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General and thermodynamic terms

Polymer Dissolution
What is solubility and what it depends on?

It should be pointed out that not all polymers can be dissolved,


and even though when they can, the dissolution process may take
up to several days or weeks. According to Rosen (1982), there is
an assembly of general rules for polymer solubility, based on
experimental observations, from which interesting conclusions
can be obtained.

Thus, it is well known that the dissolution of polymers depends


not only on their physical properties, but also on their chemical
structure, such as: polarity, molecular weight, branching,
crosslinking degree, and crystallinity. The general principle that
states like dissolves like is also appropriate in the case of
polymers. Thus, polar macromolecules like poly (acrylic acid),
poly (acrylamide) and polyvinyl alcohol, among others, are
soluble in water. Conversely, nonpolar polymers or polymer
showing a low polarity such as polystyrene, poly(methyl
methacrylate), poly(vinyl chloride), and poly(isobutylene), are
soluble in nonpolar solvents.

On the other hand, the molecular weight of polymers plays an


important role in their solubility. In a given solvent at a particular
temperature, as molecular weight increases, the solubility of a
polymer decreases. This same behavior is also noticed as
crosslinking degree increases, since strongly cross-linked
polymers will inhibit the interaction between polymer chains and
solvent molecules, preventing those polymer chains from being
transported into solution.

A similar situation occurs with crystalline macromolecules,


although in such a case the dissolution can be forced if an
appropriate solvent is available, or warming the polymer up to
temperatures slightly below its crystalline melting point (Tm). For
example, highly crystalline linear polyethylene (Tm = 135ºC) can
be dissolved in several solvents above 100ºC. Nylon 6.6 (Tm =
265ºC), a crystalline polymer which is more polar than
polyethylene, can be dissolved at room temperature in the
presence of solvents with enough ability to interact with its
chains, through for example, hydrogen bonding. Branched
polymer chains generally increase solubility, although the rate, at
which this solubility occurs, depends on the particular type of
branching. Chains containing long branches, cause dense
entanglements making difficult the penetration of solvent
molecules. Therefore the rate of dissolution in these cases
becomes slower than if it was short branching, where the
interaction between chains is practically non-existent.

How a Polymer gets dissolved?

As said earlier, the dissolution of a polymer is generally a slow


process, which can take even several weeks, depending on the
structure and the molecular weight of a given polymer.

When a low molecular weight solute such as sucrose is added to


water, the dissolution process takes place immediately. The sugar
molecules leave the crystal lattice progressively, disperse in
water, and form a solution.

But polymer molecules are rather different. They constitute long


chains with a large number of segments, forming tightly folded
coils which are even entangled to each other. Numerous cohesive
and attractive both intra and intermolecular forces hold these
coils together, such a dispersion, dipole-dipole interaction,
induction, and hydrogen bonding (Figure 1a).

Based on these features, one may expect noticeable differences


in the dissolution behavior shown by polymers. Due to their size,
coiled shape, and the attraction forces between them, polymer
molecules become dissolved quite slowly than low molecular
weight molecules. Billmeyer Jr. (1975) points out that there are
two stages involved in this process: in the first place, the polymer
swelling and next the dissolution step itself.

When a polymer is added to a given solvent, attraction as well as


dispersion forces begin acting between its segments, according to
their polarity, chemical characteristics, and solubility parameter.
If the polymer-solvent interactions are higher than the polymer-
polymer attraction forces, the chain segment start to absorb
solvent molecules, increasing the volume of the polymer matrix,
and loosening out from their coiled shape (Figure 1b). We say the
segments are now "solvated" instead of "aggregated", as they
were in the solid state.

The whole "solvation-unfolding-swelling" process takes a long


time, and given it is influenced only by the polymer-solvent
interactions, stirring plays no role in this case. However, it is
desirable to start with fine powdered material, in order to expose
more of their area for polymer-solvent interactions.

When crystalline, hydrogen bonded or highly cross-linked


substances are involved, where polymer-polymer interactions are
strong enough, the process does stop at this first stage, giving a
swollen gel as a result.

If on the contrary, the polymer-solvent interactions are still


strongly enough, the "solvation-unfolding-swelling" process will
continue until all segments are solvated. Thus, the whole loosen
coil will diffuse out of the swollen polymer, dispersing into a
solution. At this stage, the disintegration of the swollen mass can
be favored by stirring, which increases the rate of dissolution.

However, once all the chain segments have been dispersed in the
solvent phase, they still retain their coiled conformation, yet they
are now unfolded, fully solvated, and with solvent molecules
filling the empty space between the loosen segments. Hence, the
polymer coil, along with solvent molecules held within, adopts a
spherical or ellipsoid form, occupying a volume known as
hydrodynamic volume of the polymer coil (Figure 1c).

The particular behavior shown by polymer molecules, explains the


high viscosity of polymer solutions. Solvent and low molecular
weight solutes have comparable molecular size, and the solute
does not swell when dissolving. Since molecular mobility is not
restricted, and therefore intermolecular friction does not increase
drastically, the viscosity of the solvent and the solution are
similar. But the molecular size of polymer solutes is much bigger
than that of the solvent. In the dissolution process such molecules
swell appreciably, restricting their mobility, and consequently the
intermolecular friction increases. The solution in these cases,
becomes highly viscous.

Figure 1. Schematic representation of the dissolution process for polymer molecules


Thermodynamics background

The solubility of a given polymer in various solvents is largely


determined by its chemical structure. Polymers will dissolve in
solvents whose solubility parameters are not too different from
their own. This principle has become known as ‘like dissolves
like’, and, as a general rule, structural similarity favors solubility.

Dissolution of an amorphous polymer in a solvent is governed by


the free energy of mixing

(1)

where ∆Gm is the Gibbs free energy change on mixing, ∆Hm is the
enthalpy change on mixing, T is the absolute temperature, and
∆Sm is the entropy change on mixing. A negative value of the free
energy change on mixing means that the mixing process will
occur spontaneously. Otherwise, two or more phases result from
the mixing process. Since the dissolution of a high molecular
weight polymer is always associated with a very small positive
entropy change, the enthalpy term is the crucial factor in
determining the sign of the Gibbs free energy change. Solubility
parameters were developed to describe the enthalpy of mixing.

Hildebrand pointed out that the order of solubility of a given


solute in a series of solvents is determined by the internal
pressures of the solvents. Later, Scatchard introduced the concept
of ‘cohesive energy density’ into Hildebrand’s theories.
Hildebrand and Scott and Scatchard proposed that the enthalpy of
mixing is given by

(2)

where Vmix is the volume of the mixture, is the energy of


vaporization of species 1; V1 is the molar volume of species 1; and
φ1 is the volume fraction of 1 in the mixture. is the energy
change upon isothermal vaporization of the saturated liquid to the
ideal gas state at infinite volume.

The cohesive energy, E; of a material is the increase in the


internal energy per mole of the material if all of the
intermolecular forces are eliminated. The cohesive energy density
(CED) Eq. (3), is the energy required to break all intermolecular
physical links in a unit volume of the material

(3)

where ∆Hvap is the enthalpy of vaporization. The Hildebrand


solubility parameter is defined as the square root of the cohesive
energy density:

(4)

Eq. (2) can be rewritten to give the heat of mixing per unit volume
for a binary mixture:

(5)

The heat of mixing must be smaller than the entropic term in Eq.
(1) for polymer–solvent miscibility (∆Gm ≤0): Therefore, the
difference in solubility parameters (δ1 - δ2) must be small for
miscibility or dissolution over the entire volume fraction range.
However, these predictions with the Hildebrand solubility
parameters are made with the absence of any specific
interactions, especially hydrogen bonds. They also do not account
for the effects of morphology (crystallinity) and cross-linking. In
addition, there may be (non-ideal) changes with changes in
temperature and, in many cases, with changes in concentration.

One of the early schemes to overcome inconsistencies in the


Hildebrand solubility parameter introduced by hydrogen bonding
was proposed by Burrell, and is based on the assumption that
solubility is greatest between materials with similar polarities.
This method divided solvents into three categories depending on
the hydrogen bonding: poor, moderate, and strong hydrogen
bonding capabilities. The system of Burrell is summarized as
follows: weak hydrogen bonding liquids are hydrocarbons,
chlorinated hydrocarbons and nitrohydrocarbons; moderate
hydrogen bonding liquids are ketones, esters, ethers, and glycol
monoethers; and strong hydrogen bonding liquids are alcohols,
amines, acids, amides, and aldehydes.

Hansen also accounted for molecular interactions and developed


solubility parameters based on three specific interactions.

The first and most general type of interaction is the ‘non-polar’,


also termed dispersive interactions, or forces. These forces arise
because each atom consists of negatively charged electrons
orbiting around a central positively charged nucleus. The moving
negative charges create an electromagnetic field, which attracts
all atoms to one another regardless of direction. All molecules
have this type of attractive force.

Polar cohesive forces, the second type of interaction, are


produced by permanent dipole – dipole interactions. These polar
forces roughly correlate with the dipole moment of the
molecule.and the contribution to the dipole moment. They are
inherently molecular interactions and are found in most molecules
to one extent or another.

The third major interaction is hydrogen bonding. Hydrogen


bonding is a molecular interaction and resembles the polar
interactions. These bonds are considerably weaker than covalent
bonds but are much stronger than ordinary dipole–dipole
interactions.

Therefore, as Hansen proposed, the cohesive energy has three


components, corresponding to the three types of interactions:

(6)

Dividing the cohesive energy by the molar volume gives the


square of the Hildebrand solubility parameter as the sum of the
squares of the Hansen dispersion (D), polar (P), and hydrogen
bonding (H) components:
Flory Huggins Theory

A thermodynamic theory of polymer solutions, first formulated


independently by Flory and by Huggins, in which the
thermodynamic quantities of the solution are derived from a
simple concept of combinatorial entropy of mixing and a reduced
Gibbs energy parameter, the ‘χ parameter’.

Latice Model of a Polymer Solution

Boltzmann Equation
According to the Boltzmann equation the number of ways the
solids and solvent molecules can be arranged is given by the
equation.

∆Sm = K ln W (1)

where

∆Sm = entropy of mixing

K = Boltzmann constant

W = number of ways that one can accommodate the solvent


and solute
molecules arranged.

According to Flory Huggins theory, the entropy of mixing of


polymer solution is given by

∆Sm = -K [ Ns ln φs +Np ln φ p] (2)

Where the subscript

S stands for the solvent

P stands for the polymer.

The volume fraction of φs and φp in the foregoing equations are


given by.

φs = (3)

φp = (4)

Where
denotes the number of solvent molecules

denotes the number of polymer molecules.

n is the number of polymer segments

The heat of mixing of polymer solution is given by


∆ Hm = K T χ Nsφp
Where

χ - Chai is the Flory Huggins interacting parameter and which


is the measure of the solvent power.

The free energy of mixing of polymer solution in terms of χ is


given by

∆Em = K T [χ Ns φp + Ns ln φs + ln φ p] (5)

The Flory Huggins theory arrives at the equation for total free
energy of dilution based on the following train of thought. There
are two entropy factors which contribute to the free energy of
dilution: one arising from contact between the polymer segments
and solvent molecules, and the other is called conformational
entropy. Thus the overall free energy of dilution will be the sum of
the two terms as follows :

∆Fm = ∆Fconform + ∆Fcontact (6)

From thermodynamics

∆E conformation = R T [ln (1- φ p ) + (1-1/n) φ p] (7)

And ∆E contact = R T [χ φp2 ]


(8)

So that ∆Em = R T [ln (1- φ p ) + (1-1/n) φ p + χ φp2 ] (9)


This equation is derived for a mono dispersed polymer. For a
polydisperse system
the n factor in the above equation has to be replaced with its
average value denoted as . In that case for a polydisperse
system equation (9) becomes.
∆ Em = R T [ ln (1- φ p )+ (1-1/ ) φ p + χ φp2 ] (10)

in equation (10) the value of χ exceeds . some critical value than


the system will tend to separate into 2 phases. in such cases
value of ‘n’ should be,

χ c = n+ +½
(11)

(φ p)c = 1+

(12)
Here (φ p)c represents the critical composition (i.e. critical volume
fraction of the polymer), corresponding to the critical value χ c

In spite of deriving Flory Huggins equation some short comings


are noticed.
The most important correction has been done w.r.t the term

∆E contact = R T [χ φp2 ]

Above should be replaced by polynomial equation

(13)

Substitute equation (13) in equation (9) we get Flory Huggins


equation

Many parameters such as osmotic pressure, which could be


experimentally determined, may be arrived at from this theory.

The osmotic pressure ∏ is related to the free energy of dilution


through the following equation.

Where is the partial molar volume of the solvent.

On substituting for Fm from this equation in eqn (10)


in dilute solutions, the value of φ p will be far less than unity and
hence ln(1- φ p) can be written as follows

on appropriate substitution equation (19) will take the following


form [where in the osmotic pressure is related to molecular
weight ( ) and concentration (c) of the solution

Here partial specific volumeof the polymer.

equation 20 can be written as

or
When the experimental osmotic pressure data is extrapolatde to
zero concentration the higher power concentration terms can be
neglected and the eqn gets reduced to

The term on the left hand side of eqn 24 indicates at 0


concentration or infinite dilution.

Limitations to the Flory-Huggins theory


The Flory-Huggins theory is widely used still and has been
successful, largely, in
describing thermodynamics of polymer solutions. There are a
number of limitations tothe original formulation. The main ones
are

 Applicability only to solutions that are sufficiently


concentrated that they have uniform segment density
 There is no volume change of mixing (where as favorable
interactions between polymer and solvent molecules should
result in a negative volume change)
 There are no energetically preferred arrangements of
polymer segments and solvent molecules in the solution
 The interaction parameter, χ12, is independent of
composition

Nature of Polymer Molecule in Solution

Due to their large number of carbon atoms bonded together


forming a long chain, polymers can generally adopt a lot of
conformations. These conformations arise from the numerous
internal rotations that can occur through simple C-C bonds,
originating a number of rotational isomers.

Nevertheless, although the rotation of each bond is able to


originate different conformations, due to energy restrictions not
all of them have the same probability of occurrence. In such a
case, the most stable conformations predominate in solution, like
proteins and nucleic acids, that is in biopolymers mainly.

However, synthetic polymers particularly, can display a large


number of possible conformations, and even though these
conformations have not the same energy, the differences are
small enough so that the chains can change from one
conformation to another. This particularity gives a big flexibility to
the macromolecules, and due to this flexibility, the chains do not
adopt a linear form in solution, but a very characteristic
conformation, known as random coil.

Figure 4. The random coil model


Such a flexibility can be understood more clearly with the help of
molecular models, as shown in Figure 5.

Figure 5. A C-C simple-bonded chain and its spacial


representation.

Let's assume C1, C2, and C3 are carbon atoms in the same plane.
According to this, the atom C4 can occupy any place throughout
the circle, which represents the base of a cone originated by the
rotation of the bond E3. The angles of such bonds are symbolized
by w, whereas the location of atom C4 is specified by the internal
angle of rotation l.
For a macromolecule in the solid state, the angle l has a fixed
value due to the restrictions of the network packing. That is why
the possible rotational isomers do not occur. Nevertheless when
this macromolecule is dissolved, the packing disappears and the
angle l can vary widely, originating maximums and minimums of
energy. Thus, the probability of reaching diverse stable
conformations with each minimum of energy is high. On the other
hand, the variation of the internal angle of rotation is associated
to an energy change that, at minimums, is small. Hence, the
chains can move freely to adopt such stable conformations. The
fact that the chains are changing from one conformation to
another is also favored, due to the low potential energy of the
system. All these factors define, therefore, a flexible
macromolecule and from these concepts, the typical random coil
form arises.

You might ask if the "shape" or magnitude of the random coil


would remain the same once the polymer has been dissolved. You
will find that the answer is absolutely negative and that the
situation will depend not only on the kind of solvent employed,
but also on the temperature, and the molecular weight. The
polymer-solvent interactions play an important role in this case,
and its magnitude, from a thermodynamic point of view, will be
given by the solvent quality. Thus, in a "good" solvent, that is to
say that one whose solubility parameter is similar to that of the
polymer, the attraction forces between chain segments are
smaller than the polymer-solvent interactions; the random coil
adopts then, an unfolded conformation. In a "poor" solvent, the
polymer-solvent interactions are not favored, and therefore
attraction forces between chains predominate, hence the random
coil adopts a tight and contracted conformation.

In extremely "poor" solvents, polymer-solvent interactions are


eliminated thoroughly, and the random coil remains so contracted
that eventually precipitates. We say in this case, that the
macromolecule is in the presence of a "non-solvent".

The particular behavior that a polymer displays in different


solvents, allows the employ of a useful purification method,
known as fractional precipitation. For a better understanding
about how this process takes place, let’s imagine a polymer
dissolved in a "good" solvent. If a non-solvent is added to this
solution, the attractive forces between polymer segments will
become higher than the polymer-solvent interactions. At some
point, before precipitation, an equilibrium will be reached, in
which ∆G = 0, and therefore ∆H = T∆S, where ∆S reaches its
minimum value. This point, where polymer-solvent and polymer-
polymer interactions are of the same magnitude, is known as q
state and depends on: the temperature, the polymer-solvent
system (where ∆H is mainly affected) and the molecular weight of
the polymer (where ∆S is mainly affected).

It may be inferred then, that lowering the temperature or the


solvent quality, the separation of the polymer in decreasing
molecular weight fractions is obtained. Any polymer can reach its
q state, either choosing the appropriate solvent (named q
solvent) at constant temperature or adjusting the temperature
(named q temperature, or Flory temperature) in a given solvent.
Table 2 compiles some values.

q temperature
Polymer Solvent(s) (oC)
Polyethylene n-Hexane 133
n-Hexanol / Xylene (70:30) 170
n-Octane 210
Polypropylene n-Butanol / Carbon Tetrachloride
(atactic) (33:67) 25
n-Butanol / n-Hexane (32:68) 25
Cyclohexanone 92
Polystyrene Benzene / n-Butanol (58:42) 35
Cyclohexane 34-35
Cyclohexanol 79-87
Poly (vinyl acetate) Ethanol 19
Ethanol / Methanol (40:60) 36
Poly (vinyl alcohol) Ethanol / Water (41.5-58.5) 25
Water 97
Poly (vinyl chloride) Cyclohexanone 22
Dimethylformamide 36.5
Polyacrylamide Methanol / Water (2:3) 20
Polymethylmethacry
late Acetone -126
Cyclohexanol 77.6
Toluene -65
Dioxane / Water (85:15) 25
Table 2. q solvents for selected polymers.

The q temperature is a parameter arisen from Flory-Krigbaum


theory. It is used to calculate the free energy of mixing of a
polymer solution in terms of the chemical potentials of the
species. We will further study the q temperature relationship with
other important parameters that characterize dissolved polymers.

So far we have analyzed the influence of the solvent and the


temperature in the dimensions of the random coil. However is
equally important to know what happens to the viscosity of the
macromolecular solution as the solvent becomes poorer.
Considering the chain molecules as rigid spheres, when a change
from a "good" solvent to a "poor" solvent takes place, the spheres
become contracted. According to the Einstein equation, the
relative viscosity hr is obtained from:

[4]

That is to say, dividing the viscosity of the solution (h) by the


viscosity of the solvent (hs). From equation [4] it can be noticed
that hs is directly proportional to the volume fraction f that these
spheres occupy. Since, with the necessary considerations, this
reasoning can be transferred to macromolecules, which are not
rigid spheres, it may be inferred that if the segments are
contracted in a "poor" solvent, the viscosity of the solution will be
smaller. Therefore, viscosity can be adjusted according to the
solvent quality.

Temperature, however, will not affect the viscosity of a polymer


solution in a relatively "poor" solvent. In this case, it should be
considered that as the temperature increases, the viscosity of the
solvent (hs) decreases. However, on the other hand, when the
temperature is raised, a greater thermal energy will be granted to
molecules. Consequently, these molecules will tend to expand
themselves, increasing their volume fraction (f). Thus both effects
are compensated, and for this reason the change of viscosity due
to the increase of the temperature, is not significant.

The measurement of viscosity in dilute macromolecular solutions


has a fundamental importance not only in the determination of
molecular weights, but also, as we will discuss later, in the
evaluation of key parameters for the understanding of the
conformational characteristics of polymer solutions.

Statistical Parameter
According to what we have been studying so far, dissolved
polymer molecules do not remain fully extended in a stationary
state; instead they adopt a typical random coil form in continuous
motion, changing readily from one conformation to another. When
rotation around C-C simple bonds is hindered, the random coil
conformation is reached only at high temperatures, due to the
thermal energy conferred to the segments.

So you can ask the following question: it is possible to calculate


the size of a macromolecule in its typical random coil form, whose
segments are constantly changing from one conformation to
another? The answer is affirmative, only if such a size is
expressed in terms of statistical parameters, which represent an
average of all the possible conformations. To that end, there are
two very useful statistical parameters:

End-to end distance


Represents the average distance between the first and the last
segment of the macromolecule, and ranges between a maximum
value and a minimum value. The maximum value appears when
chains are fully extended, in a planar, zigzag configuration known
as "all-trans", where the contour length can be calculated easily.
The minimum value corresponds to the sum of Van der Waals
radii in each end.

Figure 6. Maximum value (left) and minimum value (right) for the
end-to-end distance r

The size of the macromolecule is given, in statistical terms, by the mean-square


end-to-end distance, (r)2. Other authors express the root mean-square end-to-end
distance, that is to say, ((r)2)½. The magnitude (r)2 is defined according to:

(5) Where W is a probability distribution


function.
The calculation of the mean-square end-to-end distance (r)2,
varies according to the chain type, and the interactions that were
taken into account.

Let's consider the simplest model of a polymer chain, i.e. an ideal


polymer, consisting of a series of N segments of length L. Let's
assume that the chain segments are bonded according to a linear
sequence, without any restriction regarding bonding angles w and
internal angles of rotation l (Figure 5), so that the atoms are
separated each other at fixed distances but located in any
direction. Thus, the calculation of (r)2 can be made by means of a
procedure known as random flight. According to this procedure
and following a mathematical reasoning equation [5] can be re-
written as follows:

(6)

Where subscript f indicates that a random flight approximation is


being considered, originating a model known as freely jointed
chain.

Nevertheless, the situation is somewhat more complicated when


trying to transfer the calculation of (r)2 to real macromolecules,
where restrictions indeed exist, and therefore chain atoms cannot
be located in any direction. Factors like solvent type, chain type,
and the groups attached to the polymer backbone, do cause
interactions, generating deviations from the freely jointed chain
model. For this reason (r)2 is higher than that obtained by
calculation of the random flight. These interactions can be divided
in: short range interactions and long range interactions.

Short range interactions are related to the structural


characteristics of the macromolecule, considering bond types and
the interactions between segments or neighboring atoms. These
factors originate steric repulsions, which limit the values of the
internal angles of rotation (figure 5) since in such a case, they are
not all equally probable. The magnitude of this effect is related to
the size of the substituent groups. Hence the random coil will
expand itself, in order to avoid such repulsions.

This model is known as unperturbed dimension, since neither


interactions between non-neighboring chain segments nor solvent
interactions (long range interactions, to be discussed later) are
being considered. To this end, the mean-square end-to-end
distance of the unperturbed dimension, (r)2o, is expressed as
follows:

(7)

Where (r)2fr represents the mean-square end-to-end distance of


the free rotation chain, that is to say, under the condition that the
bonding angles w (figure 5) remain fixed, independently of the
presence of substituent groups. The s factor, referred to as
conformation factor, is a parameter related to the impediments to
rotation that real chains show, compared to that with a free chain
rotation. The s factor depends on temperature and sometimes on
the solvent, and offers interesting information about the
conformation of a certain macromolecule and usually, it is
increased in the presence of bulky groups.

Although the corrections introduced by the short range


interactions offer a more approximate description of real
macromolecules in dilute solutions, such interactions do not
contemplate the behavior of non-neighboring chain segments,
each one occupying a certain volume from which all the other
segments are excluded. Such effect, known as excluded volume
and its influence on the dimensions of the macromolecular chains,
has been the subject of numerous studies for a long time. Its
theoretical calculation has been carried out by means of statistic
and the aid of computer simulation.

To this end, in order to make possible the calculation of the end-


to-end distance considering the excluded volume effects, the long
range interactions have been introduced, which consider both
solvent interactions and interactions between atoms or non-
neighboring segments. One may speculate that the long range
interactions can produce a bigger chain expansion over its
unperturbed dimensions, since now, due to the excluded volume
effect, such conformations where two remote segments can
occupy the same space at the same time should be eliminated.
Hence, the end-to end distance is given by:

(8)
Where a is the linear expansion factor, and (r)2o the end-to-end
distance of the unperturbed dimension.

The value of a depends on the number of segments, the


temperature, and the solvent nature. When a values are high, it is
said that the solvent is thermodynamically "good". Therefore,
remembering what we mentioned in previous pages, polymer-
solvent interactions will be favored, making the random coil to be
expanded and allowing the excluded volume effect to occur. On
the contrary, when a values are low, the solvent is considered
thermodynamically "poor" and the random coil will be contracted,
in order to minimize the contact with its segments.

Analyzing equation [8], it can be noticed that when a = 1, a


situation that can be reached with a solvent sufficiently "poor" or
at low temperatures, the dimensions of the macromolecule,
affected by long range interactions, matches those of the
unperturbed dimension. Under such conditions, the polymer-
solvent and polymer-polymer interactions are of the same
magnitude, and that particular "q state", which we mentioned
earlier, is reached. If such a condition was reached at a given
temperature, this temperature will be considered as "q
temperature" or "Flory temperature"; if it was reached in a given
solvent at T = a, this solvent will be considered as a "a solvent".

By means of the preceding discussion, the relevance in the


evaluation of the conformation factor s, and the linear expansion
factor a, while studying the conformational properties of polymers
in dilute solutions, is clearly demonstrated. While s is related to
the geometry of the chains and its structural characteristics
(considered by the short range interactions) a measures the
magnitude of the excluded volume effect as well as polymer-
solvent interactions, described through the long range
interactions. The experimental determination of factors s and a,
will be discussed briefly in the next section.

Radius of Gyration
In the case of branched chains, with a large number of ends, it
turns out more appropriate to talk about the square-mean radius
of gyration instead of the end-to-end distance, which is more
applicable to linear polymers. Represented as (s)2, the radius of
gyration is the square mean radius of each one of the elements of
the chain measured from its center of gravity. Although (s)2 is
defined according to:
(9)

Being N the number of segments, and (hi)2 the square mean


distance of i-th segment from the center of gravity, its value is
often related to the square mean distance (r)2 through a constant,
in the generic form:

(10)

Thus, it can be noticed that the dimensions of a branched chain


are smaller than those of a linear chain with the same molecular
weight, or the same number of segments. This simple relation can
be applied to the three situations considered in a), and if we
express (s)2 in terms of equations [6[, [7], and [8] we will obtain,
respectively, the value of the square-mean radius of gyration for a
"freely joined chain" (equation [11]), an "unperturbed chain"
(equation [12]) and a chain being affected by long range
interactions (equation [13]):

(11)

(12)

(13)

The following schematic representation of a random coil, shows


the differences between the end-to-end distance (r) and radius of
gyration (s).
Figure 7.

Theta Solvent

Definition: A solvent which performs in an ideal manner (activity


coefficient = 1) in dilute solution measurements of molecular
weight.

In a polymer solution, a theta solvent (or θ solvent) is a solvent


in which polymer coils act like ideal chains, assuming exactly their
random walk coil dimensions. Thermodynamically, the excess
chemical potential of mixing between a polymer and a theta
solvent is zero

Physical Interpretation

The conformation assumed by a polymer chain in dilute solution


can be modeled as a random walk of monomer subunits using a
freely jointed chain model. However, this model does not account
for steric effects. Real polymer coils are more closely represented
by a self-avoiding walk because conformations in which different
chain segments occupy the same space are not physically
possible. This excluded volume effect causes the polymer to
expand.

Chain conformation is also affected by solvent quality. The


intermolecular interactions between polymer chain segments and
coordinated solvent molecules have an associated energy of
interaction which can be positive or negative. For a good
solvent, interactions between polymer segments and solvent
molecules are energetically favorable, and will cause polymer
coils to expand. For a poor solvent, polymer-polymer self-
interactions are preferred, and the polymer coils will contract. The
quality of the solvent depends on both the chemical compositions
of the polymer and solvent molecules and the solution
temperature.

If a solvent is precisely poor enough to cancel the effects of


excluded volume expansion, the theta (θ) condition is satisfied.
For a given polymer-solvent pair, the theta condition is satisfied
at a certain temperature, called the theta (θ) temperature or
theta point. A solvent at this temperature is called a theta
solvent.

In general, measurements of the properties of polymer solutions


depend on the solvent. However, when a theta solvent is used,
the measured characteristics are independent of the solvent.
They depend only on short-range properties of the polymer such
as the bond length, bond angles, and sterically favorable
rotations. The polymer chain will behave exactly as predicted by
the random walk or ideal chain model. This makes experimental
determination of important quantities such as the root mean
square end-to-end distance or the radius of gyration much
simpler.

Additionally, the theta condition is also satisfied in the bulk


amorphous polymer phase. Thus, the conformations adopted by
polymers dissolved in theta solvents are identical to those
adopted in bulk polymer.

Theta Temperature

Definition: With respect to molecular interactions in dilute


polymer solutions, theta temperature is the temperature at which
the second virial coefficient disappears. That is, the temperature
at which the coiled polymer molecules expand to their full contour
lengths and become rod-shaped. Also known as FLORY
TEMPERATURE.

VISCOSITY OF DILUTE POLYMER SOLUTIONS

The viscosity of a dilute polymer solution depends on several


factors namely, the nature of the polymer and that of the solvent
their concentrations, the polymer molecular weight the
temperature and the shear rate.

At the molecular level, the viscosity of a polymer solution is


direct measure of the hydrodynamic volume of the polymer
molecules.Hydrodynamic volume is the apparent volume
accupied by the expanded or swollen molecular coil along with
the imbibed solvent and can be defined in terms of the expansion
factor α and unperturbed end-to end distance ((ro)2)½.Polymer will
exhibit a higher viscosity in a good solvent than in a poor solvent
and that , in the same solvent, the viscosity eill be directly
proportional to the molecular weight.

Reference
1. POLYMER SCIENCE
By V.R.Gowariker, N.V.Viswanathan, Jayadev Sreedhar

2. POLYMER SOLUTIONS
by IWAO TERAOKA

3. ESSENTIALS OF POLYMER SCIENCE AND ENGINEERING

By Paul C. Painter, Michael M. Coleman

4. TEXT BOOK OF POLYMER SCIENCE

BY Fred W. Billmeyer