3 Characterization

3.1 Introduction
Relationships between the synthesis and molecular properties of polymers
(Chapter 2), and between their molecular and bulk properties (Chapters 4
POLYMER THERMODYNAMICS
and 5), provide the foundations of Polymer Science. In order to establish
these relationships, and to test theories, it is essential to accurately and
thoroughly characterize the polymers under investigation. Furthermore,
(Young & Lovell)
use of these relationships to predict and understand the in-use performance
of a particular polymer depends upon the availability of good characteriza-
tion data for that polymer. Thus polymer characterization is of great
importance, both academically and commercially. The current chapter is
concerned with molecular characterization of polymer samples, by which is
meant the determination of their average molar masses, molar mass
distributions, molecular dimensions, overall compositions, basic chemical
structures and detailed molecular microstructures. Since most methods of
molecular characterization involve analysis of polymers in dilute solution
( < 20 g dm- 3), the relevant theories for polymers in solution will be
introduced before considering the individual methods.

Polymers in solution

3.2 Thermodynamics of polymer solutions

A solution can be defined as a homogeneous mixture of two or more
substances, i.e. the mixing is on a molecular scale. Under the usual
conditions of constant temperature T and pressure P, the thermodynamic
requirement for formation of a two-component solution is that the Gibbs
free energy G12 of the mixture must be less than the sum of the Gibbs free
energies G 1 and G2 of the pure components in isolation. This requirement
is defined in terms of the Gibbs free energy of mixing
/)'G m = G12 - (G1 + G 2 )

which must be negative (Le. /)'Gm < 0) for a solution to form. Since Gibbs
free energy is related to enthalpy H and entropy S by the standard
thermodynamic equation
G=H- TS (3.1)
 Characterization 139

a more useful expression for I'lG m is

I'lG m = I'lHm - TI'lSm (3.2)
where I'lHm is the enthalpy (or heat) of mixing and I'lSm is the entropy of
mixing.

3.2.1 Thermodynamics of ideal solutions

Ideal solutions are mixtures of molecules (i) that are identical in size and
(ii) for which the energies of like (i.e. 1-1 or 2-2) and unlike (i.e. 1-2)
molecular interactions are equal. The latter condition leads to athermal
mixing (i.e. I'lHm = 0), which also means that there are no changes in
the rotational, vibrational and translational entropies of the components
upon mixing. Thus I'lSm depends only upon the combinatorial (or configura-
tional) entropy change, I'ls~mb, which is positive because the number of
distinguishable spatial arrangements of the molecules increases when they
are mixed. Hence I'lG m is negative and formation of an ideal solution
always is favourable. The methods of statistical mechanics can be used to
derive an equation for I'ls~mb by assuming that the molecules are placed
randomly into cells which are of molecular size and which are arranged in
the form of a three-dimensional lattice (represented in two dimensions for
cubic cells in Fig. 3.1(a».
From statistical mechanics, the fundamental relation between the
entropy S of an assembly of molecules and the total number 0 of
distinguishable degenerate (i.e. of equal energy) arrangements of the
molecules is given by Boltzmann's equation
S=klnO (3.3)

•
0 0
0
••
•• • ••• 0 0
0
0 0 0 0 0 0
•--• •
0 0 000 0 0 0
0 0
I. ~t 0
I•

• • • -
0 0 0 0 0 0 1-
I'-

0 Ie 0 0 14_ 0 4t 0
•
0 0 0 0 0
• •• • • 0 0 .... 0 4~ 0

--
0 0 0 0 0
0 0 0 0 0 4~ 0 1I'"- 0
• • ••••
0 0
0 00 0 0 0 0 0 0 0
0 0 0 0 0 0 00 0 00 0 0
(0) (b)

Fig 3.1 Schematic representation of a liquid lattice. (a) mixture of molecules of equal size. (b)
mixture of solvent molecules with a polymer molecule showing the connectivity of polymer
segments.
140 Introduction to Polymers
where k is the Boltzmann constant. Application of this equation to
formation of an ideal solution gives
~s~mb = k[ln 0 12 - (In 0 1 + In O2)] (3.4)
where Ob O2 and 0 12 are respectively the total numbers of distinguishable
spatial arrangements of the molecules in the pure solvent, the pure solute
and the ideal mixture. Since all the molecules of a pure substance are
identical, there is only one distinguishable spatial arrangement of them
(i.e. of arranging N identical molecules in a lattice containing N cells).
Thus 0 1 = 1 and O2 = 1, allowing Equation (3.4) to be reduced to
(3.5)
For ideal mixing of NI molecules of solvent with N2 molecules of solute
in a lattice with (NI + N 2) cells, the total number of distinguishable spatial
arrangements of the molecules is equal to the number of permutations of
(NI + N 2) objects which fall into two classes containing Nl identical objects
of type 1 and N2 identical objects of type 2 respectively
. (Nl + N 2 )!
I.e. 0 12 = N IN I (3.6)
I· 2·

Substitution of Equation (3.6) into Equation (3.5) gives

~scomb = kl [(Nt + N 2 )!] (3.7)

m n N I·IN2·I
and introducing Stirling's approximation, InN! = NlnN - N (for large N),
leads to
L\s~mb = -k{Nlln [N1/(N 1+ N 2)] + N 2 ln [N2/(NI + N 2)]} (3.8)
It is more usual to write thermodynamic equations in terms of numbers
of moles, n, and mole fractions, X, which here are defined by nl = N1/NA ,
n2 = N 2/N A, Xl = nl/(nl + n2) and X 2 = n2/(nl + n2), where NA is the
Avogadro constant. Thus Equation (3.8) becomes
(3.9)
since the universal gas constant R = kNA . Hence for the formation of an
ideal solution
(3.10)
This important equation provides the fundamental basis from which
standard thermodynamic relationships for ideal solutions can be derived
(e.g. Raoult's Law). However, since relatively few solutions behave
ideally, the simple lattice theory requires modification to make it more
generally applicable. For mixtures of small molecules, non-ideality
 Characterization 141
'*
invariably is due to non-athermal mixing (i.e. !l.Hm 0) and so requires the
effects of non-equivalent intermolecular interactions to be taken into
account. In contrast, polymer solutions show major deviations from ideal
solution behaviour, even when !l.Hm = O. For example, the vapour
pressure of solvent above a polymer solution invariably is very much lower
than predicted from Raoult's Law. The failure of the simple lattice theory
to give realistic predictions of the thermodynamic properties of polymer
solutions arises from the assumption that the solvent and solute molecules
are identical in size. Paul Flory and Maurice Huggins independently
proposed a modified lattice theory which takes account of (i) the large
differences in size between solvent and polymer molecules, and (ii)
intermolecular interactions. This theory is described in an up-to-date form
in the following section.

3.2.2 l'lory-Hugginstheory
The theory sets out to predict !l.Gm for the formation of polymer solutions
by considering the polymer molecules to be chains of segments, each
segment being equal in size to a solvent molecule. The number, x, of
segments in the chain defines the size of a polymer molecule and is given by
the ratio of the molecular volumes of polymer and solvent (hence x is not
necessarily equal to the degree of polymerization). On this basis it is
possible to place solvent molecules and/or polymer molecules in a
three-dimensional lattice consisting of identical cells, each of which is the
same size as a solvent molecule and has z cells as first neighbours. Each
lattice cell is occupied by either a solvent molecule or a chain segment, and
each polymer molecule is placed in the lattice so that its chain segments
occupy a continuous sequence of x cells (as indicated in Fig. 3.1(b».
The first stage in the development of the Flory-Huggins theory is to
derive an expression for !l.s~mb when !l.Hm = O. As for mixing of simple
molecules this involves application of Equation (3.4), but this time with
fi2 > 1 because each molecule in a pure amorphous polymer can adopt
many different conformations (i.e. distinguishable spatial arrangements of
the chain of segments). Hence, for polymer solutions
!l.s~mb = kIn (fi 121fi2) (3.11)
The procedures and mathematical manipulations used to evaluate fi l2 ,
fi2 and !l.s~mb will only be considered in outline because they are
relatively complex. The basis of the calculations is the formation of a
theoretical polymer solution by mixing N2 polymer molecules, each
consisting of x chain segments, with Nt solvent molecules in a lattice
containing Nl + XN2 (= N) cells. The N2 polymer molecules are added
one-by-one to the lattice before adding the solvent molecules. When
142 Introduction to Polymers
adding a polymer molecule, the first segment of the chain can be placed
in any empty cell. However, for the connectivity required to represent a
polymer molecule, each successive segment of the remaining x-I seg-
ments must be placed in an empty cell adjacent to the previously-placed
segment. The individual numbers of possible placements are calculated for
each segment of the chain, and by multiplying these numbers together the
total number, v, of possible conformations of the polymer molecule in the
lattice is obtained. This series of calculations is carried out for each of
the N2 polymer molecules as they are added to the lattice. The restrictions
imposed by partial occupancy of the lattice are taken into account using a
mean-field approximation whereby the segments of the previously-added
polymer molecules are assumed to be distributed uniformly in the lattice.
Since the N} solvent molecules are identical, there is only one distinguish-
able spatial arrangement of them, namely one solvent molecule in each of
the remaining N} empty cells. Thus the total number of distinguishable
spatial arrangements of the mixture is given by
1 N2
-,IT
0 12 =
N
Vi
2 ' i =1
(3.12)

where II is the sign for a continuous product (in this case

VI x V2 X V3 X V4 X ... x VNJ The factor of lIN2! takes account of the fact
that the N2 polymer molecules are identical and therefore indistinguishable
from each other. The resulting expression for 0 12 is given below in a useful
form presented more recently by Flory

(3.13)

The first quantity in square brackets is the total number of conforma-

tions of the N2 polymer molecules when each one is given the complete
freedom of the lattice (i.e. the lattice is assumed to be empty when adding
each polymer molecule). The second quantity is the fraction of these
conformations that are allowed when the N2 polymer molecules compete
for cells in a lattice of xN2 cells (i.e. in the pure amorphous polymer). The
third quantity is the factor by which the total number of conformations of
the N2 polymer molecules is increased when they are given greater spatial
freedom by dilution with N} solvent molecules. Thus O2 is given by the
product of the first two factors in Equation (3.13) and so Equation (3.11)
simplifies to

which simplifies further to give

 Characterization 143
~s~mb = -k[NllnifJl + N2 In ifJ21 (3.14)
where ifJl and ifJ2 are the volume fractions of solvent and polymer
respectively, and are given by <PI = NI/(NI +xN2) and <P2 =
XN2/(NI + XN2)' Writing Equation (3.14) in terms ofthe number of moles,
nl and n2, of solvent and polymer in the mixture gives
~s~mb = -R[nllnifJl + n2 InifJ21 (3.15)
which may be compared to the corresponding expression for ideal mixing,
i.e. Equation (3.9). Thus the only difference is that for polymer solutions,
the mole fractions in Equation (3.9) are replaced by the corresponding
volume fractions. Equation (3.15) is in fact a more general expression for
athermal mixing and reduces to Equation (3.9) when x = l.
Having derived an expression for ~s~mb, the second stage in the
development of Flory-Huggins theory is to calculate a term which accounts
for the effects of intermolecular interactions. In the original theory, this
was considered only in terms of an enthalpy change. However, the term
subsequently was modified in recognition that there must be an entropy
change associated with the non-randomness induced by interactions. Thus
the effects of interactions will be treated here in terms of a contact Gibbs
free energy change, ~G~ntact. The calculation is simplified by restriction
to first neighbour interactions on the basis that the forces between
uncharged molecules are known to decrease rapidly with their distance of
separation. Three types of contact need to be considered, each with its own
Gibbs free energy of interaction:
Type of contact Gibbs free energy of interaction
Solvent-solvent gl1
Segment-segment g22
Solvent-segment gl2
For every two solvent-segment contacts formed on mlxmg, one
solvent-solvent and one segment-segment contact of the pure components
are lost. Thus the Gibbs free energy change, ~gI2' for the formation of a
single solvent-segment contact is given by
~g12 = gl2 - !(gl1 + g22)
If PI2 is the total number of solvent-segment contacts in the solution,
then
(3.16)
With the exception of the segments at the chain ends, each chain
segment has two connected segmental neighbours. Hence there are
(z - 2)x + 2 lattice sites adjacent to each polymer molecule. When x is
144 Introduction to Polymers
large, (z - 2)x» 2 and the total number of lattice sites adjacent to all the
polymer molecules can be taken as N 2 (z - 2)x. On the basis of the
mean-field approximation, a fraction ¢l of these sites will be occupied by
solvent molecules. Thus
P12 = Nz(z - 2)X¢1
from which x can be eliminated to give
P12 = (z - 2)N1¢2 (3.17)
because xN2¢1 = N 1¢2. Combining Equations (3.16) and (3.17) leads to
(3.18)
The lattice parameter z and the Gibbs free energy change ~g12 are not
easily accessible, and so are eliminated by introducing a single new
parameter, X, which is commonly known as the Flory-Huggins polymer-
solvent interaction parameter and is defined by
(3.19)
Thus X is a temperature-dependent dimensionless quantity which
characterizes polymer-solvent interactions and can be expressed more
simply in the form
x= a+ biT
where a and b are temperature-independent quantities. More generally X is
given as the sum of enthalpy, XH, and entropy, Xs, components
X= XH+ Xs (3.20)
from which it is simple to show that XH = biT and Xs = a, and that

XH=
ax)
-T ( aT a(Tx)
and XS=iJT

Combination of Equations (3.18) and (3.19) together with the relations

n\ = N\/NA and R = kNA leads to
(3.21)
Now all that is required to obtain the Flory-Huggins equation for the
Gibbs free energy of mixing is to combine ~s~mb (Equation (3.15)) and
~G~ntact (Equation (3.21)) as follows

~Gm = ~G~ntact - T~s~mb

to give
~Gm = RT[n1ln¢1 + n2 1n¢2 + nl¢2X] (3.22)
 Characterization 145
Using the Flory-Huggins equation it is possible to account for the
equilibrium thermodynamic properties of polymer solutions, particularly
the large negative deviations from Raoult's Law, phase-separation and
fractionation behaviour, melting-point depressions in crystalline polymers,
and swelling of networks. However, whilst the theory is able to predict
general trends, precise agreement with experimental data is not achieved.
The deficiencies of the theory result from the limitations both of the model
and of the assumptions employed in its derivation. The use of a single type
of lattice for pure solvent, pure polymer and their mixtures is unrealistic
and requires there to be no volume change upon mixing. The mathematical
procedure used to calculate the total number of possible conformations of
a polymer molecule in the lattice does not exclude self-intersections of the
chain, which clearly is physically unrealistic. Furthermore, the use of a
mean-field approximation to facilitate this calculation for placement of a
polymer molecule in a partly-filled lattice, is satisfactory only when the
volume fraction, ¢2, of polymer is high. In view of this, Flory-Huggins
theory is least satisfactory for dilute polymer solutions because the polymer
molecules in such solutions are isolated from each other by regions of pure
solvent, i.e. the segments are not uniformly distributed in the lattice.
Additionally, the interaction parameter, X, introduced to account for the
effects of contact interactions, is not a simple parameter. Equation (3.20)
resulted from a recognition that X contains both enthalpy and entropy
contributions, and X also has been shown to depend upon ¢2. Despite these
shortcomings, Flory-Huggins lattice theory was a major step forward
towards understanding the thermodynamics of polymer solutions, and is
the basis of many other theories. The theory will be developed further in
subsequent sections since the relationships obtained are instructive, though
the above limitations must be borne in mind when applying the resulting
equations. Some of the more refined theories developed since the advent
of Flory-Huggins lattice theory will be given brief consideration, but in
general are beyond the scope of this book.

3.2.3 Partial molar quantities and chemical potential

In thermodynamics it often is necessary to distinguish between extensive
and intensive properties. The value of an extensive property changes with
the amount of material in the system, whereas the value of an intensive
property is independent of the amount of material. Examples of extensive
properties are mass, volume, and total free energy, enthalpy and entropy,
whereas intensive properties include pressure, temperature, density and
molar free energy, enthalpy and entropy. Generally, systems at equilib-
rium are defined in terms of their intensive properties.
For multicomponent systems such as polymer solutions, it is important