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ENGINEERING 5473
POLYMER
CHARACTERIZATION
PROFESSOR JOHN A. NAIRN
SPRING 2003
TABLE OF CONTENTS
1 Introduction 1
1.1 Deﬁnitions of Terms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2 Course Goals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2 Molecular Conformations 7
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2 Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.3 Property Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.4 FreelyJointed Chain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.4.1 FreelyJointed Chain Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.4.2 Comment on FreelyJointed Chain . . . . . . . . . . . . . . . . . . . . . . . . 20
2.5 Equivalent Freely Jointed Chain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.6 Vector Analysis of Polymer Conformations . . . . . . . . . . . . . . . . . . . . . . . . 24
2.7 FreelyRotating Chain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.8 Hindered Rotating Chain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.9 More Realistic Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.10 Theta (Θ) Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.11 Rotational Isomeric State Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3 Polymer Molecular Weight 43
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.2 Number Average Molecular Weight . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.3 Weight Average Molecular Weight . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.4 Other Average Molecular Weights . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.5 A Distribution of Molecular Weights . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.6 Most Probable Molecular Weight Distribution . . . . . . . . . . . . . . . . . . . . . . 48
4 Polymer Solutions 57
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.2 Solution Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.3 Physical Origins of Entropy of Mixing . . . . . . . . . . . . . . . . . . . . . . . . . . 61
4.4 FloryHuggins Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
5 Colligative Properties 65
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
2
5.2 Boiling Point Elevation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
5.3 Freezing Point Depression . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
5.4 Osmotic Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
5.5 Practical Aspects of Osmotic Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . 71
5.6 Experimental Aspects of Membrane Osmometry . . . . . . . . . . . . . . . . . . . . 74
6 Viscosity 77
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
6.2 Viscosity and Viscosity Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . 77
6.3 Viscosity Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
6.4 Viscosity Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
6.4.1 Polydisperse Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
6.4.2 Experimental Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
6.5 Viscosity Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
7 Light Scattering 89
7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
7.2 Rayleigh Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
7.3 Ideal Polymer Solutions with Small Particles . . . . . . . . . . . . . . . . . . . . . . 93
7.4 NonIdeal Polymer Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
7.5 Large particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
7.6 Light Scattering Data Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
8 Miscellaneous Molecular Weight Methods 101
8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
8.2 Gel Phase Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
8.3 Field Flow Fractionation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
8.4 End Group Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
8.5 Ultracentrifugation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
8.6 Insoluble Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
9 Thermal Analysis 109
9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
9.2 Thermal Transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
9.3 Thermal Analysis of Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
10 Dilatometry 115
10.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
10.2 Amorphous Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
0
10.2.1 Pressure Dependence of T
g
. . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
10.3 Semicrystalline Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
10.3.1 Pressure Dependence of T
m
. . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
10.4 Experimental Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
10.5 Dilatometry Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
11 Diﬀerential Scanning Calorimetry 127
11.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
11.2 Diﬀerential Scanning Calorimetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
11.3 Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
11.4 Results with Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
11.4.1 Heating of Semicrystalline Polymers . . . . . . . . . . . . . . . . . . . . . . . 130
11.4.2 Cooling of Semicrystalline Polymers . . . . . . . . . . . . . . . . . . . . . . . 137
11.4.3 Amorphous Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
11.5 DSC Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
11.6 Thermogravimetric Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
12 Mechanical Properties 141
12.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
12.2 Simple Elasticity Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
12.3 StressStrain Curves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
12.3.1 StressStrain Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
12.3.2 Uses of StressStrain Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 149
12.3.3 Uniaxial Compression Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
12.3.4 Shear Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
12.3.5 Hydrostatic Compression . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
12.4 Fracture and Impact Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
12.5 Time Dependence or Viscoelasticity . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
12.5.1 Creep Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
12.5.2 FreeVolume Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
12.5.3 Stress Relaxation Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . 158
12.5.4 Dynamic Mechanical Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
Chapter 1
Introduction
The subject of polymer characterization covers the techniques that are used to give us information
about polymer materials. The type of information we can use includes thermal properties, me
chanical properties, microstructural information, time dependence of properties, and much more.
This information is obtained with a variety of experimental and theoretical approaches. In these
notes we will discuss many polymer characterization techniques. Perhaps more importantly we will
discuss the theory behind those techniques. Understanding the theory behind polymer characteri
zation techniques is an essential ingredient to making correct use of those techniques. The subject
of polymer 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 (MS&E 3410 or equivalent).
Philosophically we choose to subdivide the ﬁeld of polymer characterization into three types of
characterization methods — theoretical characterization, macroscopic property measurement, and
spectroscopic analysis. Theoretical characterization involves the detailed description of molecular
conﬁgurations and conformations. Polymers are randomcoil molecules that can exist in a variety
of conﬁgurations and conformations. We can learn much about polymer conformations purely by
theoretical analysis. 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 tech
niques used to verify the analysis. Macroscopic property measurement is what might be referred
to as conventional polymer characterization. It involves taking a macroscopic polymer specimen
or polymer solution and doing experiments that give information about properties of the polymer.
Some of the more important properties include molecular weight, thermal properties, mechanical
properties, melt viscosity, friction and wear properties, and electrical properties. Spectroscopic
analysis is aimed at characterization on the molecular scale. Some common spectroscopic tech
niques are UVvisible absorption spectroscopy, infrared spectroscopy (IR), Raman spectroscopy,
nuclear magnetic resonance (NMR), electron spin resonance (ESR), and mass spectrometry (MS).
1
2 CHAPTER 1. INTRODUCTION
These techniques are usually aimed at getting information about the chemical structure of polymer
materials.
1.1 Deﬁnitions of Terms
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 crosslinked 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, collagen, silk, cotton, wool, and natural rubber. 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 synthetic polymers are
Polyethylene (PE): (CH
2
CH
2
)
Polystyrene (PS): (CH
2
C
¨ ¨rr
r
¨ ¨
¨
rr
H)
Polyvinyl Chloride (PVC): (CH
2
C
Cl
H)
1.1. DEFINITIONS OF TERMS 3
Polytetraﬂuoroethylene (PTFE or Teﬂon): (CF
2
CF
2
)
Polypropylene (PP): (CH
2
C
CH
3
H)
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 (CH
2
CHCl) . In PE, the repeat unit listed above is
(CH
2
CH
2
) . From a topological point of view, the PE repeat unit could be (CH
2
) , but be
cause PE is polymerized from ethylene or CH
2
CH
2
, it is common practice to call (CH
2
CH
2
)
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 start
ing 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
polymers) some atoms are lost (e.g., a molecule of water (H
2
O)) from the monomer during poly
merization 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
practice to refer to such alternately copolymers as homopolymers. A good example is Nylon
6/6. The polymerization of Nylon 6/6 is shown in Fig. 1.1. Nylon 6/6 is actually an alternating
copolymer polymerized from monomers of adipic acid and hexamethyl diamine. Although it is
a copolymer, the structure on the right side Fig. 1.1 can be viewed as the single repeat unit for
Nylon 6/6. The “6/6” in the polymer name denotes the number of carbon atoms in each of the
two monomers. The ﬁrst gives the number of carbon atoms in the amine; the second gives the
number of carbon atoms in the acid. Besides Nylon 6/6, other commercial nylons include Nylon
6/12, Nylon 6/11, Nylon 6/9 and Nylon 4/6. Some nylons are followed by a single number as in
Nylon 6. These nylons are made from ωamino acids (a methylene chain with an amine group on
one end and an acid group on the other) and the single number is the number of carbon atoms in
the ωamino acid. Some examples of such commercial nylons are Nylon 6 and Nylon 11.
4 CHAPTER 1. INTRODUCTION
HO–C–(CH
2
)
4
–C–OH + H
2
N–(CH
2
)
6
–NH
2
—(N–C–(CH
2
)
4
–C–N–(CH
2
)
6
)—
O O
O O
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 –
Linear
Branched
CrossLinked
– A – A – A – A – A – A – A – A –
A – A – A
A
A
A
A
– A – A – A – A – A – A – A – A –
– A – A – A – A – A – A – A – A –
A
A
A
A
Figure 1.2: A schematic view of monomer “A” connected to make a linear, a branched, or a crosslinked
polymer.
The repeat unit can also be called the structural unit. Structural units can be connected to
make linear, branched, or crosslinked polymers. Crosslinked polymers are also called network
polymers. Figure 1.2 shows the various ways in which structural units “A” can be connected to
make a polymer molecule. The way in which structural units are connected has a profound eﬀect
on polymer properties such as toughness, viscosity, glass transition temperature, etc..
Besides the way the units are connected, the total number of units also has a profound eﬀect
on polymer properties. The more units that are connected, the higher the molecular weight. A
polymer must have a high molecular weight before it has useful properties, especially mechanical
properties. The number of monomers, or sometimes the number of repeat units, in a polymer is
called the degree of polymerization.
Polymers are often characterized as being thermoplastic or thermoset. A thermoplastic polymer
will soften as it is heated (i.e., thermal treatment leads to plastic ﬂow). This behavior has important
1.2. COURSE GOALS 5
implications about processing such polymers. Thermoplastic polymers can usually be molded and
are typically used as injection molding resins. In brief, the polymer is heated until is softens and
then is injected into a mold where it cools and solidiﬁes into a solid part. Thermoplastic behavior is
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 crosslinked 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
highmodulus and highstrength ﬁbers by a solution, ﬁberspinning method.
1.2 Course Goals
These notes will emphasize polymer characterization of high molecular weight synthetic polymers.
The focus on high molecular weight is because high molecular weight is a prerequisite 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.
The ultimate goal of polymer characterization is to understand polymer properties, how those
properties relate to polymer structure, and how they relate to potential polymer applications.
6 CHAPTER 1. INTRODUCTION
Someone well versed in polymer characterization should be able to take any polymer and decide
whether or not that polymer is suitable for some contemplated application. A longrange goal of
polymer 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 crosslinked 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 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
Molecular Conformations
2.1 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. 2.1. 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. 2.2 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 2.1: Two molecules with diﬀerent conformations. These two molecules can be made identical with
a rotation of 180
◦
about the central single bond.
7
8 CHAPTER 2. MOLECULAR CONFORMATIONS
Cl
H
Cl
H
Cl
H
H
Cl
trans
cis
Figure 2.2: 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
glasstransition temperature.
Figure 2.3 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 endtoend 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),
2.2. NOMENCLATURE 9
Figure 2.3: 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.
this type of polymer characterization is theoretical characterization.
2.2 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 1.53
˚
A long. For simplicity we will restrict ourselves
to polymers with constant bond lengths. A generalization to nonconstant 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 2.4 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
10 CHAPTER 2. MOLECULAR CONFORMATIONS
z
y
x
θ
φ
Figure 2.4: Deﬁnitions of the polar angle θ and the azimuthal angle φ for any vector in a righthanded
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, θ
i
and φ
i
, 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.
2.3. PROPERTY CALCULATION 11
φ=0˚
θ
i+1
φ=180˚
bond i+1
bond i
bond i1
x
z
l
φ
i+1
Figure 2.5: 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. 2.5, 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. 2.5). 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 θ
i+1
sweep out the cone illustrated in Fig. 2.5.
The azimuthal angle (φ) for bond i +1 is the counterclockwise 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 xyz coordinates a righthanded coordinate system.
2.3 Property Calculation
The goal of theoretical characterization of polymers is to be able to predict certain properties of
those polymers. When a polymer exists in a single conformation, the task is simple — we merely
calculate the property for that conformation. Random coil polymers, however, can exist in many
diﬀerent conformations. An observed macroscopic property of an ensemble of polymer chains will
be an average value of that property over the range of polymer conformations. We denote the
average value of any property over an ensemble of random coil polymer chains as Property.
12 CHAPTER 2. MOLECULAR CONFORMATIONS
The way to ﬁnd Property 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
Property =
i
Property(conf i) ×Probablity(conf i) (2.1)
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
pips =
6
i
i ×
1
6
=
1
6
+
2
6
+
3
6
+
4
6
+
5
6
+
6
6
= 3.5 (2.2)
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
Property ≈
1
N
Property(sample i) (2.3)
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
2.4. FREELYJOINTED CHAIN 13
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.
2.4 FreelyJointed Chain
In a freelyjointed chain all 2(n −1) angular variables are allowed to assume any values with equal
probability. In others words the direction of any bond is equally likely to occur in any of the
possible directions of space — the joints at each bond thus move freely to allow all these possible
orientations.
Let’s begin with one particular property — the polymer size. Size can be characterized by
calculating the endtoend distance, r, or the radius of gyration, s. As an average property, these
properties are usually calculated as a root mean squared endtoend distance (or a root mean
squared radius of gyration). Endtoend distance is the distance from the beginning of the chain to
the end of the chain (see Fig. 2.6). The root mean squared endtoend distance is the square root
of the average of the squared endtoend distances:
rms r =
_
r
2
=
¸
¸
¸
_
1
N
N
i=1
r
2
i
(2.4)
where N is the total number of possible conformations and r
i
is the endtoend 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:
rms s =
_
s
2
=
¸
¸
¸
_
1
N
N
i=1
s
2
i
(2.5)
where s
i
is the radius of gyration for conformation i.
14 CHAPTER 2. MOLECULAR CONFORMATIONS
r
←
Figure 2.6: The length of a vector (r) from the ﬁrst atom to the last atom on a linear polymer chain is
the endtoend distance for that polymer conformation. This ﬁgure shows the endtoend vector.
l
l cos θ
θ
Figure 2.7: The projection of a bond of length l onto the z axis is l
z
= l cos θ where θ is the angle between
the bond and the z axis.
2.4.1 FreelyJointed Chain Analysis
We begin our analysis of the freelyjointed 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 l
z
= l cos θ (see Fig. 2.7) where θ is the angle between the
bond direction and the zaxis direction. θ is also the polar angle in the coordinate system deﬁned
in Fig. 2.5 in which the z axis is along the previous bond. The average value of l
z
is found by
integrating over all possible bond projections or all possible bond directions:
l
z
=
_
l
−l
l
z
p(l
z
)dl
z
=
_ _
l cos θ p(θ, φ)dS (2.6)
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 freelyjointed chain all angles are all equally likely and therefore p(θ, φ) must be a constant;
2.4. FREELYJOINTED CHAIN 15
z
x
y
dφ
dθ
r
r sin θ
dS = r
2
sin θ dθ dφ
r sin θ dφ
r dθ
Figure 2.8: 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 = r
2
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 r
2
sin θdθdφ (see Fig. 2.8) we can integrate
over the unit sphere (r = 1) to get:
1 = k
_
2π
0
dφ
_
π
0
dθsinθ = 4πk (2.7)
or
k = p(θ, φ) =
1
4π
(2.8)
We can now insert p(θ, φ) into the expression for l
z
and integrate. The result is
l
z
=
_
2π
0
dφ
_
π
0
dθ
l cos θ sin θ
4π
=
l
2
_
π
0
cos θ sin θdθ = 0 (2.9)
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 rootmeansquared endtoend
16 CHAPTER 2. 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:
l
2
z
=
_
2π
0
dφ
_
π
0
dθ
l
2
cos
2
θ sin θ
4π
=
l
2
2
_
π
0
cos
2
θ sin θdθ (2.10)
=
l
2
2
_
−
1
3
cos
2
θ
¸
¸
¸
¸
π
0
_
=
l
2
3
(2.11)
The root mean squared distance per step is:
_
l
2
z
=
l
√
3
(2.12)
The above result gives as an average jump size per step, but we are concerned with the total
z axis rootmeansquared endtoend distance. The solution to this problem is approached by
considering a set of typical jump directions. For a chain of n bonds, some of the bonds will point in
the positive z direction and some will point in the negative z direction. If n is large, the root mean
squared length of all positive jumps will be the same as that of all negative jumps and each will be
equal to the average of all jumps. We let n
+
be the total number of jumps in the positive direction
and n
−
be the total number of jumps in the negative direction. Then the rootmeansquared
distance traveled in the z direction, denoted by z, is
z = (n
+
−n
−
)
_
l
2
z
= (n
+
−n
−
)
l
√
3
(2.13)
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:
W(z)dz =
1
√
2πσ
2
e
−z
2
2σ
2
dz =
β
√
π
e
−β
2
z
2
dz (2.14)
where σ is the standard deviation in zdirection distance and the term β is deﬁned in terms of
standard deviation by
β =
1
√
2σ
2
(2.15)
The freelyjointed chain problem is solved if we can ﬁnd the standard deviation in zdirection
distance. For a single step the variance, or the standard deviation squared, follows simply from the
formula for variance:
σ
2
1
= l
2
z
−l
z
2
= l
2
z
(2.16)
2.4. FREELYJOINTED CHAIN 17
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
= nσ
2
1
= nl
2
z
(2.17)
Substituting the above result for l
2
z
gives
β =
1
_
2nl
2
z
=
_
3
2nl
2
(2.18)
An alternate route to ﬁnding β is to ﬁnd the variance by integration (i.e., ﬁnd the average value
of z
2
and subtract the square of the average value of z, which we know to be zero). The result is
z
2
n
= l
2
z
=
λ
2
3
=
1
n
_
∞
−∞
z
2
W(z)dz =
1
2nβ
2
(2.19)
Solving for β again gives
β =
_
3
2nl
2
(2.20)
The expression for β together with the Gaussian distribution function give the distribution
function for chain length in one direction. Now we need to solve the threedimensional problem.
Because the chain is freely jointed, the three axes are independent of each other. From probability
theory, the probability that a given polymer chain jumps distances of x, y, and z in each of the three
Cartesian directions is the product of the probabilities for each of the axes considered separately.
The probability that a chain has an endtoend distance characterized by a vector (x, y, z) is thus
W(x, y, z)dxdy dz = W(x)W(y)W(z)dxdy dz (2.21)
Because the analysis for W(z)dz given above applies equally well to the x and y directions, we have
W(x, y, z)dxdy dz =
_
β
√
π
_
3
e
−β
2
r
2
dxdy dz (2.22)
where r
2
= x
2
+ 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)dxdy dz gives the probability that a chain’s endtoend 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 dxdy dz (see Fig. 2.9). One dimension of
W(x, y, z)dxdy dz is plotted in Fig. 2.9. 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)dxdy dz solves the freelyjointed 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 endtoend 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
18 CHAPTER 2. MOLECULAR CONFORMATIONS
z
y
x
dV = dx dy dz
βr
3 2 1 0 1 2 3
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Figure 2.9: 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 onedimensional plot of W(x, y, z)dxdy dz.
of width dr where
_
x
2
+y
2
+z
2
is between r and r + dr. The volume element of constant r is
a spherical shell as shown in Fig. 2.10. Integrating over this volume element yields a probability
distribution in terms of the endtoend distance r:
W(r)dr =
_
V
W(x, y, z)dxdy dz =
_
β
√
π
_
3
4πr
2
e
−β
2
r
2
dr (2.23)
This type of distribution function is called a radial distribution function.
Figure 2.11 schematically plots the endtoend 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, r
max
, occurs at
r
max
=
1
β
= l
_
2n
3
= 0.82l
√
n (2.24)
The average value of r, r, is found by integrating W(r)dr:
r =
_
∞
0
rW(r)dr =
2
β
√
π
= l
_
8n
3π
= 0.92l
√
n (2.25)
Likewise, the meansquared value of r, r
2
, is
r
2
=
_
∞
0
r
2
W(r)dr =
3
2β
2
= l
2
n (2.26)
and the root mean squared endtoend distance is
_
r
2
= l
√
n (2.27)
2.4. FREELYJOINTED CHAIN 19
z
y
x
← ←
r + dr
←
r
Shell of
width dr
Figure 2.10: Cross section of a spherical shell between radii of r and r +dr.
length (units of l √n)
W
(
r
)
d
r
0.0 0.5 1.0 1.5 2.0 2.5 3.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
r
max
= 0.82 l √n
<r> = 0.92 l √n
<r
2
> = l √n
√
Figure 2.11: A typical plot of W(r)dr. The key values r
max
, average r or r, and rootmeansquared r
are indicated on the ﬁgure.
20 CHAPTER 2. MOLECULAR CONFORMATIONS
The above key values are indicated in Fig. 2.11. For constant l and n, they always rank in the
order r
max
< r < r
2
.
The variance in the endtoend distance can be found from the mean and meansquared end
toend distances:
σ
2
= r
2
−r
2
=
3
2β
2
−
4
β
2
π
=
0.23
β
2
= 0.15nl
2
(2.28)
From this results, the coeﬃcient of variation (standard deviation divided by the mean) is
CV =
σ
r
= 42% (2.29)
This result can be characterized as a fairly large coeﬃcient of variation.
2.4.2 Comment on FreelyJointed Chain
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
standard deviation (σ =
_
nl
2
z
). The ﬁnal result predicts that the rootmeansquared endtoend
distance is
_
r
2
= l
√
n (2.30)
In other words the root mean squared endtoend 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 endtoend 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 endtoend distance is linear in bond length.
The dependence of rootmeansquared endtoend distance on the square root of the number of
bonds is a profound, or at least a nontrivial, 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 twodimensional random walks
we would ﬁnd the same result. The rootmeansquared endtoend distance is
_
r
2
= l
√
n (2.31)
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.
2.4. FREELYJOINTED CHAIN 21
Walk to the right
Walk to the left
...
...
Figure 2.12: The only two possible onedimensional, selfavoiding random walks.
To anticipate a future result that does alter the random walk nature of polymers, we consider
selfavoiding random walks. In selfavoiding 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 selfavoiding random walk is a better model for a polymer chain than the completely random
walk discussed previously. A selfavoiding 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 threedimensional selfavoiding random walks is not possible.
Onedimensional, selfavoiding random walks, however, are trivial to analyze. As shown in Fig. 2.12
there are only two possible onedimensional, selfavoiding random walks. A onedimensional 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 rootmeansquared endtoend distance for a onedimensional,
selfavoiding random walk is
_
r
2
= nl (2.32)
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 threedimensional random walks, the eﬀect of imposing self avoiding characteristics
will be less dramatic. A onedimensional, selfavoiding, 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 threedimensional, selfavoiding random walks will not restricted as much. Some
steps will be inﬂuenced by selfavoiding requirements, but most will have other options than can
be reached by random chance. Without proof, we state that the endtoend distance for two and
threedimensional 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 selfavoiding random
22 CHAPTER 2. MOLECULAR CONFORMATIONS
walks in which every step is determined by the selfavoiding requirement (power of 1.0). The
former extreme is the random walk result from above; the later extreme is the onedimensional,
selfavoiding 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 r
max
= 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
W(r)dr = (Const)4πr
2
exp
_
−β
2
r
2
_
1 +
3
10
_
r
r
max
_
2
+. . .
__
dr (2.33)
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
up to f times larger than the rootmeansquared endtoend distance (i.e., good for r ≤ f
_
r
2
)
as long as
3
10
_
f
_
r
2
r
max
_
2
=
3f
2
10n
< 0.01 or f =
_
n
30
(2.34)
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 = r
max
= 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 endtoend distance. The upper limit in r for small corrections is fl
√
n where l
√
n is the
root mean squared endtoend distance. From above, the standard deviation in endtoend distance
is 0.15l
√
n. Therefore the upper limit in r for small corrections is
fl
√
n −l
√
n
0.15l
√
n
=
_
n
30
−1
0.15
(2.35)
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
2.5. EQUIVALENT FREELY JOINTED CHAIN 23
Figure 2.13: The thin lines are a real polymer chain of n bonds. The thick lines are the superposed
equivalent freelyjointed chain of n
= 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.
2.5 Equivalent Freely Jointed Chain
Real polymers are not freely jointed; the bond directions θ and φ are not free but are restricted
by local environment to be biased towards speciﬁc values. The major restrictions are caused by
nearby bonds. In other words, the conformation of any bond is correlated with the conformations
of nearby bonds. As the distance between any two bonds increases, the correlation decreases with
the conformations of distant bonds eventually becoming uncorrelated. Say that it takes m bonds
for the correlation to drop to zero and then construct from an n bond chain an n
bond chain
with n
= n/m. Let the average length of each new bond be l
which will be proportional to l (or
l
= kl). We call the new chain of n
bonds of average length l
the equivalent freelyjointed chain
for the original n bond chain. An example equivalent freelyjointed chain is shown in Fig. 2.13.
Because the bond conformations are uncorrelated over long distances, the random walk steps
in this new chain are freelyjointed. Using the freelyjointed chain result the rootmeansquared
endtoend distance is
_
r
2
= l
√
n
= l
√
Cn (2.36)
where
C =
k
√
m
(2.37)
By using the equivalent freelyjointed chain, we have shown that the endtoend distance of a
realistic chain is proportional to l
√
n. The proportionality constant is
√
C. C is normally greater
24 CHAPTER 2. 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
C =
r
2
nl
2
(2.38)
In the freelyjointed chain, C = 1. In real polymers the characteristic ratio is a function of n or
the number of bonds and is usually greater than 1. It is customary to write the bonddependent
characteristic ratio as C
n
. In relatively ideal polymers C
n
approaches a limiting constant value for
large n. The value of C
n
at large n for such polymers characterizes the random coil nature of that
polymer. Low values of C
n
correspond to tightly coiled polymers and high values of C
n
correspond
to polymers that are loosely coiled or extended.
In real polymers, selfavoiding requirements or excluded volume eﬀects, to be described latter,
cause C
n
to increase without bound as n increases without bound. A scaling law derived by
deGennes states that for large n, C
n
increases in proportion to n
0.2
. Thus we have
C
n
=
r
2
nl
2
∝ n
0.2
(2.39)
or
_
r
2
∝ ln
0.6
(2.40)
This result agrees with the previous discussion of selfavoiding random walks which claimed that
the powerlaw 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 selfavoiding requirements).
Our discussion on the equivalent freelyjointed chain shows that any real polymer can be reduced
to any expression for endtoend 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.
2.6 Vector Analysis of Polymer Conformations
We will ﬁnd it useful to develop an alternate approach to the analysis of endtoend 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:
r =
n
i=1
u
i
(2.41)
2.6. VECTOR ANALYSIS OF POLYMER CONFORMATIONS 25
The mean squared endtoend distance is
r
2
= r · r =
n
i=1
u
i
·
n
j=1
u
j
(2.42)
Expanding this expression for a polymer chain with a constant bond length, i, results in
r
2
=
n
i=1
u
i
· u
i
+ 2
i<j
u
i
· u
j
(2.43)
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
r
2
= nl
2
+ 2l
2
i<j
cos θ
ij
(2.44)
where θ
ij
is the angle between the vectors along bond j and along bond i. If vector j is equal to
i + 1 (i.e., the bond next to bond i) then θ
ij
is the supplement of the bond angle between bonds i
and i + 1.
For the freelyjointed chain, the bond directions are uncorrelated and cos θ
ij
is zero which
yields
_
r
2
= 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 rootmeansquared endtoend distance. For more complicated models, we will
need to evaluate the term cos θ
ij
.
We can use a vector analysis to investigate the relation between endtoend distance and radius
of gyration  s. In vector notation, we can write an expression for s
2
in which r
i
is the location of
the i
th
atom along the polymer chain and z is the location of the center of mass:
s
2
=
1
n
i
( r
i
−z) · ( r
i
−z) (2.45)
Expanding this sum results in
ns
2
=
i
r
2
i
+nz
2
−2z ·
i
r
i
(2.46)
where r
i
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
z =
1
n
i
r
i
or
i
r
i
= nz (2.47)
Substituting this expression in to the above results gives
ns
2
=
i
r
2
i
−nz
2
=
i
r
2
i
−n(z · z) =
i
r
2
i
−
1
n
i
j
r
i
· r
j
(2.48)
26 CHAPTER 2. MOLECULAR CONFORMATIONS
r
i
r
ij
r
j
r
ij
2
= r
i
2
+ r
j
2
 2 r
i
r
j
cos θ
Figure 2.14: 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. 2.14. By the cosine law
the length of the vector r
ij
connecting the ends of vectors r
i
and r
j
is
r
2
ij
= r
2
i
+r
2
j
−2r
i
r
j
cos θ = r
2
i
+r
2
j
−2 r
i
· r
j
(2.49)
Solving for r
i
· r
j
gives
r
i
· r
j
=
r
2
i
+r
2
j
−r
2
ij
2
(2.50)
The expression for the radius of gyration then simpliﬁes to:
s
2
=
1
2n
2
j
i
r
2
ij
=
1
n
2
j
i<j
r
2
ij
(2.51)
In this step we made use of symmetry (r
ij
= r
ji
) and the fact that r
ii
= 0.
Because the vectors r
i
are the coordinates of the atoms in the polymer chain, the distance r
ij
is the endtoend distance for a subpolymer chain of j −i bonds. By the discussion in the section
on the equivalent freelyjointed chain, we can write this distance as
r
2
ij
= C(j −i)l
2
(2.52)
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:
s
2
=
Cl
2
n
2
n
j=1
j−1
i=1
i =
Cl
2
n
2
n
j=1
j(j −1)
2
≈
Cl
2
2n
2
n
j=1
j
2
=
Cl
2
2n
2
n(n + 1)(2n + 1)
6
(2.53)
For large polymer chains (large n) this result simpliﬁes to
_
s
2
=
_
Cnl
2
6
=
_
r
2
6
(2.54)
We conclude that whenever r
2
= Cnl
2
for a polymer, that the radius of gyration is directly
proportional to (and smaller than) the endtoend distance. This result holds for large molecules
2.7. FREELYROTATING CHAIN 27
when C
n
is independent of n. An important corollary to this result is that everything we learn
while studying the endtoend distance also applies to the radius of gyration. The reverse is also
true. Any analysis or experiments that give us information about the radius of gyration also give
us information about the endtoend distance.
The approximations used to relate radius of gyration to endtoend distance can be understood
using a matrix representation. Using the equivalent freelyjointed chain approximation, the radius
of gyration squared is the sum of all terms above the diagonal of the following matrix:
_
_
_
_
_
_
_
_
_
_
_
_
0 Cl
2
2Cl
2
3Cl
2
4Cl
2
. . .
− 0 Cl
2
2Cl
2
3Cl
2
. . .
− − 0 Cl
2
2Cl
2
. . .
− − − 0 Cl
2
. . .
− − − − 0 . . .
. . . . . . . . . . . . . . . . . .
_
_
_
_
_
_
_
_
_
_
_
_
(2.55)
The terms near the diagonal are random walk, longchain 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 s
2
and r
2
derived above will be accurate. In order for the derived relation, rewritten here as
r
2
s
2
= 6 (2.56)
to be accurate, the chain must be slightly larger than is required for r
2
to be equal to Cnl
2
.
The relation will be inaccurate for short chains or for chains that are not random walk coils (e.g.,
extended chain polymers).
2.7 FreelyRotating Chain
Commonly the bond angles in polymers are ﬁxed or narrowly ﬁxed to constant values. For example,
in polyethylene the bonds angles are all close to 112
◦
. It takes much more energy to distort bond
angles than it does to induce rotations about single bonds. We therefore consider a random walk
where all bond angles, θ
i
, are constant and equal to one value θ. The more easily moved dihedral
or rotational angles are considered to all be equally likely. Thus there is free rotation about each
bond and hence we call this model the “freelyrotating chain” model. The conformation of a given
chain is reduced to specifying the dihedral angles for n−1 bonds (all bonds except the ﬁrst bond).
To analyze the freelyrotating chain we use the vector approach outlined in the previous section.
By taking successive projections of one bond onto another, we can show (See Flory book) that
cos θ
ij
= cos
m
θ
where m = j − i where θ
= π − θ is the supplement of the ﬁxed bond angle.
28 CHAPTER 2. MOLECULAR CONFORMATIONS
The resulting vector analysis becomes
r
2
= nl
2
+ 2l
2
i<j
cos
j−i
θ
(2.57)
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
θ
:
l
2
×
_
_
_
_
_
_
_
1 cos θ
cos
2
θ
cos
3
θ
. . . cos
n−1
θ
cos θ
1 cos θ
cos
2
θ
. . . cos
n−2
θ
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
cos
n−1
θ
cos
n−2
θ
. . . cos
2
θ
cos θ
1
_
_
_
_
_
_
_
(2.58)
The n diagonal terms sum to n which give the ﬁrst term (nl
2
) in the r
2
expression. Writing out
the required terms for the summation term by inspection of this matrix gives
r
2
= nl
2
+ 2l
2
_
(n −1) cos θ
+ (n −2) cos
2
θ
+. . . + (n −(n −1)) cos
n−1
θ
¸
(2.59)
which can be written as
r
2
= nl
2
+ 2l
2
n−1
i=1
(n −i) cos
i
θ
(2.60)
We rewrite this summation in simpler terms by letting x = cosθ
:
r
2
= nl
2
+ 2l
2
(nS
1
−xS
2
) (2.61)
where
S
1
=
n−1
i=1
x
i
and S
2
=
n−1
i=1
ix
i−1
(2.62)
The terms S
1
and S
2
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 S
1
has the well known result
S
1
≈
∞
i=1
x
i
= x
_
1 +x +x
2
+x
3
+. . .
_
=
x
1 −x
(2.63)
For S
2
, we use a trick by noticing that
S
2
=
d
dx
n−1
i=1
x
i
=
dS
1
dx
(2.64)
For large n we thus have
S
2
≈
d
_
x
1−x
_
dx
=
1
(1 −x)
2
(2.65)
2.8. HINDERED ROTATING CHAIN 29
Substituting S
1
and S
2
into the expression for r
2
gives
r
2
= nl
2
+ 2l
2
_
nx
1 −x
−
x
(1 −x)
2
_
(2.66)
For large n, the second term in the brackets quickly becomes negligible and we have
r
2
= nl
2
+
2nl
2
x
1 −x
= nl
2
1 +x
1 −x
(2.67)
Finally we substitute for x and note that cos θ = −cos θ
(where θ is the bond angle and θ
= π −θ
is the supplement of the bond angle). We get
r
2
= nl
2
1 −cos θ
1 + cos θ
(2.68)
The rootmeansquared endtoend distance for large, freelyrotation chains is
_
r
2
= l
√
n
_
1 −cos θ
1 + cos θ
(2.69)
The characteristic ratio is
C
n
=
r
2
nl
2
=
1 −cos θ
1 + cos θ
(2.70)
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 S
1
and S
2
for any value of n and get an exact
result. The exact result gives a C
n
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 freelyrotating polyethylene chain
_
r
2
= l
√
2n (2.71)
and the characteristic ratio is C
n
= 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 C
n
= 2.20.
2.8 Hindered Rotating Chain
The dihedral angle is clearly not free to assume all possible values. Instead the angle is restricted
by steric interactions. Consider the potential energy for rotation about the central C C bond in
butane (CH
3
CH
2
CH
2
CH
3
) shown in Fig. 2.15. The rotations about the central C C bond
30 CHAPTER 2. MOLECULAR CONFORMATIONS
Rotational Angle
E
n
e
r
g
y
0 60 120 180 240 300 360
0
1
2
3
4
C
C
C
H
H
H
H
φ
Figure 2.15: 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. 2.15 is the lowest energy state. It is lowest
because the two CH
3
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
CH
3
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. 2.15) but
the CH
3
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 CH
3
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. 2.15,
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 freelyrotating chain with a more realistic hinderedrotating chain model.
Endtoend distance for a hinderedrotation chain is more diﬃcult to ﬁnd than the freely
2.9. MORE REALISTIC ANALYSIS 31
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 u
i
· u
j
, while accounting for unequal populations
of the possible rotational angles. The result is
_
r
2
= l
√
n
_
1 −cos θ
1 + cos θ
¸
1 −cos φ
1 +cos φ
(2.72)
where cos φ is the average value of the rotational angle. The characteristic ratio is
C
n
=
r
2
nl
2
=
1 −cos θ
1 + cos θ
1 −cos φ
1 +cos φ
(2.73)
Note that if this hinderedrotation chain becomes freelyrotating chain then cos φ = 0 and the
results reduce to the freelyrotating chain results.
For a detailed example, let’s consider polyethylene with l = 1.53
˚
A, n = 5000 bonds, and
θ = 112
◦
. The simplest model, the freelyjointed chain model, gives
_
r
2
(freely jointed) = 108
˚
A (2.74)
and a characteristic ratio of 1. The next most realistic model, the freelyrotating chain model, gives
_
r
2
(freely rotating) = 108
√
2.20
˚
A = 160
˚
A (2.75)
and a characteristic ration of 2.20. For the hinderedrotation chain model we need to know cos φ.
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
cos φ = −0.6 + 0.2 ×(0.5) + 0.2 ×(0.5) = −0.4 (2.76)
The endtoend distance for the hinderedrotation chain is
_
r
2
(hindered rotation) = 108
√
2.20
√
2.33
˚
A = 245
˚
A (2.77)
and the characteristic ratio is C
n
= 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.
2.9 More Realistic Analysis
We can list two general factors that inﬂuence the endtoend distance, but are not included in the
hindered rotation chain model — short range interactions and long range interactions. The next
step in our analysis is to include some, or preferable all, of these eﬀects.
32 CHAPTER 2. MOLECULAR CONFORMATIONS
We consider shortrange 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 jumpdirection 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 shortrange interactions, we will have a good model for polymer conformations
that are unperturbed by the longrange interactions described below. We will call the polymers
generated by this modiﬁed random walk or Markov chain process “unperturbed polymer conforma
tions.” The endtoend distance of these chains will be called the unperturbed endtoend distance
and will be denoted with a subscript zero — r
2
0
.
Longrange interactions are all interactions that are not shortrange interactions. To be more
speciﬁc, longrange 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 longrange 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 selfavoiding 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 endtoend distance and cause it to increase. Besides increasing
the endtoend distance, excluded volume will cause the rootmeansquared endtoend distance to
no longer be proportional to
√
n. When excluded volume eﬀects are signiﬁcant, we can assume
that r
2
is proportional to some power of n such as p (where p > 0.5):
r
2
∝ n
p
l
2
(2.78)
According to deGennes, p = 1.2 and therefore the characteristic ratio increases as n
0.2
:
C
n
=
r
2
nl
2
∝ n
0.2
(2.79)
A second longrange interaction is interactions between the polymer and the solvent. A solvent
can cause the unperturbed endtoend 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 polymersolvent interactions. A poor solvent will cause
the unperturbed endtoend distance to contract. The polymer wants to avoid the solvent and thus
will contract on itself to avoid polymersolvent interactions. In the extreme case, a poor solvent will
2.10. THETA (Θ) TEMPERATURE 33
cause the polymer to completely contract and precipitate out of solution. This extreme example of
a poor solvent is better characterized as a nonsolvent.
The last types of longrange 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 shortrange and longrange interactions we are led to split the problem of
theoretical polymer characterization into two parts. The ﬁrst part is the study of the unperturbed
endtoend distance. We plan to modify the hindered rotation chain model to correctly account for
shortrange interactions and thereby calculate the correct unperturbed endtoend distance. After
solving this problem we will consider what inﬂuence the longrange 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 longrange interactions:
_
r
2
= α
_
r
2
0
(2.80)
The solution to the longrange interaction problem is to ﬁnd α.
2.10 Theta (Θ) Temperature
We also need to consider temperature eﬀects. Temperature can aﬀect all types of interactions.
It can aﬀect shortrange interactions by inﬂuencing the relative probabilities of the various dihe
dral angles. Rotations about single bonds are inﬂuenced by the presence of thermal energy and
thus higher temperature will make it more likely to ﬁnd conformations in higherenergy rotational
angles. Temperature aﬀects longrange interactions mainly through polymersolvent interactions.
In general increasing the temperature improves solvent quality and lowering it decreases solvent
quality.
As discussed in the previous section, we will ﬁrst attempt to solve the shortrange interaction
problem. The ﬁrst problem we encounter is how do we know when we have the right answer? Real
polymers have longrange interactions and shortrange interactions. Thus real polymers have a
meansquared endtoend distance of r
2
and not r
2
0
. If we compare our theoretical analysis to
experimental results we will normally ﬁnd disagreement, regardless of whether the analysis to ﬁnd
r
2
0
was correct or not. Fortunately there is an experimental solution to this problem called the
theta (Θ) temperature. For any given polymersolvent pair, there is a speciﬁc temperature, called
the Θ temperature, for which the true endtoend distance is equal to the unperturbed endtoend
distance. Thus experiments at the Θ temperature can be used to measure r
2
0
which can be
compared to experimental predictions.
The concept of Θ temperature can be understood by considering the eﬀect of temperature
on polymersolvent interactions. In general the polymersolvent interactions for a given polymer
34 CHAPTER 2. MOLECULAR CONFORMATIONS
solvent pair is an increasing function of temperature. As the polymersolvent interaction increases
the solvent becomes a better solvent. Thus increasing temperature leads to a better solvent and to
a higher α; decreasing temperature leads to a poorer solvent and a lower α. For a given polymer
solvent pair, there will be some temperature for which α = 1. That temperature is called the theta
(Θ) temperature. At the Θ temperature r
2
= r
2
0
and experiments at the Θ temperature can
be used to measure r
2
0
.
Besides measuring r
2
0
, the Θ temperature has other useful properties. At the Θ temperature,
some physical properties (e.g., osmotic pressure) obey ideal laws up to high concentrations. Thus
simple theories for analysis of a physical property that do not account for longrange interactions
will still work well at the Θ temperature. There is an analogy between the Θ temperature and the
Boyle point of a gas. The Boyle point is the temperature where the repulsion between gas molecules
due to excluded volume is exactly compensated by their mutual attraction. At the Boyle point,
the ideal gas laws are obeyed to very high pressures. Note that conformity to ideal laws is one way
of determining the Θ temperature. The temperature can be varied until the measurements obey
ideal laws. That temperature is the Θ temperature.
Despite the advantages of the Θ temperature, we note that working in theta solvents is often
impractical. To get α down to one, you need a solvent that is suﬃciently poor. The solvent may
become so poor the precipitation becomes imminent. It is often better to work in a good solvent
and correct the results to the unperturbed results. For measurements of physical properties, this
correction involves correcting ideal laws for large molecules or longrange interactions.
2.11 Rotational Isomeric State Model
The rotational isomeric state model will be our solution to the problem of accounting for shortrange
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, l
i
, bond angles, θ
i
, and dihedral angels,
φ
i
. 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. 2.16).
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
2.11. ROTATIONAL ISOMERIC STATE MODEL 35
C
C
C
H
H
H
H
C
C
C
H
H
H
H
C
C
C
H
H
H
H
Trans Gauche  Gauche +
Figure 2.16: The three rotational isomeric states in polyethylene. The dihedral angle, φ, is deﬁned as the
angle between to white circles.
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 φ
i
, is given by a Boltzman factor:
P(φ
i
) =
e
−E(φ
i
)/RT
Z
(2.81)
where Z is a normalizing factor or the sum of the Boltzman energy factors for all possible angles:
Z =
3
i=1
e
−E(φ
i
)/RT
(2.82)
where E(φ
i
) is the energy associated with the state at dihedral angle φ
i
and the sum is over the
three possible states in Fig. 2.16 (Note: this equation can easily be generalized to more than three
rotational isomeric states) Because of shortrange interactions discussed above, this probability
factor is expected to be aﬀected by neighboring bonds. The simplest model is to assume that the
energy, E(φ
i
), 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(φ
i
φ
i−1
), which gives the conditional probability that bond
i has angle φ
i
given that the previous bond or bond i − 1 has angle φ
i−1
. By analogy with the
previous probability factor
P(φ
i
φ
i−1
) =
e
−E(φ
i−1
φ
i
)/RT
Z(φ
i−1
)
(2.83)
36 CHAPTER 2. MOLECULAR CONFORMATIONS
where Z(φ
i−1
) is a normalizing factor or the sum of the Boltzman energy factors for all angles φ
i
given that φ
i−1
is ﬁxed:
Z =
3
j=1
e
−E(φ
i−1
φ
j
)/RT
(2.84)
In these equations, E(φ
i−1
φ
i
) is the energy associated with two consecutive bonds with dihedral
angles φ
i−1
and φ
i
. 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 threestate polymer) we write can
write a weighting factor matrix as
U =
_
_
_
_
P(tt) P(g
+
t) P(g
−
t)
P(tg
+
) P(g
+
g
+
) P(g
−
g
+
)
P(tg
−
) P(g
+
g
−
) P(g
−
g
−
)
_
_
_
_
(2.85)
For example, the matrix element P(tg
+
) 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 E
g
or the extra energy associated with a gauche bond. We further
deﬁne
σ = e
−Eg/RT
(2.86)
and we can quickly derive Z(t) = 1 + 2σ and
P(tt) =
1
1 + 2σ
P(g
+
t) =
σ
1 + 2σ
P(g
−
t) =
σ
1 + 2σ
(2.87)
Z(t) appears in the denominator of each probability as a normalizing factor.
For the second row, we might just consider the energy associated with all the gauche bonds
and assume E(g
+
t) = E
g
and E(g
+
g
+
) = E(g
+
g
−
) = 2E
g
. The probabilities would become
P(tg
+
) =
σ
σ + 2σ
2
P(g
+
g
+
) =
σ
2
σ + 2σ
2
P(g
−
g
+
) =
σ
2
σ + 2σ
2
(2.88)
This simple analysis ignores an important shortrange interaction that occurs when two consecutive
bonds are g
+
g
−
or g
−
g
+
. Figure 2.17 illustrates a g
+
g
−
conformation. Two parts of the polymer
chain separated by four bonds are in close proximity which causes a large steric interaction. This
interaction is known as the pentane eﬀect and causes the energy of g
+
g
−
or g
−
g
+
conformations to
be much higher than that g
+
g
+
or g
−
g
−
conformations. If we let E
p
be the energy of the pentane
eﬀect interaction then E(g
−
g
+
) = 2E
g
+E
p
whereas E(g
+
g
+
) = 2E
g
. Deﬁning
ω = e
−Ep/RT
(2.89)
2.11. ROTATIONAL ISOMERIC STATE MODEL 37
C
C
C
C
C
Gauche 
Gauche +
Strong
Steric
Interactions
Figure 2.17: The steric interactions caused by the pentane eﬀect when two consecutive bonds are g
+
g
−
or g
−
g
+
.
we derive the conditional probabilities for the second row of U to be
P(tg
+
) =
σ
σ +σ
2
+σ
2
ω
=
1
1 +σ +σω
(2.90)
P(g
+
g
+
) =
σ
2
σ +σ
2
+σ
2
ω
=
σ
1 +σ +σω
(2.91)
P(g
−
g
+
) =
σ
2
ω
σ +σ
2
+σ
2
ω
=
σω
1 +σ +σω
(2.92)
Analyzing the third row similarly to the second row and collecting all probabilities in the matrix
we arrive at
U =
_
_
_
_
1
1+2σ
σ
1+2σ
σ
1+2σ
1
1+σ+σω
σ
1+σ+σω
σω
1+σ+σω
1
1+σ+σω
σ
1+σ+σω
σω
1+σ+σω
_
_
_
_
(2.93)
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
U =
_
_
_
_
1 σ σ
1 σ σω
1 σω σ
_
_
_
_
(2.94)
By theory and experiment, the energy terms for polyethylene are well known. The best results give
E
g
= 2100 J and E
p
= 8400 J. At 300
◦
C these lead to weighting factors of
σ = e
−2100J/RT
= 0.43 and ω = e
−8400J/RT
= 0.081 (2.95)
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)).
38 CHAPTER 2. 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 3
n−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.,
endtoend 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
Lattice
TM
discussed in class is an example of a program that can do Monte Carlo simulations using
the rotational isomeric state model. Programs like Lattice
TM
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 endtoend 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.
let v = (1,0,0) or the first bond is t
for bond=2 to number of bonds1
2.11. ROTATIONAL ISOMERIC STATE MODEL 39
let q=Uv be a vector giving the probabilities for t, g+, and g
pick a random number between 0 and q1+q2+q3
if (random number is between 0 and q1) then
next bond is t and v = (1,0,0)
else if (random number is between q1 and q2) then
next bond is g+ and v = (0,1,0)
else if(random number between q2 and q3) then
next bond is g and v = (0,0,1)
end if
if desired, check for excluded volume effects
if jump to occupied site, try another site, reject the entire
chain, or reject several previous bonds
if all sites occupied start new chain
end if
next bond
Now have set of n2 bond conformations which completely define the chain
Calculate properties (e.g. endtoend 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 Lattice
TM
calculates the following
properties:
1. Last r (endtoend distance of current chain)
2. rms r
3. r
4. rms s
5.
r
2
nl
2
— the characteristic ratio (equal to C
n
)
6.
r
2
s
2
— how close is it to 6?
7. % trans
8. Number of rejected steps
9. Relative entropy
40 CHAPTER 2. MOLECULAR CONFORMATIONS
In addition to the above calculations, Lattice
TM
can also plot many results. It can plot each
generated polymer in a threedimensional view. These stick ﬁgures give a feel for typical polymer
conformations. It can plot the distribution of endtoend distances and compare them to the radial
Gaussian function calculated for in the freelyjointed chain analysis.
There is one important aspect of Lattice
TM
and many rotational isomeric state solutions that
requires discussion. As implied by its name, Lattice
TM
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 carbonbackbone 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 oﬀlattice 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:
1. Polyethylene (see above)
2. Polytetraﬂuoroethylene (PTFE)
3. Copolymers
4. Polyoxymethylene (POM) (Delrin, Celcon, etc.)
5. Polypropylene (PP) — a vinyl polymer
Some results from these types of polymers are discussed in the Lattice
TM
manual and will be covered
in class.
Problems
2–1. The radial distribution function for the freelyjointed chain model was shown in class to be
W(r)dr =
_
β
√
π
_
3
4πr
2
e
−β
2
r
2
dr (2.96)
where
β =
_
3
2nl
2
(2.97)
Because the form of the radial distribution function even for nonfreelyjointed chains is similar
to the freelyjointed chain result (except with a diﬀerent value for β) it is worth studying this
function.
2.11. ROTATIONAL ISOMERIC STATE MODEL 41
a. Show that the maximum in W(r)dr occurs at r =
1
β
b. Show that the mean value of r is r =
2
β
√
π
.
c. Show that the average value of r
2
is r
2
=
3
2β
2
d. What is the standard deviation in r?
e. Express the answers to a through d in terms of number of bonds (n) and bond length
(l).
2–2. Pretend that linear polyethylene (PE or (CH
2
CH
2
)
n
) can be modeled as a freelyjointed
chain in which each bond is 1.53
˚
A long. Using the results from problem 21, evaluate the
following quantities:
a. How many bonds are in a 500,000 g/mole PE polymer chain?
b. What is the maximum length of the chain?
c. What is the most likely end to end distance?
d. What is the mean endtoend distance
e. What is the root mean squared endtoend distance?
f. What is the standard deviation in r?
g. Plot the radial distribution function for this polymer chain and indicate on your plot
the answers to c, d, and e.
2–3. Polymer A contains x freely jointed segments each of length l
a
and polymer B contains y
freely jointed segments each of length l
b
. One end of A is connected to one end of B to form
a two block, block copolymer.
a. What is the rootmeansquared endtoend distance of this 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 rootmeansquared endtoend distance of the random
copolymer?
2–4. How do each of the following aﬀect the radius of gyration?
a. Decreasing the molecular weight.
b. Decreasing the polymersolvent interaction.
c. Adding the eﬀects of excluded volume.
d. Reducing the hindrance to rotations about bonds.
42 CHAPTER 2. MOLECULAR CONFORMATIONS
2–5. 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
HO–C–(CH
2
)
4
–C–OH + H
2
N–(CH
2
)
6
–NH
2
—(N–C–(CH
2
)
4
–C–N–(CH
2
)
6
)—
O O
O O
H H
This polymer has N–CH
2
bonds, N–carbonyl bonds, carbonylCH
2
bonds, and CH
2
–CH
2
bonds. Explain, in general terms, how you would use the rotational isomeric state model to
calculate the characteristic ratio of Nylon 66.
Chapter 3
Polymer Molecular Weight
3.1 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 temperatures
and it must have mechanical properties suﬃcient to bear design loads.
For example, consider the property of tensile strength. Figure 3.1 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 strengthmolecular weight relation
can be approximated by the inverse relation
S = S
∞
−
A
M
(3.1)
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, M.
Polymer physical properties will be functions of the molecular weight distribution function as in
S = S
∞
−
A
F[P(M)]
(3.2)
43
44 CHAPTER 3. POLYMER MOLECULAR WEIGHT
Molecular Weight
S
t
r
e
n
g
t
h
S
∞
S = S
∞
–
A
M
Figure 3.1: A typical plot of tensile strength as a function of molecular weight.
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, M, and insensitive to other the details of the molecular
weight distribution function:
S = S
∞
−
A
M
(3.3)
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.
3.2 Number Average Molecular Weight
Consider a property which is only sensitive to the number of molecules present — a property that
is not inﬂuenced by the size of any particle in the mixture. The best example of such properties
are the colligative properties of solutions such as boiling point elevation, freezing point depression,
and osmotic pressure. For such properties, the most relevant average molecular weight is the total
3.2. NUMBER AVERAGE MOLECULAR WEIGHT 45
weight of polymer divided by the number of polymer molecules. This average molecular weight
follows the conventional deﬁnition for the mean value of any statistical quantity. In polymer science,
it is called the number average molecular weight — M
N
.
To get a formula for M
N
, we must ﬁrst realize that the molecular weight distribution is not a
continuous function of M. Rather, only discrete values of M are allowed. The possible values of M
are the various multiples of the monomer molecular weight — M
0
. By monomer molecular weight
we mean the weight per monomer that appears in the polymer chain. For condensation reactions,
for example, where molecules of water are typically lost from the monomers during reaction, we will
take M
0
as the monomer molecular weight less any weight loss due to the polymerization reaction.
The possible values of M make up a set of numbers with discrete values labeled M
i
. Let N
i
be the
number of polymers with molecular weight M
i
. Then the total weight of all polymers is
Total Weight =
∞
i=1
N
i
M
i
(3.4)
and the total number of polymer molecules is
Total Number =
∞
i=1
N
i
(3.5)
As discussed above, the number average molecular weight is
M
N
=
∞
i=1
N
i
M
i
∞
i=1
N
i
=
Total Weight
Number of Polymers
=
Weight
Polymer
(3.6)
The term N
i
/
N
i
is physically the number fraction of polymers with molecular weight M
i
. If we
denote number fraction as X
i
(i.e., mole fraction) the number average molecular weight is
M
N
=
∞
i=1
X
i
M
i
(3.7)
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 M
N
in
terms or weight fraction of polymers with molecular weight M
i
denoted as w
i
. First we note that
the concentration of polymer species i is (in weight per unit volume):
c
i
=
N
i
M
i
V
(3.8)
Inserting c
i
for N
i
M
i
and expressing N
i
in terms of c
i
results in
M
N
=
∞
i=1
c
i
∞
i=1
c
i
M
i
(3.9)
Dividing numerator and denominator by
c
i
results in
M
N
=
1
∞
i=1
w
i
M
i
(3.10)
46 CHAPTER 3. POLYMER MOLECULAR WEIGHT
where w
i
is the weight fraction of polymer i or the weight of polymer i divided by the total polymer
weight:
w
i
=
N
i
M
i
∞
i=1
N
i
M
i
=
c
i
∞
i=1
c
i
(3.11)
3.3 Weight Average Molecular Weight
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 N
i
in the
number average molecular weight formula with the weight of polymer having molecular weight i or
N
i
M
i
. The result is
M
W
=
∞
i=1
N
i
M
2
i
∞
i=1
N
i
M
i
(3.12)
By noting that N
i
M
i
/
N
i
M
i
is the weight fraction of polymer with molecular weight i, w
i
, an
alternative form for weight average molecular weight in terms of weight fractions
M
W
=
∞
i=1
w
i
M
i
(3.13)
Comparing this expression to the expression for number average molecular weight in terms of
number fraction (see Eq. (3.7)) we see that M
N
is the average M
i
weighted according to number
fractions and that M
W
is the average M
i
weighted according to weight fractions. The meanings of
their names are thus apparent.
3.4 Other Average Molecular Weights
To get M
W
from M
N
we replaced N
i
by N
i
M
i
. We can generalize this process and replace N
i
by
N
i
M
k
i
to get an average molecular weight denoted as M
k
:
M
k
=
∞
i=1
N
i
M
k+1
i
∞
i=1
N
i
M
k
i
(3.14)
Thus M
0
= M
N
, and M
1
= M
W
. Several other M
k
forms appear in experiments. Two examples
are M
2
= M
z
and M
3
= M
z+1
which are used in analysis of ultracentrifugation experiments.
One average molecular weight which does not ﬁt into the mold of M
k
is the viscosity average
molecular weight or M
v
. It is deﬁned by
M
v
=
_
∞
i=1
N
i
M
1+a
i
∞
i=1
N
i
M
i
_
1
a
(3.15)
3.5. A DISTRIBUTION OF MOLECULAR WEIGHTS 47
Molecular Weight
W
e
i
g
h
t
F
r
a
c
t
i
o
n
M
N M
v
M
W
M
z
M
z+1
Figure 3.2: A schematic plot of a distribution of molecular weights along with the rankings of the various
average molecular weights.
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 6.
For any molecular weight distribution, the various average molecular weights always rank in
the order
M
N
≤ M
v
≤ M
W
≤ M
z
≤ M
z+1
≤ M
4
≤ . . . (3.16)
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 M
N
and the other used
light scattering which yields M
W
. Until it was recognizes that M
N
= M
W
, it was diﬃcult to explain
diﬀering experimental results on the same polymer solution.
3.5 A Distribution of Molecular Weights
Schematically, a typical molecular weight distribution might appear as in Fig. 3.2. It resembles
a probability distribution curve. The various average molecular weights are indicated in their
expected rank.
The spread of any distribution function can be characterized by its standard deviation, or
equivalently by its coeﬃcient of variation. We can express the standard deviation of molecular
48 CHAPTER 3. POLYMER MOLECULAR WEIGHT
weight in terms of M
N
and M
W
. The deﬁnition of variance, σ
2
, is
σ
2
= M
2
−M
2
(3.17)
where angle brackets (e.g., M) denote conventional averaging. In terms of N
i
and M
i
the variance
is
σ
2
=
1
N
∞
i=1
N
i
M
2
i
−
_
1
N
∞
i=1
N
i
M
i
_
2
=
∞
i=1
N
i
M
2
i
∞
i=1
N
i
M
i
∞
i=1
N
i
∞
i=1
N
i
M
i
−M
N
2
(3.18)
which in terms of M
N
and M
W
is
σ
2
= M
W
M
N
−M
N
2
= M
N
2
_
M
W
M
N
−1
_
(3.19)
or the standard deviation is
σ = M
N
¸
M
W
M
N
−1 (3.20)
The coeﬃcient of variation is the mean divided by the standard deviation. Because M
N
is also the
conventional mean
C.V. =
σ
M
N
=
¸
M
W
M
N
−1 (3.21)
A key term in the coeﬃcient of variation is
M
W
M
N
. This term is known as the polydispersity
index. For the coeﬃcient of variation to be real (as it must), the polydispersity index must be
greater than or equal to one. When it is equal to one, the coeﬃcient of variation is zero which
means that the distribution is monodisperse. For all real polymers it is greater that one and the
amount that it is greater than one is a measure of the polydispersity of that polymer.
3.6 Most Probable Molecular Weight Distribution
Many condensation polymers are synthesized by the polymerization of bifunctional monomers. If
we denote two functional groups as A and B than a bifunctional monomer would have an A group
on one end and a B group on the other and be denoted A B. The polymerization reaction of
A B is
n(A B) → (A B)
n
(3.22)
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
( NH
2
) the A B monomer can polymerize to a polyamide. Flory considered the polymerization
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.
3.6. MOST PROBABLE MOLECULAR WEIGHT DISTRIBUTION 49
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 = 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) (3.23)
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) (3.24)
Continuing on by induction, the probability that the randomly selected molecule has a degree of
polymerization i is
P(i) = p
i−1
(1 −p) (3.25)
The p
i−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:
N
i
= Np
i−1
(1 −p) (3.26)
N is related to the initial number of monomers N
0
by N = N
0
(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 N
0
p. Now, in terms
of known quantities N
i
is
N
i
= N
0
p
i−1
(1 −p)
2
(3.27)
The above equation for N
i
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
N
i
for various values of p are given in Fig. 3.3. At all values of p, all molecular weights are present
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.
50 CHAPTER 3. POLYMER MOLECULAR WEIGHT
Degree of Polymerization
N
u
m
b
e
r
F
r
a
c
t
i
o
n
(
N
i
/
N
0
)
0 20 40 60 80 100
0.0000
0.0005
0.0010
0.0015
0.0020
0.0025
0.0030
0.0035
0.0040
p=0.94
p=0.98
p=0.96
Figure 3.3: 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.
A more familiar distribution function results if we consider the weight fraction of polymer with
length i. Weight fraction is deﬁned by
w
i
=
iM
0
N
i
N
0
M
0
=
iN
i
N
0
= ip
i−1
(1 −p)
2
(3.28)
where M
0
is the monomer molecular weight. When the repeat of the polymer has lower molecular
weight than the monomer, because of reaction products such as H
2
O loss due to condensation, M
0
should be the molecular weight of the monomer that makes it into the polymer. In other words, M
0
is the repeat unit molecular weight, iM
0
is the molecular weight of a polymer of length i, and N
0
M
0
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. 3.4. 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 M
N
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 N
i
) we can calculate
M
N
and M
W
. We can calculate M
N
for the most probable distribution using two methods. First
we evaluate the sums in the number average molecular weight formula:
M
N
=
∞
i=1
iM
0
N
i
∞
i=1
N
i
= M
0
(1 −p)
∞
i=1
ip
i−1
(3.29)
3.6. MOST PROBABLE MOLECULAR WEIGHT DISTRIBUTION 51
Degree of Polymerization
W
e
i
g
h
t
F
r
a
c
t
i
o
n
(
w
i
)
0 20 40 60 80 100
0.000
0.005
0.010
0.015
0.020
0.025
p=0.94
p=0.96
p=0.98
Figure 3.4: 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.
∞
i=1
ip
i−1
=
d
dp
∞
i=1
p
i
=
d
dp
_
p
1 −p
_
(3.30)
Evaluating the derivative gives
∞
i=1
ip
i−1
=
1
(1 −p)
2
(3.31)
Multiplying by M
0
(1 −p) gives
M
N
=
M
0
1 −p
(3.32)
An alternative and simpler method to M
N
is to realize that, by conservation of mass, the total
weight of material is always M
0
N
0
. From above, the total number of polymers is N
0
(1 −p). Thus
M
N
=
Total weight of polymer
Total number of polymers
=
M
0
N
0
N
0
(1 −p)
=
M
0
1 −p
(3.33)
To get M
W
for the most probable distribution we use the weight average molecular weight
formula in terms of weight fractions:
M
W
=
∞
i=1
w
i
iM
0
= M
0
(1 −p)
2
∞
i=1
i
2
p
i−1
(3.34)
52 CHAPTER 3. POLYMER MOLECULAR WEIGHT
We evaluate the sum using the trick used to ﬁnd M
N
and some additional work.
∞
i=1
i
2
p
i−1
=
d
dp
∞
i=1
ip
i
=
d
dp
_
p
∞
i=1
p
i−1
_
=
d
dp
_
p
(1 −p)
2
_
(3.35)
The last step uses the result from the M
N
calculation. Evaluating the derivative gives
∞
i=1
i
2
p
i−1
=
1 +p
(1 −p)
3
(3.36)
Multiplying by M
0
(1 −p)
2
gives the ﬁnal result:
M
W
= M
0
1 +p
1 −p
(3.37)
Combining the results for M
N
and M
W
, the polydispersity index for the most probable distri
bution is
M
W
M
N
= 1 +p (3.38)
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 M
N
and M
W
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 M
0
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
B−B) instead of from one monomer (A−B)). If the proportions are unequal and r = N
A
/N
B
< 1
then the results are diﬀerent. A more complicated analysis gives the following M
N
:
M
N
=
M
0
(1 +r)
1 +r −2rp
≈
M
0
(1 +r)
1 −r
(3.39)
3.6. MOST PROBABLE MOLECULAR WEIGHT DISTRIBUTION 53
where, as explained above, M
0
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 M
N
= ∞
r = 0.99 M
N
= 199M
0
r = 0.95 M
N
= 39M
0
r = 0.90 M
N
= 19M
0
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 M
N
. For example a 5% deviation of r from 1.00 reduces the molecular weight from inﬁnite to
39M
0
. But, 39M
0
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
3–1. Suppose you have n batches of polydisperse polymers. Let N
i,j
be the number of polymers
of type j with degree of polymerization i and M
i,j
be the molecular weight of that polymer.
The basic M
N
and M
W
equations for the total mixture of polymers now require double sums:
M
N
=
n
j=1
i
N
i,j
M
i,j
n
j=1
i
N
i,j
and M
W
=
n
j=1
i
N
i,j
M
2
i,j
n
j=1
i
N
i,j
M
i,j
(3.40)
Now, assume that the number average and weight average molecular weights of batch j are
M
Nj
and M
Wj
. and that you mix a weight w
j
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
M
N
=
w
1
+w
2
+· · · +w
n
w
1
M
N1
+
w
2
M
N2
+· · · +
wn
M
Nn
In other words, show that M
N
of the blend can be calculated from the individual M
Nj
of the components of the blend. Here M
Nj
has the usual deﬁnition of
M
Nj
=
i
N
i,j
M
i,j
i
N
i,j
(3.41)
or a sum over just the polymers of component j.
54 CHAPTER 3. POLYMER MOLECULAR WEIGHT
b Starting from the above basic weight average molecular weight deﬁnition, show that the
weight average molecular weight of the blend is
M
W
=
w
1
M
W1
+w
2
M
W2
+· · · +ω
n
M
Wn
w
1
+w
2
+· · · +w
n
In other words, show that M
W
of the blend can be calculated from the individual M
Wj
of the components of the blend. Here M
Wj
has the usual deﬁnition of
M
Wj
=
i
N
i,j
M
2
i,j
i
N
i,j
M
i,j
(3.42)
or a sum over just the polymers of component j.
3–2. Calcium stearate (Ca(OOC(CH
2
)
16
CH
3
)
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 M
N
= 15, 000 g/mol.
a. What is the M
N
of the PVC part of the compound? (Hint: use the blend M
N
result
from the previous problem.)
b. What is the M
W
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 M
W
while osmotic pressure
measures M
N
)
d. What is the highest possible M
N
for a polymer containing 3% by weight of calcium
stearate?
3–3. Consider the most probable molecular weight distribution:
a. Derive an expression for P(M) where P(M) is the probability that a randomly selected
polymer chain as molecular weight M. Express your result in terms of M (and not
degree of polymerization i).
b. What molecular weight has the maximum probability?
c. Derive an expression for w(M) where w(M) is the weight fraction of polymer that has
molecular weight M. Again, express your answer in terms of M (and not x).
d. What molecular weight has the largest weight fraction? Express your answer in terms
of the number average molecular weight.
3–4. Calculate the percentage conversion of functional groups required to obtain a polyester with
a numberaverage molecular weight of 24,000 g/mol from the monomer HO(CH
2
)
14
COOH.
3.6. MOST PROBABLE MOLECULAR WEIGHT DISTRIBUTION 55
3–5. 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 M
N
of the mixture. Assume it has a “most probable distibution” and also evaluate
M
W
.
56 CHAPTER 3. POLYMER MOLECULAR WEIGHT
Chapter 4
Polymer Solutions
4.1 Introduction
There are many reasons for studying polymer solutions. One obvious reason is to understand the
nature of those solutions. A practical reason is that polymer solutions are often used when measur
ing molecular weight. Some common molecular weight determination methods are osmotic pressure
measurements, solution viscosity, solution light scattering, and gelphase chromatography. Each of
these methods uses a polymer solution. Before discussing these or other polymer characterization
techniques, we therefore will spend some time discussing the thermodynamics of polymer solutions.
4.2 Solution Thermodynamics
Solutions are often characterized in terms of Gibbs free energy — G. G can be viewed as a
multivariable function that depends on temperature (T), pressure (P), and the number of moles
of each component (n
i
for i = 1 to number of components). By multivariable math analysis, the
diﬀerential in free energy following a change in any or all of the key variables is:
dG =
_
∂G
∂P
_
T,n
i
dP +
_
∂G
∂T
_
P,n
i
dT +
i
_
∂G
∂n
i
_
T,P,n
j
=n
i
dn
i
(4.1)
The subscripts on the partial derivatives mean that those variables are held constant while taking
the derivative. We will be using lower case n to mean moles of some component and upper case
N to mean molecules. The number of molecules N is always equal to nL where L is Avagadro’s
number.
We know some of the terms in the dG expression from conventional thermodynamics. Consider
a solution with constant composition (i.e., dn
i
= 0 for all i). The total free energy is
G = H −TS (4.2)
57
58 CHAPTER 4. POLYMER SOLUTIONS
The diﬀerential in free energy follows the well known relation
dG = V dP −SdT (4.3)
Comparing this expression to the solution results above gives
_
∂G
∂P
_
T,n
i
= V and
_
∂G
∂T
_
P,n
i
= −S (4.4)
We do not have a similar result for ∂G/∂n
i
. Instead ∂G/∂n
i
is given a name; it is called the
chemical potential and denoted by µ
i
or G
i
. Speciﬁcally:
_
∂G
∂n
i
_
T,P,n
j
=n
i
= µ
i
= G
i
(4.5)
Using these new results, the diﬀerential in G for a solution becomes
dG = V dP −SdT +
i
µ
i
dn
i
(4.6)
Next we consider the change in free energy upon mixing two components (A and B) at constant
temperature and pressure (dP = dT = 0). Only the chemical potential terms cause a change in G.
The diﬀerential form reduces to
dG = µ
A
dn
A
+µ
B
dn
B
(4.7)
Integrating dG from 0 to n
A
and from 0 to n
B
which corresponds to the mixing process gives
G = µ
A
n
A
+µ
B
n
B
(4.8)
If instead of mixing A and B we consider pure components A and B, the expression for G will be
the same except that the chemical potentials will be diﬀerent. If we denote the chemical potential
of pure components with a superscript “◦”, the free energy of the separated pure components is
G
◦
= µ
◦
A
n
A
+µ
◦
B
n
B
(4.9)
Comparing the solution G and the pure component G
◦
, we ﬁnd the change in free energy on mixing
or ∆G
mix
to be:
∆G
mix
= n
A
(µ
A
−µ
◦
A
) +n
B
(µ
B
−µ
◦
B
) = n
A
(G
A
−G
◦
A
) +n
B
(G
B
−G
◦
B
) (4.10)
To understand solutions we need to evaluate terms like (µ
A
−µ
◦
A
). As expressed, chemical
potential is somewhat awkward for practical use. We thus redeﬁne it in terms of activity. Ac
tivity at ﬁrst appears no better then chemical potential, but we will soon show that it has useful
interpretations under important special cases. We thus write chemical potential as
µ
A
= µ
•
A
+RT ln a
A
(4.11)
4.2. SOLUTION THERMODYNAMICS 59
where a
A
is the relative activity of component A and µ
•
A
is the chemical potential in an arbitrarily
chosen reference state. In terms of chemical potential, the activity is
a
A
= exp
_
µ
A
−µ
•
A
RT
_
(4.12)
We next apply the deﬁnition of activity to the analysis of a solution in equilibrium with its
vapor. At equilibrium the chemical potential of component A in the vapor is equal to its chemical
potential in the solution. We assume the vapor is an ideal gas and use the above result that
∂G/∂P = V to get
∂µ
vap
A
∂P
=
∂G
vap
A
∂P
=
∂
∂P
∂G
vap
∂n
A
=
∂
∂n
A
∂G
vap
∂P
=
∂V
∂n
A
= V
A
(4.13)
where V
A
is the partial molar volume of component A. In an ideal vapor of A, V = n
A
RT/P
A
where
P
A
is the partial pressure due to component A. Diﬀerentiating with respect to n
A
to get V
A
gives
∂µ
vap
A
∂P
A
=
RT
P
A
or dµ
vap
A
= RT
dP
A
P
A
(4.14)
Integrating we get
µ
vap
A
= RT ln P
A
+const (4.15)
The integration constant is found by using the reference state where µ
A
= µ
•
A
. Finding the constant
results in
µ
vap
A
= µ
•
A
+RT ln
P
A
P
•
A
(4.16)
where P
•
A
is the partial pressure of component A in the reference state.
We turn next to the chemical potential in the liquid. Because the liquid is in equilibrium
with the vapor, the chemical potential of component A in the liquid must be equal to its chemical
potential in the vapor. Thus
µ
l
A
= µ
vap
A
= µ
•
A
+RT ln
P
A
P
•
A
(4.17)
A good reference state for liquids is the chemical potential of the pure liquid. Deﬁning µ
◦
A
as the
chemical potential of the pure liquid we have
µ
◦
A
= µ
•
A
+RT ln
P
◦
A
P
•
A
(4.18)
Solving for µ
•
A
and substituting into the expression for µ
l
A
gives
µ
l
A
= µ
vap
A
= µ
◦
A
+RT ln
P
A
P
◦
A
(4.19)
In general, P
A
< P
◦
A
which implies µ
l
A
< µ
◦
A
. Physically, this observation means that compounds
are less active in solution then they are in pure form. In the above analysis we have assumed
the vapor is an ideal vapor. In eﬀect, we have proposed a physical model for the liquid/vapor
60 CHAPTER 4. POLYMER SOLUTIONS
equilibrium. In this model, the activity is no longer an abstract property; it is deﬁned in terms of
physical quantities. The activity of any component is the ratio of its partial pressure to the partial
pressure that exists over a pure liquid of that component. Thus, the activity of component A is
P
A
/P
◦
A
.
We can extend our model by introducing an assumption about the solution properties. Let’s
say that the solution (as well as the vapor) is ideal in that it obeys Raoult’s law which states
that P
A
= X
A
P
◦
A
where X
A
is the mole fraction of component A in the solution. With this new
assumption, the activity coeﬃcient of component A is X
A
and its chemical potential is
µ
A
= µ
◦
A
+RT ln X
A
(4.20)
In examining the free energy of mixing, we noted that we need terms like (µ
A
−µ
◦
A
). For an
ideal solution and an ideal vapor
µ
A
−µ
◦
A
= RT ln X
A
(4.21)
Our previous result for free energy of mixing becomes
∆G
mix
= RT (n
A
ln X
A
+n
B
ln X
B
) (4.22)
This free energy of mixing can be split up into an entropy part and an enthalpy part with
∆G
mix
= ∆H
mix
−T∆S
mix
(4.23)
We begin with entropy of mixing. A fundamental relation of thermodynamics is ∂G/∂T = −S.
Applying this relation to chemical potentials by taking the temperature derivative of µ
A
gives
S
A
= −
∂µ
A
∂T
= S
◦
A
−Rln X
A
(4.24)
Following the free energy of mixing analysis, the entropy of mixing is
∆S
mix
= n
A
(S
A
−S
◦
A
) +n
B
(S
B
−S
◦
B
) = −R(n
A
ln X
A
+n
B
ln X
B
) (4.25)
Finally, the enthalpy of mixing is
∆H
mix
= ∆G
mix
+T∆S
mix
= 0 (4.26)
∆H
mix
for an ideal solution is zero. ∆H
mix
is zero because the assumption of an ideal solution
implies no interactions between the components of the solution.
We next examine the sign of ∆G
mix
. Both n
A
and n
B
, the numbers of moles, must be positive.
Both X
A
and X
B
, the mole fractions, must between 0 and 1, which means that both ln X
A
and
ln X
B
must be negative. These facts mean that ∆G
mix
is always negative and ∆S
mix
is always
positive. In other words all two component ideal solutions are miscible in all proportions. The
driving force for this miscibility is the increase in entropy of mixed components vs. pure separated
4.3. PHYSICAL ORIGINS OF ENTROPY OF MIXING 61
A A B A B B A A
A B A A A A
B A
B A
A
B B A
A A
A
B B A A B A B
A A A B B A B
A
A B B
A
A A B A
A B A A A
B A A
Figure 4.1: A simple lattice model for a solution of A and B.
components. The fact that not all materials are soluble in all other materials means that many
solutions deviate from ideality. Deviations from ideality often mean that enthalpy is important
and not zero. To make two components immiscible, ∆G
mix
must be positive which implies that
∆H
mix
= 0 and further that ∆H
mix
is suﬃciently positive that it overwhelms the entropy or that
∆H
mix
> T∆S
mix
.
4.3 Physical Origins of Entropy of Mixing
The physical origins of the entropy of mixing can be modeled using a simple lattice model for the
structure of a solution. Say the simple lattice model in Fig. 4.1 represents a solution of A and B.
By statistical thermodynamics, entropy S is
S = k ln W (4.27)
where W is the number of possible conﬁgurations of A and B solution. In the simple lattice, it is
easy to count the number of ways of putting N
A
A units and N
B
B units into N
A
+ N
B
lattice
sites. The result from combinatorial analysis is
W =
_
N
A
+N
B
N
A
_
=
(N
A
+N
B
)!
N
A
!N
B
!
(4.28)
(Note we now use upper case N’s because they refer to individual molecules of component A and
B).
For large N
A
and N
B
(i.e., for many molecules) we can apply Stirling’s approximation for
factorials (ln n! ≈ nln n) to get
W = N
A
[ln (N
A
+N
B
) −ln N
A
] +N
B
[ln (N
A
+N
B
) −ln N
B
] (4.29)
62 CHAPTER 4. POLYMER SOLUTIONS
A A B A A A A A
A
A B A A A
A A
A A
B
B B A
B A
A
A A A B A B A
A B B B B A B
A
A B A
A
A A B A
A B B B B
B B A
Figure 4.2: Polymer molecule B in a lattice model for a solution in solvent A.
We can even replace the ≈ by a straight equal sign because N
A
and N
B
will be so large that
Stirling’s approximation is eﬀectively exact. By deﬁnition of mole fraction X
A
= N
A
/(N
A
+ N
B
)
and X
B
= N
B
/(N
A
+ N
B
). Introducing Avagadro’s number, L, and realizing that R = Lk,
N
A
= Ln
A
, and N
B
= Ln
B
, we quickly derive
∆S
mix
= −R(n
A
ln X
A
+n
B
ln X
B
) (4.30)
This result agrees exactly with the activity analysis for entropy of mixing. Thus the lattice model
recovers all details of the thermodynamics analysis. A lattice can be viewed as a good physical
picture of an ideal solution.
We ﬁnd some interesting results when we apply the lattice model to a polymer solution. The
physics of mixing is unchanged, but now we must consider the case where one molecule is much
larger than the other molecule. Figure 4.2 shows a lattice model for one polymer (component B) in
solvent A. It is clear that the number of ways of introducing the polymer molecule into solvent A
will be much less than the number of ways of introducing the same amount of monomer molecules
B into the same solvent. To count the polymer lattice conﬁgurations we could go back to the lattice
model for a solution of A and B and examine all of the W conﬁgurations. For that large set of
conﬁgurations we must now reject all conﬁgurations that do not have connected B molecules. The
remaining conﬁgurations, which will be much less than W, will be the number of conﬁgurations of
polymer B in solvent A. The conclusion is that the entropy of polymer solutions is much less that
the corresponding entropy for monomer solutions of the same weight fractions A and B.
Compared to the monomer solution problem (Fig. 4.1), it is a much harder task to count the
number of conﬁgurations in which all B units are connected into chains of length x with excluded
volume on a lattice with solvent A. An approximate calculation gives the following result for the
4.4. FLORYHUGGINS THEORY 63
entropy of mixing:
∆S
mix
= −R(n
A
ln v
A
+n
B
ln v
B
) (4.31)
where v
A
and v
B
are volume fractions of solvent (component A) and polymer (component B):
v
A
=
N
A
N
A
+xN
B
and v
B
=
xN
B
N
A
+xN
B
(4.32)
Consider two solutions of equal weight fractions of component A and B — monomer B molecules
in solvent A and a polymer of connected B monomers in solvent A. The mole fractions of A and B
in the monomer solution are identical to the volume fractions of A and B in the polymer solution.
Likewise, n
A
will be the same for both solution. The ∆S
mix
expression diﬀers only in the value for
n
B
. Because the polymer solution connects many B monomers into a single polymer, n
B
in the
polymer solution will be hundreds or thousands of times lower than n
B
in the monomer solution.
Furthermore, in dilute solutions, the n
B
ln X
B
and n
B
ln v
B
terms are the dominant entropy terms.
We thus conclude that the entropy of mixing for polymer solutions will be hundreds or thousands
of times lower than the entropy of mixing for monomer solutions.
One thing that monomer solutions and polymer solutions have in common is that they both obey
conventional thermodynamics. We do not need to derive new methods for understanding polymer
solutions. A major diﬀerence, however, is that polymer solutions are much more likely to deviate
from ideal behavior at comparable concentrations (in weight fraction solute). The deviations from
ideality are direct consequence of the size of polymer molecules. The large size reduces the entropy
of mixing which reduces the term T∆S
mix
. When the entropy of mixing term is small, it is much
easier for the ∆H
mix
term to assume a greater role. It also easy for ∆H
mix
to be greater than
T∆S
mix
and therefore for polymers to be insoluble in many solvents.
4.4 FloryHuggins Theory
We introduce a simple model for dealing with polymer solutions called the FloryHuggins theory.
In brief, the theory attempts to estimate ∆H
mix
using the lattice theory for solutions. We consider
nearest neighbor interaction between A and B molecules. Then
∆H
mix
= kTχN
A
v
B
= RTχn
A
v
B
(4.33)
where N
A
is the number of molecules of component A, n
A
is the number of moles of component
A, v
B
is the volume fraction of polymer, and χ is the Flory interaction parameter. The interaction
parameter describes the level of interaction between pairs of A and B. A high positive χ indicates
a repulsive interaction and causes a positive ∆H
mix
which tends to inhibit the solution process.
A negative χ indicates an attractive interaction and causes a negative ∆H
mix
which guarantees
dissolution.
64 CHAPTER 4. POLYMER SOLUTIONS
The free energy of mixing in the FloryHuggins theory is
∆G
mix
= RT (n
A
ln v
A
+n
B
ln v
B
+χn
A
v
B
) (4.34)
Unfortunately, the FloryHuggins theory is not very good. In practice solution property data cannot
be predicted by using a single value of the interaction parameter. The theory is particularly bad
for dilute solutions. Reasons for these problems will be discussed latter. Despite its shortcomings,
the FloryHuggins theory has some applications for physical understanding of solution properties.
We will make qualitative use of this theory when discussing osmotic pressure experiments.
Problems
4–1. Compare the entropy of mixing for two solution. The ﬁrst is a solution 1% by weight of
monomer B in solvent A (assume the molecular weights of A and B are the same). The
second is a polymer of monomer B in a 1% by weight solution in solvent A where the polymer
has a degree of polymerization of 100,000.
4–2. Explain the physical origin of each term in then FloryHuggins expression for freeenergy of
mixing in polymer solutions.
4–3. a. Explain why two components that form an ideal solution are miscible in all proportions.
b. When two components form a nonideal solution, it is common to observe that the solute
will precipitate out at low temperature and only be soluble in the solvent at elevated
temperatures. Explain why increasing the temperature often makes it more likely for
one component to dissolve in another component even when the resulting solution is
nonideal.
Chapter 5
Colligative Properties
5.1 Introduction
Properties of solutions that depend on the number of molecules present and not on the kind of
molecules are called colligative properties. These properties include boiling point elevation, freezing
point depression, and osmotic pressure. Historically, colligative properties have been one means
for determining the molecular weight of unknown compounds. In this chapter we discuss using
colligative properties to measure the molecular weight of polymers. Because colligative properties
depend on the number of molecules, we expect, and will show, that colligative property experiments
give a number average molecular weight.
5.2 Boiling Point Elevation
Figure 5.1 shows the vapor pressure of a liquid for pure liquid and for a solution with that liquid as
the solvent. In an ideal solution, the vapor pressure of the solvent, P
A
, is reduced from the vapor
pressure of a pure liquid, P
◦
A
, to X
A
P
◦
A
where X
A
is the mole fraction of liquid A. This reduction is
reﬂected in a shift to the right of the vaporpressure curves in Fig. 5.1. By deﬁnition, boiling point
is the temperature at which the vapor pressure of the liquid reaches 1 atm. Thus, the rightshift
caused by the dissolution of component B in solvent A causes the boiling point to increase. This
increase, ∆T
b
, is the boiling point elevation eﬀect.
A well known result from introductory chemistry is that the boiling point elevation is propor
tional to the molar concentration of solute particles
∆T
b
= K
b
m (5.1)
where m is the molality of solute molecules and K
b
is the boiling point elevation coeﬃcient that is
a function of only the solvent. Molality is the number of moles of component B per 1000 grams of
solvent. If we prepare a solution of an unknown compound of molecular weight B at a concentration
65
66 CHAPTER 5. COLLIGATIVE PROPERTIES
Vapor Pressure
V
a
p
o
r
P
r
e
s
s
u
r
e
Solution
Temperature
Pure Solvent
1 atm
T
b
∆T
Figure 5.1: Boiling point elevation eﬀect is a consequence of the eﬀect of solute molecules on the vapor
pressure of the solvent.
c in g/cm
3
, then
m =
1000c
M
B
ρ
(5.2)
where ρ is the density of the solvent (in g/cm
3
). Substituting into the expression for ∆T
b
gives
M
B
=
1000K
b
c
ρ∆T
b
(5.3)
or
∆T
b
c
=
1000K
b
ρM
B
(5.4)
For a given solvent (e.g., water where K
b
= 0.52 and ρ = 1.00) and concentration (c), all terms in
Eq. (5.4) are known except for M
B
. Thus, measuring ∆T
b
can be used to determine the molecular
weight M
B
.
We can also express boiling point elevation in terms of mole fraction. Mole fraction is
X
B
=
cV
M
B
ρV
M
A
+
cV
M
B
≈
cM
A
ρM
B
(5.5)
where V is total volume and M
A
is molecular weight of the solvent. The boiling point elevation
becomes
∆T
b
=
1000K
b
M
A
X
B
(5.6)
To apply boiling point elevation to polymers, we begin by using solution thermodynamics to
derive an expression for ∆T
b
. At equilibrium, the chemical potential of the vapor is equal to the
chemical potential of the liquid
µ
vap
A
= µ
liq
A
= µ
◦
A
+RT ln X
A
or
µ
vap
A
−µ
◦
A
RT
= ln X
A
(5.7)
5.2. BOILING POINT ELEVATION 67
where we have assumed an ideal solution. Diﬀerentiating both sides gives
∂
_
µ
A
T
_
∂T
=
∂
_
G
A
T
_
∂T
=
1
T
_
∂G
A
∂T
_
P
−
G
A
T
2
= −
S
A
T
−
H
A
T
2
+
S
A
T
= −
H
A
T
2
(5.8)
which is used to get
−
H
vap
A
−H
◦
A
RT
2
=
d
dT
ln X
A
(5.9)
where H
vap
A
−H
◦
A
is the heat of vaporization of the solvent or ∆H
vap
.
Now consider the process of forming a solution. As the polymer is added, the mole fraction of
A will go from 1 at the start to X
A
which is the mole fraction of the ﬁnal solution. During the
process, the boiling point will go from T
b
to T where T
b
is the boiling point of the pure liquid and
T is the boiling point of the solution. Integrating over this process gives
−
_
T
T
b
∆H
vap
RT
2
dT =
_
X
A
1
d ln X
A
(5.10)
The integrals are easily evaluated if we assume that ∆H
vap
is independent of temperature over the
small temperature range from T
b
to T. The result is
∆H
vap
R
_
1
T
−
1
T
b
_
= ln X
A
(5.11)
We can simplify this result using ∆T
b
= T −T
b
, TT
b
≈ T
2
b
, and ln X
A
= ln(1−X
B
) ≈ −X
B
. These
simpliﬁcations apply when X
B
is small (which occurs when the solution is dilute) and when ∆T
b
is
small. In general, ∆T
b
will be small when the solution is dilute. The previous equation simpliﬁes
to
∆H
vap
∆T
b
RT
2
b
= X
B
(5.12)
or
∆T
b
=
RT
2
b
∆H
vap
X
B
(5.13)
Comparison of this result to Eq. (5.6) gives a theoretical expression of K
b
:
K
b
=
M
A
RT
2
b
1000∆H
vap
(5.14)
The result is often derived in physical chemistry books.
In applying boiling point elevation to polymer solutions, we should realize that polymer solu
tions are really solutions of many components. The various components are the polymer species of
diﬀerent molecular weights. Because boiling point elevation is a colligative property, we can write
the boiling point elevation of a polymer solution as a sum over the mole fractions of each molecular
weight component:
∆H
vap
∆T
b
RT
2
b
=
i
X
i
(5.15)
68 CHAPTER 5. COLLIGATIVE PROPERTIES
where X
i
is the mole fraction of polymer with molecular weight M
i
. We more conveniently rewrite
X
i
in terms of concentration:
X
i
=
c
i
V
M
i
ρV
M
A
+
i
c
i
V
M
i
≈
c
i
M
A
ρM
i
(5.16)
where c
i
is the concentration in weight/unit volume (e.g., g/cm
3
) of polymer with molecular weight
i. The approximation in this expression is valid for dilute solutions in which the number of moles
of solvent is much greater than the total number of moles of polymer. Summing the mole fractions,
X
i
, results in
i
X
i
=
cM
A
ρ
i
c
i
M
i
i
c
i
=
cM
A
ρ
i
w
i
M
i
=
cM
A
ρM
N
(5.17)
where
c =
i
c
i
(5.18)
The ﬁnal expression for the boiling point elevation becomes
∆T
b
c
=
M
A
RT
2
b
ρ∆H
vap
M
N
(5.19)
It is common to express the boiling point elevation in terms of the latent heat of vaporization, l
vap
,
deﬁned as energy or vaporization per unit weight or
l
vap
=
∆H
vap
M
A
=
J/mole
g/mole
= heat of vaporization in J/g (5.20)
The boiling point elevation becomes
∆T
b
c
=
RT
2
b
ρl
vap
M
N
(5.21)
Except for incorporation of polydispersity, there is nothing new about the boiling point eleva
tion expression for polymer solutions vs. the comparable expression for small molecule solutions.
In polymers, however, the solution is more likely to be nonideal. For this equation to apply we
will probably need to use very low concentrations or techniques to extrapolate to very low concen
trations.
For an example, let’s consider a solution of polystyrene in benzene. For benzene ρ = 0.8787 g/cm
3
,
T
b
= 55
◦
C, and l
vap
= 104 cal/g. We assume a relatively concentrated solution of c = 1 g/cm
3
of a polymer with molecular weight M
N
= 20, 000. The change in the boiling point elevation for
this solution is ∆T
b
= 1.4 × 10
−3 ◦
C. This boiling point elevation is very small. It is probably
beyond the accuracy of most temperature measuring equipment. The small change arises despite
relatively ideal conditions of a fairly concentrated solution and a low molecular weight polymer.
More dilute solutions or higher molecular weight polymers would give an even smaller ∆T
b
. The
problem with polymer solutions is that for a given weight of material, the polymer solution will
5.3. FREEZING POINT DEPRESSION 69
have many less molecules than the comparable small molecule solution. When there are a small
number of molecules, the change in boiling point (a colligative property) is small. The problem with
the boiling point elevation method applied to polymer solutions is that it is not sensitive enough.
It has found some use with polymers but it is limited to polymers with relatively low molecular
weights. (e.g., M
N
less than 20,000 g/mol).
5.3 Freezing Point Depression
A similar analysis (but with sign changes) can be applied to the freezing point depression of a
polymer solution. The ﬁnal result is
∆T
f
c
=
RT
2
f
ρl
f
M
N
(5.22)
where T
f
is the freezing point of the solvent and l
f
is the latent heat of fusion. We consider the
same example of polystyrene in benzene with T
f
= 5.5
◦
C, l
f
= 30.45 cal/g for the freezing point
of benzene. For a c = 1 g/cm
3
solution of polystyrene with molecular weight M
N
= 20, 000, the
change in the freezing point of the solution is ∆T
f
= 2.9×10
−3 ◦
C. Like the boiling point elevation
eﬀect, the freezing point depression eﬀect is too small. The technique is insensitive and only useful
for low molecular weight polymer (e.g., M
N
less than 20,000 g/mol).
5.4 Osmotic Pressure
Another colligative property is osmotic pressure. Figure 5.2 illustrates the osmotic pressure ef
fect. Imagine a pure solvent and a solution separated by a semipermeable membrane. An ideal
semipermeable membrane will allow the solvent molecules to pass but prevent the solute molecules
(polymer molecules) from passing. The diﬀerent concentrations on the two sides of the membrane
will cause an initial diﬀerence in chemical potential. At equilibrium, this diﬀerence in potential
will be counteracted by an eﬀective pressure across the membrane. As shown in Fig. 5.2, it can be
imagined that solvent molecules pass from the pure solvent side to the solution side. The excess
height in the column of liquid above the solution side is related to the osmotic pressure by π = ρgh.
Here π is the osmotic pressure, ρ is the density of the solution, g is the acceleration of gravity
(9.81 m/sec
2
) and h is the height of the column of liquid.
We begin with a thermodynamic analysis of osmotic pressure. At equilibrium the chemical
potential in the solution will be equal to the chemical potential in the pure solvent:
µ
solvent
A
= µ
solution
A
= µ
◦
A
+RT ln a
A
(5.23)
where µ
solvent
A
is the chemical potential of the pure liquid or
µ
solvent
A
= µ
◦
A
(5.24)
70 CHAPTER 5. COLLIGATIVE PROPERTIES
Solvent
Solution
Membrane
h
π = ρgh
Figure 5.2: A schematic view of osmotic pressure across a semipermeable membrane.
The only way the chemical potentials will be equal will be if the activity of component A in the
solution is equal to 1. The activity can be raised to 1 by applying pressure. That is, activity is a
pressure dependent quantity. By applying the correct pressure, the osmotic pressure, the activity
in the solution can be changed to 1. The osmotic pressure that gets applied occurs naturally by
the tendency to approach equilibrium.
To get the pressure dependence of activity, we consider the pressure dependence of the chemical
potential
dµ
A
dP
=
d
dP
dG
dn
A
=
d
dn
A
dG
dP
=
dV
dn
A
= V
A
= RT
d
dP
ln a
A
(5.25)
Rearranging and integrating the left hand side from the original activity a
A
to the ﬁnal activity 1
and the right hand side from the initial pressure 0 to the ﬁnal pressure — the osmotic pressure π
— results in:
_
1
a
A
d ln a
A
=
_
π
0
V
A
RT
dP (5.26)
which integrates to
−ln a
A
=
πV
A
RT
(5.27)
Now, in an ideal solution
−ln a
A
= −ln X
A
≈ X
B
. (5.28)
This last approximation follows because ln(1 − x) ≈ −x for small x. Finally, as in the analysis of
boiling point elevation, we replace X
B
by
i
X
i
which was derived in Eq. (5.17) to be
i
X
i
=
cM
A
ρM
N
(5.29)
giving
cM
A
ρM
N
=
πV
A
RT
(5.30)
5.5. PRACTICAL ASPECTS OF OSMOTIC PRESSURE 71
But, M
A
/ρ is the grams per mole of solvent divided by the grams per cm
3
of solvent. The grams
cancel and we have cm
3
per mole of the solvent or the partial molar volume of component A —
V
A
. Substituting into the osmotic pressure equation thus gives:
π
c
=
RT
M
N
(5.31)
Rewriting the osmotic pressure equation gives a result that is similar to the ideal gas law
cRT = π
i
N
i
M
i
i
N
i
or
i
N
i
M
i
V
RT = π
i
N
i
M
i
i
N
i
(5.32)
which simpliﬁes to
πV =
i
N
i
RT (i.e. PV = nRT) (5.33)
For an example, let’s consider the solution of polystyrene in benzene that was used for examples
of boiling point elevation and freezing point depression; i.e., a solution of polystyrene in benzene
with M
N
= 20, 000 and a concentration of c = 1 g/cm
3
. For the correct units we use R =
8.3143 ×10
7
ergs/K/mol and calculate π = 1.24 ×10
4
dynes/cm
2
. This pressure will be measured
by a diﬀerence in heights of liquids in columns. The height diﬀerence comes from π = ρgh or
h =
1.24 ×10
4
dynes/cm
2
0.8787 g/cm
3
981 cm/sec
2
= 14.3 cm (5.34)
This height diﬀerence is large and is an easily measurable quantity. In fact we expect to be able
to measure distances at least 100 times smaller than this result. Thus osmotic pressure can, in
principle, be used to determine molecular weights in polymers with M
N
up to 2,000,000 g/mol.
5.5 Practical Aspects of Osmotic Pressure
Osmotic pressure measurements appear to be a suitable method for measuring number average
molecular weights in polymers. It is therefore worthwhile considering practical aspects of polymer
characterization by osmotic pressure. The ﬁrst practical consideration is that we expect polymer
solutions to deviate from ideal behavior and thus the osmotic pressure expression will need to be
corrected. In the limit of zero concentration, the solution will eventually become ideal. We can
therefore take a series of measurements and extrapolate back to zero concentration to get the ideal
result. In other words
lim
c→0
π
c
=
RT
M
N
(5.35)
The question which remains is “how do we extrapolate?” A common approach in thermodynamics
is to use a virial expansion. We thus write
π
c
as a sum of many terms:
π
c
=
RT
M
N
+RTA
2
c +RTA
3
c
2
+· · · (5.36)
72 CHAPTER 5. COLLIGATIVE PROPERTIES
or
π
c
=
RT
M
N
_
1 + Γ
2
c + Γ
3
c
2
+· · ·
_
(5.37)
Here A
2
, A
3
, ... and the related Γ
2
, Γ
3
, ... are called the virial coeﬃcients. If we include enough
virial coeﬃcients we will always be able ﬁt experimental data. But, how many of these terms do
we need? Furthermore, how do we analyze experimental data when virial expansion terms are
required? We consider two approaches to this problem.
In the ﬁrst approach, we assume that only the second virial coeﬃcient — A
2
or Γ
2
— will be
needed. Then π/c is predicted to be linear in concentration:
π
c
=
RT
M
N
+RTA
2
c (5.38)
A set of data for π/c vs. c can be plotted. If the results are linear, the assumption in the ﬁrst
approach is valid. When the data is linear, the intercept of the data at zero concentration will be
RT/M
N
and thus can be used to determine M
N
.
Besides an intercept, we can measure the slope which is equal to RTA
2
. In other words the
slope of the π/c vs. c plot is proportional to the second virial coeﬃcient — A
2
. We can make use
of the FloryHuggins theory to get a physical interpretation of the second virial coeﬃcient. The
FloryHuggins theory includes nonideal interactions through the Flory interaction parameter, χ.
Let’s use the FloryHuggins theory to develop an osmotic pressure theory for nonideal solutions.
We begin with an early osmotic pressure formula:
π = −
RT ln a
A
V
A
= −
µ
A
−µ
◦
A
V
A
(5.39)
The term µ
A
−µ
◦
A
is found by diﬀerentiating the free energy of mixing
d∆G
mix
dn
A
= µ
A
−µ
◦
A
(5.40)
To use the FloryHuggins theory we diﬀerentiate the ∆G
mix
from that theory. In performing the
integration we must realize that v
A
and v
B
also depend on n
A
. The work is left as an exercise to
the reader. The result is
µ
A
−µ
◦
A
= RT
_
ln v
A
+
_
1 −
1
x
_
v
B
+χv
2
B
_
(5.41)
Substituting into the osmotic pressure formula and at the same time using the approximation
ln v
A
= ln(1 −v
B
) ≈ −v
B
+v
2
B
/2 (Note that in this approximation to ln(1 −v
B
) we keep one more
term than we have used in the past. The reason for the extra term is that the µ
A
−µ
◦
A
expression
already includes terms with v
2
B
), the osmotic pressure becomes:
π =
RT
V
A
_
v
B
x
+
_
1
2
−χ
_
v
2
B
+· · ·
_
(5.42)
5.5. PRACTICAL ASPECTS OF OSMOTIC PRESSURE 73
The volume fraction of polymer, v
B
, is equal to the concentration of B in g/cm
3
divided by the
density of polymer — ρ
B
(v
B
= c/ρ
B
). The osmotic pressure is then
π
c
=
RT
V
A
xρ
B
+
RT
V
A
ρ
2
B
_
1
2
−χ
_
c +· · · (5.43)
The ﬁrst term is the ideal solution result (which can be deduced by noting that M
N
= V
B
ρ
B
and
V
B
= xV
A
in the lattice solution model).. The second term, which is proportional to concentration,
gives the second virial coeﬃcient
We return now to the slope of the linear ﬁt of π/c vs. c which gives the second virial coeﬃcient.
From the FloryHuggins analysis, the second virial coeﬃcient is:
A
2
=
1
V
A
ρ
2
B
_
1
2
−χ
_
or A
2
=
M
0
ρ
B
_
1
2
−χ
_
(5.44)
where M
0
= M
N
/x is the monomer molecular weight. When χ is large and negative, the second
virial coeﬃcient will be large and positive and the slope of π/c vs. c will be large and positive.
A negative interaction parameter also implies a favorable interaction (∆G
mix
more negative) and
therefore a good solvent will give a large positive slope. In fact the slope of the osmotic pressure
data can be thought of as a direct measure of the solvent quality — the higher the slope the better
the solvent.
The second virial coeﬃcient from the FloryHuggins result is also proportional to 1/ρ
B
or rather
is proportional to the speciﬁc volume of polymer. This result suggests an excluded volume eﬀect.
When the excluded volume eﬀect is absent, the solution will act as if the speciﬁc volume of the
polymer is zero (1/ρ
B
= 0) and the second virial coeﬃcient will therefore be zero. The excluded
volume eﬀect disappears in a theta solvent and as a result the osmotic pressure data slope will
be zero in a theta solvent. In other words a theta solvent acts as an ideal solution to fairly high
concentrations. The fact that a zero slope is a low slope illustrates a result from earlier in the
course — theta solvents in general are not very good solvents. Although working in theta solvents
would simplify data analysis (i.e., give results that obey ideal solution laws) the fact that theta
solvents are poor solvents makes working with them diﬃcult. It is usually more convenient to work
in good solvents and make use of extrapolation techniques. The observation of zero slope in osmotic
pressure data, however, is a useful method for determining theta solvent conditions.
Unfortunately, plots of π/c vs. c are often not linear. We thus need a second approach to
analysis of data from nonideal solutions. The obvious approach is to include both the second and
the third virial coeﬃcients. In other words we assume that deviations from linearity are caused by
the third virial coeﬃcient no longer being insigniﬁcant. Let’s take g as the ratio of the third virial
coeﬃcient to the second virial coeﬃcient squared (Γ
3
= gΓ
2
2
) and let’s ignore terms beyond the
third virial coeﬃcient. Then π/c becomes
π
c
=
RT
M
N
_
1 + Γ
2
c +gΓ
2
2
c
2
_
(5.45)
74 CHAPTER 5. COLLIGATIVE PROPERTIES
We now have two parameters — Γ
2
and g. Deriving two parameters for osmotic pressure data will
be more complicated than deriving the slope and intercept of simple linear ﬁts. It requires more
advanced curveﬁtting techniques. We can simplify the process by introducing some theoretical
calculations about g. For hard spheres, g can be calculated to be g = 5/8. For polymer molecules,
g has been estimated to be g = 0.25 to 0.28. The actual value of g depends on various properties such
as the expansion coeﬃcient α, the characteristic ratio, etc.. Fortunately, however, g is restricted to
a relatively narrow range for most polymers.
Because g must be positive and a polymer cannot be more impenetrable than hard spheres, g
must be between 0 and 5/8. If we pick a value for g than we are left with only one parameter (Γ
2
)
and we calculate M
N
and Γ
2
by simpler curve ﬁtting analyses. Fortunately it has been found that
the results are not very sensitive to the exact value of g. Because polymers have g’s calculated to
be near 0.25, we will assume g = 0.25. The choice of g = 0.25 is desirable because it completes the
square and the data analysis can again be done by linear ﬁts (Scientists, especially scientists that
worked before computers, like linear theories):
π
c
=
RT
M
N
_
1 + Γ
2
c +
1
4
Γ
2
2
c
2
_
or
_
π
c
=
¸
RT
M
N
_
1 +
Γ
2
c
2
_
(5.46)
When g can be assumed to be 0.25, a plot of
_
π/c vs. c should be linear. The slope will give Γ
2
and the intercept will give
_
RT/M
N
.
The advantage of setting g = 0.25 is that the data can be analyzed with a simple linear ﬁt.
This advantage was important before computers were readily available. Now we can easily treat g
as a second parameter and do a two parameter ﬁt to the data. You will try this type of analysis
in one of the class labs and be able to discuss whether the added complexity improves or weakens
the interpretation of the results.
5.6 Experimental Aspects of Membrane Osmometry
A simple type of osmometer is illustrated in Fig. 5.3. The solution is placed in a cell with membranes
on either side (one or two membranes, but two gives more area and faster equilibration). The entire
assembly is then immersed in pure solvent. The heights of the liquids in the capillaries are read and
the height diﬀerence gives the osmotic pressure. This apparatus is called a block type osmometer.
It is the type of osmometer used to get the data that will be given to you in a lab. This osmometer
uses a small cell and a large membrane. The membrane is supported by stainless steel plates with
holes. By supporting the membrane, the membrane can be made larger; with larger membrane
area equilibrium will be reached sooner.
Block osmometers are called static osmometers because they wait for the natural development
of equilibrium. The problem with static osmometers is that it can take hours (1224 hrs) to reach
5.6. EXPERIMENTAL ASPECTS OF MEMBRANE OSMOMETRY 75
SIDE VIEW FRONT VIEW
Capillaries
Outer
flange
Outer
flange
Membrance
Exploded View
Inner
flange
Solution cell
Figure 5.3: A block type, static osmometer.
an accurate equilibrium. The time depends on many factors such as the membrane area and the
speed of transport through the membrane. To quicken osmotic pressure experiments, dynamic
osmometers are sometimes used. Recall that osmotic pressure develops for the purpose of raising
the activity of the solvent in the solution to 1. By applying a pressure it is possible to do the
same thing. You will know when you have applied the correct pressure by monitoring ﬂow across
the membrane. When you apply enough pressure to stop the ﬂow you have artiﬁcially reached
equilibrium. The pressure required can be used to get the equilibrium osmotic pressure. This quick
method, unfortunately, is less accurate.
Finally, we make a few comments about what makes a good semipermeable membrane. The
membrane must be permeable to solvent and impermeable to polymer. This requirement limits the
lowend applicability of osmometry to M
N
of 20,000 g/mol or more. Note that we really require
all polymers to be above 20,000 g/mol otherwise the low molecular weight tail will pass through
membrane and the measured M
N
will be too high (do you see why it would be too high?). Therefore,
polydisperse polymers probably require M
N
greater than about 50,000 g/mol; for monodisperse
polymers it might be possible to go down to 20,000 g/mol.
There are also some material concerns for the membrane. An obvious concern is that the mem
brane not be soluble in the solvent. Perhaps the most common membrane material is gel cellulose.
76 CHAPTER 5. COLLIGATIVE PROPERTIES
Other membranes include cellulose hydrate, cellulose acetate, cellulose nitrate, polyurethanes, and
poly(chlorotriﬂuoroethylene).
Problems
5–1. In analyzing osmotic pressure data why is a plot of
_
(π/c) versus c sometimes used rather
than a plot of (π/c) versus c?
5–2. The following are data from osmotic pressure measurements on a solution of polyester in
chloroform at 20
◦
C. The results are in terms of centimeters of solvent. The density of HCCl
3
is 1.48 g/cm
3
. Plot π/c versus c and ﬁnd M
N
under the assumption that you can neglect
terms beyond the second virial coeﬃcient.
c (g/dl) h (cm of HCCl
3
)
0.57 2.829
0.28 1.008
0.17 0.521
0.10 0.275
5–3. a. Suppose that in a diﬀerent universe that the boiling point elevation was given instead
by
∆H
vap
∆T
b
R∆T
2
b
=
w
B
M
B
M
0
=
1
M
0
i
w
i
M
i
(5.47)
where w
i
is the weight fraction of polymer with molecular weight M
i
and M
0
is the
monomer molecular weight. By this law, what molecular weight average could by found
from boiling point elevation measurements and give a formula for calculating that molec
ular weight average.
b. The measurement of boiling point elevation is not very useful for ﬁnding the molecular
weight of high molecular weight polymers. If boiling point elevation was given instead by
the formula in part a, would it be a more or less useful approach to ﬁnding the molecular
weight of high molecular weight materials?
Chapter 6
Viscosity
6.1 Introduction
Viscosity of a polymer solution depends on concentration and size (i.e., molecular weight) of the
dissolved polymer. By measuring the solution viscosity we should be able to get an idea about
molecular weight. Viscosity techniques are very popular because they are experimentally simple.
They are, however less accurate and the determined molecular weight, the viscosity average molec
ular weight, is less precise. For example, M
v
depends on a parameter which depends on the solvent
used to measure the viscosity. Therefore the measured molecular weight depends on the solvent
used. Despite these drawbacks, viscosity techniques are very valuable. This chapter discusses the
theory and methods for determining polymer molecular weight by measuring solution viscosity
6.2 Viscosity and Viscosity Nomenclature
Figure 6.1 shows a piece of a liquid moving at a strain rate ˙ γ under an applied shear stress of τ.
The viscosity of the liquid is the ratio of the applied shear stress to the resulting strain rate (or
equivalently, the ratio of the shear stress required to move the solution at a ﬁxed strain rate to that
strain rate). The shear strain in Fig. 6.1 is
γ =
du
dy
(6.1)
where u is displacement in the x direction. The strain rate is therefore
˙ γ =
d
dt
du
dy
=
d
dy
du
dt
=
dv
x
dy
(6.2)
where v
x
is velocity in the x direction. The relations between viscosity (η), shear stress (τ), and
shear rate ( ˙ γ) are
τ = η ˙ γ or ˙ γ =
τ
η
or η =
τ
˙ γ
(6.3)
77
78 CHAPTER 6. VISCOSITY
F
τ =
F
A
dγ
dt
γ =
•
γ
Figure 6.1: A piece of a liquid moving at shear rate ˙ γ under an applied shear stress of τ.
A Newtonian ﬂuid is one in which the viscosity is independent of the shear rate. In other words
a plot of shear stress versus shear strain rate is linear with slope η. In Newtonian ﬂuids all the
energy goes into sliding molecules by each other. In nonNewtonian ﬂuids, the shear stress/strain
rate relation is not linear. Typically the viscosity drops at high shear rates — a phenomenon known
as shear thinning. Although the following development will not discuss shear rate eﬀects in detail,
the possibility of experimental results being aﬀected by the shear rate of the measurement should
be kept in mind. Plots of shear force vs. shear rate for Newtonian and nonNewtonian ﬂuids are
given in Fig. 6.2.
We let η
0
be the viscosity of the pure solvent and η be the viscosity of a solution using that
solvent. Several methods exist for characterizing the solution viscosity, or more speciﬁcally, the
capacity of the solute to increase the viscosity of the solution. That capacity is quantiﬁed by using
one of several diﬀerent measures of solution viscosity. The most common solution viscosity terms
are:
1. Relative viscosity
η
r
=
η
η
0
(6.4)
2. Speciﬁc viscosity
η
sp
=
η −η
0
η
0
= η
r
−1 (6.5)
3. Inherent Viscosity
η
i
=
ln η
r
c
(6.6)
4. Intrinsic Viscosity
[η] = lim
c→0
η
sp
c
(6.7)
6.2. VISCOSITY AND VISCOSITY NOMENCLATURE 79
Shear Force
NonNewtonian
Newtonian
Shear Rate
S
h
e
a
r
F
o
r
c
e
Figure 6.2: Schematic plots of shear force vs. shear rate for Newtonian and nonNewtonian ﬂuids.
In these equations, η is solution viscosity, η
0
is viscosity of the pure solvent, and c is concentration.
Relative viscosity is selfexplanatory. Speciﬁc viscosity expresses the incremental viscosity due
to the presence of the polymer in the solution. Normalizing η
sp
to concentration gives η
sp
/c which
expresses the capacity of a polymer to cause the solution viscosity to increase; i.e., the incremental
viscosity per unit concentration of polymer. As with other polymer solution properties, the solutions
used for viscosity measurements will be nonideal and therefore η
sp
/c will depend on c. As with
osmotic pressure, it will probably be useful to extrapolate to zero concentration. The extrapolated
value of η
sp
/c at zero concentration is known as the intrinsic viscosity — [η]. [η] will be shown to
be a unique function of molecular weight (for a given polymersolvent pair) and measurements of
[η] can be used to measure molecular weight.
The remaining form for the viscosity is the inherent viscosity. Like η
sp
, ln η
r
is zero for pure
solvent and increases with increasing concentration, thus ln η
r
also expresses the incremental vis
cosity due to the presence of the polymer in the solution. Normalizing ln η
r
to concentration or
ln η
r
/c gives the inherent viscosity In the limit of zero concentration, η
i
extrapolates the same as
η
sp
/c and becomes equal to the intrinsic viscosity. This can be proved by:
lim
c→0
ln η
r
c
= lim
c→0
ln (1 +η
sp
)
c
= lim
c→0
η
sp
c
= [η] (6.8)
We can thus ﬁnd [η] be extrapolating either η
sp
/c or η
i
to zero concentration. When c is not equal
to zero the speciﬁc viscosity and inherent viscosities will be diﬀerent, even for an ideal solution. In
ideal solutions η
sp
/c will be independent of concentration, but n
i
will depend on concentration.
80 CHAPTER 6. VISCOSITY
6.3 Viscosity Theory
Einstein derived the speciﬁc viscosity for a dilute solution of hard spheres. His result is
η
sp
= 2.5
N
B
V
η
V
(6.9)
where N
B
is the number of particles (hard spheres), V
η
is the hydrodynamic volume of each sphere,
and V is the total volume. For a ﬁrst approximation to polymer solutions, we will use Einstein’s
theory and assume each polymer to be a hard sphere with V
η
equal to some eﬀective hydrodynamic
volume. Letting moles of polymer be n
B
= N
B
/L, we get
η
sp
= 2.5
n
B
V
η
L
V
(6.10)
We begin with a monodisperse polymer solution with concentration c = n
B
M/V where M is
molecular weight. We can rewrite η
sp
as
η
sp
= 2.5
n
B
M
V
V
η
L
M
= 2.5c
V
η
L
M
(6.11)
or
η
sp
c
= 2.5L
V
η
M
(6.12)
This result is for an ideal solution. We see that η
sp
/c in an ideal solution is independent of
concentration. Extrapolating to zero concentration, which is trivial because η
sp
/c is independent
of c, the intrinsic viscosity of an ideal solution is
[η] = lim
c→0
η
sp
c
= 2.5L
V
η
M
(6.13)
For a hard sphere we could take V
η
to be the volume of that sphere or equal to 4πr
3
/3. Because a
polymer is not a hard sphere, we do not have so simple a result. We can, however, probably assume
that V
η
is be proportional to rootmeansquared radius cubed —
_
_
r
2
_
3
. Writing Q for the as
yet unknown proportionality constant we have V
η
= Q
_
_
r
2
_
3
. Lumping the proportionality
constant along with other constants in the above equation results in:
[η] = Φ
r
2
3
2
M
= Φ
_
r
2
M
_
3
2
M
1
2
= Φ
_
r
2
0
M
_
3
2
M
1
2
α
3
(6.14)
where Φ = 2.5LQ. In the last step of the above equation we rewrote the rootmeansquared
endtoend distance using the expansion factor α and the unperturbed endtoend distance:
r
2
= α
2
r
2
0
(6.15)
In a theta solvent the expansion factor is 1 (α = 1) and the above equation tells us that [η] is
proportional to the square root of molecule weight and the 3/2 power of r
2
0
/M
[η] = Φ
_
r
2
0
M
_
3
2
M
1
2
(6.16)
6.3. VISCOSITY THEORY 81
But, both r
2
0
and M are proportional to the number of bonds or n. Thus r
2
0
/M is a constant
for a particular polymer that is independent of molecular weight. We get in the simplest form
[η] = KM
1
2
(6.17)
where K is a constant.
The polymer size is determined by the ratio of the meansquared unperturbed endtoend
distance and its molecular weight. In terms of K and Φ, the result is
_
r
2
0
M
_
=
_
K
Φ
_2
3
(6.18)
Recall that characteristic ratio is deﬁned as the ratio of the meansquared endtoend distance,
r
2
0
, to the freelyjointed chain meansquared length, nl
2
. The characteristic ratio can thus be
written as
C
n
=
r
2
0
nl
2
or C
n
=
r
2
0
M
M
b
l
2
(6.19)
where M
b
is the molecular weight per bond or M/n. Inserting this result into the previous result
gives C
n
in terms of K and Φ.
C
n
=
_
K
Φ
_2
3
M
b
l
2
(6.20)
The viscosity constant Φ can be evaluated from theory. For polymers it is typically assumed to be
2.52.66×10
21
(when r is in cm and [η] is in dl/g). Therefore a measurement of [η] for a polymer of
known molecular weight in a theta solvent will give K, which in turn can be used to give a direct
measurement of the characteristic ratio. These types of experiments were used to check early work
on the conformations of polymers and calculations of endtoend distances.
For polymers in nontheta solvents, α will no longer be one and we lose the squareroot depen
dence of [η] on molecular weight. We instead have
[η] = KM
1
2
α
3
(6.21)
where α may have molecular weight dependence of its own. It is usually acceptable to treat non
theta solvent results by lumping the molecular weight dependence of α into one molecular weight
term to get
[η] = KM
a
(6.22)
where a is some constant that depends on the polymersolvent pair and on temperature. Values of
a are typically between 0.5 and 0.8. Close to 0.5 represents near theta solvent conditions. Farther
away from 0.5 represents large deviations from a theta solvent.
82 CHAPTER 6. VISCOSITY
6.4 Viscosity Experiments
It is usually not convenient to work in theta solvents. We thus next discuss how to use viscosity
experiments in nontheta solvents to measure molecular weight. The key experimental property
is intrinsic viscosity — [η]. You measure [η] by measuring η
sp
at several diﬀerent concentrations
and extrapolating to zero concentration (we will discuss the extrapolation further below). Once
[η] is known, it is related to molecular weight through two unknown constants — K and a. These
constants must have been previously determined by a calibration experiment. For a particular
polymersolvent pair, K and a can be measured by measuring [η] on a several batches of that poly
mer with diﬀerent, and known, molecular weights. The molecular weights might be known by some
other experimental technique such as osmotic pressure experiments. Plotting log [η] vs. log M will
easily give K and a for that polymersolvent pair. Many K’s and a’s for common polymersolvent
pairs can be found in handbooks of polymer science. Once K and a are known, a measurement
of [η] on a polymer of unknown molecular weight can be used to measure the molecular weight.
We note that this viscosity technique for measuring molecular weight is not an absolute technique
as was osmotic pressure. It requires calibration experiments using samples with known molecular.
To avoid errors resulting from the type of average molecular weights determined by osmotic pres
sure or viscosity experiments, accurate calibration experiments should be done with monodisperse
polymers.
6.4.1 Polydisperse Polymers
We next consider experiments on polydisperse polymers. How do we use viscosity experiments to
measure an average molecular weight? What sort of average molecular weight do we measure?
We cannot be as rigorous as we were for osmotic pressure on polydisperse polymers. We can,
however, make some reasonable assumptions and get a reasonable result. We make the following
three assumptions
1. η
sp
=
i
(η
sp
)
i
(6.23)
2. (η
sp
)
i
= [η]
i
c
i
(6.24)
3. [η]
i
= KM
a
i
(6.25)
The ﬁrst assumption says that the total speciﬁc viscosity is the sum of the speciﬁc viscosities for
each components (i.e., each molecular weight of the polymer). The second assumption says that
the speciﬁc weight of each component can be calculated from the intrinsic viscosity due to that
component. The third assumption says that the relation between intrinsic viscosity and molecular
weight is independent of molecular weight; i.e., K and a are independent of molecular weight.
6.4. VISCOSITY EXPERIMENTS 83
Using the above three assumptions we derive
η
sp
c
=
i
Kc
i
M
a
i
c
=
i
K
N
i
M
i
V
M
a
i
i
N
i
M
i
V
=
i
KN
i
M
1+a
i
i
N
i
M
i
(6.26)
Assumption two implies we are considering the limit of zero concentration. Thus we remove the
constant K from the summation terms and state the zeroconcentration limit to get
lim
c→0
η
sp
c
= KM
v
a
(6.27)
where
M
v
=
_
i
N
i
M
1+a
i
i
N
i
M
i
_
1
a
(6.28)
M
v
is known as the viscosity average molecular weight (for obvious reasons). When a = 1, M
v
is equal to the weight average molecule weight, M
W
; otherwise M
v
is between the weight average
molecule weight and the number average molecule weight, M
N
≤ M
v
≤ M
W
. For typical a’s (0.5
to 0.8), M
v
is closer to M
W
. This result is to be expected because viscosity properties are expected
to be a function of size and not just the number of polymers.
6.4.2 Experimental Procedures
We next discuss the experimental procedures and the equipment used to measure solution viscosity.
The experiments are simple and can all be down with a relatively simple and relatively inexpensive
piece of glassware called a viscometer (see Fig. 6.3). The experiment is to ﬁll the viscometer such
that the level on the left side is at point C and the level on the right side is at point A (i.e.,
a certain volume of liquid depending on the volume of the viscometer). Because of the height
diﬀerence between C and A (h), there is a hydrostatic head or driving pressure to cause the liquid
to ﬂow through the capillary or narrow diameter section of the viscometer. The experiment is to
measure the time it takes the liquid to ﬂow from point A to B. In other words the time it takes
the volume of liquid between A and B to ﬂow through the capillary.
Flow of a Newtonian ﬂuid through a capillary is relatively easy to analyze. The result can
be found in many ﬂuids books. If we ignore kinetic energy terms, the time is proportional to the
solution viscosity through the following relation:
η =
πr
4
c
∆P
8V
f
L
t = Aρt (6.29)
where r
c
is the radius of the capillary, V
f
if the volume of liquid that ﬂows (i.e., the volume between
points A and B), ∆P is pressure diﬀerence, and L is the length of the capillary. When ﬂowing
due to gravity only in a tube of length h, ∆P = ρgh where ρ is the solution density. The physical
constants of the viscometer can be then lumped into a single constant denoted above as A. If A is
84 CHAPTER 6. VISCOSITY
h
A
B
Capillary
C
h
Figure 6.3: Simple viscometer.
known for a particular viscometer, a measurement of ﬂow time and solution density can be used to
determine solution viscosity.
A more accurate calculation of solution viscosity in terms of ﬂow time would account for kinetic
energy of the moving liquid. The result with kinetic energy is
η = Aρ
_
t −
B
At
_
(6.30)
where B is a constant. If the ﬂow occurs rapidly (t is small), the liquid is moving fast and there
can be signiﬁcant kinetic energy. In this case it is important to correct for kinetic energy. If the
ﬂow is slow (t is large) the kinetic energy term, which is proportional to 1/t, gets small. Physically
the liquid is moving slowly and has little kinetic energy. In practice, it is simplest to use long ﬂow
times and ignore the kinetic energy term.
For most accurate results, there are several important considerations. First, the viscometer
must be clean. Any contamination from previous solutions might add to the current solution and
change its viscosity. A clean tube also means a tube that is free from dust particles. Dust particles
can add to the solution as hard spheres with a large hydrodynamic volume. They can increase
the solution viscosity and aﬀect the results, especially when working with very dilute solutions.
Third, it is best to choose a viscometer such that the ﬂow time is greater than 100 seconds. When
t > 100 seconds, it is permissible to ignore the kinetic energy terms. It is then a simple matter to
calculate relative viscosity and speciﬁc viscosity by comparing the ﬂow time of the solution, t, to
the ﬂow time of the pure solvent, t
0
:
η
r
=
t
t
0
and η
sp
=
t −t
0
t
0
(6.31)
6.4. VISCOSITY EXPERIMENTS 85
To adjust ﬂow times, viscometers are available with diﬀerent radius capillaries. The smaller the
capillary, the longer the ﬂow time. You thus select a viscometer to give good ﬂow times in the
expected viscosity range for your solutions.
To measure intrinsic viscosity requires extrapolation of η
sp
/c to zero concentration. As with
osmotic pressure, we are faced with the problem of how to extrapolate. The simplest approach is
to do a simple linear extrapolation:
η
sp
c
= [η] +kc (6.32)
Experience shows that a linear extrapolation works well as long as η
r
is restricted to less than 2.
Another consideration for viscosity experiments, therefore, is to keep the relative viscosity less than
2.
Experimental results with polymer solutions has revealed that the slope of the η
sp
/c vs. c curve,
k, depends on molecular weight of the polymer. Huggins found that a plot of k versus [η]
2
was
linear and passed through the origin. In other words
d
_
ηsp
c
_
dc
= k
[η]
2
(6.33)
Integrating this empirical result gives the Huggins’ equation:
η
sp
c
= [η] +k
[η]
2
c (6.34)
The new constant, k
, is a function of the polymer/solvent/temperature of the system, but is inde
pendent of molecular weight. Therefore once k
is known, a single relative viscosity measurement
at one concentration can be used to get the viscosity average molecular weight. The following steps
are used:
1. Measuring η
r
leads to η
sp
/c which using k
gives [η]
2. With known K and a, the measured [η] gives M
v
or the viscosity average molecular weight.
If k
is not known, the typical viscosity experiment is to measure η
sp
/c at several concentrations
and do a linear extrapolation to zero concentration to get [η]. With known K and a, the measured
[η] gives M
v
.
An alternate technique is to extrapolate inherent viscosity or ln η
r
/c to zero concentration to
get [η]. As we approach zero concentration, η
sp
will get small. Using the approximation for small
x of ln(1 +x) ≈ x −x
2
/2 we can derive
ln η
r
= ln (1 +η
sp
) ≈ η
sp
−
η
2
sp
2
(6.35)
Then
ln η
r
c
≈
η
sp
c
−
η
2
sp
2c
2
c (6.36)
86 CHAPTER 6. VISCOSITY
[η]
Concentration
η
sp
c
ln η
r
c
Figure 6.4: Typical plots of η
sp
/c and ln η
r
/c as a function of concentration. The curves extrapolate to
the same [η] at zero concentration, but approach zero concentration with diﬀerent slopes.
Using Huggins’ equation, this result gives:
ln η
r
c
≈ [η] +k
[η]
2
c −
[η]
2
c
2
−k
[η]
2
c
2
−
k
2
[η]
4
c
3
4
(6.37)
Neglecting higher order terms of order c
2
or higher gives
ln η
r
c
≈ [η] +
_
k
−
1
2
_
[η]
2
c = [η] +k
[η]
2
c (6.38)
Thus a plot of ln η
r
/c vs. c should be linear with slope k
[η]
2
and intercept [η]. The new constant,
k
, is related to k
by k
= k
−1/2. We see that plots of both η
sp
/c vs. c and ln η
r
/c vs. c will both
be linear and both extrapolate to [η] at zero concentration. The slopes of the two plots, however,
will be diﬀerent.
The terms η
sp
/c, ln η
r
/c, and [η] all have units of 1/concentration (e.g., a common convenient
unit is deciliters per gram — dl/g). Because [η]
2
c also has units of 1/c, k
and k
are dimensionless.
For many polymers k
≈ 1/3 which makes k
≈ −1/6. This diﬀerence in signs makes plots of
both types of data useful. The two types of plots converge on the same intrinsic viscosity but from
diﬀerent directions — one has a positive slope and the other a negative one. Plotting of both types
of data will often give a good feeling for the accuracy of the extrapolated intrinsic viscosity. Typical
plots will resemble the curves in Fig. 6.4.
One ﬁnal complication arises if [η] is large. A high intrinsic viscosity probably means that the
viscosity depends on the shear rate of the test. Likewise, the extrapolation to zero concentration
will also depend on shear rate. To remove shear rate eﬀect it is sometimes necessary to get [η] at
several shear rates and do a second extrapolation of [η] to zero shear rate. The zero shearrate
6.5. VISCOSITY SUMMARY 87
intrinsic viscosity is the intrinsic viscosity that should be used in molecular weight calculations. If
[η] is not too high, the measured value of [η] at some nonzero shear rate can probably be assumed
to be a good estimate of the zero shearrate viscosity.
6.5 Viscosity Summary
In summary, the work you need to do to get useful results from viscosity experiments depends on the
prior knowledge you might have about the constants relevant to your particular polymer/solvent
pair. We consider four situations:
1. Known K, a, k
(or k
): If all these constants are all known, then measurement of η
0
and
η at one concentration will lead directly to M
v
. Many of these constants are tabulated for
common polymers. Thus when you are working with common polymers it is relatively easy
to get a good estimate of molecular weight.
2. Known K and a, but unknown k
(and k
): Tables of K and a are common, but there is less
data about k
(or k
). When these constants are not known, you have to measure η
0
and
measure η at several concentrations. These results can be used to linearly extrapolate η
sp
/c
and ln η
r
/c to zero concentration to get [η] which will lead to M
v
. Although this situation
requires more work than using a known k
(or k
), it is less prone to errors; it is less prone to
uncertainties in the tabulated values of k
(or k
).
3. No constants known: If you are working with a new polymer or an unusual solvent, it is
likely that none of the constants (K, a, k
, or k
) will be known. For such polymers you
can still measure [η] by extrapolating η
sp
/c and ln η
r
/c to zero concentration. Although you
cannot use [η] to determine molecular weight, you can compare values of [η] from the same
polymer/solvent pair to get relative molecular weights. The higher the value of [η], the higher
the molecular weight. Relative molecular weights are often enough. If they are not enough it
might be useful to do calibration experiments to ﬁnd K and a. The calibration experiments
will require monodisperse polymers whose molecular weight has been absolutely determined
by some other method (e.g., osmotic pressure or light scattering). The use of monodisperse
polymers avoids problems of diﬀerences in M
N
, M
W
, and M
v
.
4. Insoluble polymer: Solution viscosity techniques assume that you can dissolve the polymer
in some solvent. Obviously the techniques cannot be used with polymers that cannot be
dissolved in any solvent. For such polymers it is often possible to measure the zero shearrate
viscosity of the polymer melt. The zero shearrate melt viscosity increases as the molecular
weight increases. A crude, but standardized method of estimating melt viscosity is called the
melt index. The melt index test measures the mass of material that ﬂows through a standard
88 CHAPTER 6. VISCOSITY
oriﬁce in a ﬁxed amount of time. The more material that ﬂows, and hence the higher the
melt index, the lower the melt viscosity and thus the lower the molecular weight.
Problems
6–1. Two “monodisperse” polystyrenes are mixed in equal quantities by weight. One polymer has
molecular weight 39,000 and the other molecular weight of 292,000. What is the intrinsic vis
cosity of the blend in benzene at 25
◦
C. The MarkHouwink constants for polystyrene/benzene
at 25
◦
C are K = 9.18 ×10
−5
dl/g and a = 0.74.
6–2. With enough predetermined constants for a particular polymersolvent pair, it is possible to
determine molecular weight of a polymer by doing only two viscosity measurements. What
two viscosity measurements are required? What constants for the particular polymersolvent
pair are required and how are they used?
6–3. Solution viscosities for a particular polymer and solvent are plotted in the form (η −η
0
)/(cη
0
)
versus c, where η is the viscosity of the polymer solution at concentration c in g/cm
3
and η
0
is the viscosity of the pure solvent. The plot is a straight line with intercept of 1.50 cm
3
/g
and a slope of 0.9 cm
6
/g
2
. Give the magnitude and the units for the Huggin’s constant for
this polymersolvent pair.
Chapter 7
Light Scattering
7.1 Introduction
Figure 7.1 shows light scattering oﬀ a particle in solution or in vacuum. The incident light scatters
in all diﬀerent directions. The intensity of the scattered light depends on the polarizability (to
be deﬁned later) and the polarizability depends on the molecular weight. This property of light
scattering makes it a valuable tool for measuring molecular weight.
Because the intensity of scattered light depends on molecular weight of the particle, light
scattering will depend on weight average molecular weight. This result contrasts to colligative
properties, such as osmotic pressure, which only depended on number of particles and therefore
gave the number average molecular weight. Besides molecular weight dependence, light scattering
also has a direct dependence on particle size. For polymer solutions, this dependence on size can
be used to measure the radius of gyration of the polymer molecule. As with osmotic pressure, we
expect all light scattering experiments to be done in nonideal solutions. Nonideality complicates
the data analysis, but, like osmotic pressure, allows you to determining a virial coeﬃcient, A
2
.
In summary, light scattering experiments can be used to measure three things: weight average
molecular weight (M
W
), meansquared radius of gyration (s
2
), and the second virial coeﬃcient
(A
2
or Γ
2
).
To interpret light scattering experiments, we begin with a discussion of light scattering theories.
Classical light scattering theory was derived by Lord Rayleigh and is now called Rayleigh theory.
Rayleigh theory applies to small particles. By small particles, we mean particles whose size is much
less than λ or the wavelength of the light that is being scattered. By “much less” we mean
_
s
2
< λ/20 (7.1)
Because visible light has λ between 4000
˚
A and 8000
˚
A, we need the root mean squared radius of
gyration
_
s
2
< 200 to 400
˚
A. Many polymers will violate this criterion and the light scattering
results will have to be corrected for large particle size eﬀects.
89
90 CHAPTER 7. LIGHT SCATTERING
Incident Light
Scattered
Light
Figure 7.1: Scattering of incident light oﬀ a particle in solution or in vacuum.
A light scattering theory known as the RayleighGans theory was developed to extend Rayleigh
theory to particles that are not optically small. The correction method involves extrapolation
techniques that extrapolate light scattering intensity to zero scattering angle. This correction
technique is important for analyzing results on polymer solutions.
Analysis of osmotic pressure experiments requires extrapolation techniques to account for non
ideal solutions. In light scattering there are two nonideal eﬀect — nonideal solutions and large
particle size eﬀects. Thus, analysis or deconvolution of light scattering data requires two extrapo
lations. One is an extrapolation to small particle size to remove the large particle size eﬀect. The
other is an extrapolation to zero concentration to remove the eﬀect of nonideal solutions. The slope
of the ﬁrst extrapolation gives the mean squared radius of gyration (s
2
). The slope of the second
extrapolation gives the second virial coeﬃcient (A
2
). The intercept of the two extrapolations gives
the weight average molecular weight (M
W
).
7.2 Rayleigh Theory
We begin by describing the theory for light scattering oﬀ a small particle in an ideal solution. Light
is an electromagnetic ﬁeld. At the origin the ﬁeld is time dependent and described by:
E
z
= E
0
cos
_
2πct
λ
_
(7.2)
where E
0
is the amplitude of the electric ﬁeld, c is the speed of light, and λ is the wavelength of
light. The subscript z on E means we are considering plane polarized light with the light polarized
along the z axis. An incident beam of light polarized in the z direction is shown in Fig. 7.2.
If the particle at the origin in Fig. 7.2 is polarizable, the incident electric ﬁeld will induce a
dipole moment in that particle. The magnitude of the dipole moment is proportional to the ﬁeld.
7.2. RAYLEIGH THEORY 91
Incident Polarized Light
z
Figure 7.2: Plane polarized light polarized in the z direction and incident on a small particle.
The proportionality constant is called the polarizability — α
p
. The higher a particle’s polarizability
the higher will be the magnitude of the dipole moment induced by a given electromagnetic ﬁeld.
The dipole moment is
p = α
p
E
0
cos
_
2πct
λ
_
(7.3)
The induced dipole moment will radiate light in all directions. We consider observing the radiated
or scattered light at a distance r from the origin along a line that makes an angle θ
z
with the z
axis (see Fig. 7.3). The scattered light ﬁeld will be proportional to (1/c
2
)(d
2
p/dt
2
). The second
derivative of p is the acceleration of the charge on the dipole moment. To include spatial eﬀects,
the scattered light is also proportional to 1/r (electromagnetic ﬁelds die oﬀ as 1/r) and to sin θ
z
(the projection of the dipole moment on the observation direction). Combining all these eﬀects,
the electric ﬁeld for light scattered in the θ
z
direction is
E
s
=
1
r
1
c
2
d
2
p
dt
2
= −
1
c
2
α
p
E
0
4π
2
c
2
rλ
2
sin θ
z
cos
_
2πct
λ
_
(7.4)
Equipment that measures scattered light is typically only sensitive to the intensity of light. The
intensity of light is equal to the amplitude of the electromagnetic ﬁeld squared. Thus, squaring the
amplitude of E
s
gives the scattered light intensity at r and θ
z
:
I
s
= α
2
p
I
0z
16π
4
r
2
λ
4
sin
2
θ
z
(7.5)
where I
0z
is the intensity of the z polarized incident light.
I
0z
= E
2
0
(7.6)
92 CHAPTER 7. LIGHT SCATTERING
Incident Polarized Light
z
r
θ
z
Figure 7.3: Observation direction for light scattered oﬀ a particle at the origin in a direction that makes
an angle θ
z
with respect to the z axis. The observation distance is r.
The above results are for incident light polarized in the z direction. Experiments, however, are
usually done with unpolarized light. We can account for unpolarized incident light by summing
the intensity of equal parts of incident light polarized in both the z direction and the y direction.
The incident intensity becomes
I
0
=
1
2
I
0z
+
1
2
I
0y
(7.7)
and the intensity of scattered light becomes
I
s
=
1
2
I
sz
+
1
2
I
sy
= I
0
8π
4
α
2
p
r
2
λ
4
_
sin
2
θ
z
+ sin
2
θ
y
_
(7.8)
where θ
y
is the angle the observation direction makes with the y axis. Scattering of unpolarized
light is illustrated in Fig. 7.4.
By geometry the θ
z
and θ
y
terms can be related to the angle θ
x
that the observation direction
makes with the x axis (see Fig. 7.4). This angle will simply be referred to as θ. Because the sum
of the direction cosines is 1:
cos
2
θ
x
+ cos
2
θ
y
+ cos
2
θ
z
= 1 (7.9)
the geometric result is easily derived to be
sin
2
θ
z
+ sin
2
θ
y
= 1 + cos
2
θ (7.10)
We now have the scattered light intensity for scattering oﬀ a single particle. For scattering oﬀ n
moles of particles or nL particles (L is Avagadro’s number) in a dilute solution of volume V , the
7.3. IDEAL POLYMER SOLUTIONS WITH SMALL PARTICLES 93
Incident Unpolarized Light
z
θ
Figure 7.4: Scattering of unpolarized light is analyzed by considering scattering of incident light polarized
in both the z and y directions.
scattered intensity at θ is:
i
0
θ
=
I
0
nL
V
8π
4
α
2
p
r
2
λ
4
_
1 + cos
2
θ
_
(7.11)
The superscript 0 on the i indicates that this is scattering due to small molecules.
The light scattering intensity depends on scattering angle. The shape of the diagram is deter
mined by the (1 + cos
2
θ) term. A plot of this term is given in Fig. 7.5. The maximum scattering
intensity is at θ = 0. The minimum scattering intensity is at θ = 90. The scattering intensity for
forward scattering is equal to the intensity for back scattering at the corresponding angle. In other
words, the scattering intensity at angle θ is equal to the scattering intensity at angle 180 −θ.
As a function of λ, the scattered intensity is proportional 1/λ
4
. This strong wavelength depen
dence makes short wavelength light scatter more than long wavelength light. This eﬀect explains
why the sky is blue. Short wavelength or blue light scatters the most. Normally we do not look
at the sun and θ is not zero. When θ is not zero you see the scattered light or the blue light. At
sunset you normally do look in the direction of the sun and θ is zero or near zero. Because blue
light is scattered away, you are left with the red light and sunsets appear red.
7.3 Ideal Polymer Solutions with Small Particles
For practical results, we need to make a connection between the scattering intensity derived in the
previous section and molecular weight of the polymer particles in solution. The connection arises
because polarizability depends on molecular weight. First, the polarizability can be thought of as
94 CHAPTER 7. LIGHT SCATTERING
2 1 1 2
1
0.5
1
θ
Figure 7.5: Shape of the scattering intensity as a function of scattering angle for scattering oﬀ a small
particle.
a diﬀerence in the index of refraction between the polymer and the solvent. In other words light
scattering only occurs in mediums that have an inhomogeneous index of refraction. Speciﬁcally,
the polarizability of particles at concentration c is
α
p
=
n
0
cV
2πnL
dn
0
dc
(7.12)
where n
0
is the index of refraction of the solution and dn
0
/dc is the concentration dependence of
the index of refraction. Note that if the index of refraction of the solvent and of the polymer are
the same then dn
0
/dc will be zero and there would be no polarizability and therefore no scattered
light. Writing c as nM/V (in units of g/ml) yields
α
p
=
n
0
M
2πL
dn
0
dc
(7.13)
and substituting into the scattered light intensity gives (where we also replace n/V by c/M):
i
0
θ
I
0
=
2π
2
r
2
λ
4
n
2
0
L
_
dn
0
dc
_
2
Mc
_
1 + cos
2
θ
_
(7.14)
In a given scattering experiment, I
0
and r will be ﬁxed and we will measure i
0
θ
. These measured
quantities can be combined into one quantity called the Rayleigh ratio — R
0
θ
:
R
0
θ
=
r
2
i
0
θ
I
0
(7.15)
The advantage of the Rayleigh ratio is that it is independent of the incident light intensity and
the distance to the scattered light detector (i.e., independent of I
0
and r). From the scattering
equation, the Rayleigh ratio can be written as:
R
0
θ
= KMc (7.16)
7.4. NONIDEAL POLYMER SOLUTIONS 95
where
K =
2π
2
n
2
0
λ
4
L
_
dn
0
dc
_
2
_
1 + cos
2
θ
_
(7.17)
The constant K depends only on the solvent properties, on λ, and on θ. K is therefore a system
constant that is independent of the concentration of the solution and the molecular weight of the
polymer.
For a dilute, polydisperse polymer solution, the total Rayleigh ratio can be written as a sum of
the Rayleigh ratios for scattering of polymers of each possible molecular weight:
R
0
θ
= K
i
c
i
M
i
(7.18)
or
Kc
R
0
θ
=
i
c
i
i
c
i
M
i
=
i
N
i
M
i
i
N
i
M
2
i
=
1
M
W
(7.19)
The Rayleigh ratio for an ideal polymer solution with small particles is thus directly related to the
weight average molecular weight (M
W
).
7.4 NonIdeal Polymer Solutions
As done with osmotic pressure, the possibility of nonideal solutions is handled by adding virial
coeﬃcients and concentration terms to the ideal result. Thus expanding Kc/R
0
θ
gives
Kc
R
0
θ
=
1
M
W
+ 2A
2
c + 3A
3
c
2
+· · · (7.20)
The virial coeﬃcients A
2
and A
3
are the same as the virial coeﬃcients we discussed in osmotic
pressure theory. The factors of 2, 3, etc., come from the thermodynamic theory of ﬂuctuations
which can be used to show that
Kc
R
0
θ
=
1
RT
∂π
∂c
(7.21)
where π is osmotic pressure. In a virial expansion
π =
RT
M
N
c +RTA
2
c
2
+RTA
3
c
3
+· · · (7.22)
To convert to the light scattering experiment, the M
N
in the π expression must be changed to M
W
.
The only diﬀerence between the A
2
in osmotic pressure and the A
2
in light scattering is that the
light scattering A
2
is formally a weightaverage virial coeﬃcient. Besides that diﬀerence, the light
scattering A
2
gives similar information, notably information about the quality of the solvent.
Typically, we will ignore terms beyond the second virial coeﬃcient. Then Kc/R
0
θ
is predicted to
be linear in c. From experiments we can plot Kc/R
0
θ
as a function of c. The slope will give the second
virial coeﬃcient (slope = 2A
2
) and the intercept will give the molecular weight (intercept = 1/M
W
).
This extrapolation, however, ignores any possible large particle size eﬀects The extrapolated M
W
will therefore be in error. The next section considers how to correct for large particle size.
96 CHAPTER 7. LIGHT SCATTERING
Scattering from different
parts of the particle
Path length difference
causes destructive interference
Figure 7.6: Scattering of light of two diﬀerent parts of a large polymer molecule.
7.5 Large particles
If a particle is not small compared to the wavelength of light, the light can scatter from diﬀerent
parts of the particle. Fig. 7.6 shows a large polymer that is scattering light. Light scattering
from diﬀerent parts of the particle will reach the detector by traveling diﬀerent path lengths. The
diﬀerence in path lengths can lead to destructive interference that reduces the intensity of the
scattered light. The net eﬀect is that the scattering diagram for large particles is reduced in
intensity from the scattering diagram for small particles (see Fig. 7.5).
The amount of intensity reduction or the amount of destructive interference depends on the
scattering angle. At θ equal to zero, the path lengths will always be identical. With identical path
lengths, there will be no destructive interference. In other words at θ = 0, the intensity of scattered
light will be identical to i
0
θ
. At θ not equal to zero there will be destructive interference. As θ
increases, the interference will increase reaching a maximum and θ = 180
◦
. A comparison of the
scattering diagrams for large particles vs. small particles is given in Fig. 7.7. The large particle
scattering diagram shows the eﬀect of large particles and now shows asymmetry in scattering; i.e.,
the back scattering intensity is much reduced from the forward scattering intensity.
To correct for large particles, we merely need to do the light scattering experiments at zero
scattering angle (θ = 0). Unfortunately, these experiments cannot be done. At θ = 0 most light
will be transmitted light that is not scattered. The transmitted light will swamp the scattered
light preventing its measurement. Because scattered light and transmitted light have the same
wavelength, there is no way to distinguish between them. Instead, we must do experiments at
θ > 0 and extrapolate to θ = 0. We thus do a second extrapolation, an extrapolation to zero
scattering angle.
To develop an extrapolation method, we deﬁne a new function, P(θ), that describes the large
7.5. LARGE PARTICLES 97
2 1 1 2
1
0.5
1
Large
Particles
Small
Particles
θ
Figure 7.7: Scattering diagrams for both small particles and large particles.
particle size eﬀect. P(θ) is the ratio between the actual scattering (i
θ
) and the scattering that
would occur oﬀ small particles (i
0
θ
)
P(θ) =
i
θ
i
0
θ
=
R
θ
R
0
θ
(7.23)
From the above discussions we know that P(0) = 1 (there is no eﬀect at zero scattering angle)
and P(θ) < 1 for all other θ (destructive interference can only cause a reduction in intensity). The
larger eﬀect on back scattering than on forward scatter means that P(θ < 90) > P(180 −θ).
First consider an ideal solution. The measured Rayleigh ratio, written as R
θ
, includes the large
particle size eﬀect. Using P(θ) we can write R
θ
= P(θ)R
0
θ
. The key measured quantity becomes
Kc
R
θ
=
Kc
P(θ)R
0
θ
=
1
M
W
P(θ)
(7.24)
The second equality follows from the previously derived ideal solution result with small particles.
To use this equation, we need some information about P(θ). That information can sometimes be
derived by theoretical analysis of largeparticle scattering. Fortunately, some theoretical results are
available for scattering oﬀ a large random coil. The results are accurate as long as the particle size
is not too large. Instead of requiring
_
s
2
< λ/20 as done before for small particles, we can use
the theoretical result to handle particles with
_
s
2
< λ/2. For scattering with visible light we
now can use
_
s
2
< 2000
˚
A to 4000
˚
A. Most polymers fall within or below this range and thus we
can derive eﬀective extrapolation methods for scattering oﬀ polymer molecules.
The theoretical result for P(θ) is
1
P(θ)
= 1 +
16π
2
3λ
2
s
2
sin
2
θ
2
+· · · (7.25)
The “· · ·” means that there are higher order terms in sin(θ/2). Those terms are normally assumed
to be negligible. For a polydisperse polymer, the scattering intensity as a function of scattering
98 CHAPTER 7. LIGHT SCATTERING
angle becomes
Kc
R
θ
=
1
M
W
_
1 +
16π
2
3λ
2
s
2
w
sin
2
θ
2
_
(7.26)
Note we have changed s
2
to s
2
w
, the weight average radius of gyration squared. In terms of the
various polymer weights, the relevant radius of gyration squared is
s
2
w
=
i
N
i
M
i
s
2
i
i
N
i
M
i
=
i
w
i
s
2
i
(7.27)
where s
2
i
is the average squared radius of gyration for polymers with molecular weight M
i
To ﬁnd weightaverage molecular weight (M
W
) in ideal solutions, we truncate 1/P(θ) after the
sin
2
(θ/2) term and plot Kc/R
θ
as a function of sin
2
(θ/2). That plot should be linear. The intercept
will give the molecular weight:
intercept =
1
M
W
(7.28)
The slope divided by the intercept will give the radius of gyration
slope/intercept =
16π
2
s
2
w
3λ
2
(7.29)
7.6 Light Scattering Data Reduction
To handle both nonideal solutions and large particle eﬀects, we need to do two extrapolations.
First, we introduce nonideal solution eﬀects into the large particle analysis in the previous section.
Instead of using P(θ) to correct the ideal solution result, we use it to correct the nonideal solution
result. Thus the actually measured Kc/R
θ
is
Kc
R
θ
=
Kc
P(θ)R
0
θ
=
_
1
M
W
+ 2A
2
c
_
1
P(θ)
(7.30)
where we have truncated the nonideal solution result to a single virial coeﬃcient. Inserting the
theoretical result for P(θ) truncated after the sin
2
(θ/2) term gives
Kc
R
θ
=
_
1
M
W
+ 2A
2
c
__
1 +
16π
2
3λ
2
s
2
w
sin
2
θ
2
_
(7.31)
A set of light scattering experiments consists of measure Kc/R
θ
for various concentrations and
at various scattering angles. To get M
W
, we do two extrapolations. First, plotting Kc/R
θ
as a
function of sin
2
(θ/2) at constant c gives a straight line with the following slope and intercept:
slope =
_
1
M
W
+ 2A
2
c
_
16π
2
3λ
2
s
2
w
(7.32)
intercept =
_
1
M
W
+ 2A
2
c
_
(7.33)
7.6. LIGHT SCATTERING DATA REDUCTION 99
c=0
c1
c2
c3
c4
c5
θ=0
θ1
θ2
θ3
θ4
θ5
θ6
sin
2
θ
+ kc
2
Kc
R
θ
Figure 7.8: Typical Zimm plot. The experimental data points are at the grid intersection points except
along the θ = 0 and c = 0 lines.
Next we plot the intercepts of the ﬁrst plots as a function of concentration. The resulting plot
should be a straight line with
slope = 2A
2
(7.34)
intercept =
1
M
W
(7.35)
The slope and intercept of the second line gives us M
W
and A
2
. Substituting these results into the
slope of the ﬁrst line allows us to ﬁnd s
2
w
. We could achieve similar results by ﬁrst plotting as a
function of concentration and then plotting the intercept of those plots as a function of sin
2
(θ/2).
The above analysis assumes that all c’s are low enough such that the concentration dependence
is linear in concentration and only requires the second virial coeﬃcient. It also assumes all scattering
angles are low enough that terms higher than the sin
2
(θ/2) can be neglected. Both these conditions
are easy to satisfy for light scattering with polymer solutions.
The analysis method described above is easy to do in a personal computer. When light scatter
ing techniques were ﬁrst developed, however, computers were not available and the numerous linear
ﬁts were tedious. To avoid the tedium the Zimm plot was developed. In the Zimm plot technique,
you plot Kc/R
θ
versus sin
2
(θ/2) +kc where k is a constant. k is chosen to spread out the plot and
give equal weights to each variable. For example sin
2
(θ/2) is always less than 1 or has a maximum
of 1. The range in kc should also go from 0 to 1 or kc
max
= 1 which means a good k might be
1/c
max
where c
max
is the maximum concentration used. A typical Zimm plot is given in Fig. 7.8.
Plotting all Kc/R
θ
points on a Zimm plot should result in a grid such as the one shown in
100 CHAPTER 7. LIGHT SCATTERING
Fig. 7.8. There will be experimental points at all grid points except along the lower line (the θ = 0
line) and the leftmost line (the c = 0) line. Connecting all the grid lines and extrapolating to the
lowerleft corner, the intercept point gives the molecular weight (intercept = 1/M
W
). Incorporating
the k constant, the Zimm plot is plotting
Kc
R
θ
=
_
1
M
W
+
2A
2
k
kc
__
1 +
16π
2
3λ
2
s
2
w
sin
2
θ
2
_
(7.36)
The slopes of the two directions in the parallelogram have physical meaning. The lines labeled θ
1
,
θ
2
, etc., are lines at constant θ. Inspection of the Zimm equation shows that the slopes of these
lines are:
slope of the contant θ lines =
2A
2
k
_
1 +
16π
2
3λ
2
s
2
w
sin
2
θ
2
_
(7.37)
Notice that these slopes are a function of θ. Thus the slope of the θ = 0 line and the θ
5
(or any θ
i
line) are diﬀerent. In other words the Zimm plot is not actually a parallelogram. The lines labeled
c
1
, c
2
, etc., are lines at constant concentration. Inspection of the Zimm equation shows that the
slopes of these lines are:
slope of the constant c lines =
_
1
M
W
+ 2A
2
c
_
16π
2
3λ
2
s
2
w
(7.38)
Notice that these slopes are a function of c. Thus the slope of the c = 0 line and the c
5
(or any
c
i
line) are diﬀerent. In other words the Zimm plot is not actually a parallelogram. The slopes
of constant θ and constant c lines both depend on A
2
and on s
2
w
. The slopes of the constant θ
lines are mostly sensitive to A
2
. The slopes of the constant c lines are mostly sensitive to s
2
w
.
Because A
2
and s
2
w
are independent physical quantities, it is possible to get Zimm plots that
are inverted from the plot in Fig. 7.8. If A
2
increases and/or s
2
w
decreases, it is possible for the
steeper lines to be the constant θ lines and for the shallower lines to be the constant c lines.
Chapter 8
Miscellaneous Molecular Weight
Methods
8.1 Introduction
The previous three chapters described several methods for determining the molecular weight, or an
average molecular weight for a polymer dissolved in solution. This chapter brieﬂy describes a few
more techniques. At the end there is a short discussion about polymers that cannot be dissolved
into any solvent.
8.2 Gel Phase Chromatography
Gel phase chromatography is also called size exclusion chromatography; the reason for this second
name will become apparent shortly. In gel phase chromatography, a standard chromatographic col
umn is ﬁlled with beads of a rigid porous gel (e.g., porous glass or highly crosslinked polystyrene).
The beads are selected such that the size of its pores are in the range of the sizes of polymer
molecules. Figure 8.1 illustrates what happens when a dilute polymer solution is introduced into
the column. The larger molecules do not ﬁt into the pores and thus they take the easier and faster
route around the ﬁller particles and out the bottom of the column. The smaller molecules are able
to get into the pores and thus they follow a path that sometimes travels through the ﬁller particles.
Because passage through a ﬁller particle presents a more tortuous path, the smaller molecules spend
more time in the column before coming out the bottom.
A typical gel phase chromatography experiment consists of collecting elution fractions as they
elute from the bottom of the column. The ﬁrst fractions will be more concentrated in high molecular
weight polymer. As a function of time (or as a function of total volume that has eluted — the
elution volume) the elution fraction will be more concentrated in increasingly lower molecular weight
101
102 CHAPTER 8. MISCELLANEOUS MOLECULAR WEIGHT METHODS
Figure 8.1: Schematic drawing of a gel phase chromatographic column. The line represents a path of a
polymer. The solution that comes out the bottom can be collected in ﬂasks.
polymer. By many means (e.g., absorption spectroscopy or index of refraction) it is possible to
determine the concentration of polymer in each fraction. Plotting these concentrations as a function
of time or elution volume will give the complete molecular weight distribution (see Fig. 8.2). Because
high molecular weight fractions come out ﬁrst, the plot of raw data will be a mirror image of the
molecular weight distribution.
Like viscosity experiments, the results from gel phase chromatography experiments are not
absolute. You need a calibration experiment to convert the concentration data versus elution
volume to concentration data versus molecular weight or true molecular weight distribution. The
calibration procedure typically uses calibrated viscosity experiments. From the viscosity theory
(see Chapter 6), the intrinsic viscosity is
[η] = Φ
_
r
2
M
_
3
2
M
1
2
= Φ
_
r
2
_3
2
M
−1
(8.1)
where Φ is a constant (relatively ﬁxed for polymer solutions), r
2
is the mean squared endtoend
distance of the polymer (hence (r
2
)
3/2
is proportional to total volume of the polymer), and M is
molecular weight. This equation can be rearranged to give
[η]M = Φ
_
r
2
_3
2
(8.2)
Because Φ is a relatively polymerinsensitive constant and (r
2
)
3/2
merely expresses volume, a
plot of [η]M as a function of any property that depends only on polymer volume should produce a
8.2. GEL PHASE CHROMATOGRAPHY 103
Concentration
High MW
Time Low MW
Elution Volume
C
o
n
c
e
n
t
r
a
t
i
o
n
Figure 8.2: Molecular weight distribution curve from gel phase chromatography. The high molecular
weight polymers come out at early time and the low molecular weight polymers come out a latter time.
universal or master curve. In other words the curve would be the same for all polymer/solvent/
temperature systems.
Passage time through a gel phase chromatography column is one such property that depends
only on polymer volume. We can expect or assume that all polymers with the same value of
[η]M will elute at the same time in that column. The calibration procedure uses this assumption.
Calibration data consists of a plot of [η]M versus elution volume. [η]M is measured using viscosity
experiments on polymers of known molecular weight. For greatest accuracy and elimination of
ambiguity about the type of average molecule weight, the preferred experiments use monodisperse
polymers. The elution time is measured in a chromatographic column. A plot of [η]M should
be a universal calibration curve for that speciﬁc gel phase chromatographic column. Because the
calibration curve should be independent of polymer type, the calibration experiment can be done
with any convenient polymer. A typical calibration curve is shown in Fig. 8.3. As [η]M increases
the elution volume (or elution time) decreases. Because [η]M increases with molecular weight, the
curve expresses the tendency of high molecular weight polymer to elute faster than low molecular
weight polymer.
Once you have a calibration curve, you can use that column to measure the molecular weight
distribution of any soluble polymer. For the unknown polymer, data of concentration versus elution
volume is collected. For each elution volume, the calibration curve is used to calculate the [η]M
corresponding to that elution time. By viscosity theory, a given calibration value for [η]M (here
denoted as ([η]M)
c
is related to the molecular weight of the unknown polymer by
([η]M)
c
= KM
a+1
(8.3)
104 CHAPTER 8. MISCELLANEOUS MOLECULAR WEIGHT METHODS
Calibration Curve
Elution Volume
[
η
]
M
Figure 8.3: A typical calibration curve for gel phase. chromatography
where K and a are the viscositymolecular weight constants for the unknown polymer being studied.
Solving for molecular weight gives
M =
_
([η]M)
c
K
_ 1
a+1
(8.4)
Formally this M is a viscosity average molecular weight. Because each elution fraction, however, is
close to monodisperse polymer, we can treat it is an absolute molecular weight and not an average
molecular weight.
In summary, gel phase chromatography gives information about complete molecular weight
distribution. Its only drawbacks are that it requires calibration experiments, it requires the polymer
to be soluble, and requires a modest amount of specialized equipment.
8.3 Field Flow Fractionation
Field ﬂow fractionation or FFF is a powerful and ﬂexible technique that was developed at the
University of Utah. There is currently no information on FFF in these notes, but the technique
will be discussed in class.
8.4 End Group Analysis
Consider the polymer shown in Fig. 8.4. The two ends have acid groups ( COOH groups) and the
reminder of the polymer backbone has no acid groups. The situation in Fig. 8.4 is common to many
polymers. The common situation is not that many polymers have COOH end groups, but that
the end groups are often chemically distinguishable from the backbone of the polymer. When the
8.4. END GROUP ANALYSIS 105
COOH
HOOC
Figure 8.4: A typical polymer having chemically distinguishable end groups.
backbones are chemically unique it is sometimes possible to use analytical chemistry techniques to
measure the concentration of end groups. Some typical analytical methods are: chemical methods
(e.g., titration of acid groups as for Fig. 8.4 or of basic groups), spectroscopic measurements, or
radioactive measurements (e.g., for polymers with labeled endgroups).
Measuring the concentration of end groups allows you to measure the number of end groups.
Assuming the polymer is linear, each polymer will have two end groups. Thus dividing the number
of end groups by two will give the total number of polymer molecules. In some polymers the two
end groups are distinguishable from each other. In this case, measuring the number of one type of
end group will be equal the number of polymer molecules (without dividing by two). The average
molecular weight, which in this case will be the number average molecular weight, can be calculated
from
Total Weight
Number of Polymers
=
i
N
i
M
i
i
N
i
= M
N
(8.5)
When endgroup analysis works, it can be a useful technique to measure an absolute molecular
weight. Unfortunately, it often has problems that make it impractical. First the ratio of end
groups to total amount of polymer is small. Thus when using dilute concentrations of polymers,
an accurate end group analysis will require extremely sensitive techniques. The sensitivity problem
gets worse as the molecular weight gets higher, because the number of end groups decreases as the
molecular weight increases. As a result, endgroup analysis is limited to relatively low molecular
weight polymers.
Another problem is that use of endgroup analysis assumes you know the structure of the
polymer. You must know the chemical nature of the end groups and know that the polymer is linear.
Furthermore, the chemical nature of the end groups must be such that they can be distinguished
from the rest of the polymer. Endgroup analysis cannot be used when the end groups are uncertain
(a situation that arises in some polymer synthesis schemes) or when the polymer is branched or
crosslinked. In principle, if you knew the number of branches per polymer, you could divide the
total number of end groups by that number and still calculate the number of polymer molecules.
Unfortunately, the extent of branching is not often characterized so precisely. If the polymer is
106 CHAPTER 8. MISCELLANEOUS MOLECULAR WEIGHT METHODS
linear you can be sure it has two ends; if it is branched you cannot be sure how many ends it has.
8.5 Ultracentrifugation
In the ultracentrifugation method, a polymer solution is placed in a centrifuge and the rate of
sedimentation or the equilibrium position of polymer after centrifugation is measured. These quan
tities are typically measured by some spatially resolved optical means that is scanned along the
length of the centrifugation tube. The diﬀusion process under centrifugal force is related to the
size or molecular weight of the polymer. The polymer concentration along the tube as a function
of position can be reduced to give average molecular weights. At its best, the results can even give
information about distribution of molecular weights by ﬁnding M
N
, M
W
, M
z
, and M
z+1
, etc..
Ultracentrifugation works well and is used often when working with biological macromolecules
(e.g., proteins). These macromolecules usually have ﬁxed structures and are close to being spherical.
As a result they do not entangle with each other and simple sedimentation theories are applicable.
In contrast polymers are often random coils. They will often entangle with each other and the
sedimentation will be strongly eﬀected by the amount of entanglement. The technique is less useful
for high molecular weight random coil polymers.
8.6 Insoluble Polymers
If a polymer is insoluble, then most of the previously discussed techniques cannot be used to get
molecular weights. Colligative properties (e.g., osmotic pressure), solution viscosity, light scat
tering, gel phase chromatography, ﬁeldﬂow fraction, endgroup analysis, and ultracentrifugation
always use polymer solutions. If the polymer cannot be dissolved in any solvent, those techniques
will not be applicable. One technique available which is sensitive to molecular weight is melt
rheology (i.e., melt viscosity experiments).
On a theoretical basis one can take a known molecular weight distribution and make a reasonable
calculation of melt rheology data. Recent workers have suggested that the reverse calculation can
be made. Given melt rheology data, they claim to be able to calculate the molecular weight
distribution. These techniques make many assumptions and are probably only qualitative at best.
Their work indicates, however, that melt rheology data can be used to get at least qualitative and
comparative data about molecular weights in various insoluble polymers.
One crude standard technique is called melt index. It measures the amount of molten polymer
that ﬂows through a standard opening in a ﬁxed amount of time. The higher the melt index, the
lower the viscosity of the polymer melt and thus the lower the molecular weight. Although this
technique is crude, it is often used by industry and reported in company literature on various grades
of polymers.
8.6. INSOLUBLE POLYMERS 107
Problems
8–1. Nylon11 is poly(11aminoundecanoic acid). This polymer has a crystal melting point around
190
◦
C and has lower water absorption than Nylon 6,6 or Nylon 6. It can be used to make
mechanical parts, packaging ﬁlms, gristles, monoﬁlaments, and sprayed and ﬂuidized coatings.
It is formed via polymerization of the following monomer:
HO–C–(CH
2
)
10
–NH
2
O
a. If 2.65 grams of nylon 11 was dissolved in 450 ml of Formic acid and it was subsequently
determined that the concentration of amine groups was [NH
2
]=3.56 ×10
−4
moles/liter,
what would be the average molecular weight of the polymer?
b. In part a, what type of molecular weight average was determined?
c. Without any additional information, what would be the “most probable” polydispersity
index M
W
/M
N
. From your guessed polydispersity index, write down both M
N
and M
W
for this polymer.
108 CHAPTER 8. MISCELLANEOUS MOLECULAR WEIGHT METHODS
Chapter 9
Thermal Analysis
9.1 Introduction
As temperature changes polymers undergo transitions (e.g., melting, glasstransition, subglass
transitions, crystallization, etc.). In thermal analysis we do two things. First, we ﬁnd the temper
atures where the various transitions occur, and second, we evaluate the change in properties the
might occur as the temperature is varied from below the transition to above the transition.
9.2 Thermal Transitions
The wellknown thermodynamicist Ehrenfest, developed a scheme for classifying thermal transi
tions. He classiﬁed transitions as ﬁrst order, second, order, third order, etc.. In practice, we only
encounter ﬁrst and second order transitions. In this section we discuss Ehrenfest’s classiﬁcation
scheme and consider speciﬁcally ﬁrst order and second order transitions.
A ﬁrst order transition is a transition that involves a discontinuous change in a ﬁrst derivative
of the free energy. Free energy is a function of temperature (T) and pressure (P). From our earlier
solution thermodynamics, but now considering constant composition, the ﬁrst diﬀerential of free
energy, or the change in free energy (dG) following a change in pressure (dP) and/or a change in
temperature (dT) is
dG = V dP −SdT (9.1)
From this diﬀerential expression, the ﬁrst derivatives of free energy are
_
∂G
∂P
_
T
= V (9.2)
_
∂G
∂T
_
P
= −S (9.3)
These ﬁrst derivatives have physical interpretations. The ﬁrst derivative with respect to pressure
is volume (V ). The ﬁrst derivative with respect to temperature is minus the entropy (−S). By
109
110 CHAPTER 9. THERMAL ANALYSIS
V
o
l
u
m
e
(
V
)
E
n
t
r
o
p
y
(
S
)
First Order Transitions
Temperature
Temperature
Figure 9.1: Typical observation of a ﬁrst order transition while measuring volume or entropy (ﬁrst deriva
tives of free energy).
Ehrenfest’s classiﬁcation scheme, a ﬁrst order transition occurs when the volume or entropy of a
material undergoes a discontinuous change at some temperature. The temperature at which the
change occurs is called the transition temperature.
Volume can be measured by dilatometry and entropy can be measured by calorimetry (S =
q/T). A typical ﬁrst order transition observed by either dilatometry or calorimetry is given in
Fig. 9.1. Both volume and entropy are expected to be higher above the transition temperature than
below it. Thus there is a discontinuous change to a higher value at the transition temperature.
An example of a ﬁrst order transition is the melting transition which occurs at the melting
point. The change in volume, ∆V
m
, and the change in entropy, ∆S
m
, describe the magnitude of
the discontinuous change. Other changes, such as the change in enthalpy can also be measured.
For melting, the change in enthalpy is the heat of fusion (∆H
m
or ∆H
f
). Note that a change in
ﬁrst derivative implies a change in slope in the function itself. Thus at a ﬁrst order transition, G
will change in slope but not change in value. We then have the result that ∆G
m
= 0. Because
∆G
m
= 0 = ∆H
m
−T
m
∆S
m
, we have
∆H
m
= T
m
∆S
m
or T
m
=
∆H
m
∆S
m
(9.4)
A second order transition is a transition that involves a discontinuous change in a second
derivative of the free energy. We can ﬁnd the possible second derivatives by diﬀerentiating V or
S (the ﬁrst derivatives) with respect to pressure or temperature. Of the four possible derivatives,
three are related to common physical properties:
_
∂
2
G
∂P
2
_
T
=
_
∂V
∂P
_
T
= −V K (9.5)
_
∂
2
G
∂T
2
_
P
= −
_
∂S
∂T
_
P
= −
C
P
T
+
S
T
(9.6)
9.2. THERMAL TRANSITIONS 111
Second Order Transitions
K C
p
Temperature Temperature
Figure 9.2: Typical observation of a second order transition while measuring compressibility or constant
pressure heat capacity (second derivatives of free energy).
_
∂
∂T
_
∂G
∂P
_
T
_
P
=
_
∂V
∂T
_
P
= V β (9.7)
(9.8)
where K is compressibility, C
P
is the constantpressure heat capacity, and β is the volumetric ther
mal expansion coeﬃcient. Second order transitions can be observed be measuring a discontinuous
change in K, in C
P
, or in β. K and β can be measured by dilatometry; C
P
can be measured by
calorimetry. Some typical dilatometry and calorimetry data at a second order transition are given
in Fig. 9.2. K, C
P
, and β are all expected to by higher above the transition temperature than
below it. Thus there is a discontinuous change to a higher value at the transition temperature.
Suppose that instead of measuring K, C
P
, or β, you were measuring V or S during a second
order transition. In other words you were measuring a ﬁrst derivative of free energy instead of a
second derivative of G. From the mathematical deﬁnition of derivatives, when the second deriva
tive of a function undergoes a discontinuous change, the ﬁrst derivative will undergo a change in
slope. Thus when K, C
P
, and β undergo a discontinuous change at a second order transition, V
and S will change in slope (but not value, i.e., ∆V = ∆S = 0) at the transition temperature.
Figure 9.3 shows typical second order transitions when observed by measuring a ﬁrst derivative of
free energy. Because K, C
P
, and β change to a higher value above the transition, the slopes of V
or S vs. temperature become higher above the transition.
Second order transitions are less common than ﬁrst order transitions. Some typical second
order transitions are orderdisorder transitions, rotational transitions, the disappearance of ferro
magnetism at the Curie point, and a transition in Helium at 2.2K. In polymers, the glass transition
is often treated as a second order transition. We will see that it has much in common with sec
ond order transitions, but on closer inspection it is not a true second order transition. The glass
transition is sometimes called a pseudo second order transition.
112 CHAPTER 9. THERMAL ANALYSIS
V
o
l
u
m
e
(
V
)
E
n
t
r
o
p
y
(
S
)
Second Order Transitions
Temperature
Temperature
Figure 9.3: Observation of a second order transition when observing volume or entropy (ﬁrst derivatives
of free energy).
First Order Transitions
K C
p
Temperature Temperature
Figure 9.4: Observation of a ﬁrst order transition when observing compressibility or constant pressure
heat capacity (second derivatives of free energy).
Suppose you were measuring K, C
P
, or β, perhaps in search of a second order transition, and
your material goes through a ﬁrst order transition. At the transition, the ﬁrst derivative of free
energy would have just undergone a discontinuous change. When measuring a second derivative of
free energy, a discontinuous change in the ﬁrst derivative of free energy will show up as a peak. If
the transition was very sharp, the peak would be very high and very narrow. For many practical
materials (especially polymers), the peak is less high and somewhat broad. Figure 9.4 shows typical
ﬁrst order transitions that are observed while measuring a second derivative of free energy.
A generalization of Ehrenfest’s classiﬁcation scheme is to call a transition an n
th
order transi
tions when the material undergoes a discontinuous change in an n
th
derivative of free energy at the
transition temperature. Transitions higher than second order are rare. For polymers we will only
deal with ﬁrst and second order transitions.
9.3. THERMAL ANALYSIS OF POLYMERS 113
9.3 Thermal Analysis of Polymers
This sections lists some of the common types of transitions observed in organic materials. Some of
them are common in polymers; others are rarely or never observed.
1. Vaporization: ﬁrst order transition that occurs at the boiling point and marks the transition
from liquid to gas (vapor). Vaporization transitions are almost never studied in polymers.
Because polymers are high molecular weight materials, their boiling points are very high. In
fact, almost all polymers will thermally degrade before they vaporize.
2. Melting: ﬁrst order transition that occurs at the melting point and marks the transition from
solid to liquid. Melting is a transition from solid to liquid, but is better characterized as a
disappearance of crystals. Because only semicrystalline polymers have crystals (amorphous
polymers have none), melting is only observed in semicrystalline polymers. There are some
important diﬀerences between disappearance of crystals on heating and their reappearance
on cooling. Melting is the disappearance of crystals and thus is observed while heating.
3. Crystallization: occurs when cooling from above the melting temperature to a low tempera
ture. Like melting, crystallization is a ﬁrst order transition. It corresponds to the formation
of crystals while cooling. As will be explained latter, the melting point and the crystallization
temperature are usually diﬀerent. Because only semicrystalline polymers can form crystals
(amorphous polymers have none), crystallization is only observed in semicrystalline polymers.
4. Glass transition: pseudo second order transition that occurs in amorphous polymers or in
the amorphous phase of semicrystalline polymers. The glass transition occurs when long
range motions become very slow with respect to the observation time scale. Formally, the
glasstransition is not a true thermodynamic second order transition but many aspects of
the thermal analysis of glass transitions are similar to true second order transitions. It is
thus often useful to treat it as a second order transitions. Because no polymers are 100%
crystalline, all polymers will have an amorphous fraction and will exhibit a glass transition.
The glass transition temperature is always lower than the melting or crystallization transition
temperature (can you explain why?).
5. Subglass transitions. a transition that occurs below the glass transition temperature. Sub
glass transitions are typically second order transitions. The transitions can occur in either
the amorphous fraction or in the crystal fraction. The physical processes that correspond to
subglass transitions will vary from polymer to polymer.
The above transitions in polymers are observed using various thermal analysis techniques. Sev
eral thermal analysis techniques will be discussed in the following three chapters. Those techniques
and what they measure are listed below:
114 CHAPTER 9. THERMAL ANALYSIS
1. Dilatometry (PVT or TMA): Measures volume as a function of temperature and/or pressure
(see Chapter 10).
2. Diﬀerential Scanning Calorimetry (DSC): Measures constantpressure heat capacity as a func
tion of temperature (see Chapter 11).
3. Thermogravimetric Analysis (TGA): Measures weight as a function of temperature and time.
This method is aimed at providing information about polymer degradation rather than ther
modynamic transitions (see Chapter 11).
4. Dynamic Mechanical Analysis (DMA): Measures stiﬀness and energy losses as a function of
temperature. By measuring a mechanical property, DMA can determine transition tempera
tures and simultaneously determine the eﬀect of the transition on properties (i.e., on stiﬀness)
(see Chapter 12).
Chapter 10
Dilatometry
10.1 Introduction
The technique of dilatometry measures volume (V ) as a function of temperature (T) and pressure
(P). The method is sometimes referred to as PV T measurements. In equilibrium systems, the
V is a unique function of T and P, i.e., V does not depend on the path taken or on the sample
history. In equilibrium systems, dilatometry is used to study the relation between P, V , and T
and to develop or test equations of state. Polymer melts are close to equilibrium systems. PV T
experiments on polymer melts have been used to check theoretical equations of state for polymer
melts. Note that equilibrium systems also require that no chemistry is occurring. If cross linking or
polymerization occurs at the test temperature than volume will change because of these reactions
and not because of T and P. Such results will not be an equilibrium system and cannot be analyzed
with an equation of state.
Polymers in solid form will not be equilibrium (e.g., glassy and semicrystalline polymers). Their
volume as a function of T and P will depend on the formation history (e.g., cooling rate, formation
pressure, and time at temperature and pressure). The formation history can eﬀect such things as
the degree of crystallinity, the crystal morphology, and the glass density. Much interesting PV T
work is done on nonequilibrium systems, and the results are useful despite the material being in
nonequilibrium conditions.
Many times it is possible to do quasiequilibrium experiments on nonequilibrium systems. For
example, if you form a solid by lowering the temperature below the glass transition temperature
and then do all experiments on that solid, the results might be considered to be in a state of quasi
equilibrium; i.e., a set of experiments on samples with the same formation history. The results
will be quasiequilibrium if it can be demonstrated that the process of approaching equilibrium is
much slower than the time scale of observation for all observation temperatures. For polymers, this
condition holds as long as the sample remains far enough below the glass transition temperature
115
116 CHAPTER 10. DILATOMETRY
P=0
Increasing P
V
o
l
u
m
e
Temperature
Figure 10.1: Typical PV T data for an amorphous polymer. The curves are data at constant pressure. As
the pressure increases, the curves move down and to the right.
(perhaps 30
◦
C or more below). Such quasiequilibrium data can give much useful information.
Because it is not a true equilibrium, the results might change with time. These changes, however,
are often very slow.
10.2 Amorphous Polymers
Some typical PV T data for an amorphous polymer are give in Fig. 10.1. There are several curves.
Each curve plots the volume as a function of pressure for some constant pressure. As the pressure
increases, the curves move down and to the right. The breaks in the curves are the glass transition
temperatures — T
g
. At T
g
, the slopes of the volume vs. temperature curves change. This change
in slope is an indication that the glass transition is a second order transition (see Chapter 9). At
higher pressures, the sample is more dense and the volume is lower. The T
g
always shifts to a
higher temperature at higher pressures. The glass transition is associated with mobility. At higher
pressures, the transition to higher mobility is more diﬃcult and thus requires higher thermal energy
or a higher transition temperature.
Besides a direct measure of volume as a function of temperature, dilatometry data can be
used to determine other physical properties of the material. We consider ﬁrst determination of the
thermal expansion coeﬃcient. Consider a transition from V
1
to V
2
and from T
1
to T
2
at constant
pressure P. The new volume can be expressed as
V
2
=
_
1 +β(T
2
−T
1
)
_
V
1
(10.1)
where β is the thermal expansion per degree — the volumetric thermal expansion coeﬃcient.
10.2. AMORPHOUS POLYMERS 117
L
0
L=(1+α∆T)L
0
Figure 10.2: Linear thermal expansion. a is the linear thermal expansion coeﬃcient.
Rearranging this expression gives
β =
1
V
1
V
2
−V
1
T
2
−T
1
(10.2)
For a small temperature change, this expression becomes a derivative and the thermal expansion
coeﬃcient is deﬁned as
β(P, T) =
1
V (P, T)
_
∂V (P, T)
∂T
_
P
=
_
∂ ln V (P, T)
∂T
_
P
(10.3)
Any one of these expressions can be used with dilatometry data to measure β. The discrete forms
are easiest to use with discrete dilatometry data. Dilatometry data is sometimes reported as an
empirical ﬁt to an equation of state (see below). In these cases the equation of state can be
diﬀerentiated to measure β using the deﬁnition in terms of derivatives.
Below T
g
, β is usually nearly constant. Hence volume vs. temperature is close to a straight
line. At T
g
, β undergoes a discontinuous change to a higher value. The higher value remains
roughly constant above T
g
. Hence volume vs. temperature is close to a straight line above T
g
. The
discontinuous change in β is another manifestation of the glass transition being a second order
transition — β is a second derivative of free energy and it undergoes a discontinuous change at T
g
.
Consider thermal expansion of an isotropic material. Because of isotropy, the amount of ther
mal expansion along each of the three axes will be the same. If we deﬁne α as the linear thermal
expansion coeﬃcient, then the change in lineal dimension (L) is illustrated in Fig. 10.2. Follow
ing the interpretation of volumetric thermal expansion coeﬃcient, the linear thermal expansion
coeﬃcient (or commonly just the thermal expansion coeﬃcient) is deﬁned by
α(P, T) =
1
L(P, T)
_
∂L(P, T)
∂T
_
P
=
_
∂ ln L(P, T)
∂T
_
P
(10.4)
β and α both describe thermal expansion and thus can be related to each other. Consider
thermal expansion from V
1
to V
2
after a temperature change of 1
◦
C (T
2
−T
1
= 1) where
V
1
= L
1
L
2
L
3
and V
2
= (1 +α)
3
L
1
L
2
L
3
= (1 +β)V
1
(10.5)
Comparing these expressions
1 +β = 1 + 3α + 3α
2
+α
3
(10.6)
Because α is usually small (≈ 10
−5
) we can ignore higher order terms (3α
2
and α
3
) and write with
suﬃcient accuracy
β ≈ 3α (10.7)
118 CHAPTER 10. DILATOMETRY
This result assumes an isotropic material. It is easy to generalize it to an anisotropic material by
allowing the linear thermal expansion coeﬃcients in the three directions to be diﬀerent. Thus
β ≈ α
1
+α
2
+α
3
(10.8)
where α
i
is the thermal expansion coeﬃcient for thermal expansion in the i
th
direction.
The values of α and β do not vary dramatically from polymer to polymer. At most we might
expect a factor of two diﬀerence between any two polymers. Typical values for isotropic, amorphous
polymers
Below T
g
: α = 50 −100 ppm/
◦
C (β = 150 −300 ppm/
◦
C)
Above T
g
: α = 150 −300 ppm/
◦
C (β = 450 −900 ppm/
◦
C)
The designation “ppm/
◦
C” means parts per million per degree C. These units are convenient for
thermal expansion coeﬃcients. Without the“ppm” designation the numbers should include a factor
of 10
−6
. For example the typical α below T
g
is 5 ×10
−5
to 1 ×10
−4
.
The pressure dependence of PV T data at constant temperature can be used to calculate the
isothermal compressibility. In analogy with volumetric thermal expansion coeﬃcient, compressibil
ity is deﬁned by
K(P, T) = −
1
V (P, T)
_
∂V (P, T)
∂P
_
T
= −
_
∂ ln V (P, T)
∂P
_
T
(10.9)
The minus sign is included to make K positive. When K is large, the material is compressible or
soft. When K is small, the material is incompressible or hard. K undergoes a discontinuous change
from a low to a higher value at T
g
. The discontinuous change in K is another manifestation of the
glass transition being a second order transition — K is a second derivative of free energy and it
undergoes a discontinuous change at T
g
.
Empirically, the PV T properties of many amorphous polymers can be ﬁt using the Tait equa
tion. The Tait equation was derived in the nineteenth century from experiments on sea water. It
empirically explains sea water results (volume as a function of pressure and temperature) and also
the PV T properties of many other amorphous materials such as amorphous polymers. The Tait
equation is:
V (P, T) = V (0, T)
_
1 −0.0894 ln
_
1 +
P
B(T)
__
(10.10)
where V (0, T) is the volume at zero applied pressure (or atmospheric pressure) and B(T) is
B(T) = B
0
e
−B
1
T
(10.11)
where B
0
and B
1
are constants. Over a restricted temperature range, V (0, T) can often be expressed
as a polynomial. For example, we can write
V (0, T) = A
0
+A
1
T +A
2
T
2
+A
3
T
3
+· · · (10.12)
10.2. AMORPHOUS POLYMERS 119
where A
0
, A
1
, . . . are constants. Alternatively, if we assume that the volumetric thermal expansion
coeﬃcient is independent of temperature for some temperature range, we can integrate the deﬁnition
of β to get
V (0, T) = A
0
e
β(0)T
(10.13)
where A
0
is a constant and β(0) is the volumetric thermal expansion coeﬃcient at zero (or atmo
spheric) pressure.
Fitting experimental PV T data to the Tait equation is often a useful exercise. The Tait
equation has several ﬁtting constants. There are ﬁtting constants when ﬁtting V (0, T) (A
0
, A
1
,
. . . or A
0
and β(0)); there are two additional ﬁtting constants in B(T) (B
1
and B
0
). Over some
restricted temperature range all the PV T data can be reduced to 4 to 6 Tait parameters. Once
these parameters are known, it is possible to calculate volume for any temperature and pressure
within that temperature range. By diﬀerentiated the Tait equation with respect to temperature
or pressure, it is also possible to calculate the volumetric thermal expansion coeﬃcient and the
isothermal compressibility as functions of temperature and pressure. Because Tait equation ﬁts
can typically reproduce all the experimental results to four signiﬁcant ﬁgures, the Tait parameters
are a useful way to tabulate PVT data. Thus instead of storing a large amount of raw data,
one can record several sets of Tait parameters for temperature ranges of interest. Indeed, there
are polymer handbooks that list Tait parameters for common polymers. Another advantage of
using the Tait equation vs. the raw data is that it is more reliable to calculate volumetric thermal
expansion coeﬃcient and the isothermal compressibility by diﬀerentiating the Tait equation than
it is to numerically diﬀerentiate the raw data.
10.2.1 Pressure Dependence of T
g
Although the glass transition is not a true secondorder transtion, it is possible to calculate the
pressure dependence of T
g
by using thermodynamics methods. If one is careful in analysis of
experiments, this result is correct for polymer glass transitions. Two key results, ﬁrst derived by
Ehrenfest, are:
dT
g
dP
=
∆K
∆β
and
dT
g
dP
=
V T∆β
∆C
p
(10.14)
where the “∆” terms are changes in thermodynamic properties at the glass transition. Each of
these properties (compressibility (K), volumetric thermal expansion coeﬃcient (β), and constant
pressure heat capacity (C
p
)) has a discontinuous change at a secondorder transition. Because both
results are exact thermodynamics results, they can be equated to deﬁne the PrigogineDefray ratio
(R) or
R =
∆K∆C
p
V T(∆β)
2
= 1 (10.15)
This ratio must hold at any secondorder transition.
120 CHAPTER 10. DILATOMETRY
T
c
V
o
l
u
m
e
Temperature
T
g
T
m
Cooling Heating
Figure 10.3: Typical PV T data for a semicrystalline polymer at a single pressure. The solid curve is
obtained during heating, the dashed curved is obtained during cooling.
10.3 Semicrystalline Polymers
Some typical PV T data for a semicrystalline polymer are give in Fig. 10.3. The single curve
plots the volume as a function of pressure for some constant pressure. If we included curves for
several pressures (as in Fig. 10.1), the curves would move down and to the right as the pressure
increased. The break in the curve at low temperature is the glass transition temperatures — T
g
.
Because all semicrystalline polymers are also partially amorphous, they exhibit a glass transition
that is characteristic of amorphous polymers. At T
g
, the slope of the volume vs. temperature
curve changes. The magnitude of the change will reﬂect the amount of amorphous polymer that
is present. As the polymer gets more crystalline, the change in slope will get smaller. For some
highly crystalline polymers (e.g., polyethylene), the change in slope may be undetectable.
Figure 10.3 shows PV T results for both heating (solid curve) and cooling (dashed curve). In
addition to a glass transition, the heating curve shows a melting transition. The melting transition
temperature is always above the glass transition temperature. Melting of polymers is a ﬁrst order
transition and we expect a discontinuous change in volume. The change is never exactly discontin
uous but occurs over a relatively narrow temperature range of 2040
◦
C. The melting temperature
is usually deﬁned as the end of the melting range or the temperature at which all crystals have
completely melted. Most materials melt in a much narrower temperature ranges (< 1
◦
C). One
reason that polymers melt over a broad temperature range is that polymers have a distribution of
molecular weights. It can be demonstrated that melting point is a function of molecular weight.
Thus a polydisperse sample naturally shows a distribution in melting points or a temperature range
for melting.
10.4. EXPERIMENTAL TECHNIQUES 121
Above T
m
, the material is called a polymer melt. The PV T properties of polymer melts are
nearly equilibrium properties. There are equations of state which can predict this data. Polymer
melts are also amorphous liquids and thus the data can be ﬁt with the Tait equation if desired.
Below T
m
, the results are largely empirical. The Tait equation can be used well below the melting
transition. Near the melting transition, the melting process is too complex to be described by the
Tait equation. The Tait equation is an empirical equation that can describe amorphous materials.
The Tait equation, however, is not a thermodynamic equation of state and thus says nothing about
the occurrence of transitions. When the Tait equation cannot be used, α and K can still be found
by numerical diﬀerentiation of the raw data.
Heating and cooling experiments on semicrystalline polymers are diﬀerent. A thermodynamic
deﬁnition of T
m
is the temperature at which the free energy of the crystals and the melt are equal.
Above T
m
the free energy of the melt is lower. Below T
m
, the free energy of the crystals is lower.
Thus, on cooling, it is theoretically possible (by thermodynamic data) for new crystals to form
when the temperature ﬁrst reaches T
m
. In polymers, however, the crystals never form at T
m
.
Instead, there are energy barriers associated with nucleation and growth of the crystals that must
be overcome. These barriers are eventually overcome at some temperature below T
m
called the
crystallization temperature T
c
. The phenomenon whereby the temperature decreases below T
m
to
T
c
before crystallization occurs is called supercooling. The amount of supercooling depends on the
cooling rate, the properties of the sample, and the presence of heterogeneous nucleating agents.
The amount of supercooling can be large and in fact if cooled fast enough the crystallization can
be prevented entirely giving an amorphous polymer.
10.3.1 Pressure Dependence of T
m
Th pressure dependence of the melting point is easy to determine by thermodynamics analysis of
the ﬁrstorder transition. The result is
dT
m
dP
=
T
m
∆V
∆H
f
(10.16)
where ∆V is the volume change at the melting point and ∆H
f
is the heat of fusion of the pure
crystals (or the enthalpy change at the melting point).
10.4 Experimental Techniques
A simple, but not very accurate, dilatometer is called a thermal mechanical analyzer (TMA). A
TMA measures linear thermal expansion of a specimen. A schematic of a TMA apparatus is show
in Fig. 10.4. In brief, a probe rests on a sample with some weight (note: the probe shape may
be important). The probe is attached to a rod which passes into an linear variable displacement
transducer (LVDT). As the rod moves in the LVDT, the voltage output changes in proportion to
122 CHAPTER 10. DILATOMETRY
LVDT
Sample
Weights
Figure 10.4: Schematic drawing of a thermomechanical analyzer or TMA.
displacement. The LVDT thus converts a linear displacement to a voltage which can be recorded
by many types of scientiﬁc instruments. In a TMA experiment, the temperature is scanned and
the displacement is measured as a function of temperature.
The TMA method has several limitations. First, the probe must rest on the sample. The
sample must therefore remain solid over the entire temperature range of the tests. For polymers
TMA can be used as long as the temperature is kept well below T
g
. At higher temperature, the
probe may start to penetrate the specimen and give erroneous expansion results. If the probe
penetrated deeply, the TMA may report an illogical negative thermal expansion coeﬃcient. The
temperature at which penetration becomes signiﬁcant depends on the shape of the probe and the
amount of weight used to hold the probe on the surface. A second disadvantage of TMA is that
it only measures linear thermal expansion. To calculate volumetric thermal expansion, you must
either assume the specimen is isotropic (same thermal expansion in all directions) or you must
measure thermal expansion in all directions. In summary, TMA is does not give quantitative
results about transition temperatures (because of probe penetration problems) or about thermal
expansion coeﬃcient (because of uncertainty about specimen isotropy).
Unlike TMA, true dilatometry experiments measure total volume change. A simple dilatometer
can be constructed from simple glass ware — a beaker and a capillary (see Fig. 10.5). A sample is
immersed in a liquid. The experiment is to measure total volume of the liquid and polymer as a
function of temperature. The volume can be accurately measured by observing height of the liquid
in a narrow capillary on top of the beaker. To get the volume of the polymer, you must subtract the
volume of the pure liquid which can be measured by a calibration experiment. In the calibration
experiment you measure value of the pure liquid in the same dilatometer
To calibrate such a dilatometer you begin with an experiment on the pure liquid. Let m
l0
be
the mass of the liquid in the calibration experiment. Then you can measure the liquid volume as
a function of temperature, V
0
(T). It will be equal to
V
0
(T) =
m
l0
ρ
l
(T)
(10.17)
10.4. EXPERIMENTAL TECHNIQUES 123
Capillary
Sample
Figure 10.5: A simple dilatometry for measure volume of a polymer at atmospheric pressure.
where ρ
l
(T) is the density of the liquid at temperature T. Now do a real experiment combining a
mass m
s
of a specimen with a mass m
l
of liquid. The speciﬁc volume of the specimen is
v =
V
s
(T)
m
s
=
V (T) −V
l
(T)
m
s
(10.18)
where V
s
(T) is the volume of the specimen, V (T) is the total measured volume, and V
l
(T) is the
volume of the liquid, all at temperature T. The volume of the liquid is
V
l
(T) =
m
l
ρ
l
(T)
(10.19)
which gives
v =
1
m
s
_
V (T) −
m
l
ρ
l
(T)
_
(10.20)
In terms of the calibration data, V
0
(T), this equation can be rewritten as
v =
1
m
s
_
V (T) −
m
l
m
l0
V
0
(T)
_
(10.21)
Thus the speciﬁc volume of the specimen is given in terms of the masses (m
l
and m
s
), the mea
sured total volume (V (T)), the mass used in the calibration experiment (m
l0
) and the measured
calibration volume (V
0
(T)).
There are two other considerations when doing dilatometry experiments. First, there must be
no chemical reactions, either in the polymer, or between the liquid and the polymer. A chemical
reaction would cause a volume change not associated with PV T physical properties. Second, the
liquid must not undergo any transitions which would mask the sample volume change. In other
words, the conﬁning liquid must remain liquid over the entire temperature range of the experi
ments. If the liquid started to boil, the large volume changes associated with vaporization would
mask the polymer volume changes. If the liquid froze, it would no longer communicate polymer
volume changes to height changes in the capillary. A good conﬁning liquid for studying polymers
124 CHAPTER 10. DILATOMETRY
LVDT
Bellows
Sample
Heated
Jacket
Hydraulic Fluid Inlet
Figure 10.6: Schematic drawing of a PVT apparatus.
is mercury. It is relatively inert and reacts with very few polymers (but can react with ﬂuoropoly
mers). It is also a liquid at room temperature and remains a liquid to very high temperature. Its
liquid temperature range makes its suitable for studying glass transitions, melting transitions and
crystallization transitions in all but the highest melting point polymers. The main problem with
mercury is that its vapors are toxic.
Neither TMA nor simple dilatometry in a beaker are suitable to applying pressure and therefore
to getting volume data as a function of temperature and pressure. Equipment that can vary both
temperature and pressure is called PV T equipment. A good PV T technique is to apply pressure
using hydraulic ﬂuid. A schematic drawing of a highpressure PV T apparatus is given in Fig. 10.6.
The specimen is conﬁned in a liquid as described above for simple dilatometry. The same concerns
that apply to liquids for simple dilatometry also apply to highpressure PV T experiments. The
specimen plus liquid volume is measured by converting the volume expansion into a linear expansion
through the use of a bellows. The linear change in the bellows is measured with an LVDT. The
pressure is applied by hydraulic ﬂuid; the ﬂuid surrounds the sample and cell and is inside the
bellows. As the hydraulic ﬂuid is pressurized, movement of the bellows applies pressure to the
sample. Like simple dilatometry, the volume expansion of the conﬁning liquid is subtracted out by
doing a calibration experiment on pure liquid.
10.5 Dilatometry Summary
Dilatometry can be used to measure thermal transitions, PV T properties, thermal expansion coef
ﬁcients and isothermal compressibility. Although not discussed above, dilatometry can be extended
to many other polymer processes that involve volume changes. Two examples are the kinetics of
crystallization or the kinetics of cure in thermoset polymers.
10.5. DILATOMETRY SUMMARY 125
Dilatometry results are potentially of great importance to the ﬁeld of polymer processing. For
example, polymers are often heated, and than molded at high pressures. The amount of volume
change during the pressure and temperature conditions of the molding cycle are important. Size
can be of critical importance for plastic parts such as gears, LEGOs, etc.. For molding of such parts
the entire molding process must be controlled to tight tolerances and speciﬁcally to tolerances on
volume change. PV T data can help develop these controls. Unfortunately, many polymer processes
work by empiricism. They play with the molding conditions until they get acceptable part sizes.
There is probably room for a more scientiﬁc approach that would use PV T data to predict the
required molding conditions.
Another molding consideration is the pressure dependence of the thermal transitions (T
m
and
T
g
). PV T experiments can measure T
m
and T
g
as a function of pressure. The ﬁndings with poly
mers is that the transition temperatures can change by 50100
◦
C between atmospheric pressure
and molding pressure. If T
m
is 50
◦
C higher at the molding pressure, than the molding temperature
better be more than 50
◦
C higher than T
m
or the sample will never melt. Again, problems associ
ated with molding temperature are often handled by empiricism. Some simple reﬂecting on PV T
experiments could save polymer molders a lot of trial and error experimentation.
Problems
10–1. Derive an expression for the compressibility of a material which obeys the Tait equation.
10–2. Derive an expression for the volumetric thermal expansion coeﬃcient of a material which
obeys the Tait equation.
126 CHAPTER 10. DILATOMETRY
Chapter 11
Diﬀerential Scanning Calorimetry
11.1 Introduction
Calorimetry with polymers is normally done using diﬀerential scanning calorimetry or DSC. In
brief, DSC scans temperature and measures heat capacity of a specimen. The experiments are typ
ically done at atmospheric pressure and thus DSC measures the constantpressure heat capacity.
Another thermal analysis technique that typically involves temperature scanning is thermogravi
metric analysis or TGA. In TGA experiments, the temperature is scanned while measuring the
weight of a specimen. Thermal degradation reactions typically cause the weight to decrease and
thus decreases in weight are a sign of thermal instabilities. This chapter discusses both DSC and
TGA.
11.2 Diﬀerential Scanning Calorimetry
DSC measures a specimen’s heat capacity at constant pressure — C
P
. Heat capacity units are
cal/
◦
K or J/
◦
K. It measures the amount of heat input (q) required to raise the temperature of the
specimen by one degree Celsius while at constant pressure. Heat capacity is usually normalized by
dividing the specimen heat capacity by the number of grams to get the heat required to raise one
gram of specimen by one degree Celsius. If desired, heat capacity can be normalized by the number
of moles. When observing thermal transitions, we note that heat capacity is related to the second
derivative of free energy:
_
∂G
∂T
_
P
= −S = −
q
T
(11.1)
_
∂
2
G
∂T
2
_
P
= −
_
∂(q/T)
∂T
_
P
=
S
T
−
1
T
_
∂q
∂T
_
P
=
S
T
−
C
P
T
(11.2)
127
128 CHAPTER 11. DIFFERENTIAL SCANNING CALORIMETRY
and constantpressure heat capacity is deﬁned by
C
P
=
_
∂q
∂T
_
P
= S −T
_
∂
2
G
∂T
2
_
P
(11.3)
At the second order transition, there will be a discontinuity in the second derivative of free energy.
Because S will be continuous at the second order transition (S is the ﬁrst derivative of free en
ergy), a second order transition will show a discontinuous change in heat capacity at the transition
temperature. A ﬁrst order transition will show up as a peak in heat capacity.
DSC is a form of calorimetry and in fact gives the same information as conventional calorimetry.
In conventional calorimetry (e.g., bomb calorimeters you may have used in freshman chemistry),
you are usually concerned with measuring the heat of some reaction or some process. The method
is to carry out the reaction adiabatically (i.e., with no heat ﬂow) and measure the change in
temperature within the calorimeter. If the temperature changes from T
0
to T
1
, the enthalpy of the
reaction (∆H) is
∆H =
_
T
1
T
0
C
P
dT (11.4)
where C
P
the heat capacity of your system. C
P
of your system can be found by a calibration
experiment in which the temperature is changed by providing a known amount of heat in the form
of supplied electrical energy. Usually ∆T is small and C
P
is independent of temperature between
T
0
and T
1
. The integral thus reduces to
∆H = C
P
(T
1
−T
0
) = C
P
∆T (11.5)
The experiment consists of measuring ∆T. The only problem is determining the ﬁnal temperature
T
1
. Usually the calorimeter will not be perfectly adiabatic and there will be a slow decrease
in temperature as heat escapes to the surroundings. The standard approach is to record T
0
at
the beginning and then to monitor temperature during and after the reaction. Eventually the
temperature will enter a steady decrease and return to T
0
. Extrapolating this portion of the curve
back to zero time will give the true T
1
or the ideal adiabatic T
1
.
Conventional calorimetry is accurate and has been an important part of chemistry for several
centuries. Unfortunately, it is slow and not adaptable to scanned experiments or to studying thermal
transitions. When we want faster calorimetry and/or scanned results, DSC is the calorimetry
method of choice. DSC is fast and easy. It is not as accurate as conventional calorimetry but it
is still within 12%; an accuracy that is more than suﬃcient for most polymer applications. As
discussed above, DSC measures heat capacity which is a second derivative of free energy. Second
order transitions, such as the glass transition, will show up as a discrete change in C
P
. DSC will
give the ∆C
P
of transition and the temperature of the transition. First order transitions, such as
melting or crystallization, will appear as a spike or peak. The area under the peak will be the
heat evolved or absorbed during the transition. This information will give, for example, the heat of
11.3. INSTRUMENTATION 129
Sample
Reference
Heaters
Difference of two
channels to
recorder
amp
amp
Error
Error
Programmed
Temp
Programmed
Temp
Measured
Temp
Measured
Temp
Figure 11.1: Schematic drawing of a DSC.
fusion, ∆H
f
, or the heat of crystallization, ∆H
crys
. The area under the curve analysis is similar to
the conventional calorimetry method discussed above where T
0
and T
1
are the beginning and the
end of the thermal transition and C
P
is the measured heat capacity. During a transition, however,
C
P
does not remain constant and we must use the integral expression or the area under the C
P
curve.
11.3 Instrumentation
A schematic drawing of a DSC instrument is given in Fig. 11.1. There are two sample chambers — a
“reference” chamber and the“sample” chamber. An empty pan is placed in the reference chamber
and a pan ﬁlled with a polymer specimen is placed in the sample chamber. The two chambers
are then heated or cooled until they each reach the selected starting temperature. A temperature
program is then begun; a typical temperature program would be to increase the temperature to
some higher temperature at some ﬁxed rate or ﬁxed number of degrees Celsius per minute. As the
program runs, the system monitors the temperature in each chamber. If the temperature diﬀers
from the programmed temperature in either chamber, heat or coolant is supplied to that chamber
to make the temperature equal the program temperature. The diﬀerence in the energy supplied to
the two chambers per unit time (or dq/dt) is proportional to the heat capacity of the sample. That
energy diﬀerence is monitored electronically and output to the recorder.
The instrument shown in Fig. 11.1 is a true calorimetry. It measures heat ﬂow which is converted
into heat capacity. An alternative approach to DSC is to measure temperature diﬀerence. In
particular, the reference and sample chamber can be supplied with the same amount of heat.
130 CHAPTER 11. DIFFERENTIAL SCANNING CALORIMETRY
The amount of heat supplied can be adjusted to give various heating rates. Then instead of
maintaining equal temperatures and measuring diﬀerential heat ﬂow, it is possible to maintain
constant heat ﬂow and measure the diﬀerence in temperature between the reference and sample
chambers. The temperature diﬀerence will give a good measure of the heat capacity. When
the heat capacity of the sample chamber increases (because of a heat absorbing or endothermic
transition) the temperature in the sample chamber will lag behind the reference chamber and
there will be a negative temperature diﬀerential (T
sample
− T
ref
< 0). Conversely, when the heat
capacity of the sample chamber decreases (because of a heat generating or exothermic transition)
the temperature in the sample chamber will be ahead of the reference chamber and there will be a
positive temperature diﬀerential (T
sample
−T
ref
> 0).
DSCs that measure temperature diﬀerential are not true DSCs or true calorimeters. They are
more accurately labeled as diﬀerential thermal analyzers or DTAs. They were originally developed
by many manufacturers to avoid patent protection of the DSC mode of operation and because the
instrumentation is slightly simpler. Many such DTAs are inaccurately labels as DSCs by those
manufacturers. Fortunately both DSCs and DTAs can give suitable heat capacity results when
working with polymers. DTAs are perhaps slightly less quantitative than DSCs. When using a new
DSC, it is advisable to determine whether it is a DSC or a DTA.
11.4 Results with Polymers
11.4.1 Heating of Semicrystalline Polymers
A typical plot of dq/dT (or heat capacity) vs. T for the DSC of a semicrystalline polymer is given
in Fig. 11.2. If the same experiment was done on a DTA, it would instead be a plot of −∆Tvs. T.
In such a DSC plot, higher heat capacity is up and lower heat capacity is down. Endothermic ﬁrst
order transitions or transitions that absorb heat have a high heat capacity and thus show positive
peaks. Exothermic ﬁrst order transitions or transitions that release heat have a low or negative
heat capacity and thus show negative peaks. Some DTAs plot ∆T instead of −∆T and thus the
entire plot in Fig. 11.2 would be inverted. Lower heat capacity is up, higher heat capacity is down,
endothermic ﬁrst order transitions show negative peaks and exothermic ﬁrst order transitions show
positive peaks. When interpreting DSC data, you must verify the sign convention used by your DSC
instrument. The sign used in Fig. 11.2 is the most logical one and the one that is used throughout
these notes.
The lowest temperature transition in Fig. 11.2 is the glass transition or T
g
. Around T
g
, C
P
undergoes a quasidiscontinuous change from a lower value to a higher value. This behavior is
typical for a second order transition. Polymers always have a higher heat capacity above T
g
than
below T
g
because there are more degrees of freedom that can absorb energy above T
g
. We called
11.4. RESULTS WITH POLYMERS 131
+

Temperature
dq
dT T
g
T
c
T
m
Figure 11.2: Typical DSC data while heating a semicrystalline polymer. The lowtemperature second order
transition is the glass transition. The exothermic transition is crystallization. The endothermic transition is
melting.
the change at T
g
a quasidiscontinuous change because it is not sharp, but happens over a range
of about 10
◦
C. Many polymer handbooks list a single T
g
; the question remains: which part of
the curve deﬁnes the actual T
g
? The answer depends on who is determining T
g
. Some possible
answers are the temperature at the onset of the discontinuous change (the ﬁrst line in Fig. 11.3),
the inﬂection point of the change (the second line in Fig. 11.3), or the end of the discontinuous
change (the last line in Fig. 11.3). The most common convention is to take the inﬂection point.
The results in the glass transition temperature depend on the rate of the test. One eﬀect is a
material property; namely, the glass transition temperature is a rate dependent property. Its true
value will be diﬀerent at diﬀerent rates and thus DSC will be sensitive to rate. T
g
increases with
increasing heating rate. Recall that T
g
is the temperature at which longrange relaxations become
slow with respect to the observation time. If the observation time is shorter, the relaxations do not
need to be as fast to be at T
g
; thus the glass transition occurs at a higher temperature. Conversely,
T
g
decreases with decreasing heating rate. The eﬀect of rate on T
g
is not large. T
g
changes about
3
◦
C for each order of magnitude change in heating rate.
Another heating rate eﬀect depends on sample preparation. Before doing the heating experi
ment, the sample must be cooled down to the testing temperature. Even if you do not cool the
sample down, the sample was cooled down by the material supplier before you bought it. The
glass transition region will depend on the heating rate (see above) and on the diﬀerence between
the heating rate and the cooling rate used in preparing the sample. The results might also depend
on aging time or the length of time that has elapsed since the polymer was cooled down. If you
bought the sample and have not yet heated it, the aging time could be several years. Speaking
qualitatively, if the heating rate is slower than or similar to the cooling rate and the sample has
132 CHAPTER 11. DIFFERENTIAL SCANNING CALORIMETRY
Glass Transition
Temperature
C
p
Onset
End
Inflection
Figure 11.3: Blow up of the glass transition region. The vertical lines show two possible methods for
determining T
g
. The infection point method is the most common one.
not aged long, the glass transition will resemble the one in Fig. 11.3. In other words, there will be
a smooth transition from a low heat capacity below T
g
to a higher heat capacity above T
g
. If the
heating rate is much faster than the cooling rate or the sample has aged signiﬁcantly before testing,
it is possible to get a glass transition that resembles the trace in Fig. 11.4. The heat capacity passes
through a peak on preceding from the low heat capacity below T
g
to the higher heat capacity above
T
g
. This peak resembles an endothermic, ﬁrst order transition. Some researchers have, indeed,
misinterpreted such peaks as endothermic transitions. The peak, however, has nothing to do with
a ﬁrst order transitions and can be completely explained by a detailed analysis of the kinetics of
the glass transition.
If a semicrystalline polymer did not crystallize to the limit of its ability when cooled, it is
possible to see some additional crystallization during the heating DSC. Crystallization shows up
as an exothermic peak (negative peak or peak that gives oﬀ heat); the crystallization temperature,
T
c
, is always between T
g
and the melting temperature T
m
. To emphasize, crystallization will only
occur in samples that can crystallize (semicrystalline polymers) and in samples that are not already
crystallized as far as they can be crystallized (because of incomplete crystallization during cooling).
A typical crystallization peak is shown in Fig. 11.5. The crystallization temperature is sometimes
taken as the onset of crystallization, but is more commonly assigned to the peak temperature.
Both the onset and peak temperature are sensitive to rate. During heating, these temperatures
may increase with increasing rate. The total heat evolved, q
c
or ∆H
c
, can be determined from the
area under the peak (the shaded portion in Fig. 11.5).
The highest temperature peak in Fig. 11.2 is the melting transition. Melting is a ﬁrst order,
endothermic transition (i.e., it requires heat); it thus occurs as a positive peak on a DSC trace.
DSC can also be used to study low molecular weight samples. A typical small molecule would
11.4. RESULTS WITH POLYMERS 133
Glass Transition
Temperature
C
p
Figure 11.4: Glass transition with an overshoot due to kinetic eﬀects in the glass transition process. The
overshoot is accentuated by using faster heating times or by aging the sample before heating.
Crystallization
Onset
T
1 T
2
Peak
C
p
Temperature
Figure 11.5: A typical exothermic crystallization peak. The shaded area is the area under the curve.
134 CHAPTER 11. DIFFERENTIAL SCANNING CALORIMETRY
Polymer Melting
Onset
Peak
C
p
Temperature
End
Small MW Melting
C
p
Temperature
Figure 11.6: The melting transition for typical polymer molecules and a typical monodisperse low molecular
weight molecule.
show neither a glass transition (there are no amorphous parts of most small molecules) nor a
crystallization peak (because the sample could not be prevented from crystallizing during the initial
cool down). It would show a melting point, but the melting transition would be much sharper than
the corresponding transition in a polymer sample (see Fig. 11.6). For small molecules, the peak
is very sharp, and the melting temperature is taken as the peak temperature. For polymers, the
melting transition is broad. As explained in the dilatometry section, the breadth of the peak is due
to the polydispersity of polymer molecular weights. The melting temperature is sometimes taken
as the onset temperature, the peak temperature, or the end temperature (see Fig. 11.6). The end
temperature is perhaps the most logical because it deﬁnes the temperature at which all crystals
disappear. By convention, however, a melting temperature determined by DSC is usually taken as
the peak temperature. The discrepancy between the peak temperature and the end temperature is
minute for low molecular weight materials, but can be signiﬁcant for polymer materials.
The area under a melting transition curve is the total amount of heat absorbed during the
melting process. The relevant area is shown as the shaded portion in Fig. 11.6. This area is used
below to calculate the fraction crystallinity that existed before the polymer was heated.
Some polymers can crystallize into more than one form of crystal. When there are two types
of crystals, it is possible for them to have diﬀerent melting point. This complicating feature
in the polymer structure can lead to a complicated melting transition region in the DSC trace.
One possible eﬀect is shown in the left half of Fig. 11.7 where the two types of crystals give two
independent melting transitions. There are thus two peaks in the DSC trace. It is even possible for
crystals that melt at the lower temperature to recrystallize into the higher melting point crystal and
then melt at the higher temperature. The melting point region would than be the superposition of
two melting peaks and one crystallization peak (see right half of Fig. 11.7)
11.4. RESULTS WITH POLYMERS 135
C
p
C
p
Temperature Temperature
Two melting peaks
Two melting and one
crstallization peak
Figure 11.7: Melting transition region of a polymer with more than one type of crystal forms. The left side
shows two melting transitions. The right side shows two melting transitions and a crystallization transition.
The area under any ﬁrst order transition peak in a DSC trace gives the heat evolved during
that transition (see Figs. 11.5 and 11.6). DSC data measures heat capacity or dq/dT. Integrating
dq/dT clearly gives heat or q:
_
T
2
T
1
dq
dT
dT = q (11.6)
Many DSCs print the trace onto chart paper (e.g., one of the DSCs in the Material Science De
partment). If we let A be the area under the peak on the chart in square inches (in
2
), R be the
machine sensitivity or range in cal/sec/in, and S be the chart speed in in/sec, then the heat per
gram or enthalpy per gram (∆H) of the transition is
∆H =
K A(in
2
) R(cal/sec/in)
m(g) S(in/sec)
(11.7)
where ∆H is in cal/g and K is a calibration constant. The calibration constant is determined by
measuring the heat evolved in a transition with known ∆H. Now consider applying this formula
to the melting transition. The entire heat of evolution is due to melting of the crystal fraction. If
the sample is χ% crystalline by weight, you can get the heat of fusion of the crystals by replacing
total mass of the specimen (m) by the mass of the crystals which would be mχ/100. Substituting
into the above equation:
∆H
f
=
100KAR
mχS
=
100∆H
χ
(11.8)
or
χ =
100∆H
∆H
f
(11.9)
The equation for χ is perhaps the more intuitive of the two equations. It says that fraction
crystallinity on any sample is equal to the ratio of ∆H to ∆H
f
. ∆H
f
is the enthalpy of fusion
136 CHAPTER 11. DIFFERENTIAL SCANNING CALORIMETRY
and is deﬁned as the calories required to melt one gram of crystal or cal/g or crystal. ∆H is
experimental data and it is the calories required to melt one gram of sample or cal/g of sample.
Their ratio is
∆H cal/g of sample
∆H
f
cal/g of crystal
=
g of crystal
g of sample
(11.10)
or the mass fraction of crystal in the sample. Multiplying this fraction by 100 gives the percent
crystallinity.
The ease of measuring areas under melting transitions makes DSC a good tool for measuring
percent crystallinity. The method, however, requires that you know the heat of fusion for the
polymer, ∆H
f
. If the polymer could be obtained in 100% crystalline form, ∆H
f
could be measured
by a simple DSC experiment. Unfortunately, all crystalline polymers are semicrystalline and we
need some alternative method for determining ∆H
f
or the enthalpy of fusion of the pure crystal.
There are two approaches. One is a noncalorimetric method for determining ∆H
f
. The other is to
do DSC on a sample with known fraction crystallinity. We describe each method.
The ClausiusClapeyron equation is a simpletoderive thermodynamic relation that predicts
the pressure dependence of the melting point. Solving that equation for heat of fusion gives:
∆H
f
=
T
m
(V
a
−V
c
)
dTm
dP
(11.11)
where T
m
is the melting point, dT
m
/dP is the pressure dependence of the melting point, V
a
is
the speciﬁc volume of amorphous material at the melting point, and V
c
is the speciﬁc volume of
the crystal at the melting point. T
m
, dT
m
/dP, and V
a
can all be determine by PV T experiments
or dilatometry. T
m
is easy; it is the temperature at which all crystals disappear. dT
m
/dP is
determined by determining T
m
at several diﬀerent pressures. T
m
always increases with pressure
and thus dT
m
/dP is greater than zero. V
a
is determined by measuring the volume in the melt and
extrapolating back to the melting temperature. Although dilatometry measures volumes, it cannot
determine V
c
. V
c
is the speciﬁc volume of the pure crystal and polymers cannot be obtained in
a purely crystalline form. V
c
can, however, be determined by Xray crystallography. The speciﬁc
volume can be calculated from unit cell dimensions. The Xray experiments should be done at
temperatures near T
m
and extrapolated up to T
m
to get the most accurate results.
Once T
m
, V
a
, V
c
, and dT
m
/dP are known, ∆H
f
can be calculated using the ClausiusClapeyron
equation. Note that neither dilatometry nor Xray crystallography are calorimetric techniques.
This method thus provides an independent, noncalorimetric route to ﬁnding ∆H
f
. Once ∆H
f
is
known, DSC can be used on any sample of that polymer to ﬁnd the percent crystallinity. The
ClausiusClapeyron equation is an exact thermodynamic equation. The only potential problem
with applying it to polymers is diﬃculty in obtaining reliable results for T
m
, V
a
, V
c
, and dT
m
/dP.
Fortunately, dilatometry and Xray of polymers gives data that is accurate enough for calculating
∆H
f
.
11.4. RESULTS WITH POLYMERS 137
Instead of measuring ∆H
f
, an alternative approach is to do a DSC on a sample with a known
χ. If χ can be accurately determined by some noncalorimetric method, than the heat of fusion can
be calculated from DSC data by
∆H
f
=
100∆H
χ
(11.12)
The problem thus reduces to ﬁnding a second method for determining the percent crystallinity. We
discuss two methods:
1. Sample density method: a sample of density ρ has a fraction crystallinity of
χ =
ρ
c
V
c
ρV
(11.13)
where V
c
is the total volume of crystal, V is the total volume of sample, and ρ
c
is the density
of a 100% crystalline polymer. The ratio of volumes is
V
c
V
=
ρ −ρ
a
ρ
c
−ρ
a
(11.14)
where ρ
a
is the density of a 100% amorphous polymer. Thus, in terms of densities
χ =
ρ
c
ρ
ρ −ρ
a
ρ
c
−ρ
a
(11.15)
The amourphous density, ρ
a
can often be determined by quenching or rapidly cooling a
sample to prevent crystallization and then measuring density. The crystalline density, ρ
c
is
best determined by Xray crystallography and unit cell dimensions. Note that the V
c
/V or
the volume fraction of crystals was used above. It comes from a simple linear interpolation
between the volume of a pure crystal and the volume of a pure amorphous sample.
ρV = ρ
c
V
c
+ρ
a
V
a
= ρ
c
V
c
+ρ
a
(V −V
c
) (11.16)
To be successful, the density method requires use of voidfree samples.
2. Spectroscopic methods: many spectroscopic methods (e.g., IR, NMR, Xray, etc.) sometimes
show peaks that result from the crystalline fraction and are not present in the amorphous
fraction. Conversely, they sometimes show peaks in the amorphous fraction that are not
present in the crystalline fraction. Careful analysis of these peaks with suitable normal
ization can be used to determine the fraction crystallinity in a sample. To be successful,
spectroscopic methods require careful characterization of the origins of the observed signals.
This characterization might entail much extra work.
11.4.2 Cooling of Semicrystalline Polymers
Cooling of semicrystalline polymers will typically give a trace similar to the heating trace except
that there will never be a melting transition. There will probably also be signiﬁcant diﬀerences
138 CHAPTER 11. DIFFERENTIAL SCANNING CALORIMETRY
in the crystallization region. When approaching T
c
from high temperature, the sample is 100%
noncrystalline and is thus ready to crystallize as much as possible. Typically the crystallization
peak will be more pronounced in cooling curves than in heating curves. Cooling rate will have a
signiﬁcant eﬀect. The rate will aﬀect the crystallization temperature, with higher rates tending to
decrease T
c
. More importantly, higher rates will aﬀect the amount of crystals that form. Higher
rates tend to reduce the area under the peak and thus reduce the amount of crystallization. Many
polymers crystallize so sluggishly that they can be entirely prevented from crystallizing by cooling
at a high rate or by quenching to well below T
c
. The DSC of a polymer that is prevented from
crystallization will not show any crystallization peak.
11.4.3 Amorphous Polymers
Amorphous polymers have no crystals and thus never show melting transitions or crystallization
transitions. Amorphous polymers show only the glass transition region. The discussion of the
glass transition region given above applies also to amorphous polymers. The only diﬀerence is that
because amorphous polymers are 100% amorphous, the glass transition will be more pronounced
or will show a larger change in heat capacity.
11.5 DSC Summary
DSC ﬁnds many uses in calorimetry and in polymer science. We list a few of the properties that
can be measured by DSC. Many of these were discussed above. Others can be found discussed in
the literature or in text books:
1. Temperature for thermal transitions: T
g
, T
c
, and T
m
2. Heat and entropy of transition: ∆H and ∆S (from q/T)
3. Heat capacity: C
P
4. Percent crystallinity: χ (assuming ∆H
f
is known)
5. Heat absorbed or evolved during cure reactions or decomposition reactions
6. Subglass or solid state transitions
7. Crystallization kinetics (heat evolved during isothermal crystallization)
11.6 Thermogravimetric Analysis
Thermogravimetric analysis or TGA involves heating a sample to some temperature and then
monitoring its weight as a function of time. It is commonly used to monitor polymer degradation
11.6. THERMOGRAVIMETRIC ANALYSIS 139
reactions. TGA only requires a sensitive method for monitoring weight and a method for setting
the temperature of the sample. Ideally the sample chamber should have a controllable environment
to allow you to monitor degradation under various conditions (e.g., in the presence of oxygen or
under dry nitrogen).
The most accurate TGA experiments are to set the temperature to some constant value and
follow weight as a function of time. The results will give quantitative information about the rate
of degradation at that temperature. Repeating this experiment for several temperatures will give
information about the temperature range under which this polymer can be used. Usually, people
(i.e., industry) are not patient enough to do all those required experiments. Therefore, most TGAs
are set up to scan temperature. Monitoring weight while scanning temperature will give useful
results, but it must be realized that if the degradation is slow, the polymer will appear to survive
to higher temperatures than it would actually survive under long term exposure. In other words,
the results will also be very sensitive to rate. The sensitivity is large because degradation rates
may be slow when compared to typical scanning rates such as 1020
◦
C/min.
Coupling the byproducts of a TGA experiment or the degradation products from the polymer
to other instruments such as mass spectrometer, infrared spectrometry, gas chromatography, etc.,
can be useful in studying the mechanisms of polymer degradation. The coupled instruments can
be used to identify the structure of the degradation products. Combining structural information
with kinetics information can give a complete picture of the degradation process.
Problems
11–1. Most polymers crystallize by heterogeneous crystallization at nucleating agents. Nucleating
agents help the crystallization process to get started. Suppose you wanted to add a nucleating
agent to promote rapid crystallization during processing and that you have several nucleating
agents to choose from. Describe some DSC experiments (including control experiments) that
would enable you to decide which nucleating agent would be the best. (Hints: nucleating
agents will change the crystallization temperature (specify which way) and will change the
level of crystallization for a given amount of crystallization time).
11–2. Because it is easy to measure sample density, the density method appears to provide and
ideal way to measure the weight fraction crystallinity. Unfortunately reallife experiments
are not always trouble free. Describe problems that might arise in the following parts of the
analysis:
a. Accurately knowing ρ
a
:
b. Accurately knowing ρ
c
:
c. Polymers that have ρ
a
≈ ρ
c
:
140 CHAPTER 11. DIFFERENTIAL SCANNING CALORIMETRY
Chapter 12
Mechanical Properties
12.1 Introduction
Polymers are often used in applications that involve stresses. Examples include housings, gears,
ropes, structures, composites, etc.. Before using polymers in loadbearing applications, we must
study the eﬀect that stress has on them. In the ﬁeld of polymer characterization, there are numerous
tests aimed as characterizing the mechanical properties of polymers. Some of tests and the type of
information measured are:
1. Static testing: tensile, compressive and shear properties; stressstrain curves; stiﬀness, strength,
and toughness.
2. Creep test: time dependencies of elongation; viscoelastic properties.
3. Relaxation test: time dependencies of stress; viscoelastic properties.
4. Dynamic mechanical test: viscoelastic properties; thermal transitions; molecular relaxations.
5. Fatigue test: lifetimes or durability
6. Impact tests: highrate properties; impact strength.
All these mechanical characterization tests measure some mechanical properties. Because any
mechanical property may be aﬀected by temperature and environment, the tests sometimes need to
be done at various temperatures and in various environments. The test results for many mechanical
properties (e.g., toughness and impact strength) depend on sample geometry. For such properties
it is important to have a detailed understanding of geometry eﬀects and to avoid oversimpliﬁed
interpretations such as merely dividing by the crosssectional area of the specimen.
141
142 CHAPTER 12. MECHANICAL PROPERTIES
12.2 Simple Elasticity Theory
Our basis for understanding the inﬂuence of stress on materials is the theory of elasticity. Although
polymers often deviate from smallstrain elasticity theory, the theory is still useful. It can be directly
applied to many polymer problems and it helps in the understanding of other polymer problems.
The simplest elasticity problem is the one dimensional problem of a tensile load being applied
to a bar of constant cross section. According to Hooke’s law, such a bar made of a linear elastic
material acts like a spring. The force applied to the bar, F, is proportional to the extension of the
bar, x:
F = kx (12.1)
where x is the extension of the bar or (L −L
0
) where L is the extended length of the bar and L
0
is the original length of the bar. Thus
F = k(L −L
0
) (12.2)
The spring constant, or the stiﬀness, k, will depend on the size of the sample (i.e., on the size of
the spring) and on the mechanical properties of the sample. To eliminate size eﬀects, it is desirable
to normalize out the sample size eﬀect using
k =
EA
0
L
0
(12.3)
where E is the Young’s modulus of the material and A
0
is the initial crosssectional area. Then
F
A
0
= E
L −L
0
L
0
(12.4)
The term on the left is called the stress, σ, or the force per unit area. It has the same units
as pressure. The term (L − L
0
)/L
0
is the strain, ε, or the fractional increase in length; it is
dimensionless. The ﬁnal onedimensional elasticity equation is
σ = Eε (12.5)
Analyzing one dimension is enough when you are working only with simple springs. For solid or
three dimensional materials, we must consider length changes in all directions. First assume that
a onedimensional stress is applied along the z axis and that the z axis stress causes dimensional
changes only in the z direction. In this case the change in volume is
∆V = V −V
0
= L
x
L
y
(1 +ε
z
)L
z
−L
x
L
y
L
z
= ε
z
V
0
(12.6)
Simple dilatometry experiments during loading can show that this large a volume change does not
occur. What must be happening is that the x and y dimensions contract slightly to reduce ∆V .
In essence, a solid material wants to resist a change in volume. Thus an application of a tensile
12.2. SIMPLE ELASTICITY THEORY 143
stress in one direction causes the other two direction to contract in order to minimize the increase
in volume. Poisson assumed that the contractions in the x and y directions are proportional to the
extension in the z direction or:
ε
x
= −νε
z
and ε
y
= −νε
z
(12.7)
where ν is called the Poisson’s ratio. The volume change on extension in the z direction is now
∆V = (1 +ε
x
)(1 +ε
y
)(1 +ε
z
)V
0
−V
0
≈ (ε
x
+ε
y
+ε
z
)V
0
= (1 −2ν)ε
z
V
0
(12.8)
where the indicated approximations assumes all strains are small and thus higher order terms in
strain can be neglected. When ν = 1/2, ∆V is equal to zero. This is approximately true for many
rubberlike materials. Most metals, and glassy or semicrystalline polymers have ν of about 1/3.
Considering strains in all directions, a stress of σ
z
in the z direction induces the following
strains:
ε
x
= −
ν
E
σ
z
(12.9)
ε
y
= −
ν
E
σ
z
(12.10)
ε
z
=
1
E
σ
z
(12.11)
Of course we are not limited to applying stress in only one direction. We may apply stresses in the
x, y, and z directions simultaneously. Because linear elasticity is a linear theory, the response of
a solid to stress in all direction is just the superposition of the individual responses. We can thus
generalize Hooke’s law for tensile loading to get
ε
x
=
1
E
[σ
x
−ν(σ
y
+σ
z
)] (12.12)
ε
y
=
1
E
[σ
y
−ν(σ
x
+σ
z
)] (12.13)
ε
z
=
1
E
[σ
z
−ν(σ
x
+σ
y
)] (12.14)
Besides tensile loading, polymers may also be subjected to shear loading and shear stresses.
Unlike tensile loading, shear loading causes no change in volume and thus the responses due to
shear loading in the three directions are uncoupled. Hooke’s law for shear loading are
γ
xy
= γ
yx
=
τ
xy
G
(12.15)
γ
xz
= γ
zx
=
τ
xz
G
(12.16)
γ
yz
= γ
zy
=
τ
yz
G
(12.17)
where γ
ij
are shear strains and G is the shear modulus. For isotropic materials, the shear modulus
is related to E and ν by
G =
E
2(1 +ν)
(12.18)
144 CHAPTER 12. MECHANICAL PROPERTIES
The above discussion was all about isotropic materials. In polymer science, one often encoun
ters anisotropic materials. Two examples are composite materials and oriented polymer specimens.
For anisotropic materials, the mechanical properties depend on the direction of the applied load.
Dealing with general anisotropy is very complex. Here we introduce a single example of an or
thotropic material. An orthotropic material has diﬀerent properties in the x, y, and z directions,
but still has no coupling between shear and tensile deformation. Orthotropic materials are usually
the most complex situation encountered in analysis of polymeric specimens. For an orthotropic
material, Hooke’s law becomes
ε
x
=
σ
x
E
x
−
ν
xy
σ
y
E
x
−
ν
xz
σ
z
E
x
(12.19)
ε
y
= −
ν
xy
σ
x
E
x
+
σ
y
E
y
−
ν
yz
σ
z
E
y
(12.20)
ε
y
= −
ν
xz
σ
x
E
x
−
ν
yz
σ
y
E
y
+
σ
z
E
z
(12.21)
γ
xy
=
τ
xy
G
xy
(12.22)
γ
xz
=
τ
xz
G
xz
(12.23)
γ
yz
=
τ
yz
G
yz
(12.24)
where the E
i
’s are the tensile moduli for loading in the i direction, the G
ij
’s are the shear moduli
for shear deformation in the ij plane, and the ν
ij
’s are the generalized Poisson ratios; ν
ij
is the
ratio of the strain in the j direction to the strain in the i direction when the specimen is under
uniaxial load in the i direction.
This discussion of elasticity theory has been extremely brief, It should suﬃce for the material
covered in this chapter. If you need more information, you may want to refer to any text of
mechanics of materials or elasticity theory.
12.3 StressStrain Curves
A stressstrain curve is measured by monotonically increasing stress or strain and measuring the
other quantity. Plotting the results gives a stress strain curve. Consider ﬁrst a tensile stressstrain
curve measured by pulling in one direction. As the sample extends, the crosssectional area changes
due to Poisson contraction eﬀects. The “true” stress and “true” strain should be deﬁned in terms
of the current sample dimensions. That reﬁnement, however, is rarely used when characterizing
polymers. Instead, we measure engineering stress and stress. Engineering stress is the total load
divided by the original crosssectional area. Engineering strain is the total elongation divided by the
original length. Some typical polymer engineering stressstrain curves are illustrated in Fig. 12.1.
Curve a in Fig. 12.1 is for a linear elastic polymer. The stress increases linearly with strain (or
very nearly linearly) until ultimate failure. Curve b is for a polymer that yields and then breaks.
12.3. STRESSSTRAIN CURVES 145
a
b c
d
S
t
r
e
s
s
Strain
Figure 12.1: Some typical stressstrain curves. a: linear elastic; b. nonlinear with yield; c. yielding
followed by necking and high elongation; d. rubberelastic curve.
Yielding shows up as deviations from linearity. In metals, yield stress is often deﬁned as some ﬁxed
amount of deviation from linearity. In polymers, this approach is often unworkable and yield stress
is, by convention, the peak stress. A peak stress will not always be observed, but it shows up barely
in curve b and clearly in curve c. Thus curve c is for a material that yields and then continues
to elongate. After yielding, a neck will form. Then the neck region elongates or grows, sometimes
to several hundred percent strains. Eventually the polymer chains can align in the necked region.
Upon alignment, the material will get stiﬀer and soon break. Figure 12.2 shows the process of neck
formation followed by neck elongation.
Curve d in Fig. 12.1 is typical for rubbers or for materials that exhibit rubber elasticity. Rubber
elastic deformation is characterized by high recoverable extension; there is no necking. At the
highest elongations, the polymer chains can align and crystallize. These eﬀects will cause a stiﬀening
and the curve turns up before failure.
12.3.1 StressStrain Properties
The raw curves in Fig. 12.1 tell you much about the mechanical properties of polymers. It is useful,
however, to reduce the data in the raw curves to a set of mechanical properties. We next consider
typical properties measured from stressstrain curves, how they are measured, and what they mean.
The stiﬀness or modulus of a polymer is usually taken from the slope of the stressstrain curve at
very low strains — the initial slope. As the strain increases, the meaning of the slope of the stress
strain curve decreases. The problem is that engineering stress and strain are no longer close to true
stress and strain. Thus, for example the negative slopes in curve c have no physical meaning. If we
146 CHAPTER 12. MECHANICAL PROPERTIES
Yielding
Necking
Figure 12.2: The appearance of a specimen that necks and follows curve c in Fig. 12.1.
did plot true stresstrue strain curves, the slopes would give the strain dependence of the stiﬀness.
We would also ﬁnd that the true stress never decreases as in curve c. A high slope is a hard or
a stiﬀ sample; a low slope is a soft or a compliant sample. The modulus of unoriented polymers
are almost universally in the range of 1 to 4 GPa. Polymers are all made up from similar organic
bonds and thus we never expect to ﬁnd unoriented polymers with moduli signiﬁcantly outside this
range. If a polymer is oriented, however, such that the backbone chains are all aligned with the
applied load, it is possible to have a very high modulus when the load is applied in the direction
of the orientation. Highly oriented polymers can have moduli as high as 300 GPa which is higher
than the modulus of steel. Unfortunately, you do not get something for nothing when orienting a
polymer. The increase in modulus in oriented polymers applies only to loading in the direction of
orientation. The oriented polymer is anisotropic and the modulus in the other directions decreases
as the orientationdirection modulus increases.
The strength of a polymer is usually deﬁned as the maximum stress reached during the stress
strain curve, or the stress when the sample breaks. Strength is often a poor way to characterize
polymer failure properties. The results are usually highly variable and are also a strong function of
the sample size and shape. The strengths of unoriented polymer are in the range of 10 to 100 MPa.
Highly oriented polymers can have strengths up to 4 GPa.
A formal deﬁnition of yielding is the point at which the stressstrain response becomes nonlinear
and irreversible. In polymers, it is diﬃcult to deﬁne irreversibility, because if you wait long enough,
the viscoelastic nature of polymers can make extreme nonlinearities reversible. By convention,
yield strength in polymers is often assigned to the peak of the stressstrain curve that occurs prior
to necking. Measuring the yield strength of polymers that do not neck can be a problem. Many
such polymers, however, can be induced to neck when tested in suﬃciently thin specimens and at
suﬃciently slow rates. High yield strength is associated with brittle and linear elastic materials;
12.3. STRESSSTRAIN CURVES 147
low yield strength is associated with ductile materials. Like strengths, yield strengths of unoriented
polymers are usually 10 to 100 MPa. Highly oriented polymers will not yield and thus do not have
a yield strength.
Elongation to break is the total elongation at the time the sample breaks. High elongation
means a ductile failure; low elongation means a brittle failure. Elongation is a nearly useless
material property. It is highly dependent on sample size and testing conditions. High elongation
is obtained by promoting necking. Necking is promoted by slow testing rates and by using thin
samples. Also many polymer applications will not involve large strains. If the designed part will
only experience 5% strain, who cares if the polymer can extend to 250% or to 1000%? In summary,
elongation to break is easy to measure and is commonly reported. Without additional experiments
and additional information about testing conditions, it is not a useful material property.
Toughness is deﬁned as the amount of energy or work required to break the sample. Because
work is force × distance, stress × strain is work per unit volume. Thus the area under the stress
strain curve is the total work per unit crosssectional area to break the sample. This work is often
equated with toughness. High area is for tough samples or ductile samples; low area is for brittle
samples. Although toughness is an important material property, the area under the curve is not a
good way to measure the toughness. The main problem is that the total area is a sensitive function
of the elongation to break. As stated above, elongation to break is very sample size and test
condition dependent. Useful values of toughness are normally measured by techniques of fracture
mechanics and not by areas under the curve.
Unlike most metals, the stressstrain behavior of polymers is very sensitive to testing rate and
temperature. Large eﬀects can be seen at ordinary temperatures and testing rates. The eﬀect
of temperature is illustrated in Fig. 12.3. At low temperatures, the polymer becomes hard and
brittle. As the temperature increases, polymers typically become softer and more ductile. In short,
one polymer can exhibit all the possible stressstrain curve types by changing the temperature.
The eﬀect is connected with the glass transition. Well below the glass transition temperature the
polymer is immobile and behaves as a brittle material. As the temperature is raised and the glass
transition is approached or passed, the material becomes more ductile and softer.
The testing rate eﬀect is illustrated in Fig. 12.4. The rate eﬀect is the opposite of the tempera
ture eﬀect. Increasing the rate is like decreasing the temperature; it causes the polymer to become
harder and more brittle. This eﬀect is again associated with the glass transition. At slow rates the
polymer has time to rearrange and on the time scale of the test, it can be said to be eﬀectively
above the glass transition temperature. At high rates, no motion is possible and it can be said to
be eﬀectively below the glass transition temperature.
The similarity between temperature eﬀects and rate eﬀects suggests that time and temperature
are related. We will see later in the chapter that we can exploit the relation using a principle
known as timetemperature superposition. Suppose you want to do a very slow test at room
148 CHAPTER 12. MECHANICAL PROPERTIES
Low Temp
Room Temp
High Temp
Increasing Temp
Figure 12.3: The eﬀect of temperature on the stressstrain curve of polymers.
High Rate
Moderate Rate
Low Rate
Increasing Rate
Figure 12.4: The eﬀect of testing rate on the stressstrain curve of polymers.
12.3. STRESSSTRAIN CURVES 149
temperature. One method would be to use the very slow rate that you are interested in. This
slow rate, however, might be very slow and in fact might involving testing over many years. A
better method is to use the timetemperature superposition principle which states that the eﬀect of
slowing done the rate by some amount is equivalent to lowering the temperature by some amount.
You can therefore get reasonable very slow rate, room temperature data by doing higher rate tests
at a higher temperature. The only problem is knowing how much to increase the temperature to
simulate a given slow rate. This subject will be discussed latter.
When measuring stressstrain curves, there are many possible sources of error. One common
error is slippage of the specimen in the grips. If the specimen slips, the measured grip displacement
will be diﬀerent that the actual specimen displacement resulting in large errors in the measured
strain. For this reason, in quantitative work it is important to measure displacements or strains
directly on the sample by using strain gages or extensometers instead of measuring strain from
grip displacement. Grip slippage will not aﬀect measured load and therefore loads will always be
accurate assuming the load cell in accurate and well calibrated. Specimen geometry and quality
can have a large eﬀect of the stressstrain curve. If necking is part of the specimen deformation,
the amount of deformation will be very dependent on sample thickness. In other words necking is a
specimen property and only partially a material property. Although some materials are more likely
to neck than other materials, the amount of necking will be determined by sample geometry. Thin
samples will neck more than thick samples. Sample geometry and quality can dramatically aﬀect
ultimate failure loads. For example, samples with stress concentrations, such as scratches on the
surface, can prematurely fail at the sample imperfections. Thus, reproducibly measuring sample
strength requires great attention to specimen design and quality.
Polymer stressstrain curves are often nonlinear. The nonlinearity can be caused by plastic
deformation (yielding) or by rate/temperature eﬀects (low rate or high temperature promotes
curvature). It can be diﬃcult to separate plastic aﬀects from viscoelastic eﬀects. Additional
experiments, besides stressstrain experiments, may be needed to fully characterize the mechanical
response of a polymer.
12.3.2 Uses of StressStrain Properties
The reason for measuring stressstrain properties, such as modulus, strength, or toughness, is
because they are useful in polymer applications. We next give a few comments about using stress
strain properties.
Stiﬀness or modulus is a key input into Hooke’s laws and they are used to calculate deformations
under load. The importance of knowing deformation for polymer design problems should be self
evident. An important aspect of stiﬀness is that it is a function of temperature. A common
and quick stiﬀness/temperature experiment is called the heat deﬂection temperature. In brief, a
150 CHAPTER 12. MECHANICAL PROPERTIES
cantilever beam is loaded with a ﬁxed amount of load and the deformation of the beam is measured
as a function of temperature. A large deﬂection means that the polymer stiﬀness has become low
and will probably no longer be suitable for stiﬀnesscritical applications. In general polymers should
only be used at temperatures well below the heat deﬂection temperature. In amorphous polymers,
the heat deﬂection temperature is always below, but near T
g
; in semicrystalline polymers, the heat
deﬂection temperature can be above T
g
, but it is always below T
m
.
Failure properties describe the conditions under which a polymer will either break or become
so distorted that it can be considered failed. Of the previously discussed properties, strength, yield
strength, elongation to break, and toughness are failure properties. Although failure properties are
important, a stressstrain experiment is not the ideal way to study failure. Better information about
failure, especially about toughness, can be derived by using the techniques of fracture mechanics.
12.3.3 Uniaxial Compression Testing
If instead of loading the sample in tension, you load it in compression, you can record a compression
stressstrain curve. Many features of compression stressstrain curves are similar to tensile stress
strain curves. You can, for example measure stiﬀness, strength, and toughness. There are, how
ever, some important diﬀerences. First yielding will be very diﬀerent in compression. In particular,
there will be no necking and there will be no opportunity for very large elongations (the maximum
compression strain is 100% and this amount of strain means the sample has disappeared). Sec
ond, when testing samples in compression, you are often limited by buckling rather than by the
true compressive strength of the material. Buckling is a geometric instability and not a material
property. If buckling can be prevented, most polymers will be able to sustain 2 to 3 times more
stress in compression than they can in tension.
12.3.4 Shear Testing
This topic may be discussed and involves loading the sample in shear and measuring shear strain.
12.3.5 Hydrostatic Compression
The pressuredependent dilatometry experiments discussed in Chapter 10 involved immersing a
sample in a conﬁning liquid and applying a pressure. This type of pressure application results in a
form of stress known as hydrostatic compression. In a state of hydrostatic compression, all three
axial stresses are equal and the shear stresses are all zero. Thus
σ
x
= σ
y
= σ
z
= −p or p = −
1
3
(σ
x
+σ
y
+σ
z
) (12.25)
where p is the pressure. Plugging this stress state into the generalized Hooke’s laws gives:
ε
x
= ε
y
= ε
z
= −
p(1 −2ν)
E
(12.26)
12.4. FRACTURE AND IMPACT TESTING 151
and the change in volume is
∆V = (e
x
+e
y
+e
x
)V
0
= −
3p(1 −2ν)
E
V
0
(12.27)
In the discussion of dilatometry in Chapter 10, we deﬁned the isothermal compressibility as
K = −
1
V
_
∂V
∂P
_
T
= −
∆V
V
0
p
(12.28)
Substituting ∆V for hydrostatic compression gives K in terms of E and ν:
K =
3(1 −2ν)
E
(12.29)
Hydrostatic compression call also be viewed as plotting pressure vs. volumetric stain. By
analogy with tensile strain, we deﬁne volumetric strain as ∆V/V
0
. The volumetric strain/pressure
relation then becomes
−p =
1
K
∆V
V
0
(12.30)
Comparing this expression to the onedimensional Hooke’s law, we see that 1/K plays the role of
modulus. The quantity 1/K is known as the bulk modulus of the material. In terms of E and ν:
1
K
=
E
3(1 −2ν)
(12.31)
Note the factor of 1 −2ν in the denominator. Many rubbers which are very soft also have ν ≈ 1/2.
When ν is equal to 1/2, the bulk modulus is predicted to be inﬁnite. In reality, ν is never quite 1/2
and it turns out that the increase in ν in soft materials is roughly compensated by the decrease in
E. In the end the variability of bulk moduli over a wide range of polymer materials is not large.
This is reasonable because most polymers are made up of units of similar chemical composition and
the compression of these units under hydrostatic compression in not overly sensitive to the nature
of how these units are connected together. Note this statement only applies to hydrostatic stress.
When the stresses in one or more directions are signiﬁcantly diﬀerent, then the nature in which the
chemical units are connected becomes more important.
Another unique aspect of hydrostatic stress is the absence or near absence of yielding. In
general, yielding requires shear stresses. When none are present, as in hydrostatic stress, the yield
strength is predicted to be inﬁnite. In compression, a material under hydrostatic stress will not
yield. In hydrostatic tension, all polymers will be brittle and will not yield, or at least will not
yield until high stress.
12.4 Fracture and Impact Testing
This topic may be discussed and inolve loading a sample until in cracks or hitting with an object
in impact. The analysis of the results can be complicated.
152 CHAPTER 12. MECHANICAL PROPERTIES
12.5 Time Dependence or Viscoelasticity
In elastic materials (linear or nonlinear) the strain is a function of the stress only, or the stress is
a function of the strain only:
ε = f(σ) (12.32)
In polymers, the stress and strain are often time dependent; in other words, polymers are viscoelas
tic:
ε = f(σ, t) (12.33)
The are several ways to observe and quantify time dependence of the mechanical properties of
polymers. One method is a creep test. In a creep test, the stress is held constant, and the strain
is measured as a function of time. Let’s assume that the stresstime dependencies of the strain can
be separated. In a creep test we then write the strain as the product of two functions, J(t) and
f(σ). One depends only on time and the other depends only on stress:
ε(t) = J(t)f(σ) (12.34)
We next assume the material is linear viscoelastic, that is, we assume that f(σ) includes only terms
that are linear in σ. Because the coeﬃcient of the linear term can be included in J(t), we can write:
e(t) = J(t)σ (12.35)
J(t) is a new material property; it is called the creep compliance. It is time dependent and it can
be measured in a creep test. The stress is set to some constant value, σ
0
, and the strain is measured
as a function of time. The creep compliance is
J(t) =
ε(t)
σ
0
(12.36)
If the material was linear elastic then ε = (1/E)σ. The creep compliance of a linear elastic material
is just 1/E or the compliance.
The above analysis describes the creep behavior of a linear viscoelastic material. But, what
does linear viscoelastic mean? By the equation above, J(t) was written to be independent of stress;
in other words, you would ﬁnd the same J(t) no matter what value of σ
0
was used in the creep
test. To the extent that this is true, the material under test is linear viscoelastic. When J(t) is
observed to depend on the level of constant stress, the material is said to be nonlinear viscoelastic.
Most analyses of polymer viscoelasticity assume linear viscoelasticity. That assumption is good for
small strains. It could be called the analog of the smallstrain assumption in linear elasticity.
The complementary experiment to a creep test is a stress relaxation test. In the stress relaxation
test, the strain is held constant, and the stress is measured as a function of time. In analogy with
the development above, the stress relaxation test is described by:
σ(t) = G(t)ε
0
or G(t) =
σ(t)
ε
0
(12.37)
12.5. TIME DEPENDENCE OR VISCOELASTICITY 153
where G(t) is the relaxation modulus and ε
0
is the constant strain level used during the test.
For a linear elastic material, the relaxation modulus would be just the modulus E. For a linear
viscoelastic material, the relaxation modulus depends on time, but not on the level of applied strain,
ε
0
. For a nonlinear viscoelastic material, the relaxation modulus depends both on time and on the
level of the applied strain.
Creep and stress relaxation experiments can be done using a variety of loading conditions.
Some examples include tensile loading, shear loading, torsional loading, compressional loading, and
even hydrostatic compression. You can imagine that in hydrostatic compression where yielding
and therefore most ﬂow is eliminated, that there is much less time dependence in the mechanical
properties. The other loading conditions, however often show signiﬁcant time dependencies.
Time dependence of mechanical properties is an important piece of information about the
response of polymers to stress. Polymers are often used in applications that may experience long
term loads. It is important to know not only if the polymer can sustain a given load but if it
can sustain the load for a long period of time. For an example consider the recent development of
polyethylene ropes. By orienting PE, it is possible to create stiﬀ and strong ﬁbers. The ﬁbers can
be woven into ropes. As with the ﬁber, the rope is very stiﬀ and very strong in short time scale
static tests. Because it is made from PE, the rope is potentially cheap. There are many potential
problems, however, that have not yet been considered. First, PE is above T
g
at room temperature
and therefore can be expected to be strongly viscoelastic. While the rope may be strong, it also
may rapidly creep. A large amount of creep would make the rope useless. The viscoelastic eﬀect
will also be compounded by high levels of stress. A high uniaxial stress will increase the volume;
it will increase the volume by the amount equivalent to a hydrostatic tension equal to 1/3 of the
axial tensile stress. In other words, the uniaxial tensile stress can be considered to be a negative
pressure. While positive pressures always increase T
m
and T
g
, a negative pressure will cause T
m
and T
g
to decrease. Therefore at a given temperature, the rope will be farther above T
g
when
under stress than it will be when unloaded. If the stress is high enough the rope may even melt by
the application of load. This lowering of T
g
and T
m
will have the eﬀect of magnifying any possible
viscoelastic eﬀects.
12.5.1 Creep Experiments
Depending on temperature, it can take a long time to run a creep experiment that shows a signiﬁcant
amount of creep. Therefore, it is typical to plot the creep compliance as a function of log time.
Some typical creep data at one speciﬁc temperature are given on the right side of Fig. 12.5. The
time scales in such plots can be so long that it is impractical to rely on isothermal creep tests. To
get the long time scales that might be of interest, we instead use the principle of timetemperature
superposition that was introduced earlier in this chapter. We call the temperature we care about the
154 CHAPTER 12. MECHANICAL PROPERTIES
J(t) J(t)
log t log t
r
Figure 12.5: Left side is a set of creep experiments as a function of temperature. The lower curves are for
lower temperatures; the higher curves are for higher temperatures. The right side is the master curve for
creep compliance. It is obtained from the creep data on the left by using timetemperature superposition.
reference temperature. By the principle of timetemperature superposition, the creep at very long
times at the reference temperature, can be expected to be equivalent to the creep at shorter times
at some higher temperature. Conversely, the creep at short times at the reference temperature,
can be expected to be equivalent to the creep at longer times at some lower temperature. A set of
creep experiments thus consists of measuring creep over a relatively short amount of time (10
5
to
10
6
seconds) at a series of diﬀerent temperatures. The temperatures will probably be both above
and below the reference temperature. A typical set of data for creep as a function of time at many
temperatures is shown in the left side of Fig. 12.5.
The question is how do we relate the times at one temperature to the times at another tem
perature? If the temperatures are not too far apart, and the measurement time is not too short,
than the creep data can be expected to overlap. That is, the creep compliance near the end of the
measurement time for one temperature will be identical or higher than the creep compliance near
the beginning of the measurement time at a slightly higher temperature. It has been experimentally
observed that the log time plots can usually be overlapped by a simple linear shift along the time
axis. A typical result is illustrated in the right side of Fig. 12.5. The master curve was obtained
from the raw data on the left by ﬁxing the curve at the reference temperature and then shifting
all other curves horizontally until they achieve the maximum overlap with data at the reference
temperature.
The master curve on the right side of Fig. 12.5 is plot as a function of log t
r
where t
r
is called
the reduced time. Reduced time is actual time for experiments run at the reference temperature.
12.5. TIME DEPENDENCE OR VISCOELASTICITY 155
log a
T
T
REF
Temperature
l
o
g
a
T
0
Figure 12.6: Typical shift factor plot for log a
T
as a function of temperature.
For experiments at other temperatures, reduced time is related to real time by:
log t
r
= log
t
a
T
= log t −log a
T
(12.38)
To move a curve at a given temperature in the plot of the left half of Fig. 12.5 to the master curve
on the right half of Fig. 12.5, the curve is shifted horizontally by the amount −log a
T
( the curve
is shifted to the right if log a
T
< 0 and to the left if log a
T
> 0). The term log a
T
is thus known
as the shift factor. Because for T > T
ref
, the curves are shifted to the right, log a
T
is less than
zero. At T
ref
, log a
T
is equal to zero. For T < T
ref
, log a
T
is greater than zero. A schematic plot
of log a
T
versus T is shown in Fig. 12.6. Plots such as Fig. 12.6 quantify the timetemperature
superposition principle. They tell you how to convert the time at one temperature to the time at
another temperature.
We next examine the physical meaning of the creep compliance plot of the right side of Fig. 12.5.
At early times J(t) is increasing. This region is known as viscoelastic response. If the experiments
included data to very short times (or low temperatures), J(t) would level oﬀ at a constant value
equal to 1/E for the material at that time (or temperature). This region of the curve would be the
elastic response region. The plateau region at middle times is known as the rubbery plateau. In this
region the polymer acts like a rubber or a polymer that is above the glasstransition temperature.
The transition of J(t) from a low value to the plateau is a measurement of the glasstransition on
a timescale plot. The time to reach the rubbery plateau is termed the glasstransition time. At
late times, J(t) begins to rapidly increase. The polymer is now acting like a liquid and the region
is called the viscous ﬂow region. If the material is crosslinked and thus prevented from ﬂowing,
this terminal region would not occur.
156 CHAPTER 12. MECHANICAL PROPERTIES
12.5.2 FreeVolume Theory
With suﬃcient data, log a
T
can be found experimentally by shifting creep curves to obtain the max
imum amount of overlap. This measured log a
T
can then be used to quantify the timetemperature
superposition principle. It would be nice, however, to be able to predict log a
T
. There is an empir
ical equation, the WLF equation (for WilliamsLandelFerry), and that equation can be justiﬁed
with freevolume theory. The theory was originally developed for amorphous polymers and the
glasstransition in those polymers. Because semicrystalline polymers also have amorphous regions,
the theory can be applied to semicrystalline polymers. The most quantitative results, however, are
obtained when working with amorphous polymers.
An amorphous polymer can be considered to be made up of occupied volume and free volume.
As the temperature is changed, the free volume and the occupied volume will both change in speciﬁc
volume or density. The occupied volume might be expected to expand with an expansion coeﬃcient
appropriate to a solid polymer or close to the expansion coeﬃcient that exists below T
g
. Above
T
g
, the solid part or occupied volume should continue expanding at the same rate and the excess
expansion observed above T
g
can be attributed to expansion in the free volume. Expansion of the
total, free, and occupied volume is illustrated schematically in the dilatometry data in Fig. 12.7.
At any given temperature, the fraction of the total volume that is free volume is
f(T) =
V
f
V
f
+V
0
≈
V
f
V
0
(12.39)
where the approximation is based on V
f
<< V
0
. Around T
g
and above T
g
, the fraction of free
volume can be expressed as
f(T) = f
g
+α
f
(T −T
g
) (12.40)
where f
g
is the fraction of free volume at T
g
and α
f
is an expansion coeﬃcient for the fraction
free volume (see Fig. 12.7). α
f
is approximately α
m
− α
g
, or the diﬀerence between the thermal
expansion coeﬃcients of the polymer above (α
m
where m stands for melt) and below (α
g
where g
stands for glass) T
g
. According to free volume theory, viscosity can be related to the fraction of
free volume by
ln η(T) = A+
B
f(T)
(12.41)
This equation states that as the fraction of free volume increases, the viscosity decreases. This
equation is known as the Doolittle equation.
The shift factor can be expected to be related to the relative viscosities at two temperatures.
If we select T
g
as the reference temperature, then the shift factor at any other T (≥ T
g
) is given by
ln a
T
= ln
η(T)
η(T
g
)
= ln η(T) −ln η(T
g
) = B
_
1
f(T)
−
1
f
g
_
(12.42)
12.5. TIME DEPENDENCE OR VISCOELASTICITY 157
V
V
total
V
free
V
occupied
α
f
Temperature
Figure 12.7: Plots of total volume and occupied volume for an amorphous polymer both above and below
the glasstransition temperature.
158 CHAPTER 12. MECHANICAL PROPERTIES
Substituting in f(T) from above, this expression can be rearranged to get:
log a
T
=
−
_
B
2.303fg
_
(T −T
g
)
_
fg
α
f
_
+ (T −T
g
)
(12.43)
or
log a
T
=
−C
1
(T −T
g
)
C
2
+ (T −T
g
)
(12.44)
where C
1
and C
2
are two constants for a given polymer. This shiftfactor equation is the WLF
equation.
There is nothing special about the choice of T
g
in the above derivation. In fact any reference
temperature, T
ref
, could be used as long as the fraction of freevolume can be expressed by the
equation give earlier. In general, this requirement limits T’s to near T
g
and equations like the WLF
equation can only be expected to be quantitative near and above T
g
. There is an advantage to
choosing T
g
as the reference temperature. If we restrict the reference temperature to T
g
, it has
been observed that the constants in the expressions above (C
1
and C
2
) appear to be universal for
all polymers. In other words, the constants C
1
and C
2
are relatively invariant to the nature of the
polymer. For a wide variety of polymers the shift factor is given by:
log a
T
=
−17.44(T −T
g
)
51.6 + (T −T
g
)
(12.45)
A plot of this equation would be similar to the plot in Fig. 12.6. The universal constants come from
ﬁtting the WLF equation to a wide variety of polymers. We note that the variation from polymer
to polymer can be signiﬁcant. In practice, it is recommended that the WLF universal constants
only be used as a last resort. It is better to determine shift factors experimentally or to ﬁnd WLF
constants speciﬁc to the polymer of interest.
The WLF equation gives us information about the eﬀect of rate on T
g
. The predicted eﬀect
is about a 3
◦
C change in T
g
for each order of magnitude change in rate. The reasons behind this
result will be discussed in class.
In some cases, the shift factors cannot be observed experimentally. This can occur when the
creep compliance remains constant over a long period of time. The shift can only be measured if
there are features (i.e., changes) in the creep compliance data at all temperatures. If there is no
change at several temperatures, there is no way of knowing how far to shift.
12.5.3 Stress Relaxation Experiments
The complementary experiment to creep experiments is stress relaxation experiments. Like creep
tests, longterm stress relaxation tests are done using timetemperature superposition. The left side
of Fig. 12.8 shows several stress relaxation tests at various temperature. The higher curves are for
lower temperatures and the lower curves are for higher temperatures. The right side of Fig. 12.8
12.5. TIME DEPENDENCE OR VISCOELASTICITY 159
G(t) G(t)
log t log t
r
Glassy
Viscoelastic
Rubbery
Viscous
Flow
Figure 12.8: Left side is a set of stress relaxation experiments as a function of temperature. The higher
curves are for lower temperatures; the lower curves are for higher temperatures. The right side is the
master curve for relaxation modulus. It is obtained from the raw data on the left by using timetemperature
superposition.
shows the master plot for relaxation modulus plot that was obtained by appropriately shifting the
raw data in the left side plot.
The master relaxation modulus curve resembles a ﬂipped over version of the master creep
compliance curve. Furthermore the various regions of the relaxation modulus curve correspond to
the regions of the creep compliance curve. The earliest time data, where G(t) is ﬂat, is the glassy
region. In this region the response is elastic and G(t) is approximately equal to the static tensile
test modulus, E. The next region is called the viscoelastic region. The middle region is called
the rubbery plateau. The transition from the glassy region to the rubbery plateau is the glass
transition visualized on a time scale. The ﬁnal or terminal region represents viscous ﬂow.
12.5.4 Dynamic Mechanical Analysis
While creep and stress relaxation tests can be used to characterize viscoelastic materials, they can
often be impractical because they require much time. They require several experiments at various
temperatures, each of which can take 10
5
to 10
6
seconds (1 to 10 days). A more common technique
for characterizing viscoelastic polymers is dynamic mechanical analysis (DMA). In DMA, instead
of keeping the strain constant, as in a stress relaxation test, the strain is oscillated at a constant
amplitude, ε
0
, and a constant frequency, ω. Thus the strain input is
ε(t) = ε
0
sin ωt (12.46)
160 CHAPTER 12. MECHANICAL PROPERTIES
As in most physical response problems, when the system is driven by a constant frequency, it will
respond at the same frequency but may have a phase diﬀerence and a diﬀerent amplitude. In other
words, the stress will be given by:
σ(t) = σ
0
sin(ωt +δ) = G(ω)ε
0
sin(ωt +δ) (12.47)
where G(ω) is the dynamic modulus and δ is the phase angle.
In analogy with other deﬁnitions of moduli, the dynamic modulus G(ω) is the ratio of stress to
strain; in this case we take the ratio of the amplitudes of the stress and the strain:
G(ω) =
σ
0
ε
0
(12.48)
G(ω) or the dynamic modulus deﬁnes the modulus of a viscoelastic material. The phase angle,
δ, describes the viscous character of the material. If δ = 0, the stress is in phase with the strain and
the material is totally elastic. If δ = π/2, the stress is completely out of phase and is completely
viscous. In general, δ will be between 0 and π/2 and the material will be viscoelastic.
Some people prefer other ways to describe DMA data. To see alternative representations, we
can expand the stress function:
σ(t) = G(ω)ε
0
cos δ sin ωt +G(ω)ε
0
sin δ cos ωt (12.49)
= G
(ω)ε
0
sin ωt +G
(ω)ε
0
cos ωt (12.50)
where
G
(ω) = G(ω) cos δ and G
(ω) = G(ω) sin δ (12.51)
G
(ω) is known as the storage modulus. It is proportional to that part of the strain energy that
is stored and then recovered during one cycle. It also describes the elastic part of the stress
response, or the part of the stress in phase with the strain. G
(ω) is known as the loss modulus.
It is proportional to that part of the strain energy that is lost during a cycle due to viscoelastic
dampening. It also describes the viscoelastic part of the stress response, or that part of the stress
that is out of phase with the strain.
The above expressions give G
(ω) and G
(ω) in terms of G(ω) and δ. The inverse relations can
easily be derived:
G(ω) =
_
G
(ω)
2
+G
(ω)
2
(12.52)
tan δ =
G
(ω)
G
(ω)
(12.53)
These two relations are reminiscent of complex numbers. It is common practice to deﬁne a complex
modulus:
G
∗
(ω) = G
(ω) +iG
(ω) (12.54)
12.5. TIME DEPENDENCE OR VISCOELASTICITY 161
n
G'(ω)
tan δ
G
'
(
ω
)
o
r
t
a
n
δ
T
g
Temperature
Figure 12.9: Typical DMA data for an amorphous polymer.
The storage modulus is the real part of G
∗
(ω), the loss modulus is the imaginary part of G
∗
(ω), the
dynamic modulus is the amplitude of G
∗
(ω), and tan δ is the tangent of the angle between G
∗
(ω)
and the positive real axis when G
∗
(ω) is plotted in the complex plane.
We have deﬁned four types of dynamic properties — G(ω), δ, G
(ω), and G
(ω). Only two of
these are independent and it is only useful or rather necessary to measure two of them. Common,
but not universal practice, is to measure G
(ω) and tan δ. Some typical DMA data for an amorphous
polymer as a function of temperature are plotted in Fig. 12.9. Below T
g
, G
(ω) is fairly constant,
and because tan δ and therefore also G
(ω) are both small, G
(ω) is close to the modulus of the
material that would be measured in a static test. At T
g
, G
(ω) drops dramatically, while tan δ goes
through a peak. The peak is often used to measure the glass transition temperature. Peaks in tan δ
can also be observed below T
g
. Observing these smaller peaks is one of the best ways of observing
subglass relaxations.
Some typical DMA data for semicrystalline polymers as a function of temperature are given
in Fig. 12.10. Below Tg these data are similar to the amorphous polymer data including peaks in
tan δ at subglass relaxations and at T
g
. At T
g
, however, G
(ω) does not drop nearly as far. The
crystal fraction contributes stiﬀness and prevents overall viscous ﬂow. At T
m
, the crystals melt
and a second drop in G
(ω) results in a very low ﬁnal value. The relative drops at T
g
and T
m
are
sensitive to the percent crystallinity.
The stress relaxation experiments measure a relaxation modulus known as G(t). DMA experi
ments measure a new viscoelastic modulus called the complex dynamic modulus of G
∗
(ω). G(t) and
G
∗
(ω), however, are not independent quantities. It is easy to show that G
∗
(ω) can be calculated
from a Fourier transform of G(t). Thus G
∗
(ω) is the frequency domain version of the relaxation
162 CHAPTER 12. MECHANICAL PROPERTIES
n
G'(ω)
tan δ
G
'
(
ω
)
o
r
t
a
n
δ
T
g
T
m
Temperature
Figure 12.10: Typical DMA data for an semicrystalline polymer.
modulus.
In analogy with creep experiments, we could imagine dynamic stress experiments in which the
sample is subjected to an oscillating stress and we measure the amplitude and the phase angle of
the strain response. These dynamic experiments will give a dynamic complex compliance, J
∗
(ω),
which can be shown to be the Fourier transform of J(t). Like dynamic modulus, J
∗
(ω) can be
broken up to component functions of J
(ω) (the storage compliance), J
(ω) (the loss compliance),
J(ω) (the dynamic modulus), and δ (phase angle). The analysis of dynamic stress experiments
is identical to the above analysis of DMA experiments. Most commercial instruments are limited
to oscillating strains or displacements. Thus must dynamic tests on polymers measure dynamic
modulus instead of dynamic compliance.
Problems
12–1. Show that Eq. (12.27) is valid for any stress state and not just for hydrostatic compression.
TABLE OF CONTENTS
1 Introduction 1.1 1.2 Deﬁnitions of Terms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Course Goals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1 2 5 7 7 9
2 Molecular Conformations 2.1 2.2 2.3 2.4 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Property Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 FreelyJointed Chain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 2.4.1 2.4.2 FreelyJointed Chain Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 Comment on FreelyJointed Chain . . . . . . . . . . . . . . . . . . . . . . . . 20
2.5 2.6 2.7 2.8 2.9
Equivalent Freely Jointed Chain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 Vector Analysis of Polymer Conformations . . . . . . . . . . . . . . . . . . . . . . . . 24 FreelyRotating Chain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 Hindered Rotating Chain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29 More Realistic Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.10 Theta (Θ) Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33 2.11 Rotational Isomeric State Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 3 Polymer Molecular Weight 3.1 3.2 3.3 3.4 3.5 3.6 43
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 Number Average Molecular Weight . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44 Weight Average Molecular Weight . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46 Other Average Molecular Weights . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46 A Distribution of Molecular Weights . . . . . . . . . . . . . . . . . . . . . . . . . . . 47 Most Probable Molecular Weight Distribution . . . . . . . . . . . . . . . . . . . . . . 48 57
4 Polymer Solutions 4.1 4.2 4.3 4.4
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57 Solution Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57 Physical Origins of Entropy of Mixing . . . . . . . . . . . . . . . . . . . . . . . . . . 61 FloryHuggins Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63 65
5 Colligative Properties 5.1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
2 5.2 5.3 5.4 5.5 5.6 Boiling Point Elevation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
Freezing Point Depression . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69 Osmotic Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69 Practical Aspects of Osmotic Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . 71 Experimental Aspects of Membrane Osmometry . . . . . . . . . . . . . . . . . . . . 74 77
6 Viscosity 6.1 6.2 6.3 6.4
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77 Viscosity and Viscosity Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . 77 Viscosity Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80 Viscosity Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82 6.4.1 6.4.2 Polydisperse Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82 Experimental Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
6.5
Viscosity Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87 89
7 Light Scattering 7.1 7.2 7.3 7.4 7.5 7.6
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89 Rayleigh Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90 Ideal Polymer Solutions with Small Particles . . . . . . . . . . . . . . . . . . . . . . 93 NonIdeal Polymer Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95 Large particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96 Light Scattering Data Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98 101
8 Miscellaneous Molecular Weight Methods 8.1 8.2 8.3 8.4 8.5 8.6
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101 Gel Phase Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101 Field Flow Fractionation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104 End Group Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104 Ultracentrifugation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106 Insoluble Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106 109
9 Thermal Analysis 9.1 9.2 9.3
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109 Thermal Transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109 Thermal Analysis of Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113 115
10 Dilatometry
10.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115 10.2 Amorphous Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
. .4. . . . . . . . . . . . . . .3. . . . . . .3 Instrumentation .5. . . 138 11. . . . . . . . . . . . . . . . .2 Uses of StressStrain Properties . . . .4 Shear Testing . . .1 Introduction . .1 Introduction . . . . . . . . . . 127 11. . . . . . . . . . . . . . . . . . . 137 11. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5 Time Dependence or Viscoelasticity . .4 Experimental Techniques . . . . . . . . . . . . . . . . . . . . . .4. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120 10. . . . . . . . . . . . . 127 11. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3 Stress Relaxation Experiments . . . . . . . . . . . . . . . . . . . . . . . . 130 11. . . . . . . . . . . . . . .1 Heating of Semicrystalline Polymers . 149 12. . . .2 Simple Elasticity Theory . . . . . .2 FreeVolume Theory . . . . . . . . 145 12. . . . . . . . . . . . . . . 142 12. . . . . . . . . . . . . .1 Creep Experiments . .3. . 150 12. . . . .5 Hydrostatic Compression . . . . . . . . . . . . . 150 12. 119 10.0 10. . .1 Pressure Dependence of Tg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141 12. . . . . . . . . . 138 12 Mechanical Properties 141 12. . . . . . . 151 12. . . . . . 158 12. . . . . . . . . . . . . . . . . . 144 12.5. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138 11. . . . . . . . . . . . . . . .5. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2 Diﬀerential Scanning Calorimetry . . . . 121 10. . . . . . . . . . . . . . . . . . . . . 121 10. . . . . . . . . . . . .4. . . . . . . . . . . . . . . . . . .5 DSC Summary . . . . . . .2. .3 Semicrystalline Polymers . . . . . .2 Cooling of Semicrystalline Polymers . . . . . . . . . . . . . . 153 12. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3 Uniaxial Compression Testing . . . . . . . . . . . . . . . . .4 Dynamic Mechanical Analysis . . . .6 Thermogravimetric Analysis . . . . . . . . .4 Fracture and Impact Testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3. . . . . . . . . . . . . . . . . . . . . . . .1 Pressure Dependence of Tm . . . .4 Results with Polymers . . . . . . . . 150 12. . . . . . .3 Amorphous Polymers . . . . . . . . . . . . . . . . 156 12.1 StressStrain Properties . . . 124 11 Diﬀerential Scanning Calorimetry 127 11. .5 Dilatometry Summary . 152 12. . . . .3. . . . . . . . . . . . 130 11. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3. . . . . . . . . . . . . . . . . . . . . . . .5. . 129 11. . . .3 StressStrain Curves . . . . . .3. . . . . . . . 159 . . . . . . . . . . . . . . . . . . . . .
and much more. Perhaps more importantly we will discuss the theory behind those techniques. as a prerequisite. Spectroscopic analysis is aimed at characterization on the molecular scale. Understanding the theory behind polymer characterization techniques is an essential ingredient to making correct use of those techniques. As such it will be assumed that all students have completed. and mass spectrometry (MS). and spectroscopic analysis. macroscopic property measurement. The subject of polymer characterization is typically a second course in polymer science. Polymers are randomcoil molecules that can exist in a variety of conﬁgurations and conformations. 1 . infrared spectroscopy (IR).Chapter 1 Introduction The subject of polymer characterization covers the techniques that are used to give us information about polymer materials. 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. Some of the more important properties include molecular weight. time dependence of properties. Raman spectroscopy. The type of information we can use includes thermal properties. melt viscosity. mechanical properties. Many of the theoretical results can be veriﬁed by experiment. electron spin resonance (ESR). an introduction to polymer materials course (MS&E 3410 or equivalent). nuclear magnetic resonance (NMR). mechanical properties. In these notes we will discuss many polymer characterization techniques. We can learn much about polymer conformations purely by theoretical analysis. Theoretical characterization involves the detailed description of molecular conﬁgurations and conformations. thermal properties. Philosophically we choose to subdivide the ﬁeld of polymer characterization into three types of characterization methods — theoretical characterization. It involves taking a macroscopic polymer specimen or polymer solution and doing experiments that give information about properties of the polymer. Macroscopic property measurement is what might be referred to as conventional polymer characterization. friction and wear properties. This information is obtained with a variety of experimental and theoretical approaches. microstructural information. Some common spectroscopic techniques are UVvisible absorption spectroscopy. and electrical properties.
and natural rubber. as expected. physical chemistry of polymers and polymer characterization can be thought of as a subset of physical chemistry. Some example synthetic polymers are Polyethylene (PE): Polystyrene (PS): (CH2 (CH2 CH2 ) C H) ¨r r ¨ r¨ Polyvinyl Chloride (PVC): (CH2 C H) Cl . proteins. In the ﬁeld of polymer characterization. we will ﬁnd that most of the principles of chemistry (e.e.g. In one sense. we can therefore draw on all the knowledge of the physical chemistry of small molecules.. wool. Historically. enzymes. 1. The key word is “large. chemical reactions) and physics (e. 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. Natural polymers include DNA. A polymer is molecule formed by covalent chemical bonds between atoms (or groups of atoms) to give a large structure (linear chains.. Despite the unquestioned importance of natural polymers. Two types of polymers are natural polymers and synthetic polymers.1 Deﬁnitions of Terms The most basic deﬁnition is that of a polymer. Because this old thinking was wrong and instead polymers are large molecules (or macromolecules). collagen. RNA.. the fact that polymers are molecules with ordinary chemical bonds (i. physical properties) apply to polymers just as they do to conventional molecules. naturally occurring macromolecules. INTRODUCTION These techniques are usually aimed at getting information about the chemical structure of polymer materials. 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. cotton.g. however.” The word polymer is usually reserved for high molecular weight molecules. Before applying any traditional physical chemistry analysis. we must ﬁrst ask about the eﬀect that large molecular size has on the traditional analysis and then correct for those eﬀects. branched chains. silk. 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. or crosslinked networks).2 CHAPTER 1. Natural polymers are.
From a topological point of view. The above structures show the repeat unit of the polymer. Sometimes (e. . other commercial nylons include Nylon 6/12. If a polymer is made from only one type of monomer or if it has a single repeat unit. Monomers are the starting materials used in synthesizing polymers. In polyvinyl chloride the repeat unit is (CH2 (CH2 CHCl) . Some polymers are made up of alternating monomers or alternating repeat units. In PE. The ﬁrst gives the number of carbon atoms in the amine. Besides Nylon 6/6. The repeat unit is usually the smallest piece of the polymer that can be said to “repeat” periodically to give the polymer chain. the structure on the right side Fig. polyethylene terepthalate (polyester.. The names of polymers often indicate the starting monomer material. However. As there is then only one type of repeat unit. Nylon 6/9 and Nylon 4/6. it is called a homopolymer. Some nylons are followed by a single number as in Nylon 6. The polymerization of Nylon 6/6 is shown in Fig. The word polymer literally means many “mers” or many monomers. the repeat unit listed above is (CH2 ) . the PE repeat unit could be CH2 ..1. epoxy. but be(CH2 CH2 ) CH2 ) . The “6/6” in the polymer name denotes the number of carbon atoms in each of the two monomers. 1. in condensation polymers) some atoms are lost (e. Some examples of such commercial nylons are Nylon 6 and Nylon 11. it is common practice to refer to such alternately copolymers as homopolymers.1.1. Nylon 6/6 is actually an alternating copolymer polymerized from monomers of adipic acid and hexamethyl diamine.g. 1. Such polymers are often made from two types of monomers and thus are formally copolymers. Thus polytetraﬂuoroetheylene is a polymer made by polymerizing tetraﬂuoroethylene monomers. it is common practice to call cause PE is polymerized from ethylene or CH2 the repeat unit although it is not the smallest periodically repeating unit. and polyoxymethlyene. polymethyl methacrylate (lucite). These nylons are made from ωamino acids (a methylene chain with an amine group on one end and an acid group on the other) and the single number is the number of carbon atoms in the ωamino acid. mylar). the second gives the number of carbon atoms in the acid. Polymers are made by combining many monomers. it is possible to consider two consecutive monomer units in the polymer chain as a single repeat unit. it is called a copolymer. a molecule of water (H2 O)) from the monomer during polymerization and the repeat unit will diﬀer slightly from the monomer. Although it is a copolymer. A good example is Nylon 6/6.g. DEFINITIONS OF TERMS Polytetraﬂuoroethylene (PTFE or Teﬂon): Polypropylene (PP): (CF2 (CH2 CF2 ) C H) CH3 3 Other examples of synthetic polymers include nylon. polycarbonate. The repeat unit and the monomer are usually closely related. Nylon 6/11. If a polymer is made from more than one type of monomer or has more than a single repeat unit.1 can be viewed as the single repeat unit for Nylon 6/6.
viscosity. a branched. in a polymer is called the degree of polymerization. Structural units can be connected to make linear. The number of monomers.. or sometimes the number of repeat units. Besides the way the units are connected. especially mechanical properties. A polymer must have a high molecular weight before it has useful properties.2: A schematic view of monomer “A” connected to make a linear.2 shows the various ways in which structural units “A” can be connected to make a polymer molecule.. result in synthesis of the polymer Nylon 6/6. The way in which structural units are connected has a profound eﬀect on polymer properties such as toughness. glass transition temperature.4 CHAPTER 1.1: Copolymerization of the two monomers. or crosslinked polymers. The repeat unit can also be called the structural unit.e. or a crosslinked polymer. branched. Figure 1. A thermoplastic polymer will soften as it is heated (i. thermal treatment leads to plastic ﬂow). the higher the molecular weight. Crosslinked polymers are also called network polymers. –A–A–A–A–A–A–A–A– Linear A–A–A A A –A–A–A–A–A–A–A–A– A A Branched – A– A– A– A– A– A– A– A– A A A A – A– A– A– A– A– A– A– A– CrossLinked Figure 1. adipic acid and hexamethyl diamine. The more units that are connected. the total number of units also has a profound eﬀect on polymer properties. This behavior has important . etc. 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. Polymers are often characterized as being thermoplastic or thermoset.
1.2. COURSE GOALS
5
implications about processing such polymers. Thermoplastic polymers can usually be molded and are typically used as injection molding resins. In brief, the polymer is heated until is softens and then is injected into a mold where it cools and solidiﬁes into a solid part. Thermoplastic behavior is 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 crosslinked 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 highmodulus and highstrength ﬁbers by a solution, ﬁberspinning method.
1.2
Course Goals
These notes will emphasize polymer characterization of high molecular weight synthetic polymers. The focus on high molecular weight is because high molecular weight is a prerequisite 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. The ultimate goal of polymer characterization is to understand polymer properties, how those properties relate to polymer structure, and how they relate to potential polymer applications.
6
CHAPTER 1. INTRODUCTION
Someone well versed in polymer characterization should be able to take any polymer and decide whether or not that polymer is suitable for some contemplated application. A longrange goal of polymer 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 crosslinked 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 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
Molecular Conformations
2.1 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. 2.1. 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. 2.2 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 2.1: Two molecules with diﬀerent conformations. These two molecules can be made identical with a rotation of 180◦ about the central single bond.
7
The random coil picture.3 shows an extended chain polymer and a random coil polymer. As discussed in the Introduction chapter (chapter 1). solution. The diﬀerent conformations arise by thermal energy and the relatively low barrier to rotations about single bonds. Figure 2. We will therefore spend some time studying the conformations of isolated polymer chains. The major results will be predictions of the endtoend distance for linear polymers. It turns out that the description of an isolated polymer chain is also a good description for polymer chains in concentrated solutions. The ideas that enter into the analysis give insight about the shape of polymers. . To understand polymers. rigid rod polymers are generally stiﬀer and have a higher glasstransition temperature. The shapes of the possible conformations have a direct bearing on the physical properties of the polymer. is a more realistic view of the shape of real polymer molecules. An isolated polymer chain is clearly a good model for a gas phase or a dilute solution polymer. Some properties that can be inﬂuenced included solution viscosity. For example. solution light scattering.8 CHAPTER 2. In a collection of polymers (gas phase.2: Two distinct conﬁgurations of polymers can exist at asymmetric carbon atoms (top) and across double bonds (bottom). To be speciﬁc. however. These more extended shapes give rigid rod polymers very diﬀerent properties. and mechanical properties. Each conformation will be a diﬀerent variation on a random coil. or solid state). MOLECULAR CONFORMATIONS Cl H Cl H Cl H H Cl trans cis Figure 2. The ﬁrst thing to realize about polymers is that they are usually very long and are best described as resembling a random coil . In this chapter we will discuss various theoretical methods for characterizing the shape of random coil polymers. the various individual polymer molecules will assume many possible conformations. or even in the solid state. rigid rod polymers generally assume more extended conformations than polymers with more ﬂexible backbones. The extended chain picture is the way we might choose to draw a polymer structure. we must understand the shape or the form that polymers have in solution as well as in solid state.
2. Blue is for trans bonds while read and green are for gauche bonds. A generalization to nonconstant bond lengths can be made later if necessary. With constant bond lengths. 2. The colors indicate rotation angle about each bond. Figure 2. we can consider a polymer conformation as a 3D random walk of n steps where each step has length l.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. These n bonds connect n + 1 backbone atoms. This nomenclature works but is normally more cumbersome than desired and we thus make some simpliﬁcations.3: Extended chain polymer on the left. this type of polymer characterization is theoretical characterization. In many polymers the bonds in the polymer backbone are all identical and therefore have a constant bond length. we choose to describe a polymer by listing the relative directions of each step in the random walk. A more realistic picture of a polymer as a random coil on the right. in PE the bonds are all carbon˚ carbon bonds and they are all typically about 1. NOMENCLATURE 9 Figure 2.4 shows an arbitrary direction in space emanating from the origin of a coordinate system. For example. Instead of listing absolute coordinates of each atom in the backbone.2. We begin with a polymer having n bonds. Directions in space are most conveniently described using polar angles. The angle that the . The angle with respect to the z axis is called the polar angle and is usually denoted by θ.53A long. We can thus deﬁne any conformation by giving the 3(n + 1) Cartesian coordinates of the n + 1 atoms along the polymer backbone. For simplicity we will restrict ourselves to polymers with constant bond lengths. We begin with the bond length (l).
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.10 CHAPTER 2. If we ever generalize to diﬀerent l’s for each bond. each step can be described by polar and azimuthal angles. where those angles are given with respect to an axis system centered on the atom at the start of that bond.4: Deﬁnitions of the polar angle θ and the azimuthal angle φ for any vector in a righthanded coordinate system. For n bonds. Normally we will not be concerned with the absolute location in space of the polymer chain. MOLECULAR CONFORMATIONS z θ y φ x Figure 2. we must add to these 2(n − 1) variables. θi and φi . some repeat units have more than one bond and for n we count all of these bonds). then we do not need to know the 3 original coordinates nor the 2 polar angles of the ﬁrst bond. we can deﬁne an arbitrary polymer conformation with 2n − 2 or 2(n − 1) variables. If we do everything relative to the location of the ﬁrst bond. each bond will have its own angles. Subtracting these ﬁve variables. n new variables which specify the length of each bond. 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. All possible directions in space can be spanned by choosing θ from 0 to π and φ from 0 to 2π. In other words. The 2(n − 1) variables are the polar and azimuthal angles for each bond except the ﬁrst bond. In the random walk. . any direction from the origin can be deﬁned by a unique pair of θ and φ. We thus require 2n + 3 variables to specify a conformation of a polymer with constant bond length. 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. θ and φ.
5. We denote the average value of any property over an ensemble of random coil polymer chains as P roperty . and z axes.5. the task is simple — we merely calculate the property for that conformation. When a polymer exists in a single conformation. 2. As illustrated in Fig.3.2. 2. An observed macroscopic property of an ensemble of polymer chains will be an average value of that property over the range of polymer conformations. can exist in many diﬀerent conformations. the polar angle for bond i + 1 is just the bond angle between bond i and bond i + 1 (see Fig. From now on. y. 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.5).5: Deﬁnition of polar and azimuthal angles for bond i. however. PROPERTY CALCULATION 11 φ=180˚ bond i+1 φi+1 x bond i1 φ=0˚ l z θi+1 bond i Figure 2. 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). Random coil polymers. 2. we consider the central bond as bond i and take the z axis to point back along bond i. we will refer to the polar angle as the bond angle. With the illustrated selection of x. 2. The possible orientations for bond i + 1 when the bond angle is θi+1 sweep out the cone illustrated in Fig. With this choice for the z axis.3 Property Calculation The goal of theoretical characterization of polymers is to be able to predict certain properties of those polymers. This choice is arbitrary. Another term for such an azimuthal angle is the dihedral angle for bond i + 1 — a term that we will adopt throughout these notes. The azimuthal angle (φ) for bond i + 1 is the counterclockwise angle around that cone from some suitably selected reference point. Finally. . the y axis is chosen to be perpendicular to the x and z axes and directed to make the xyz coordinates a righthanded coordinate system. 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. the polar angle is the bond angle for bond i + 1 and the azimuthal angle is the dihedral angle for bond i + 1.
. we can average them to get the average of that property for the bulk polymer sample. consider the roll of a single dice and consider the property of the number of pips showing on each role.3) where N is the number of randomly generated polymer chains. We can illustrate the Monte Carlo method with the dice problem. ﬁnd the probability and property of each conformation.) for each speciﬁc conformation.2) For polymer calculations there will usually be too many conformations to make the above exact calculation procedure possible. In other words you can enumerate all possible conformations. total the pips.5 6 6 6 6 6 6 6 (2. A Monte Carlo solution to the dice problem would be to roll a die many times.12 CHAPTER 2. For small molecules you can often do the above averaging process exactly.1) 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 the simplest models (models of short chains) we will be able to examine all possible random walks. The average property is deﬁned by P roperty = i Property(conf i) × Probablity(conf i) (2. 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. For a non chemistry example. the Property(conf i) = i. The property of the number of pips therefore has the exact average value of 6 pips = i i× 1 2 3 4 5 6 1 = + + + + + = 3. than the average property for a polymer sample can be approximated by P roperty ≈ 1 N Property(sample i) (2.. size.e. MOLECULAR CONFORMATIONS The way to ﬁnd P roperty is to examine a large number of polymer chains by considering a large number of random walks. When counting pips. if the probability of selecting a particular conformation at random is proportional to the actual probability of conformation i (selection probability ∝ Probablity(conf i)). etc. and then ﬁnd the average property by averaging the results. A die has six faces which represent six possible conformations of the die after each roll. Assuming the die is a fair die (i. not loaded) the probability of each conformation is the same and equal to 1/6 (thus Probablity(conf i) = 1/6). stiﬀness. By the Monte Carlo procedure.g. Assuming we can calculate some polymer property (e. Instead we will select conformations at random and use a Monte Carlo procedure to get the average property. and divide by the number of . the more accurate will be the calculated average property. Other molecules have only a few conformations and the task is still relatively simple. 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. The larger N .
FREELYJOINTED CHAIN 13 rolls.. Instead we have to generate conformations mathematically or in a computer. If the die was rolled suﬃciently many times and if the die was fair (i. In others words the direction of any bond is equally likely to occur in any of the possible directions of space — the joints at each bond thus move freely to allow all these possible orientations. Let’s begin with one particular property — the polymer size. The success of the Monte Carlo procedure is dependent on ones ability to select polymer conformations with realistic probabilities that accurately reﬂect the true distribution of conformations. s. the answer would be very unlikely to show much deviation from 3.4) where N is the total number of possible conformations and ri is the endtoend distance for conformation 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.e. As an average property.4. After many rolls. The problem we must solve is the development of rules or algorithms for realistically generating conformations. the answer might diﬀer from 3. At each subsequent step we will add more realism to the procedure used to generate the random conformations. or the radius of gyration.5. symmetric and not loaded). The ﬁnal results can be used to accurately predict many polymer properties.5) where si is the radius of gyration for conformation i. these properties are usually calculated as a root mean squared endtoend distance (or a root mean squared radius of gyration).2. Size can be characterized by calculating the endtoend distance.4 FreelyJointed Chain In a freelyjointed chain all 2(n − 1) angular variables are allowed to assume any values with equal probability. After a few rolls. the Monte Carlo solution would be very close to the exact answer of 3. Endtoend distance is the distance from the beginning of the chain to the end of the chain (see Fig. 2. We will begin with the simplest possible rules.5. Unfortunately for polymer problems we cannot physically select real polymers. The root mean squared endtoend distance is the square root of the average of the squared endtoend distances: r2 = 1 N N 2 ri i=1 rms r = (2.5. however. The root mean squared radius of gyration is the square root of the average of the squared radius of gyrations: s2 1 N N rms s = = s2 i i=1 (2.6). We will approach this problem in a series of steps. This problem is easily solved in the dice problem by rolling a die. r. 2.
5 in which the z axis is along the previous bond. φ) is the probability that any given bond has directional angles of θ and φ.7) where θ is the angle between the bond direction and the zaxis direction.6: The length of a vector (r) from the ﬁrst atom to the last atom on a linear polymer chain is the endtoend distance for that polymer conformation. φ) must be a constant. the bond length along the z axis is lz = l cos θ (see Fig.1 FreelyJointed Chain Analysis We begin our analysis of the freelyjointed chain by analyzing a single direction in space — we will analyze the z axis direction. For a freelyjointed chain all angles are all equally likely and therefore p(θ. The average value of lz is found by integrating over all possible bond projections or all possible bond directions: l lz = −l lz p(lz )dlz = where p(θ. φ)dS (2. MOLECULAR CONFORMATIONS Figure 2. Figure 2.6) .14 CHAPTER 2. The integration is over the surface of a sphere centered on the origin and dS is the diﬀerential of surface area. For any of the bonds in the chain (or steps in the random walk).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. 2. 2. 2. This ﬁgure shows the endtoend vector. ← r l θ l cos θ l cos θ p(θ. θ is also the polar angle in the coordinate system deﬁned in Fig.4.
The result is k = p(θ. These equally likely jumps cancel out to give zero average jump size. and note that the integral over p(θ. φ) = 2π π (2. which is a probability distribution function. FREELYJOINTED CHAIN 15 z dS = r2 sin θ dθ dφ dφ r dθ r sin θ r r sin θ dφ y dθ x Figure 2. φ).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. To ﬁnd k. When random walk steps in all directions are equally likely. For small angles this area is dS = r2 sin θdθdφ. we call it k. It is for this reason that we constantly work with rootmeansquared endtoend .8) lz = 0 dφ 0 dθ l l cos θ sin θ = 4π 2 π cos θ sin θdθ = 0 0 (2. which represents all possible directions in space. Because dS for surface integration over a sphere is r2 sin θdθdφ (see Fig.2.4.7) or 1 4π We can now insert p(θ. we integrate over the surface of sphere. 2.9) This result could have been anticipated.8) we can integrate over the unit sphere (r = 1) to get: 2π π 1=k 0 dφ 0 dθsinθ = 4πk (2. we are equally likely to jump in the positive direction as in the negative directions. φ) into the expression for lz and integrate. A simple average step size is not useful and we therefore instead consider the average squared step length. must be 1.
we can easily calculate the mean squared jump size: 2π 2 lz = 0 π dφ 0 dθ l2 cos2 θ sin θ 4π = = l2 π cos2 θ sin θdθ 2 0 π 1 l2 l2 − cos2 θ = 2 3 3 0 (2. or more usefully the distance in the z direction. If n is large. φ) function. Squaring each step length makes all step size positive and we are guaranteed to get a nonzero result.14) where σ is the standard deviation in zdirection distance and the term β is deﬁned in terms of standard deviation by β=√ 1 2σ 2 (2. 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). but we are concerned with the total z axis rootmeansquared endtoend distance. In the coin toss results.16 CHAPTER 2.16) .10) (2. Each step is considered a coin toss. follows simply from the formula for variance: 2 2 σ1 = lz − lz 2 2 = lz (2. the coin toss result is tails. the root mean squared length of all positive jumps will be the same as that of all negative jumps and each will be equal to the average of all jumps. with the following Gaussian distribution function: W (z)dz = √ −z 2 β 2 2 e 2σ2 dz = √ e−β z dz π 2πσ 2 1 (2. is z = (n+ − n− ) l 2 lz = (n+ − n− ) √ (2. if z increases on the step the coin toss result is heads. The factor(n+ − n− ) is like the result of a coin toss experiment. For a single step the variance. MOLECULAR CONFORMATIONS distances in our discussion of polymer size. The solution to this problem is approached by considering a set of typical jump directions. some of the bonds will point in the positive z direction and some will point in the negative z direction. We can thus represent the factor (n+ − n− ).13) 3 To solve for z we must determine (n+ − n− ).15) The freelyjointed chain problem is solved if we can ﬁnd the standard deviation in zdirection distance. the expected result is to have equal numbers of heads and tails. or the standard deviation squared.12) 3 The above result gives as an average jump size per step. For a chain of n bonds. if z decreases. denoted by z. We let n+ be the total number of jumps in the positive direction and n− be the total number of jumps in the negative direction. With the known p(θ.11) The root mean squared distance per step is: l 2 lz = √ (2. Then the rootmeansquared distance traveled in the z direction.
18) An alternate route to ﬁnding β is to ﬁnd the variance by integration (i. z)dx dy dz gives the probability that a chain’s endtoend vector is characterized by a vector (x. In other words. the three axes are independent of each other. As stated above. z)dx dy dz = W (x)W (y)W (z)dx dy dz (2. z) coordinates that give the same r value. FREELYJOINTED CHAIN 17 Statistical analysis tells us that for n steps.e. z)dx dy dz solves the freelyjointed chain problem. One dimension of W (x. y. z) is thus W (x.e. y.19) The expression for β together with the Gaussian distribution function give the distribution function for chain length in one direction.. y. y. z)dx dy dz = β √ π 3 e−β 2 r2 dx dy dz (2. Now we need to solve the threedimensional problem. 2. y. In other words. and z in each of the three Cartesian directions is the product of the probabilities for each of the axes considered separately. The function W (x. but rather with the endtoend distance r. but it is not in the most useful form. z)). We are normally not concerned with absolute end of the chain (i.17) β= 1 2n 2 lz = 3 2nl2 (2.9). From probability theory. y. z). the standard deviation in z is n times the standard deviation for a single step or 2 2 σ 2 = nσ1 = n lz 2 Substituting the above result for lz gives (2. The function is a Gaussian distribution function centered at the origin or centered about the mean value of zero. y. y.20) ∞ z 2 W (z)dz = −∞ 1 2nβ 2 (2. To ﬁnd this result we sum up all possible (x.9. location (x. we have W (x. ﬁnd the average value of z2 and subtract the square of the average value of z. we integrate over the volume element V . which we know to be zero). y.21) Because the analysis for W (z)dz given above applies equally well to the x and y directions. it is the probability that a chain that begins at the origin ends in a box center at the point (x. The result is z2 λ2 1 2 = lz = = n 3 n Solving for β again gives β= 3 2nl2 (2.. y.22) where r2 = x2 + y 2 + z 2 is the square of the distance from the origin to the end of the chain at (x. The probability that a chain has an endtoend distance characterized by a vector (x. Because the chain is freely jointed. W (x. z)dx dy dz is plotted in Fig. z). y. y. 2.2.4. z) or size dx dy dz (see Fig. the probability that a given polymer chain jumps distances of x.
The function W (r)dr always increases to some maximum and then decrease towards zero. is ∞ r2 = 0 r2 W (r)dr = 3 = l2 n 2β 2 (2.4 y 0.5 0. The maximum value.82l n 3 (2. The right side is a onedimensional plot of W (x. z)dx dy dz.25) Likewise.1 0. Figure 2. rmax . Integrating over this volume element yields a probability distribution in terms of the endtoend distance r: W (r)dr = V 3 W (x. We can characterize the distribution function by ﬁnding some key points. y.27) .23) This type of distribution function is called a radial distribution function. of width dr where x2 + y 2 + z 2 is between r and r + dr. is found by integrating W (r)dr: ∞ r = 0 rW (r)dr = 2 √ =l β π √ 8n = 0. r .0 3 2 1 0 βr 1 2 3 x Figure 2. 2.10. W (r)dr. the meansquared value of r.9 0. r2 .24) The average value of r.2 0.9: The left side shows a chain that starts at the origin and ends in a box centered a (x.7 0. y.6 0. z)dx dy dz = β √ π 4πr2 e−β 2 r2 dr (2.0 0.92l n 3π (2.3 0.26) and the root mean squared endtoend distance is √ r2 = l n (2. z). The peak value is found by ﬁnding where the derivative of W (r)dr is zero. The volume element of constant r is a spherical shell as shown in Fig.18 CHAPTER 2. y. MOLECULAR CONFORMATIONS z dV = dx dy dz 1.8 0. occurs at rmax = 1 =l β √ 2n = 0.11 schematically plots the endtoend distance distribution function.
11: A typical plot of W (r)dr.7 0.2 0.0 rmax = 0. FREELYJOINTED CHAIN 19 z r + dr y x Figure 2.4.82 l √n <r> = 0. ← ← Shell of width dr ← r .92 l √n √ <r2> = l √n Figure 2.3 0. average r or r .0 0. 0. and rootmeansquared r are indicated on the ﬁgure.5 3.0 1. The key values rmax .2.5 W(r) dr 0.6 0.0 0.4 0.5 1.10: Cross section of a spherical shell between radii of r and r + dr.0 length (units of l √n) 2.5 2.1 0.
or at least a nontrivial. This expected result will only occur if the endtoend distance is linear in bond length.30) In other words the root mean squared endtoend distance is proportional to the square root of the number of bonds and linear in the bond length. The variance in the endtoend distance can be found from the mean and meansquared endtoend distances: σ2 = r2 − r 2 = 4 0. . First we assumed that the chain can be simulated by a random walk. 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. It is merely a scaling parameter. The dependence of rootmeansquared endtoend distance on the square root of the number of bonds is a profound. 2.28) From this results. result. The square root of n dependence comes from the expression for the standard deviation of √ the walk which contains n. they always rank in the order rmax < r < r2 .20 CHAPTER 2. It can also be thought of as a consequence of units. Thus if we double all bond lengths we double the endtoend distance. MOLECULAR CONFORMATIONS The above key values are indicated in Fig.4.4. The rootmeansquared endtoend distance is √ r2 = l n (2.2 Comment on FreelyJointed Chain We only used two facts in deriving W (r). If we solve the problem in inches and then in millimeters.15nl2 2 2β β π β (2. we assumed there are enough steps to make the random walk a Gaussian distribution.or twodimensional random walks we would ﬁnd the same result. If we repeated the analysis for one. The linear dependence on bond length is a trivial result. the coeﬃcient of variation (standard deviation divided by the mean) is CV = σ = 42% r (2. 2. Only polymer features that alter the random walk nature of the chain can alter the square root dependence on n. The ﬁnal result predicts that the rootmeansquared endtoend √ r2 = l n (2.29) This result can be characterized as a fairly large coeﬃcient of variation.11. Second. Let’s consider the origins of the square root dependence on bond length.31) in any dimension. we should get answers that diﬀer only by the units conversion factor for inches to millimeters of 25. Our analysis is one of a completely random three dimensional random walk. For constant l and n. To ﬁnd the Gaussian curve we therefore only had to ﬁnd the mean (mean = 0) and the standard deviation (σ = distance is 2 n lz ).23 3 − 2 = 2 = 0.
the next step must also be to the left because a step to the right would revisit the starting location. A onedimensional random walk must begin with one step to the left or to the right.4.0. In two. is not a completely random walk because some steps may be inﬂuenced by previous steps. selfavoiding random walk is r2 = nl (2. 2. Without proof. All steps (except the ﬁrst one) are determined by the requirement of being self avoiding and not by random chance.and threedimensional random walks will be proportional to n to some power between 0. selfavoiding random walks will not restricted as much. selfavoiding random walks.32) In contrast to the completely random walk.and threedimensional. selfavoiding random walks. random walk is hardly random. however. the chain that starts to the left must make all steps to the left. Averaging over all possible chain conformations. we state that the endtoend distance for two.. A onedimensional. this result is now linear in n. are trivial to analyze.. Because of scaling requirements it remains linear in l. Some steps will be inﬂuenced by selfavoiding requirements. To anticipate a future result that does alter the random walk nature of polymers. the eﬀect of imposing self avoiding characteristics will be less dramatic. a selfavoiding random walk is a better model for a polymer chain than the completely random walk discussed previously. we consider selfavoiding random walks.2. selfavoiding. The two extremes are completely random walks (power equal to 0.12 there are only two possible onedimensional. but most will have other options than can be reached by random chance. selfavoiding random walks. Onedimensional. Because no two atoms in a polymer chain can occupy the same space. One makes all n steps to the left and its length is nl. If the ﬁrst step is to the left. some steps may be biased away from moving in a given direction because doing so would revisit a previous part of the random walk. There are thus only two possible chains.12: The only two possible onedimensional. As shown in Fig. The other possible chain is the one that starts with its ﬁrst step to the right.5 and 1. In other words. This chain can only continue with repeated steps to the right. Continuing on. A selfavoiding random walk. In selfavoiding random walks.and threedimensional selfavoiding random walks is not possible. the path cannot revisit any spot that was previously visited. Walk to the left Figure 2.5) and selfavoiding random . the rootmeansquared endtoend distance for a onedimensional. The exact analysis of two... . FREELYJOINTED CHAIN 21 Walk to the right . however. The other makes all n steps to the right and its length is also nl.and threedimensional random walks. Two.
From above. Therefore the ﬁrst correction term in W (r)dr is less than 1% for √ 0 < r < 1. In . W (r)dr will then be good for a chain that is up to f times larger than the rootmeansquared endtoend distance (i.15 0. some researchers have constructed more detailed analyses that account for deviations from Gaussian behavior at large r. We can relate the range of small correction terms to the standard deviation in root mean √ √ squared endtoend distance.0).83l n = 18.34) For example consider a chain of n = 100 bonds (a fairly short polymer chain). In each of these cases n+ − n−  = n and the requirement that n+ − n−  be much less than n is violated. W (r)dr is accurate as long as this inequality is true.83. the standard deviation in endtoend distance √ is 0. the chain becomes less Gaussian and W (r)dr becomes increasing inaccurate. 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.50 standard deviations above the mean.15l n standard deviations above the mean.22 CHAPTER 2. W (r)dr. MOLECULAR CONFORMATIONS walks in which every step is determined by the selfavoiding requirement (power of 1. For large chains with random n+ and n− jumps.e. the later extreme is the onedimensional.01 10n or f= n 30 (2. 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. dr (2. Therefore the upper limit in r for small corrections is √ √ n −1 fl n − l n √ = 30 (2. is supposed to work for all values of r which includes r near rmax = nl. The upper limit in r for small corrections is f l n where l n is the root mean squared endtoend distance.3l < r < nl = rmax = 100l the ﬁrst correction term is greater than 1%.. selfavoiding random walk result.. we require n+ − n−  n. In other words. as r gets large. How big do the chains have to be to be large enough? The Gaussian distribution was applied to the factor (n+ − n− ). For the above example with n = 100 bonds. To assess the accuracy of W (r)dr. The former extreme is the random walk result from above. When 18. Only the ﬁrst and largest correction term is given. 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+ = 0.3l. One published result is W (r)dr = (Const)4πr exp −β r 2 2 2 2 3 1+ 10 r rmax + .01 (or less than 1%). good for r ≤ f as long as 3 10 f r2 rmax 2 r2 ) = 3f 2 < 0.33) The ﬁrst term within the square brackets is 1 which is the previous result for a Gaussian distribution.15l n. this equation shows the W (r)dr is accurate as long as r is less than 5. however.35) 0. Solving this equation for f results in f = 1. 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..
We conclude that the correction factors are insigniﬁcant for most real polymer chains.2. C is normally greater . As the distance between any two bonds increases. EQUIVALENT FREELY JOINTED CHAIN 23 Figure 2. The thick lines are the superposed equivalent freelyjointed chain of n = n/m bonds.5.50 standard deviations above the mean. The major restrictions are caused by nearby bonds. the correction factor is insigniﬁcant.37) √ √ n = l Cn (2. We call the new chain of n bonds of average length l the equivalent freelyjointed chain for the original n bond chain.36) By using the equivalent freelyjointed chain. In other words. An example equivalent freelyjointed chain is shown in Fig. Let the average length of each new bond be l which will be proportional to l (or l = kl). The proportionality constant is C. the correlation decreases with the conformations of distant bonds eventually becoming uncorrelated. a normal distribution very few chains will be more than 5. Say that it takes m bonds for the correlation to drop to zero and then construct from an n bond chain an n bond chain with n = n/m.13: The thin lines are a real polymer chain of n bonds.13. Because the bond conformations are uncorrelated over long distances.5 Equivalent Freely Jointed Chain Real polymers are not freely jointed. the bond directions θ and φ are not free but are restricted by local environment to be biased towards speciﬁc values. Thus even for a relatively short 100 bond chain. the conformation of any bond is correlated with the conformations of nearby bonds. 2. the random walk steps in this new chain are freelyjointed. 2. we have shown that the endtoend distance of a √ √ realistic chain is proportional to l n. Using the freelyjointed chain result the rootmeansquared endtoend distance is r2 = l where k C=√ m (2.
for the moment.2 nl2 (2. excluded volume eﬀects). The thing that distinguishes one polymer from another is the characteristic ratio C. The square of the expansion factor. selfavoiding requirements or excluded volume eﬀects. or C. It tells how much the real chain is expanded relative to a freely jointed chain. Cn increases in proportion to n0. Our discussion on the equivalent freelyjointed chain shows that any real polymer can be reduced √ to any expression for endtoend distance that is proportional to l n (provided we ignore. We associate with each bond a vector. It is deﬁned by C= r2 nl2 (2. In real polymers.6 (2. 2.39) This result agrees with the previous discussion of selfavoiding random walks which claimed that the powerlaw dependence on n for a real chain is between 0. A scaling law derived by deGennes states that for large n. The value of Cn at large n for such polymers characterizes the random coil nature of that polymer.24 than one and therefore √ CHAPTER 2. to be described latter.41) .6 Vector Analysis of Polymer Conformations We will ﬁnd it useful to develop an alternate approach to the analysis of endtoend distance in polymers.0 (for a chain with all steps controlled by selfavoiding requirements).38) In the freelyjointed chain. We thus embark on a series of models whose main purpose is to use theoretical arguments for calculating the characteristic ratio. In relatively ideal polymers Cn approaches a limiting constant value for large n.5 (for a completely random chain) and 1.40) r2 ∝ n0.2 . is known as the characteristic ratio. Low values of Cn correspond to tightly coiled polymers and high values of Cn correspond to polymers that are loosely coiled or extended. cause Cn to increase without bound as n increases without bound. MOLECULAR CONFORMATIONS C is sometimes called the expansion factor and sometimes denoted as α. Thus we have Cn = or r2 ∝ ln0. The new analysis will be based on vectors and analytical geometry. C = 1. Let the vectors u1 to un be the vectors along the n bonds. It is customary to write the bonddependent characteristic ratio as Cn . In real polymers the characteristic ratio is a function of n or the number of bonds and is usually greater than 1. Then a vector from one end of the chain to the other is simple the sum of these vectors: n r= i=1 ui (2.
s. i. The factor of 2 in front of the sum includes.e.44) where θij is the angle between the vectors along bond j and along bond i. VECTOR ANALYSIS OF POLYMER CONFORMATIONS The mean squared endtoend distance is n n 25 r 2 = r·r = i=1 ui · j=1 uj (2.46) 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 dot product of a vector with itself is simply the square of the length of the vector. we can write an expression for s2 in which ri is the location of the ith atom along the polymer chain and z is the location of the center of mass: s2 = Expanding this sum results in ns2 = i 2 ri + nz 2 − 2z · i 1 n (ri − z) · (ri − z) i (2. For the freelyjointed chain. however gave a full distribution function (a Gaussian distribution) while this one only gives the rootmeansquared endtoend distance.2. yields The previous analysis. results in n r2 = i=1 ui · ui + 2 i<j ui · u j (2.6. the bond next to bond i) then θij is the supplement of the bond angle between bonds i and i + 1. For more complicated models. we will need to evaluate the term cos θij .43) where the sum over i < j means all combinations of i and j such that i is less than j.47) Substituting this expression in to the above results gives ns2 = i 2 ri − nz 2 = i 2 ri − n(z · z) = i 2 ri − 1 n ri · rj i j (2. the bond directions are uncorrelated and cos θij is zero which √ r2 = l n as before. Thus we can write r2 = nl2 + 2l2 i<j cos θij (2.48) . In vector notation.. by symmetry.45) ri (2. This result was obtained with less work than the previous analysis. the terms when i is greater than j. The deﬁnition of the center of mass is z= 1 n ri i or i ri = nz (2. We can use a vector analysis to investigate the relation between endtoend distance and radius of gyration .42) Expanding this expression for a polymer chain with a constant bond length. If vector j is equal to i + 1 (i.
2.26 CHAPTER 2. By the cosine law the length of the vector rij connecting the ends of vectors ri and rj is 2 2 2 2 2 rij = ri + rj − 2ri rj cos θ = ri + rj − 2ri · rj (2. MOLECULAR CONFORMATIONS ri rj rij rij2 = ri2 + rj2 . To evaluate the vector dot product ri · rj .51) In this step we made use of symmetry (rij = rji ) and the fact that rii = 0. we can write this distance as 2 rij = C(j − i)l2 (2.50) The expression for the radius of gyration then simpliﬁes to: s2 = 1 2n2 2 rij = j i 1 n2 2 rij j i<j (2. By the discussion in the section on the equivalent freelyjointed chain. The vector rij connects the two ends of vectors ri and rj .54) We conclude that whenever r2 = Cnl2 for a polymer. This result holds for large molecules . consider the triangle in Fig.53) For large polymer chains (large n) this result simpliﬁes to s2 = Cnl2 = 6 r2 6 (2. the distance rij is the endtoend distance for a subpolymer chain of j − i bonds. Because the vectors ri are the coordinates of the atoms in the polymer chain.14: A triangle framed by vectors ri and rj .2 ri rj cos θ Figure 2. Ignoring the j − i dependence of C.49) Solving for ri · rj gives 2 2 2 ri + rj − rij ri · rj = 2 (2.52) 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). inserting this result.14. and reordering the summation over i yields: s2 = Cl2 n2 n j−1 i= j=1 i=1 Cl2 n2 n j=1 Cl2 j(j − 1) ≈ 2 2 2n n j2 = j=1 Cl2 n(n + 1)(2n + 1) 2n2 6 (2. that the radius of gyration is directly proportional to (and smaller than) the endtoend distance.
. The approximations used to relate radius of gyration to endtoend distance can be understood using a matrix representation. the inaccuracies in the terms close to the diagonal will have only a negligible eﬀect on the sum of all terms. Thus there is free rotation about each bond and hence we call this model the “freelyrotating chain” model. 2. For large matrices. Any analysis or experiments that give us information about the radius of gyration also give us information about the endtoend distance. .. the chain must be slightly larger than is required for r2 to be equal to Cnl2 . In order for the derived relation. It takes much more energy to distort bond angles than it does to induce rotations about single bonds. . . . The relation will be inaccurate for short chains or for chains that are not random walk coils (e...... The more easily moved dihedral or rotational angles are considered to all be equally likely.. in polyethylene the bonds angles are all close to 112◦ . − 0 Cl 2Cl 2 − − 0 Cl ..g. we can show (See Flory book) that cos θij = cosm θ where m = j − i where θ = π − θ is the supplement of the ﬁxed bond angle.. (2.7 FreelyRotating Chain Commonly the bond angles in polymers are ﬁxed or narrowly ﬁxed to constant values. . By taking successive projections of one bond onto another. are constant and equal to one value θ.. there will be many more terms far from the diagonal then close to the diagonal. The reverse is also true. FREELYROTATING CHAIN 27 when Cn is independent of n. To analyze the freelyrotating chain we use the vector approach outlined in the previous section..55) The terms near the diagonal are random walk. Using the equivalent freelyjointed chain approximation. extended chain polymers). If the matrix is large.56) to be accurate. . terms above the diagonal of the following matrix: Cl2 2Cl2 3Cl2 4Cl2 . .. For example.2. . rewritten here as r2 =6 s2 (2. The conformation of a given chain is reduced to specifying the dihedral angles for n − 1 bonds (all bonds except the ﬁrst bond)... . 0 Cl2 2Cl2 3Cl2 . We therefore consider a random walk where all bond angles. 2 2 . however.. Thus the relation between s2 and r2 derived above will be accurate. the radius of gyration squared is the sum of all 0 − − − − ..7. longchain approximations for short chains and may be inaccurate.. − − − 0 .. θi .. An important corollary to this result is that everything we learn while studying the endtoend distance also applies to the radius of gyration.
.59) r 2 = nl + 2l 2 2 i=1 (n − i) cosi θ (2. cos2 θ . .60) We rewrite this summation in simpler terms by letting x = cosθ : r2 = nl2 + 2l2 (nS1 − xS2 ) where n−1 n−1 (2. MOLECULAR CONFORMATIONS i<j r 2 = nl + 2l 2 2 cosj−i θ (2. . we use a trick by noticing that d S2 = dx For large n we thus have d S2 ≈ x 1−x n−1 xi = i=1 dS1 dx (2.65) . = x 1−x (2.58) The n diagonal terms sum to n which give the ﬁrst term (nl2 ) in the r2 expression. Writing out the required terms for the summation term by inspection of this matrix gives r2 = nl2 + 2l2 (n − 1) cos θ + (n − 2) cos2 θ + .. . . . . . 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. .64) dx = 1 (1 − x)2 (2.63) For S2 . + (n − (n − 1)) cosn−1 θ which can be written as n−1 (2. . . . cos θ cosn−1 θ cosn−2 θ .. For polymer problems..62) The terms S1 and S2 can be evaluated in closed form for all values of n.. .57) 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 cosj−i θ : 1 cos θ cos2 θ cos θ 1 cos θ l2 × .. . . .61) S1 = i=1 x i and S2 = i=1 ixi−1 (2. . cos3 θ cos2 θ . The inﬁnite geometric series S1 has the well known result ∞ S1 ≈ i=1 xi = x 1 + x + x2 + x3 + . .28 The resulting vector analysis becomes CHAPTER 2. 1 (2. cosn−1 θ cosn−2 θ .. . .
This slight increase in bond angle increases the characteristic ratio by 10% to Cn = 2. the second term in the brackets quickly becomes negligible and we have r2 = nl2 + 2nl2 x 1+x = nl2 1−x 1−x (2. Real polyethylene is not totally symmetric and thus the C C C bonds deviate slightly from 109. The rotations about the central C . 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 109.67) Finally we substitute for x and note that cos θ = − cos θ (where θ is the bond angle and θ = π − θ is the supplement of the bond angle). It is possible to evaluate S1 and S2 for any value of n and get an exact result.47◦ ).20. HINDERED ROTATING CHAIN Substituting S1 and S2 into the expression for r2 gives r2 = nl2 + 2l2 nx x − 1 − x (1 − x)2 29 (2. freelyrotation chains is √ r2 = l n The characteristic ratio is Cn = 1 − cos θ 1 + cos θ (2. This independence is a consequence of our assumption of large n.70) Note that the characteristic ratio is independent of n. 2. For an example we consider polyethylene.15.8. All carbon bonds are in approximately tetrahedral geometries.47◦ to 112◦ .68) The rootmeansquared endtoend distance for large. The C C H and H C H bonds shrink slightly to compensate.8 Hindered Rotating Chain C bond in C bond The dihedral angle is clearly not free to assume all possible values. Consider the potential energy for rotation about the central C butane (CH3 CH2 CH2 CH3 ) shown in Fig.71) and the characteristic ratio is Cn = 2.2.66) For large n. 2. Instead the angle is restricted by steric interactions. We get r2 = nl2 1 − cos θ 1 + cos θ (2. The exact result gives a Cn that depends on n but rapidly converges to the above result for large n.69) r2 1 − cos θ = 2 nl 1 + cos θ (2. For a freelyrotating polyethylene chain √ r2 = l 2n (2.
A preferred analogy would be higher molecular weight alkanes. MOLECULAR CONFORMATIONS C H H 4 3 C H Energy φ H 2 1 C 0 0 60 120 180 240 Rotational Angle 300 360 Figure 2. but with more eﬀort and less accuracy than available for butane. Those experiments and their analysis have been done. As rotations occur the groups appended to each of the central C atoms come into closer proximity and the steric energy increases.15: Left side is an end view of the central C–C bond in butane. For butane. When rotations are hindered by potential energy functions such as those shown in Fig. most bonds will be at or near the trans state (φ = 180◦ ) or at or near the local gauche minima (φ = ±60◦ ). 2. The trans state illustrated on the left side of Fig.15 is the lowest energy state. which are larger than the H atoms. 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.states. it is clear that the rotations will not be free. Finally there is a local maximum at φ = 0◦ .15. 2. It is lowest because the two CH3 groups. There are local maxima at φ = ±120◦ .30 CHAPTER 2. are as far apart as possible. will not be equal. All rotational angles are perhaps possible. These local minima are called the gauche+ and gauche. Endtoend distance for a hinderedrotation chain is more diﬃcult to ﬁnd than the freely . Thermal energy will allow the angles to deviate from these states and to overcome the barriers to transitions from one state to another. which occurs when the two CH3 groups on either end of the butane chain are aligned and as close together as possible. These minima occur when all the groups are staggered (as in the left of Fig. 2.15) but the CH3 groups are adjacent to each other rather than opposite each other as in the trans state. We thus replace the freelyrotating chain with a more realistic hinderedrotating chain model. There are local minima when φ = ±60◦ . in butane are a reasonable model for the C C rotations in polyethylene. but the dihedral angles will have a preference for the low energy states. however. The populations of all rotational angles. These maxima occur when the CH3 groups are aligned with H atoms on the other carbon atom.
5) + 0. gives √ r2 (freely rotating) = 108 2. . 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). the freelyjointed chain model. Then the average dihedral angle gives cos φ = −0. The characteristic ratio is Cn = r2 1 − cos θ 1 − cos φ = nl2 1 + cos θ 1 + cos φ (2. We omit the details and give the results.20˚ = 160˚ A A (2. n = 5000 bonds. while accounting for unequal populations of the possible rotational angles. and A θ = 112◦ . The next most realistic model.72) where cos φ is the average value of the rotational angle.2 × (0.2. but are not included in the hindered rotation chain model — short range interactions and long range interactions. 2.5) = −0.13. The hindered rotating chain gives a result that is close to the correct results. The ﬁnal equation is found using the vector analysis and averaging the dot products ui · uj . or preferable all. In the next section we consider improvements on the hindered rotating chain model. The next step in our analysis is to include some. For a detailed example. MORE REALISTIC ANALYSIS 31 rotating chain model. let’s consider polyethylene with l = 1.76) and the characteristic ratio is Cn = 5. of these eﬀects.53˚.20.9 More Realistic Analysis We can list two general factors that inﬂuence the endtoend distance. For example.77) (2. gives r2 (freely jointed) = 108˚ A (2. We can compare this result to the experimental result for polyethylene which is 6 to 7 (depending on temperature).75) and a characteristic ration of 2. but is still too low. the freelyrotating chain model.33˚ = 245˚ A A (2. For the hinderedrotation chain model we need to know cos φ .20 2. We thus need some new information.2 × (0. The result is √ r2 = l n 1 − cos θ 1 + cos θ 1 − cos φ 1 + cos φ (2.6 + 0.74) and a characteristic ratio of 1.9. The simplest model.73) Note that if this hinderedrotation chain becomes freelyrotating chain then cos φ = 0 and the results reduce to the freelyrotating chain results.4 The endtoend distance for the hinderedrotation chain is √ √ r2 (hindered rotation) = 108 2.
The polymer wants to avoid the solvent and thus will contract on itself to avoid polymersolvent interactions.5): r 2 ∝ np l 2 According to deGennes. We need to account for the eﬀect of neighboring bonds. To be more speciﬁc. In eﬀect the polymer will prefer interactions with the solvent over interactions with itself and therefore will expand to maximize polymersolvent interactions. The ﬁrst important perturbation to random walks is that while random walks can cross their own path. When we include short range interactions we cannot take a simple average of cos φ as in the hindered rotation model. Deﬁned this way. Some probability analysts call such models Markov chains instead of random walks.32 CHAPTER 2. MOLECULAR CONFORMATIONS We consider shortrange interactions as interactions with neighboring bonds that aﬀect the relative probabilities of the dihedral angle. longrange interactions are interactions between atoms or molecular units that are not covalently bonded to each other. A poor solvent will cause the unperturbed endtoend distance to contract. a polymer conformation cannot — random walks used to simulate polymer chains should be selfavoiding random walks. We discuss three types of longrange interactions. long range interactions include interactions between two parts of the polymer that are separated by many bonds or between the polymer and solvent molecules.2 nl2 (2. a poor solvent will . When excluded volume eﬀects are signiﬁcant. A good solvent will cause it to increase. This new feature is called the eﬀect of excluded volume. Besides increasing the endtoend distance. we can assume that r2 is proportional to some power of n such as p (where p > 0. If included in the analysis.2 and therefore the characteristic ratio increases as n0.79) (2.78) A second longrange interaction is interactions between the polymer and the solvent. p = 1. excluded volume will cause the rootmeansquared endtoend distance to √ no longer be proportional to n. A solvent can cause the unperturbed endtoend distance to increase or decrease. we will have a good model for polymer conformations that are unperturbed by the longrange interactions described below. After we develop a model that does a good job of accounting for shortrange interactions. We will call the polymers generated by this modiﬁed random walk or Markov chain process “unperturbed polymer conformations. 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. excluded volume will perturb the endtoend distance and cause it to increase. Each step of the random walk then requires an adjustment of the jumpdirection probabilities according to the conformation of the previous bond.2 : Cn = r2 ∝ n0.” The endtoend distance of these chains will be called the unperturbed endtoend distance and will be denoted with a subscript zero — r2 0 . Longrange interactions are all interactions that are not shortrange interactions. In the extreme case. The elements of the chain exclude other elements from their occupied volume.
for which the true endtoend distance is equal to the unperturbed endtoend distance. there is a speciﬁc temperature. In general the polymersolvent interactions for a given polymer0 which can be . 2. The concept of Θ temperature can be understood by considering the eﬀect of temperature on polymersolvent interactions. This extreme example of a poor solvent is better characterized as a nonsolvent. Rotations about single bonds are inﬂuenced by the presence of thermal energy and thus higher temperature will make it more likely to ﬁnd conformations in higherenergy rotational angles. Temperature can aﬀect all types of interactions. If we compare our theoretical analysis to experimental results we will normally ﬁnd disagreement. It can aﬀect shortrange interactions by inﬂuencing the relative probabilities of the various dihedral angles. called the Θ temperature. Two examples are hydrogen bonding and ionic interactions. After solving this problem we will consider what inﬂuence the longrange interactions (including excluded volume eﬀects) have on the results. After considering both shortrange and longrange interactions we are led to split the problem of theoretical polymer characterization into two parts. Temperature aﬀects longrange interactions mainly through polymersolvent interactions. Thus experiments at the Θ temperature can be used to measure r2 compared to experimental predictions.10. For any given polymersolvent pair. Thus real polymers have a meansquared endtoend distance of r2 and not r2 0 . As discussed in the previous section. regardless of whether the analysis to ﬁnd r2 0 was correct or not. In general increasing the temperature improves solvent quality and lowering it decreases solvent quality.10 Theta (Θ) Temperature We also need to consider temperature eﬀects. Let’s deﬁne α to be the factor by which the linear dimension expands (α > 1) or contracts (α < 1) due to longrange interactions: r2 = α r2 0 (2. The last types of longrange interactions are speciﬁc interactions. The ﬁrst part is the study of the unperturbed endtoend distance.2.80) The solution to the longrange interaction problem is to ﬁnd α. we will ﬁrst attempt to solve the shortrange interaction problem. Fortunately there is an experimental solution to this problem called the theta (Θ) temperature. The ﬁrst problem we encounter is how do we know when we have the right answer? Real polymers have longrange interactions and shortrange interactions. We plan to modify the hindered rotation chain model to correctly account for shortrange interactions and thereby calculate the correct unperturbed endtoend distance. THETA (Θ) TEMPERATURE 33 cause the polymer to completely contract and precipitate out of solution. By speciﬁc interactions we mean identiﬁable interactions between remote parts of the chains.
and dihedral angels. we assume that the polymer is restricted to certain types of conformations or to certain isomeric states. but instead are assumed to be restricted to a small number of discrete values. θi . At the Θ temperature. the eﬀect of excluded volume). 0 and experiments at the Θ temperature can Besides measuring r2 0 .11 Rotational Isomeric State Model The rotational isomeric state model will be our solution to the problem of accounting for shortrange interactions and some long range interactions (e. 2. some physical properties (e. In the rotational isomeric state model. We will illustrate with polyethylene. At the Θ temperature r2 = r2 be used to measure r2 0. Despite the advantages of the Θ temperature. As the polymersolvent interaction increases the solvent becomes a better solvent. That temperature is called the theta (Θ) temperature. any polymer conformation is deﬁned by a set of bond lengths.g. thermal ﬂuctuations about the minima in . In the rotational isomeric state model. Bond lengths are likely to vary only ±3% and thus as before we consider them to be ﬁxed at l.g. The possible discrete dihedral angles deﬁne the set of rotational isomeric states for each bond. bond angles. It is often better to work in a good solvent and correct the results to the unperturbed results. The trans state (φ = +180◦ ). this correction involves correcting ideal laws for large molecules or longrange interactions. you need a solvent that is suﬃciently poor. the ideal gas laws are obeyed to very high pressures. The dihedral angles are not allowed to assume any possible angle. The temperature can be varied until the measurements obey ideal laws.. These ideas will be extended to other polymers latter. In reality. we note that working in theta solvents is often impractical. Due to symmetry of polyethylene there are three possible rotational isomeric states (see Fig. For a given polymersolvent pair. At the Boyle point. Note that conformity to ideal laws is one way of determining the Θ temperature. osmotic pressure) obey ideal laws up to high concentrations.34 CHAPTER 2. li .. There is an analogy between the Θ temperature and the Boyle point of a gas. In general. there will be some temperature for which α = 1. the gauche+ state (φ = +60◦ ) and the gauche. Likewise.16). The solvent may become so poor the precipitation becomes imminent. That temperature is the Θ temperature. bond angles are likely to vary only ±5 degrees and we consider them to be ﬁxed at θ. each bond of polyethylene is assumed to be in one of these three states. For measurements of physical properties. MOLECULAR CONFORMATIONS solvent pair is an increasing function of temperature. Thus increasing temperature leads to a better solvent and to a higher α. Thus simple theories for analysis of a physical property that do not account for longrange interactions will still work well at the Θ temperature. the Θ temperature has other useful properties. φi . To get α down to one. decreasing temperature leads to a poorer solvent and a lower α.state (φ = −60◦ ). The Boyle point is the temperature where the repulsion between gas molecules due to excluded volume is exactly compensated by their mutual attraction. 2. No other values of φ are allowed.
This important nearestneighbor interaction is ignored in the hindered rotation chain model. In our random walk analysis of the rotational isomeric state. By analogy with the previous probability factor P (φi φi−1 ) = e−E(φi−1 φi )/RT Z(φi−1 ) (2. we must consider all bond pairs and all possible conditional probabilities of the form P (φi φi−1 ).16: The three rotational isomeric states in polyethylene.82) 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. ROTATIONAL ISOMERIC STATE MODEL 35 C C C H H H H H H C H H C C C H H C H H C Gauche + Trans Gauche  Figure 2.2. 2.81) where Z is a normalizing factor or the sum of the Boltzman energy factors for all possible angles: 3 Z= i=1 e−E(φi )/RT (2. which gives the conditional probability that bond i has angle φi given that the previous bond or bond i − 1 has angle φi−1 . potential energy will lead to a distribution in φ’s around these three local minima. Its inclusion in the rotational isomeric state model is the major advance in realism in this new model. the probability of any bond existing in one of the rotational state i characterized by angle φi . The rotational isomeric state model asserts that we can realistically simulate a polymer chain by ignoring variations in φ around the local minima. The simplest model is to assume that the energy. is given by a Boltzman factor: P (φi ) = e−E(φi )/RT Z (2. To account for nearest neighbor interactions. φ. The dihedral angle.16 (Note: this equation can easily be generalized to more than three rotational isomeric states) Because of shortrange interactions discussed above. this probability factor is expected to be aﬀected by neighboring bonds. E(φi ).83) .11. is deﬁned as the angle between to white circles. is aﬀected by the bond conformation of the previous bond.
89) . For polyethylene (or for any threestate polymer) we write can write a weighting factor matrix as (2. We let that excess energy be Eg or the extra energy associated with a gauche bond. This interaction is known as the pentane eﬀect and causes the energy of g + g − or g − g + conformations to be much higher than that g + g + or g − g − conformations.84) In these equations. the excess energy associated with the two possible gauche bonds will be the same. The tg + and tg − bond pairs will each be higher in energy than the tt bond pair. Let’s begin with the ﬁrst row and arbitrarily assign the tt state to the ground state.88) This simple analysis ignores an important shortrange interaction that occurs when two consecutive bonds are g + g − or g − g + .. Deﬁning ω = e−Ep /RT (2.85) P (tt) P (g + t) P (g − t) U = P (tg + ) P (g + g + ) P (g − g + ) P (tg − ) P (g + g − ) P (g − g − ) For example. We further deﬁne σ = e−Eg /RT and we can quickly derive Z(t) = 1 + 2σ and P (tt) = 1 1 + 2σ P (g + t) = σ 1 + 2σ P (g − t) = σ 1 + 2σ (2. E(φi−1 φi ) is the energy associated with two consecutive bonds with dihedral angles φi−1 and φi . gauche+ (g + ). 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 Z= j=1 e−E(φi−1 φj )/RT (2. and gauche. E(tg + ). Thus we assume E(tt) = 0. the matrix element P (tg + ) gives the probability that the next bond is trans given that the previous bond was gauche+. The probabilities would become P (tg + ) = σ σ + 2σ 2 P (g + g + ) = σ2 σ + 2σ 2 P (g − g + ) = σ2 σ + 2σ 2 (2.87) (2. The conditional probabilities we are concerned with can conveniently be tabulated in a matrix called the weighting factor matrix. Figure 2. Two parts of the polymer chain separated by four bonds are in close proximity which causes a large steric interaction. In this section we are restricting ourselves to three rotational states of trans (t). The energy factors we care about are E(tt).17 illustrates a g + g − conformation. etc.36 CHAPTER 2. If we let Ep be the energy of the pentane eﬀect interaction then E(g − g + ) = 2Eg + Ep whereas E(g + g + ) = 2Eg .86) Z(t) appears in the denominator of each probability as a normalizing factor. For the second row. E(tg − ). we might just consider the energy associated with all the gauche bonds and assume E(g + t) = Eg and E(g + g + ) = E(g + g − ) = 2Eg . In polyethylene.(g − ).
By convention we normalize each row to the ﬁrst element in that row.17: The steric interactions caused by the pentane eﬀect when two consecutive bonds are g + g − or g − g + .43 and ω = e−8400J/RT = 0. At 300◦ C these lead to weighting factors of σ = e−2100J/RT = 0.90) (2.95) Thus gauche bonds are only about 46% as likely as trans bonds (2σ/(1 + 2σ)) and g + g − conformations are only about 2. The best results give Eg = 2100 J and Ep = 8400 J.94) By theory and experiment. the energy terms for polyethylene are well known. ROTATIONAL ISOMERIC STATE MODEL 37 Gauche  C Gauche + Strong Steric Interactions C C C C Figure 2. we write the weighting matrix of relative probabilities as 1 σ σ 1 σ σω U = 1 σω σ (2. .081 (2. For a simple polymer like polyethylene.91) (2.92) Analyzing the third row similarly to the second row and collecting all probabilities in the matrix we arrive at U = 1 1+2σ 1 1+σ+σω 1 1+σ+σω σ 1+2σ σ 1+σ+σω σ 1+σ+σω σ 1+2σ σω 1+σ+σω σω 1+σ+σω (2.11.4% as likely (σω/(1 + σ + σω)).2. we derive the conditional probabilities for the second row of U to be P (tg + ) = P (g + g + ) = P (g − g + ) = σ 1 = 2ω σ+ +σ 1 + σ + σω σ2 σ = 2 + σ2ω σ+σ 1 + σ + σω σ2ω σω = 2 + σ2ω σ+σ 1 + σ + σω σ2 (2.93) It usually suﬃces to work with relative probabilities rather than absolute probabilities.
For each chain we can calculate a property of interest (e. let v = (1. even on the fastest supercomputer. but it could easily be generalized to handle any number of states. 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. but soon becomes impractical for large n’s typical of real polymers. The ﬁrst bond can be ignored because it only serves to locate the start of the polymer in space.. endtoend distance. We generate a large number of chains using a random walk or Markov chain process. These computer experimental results can be compared to real experimental results. The second bond direction is determined by the rotational state of bond 1.g. in eﬀect. There are two possible solutions to the rotational isomeric state model. Programs like LatticeTM are.).0) or the first bond is t for bond=2 to number of bonds1 . One possible approach is to enumerate all possible conformations and calculate properties using the exact process discussed earlier in this chapter. the total number of polymer conformations is ﬁnite. MOLECULAR CONFORMATIONS We next consider how to use the rotational isomeric state model to predict polymer properties. For large polymers. Because each bond has a small number of discrete states.. radius of gyration. The following pseudo computer code is the program logic. you have evidence that the rotational isomeric state is a valid model for polymers. Then you run the program and calculate the endtoend distance or the radius of gyration. Imagine a polymer chain of n bonds. or ﬂow chart. etc. The above Monte Carlo random walk process requires a computer. g + . We can ignore the ﬁrst two bonds and thus we need to set the states of the terminal n − 2 bonds. excluded volume.38 CHAPTER 2. temperature. When n is large the total number of conformations is too large to enumerate. of the main part of any program that does Monte Carlo solutions using the rotational isomeric state model. The remaining n − 2 bonds need to be determined. The average value of that property after generating suﬃciently many chains will be our Monte Carlo solution to the problem. 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 a polymer with n bonds of which each bond can be in one of three states. This exact solution can be done for small n. This ﬂow chart assumes a three rotational isomeric states. computer experiments. or g − .0. Furthermore the physical concepts of the rotational isomeric state model give you insight about the polymer molecules and the factors that control conformations. a preferred approach is to use the Monte Carlo method. the total number of polymer conformations is 3n−2 . etc. each bond can be t. You set polymer properties by selecting weighting factors. A polymer conformation of this chain is determined by setting the states of each bond. but this state only serves to locate the initial direction of the random walk. If the two results agree.
check for excluded volume effects if jump to occupied site. and gpick a random number between 0 and q1+q2+q3 if (random number is between 0 and q1) then next bond is t and v = (1.g. Number of rejected steps 9. endtoend distance. Relative entropy . r 4.0. You can calculate any property than can be reliably calculated for a given polymer conformation. or reject several previous bonds if all sites occupied start new chain end if next bond Now have set of n2 bond conformations which completely define the chain Calculate properties (e. The simplest and most reliable properties are size properties.1) end if if desired. radius of gyration. try another site.0) else if (random number is between q1 and q2) then next bond is g+ and v = (0. The program LatticeTM calculates the following properties: 1.0) else if(random number between q2 and q3) then next bond is g.11. ROTATIONAL ISOMERIC STATE MODEL let q=Uv be a vector giving the probabilities for t. etc. rms s 5.1.0. % trans 8. Last r (endtoend distance of current chain) 2. 6. r2 nl2 r2 s2 — the characteristic ratio (equal to Cn ) — how close is it to 6? 7.) Start over with another chain and continue until results converge 39 The key part of this loop is calculating the properties of each generated chain. rms r 3.and v = (0.2. g+. reject the entire chain.
It can plot each generated polymer in a threedimensional view. Copolymers 4. LatticeTM generates chains on a tetrahedral lattice.47◦ in a tetrahedral lattice) and cannot simulate polymers with diﬀerent bond lengths. Celcon. Some interesting polymers are: 1. etc. Polytetraﬂuoroethylene (PTFE) 3. Polypropylene (PP) — a vinyl polymer Some results from these types of polymers are discussed in the LatticeTM manual and will be covered in class. This requires all bonds angles to be the tetrahedral bond angle of 109. β √ π 3 4πr2 e−β 2 r2 dr (2. cannot give you information about the eﬀect of bond angle (e. We can simulate many polymers using the rotational isomeric state model. Lattice simulations. The advantage of lattice simulations is that they are fast.96) . however. it also requires all bonds lengths to be the same. As implied by its name. The use of a lattice makes it possible to do meaningful simulations in personal computers such as Macintoshes. They can do most of the work with integer arithmetic which is much faster in computers.97) 2nl2 Because the form of the radial distribution function even for nonfreelyjointed chains is similar β= to the freelyjointed chain result (except with a diﬀerent value for β) it is worth studying this function. The radial distribution function for the freelyjointed chain model was shown in class to be W (r)dr = where 3 (2. Problems 2–1. An oﬀlattice calculation on a Macintosh would be limited to much more rudimentary work and to much shorter chains. MOLECULAR CONFORMATIONS In addition to the above calculations. There is one important aspect of LatticeTM and many rotational isomeric state solutions that requires discussion. the 109.47◦ . LatticeTM can also plot many results. Polyoxymethylene (POM) (Delrin. 112◦ in real polyethylene vs. It can plot the distribution of endtoend distances and compare them to the radial Gaussian function calculated for in the freelyjointed chain analysis.g. Polyethylene (see above) 2. Because it is a regular lattice. This type of simulation is reasonably accurate for polyethylene and for many other carbonbackbone polymers..40 CHAPTER 2.) 5. These stick ﬁgures give a feel for typical polymer conformations.
c. Adding the eﬀects of excluded volume. How many bonds are in a 500. One end of A is connected to one end of B to form a two block. How do each of the following aﬀect the radius of gyration? a. Decreasing the polymersolvent interaction. Show that the maximum in W (r)dr occurs at r = b. d. a. and e. β π 3 2β 2 1 β 41 c. What is the standard deviation in r? e. What is the mean endtoend distance e.11. What is the maximum length of the chain? c. If segments of A are randomly interspersed with segments of B and the segments are still freely jointed. Pretend that linear polyethylene (PE or (CH2 CH2 )n ) can be modeled as a freelyjointed ˚ chain in which each bond is 1. what would be the rootmeansquared endtoend distance of the random copolymer? 2–4. Decreasing the molecular weight. 2–2.53A long. Show that the average value of r2 is r2 = d. What is the most likely end to end distance? d. Show that the mean value of r is r = 2 √ . What is the standard deviation in r? g. Reducing the hindrance to rotations about bonds.2. What is the rootmeansquared endtoend distance of this block copolymer? b. Plot the radial distribution function for this polymer chain and indicate on your plot the answers to c. block copolymer. Polymer A contains x freely jointed segments each of length la and polymer B contains y freely jointed segments each of length lb . Express the answers to a through d in terms of number of bonds (n) and bond length (l). . evaluate the following quantities: a.000 g/mole PE polymer chain? b. b. ROTATIONAL ISOMERIC STATE MODEL a. What is the root mean squared endtoend distance? f. Using the results from problem 21. 2–3. d.
how you would use the rotational isomeric state model to calculate the characteristic ratio of Nylon 66. in general terms. carbonylCH2 bonds. N –carbonyl bonds.42 CHAPTER 2. . Many polymers have more than one type of bond the diﬀerent types of bonds may have more the one value for bond length. MOLECULAR CONFORMATIONS 2–5. and CH2 –CH2 bonds. Explain. 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.
consider the property of tensile strength. Figure 3. They start at a low value and eventually saturate at a high value that is characteristic for inﬁnite or very large molecular weight. strength.Chapter 3 Polymer Molecular Weight 3. the molecular weight of a polymer is not one unique value. Some examples include the temperatures for transitions from liquids to waxes to rubbers to solids and mechanical properties such as stiﬀness. Many properties have similar molecular weight dependencies. and viscosity. a given polymer will have a distribution of molecular weights. The distribution will depend on the way the polymer is produced. If molecular weight is too low. For example. but rather of the distribution of molecular weight. the transition temperatures and the mechanical properties will generally be too low for the polymer material to have any useful commercial applications.1 Introduction Polymer molecular weight is important because it determines many physical properties. Polymer physical properties will be functions of the molecular weight distribution function as in S = S∞ − A F [P (M )] (3.1 shows a typical plot of strength as a function of molecular weight. Unlike small molecules. viscoelasticity. At high molecular weight.1) where A is a constant and M is the molecular weight. The strengthmolecular weight relation can be approximated by the inverse relation S = S∞ − A M (3. or of the average molecular weight. For polymers we should not speak of a molecular weight. the strength is too low for the polymer material to be useful. For a polymer to be useful it must have transition temperatures to waxes or liquids that are above room temperatures and it must have mechanical properties suﬃcient to bear design loads. however.2) 43 . P (M ). the strength increases eventually saturating to the inﬁnite molecular weight result of S∞ . Rather. toughness. At low molecular weight. M .
M . freezing point depression.3) M There are many ways. The property will thus be a function of the average molecular weight. For such properties. we consider typical distributions of molecular weights. and insensitive to other the details of the molecular weight distribution function: A (3. 3.1: A typical plot of tensile strength as a function of molecular weight. and osmotic pressure. We also consider the meanings of those averages.44 CHAPTER 3. where F [P (M )] is some function of the complete molecular weight distribution function. POLYMER MOLECULAR WEIGHT S∞ Strength S = S∞ – A M Molecular Weight Figure 3. For example. F [P (M )] my reduce to simply an average molecular weight. In this chapter we consider several ways of calculating molecular weights. The question therefore S = S∞ − 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. to calculate an average molecular weight. 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. For some properties.2 Number Average Molecular Weight Consider a property which is only sensitive to the number of molecules present — a property that is not inﬂuenced by the size of any particle in the mixture. The best example of such properties are the colligative properties of solutions such as boiling point elevation. Finally. however. the most relevant average molecular weight is the total .
The possible values of M are the various multiples of the monomer molecular weight — M0 . The possible values of M make up a set of numbers with discrete values labeled Mi . Rather.. it is called the number average molecular weight — MN . In polymer science. we will take M0 as the monomer molecular weight less any weight loss due to the polymerization reaction.7) In lab experiments it is more common to measure out certain weights of a polymer rather than certain numbers of moles of a polymer. For condensation reactions. NUMBER AVERAGE MOLECULAR WEIGHT 45 weight of polymer divided by the number of polymer molecules.8) Inserting ci for Ni Mi and expressing Ni in terms of ci results in MN = Dividing numerator and denominator by (3. Let Ni be the number of polymers with molecular weight Mi .6) Ni is physically the number fraction of polymers with molecular weight Mi . To get a formula for MN .2. By monomer molecular weight we mean the weight per monomer that appears in the polymer chain.4) and the total number of polymer molecules is ∞ Total Number = i=1 Ni (3. the number average molecular weight is MN = The term Ni / ∞ i=1 Ni Mi ∞ i=1 Ni = Total Weight Weight = Number of Polymers Polymer (3. only discrete values of M are allowed. This average molecular weight follows the conventional deﬁnition for the mean value of any statistical quantity.10) .5) As discussed above. mole fraction) the number average molecular weight is MN = i=1 X i Mi (3. Then the total weight of all polymers is ∞ Total Weight = i=1 N i Mi (3. we must ﬁrst realize that the molecular weight distribution is not a continuous function of M .3. where molecules of water are typically lost from the monomers during reaction. First we note that the concentration of polymer species i is (in weight per unit volume): ci = N i Mi V ∞ i=1 ci ∞ ci i=1 Mi (3. 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 .e.9) ci results in MN = 1 ∞ wi i=1 Mi (3. for example. If we ∞ denote number fraction as Xi (i.
14) Thus M0 = MN . The result is MW = By noting that Ni Mi / ∞ 2 i=1 Ni Mi ∞ i=1 Ni Mi (3.11) 3. The meanings of their names are thus apparent. It is deﬁned by Mv = ∞ 1+a i=1 Ni Mi ∞ i=1 Ni Mi 1 a (3.3 Weight Average Molecular Weight Consider of polymer property which depends not just on the number of polymer molecules but on the size or weight of each polymer molecule. POLYMER MOLECULAR WEIGHT where wi is the weight fraction of polymer i or the weight of polymer i divided by the total polymer weight: wi = N i Mi ∞ i=1 Ni Mi = ci ∞ i=1 ci (3. To derive the weight average molecular weight.15) .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. Two examples are M2 = Mz and M3 = Mz+1 which are used in analysis of ultracentrifugation experiments. We can generalize this process and replace Ni by Ni Mik to get an average molecular weight denoted as Mk : Mk = ∞ k+1 i=1 Ni Mi ∞ k i=1 Ni Mi (3. 3. A classic example is light scattering. One average molecular weight which does not ﬁt into the mold of Mk is the viscosity average molecular weight or Mv . (3. Several other Mk forms appear in experiments. an alternative form for weight average molecular weight in terms of weight fractions ∞ MW = i=1 wi Mi (3. For such a property we need a weight average molecular weight. wi . and M1 = MW .4 Other Average Molecular Weights To get MW from MN we replaced Ni by Ni Mi . 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 .12) Ni Mi is the weight fraction of polymer with molecular weight i.13) Comparing this expression to the expression for number average molecular weight in terms of number fraction (see Eq.46 CHAPTER 3.
the average molecular weights will all be diﬀerent and will rank in the above order. . For monodisperse polymers all molecular weight averages are the same and equal to the one molecular weight. or equivalently by its coeﬃcient of variation. but one used a colligative property which yields MN and the other used light scattering which yields MW .5.3. 3. Viscosity average molecular weight and viscosity experiments are discussed in Chapter 6. i. It resembles a probability distribution curve. We can express the standard deviation of molecular . (3. .2.16) The equalities hold only when the polymer is monodisperse. only when all molecules have the same molecular weight.2: A schematic plot of a distribution of molecular weights along with the rankings of the various average molecular weights.5 A Distribution of Molecular Weights Schematically. Until it was recognizes that MN = MW .. it was diﬃcult to explain diﬀering experimental results on the same polymer solution. the various average molecular weights always rank in the order MN ≤ Mv ≤ MW ≤ Mz ≤ Mz+1 ≤ M4 ≤ . For polydisperse polymers. For any molecular weight distribution. a typical molecular weight distribution might appear as in Fig. A DISTRIBUTION OF MOLECULAR WEIGHTS MN Mv 47 MW Mz Weight Fraction Mz+1 Molecular Weight Figure 3. Historically this fact was not always recognized thus it was sometimes diﬃcult to reconcile conﬂicting experimental results. Say two scientists measured average molecular weight. where a is a constant that depends on the polymer/solvent pair used in the viscosity experiments. The various average molecular weights are indicated in their expected rank.e. 3. The spread of any distribution function can be characterized by its standard deviation.
Or. the A B monomer can polymerize to a polyester. If we denote two functional groups as A and B than a bifunctional monomer would have an A group on one end and a B group on the other and be denoted A A B is n(A For example if A is an acid group ( ( NH2 ) the A of A B) → (A B)n (3.. or most probable distribution of molecular weights. = σ = MN MW MN MW −1 MN (3. M ) denote conventional averaging.20) 2 2 MW −1 MN (3.22) B. In terms of Ni and Mi the variance is 1 σ = N 2 ∞ Ni Mi2 i=1 − 1 N ∞ 2 N i Mi i=1 = ∞ ∞ 2 i=1 Ni Mi i=1 Ni Mi ∞ N i ∞ N i Mi i=1 i=1 − MN 2 (3. σ 2 .V. . Flory considered the polymerization B type monomers and used simple statistical arguments to calculate the expected. if A is an acid group ( COOH) and B is an amine group B monomer can polymerize to a polyamide. Because MN is also the conventional mean C. This term is known as the polydispersity index.18) which in terms of MN and MW is σ 2 = MW M N − M N = MN or the standard deviation is σ = MN MW −1 MN (3. His results give us insight into typical molecular weight distributions.19) The coeﬃcient of variation is the mean divided by the standard deviation. the polydispersity index must be greater than or equal to one. 3.21) A key term in the coeﬃcient of variation is . For all real polymers it is greater that one and the amount that it is greater than one is a measure of the polydispersity of that polymer. POLYMER MOLECULAR WEIGHT weight in terms of MN and MW .48 CHAPTER 3.6 Most Probable Molecular Weight Distribution Many condensation polymers are synthesized by the polymerization of bifunctional monomers.g. For the coeﬃcient of variation to be real (as it must). is σ2 = M 2 − M 2 (3.17) where angle brackets (e. When it is equal to one. the coeﬃcient of variation is zero which means that the distribution is monodisperse. The polymerization reaction of COOH) and B is an alcohol group ( OH). The deﬁnition of variance.
. Thus the probability that the randomly selected molecule is a monomer is P (i = 1) = (1 − p) (3. MOST PROBABLE MOLECULAR WEIGHT DISTRIBUTION 49 We deﬁne p as the fraction of functional groups of type A that have reacted at a given stage of polymerization.3. For example. the total number of molecules is reduced by N0 p. We begin at one end of the molecule which will be an unreacted A group. after some amount of polymerization (i. p = 0) we select a molecule at random. one could use simple acid/base titration experiments. This monotonically decreasing function is not the type commonly drawn to illustrate distribution functions.3. all molecular weights are present to some extent.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. Because A reacts by reacting with B.24) Continuing on by induction. . The probability that the adjacent B group is also unreacted is simply (1 − p) — one minus the probability that a B group has reacted. The surprising results is that at all values of p. the probability that the randomly selected molecule has a degree of polymerization i is P (i) = pi−1 (1 − p) (3.6. the most probable species is the monomer. 3. Now. Virtually all condensation polymers no matter how they are formed will end up with a distribution resembling the most probable distribution. For extent of reaction p. Next. We deﬁne p in mathematical terms but note that in practical terms it is often easily accessible by measurement. then the number of polymer chains of length i is N times the probability of having length i: Ni = N pi−1 (1 − p) (3. At all values of p.26) N is related to the initial number of monomers N0 by N = N0 (1 − p). in terms of known quantities Ni is Ni = N0 pi−1 (1 − p)2 (3. Plots of Ni for various values of p are given in Fig. the fraction of functional groups of type B that have reacted at the same stage of polymerization is also p. If there are N molecules in the polymerizing mixture. It is called the most probable distribution or the Flory Distribution.23) The probability that the randomly selected molecule is a dimer is equal the product of the independent probabilities that the ﬁrst group is reacted (p) and the second in unreacted (1 − p): P (i = 2) = p(1 − p) (3.e. to ﬁnd the fraction of reacted acid A groups of type COOH.27) The above equation for Ni describes the complete polymer distribution. This relation can easily be derived be realizing that each reaction of a functional group reduces the total number of molecules by one.
3. M0 is the repeat unit molecular weight. which increases p. The three curves are for three values of p. The most prevalent species is no longer the monomer.4. First we evaluate the sums in the number average molecular weight formula: MN = ∞ i=1 iM0 Ni ∞ i=1 Ni ∞ = M0 (1 − p) i=1 ipi−1 (3.29) . When the repeat of the polymer has lower molecular weight than the monomer. an equation for Ni ) we can calculate MN and MW . POLYMER MOLECULAR WEIGHT 0. the peak in the weight fraction shifts to higher values and the distribution curve broadens. A more familiar distribution function results if we consider the weight fraction of polymer with length i.50 CHAPTER 3. each monomer weighs very little. As time of reaction increases.98 20 40 60 Degree of Polymerization 80 100 Figure 3. M0 should be the molecular weight of the monomer that makes it into the polymer. 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. Although there will be a lot of monomers. Some plots of weight fraction for various values of p are given in Fig. We can calculate MN for the most probable distribution using two methods..0035 Number Fraction (Ni/N0) 0. In other words.0005 0.0030 0.0000 0 p=0. because of reaction products such as H2 O loss due to condensation. Weight fraction is deﬁned by wi = iM0 Ni iNi = = ipi−1 (1 − p)2 N 0 M0 N0 (3.96 p=0.0040 0.0020 0.28) where M0 is the monomer molecular weight.0015 0. 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.3: The number fraction as a function of degree of polymerization for the most probable molecular weight distribution.0025 0.94 p=0.e.0010 0.
The sum.96 p=0.33) To get MW for the most probable distribution we use the weight average molecular weight formula in terms of weight fractions: ∞ ∞ MW = i=1 wi iM0 = M0 (1 − p)2 i=1 i2 pi−1 (3.32) An alternative and simpler method to MN is to realize that.31) Multiplying by M0 (1 − p) gives MN = M0 1−p (3.005 0.000 0 20 40 60 Degree of Polymerization 80 100 Figure 3. however. ∞ ip i=1 i−1 d = dp ∞ pi = i=1 d dp p 1−p (3.3. The evaluation of the sum is nontrivial. Thus MN = Total weight of polymer M0 N 0 M0 = = Total number of polymers N0 (1 − p) 1−p (3.34) . by conservation of mass.98 0. the total number of polymers is N0 (1 − p). can be expressed as the derivative of another sum which is simpler to evaluate.94 0.30) Evaluating the derivative gives ∞ ipi−1 = i=1 1 (1 − p)2 (3.6. the total weight of material is always M0 N0 .025 p=0.015 0. The three curves are for three values of p. From above.020 Weight Fraction (wi) 0.010 p=0. MOST PROBABLE MOLECULAR WEIGHT DISTRIBUTION 51 0.4: The weight fraction as a function of degree of polymerization for the most probable molecular weight distribution.
there are more reactions (albeit at a slow rate) which cause p to increase. both MN and MW approach inﬁnity.37) Combining the results for MN and MW . they would not ﬂow when melted. It is usually not desirable to have molecular weights that are too high.36) Multiplying by M0 (1 − p)2 gives the ﬁnal result: MW = M0 1+p 1−p (3. To avoid unprocessible polymers. Instability occurs if over long times. A more complicated analysis gives the following MN : MN = M0 (1 + r) M0 (1 + r) ≈ 1 + r − 2rp 1−r (3.38) As the reaction nears completion. If the two monomers are mixed in equal proportions.35) The last step uses the result from the MN calculation. One solution to molecular weight control is to polymerize the two monomers A instead of the single monomer A A and B B B. POLYMER MOLECULAR WEIGHT We evaluate the sum using the trick used to ﬁnd MN and some additional work. This scheme. p approaches one and the polydispersity index approaches 2. One way to control molecular weight would be to freeze the reaction at some p less than one. That large of a coeﬃcient of variation means that the molecular weight distribution is relatively broad. ∞ i2 pi−1 = i=1 d dp ∞ ipi = i=1 d dp ∞ p i=1 pi−1 = d dp p (1 − p)2 (3. This limit means that all the monomers will be in a single polymer molecule. the polymer properties change with time and might eventually give a molecular weight that is too high to be processible. 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 B − B) instead of from one monomer (A − B)). When p increases. however. That is the coeﬃcient of variation of the most probable distribution is 100%. the analysis will be identical to the one above and there will be no molecular weight control (note: although the analysis is the same. Evaluating the derivative gives ∞ i2 pi−1 = i=1 1+p (1 − p)3 (3.39) . the polydispersity index for the most probable distribution is MW =1+p MN (3. We also notice that as p approaches one.52 CHAPTER 3. it is desirable to use methods to control molecular weight. can produce a material that is unstable with time. Such polymers would not be processible. If the proportions are unequal and r = NA /NB < 1 then the results are diﬀerent.
assume that the number average and weight average molecular weights of batch j are MN j and MW j . show that the number average molecular weight of the blend is MN = w1 MN 1 w1 + w2 + · · · + wn w w + M 2 + ··· + M n N2 Nn In other words.j Mi. M0 is half the repeat unit molecular weight. Sample calculations for various values of r give r = 1.40) Now.j Mi. But. The second part of this equation assumes p is equal to one.99 r = 0.6.90 MN = ∞ MN = 199M0 MN = 39M0 MN = 19M0 By selecting r.j i Ni. MOST PROBABLE MOLECULAR WEIGHT DISTRIBUTION 53 where.j n j=1 i Ni.j (3.95 r = 0. Starting from the above basic number average molecular weight deﬁnition.41) or a sum over just the polymers of component j. the reaction stops at a ﬁnite molecular weight. you must have accurate control over r.j be the molecular weight of that polymer. . Here MN j has the usual deﬁnition of MN j = i Ni. Suppose you have n batches of polydisperse polymers. Problems 3–1.00 r = 0. Let Ni. show that MN of the blend can be calculated from the individual MN j of the components of the blend. Physically what happens is that the monomer mixture runs out of A with B A and all polymers are end capped B monomers. a. 39M0 is not a very high molecular weight and may not be high enough to be useful.j Mi. To prevent polymerization from stopping at low molecular weights.j Mi. Also you must account for any side reactions and monomer volatility which might remove monomer of one type and eﬀectively change r. we see it is possible to control molecular weight to some ﬁnite value. Because B can only react with A and no unreacted A remains. and that you mix a weight wj of each batch to make a new polymer blend. The basic MN and MW equations for the total mixture of polymers now require double sums: MN = n j=1 i Ni.j n j=1 n j=1 and MW = 2 i Ni.00 reduces the molecular weight from inﬁnite to 39M0 .j (3.3. For example a 5% deviation of r from 1.j be the number of polymers of type j with degree of polymerization i and Mi. as explained above.j i Ni. The only problem is that small changes in r lead to large changes in MN .
What is the highest possible MN for a polymer containing 3% by weight of calcium stearate? 3–3. 000 g/mol. Again. A sample of pure PVC polymer with a polydispersity index of 2. a. Derive an expression for w(M ) where w(M ) is the weight fraction of polymer that has molecular weight M . What is the MN of the PVC part of the compound? (Hint: use the blend MN result from the previous problem. 3–4.j i Ni. b. What is the MW of the blend? c. What molecular weight has the largest weight fraction? Express your answer in terms of the number average molecular weight. 3–2.54 CHAPTER 3. Consider the most probable molecular weight distribution: a.j Mi.j Mi. . Calculate the percentage conversion of functional groups required to obtain a polyester with a numberaverage molecular weight of 24. Calcium stearate (Ca(OOC(CH2 )16 CH3 )2 . show that the weight average molecular weight of the blend is MW = w1 MW 1 + w2 MW 2 + · · · + ωn MW n w1 + w2 + · · · + wn In other words. Express your result in terms of M (and not degree of polymerization i).000 g/mol from the monomer HO(CH2 )14 COOH.8 is modifed by the addition of 3% by weight of calcium stearate. 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. show that MW of the blend can be calculated from the individual MW j of the components of the blend. d. POLYMER MOLECULAR WEIGHT b Starting from the above basic weight average molecular weight deﬁnition. Here MW j has the usual deﬁnition of MW j = 2 i Ni. Derive an expression for P (M ) where P (M ) is the probability that a randomly selected polymer chain as molecular weight M . express your answer in terms of M (and not x). What molecular weight has the maximum probability? c. TYhe mixture of PVC and salcium stearate is found to have MN = 15.) b.42) or a sum over just the polymers of component j.j (3. molecular weight = 607) is sometimes used as a lubricant in the processing of poly(vinyl chloride).
2 g and molecular weight 166) at 280◦ C. .22 g and molecular weight 116) and adipic acid (13.6. A polyamide was prepared by bulk polymerization of hexamethyl diamine (9. Analysis of the whole reaction product showed that it contained 2.6 × 10−3 moles of carboxylic acid groups.3. Assume it has a “most probable distibution” and also evaluate MW . MOST PROBABLE MOLECULAR WEIGHT DISTRIBUTION 55 3–5. Evaluate MN of the mixture.
POLYMER MOLECULAR WEIGHT .56 CHAPTER 3.
Chapter 4
Polymer Solutions
4.1 Introduction
There are many reasons for studying polymer solutions. One obvious reason is to understand the nature of those solutions. A practical reason is that polymer solutions are often used when measuring molecular weight. Some common molecular weight determination methods are osmotic pressure measurements, solution viscosity, solution light scattering, and gelphase chromatography. Each of these methods uses a polymer solution. Before discussing these or other polymer characterization techniques, we therefore will spend some time discussing the thermodynamics of polymer solutions.
4.2
Solution Thermodynamics
Solutions are often characterized in terms of Gibbs free energy — G. G can be viewed as a multivariable function that depends on temperature (T ), pressure (P ), and the number of moles of each component (ni for i = 1 to number of components). By multivariable math analysis, the diﬀerential in free energy following a change in any or all of the key variables is: dG = ∂G ∂P dP +
T,ni
∂G ∂T
dT +
P,ni i
∂G ∂ni
dni
T,P,nj =ni
(4.1)
The subscripts on the partial derivatives mean that those variables are held constant while taking the derivative. We will be using lower case n to mean moles of some component and upper case N to mean molecules. The number of molecules N is always equal to nL where L is Avagadro’s number. We know some of the terms in the dG expression from conventional thermodynamics. Consider a solution with constant composition (i.e., dni = 0 for all i). The total free energy is G = H − TS 57 (4.2)
58
CHAPTER 4. POLYMER SOLUTIONS
The diﬀerential in free energy follows the well known relation dG = V dP − SdT Comparing this expression to the solution results above gives ∂G ∂P =V
T,ni
(4.3)
and
∂G ∂T
= −S
P,ni
(4.4)
We do not have a similar result for ∂G/∂ni . Instead ∂G/∂ni is given a name; it is called the chemical potential and denoted by µi or Gi . Speciﬁcally: ∂G ∂ni = µi = Gi
T,P,nj =ni
(4.5)
Using these new results, the diﬀerential in G for a solution becomes dG = V dP − SdT +
i
µi dni
(4.6)
Next we consider the change in free energy upon mixing two components (A and B) at constant temperature and pressure (dP = dT = 0). Only the chemical potential terms cause a change in G. The diﬀerential form reduces to dG = µA dnA + µB dnB (4.7)
Integrating dG from 0 to nA and from 0 to nB which corresponds to the mixing process gives G = µA nA + µB nB (4.8)
If instead of mixing A and B we consider pure components A and B, the expression for G will be the same except that the chemical potentials will be diﬀerent. If we denote the chemical potential of pure components with a superscript “◦”, the free energy of the separated pure components is G◦ = µ◦ nA + µ◦ nB A B (4.9)
Comparing the solution G and the pure component G◦ , we ﬁnd the change in free energy on mixing or ∆Gmix to be: ∆Gmix = nA (µA − µ◦ ) + nB (µB − µ◦ ) = nA (GA − G◦ ) + nB (GB − G◦ ) A B A B (4.10)
To understand solutions we need to evaluate terms like (µA − µ◦ ). As expressed, chemical A potential is somewhat awkward for practical use. We thus redeﬁne it in terms of activity. Activity at ﬁrst appears no better then chemical potential, but we will soon show that it has useful interpretations under important special cases. We thus write chemical potential as µA = µ• + RT ln aA A (4.11)
4.2. SOLUTION THERMODYNAMICS
59
where aA is the relative activity of component A and µ• is the chemical potential in an arbitrarily A chosen reference state. In terms of chemical potential, the activity is aA = exp µA − µ• A RT (4.12)
We next apply the deﬁnition of activity to the analysis of a solution in equilibrium with its vapor. At equilibrium the chemical potential of component A in the vapor is equal to its chemical potential in the solution. We assume the vapor is an ideal gas and use the above result that ∂G/∂P = V to get ∂Gvap ∂µvap ∂ ∂Gvap ∂ ∂Gvap ∂V A A = = = = = VA ∂P ∂P ∂P ∂nA ∂nA ∂P ∂nA (4.13)
where VA is the partial molar volume of component A. In an ideal vapor of A, V = nA RT /PA where PA is the partial pressure due to component A. Diﬀerentiating with respect to nA to get VA gives ∂µvap RT A = ∂PA PA Integrating we get µvap = RT ln PA + const A (4.15) or dµvap = RT A dPA PA (4.14)
The integration constant is found by using the reference state where µA = µ• . Finding the constant A results in µvap = µ• + RT ln A A PA • PA (4.16)
• where PA is the partial pressure of component A in the reference state.
We turn next to the chemical potential in the liquid. Because the liquid is in equilibrium with the vapor, the chemical potential of component A in the liquid must be equal to its chemical potential in the vapor. Thus µl = µvap = µ• + RT ln A A A PA • PA (4.17)
A good reference state for liquids is the chemical potential of the pure liquid. Deﬁning µ◦ as the A chemical potential of the pure liquid we have µ◦ = µ• + RT ln A A
◦ PA • PA
(4.18)
Solving for µ• and substituting into the expression for µl gives A A µl = µvap = µ◦ + RT ln A A A PA ◦ PA (4.19)
◦ In general, PA < PA which implies µl < µ◦ . Physically, this observation means that compounds A A
are less active in solution then they are in pure form. In the above analysis we have assumed the vapor is an ideal vapor. In eﬀect, we have proposed a physical model for the liquid/vapor
it is deﬁned in terms of physical quantities. the entropy of mixing is ◦ ◦ ∆Smix = nA (SA − SA ) + nB (SB − SB ) = −R (nA ln XA + nB ln XB ) (4. The activity of any component is the ratio of its partial pressure to the partial pressure that exists over a pure liquid of that component.22) (4.25) Finally. we noted that we need terms like (µA − µ◦ ).20) In examining the free energy of mixing. pure separated . the activity coeﬃcient of component A is XA and its chemical potential is µA = µ◦ + RT ln XA A (4. the enthalpy of mixing is ∆Hmix = ∆Gmix + T ∆Smix = 0 (4.26) ∆Hmix for an ideal solution is zero. These facts mean that ∆Gmix is always negative and ∆Smix is always positive.21) This free energy of mixing can be split up into an entropy part and an enthalpy part with ∆Gmix = ∆Hmix − T ∆Smix (4. the mole fractions. POLYMER SOLUTIONS equilibrium. which means that both ln XA and ln XB must be negative. The driving force for this miscibility is the increase in entropy of mixed components vs. the numbers of moles. Both XA and XB . Let’s say that the solution (as well as the vapor) is ideal in that it obeys Raoult’s law which states ◦ that PA = XA PA where XA is the mole fraction of component A in the solution. We next examine the sign of ∆Gmix .60 CHAPTER 4. ∆Hmix is zero because the assumption of an ideal solution implies no interactions between the components of the solution.23) We begin with entropy of mixing. the activity is no longer an abstract property. Thus. A fundamental relation of thermodynamics is ∂G/∂T = −S. must be positive. In other words all two component ideal solutions are miscible in all proportions. With this new assumption. must between 0 and 1. the activity of component A is ◦ PA /PA .24) Following the free energy of mixing analysis. For an A ideal solution and an ideal vapor µA − µ◦ = RT ln XA A Our previous result for free energy of mixing becomes ∆Gmix = RT (nA ln XA + nB ln XB ) (4. Applying this relation to chemical potentials by taking the temperature derivative of µA gives SA = − ∂µA ◦ = SA − R ln XA ∂T (4. Both nA and nB . We can extend our model by introducing an assumption about the solution properties. In this model.
29) . it is easy to count the number of ways of putting NA A units and NB B units into NA + NB lattice sites. ∆Gmix must be positive which implies that ∆Hmix = 0 and further that ∆Hmix is suﬃciently positive that it overwhelms the entropy or that ∆Hmix > T ∆Smix .1: A simple lattice model for a solution of A and B.. Deviations from ideality often mean that enthalpy is important and not zero.4.1 represents a solution of A and B. In the simple lattice. for many molecules) we can apply Stirling’s approximation for factorials (ln n! ≈ n ln n) to get W = NA [ln (NA + NB ) − ln NA ] + NB [ln (NA + NB ) − ln NB ] (4.e. By statistical thermodynamics. 4. entropy S is S = k ln W (4.27) where W is the number of possible conﬁgurations of A and B solution. For large NA and NB (i. The fact that not all materials are soluble in all other materials means that many solutions deviate from ideality.3. 4. components.3 Physical Origins of Entropy of Mixing The physical origins of the entropy of mixing can be modeled using a simple lattice model for the structure of a solution. PHYSICAL ORIGINS OF ENTROPY OF MIXING 61 A A B A A A A A B A B A B B B A A B A B A A A B A B A A B A B A B A A B A A B A A B A B A A B B A A A A B A A A Figure 4. Say the simple lattice model in Fig. To make two components immiscible. The result from combinatorial analysis is W = NA + NB NA = (NA + NB )! NA !NB ! (4.28) (Note we now use upper case N ’s because they refer to individual molecules of component A and B).
1).2 shows a lattice model for one polymer (component B) in solvent A. Compared to the monomer solution problem (Fig. 4.30) This result agrees exactly with the activity analysis for entropy of mixing. and NB = LnB . The conclusion is that the entropy of polymer solutions is much less that the corresponding entropy for monomer solutions of the same weight fractions A and B. it is a much harder task to count the number of conﬁgurations in which all B units are connected into chains of length x with excluded volume on a lattice with solvent A. We ﬁnd some interesting results when we apply the lattice model to a polymer solution. By deﬁnition of mole fraction XA = NA /(NA + NB ) and XB = NB /(NA + NB ). we quickly derive ∆Smix = −R(nA ln XA + nB ln XB ) (4.2: Polymer molecule B in a lattice model for a solution in solvent A. An approximate calculation gives the following result for the . which will be much less than W . and realizing that R = Lk. Thus the lattice model recovers all details of the thermodynamics analysis. It is clear that the number of ways of introducing the polymer molecule into solvent A will be much less than the number of ways of introducing the same amount of monomer molecules B into the same solvent. will be the number of conﬁgurations of polymer B in solvent A. The physics of mixing is unchanged. POLYMER SOLUTIONS A A A A A A A A A A A B B B B B B A B A B A A B A B A B A A B B B A B A A A A A A B A A B B B B B A A A A A A A Figure 4. For that large set of conﬁgurations we must now reject all conﬁgurations that do not have connected B molecules. but now we must consider the case where one molecule is much larger than the other molecule. We can even replace the ≈ by a straight equal sign because NA and NB will be so large that Stirling’s approximation is eﬀectively exact. NA = LnA . L. A lattice can be viewed as a good physical picture of an ideal solution. Introducing Avagadro’s number. Figure 4. The remaining conﬁgurations. To count the polymer lattice conﬁgurations we could go back to the lattice model for a solution of A and B and examine all of the W conﬁgurations.62 CHAPTER 4.
. In brief. it is much easier for the ∆Hmix term to assume a greater role. Then ∆Hmix = kT χNA vB = RT χnA vB (4.31) where vA and vB are volume fractions of solvent (component A) and polymer (component B): vA = NA NA + xNB and vB = xNB NA + xNB (4. When the entropy of mixing term is small. the theory attempts to estimate ∆Hmix using the lattice theory for solutions. 4. nA will be the same for both solution. Likewise. Because the polymer solution connects many B monomers into a single polymer.4.33) where NA is the number of molecules of component A. Furthermore.4. in dilute solutions. The mole fractions of A and B in the monomer solution are identical to the volume fractions of A and B in the polymer solution. We do not need to derive new methods for understanding polymer solutions. It also easy for ∆Hmix to be greater than T ∆Smix and therefore for polymers to be insoluble in many solvents.32) Consider two solutions of equal weight fractions of component A and B — monomer B molecules in solvent A and a polymer of connected B monomers in solvent A. One thing that monomer solutions and polymer solutions have in common is that they both obey conventional thermodynamics. A negative χ indicates an attractive interaction and causes a negative ∆Hmix which guarantees dissolution. We thus conclude that the entropy of mixing for polymer solutions will be hundreds or thousands of times lower than the entropy of mixing for monomer solutions. nB in the polymer solution will be hundreds or thousands of times lower than nB in the monomer solution. The deviations from ideality are direct consequence of the size of polymer molecules. The ∆Smix expression diﬀers only in the value for nB . the nB ln XB and nB ln vB terms are the dominant entropy terms. A high positive χ indicates a repulsive interaction and causes a positive ∆Hmix which tends to inhibit the solution process. FLORYHUGGINS THEORY entropy of mixing: ∆Smix = −R (nA ln vA + nB ln vB ) 63 (4. The large size reduces the entropy of mixing which reduces the term T ∆Smix .4 FloryHuggins Theory We introduce a simple model for dealing with polymer solutions called the FloryHuggins theory. is that polymer solutions are much more likely to deviate from ideal behavior at comparable concentrations (in weight fraction solute). We consider nearest neighbor interaction between A and B molecules. nA is the number of moles of component A. The interaction parameter describes the level of interaction between pairs of A and B. however. and χ is the Flory interaction parameter. vB is the volume fraction of polymer. A major diﬀerence.
We will make qualitative use of this theory when discussing osmotic pressure experiments. Compare the entropy of mixing for two solution. the FloryHuggins theory has some applications for physical understanding of solution properties. Explain the physical origin of each term in then FloryHuggins expression for freeenergy of mixing in polymer solutions. 4–3. The ﬁrst is a solution 1% by weight of monomer B in solvent A (assume the molecular weights of A and B are the same). it is common to observe that the solute will precipitate out at low temperature and only be soluble in the solvent at elevated temperatures. When two components form a nonideal solution. a. The theory is particularly bad for dilute solutions. The second is a polymer of monomer B in a 1% by weight solution in solvent A where the polymer has a degree of polymerization of 100. Explain why two components that form an ideal solution are miscible in all proportions. Problems 4–1. the FloryHuggins theory is not very good. 4–2. Reasons for these problems will be discussed latter. . b.34) Unfortunately. POLYMER SOLUTIONS The free energy of mixing in the FloryHuggins theory is ∆Gmix = RT (nA ln vA + nB ln vB + χnA vB ) (4. Explain why increasing the temperature often makes it more likely for one component to dissolve in another component even when the resulting solution is nonideal. Despite its shortcomings.64 CHAPTER 4.000. In practice solution property data cannot be predicted by using a single value of the interaction parameter.
we expect. ∆Tb . freezing point depression.1) where m is the molality of solute molecules and Kb is the boiling point elevation coeﬃcient that is a function of only the solvent. A well known result from introductory chemistry is that the boiling point elevation is proportional to the molar concentration of solute particles ∆Tb = Kb m (5. colligative properties have been one means for determining the molecular weight of unknown compounds. and will show. In an ideal solution. PA .2 Boiling Point Elevation Figure 5. These properties include boiling point elevation. Historically.Chapter 5 Colligative Properties 5. 5. that colligative property experiments give a number average molecular weight. is reduced from the vapor ◦ ◦ pressure of a pure liquid. In this chapter we discuss using colligative properties to measure the molecular weight of polymers. and osmotic pressure. boiling point is the temperature at which the vapor pressure of the liquid reaches 1 atm. This reduction is reﬂected in a shift to the right of the vaporpressure curves in Fig. Because colligative properties depend on the number of molecules. PA . This increase. Molality is the number of moles of component B per 1000 grams of solvent. the vapor pressure of the solvent.1. is the boiling point elevation eﬀect.1 Introduction Properties of solutions that depend on the number of molecules present and not on the kind of molecules are called colligative properties. If we prepare a solution of an unknown compound of molecular weight B at a concentration 65 . 5. By deﬁnition. Thus. to XA PA where XA is the mole fraction of liquid A. the rightshift caused by the dissolution of component B in solvent A causes the boiling point to increase.1 shows the vapor pressure of a liquid for pure liquid and for a solution with that liquid as the solvent.
00) and concentration (c). water where Kb = 0. COLLIGATIVE PROPERTIES Pure Solvent Vapor Pressure 1 atm Solution Vapor Pressure ∆T Temperature Tb Figure 5.3) For a given solvent (e. Substituting into the expression for ∆Tb gives MB = or ∆Tb 1000Kb = c ρMB (5.7) . At equilibrium.5) where V is total volume and MA is molecular weight of the solvent. Thus.1: Boiling point elevation eﬀect is a consequence of the eﬀect of solute molecules on the vapor pressure of the solvent.2) where ρ is the density of the solvent (in g/cm3 ). measuring ∆Tb can be used to determine the molecular weight MB . Mole fraction is XB = cV MB ρV MA + cV MB ≈ cMA ρMB (5. We can also express boiling point elevation in terms of mole fraction.66 CHAPTER 5.52 and ρ = 1.4) are known except for MB .6) MA To apply boiling point elevation to polymers. we begin by using solution thermodynamics to ∆Tb = derive an expression for ∆Tb . the chemical potential of the vapor is equal to the chemical potential of the liquid µvap = µliq = µ◦ + RT ln XA A A A or µvap − µ◦ A A = ln XA RT (5. c in g/cm3 ..4) (5. then m= 1000c MB ρ 1000Kb c ρ∆Tb (5.g. (5. all terms in Eq. The boiling point elevation becomes 1000Kb XB (5.
2.13) Comparison of this result to Eq. Integrating over this process gives T − Tb ∆Hvap dT = RT 2 XA d ln XA 1 (5. T Tb ≈ Tb2 . we should realize that polymer solutions are really solutions of many components.5. These simpliﬁcations apply when XB is small (which occurs when the solution is dilute) and when ∆Tb is small.10) The integrals are easily evaluated if we assume that ∆Hvap is independent of temperature over the small temperature range from Tb to T . and ln XA = ln(1 − XB ) ≈ −XB .9) vap ◦ where HA − HA is the heat of vaporization of the solvent or ∆Hvap .14) The result is often derived in physical chemistry books. During the process.6) gives a theoretical expression of Kb : Kb = MA RTb2 1000∆Hvap (5. BOILING POINT ELEVATION where we have assumed an ideal solution. In applying boiling point elevation to polymer solutions. The previous equation simpliﬁes to ∆Hvap ∆Tb = XB RTb2 or ∆Tb = RTb2 XB ∆Hvap (5. Because boiling point elevation is a colligative property. The result is ∆Hvap R 1 1 − T Tb = ln XA (5.15) . the boiling point will go from Tb to T where Tb is the boiling point of the pure liquid and T is the boiling point of the solution. we can write the boiling point elevation of a polymer solution as a sum over the mole fractions of each molecular weight component: ∆Hvap ∆Tb = RTb2 Xi i (5.11) We can simplify this result using ∆Tb = T − Tb . Diﬀerentiating both sides gives ∂ µA T 67 ∂ = GA T ∂T which is used to get ∂T = 1 T ∂GA ∂T − P GA SA H A SA HA =− − 2 + =− 2 2 T T T T T (5. (5.12) (5. As the polymer is added. Now consider the process of forming a solution. The various components are the polymer species of diﬀerent molecular weights. ∆Tb will be small when the solution is dilute.8) − vap ◦ HA − H A d = ln XA 2 RT dT (5. In general. the mole fraction of A will go from 1 at the start to XA which is the mole fraction of the ﬁnal solution.
21) Except for incorporation of polydispersity. however. deﬁned as energy or vaporization per unit weight or lvap = ∆Hvap J/mole = = heat of vaporization in J/g MA g/mole (5. the solution is more likely to be nonideal. the polymer solution will . 000. Summing the mole fractions. In polymers. results in Xi = i cMA ρ ci i Mi i ci = cMA ρ i wi cMA = Mi ρMN (5. For an example.20) The boiling point elevation becomes RTb2 ∆Tb = c ρlvap MN (5.17) where c= i ci (5.8787 g/cm3 .g. the comparable expression for small molecule solutions. We more conveniently rewrite Xi in terms of concentration: Xi = ρV MA ci V Mi + ci V i Mi ≈ ci MA ρMi (5. The approximation in this expression is valid for dilute solutions in which the number of moles of solvent is much greater than the total number of moles of polymer.4 × 10−3 ◦ C. Xi . We assume a relatively concentrated solution of c = 1 g/cm3 of a polymer with molecular weight MN = 20. The problem with polymer solutions is that for a given weight of material. More dilute solutions or higher molecular weight polymers would give an even smaller ∆Tb .68 CHAPTER 5. This boiling point elevation is very small. The small change arises despite relatively ideal conditions of a fairly concentrated solution and a low molecular weight polymer. For benzene ρ = 0. The change in the boiling point elevation for this solution is ∆Tb = 1. let’s consider a solution of polystyrene in benzene. For this equation to apply we will probably need to use very low concentrations or techniques to extrapolate to very low concentrations. there is nothing new about the boiling point elevation expression for polymer solutions vs. It is probably beyond the accuracy of most temperature measuring equipment. COLLIGATIVE PROPERTIES where Xi is the mole fraction of polymer with molecular weight Mi . g/cm3 ) of polymer with molecular weight i.. and lvap = 104 cal/g.16) where ci is the concentration in weight/unit volume (e.19) It is common to express the boiling point elevation in terms of the latent heat of vaporization.18) The ﬁnal expression for the boiling point elevation becomes MA RTb2 ∆Tb = c ρ∆Hvap MN (5. lvap . Tb = 55◦ C.
. Like the boiling point elevation eﬀect.2. It has found some use with polymers but it is limited to polymers with relatively low molecular weights.000 g/mol). FREEZING POINT DEPRESSION 69 have many less molecules than the comparable small molecule solution.24) (5. MN less than 20.22) where Tf is the freezing point of the solvent and lf is the latent heat of fusion. An ideal semipermeable membrane will allow the solvent molecules to pass but prevent the solute molecules (polymer molecules) from passing. ρ is the density of the solution. (e.2 illustrates the osmotic pressure effect. 5. When there are a small number of molecules. the change in the freezing point of the solution is ∆Tf = 2. The technique is insensitive and only useful for low molecular weight polymer (e. the change in boiling point (a colligative property) is small. lf = 30. For a c = 1 g/cm3 solution of polystyrene with molecular weight MN = 20. The problem with the boiling point elevation method applied to polymer solutions is that it is not sensitive enough. g is the acceleration of gravity (9. 5. The ﬁnal result is 2 RTf ∆Tf = c ρlf MN (5. the freezing point depression eﬀect is too small. At equilibrium.9 × 10−3 ◦ C. The excess height in the column of liquid above the solution side is related to the osmotic pressure by π = ρgh.g.23) .3 Freezing Point Depression A similar analysis (but with sign changes) can be applied to the freezing point depression of a polymer solution. it can be imagined that solvent molecules pass from the pure solvent side to the solution side. Figure 5.000 g/mol).45 cal/g for the freezing point of benzene. Here π is the osmotic pressure. The diﬀerent concentrations on the two sides of the membrane will cause an initial diﬀerence in chemical potential. As shown in Fig.5◦ C. 5. 000.81 m/sec2 ) and h is the height of the column of liquid.5.. We begin with a thermodynamic analysis of osmotic pressure. At equilibrium the chemical potential in the solution will be equal to the chemical potential in the pure solvent: µsolvent = µsolution = µ◦ + RT ln aA A A A where µsolvent is the chemical potential of the pure liquid or A µsolvent = µ◦ A A (5.4 Osmotic Pressure Another colligative property is osmotic pressure. this diﬀerence in potential will be counteracted by an eﬀective pressure across the membrane.3. Imagine a pure solvent and a solution separated by a semipermeable membrane. MN less than 20. We consider the same example of polystyrene in benzene with Tf = 5.g.
The only way the chemical potentials will be equal will be if the activity of component A in the solution is equal to 1. COLLIGATIVE PROPERTIES π = ρgh h Membrane Solvent Solution Figure 5.28) πVA RT (5. the osmotic pressure. we replace XB by i Xi which was derived in Eq. the activity in the solution can be changed to 1.70 CHAPTER 5. To get the pressure dependence of activity. Finally. The activity can be raised to 1 by applying pressure. That is. as in the analysis of boiling point elevation. (5. in an ideal solution − ln aA = − ln XA ≈ XB . activity is a pressure dependent quantity.25) dP dP dnA dnA dP dnA dP Rearranging and integrating the left hand side from the original activity aA to the ﬁnal activity 1 and the right hand side from the initial pressure 0 to the ﬁnal pressure — the osmotic pressure π — results in: 1 π d ln aA = aA 0 VA dP RT (5. By applying the correct pressure.29) Xi = i giving cMA πVA = RT ρMN (5.2: A schematic view of osmotic pressure across a semipermeable membrane.17) to be cMA ρMN (5.30) .27) This last approximation follows because ln(1 − x) ≈ −x for small x. we consider the pressure dependence of the chemical potential d dG d dG dV d dµA = = = = VA = RT ln aA (5. The osmotic pressure that gets applied occurs naturally by the tendency to approach equilibrium. (5.26) which integrates to − ln aA = Now.
32) Ni RT (i. MA /ρ is the grams per mole of solvent divided by the grams per cm3 of solvent. 5. P V = nRT ) (5.5.5 Practical Aspects of Osmotic Pressure Osmotic pressure measurements appear to be a suitable method for measuring number average molecular weights in polymers.24 × 104 dynes/cm2 h= = 14.000. In the limit of zero concentration. In fact we expect to be able to measure distances at least 100 times smaller than this result. be used to determine molecular weights in polymers with MN up to 2. We thus write π c (5. Substituting into the osmotic pressure equation thus gives: RT π = c MN (5. The grams cancel and we have cm3 per mole of the solvent or the partial molar volume of component A — VA .31) Rewriting the osmotic pressure equation gives a result that is similar to the ideal gas law cRT = π which simpliﬁes to πV = i i N i Mi i Ni or i N i Mi V RT = π i N i Mi i Ni (5. In other words π RT = c→0 c MN lim is to use a virial expansion. This pressure will be measured by a diﬀerence in heights of liquids in columns. For the correct units we use R = 8.33) For an example. We can therefore take a series of measurements and extrapolate back to zero concentration to get the ideal result.36) π RT = + RT A2 c + RT A3 c2 + · · · c MN . Thus osmotic pressure can. PRACTICAL ASPECTS OF OSMOTIC PRESSURE 71 But.e. The ﬁrst practical consideration is that we expect polymer solutions to deviate from ideal behavior and thus the osmotic pressure expression will need to be corrected. a solution of polystyrene in benzene with MN = 20.3143 × 107 ergs/K/mol and calculate π = 1.8787 g/cm3 981 cm/sec2 (5.5.34) This height diﬀerence is large and is an easily measurable quantity.3 cm 0.e. It is therefore worthwhile considering practical aspects of polymer characterization by osmotic pressure.24 × 104 dynes/cm2 .000 g/mol.35) The question which remains is “how do we extrapolate?” A common approach in thermodynamics as a sum of many terms: (5.. let’s consider the solution of polystyrene in benzene that was used for examples of boiling point elevation and freezing point depression. i. in principle. The height diﬀerence comes from π = ρgh or 1. the solution will eventually become ideal. 000 and a concentration of c = 1 g/cm3 .
The result is µA − µ◦ = RT ln vA + 1 − A 1 x 2 vB + χvB (5. Then π/c is predicted to be linear in concentration: π RT = + RT A2 c c MN (5. Besides an intercept.. In the ﬁrst approach. and the related Γ2 .37) Here A2 . the intercept of the data at zero concentration will be RT /MN and thus can be used to determine MN . In performing the integration we must realize that vA and vB also depend on nA .41) Substituting into the osmotic pressure formula and at the same time using the approximation 2 ln vA = ln(1 − vB ) ≈ −vB + vB /2 (Note that in this approximation to ln(1 − vB ) we keep one more term than we have used in the past. In other words the slope of the π/c vs.72 or CHAPTER 5. We can make use of the FloryHuggins theory to get a physical interpretation of the second virial coeﬃcient. are called the virial coeﬃcients. When the data is linear. χ. c plot is proportional to the second virial coeﬃcient — A2 . If the results are linear.. the osmotic pressure becomes: π= RT VA vB + x 1 2 − χ vB + · · · 2 (5. Let’s use the FloryHuggins theory to develop an osmotic pressure theory for nonideal solutions. The work is left as an exercise to the reader. But. we can measure the slope which is equal to RT A2 . The reason for the extra term is that the µA − µ◦ expression A 2 already includes terms with vB ). A3 . we assume that only the second virial coeﬃcient — A2 or Γ2 — will be needed. . how do we analyze experimental data when virial expansion terms are required? We consider two approaches to this problem. the assumption in the ﬁrst approach is valid.40) To use the FloryHuggins theory we diﬀerentiate the ∆Gmix from that theory..38) A set of data for π/c vs.42) .39) The term µA − µ◦ is found by diﬀerentiating the free energy of mixing A d∆Gmix = µA − µ◦ A dnA (5. COLLIGATIVE PROPERTIES π RT = 1 + Γ2 c + Γ3 c2 + · · · c MN (5. . We begin with an early osmotic pressure formula: π=− µA − µ◦ RT ln aA A =− VA VA (5.. c can be plotted. If we include enough virial coeﬃcients we will always be able ﬁt experimental data. how many of these terms do we need? Furthermore. Γ3 . The FloryHuggins theory includes nonideal interactions through the Flory interaction parameter.
c will be large and positive. c are often not linear.5. In fact the slope of the osmotic pressure data can be thought of as a direct measure of the solvent quality — the higher the slope the better the solvent.45) . Unfortunately.44) where M0 = MN /x is the monomer molecular weight.. When the excluded volume eﬀect is absent.43) The ﬁrst term is the ideal solution result (which can be deduced by noting that MN = VB ρB and VB = xVA in the lattice solution model).. Let’s take g as the ratio of the third virial coeﬃcient to the second virial coeﬃcient squared (Γ3 = gΓ2 ) and let’s ignore terms beyond the 2 third virial coeﬃcient. vB . which is proportional to concentration. the solution will act as if the speciﬁc volume of the polymer is zero (1/ρB = 0) and the second virial coeﬃcient will therefore be zero. We thus need a second approach to analysis of data from nonideal solutions. The fact that a zero slope is a low slope illustrates a result from earlier in the course — theta solvents in general are not very good solvents. The second virial coeﬃcient from the FloryHuggins result is also proportional to 1/ρB or rather is proportional to the speciﬁc volume of polymer. The obvious approach is to include both the second and the third virial coeﬃcients. The observation of zero slope in osmotic pressure data. The second term. the second virial coeﬃcient will be large and positive and the slope of π/c vs. In other words a theta solvent acts as an ideal solution to fairly high concentrations. From the FloryHuggins analysis. In other words we assume that deviations from linearity are caused by the third virial coeﬃcient no longer being insigniﬁcant. A negative interaction parameter also implies a favorable interaction (∆Gmix more negative) and therefore a good solvent will give a large positive slope.e. PRACTICAL ASPECTS OF OSMOTIC PRESSURE 73 The volume fraction of polymer. This result suggests an excluded volume eﬀect. c which gives the second virial coeﬃcient. is equal to the concentration of B in g/cm3 divided by the density of polymer — ρB (vB = c/ρB ). The excluded volume eﬀect disappears in a theta solvent and as a result the osmotic pressure data slope will be zero in a theta solvent. the second virial coeﬃcient is: A2 = 1 V A ρ2 B 1 −χ 2 or A2 = M0 ρB 1 −χ 2 (5. The osmotic pressure is then π RT RT = + c VA xρB V A ρ2 B 1 − χ c + ··· 2 (5. Although working in theta solvents would simplify data analysis (i. gives the second virial coeﬃcient We return now to the slope of the linear ﬁt of π/c vs.5. plots of π/c vs. It is usually more convenient to work in good solvents and make use of extrapolation techniques. however. is a useful method for determining theta solvent conditions. When χ is large and negative. give results that obey ideal solution laws) the fact that theta solvents are poor solvents makes working with them diﬃcult. Then π/c becomes RT π = 1 + Γ2 c + gΓ2 c2 2 c MN (5.
It is the type of osmometer used to get the data that will be given to you in a lab. etc. but two gives more area and faster equilibration). Because g must be positive and a polymer cannot be more impenetrable than hard spheres. Block osmometers are called static osmometers because they wait for the natural development of equilibrium. The solution is placed in a cell with membranes on either side (one or two membranes. We can simplify the process by introducing some theoretical calculations about g.74 CHAPTER 5. g has been estimated to be g = 0. For polymer molecules. π/c vs.25.46) When g can be assumed to be 0. The actual value of g depends on various properties such as the expansion coeﬃcient α.25. the membrane can be made larger. For hard spheres. The heights of the liquids in the capillaries are read and the height diﬀerence gives the osmotic pressure. The choice of g = 0. the characteristic ratio. 5. The slope will give Γ2 The advantage of setting g = 0.28.3. Fortunately it has been found that the results are not very sensitive to the exact value of g.25. g must be between 0 and 5/8.25 to 0. This advantage was important before computers were readily available. g can be calculated to be g = 5/8. especially scientists that worked before computers. with larger membrane area equilibrium will be reached sooner. Now we can easily treat g as a second parameter and do a two parameter ﬁt to the data. By supporting the membrane. This apparatus is called a block type osmometer. a plot of and the intercept will give RT /MN . You will try this type of analysis in one of the class labs and be able to discuss whether the added complexity improves or weakens the interpretation of the results. COLLIGATIVE PROPERTIES We now have two parameters — Γ2 and g. we will assume g = 0. 5. Fortunately. g is restricted to a relatively narrow range for most polymers. like linear theories): π RT = c MN 1 1 + Γ2 c + Γ2 c2 4 2 or π = c RT MN 1+ Γ2 c 2 (5. Because polymers have g’s calculated to be near 0. If we pick a value for g than we are left with only one parameter (Γ2 ) and we calculate MN and Γ2 by simpler curve ﬁtting analyses.25 is desirable because it completes the square and the data analysis can again be done by linear ﬁts (Scientists. The membrane is supported by stainless steel plates with holes. This osmometer uses a small cell and a large membrane. Deriving two parameters for osmotic pressure data will be more complicated than deriving the slope and intercept of simple linear ﬁts. The problem with static osmometers is that it can take hours (1224 hrs) to reach . however. It requires more advanced curveﬁtting techniques. The entire assembly is then immersed in pure solvent. c should be linear.25 is that the data can be analyzed with a simple linear ﬁt..6 Experimental Aspects of Membrane Osmometry A simple type of osmometer is illustrated in Fig.
000 g/mol or more. Perhaps the most common membrane material is gel cellulose. unfortunately. This quick method. Note that we really require all polymers to be above 20. This requirement limits the lowend applicability of osmometry to MN of 20. To quicken osmotic pressure experiments. polydisperse polymers probably require MN greater than about 50. The pressure required can be used to get the equilibrium osmotic pressure. static osmometer.000 g/mol. . for monodisperse polymers it might be possible to go down to 20. When you apply enough pressure to stop the ﬂow you have artiﬁcially reached equilibrium.3: A block type.000 g/mol otherwise the low molecular weight tail will pass through membrane and the measured MN will be too high (do you see why it would be too high?).5. EXPERIMENTAL ASPECTS OF MEMBRANE OSMOMETRY 75 Capillaries Outer flange Membrance Inner flange Solution cell Outer flange Exploded View SIDE VIEW FRONT VIEW Figure 5. The time depends on many factors such as the membrane area and the speed of transport through the membrane.6. There are also some material concerns for the membrane. an accurate equilibrium. By applying a pressure it is possible to do the same thing. You will know when you have applied the correct pressure by monitoring ﬂow across the membrane. we make a few comments about what makes a good semipermeable membrane.000 g/mol. is less accurate. The membrane must be permeable to solvent and impermeable to polymer. Finally. dynamic osmometers are sometimes used. An obvious concern is that the membrane not be soluble in the solvent. Therefore. Recall that osmotic pressure develops for the purpose of raising the activity of the solvent in the solution to 1.
b.28 0.47) where wi is the weight fraction of polymer with molecular weight Mi and M0 is the monomer molecular weight. The measurement of boiling point elevation is not very useful for ﬁnding the molecular weight of high molecular weight polymers.521 0. If boiling point elevation was given instead by the formula in part a. cellulose nitrate. Problems 5–1.275 (π/c) versus c sometimes used rather a. and poly(chlorotriﬂuoroethylene). In analyzing osmotic pressure data why is a plot of than a plot of (π/c) versus c? 5–2.10 5–3. h (cm of HCCl3 ) 2. The density of HCCl3 is 1. The following are data from osmotic pressure measurements on a solution of polyester in chloroform at 20◦ C.008 0. The results are in terms of centimeters of solvent. what molecular weight average could by found from boiling point elevation measurements and give a formula for calculating that molecular weight average.76 CHAPTER 5.17 0. Plot π/c versus c and ﬁnd MN under the assumption that you can neglect terms beyond the second virial coeﬃcient.57 0. cellulose acetate.48 g/cm3 . COLLIGATIVE PROPERTIES Other membranes include cellulose hydrate. By this law. would it be a more or less useful approach to ﬁnding the molecular weight of high molecular weight materials? .829 1. c (g/dl) 0. polyurethanes. Suppose that in a diﬀerent universe that the boiling point elevation was given instead by ∆Hvap ∆Tb wB MB 1 = = 2 M0 M0 R∆Tb wi Mi i (5.
1 is γ= du dy (6. ˙ The viscosity of the liquid is the ratio of the applied shear stress to the resulting strain rate (or equivalently.2) where vx is velocity in the x direction. viscosity techniques are very valuable. is less precise. By measuring the solution viscosity we should be able to get an idea about molecular weight. They are. molecular weight) of the dissolved polymer. The relations between viscosity (η).Chapter 6 Viscosity 6. Therefore the measured molecular weight depends on the solvent used. Viscosity techniques are very popular because they are experimentally simple. the viscosity average molecular weight. The shear strain in Fig. Despite these drawbacks. however less accurate and the determined molecular weight.1) where u is displacement in the x direction.1 Introduction Viscosity of a polymer solution depends on concentration and size (i.2 Viscosity and Viscosity Nomenclature Figure 6.e. This chapter discusses the theory and methods for determining polymer molecular weight by measuring solution viscosity 6.. the ratio of the shear stress required to move the solution at a ﬁxed strain rate to that strain rate). and shear rate (γ) are ˙ τ = ηγ ˙ or γ= ˙ 77 τ η or η= τ γ ˙ (6. shear stress (τ ). The strain rate is therefore γ= ˙ d du dvx d du = = dt dy dy dt dy (6. For example. 6.3) . Mv depends on a parameter which depends on the solvent used to measure the viscosity.1 shows a piece of a liquid moving at a strain rate γ under an applied shear stress of τ .
shear rate for Newtonian and nonNewtonian ﬂuids are given in Fig. the shear stress/strain rate relation is not linear.5) (6. The most common solution viscosity terms are: 1.2. Plots of shear force vs. ˙ A Newtonian ﬂuid is one in which the viscosity is independent of the shear rate. Speciﬁc viscosity ηsp = 3.4) η − η0 = ηr − 1 η0 ln ηr c ηsp c (6.78 CHAPTER 6. Several methods exist for characterizing the solution viscosity. the possibility of experimental results being aﬀected by the shear rate of the measurement should be kept in mind. In other words a plot of shear stress versus shear strain rate is linear with slope η. In Newtonian ﬂuids all the energy goes into sliding molecules by each other. Intrinsic Viscosity [η] = lim c→0 η η0 (6.7) . That capacity is quantiﬁed by using one of several diﬀerent measures of solution viscosity. the capacity of the solute to increase the viscosity of the solution. 6. Although the following development will not discuss shear rate eﬀects in detail. Typically the viscosity drops at high shear rates — a phenomenon known as shear thinning.6) (6. We let η0 be the viscosity of the pure solvent and η be the viscosity of a solution using that solvent. or more speciﬁcally. In nonNewtonian ﬂuids. Inherent Viscosity ηi = 4. VISCOSITY τ= F A F • dγ γ= dt γ Figure 6.1: A piece of a liquid moving at shear rate γ under an applied shear stress of τ . Relative viscosity ηr = 2.
η0 is viscosity of the pure solvent. Like ηsp . even for an ideal solution.8) We can thus ﬁnd [η] be extrapolating either ηsp /c or ηi to zero concentration. and c is concentration. The extrapolated value of ηsp /c at zero concentration is known as the intrinsic viscosity — [η]. .2: Schematic plots of shear force vs. The remaining form for the viscosity is the inherent viscosity. it will probably be useful to extrapolate to zero concentration. VISCOSITY AND VISCOSITY NOMENCLATURE 79 NonNewtonian Shear Force Shear Force Newtonian Shear Rate Figure 6. ln ηr is zero for pure solvent and increases with increasing concentration. but ni will depend on concentration.e. In ideal solutions ηsp /c will be independent of concentration. This can be proved by: ln (1 + ηsp ) ηsp ln ηr = lim = lim = [η] c→0 c c→0 c→0 c c lim (6. Relative viscosity is selfexplanatory. Normalizing ln ηr to concentration or ln ηr /c gives the inherent viscosity In the limit of zero concentration. shear rate for Newtonian and nonNewtonian ﬂuids. thus ln ηr also expresses the incremental viscosity due to the presence of the polymer in the solution. Speciﬁc viscosity expresses the incremental viscosity due to the presence of the polymer in the solution. When c is not equal to zero the speciﬁc viscosity and inherent viscosities will be diﬀerent. η is solution viscosity. As with other polymer solution properties.. the incremental viscosity per unit concentration of polymer. In these equations. ηi extrapolates the same as ηsp /c and becomes equal to the intrinsic viscosity. Normalizing ηsp to concentration gives ηsp /c which expresses the capacity of a polymer to cause the solution viscosity to increase. i. As with osmotic pressure. the solutions used for viscosity measurements will be nonideal and therefore ηsp /c will depend on c.2.6. [η] will be shown to be a unique function of molecular weight (for a given polymersolvent pair) and measurements of [η] can be used to measure molecular weight.
80 CHAPTER 6.13) Vη L nB M V η L = 2. we get ηsp = 2. VISCOSITY 6. which is trivial because ηsp /c is independent of c. and V is the total volume.5 NB Vη V (6.12) c M This result is for an ideal solution. probably assume that Vη is be proportional to rootmeansquared radius cubed — yet unknown proportionality constant we have Vη = Q 3 3 2 r2 3 3 .5c V M M (6.16) . His result is ηsp = 2.5LQ. the intrinsic viscosity of an ideal solution is [η] = lim ηsp Vη = 2. Writing Q for the as r2 . Because a polymer is not a hard sphere.9) where NB is the number of particles (hard spheres).10) We begin with a monodisperse polymer solution with concentration c = nB M/V where M is molecular weight.5 or ηsp Vη = 2.14) where Φ = 2.5 nB Vη L V (6.11) For a hard sphere we could take Vη to be the volume of that sphere or equal to 4πr3 /3.15) In a theta solvent the expansion factor is 1 (α = 1) and the above equation tells us that [η] is proportional to the square root of molecule weight and the 3/2 power of r2 0 /M [η] = Φ r2 0 M 3 2 M2 1 (6. Letting moles of polymer be nB = NB /L. we will use Einstein’s theory and assume each polymer to be a hard sphere with Vη equal to some eﬀective hydrodynamic volume.5L c→0 c M (6.3 Viscosity Theory Einstein derived the speciﬁc viscosity for a dilute solution of hard spheres. Vη is the hydrodynamic volume of each sphere. we do not have so simple a result. For a ﬁrst approximation to polymer solutions. We can. We can rewrite ηsp as ηsp = 2. We see that ηsp /c in an ideal solution is independent of concentration.5L (6. Lumping the proportionality 3 2 constant along with other constants in the above equation results in: r2 2 [η] = Φ =Φ M r2 M M =Φ 1 2 r2 0 M M 2 α3 1 (6. however. In the last step of the above equation we rewrote the rootmeansquared endtoend distance using the expansion factor α and the unperturbed endtoend distance: r 2 = α2 r 2 0 (6. Extrapolating to zero concentration.
. Values of a are typically between 0. Cn = K Φ 2 3 Mb l2 (6. which in turn can be used to give a direct measurement of the characteristic ratio. These types of experiments were used to check early work on the conformations of polymers and calculations of endtoend distances. Inserting this result into the previous result gives Cn in terms of K and Φ. We get in the simplest form [η] = KM 2 where K is a constant.66 × 1021 (when r is in cm and [η] is in dl/g). the result is r2 0 M K Φ 2 3 1 (6. Thus r2 0 /M is a constant for a particular polymer that is independent of molecular weight. For polymers in nontheta solvents.52.5 represents near theta solvent conditions. Close to 0.19) where Mb is the molecular weight per bond or M/n.5 and 0. nl2 .21) where α may have molecular weight dependence of its own. It is usually acceptable to treat nontheta solvent results by lumping the molecular weight dependence of α into one molecular weight term to get [η] = KM a (6.20) The viscosity constant Φ can be evaluated from theory. For polymers it is typically assumed to be 2. both r2 0 81 and M are proportional to the number of bonds or n. The polymer size is determined by the ratio of the meansquared unperturbed endtoend distance and its molecular weight. Farther away from 0. VISCOSITY THEORY But.22) where a is some constant that depends on the polymersolvent pair and on temperature.3. The characteristic ratio can thus be written as Cn = r2 0 nl2 or Cn = r 2 0 Mb M l2 (6. Therefore a measurement of [η] for a polymer of known molecular weight in a theta solvent will give K.8. α will no longer be one and we lose the squareroot dependence of [η] on molecular weight.17) = (6. We instead have [η] = KM 2 α3 1 (6.6. In terms of K and Φ. r2 0 . to the freelyjointed chain meansquared length.5 represents large deviations from a theta solvent.18) Recall that characteristic ratio is deﬁned as the ratio of the meansquared endtoend distance.
it is related to molecular weight through two unknown constants — K and a. To avoid errors resulting from the type of average molecular weights determined by osmotic pressure or viscosity experiments.e. 6. however..4 Viscosity Experiments It is usually not convenient to work in theta solvents. The key experimental property is intrinsic viscosity — [η].1 Polydisperse Polymers We next consider experiments on polydisperse polymers. We note that this viscosity technique for measuring molecular weight is not an absolute technique as was osmotic pressure. VISCOSITY 6. We can. Once [η] is known.82 CHAPTER 6. You measure [η] by measuring ηsp at several diﬀerent concentrations and extrapolating to zero concentration (we will discuss the extrapolation further below). accurate calibration experiments should be done with monodisperse polymers.4.. How do we use viscosity experiments to measure an average molecular weight? What sort of average molecular weight do we measure? We cannot be as rigorous as we were for osmotic pressure on polydisperse polymers. The molecular weights might be known by some other experimental technique such as osmotic pressure experiments.23) (6. We make the following three assumptions 1. K and a are independent of molecular weight.e. each molecular weight of the polymer). ηsp = i (ηsp )i (6. The third assumption says that the relation between intrinsic viscosity and molecular weight is independent of molecular weight. K and a can be measured by measuring [η] on a several batches of that polymer with diﬀerent. log M will easily give K and a for that polymersolvent pair. 3. Once K and a are known. Many K’s and a’s for common polymersolvent pairs can be found in handbooks of polymer science.25) (ηsp )i = [η]i ci [η]i = KMia The ﬁrst assumption says that the total speciﬁc viscosity is the sum of the speciﬁc viscosities for each components (i. Plotting log [η] vs.24) (6. make some reasonable assumptions and get a reasonable result. These constants must have been previously determined by a calibration experiment. For a particular polymersolvent pair. a measurement of [η] on a polymer of unknown molecular weight can be used to measure the molecular weight. i. molecular weights. We thus next discuss how to use viscosity experiments in nontheta solvents to measure molecular weight. 2. and known. . It requires calibration experiments using samples with known molecular. The second assumption says that the speciﬁc weight of each component can be calculated from the intrinsic viscosity due to that component.
The experiments are simple and can all be down with a relatively simple and relatively inexpensive piece of glassware called a viscometer (see Fig. The result can be found in many ﬂuids books. If we ignore kinetic energy terms. Flow of a Newtonian ﬂuid through a capillary is relatively easy to analyze.3). a certain volume of liquid depending on the volume of the viscometer).27) where Mv = (6.e.28) Mv is known as the viscosity average molecular weight (for obvious reasons). the time is proportional to the solution viscosity through the following relation: η= 4 πrc ∆P t = Aρt 8Vf L (6. The experiment is to measure the time it takes the liquid to ﬂow from point A to B. VISCOSITY EXPERIMENTS Using the above three assumptions we derive ηsp = c a i Kci Mi 83 c = iK Ni Mi a V Mi Ni M i i V = 1+a i KNi Mi i N i Mi (6.29) where rc is the radius of the capillary.2 Experimental Procedures We next discuss the experimental procedures and the equipment used to measure solution viscosity. and L is the length of the capillary..e.4.5 to 0. the volume between points A and B).. MW . When a = 1.26) Assumption two implies we are considering the limit of zero concentration. 6. The experiment is to ﬁll the viscometer such that the level on the left side is at point C and the level on the right side is at point A (i. Because of the height diﬀerence between C and A (h). The physical constants of the viscometer can be then lumped into a single constant denoted above as A.4. For typical a’s (0. This result is to be expected because viscosity properties are expected to be a function of size and not just the number of polymers. When ﬂowing due to gravity only in a tube of length h. 6. Vf if the volume of liquid that ﬂows (i. Thus we remove the constant K from the summation terms and state the zeroconcentration limit to get lim ηsp a = KMv c 1+a i N i Mi i N i Mi 1 a c→0 (6. otherwise Mv is between the weight average molecule weight and the number average molecule weight.8). In other words the time it takes the volume of liquid between A and B to ﬂow through the capillary. Mv is closer to MW .6. there is a hydrostatic head or driving pressure to cause the liquid to ﬂow through the capillary or narrow diameter section of the viscometer. Mv is equal to the weight average molecule weight. If A is . ∆P = ρgh where ρ is the solution density. ∆P is pressure diﬀerence. MN ≤ Mv ≤ MW .
In this case it is important to correct for kinetic energy. In practice. The result with kinetic energy is η = Aρ t − B At (6. Dust particles can add to the solution as hard spheres with a large hydrodynamic volume. For most accurate results. A clean tube also means a tube that is free from dust particles. A more accurate calculation of solution viscosity in terms of ﬂow time would account for kinetic energy of the moving liquid. First. It is then a simple matter to calculate relative viscosity and speciﬁc viscosity by comparing the ﬂow time of the solution. VISCOSITY A B h h Capillary C Figure 6. which is proportional to 1/t.84 CHAPTER 6. gets small. t0 : ηr = t t0 and ηsp = t − t0 t0 (6. known for a particular viscometer. a measurement of ﬂow time and solution density can be used to determine solution viscosity. Physically the liquid is moving slowly and has little kinetic energy.31) . it is permissible to ignore the kinetic energy terms. especially when working with very dilute solutions. t. it is simplest to use long ﬂow times and ignore the kinetic energy term. the viscometer must be clean. Any contamination from previous solutions might add to the current solution and change its viscosity. to the ﬂow time of the pure solvent.3: Simple viscometer. When t > 100 seconds. it is best to choose a viscometer such that the ﬂow time is greater than 100 seconds. They can increase the solution viscosity and aﬀect the results.30) where B is a constant. If the ﬂow is slow (t is large) the kinetic energy term. there are several important considerations. the liquid is moving fast and there can be signiﬁcant kinetic energy. If the ﬂow occurs rapidly (t is small). Third.
4. is to keep the relative viscosity less than 2. You thus select a viscometer to give good ﬂow times in the expected viscosity range for your solutions. The simplest approach is to do a simple linear extrapolation: ηsp = [η] + kc c (6. An alternate technique is to extrapolate inherent viscosity or ln ηr /c to zero concentration to get [η]. ηsp will get small. In other words d ηsp c dc = k [η]2 (6.36) . k . If k is not known. the typical viscosity experiment is to measure ηsp /c at several concentrations and do a linear extrapolation to zero concentration to get [η]. c curve. k. Therefore once k is known. is a function of the polymer/solvent/temperature of the system.32) Experience shows that a linear extrapolation works well as long as ηr is restricted to less than 2. The smaller the capillary. VISCOSITY EXPERIMENTS 85 To adjust ﬂow times. a single relative viscosity measurement at one concentration can be used to get the viscosity average molecular weight. but is independent of molecular weight. Huggins found that a plot of k versus [η]2 was linear and passed through the origin. As we approach zero concentration.35) (6. depends on molecular weight of the polymer. viscometers are available with diﬀerent radius capillaries. With known K and a. With known K and a. the measured [η] gives Mv or the viscosity average molecular weight. therefore. the measured [η] gives Mv . Measuring ηr leads to ηsp /c which using k gives [η] 2. the longer the ﬂow time. Experimental results with polymer solutions has revealed that the slope of the ηsp /c vs.34) The new constant.33) Integrating this empirical result gives the Huggins’ equation: ηsp = [η] + k [η]2 c c (6. The following steps are used: 1. we are faced with the problem of how to extrapolate. Using the approximation for small x of ln(1 + x) ≈ x − x2 /2 we can derive ln ηr = ln (1 + ηsp ) ≈ ηsp − Then 2 ηsp ηsp ln ηr ≈ − 2c c c 2c 2 ηsp 2 (6. As with osmotic pressure. To measure intrinsic viscosity requires extrapolation of ηsp /c to zero concentration.6. Another consideration for viscosity experiments.
VISCOSITY ηsp c [η] ln ηr c Concentration Figure 6.4. this result gives: ln ηr [η]2 c k 2 [η]4 c3 ≈ [η] + k [η]2 c − − k [η]2 c2 − c 2 4 Neglecting higher order terms of order c2 or higher gives ln ηr 1 ≈ [η] + k − c 2 [η]2 c = [η] + k [η]2 c (6. and [η] all have units of 1/concentration (e. the extrapolation to zero concentration will also depend on shear rate.4: Typical plots of ηsp /c and ln ηr /c as a function of concentration. Typical plots will resemble the curves in Fig. c will both be linear and both extrapolate to [η] at zero concentration. ln ηr /c. Because [η]2 c also has units of 1/c.. Plotting of both types of data will often give a good feeling for the accuracy of the extrapolated intrinsic viscosity. 6. k . will be diﬀerent.86 CHAPTER 6. The terms ηsp /c. This diﬀerence in signs makes plots of both types of data useful. c and ln ηr /c vs. k and k are dimensionless. Likewise. To remove shear rate eﬀect it is sometimes necessary to get [η] at several shear rates and do a second extrapolation of [η] to zero shear rate. The new constant. c should be linear with slope k [η]2 and intercept [η]. The two types of plots converge on the same intrinsic viscosity but from diﬀerent directions — one has a positive slope and the other a negative one. however. The curves extrapolate to the same [η] at zero concentration. but approach zero concentration with diﬀerent slopes. For many polymers k ≈ 1/3 which makes k ≈ −1/6. A high intrinsic viscosity probably means that the viscosity depends on the shear rate of the test.38) (6. The zero shearrate . The slopes of the two plots. Using Huggins’ equation. is related to k by k = k − 1/2.37) Thus a plot of ln ηr /c vs. We see that plots of both ηsp /c vs. One ﬁnal complication arises if [η] is large.g. a common convenient unit is deciliters per gram — dl/g).
Known K.5. The melt index test measures the mass of material that ﬂows through a standard . but standardized method of estimating melt viscosity is called the melt index. Known K and a. Although this situation requires more work than using a known k (or k ). it is less prone to uncertainties in the tabulated values of k (or k ). then measurement of η0 and η at one concentration will lead directly to Mv . Relative molecular weights are often enough. and Mv . 4.5 Viscosity Summary In summary. or k ) will be known. These results can be used to linearly extrapolate ηsp /c and ln ηr /c to zero concentration to get [η] which will lead to Mv . Insoluble polymer: Solution viscosity techniques assume that you can dissolve the polymer in some solvent. For such polymers it is often possible to measure the zero shearrate viscosity of the polymer melt. MW . No constants known: If you are working with a new polymer or an unusual solvent. Obviously the techniques cannot be used with polymers that cannot be dissolved in any solvent. Many of these constants are tabulated for common polymers.6. k (or k ): If all these constants are all known. a. 6. The higher the value of [η]. osmotic pressure or light scattering). For such polymers you can still measure [η] by extrapolating ηsp /c and ln ηr /c to zero concentration. The calibration experiments will require monodisperse polymers whose molecular weight has been absolutely determined by some other method (e. When these constants are not known.. A crude. Thus when you are working with common polymers it is relatively easy to get a good estimate of molecular weight. k . you can compare values of [η] from the same polymer/solvent pair to get relative molecular weights. 3. Although you cannot use [η] to determine molecular weight. VISCOSITY SUMMARY 87 intrinsic viscosity is the intrinsic viscosity that should be used in molecular weight calculations. the higher the molecular weight. The use of monodisperse polymers avoids problems of diﬀerences in MN . it is less prone to errors. but there is less data about k (or k ). the measured value of [η] at some nonzero shear rate can probably be assumed to be a good estimate of the zero shearrate viscosity. 2. The zero shearrate melt viscosity increases as the molecular weight increases. If they are not enough it might be useful to do calibration experiments to ﬁnd K and a.g. a. If [η] is not too high. the work you need to do to get useful results from viscosity experiments depends on the prior knowledge you might have about the constants relevant to your particular polymer/solvent pair. We consider four situations: 1. you have to measure η0 and measure η at several concentrations. but unknown k (and k ): Tables of K and a are common. it is likely that none of the constants (K.
. 6–2.50 cm3 /g and a slope of 0. Two “monodisperse” polystyrenes are mixed in equal quantities by weight. where η is the viscosity of the polymer solution at concentration c in g/cm3 and η0 is the viscosity of the pure solvent. The plot is a straight line with intercept of 1. the lower the melt viscosity and thus the lower the molecular weight. Give the magnitude and the units for the Huggin’s constant for this polymersolvent pair. The more material that ﬂows.18 × 10−5 dl/g and a = 0. and hence the higher the melt index.9 cm6 /g2 . it is possible to determine molecular weight of a polymer by doing only two viscosity measurements. What is the intrinsic viscosity of the blend in benzene at 25◦ C.000. One polymer has molecular weight 39. The MarkHouwink constants for polystyrene/benzene at 25◦ C are K = 9. VISCOSITY oriﬁce in a ﬁxed amount of time.74.000 and the other molecular weight of 292.88 CHAPTER 6. With enough predetermined constants for a particular polymersolvent pair. Problems 6–1. What two viscosity measurements are required? What constants for the particular polymersolvent pair are required and how are they used? 6–3. Solution viscosities for a particular polymer and solvent are plotted in the form (η − η0 )/(cη0 ) versus c.
such as osmotic pressure. we expect all light scattering experiments to be done in nonideal solutions. allows you to determining a virial coeﬃcient. This property of light scattering makes it a valuable tool for measuring molecular weight. and the second virial coeﬃcient (A2 or Γ2 ).Chapter 7 Light Scattering 7. Many polymers will violate this criterion and the light scattering ˚ s gyration results will have to be corrected for large particle size eﬀects. light scattering also has a direct dependence on particle size. Besides molecular weight dependence. we mean particles whose size is much less than λ or the wavelength of the light that is being scattered. Classical light scattering theory was derived by Lord Rayleigh and is now called Rayleigh theory. By “much less” we mean s2 < λ/20 (7. light scattering experiments can be used to measure three things: weight average molecular weight (MW ). By small particles. which only depended on number of particles and therefore gave the number average molecular weight. For polymer solutions. we need the root mean squared radius of A A 2 < 200 to 400A. In summary.1 shows light scattering oﬀ a particle in solution or in vacuum. like osmotic pressure.1) Because visible light has λ between 4000˚ and 8000˚. A2 .1 Introduction Figure 7. but. This result contrasts to colligative properties. The intensity of the scattered light depends on the polarizability (to be deﬁned later) and the polarizability depends on the molecular weight. light scattering will depend on weight average molecular weight. Because the intensity of scattered light depends on molecular weight of the particle. As with osmotic pressure. this dependence on size can be used to measure the radius of gyration of the polymer molecule. 89 . meansquared radius of gyration ( s2 ). Nonideality complicates the data analysis. To interpret light scattering experiments. we begin with a discussion of light scattering theories. The incident light scatters in all diﬀerent directions. Rayleigh theory applies to small particles.
Analysis of osmotic pressure experiments requires extrapolation techniques to account for nonideal solutions. Light is an electromagnetic ﬁeld. At the origin the ﬁeld is time dependent and described by: Ez = E0 cos 2πct λ (7. A light scattering theory known as the RayleighGans theory was developed to extend Rayleigh theory to particles that are not optically small. The correction method involves extrapolation techniques that extrapolate light scattering intensity to zero scattering angle. c is the speed of light. the incident electric ﬁeld will induce a dipole moment in that particle.90 CHAPTER 7.2 is polarizable. If the particle at the origin in Fig. LIGHT SCATTERING Scattered Light Incident Light Figure 7. In light scattering there are two nonideal eﬀect — nonideal solutions and large particle size eﬀects. 7.2. analysis or deconvolution of light scattering data requires two extrapolations. This correction technique is important for analyzing results on polymer solutions. Thus. The subscript z on E means we are considering plane polarized light with the light polarized along the z axis. One is an extrapolation to small particle size to remove the large particle size eﬀect. and λ is the wavelength of light. The other is an extrapolation to zero concentration to remove the eﬀect of nonideal solutions.2 Rayleigh Theory We begin by describing the theory for light scattering oﬀ a small particle in an ideal solution. 7. The intercept of the two extrapolations gives the weight average molecular weight (MW ). The slope of the second extrapolation gives the second virial coeﬃcient (A2 ). The magnitude of the dipole moment is proportional to the ﬁeld. An incident beam of light polarized in the z direction is shown in Fig. 7. . The slope of the ﬁrst extrapolation gives the mean squared radius of gyration ( s2 ).2) where E0 is the amplitude of the electric ﬁeld.1: Scattering of incident light oﬀ a particle in solution or in vacuum.
the electric ﬁeld for light scattered in the θz direction is Es = 1 1 1 d2 p 4π 2 c2 2 dt2 = − c2 αp E0 rλ2 sin θz cos rc 2πct λ (7. We consider observing the radiated or scattered light at a distance r from the origin along a line that makes an angle θz with the z axis (see Fig. Thus. RAYLEIGH THEORY 91 z Incident Polarized Light Figure 7. The second derivative of p is the acceleration of the charge on the dipole moment. The intensity of light is equal to the amplitude of the electromagnetic ﬁeld squared.3) The induced dipole moment will radiate light in all directions. squaring the amplitude of Es gives the scattered light intensity at r and θz : 2 Is = αp I0z 16π 4 sin2 θz r 2 λ4 (7. The dipole moment is p = αp E0 cos 2πct λ (7.6) . To include spatial eﬀects. Combining all these eﬀects. The proportionality constant is called the polarizability — αp . 7.3). The higher a particle’s polarizability the higher will be the magnitude of the dipole moment induced by a given electromagnetic ﬁeld. The scattered light ﬁeld will be proportional to (1/c2 )(d2 p/dt2 ). 2 I0z = E0 (7.4) Equipment that measures scattered light is typically only sensitive to the intensity of light.2: Plane polarized light polarized in the z direction and incident on a small particle.7. the scattered light is also proportional to 1/r (electromagnetic ﬁelds die oﬀ as 1/r) and to sin θz (the projection of the dipole moment on the observation direction).5) where I0z is the intensity of the z polarized incident light.2.
Because the sum of the direction cosines is 1: cos2 θx + cos2 θy + cos2 θz = 1 the geometric result is easily derived to be sin2 θz + sin2 θy = 1 + cos2 θ (7.4). The incident intensity becomes 1 1 I0 = I0z + I0y 2 2 and the intensity of scattered light becomes 2 8π 4 αp 1 1 Is = Isz + Isy = I0 2 4 sin2 θz + sin2 θy 2 2 r λ (7. 7. Scattering of unpolarized light is illustrated in Fig. The above results are for incident light polarized in the z direction.7) (7. The observation distance is r. however.4. 7. LIGHT SCATTERING z θz Incident Polarized Light r Figure 7. Experiments.10) (7. are usually done with unpolarized light.92 CHAPTER 7. We can account for unpolarized incident light by summing the intensity of equal parts of incident light polarized in both the z direction and the y direction. This angle will simply be referred to as θ.8) where θy is the angle the observation direction makes with the y axis. the . By geometry the θz and θy terms can be related to the angle θx that the observation direction makes with the x axis (see Fig. For scattering oﬀ n moles of particles or nL particles (L is Avagadro’s number) in a dilute solution of volume V .3: Observation direction for light scattered oﬀ a particle at the origin in a direction that makes an angle θz with respect to the z axis.9) We now have the scattered light intensity for scattering oﬀ a single particle.
7.3. IDEAL POLYMER SOLUTIONS WITH SMALL PARTICLES
93
z
Incident Unpolarized Light θ
Figure 7.4: Scattering of unpolarized light is analyzed by considering scattering of incident light polarized in both the z and y directions.
scattered intensity at θ is: i0 = θ
2 I0 nL 8π 4 αp 1 + cos2 θ V r 2 λ4
(7.11)
The superscript 0 on the i indicates that this is scattering due to small molecules. The light scattering intensity depends on scattering angle. The shape of the diagram is determined by the (1 + cos2 θ) term. A plot of this term is given in Fig. 7.5. The maximum scattering intensity is at θ = 0. The minimum scattering intensity is at θ = 90. The scattering intensity for forward scattering is equal to the intensity for back scattering at the corresponding angle. In other words, the scattering intensity at angle θ is equal to the scattering intensity at angle 180 − θ. As a function of λ, the scattered intensity is proportional 1/λ4 . This strong wavelength dependence makes short wavelength light scatter more than long wavelength light. This eﬀect explains why the sky is blue. Short wavelength or blue light scatters the most. Normally we do not look at the sun and θ is not zero. When θ is not zero you see the scattered light or the blue light. At sunset you normally do look in the direction of the sun and θ is zero or near zero. Because blue light is scattered away, you are left with the red light and sunsets appear red.
7.3
Ideal Polymer Solutions with Small Particles
For practical results, we need to make a connection between the scattering intensity derived in the previous section and molecular weight of the polymer particles in solution. The connection arises because polarizability depends on molecular weight. First, the polarizability can be thought of as
94
1
CHAPTER 7. LIGHT SCATTERING
θ 2 1 0.5 1 2
1
Figure 7.5: Shape of the scattering intensity as a function of scattering angle for scattering oﬀ a small particle.
a diﬀerence in the index of refraction between the polymer and the solvent. In other words light scattering only occurs in mediums that have an inhomogeneous index of refraction. Speciﬁcally, the polarizability of particles at concentration c is αp = n0 cV dn0 2πnL dc (7.12)
where n0 is the index of refraction of the solution and dn0 /dc is the concentration dependence of the index of refraction. Note that if the index of refraction of the solvent and of the polymer are the same then dn0 /dc will be zero and there would be no polarizability and therefore no scattered light. Writing c as nM/V (in units of g/ml) yields αp = n0 M dn0 2πL dc (7.13)
and substituting into the scattered light intensity gives (where we also replace n/V by c/M ): i0 2π 2 n2 θ = 2 4 0 I0 r λ L dn0 dc
2
M c 1 + cos2 θ
(7.14)
In a given scattering experiment, I0 and r will be ﬁxed and we will measure i0 . These measured θ
0 quantities can be combined into one quantity called the Rayleigh ratio — Rθ : 0 Rθ =
r2 i0 θ I0
(7.15)
The advantage of the Rayleigh ratio is that it is independent of the incident light intensity and the distance to the scattered light detector (i.e., independent of I0 and r). From the scattering equation, the Rayleigh ratio can be written as:
0 Rθ = KM c
(7.16)
7.4. NONIDEAL POLYMER SOLUTIONS where
95
2π 2 n2 dn0 2 0 1 + cos2 θ (7.17) λ4 L dc The constant K depends only on the solvent properties, on λ, and on θ. K is therefore a system K= constant that is independent of the concentration of the solution and the molecular weight of the polymer. For a dilute, polydisperse polymer solution, the total Rayleigh ratio can be written as a sum of the Rayleigh ratios for scattering of polymers of each possible molecular weight:
0 Rθ = K i
ci Mi
i N i Mi 2 i N i Mi
(7.18)
or 1 (7.19) MW i ci Mi The Rayleigh ratio for an ideal polymer solution with small particles is thus directly related to the = = weight average molecular weight (MW ). Kc 0 = Rθ
i ci
7.4
NonIdeal Polymer Solutions
As done with osmotic pressure, the possibility of nonideal solutions is handled by adding virial
0 coeﬃcients and concentration terms to the ideal result. Thus expanding Kc/Rθ gives
1 Kc + 2A2 c + 3A3 c2 + · · · 0 = Rθ MW
(7.20)
The virial coeﬃcients A2 and A3 are the same as the virial coeﬃcients we discussed in osmotic pressure theory. The factors of 2, 3, etc., come from the thermodynamic theory of ﬂuctuations which can be used to show that 1 ∂π Kc 0 = RT ∂c Rθ where π is osmotic pressure. In a virial expansion π= RT c + RT A2 c2 + RT A3 c3 + · · · MN (7.22) (7.21)
To convert to the light scattering experiment, the MN in the π expression must be changed to MW . The only diﬀerence between the A2 in osmotic pressure and the A2 in light scattering is that the light scattering A2 is formally a weightaverage virial coeﬃcient. Besides that diﬀerence, the light scattering A2 gives similar information, notably information about the quality of the solvent.
0 Typically, we will ignore terms beyond the second virial coeﬃcient. Then Kc/Rθ is predicted to 0 be linear in c. From experiments we can plot Kc/Rθ as a function of c. The slope will give the second
virial coeﬃcient (slope = 2A2 ) and the intercept will give the molecular weight (intercept = 1/MW ). This extrapolation, however, ignores any possible large particle size eﬀects The extrapolated MW will therefore be in error. The next section considers how to correct for large particle size.
7.5). small particles is given in Fig. i. At θ equal to zero. Because scattered light and transmitted light have the same wavelength. the light can scatter from diﬀerent parts of the particle. The large particle scattering diagram shows the eﬀect of large particles and now shows asymmetry in scattering. At θ = 0 most light will be transmitted light that is not scattered.. At θ not equal to zero there will be destructive interference. these experiments cannot be done. we merely need to do the light scattering experiments at zero scattering angle (θ = 0). To develop an extrapolation method. The transmitted light will swamp the scattered light preventing its measurement. A comparison of the scattering diagrams for large particles vs. P (θ). the interference will increase reaching a maximum and θ = 180◦ . we must do experiments at θ > 0 and extrapolate to θ = 0. The amount of intensity reduction or the amount of destructive interference depends on the scattering angle. that describes the large . there will be no destructive interference. Fig.5 Large particles If a particle is not small compared to the wavelength of light. the back scattering intensity is much reduced from the forward scattering intensity. To correct for large particles. As θ θ increases. The diﬀerence in path lengths can lead to destructive interference that reduces the intensity of the scattered light. 7.96 CHAPTER 7. Instead.e. 7. Light scattering from diﬀerent parts of the particle will reach the detector by traveling diﬀerent path lengths. The net eﬀect is that the scattering diagram for large particles is reduced in intensity from the scattering diagram for small particles (see Fig. the path lengths will always be identical. LIGHT SCATTERING Scattering from different parts of the particle Path length difference causes destructive interference Figure 7.6 shows a large polymer that is scattering light. Unfortunately. we deﬁne a new function.6: Scattering of light of two diﬀerent parts of a large polymer molecule. the intensity of scattered light will be identical to i0 . 7.7. We thus do a second extrapolation. In other words at θ = 0. With identical path lengths. there is no way to distinguish between them. an extrapolation to zero scattering angle.
That information can sometimes be derived by theoretical analysis of largeparticle scattering. Those terms are normally assumed to be negligible. The larger eﬀect on back scattering than on forward scatter means that P (θ < 90) > P (180 − θ). First consider an ideal solution. Fortunately. some theoretical results are available for scattering oﬀ a large random coil. includes the large 0 particle size eﬀect.5.5 1 2 97 1 Figure 7. Instead of requiring s2 < λ/20 as done before for small particles.7: Scattering diagrams for both small particles and large particles. particle size eﬀect. P (θ) is the ratio between the actual scattering (iθ ) and the scattering that would occur oﬀ small particles (i0 ) θ P (θ) = Rθ iθ 0 = R0 iθ θ (7. LARGE PARTICLES 1 Small Particles Large Particles θ 2 1 0.7. Most polymers fall within or below this range and thus we A A can derive eﬀective extrapolation methods for scattering oﬀ polymer molecules. For a polydisperse polymer. The results are accurate as long as the particle size is not too large. The measured Rayleigh ratio. For scattering with visible light we now can use s2 < 2000˚ to 4000˚.24) The second equality follows from the previously derived ideal solution result with small particles. we need some information about P (θ).23) From the above discussions we know that P (0) = 1 (there is no eﬀect at zero scattering angle) and P (θ) < 1 for all other θ (destructive interference can only cause a reduction in intensity). we can use the theoretical result to handle particles with s2 < λ/2. To use this equation. Using P (θ) we can write Rθ = P (θ)Rθ . written as Rθ . the scattering intensity as a function of scattering .25) The “· · ·” means that there are higher order terms in sin(θ/2). The key measured quantity becomes 1 Kc Kc = 0 = Rθ P (θ)Rθ MW P (θ) (7. The theoretical result for P (θ) is 1 16π 2 2 θ =1+ s sin2 + · · · 2 P (θ) 3λ 2 (7.
The intercept will give the molecular weight: intercept = 1 MW (7. Inserting the theoretical result for P (θ) truncated after the sin2 (θ/2) term gives Kc = Rθ 1 + 2A2 c MW 1+ 16π 2 2 s 3λ2 w sin2 θ 2 (7. we do two extrapolations. plotting Kc/Rθ as a function of sin2 (θ/2) at constant c gives a straight line with the following slope and intercept: slope = intercept = 1 + 2A2 c MW 1 + 2A2 c MW 16π 2 2 s 3λ2 w (7. Instead of using P (θ) to correct the ideal solution result.30) where we have truncated the nonideal solution result to a single virial coeﬃcient.31) A set of light scattering experiments consists of measure Kc/Rθ for various concentrations and at various scattering angles. we truncate 1/P (θ) after the sin2 (θ/2) term and plot Kc/Rθ as a function of sin2 (θ/2). Thus the actually measured Kc/Rθ is Kc Kc = 0 = Rθ P (θ)Rθ 1 + 2A2 c MW 1 P (θ) (7. First.27) i is the average squared radius of gyration for polymers with molecular weight Mi To ﬁnd weightaverage molecular weight (MW ) in ideal solutions. we use it to correct the nonideal solution result. First.26) the weight average radius of gyration squared. we need to do two extrapolations.33) .28) The slope divided by the intercept will give the radius of gyration slope/intercept = 16π 2 s2 3λ2 w (7.6 Light Scattering Data Reduction To handle both nonideal solutions and large particle eﬀects.32) (7. That plot should be linear. CHAPTER 7. the relevant radius of gyration squared is s2 where s2 w = i N i Mi s2 i N i Mi i = i wi s2 i (7. To get MW .98 angle becomes Kc 1 = Rθ MW Note we have changed s2 to s2 w. we introduce nonideal solution eﬀects into the large particle analysis in the previous section. LIGHT SCATTERING 1+ 16π 2 2 s 3λ2 w sin2 θ 2 (7.29) 7. In terms of the various polymer weights.
In the Zimm plot technique. (7. Next we plot the intercepts of the ﬁrst plots as a function of concentration. you plot Kc/Rθ versus sin2 (θ/2) + kc where k is a constant.34) (7. Both these conditions are easy to satisfy for light scattering with polymer solutions. 7. Plotting all Kc/Rθ points on a Zimm plot should result in a grid such as the one shown in . Substituting these results into the We could achieve similar results by ﬁrst plotting as a function of concentration and then plotting the intercept of those plots as a function of sin2 (θ/2). For example sin2 (θ/2) is always less than 1 or has a maximum of 1.8: Typical Zimm plot. The analysis method described above is easy to do in a personal computer. computers were not available and the numerous linear ﬁts were tedious. LIGHT SCATTERING DATA REDUCTION 99 c4 c5 c2 c3 θ6 c=0 c1 θ5 Kc Rθ θ=0 θ4 θ3 θ2 θ1 sin2 θ + kc 2 Figure 7.7. The above analysis assumes that all c’s are low enough such that the concentration dependence is linear in concentration and only requires the second virial coeﬃcient.6. The range in kc should also go from 0 to 1 or kcmax = 1 which means a good k might be 1/cmax where cmax is the maximum concentration used. A typical Zimm plot is given in Fig. The resulting plot should be a straight line with slope = 2A2 1 intercept = MW slope of the ﬁrst line allows us to ﬁnd s2 w. When light scattering techniques were ﬁrst developed. It also assumes all scattering angles are low enough that terms higher than the sin2 (θ/2) can be neglected. To avoid the tedium the Zimm plot was developed. The experimental data points are at the grid intersection points except along the θ = 0 and c = 0 lines. k is chosen to spread out the plot and give equal weights to each variable. however.8.35) The slope and intercept of the second line gives us MW and A2 .
. Incorporating the k constant. etc. There will be experimental points at all grid points except along the lower line (the θ = 0 line) and the leftmost line (the c = 0) line. are lines at constant concentration. are lines at constant θ. The slopes of the constant θ w. The lines labeled θ1 . 7.8. it is possible to get Zimm plots that w are inverted from the plot in Fig.8. The slopes of the constant c lines are mostly sensitive to s2 w are independent physical quantities. Inspection of the Zimm equation shows that the slopes of these lines are: slope of the contant θ lines = 2A2 k 1+ 16π 2 2 s 3λ2 sin2 θ 2 (7. Inspection of the Zimm equation shows that the slopes of these lines are: slope of the constant c lines = 1 + 2A2 c MW 16π 2 2 s 3λ2 w (7.100 CHAPTER 7. The lines labeled c1 . Connecting all the grid lines and extrapolating to the lowerleft corner. If A2 increases and/or s2 decreases. the intercept point gives the molecular weight (intercept = 1/MW ).37) w Notice that these slopes are a function of θ. it is possible for the steeper lines to be the constant θ lines and for the shallower lines to be the constant c lines. c2 . Thus the slope of the θ = 0 line and the θ5 (or any θi line) are diﬀerent. In other words the Zimm plot is not actually a parallelogram. lines are mostly sensitive to A2 .. The slopes of constant θ and constant c lines both depend on A2 and on s2 Because A2 and s2 w. . Thus the slope of the c = 0 line and the c5 (or any ci line) are diﬀerent. 7. In other words the Zimm plot is not actually a parallelogram. θ2 .36) The slopes of the two directions in the parallelogram have physical meaning. etc.38) Notice that these slopes are a function of c. LIGHT SCATTERING Fig. the Zimm plot is plotting Kc = Rθ 1 2A2 + kc k MW 1+ 16π 2 2 s 3λ2 w sin2 θ 2 (7.
At the end there is a short discussion about polymers that cannot be dissolved into any solvent. porous glass or highly crosslinked polystyrene).2 Gel Phase Chromatography Gel phase chromatography is also called size exclusion chromatography. The beads are selected such that the size of its pores are in the range of the sizes of polymer molecules. As a function of time (or as a function of total volume that has eluted — the elution volume) the elution fraction will be more concentrated in increasingly lower molecular weight 101 . This chapter brieﬂy describes a few more techniques. The ﬁrst fractions will be more concentrated in high molecular weight polymer. Figure 8. The smaller molecules are able to get into the pores and thus they follow a path that sometimes travels through the ﬁller particles.g.1 illustrates what happens when a dilute polymer solution is introduced into the column. Because passage through a ﬁller particle presents a more tortuous path. 8.1 Introduction The previous three chapters described several methods for determining the molecular weight. The larger molecules do not ﬁt into the pores and thus they take the easier and faster route around the ﬁller particles and out the bottom of the column. In gel phase chromatography.Chapter 8 Miscellaneous Molecular Weight Methods 8. or an average molecular weight for a polymer dissolved in solution.. the reason for this second name will become apparent shortly. the smaller molecules spend more time in the column before coming out the bottom. A typical gel phase chromatography experiment consists of collecting elution fractions as they elute from the bottom of the column. a standard chromatographic column is ﬁlled with beads of a rigid porous gel (e.
102
CHAPTER 8. MISCELLANEOUS MOLECULAR WEIGHT METHODS
Figure 8.1: Schematic drawing of a gel phase chromatographic column. The line represents a path of a polymer. The solution that comes out the bottom can be collected in ﬂasks.
polymer. By many means (e.g., absorption spectroscopy or index of refraction) it is possible to determine the concentration of polymer in each fraction. Plotting these concentrations as a function of time or elution volume will give the complete molecular weight distribution (see Fig. 8.2). Because high molecular weight fractions come out ﬁrst, the plot of raw data will be a mirror image of the molecular weight distribution. Like viscosity experiments, the results from gel phase chromatography experiments are not absolute. You need a calibration experiment to convert the concentration data versus elution volume to concentration data versus molecular weight or true molecular weight distribution. The calibration procedure typically uses calibrated viscosity experiments. From the viscosity theory (see Chapter 6), the intrinsic viscosity is r2 M
3 2 1
[η] = Φ
M2 =Φ
r2
3 2
M −1
(8.1)
where Φ is a constant (relatively ﬁxed for polymer solutions), r2 is the mean squared endtoend distance of the polymer (hence ( r2 )3/2 is proportional to total volume of the polymer), and M is molecular weight. This equation can be rearranged to give [η]M = Φ r2
3 2
(8.2)
Because Φ is a relatively polymerinsensitive constant and ( r2 )3/2 merely expresses volume, a plot of [η]M as a function of any property that depends only on polymer volume should produce a
8.2. GEL PHASE CHROMATOGRAPHY
103
Concentration
Concentration
High MW
Time Elution Volume
Low MW
Figure 8.2: Molecular weight distribution curve from gel phase chromatography. The high molecular weight polymers come out at early time and the low molecular weight polymers come out a latter time.
universal or master curve. In other words the curve would be the same for all polymer/solvent/temperature systems. Passage time through a gel phase chromatography column is one such property that depends only on polymer volume. We can expect or assume that all polymers with the same value of [η]M will elute at the same time in that column. The calibration procedure uses this assumption. Calibration data consists of a plot of [η]M versus elution volume. [η]M is measured using viscosity experiments on polymers of known molecular weight. For greatest accuracy and elimination of ambiguity about the type of average molecule weight, the preferred experiments use monodisperse polymers. The elution time is measured in a chromatographic column. A plot of [η]M should be a universal calibration curve for that speciﬁc gel phase chromatographic column. Because the calibration curve should be independent of polymer type, the calibration experiment can be done with any convenient polymer. A typical calibration curve is shown in Fig. 8.3. As [η]M increases the elution volume (or elution time) decreases. Because [η]M increases with molecular weight, the curve expresses the tendency of high molecular weight polymer to elute faster than low molecular weight polymer. Once you have a calibration curve, you can use that column to measure the molecular weight distribution of any soluble polymer. For the unknown polymer, data of concentration versus elution volume is collected. For each elution volume, the calibration curve is used to calculate the [η]M corresponding to that elution time. By viscosity theory, a given calibration value for [η]M (here denoted as ([η]M )c is related to the molecular weight of the unknown polymer by ([η]M )c = KM a+1 (8.3)
104
CHAPTER 8. MISCELLANEOUS MOLECULAR WEIGHT METHODS
Calibration Curve [η] M
Elution Volume
Figure 8.3: A typical calibration curve for gel phase. chromatography
where K and a are the viscositymolecular weight constants for the unknown polymer being studied. Solving for molecular weight gives M= ([η]M )c K
1 a+1
(8.4)
Formally this M is a viscosity average molecular weight. Because each elution fraction, however, is close to monodisperse polymer, we can treat it is an absolute molecular weight and not an average molecular weight. In summary, gel phase chromatography gives information about complete molecular weight distribution. Its only drawbacks are that it requires calibration experiments, it requires the polymer to be soluble, and requires a modest amount of specialized equipment.
8.3
Field Flow Fractionation
Field ﬂow fractionation or FFF is a powerful and ﬂexible technique that was developed at the University of Utah. There is currently no information on FFF in these notes, but the technique will be discussed in class.
8.4
End Group Analysis
COOH groups) and the
Consider the polymer shown in Fig. 8.4. The two ends have acid groups ( polymers. The common situation is not that many polymers have
reminder of the polymer backbone has no acid groups. The situation in Fig. 8.4 is common to many COOH end groups, but that the end groups are often chemically distinguishable from the backbone of the polymer. When the
g. measuring the number of one type of end group will be equal the number of polymer molecules (without dividing by two). The sensitivity problem gets worse as the molecular weight gets higher. Assuming the polymer is linear. Another problem is that use of endgroup analysis assumes you know the structure of the polymer.4. titration of acid groups as for Fig.4 or of basic groups). In this case. backbones are chemically unique it is sometimes possible to use analytical chemistry techniques to measure the concentration of end groups. Some typical analytical methods are: chemical methods (e. Furthermore. You must know the chemical nature of the end groups and know that the polymer is linear. Thus dividing the number of end groups by two will give the total number of polymer molecules. END GROUP ANALYSIS 105 COOH HOOC Figure 8. an accurate end group analysis will require extremely sensitive techniques. Endgroup analysis cannot be used when the end groups are uncertain (a situation that arises in some polymer synthesis schemes) or when the polymer is branched or crosslinked. The average molecular weight. the chemical nature of the end groups must be such that they can be distinguished from the rest of the polymer. Thus when using dilute concentrations of polymers. As a result. it can be a useful technique to measure an absolute molecular weight. or radioactive measurements (e. 8. for polymers with labeled endgroups). In principle. endgroup analysis is limited to relatively low molecular weight polymers. it often has problems that make it impractical. which in this case will be the number average molecular weight.4: A typical polymer having chemically distinguishable end groups. because the number of end groups decreases as the molecular weight increases.5) When endgroup analysis works. Unfortunately. Unfortunately. can be calculated from Total Weight = Number of Polymers i N i Mi i Ni = MN (8. First the ratio of endgroups to total amount of polymer is small. the extent of branching is not often characterized so precisely.. If the polymer is . you could divide the total number of end groups by that number and still calculate the number of polymer molecules.. In some polymers the two end groups are distinguishable from each other. each polymer will have two end groups. Measuring the concentration of end groups allows you to measure the number of end groups. if you knew the number of branches per polymer.g.8. spectroscopic measurements.
Ultracentrifugation works well and is used often when working with biological macromolecules (e. and Mz+1 . Although this technique is crude.5 Ultracentrifugation In the ultracentrifugation method. . that melt rheology data can be used to get at least qualitative and comparative data about molecular weights in various insoluble polymers. One crude standard technique is called melt index. One technique available which is sensitive to molecular weight is melt rheology (i. however. they claim to be able to calculate the molecular weight distribution. Recent workers have suggested that the reverse calculation can be made.106 CHAPTER 8. osmotic pressure). As a result they do not entangle with each other and simple sedimentation theories are applicable. The diﬀusion process under centrifugal force is related to the size or molecular weight of the polymer. light scattering. They will often entangle with each other and the sedimentation will be strongly eﬀected by the amount of entanglement. if it is branched you cannot be sure how many ends it has. It measures the amount of molten polymer that ﬂows through a standard opening in a ﬁxed amount of time.g. The higher the melt index. At its best.. If the polymer cannot be dissolved in any solvent. The polymer concentration along the tube as a function of position can be reduced to give average molecular weights.. 8. proteins). ﬁeldﬂow fraction. Given melt rheology data. These quantities are typically measured by some spatially resolved optical means that is scanned along the length of the centrifugation tube.. In contrast polymers are often random coils. those techniques will not be applicable. gel phase chromatography. the lower the viscosity of the polymer melt and thus the lower the molecular weight. a polymer solution is placed in a centrifuge and the rate of sedimentation or the equilibrium position of polymer after centrifugation is measured. melt viscosity experiments). the results can even give information about distribution of molecular weights by ﬁnding MN . The technique is less useful for high molecular weight random coil polymers. 8. MISCELLANEOUS MOLECULAR WEIGHT METHODS linear you can be sure it has two ends.6 Insoluble Polymers If a polymer is insoluble. and ultracentrifugation always use polymer solutions. MW . solution viscosity. endgroup analysis..e.g. then most of the previously discussed techniques cannot be used to get molecular weights. On a theoretical basis one can take a known molecular weight distribution and make a reasonable calculation of melt rheology data. etc. Colligative properties (e. These macromolecules usually have ﬁxed structures and are close to being spherical. it is often used by industry and reported in company literature on various grades of polymers. Mz . Their work indicates. These techniques make many assumptions and are probably only qualitative at best.
6 or Nylon 6. packaging ﬁlms. what type of molecular weight average was determined? c. Without any additional information. monoﬁlaments.6. . It is formed via polymerization of the following monomer: O HO–C–(CH2)10–NH2 a. write down both MN and MW for this polymer. From your guessed polydispersity index.65 grams of nylon 11 was dissolved in 450 ml of Formic acid and it was subsequently determined that the concentration of amine groups was [NH2 ]=3. INSOLUBLE POLYMERS 107 Problems 8–1. gristles. In part a. Nylon11 is poly(11aminoundecanoic acid).56 × 10−4 moles/liter. If 2.8. It can be used to make mechanical parts. This polymer has a crystal melting point around 190◦ C and has lower water absorption than Nylon 6. and sprayed and ﬂuidized coatings. what would be the “most probable” polydispersity index MW /MN . what would be the average molecular weight of the polymer? b.
MISCELLANEOUS MOLECULAR WEIGHT METHODS .108 CHAPTER 8.
First. A ﬁrst order transition is a transition that involves a discontinuous change in a ﬁrst derivative of the free energy.g.3) = −S P These ﬁrst derivatives have physical interpretations. The ﬁrst derivative with respect to pressure is volume (V ). etc. crystallization. developed a scheme for classifying thermal transitions. In this section we discuss Ehrenfest’s classiﬁcation scheme and consider speciﬁcally ﬁrst order and second order transitions. etc. or the change in free energy (dG) following a change in pressure (dP ) and/or a change in temperature (dT ) is dG = V dP − SdT From this diﬀerential expression.1) (9. the ﬁrst diﬀerential of free energy.. Free energy is a function of temperature (T ) and pressure (P ).1 Introduction As temperature changes polymers undergo transitions (e. melting. we only encounter ﬁrst and second order transitions. we evaluate the change in properties the might occur as the temperature is varied from below the transition to above the transition. By 109 . second.2) (9. but now considering constant composition. From our earlier solution thermodynamics. 9. In practice. order. third order. the ﬁrst derivatives of free energy are ∂G ∂P ∂G ∂T = V T (9. subglass transitions. The ﬁrst derivative with respect to temperature is minus the entropy (−S).. glasstransition.2 Thermal Transitions The wellknown thermodynamicist Ehrenfest. we ﬁnd the temperatures where the various transitions occur. and second. He classiﬁed transitions as ﬁrst order. In thermal analysis we do two things.).Chapter 9 Thermal Analysis 9.
We can ﬁnd the possible second derivatives by diﬀerentiating V or S (the ﬁrst derivatives) with respect to pressure or temperature. Thus at a ﬁrst order transition. a ﬁrst order transition occurs when the volume or entropy of a material undergoes a discontinuous change at some temperature.1: Typical observation of a ﬁrst order transition while measuring volume or entropy (ﬁrst derivatives of free energy). and the change in entropy. Of the four possible derivatives. THERMAL ANALYSIS First Order Transitions Entropy (S) Temperature Volume (V) Temperature Figure 9. such as the change in enthalpy can also be measured. G will change in slope but not change in value.6) = − P =− P CP S + T T . Other changes. Volume can be measured by dilatometry and entropy can be measured by calorimetry (S = q/T ). three are related to common physical properties: ∂2G ∂P 2 ∂2G ∂T 2 = T ∂V ∂P ∂S ∂T = −V K T (9.5) (9. Both volume and entropy are expected to be higher above the transition temperature than below it. the change in enthalpy is the heat of fusion (∆Hm or ∆Hf ). For melting. We then have the result that ∆Gm = 0.1. Because ∆Gm = 0 = ∆Hm − Tm ∆Sm . ∆Sm . ∆Vm . Note that a change in ﬁrst derivative implies a change in slope in the function itself.110 CHAPTER 9. Ehrenfest’s classiﬁcation scheme.4) A second order transition is a transition that involves a discontinuous change in a second derivative of the free energy. An example of a ﬁrst order transition is the melting transition which occurs at the melting point. A typical ﬁrst order transition observed by either dilatometry or calorimetry is given in Fig. we have ∆Hm = Tm ∆Sm or Tm = ∆Hm ∆Sm (9. The change in volume. Thus there is a discontinuous change to a higher value at the transition temperature. describe the magnitude of the discontinuous change. The temperature at which the change occurs is called the transition temperature. 9.
or β. but on closer inspection it is not a true second order transition. K. and β are all expected to by higher above the transition temperature than below it.2.7) (9.e. Some typical second order transitions are orderdisorder transitions. ∆V = ∆S = 0) at the transition temperature.3 shows typical second order transitions when observed by measuring a ﬁrst derivative of free energy. CP . and a transition in Helium at 2. 9. From the mathematical deﬁnition of derivatives. and β change to a higher value above the transition. We will see that it has much in common with second order transitions. ∂ ∂T ∂G ∂P = T P ∂V ∂T =Vβ P (9. when the second derivative of a function undergoes a discontinuous change. V and S will change in slope (but not value. CP . rotational transitions. Second order transitions can be observed be measuring a discontinuous change in K. K and β can be measured by dilatometry. Suppose that instead of measuring K. Thus there is a discontinuous change to a higher value at the transition temperature. in CP . CP . THERMAL TRANSITIONS 111 Second Order Transitions K Cp Temperature Temperature Figure 9. CP .2.9. The glass transition is sometimes called a pseudo second order transition. the ﬁrst derivative will undergo a change in slope. Some typical dilatometry and calorimetry data at a second order transition are given in Fig. the glass transition is often treated as a second order transition. . In polymers. and β is the volumetric thermal expansion coeﬃcient. you were measuring V or S during a second order transition.. In other words you were measuring a ﬁrst derivative of free energy instead of a second derivative of G. CP is the constantpressure heat capacity. Second order transitions are less common than ﬁrst order transitions. the disappearance of ferromagnetism at the Curie point. temperature become higher above the transition. Because K. Figure 9. Thus when K. i. the slopes of V or S vs. CP can be measured by calorimetry. and β undergo a discontinuous change at a second order transition.2: Typical observation of a second order transition while measuring compressibility or constantpressure heat capacity (second derivatives of free energy).2K.8) where K is compressibility. or in β.
Transitions higher than second order are rare.4: Observation of a ﬁrst order transition when observing compressibility or constant pressure heat capacity (second derivatives of free energy). the ﬁrst derivative of free energy would have just undergone a discontinuous change. Figure 9. If the transition was very sharp. the peak would be very high and very narrow. CP . Suppose you were measuring K. or β. a discontinuous change in the ﬁrst derivative of free energy will show up as a peak. and your material goes through a ﬁrst order transition. THERMAL ANALYSIS Second Order Transitions Entropy (S) Temperature Volume (V) Temperature Figure 9.112 CHAPTER 9. the peak is less high and somewhat broad.3: Observation of a second order transition when observing volume or entropy (ﬁrst derivatives of free energy). perhaps in search of a second order transition. . First Order Transitions K Cp Temperature Temperature Figure 9. A generalization of Ehrenfest’s classiﬁcation scheme is to call a transition an nth order transitions when the material undergoes a discontinuous change in an nth derivative of free energy at the transition temperature. At the transition. For many practical materials (especially polymers). For polymers we will only deal with ﬁrst and second order transitions.4 shows typical ﬁrst order transitions that are observed while measuring a second derivative of free energy. When measuring a second derivative of free energy.
Some of them are common in polymers. Melting: ﬁrst order transition that occurs at the melting point and marks the transition from solid to liquid. 5. Those techniques and what they measure are listed below: . Crystallization: occurs when cooling from above the melting temperature to a low temperature. THERMAL ANALYSIS OF POLYMERS 113 9. The physical processes that correspond to subglass transitions will vary from polymer to polymer. crystallization is only observed in semicrystalline polymers. a transition that occurs below the glass transition temperature. There are some important diﬀerences between disappearance of crystals on heating and their reappearance on cooling. As will be explained latter. Because polymers are high molecular weight materials. almost all polymers will thermally degrade before they vaporize. Melting is a transition from solid to liquid. the melting point and the crystallization temperature are usually diﬀerent. but is better characterized as a disappearance of crystals. Glass transition: pseudo second order transition that occurs in amorphous polymers or in the amorphous phase of semicrystalline polymers. Because no polymers are 100% crystalline. The above transitions in polymers are observed using various thermal analysis techniques. It corresponds to the formation of crystals while cooling. crystallization is a ﬁrst order transition. It is thus often useful to treat it as a second order transitions. Because only semicrystalline polymers can form crystals (amorphous polymers have none). 3. melting is only observed in semicrystalline polymers.9. The glass transition temperature is always lower than the melting or crystallization transition temperature (can you explain why?). Formally. In fact. others are rarely or never observed. Vaporization: ﬁrst order transition that occurs at the boiling point and marks the transition from liquid to gas (vapor). Melting is the disappearance of crystals and thus is observed while heating. the glasstransition is not a true thermodynamic second order transition but many aspects of the thermal analysis of glass transitions are similar to true second order transitions.3 Thermal Analysis of Polymers This sections lists some of the common types of transitions observed in organic materials. The transitions can occur in either the amorphous fraction or in the crystal fraction. The glass transition occurs when longrange motions become very slow with respect to the observation time scale. Vaporization transitions are almost never studied in polymers. Subglass transitions. Subglass transitions are typically second order transitions. Because only semicrystalline polymers have crystals (amorphous polymers have none).3. 2. 1. 4. Like melting. their boiling points are very high. Several thermal analysis techniques will be discussed in the following three chapters. all polymers will have an amorphous fraction and will exhibit a glass transition.
Dynamic Mechanical Analysis (DMA): Measures stiﬀness and energy losses as a function of temperature.114 CHAPTER 9. Thermogravimetric Analysis (TGA): Measures weight as a function of temperature and time.. Diﬀerential Scanning Calorimetry (DSC): Measures constantpressure heat capacity as a function of temperature (see Chapter 11). By measuring a mechanical property.e. 2. on stiﬀness) (see Chapter 12). THERMAL ANALYSIS 1. DMA can determine transition temperatures and simultaneously determine the eﬀect of the transition on properties (i. Dilatometry (PVT or TMA): Measures volume as a function of temperature and/or pressure (see Chapter 10). 4. 3. This method is aimed at providing information about polymer degradation rather than thermodynamic transitions (see Chapter 11). .
Much interesting P V T work is done on nonequilibrium systems. Such results will not be an equilibrium system and cannot be analyzed with an equation of state. and the glass density. The formation history can eﬀect such things as the degree of crystallinity. V does not depend on the path taken or on the sample history. i. the crystal morphology. and time at temperature and pressure). dilatometry is used to study the relation between P ...1 Introduction The technique of dilatometry measures volume (V ) as a function of temperature (T ) and pressure (P ).. formation pressure. and T and to develop or test equations of state. Polymers in solid form will not be equilibrium (e. glassy and semicrystalline polymers). this condition holds as long as the sample remains far enough below the glass transition temperature 115 .e.g. Note that equilibrium systems also require that no chemistry is occurring.e. For polymers. if you form a solid by lowering the temperature below the glass transition temperature and then do all experiments on that solid. Their volume as a function of T and P will depend on the formation history (e. i. P V T experiments on polymer melts have been used to check theoretical equations of state for polymer melts.g. If cross linking or polymerization occurs at the test temperature than volume will change because of these reactions and not because of T and P . a set of experiments on samples with the same formation history. V . Polymer melts are close to equilibrium systems. the V is a unique function of T and P . The method is sometimes referred to as P V T measurements. and the results are useful despite the material being in nonequilibrium conditions. Many times it is possible to do quasiequilibrium experiments on nonequilibrium systems. the results might be considered to be in a state of quasiequilibrium.Chapter 10 Dilatometry 10. In equilibrium systems. cooling rate.. The results will be quasiequilibrium if it can be demonstrated that the process of approaching equilibrium is much slower than the time scale of observation for all observation temperatures. In equilibrium systems. For example.
We consider ﬁrst determination of the thermal expansion coeﬃcient. however.1) where β is the thermal expansion per degree — the volumetric thermal expansion coeﬃcient. Consider a transition from V1 to V2 and from T1 to T2 at constant pressure P . The curves are data at constant pressure. Because it is not a true equilibrium. (perhaps 30◦ C or more below). the curves move down and to the right. As the pressure increases. are often very slow. the results might change with time. 10.1: Typical P V T data for an amorphous polymer. the transition to higher mobility is more diﬃcult and thus requires higher thermal energy or a higher transition temperature. The Tg always shifts to a higher temperature at higher pressures.116 CHAPTER 10. As the pressure increases. Such quasiequilibrium data can give much useful information. At higher pressures.1.2 Amorphous Polymers Some typical P V T data for an amorphous polymer are give in Fig. dilatometry data can be used to determine other physical properties of the material. DILATOMETRY Increasing P P=0 Volume Temperature Figure 10. the slopes of the volume vs. temperature curves change. The new volume can be expressed as V2 = 1 + β(T2 − T1 ) V1 (10. The breaks in the curves are the glass transition temperatures — Tg . . the sample is more dense and the volume is lower. Each curve plots the volume as a function of pressure for some constant pressure. At Tg . This change in slope is an indication that the glass transition is a second order transition (see Chapter 9). These changes. The glass transition is associated with mobility. the curves move down and to the right. 10. Besides a direct measure of volume as a function of temperature. There are several curves. At higher pressures.
The higher value remains roughly constant above Tg .6) and V2 = (1 + α)3 L1 L2 L3 = (1 + β)V1 (10. T ) ∂T = P ∂ ln L(P. T ) ∂V (P. T ) ∂L(P. T ) = 1 L(P.7) . At Tg . 10. this expression becomes a derivative and the thermal expansion β= coeﬃcient is deﬁned as β(P. T ) ∂T (10. the amount of thermal expansion along each of the three axes will be the same. T ) ∂T (10. If we deﬁne α as the linear thermal expansion coeﬃcient. temperature is close to a straight line. the linear thermal expansion coeﬃcient (or commonly just the thermal expansion coeﬃcient) is deﬁned by α(P. In these cases the equation of state can be diﬀerentiated to measure β using the deﬁnition in terms of derivatives. Consider thermal expansion of an isotropic material.2: Linear thermal expansion. Below Tg .10. temperature is close to a straight line above Tg .2) V1 T2 − T1 For a small temperature change.4) P β and α both describe thermal expansion and thus can be related to each other.2. Dilatometry data is sometimes reported as an empirical ﬁt to an equation of state (see below). Consider thermal expansion from V1 to V2 after a temperature change of 1◦ C (T2 − T1 = 1) where V1 = L1 L2 L3 Comparing these expressions 1 + β = 1 + 3α + 3α2 + α3 (10. a is the linear thermal expansion coeﬃcient. Because of isotropy. then the change in lineal dimension (L) is illustrated in Fig. Rearranging this expression gives 1 V2 − V 1 (10.2.3) P Any one of these expressions can be used with dilatometry data to measure β. Hence volume vs. T ) = 1 V (P. The discrete forms are easiest to use with discrete dilatometry data. β undergoes a discontinuous change to a higher value. AMORPHOUS POLYMERS 117 L0 L=(1+α∆T)L0 Figure 10. Following the interpretation of volumetric thermal expansion coeﬃcient. The discontinuous change in β is another manifestation of the glass transition being a second order transition — β is a second derivative of free energy and it undergoes a discontinuous change at Tg . Hence volume vs.5) Because α is usually small (≈ 10−5 ) we can ignore higher order terms (3α2 and α3 ) and write with suﬃcient accuracy β ≈ 3α (10. β is usually nearly constant. T ) ∂T = P ∂ ln V (P.
T ) = A0 + A1 T + A2 T 2 + A3 T 3 + · · · (10. These units are convenient for thermal expansion coeﬃcients. DILATOMETRY This result assumes an isotropic material. T ) = V (0. In analogy with volumetric thermal expansion coeﬃcient.118 CHAPTER 10. the material is compressible or soft. the material is incompressible or hard. V (0. T ) ∂V (P.8) ∂ ln V (P. It empirically explains sea water results (volume as a function of pressure and temperature) and also the P V T properties of many other amorphous materials such as amorphous polymers. Over a restricted temperature range. The Tait equation was derived in the nineteenth century from experiments on sea water. The Tait equation is: V (P. T ) can often be expressed as a polynomial. Thus β ≈ α1 + α2 + α3 where αi is the thermal expansion coeﬃcient for thermal expansion in the ith direction. At most we might expect a factor of two diﬀerence between any two polymers. T ) ∂P (10. It is easy to generalize it to an anisotropic material by allowing the linear thermal expansion coeﬃcients in the three directions to be diﬀerent. The values of α and β do not vary dramatically from polymer to polymer. Empirically. T ) 1 − 0. amorphous polymers Below Tg : α = 50 − 100 ppm/◦ C (β = 150 − 300 ppm/◦ C) Above Tg : α = 150 − 300 ppm/◦ C (β = 450 − 900 ppm/◦ C) The designation “ppm/◦ C” means parts per million per degree C. For example the typical α below Tg is 5 × 10−5 to 1 × 10−4 .9) T The minus sign is included to make K positive. K undergoes a discontinuous change from a low to a higher value at Tg . we can write V (0.0894 ln 1 + P B(T ) (10. the P V T properties of many amorphous polymers can be ﬁt using the Tait equation. T ) is the volume at zero applied pressure (or atmospheric pressure) and B(T ) is B(T ) = B0 e−B1 T (10. compressibility is deﬁned by K(P. The discontinuous change in K is another manifestation of the glass transition being a second order transition — K is a second derivative of free energy and it undergoes a discontinuous change at Tg . T ) = − 1 V (P. When K is large.10) where V (0. The pressure dependence of P V T data at constant temperature can be used to calculate the isothermal compressibility. T ) ∂P =− T (10.11) where B0 and B1 are constants. For example. Without the“ppm” designation the numbers should include a factor of 10−6 .12) . Typical values for isotropic. When K is small.
T ) = A0 eβ(0)T (10. T ) (A0 . . Because Tait equation ﬁts can typically reproduce all the experimental results to four signiﬁcant ﬁgures. they can be equated to deﬁne the PrigogineDefray ratio (R) or R= ∆K∆Cp =1 V T (∆β)2 (10. . 10. are: dTg ∆K = dP ∆β and dTg V T ∆β = dP ∆Cp (10. There are ﬁtting constants when ﬁtting V (0. and constantpressure heat capacity (Cp )) has a discontinuous change at a secondorder transition. By diﬀerentiated the Tait equation with respect to temperature or pressure. . this result is correct for polymer glass transitions. one can record several sets of Tait parameters for temperature ranges of interest. Alternatively. it is possible to calculate volume for any temperature and pressure within that temperature range. volumetric thermal expansion coeﬃcient (β). Fitting experimental P V T data to the Tait equation is often a useful exercise. . Indeed. If one is careful in analysis of experiments. Over some restricted temperature range all the P V T data can be reduced to 4 to 6 Tait parameters. the Tait parameters are a useful way to tabulate PVT data. Because both results are exact thermodynamics results.15) This ratio must hold at any secondorder transition. Once these parameters are known. there are two additional ﬁtting constants in B(T ) (B1 and B0 ). or A0 and β(0)). we can integrate the deﬁnition of β to get V (0. AMORPHOUS POLYMERS 119 where A0 . if we assume that the volumetric thermal expansion coeﬃcient is independent of temperature for some temperature range. .10. .14) where the “∆” terms are changes in thermodynamic properties at the glass transition. the raw data is that it is more reliable to calculate volumetric thermal expansion coeﬃcient and the isothermal compressibility by diﬀerentiating the Tait equation than it is to numerically diﬀerentiate the raw data.13) where A0 is a constant and β(0) is the volumetric thermal expansion coeﬃcient at zero (or atmospheric) pressure. are constants. The Tait equation has several ﬁtting constants. . A1 . it is also possible to calculate the volumetric thermal expansion coeﬃcient and the isothermal compressibility as functions of temperature and pressure. Two key results.1 Pressure Dependence of Tg Although the glass transition is not a true secondorder transtion. A1 .2. there are polymer handbooks that list Tait parameters for common polymers. Each of these properties (compressibility (K). it is possible to calculate the pressure dependence of Tg by using thermodynamics methods.2. Another advantage of using the Tait equation vs. ﬁrst derived by Ehrenfest. Thus instead of storing a large amount of raw data.
Most materials melt in a much narrower temperature ranges (< 1◦ C). the change in slope will get smaller. . Figure 10. At Tg . The single curve plots the volume as a function of pressure for some constant pressure. As the polymer gets more crystalline. the heating curve shows a melting transition. It can be demonstrated that melting point is a function of molecular weight. One reason that polymers melt over a broad temperature range is that polymers have a distribution of molecular weights. the dashed curved is obtained during cooling. they exhibit a glass transition that is characteristic of amorphous polymers. DILATOMETRY Tc Volume Cooling Heating Tg Temperature Tm Figure 10. temperature curve changes.3: Typical P V T data for a semicrystalline polymer at a single pressure. The change is never exactly discontinuous but occurs over a relatively narrow temperature range of 2040◦ C. The solid curve is obtained during heating.120 CHAPTER 10.3 shows P V T results for both heating (solid curve) and cooling (dashed curve).g. 10. In addition to a glass transition. The magnitude of the change will reﬂect the amount of amorphous polymer that is present. Because all semicrystalline polymers are also partially amorphous. The break in the curve at low temperature is the glass transition temperatures — Tg .1). Melting of polymers is a ﬁrst order transition and we expect a discontinuous change in volume.3 Semicrystalline Polymers Some typical P V T data for a semicrystalline polymer are give in Fig. The melting temperature is usually deﬁned as the end of the melting range or the temperature at which all crystals have completely melted. the curves would move down and to the right as the pressure increased. The melting transition temperature is always above the glass transition temperature.3. the slope of the volume vs. 10. For some highly crystalline polymers (e. 10.. the change in slope may be undetectable. If we included curves for several pressures (as in Fig. Thus a polydisperse sample naturally shows a distribution in melting points or a temperature range for melting. polyethylene).
Polymer melts are also amorphous liquids and thus the data can be ﬁt with the Tait equation if desired. a probe rests on a sample with some weight (note: the probe shape may be important). A TMA measures linear thermal expansion of a specimen. The phenomenon whereby the temperature decreases below Tm to Tc before crystallization occurs is called supercooling. Instead. The result is Tm ∆V dTm = dP ∆Hf crystals (or the enthalpy change at the melting point). A thermodynamic deﬁnition of Tm is the temperature at which the free energy of the crystals and the melt are equal. dilatometer is called a thermal mechanical analyzer (TMA). the material is called a polymer melt. the melting process is too complex to be described by the Tait equation.10. The Tait equation. Heating and cooling experiments on semicrystalline polymers are diﬀerent. α and K can still be found by numerical diﬀerentiation of the raw data. The amount of supercooling can be large and in fact if cooled fast enough the crystallization can be prevented entirely giving an amorphous polymer.3. the free energy of the crystals is lower. When the Tait equation cannot be used.4. Thus. it is theoretically possible (by thermodynamic data) for new crystals to form when the temperature ﬁrst reaches Tm . A schematic of a TMA apparatus is show in Fig.16) where ∆V is the volume change at the melting point and ∆Hf is the heat of fusion of the pure 10. In polymers. Below Tm . In brief. the crystals never form at Tm . Above Tm the free energy of the melt is lower. is not a thermodynamic equation of state and thus says nothing about the occurrence of transitions. 10.1 Pressure Dependence of Tm Th pressure dependence of the melting point is easy to determine by thermodynamics analysis of the ﬁrstorder transition. on cooling. but not very accurate. The probe is attached to a rod which passes into an linear variable displacement transducer (LVDT). the results are largely empirical. there are energy barriers associated with nucleation and growth of the crystals that must be overcome. Below Tm . The Tait equation is an empirical equation that can describe amorphous materials.4 Experimental Techniques A simple.4. As the rod moves in the LVDT. however. The amount of supercooling depends on the cooling rate. The P V T properties of polymer melts are nearly equilibrium properties. the properties of the sample. The Tait equation can be used well below the melting transition. 10. These barriers are eventually overcome at some temperature below Tm called the crystallization temperature Tc . Near the melting transition. (10. and the presence of heterogeneous nucleating agents. There are equations of state which can predict this data. the voltage output changes in proportion to . EXPERIMENTAL TECHNIQUES 121 Above Tm . however.
For polymers TMA can be used as long as the temperature is kept well below Tg . the probe must rest on the sample. 10. First. you must either assume the specimen is isotropic (same thermal expansion in all directions) or you must measure thermal expansion in all directions. In summary. In a TMA experiment. A simple dilatometer can be constructed from simple glass ware — a beaker and a capillary (see Fig. TMA is does not give quantitative results about transition temperatures (because of probe penetration problems) or about thermal expansion coeﬃcient (because of uncertainty about specimen isotropy). The TMA method has several limitations. the probe may start to penetrate the specimen and give erroneous expansion results. Unlike TMA.5). V0 (T ). A second disadvantage of TMA is that it only measures linear thermal expansion. Let ml0 be the mass of the liquid in the calibration experiment. A sample is immersed in a liquid. the TMA may report an illogical negative thermal expansion coeﬃcient. Then you can measure the liquid volume as a function of temperature.122 CHAPTER 10. If the probe penetrated deeply. DILATOMETRY LVDT Weights Sample Figure 10. It will be equal to V0 (T ) = ml0 ρl (T ) (10. To calculate volumetric thermal expansion. The experiment is to measure total volume of the liquid and polymer as a function of temperature. At higher temperature. The sample must therefore remain solid over the entire temperature range of the tests. To get the volume of the polymer. The temperature at which penetration becomes signiﬁcant depends on the shape of the probe and the amount of weight used to hold the probe on the surface.4: Schematic drawing of a thermomechanical analyzer or TMA. displacement. the temperature is scanned and the displacement is measured as a function of temperature. true dilatometry experiments measure total volume change. The LVDT thus converts a linear displacement to a voltage which can be recorded by many types of scientiﬁc instruments.17) . In the calibration experiment you measure value of the pure liquid in the same dilatometer To calibrate such a dilatometer you begin with an experiment on the pure liquid. you must subtract the volume of the pure liquid which can be measured by a calibration experiment. The volume can be accurately measured by observing height of the liquid in a narrow capillary on top of the beaker.
First.10.19) In terms of the calibration data. either in the polymer. A chemical reaction would cause a volume change not associated with P V T physical properties. V0 (T ). In other words. where ρl (T ) is the density of the liquid at temperature T .21) Thus the speciﬁc volume of the specimen is given in terms of the masses (ml and ms ). the measured total volume (V (T )).18) where Vs (T ) is the volume of the specimen. A good conﬁning liquid for studying polymers . the liquid must not undergo any transitions which would mask the sample volume change. Second. There are two other considerations when doing dilatometry experiments. the mass used in the calibration experiment (ml0 ) and the measured calibration volume (V0 (T )). The speciﬁc volume of the specimen is v= Vs (T ) V (T ) − Vl (T ) = ms ms (10. Now do a real experiment combining a mass ms of a specimen with a mass ml of liquid. the large volume changes associated with vaporization would mask the polymer volume changes. it would no longer communicate polymer volume changes to height changes in the capillary. the conﬁning liquid must remain liquid over the entire temperature range of the experiments. this equation can be rewritten as v= 1 ms V (T ) − ml V0 (T ) ml0 (10. and Vl (T ) is the volume of the liquid. The volume of the liquid is Vl (T ) = which gives v= 1 ms V (T ) − ml ρl (T ) (10. If the liquid started to boil. EXPERIMENTAL TECHNIQUES 123 Capillary Sample Figure 10. V (T ) is the total measured volume.4. there must be no chemical reactions. all at temperature T .5: A simple dilatometry for measure volume of a polymer at atmospheric pressure. or between the liquid and the polymer.20) ml ρl (T ) (10. If the liquid froze.
Two examples are the kinetics of crystallization or the kinetics of cure in thermoset polymers. The specimen plus liquid volume is measured by converting the volume expansion into a linear expansion through the use of a bellows. . DILATOMETRY LVDT Heated Jacket Bellows Sample Hydraulic Fluid Inlet Figure 10. It is relatively inert and reacts with very few polymers (but can react with ﬂuoropolymers).6: Schematic drawing of a PVT apparatus. Neither TMA nor simple dilatometry in a beaker are suitable to applying pressure and therefore to getting volume data as a function of temperature and pressure. the volume expansion of the conﬁning liquid is subtracted out by doing a calibration experiment on pure liquid. A schematic drawing of a highpressure P V T apparatus is given in Fig. A good P V T technique is to apply pressure using hydraulic ﬂuid. As the hydraulic ﬂuid is pressurized. the ﬂuid surrounds the sample and cell and is inside the bellows. The main problem with mercury is that its vapors are toxic. movement of the bellows applies pressure to the sample. The pressure is applied by hydraulic ﬂuid. Like simple dilatometry. The same concerns that apply to liquids for simple dilatometry also apply to highpressure P V T experiments. Its liquid temperature range makes its suitable for studying glass transitions. thermal expansion coefﬁcients and isothermal compressibility. The linear change in the bellows is measured with an LVDT. 10. P V T properties. is mercury.5 Dilatometry Summary Dilatometry can be used to measure thermal transitions.6. Equipment that can vary both temperature and pressure is called P V T equipment. The specimen is conﬁned in a liquid as described above for simple dilatometry. Although not discussed above. It is also a liquid at room temperature and remains a liquid to very high temperature. 10. dilatometry can be extended to many other polymer processes that involve volume changes.124 CHAPTER 10. melting transitions and crystallization transitions in all but the highest melting point polymers.
They play with the molding conditions until they get acceptable part sizes. There is probably room for a more scientiﬁc approach that would use P V T data to predict the required molding conditions. many polymer processes work by empiricism. Unfortunately. than the molding temperature better be more than 50◦ C higher than Tm or the sample will never melt. If Tm is 50◦ C higher at the molding pressure. The amount of volume change during the pressure and temperature conditions of the molding cycle are important. Again. etc. P V T data can help develop these controls.5. Another molding consideration is the pressure dependence of the thermal transitions (Tm and Tg ). DILATOMETRY SUMMARY 125 Dilatometry results are potentially of great importance to the ﬁeld of polymer processing. P V T experiments can measure Tm and Tg as a function of pressure. 10–2. . Derive an expression for the volumetric thermal expansion coeﬃcient of a material which obeys the Tait equation. For example. polymers are often heated. The ﬁndings with polymers is that the transition temperatures can change by 50100◦ C between atmospheric pressure and molding pressure. For molding of such parts the entire molding process must be controlled to tight tolerances and speciﬁcally to tolerances on volume change. Some simple reﬂecting on P V T experiments could save polymer molders a lot of trial and error experimentation. problems associated with molding temperature are often handled by empiricism. and than molded at high pressures. Derive an expression for the compressibility of a material which obeys the Tait equation. Size can be of critical importance for plastic parts such as gears.10. Problems 10–1.. LEGOs.
126 CHAPTER 10. DILATOMETRY .
2) 127 .2 Diﬀerential Scanning Calorimetry DSC measures a specimen’s heat capacity at constant pressure — CP . the temperature is scanned while measuring the weight of a specimen. Heat capacity units are cal/◦ K or J/◦ K. Another thermal analysis technique that typically involves temperature scanning is thermogravimetric analysis or TGA. Heat capacity is usually normalized by dividing the specimen heat capacity by the number of grams to get the heat required to raise one gram of specimen by one degree Celsius. This chapter discusses both DSC and TGA. Thermal degradation reactions typically cause the weight to decrease and thus decreases in weight are a sign of thermal instabilities. we note that heat capacity is related to the second derivative of free energy: ∂G ∂T ∂2G ∂T 2 q T = P = −S = − P (11. If desired. When observing thermal transitions. In brief.1) S 1 − T T ∂q ∂T = P = − P ∂(q/T ) ∂T S CP − T T (11. In TGA experiments. 11.1 Introduction Calorimetry with polymers is normally done using diﬀerential scanning calorimetry or DSC. DSC scans temperature and measures heat capacity of a specimen. heat capacity can be normalized by the number of moles. It measures the amount of heat input (q) required to raise the temperature of the specimen by one degree Celsius while at constant pressure.Chapter 11 Diﬀerential Scanning Calorimetry 11. The experiments are typically done at atmospheric pressure and thus DSC measures the constantpressure heat capacity.
If the temperature changes from T0 to T1 . will show up as a discrete change in CP . The standard approach is to record T0 at the beginning and then to monitor temperature during and after the reaction. the heat of . DSC is fast and easy.g. In conventional calorimetry (e. the enthalpy of the reaction (∆H) is T1 ∆H = T0 CP dT (11. such as melting or crystallization. DSC is the calorimetry method of choice. CP of your system can be found by a calibration experiment in which the temperature is changed by providing a known amount of heat in the form of supplied electrical energy. The area under the peak will be the heat evolved or absorbed during the transition. Extrapolating this portion of the curve back to zero time will give the true T1 or the ideal adiabatic T1 . DSC will give the ∆CP of transition and the temperature of the transition. such as the glass transition..3) P At the second order transition. Second order transitions.5) The experiment consists of measuring ∆T . for example.128 CHAPTER 11. it is slow and not adaptable to scanned experiments or to studying thermal transitions. As discussed above. A ﬁrst order transition will show up as a peak in heat capacity. Usually ∆T is small and CP is independent of temperature between T0 and T1 . The integral thus reduces to ∆H = CP (T1 − T0 ) = CP ∆T (11. This information will give. It is not as accurate as conventional calorimetry but it is still within 12%. Because S will be continuous at the second order transition (S is the ﬁrst derivative of free energy). When we want faster calorimetry and/or scanned results. with no heat ﬂow) and measure the change in temperature within the calorimeter. Usually the calorimeter will not be perfectly adiabatic and there will be a slow decrease in temperature as heat escapes to the surroundings. DSC is a form of calorimetry and in fact gives the same information as conventional calorimetry. you are usually concerned with measuring the heat of some reaction or some process. First order transitions.4) where CP the heat capacity of your system. DSC measures heat capacity which is a second derivative of free energy. bomb calorimeters you may have used in freshman chemistry). DIFFERENTIAL SCANNING CALORIMETRY and constantpressure heat capacity is deﬁned by CP = ∂q ∂T =S−T P ∂2G ∂T 2 (11. Conventional calorimetry is accurate and has been an important part of chemistry for several centuries.e. there will be a discontinuity in the second derivative of free energy. The only problem is determining the ﬁnal temperature T1 . Eventually the temperature will enter a steady decrease and return to T0 . an accuracy that is more than suﬃcient for most polymer applications. a second order transition will show a discontinuous change in heat capacity at the transition temperature.. The method is to carry out the reaction adiabatically (i. will appear as a spike or peak. Unfortunately.
A temperature program is then begun. The area under the curve analysis is similar to the conventional calorimetry method discussed above where T0 and T1 are the beginning and the end of the thermal transition and CP is the measured heat capacity.1: Schematic drawing of a DSC.11. There are two sample chambers — a “reference” chamber and the“sample” chamber. a typical temperature program would be to increase the temperature to some higher temperature at some ﬁxed rate or ﬁxed number of degrees Celsius per minute. In particular. the system monitors the temperature in each chamber. however. If the temperature diﬀers from the programmed temperature in either chamber. the reference and sample chamber can be supplied with the same amount of heat.3. INSTRUMENTATION 129 Sample Reference Heaters Difference of two channels to recorder Measured Temp Measured Temp Programmed Temp Programmed Temp Error amp Error amp Figure 11. An alternative approach to DSC is to measure temperature diﬀerence. 11. The diﬀerence in the energy supplied to the two chambers per unit time (or dq/dt) is proportional to the heat capacity of the sample. During a transition. CP does not remain constant and we must use the integral expression or the area under the CP curve. or the heat of crystallization.1 is a true calorimetry.3 Instrumentation A schematic drawing of a DSC instrument is given in Fig. The instrument shown in Fig. 11. fusion. It measures heat ﬂow which is converted into heat capacity. . That energy diﬀerence is monitored electronically and output to the recorder.1. heat or coolant is supplied to that chamber to make the temperature equal the program temperature. ∆Hf . An empty pan is placed in the reference chamber and a pan ﬁlled with a polymer specimen is placed in the sample chamber. 11. ∆Hcrys . As the program runs. The two chambers are then heated or cooled until they each reach the selected starting temperature.
you must verify the sign convention used by your DSC instrument. 11. 11. 11.2. They were originally developed by many manufacturers to avoid patent protection of the DSC mode of operation and because the instrumentation is slightly simpler. They are more accurately labeled as diﬀerential thermal analyzers or DTAs. Fortunately both DSCs and DTAs can give suitable heat capacity results when working with polymers. DSCs that measure temperature diﬀerential are not true DSCs or true calorimeters.2 is the glass transition or Tg . DIFFERENTIAL SCANNING CALORIMETRY The amount of heat supplied can be adjusted to give various heating rates. Some DTAs plot ∆T instead of −∆T and thus the entire plot in Fig. CP undergoes a quasidiscontinuous change from a lower value to a higher value. higher heat capacity is up and lower heat capacity is down. DTAs are perhaps slightly less quantitative than DSCs. higher heat capacity is down. The temperature diﬀerence will give a good measure of the heat capacity. 11. We called .2 is the most logical one and the one that is used throughout these notes. This behavior is typical for a second order transition. Around Tg .130 CHAPTER 11. When the heat capacity of the sample chamber increases (because of a heat absorbing or endothermic transition) the temperature in the sample chamber will lag behind the reference chamber and there will be a negative temperature diﬀerential (Tsample − Tref < 0). T for the DSC of a semicrystalline polymer is given in Fig. Exothermic ﬁrst order transitions or transitions that release heat have a low or negative heat capacity and thus show negative peaks.4. 11. endothermic ﬁrst order transitions show negative peaks and exothermic ﬁrst order transitions show positive peaks. when the heat capacity of the sample chamber decreases (because of a heat generating or exothermic transition) the temperature in the sample chamber will be ahead of the reference chamber and there will be a positive temperature diﬀerential (Tsample − Tref > 0). Then instead of maintaining equal temperatures and measuring diﬀerential heat ﬂow. Lower heat capacity is up. In such a DSC plot. If the same experiment was done on a DTA. When using a new DSC. it would instead be a plot of −∆T vs. When interpreting DSC data. T .2 would be inverted. Many such DTAs are inaccurately labels as DSCs by those manufacturers. Conversely. The sign used in Fig. Polymers always have a higher heat capacity above Tg than below Tg because there are more degrees of freedom that can absorb energy above Tg . it is advisable to determine whether it is a DSC or a DTA.1 Results with Polymers Heating of Semicrystalline Polymers A typical plot of dq/dT (or heat capacity) vs. it is possible to maintain constant heat ﬂow and measure the diﬀerence in temperature between the reference and sample chambers.4 11. Endothermic ﬁrst order transitions or transitions that absorb heat have a high heat capacity and thus show positive peaks. The lowest temperature transition in Fig.
The results in the glass transition temperature depend on the rate of the test. Tg increases with increasing heating rate. If you bought the sample and have not yet heated it. The glass transition region will depend on the heating rate (see above) and on the diﬀerence between the heating rate and the cooling rate used in preparing the sample.2: Typical DSC data while heating a semicrystalline polymer.4. or the end of the discontinuous change (the last line in Fig.3). the aging time could be several years. Even if you do not cool the sample down. 11. Tg decreases with decreasing heating rate. Conversely.3). namely. The results might also depend on aging time or the length of time that has elapsed since the polymer was cooled down. thus the glass transition occurs at a higher temperature. The most common convention is to take the inﬂection point. the sample must be cooled down to the testing temperature. Some possible answers are the temperature at the onset of the discontinuous change (the ﬁrst line in Fig. RESULTS WITH POLYMERS 131 + dq dT Tg Tc Tm Temperature Figure 11. Tg changes about 3◦ C for each order of magnitude change in heating rate. If the observation time is shorter. The endothermic transition is melting. the glass transition temperature is a rate dependent property. The lowtemperature second order transition is the glass transition. Its true value will be diﬀerent at diﬀerent rates and thus DSC will be sensitive to rate. the inﬂection point of the change (the second line in Fig. the sample was cooled down by the material supplier before you bought it. 11.11. The exothermic transition is crystallization. 11. Another heating rate eﬀect depends on sample preparation. but happens over a range of about 10◦ C. if the heating rate is slower than or similar to the cooling rate and the sample has . Recall that Tg is the temperature at which longrange relaxations become slow with respect to the observation time. One eﬀect is a material property. the question remains: which part of the curve deﬁnes the actual Tg ? The answer depends on who is determining Tg . Many polymer handbooks list a single Tg . the change at Tg a quasidiscontinuous change because it is not sharp. Before doing the heating experiment. The eﬀect of rate on Tg is not large. Speaking qualitatively.3). the relaxations do not need to be as fast to be at Tg .
Both the onset and peak temperature are sensitive to rate.132 CHAPTER 11.5. The total heat evolved.. but is more commonly assigned to the peak temperature. In other words. 11. it is possible to get a glass transition that resembles the trace in Fig. The heat capacity passes through a peak on preceding from the low heat capacity below Tg to the higher heat capacity above Tg . it is possible to see some additional crystallization during the heating DSC. 11. A typical crystallization peak is shown in Fig.e. The peak. these temperatures may increase with increasing rate. however. The infection point method is the most common one. there will be a smooth transition from a low heat capacity below Tg to a higher heat capacity above Tg . it requires heat). If a semicrystalline polymer did not crystallize to the limit of its ability when cooled. Melting is a ﬁrst order. crystallization will only occur in samples that can crystallize (semicrystalline polymers) and in samples that are not already crystallized as far as they can be crystallized (because of incomplete crystallization during cooling). has nothing to do with a ﬁrst order transitions and can be completely explained by a detailed analysis of the kinetics of the glass transition.3: Blow up of the glass transition region. can be determined from the area under the peak (the shaded portion in Fig. the glass transition will resemble the one in Fig. 11. 11. indeed. DSC can also be used to study low molecular weight samples.5). Some researchers have. If the heating rate is much faster than the cooling rate or the sample has aged signiﬁcantly before testing. This peak resembles an endothermic. ﬁrst order transition. it thus occurs as a positive peak on a DSC trace. not aged long. During heating. The highest temperature peak in Fig.4. The vertical lines show two possible methods for determining Tg .2 is the melting transition. the crystallization temperature. Crystallization shows up as an exothermic peak (negative peak or peak that gives oﬀ heat). A typical small molecule would . misinterpreted such peaks as endothermic transitions.3. is always between Tg and the melting temperature Tm . To emphasize. The crystallization temperature is sometimes taken as the onset of crystallization. DIFFERENTIAL SCANNING CALORIMETRY Glass Transition End Cp Onset Inflection Temperature Figure 11. Tc . 11. endothermic transition (i. qc or ∆Hc .
Crystallization T1 Onset T2 Cp Peak Temperature Figure 11. RESULTS WITH POLYMERS 133 Glass Transition Cp Temperature Figure 11.5: A typical exothermic crystallization peak.11. . The overshoot is accentuated by using faster heating times or by aging the sample before heating. The shaded area is the area under the curve.4.4: Glass transition with an overshoot due to kinetic eﬀects in the glass transition process.
the peak is very sharp. The melting temperature is sometimes taken as the onset temperature. but can be signiﬁcant for polymer materials. As explained in the dilatometry section. Some polymers can crystallize into more than one form of crystal. and the melting temperature is taken as the peak temperature. it is possible for them to have diﬀerent melting point. or the end temperature (see Fig.6). The relevant area is shown as the shaded portion in Fig. 11. The discrepancy between the peak temperature and the end temperature is minute for low molecular weight materials. This complicating feature in the polymer structure can lead to a complicated melting transition region in the DSC trace. There are thus two peaks in the DSC trace. the breadth of the peak is due to the polydispersity of polymer molecular weights. show neither a glass transition (there are no amorphous parts of most small molecules) nor a crystallization peak (because the sample could not be prevented from crystallizing during the initial cool down). but the melting transition would be much sharper than the corresponding transition in a polymer sample (see Fig. the peak temperature. 11. 11. the melting transition is broad.6.6: The melting transition for typical polymer molecules and a typical monodisperse low molecular weight molecule. When there are two types of crystals. The area under a melting transition curve is the total amount of heat absorbed during the melting process. The end temperature is perhaps the most logical because it deﬁnes the temperature at which all crystals disappear. This area is used below to calculate the fraction crystallinity that existed before the polymer was heated.7) . It is even possible for crystals that melt at the lower temperature to recrystallize into the higher melting point crystal and then melt at the higher temperature. For small molecules. One possible eﬀect is shown in the left half of Fig. 11. It would show a melting point.7 where the two types of crystals give two independent melting transitions.134 CHAPTER 11. however. By convention. The melting point region would than be the superposition of two melting peaks and one crystallization peak (see right half of Fig. DIFFERENTIAL SCANNING CALORIMETRY Polymer Melting Peak Cp Onset End Cp Small MW Melting Temperature Temperature Figure 11. For polymers.6). a melting temperature determined by DSC is usually taken as the peak temperature. 11.
Substituting into the above equation: ∆Hf = or χ= 100∆H ∆Hf (11. ∆Hf is the enthalpy of fusion . one of the DSCs in the Material Science Department).6) Many DSCs print the trace onto chart paper (e. R be the machine sensitivity or range in cal/sec/in. Integrating dq/dT clearly gives heat or q: T2 T1 dq dT = q dT (11. If the sample is χ% crystalline by weight.9) 100∆H 100KAR = mχS χ (11.. The area under any ﬁrst order transition peak in a DSC trace gives the heat evolved during that transition (see Figs. RESULTS WITH POLYMERS 135 Two melting peaks Two melting and one crstallization peak Cp Cp Temperature Temperature Figure 11.11. you can get the heat of fusion of the crystals by replacing total mass of the specimen (m) by the mass of the crystals which would be mχ/100. DSC data measures heat capacity or dq/dT . The entire heat of evolution is due to melting of the crystal fraction. It says that fraction crystallinity on any sample is equal to the ratio of ∆H to ∆Hf .7) where ∆H is in cal/g and K is a calibration constant. 11.7: Melting transition region of a polymer with more than one type of crystal forms.g. Now consider applying this formula to the melting transition. If we let A be the area under the peak on the chart in square inches (in2 ). then the heat per gram or enthalpy per gram (∆H) of the transition is ∆H = K A(in2 ) R(cal/sec/in) m(g) S(in/sec) (11. and S be the chart speed in in/sec. The calibration constant is determined by measuring the heat evolved in a transition with known ∆H.8) The equation for χ is perhaps the more intuitive of the two equations.4. The right side shows two melting transitions and a crystallization transition.5 and 11. The left side shows two melting transitions.6).
The speciﬁc volume can be calculated from unit cell dimensions. The other is to do DSC on a sample with known fraction crystallinity. Solving that equation for heat of fusion gives: ∆Hf = Tm (Va − Vc ) dTm dP (11. ∆H is experimental data and it is the calories required to melt one gram of sample or cal/g of sample. and dTm /dP . Va . Vc can. Fortunately. . ∆Hf . Tm is easy. Once ∆Hf is known. ∆Hf could be measured by a simple DSC experiment. it cannot determine Vc . and dTm /dP are known. Va is the speciﬁc volume of amorphous material at the melting point. Unfortunately. Note that neither dilatometry nor Xray crystallography are calorimetric techniques. Tm . DSC can be used on any sample of that polymer to ﬁnd the percent crystallinity. and Va can all be determine by P V T experiments or dilatometry. dTm /dP is determined by determining Tm at several diﬀerent pressures. noncalorimetric route to ﬁnding ∆Hf . dTm /dP . The ease of measuring areas under melting transitions makes DSC a good tool for measuring percent crystallinity. Va . DIFFERENTIAL SCANNING CALORIMETRY and is deﬁned as the calories required to melt one gram of crystal or cal/g or crystal. There are two approaches. all crystalline polymers are semicrystalline and we need some alternative method for determining ∆Hf or the enthalpy of fusion of the pure crystal. The only potential problem with applying it to polymers is diﬃculty in obtaining reliable results for Tm . it is the temperature at which all crystals disappear. and Vc is the speciﬁc volume of the crystal at the melting point.10) ∆Hf cal/g of crystal g of sample or the mass fraction of crystal in the sample. Once Tm . Vc . We describe each method. Tm always increases with pressure and thus dTm /dP is greater than zero. be determined by Xray crystallography. Although dilatometry measures volumes. The ClausiusClapeyron equation is an exact thermodynamic equation. Vc is the speciﬁc volume of the pure crystal and polymers cannot be obtained in a purely crystalline form. Vc . The method.11) where Tm is the melting point.136 CHAPTER 11. Multiplying this fraction by 100 gives the percent crystallinity. Their ratio is g of crystal ∆H cal/g of sample = (11. dTm /dP is the pressure dependence of the melting point. ∆Hf can be calculated using the ClausiusClapeyron equation. The ClausiusClapeyron equation is a simpletoderive thermodynamic relation that predicts the pressure dependence of the melting point. requires that you know the heat of fusion for the polymer. dilatometry and Xray of polymers gives data that is accurate enough for calculating ∆Hf . however. This method thus provides an independent. The Xray experiments should be done at temperatures near Tm and extrapolated up to Tm to get the most accurate results. however. One is a noncalorimetric method for determining ∆Hf . If the polymer could be obtained in 100% crystalline form. Va is determined by measuring the volume in the melt and extrapolating back to the melting temperature.
13) where Vc is the total volume of crystal. than the heat of fusion can be calculated from DSC data by 100∆H (11.14) The amourphous density. If χ can be accurately determined by some noncalorimetric method.. NMR.12) χ The problem thus reduces to ﬁnding a second method for determining the percent crystallinity.4. IR. Thus. (11. We ∆Hf = discuss two methods: 1.2 Cooling of Semicrystalline Polymers Cooling of semicrystalline polymers will typically give a trace similar to the heating trace except that there will never be a melting transition. the density method requires use of voidfree samples. an alternative approach is to do a DSC on a sample with a known χ. ρV = ρc Vc + ρa Va = ρc Vc + ρa (V − Vc ) To be successful. Spectroscopic methods: many spectroscopic methods (e. V is the total volume of sample. The ratio of volumes is Vc ρ − ρa = V ρc − ρa where ρa is the density of a 100% amorphous polymer. Sample density method: a sample of density ρ has a fraction crystallinity of χ= ρc V c ρV (11. spectroscopic methods require careful characterization of the origins of the observed signals. There will probably also be signiﬁcant diﬀerences . 2. ρa can often be determined by quenching or rapidly cooling a sample to prevent crystallization and then measuring density.) sometimes show peaks that result from the crystalline fraction and are not present in the amorphous fraction.g. in terms of densities χ= ρc ρ − ρa ρ ρc − ρa (11. This characterization might entail much extra work.4. The crystalline density.16) 11. Careful analysis of these peaks with suitable normalization can be used to determine the fraction crystallinity in a sample. etc. Note that the Vc /V or the volume fraction of crystals was used above. and ρc is the density of a 100% crystalline polymer. Conversely. they sometimes show peaks in the amorphous fraction that are not present in the crystalline fraction. ρc is best determined by Xray crystallography and unit cell dimensions. Xray.15) (11.11. It comes from a simple linear interpolation between the volume of a pure crystal and the volume of a pure amorphous sample. To be successful. RESULTS WITH POLYMERS 137 Instead of measuring ∆Hf .
the sample is 100% noncrystalline and is thus ready to crystallize as much as possible. More importantly. Temperature for thermal transitions: Tg . Subglass or solid state transitions 7. with higher rates tending to decrease Tc . Percent crystallinity: χ (assuming ∆Hf is known) 5. The only diﬀerence is that because amorphous polymers are 100% amorphous. Many of these were discussed above. higher rates will aﬀect the amount of crystals that form. DIFFERENTIAL SCANNING CALORIMETRY in the crystallization region. Amorphous polymers show only the glass transition region. 11. Others can be found discussed in the literature or in text books: 1. The discussion of the glass transition region given above applies also to amorphous polymers. Heat capacity: CP 4.138 CHAPTER 11. When approaching Tc from high temperature. We list a few of the properties that can be measured by DSC. Heat absorbed or evolved during cure reactions or decomposition reactions 6. 11. and Tm 2.3 Amorphous Polymers Amorphous polymers have no crystals and thus never show melting transitions or crystallization transitions.5 DSC Summary DSC ﬁnds many uses in calorimetry and in polymer science. Higher rates tend to reduce the area under the peak and thus reduce the amount of crystallization.6 Thermogravimetric Analysis Thermogravimetric analysis or TGA involves heating a sample to some temperature and then monitoring its weight as a function of time. Heat and entropy of transition: ∆H and ∆S (from q/T ) 3. Many polymers crystallize so sluggishly that they can be entirely prevented from crystallizing by cooling at a high rate or by quenching to well below Tc . Tc . the glass transition will be more pronounced or will show a larger change in heat capacity. Typically the crystallization peak will be more pronounced in cooling curves than in heating curves. The DSC of a polymer that is prevented from crystallization will not show any crystallization peak. It is commonly used to monitor polymer degradation . The rate will aﬀect the crystallization temperature.4. Crystallization kinetics (heat evolved during isothermal crystallization) 11. Cooling rate will have a signiﬁcant eﬀect.
but it must be realized that if the degradation is slow. Monitoring weight while scanning temperature will give useful results.11. Ideally the sample chamber should have a controllable environment to allow you to monitor degradation under various conditions (e. in the presence of oxygen or under dry nitrogen). The sensitivity is large because degradation rates may be slow when compared to typical scanning rates such as 1020◦ C/min. infrared spectrometry. the results will also be very sensitive to rate.. most TGAs are set up to scan temperature. Repeating this experiment for several temperatures will give information about the temperature range under which this polymer can be used. (Hints: nucleating agents will change the crystallization temperature (specify which way) and will change the level of crystallization for a given amount of crystallization time). Problems 11–1.e. Accurately knowing ρc : c.g. THERMOGRAVIMETRIC ANALYSIS 139 reactions. The coupled instruments can be used to identify the structure of the degradation products. can be useful in studying the mechanisms of polymer degradation. Most polymers crystallize by heterogeneous crystallization at nucleating agents. Accurately knowing ρa : b. Because it is easy to measure sample density. Describe some DSC experiments (including control experiments) that would enable you to decide which nucleating agent would be the best..6. TGA only requires a sensitive method for monitoring weight and a method for setting the temperature of the sample. Usually.. Suppose you wanted to add a nucleating agent to promote rapid crystallization during processing and that you have several nucleating agents to choose from. 11–2. Therefore. the polymer will appear to survive to higher temperatures than it would actually survive under long term exposure. gas chromatography. people (i. The most accurate TGA experiments are to set the temperature to some constant value and follow weight as a function of time. Unfortunately reallife experiments are not always trouble free. Combining structural information with kinetics information can give a complete picture of the degradation process. The results will give quantitative information about the rate of degradation at that temperature. In other words. Polymers that have ρa ≈ ρc : . Nucleating agents help the crystallization process to get started. etc. Describe problems that might arise in the following parts of the analysis: a. industry) are not patient enough to do all those required experiments. the density method appears to provide and ideal way to measure the weight fraction crystallinity. Coupling the byproducts of a TGA experiment or the degradation products from the polymer to other instruments such as mass spectrometer.
DIFFERENTIAL SCANNING CALORIMETRY .140 CHAPTER 11.
Relaxation test: time dependencies of stress. For such properties it is important to have a detailed understanding of geometry eﬀects and to avoid oversimpliﬁed interpretations such as merely dividing by the crosssectional area of the specimen. 2. the tests sometimes need to be done at various temperatures and in various environments. there are numerous tests aimed as characterizing the mechanical properties of polymers. gears. 5. composites. thermal transitions. Some of tests and the type of information measured are: 1. and toughness. 3. ropes.Chapter 12 Mechanical Properties 12. 141 . Static testing: tensile.. Dynamic mechanical test: viscoelastic properties. we must study the eﬀect that stress has on them. Before using polymers in loadbearing applications. stiﬀness. In the ﬁeld of polymer characterization.. etc. stressstrain curves. impact strength. viscoelastic properties. viscoelastic properties. 4.g. molecular relaxations. All these mechanical characterization tests measure some mechanical properties. toughness and impact strength) depend on sample geometry. strength. The test results for many mechanical properties (e. Because any mechanical property may be aﬀected by temperature and environment. Creep test: time dependencies of elongation. Fatigue test: lifetimes or durability 6.1 Introduction Polymers are often used in applications that involve stresses. Impact tests: highrate properties. Examples include housings. structures. compressive and shear properties.
the theory is still useful.6) Simple dilatometry experiments during loading can show that this large a volume change does not occur. It has the same units as pressure. will depend on the size of the sample (i. ε. Then F L − L0 =E A0 L0 (12. or the stiﬀness. In this case the change in volume is ∆V = V − V0 = Lx Ly (1 + εz )Lz − Lx Ly Lz = εz V0 (12. For solid or three dimensional materials. To eliminate size eﬀects. Although polymers often deviate from smallstrain elasticity theory. such a bar made of a linear elastic material acts like a spring. In essence. F . MECHANICAL PROPERTIES 12. it is desirable to normalize out the sample size eﬀect using k= EA0 L0 (12. σ. The force applied to the bar.2) The spring constant.142 CHAPTER 12. What must be happening is that the x and y dimensions contract slightly to reduce ∆V .2 Simple Elasticity Theory Our basis for understanding the inﬂuence of stress on materials is the theory of elasticity.5) Analyzing one dimension is enough when you are working only with simple springs. Thus an application of a tensile .e. The term (L − L0 )/L0 is the strain. The simplest elasticity problem is the one dimensional problem of a tensile load being applied to a bar of constant cross section. First assume that a onedimensional stress is applied along the z axis and that the z axis stress causes dimensional changes only in the z direction. it is dimensionless.4) The term on the left is called the stress. or the force per unit area.1) where x is the extension of the bar or (L − L0 ) where L is the extended length of the bar and L0 is the original length of the bar. we must consider length changes in all directions. on the size of the spring) and on the mechanical properties of the sample. is proportional to the extension of the bar. Thus F = k(L − L0 ) (12. According to Hooke’s law. The ﬁnal onedimensional elasticity equation is σ = Eε (12. x: F = kx (12.. It can be directly applied to many polymer problems and it helps in the understanding of other polymer problems. or the fractional increase in length. a solid material wants to resist a change in volume.3) where E is the Young’s modulus of the material and A0 is the initial crosssectional area. k.
9) (12. This is approximately true for many rubberlike materials. the shear modulus is related to E and ν by G= E 2(1 + ν) (12. SIMPLE ELASTICITY THEORY 143 stress in one direction causes the other two direction to contract in order to minimize the increase in volume. Poisson assumed that the contractions in the x and y directions are proportional to the extension in the z direction or: εx = −νεz and εy = −νεz (12. the response of a solid to stress in all direction is just the superposition of the individual responses.15) (12.18) .12) (12. and z directions simultaneously. y.13) (12.10) (12.7) where ν is called the Poisson’s ratio. For isotropic materials. polymers may also be subjected to shear loading and shear stresses. ∆V is equal to zero. Hooke’s law for shear loading are γxy = γyx = γxz γyz τxy G τxz = γzx = G τyz = γzy = G (12.12.11) Of course we are not limited to applying stress in only one direction. We may apply stresses in the x. We can thus generalize Hooke’s law for tensile loading to get εx = εy = εz = 1 [σx − ν(σy + σz )] E 1 [σy − ν(σx + σz )] E 1 [σz − ν(σx + σy )] E (12.17) where γij are shear strains and G is the shear modulus. and glassy or semicrystalline polymers have ν of about 1/3. Considering strains in all directions.16) (12. shear loading causes no change in volume and thus the responses due to shear loading in the three directions are uncoupled. Because linear elasticity is a linear theory. Most metals. When ν = 1/2. a stress of σz in the z direction induces the following strains: εx = − εy εz ν σz E ν = − σz E 1 = σz E (12. The volume change on extension in the z direction is now ∆V = (1 + εx )(1 + εy )(1 + εz )V0 − V0 ≈ (εx + εy + εz )V0 = (1 − 2ν)εz V0 (12.8) where the indicated approximations assumes all strains are small and thus higher order terms in strain can be neglected. Unlike tensile loading.14) Besides tensile loading.2.
Engineering strain is the total elongation divided by the original length. Dealing with general anisotropy is very complex. the crosssectional area changes due to Poisson contraction eﬀects. As the sample extends. Two examples are composite materials and oriented polymer specimens. 12.19) (12. Instead. y. 12. An orthotropic material has diﬀerent properties in the x. and the νij ’s are the generalized Poisson ratios. Engineering stress is the total load divided by the original crosssectional area. 12. Here we introduce a single example of an orthotropic material. Some typical polymer engineering stressstrain curves are illustrated in Fig. For anisotropic materials. you may want to refer to any text of mechanics of materials or elasticity theory.1.1 is for a linear elastic polymer. That reﬁnement.23) (12. If you need more information. It should suﬃce for the material covered in this chapter. however. and z directions. In polymer science. we measure engineering stress and stress. For an orthotropic material. Plotting the results gives a stress strain curve. the Gij ’s are the shear moduli for shear deformation in the ij plane. Hooke’s law becomes εx = εy = εy = γxy = γxz = γyz = νxy σy νxz σz σx − − Ex Ex Ex νxy σx σy νyz σz − + − Ex Ey Ey σz νxz σx νyz σy − + − Ex Ey Ez τxy Gxy τxz Gxz τyz Gyz (12. . The “true” stress and “true” strain should be deﬁned in terms of the current sample dimensions.22) (12. is rarely used when characterizing polymers. The stress increases linearly with strain (or very nearly linearly) until ultimate failure. MECHANICAL PROPERTIES The above discussion was all about isotropic materials.21) (12.144 CHAPTER 12. but still has no coupling between shear and tensile deformation. νij is the ratio of the strain in the j direction to the strain in the i direction when the specimen is under uniaxial load in the i direction. This discussion of elasticity theory has been extremely brief. Consider ﬁrst a tensile stressstrain curve measured by pulling in one direction.3 StressStrain Curves A stressstrain curve is measured by monotonically increasing stress or strain and measuring the other quantity.20) (12. the mechanical properties depend on the direction of the applied load. Curve b is for a polymer that yields and then breaks.24) where the Ei ’s are the tensile moduli for loading in the i direction. one often encoun ters anisotropic materials. Orthotropic materials are usually the most complex situation encountered in analysis of polymeric specimens. Curve a in Fig.
d. After yielding. At the highest elongations. the polymer chains can align and crystallize.1 is typical for rubbers or for materials that exhibit rubber elasticity. Yielding shows up as deviations from linearity. Curve d in Fig. Thus. how they are measured. the meaning of the slope of the stressstrain curve decreases. 12. The problem is that engineering stress and strain are no longer close to true stress and strain. 12. Thus curve c is for a material that yields and then continues to elongate. the peak stress. We next consider typical properties measured from stressstrain curves. the material will get stiﬀer and soon break. this approach is often unworkable and yield stress is. As the strain increases.3. by convention. The stiﬀness or modulus of a polymer is usually taken from the slope of the stressstrain curve at very low strains — the initial slope. b. yielding followed by necking and high elongation. to reduce the data in the raw curves to a set of mechanical properties.1: Some typical stressstrain curves. STRESSSTRAIN CURVES 145 a Stress b c d Strain Figure 12. a neck will form. a: linear elastic. there is no necking. It is useful. rubberelastic curve. Rubber elastic deformation is characterized by high recoverable extension. 12. Upon alignment. yield stress is often deﬁned as some ﬁxed amount of deviation from linearity. Then the neck region elongates or grows. In metals.1 tell you much about the mechanical properties of polymers. A peak stress will not always be observed. If we . Figure 12. c. for example the negative slopes in curve c have no physical meaning. Eventually the polymer chains can align in the necked region.12. sometimes to several hundred percent strains. but it shows up barely in curve b and clearly in curve c. however. These eﬀects will cause a stiﬀening and the curve turns up before failure. nonlinear with yield. and what they mean.1 StressStrain Properties The raw curves in Fig.3. In polymers.2 shows the process of neck formation followed by neck elongation.
The modulus of unoriented polymers are almost universally in the range of 1 to 4 GPa. Many such polymers. We would also ﬁnd that the true stress never decreases as in curve c. because if you wait long enough.1. Strength is often a poor way to characterize polymer failure properties. The strength of a polymer is usually deﬁned as the maximum stress reached during the stressstrain curve. or the stress when the sample breaks. did plot true stresstrue strain curves. it is possible to have a very high modulus when the load is applied in the direction of the orientation.146 CHAPTER 12. however. The results are usually highly variable and are also a strong function of the sample size and shape. If a polymer is oriented.2: The appearance of a specimen that necks and follows curve c in Fig. Measuring the yield strength of polymers that do not neck can be a problem. such that the backbone chains are all aligned with the applied load. Highly oriented polymers can have moduli as high as 300 GPa which is higher than the modulus of steel. MECHANICAL PROPERTIES Yielding Necking Figure 12. the viscoelastic nature of polymers can make extreme nonlinearities reversible. The strengths of unoriented polymer are in the range of 10 to 100 MPa. a low slope is a soft or a compliant sample. can be induced to neck when tested in suﬃciently thin specimens and at suﬃciently slow rates. 12. it is diﬃcult to deﬁne irreversibility. yield strength in polymers is often assigned to the peak of the stressstrain curve that occurs prior to necking. however. Highly oriented polymers can have strengths up to 4 GPa. In polymers. The oriented polymer is anisotropic and the modulus in the other directions decreases as the orientationdirection modulus increases. you do not get something for nothing when orienting a polymer. High yield strength is associated with brittle and linear elastic materials. The increase in modulus in oriented polymers applies only to loading in the direction of orientation. . the slopes would give the strain dependence of the stiﬀness. A formal deﬁnition of yielding is the point at which the stressstrain response becomes nonlinear and irreversible. By convention. Polymers are all made up from similar organic bonds and thus we never expect to ﬁnd unoriented polymers with moduli signiﬁcantly outside this range. A high slope is a hard or a stiﬀ sample. Unfortunately.
the polymer becomes hard and brittle. This work is often equated with toughness. Elongation to break is the total elongation at the time the sample breaks. High area is for tough samples or ductile samples. The similarity between temperature eﬀects and rate eﬀects suggests that time and temperature are related. who cares if the polymer can extend to 250% or to 1000%? In summary. As stated above. 12. no motion is possible and it can be said to be eﬀectively below the glass transition temperature. Elongation is a nearly useless material property. STRESSSTRAIN CURVES 147 low yield strength is associated with ductile materials. At slow rates the polymer has time to rearrange and on the time scale of the test. yield strengths of unoriented polymers are usually 10 to 100 MPa. Large eﬀects can be seen at ordinary temperatures and testing rates. one polymer can exhibit all the possible stressstrain curve types by changing the temperature. stress × strain is work per unit volume. If the designed part will only experience 5% strain. High elongation is obtained by promoting necking. Highly oriented polymers will not yield and thus do not have a yield strength. We will see later in the chapter that we can exploit the relation using a principle known as timetemperature superposition. elongation to break is easy to measure and is commonly reported. The testing rate eﬀect is illustrated in Fig. Well below the glass transition temperature the polymer is immobile and behaves as a brittle material. it is not a useful material property. Suppose you want to do a very slow test at room . The eﬀect of temperature is illustrated in Fig. Useful values of toughness are normally measured by techniques of fracture mechanics and not by areas under the curve. At high rates. 12. Although toughness is an important material property. it can be said to be eﬀectively above the glass transition temperature.4. Necking is promoted by slow testing rates and by using thin samples. Also many polymer applications will not involve large strains. Toughness is deﬁned as the amount of energy or work required to break the sample. In short.3. polymers typically become softer and more ductile. High elongation means a ductile failure. The eﬀect is connected with the glass transition. At low temperatures. Without additional experiments and additional information about testing conditions. Increasing the rate is like decreasing the temperature.12. low area is for brittle samples. it causes the polymer to become harder and more brittle. low elongation means a brittle failure. Because work is force × distance. As the temperature increases. The main problem is that the total area is a sensitive function of the elongation to break. the area under the curve is not a good way to measure the toughness. It is highly dependent on sample size and testing conditions.3. Like strengths. the material becomes more ductile and softer. Thus the area under the stressstrain curve is the total work per unit crosssectional area to break the sample. Unlike most metals. This eﬀect is again associated with the glass transition. The rate eﬀect is the opposite of the temperature eﬀect. As the temperature is raised and the glass transition is approached or passed. elongation to break is very sample size and test condition dependent. the stressstrain behavior of polymers is very sensitive to testing rate and temperature.
.4: The eﬀect of testing rate on the stressstrain curve of polymers. High Rate Moderate Rate Low Rate Increasing Rate Figure 12. MECHANICAL PROPERTIES Low Temp Room Temp High Temp Increasing Temp Figure 12.3: The eﬀect of temperature on the stressstrain curve of polymers.148 CHAPTER 12.
When measuring stressstrain curves. It can be diﬃcult to separate plastic aﬀects from viscoelastic eﬀects. 12. is because they are useful in polymer applications. The importance of knowing deformation for polymer design problems should be self evident. One common error is slippage of the specimen in the grips. An important aspect of stiﬀness is that it is a function of temperature.3. the amount of necking will be determined by sample geometry. Polymer stressstrain curves are often nonlinear. One method would be to use the very slow rate that you are interested in. there are many possible sources of error. In brief. the amount of deformation will be very dependent on sample thickness.2 Uses of StressStrain Properties The reason for measuring stressstrain properties. This slow rate. A common and quick stiﬀness/temperature experiment is called the heat deﬂection temperature. such as scratches on the surface. Sample geometry and quality can dramatically aﬀect ultimate failure loads. however. The nonlinearity can be caused by plastic deformation (yielding) or by rate/temperature eﬀects (low rate or high temperature promotes curvature). or toughness. You can therefore get reasonable very slow rate. the measured grip displacement will be diﬀerent that the actual specimen displacement resulting in large errors in the measured strain.12. In other words necking is a specimen property and only partially a material property. such as modulus. strength. If necking is part of the specimen deformation. Thus. may be needed to fully characterize the mechanical response of a polymer. For this reason. a . Specimen geometry and quality can have a large eﬀect of the stressstrain curve.3. besides stressstrain experiments. might be very slow and in fact might involving testing over many years. samples with stress concentrations. STRESSSTRAIN CURVES 149 temperature. For example. room temperature data by doing higher rate tests at a higher temperature. If the specimen slips. in quantitative work it is important to measure displacements or strains directly on the sample by using strain gages or extensometers instead of measuring strain from grip displacement. A better method is to use the timetemperature superposition principle which states that the eﬀect of slowing done the rate by some amount is equivalent to lowering the temperature by some amount. The only problem is knowing how much to increase the temperature to simulate a given slow rate. Thin samples will neck more than thick samples. Grip slippage will not aﬀect measured load and therefore loads will always be accurate assuming the load cell in accurate and well calibrated. Additional experiments. We next give a few comments about using stressstrain properties. This subject will be discussed latter. Although some materials are more likely to neck than other materials. reproducibly measuring sample strength requires great attention to specimen design and quality. can prematurely fail at the sample imperfections. Stiﬀness or modulus is a key input into Hooke’s laws and they are used to calculate deformations under load.
26) . Plugging this stress state into the generalized Hooke’s laws gives: εx = εy = εz = − (12. 12. First yielding will be very diﬀerent in compression. If buckling can be prevented. Of the previously discussed properties. Although failure properties are important. Second. In particular.3. all three axial stresses are equal and the shear stresses are all zero. You can.3. for example measure stiﬀness. some important diﬀerences. This type of pressure application results in a form of stress known as hydrostatic compression. but near Tg . however. 12. There are. A large deﬂection means that the polymer stiﬀness has become low and will probably no longer be suitable for stiﬀnesscritical applications. Buckling is a geometric instability and not a material property. In general polymers should only be used at temperatures well below the heat deﬂection temperature. when testing samples in compression. In a state of hydrostatic compression. strength. can be derived by using the techniques of fracture mechanics. Failure properties describe the conditions under which a polymer will either break or become so distorted that it can be considered failed. and toughness are failure properties.4 Shear Testing This topic may be discussed and involves loading the sample in shear and measuring shear strain. there will be no necking and there will be no opportunity for very large elongations (the maximum compression strain is 100% and this amount of strain means the sample has disappeared). a stressstrain experiment is not the ideal way to study failure. especially about toughness. Better information about failure. but it is always below Tm . you are often limited by buckling rather than by the true compressive strength of the material.5 Hydrostatic Compression The pressuredependent dilatometry experiments discussed in Chapter 10 involved immersing a sample in a conﬁning liquid and applying a pressure. you load it in compression.25) where p is the pressure. strength.3. in semicrystalline polymers.3 Uniaxial Compression Testing If instead of loading the sample in tension. Many features of compression stressstrain curves are similar to tensile stress strain curves. 12. you can record a compression stressstrain curve. MECHANICAL PROPERTIES cantilever beam is loaded with a ﬁxed amount of load and the deformation of the beam is measured as a function of temperature. and toughness. In amorphous polymers. most polymers will be able to sustain 2 to 3 times more stress in compression than they can in tension.150 CHAPTER 12. the heat deﬂection temperature is always below. yield strength. Thus σx = σy = σz = −p or 1 p = − (σx + σy + σz ) 3 p(1 − 2ν) E (12. the heat deﬂection temperature can be above Tg . elongation to break.
The volumetric strain/pressure relation then becomes 1 ∆V (12. In reality. then the nature in which the chemical units are connected becomes more important.27) In the discussion of dilatometry in Chapter 10. . The analysis of the results can be complicated. or at least will not yield until high stress. we deﬁned the isothermal compressibility as K=− 1 V ∂V ∂P =− T ∆V V0 p (12. we see that 1/K plays the role of −p = modulus. all polymers will be brittle and will not yield. In the end the variability of bulk moduli over a wide range of polymer materials is not large.29) Hydrostatic compression call also be viewed as plotting pressure vs.31) Note the factor of 1 − 2ν in the denominator. as in hydrostatic stress. This is reasonable because most polymers are made up of units of similar chemical composition and the compression of these units under hydrostatic compression in not overly sensitive to the nature of how these units are connected together. In general. Many rubbers which are very soft also have ν ≈ 1/2. When ν is equal to 1/2. In compression.4 Fracture and Impact Testing This topic may be discussed and inolve loading a sample until in cracks or hitting with an object in impact. the yield strength is predicted to be inﬁnite. a material under hydrostatic stress will not yield. the bulk modulus is predicted to be inﬁnite. FRACTURE AND IMPACT TESTING and the change in volume is ∆V = (ex + ey + ex )V0 = − 3p(1 − 2ν) V0 E 151 (12. In terms of E and ν: 1 E = K 3(1 − 2ν) (12. ν is never quite 1/2 and it turns out that the increase in ν in soft materials is roughly compensated by the decrease in E.30) K V0 Comparing this expression to the onedimensional Hooke’s law. The quantity 1/K is known as the bulk modulus of the material. 12. Note this statement only applies to hydrostatic stress. By analogy with tensile strain. In hydrostatic tension.4. yielding requires shear stresses. volumetric stain.28) Substituting ∆V for hydrostatic compression gives K in terms of E and ν: K= 3(1 − 2ν) E (12. When none are present. When the stresses in one or more directions are signiﬁcantly diﬀerent. Another unique aspect of hydrostatic stress is the absence or near absence of yielding. we deﬁne volumetric strain as ∆V /V0 .12.
polymers are viscoelastic: ε = f (σ.5 Time Dependence or Viscoelasticity In elastic materials (linear or nonlinear) the strain is a function of the stress only. But. the stress is held constant. what does linear viscoelastic mean? By the equation above.32) In polymers. and the stress is measured as a function of time. It could be called the analog of the smallstrain assumption in linear elasticity. the strain is held constant. Most analyses of polymer viscoelasticity assume linear viscoelasticity. that is. you would ﬁnd the same J(t) no matter what value of σ0 was used in the creep test. we can write: e(t) = J(t)σ (12. In the stress relaxation test. the stress and strain are often time dependent. J(t) and f (σ). That assumption is good for small strains. When J(t) is observed to depend on the level of constant stress. In a creep test. Because the coeﬃcient of the linear term can be included in J(t). in other words. The above analysis describes the creep behavior of a linear viscoelastic material. The creep compliance is J(t) = ε(t) σ0 (12.33) The are several ways to observe and quantify time dependence of the mechanical properties of polymers. The creep compliance of a linear elastic material is just 1/E or the compliance. MECHANICAL PROPERTIES 12. One depends only on time and the other depends only on stress: ε(t) = J(t)f (σ) (12. The stress is set to some constant value. In a creep test we then write the strain as the product of two functions. in other words. J(t) was written to be independent of stress. One method is a creep test. it is called the creep compliance. σ0 . and the strain is measured as a function of time. t) (12. It is time dependent and it can be measured in a creep test. and the strain is measured as a function of time. the material under test is linear viscoelastic. the material is said to be nonlinear viscoelastic.37) .34) We next assume the material is linear viscoelastic. The complementary experiment to a creep test is a stress relaxation test. In analogy with the development above. the stress relaxation test is described by: σ(t) = G(t)ε0 or G(t) = σ(t) ε0 (12. or the stress is a function of the strain only: ε = f (σ) (12. Let’s assume that the stresstime dependencies of the strain can be separated. we assume that f (σ) includes only terms that are linear in σ.152 CHAPTER 12.35) J(t) is a new material property. To the extent that this is true.36) If the material was linear elastic then ε = (1/E)σ.
Some examples include tensile loading. 12. By orienting PE. Time dependence of mechanical properties is an important piece of information about the response of polymers to stress. The time scales in such plots can be so long that it is impractical to rely on isothermal creep tests. that there is much less time dependence in the mechanical properties. a negative pressure will cause Tm and Tg to decrease. For an example consider the recent development of polyethylene ropes. While positive pressures always increase Tm and Tg . however. the rope is very stiﬀ and very strong in short time scale static tests. but not on the level of applied strain. and even hydrostatic compression. First. Polymers are often used in applications that may experience long term loads. it can take a long time to run a creep experiment that shows a signiﬁcant amount of creep. While the rope may be strong.5. it is possible to create stiﬀ and strong ﬁbers.5. PE is above Tg at room temperature and therefore can be expected to be strongly viscoelastic.1 Creep Experiments Depending on temperature. There are many potential problems. Because it is made from PE. You can imagine that in hydrostatic compression where yielding and therefore most ﬂow is eliminated. the relaxation modulus depends both on time and on the level of the applied strain. the uniaxial tensile stress can be considered to be a negative pressure. it will increase the volume by the amount equivalent to a hydrostatic tension equal to 1/3 of the axial tensile stress. For a linear viscoelastic material. For a nonlinear viscoelastic material. In other words. The other loading conditions. that have not yet been considered. We call the temperature we care about the . the relaxation modulus depends on time. To get the long time scales that might be of interest. the rope is potentially cheap. ε0 . A high uniaxial stress will increase the volume. however often show signiﬁcant time dependencies. It is important to know not only if the polymer can sustain a given load but if it can sustain the load for a long period of time. we instead use the principle of timetemperature superposition that was introduced earlier in this chapter. For a linear elastic material. Therefore at a given temperature. it is typical to plot the creep compliance as a function of log time. Some typical creep data at one speciﬁc temperature are given on the right side of Fig. torsional loading. compressional loading. The viscoelastic eﬀect will also be compounded by high levels of stress. shear loading. it also may rapidly creep. the relaxation modulus would be just the modulus E.5. TIME DEPENDENCE OR VISCOELASTICITY 153 where G(t) is the relaxation modulus and ε0 is the constant strain level used during the test. A large amount of creep would make the rope useless. The ﬁbers can be woven into ropes. As with the ﬁber. Therefore. Creep and stress relaxation experiments can be done using a variety of loading conditions. the rope will be farther above Tg when under stress than it will be when unloaded.12. This lowering of Tg and Tm will have the eﬀect of magnifying any possible viscoelastic eﬀects. 12. If the stress is high enough the rope may even melt by the application of load.
5 is plot as a function of log tr where tr is called the reduced time.154 CHAPTER 12. the higher curves are for higher temperatures. The temperatures will probably be both above and below the reference temperature. the creep at short times at the reference temperature. than the creep data can be expected to overlap. Reduced time is actual time for experiments run at the reference temperature.5. . The lower curves are for lower temperatures. can be expected to be equivalent to the creep at shorter times at some higher temperature. A typical set of data for creep as a function of time at many temperatures is shown in the left side of Fig. The question is how do we relate the times at one temperature to the times at another temperature? If the temperatures are not too far apart. A typical result is illustrated in the right side of Fig. the creep at very long times at the reference temperature. 12. 12. The right side is the master curve for creep compliance. The master curve was obtained from the raw data on the left by ﬁxing the curve at the reference temperature and then shifting all other curves horizontally until they achieve the maximum overlap with data at the reference temperature. The master curve on the right side of Fig. and the measurement time is not too short. Conversely. can be expected to be equivalent to the creep at longer times at some lower temperature. That is. reference temperature. MECHANICAL PROPERTIES J(t) J(t) log t log tr Figure 12. By the principle of timetemperature superposition.5. 12. It has been experimentally observed that the log time plots can usually be overlapped by a simple linear shift along the time axis. the creep compliance near the end of the measurement time for one temperature will be identical or higher than the creep compliance near the beginning of the measurement time at a slightly higher temperature. A set of creep experiments thus consists of measuring creep over a relatively short amount of time (105 to 106 seconds) at a series of diﬀerent temperatures.5: Left side is a set of creep experiments as a function of temperature. It is obtained from the creep data on the left by using timetemperature superposition.
12.5. If the experiments included data to very short times (or low temperatures). This region of the curve would be the elastic response region.5. log aT is less than zero.6 quantify the timetemperature superposition principle. this terminal region would not occur. We next examine the physical meaning of the creep compliance plot of the right side of Fig.38) To move a curve at a given temperature in the plot of the left half of Fig. reduced time is related to real time by: log tr = log t = log t − log aT aT (12. In this region the polymer acts like a rubber or a polymer that is above the glasstransition temperature.6: Typical shift factor plot for log aT as a function of temperature. log aT is greater than zero. The time to reach the rubbery plateau is termed the glasstransition time. For T < Tref . 12. . 12.5. the curve is shifted horizontally by the amount − log aT ( the curve is shifted to the right if log aT < 0 and to the left if log aT > 0). This region is known as viscoelastic response.5 to the master curve on the right half of Fig. The polymer is now acting like a liquid and the region is called the viscous ﬂow region. If the material is crosslinked and thus prevented from ﬂowing. They tell you how to convert the time at one temperature to the time at another temperature.6. 12. J(t) would level oﬀ at a constant value equal to 1/E for the material at that time (or temperature). A schematic plot of log aT versus T is shown in Fig. TIME DEPENDENCE OR VISCOELASTICITY 155 log aT T log a 0 TREF Temperature Figure 12. Because for T > Tref . 12. At Tref . J(t) begins to rapidly increase. The plateau region at middle times is known as the rubbery plateau. the curves are shifted to the right. The term log aT is thus known as the shift factor.12. log aT is equal to zero. For experiments at other temperatures. Plots such as Fig. The transition of J(t) from a low value to the plateau is a measurement of the glasstransition on a timescale plot. At late times. At early times J(t) is increasing.
This equation is known as the Doolittle equation. Around Tg and above Tg . The most quantitative results. Expansion of the total. Above Tg . free.7. αf is approximately αm − αg . however. the theory can be applied to semicrystalline polymers. 12. The occupied volume might be expected to expand with an expansion coeﬃcient appropriate to a solid polymer or close to the expansion coeﬃcient that exists below Tg . The shift factor can be expected to be related to the relative viscosities at two temperatures. An amorphous polymer can be considered to be made up of occupied volume and free volume. are obtained when working with amorphous polymers. Because semicrystalline polymers also have amorphous regions. the solid part or occupied volume should continue expanding at the same rate and the excess expansion observed above Tg can be attributed to expansion in the free volume.42) . If we select Tg as the reference temperature. As the temperature is changed. At any given temperature. or the diﬀerence between the thermal expansion coeﬃcients of the polymer above (αm where m stands for melt) and below (αg where g stands for glass) Tg .40) where fg is the fraction of free volume at Tg and αf is an expansion coeﬃcient for the fraction free volume (see Fig. the fraction of the total volume that is free volume is f (T ) = Vf Vf ≈ Vf + V0 V0 (12.156 CHAPTER 12. MECHANICAL PROPERTIES 12. According to free volume theory. to be able to predict log aT . It would be nice. 12. The theory was originally developed for amorphous polymers and the glasstransition in those polymers. the WLF equation (for WilliamsLandelFerry). however.2 FreeVolume Theory With suﬃcient data. There is an empirical equation.39) where the approximation is based on Vf << V0 .5. and that equation can be justiﬁed with freevolume theory. This measured log aT can then be used to quantify the timetemperature superposition principle. log aT can be found experimentally by shifting creep curves to obtain the maximum amount of overlap. viscosity can be related to the fraction of free volume by ln η(T ) = A + B f (T ) (12. and occupied volume is illustrated schematically in the dilatometry data in Fig. the fraction of free volume can be expressed as f (T ) = fg + αf (T − Tg ) (12.7). the free volume and the occupied volume will both change in speciﬁc volume or density.41) This equation states that as the fraction of free volume increases. then the shift factor at any other T (≥ Tg ) is given by ln aT = ln η(T ) = ln η(T ) − ln η(Tg ) = B η(Tg ) 1 1 − f (T ) fg (12. the viscosity decreases.
.7: Plots of total volume and occupied volume for an amorphous polymer both above and below the glasstransition temperature.5.12. TIME DEPENDENCE OR VISCOELASTICITY 157 Vtotal Vfree αf Voccupied V Temperature Figure 12.
Tref . 12. The higher curves are for lower temperatures and the lower curves are for higher temperatures. There is an advantage to choosing Tg as the reference temperature. the constants C1 and C2 are relatively invariant to the nature of the polymer. 12. In general. it has been observed that the constants in the expressions above (C1 and C2 ) appear to be universal for all polymers. 12. this expression can be rearranged to get: − log aT = or log aT = B 2.44(T − Tg ) 51. This can occur when the creep compliance remains constant over a long period of time. there is no way of knowing how far to shift. longterm stress relaxation tests are done using timetemperature superposition. The left side of Fig. the shift factors cannot be observed experimentally. The reasons behind this result will be discussed in class. 12.44) where C1 and C2 are two constants for a given polymer. For a wide variety of polymers the shift factor is given by: log aT = −17. We note that the variation from polymer to polymer can be signiﬁcant. In fact any reference temperature.6. it is recommended that the WLF universal constants only be used as a last resort.3 Stress Relaxation Experiments The complementary experiment to creep experiments is stress relaxation experiments. The universal constants come from ﬁtting the WLF equation to a wide variety of polymers.303fg fg αf (T − Tg ) (12. The shift can only be measured if there are features (i. The predicted eﬀect is about a 3◦ C change in Tg for each order of magnitude change in rate. changes) in the creep compliance data at all temperatures.. It is better to determine shift factors experimentally or to ﬁnd WLF constants speciﬁc to the polymer of interest. MECHANICAL PROPERTIES Substituting in f (T ) from above. If there is no change at several temperatures.158 CHAPTER 12.8 . could be used as long as the fraction of freevolume can be expressed by the equation give earlier.e. There is nothing special about the choice of Tg in the above derivation. In other words. If we restrict the reference temperature to Tg .5. The right side of Fig.6 + (T − Tg ) (12. this requirement limits T ’s to near Tg and equations like the WLF equation can only be expected to be quantitative near and above Tg .8 shows several stress relaxation tests at various temperature. In practice. The WLF equation gives us information about the eﬀect of rate on Tg . Like creep tests.45) A plot of this equation would be similar to the plot in Fig. In some cases.43) + (T − Tg ) −C1 (T − Tg ) C2 + (T − Tg ) (12. This shiftfactor equation is the WLF equation.
The master relaxation modulus curve resembles a ﬂipped over version of the master creep compliance curve. Thus the strain input is ε(t) = ε0 sin ωt (12. and a constant frequency. they can often be impractical because they require much time. as in a stress relaxation test.46) . The ﬁnal or terminal region represents viscous ﬂow. instead of keeping the strain constant. each of which can take 105 to 106 seconds (1 to 10 days). They require several experiments at various temperatures.5. The higher curves are for lower temperatures. The transition from the glassy region to the rubbery plateau is the glass transition visualized on a time scale. In this region the response is elastic and G(t) is approximately equal to the static tensile test modulus. the lower curves are for higher temperatures.4 Dynamic Mechanical Analysis While creep and stress relaxation tests can be used to characterize viscoelastic materials. TIME DEPENDENCE OR VISCOELASTICITY 159 Glassy Viscoelastic G(t) G(t) Rubbery Viscous Flow log t log tr Figure 12. The earliest time data. The next region is called the viscoelastic region. Furthermore the various regions of the relaxation modulus curve correspond to the regions of the creep compliance curve. It is obtained from the raw data on the left by using timetemperature superposition. where G(t) is ﬂat. A more common technique for characterizing viscoelastic polymers is dynamic mechanical analysis (DMA). the strain is oscillated at a constant amplitude. E.8: Left side is a set of stress relaxation experiments as a function of temperature. In DMA.5. 12. shows the master plot for relaxation modulus plot that was obtained by appropriately shifting the raw data in the left side plot.12. is the glassy region. The right side is the master curve for relaxation modulus. ω. The middle region is called the rubbery plateau. ε0 .
52) (12.49) (12. in this case we take the ratio of the amplitudes of the stress and the strain: G(ω) = σ0 ε0 (12. The inverse relations can easily be derived: G(ω) = tan δ = G (ω)2 + G (ω)2 G (ω) G (ω) (12. it will respond at the same frequency but may have a phase diﬀerence and a diﬀerent amplitude. In other words.54) . It also describes the elastic part of the stress response. The phase angle. It is common practice to deﬁne a complex modulus: G∗ (ω) = G (ω) + iG (ω) (12. MECHANICAL PROPERTIES As in most physical response problems. δ will be between 0 and π/2 and the material will be viscoelastic. If δ = 0. describes the viscous character of the material. It is proportional to that part of the strain energy that is lost during a cycle due to viscoelastic dampening. In general. In analogy with other deﬁnitions of moduli. we can expand the stress function: σ(t) = G(ω)ε0 cos δ sin ωt + G(ω)ε0 sin δ cos ωt = G (ω)ε0 sin ωt + G (ω)ε0 cos ωt where G (ω) = G(ω) cos δ and G (ω) = G(ω) sin δ (12.47) G(ω) or the dynamic modulus deﬁnes the modulus of a viscoelastic material. δ.50) G (ω) is known as the storage modulus.160 CHAPTER 12.51) (12.48) (12. Some people prefer other ways to describe DMA data. It also describes the viscoelastic part of the stress response. If δ = π/2. G (ω) is known as the loss modulus. when the system is driven by a constant frequency. To see alternative representations. the stress is completely out of phase and is completely viscous. or that part of the stress that is out of phase with the strain. The above expressions give G (ω) and G (ω) in terms of G(ω) and δ. or the part of the stress in phase with the strain. It is proportional to that part of the strain energy that is stored and then recovered during one cycle. the stress is in phase with the strain and the material is totally elastic.53) These two relations are reminiscent of complex numbers. the stress will be given by: σ(t) = σ0 sin(ωt + δ) = G(ω)ε0 sin(ωt + δ) where G(ω) is the dynamic modulus and δ is the phase angle. the dynamic modulus G(ω) is the ratio of stress to strain.
is to measure G (ω) and tan δ. δ.9: Typical DMA data for an amorphous polymer. Only two of these are independent and it is only useful or rather necessary to measure two of them. The crystal fraction contributes stiﬀness and prevents overall viscous ﬂow. 12. The relative drops at Tg and Tm are sensitive to the percent crystallinity. Observing these smaller peaks is one of the best ways of observing subglass relaxations.10. but not universal practice. It is easy to show that G∗ (ω) can be calculated from a Fourier transform of G(t). while tan δ goes through a peak. We have deﬁned four types of dynamic properties — G(ω). At Tg . Some typical DMA data for an amorphous polymer as a function of temperature are plotted in Fig. Below Tg these data are similar to the amorphous polymer data including peaks in tan δ at subglass relaxations and at Tg .9. however. and G (ω). DMA experiments measure a new viscoelastic modulus called the complex dynamic modulus of G∗ (ω). the loss modulus is the imaginary part of G∗ (ω). Some typical DMA data for semicrystalline polymers as a function of temperature are given in Fig. G (ω) drops dramatically. G (ω) is fairly constant. TIME DEPENDENCE OR VISCOELASTICITY 161 G'(ω) G'(ω) or tan δ Tg n tan δ Temperature Figure 12. and tan δ is the tangent of the angle between G∗ (ω) and the positive real axis when G∗ (ω) is plotted in the complex plane. however. the crystals melt and a second drop in G (ω) results in a very low ﬁnal value. At Tg . 12. The stress relaxation experiments measure a relaxation modulus known as G(t). At Tm . G (ω) does not drop nearly as far. Below Tg . G (ω) is close to the modulus of the material that would be measured in a static test. G(t) and G∗ (ω). Thus G∗ (ω) is the frequency domain version of the relaxation . G (ω). and because tan δ and therefore also G (ω) are both small.5. The peak is often used to measure the glass transition temperature. Peaks in tan δ can also be observed below Tg . Common. are not independent quantities. the dynamic modulus is the amplitude of G∗ (ω).12. The storage modulus is the real part of G∗ (ω).
J ∗ (ω). Most commercial instruments are limited to oscillating strains or displacements. In analogy with creep experiments.10: Typical DMA data for an semicrystalline polymer. Problems 12–1. The analysis of dynamic stress experiments is identical to the above analysis of DMA experiments. J(ω) (the dynamic modulus). and δ (phase angle). J (ω) (the loss compliance).162 CHAPTER 12. J ∗ (ω) can be broken up to component functions of J (ω) (the storage compliance). modulus. Show that Eq. These dynamic experiments will give a dynamic complex compliance. . (12. which can be shown to be the Fourier transform of J(t). Like dynamic modulus. we could imagine dynamic stress experiments in which the sample is subjected to an oscillating stress and we measure the amplitude and the phase angle of the strain response.27) is valid for any stress state and not just for hydrostatic compression. Thus must dynamic tests on polymers measure dynamic modulus instead of dynamic compliance. MECHANICAL PROPERTIES G'(ω) G'(ω) or tan δ Tg Tm n tan δ Temperature Figure 12.
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