Characterization PDF
Characterization PDF
Characterization PDF
STRUCTURE AND
CHARACTERIZATION
1 INTRODUCTION 1
1.1 Definitions of Terms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2 Course Goals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3 MOLECULAR CONFORMATIONS 21
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.2 Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.3 Property Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.4 Freely-Jointed Chain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.4.1 Freely-Jointed Chain Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3.4.2 Comment on Freely-Jointed Chain . . . . . . . . . . . . . . . . . . . . . . . . 34
3.5 Equivalent Freely Jointed Chain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.6 Vector Analysis of Polymer Conformations . . . . . . . . . . . . . . . . . . . . . . . . 38
3.7 Freely-Rotating Chain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.8 Hindered Rotating Chain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.9 More Realistic Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.10 Theta (Θ) Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.11 Rotational Isomeric State Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
4 RUBBER ELASTICITY 57
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.2 Historical Observations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.3 Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.4 Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
4.5 Making Elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
4.5.1 Diene Elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
0
5 AMORPHOUS POLYMERS 73
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
5.2 The Glass Transition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
5.3 Free Volume Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
5.4 Physical Aging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
6 SEMICRYSTALLINE POLYMERS 75
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
6.2 Degree of Crystallization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
6.3 Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Chapter 1
INTRODUCTION
The topic of polymer structure and characterization covers molecular structure of polymer molecules,
the arrangement of polymer molecules within a bulk polymer material, and techniques used to give
information about structure or properties of polymers. The subjects are logically combined because
understanding how structure affects properties, as measured in characterization, is a key element of
polymer materials science and engineering. The subject of polymer structure and characterization
is typically a second course in polymer science. As such it will be assumed that all students have
completed, as a prerequisite, an introduction to polymer materials course.
We choose to subdivide polymer structure into two areas. The first area is analysis of individual
polymer molecules. Molecular structure involves the detailed description of polymer molecules, their
molecular weights, and their molecular configurations and conformations. Polymers are random-
coil molecules that can exist in a variety of lengths, configurations, and conformations. We can
learn much about polymer materials purely by theoretical analysis of their conformations. Many
of the theoretical results can be verified by experiment, but most of our insight is gained by the
process of doing the theoretical analysis and not by learning about techniques used to verify the
analysis. The second area is the study of how individual polymer molecules pack into a solid
material to make a bulk polymer. Polymer solids are either amorphous or semicrystalline. An
amorphous polymer means a non-crystalline material. A semicrystalline polymer means a mixture
of polymer single crystals (polymer lamellae) and amorphous polymer. These components combine
into supramolecular structures that pack into the bulk material. A polymer’s properties are strongly
affected by whether or not is is semicrystalline. For semicrystalline polymers, the properties are
strongly affected by the amount of crystalline material and the arrangement of the supramolecular
structures.
Polymer characterization involves measuring any kind of property of a polymer material. It
includes both molecular characterization, such as molecular weight, microstructural information,
degree of crystallinity, etc., and macroscopic property measurement, such as thermal properties,
1
2 CHAPTER 1. INTRODUCTION
The most basic definition is that of a polymer. A polymer is molecule formed by covalent chemical
bonds between atoms (or groups of atoms) to give a large structure (linear chains, branched chains,
or cross-linked networks). The key word is “large.” The word polymer is usually reserved for high
molecular weight molecules. Historically, the fact that polymers are molecules with ordinary chem-
ical bonds (i.e., with chemical bonds identical to those found in low molecular weight molecules)
was not recognized and polymers were once thought to be a distinct state of matter. Because
this old thinking was wrong and instead polymers are large molecules (or macromolecules), we will
find that most of the principles of chemistry (e.g., chemical reactions) and physics (e.g., physical
properties) apply to polymers just as they do to conventional molecules. In the field of polymer
characterization, we can therefore draw on all the knowledge of the physical chemistry of small
molecules. Before applying any traditional physical chemistry analysis, however, we must first ask
about the effect that large molecular size has on the traditional analysis and then correct for those
effects. In one sense, physical chemistry of polymers and polymer characterization can be thought
of as a subset of physical chemistry. Fortunately the effect of large molecular size is of enough
significance that polymer science is not a trivial subset of physical chemistry — it is a challenging
and important subset.
Two types of polymers are natural polymers and synthetic polymers. Natural polymers are,
as expected, naturally occurring macromolecules. Natural polymers include DNA, RNA, proteins,
enzymes, cellulose, collagen, silk, cotton, wool, and natural rubber. Cellulose is the most abundant
polymer, natural or synthetic, on the earth. Despite the unquestioned importance of natural
polymers, most of the polymer and chemical industry is based on synthetic polymers or polymers
that can be synthesized by polymerization of low molecular weight monomers. Some example
1.1. DEFINITIONS OF TERMS 3
Cl
CH3
Other examples of synthetic polymers include nylon, polycarbonate, polymethyl methacrylate (lu-
cite), epoxy, polyethylene terepthalate (polyester, mylar), and polyoxymethlyene.
The above structures show the repeat unit of the polymer. The repeat unit is usually the
smallest piece of the polymer that can be said to “repeat” periodically to give the polymer chain.
In polyvinyl chloride the repeat unit is (CH2 CHCl) . In PE, the repeat unit listed above is
(CH2 CH2 ) . From a topological point of view, the PE repeat unit could be (CH2 ) , but be-
cause PE is polymerized from ethylene or CH2 CH2 , it is common practice to call (CH2 CH2 )
the repeat unit although it is not the smallest periodically repeating unit.
The word polymer literally means many “mers” or many monomers. Monomers are the starting
materials used in synthesizing polymers. Polymers are made by combining many monomers. The
repeat unit and the monomer are usually closely related. Sometimes (e.g., in condensation and most
step-reaction polymers) some atoms are lost (e.g., a molecule of water (H2 O)) from the monomer
during polymerization and the repeat unit will differ slightly from the monomer. The names of
polymers often indicate the starting monomer material. Thus polytetrafluoroetheylene is a polymer
made by polymerizing tetrafluoroethylene monomers.
If a polymer is made from only one type of monomer or if it has a single repeat unit, it is called
a homopolymer. If a polymer is made from more than one type of monomer or has more than a
single repeat unit, it is called a copolymer. Some polymers are made up of alternating monomers
or alternating repeat units. Such polymers are often made from two types of monomers and thus
are formally copolymers. However, it is possible to consider two consecutive monomer units in the
polymer chain as a single repeat unit. As there is then only one type of repeat unit, it is common
4 CHAPTER 1. INTRODUCTION
O O
HO–C–(CH2)4–C–OH + H2N–(CH2)6–NH2
O O
—(N–C–(CH2)4–C–N–(CH2)6)—
H H
Figure 1.1: Copolymerization of the two monomers, adipic acid and hexamethyl diamine, result in synthesis
of the polymer Nylon 6/6.
–A–A–A–A–A–A–A–A–
A–A–A
Linear
A
A
–A–A–A–A–A–A–A–A–
A
– A– A– A– A– A– A– A– A–
A A A
A A Branched
– A– A– A– A– A– A– A– A–
Cross-Linked
Figure 1.2: A schematic view of monomer “A” connected to make a linear, a branched, or a cross-linked
polymer.
a physically change that is reversible; the polymer can be heated and soften and cooled and solidified
many times. In contrast, a thermoset polymer sets up when heated. Thermoset polymers undergo
irreversible chemical reactions on heating. Such polymers cannot be reheated and soften; instead
they normally degrade when reheated. They are never processed by thermal injection molding, but
instead required other processing methods such as liquid casting or reaction injection molding.
Thermoplastic polymers typically have linear polymers with few or no cross links. Thermoset
polymers are typically highly cross-linked or are network polymers. It is the cross linking reactions
that cause the “setting” at high temperatures. An important use of the thermoplastic and thermoset
terminology is to decide how to process a given polymer. Thermoplastic polymers are processed
by heating, molding, and solidification; thermoset polymers are processed by liquid or gel methods
followed by chemical reactions. Some polymers fall between these two categories. For example,
some polymers with no cross linking may have very high melting points and may undergo thermal
degradation before they soften enough to allow molding. With regards to polymer structure, such
polymers have more in common with thermoplastic polymers than with thermoset polymers. They
require, however, different processing methods than thermoplastic polymers. For example, Kevlar
R
aramid polymer is a linear polymer, but it cannot be processed by molding. It is processed into
high-modulus and high-strength fibers by a solution, fiber-spinning method.
These notes will emphasize polymer structure and characterization of high molecular weight syn-
thetic polymers. The focus on high molecular weight is because high molecular weight is a prerequi-
6 CHAPTER 1. INTRODUCTION
site for an organic material to have useful physical properties. It takes high molecular weight before
a polymer has sufficient stiffness or strength to be useful for making things ranging from clothing to
airplanes. One finds high molecular weight polymers in plastic parts, synthetic fibers (both textile
fibers and high performance fibers), elastomers (synthetic rubbers), glues, and composites. These
uses are the ones that are important to most of the polymer industry and thus these notes focus
on polymers of commercial interest. Likewise, the focus on synthetic polymers reflects the current
emphasis of the polymer and chemical industry. In fact, synthetic polymers not only dominate
the polymer industry, they even dominate the chemical industry as a whole. This dominance in
illustrated by the fact that more than half the chemists and chemical engineers employed in this
country are involved with polymers. Although the emphasis is on synthetic polymers, most of the
methods work for natural polymers too. Natural polymers, however, sometimes require additional
considerations to get valid results.
The ultimate goal of polymer structure and characterization is to understand polymer proper-
ties, how those properties relate to polymer structure, and how they relate to potential polymer
applications. Someone well versed in polymer structure and characterization should be able to take
any polymer and decide whether or not that polymer is suitable for some contemplated applica-
tion. A long-range goal of polymer structure and characterization is also to design new polymer
materials. With knowledge of how various polymer structures translate into polymer properties (as
measured using polymer characterization), the astute polymer engineer could recommend molecular
and structural modifications that could be used to create new and more useful polymers.
Problems
1–1. What are the repeat units for the following polymers: Nylon 6, Nylon 11, Polymethyl
methacrylate, and polypropylene?
1–2. What is the difference between natural polymers and synthetic polymers?
1–3. What is the difference between a branched polymer and a cross-linked polymer?
1–4. What is the difference between a thermoplastic polymer and a Thermoset polymer?
1–5. Search the Internet and find the top five synthetic polymers on the basis of volume sold.
1–6. Search the Internet and find product information on two commercial copolymers. Give the
chemical structures of the monomers used to synthesize the polymer.
Chapter 2
2.1 Introduction
Polymer molecular weight is important because it determines many physical properties. Some
examples include the temperatures for transitions from liquids to waxes to rubbers to solids and
mechanical properties such as stiffness, strength, viscoelasticity, toughness, and viscosity. If molec-
ular weight is too low, the transition temperatures and the mechanical properties will generally be
too low for the polymer material to have any useful commercial applications. For a polymer to be
useful it must have transition temperatures to waxes or liquids that are above room temperature
(i.e., be a solid at room temperature) and it must have mechanical properties sufficient to bear
design loads.
For example, consider the property of tensile strength. Figure 2.1 shows a typical plot of
strength as a function of molecular weight. At low molecular weight, the strength is too low for
the polymer material to be useful. At high molecular weight, the strength increases eventually
saturating to the infinite molecular weight result of S∞ . The strength-molecular weight relation
can be approximated by the inverse relation
A
S = S∞ − (2.1)
M
where A is a constant and M is the molecular weight. Many properties have similar molecular
weight dependencies. They start at a low value and eventually saturate at a high value that is
characteristic for infinite or very large molecular weight.
Unlike small molecules, however, the molecular weight of a polymer is not one unique value.
Rather, a given polymer will have a distribution of molecular weights. The distribution will depend
on the way the polymer is produced. For polymers we should not speak of a molecular weight,
but rather of the distribution of molecular weight, P (M ), or of the average molecular weight, hM i.
7
8 CHAPTER 2. POLYMER MOLECULAR WEIGHT
S∞
Strength
A
S = S∞ –
M
Molecular Weight
Figure 2.1: A typical plot of tensile strength as a function of molecular weight.
Polymer physical properties will be functions of the molecular weight distribution function as in
A
S = S∞ − (2.2)
F [P (M )]
where F [P (M )] is some function of the complete molecular weight distribution function. For some
properties, F [P (M )] my reduce to simply an average molecular weight. The property will thus be a
function of the average molecular weight, hM i, and insensitive to other the details of the molecular
weight distribution function:
A
S = S∞ − (2.3)
hM i
There are many ways, however, to calculate an average molecular weight. The question therefore
is how do you define the average molecular weight for a given distribution of molecular weights.
The answer is that the type of property being studied will determine the desired type of average
molecular weight. For example, strength properties may be influenced more by high molecular
weight molecules than by low molecular weight molecules and thus the average molecular weight
for strength properties should be weighted to emphasize the presence of high molecular weight
polymer. In this chapter we consider several ways of calculating molecular weights. We also
consider the meanings of those averages. Finally, we consider typical distributions of molecular
weights.
2.2. NUMBER AVERAGE MOLECULAR WEIGHT 9
In lab experiments it is more common to measure out certain weights of a polymer rather than
certain numbers of moles of a polymer. It is thus useful to derive an alternate form for MN in
terms or weight fraction of polymers with molecular weight Mi denoted as wi . First we note that
the concentration of polymer species i is (in weight per unit volume):
Ni Mi
ci = (2.8)
V
10 CHAPTER 2. POLYMER MOLECULAR WEIGHT
1
MN = P∞ wi (2.10)
i=1 Mi
where wi is the weight fraction of polymer i or the weight of polymer i divided by the total polymer
weight:
Ni Mi ci
wi = P∞ = P∞ (2.11)
i=1 Ni Mi i=1 ci
Consider of polymer property which depends not just on the number of polymer molecules but
on the size or weight of each polymer molecule. A classic example is light scattering. For such
a property we need a weight average molecular weight. To derive the weight average molecular
weight, replace the appearance of the number of polymers of molecular weight i or Ni in the
number average molecular weight formula with the weight of polymer having molecular weight i or
Ni Mi . The result is P∞
Ni Mi2
MW = Pi=1
∞ (2.12)
i=1 Ni Mi
P
By noting that Ni Mi / Ni Mi is the weight fraction of polymer with molecular weight i, wi , an
alternative form for weight average molecular weight in terms of weight fractions
∞
X
MW = wi M i (2.13)
i=1
Comparing this expression to the expression for number average molecular weight in terms of
number fraction (see Eq. (2.7)) we see that MN is the average Mi weighted according to number
fractions and that MW is the average Mi weighted according to weight fractions. The meanings of
their names are thus apparent.
where a is a constant that depends on the polymer/solvent pair used in the viscosity experiments.
Viscosity average molecular weight and viscosity experiments are discussed in Chapter ??.
For any molecular weight distribution, the various average molecular weights always rank in
the order
MN ≤ Mv ≤ MW ≤ Mz ≤ Mz+1 ≤ M4 ≤ . . . (2.16)
The equalities hold only when the polymer is monodisperse; i.e., only when all molecules have the
same molecular weight. For monodisperse polymers all molecular weight averages are the same and
equal to the one molecular weight. For polydisperse polymers, the average molecular weights will all
be different and will rank in the above order. Historically this fact was not always recognized thus
it was sometimes difficult to reconcile conflicting experimental results. Say two scientists measured
average molecular weight, but one used a colligative property which yields MN and the other used
light scattering which yields MW . Until it was recognizes that MN 6= MW , it was difficult to explain
differing experimental results on the same polymer solution.
σ 2 = hM 2 i − hM i2 (2.17)
where angle brackets (e.g., hM i) denote conventional averaging. In terms of Ni and Mi the variance
is !2
∞ ∞ P∞
Ni Mi2 ∞
P
1 X 1 X NM 2
σ2 = Ni Mi2 − Ni Mi i=1
= P∞ P∞i=1 i i − MN (2.18)
N N i=1 Ni i=1 Ni Mi
i=1 i=1
MN Mv
MW
Mz
Weight Fraction
Mz+1
Molecular Weight
Figure 2.2: A schematic plot of a distribution of molecular weights along with the rankings of the various
average molecular weights.
For example if A is an acid group ( COOH) and B is an alcohol group ( OH), the A B monomer
can polymerize to a polyester. Or, if A is an acid group ( COOH) and B is an amine group
( NH2 ) the A B monomer can polymerize to a polyamide. Flory considered the polymerization
2.6. MOST PROBABLE MOLECULAR WEIGHT DISTRIBUTION 13
of A B type monomers and used simple statistical arguments to calculate the expected, or most
probable distribution of molecular weights. His results give us insight into typical molecular weight
distributions.
We define p as the fraction of functional groups of type A that have reacted at a given stage of
polymerization. Because A reacts by reacting with B, the fraction of functional groups of type B
that have reacted at the same stage of polymerization is also p. We define p in mathematical terms
but note that in practical terms it is often easily accessible by measurement. For example, to find
the fraction of reacted acid A groups of type COOH, one could use simple acid/base titration
experiments. Next, after some amount of polymerization (i.e., p 6= 0) we select a molecule at
random. We begin at one end of the molecule which will be an unreacted A group. The probability
that the adjacent B group is also unreacted is simply (1 − p) — one minus the probability that a
B group has reacted. Thus the probability that the randomly selected molecule is a monomer is
P (i = 1) = (1 − p) (2.23)
The probability that the randomly selected molecule is a dimer is equal the product of the inde-
pendent probabilities that the first group is reacted (p) and the second in unreacted (1 − p):
P (i = 2) = p(1 − p) (2.24)
Continuing on by induction, the probability that the randomly selected molecule has a degree of
polymerization i is
P (i) = pi−1 (1 − p) (2.25)
The pi−1 term is for the i − 1 reacted functional groups in the chain and the 1 − p term is for the
terminal unreacted functional group.
If there are N molecules in the polymerizing mixture, then the number of polymer chains of
length i is N times the probability of having length i:
Ni = N pi−1 (1 − p) (2.26)
N is related to the initial number of monomers N0 by N = N0 (1 − p). This relation can easily be
derived be realizing that each reaction of a functional group reduces the total number of molecules
by one. For extent of reaction p, the total number of molecules is reduced by N0 p. Now, in terms
of known quantities Ni is
Ni = N0 pi−1 (1 − p)2 (2.27)
The above equation for Ni describes the complete polymer distribution. It is called the most
probable distribution or the Flory Distribution. Virtually all condensation polymers no matter how
they are formed will end up with a distribution resembling the most probable distribution. Plots of
Ni for various values of p are given in Fig. 2.3. At all values of p, all molecular weights are present
14 CHAPTER 2. POLYMER MOLECULAR WEIGHT
0.0040
0.0035
0.0030
Number Fraction (Ni/N0)
p=0.94
0.0025
0.0020
0.0015
p=0.96
0.0010
0.0005 p=0.98
0.0000
0 20 40 60 80 100
Degree of Polymerization
Figure 2.3: The number fraction as a function of degree of polymerization for the most probable molecular
weight distribution. The three curves are for three values of p.
to some extent. The surprising results is that at all values of p, the most probable species is the
monomer. This monotonically decreasing function is not the type commonly drawn to illustrate
distribution functions.
A more familiar distribution function results if we consider the weight fraction of polymer with
length i. Weight fraction is defined by
iM0 Ni iNi
wi = = = ipi−1 (1 − p)2 (2.28)
N0 M0 N0
where M0 is the monomer molecular weight. When the repeat of the polymer has lower molecular
weight than the monomer, because of reaction products such as H2 O loss due to condensation, M0
should be the molecular weight of the monomer that makes it into the polymer. In other words, M0
is the repeat unit molecular weight, iM0 is the molecular weight of a polymer of length i, and N0 M0
is the total weight of monomer that ends up in a polymer. Some plots of weight fraction for various
values of p are given in Fig. 2.4. The most prevalent species is no longer the monomer. Although
there will be a lot of monomers, each monomer weighs very little. As time of reaction increases,
which increases p, the peak in the weight fraction shifts to higher values and the distribution curve
broadens. The peak molecular weight turns out to be very close to MN expecially as p is close to
1 (see problem 3 at end of this chapter)
Now that we have a complete distribution function (i.e., an equation for Ni ) we can calculate
MN and MW . We can calculate MN for the most probable distribution using two methods. First
2.6. MOST PROBABLE MOLECULAR WEIGHT DISTRIBUTION 15
0.025
p=0.94
0.020
Weight Fraction (wi)
p=0.96
0.015
0.010
p=0.98
0.005
0.000
0 20 40 60 80 100
Degree of Polymerization
Figure 2.4: The weight fraction as a function of degree of polymerization for the most probable molecular
weight distribution. The three curves are for three values of p.
The evaluation of the sum is nontrivial. The sum, however, can be expressed as the derivative of
another sum which is simpler to evaluate.
∞ ∞
X d X i d p
ipi−1 = p = (2.30)
dp dp 1−p
i=1 i=1
Multiplying by M0 (1 − p) gives
M0
MN = (2.32)
1−p
An alternative and simpler method to MN is to realize that, by conservation of mass, the total
weight of material is always M0 N0 . From above, the total number of polymers is N0 (1 − p). Thus
To get MW for the most probable distribution we use the weight average molecular weight
formula in terms of weight fractions:
∞
X ∞
X
MW = wi iM0 = M0 (1 − p)2 i2 pi−1 (2.34)
i=1 i=1
We evaluate the sum using the trick used to find MN and some additional work.
∞ ∞ ∞
!
X
2 i−1 d X
i d X
i−1 d p
i p = ip = p p = (2.35)
dp dp dp (1 − p)2
i=1 i=1 i=1
The last step uses the result from the MN calculation. Evaluating the derivative gives
∞
X 1+p
i2 pi−1 = (2.36)
(1 − p)3
i=1
1+p
MW = M0 (2.37)
1−p
Combining the results for MN and MW , the polydispersity index for the most probable distri-
bution is
MW
=1+p (2.38)
MN
As the reaction nears completion, p approaches one and the polydispersity index approaches 2.
That is the coefficient of variation of the most probable distribution is 100%. That large of a
coefficient of variation means that the molecular weight distribution is relatively broad.
We also notice that as p approaches one, both MN and MW approach infinity. This limit
means that all the monomers will be in a single polymer molecule. It is usually not desirable to
have molecular weights that are too high. Such polymers would not be processible; they would
not flow when melted. To avoid unprocessible polymers, it is desirable to use methods to control
molecular weight. One way to control molecular weight would be to freeze the reaction at some p
less than one. This scheme, however, can produce a material that is unstable with time. Instability
occurs if over long times, there are more reactions (albeit at a slow rate) which cause p to increase.
When p increases, the polymer properties change with time and might eventually give a molecular
weight that is too high to be processible.
One solution to molecular weight control is to polymerize the two monomers A A and B B
instead of the single monomer A B. If the two monomers are mixed in equal proportions, the
analysis will be identical to the one above and there will be no molecular weight control (note:
although the analysis is the same, the meaning of M0 has to be changed to be half the repeat
unit molecular weight to account for the fact that the synthesis is from two monomers (A − A and
2.6. MOST PROBABLE MOLECULAR WEIGHT DISTRIBUTION 17
B − B) instead of from one monomer (A − B)). If the proportions are unequal and r = NA /NB < 1
then the results are different. A more complicated analysis gives the following MN :
M0 (1 + r) M0 (1 + r)
MN = ≈ (2.39)
1 + r − 2rp 1−r
where, as explained above, M0 is half the repeat unit molecular weight. The second part of this
equation assumes p is equal to one. Sample calculations for various values of r give
r = 1.00 MN = ∞
r = 0.99 MN = 199M0
r = 0.95 MN = 39M0
r = 0.90 MN = 19M0
By selecting r, we see it is possible to control molecular weight to some finite value. Physically
what happens is that the monomer mixture runs out of A A and all polymers are end capped
with B B monomers. Because B can only react with A and no unreacted A remains, the reaction
stops at a finite molecular weight. The only problem is that small changes in r lead to large changes
in MN . For example a 5% deviation of r from 1.00 reduces the molecular weight from infinite to
39M0 . But, 39M0 is not a very high molecular weight and may not be high enough to be useful.
To prevent polymerization from stopping at low molecular weights, you must have accurate control
over r. Also you must account for any side reactions and monomer volatility which might remove
monomer of one type and effectively change r.
Problems
2–1. Suppose you have n batches of polydisperse polymers. Let Ni,j be the number of polymers
of type j with degree of polymerization i and Mi,j be the molecular weight of that polymer.
The basic MN and MW equations for the total mixture of polymers now require double sums:
Pn P Pn P 2
j=1 i Ni,j Mi,j j=1 i Ni,j Mi,j
M N = Pn P and MW = Pn P (2.40)
j=1 i Ni,j j=1 i Ni,j Mi,j
Now, assume that the number average and weight average molecular weights of batch j are
MN j and MW j . and that you mix a weight wj of each batch to make a new polymer blend.
a. Starting from the above basic number average molecular weight definition, show that
the number average molecular weight of the blend is
w1 + w2 + · · · + wn
MN = w1
M
+ Mw2 + · · · + Mwn
N1 N2 Nn
In other words, show that MN of the blend can be calculated from the individual MN j
of the components of the blend. Here MN j has the usual definition of
P
i Ni,j Mi,j
MN j = P (2.41)
i Ni,j
18 CHAPTER 2. POLYMER MOLECULAR WEIGHT
2–2. Calcium stearate (Ca(OOC(CH2 )16 CH3 )2 , molecular weight = 607) is sometimes used as a
lubricant in the processing of poly(vinyl chloride). A sample of pure PVC polymer with a
polydispersity index of 2.8 is modifed by the addition of 3% by weight of calcium stearate.
TYhe mixture of PVC and salcium stearate is found to have MN = 15, 000 g/mol.
a. What is the MN of the PVC part of the compound? (Hint: use the blend MN result
from the previous problem.)
b. What is the MW of the blend?
c. What effect does the calcium stearate have on the light scattering and osmotic pressure
properties of the polymer? (Hint: light scattering measures MW while osmotic pressure
measures MN )
d. What is the highest possible MN for a polymer containing 3% by weight of calcium
stearate?
2–4. Calculate the percentage conversion of functional groups required to obtain a polyester with
a number-average molecular weight of 24,000 g/mol from the monomer HO(CH2 )14 COOH.
2.6. MOST PROBABLE MOLECULAR WEIGHT DISTRIBUTION 19
2–5. A polyamide was prepared by bulk polymerization of hexamethyl diamine (9.22 g and molec-
ular weight 116) and adipic acid (13.2 g and molecular weight 166) at 280◦ C. Analysis of the
whole reaction product showed that it contained 2.6 × 10−3 moles of carboxylic acid groups.
Evaluate MN of the mixture. Assume it has a “most probable distibution” and also evaluate
MW .
20 CHAPTER 2. POLYMER MOLECULAR WEIGHT
Chapter 3
MOLECULAR CONFORMATIONS
3.1 Introduction
Polymers can exist in various conformations and various configurations. Two polymers which differ
only by rotations about single bonds are said to be two different conformations of that polymer.
A schematic view of two polymer conformations is show in Fig. 3.1. Two polymers which have the
same chemical composition but can only be made identical (e.g., superposable) by breaking and
reforming bonds are said to be two configurations of that polymer. Two examples in Fig. 3.2 are
polymers that contain asymmetric carbon atoms or that contain double bonds. Asymmetric carbon
atoms can exist in d or l states while double bonds can exist in cis or trans states. No manner of
rotations about single bonds can turn polymers in different configuration states into superposable
polymers.
The above definitions of conformation and configuration are standard, but they have not always
been rigorously followed in the literature. For example, Paul Flory, who won a Nobel prize for
studies of polymer conformations, used configuration in his writings when he meant conformation.
Fortunately a writer’s meaning is usually obvious from context. It is recommended that you strive
to use the correct terminology as defined above. These notes strive to follow that convention.
Figure 3.1: Two molecules with different conformations. These two molecules can be made identical with
a rotation of 180◦ about the central single bond.
21
22 CHAPTER 3. MOLECULAR CONFORMATIONS
H H Cl H H Cl
Cl Cl
trans cis
Figure 3.2: Two distinct configurations of polymers can exist at asymmetric carbon atoms (top) and across
double bonds (bottom).
To understand polymers, we must understand the shape or the form that polymers have in
solution as well as in solid state. We will therefore spend some time studying the conformations
of isolated polymer chains. An isolated polymer chain is clearly a good model for a gas phase or
a dilute solution polymer. It turns out that the description of an isolated polymer chain is also a
good description for polymer chains in concentrated solutions, or even in the solid state.
The first thing to realize about polymers is that they are usually very long and are best de-
scribed as resembling a random coil . In a collection of polymers (gas phase, solution, or solid
state), the various individual polymer molecules will assume many possible conformations. Each
conformation will be a different variation on a random coil. The different conformations arise by
thermal energy and the relatively low barrier to rotations about single bonds. The shapes of the
possible conformations have a direct bearing on the physical properties of the polymer. Some
properties that can be influenced included solution viscosity, solution light scattering, and mechan-
ical properties. For example, rigid rod polymers generally assume more extended conformations
than polymers with more flexible backbones. These more extended shapes give rigid rod polymers
very different properties. To be specific, rigid rod polymers are generally stiffer and have a higher
glass-transition temperature.
Figure 3.3 shows an extended chain polymer and a random coil polymer. The extended chain
picture is the way we might choose to draw a polymer structure. The random coil picture, however,
is a more realistic view of the shape of real polymer molecules. In this chapter we will discuss various
theoretical methods for characterizing the shape of random coil polymers. The major results will
be predictions of the end-to-end distance for linear polymers. The ideas that enter into the analysis
give insight about the shape of polymers. As discussed in the Introduction chapter (chapter 1),
3.2. NOMENCLATURE 23
Figure 3.3: Extended chain polymer on the left. A more realistic picture of a polymer as a random coil on
the right. The colors indicate rotation angle about each bond. Blue is for trans bonds while read and green
are for gauche bonds.
3.2 Nomenclature
We will restrict ourselves to linear polymers and we will consider all their possible conformations.
To describe any given conformation we must first define a nomenclature or coordinate system. We
begin with a polymer having n bonds. These n bonds connect n + 1 backbone atoms. We can thus
define any conformation by giving the 3(n + 1) Cartesian coordinates of the n + 1 atoms along the
polymer backbone. This nomenclature works but is normally more cumbersome than desired and
we thus make some simplifications.
We begin with the bond length (l). In many polymers the bonds in the polymer backbone are all
identical and therefore have a constant bond length. For example, in PE the bonds are all carbon-
carbon bonds and they are all typically about 1.53Å long. For simplicity we will restrict ourselves
to polymers with constant bond lengths. A generalization to non-constant bond lengths can be
made later if necessary. With constant bond lengths, we can consider a polymer conformation as
a 3D random walk of n steps where each step has length l. Instead of listing absolute coordinates
of each atom in the backbone, we choose to describe a polymer by listing the relative directions of
each step in the random walk.
Directions in space are most conveniently described using polar angles. Figure 3.4 shows an
arbitrary direction in space emanating from the origin of a coordinate system. The angle with
respect to the z axis is called the polar angle and is usually denoted by θ. The angle that the
24 CHAPTER 3. MOLECULAR CONFORMATIONS
x
Figure 3.4: Definitions of the polar angle θ and the azimuthal angle φ for any vector in a right-handed
coordinate system.
projection of the direction onto the x–y plane makes with any consistently chosen reference point
in that plane is called the azimuthal angle and is usually denoted by φ. All possible directions in
space can be spanned by choosing θ from 0 to π and φ from 0 to 2π. In other words, any direction
from the origin can be defined by a unique pair of θ and φ.
We will represent a polymer as a 3D random walk of n steps where n is the number of bonds
(note that n is not necessarily the same as the degree of polymerization or the number of repeat
units; some repeat units have more than one bond and for n we count all of these bonds). In the
random walk, each step can be described by polar and azimuthal angles, θ and φ, where those
angles are given with respect to an axis system centered on the atom at the start of that bond. For
n bonds, each bond will have its own angles, θi and φi , and the complete chain will be described
with the 3 original coordinates for the first atom and the 2n angles for the steps of the random
walk. We thus require 2n + 3 variables to specify a conformation of a polymer with constant bond
length.
Normally we will not be concerned with the absolute location in space of the polymer chain.
If we do everything relative to the location of the first bond, then we do not need to know the 3
original coordinates nor the 2 polar angles of the first bond. Subtracting these five variables, we can
define an arbitrary polymer conformation with 2n − 2 or 2(n − 1) variables. The 2(n − 1) variables
are the polar and azimuthal angles for each bond except the first bond. If we ever generalize to
different l’s for each bond, we must add to these 2(n − 1) variables, n new variables which specify
the length of each bond.
3.3. PROPERTY CALCULATION 25
φ=180˚
l bond i+1
θi+1
bond i
z φi+1
x
φ=0˚
bond i-1
Figure 3.5: Definition of polar and azimuthal angles for bond i. With the illustrated selection of x, y, and
z axes, the polar angle is the bond angle for bond i + 1 and the azimuthal angle is the dihedral angle for
bond i + 1.
It is convenient to choose a coordinate system that lends physical interpretations to the polar
and azimuthal angles of each bond in the polymer chain. As illustrated in Fig. 3.5, we consider
the central bond as bond i and take the z axis to point back along bond i. With this choice for
the z axis, the polar angle for bond i + 1 is just the bond angle between bond i and bond i + 1
(see Fig. 3.5). From now on, we will refer to the polar angle as the bond angle. The possible
orientations for bond i + 1 when the bond angle is θi+1 sweep out the cone illustrated in Fig. 3.5.
The azimuthal angle (φ) for bond i + 1 is the counter-clockwise angle around that cone from some
suitably selected reference point. We choose the x axis to define the reference point such that the
azimuthal angle for bond i + 1 is 180◦ when bond i is a trans bond. This choice is arbitrary, but
is consistent with the bulk of the modern literature (note: Flory choose φ = 0 to correspond to
trans bonds which makes his results shifted by 180◦ from these notes). Another term for such an
azimuthal angle is the dihedral angle for bond i + 1 — a term that we will adopt throughout these
notes. Finally, the y axis is chosen to be perpendicular to the x and z axes and directed to make
the x-y-z coordinates a right-handed coordinate system.
The way to find hP ropertyi is to examine a large number of polymer chains by considering
a large number of random walks. For the simplest models (models of short chains) we will be
able to examine all possible random walks. When we can consider all possible random walks we
can assign to each random walk a probability which equals the probability that that conformation
will be selected when one polymer is selected from an ensemble of random coils. Assuming we
can calculate some polymer property (e.g., size, stiffness, etc.) for each specific conformation, we
can average them to get the average of that property for the bulk polymer sample. The average
property is defined by
X
hP ropertyi = Property(conf i) × Probablity(conf i) (3.1)
i
where Property(conf i) is the value of the property calculated for conformation i and Probablity(conf i)
is the probability of that conformation occurring.
For small molecules you can often do the above averaging process exactly. In other words you
can enumerate all possible conformations, find the probability and property of each conformation,
and then find the average property by averaging the results. Some small molecules have only one
conformation and the task is relatively simple — the average property is equal to the property
of the single conformation. Other molecules have only a few conformations and the task is still
relatively simple. For a non chemistry example, consider the roll of a single dice and consider the
property of the number of pips showing on each role. A die has six faces which represent six possible
conformations of the die after each roll. When counting pips, the Property(conf i) = i. Assuming
the die is a fair die (i.e., not loaded) the probability of each conformation is the same and equal to
1/6 (thus Probablity(conf i) = 1/6). The property of the number of pips therefore has the exact
average value of
6
X 1 1 2 3 4 5 6
hpipsi = i× = + + + + + = 3.5 (3.2)
6 6 6 6 6 6 6
i
For polymer calculations there will usually be too many conformations to make the above
exact calculation procedure possible. Instead we will select conformations at random and use
a Monte Carlo procedure to get the average property. By the Monte Carlo procedure, if the
probability of selecting a particular conformation at random is proportional to the actual probability
of conformation i (selection probability ∝ Probablity(conf i)), than the average property for a
polymer sample can be approximated by
1 X
hP ropertyi ≈ Property(sample i) (3.3)
N
where N is the number of randomly generated polymer chains. The larger N , the more accurate
will be the calculated average property.
We can illustrate the Monte Carlo method with the dice problem. A Monte Carlo solution to
the dice problem would be to roll a die many times, total the pips, and divide by the number of
3.4. FREELY-JOINTED CHAIN 27
rolls. If the die was rolled sufficiently many times and if the die was fair (i.e., symmetric and not
loaded), the Monte Carlo solution would be very close to the exact answer of 3.5. After a few rolls,
the answer might differ from 3.5. After many rolls, however, the answer would be very unlikely to
show much deviation from 3.5.
The success of the Monte Carlo procedure is dependent on ones ability to select polymer confor-
mations with realistic probabilities that accurately reflect the true distribution of conformations.
This problem is easily solved in the dice problem by rolling a die. Unfortunately for polymer
problems we cannot physically select real polymers. Instead we have to generate conformations
mathematically or in a computer. The problem we must solve is the development of rules or al-
gorithms for realistically generating conformations. We will approach this problem in a series of
steps. We will begin with the simplest possible rules. At each subsequent step we will add more
realism to the procedure used to generate the random conformations. The final results can be used
to accurately predict many polymer properties.
where N is the total number of possible conformations and ri is the end-to-end distance for confor-
mation i. The radius of gyration is the average of the distances of each of the atoms in the polymer
chain to the center of mass of the polymer. The root mean squared radius of gyration is the square
root of the average of the squared radius of gyrations:
v
p
u
u1 X N
2
rms s = hs i = t s2i (3.5)
N
i=1
←
r
Figure 3.6: The length of a vector (~r) from the first atom to the last atom on a linear polymer chain is
the end-to-end distance for that polymer conformation. This figure shows the end-to-end vector.
l
θ
l cos θ
Figure 3.7: The projection of a bond of length l onto the z axis is lz = l cos θ where θ is the angle between
the bond and the z axis.
We begin our analysis of the freely-jointed chain by analyzing a single direction in space — we
will analyze the z axis direction. For any of the bonds in the chain (or steps in the random walk),
the bond length along the z axis is lz = l cos θ (see Fig. 3.7) where θ is the angle between the
bond direction and the z-axis direction. θ is also the polar angle in the coordinate system defined
in Fig. 3.5 in which the z axis is along the previous bond. The average value of lz is found by
integrating over all possible bond projections or all possible bond directions:
Z l Z Z
hlz i = lz p(lz )dlz = l cos θ p(θ, φ)dS (3.6)
−l
where p(θ, φ) is the probability that any given bond has directional angles of θ and φ. The inte-
gration is over the surface of a sphere centered on the origin and dS is the differential of surface
area.
For a freely-jointed chain all angles are all equally likely and therefore p(θ, φ) must be a constant;
3.4. FREELY-JOINTED CHAIN 29
z
dS = r2 sin θ dθ dφ
dφ
r sin θ
r dθ
r r sin θ dφ
dθ
y
x
Figure 3.8: The differential of surface integration for polar coordinates is the area of the surface element on
the right side of the figure which is a top view of the left side. For small angles this area is dS = r2 sin θdθdφ.
we call it k. To find k, we integrate over the surface of sphere, which represents all possible directions
in space, and note that the integral over p(θ, φ), which is a probability distribution function, must
be 1. Because dS for surface integration over a sphere is r2 sin θdθdφ (see Fig. 3.8) we can integrate
over the unit sphere (r = 1) to get:
Z 2π Z π
1=k dφ dθsinθ = 4πk (3.7)
0 0
or
1
k = p(θ, φ) = (3.8)
4π
We can now insert p(θ, φ) into the expression for hlz i and integrate. The result is
Z 2π Z π
l π
Z
l cos θ sin θ
hlz i = dφ dθ = cos θ sin θdθ = 0 (3.9)
0 0 4π 2 0
This result could have been anticipated. When random walk steps in all directions are equally
likely, we are equally likely to jump in the positive direction as in the negative directions. These
equally likely jumps cancel out to give zero average jump size.
A simple average step size is not useful and we therefore instead consider the average squared
step length. It is for this reason that we constantly work with root-mean-squared end-to-end
30 CHAPTER 3. MOLECULAR CONFORMATIONS
distances in our discussion of polymer size. Squaring each step length makes all step size positive
and we are guaranteed to get a nonzero result. With the known p(θ, φ) function, we can easily
calculate the mean squared jump size:
2π π
l2 cos2 θ sin θ l2 π
Z Z Z
hlz2 i = dφ dθ = cos2 θ sin θdθ (3.10)
0 0 4π 2 0
π
l2 l2
1
− cos2 θ =
= (3.11)
2 3 0 3
To solve for z we must determine (n+ − n− ). The factor(n+ − n− ) is like the result of a coin
toss experiment. Each step is considered a coin toss, if z increases on the step the coin toss result
is heads, if z decreases, the coin toss result is tails. In the coin toss results, the expected result is to
have equal numbers of heads and tails. If a large number of coin tosses are made the distribution
of (n+ − n− ) will be a Gaussian function centered at zero (mean of zero). We can thus represent
the factor (n+ − n− ), or more usefully the distance in the z direction, with the following Gaussian
distribution function:
1 −z 2 β 2 2
W (z)dz = √ e 2σ2 dz = √ e−β z dz (3.14)
2πσ 2 π
where σ is the standard deviation in z-direction distance and the term β is defined in terms of
standard deviation by
1
β=√ (3.15)
2σ 2
The freely-jointed chain problem is solved if we can find the standard deviation in z-direction
distance. For a single step the variance, or the standard deviation squared, follows simply from the
formula for variance:
σ12 = hlz2 i − hlz i2 = hlz2 i (3.16)
3.4. FREELY-JOINTED CHAIN 31
Statistical analysis tells us that for n steps, the standard deviation in z is n times the standard
deviation for a single step or
σ 2 = nσ12 = nhlz2 i (3.17)
An alternate route to finding β is to find the variance by integration (i.e., find the average value
of z2 and subtract the square of the average value of z, which we know to be zero). The result is
∞
hz 2 i λ2
Z
1 1
= hlz2 i = = z 2 W (z)dz = (3.19)
n 3 n −∞ 2nβ 2
Because the analysis for W (z)dz given above applies equally well to the x and y directions, we have
3
β 2 r2
W (x, y, z)dx dy dz = √ e−β dx dy dz (3.22)
π
where r2 = x2 + y 2 + z 2 is the square of the distance from the origin to the end of the chain at
(x, y, z).
As stated above, W (x, y, z)dx dy dz gives the probability that a chain’s end-to-end vector is
characterized by a vector (x, y, z). In other words, it is the probability that a chain that begins at
the origin ends in a box center at the point (x, y, z) or size dx dy dz (see Fig. 3.9). One dimension of
W (x, y, z)dx dy dz is plotted in Fig. 3.9. The function is a Gaussian distribution function centered
at the origin or centered about the mean value of zero.
The function W (x, y, z)dx dy dz solves the freely-jointed chain problem, but it is not in the most
useful form. We are normally not concerned with absolute end of the chain (i.e., location (x, y, z)),
but rather with the end-to-end distance r. To find this result we sum up all possible (x, y, z)
coordinates that give the same r value. In other words, we integrate over the volume element V
32 CHAPTER 3. MOLECULAR CONFORMATIONS
dV = dx dy dz 1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
y
0.1
0.0
-3 -2 -1 0 1 2 3
βr
Figure 3.9: The left side shows a chain that starts at the origin and ends in a box centered a (x, y, z). The
right side is a one-dimensional plot of W (x, y, z)dx dy dz.
p
of width dr where x2 + y 2 + z 2 is between r and r + dr. The volume element of constant r is
a spherical shell as shown in Fig. 3.10. Integrating over this volume element yields a probability
distribution in terms of the end-to-end distance r:
β 3
Z
2 2
W (r)dr = W (x, y, z)dx dy dz = √ 4πr2 e−β r dr (3.23)
V π
This type of distribution function is called a radial distribution function.
Figure 3.11 schematically plots the end-to-end distance distribution function, W (r)dr. We can
characterize the distribution function by finding some key points. The function W (r)dr always
increases to some maximum and then decrease towards zero. The peak value is found by finding
where the derivative of W (r)dr is zero. The maximum value, rmax , occurs at
r
1 2n √
rmax = = l = 0.82l n (3.24)
β 3
The average value of r, hri, is found by integrating W (r)dr:
Z ∞ r
2 8n √
hri = rW (r)dr = √ = l = 0.92l n (3.25)
0 β π 3π
←
Shell of r ← ←
r + dr
width dr
x
Figure 3.10: Cross section of a spherical shell between radii of r and r + dr.
0.7
0.3
0.2
0.1
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
length (units of l √n)
Figure 3.11: A typical plot of W (r)dr. The key values rmax , average r or hri, and root-mean-squared r
are indicated on the figure.
34 CHAPTER 3. MOLECULAR CONFORMATIONS
The above key values are indicated in Fig. 3.11. For constant l and n, they always rank in the
order rmax < hri < hr2 i.
The variance in the end-to-end distance can be found from the mean and mean-squared end-
to-end distances:
3 4 0.23
σ 2 = hr2 i − hri2 = 2
− 2 = 2 = 0.15nl2 (3.28)
2β β π β
From this results, the coefficient of variation (standard deviation divided by the mean) is
σ
CV = = 42% (3.29)
hri
We only used two facts in deriving W (r). First we assumed that the chain can be simulated by a
random walk. Second, we assumed there are enough steps to make the random walk a Gaussian
distribution. To find the Gaussian curve we therefore only had to find the mean (mean = 0) and the
p
standard deviation (σ = nhlz2 i). The final result predicts that the root-mean-squared end-to-end
distance is
p √
hr2 i = l n (3.30)
In other words the root mean squared end-to-end distance is proportional to the square root of the
number of bonds and linear in the bond length.
The linear dependence on bond length is a trivial result. It is merely a scaling parameter.
Thus if we double all bond lengths we double the end-to-end distance. It can also be thought of
as a consequence of units. If we solve the problem in inches and then in millimeters, we should
get answers that differ only by the units conversion factor for inches to millimeters of 25.4. This
expected result will only occur if the end-to-end distance is linear in bond length.
The dependence of root-mean-squared end-to-end distance on the square root of the number of
bonds is a profound, or at least a non-trivial, result. Let’s consider the origins of the square root
dependence on bond length. Our analysis is one of a completely random three dimensional random
walk. The square root of n dependence comes from the expression for the standard deviation of
√
the walk which contains n. If we repeated the analysis for one- or two-dimensional random walks
we would find the same result. The root-mean-squared end-to-end distance is
p √
hr2 i = l n (3.31)
in any dimension. We thus conclude that the square root of n dependence is a property of the
random walk nature of polymers and unrelated to geometrical effects. Only polymer features that
alter the random walk nature of the chain can alter the square root dependence on n.
3.4. FREELY-JOINTED CHAIN 35
To anticipate a future result that does alter the random walk nature of polymers, we consider
self-avoiding random walks. In self-avoiding random walks, the path cannot revisit any spot that
was previously visited. Because no two atoms in a polymer chain can occupy the same space,
a self-avoiding random walk is a better model for a polymer chain than the completely random
walk discussed previously. A self-avoiding random walk, however, is not a completely random walk
because some steps may be influenced by previous steps. In other words, some steps may be biased
away from moving in a given direction because doing so would revisit a previous part of the random
walk.
The exact analysis of two- and three-dimensional self-avoiding random walks is not possible.
One-dimensional, self-avoiding random walks, however, are trivial to analyze. As shown in Fig. 3.12
there are only two possible one-dimensional, self-avoiding random walks. A one-dimensional random
walk must begin with one step to the left or to the right. If the first step is to the left, the next step
must also be to the left because a step to the right would revisit the starting location. Continuing
on, the chain that starts to the left must make all steps to the left. The other possible chain is the
one that starts with its first step to the right. This chain can only continue with repeated steps
to the right. There are thus only two possible chains. One makes all n steps to the left and its
length is nl. The other makes all n steps to the right and its length is also nl. Averaging over
all possible chain conformations, the root-mean-squared end-to-end distance for a one-dimensional,
self-avoiding random walk is
p
hr2 i = nl (3.32)
In contrast to the completely random walk, this result is now linear in n. Because of scaling
requirements it remains linear in l.
In two- and three-dimensional random walks, the effect of imposing self avoiding characteristics
will be less dramatic. A one-dimensional, self-avoiding, random walk is hardly random. All steps
(except the first one) are determined by the requirement of being self avoiding and not by random
chance. Two- and three-dimensional, self-avoiding random walks will not restricted as much. Some
steps will be influenced by self-avoiding requirements, but most will have other options than can
be reached by random chance. Without proof, we state that the end-to-end distance for two- and
three-dimensional random walks will be proportional to n to some power between 0.5 and 1.0.
The two extremes are completely random walks (power equal to 0.5) and self-avoiding random
36 CHAPTER 3. MOLECULAR CONFORMATIONS
walks in which every step is determined by the self-avoiding requirement (power of 1.0). The
former extreme is the random walk result from above; the later extreme is the one-dimensional,
self-avoiding random walk result.
We now return to the random walk analysis and its assumption that the polymer chains are
long enough such that a Gaussian distribution function accurately represents the results. How big
do the chains have to be to be large enough? The Gaussian distribution was applied to the factor
(n+ − n− ). For large chains with random n+ and n− jumps, we require |n+ − n− | n. W (r)dr is
accurate as long as this inequality is true. W (r)dr, however, is supposed to work for all values of
r which includes r near rmax = nl. The maximum value of r can only occur when all jumps are in
the same direction which means either n+ = n and n− = 0 or n− = n and n+ = 0. In each of these
cases |n+ − n− | = n and the requirement that |n+ − n− | be much less than n is violated. In other
words, as r gets large, the chain becomes less Gaussian and W (r)dr becomes increasing inaccurate.
To assess the accuracy of W (r)dr, some researchers have constructed more detailed analyses
that account for deviations from Gaussian behavior at large r. One published result is
( " 2 #)
2 2 2 3 r
W (r)dr = (Const)4πr exp −β r 1 + + ... dr (3.33)
10 rmax
The first term within the square brackets is 1 which is the previous result for a Gaussian distribution.
The rest of the terms within the square brackets are correction terms that are small for small r
and become more significant for large r. Only the first and largest correction term is given. Let’s
consider a chain of n bonds and say that the uncorrected W (r)dr is adequate as long as the
correction term is less than 0.01 (or less than 1%). W (r)dr will then be good for a chain that is
p
up to f times larger than the root-mean-squared end-to-end distance (i.e., good for r ≤ f hr2 i)
as long as
p !2
3f 2
r
3 f hr2 i n
= < 0.01 or f= (3.34)
10 rmax 10n 30
For example consider a chain of n = 100 bonds (a fairly short polymer chain). Solving this
equation for f results in f = 1.83. Therefore the first correction term in W (r)dr is less than 1% for
√
0 < r < 1.83l n = 18.3l. When 18.3l < r < nl = rmax = 100l the first correction term is greater
than 1%.
We can relate the range of small correction terms to the standard deviation in root mean
√ √
squared end-to-end distance. The upper limit in r for small corrections is f l n where l n is the
root mean squared end-to-end distance. From above, the standard deviation in end-to-end distance
√
is 0.15l n. Therefore the upper limit in r for small corrections is
√ √ pn
fl n − l n −1
√ = 30 (3.35)
0.15l n 0.15
standard deviations above the mean. For the above example with n = 100 bonds, this equation
shows the W (r)dr is accurate as long as r is less than 5.50 standard deviations above the mean. In
3.5. EQUIVALENT FREELY JOINTED CHAIN 37
Figure 3.13: The thin lines are a real polymer chain of n bonds. The thick lines are the superposed
equivalent freely-jointed chain of n0 = n/m bonds.
a normal distribution very few chains will be more than 5.50 standard deviations above the mean.
Thus even for a relatively short 100 bond chain, the correction factor is insignificant. We conclude
that the correction factors are insignificant for most real polymer chains.
where
k
C=√ (3.37)
m
By using the equivalent freely-jointed chain, we have shown that the end-to-end distance of a
√ √
realistic chain is proportional to l n. The proportionality constant is C. C is normally greater
38 CHAPTER 3. MOLECULAR CONFORMATIONS
√
than one and therefore C is sometimes called the expansion factor and sometimes denoted as α.
It tells how much the real chain is expanded relative to a freely jointed chain. The square of the
expansion factor, or C, is known as the characteristic ratio. It is defined by
hr2 i
C= (3.38)
nl2
hr2 i
Cn = ∝ n0.2 (3.39)
nl2
or
p
hr2 i ∝ ln0.6 (3.40)
This result agrees with the previous discussion of self-avoiding random walks which claimed that
the power-law dependence on n for a real chain is between 0.5 (for a completely random chain) and
1.0 (for a chain with all steps controlled by self-avoiding requirements).
Our discussion on the equivalent freely-jointed chain shows that any real polymer can be reduced
√
to any expression for end-to-end distance that is proportional to l n (provided we ignore, for the
moment, excluded volume effects). The thing that distinguishes one polymer from another is
the characteristic ratio C. We thus embark on a series of models whose main purpose is to use
theoretical arguments for calculating the characteristic ratio.
We will find it useful to develop an alternate approach to the analysis of end-to-end distance in
polymers. The new analysis will be based on vectors and analytical geometry. We associate with
each bond a vector. Let the vectors u~1 to u~n be the vectors along the n bonds. Then a vector from
one end of the chain to the other is simple the sum of these vectors:
n
X
~r = u~i (3.41)
i=1
3.6. VECTOR ANALYSIS OF POLYMER CONFORMATIONS 39
Expanding this expression for a polymer chain with a constant bond length, i, results in
n
X X
hr2 i = u~i · u~i + 2 hu~i · u~j i (3.43)
i=1 i<j
where the sum over i < j means all combinations of i and j such that i is less than j. The factor of
2 in front of the sum includes, by symmetry, the terms when i is greater than j. The dot product
of a vector with itself is simply the square of the length of the vector. Thus we can write
X
0
hr2 i = nl2 + 2l2 hcos θij i (3.44)
i<j
0 is the angle between the vectors along bond j and along bond i. If vector j is equal to
where θij
0 is the supplement of the bond angle between bonds i
i + 1 (i.e., the bond next to bond i) then θij
and i + 1.
0 i is zero which
For the freely-jointed chain, the bond directions are uncorrelated and hcos θij
p √
yields hr2 i = l n as before. This result was obtained with less work than the previous analysis.
The previous analysis, however gave a full distribution function (a Gaussian distribution) while this
one only gives the root-mean-squared end-to-end distance. For more complicated models, we will
0 i.
need to evaluate the term hcos θij
We can use a vector analysis to investigate the relation between end-to-end distance and radius
of gyration - s. In vector notation, we can write an expression for s2 in which r~i is the location of
the ith atom along the polymer chain and ~z is the location of the center of mass:
1X
s2 = ri − ~z) · (~
(~ ri − ~z) (3.45)
n
i
where ri is the distance from the origin to atom i and z is the distance from the origin to the center
of mass. The definition of the center of mass is
1X X
~z = r~i or r~i = n~z (3.47)
n
i i
ri
rij rij2 = ri2 + rj2 - 2 ri rj cos θ
rj
Figure 3.14: A triangle framed by vectors r~i and r~j . The vector r~ij connects the two ends of vectors r~i
and r~j .
To evaluate the vector dot product r~i · r~j , consider the triangle in Fig. 3.14. By the cosine law
the length of the vector r~ij connecting the ends of vectors r~i and r~j is
2
rij = ri2 + rj2 − 2ri rj cos θ = ri2 + rj2 − 2~
ri · r~j (3.49)
In this step we made use of symmetry (rij = rji ) and the fact that rii = 0.
Because the vectors r~i are the coordinates of the atoms in the polymer chain, the distance rij
is the end-to-end distance for a sub-polymer chain of j − i bonds. By the discussion in the section
on the equivalent freely-jointed chain, we can write this distance as
2
rij = C(j − i)l2 (3.52)
We do not know the value of C but it is the characteristic ratio for the polymer under consideration
and may depend on j − i (especially for small j − i). Ignoring the j − i dependence of C, inserting
this result, and reordering the summation over i yields:
n j−1 n n
Cl2 X X Cl2 X j(j − 1) Cl2 X 2 Cl2 n(n + 1)(2n + 1)
s2 = i = ≈ j = 2 (3.53)
n2 n2 2 2n2 2n 6
j=1 i=1 j=1 j=1
The terms near the diagonal are random walk, long-chain approximations for short chains and may
be inaccurate. If the matrix is large, however, there will be many more terms far from the diagonal
then close to the diagonal. For large matrices, the inaccuracies in the terms close to the diagonal
will have only a negligible effect on the sum of all terms. Thus the relation between hs2 i and hr2 i
derived above will be accurate. In order for the derived relation, rewritten here as
hr2 i
=6 (3.56)
hs2 i
to be accurate, the chain must be slightly larger than is required for hr2 i to be equal to Cnl2 .
The relation will be inaccurate for short chains or for chains that are not random walk coils (e.g.,
extended chain polymers).
This expression can be imagined as the sum of all the terms in the matrix of size n × n in which
the element at row i and column j is cos|j−i| θ0 :
1 cos θ0 cos2 θ0 cos3 θ0 . . . cosn−1 θ0
cos θ0 1 cos θ0 cos2 θ0 . . . cosn−2 θ0
l2 × (3.58)
.. .. .. .. .. ..
. . . . . .
cosn−1 θ0 cosn−2 θ0 ... cos2 θ0 cos θ0 1
The n diagonal terms sum to n which give the first term (nl2 ) in the hr2 i expression. Writing out
the required terms for the summation term by inspection of this matrix gives
where
n−1
X n−1
X
i
S1 = x and S2 = ixi−1 (3.62)
i=1 i=1
The terms S1 and S2 can be evaluated in closed form for all values of n. For polymer problems,
we are normally concerned with large n for which these sums converge to constant values and we
can treat the two sums as infinite series. The infinite geometric series S1 has the well known result
∞
X x
xi = x 1 + x + x2 + x3 + . . . =
S1 ≈ (3.63)
1−x
i=1
For large n, the second term in the brackets quickly becomes negligible and we have
2nl2 x 1+x
hr2 i = nl2 + = nl2 (3.67)
1−x 1−x
Finally we substitute for x and note that cos θ = − cos θ0 (where θ is the bond angle and θ0 = π − θ
is the supplement of the bond angle). We get
1 − cos θ
hr2 i = nl2 (3.68)
1 + cos θ
The root-mean-squared end-to-end distance for large, freely-rotation chains is
r
p √ 1 − cos θ
hr2 i = l n (3.69)
1 + cos θ
The characteristic ratio is
hr2 i 1 − cos θ
Cn = 2
= (3.70)
nl 1 + cos θ
Note that the characteristic ratio is independent of n. This independence is a consequence of our
assumption of large n. It is possible to evaluate S1 and S2 for any value of n and get an exact
result. The exact result gives a Cn that depends on n but rapidly converges to the above result for
large n.
For an example we consider polyethylene. All carbon bonds are in approximately tetrahedral
geometries. We can thus approximate all bond angles by the tetrahedral angle of θ = 109.47◦ or
cos θ = −1/3 (note: it is easier to remember the tetrahedral angle as the cos−1 (−1/3) than it is to
remember it as 109.47◦ ). For a freely-rotating polyethylene chain
p √
hr2 i = l 2n (3.71)
and the characteristic ratio is Cn = 2. Real polyethylene is not totally symmetric and thus the
C C C bonds deviate slightly from 109.47◦ to 112◦ . The C C H and H C H bonds shrink
slightly to compensate. This slight increase in bond angle increases the characteristic ratio by 10%
to Cn = 2.20.
4
C
H H 3
Energy
C 2
H H 1
C
0
0 60 120 180 240 300 360
Rotational Angle
Figure 3.15: Left side is an end view of the central C–C bond in butane. The right side plots to potential
energy as a function of angle with φ = 180◦ defined as the trans position illustrated on the left side.
in butane are a reasonable model for the C C rotations in polyethylene. A preferred analogy
would be higher molecular weight alkanes. Those experiments and their analysis have been done,
but with more effort and less accuracy than available for butane.
The trans state illustrated on the left side of Fig. 3.15 is the lowest energy state. It is lowest
because the two CH3 groups, which are larger than the H atoms, are as far apart as possible. As
rotations occur the groups appended to each of the central C atoms come into closer proximity and
the steric energy increases. There are local maxima at φ = ±120◦ . These maxima occur when the
CH3 groups are aligned with H atoms on the other carbon atom. There are local minima when
φ = ±60◦ . These minima occur when all the groups are staggered (as in the left of Fig. 3.15) but
the CH3 groups are adjacent to each other rather than opposite each other as in the trans state.
These local minima are called the gauche+ and gauche- states. Finally there is a local maximum
at φ = 0◦ , which occurs when the two CH3 groups on either end of the butane chain are aligned
and as close together as possible.
When rotations are hindered by potential energy functions such as those shown in Fig. 3.15,
it is clear that the rotations will not be free. All rotational angles are perhaps possible, but the
dihedral angles will have a preference for the low energy states. For butane, most bonds will be
at or near the trans state (φ = 180◦ ) or at or near the local gauche minima (φ = ±60◦ ). Thermal
energy will allow the angles to deviate from these states and to overcome the barriers to transitions
from one state to another. The populations of all rotational angles, however, will not be equal. We
thus replace the freely-rotating chain with a more realistic hindered-rotating chain model.
End-to-end distance for a hindered-rotation chain is more difficult to find than the freely-
3.9. MORE REALISTIC ANALYSIS 45
rotating chain model. We omit the details and give the results. The final equation is found using
the vector analysis and averaging the dot products ~ui · ~uj , while accounting for unequal populations
of the possible rotational angles. The result is
r s
p √ 1 − cos θ 1 − hcos φi
hr2 i = l n (3.72)
1 + cos θ 1 + hcos φi
where hcos φi is the average value of the rotational angle. The characteristic ratio is
and a characteristic ratio of 1. The next most realistic model, the freely-rotating chain model, gives
p √
hr2 i (freely rotating) = 108 2.20Å = 160Å (3.75)
and a characteristic ration of 2.20. For the hindered-rotation chain model we need to know hcos φi.
We thus need some new information. For example, we will say that experiments show that 60% of
the bonds have φ = 180◦ (trans) and 20% each have φ’s of +60◦ or −60◦ (gauche+ or gauche-).
Then the average dihedral angle gives
and the characteristic ratio is Cn = 5.13. We can compare this result to the experimental result
for polyethylene which is 6 to 7 (depending on temperature). The hindered rotating chain gives
a result that is close to the correct results, but is still too low. In the next section we consider
improvements on the hindered rotating chain model.
We consider short-range interactions as interactions with neighboring bonds that affect the
relative probabilities of the dihedral angle. When we include short range interactions we cannot
take a simple average of cos φ as in the hindered rotation model. We need to account for the effect
of neighboring bonds. In its simplest implementation we might assume that the conformation of
one bond depends on relative energies that are influenced by the conformation of the previous
bond. Each step of the random walk then requires an adjustment of the jump-direction proba-
bilities according to the conformation of the previous bond. Some probability analysts call such
models Markov chains instead of random walks. After we develop a model that does a good job
of accounting for short-range interactions, we will have a good model for polymer conformations
that are unperturbed by the long-range interactions described below. We will call the polymers
generated by this modified random walk or Markov chain process “unperturbed polymer conforma-
tions.” The end-to-end distance of these chains will be called the unperturbed end-to-end distance
and will be denoted with a subscript zero — hr2 i0 .
Long-range interactions are all interactions that are not short-range interactions. To be more
specific, long-range interactions are interactions between atoms or molecular units that are not
covalently bonded to each other. Defined this way, long range interactions include interactions
between two parts of the polymer that are separated by many bonds or between the polymer and
solvent molecules. We discuss three types of long-range interactions.
The first important perturbation to random walks is that while random walks can cross their
own path, a polymer conformation cannot — random walks used to simulate polymer chains should
be self-avoiding random walks. This new feature is called the effect of excluded volume. The
elements of the chain exclude other elements from their occupied volume. If included in the analysis,
excluded volume will perturb the end-to-end distance and cause it to increase. Besides increasing
the end-to-end distance, excluded volume will cause the root-mean-squared end-to-end distance to
√
no longer be proportional to n. When excluded volume effects are significant, we can assume
that hr2 i is proportional to some power of n such as p (where p > 0.5):
hr2 i ∝ np l2 (3.78)
According to deGennes, p = 1.2 and therefore the characteristic ratio increases as n0.2 :
hr2 i
Cn = ∝ n0.2 (3.79)
nl2
A second long-range interaction is interactions between the polymer and the solvent. A solvent
can cause the unperturbed end-to-end distance to increase or decrease. A good solvent will cause
it to increase. In effect the polymer will prefer interactions with the solvent over interactions with
itself and therefore will expand to maximize polymer-solvent interactions. A poor solvent will cause
the unperturbed end-to-end distance to contract. The polymer wants to avoid the solvent and thus
will contract on itself to avoid polymer-solvent interactions. In the extreme case, a poor solvent will
3.10. THETA (Θ) TEMPERATURE 47
cause the polymer to completely contract and precipitate out of solution. This extreme example of
a poor solvent is better characterized as a non-solvent.
The last types of long-range interactions are specific interactions. By specific interactions we
mean identifiable interactions between remote parts of the chains. Two examples are hydrogen
bonding and ionic interactions.
After considering both short-range and long-range interactions we are led to split the problem of
theoretical polymer characterization into two parts. The first part is the study of the unperturbed
end-to-end distance. We plan to modify the hindered rotation chain model to correctly account for
short-range interactions and thereby calculate the correct unperturbed end-to-end distance. After
solving this problem we will consider what influence the long-range interactions (including excluded
volume effects) have on the results. Let’s define α to be the factor by which the linear dimension
expands (α > 1) or contracts (α < 1) due to long-range interactions:
p p
hr2 i = α hr2 i0 (3.80)
The rotational isomeric state model will be our solution to the problem of accounting for short-range
interactions and some long range interactions (e.g., the effect of excluded volume). In general, any
polymer conformation is defined by a set of bond lengths, li , bond angles, θi , and dihedral angels,
φi . In the rotational isomeric state model, we assume that the polymer is restricted to certain
types of conformations or to certain isomeric states. Bond lengths are likely to vary only ±3% and
thus as before we consider them to be fixed at l. Likewise, bond angles are likely to vary only ±5
degrees and we consider them to be fixed at θ. The dihedral angles are not allowed to assume any
possible angle, but instead are assumed to be restricted to a small number of discrete values. The
possible discrete dihedral angles define the set of rotational isomeric states for each bond.
We will illustrate with polyethylene. These ideas will be extended to other polymers latter.
Due to symmetry of polyethylene there are three possible rotational isomeric states (see Fig. 3.16).
The trans state (φ = +180◦ ), the gauche+ state (φ = +60◦ ) and the gauche- state (φ = −60◦ ).
In the rotational isomeric state model, each bond of polyethylene is assumed to be in one of these
three states. No other values of φ are allowed. In reality, thermal fluctuations about the minima in
3.11. ROTATIONAL ISOMERIC STATE MODEL 49
C C C
C H H H H C
C C C
H H H H H H
H C H
potential energy will lead to a distribution in φ’s around these three local minima. The rotational
isomeric state model asserts that we can realistically simulate a polymer chain by ignoring variations
in φ around the local minima.
In our random walk analysis of the rotational isomeric state, the probability of any bond existing
in one of the rotational state i characterized by angle φi , is given by a Boltzman factor:
e−E(φi )/RT
P (φi ) = (3.81)
Z
where Z is a normalizing factor or the sum of the Boltzman energy factors for all possible angles:
3
X
Z= e−E(φi )/RT (3.82)
i=1
where E(φi ) is the energy associated with the state at dihedral angle φi and the sum is over the
three possible states in Fig. 3.16 (Note: this equation can easily be generalized to more than three
rotational isomeric states) Because of short-range interactions discussed above, this probability
factor is expected to be affected by neighboring bonds. The simplest model is to assume that the
energy, E(φi ), is affected by the bond conformation of the previous bond. This important nearest-
neighbor interaction is ignored in the hindered rotation chain model. Its inclusion in the rotational
isomeric state model is the major advance in realism in this new model.
To account for nearest neighbor interactions, we must consider all bond pairs and all possible
conditional probabilities of the form P (φi |φi−1 ), which gives the conditional probability that bond
i has angle φi given that the previous bond or bond i − 1 has angle φi−1 . By analogy with the
previous probability factor
e−E(φi−1 φi )/RT
P (φi |φi−1 ) = (3.83)
Z(φi−1 )
50 CHAPTER 3. MOLECULAR CONFORMATIONS
where Z(φi−1 ) is a normalizing factor or the sum of the Boltzman energy factors for all angles φi
given that φi−1 is fixed:
3
X
Z= e−E(φi−1 φj )/RT (3.84)
j=1
In these equations, E(φi−1 φi ) is the energy associated with two consecutive bonds with dihedral
angles φi−1 and φi . In this section we are restricting ourselves to three rotational states of trans
(t), gauche+ (g + ), and gauche- (g − ). The energy factors we care about are E(tt), E(tg + ), E(tg − ),
etc.. The conditional probabilities we are concerned with can conveniently be tabulated in a matrix
called the weighting factor matrix. For polyethylene (or for any three-state polymer) we write can
write a weighting factor matrix as
P (t|t) P (g + |t) P (g − |t)
U = P (t|g + ) P (g + |g + ) P (g − |g + ) (3.85)
P (t|g − ) P (g + |g − ) P (g − |g − )
For example, the matrix element P (t|g + ) gives the probability that the next bond is trans given
that the previous bond was gauche+.
Let’s begin with the first row and arbitrarily assign the tt state to the ground state. Thus we
assume E(tt) = 0. The tg + and tg − bond pairs will each be higher in energy than the tt bond pair.
In polyethylene, the excess energy associated with the two possible gauche bonds will be the same.
We let that excess energy be Eg or the extra energy associated with a gauche bond. We further
define
σ = e−Eg /RT (3.86)
Gauche - C
C Gauche +
C
Strong
C
Steric C
Interactions
Figure 3.17: The steric interactions caused by the pentane effect when two consecutive bonds are g + |g −
or g − |g + .
It usually suffices to work with relative probabilities rather than absolute probabilities. By conven-
tion we normalize each row to the first element in that row. For a simple polymer like polyethylene,
we write the weighting matrix of relative probabilities as
1 σ σ
U = 1 σ σω
(3.94)
1 σω σ
By theory and experiment, the energy terms for polyethylene are well known. The best results give
Eg = 2100 J and Ep = 8400 J. At 300◦ C these lead to weighting factors of
Thus gauche bonds are only about 46% as likely as trans bonds (2σ/(1 + 2σ)) and g + |g − confor-
mations are only about 2.4% as likely (σω/(1 + σ + σω)).
52 CHAPTER 3. MOLECULAR CONFORMATIONS
We next consider how to use the rotational isomeric state model to predict polymer properties.
Imagine a polymer chain of n bonds. A polymer conformation of this chain is determined by setting
the states of each bond; each bond can be t, g + , or g − . We can ignore the first two bonds and thus
we need to set the states of the terminal n − 2 bonds. The first bond can be ignored because it only
serves to locate the start of the polymer in space. The second bond direction is determined by the
rotational state of bond 1, but this state only serves to locate the initial direction of the random
walk. The remaining n − 2 bonds need to be determined.
There are two possible solutions to the rotational isomeric state model. Because each bond
has a small number of discrete states, the total number of polymer conformations is finite. For
a polymer with n bonds of which each bond can be in one of three states, the total number of
polymer conformations is 3n−2 . One possible approach is to enumerate all possible conformations
and calculate properties using the exact process discussed earlier in this chapter. This exact solution
can be done for small n, but soon becomes impractical for large n’s typical of real polymers.
When n is large the total number of conformations is too large to enumerate, even on the fastest
supercomputer.
For large polymers, a preferred approach is to use the Monte Carlo method. We generate a large
number of chains using a random walk or Markov chain process. For each bond the probabilities of
the next bond being in a given state are determined by the weighting matrix like the one given above
and by the state of the previous bond. For each chain we can calculate a property of interest (e.g.,
end-to-end distance, radius of gyration, etc.). The average value of that property after generating
sufficiently many chains will be our Monte Carlo solution to the problem.
The above Monte Carlo random walk process requires a computer. The computer program
LatticeTM discussed in class is an example of a program that can do Monte Carlo simulations using
the rotational isomeric state model. Programs like LatticeTM are, in effect, computer experiments.
You set polymer properties by selecting weighting factors, excluded volume, temperature, etc..
Then you run the program and calculate the end-to-end distance or the radius of gyration. These
computer experimental results can be compared to real experimental results. If the two results
agree, you have evidence that the rotational isomeric state is a valid model for polymers. Fur-
thermore the physical concepts of the rotational isomeric state model give you insight about the
polymer molecules and the factors that control conformations.
The following pseudo computer code is the program logic, or flow chart, of the main part of
any program that does Monte Carlo solutions using the rotational isomeric state model. This flow
chart assumes a three rotational isomeric states, but it could easily be generalized to handle any
number of states.
next bond
Now have set of n-2 bond conformations which completely define the chain
Calculate properties (e.g. end-to-end distance, radius of gyration, etc.)
Start over with another chain and continue until results converge
The key part of this loop is calculating the properties of each generated chain. You can calculate
any property than can be reliably calculated for a given polymer conformation. The simplest
and most reliable properties are size properties. The program LatticeTM calculates the following
properties:
2. rms r
3. hri
4. rms s
r2
5. nl2
— the characteristic ratio (equal to Cn )
r2
6. s2
— how close is it to 6?
7. % trans
9. Relative entropy
54 CHAPTER 3. MOLECULAR CONFORMATIONS
In addition to the above calculations, LatticeTM can also plot many results. It can plot each
generated polymer in a three-dimensional view. These stick figures give a feel for typical polymer
conformations. It can plot the distribution of end-to-end distances and compare them to the radial
Gaussian function calculated for in the freely-jointed chain analysis.
There is one important aspect of LatticeTM and many rotational isomeric state solutions that
requires discussion. As implied by its name, LatticeTM generates chains on a tetrahedral lattice.
This requires all bonds angles to be the tetrahedral bond angle of 109.47◦ . Because it is a regular
lattice, it also requires all bonds lengths to be the same. This type of simulation is reasonably
accurate for polyethylene and for many other carbon-backbone polymers. Lattice simulations,
however, cannot give you information about the effect of bond angle (e.g., 112◦ in real polyethylene
vs. the 109.47◦ in a tetrahedral lattice) and cannot simulate polymers with different bond lengths.
The advantage of lattice simulations is that they are fast. They can do most of the work with
integer arithmetic which is much faster in computers. The use of a lattice makes it possible to do
meaningful simulations in personal computers such as Macintoshes. An off-lattice calculation on a
Macintosh would be limited to much more rudimentary work and to much shorter chains.
We can simulate many polymers using the rotational isomeric state model. Some interesting
polymers are:
2. Polytetrafluoroethylene (PTFE)
3. Copolymers
Some results from these types of polymers are discussed in the LatticeTM manual and will be covered
in class.
Problems
3–1. The radial distribution function for the freely-jointed chain model was shown in class to be
β 3
2 2
W (r)dr = √ 4πr2 e−β r dr (3.96)
π
where r
3
β= (3.97)
2nl2
Because the form of the radial distribution function even for non-freely-jointed chains is similar
to the freely-jointed chain result (except with a different value for β) it is worth studying this
function.
3.11. ROTATIONAL ISOMERIC STATE MODEL 55
1
a. Show that the maximum in W (r)dr occurs at r = β
2
b. Show that the mean value of r is hri = √
β π
.
3
c. Show that the average value of r2 is hr2 i = 2β 2
e. Express the answers to a through d in terms of number of bonds (n) and bond length
(l).
3–2. Pretend that linear polyethylene (PE or (CH2 CH2 )n ) can be modeled as a freely-jointed
chain in which each bond is 1.53Å long. Using the results from problem 2-1, evaluate the
following quantities:
g. Plot the radial distribution function for this polymer chain and indicate on your plot
the answers to c, d, and e.
3–3. Polymer A contains x freely jointed segments each of length la and polymer B contains y
freely jointed segments each of length lb . One end of A is connected to one end of B to form
a two block, block copolymer.
b. If segments of A are randomly interspersed with segments of B and the segments are still
freely jointed, what would be the root-mean-squared end-to-end distance of the random
copolymer?
3–5. Many polymers have more than one type of bond the different types of bonds may have
more the one value for bond length. One example is Nylon 66 whose repeat unit structure is
O O
HO–C–(CH2)4–C–OH + H2N–(CH2)6–NH2
O O
—(N–C–(CH2)4–C–N–(CH2)6)—
H H
This polymer has N –CH2 bonds, N –carbonyl bonds, carbonyl-CH2 bonds, and CH2 –CH2
bonds. Explain, in general terms, how you would use the rotational isomeric state model to
calculate the characteristic ratio of Nylon 66.
Chapter 4
RUBBER ELASTICITY
4.1 Introduction
The mechanical properties that define a rubber elastic material are:
2. Much of the elongation is recoverable (it returns to its original shape when unloaded)
Many polymers exhibit such rubber elasticity over some range in temperatures. Those polymers
that exhibit rubber elasticity at room temperature are caller elastomers. Furthermore, it is only
polymeric materials that can be elastomers (with some commercially-unimportant exceptions in
inorganic gels). Since the main unique feature of polymers is that they are large molecules, it is
logical to assume that rubber elasticity is a potential property of large, covalently bonded molecules.
But, what is it about polymers that makes it possible for them to be elastomers? What are the
mechanical properties of elastomers? How does one design new and improved elastiomers? Those
questions are discussed in this chapter.
57
58 CHAPTER 4. RUBBER ELASTICITY
Rubber
Heat
Weight
Figure 4.1: A specimen of rubber loaded under a constant weight and then heated. Upon heating the
specimen decreases in length.
Prior to vulcanized rubber, natural rubber from various sources existed and was studied in the
literature. In 1805, John Gough described a series of experiments on caoutchouc or Indian rubber.3
His first experiment was to monitor the temperature during elongation. He did not have elaborate
equipment, but was able to observe a temperature rise by stretching a rubber and bringing the
specimen into contact with his lips:
“For the resin evidently grows warmer the further it is extended; and the edges of the
lips possess a high degree of sensibility, which enables them to discover these changes
with greater facility than other parts of the body.”
The expectation for an elastic material (i.e., a material that recovers its shape when unloaded), is
that all the energy put into a specimen is stored as mechanical energy and then recovered when the
sample is unloaded. During such reversible unloading, it is unexpected to experience heat. Thus,
the behavior or rubber is unusual compared to other materials. Even though rubber increases in
temperature on elongation, it is still able to be reversible because it cools when unloaded.
Gough’s second experiment was to hang a weight on a piece of rubber (i.e., load a piece of
rubber at constant force) and then heat the specimen (see Fig. 4.1). The result of heating was that
the sample decreased in length. All other types of materials get slightly longer when heated due to
thermal expansion. In fact even a piece or rubber will thermally expand when it is not under load.
Rubber specimens under load, however, have the unusual property of getting shorter when heated.
Gough’s final experiments where to stretch rubber samples under water at different tempera-
tures. The elastomeric nature of the rubbers was preserved in warm water but was impaired in
cold water. It is not ususual for the elongation of materials to depend on temperature, but rubbery
materials depend dramatically on temperature. In fact the rubber elasticity effects disappear at
sufficiently low temperature. A common science demonstration is to bounce a rubber ball, dip it in
liquid nitrogen, and then show that it shatters like glass when bounced again. This effect is loss of
4.2. HISTORICAL OBSERVATIONS 59
Random Coil
F F
Elongated Coil
Figure 4.2: A single polymer molecule in the random coil state and in a more-ordered state when elogated
by a force.
rubber elasticity at lower temperature. The shattering like glass is a consequence of the polymer
now being well below its glass transition.
All these experiments on rubber, and more, can be explained as a consequence of changes in
entropy while stretching a rubber. Polymers are random coils. When they are stretched in one
direction, it is possible for the coil to become more ordered. This higher-order state is less random
and thus has less entropy. The process is illustrated in Fig. 4.2. In other words, the change in
entropy, ∆S, is negative upon loading (∆S < 0). The restoring force in rubbery materials is a result
of this entropy decrease. For this reason, elastomers are accurately called “entropy springs.” Now
all materials must follow the laws of thermodynamics and thus the restoring force in all materials
is consequence of both internal energy change and entropy change. In virtually all materials, the
internal energy change dominates and entropy effects can be ignored. Rubber elastic materials are
unique in that it is the internal energy effects that are small and the entropy effects dominate.
We can outline the three requirements for a polymer molecule to be rubber elastic:
3. The polymer molecules must be lightly crosslinked. The cross links may be either chemical
cross links or physical entanglements between large polymer molecules.
The first two criteria relate to the need for the polymer chain to be mobile and the need for internal
energy effects to be small. The only way entropy effects can be large is when the polymer chains
become ordered on elongation such as in Fig. 4.2. This ordering is only possible when the polymer is
at sufficiently high temperature. For polymers, the characteristic temperature is the glass transition
temperature or Tg . By definition, Tg is the temperature where molecular motions become slow and
60 CHAPTER 4. RUBBER ELASTICITY
difficult. Thus whenever T > Tg molecular motions are easy and rubber elasticity is possible. The
requirement to be an amorphous material is similar. A crystalline structure is not mobile and
deformations of crystals result in internal energy changes that impair rubber elasticity. The last
criteria is less obvious. The need for cross linking is to make the material a solid rather than a liquid.
After all, many materials are highly mobile and non-crystalline but are still not rubber elastic; they
are liquids. To be rubber elastic, a liquid-like material has to be cross linked to prevent viscous
flow. It is the cross links that allow the material to recover when unloaded. Goodyear’s invention
of vulcanization was actually an invention of a process for cross linking natural rubber. Natural
rubber, in its native state, is slightly crystalline and too fluid for significant commercial uses. By
cross linking using vulcanization, the crystallinity disappears and the mechanical properties become
much more useful. Finally, it is the need for cross linking that makes polymers the only materials
that can be elastomers. They are the only liquid-like materials that can be readily cross linked.
4.3 Thermodynamics
The deformation of elastomers and how they differ from most other materials can be understood
by simple (albeit non-rigorous) thermodynamics analysis for uniaxial loading. The first law of
thermodynamics is
dQ + dW = dU (4.1)
where dQ is heat added to the sample, dW is work done on the sample, and dU is the change in
internal energy. (Note that chemical engineers frequently define work done by a sample and thus
the dW term changes sign. In mechanics, it is more natural to think in terms of work done on a
sample). In a reversible process (such as loading an elastic material), the heat term is dQ = T dS
where T is absolute temperature and dS is the change in entropy. The work term is
dW = F d` − P dV (4.2)
The first term is work of extension (force F times distance of extension or change in length d`). The
second term is expansion work, but it is generally very small during uniaxial loading. Substitution
into the first law of thermodynamics gives
T dS + F d` = dU + P dV = dH (4.3)
where dH is the enthalpy change (by definition dH = dU + P dV ). Finally, solve for the force of
elongation gives
∂H ∂S
F = −T (4.4)
∂` T,P ∂` T,P
The first term in the extension force is the force due to enthalpy change, which is very close
to the internal energy change (since P dV is small). For nearly all engineering materials, such as
4.3. THERMODYNAMICS 61
metals, ceramics, polymers (with T < Tg ), etc., this first term dominates as the force is equal to
the internal energy change per unit length change. For elastomers, however, the converse is true.
The internal energy change is small while the entropy change is large. Thus for elastomers, the
force of extension is
∂S
F ≈ −T (4.5)
∂` T,P
Because extension (∂` > 0) causes a decrease in entropy (∂S < 0), the negative sign is correct
and leads to a positive force. Conventional engineering materials and elastomers are two extremes
of the force equation in which one of the two terms dominates. It is possible for materials to be
between these two extremes where the internal energy and entropy terms are of similar magnitude,
but such materials are uncommon.
To explain temperature effects in Gough’s experiments3 requires slightly more advanced ther-
modynamics. The free energy change, dG, on extension is:1
dG = V dP − S dT + F d` (4.6)
Thus, when an elastomer is stretched (∂` > 0) causing the entropy to decrease (∂S < 0), the left
hand side (with the minus sign) is positive. This result implies that whenever the force increases
(∂F > 0) that the temperature must increase too (∂T > 0). This relation thus explains Gough’s
first experiment. Gough’s second experiment is length as a function of temperature at constant
force. This experiment can be explained by more involved thermodynamics,1 but will not be
discussed here.
Actually, Eq. (4.7) is true for any material, but it is only elastomers for which the decrease
in entropy is sufficient to cause an easily observable temperature increase. Equation (4.7) gives
a simple experiment to verify this dominant role of entropy in elastomers. The experiment is to
measure force as a function of temperature at constant length and pressure. The slope of the results
is (∂F/∂T )`,P , which by Eq. (4.7) is equal to −(∂S/∂`)T,P . Substitution of this entropy result into
Eq. (4.4) provides simultaneous measurement of enthalpy (or approximately internal energy) change
during elongation. The results for such experiments on elastomers and conventional materials are
shown schematically in Fig. 4.3. For elastomers, the slope is large and positive and the energy
terms can be shown to be small. For most other materials the slope is close to zero. As shown in
Fig. 4.3, most materials have a slightly negative slope due to thermal expansion. As the material
expands when held at fixed length, it expands against the grips and therefore reduces the force.
Such experiments can prove the dominance of entropy effects in elastomers and their absence in
other materials.
62 CHAPTER 4. RUBBER ELASTICITY
Elastomers
Force
Other Materials
Temperature
Figure 4.3: Force as a function of temperature for a specimen held at constant length and external pressure.
where k is Boltzman’s constant and Ω is the number of possible configurations. The number of
configurations per unit volume is equal to the distribution function for random-coil chain end:
3
β 2 r2
Ω ∝ W (x, y, z) = √ e−β (4.9)
π
where W (x, y, z) is the probability that a polymer chain starting at the origin ends at location
p
(x, y, z) which is a distance r = x2 + y 2 + z 2 from the origin. The derivation of this equation was
given in Chapter 3. The distribution is picture in Fig. 4.4, which is repeated from the Chapter 3.
W (x, y, z) is the probability that the random coil on the left starts at the origin and ends in the
box centered on (x, y, z). Substitution into the entropy equation gives the entropy of a single chain
as
S = c − kβ 2 r2 (4.10)
dV = dx dy dz 1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
y
0.1
0.0
-3 -2 -1 0 1 2 3
βr
Figure 4.4: The left side shows a chain that starts at the origin and ends in a box centered a (x, y, z). The
right side is a one-dimensional plot of W (x, y, z)dx dy dz.
lengths in the x, y, and z directions before deformation and Lx , Ly , and Lz be the lengths after
deformation. Now define elongation ratios
Lx Ly Lz
λx = , λy = , and λz = (4.11)
Lx0 Ly0 Lz0
An “affine” deformation means that each location in space transforms the same way as the global
lengths. Thus a point initially at (x, y, z) will be at (λx x, λy y, λz z) in the deformed space. Thus
the entropy of a single chain will change from
Si = c − kβ 2 (x2 + y 2 + z 2 ) (4.12)
to
Si = c − kβ 2 (λ2x x2 + λ2y y 2 + λ2y z 2 ) (4.13)
The total entropy change per unit volume is found by integrating the single-chain result over
all space using the random coil distribution function
Z ∞Z ∞Z ∞
∆S = N ∆Si W (x, y, z) dx dy dz (4.15)
−∞ −∞ −∞
where N is the number of random coils per unit volume. Using the integration result that
Z ∞Z ∞Z ∞
1
β 2 x2 W (x, y, z) dx dy dz = (4.16)
−∞ −∞ −∞ 2
64 CHAPTER 4. RUBBER ELASTICITY
1
∆S = − N k(λ2x + λ2y + λ2z − 3) (4.17)
2
ρL
N= (4.18)
Mc
1 ρLk ρR G0
Nk = = = (4.19)
2 2Mc 2Mc 2T
ρRT
G0 = (4.20)
Mc
Here G0 is just a defined constant, but as discussed below it is equal to the shear modulus of
the elastomer. The key molecular property that affects G0 is Mc and that property is a function
of the amount of cross-linking. As the amount of cross linking increases, the distance between
cross links, and therefore also Mc , decreases. The shear modulus therefore increases. Thus, a
lightly cross-linked elastomer will have a low shear modulus (or stiffness). As the amount of cross
linking increases, it will get stiffer. If the amount gets too high, it will eventually become a non-
elastomeric, rigid polymer. A key requirement when making elastomers is to get the ideal amount
of cross linking.
We can apply the above entropy change result to analysis of deformation experiments on elas-
tomers. First consider uniaxial loading of extension λ = λx . Under such loading the specimen will
contract in the y and z directions. For an isotropic material, the contractions will be the same or
λy = λz = λT . After elongation, the new volume will be V = λλ2T V0 where V0 = Lx0 Ly0 Lz0 is
the initial volume. All experiments with elastomers shows that the volume change is always very
small. In other words V = V0 , which for unixial loading implies λλ2T = 1. Unaxial loading in the x
direction is thus represented by one variable, λ using:
1 1
λx = λ, λy = √ , and λz = √ (4.21)
λ λ
From Eq. (4.5), the force for uniaxial loading of a collection of networked random coils is
d∆S
F = −T V (4.22)
dLx
4.4. MECHANICAL PROPERTIES 65
6 True
4 Engineering
Stress/G0
0
-2
-4
-6
-8
0 1 2 3 4
Elongation
Figure 4.5: Theoretical predictions for engineering and true stress as a function of elongation for a net-
worked polymer of random coils. The force is assumed to be due solely to entropy change on elongation.
The V is needed because ∆S was derived per unit volume. Substituting Lx = λLx0 , V = Lx0 Ly0 Lz0
(and constant), and ∆S gives
G0 d 2 1
F = Ly0 Lz0 λ2 + − 3 = Ly0 Lz0 G0 λ − 2 (4.23)
2 dλ λ λ
Now Ly0 Lz0 = A0 or the initial cross-sectional area normal to the loading direction. The definition
of engineering stress, σ, is the force divided by the initial area or
F 1
σ= = G0 λ − 2 (4.24)
A0 λ
The definition of true stress is the force divided by the current area A = Ly Lz = λy λz Ly0 Lz0 =
A0 /λ. Thus true stress is
true λF 2 1
σ = = G0 λ − (4.25)
A0 λ
Plots of engineering and true stress predicted for an elastomer are in Fig. 4.5. The curves are
nonlinear. The engineering stress has decreasing slope as the elongation increases. The true stress
increases more rapidly due the decreasing cross sectional area. Both curves get stiff in compression
because compression elongation can never reach zero. Real elastomers have similar curves at modest
elongation but differ at very high elongations. At very high elongations, the molecular chains can
become sufficiently aligned that the sample gets much stiffer. The curves thus turn up to very high
stress just prior to failure. This transition is due to molecular alignment rather then entropy effects
and thus is not reproduced in entropy elasticity theories.
Shear Loading can be pictured as pulling in one direction (say the x direction) while pushing
in a perpendicular direction (say the y direction) by the same amount. If the equal stresses are
66 CHAPTER 4. RUBBER ELASTICITY
equal to σ, it produces a pure shear stress state with τ = σ/2. This pure shear deformation state
is represented by elongation ratios
1
λx = λ, λy = , and λz = 1 (4.26)
λ
The λx and λy values are for equal, but opposite forces. The λz value is required by the criterion
for zero volume change. The equal and opposite stresses are
1 2
F G0 d 2 1 G0 d 1 1
σ= = λ −2+ 2 = λ− = G0 λ − 1+ 2 (4.27)
A0 2 dλ λ 2 dλ λ λ λ
1
γ =λ− (4.29)
λ
Expressing the tensile test in terms of ε and the shear test in terms of γ, taking the limits as λ → 1
(i.e., as ε → 0 and γ → 0), and keeping only the linear terms results in
In other words, G0 is the shear modulus of an elastomer or the slope of the shear stress-strain curve
around λ = 1. Similarly, the tensile modulus, or the slope of the tensile stress-strain curve around
λ = 1, is E = 3G0 . For an isotropic, linear elastic material, E and G0 are related by
E
= 2(1 + ν) (4.31)
G0
where ν is the low-strain Poisson’s ratio of the material. Using the ratio of 3 implies ν = 1/2. A
Poisson ratio of 1/2 is characteristic for a material with no volume change upon deformation as
was assumed above for elastomers.
The section concludes with some example calculations. Consider an elastomer with density
ρ = 900 kg/m3 and molecular weight between cross links of Mc = 20, 000 g/mol. What is the shear
modulus at 0◦ C? The shear modulus is equal to G0 , which is defined by
A typical engineering polymer with T < Tg will have G0 ≈ 1000 MPa. Thus, this elastomer with
T > Tg is 10,000 times less stiff than a typical engineering plastic. This problem solved for modulus
as a function of Mc .
4.4. MECHANICAL PROPERTIES 67
The previous example can be inverted. In other words, a good way to determine the molecular
weight between cross links is to measure the shear modulus and then use
ρRT
Mc = (4.33)
G0
For example, consider a piece of rubber that is 12.7 mm × 1 mm × 40 mm with a shear modulus
of G0 = 2 MPa at 25◦ C and ρ = 900 kg/m3 . What is the molecular weight between cross links?
Substitution gives
Finally, estimate the temperature rise of the specimen during this experiment (i.e., Gough’s first ex-
periment). Assume the heat capacity of the elastomer is typical for a polymer or Cp = 1.5 J/(g · K).
The total heat is
∆Q = −∆W = −3.382 J (4.37)
The heat is less than zero since ∆Q is defined as heated added to the sample. For an elastomer
during elongation, the sample heats up and thus the specimen releases heat. This heat will raise
the sample temperature by
∆Q
∆T = − (4.38)
mCp
where m is the mass of the specimen:
∆Q = ∆U − ∆W ≈ 0 (4.41)
In other words, there is no noticeable temperature rise for most materials during elongation.
68 CHAPTER 4. RUBBER ELASTICITY
1. Diene elastomers - if the main polymer chain has double bonds, they can act as reaction sites
to add cross links between chains.
2. Nondiene elastomers - if the main chain does not have any double bonds, cross linking has to
be done by other methods. One common approach is to copolymerize with a small amount
of a monomer having main-chain dienes and cross linking at those diene sites. This approach
might be considered a diene ealstomer, but since most of the network is mostly a nondiene
monomer, they are still called nondiene elastomers.
3. Thermoplastic elastomers - these elastomers do not have chemical cross links. They rely on
physical entanglements to act like cross links. As long as the cross links maintain connection
on the time scale of deformation, they are just as effective as chemical cross links. An
advantage of physical cross links is that the material can be melted and processed by typical
thermoplastic means such as injection molding or extrusion.
A common building block for many commerical diene elastomers is the diene monomer
R
CH2 C CH CH2
When R = H, the monomer is butadiane; when R = CH2 , the monomer is isoprene; when R = Cl,
the monomer is chloroprene. When butadiene is polymerized by non-specific methods, it generates
a mixture of three different polymers depending on how the double bond reacts and the location
of the double bond that remains in the polymer:
Each polymer in the mixture has one remaining double bond per repeat unit. The second step in
making butadiene rubber is to use those double bonds to cross link the chains. Although it can
4.5. MAKING ELASTOMERS 69
be done with a mixture of stereochemistries, it is usually preferrable to start with a pure polymer
(e.g., all cis or all trans) by using a stereo-specific polymerization process. A common cross linking
process is sulfur vulcanization invented by Goodyear.2 The process is to heat in the presence of
sulfur and various additives (fatty acids, ZnO2 , and accelerators). This step creates Sx linkages
between polymer chains. The process is run until light cross linking is achieved. Too little cross
linking and the product will be too soft. Too much cross linking and it will lose rubber elasticity.
Besides sulfur vulcanization, other methods of cross linking include using peroxides or ionizing
radiation.
Elastomers made with butadiene include butadiene rubber (BR), styrene-butadiene rubber
(SBR), and nitrile rubber (NBR). SBR starts with a copolymer of styrene (10-25%) and butadiene.
The addition of styrene makes the rubber cheaper and improves wear resistance. One application
is for tires. NBR starts with a copolymer of acrylonitrile (15-40%) and butadiene. The addition of
acrylonitrile improves the solvent resistance. One application is for gaskets.
The monomer for natural rubber (NR) is isoprene. Like butadiene, non-specific polymerization
of isoprene results in a mixture of polymers. In contrast, natural rubber from plants is stereospecific.
The all trans version of polyisoprene is known as Hevea rubber. When vulcanized, it is used in
tires. The all cis version is known as Gutta Percha rubber. When vulcanized, it is harder than
Hevea rubber. One application is in covers for golf balls. Unvulcanized natural rubber is crystalline
due to the stereoregular nature of the polymers. The vulcanization breaks up the crystallization
as well as creating the cross links - the two things need to create the low-Tg polyisoprene into an
elastomer. Synthetic versions of natural rubber are possible, but they require use of stereospecific
polymerization methods to start with all trans or all cis polyisoprene polymers.
Rubbers starting with polychloroprene are called Neoprene rubber (CR). These rubbers have
improved solvent resistance. Common applications are for gaskets and O-rings.
Numerous polymers based on aliphatic hydrocarbon chains (e.g., polyethylene, polypropylene, etc.)
are inexpensive and have low Tg , but are not elastomeric unless further processed. For example,
polyisobutylene has the repeat unit
CH3
( CH2 C )
CH3
The main chain has no double bonds and therefore this polymer can not be cross linked by standard
double bond methods. The solution is to copolymerize with a small amount of isoprene. This co-
monomer adds doubles bounds to the main chain which can be reactive sights for cross linking.
70 CHAPTER 4. RUBBER ELASTICITY
Even though cross linking is done with dienes, this rubber is called a non-diene rubber because
most of the main chain lacks double bonds. The resulting elastomer is called Butyl Rubber. It has
lower permeability to oxygen than other elastomers and therefore has application in inner tubes
(e.g., bicycle tires) and weather stripping.
Polyethylene and polypropylene are two of the most widely-produced synthetic polymers. They
are both inexpensive and have Tg ’s well below room temperature. Both, however, are highly
crystalline (otherwise they would not be commercially significant polymers due to their low Tg ’s).
The first step to using them for elastomers, is to eliminate the crystallinity. This step can be
achieved by an ethylene-polypropylene random copolymer. The random arrangement of monomers
breaks up the regularity needed for crystallization. The next step is to cross link. The copolymer
can be cross linked using peroxides. The resulting elastomer is ethylene-propylene rubber (EPR or
EPM). An alternative is the approach taken with butyl rubber to copolymerize with a third diene
monomer, such as isoprene, and cross link at the added double bond sites. The resulting elastomer
is called ethylene-propylene-diene rubber (EPDM).
If all, or most, of the hydrogens in the above olefinic elastomers are replaced by fluorine (e.g.,
replace ethylene and propylene monomers with tetrafluoroethylene and hexafluoropropylene), the
polymers still have low Tg ’s, but have much higher temperature resistance and improved solvent
resistance. When these polymers are lightly cross linked they produce fluoroelastomers. Common
applications are hoses, O-rings, gaskets, tubing, and hydraulics.
Silicone elastomers are made from polymers derived from polysiloxanes with repeat unit
CH3
(O Si )
CH3
They have good low-temperature properties, good electrical properties, good resistance to solvents
(e.g., oil), and weather well. Cross linking is done by compolymerizing with silanes that have
functional groups or with peroxides.
An alternative to chemical cross linking is to prevent flow by physical cross links. Two types of
physical cross links are shown in Fig. 4.6. The top of the figure shows two entangled polymers
being pulled apart. As long as the chains do not break, this arrangement is an effective cross link
that will prevent flow. In real polymers, one does not pull individual molecules, but the result is
similar if the molecular weight is sufficiently high. Given enough time, such entanglements will
unravel allowing flow. On time scales much shorter that this time, the polymer will act like an
elastomer. In fact all amorphous polymers have a region above Tg up to some higher temperature
4.5. MAKING ELASTOMERS 71
Figure 4.6: The top shows two polymer molecules entangles. A short time scales this molecules will not
pull apart and the entanglement will act like a cross link. The bottom shows a block copolymer with flexible
blocks and semicrystalline blocks. The semicrystalline blocks can organize to create regions that act like
cross links.
with elastomeric properties known at the “rubbery plateau.” The rubbery plateau gets longer
as the molecular weight gets higher. Thus any high molecular weight, amorphous polymer with
Tg below room temperature, will have some elastomeric properties or some temperature and time
range without adding chemical cross links.
The bottom half of Fig. 4.6 shows a different type of physical cross linking and an important
type in the polymer industry. This schematic diagram is for a block copolymer having soft segments
(low Tg amorphous polymer) and hard segments (a semicystalline polymer). When copolymerized
into a block copolymer, the hard segments can segregate in to crystalline regions that act as cross
links for the remaining soft material. It is crucial that the two blocks are from incompatible
polymers such that they segregate into separate regions when solidified. If this polymer is heated
above the melting point of the crystalline region, the cross links will melt and the polymer will flow.
Thus, there elastomers are known as thermoplastic elastomers. When heated then can be molded
72 CHAPTER 4. RUBBER ELASTICITY
or melt spun into fibers. When they cool down, the cross links form again to make an elastomer.
On example is Lycra
R
spandex fibers.
Problems
4–1. a. Give three characteristics that a polymer must have for it to have elastomeric properties
at room temperature
b. For each of the characteristics listed in part a, give a physical explanation of why it is
needed for elastomeric properties.
4–2. A rubber consists of a cross-linked network of chains with the molecular weight between cross
links equal to Mc = 15,000 g/mol. The density of the specimen is 0.92 g/cm3 .
4–3. Polyethylene (PE) is highly crystalline and not elastomeric at room temperature. By copoly-
merizing with two other monomers and further processing it can be converted into an elas-
tomeric product (olefinic rubbers).
a. Describe two co-monomers and the further processing that can be used to convert PE into
olefinic rubber. Explain the reasons for each co-monomer and for the extra processing.
a. If the resulting elastomer is found to have a shear modulus of 100 kPa at 25◦ C and a
density of 0.95 g/cm3 , find the molecular weight between cross links and the cross link
density of the polymer.
4–4. Imagine an elastomer subjected to biaxial loading in the x and y directions such that λx =
λy = λ. Find the stress-elongation curve and compare to the result for unaxial loading.
Chapter 5
AMORPHOUS POLYMERS
5.1 Introduction
Polymer solids
73
74 CHAPTER 5. AMORPHOUS POLYMERS
Chapter 6
SEMICRYSTALLINE POLYMERS
6.1 Introduction
Polymer solids
6.3 Structures
Unit cell, lamallae, spherulites, etc.
75
76 CHAPTER 6. SEMICRYSTALLINE POLYMERS
Bibliography
77