Thermodynamic Modeling of Polymer Solution Interface: Full Paper

Thermodynamic Modeling of Polymer
Solution Interface
Majid Ghiass, Alejandro D. Rey
*
Introduction
Interfacial equilibrium thermodynamic models are based
on the essential postulate that the free energy density of a
polymer solution f f; rf at xed temperature is deter-
mined by the local concentration, (i.e., volume fraction of
polymer f) and its gradient rf,
[1,2]
f f; rf f
h
f K rf
2
(1)
where f
h
f is the homogeneous contribution of the free
energy, and K is the gradient concentration (energy)
coefcient.
[2]
The formulation of the free energy as the sum
of the homogeneous and gradient parts was introduced by
van der Waals,
[1]
equivalently by Landau and Lifshitzs
theory of magnetic domain structure,
[3]
and in reformu-
lated and extended form by Cahn and Hilliard.
[2]
Neglect-
ing the inhomogeneous contribution of the local free
energy density leads to a vanishing interfacial tension and
to a step-function-like concentration prole. The role of
this contribution is to impose a characteristic correlation
limit in the uid which leads to a non-zero thickness of
interfacial zone after minimization of the integrated free
energy density.
[4]
The coefcient of concentration gradi-
ent, K, is a measure of the strength and the range of forces
of attraction between the molecules, or, more accurately, it
is proportional to the attractive component of intermole-
cular interactive potential.
[4,5]
Using the density functional
approximation, the total free energy can be expressed as
[6]
F
f
h
f dx
fx dx
rc
Urfx r fx dx
(2)
Full Paper
M. Ghiass, A. D. Rey
Department of Chemical Engineering, McGill University, 3610
University Street, Montreal, Quebec H3A 2B2, Canada
E-mail: alejandro.rey@mcgill.ca
A new method is presented to characterize the interfacial concentration eld and interfacial
tension between equilibrium polymer solution phases, using readily accessible equilibrium
concentration data. The new method is tested and validated using experimental data from
different polystyrene solutions and it consists of
i) calculation of a universal expression for the
concentration gradient coefcient based on the
Cahn-Hilliard model and the Wolf interfacial ten-
sion master equation, and ii) development of a
highly accurate algebraic function (Kappa distri-
bution) that, for a given equilibrium polymer
concentration set, yields the essentially exact
interfacial prole predicted by the classical gra-
dient theory for polymer solutions.
Square Gradient theory
Flory-Huggins model
Wolfs Master
equation
Polystyrene
Solutions
literature data
Parameters of
Kappa dist.
Universal
concentration gradient
coefficient
Concentration profile
using
Kappa distribution function
Square Gradient theory
Flory-Huggins model
Wolfs Master
equation
Polystyrene
Solutions
literature data
Parameters of
Kappa dist.
Universal
concentration gradient
coefficient
Concentration profile
using
Kappa distribution function
Macromol. Theory Simul. 2009, 18, 127137
2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/mats.200800066 127
where x and r are displacement and U(r) is the attractive
pair interaction kernel with cut-off radius r
c
. Expanding
the integrand in the second term of Equation (2) and using
spherical symmetry, it is found that:
fx dx
r>rc
Urfx r fx dx

p
3
r>rc
Urr
4
dr
rf
2
dx
(3)
where the positive gradient energy coefcient K is
[4,6]
K
p
3
1
r>rc
Urr
4
dr (4)
Knowledge of K is required to determine the interfacial
tension and the concentration prole across the interface
region. Although lattice models,
[79]
statistical mod-
els,
[10,11]
and molecular dynamic and Monte Carlo
methods
[12,13]
do not explicitly introduce the concept of
concentration gradient and do not depend on the value of
the concentration gradient coefcient, so far such techni-
ques have been applied only to obtain the interfacial
properties of short alkanes.
[13]
The value of the gradient concentration coefcient K is
essentially assumed to be constant for polymer solutions,
but there have been theoretical and experimental relation-
ships established that relate it to the local concentra-
tion.
[14]
This paper focuses on the estimation of a universal
concentration gradient coefcient K, an essential piece of
information in modeling of the interfacial properties and
phase separation kinetics of polymer solutions and blends.
Determination of the polymer concentration prole
across the planar interfacial region of two equilibrium
polymer solution phases is the second objective of this
paper. In most interfacial models, the concentration prole
is assumed to be a hyperbolic tangent function that
smoothly interpolates between the two equilibrium
concentrations (f
a
, f
b
),
[4,9,1518]
fx
f
b
f
a
2

f
b
f
a
2
tanh
x x
0
j
(5)
where x
0
is the Gibbs dividing surface and j is a measure of
the interfacial thickness. This function is antisymmetric
and its derivative is symmetric. This representation is valid
in the vicinity of the critical region, where the assumption
of symmetry holds.
[4,19,20]
This is due to the fact that, in the
neighborhood of the critical point, the chemical composi-
tion and the physical properties of the two equilibrium
phases are identical, leading to scaling relationships and
universal behavior. On the other hand, in regions far from
the critical temperature, the polymer concentration in the
solvent-rich phase is very small in comparison to the more
concentrated or polymer-rich phase.
Figure 1 shows a qualitative outline of a typical polymer
concentration prole across the interfacial region which
has been studied in this work. Figure 1a shows a
temperature-concentration, asymmetric upper critical
solution temperature (UCST) phase diagram, which is a
general characteristic of polymer solutions. Each horizon-
tal line or constant temperature path or tie-line in the Tf
phase diagramshows the equilibriumconcentration of the
two equilibrium phases, that is, solvent-rich phase on the
left-hand side and polymer-rich phase on the right-hand
side of the phase diagram. The gure shows two tie-lines,
T
1
and T
2
, close and far fromthe critical point, respectively.
Figure 1b shows the qualitative concentration prole f,
(thick line), and concentration gradient df/dx, (thin line),
in the interfacial region between two equilibrium phases
at temperature T
1
, very close to the critical temperature.
The interface region is essentially diffusive, the concen-
tration prole is antisymmetric and smoothly starts from
binodal concentration in one phase (f
a
) to binodal
concentration in the other phase (f
b
), and the gradient
concentration is symmetric. Thus, the concentration
prole can be represented and tted well by tangent
hyperbolic function such as Equation (5).
[4,19,21]
Figure 1c
shows the corresponding proles for tie-line T
2
, far away
from the critical temperature. The interfacial region is of
the sharp interface type, the concentration prole is
skewed towards the more concentrated phase, and the
asymmetric behavior in the concentration gradient is
signicant.
[21,22]
Figure 1d shows a qualitative representa-
tion of concentration prole of tie-line T
2
(thick line) and
the concentration predicted (thin line) by Equation (5). It
clearly demonstrates that Equation (5) is not an accurate
representation for the polymer concentration prole in the
region far from the critical point.
In the simplest mean-eld theory, the interface has a
thickness of the order of the chain segment in the polymer-
rich phase but is essentially innitely sharp in the solvent-
rich phase,
[21]
and the concentration prole increases
sharply in the more dilute phase but with a weaker slope
in the concentrated phase. This asymmetric behavior
away from the critical point has been remarked on by
Widom
[21]
and Nose.
[22]
Thus, the tangent hyperbolic t to
the polymer concentration prole is not accurate in the
region far from the critical point. A single formula that
represents the polymer concentration prole, captures the
skewness of the prole and can be used for the entire phase
diagram both very close to and far from the critical point
has not, to the best of our knowledge, been reported.
In this paper, we present a new and accurate expres-
sion for the concentration prole in the interfacial region
betweentwoequilibriumphasesof apolymer solutionwith
minimal knowledge of the polymer concentration in the
128
2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/mats.200800066
equilibriumphases. The approach is based on identifying a
versatile function that lacks the weaknesses of the
hyperbolic tangent function in conjunction with an
accurate method to calculate the gradient coefcient, K.
While in the thermodynamic interface models the inter-
facial tensioncan be determined without knowledge of the
concentration prole, use of the Kappa distribution
function for the concentration prole provides a quick
and easy method to determine the interfacial tension and
thickness based on the properties of polymer solutions.
The specic objectives of this work are:
1) To develop a generalized equation for the concentration
gradient coefcient, K, based on the classical Cahn-
Hilliard model and the well known Wolf interfacial
tension equation;
[23]
2) To identify a proper interpolating
function that lacks the inaccura-
cies of the hyperbolic tangent
function and captures the asym-
metries inherent in high molecu-
lar weight polymer solutions; and,
3) To develop and validate a scheme
to compute interfacial tension
and interfacial polymer concen-
tration proles based on equili-
brium polymer concentration,
accurate at temperature close
and far from the critical point.
The organization of this paper is
shown in Scheme 1 and described
below.
Model Section
A) Basedonthesquaregradienttheory
[Equation (7)] and Flory-Huggins
free energy function for polymer
solutions [Equation (13)], the gen-
eral expressions for calculation of
the concentration prole [Equation
(14)] and the interfacial tension
[Equation(15)] are presented. Then,
the expression for interfacial ten-
sion [Equation (15)] is compared
with an empirical relationship for
interfacial tension [Equation (17)],
and a universal relationship for the
concentrationgradient coefcient
[Equation (18)] is presented.
B) The Kappa distribution function
is introduced as a novel mathe-
matical expression for tting the concentration prole
in the interface region between two equilibriumphases
of a polymer solution. The procedure to determine the
Kappa distribution function parameters are developed,
and the expressions to calculate the concentration
prole, interfacial tension, and the interface thickness
[Equation (2224)] are represented.
Results and Discussion Section
A) By use of data reported in the literature for different
polystyrene polymer solutions (Table 1) the Flory-
Huggins model [Equation (13)] and Equation (18), a
universal numerical value for concentration gradient
coefcient [Equation (27)] is reported.
Thermodynamic Modeling of Polymer Solution Interface
Figure 1. Outline of polymer concentration prole across the interfacial region between two
equilibrium phases of polymer solution. a) Typical phase diagram of a polymer solution and
two tie-lines T
1
and T
2
(dashed lines) very close to and far from the critical temperature,
respectively. b) Concentration prole (thick line) and concentration gradient (thin line) in the
interfacial region for a polymer solution at temperature T
1
, very close to the critical point. This
case shows a diffusive interface prole. c) Concentration prole (thick line) and concentration
gradient (thin line) in the interfacial region (sharp interface prole) for a polymer solution at
temperature T
2
, very close to the critical point. d) Concentration prole at a temperature far
away from the critical point calculated by a typical interface model (thick line) and the
corresponding prole predicted by Equation (5) (thin line).
2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.mts-journal.de 129
B) The parameters of the Kappa distribution [Equation
(29)] are determined by use of the literature data
(Table 1), the free energy model [Equation (13)] and
procedures shown in the Appendix.
C) The expression for interfacial tension based on the
Kappa distribution function [Equation (23)] is com-
pared with empirical relationship [Equation (17)].
D) The expression for concentration prole based on the
Kappa distribution [Equation (22)] is compared with
the results of the concentration prole from Equation
(14).
Model
(A) Interfacial Tension and Concentration
In the Cahn-Hilliard
[2]
non-linear theory of phase separa-
tion, the free energy is expressed as the sum of the
homogeneous and nonhomogeneous or gradient parts, as
shown in Equation (1). Taking into account the mass
conservation constraint on a binary polymer solution,
c f f
s
1 0 (6)
where f
s
is the solvent volume fraction.
Minimizing of the total free energy of
the system leads to
@f
h
f
@f
l 2Kr
2
f (7)
where l is the Lagrange multiplier from
the mass conservation constraint. To
determine the value of l, we use the
fact that, in the bulk of either phase, the
solution is homogeneous and the con-
centration gradient vanishes. Applying
this condition to Equation (7)
leads to:
@f
h
f
@f
m
p
m
s
2Kr
2
f (8)
where m
s
and m
p
are the chemical
potentials of the solvent and polymer,
respectively, at equilibrium conditions,
expressed in energy per unit volume.
We consider a 1-D planar interface
separating two equilibrium polymer
solution phases, the solvent-rich phase
a on the left side of interface and the
polymer-rich phase b on the right
side of interface, with a concentration gradient in the x
direction. Integration of Equation (8) between the bulk of
one phase, where the equilibrium concentration is f
e
, to a
point within the interface (x, f) gives:
f
h
f f
h
f
e
m
p
m
s
f f
e
K
df
dx

2
(9)
Which, upon integration leads to:
x x
0

f
f
e
K
p
f
h
f f
h
f
e
m
p
m
s
f f
e
1=2
df
(10)
Assuming the interface extends from 1to 1, the
interfacial tension is calculated by:
[2,24,25]
g
1
1
2K
df
dx

2
dx 11
-Interfacial tension,
kappa ,
eq. (23)
-Concentration profile,
kappa
(x), eq. (22)
-Interface thickness,
L, eq. (24)
-Formula of K, Eq. (18)
-Flory-Huggins model,
eq. (13)
A
D
C
eq. (13)
-Concentration Gradient
coefficient, K, eq. (18)
-Polystyrene solutions,
Table 1
-Numerical value of K,
eq. (27)
-Empirical relation of
interfacial tension,
wolf
,
eq. (17)
SGFH
, eq. (15)
SGFH
(x), eq. (14)
Concentration Gradient
coefficient, K,
eq. (18)
kappa
, eq. (22)
compare with eq. (14)
kappa
, eq. (23)
Model
-Square Gradient theory,
eq. (7)
eq. (13)
A
Parameters
of Kappa dist.
function, h,
B
Results (Validation)
-Eqs. (A2, A6)
eq. (13)
B
Table 1
-Kappa dist. parameters,
h, , eq. (29)
kappa ,
eq. (23)
kappa
(x), eq. (22)
-Interface thickness,
L, eq. (24)
-Formula of K, Eq. (18)
eq. (13)
A
D
C
eq. (13)
-Concentration Gradient
coefficient, K, eq. (18)
Table 1
-Numerical value of K,
eq. (27)
-Empirical relation of
interfacial tension,
wolf
,
eq. (17)
SGFH
, eq. (15)
SGFH
(x), eq. (14)
Concentration Gradient
coefficient, K,
eq. (18)
kappa
, eq. (22)
kappa
, eq. (23)
Model
-Square Gradient theory,
eq. (7)
eq. (13)
A
Parameters
of Kappa dist.
function, h,
B
Results (Validation)
-Eqs. (A2, A6)
eq. (13)
B
Table 1
-Kappa dist. parameters,
h, , eq. (29)
Scheme 1. Outline of the modeling and validation procedure.
130
A change of variable in the interfacial tension
[Equation (11)] from x to f gives:
g
f
b
f
a
2
K
p
f
h
f f
h
f
e
m
p
m
s
f f
e
1=2
df
(12)
where f
a
and f
b
are the equilibrium concentration of two
phases known from a computed equilibrium phase
diagram. Equation (10) and (12) provide a framework for
determination of the concentration prole along the
interface fx, the interfacial thickness, and the interfacial
tension between two equilibrium phases.
In this work, the well-known Flory-Huggins (FH) theory
is used to describe the equilibrium phase behavior of a
binary polymer solution. We use an improved version of
the FH theory in which the interaction parameter is a
function of concentration. For the polystyrene solutions,
the following expression of the FH model as the
homogeneous part of the free energy, f
h
f, has been
frequently used:
[2629]
f
h
f
RT
v
1 f
r
1
ln1 f
f
r
2
lnf
bf1 f
T1 pf

(13)
where b and p are parameters of the polymer solution, n is
a reference molar volume (i.e., solvent molar volume), and
r
i
are the effective number of segments,
[29]
dening a
segment in terms of a molar volume of 100 cm
3
mol
1
.
[27]
This effective number of segments is quite similar (but not
precisely identical) to the degree of the polymerization of
polymer.
[29]
Determination of equilibrium chemical potentials from
Equation (13) and substituting them in Equation (10) and
(12) leads to expressions for the 1-D concentration prole
Table 1. Properties and parameters of different polystyrene solutions. Here, M
w
is molecular weight, r
2
is the ratio of polymer segment
molar volume to the solvent molar volume, T
c
and f
c
are the critical temperature and volume fraction, respectively, and, b and p are the
parameters in Equation (13) for each polymer.
No. Reference Solvent
M
w
r
2
T
c
f
c
b p
kg mol
S1
K
1 [33] MCH 9 83 281.2 0.199 221.179 0.3151
2 [35] MCH 10.2 94 285.71 0.199 222.654 0.3099
3 [35] MCH 16.1 150 295.98 0.172 227.228 0.3120
4 [35] MCH 17.3 161 296.13 0.167 228.011 0.3122
5 [23] MCH 17.5 163 296.05 0.169 227.135 0.3140
6 [35] MCH 20.2 189 298.95 0.159 226.646 0.3110
7 [35] MCH 34.9 328 309 0.129 232.206 0.3103
8 [33] MCH 37 348 309.65 0.125 233.627 0.3152
9 [23] MCH 42.5 452 311.55 0.121 234.318 0.3165
10 [23] CH 42.5 452 287.35 0.162 223.718 0.3491
11 [35] MCH 46.4 436 312.61 0.117 233.825 0.3109
12 [34] MCH 50 471 313.25 0.109 232.512 0.3051
13 [23] MCH 86.3 816 320.05 0.096 238.318 0.3152
14 [27] CH 96 894 293.65 0.075 211.834 0.2886
15 [35] MCH 109 1 032 322.17 0.084 238.441 0.3103
16 [33] MCH 110 1 042 323.24 0.088 240.317 0.3189
17 [23] MCH 175 1 660 326.65 0.071 241.068 0.3129
18 [23] CH 175 1 660 297.35 0.07 218.834 0.3104
19 [35] MCH 181 1 718 327 0.07 241.089 0.3123
20 [33] MCH 233 2 216 329.93 0.059 241.769 0.3089
21 [35] MCH 719 6 855 334.82 0.041 245.601 0.314
22 [33] MCH 1260 12 034 336.97 0.028 243.799 0.3074
f
SGFH
(x) and interfacial tension g:
x x
0

Kv=RT

f
f
a
Af
1=2
df (14)
g
SGFH
2
KRT=v

f
b
f
a
Af
1=2
df (15)
where the subscript SGFH denotes the square gradient
Flory-Huggins and A(f) is the hump function,
[4,21]
dened as:
Af
1 f
r
1
ln
1 f
1 f
e
f
r
2
ln
f
f
e
1
r
1
1
r
2

f f
e
b1 pf f
e
2
T1 pf1 pf
e
2
(16)
Here f
e
is either f
a
or f
b
, obtained from the equilibrium
phase diagram.
The empirical results to correlate the interfacial tension
to the properties of the polymer solution such as binodal
concentration and molecular weight, has led to the
following well-known master equation:
[23]
g
Wolf
a
N
p
f
b
f
a
3:85
(17)
where a1.5310
4
J m
2
, and N is the degree of
polymerization of polymer.
Comparing Equation (15) and (17) leads to a relationship
to express the concentration gradient coefcient as:
K
a
2
vN
4RT
f
b
f
a
7:7
c
2
(18)
Where:
cf
a
; f
b

f
b
f
a
Af
1=2
df (19)
Thus, for a polymer solution, if the values of N(or r
2
), p, b,
f
a
and f
b
are known, at each temperature, a value for the
concentration gradient coefcient can be determined. All
quantities in Equation (18) come from the experimental
phase diagram, along with an expression for the free
energy function such as Equation (13). Equation (18)
expresses the universal behavior of the concentration
gradient coefcient K with respect to the binodal point
concentration difference f
b
f
a
.
(B) Concentration Prole
In this section, we focus on the concentration prole in the
interface region of a polymer solution. For any constant
temperaturepathor tie-line(inatemperature-concentration
phase diagram), the concentration prole across the inter-
face interpolates between
x !1 f f
a
x !1 f f
b
(20)
As mentioned above (see Figure 1b and c), at the region
away from (close to) the critical point, the concentration
prole and its gradient are skewed (symmetric). Thus, a
suitable mathematical expression for the concentration
prole should be able to showthe appropriate behaviors in
the vicinity of and far away from the critical point. Here,
we propose the use of the Kappa distribution function for
expressing the concentration prole in the interfacial
region between equilibrium phases of a polymer solution
or blends.
The Kappa distribution is a versatile four-parameter
distribution that ts a wide range of experimental
data.
[3032]
A special case of the Kappa distribution is
the general 3-parameter logistic distribution function
Fx:
Fx
1
1 he
xj=a

1
=
h
(21)
In this distribution, j is the location parameter, a the
scale parameter and h the shape parameter, which controls
the skewness of the distribution and varies between zero
and one (for a right-hand-side skewed distribution). When
h1, the distribution is antisymmetric (its derivative is
symmetric) and it is known as the logistic distribution.
Once the three parameters (h, a and j) are determined from
simulation or experimental results, the concentration
prole and interfacial thickness can be analytically derived
from the Kappa distribution. The benet of having the
concentration prole based on an analytical expression is
that it is not necessary to solve the interface model
differential equation to calculate the interfacial tension
and interface thickness of equilibrium solution. If an
expression for the concentration gradient coefcient is
available, the concentration prole can be predicted by
using only the phase diagram and free energy function
information.
Here we propose the following form of the Kappa or
general logistic distribution function as a suitable
representation of the concentration prole across the
interfacial region between the two equilibrium polymer
132
solution phases,
f
kappa
x f
a
f
b
f
a
1 he
xj=
K=a
p
1=h
(22)
where the condition in Equation (20) is satised, h, a and j
are parameters of the expression, and
K=a
is a measure
of the thickness of the interface, known as the Cahn or
capillary number. Substituting the derivative of Equation
(22) in Equation (15) and integrating leads to
g
kappa

Ka
p
f
b
f
a
2
h 2
(23)
Using the denition of the interfacial thickness,
[2]
the
thickness of interfacial region is
L
K=a
1 h
11=h
(24)
Thus, if the concentration gradient coefcient K, the
binodal concentrations from a phase diagram f
a
and f
b
,
and the parameters of the Kappa distribution h, a, and j are
available, the interfacial tension and the interface thick-
ness can be easily determined from Equation (23) and (24).
The procedure for determining the Kappa distribution
parameters is shown in the Appendix.
In this work, we use polystyrene as a representative
polymer for the study of interfacial phenomena in
incompressible polymer solutions. Polystyrene is assumed
to be monodisperse in the phase equilibrium calculations.
We use experimental data from 22 polystyrene solutions
withdifferent molecular weights intwosolvents, cyclohex-
ane (CH) and methylcyclohexane (MCH).
[2729,3335]
An
extendedFlory-Huggins freeenergymodel is used, inwhich
the interaction parameter is considered as a function of
temperature and concentration and UCST-type phase
diagram was generated for each solution.
[28,29]
Table 1
shows the data for the different polystyrene solutions: the
nature of the solvents, the molecular weights of the
polymers, the degree of polymerizationor segment volume
of polymer chain, the critical temperature and concentra-
tion and the required parameters for calculating the T-f
equilibrium phase diagram. The molecular weight of
polymers covers several orders of magnitude. The concen-
tration-dependant interaction parameter enables the
reproduction of the phase diagramof the polymer solution
with a high degree of accuracy.
[2729]
The calculation procedure is as follows:
a) For each polystyrene/solvent system in Table 1, the
temperature/concentration UCST phase diagram is
generated using standard chemical equilibrium proce-
dure;
b) At each temperature in the phase diagram of Step (a),
the tie-line length, (f
b
f
a
), and the value of Equation
(19) is calculated;
c) At the same temperature, the value of concentration
gradient coefcient from Equation (18) is calculated;
and,
d) At the same temperature, by use of the value of the
concentration gradient coefcient and Equation (14),
the concentration prole is determined.
Step (bd) are repeated for all temperatures in the
specied phase diagram of Step (a), and the whole
procedure is repeated for all 22 polystyrene solution
systems in Table 1.
Results and Discussions
In this section we present rst the results of the
determination of concentration gradient coefcient, then
the Kappa distribution parameters (h, a), and interfacial
tension in terms of polymer molecular weight N and
equilibrium concentrations (f
a
, f
b
), and, nally, the
validation of the Kappa-tting formula is established.
(A) Calculation of the Gradient Elastic Coefcient K
This section is related to calculation of a universal
concentration gradient coefcient K. According to Equa-
tion (18) and (19), the concentration gradient coefcient
depends on the termc. This integral can be calculated only
by using the free energy function given in Equation (13).
Figure 2 shows the value of cwith respect to the binodal
concentration difference or tie-line length for eight
different polystyrene solutions in Table 1. These systems
have been selected in a way to cover different solvents and
a broad range of molecular weight, (i.e., 4 orders of
magnitude in molecular weight). The results of Figure 2
can be represented by a power-law relationship (the same
behavior has been observed for all 22 polymer solutions in
Table 1, but is not shown here for brevity),
c f
b
f
a
3:090:02
(25)
Substituting Equation (25) in Equation (18) leads to:
K Nf
b
f
a
1:520:04
(26)
Figure 3 shows the calculated concentration gradient
coefcient, K, with respect to the binodal concentration
difference for the same systems as in Figure 2 (The same
behavior was observed for all the polystyrene solutions in
Table 1). All the graphs display essentially the same slope
and at large values of the concentration difference the
slopes are slightly decreasing. The results from Figure 3
(and similar results for all systems in Table 1) suggest a
power law relationship between concentration gradient
coefcient and binodal point concentrations for a wide
range of molecular weights. This relationship is a scaling
equation that gives K in terms of the polymer molecular
weight N, and the binodal concentration difference as
K 3:1875 10
14
Nf
b
f
a
1:5270:045
J=m (27)
or, more simply, by
K 3:1875 10
14
Nf
b
f
a
1:5
J=m (28)
Equation (27) or, equivalently, Equation (28) provide a
very good universal concentration gradient coefcient for
polymer solutions which is an essential quantity for the
calculation of polymer interfacial properties.
(B) Determination of the Parameters of the Kappa
Distribution Function
As shown in the Appendix, the values of h and a in
Equation (22) can be determined for each polymer solution
system and at each temperature by using Equation (A2)
and (A6), the phase diagram, and the selected free energy
function [i.e., Equation (13)]. These values are required to
determine the interfacial tension [Equation (23)]. Using the
data in Table 1 for all polystyrene solutions results shows
the following scaling relationships involving the Kappa
distribution parameters (a, h) and the equilibriumpolymer
concentration f
b
f
a
or tie-line length:
a f
b
f
a
2:0570:079
(29a)
h 2 f
b
f
a
0:1850:028
(29b)
1 h
11=h
f
b
f
a
0:1870:013
(29c)
The latter two terms are evaluated in the form they
appear in Equation (23) and (24). Equation (29) shows that
there is a unique power law relationship between the
Kappa distribution parameters and equilibrium concen-
trations. Use of these relationships in Equation (23) and
(24) yields an efcient way to go from equilibrium bulk
values to knowledge of the interfacial region.
(C) Calculation of the Interfacial Tension from the
Kappa distribution Function
Substituting the value of the concentration gradient
coefcient from Equation (27) and the Kappa distribution
parameters [Equation (29a,b)] into Equation (23) leads to a
the following relationship for interfacial tension based on
Figure 3. The concentration gradient coefcient with respect to
the equilibrium concentration difference or tie-line length for 8
different molecular weights of polystyrene solution systems. The
numbers in the legend correspond to those in Table 1.
Figure 2. Magnitude of c in Equation (18) and (19) with respect to
the equilibrium concentration difference or tie-line length for 8
different molecular weights of polystyrene solution systems. The
numbers in the legend correspond to those in Table 1.
134
the Kappa distribution function:
g
kappa
N
0:5
f
b
f
a
3:970:09
(30)
This shows very close agreement with the experimental
relationship of Equation (17).
[23]
Equation (30) is a
theoretically-based power law relationship that incorpo-
rates the molecular weight Ndependence of the interfacial
tension g, is in excellent agreement with the experimen-
tally-based relationship [Equation (17)], and is able to
accurately predict interfacial tension from equilibrium
data, f
a
, and f
b
.
(D) Validation of the Kappa Distribution Function
Predictions of Concentration Proles
To validate the use of the proposed concentration prole
[Equation (22)], we compare the results with the computed
concentration prole, Equation (14), as follows. For each
temperature of the UCST-type phase diagram of the 22
polystyrene solutions (see Table 1), the parameters of
Equation (22) were determined and the concentration
prole evaluated (according to the method shown in the
Appendix). At the same temperature, the concentration
prole was also determined by solving the differential
Equation (14), then at each point (distance x), the
difference between these two values was calculated
and, for the whole range of concentration, the total
difference or error is reected by the absolute average
deviation percentage (AAD%) as:
AAD%
1
n
f
Calc
f
Pred
f
Calc
% (31)
Where f
calc
and f
pred
are the concentrations determined by
Equation (14) and (22), respectively, and n is the number of
data points. Figure 4 shows the values of AAD% in the
prediction of the concentration prole for the highest
molecular weight polystyrene, M
w
1 260 kg mol
1
, as a
function of the binodal concentration difference or tie-line
length (f
b
f
a
). The AAD% is evaluated over a broad range
of binodal concentrations difference, starting from the
neighborhood of the critical point (where the concentra-
tion difference is almost zero) to a region far from the
critical point. As Figure 4 shows, the total error or deviation
in the use of the concentration prole given by the Kappa
function [Equation (22)] is, at worst, less than 1.5%. The
total deviation increases with increasing distance fromthe
critical point (increase in tie-line length), but it is not
signicant within the experimental range of temperature
and concentration difference between two equilibrium
phases. The same behavior is observed for all the 22
polymer solutions in Table 1. For lower molecular weights,
the error is lower; Figure 4 shows the worst case scenario.
The results of Figure 4 and for all systems in Table 1
conrm that the proposed expression [Equation (22)] can
be successfully used to predict the concentration prole of
polymer in the interfacial region between two equilibrium
phases of a polymer solution or polymer blend.
Conclusion
A square gradient thermodynamic model, based on the
classical approach of van der Waals and Cahn-Hilliard, was
used to determine the interfacial tension g and interfacial
thickness of a planar interface between two equilibrium
phases of a phase separated incompressible polymer
solution [Equation (14) and (15)]. The equilibrium volume
fractions (f
a
, f
b
) and chemical potential of each compo-
nent within each phase, are computed using a generalized
Flory-Huggins model, which uses a temperature and
concentration dependent interaction parameter [Equation
(13)]. Cyclohexane and methylcyclohexane polystyrene
solutions of different molecular weights were selected and
used (Table 1). The value of the concentration gradient
coefcient, K, as a function of the tie-line length and the
molecular weight of polymer (number of monomeric unit)
was estimated [Equation (27) and (28) and Figure 3]. The
Kappa distribution [Equation (22)] was proposed as an
alternative for the classical sigmoid or tangent hyperbolic
functions [Equation (5)] to represent the polymer con-
Figure 4. The absolute average deviation percentage, AAD%,
between the proposed concentration prole function and the
calculated one for the polystyrene/methylcyclohexane system
(no. 22 in Table 1), corresponding to the highest-molecular-weight
polystyrene (M
w
1 260 kg mol
1
).
centration prole within the interfacial region. The Kappa
distribution function can be used to calculate the
concentration prole for the entire temperature-concen-
tration phase diagram, both very close to and far from the
critical region. It was shown that the concentration prole
parameters can be easily determined directly from
equilibrium thermodynamic information [Equation (A2)
and (A6)]. The integration of the gradient constant power
lawwith the Kappa distribution predictions, yields the key
result of this paper: g N
0:5
f
b
f
a
3:970:09
, which is a
new tool to predict the interfacial tension in equilibrium
polymer solutions.
Acknowledgements: This work was supported by a grant from
the Natural Science and Engineering Research Council of Canada
and NOVA Chem. Inc. The authors are thankful to Dr. Eric Cheluget
for many technical discussions.
Appendix
Parametric Determination of the
Kappa Distribution
Thepurposeof this appendixis todeterminethethree
parameters h, a, j, in Equation (22) from thermo-
dynamic information, consisting of the phase dia-
gram and the free energy function of the polymer
solution.
The rst derivative of Equation (22) shows a
maximumvalue at x j, and the second derivative is
zero at the same point. Thus choosing j 0 means
the concentration gradient has a maximum at x 0.
This condition is
f f
m
;
df
dx
max;
d
2
f
dx
2
0 at x 0 (A1)
Substitution of this condition in Equation (22) and
its rst derivative gives
f
m
f
a
f
b
f
a
1
1 h
1
=
h
(A2)
df
dx

f
m
f
b
f
a
K=a
1 h
11=h
(A3)
Applying the condition in Equation (A1) in
Equation (8) gives
@f
h
@f

f
m
m
p
m
s
(A4)
From which the value of f
m
can be determined, if
the function of free energy [such as Equation (13)] is
known. By substituting the value of f
m
from
Equation (A4) into Equation (A2), the value of h
can be determined.
Substitution of the value of f
m
in Equation (9)
gives
f
h
f
m
m
p
f
m
m
s
1 f
m
K
df
dx

2
f
m
(A5)
Comparing Equation (A3) and (A5):
f
h
f
m
m
p
f
m
m
s
1 f
m

af
b
f
a
2
1 h
2=h
(A6)
From which the value of a can be calculated. The
overall procedure is:
i) From Equation (A4) the value of f
m
is calculated;
ii) With f
m
known, the value of h is calculated from
Equation (A2);
iii) With f
m
and h known, the value of a is calculated
from Equation (A6).
Received: September 12, 2008; Revised: November 17, 2008;
Accepted: November 17, 2008; DOI: 10.1002/mats.200800066
Keywords: computational modeling; concentration gradient;
interface; phase separation; polystyrene
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