JOURNAL OF CHEMICAL PHYSICS VOLUME 121, NUMBER 10 8 SEPTEMBER 2004

A theory of polymer solutions without the mean-field approximation

in Flory-Huggins theory
Baofu Qiao and Delu Zhao
State Key Laboratory of Polymer Physics and Chemistry, Institute of Chemistry,
Chinese Academy of Science, Beijing 100080, China
~Received 11 May 2004; accepted 16 June 2004!
The concept of the volume fraction at chain end is proposed, which is the conditional probability for
a site having been occupied, knowing that an adjacent site is occupied by polymer end. The overall
entropy of polymer/solvent system is separated into two fundamentally different parts, i.e., the
translational entropy and the conformational entropy. Based on these a theory of polymer solutions
is established. When a mean-field approximation is introduced, Flory-Huggins ~FH! theory is
recovered. The FH interaction parameters and spinodal curves of the polystyrene/cyclohexane
system are calculated and compared with the experimental data. The good prediction of them two
is achieved. © 2004 American Institute of Physics. @DOI: 10.1063/1.1781091#

I. INTRODUCTION polymer fluids and polymer solutions, respectively. Their

For polymer solutions, the most widely used model is
Flory-Huggins ~FH! theory, proposed by Flory and Huggins
in 1940s.1– 6 In FH theory, a mean-field approximation and
an approximation that the entropy of the system is indepen-
dent of the interaction energy, which is called as athermal
entropy approximation in this work, are introduced, and the
Gibbs free energy of mixing DG is given by
DG f
5 ln f 1 ~ 12 f ! ln~ 12 f ! 1 x f ~ 12 f ! , ~1!
kT N
where k is the Boltzmann constant, T is the absolute tempera-
ture, f is the volume fraction of polymer, N is the ratio of
molar volume of polymer to that of solvent, and x is the FH
interaction parameter.
Based on FH theory, Guggenheim proposed a qua-
sichemical model.7,8 Freed and co-workers designed a lattice
field theory.9,10 Besides these three, the lattice fluid
theory11–13 and the recently developed local composition
theory14 –17 also promoted the development of theory of poly-
mer solutions.
Experimentally, Krigbaum and Geymer investigated the
polystyrene/cyclohexane system across the concentration
range by combining osmotic pressure, isothermal distillation,
and differential vapor pressure measurements.18 Scholte
studied the PS/cyclohexane system with the methods of
light-scattering19,20 and sedimentation-diffusion equilibrium
in the ultracentrifuge,21 and calculated the FH interaction
parameter and spinodal curves according to FH model.
Koningsveld and co-workers investigated the critical points
of PS/cyclohexane systems with different molecular weights
of PS by using the critical miscibility method, and calculated
the FH interaction parameters and spinodal curves.22–25
There are some other experiments that investigated the FH
interaction parameter.26 –29 In Ref. 30, the researches on the
FH interaction parameter are reviewed.
In Refs. 31 and 32, Li and Zhao presented a polymer
theory from statistical thermodynamics and studied the pure
theory avoids the athermal entropy approximation in FH
theory. In this work, we introduce the concept of the volume
fraction at chain end, and obtain a new polymer theory with-
out the mean-field approximation in FH theory.
II. DESCRIPTION OF THE MODEL
A simple cubic lattice model is used, just as in FH
theory. Only the nearest-neighboring interaction is consid-
ered. Each site is occupied by either one polymer monomer
or one solvent molecule. One polymer molecule occupies
sequentially neighboring sites. In this model with a volume
V, first, n lattice sites are selected randomly as the positions
of chain heads; second, each chain increases its length by
one monomer ~sites! in turn according to the self-avoiding
walk principle; then the second step is repeated for N22
times, thus a system of n chains with chain length N ~N
monomers! is achieved, and then all the rest n s sites are filled
with solvent molecules. In this polymer/solvent system, the
volume fractions of polymer and solvent are
nN
f5 ,
V
~2!
ns
f s5 512 f ,
V
respectively.
Keeping the athermal entropy approximation, the Gibbs
free energy of mixing can be written as
DG5DH2TDS, ~3!
where DH and DS are the enthalpy of mixing and entropy of
mixing, respectively.
A. The entropy of mixing
The entropy is divided into two parts, i.e., the transla-
tional one and the conformational one. The former describes
the distribution of polymer chain heads. The latter describes

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J. Chem. Phys., Vol. 121, No. 10, 8 September 2004 A theory of polymer solutions 4969

the conformations, which represents the linkage among S ST SC f f

monomers and distinguishes polymer molecules from small 5 1 52 ln 1 f ln~ z21 !
k k k N N
molecules.
f
First, the number of arranging the n polymer chain heads
is calculated, 1 E 0
ln~ 12 f end! d f . ~12!

V! Therefore, the concentration of the entropy of mixing DS is

V T5 . ~4! obtained
~ V2n ! !n!
DS f f
When V@n@1, introducing the Stirling approximation, the
concentration of the translational entropy S T is yielded, k
52 ln f 1
N
E0
ln~ 12 f end! d f

1
S T ln V T
k
5
V
f f
52 ln .
N N
~5!
2f E0
ln~ 12 f end! d f . ~13!

Second, the conformational entropy can be calculated B. The enthalpy of mixing

through defining a quantity
When the chain increases its length by one monomer,
V ~ N11 ! one covalent bond is generated, and the new chain end has
v~ N !5 , ~6! (z21) f end nonbonded monomer-monomer contact, but the
V~ N !
number of nonbonded monomer-monomer contact of the
where V(N) is the conformation number when the length of monomer next to last decreases f end ; thus the number of
the chain is N, thus v (N) is the void site number at chain monomer-solvent ~1-2! contact C 12 increases by
end when the chain length is N. In the lattice model, the DC 125z22DC 115z2222 ~ z21 ! f end12 f end
maximum of v (N) is z21, where z is the coordination num-
ber. Hence the average void site number at chain end is ob- 5 ~ z22 !~ 122 f end! . ~14!
tained under the mean-field approximation, For N@1, the overall number of monomer-solvent contact
can be written as
v ~ N ! 5 ~ z21 !~ 12 f ! , ~7!
nN
where f is the volume fraction of polymer. Here a concept of C 12' E1
@~ z22 !~ 122 f end!# dl. ~15!
the volume fraction at chain end f end is introduced, which is
the conditional probability for a site having been occupied, The concentration of monomer-solvent contact is
knowing that an adjacent site is occupied by polymer end. C 12 f
Thus the average void site number at chain end is rewritten
as
c 125
V
' ~ z22 ! f 22 ~ z22 ! Ef0
endd f . ~16!

Therefore, the concentration of the enthalpy of mixing is

v ~ N ! 5 ~ z21 !~ 12 f end! . ~8!
DH5c 12D e , ~17!
When the chain length N increases by 1 (DN51), the
where D e 5 e 122( e 111 e 22)/2 is the interaction energy of
concentration of conformational entropy S C increases by
mixing.
By substituting Eqs. ~13! and ~17! into Eq. ~3!, a theory
DS C ln v ~ N ! DN
5 5ln v ~ N ! . ~9! of polymer solutions is established,
k V V
DG f f 1
When nN@1, the effect of chain end can be ignored; it 5 ln f 2
kT N
E 0
ln~ 12 f end! d f 1 f E 0
ln~ 12 f end! d f
yields

SC
k
5 E n ~ N21 ! dl
ln v ~ l ! .
V
~10!
F
1 ~ z22 ! f 22 ~ z22 ! E f fG
f

0
endd
De
kT
. ~18!
1
When the mean-field approximation is introduced, that is
For dl/V5d f , substitution of Eq. ~8! into Eq. ~10! yields f 5 f end , Eq. ~18! comes back to the result of FH theory
@Eq. ~1!#.
SC f

k
' E0
@ ln~ z21 ! 1ln~ 12 f end!# d f

f C. Chemical potential and phase separation

5 f ln~ z21 ! 1 E 0
ln~ 12 f end! d f . ~11!
In order to evaluate the present theory, we will calculate
spinodal curves and FH interaction parameter for which the
From Eqs. ~5! and ~11!, the concentration of the overall chemical potential of solvent is required. In FH theory, this is
entropy S is given by

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4970 J. Chem. Phys., Vol. 121, No. 10, 8 September 2004 B. Qiao and D. Zhao

Dms
kT
5ln~ 12 f ! 1 12
1
N S D
f 1 x 1f 2, ~19!

where x 1 5 x 2(12 f ) ]x / ] f . Since it is the chemical po-

tential of solvent that is normally measured, x 1 is practically
the only parameter that can be directly obtained. In the fol-
lowing text, the term ‘‘FH interaction parameter’’ is, there-
fore, exclusively applied to x 1 .
From the present theory, the chemical potential of sol-
vent is given by
Dms f f

kT
52 2
N
E 0
ln~ 12 f end! d f 1 f ln~ 12 f end!

22 ~ z22 ! FE0
f
f endd f 2 ff end G De
kT
. ~20!

Therefore,
FIG. 1. f end dependence on f. The simulation conditions are j (5,108 ,8),
f and d (20,107 ,8). The three numbers in brackets represent the side length of
2 E0
ln~ 12 f end! d f 1 f ln~ 12 f end! 22 ~ z22 ! periodic boundary, number of sample and number of chains for each sample,
respectively.

3 FE0
f
f endd f 2 ff end G De
kT
~1! Watt pointed out from the renormalization theory
5 f 1ln~ 12 f ! 1 x 1 f 2 . ~21! that the average number for walking forward for an isolated
chain is 4.6838 in a simple cubic lattice model.33
From Eq. ~21!, the FH interaction parameter can be calcu- ~2! Shita and co-workers simulated the ‘‘effective coor-
lated. dination number,’’ which seems to converge linearly to
In a phase diagram, the spinodal curve separates the 4.6838 when the volume fraction of segments is small.34
metastable regime and the unstable one. Thus, information of ~3! De Gennes pointed out ‘‘the concentration of end
phase separation can be obtained in studies of the spinodal points must be proportional to c,’’ where c is the order pa-
curve. In the present theory, the spinodal curve is given by rameter for polymer solution.35
solving the following equation: The Monte Carlo statistical counting method36,37 is used
to simulate the volume fraction at chain end under the ather-
]2
]f 2 S D DG
kT
5
1
1
1 ] f end
N f 12 f end ] f
22 ~ z22 !
] f end D e
] f kT
50 mal condition. The simulation results are plotted in Fig. 1.
From Watt’s result, the volume fraction at chain end in ex-
~22! tremely dilute solution is ~524.6838!/550.063 24, which is
and the critical point by consistent with our simulation results. It is also found that
the longer the chain is the better our result in extremely
]3 2

]f3
S D DG
kT
52
1
Nf 2
1
12
1
f
] f end
end ] f
F G dilute solution approaches 0.063 24. From our simulation re-
sults, the following equation is accepted to express the vol-
ume fraction at chain end:
1 ] 2 f end ] 2 f end D e f end512a ~ 12 f ! b . ~24!
1 22 ~ z22 !
12 f end ] f 2 ] f 2 kT Under the athermal condition, a50.94 and b50.65.
50. ~23!
B. FH interaction parameter and spinodal curve
III. RESULTS AND DISCUSSIONS
The model presented here has two parameters a and b.
A. The volume fraction at chain end
For true polymer solution systems, they should be treated as
The volume fraction at chain end reflects the local con- adjustable parameters.
dition at chain end, which is different from the volume frac- We will compare our results with the experimental data
tion, the interaction surface fraction ~the conditional prob- of the PS/cyclohexane system, because the FH interaction
ability for a monomer to occupy a site, knowing that an parameter in this system has been measured in the vicinity of
adjacent site is occupied by another monomer! used by the u temperature across the concentration range, and also its
Guggenheim and Koningsveld, and the local composition spinodal curve is studied by many workers. The result of
~describing the monomer-solvent interaction! in local com- Koningsveld24 is given for comparison, which is a semi-
position theory. To our knowledge, researches on the volume empirical result, and is the most convincing one from the
fraction at chain end up to now are as given below. theoretical viewpoint.

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J. Chem. Phys., Vol. 121, No. 10, 8 September 2004 A theory of polymer solutions 4971

TABLE I. Experimental critical data ( f c ,T c ) for the PS/cyclohexane

system.a

Sample no. MW fc T c (K)

1 51 000 0.1126 288.85

2 93 000 0.0895 293.65
3 166 000 0.0754 296.60
4 394 000 0.0525 300.70
5 527 000 0.0483 301.15
6 1 500 000 0.0308 303.20
a
See Ref. 23.

Substitution of Eq. ~24! into Eqs. ~21!, ~22!, and ~23!

yields
T* 1
~ b21 !@ f 1ln~ 12 f !# 2 @~ 11b f !~ 12 f ! b 21 #
T b11
FIG. 2. Plot of FH interaction parameter of the PS/cyclohexane systems.
5 x 1f 2, ~25!
1 b T*
1 2 b ~ 12 f ! b21 50, ~26! concentration range is very small. From Fig. 2, we can see
N f 12 f T
that the volume fraction dependence of FH interaction pa-
1 b T* rameter calculated from the present theory is consistent with
2 1 1 b ~ b21 !~ 12 f ! b22 50, ~27! the experimental data across the concentration range, except
Nf 2
~ 12 f ! 2 T
that our results are a little bigger for some points. We also
where noticed that in the extremely concentrated range, the present
T * 52 ~ z22 ! aD e /k. ~28! theory is much better than Koningsveld’s theory.
The calculated spinodal curves are compared with ex-
The values of b and T * can be obtained by fitting Eqs. perimental results reported by Scholte, as shown in Figs. 3,
~26! and ~27! to the experimental critical points in Table I 4, and 5. It can be seen that our results are consistent with the
reported by Koningsveld and co-workers.23 The calculated experimental data. In our opinion, the small deviations exist
values of b and T * are listed in Table II. for the following reasons:
With the values of b and T * obtained, the FH interaction ~1! The spinodal curves of Scholte and the critical
parameters and the spinodal curves for three systems of dif- points of Koningsveld are not consistent with each other, as
ferent molecular weights (M W 551 000, 166 000, 527 000) shown in Fig. 5.
are calculated. ~2! The parameters b and T * used to calculate the spin-
The calculated FH interaction parameters are plotted in odal curves are obtained at temperature T c , while in practice
Fig. 2, also given is Koningsveld’s result. For FH theory it is quite possible that they are not constant at different
x 1 5 x 5(z22)D e /kT, which is not plotted in Fig. 2 for it is temperatures.
independent of the molecular weight and volume fraction of ~3! The calculated spinodal curves are narrower than the
PS. The experimental data plotted in Fig. 2 are those ob-
tained by Krigbaum et al. and Scholte. Krigbaum et al. stud-
ied three systems with molecular weights M n 525 100,
72 000, 440 000. Scholte worked on three systems with mo-
lecular weights M W 551 000, 163 000, 520 000. From these
experimental data, it is hard to conclude whether the molecu-
lar weight of polymer affects the FH interaction parameter or
not. From our results, it can be found that the molecular
weight dependence of FH interaction parameter across the

TABLE II. Values of b and T * for the present theory.

Sample no. N b T * (K)

1 447 0.3870 316.30

2 816 0.3670 314.26
3 1456 0.3300 312.14
4 3455 0.3128 310.92
5 4622 0.2950 310.00
6 13 155 0.2775 308.48
FIG. 3. Spinodal curve of PS/cyclohexane for M W 551 000.

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4972 J. Chem. Phys., Vol. 121, No. 10, 8 September 2004
FIG. 4. Spinodal curve of PS/cyclohexane for M W 5163 000.
experimental ones, which exists in other theories, as shown
in Figs. 3–5.
~4! For true polymer solutions, our expression of the
volume fraction at chain end @Eq. ~24!# does not hold exactly
because of the interaction energy, which affects the exactness
of Eqs. ~25!, ~26!, and ~27!.
~5! The present theory does not avoid the athermal en-
tropy approximation.
In Figs. 3–5, the results of FH theory and Koningsveld’s
results are also plotted. It can be seen that the results of FH
theory are the worst. Its spinodal curves are too narrow, and
its critical points depend on the chain length exclusively and
are much smaller than the true values. Koningsveld’s results
are almost as good as those of the present theory, while the
present theory is deduced without empirical fitting to experi-
mental data, and is simpler than the Koningsveld’s theory.
FIG. 5. Spinodal curve of PS/cyclohexane for M W 5520 000.
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B. Qiao and D. Zhao
IV. SUMMARY AND CONCLUSIONS
A concept of the volume fraction at chain end is pro-
posed. Though it is important in studying order parameters as
pointed out by de Gennes, it is rarely investigated. In this
work, the Monte Carlo statistical counting method is used to
simulate it.
By keeping the athermal entropy approximation and
separating the entropy into two parts, i.e., the translational
part and the conformational part, a theory of polymer solu-
tions is established. When the mean-field approximation is
introduced, the theory becomes identical with FH theory.
Using the present theory, the FH interaction parameters
and spinodal curves of the PS/cyclohexane system are pre-
dicted, and the dependence of FH interaction parameter on
molecular weight and volume fraction of PS is investigated.
Our calculated results, both the FH interaction parameter and
the spinodal curves, are in reasonably good correspondence
with the experimental data. And the experimental spinodal
data for high molecular weight are better reproduced than
those for low molecular weight.
Comparing with other theories of polymer solutions, the
present theory is more concise. And even with some approxi-
mations retained, the present theory improves greatly the FH
theory in describing the FH interaction parameter and spin-
odal curve. It can be seen that the concept of the volume
fraction at chain end plays an important role.
ACKNOWLEDGMENTS
This work was subsidized by the Special Funds for Ma-
jor State Basic Research Projects of China ~Grant No.
G1999064808! and 863 Project ~Contract No.
2002AA336120!.
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