Chapter 12

Polymer blends, copolymers and liquidcrystal

polymers
12.1 Introduction
Although the properties of the polymers in the three groups considered in this chapter are in some ways
very different, they share the possibility, under suitable circumstances, of self-organisation into supermolecular
structures that are of different kinds from the crystallites and spherulites typical of the semicrystalline polymers
discussed in the earlier chapters. These kinds of organisation give rise to properties that are of great interest both
scientifically and commercially and it is the aim of this chapter to indicate some of the factors that control the
various kinds of organization and to give some indication of the wide variety of structures and properties that can be
obtained.
Two or more existing polymers may be blended for various reasons. One reason is to achieve a material
that has a combination of the properties of the constituents, e.g. a blend of two polymers, one of which is chemically
resistant and the other tough. Another reason is to save costs by blending a high performance polymer with a
cheaper material. A very important use of blending is the combination of an elastomer with a rigid polymer in order
to reduce the brittleness of the rigid polymer. It is in the latter use
that the self-organising feature of some blends is seen to play a part. This feature arises when the components of the
blend are incompatible, i.e. they do not mix, and they segregate into different regions within the material.
Copolymerisation might at first sight be thought to be a route for compelling two polymers to mix. If, however, the
polymer is a block copolymer it is still possible, and indeed usual, for the components to segregate, which can give
rise to interesting and useful structures.
The materials of the third group to be discussed in this chapter, liquidcrystal polymers, possess the property
of self-organisation into highly oriented local regions that can be further aligned very easily to give solid structures
with high modulus and strength, which makes them important materials for many applications.

12.2 Polymer blends

12.2.1 Introduction
When any two materials are mixed together, or blended, the properties of the resulting mixture depend on
the level at which intimate mixing takes place and on whether any chemical reactions between the components of
the mixture take place. An example of a very coarse level of mixing is concrete, formed by the mixing of pebbles
and mortar. The mortar itself is a somewhat finer mixture of sand and cement and the setting process involves
chemical reactions between the cement and both the sand and the pebbles. The most intimate form of mixing is at
the molecular level; two substances that have mixed at this level may each be said to have dissolved in the other. If
the molecules have similar sizes, each type of molecule is then surrounded, on average, by molecules of the two
types in proportion to the numbers of the two types in the mixture.
Some polymers can be mixed homogeneously with others at a molecular level over a wide range of
compositions in such a way that there is only one phase present, but most cannot. Immiscible polymer compositions
can, however, often be induced to coexist at a variety of coarser levels of mixing, similar in some instances to the
structure of cement, but on a much finer scale. In the next section the factors that determine the mixing behavior are
considered. First it is useful to give some definitions. A miscible npolymer blend is one for which the miscibility and
homogeneity extend down to the molecular level, so that there is no phase separation. An immiscible blend is one
for which phase separation occurs, as
described in the next section. An immiscible blend is called compatible if it is a useful blend wherein the
inhomogeneity caused by the different phases is on a small enough scale not to be apparent in use. (Blends that are
miscible in certain useful ranges of composition and temperature, but immiscible in others, are also sometimes
called compatible blends.) Most blends are immiscible and can be made compatible only by a variety of
compatibilisation techniques, which are described in section 12.2.4. Such
compatibilised blends are sometimes called polymer alloys.

12.2.2 Conditions for polymer–polymer miscibility

The necessary condition for two substances A and B to mix is that the Gibbs free energy of the mixture must be less
than the sum of the Gibbs free energies of the separate constituents, i.e. that _Gmix, the increase in free energy on
mixing, should be < 0. The free energy is given by G ¼ H _ TS, where H is the enthalpy and S is the entropy, so that
the necessary condition for mixing at temperature T is _Gmix ¼ _Hmix _ T _Smix < 0 ð12:1Þ where _Hmix is the
enthalpy of mixing and _Smix is the entropy of mixing. Unless there are special attractive forces, such as hydrogen-
bonding, between molecules of the two different types A and B, there is usually a stronger attraction between
molecules A and A and molecules B and B than there is between molecules A and B. This means that if A and B
molecules mix randomly, _Hmix > 0. For this (hypothetical) random mixing, _Hmix per mole is usually written in the
form
_Hmix ¼ RT_AB_A_B ð12:2Þ
where _A and _B are the volume fractions of molecules A and B, respectively, in the mixture and _AB is the
Flory–Huggins interaction parameter. Consider first two small-molecule compounds, A and B, and assume that there
are no special interaction forces, such as hydrogen-bonding, between A molecules, between B molecules and
between A and B molecules. The change in enthalpy when the two compounds mix is then likely to be small. If
there is no change of enthalpy, the mixing is said to be athermal mixing because it takes place without heat being
emitted or absorbed. The free energy of mixing is then entirely due to the increase in entropy on mixing, which is
always positive, so that mixing takes place for all concentrations. Even if the mixing is not athermal and _Hmix is
positive, the increase in entropy is often sufficient to allow mixing at least for some concentration range, because
there are enormously more ways in which the molecules can be arranged in the mixture than there are for the
separated pure constituents. For polymers this is not so. Consider the mixing of two polymers A and B and suppose
for simplicity that each is mono-disperse and that the lengths, thicknesses and flexibilities
of the two types of molecule are very closely the same. Imagine that equal amounts of the two polymers are mixed,
say n molecules of each. If the polymers were truly indistinguishable, the entropy of the mixture would be equal to
exactly twice the entropy of each of the component sets of n molecules before mixing. If, on the other hand, the
molecules are different, however slightly, there will be an increase in entropy when they mix, because of the number
of different arrangements that can be produced by interchanging molecules of the two different types. Imagine any
particular state of the mixture, with each of the molecules in one specific conformation out of the many that it can
take up. Whatever this state, it can be arrived at in (2n)!/(n!)2 ways. The factor (2n)! is the number of ways of
arranging 2n distinguishable molecules on 2n sites, which must be divided by (n!)2 to take account of the identity of
the n molecules of type A and the n molecules of type B. The total number N of ways of arranging the 2n molecules
in the mixture is thus given by
N ¼ Noð2nÞ!=ðn!Þ2 ð12:3Þ
where No is the total number of conformational states available to the mixture when the difference between A and B
molecules is neglected. If So is the total entropy of the unmixed polymers, then using Boltzmann’s expression S ¼ k
lnN for the entropy of the mixture leads to
_Smix ¼ S _ So ¼ k lnN _ So ¼ k lnNo þ k ln ð2nÞ!
ðn!Þ2
__
_ So
¼ k ln ð2nÞ!
ðn!Þ2
_ _ ð12:4Þ
because So ¼ k lnNo. Using Stirling’s approximation for large m, namely
ln(m!) ¼ mlnm _ m, leads to
_Smix ¼ k½ð2nÞ lnð2nÞ _ 2n _ 2ðn ln n _ nÞ_ ¼ k½2n lnð2nÞ _ 2n ln n_
¼ 2nk ln 2
ð12:5Þ
Suppose now that each polymer chain is made up of x monomer units joined together and consider what the
corresponding value of _Smix would be if the monomers were separate molecules, so that the monomers of A could
mix totally freely with those of B when the substances were mixed. It is merely necessary to replace n in the above
argument by xn, so that, for this mixture, _Smix ¼ 2xnk ln 2, which is x times greater than for the polymer mixture.
Because the value of x may easily be 1000 or much larger, the entropy of mixing of polymers is usually thousands
of times smaller than it would be for the mixing of the corresponding monomers, so that even a small positive value
of _Hmix is likely to prevent mixing from taking place.
The above argument somewhat overemphasises the immiscibility of polymers, because it considers only
the mixing of polymers of high molar mass at equal concentrations of the two components. Considering the entropy
of mixing more generally shows that mixing becomes more likely for low molar masses and small concentrations of
the minority component and that all polymers are miscible at low enough concentrations of the minority component.
It is therefore useful to consider how miscibility actually varies with composition in polymer blends before
considering the modifications that need to be made to the theory to account for the fact that some pairs of polymers
are miscible over ranges of composition rather larger than might be expected.
When _Gmix at a particular temperature is plotted against composition for a blend of two polymers, a curve
of the type shown schematically in fig. 12.1(a) is obtained in the simplest case. The quantity _Gmix is usually taken
to be the free energy per unit volume and represents the value that would be obtained if the two components could
be uniformly molecularly mixed at the corresponding composition, which is usually specified in terms of the volume
fraction _ of one of the components. The points B represent the
points where the straight line shown is tangential to the curve and are called the binodal points. The points S are the
points of inflection, where the curvature changes sign, and are called the spinodal points.
In discussing the implications of this curve it is useful to consider the diagram shown in fig. 12.1(b). Suppose that a
particular mixture corresponding to the composition _o is made, so that _Gmix is represented by the point O. Assume
that, by some mechanism, the mixture actually splits into two phases represented by the points P 1 and P2,
corresponding to compositions _1 and _2, respectively. Because the overall composition of the mixture cannot
change, the actual volumes of the two phases depend on the values of _o, _1 and _2. Provided that there are no
changes of volume on mixing, it can be shown (see problem 12.1) that the overall value of _Gmix is now given by the
point P on the chord P1P2 where it
crosses a line parallel to the _Gmix axis drawn at composition _o. For the particular compositions illustrated, this
value of _Gmix would be greater than the value corresponding to a single phase of composition _o. It follows from
the construction in fig. 12.1(b) that for any composition between one end of the curve of fig. 12.1(a) and the nearest
point B, partition of the mixture into two phases of different compositions would lead to an increase in the total
value of _Gmix. Compositions in the two corresponding
regions are therefore stable against fluctuations of composition. In contrast, for any composition between the two
points B where the common tangent touches the curve, the lowest free energy of mixing is obtained by the
coexistence of two separate phases corresponding to the points B. This is actually an example of a more general
thermodynamic rule for determining the equilibrium concentrations of phases in mixtures. When changes in volume
take place on mixing, the argument holds if molar free energies and mole fractions, rather than volume fractions, are
used. A further example of the application of this common-tangent construction is given in section 12.4.4 in
connection with the theory of liquid-crystal polymers.

Fig. 12.1 (a) Gmix plotted against composition for a partially miscible polymer. The points B are the
binodal points, where a common tangent touches the two sections of the curve near the minima. The points S are the
spinodal points, where the curve has points of inflection. M is the maximum between the spinodal points. (b) See the
text.

A closer look at the application of the construction of fig. 12.1(b) to the region between the two points B
shows that any composition between the two points S, called the spinodal region, is unstable against small
fluctuations in composition and the lowest free energy can be obtained by splitting into two phases with
compositions corresponding to the points B. This is called spinodal decomposition (SD). The two regions between
consecutive points B and S, called the binodal regions, are more interesting. The curvature in these regions is such
that for small fluctuations in composition the free energy increases, but for larger fluctuations it can decrease if the
mixture splits into two phases of compositions corresponding to the two points B. This kind of decomposition is
called binodal decomposition (BD). Unlike SD, BD is not spontaneous, because small variations of composition
lead to an increase in the free energy and therefore tend to die out. If, however, a large enough fluctuation takes
place, a concentration within the spinodal region may be achieved and then phase separation will take place
spontaneously. The mechanism for phase separation in the binodal region is thus nucleation and growth. Droplets of
the equilibrium phase corresponding to one of the points B form by nucleation and then grow by a process of
diffusion of the polymer molecules from the surrounding matrix. Eventually coalescence of droplets takes place.
The phase separation in SD takes place in a completely different way. There is no nucleation stage because
any slight change in the composition lowers the free energy. The process therefore takes place in three stages,
diffusion, liquid flow and finally coalescence. In the early stages the different regions have compositions that are
somewhere between those of the two points B and their boundaries are ill-defined, with the composition changing
smoothly from one region to another. It must be emphasised that the various stages of phase separation and the final
structures obtained depend on many factors, some of which are considered in later sections. The previous paragraphs
represent idealisations of what may happen during real polymer blend processing. One of the most important factors
that determine the behaviour of a polymer blend is the way that temperature affects the _Gmix curve, which is now
considered.
The curve obtained by plotting the points B on a temperature–composition plot, or phase diagram, is called the
binodal curve or simply the binodal. A similar curve for the spinodal points is called the spinodal. There are two
simple possible ways in which the curve of fig. 12.1(a) can change when the temperature T is changed. Either the
points B get closer together as T decreases and finally coalesce or they get closer together as T increases and finally
coalesce. In the first type of behaviour, illustrated in fig. 12.2(a), there is a lower critical solution temperature
(LCST) below which there is a single phase for all compositions and above which there are two phases for a certain
range of concentrations that increases in width with increasing T. In the second type of behaviour, illustrated in fig.
12.2(b), there is an upper critical solution temperature (UCST) above which there is a single phase for all
compositions and below which there are two phases for a certain range of concentrations that increases in width with
decreasing T. Many polymer systems have LCSTs, whereas most solutions of small molecules have UCSTs. More
complicated types of behaviour are also observed for polymers, with more than one UCST or LCST or neither type
of critical solution temperature. As already explained, the simplest forms of the theory of mixing suggest that
polymers of high molar mass should not be miscible over significant ranges of composition in the absence of
specific attractive interaction forces between the molecules. The theories cannot explain the existence of a LCST
either, because they suggest that the only temperature-dependent term in _Gmix is the entropic term _T_Smix and that,
if it plays any significant part, it must increase the likelihood of mixing as the temperature is raised. The
fundamental assumption behind the simplest attempts to calculate _Gmix is that it can be neatly split into two
contributions, the entropic contribution, which does not contain any part arising from the interaction between the
different types of molecule, and a part that depends only on the interactions and is purely enthalpic. More advanced
theories in which the interaction term contains both entropic and enthalpic parts have therefore been developed. In
order to allow for the existence of a LCST, this term is also made temperature-dependent.
The physical origin of the contribution of the interaction term to the entropy of mixing is that the interaction causes
one or both of the two constituent polymers to take up a different distribution of conformations
from that taken up in the pure state. The temperature dependence is introduced most simply by allowing the mixture
to have a larger volume than the sum of the volumes of its constituent molecules, i.e. by introducing the idea of free
volume and allowing this free volume to change with temperature. According to Koningsveld et al., if the
configurational entropy term is sufficiently small that it can be neglected, _Gmix per mole can be expressed in its
simplest form as
_Gmix=ðRTÞ " _0AB_A_B ¼ ða0 þ a1=T þ a2TÞðb0 þ b1_B þ b2_2
BÞ_A_B
ð12:6Þ
where T is the temperature, _A and _B are the volume fractions of components A and B and _0AB is the polymer–
polymer interaction parameter, which now includes both entropic and enthalpic contributions. The parameters a0, a1,
a2, b0, b1 and b2 depend on the nature of the polymers and must usually be determined by experiment.