08 0.12
80,000-90,000 0.04 0.07

3. Molecular Structure and Copolymers

3.1 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. There are four types of molecular structures, namely: linear,
branched, crosslinked and network.

Linear polymers
The repeat units of linear polymers are joined end to end in single chains. These long chains are flexible and may
be thought of as a mass of spaghetti. Each circle in the illustration below of a linear polymer represents a repeat
unit. Examples of polymers with linear structures are polyethylene, poly vinyl chloride, polystyrene, nylon and
the fluorocarbons.

Branched polymers
In branched polymers, there are side branches that are connected to the main chain and is considered as a part
of the main-chain molecule. The chain packing efficiency is reduced with the formation of side branches, which
results in lowering the polymer density. Polymers with linear structure may also form the branched chain.

Crosslinked polymers
In crosslinked polymers, the 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 non-reversible chemical reactions.
But often, this crosslinking is accomplished by additive atoms or molecules that are covalently bonded to the
chains. Many of rubber elastic materials are crosslinked.

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Network polymers
Multifunctional monomers forming three or more active covalent bonds, make three dimensional networks
termed network polymers. A polymer that is highly crosslinked may also be classified as network polymer.
These materials have distinctive mechanical and thermal properties. Examples of network polymers are
epoxies, polyurethanes, and phenol formaldehyde.

3.2 Copolymers
Polymer chemists and scientist continuously search for new materials that can easily and economically be
synthesized and fabricated with improved properties or better property combinations than those offered by
homopolymers. One group of these materials that are being studied is copolymers. A copolymer is composed
of two different repeat units as represented by • and • circles in Figure 6.2. Depending on the polymerization
process, different sequencing arrangements along the polymer chain is possible. A randomly dispersed units
along the chain is termed random copolymers (Figure 6. 2a). When two repeat units are in alternate position, it
is termed alternating copolymer (Figure 6.2b). When identical repeat units are clustered in blocks along the
chain, it is termed block copolymer (Figure 6.2c). And finally, when a homopolymer of one type is grafted (or
side branch) to a homopolymer main chain that is composed of a different repeat unit, it is termed as graft
copolymer (Figure 6.2d).

Figure 6.2 Representation of a) random, b) alternating, c) block, and d) graft copolymers

(Source: Callister Jr, W.D. (2007). Materials Science and Engineering: An Introduction)

4. Thermoplastic and Thermosetting Behavior of Polymers

One classification scheme of polymers is according to behavior with rising temperature. The response of the
polymer to mechanical forces at elevated temperatures is related to its dominant molecular structure.
Thermoplastics and thermosets are the two subdivisions under the classification of polymers in terms of its
behavior with rising temperature.

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4.1 Thermoplastic polymers
Thermosplastic polymers (or thermoplast polymers) softens when heated and eventually liquefy, and when
cooled it hardened. Thermoplastics are relatively soft. Most linear polymers and those having some branched
structures with flexible chains are thermoplastics. Examples of common thermosplastic polymers include
polyethylene, polystyrene and poly vinyl chloride.

4.2 Thermosetting polymers

Thermosetting polymers (thermoset polymers) do not soften upon heating, it becomes permanently hard when
heated. Thermoset polymers are generally harder and stronger than thermosplastic polymers and have better
dimensional stability. Most of the crosslinked and network polymers which include epoxies, some polyester
resins, vulcanized rubbers, and phenolics are thermosetting.

5. Polymer Crystallinity
Polymeric materials may exist in crystalline state or amorphous state. But since atomic and chain arrangement
are very complex, polymers are often only partially crystalline or semi crystalline. Semi-crystalline polymers
have two phase regions, the amorphous and crystalline regions; the crystalline region is dispersed within the
remaining amorphous material.

Polymer crystallinity is the packing of molecular chains to produce an ordered atomic array. Any chain disorder
or misalignment will result in an amorphous region because twisting, kinking and coiling of the chains prevent
strict ordering of the chains. So, the degree of crystallinity may range from completely amorphous to almost
entirely (up to 95%) crystalline. The degree of crystallinity by weight is determined from accurate density
measurements computed according to:

𝜌𝑐 (𝜌𝑠−𝜌𝑎)
% crystallinity = 𝜌𝑠 (𝜌𝑐−𝜌𝑎) x 100

where: ρs = density of specimen for which % crystallinity is to be determined.

ρa = density of totally amorphous polymer
ρc = density of perfectly crystalline polymer

The degree of crystallinity of polymer depends on the rate of cooling during solidification as well as the chain
configuration. During crystallization, the chains which are highly random and entangled in the viscous fluid need
sufficient time for the chain to move and align themselves, hence, longer time is required to crystallize.

Molecular chemistry and chain configuration also influences the ability of the polymer to crystallize.
Crystallization is not favored in polymers that are composed of complex repeat units; crystallization is easy then
for simple repeat units. Linear polymers crystallize easily because there are few restrictions to prevent chain
alignment. Side branches interfere with crystallization, so branched polymers never are highly crystalline;
excessive branching may even prevent crystallization. Most network and crosslinked polymers are almost
totally amorphous because the crosslinks prevent the polymer chains from rearranging and aligning into a
crystalline structure.

For copolymers, the more irregular and random the arrangement of repeat units, the greater the tendency for
the development of non-crystallinity. So, alternating and block copolymers have some likelihood of
crystallinity. On the other hand, the graft and random copolymers are normally amorphous.

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The degree of crystallinity is influenced by the physical properties of polymeric materials. Crystalline polymers
are usually stronger and more resistant to dissolution and softening by heat.

Example 4. Calculate the % crystallinity of the branched polyethylene with ρc = 0.998 g/cm3, ρa = 0.870 g/cm3
and ρs = 0.925 g/cm3.

Given: ρc = 0.998 g/cm3

ρa = 0.870 g/cm3
ρs = 0.925 g/cm3
Required: % crystallinity

Solution:
𝜌𝑐 (𝜌𝑠−𝜌𝑎)
% crystallinity = 𝜌𝑠 (𝜌𝑐−𝜌𝑎) x 100

𝑔 𝑔 𝑔
0.998 ( 0.925 − 0.870 )
𝑐𝑚3 𝑐𝑚3 𝑐𝑚3
% crystallinity = 𝑔 𝑔 𝑔 x 100
0.925 (0.998 − 0.870 )
𝑐𝑚3 𝑐𝑚3 𝑐𝑚3

% crystallinity = 46.4%

6. Diffusion in Polymeric Materials

Polymeric materials are often in diffusive motion of small foreign molecules (e.g. O2, CO2, H2O, CH4) between
the molecular chains. The polymer’s permeability and absorption characteristics relate to the degree to which
foreign substances diffuse into the material. Penetration of these substances can lead to swelling and/or
chemical reactions with the polymer molecules which may result to degradation of the material’s mechanical
and physical properties.

Rates of diffusion is greater through amorphous regions than through crystalline regions. The size of the foreign
molecules also affects the diffusion rate; smaller molecules diffuse faster than larger ones. Diffusion is also more
rapid to foreign molecules that are chemically inert than those that react with the polymer.

Diffusion properties of polymers are characterized in terms of permeability coefficient (PM), and for a steady-
state diffusion through a polymer membrane the diffusion flux is calculated as: J = PM (ΔP/Δx)

where: J is the diffusion flux of gas through a membrane (cm3 STP/ cm2-s)
PM is the permeability coefficient (cm3 STP cm / cm3-s-Pa)
Δx is the membrane thickness (cm)
ΔP is the difference in pressure of the gas across the membrane (Pa)

Table 6.2 lists the permeability coefficients of oxygen, nitrogen, carbon dioxide and water vapor in several
common polymers. In some applications, low permeability rates through polymeric materials are desirable, as
with food and beverages packaging and automobile tires and inner tubes. In another case like when polymeric
material is used as filters, the permeation rate of the substance to be filtered should be higher than for other
substances.

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Table 6.2 Permeability coefficients(PM) at 25 ºC in a variety of polymers
PM [ x 10-13 cm3 STP cm / cm3-s-Pa]
Polymer Acronym O2 N2 CO2 H2O
Polyethylene (low density) LDPE 2.2 0.73 9.5 68
Polyethylene (high density) HDPE 0.30 0.11 0.27 9.0
Polypropylene PP 1.2 0.22 5.4 38
Polyvinyl chloride PVC 0.034 0.0089 0.012 206
Polystyrene PS 2.0 0.59 7.9 840
Polyvinylidence chloride PVDC 0.0025 0.00044 0.015 7.0
Polyethylene terephthalate PET 0.044 0.011 0.23 -
Polyethyl methacrylate PEMA 0.89 0.17 3.8 2380
Source: Polymer Handbook, 4th edition, copyright 1999, John Wiley & Sons

Example 5. The clear plastic bottle used for carbonated beverages are made from polyethylene terephthalate
(PET). The “fizz” in soda pop results from carbon dioxide (CO2), and because PET is permeable to CO2, the pop
stored in PET bottles will eventually go “flat” (loose its fizz). A 20 oz bottle of pop has a CO2 pressure of about
400 kPa inside the bottle and the CO2 pressure outside the bottle is 0.4 kPa. Assume that each bottle has a
surface area of 500 cm2 and a wall thickness of 0.05 cm.
a. Assuming conditions of steady state, calculate the diffusion flux of CO2 through the wall of the bottle.
b. If the bottle must lose 750 cm3 STP of CO2 before the pop tastes flat, what is the shelf life for a bottle of pop?

Given: Pressure inside the bottle = 400 kPa Pressure outside the bottle = 0.4 kPa
3
Volume of lost CO2 = 750 cm STP Area of bottle = 500 cm2
Thickness of bottle = 0.05 cm
PM (from Table 6.1) = 0.23 x 10-13 cm3 STP cm/cm2 –s-Pa
Required: a. Diffusion flux (J)
b. shelf life of pop in the PET bottle (time)

Solution:
a. Solve for the diffusion flux: J = PM (ΔP/Δx)
J = PM (ΔP/Δx)
J = - PM (P2-P1)/ Δx
J = - [0.23 x 10-13 (cm3 STP) cm/cm2 s Pa] * [(400 Pa - 400,000Pa)/ 0.05 cm]
J = 1.8 x 10-7 cm3 STP/ cm2 s

b. Solve for the shelf life of pop in the bottle: time = V/Vf CO2
V of lost CO2 = 750 cm3 STP
Vf CO2 = volume flowrate of CO2

Calculate first Vf CO2: Vf CO2 =J*A

Vf CO2 = J*A
Vf CO2 = 1.8 x 10-7 cm3 STP/cm2-s * 500 cm2
Vf CO2 = 9 x 10-5 cm3 STP/ s

time= = V/Vf CO2

time = 750 cm3 STP / 9 x 10-5 cm3 STP / s
time = 8.3 x 106 s
time = 8.3 x 106 s * 1 day/ 86,400 s
time = 96 days (about 3 months)
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Clicker Exercise 2
1. The density and associated percent crystallinity for two polyethylene terephthalate materials are as follows:
ρ (g/cm3) Crystallinity (%)
1.408 74.3
1.343 31.2

a. Compute the densities of totally crystalline and totally amorphous polyethylene terephthalate.
b. Determine the percent crystallinity of a specimen having a density of 1.382 g/cm3.

2. Consider the diffusion of oxygen through a low density polyethylene (LDPE) sheet 15 mm thick. The pressures
of oxygen at the two faces are 2000 kPa and 150 kPa, which are maintained constant. Assuming conditions of
steady state, what is the diffusion flux (in cm3 STP/ cm2-s) at 298 K?

Reference
1. Callister Jr, WD. (2007). Materials Science and Engineering: An Introduction. John Wiley and Sons, Inc.

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