544 Macromol. Theory Simul.

8, 544–550 (1999)

Phase behaviour of nematic liquid crystal/linear polymer systems:

Applicability of the extended Flory-Huggins theory

Yong Seok Lee, Young Chan Bae*

Division of Chemical Engineering and Molecular Thermodynamics Laboratory, Hanyang University,
Seoul 133-791, Korea
(Received: February 16, 1999; revised: May 27, 1999)

SUMMARY: Phase behaviour of nematic liquid crystals (N-(p-ethoxybenzylidene)-p-butylaniline and N-

(p-methoxybenzylidene)-p-butylaniline) in linear polystyrene are investigated by thermo-optical analysis.
Results are compared to the model based on the extended Flory-Huggins equation. The model used in this
work includes two adjustable model parameters (d0, d1). The proposed semi-empirical model gives a very
good agreement with new data obtained for liquid crystal and polystyrene systems.

Introduction together flexibly. The free volume which is known to be

Liquid crystal technology has a major effect in many
areas of science and engineering as well as device tech-
nology. Applications for this special kind of material are
still being discovered and continue to provide effective
solutions to many different problems.
Many statistical theories of the nematic phase have
been presented. The best known theories among them are
those suggested by Onsager1), Maier and Saupe2, 3) and
Flory4). The Onsager treatment has proven successful in
the description of rigid molecules of high axial ratio
which display lyotropic behavior while the Maier-Saupe
treatment has found application to lower axial ratio mole-
cules displaying thermotropic behaviour5). Maier and
Saupe2, 3) postulated that the orientation-dependent inter-
action between nematogenic molecules arises from the
anisotropy of their dispersion interaction. They sought to
account for the stability and properties of the nematic
phase solely on the basis of the anisotropy of the forces
of attraction, disregarding the steric or space filling, and
characteristics of the asymmetric molecules comprising
typical nematogenic substances.
Flory and Ronca6, 7) extended the original Flory lattice
model to include anisotropic molecular forces. They have
created a theoretical framework which is particularly well
suited for the description of mixtures containing nemato-
gens6, 8, 9). They combined an orientation-dependent
energy with a partition function derived for a system of
“hard” rodlike molecules in which the intermolecular
energy is the same for all configurations that are devoid
of overlaps. Their treatment of a mixture consisting of
rods, coils and a solvent allowed a successful comparison
with experimental data.
The Flory-Ronca treatment was extended by Ballauff10)
to binary mixtures of a thermotropic nematogen and a
coiled species consisting of isodiametric segments linked
of utmost importance in describing thermotropic systems
was introduced by the methods devised previously8, 9). In
this work, the comparison of the model with experimental
results was made only for polymers of relatively low
molecular weight. Dorgan and Soane11) reported nematic
liquid crystal systems with a wider range of the polymer
molecular weight.
Experimentally, as first discovered by de Kock12), the
presence of a nonmesomorphic solute leads in general to
a depression of the nematic-isotropic transition tempera-
ture. The transition in fact occurs over a temperature
range where the nematic and isotropic phases are in equi-
librium. Thus, at a given solute concentration, there is a
characteristic temperature, at which a two phase region is
formed upon cooling from the isotropic state; further
cooling leads to a homogeneous nematic phase. Demus et
al.13) and Kuss14) reported the melting and pour point of
several homogeneous series of liquid crystals.
In this study, we propose a semi-empirical molecular-
thermodynamic framework for correlating phase equi-
libria in nematic liquid crystal/polymer systems. In the
classical Flory-Huggins lattice theory, the interaction
parameter (vFH) is independent of composition and
inversely proportional to temperature. However, exten-
sive experimental results by many researchers clearly
show that vFH is a function of both polymer concentra-
tion and temperature. Furthermore, its temperature
dependence is not a simple proportionality to inverse
temperature. We modify vFH to take into account both
polymer concentration and temperature and develop a
model by combining Ballauff’s model with the
extended Flory-Huggins model. We also quantitatively
investigate the nematic-isotropic phase transition beha-
viors of nematic liquid crystal/linear PS systems using
thermo-optical analysis (TOA)11).

Macromol. Theory Simul. 8, No. 6 i WILEY-VCH Verlag GmbH, D-69451 Weinheim 1999 1022-1344/99/0611–0544$17.50+.50/0
Phase behaviour of nematic liquid crystal/linear polymer systems: ... 545

Experimental part on the polymer coils residing therein. The quantity, speci-
fies the disorientation of the rodlike particles. For a mole-
Materials cule with the long axis at an angle w with respect to the
Liquid Crystals: Liquid crystals used in this study were domain axis7)
EBBA (N-(p-ethoxybenzylidene)-p-butylaniline) and MBBA
4
(N-(p-methoxybenzylidene)-p-butylaniline) obtained from yˆ xr sin w …2†
Sigma Aldrich Co. Nematic-isotropic transition temperatures p
of EBBA and MBBA measured by TOA are 76.4 8C and with the orientational distribution function for the rodlike
43.6 8C, respectively.
component being given by the ratio nxy/nx of the number
Polymers: Polystyrene (PS) samples were synthesized by
the anionic polymerization method. Their molecular weights of molecules with disorientation y to the total number nx,
— — — — the mean value y follows as
were 39 000 (Mw/Mn = 1.06), 56 000 (Mw/Mn = 1.06), 60 000
— — — —
(Mw/Mn = 1.06), 71 000 (Mw/Mn = 1.06), respectively. X nxy
yˆ y …3†
y
nx
Sample preparation
Samples were prepared by the solvent casting method with As shown in ref. 15, ZM is given by
various compositions: The materials were weighed-out into
clean sample vials. EBBA/polymer samples were dissolved …n0 ÿ nx …xr ÿ y††!
ZM ˆ Zorient
in chloroform and stirred at 50 8C for 15 h until samples …n0 ÿ nx xr † ! nx ! n0nx …yÿ1†
became homogeneous. The samples were then dried in a
vacuum oven at 60 8C for 30 h. MBBA/polymer samples …n0 ÿ nx xr †!
were also prepared in the same way. …4†
…n0 ÿ nx xr ÿ nc xc † ! nc ! n0nc …xc ÿ1†

Thermo-optical analysis (TOA) The orientational partition function Zorient may be ex-
A sample was placed in the microscope heating stage and pressed as7, 9):
heated to 100 8C to achieve homogenization. The sample
was repeatedly heated and cooled over a temperature range Y xy nx  nxy
Zorient ˆ exp…ÿxr ey =…2kB T†† …5†
near the clearing temperature of the pure nematogen while y
nxy
the light intensity was monitored. If the measured transition
points upon heating and cooling agreed with each other, the where
point was taken as the equilibrium transition temperature. If
these temperatures were different, slower heating and cool- xy ˆ sin w …6†
ing rates were employed. In the case of a slight discrepancy,
the transition temperature upon cooling, corresponding to the is the a priori probability of disorientation y for a rodlike
traditional cloud point, has been taken as the equilibrium solute6), ey is the orientation dependent interaction energy
temperature. and kB is the Boltzmann constant.
The first factor in Eq. (4) expresses the expected num-
Theoretical considerations ber of configurations for the rodlike species on the empty
lattice. The last term takes into account the configurations
Consider a binary system consisting of a rodlike nemato- accessible to the nc coiled molecules which have been
gen and a random coil polymer. The diameters of the added to the lattice subsequently.
components are assumed to be equal to the size of the lat- The inclusion of anisotropic molecular dispersion
tice cell. The axial ratio of the rodlike particle is and the forces is accomplished by introducing the mean energy of
contour length of the random coil is. The free volume a rodlike segment expressed as 6, 15)
present in the system is introduced by allowing a corre-
   
sponding fraction of the lattice sites to remain vacant. kB T  3
ey ˆ ÿ vr s 1 ÿ sin w
2
…7†
The combinatorial analysis along the lines given by V~ 2
Flory15) may be readily adapted for the system under con-
sideration. As usually7, 8, 9), the mixing partition function For the entire system, this energy is summed over all
ZM is subdivided into a combinatorial, an orientational, segment pairs,
and a configurational part.
1 kB T 
Eorient ˆ ÿ nr xr mr s2 …8†
ZM ˆ Zcomb Zorient Zconfig …1† 2 V~

where Zconfig is a constant. Thus, this treatment excludes where the characteristic temperature T* expresses the
the possibility of any ordering effect of the nematic phase strength of the orientation-dependent forces for a given
546 Y. S. Lee, Y. C. Bae

~ is the reduced volume, i. e., the ratio

nematic species6). V Qian et al.16, 17) and Bae et al.19) proposed that v is given
of the volume V of the system to the occupied volume V*. by the product of a temperature-dependent term, D (T),
and a concentration-dependent term, B (vr)
~ˆ V
V …9†
V v…T; vr † ˆ D…T†B…vr † …18†

and the order parameter s is expressed as10) d1

D…T† ˆ d0 ‡ …19†
2 T
s ˆ 1 ÿ hsin2 wi …10†
3 1
B…vr † ˆ …20†

Let V denote a segment volume, then it follows 1 ÿ bvr
1

~ 1
n0 V1 ˆ V ˆ …nx xr ‡ nc xc †VV …11†
where, d0, d1 and b are adjustable model parameters.
The enthalpy then is given by
Thus
DHM ˆ nc xc vr v ˆ nc xc vr D…T†B…vr † …21†
~
n0 …nx xr ‡ nc xc †V …12†
The chemical potential of the components is
Also, we have  
vr9 ~r
V
Dlr9=…RT† ˆ ln ‡ vr9…y ÿ 1† ‡ vc9xr 1 ÿ
~ ˆ …V
V ~c nc xc †=…nx xr ‡ nc xc †
~ r nx x r ‡ V …13† ~r
xr V ~ c xc
V

~r and V
~c being the reduced volume of the nemato-     
with V ~r
V 1
‡xr ~
ÿ 1 ‡ xr …Vr ÿ 1† a ‡ ln 1 ÿ
gen and the coiled solute, respectively. Hence, the volume ~
V9 ~
V9
fractions vr and vc of the rodlike and the coiled species
  
follow as: xr vr9s 1 1 ~
V9
ÿln f1 ÿ 1 ÿ s ÿ svr9 1 ÿ
~
V9h 2 2 ~r
V
V~r nx xr
vr ˆ …14† !
~
…nx xr ‡ nc xc †V   
1 d1 1
‡ svc9 ‡ d0 ‡
…1 ÿ bvr9†
2
2 T
~c nc xc
V
vc ˆ …15†
~
…nx xr ‡ nc xc †V  
~ r xr
V
vc9 …22†
2

Combining Eqs. (3), (4), (14) and (15) and employing ~c

V
Stirling’s approximation for the factorials, the reduced  
free energy is obtained18) vc9 ~ c xc
V ~c
V
Dlc9=…RT† ˆ ln ‡ vr9 …y ÿ 1† ‡ vc9 xc ÿ 1
   ~r
xr V ~ r xr
V ~r
V
nx x r y
ÿln ZM ˆ ÿ…n0 ÿ nx xr ‡ nx y† ln 1 ÿ 1ÿ    
n0 xr 1 1 1
~c
‡ xc V ÿ ~ ~
‡ Vc xc a ‡ xc …Vc ÿ 1†ln 1 ÿ
~
V9 ~
Vr ~
V9
nx nc
‡ nx ln ‡ nc ln ‡ nx …y ÿ 1† ‡ nc …xc ÿ 1† !
n0 n0   
d1 1 ~
2 Vr x r
‡ d0 ‡ vc9 …23†
‡ …n0 ÿ nx xr ÿ nc xc †ln‰…nc ÿ nx xr ÿ nc xc †=n0 Š T …1 ÿ bvr9†
2 ~c
V

X nxy nxy nx x r 2 and

ÿ nz ln ÿ s …16†
y
nx nx x y ~
2Vh
 
vr ~r
V
In Dorgan’s treatment, the dipole moments are ignored. Dlr =…RT† ˆ ln ‡ vr …xr ÿ 1† ‡ vc xr 1 ÿ
~r
xr V ~c xc
V
These forces scale with the other parameter rather than
the order parameter squared. Isotropic energetics may be    
~r
V
included in the form of a characteristic temperature for an ‡ xr ~r ÿ 1†ln 1 ÿ 1
ÿ 1 ‡ xr …V
~
V ~
V
isotropic interaction17).
    !

Tiso d1 1ÿb
DHM ˆ nc xc mr ˆ nc xc mr v …17† ‡ d0 ‡ …v2r xc † …24†
…1 ÿ bvr †
2
T T
Phase behaviour of nematic liquid crystal/linear polymer systems: ... 547
 
vc ~c xc
V 1 follows: the NEQNF method of IMSL in FORTRAN was
Dlc =…RT† ˆ ln ‡ vr 1ÿ
~c
xc V ~r
V xr chosen as a method of calculating three parameters (d0,
~r , V
d1, b). If xr, xc, V ~c and T* are known, first, provisional
    values of vr9, y, s serve for the numerical evaluation of fp,
~c
V
‡ vc ~c 1 ÿ 1
xc ÿ 1 ‡ xc V which subsequently yield improved values of y and s via
~r
V ~
V ~r
V
Eq. (26) and (27). From the experimental data, three
  unknown parameters, (d0, d1, b), are obtained by solving
~c ÿ 1†ln 1 ÿ 1
‡ xc …V three equations using the NEQNF method. And by insert-
~
V
ing calculated values of three parameters into the chemi-
  ! cal potential, the condition Dli9 = Dli may be solved for
d1 1ÿb ~ By
‡ d0 ‡ …v2r xc † …25† vr which in turn leads to an improved volume of V.
…1 ÿ bvr †
2
T iterating the above steps, the nematic-isotropic transition
temperature is theoretically calculated.
where primed and unprimed symbols represent quantities
in the nematic phase and the isotropic phase, respectively.
The order parameter s and disorientation index y are
defined as follows: Results and conclusion
  As Dorgan et al.11) reported previously, LC/polymer blend
4 f2 systems exhibit competing effects between entropy and
yˆ xr …26†
p f1 enthalpy contributions. It is a tradeoff between unfavor-
  able entropy effect and favorable energetic effect to the
3 f3 free energy which leads to the formation of a nematic
sˆ1ÿ …27†
2 f1 phase. This shows that the phase behaviour becomes
dominated by entropy effects with increasing molecular
where weight of the polymer. The extended interaction between
Z p=2  rod-like molecules only is considered in the present study
4
fp ˆ sin w exp ÿ
p
xr a sin w and our energetic considerations show good agreement
p
0
with our model for the given systems.
   We used the TOA technique to investigate the nematic-
3 xr vr s —
ÿ sin w dw
2
…28† isotropic transition temperatures of EBBA/PS (Mw =
2 ~
Vh —
39 000, 56 000, 60 000, 71 000) and MBBA/PS (Mw =
25 000, 56 000) systems. The use of the TOA technique
a is defined as
gives a significant advantage over the use of Differential
   Scanning Calorimetry (DSC), which is the classical
vr y
a ˆ ÿln 1 ÿ 1ÿ …29† measurement technique to determine the phase behaviors
~r
V xr
of polymer systems. Most importantly, it allowed the use
of samples in the form of thin films. This promoted
kinetics of the phase separation process and eliminated
major spatial or temporal inhomogeneities. Hence, the
Numerical calculations transition between one-phase and two-phase regions as
Temperature-composition phase diagrams may be found measured by DSC was less sharp than in the method used
through solution for the rodlike component volume frac- in this study.
tions from the equilibrium condition Dli9 = Dli, for each We employed the extended Flory-Huggins equation to
species. For, xc F 50, however, the nematogen rich phase describe phase behaviours of the liquid crystal/PS sys-
approaches complete exclusion of the random coil. This tems. Thermodynamic properties of EBBA and MBBA
leads to a numerical difficulty for higher molecular are summarized in Tab. 1. There are three adjustable
weight as the nematic rich phase composition exceeds the model parameters (d0, d1, b) in the proposed model. The
number of repeating nines available as significant digits parameter b appeared to be unity for all given systems
in double precision FORTRAN. Therefore, calculations based on our calculation and was fixed to be unity
of high molecular weight are performed by setting the through our prediction. We, therefore, use two adjustable
composition of the ordered phase to unity and solving model parameters (d0, d1) to describe phase behaviours of
one remaining equation for the isotropic phase composi- the given systems. All the adjustable model parameters
tion. are listed in Tab. 2 and Tab. 3.
The the calculation step for obtaining three adjustable Fig. 1 – 6 show phase diagrams of EBBA/PS systems.
model parameters (d0, d1, b) proposed in this study is as In these figures, solid lines are the nematic-isotropic tran-
548 Y. S. Lee, Y. C. Bae

Tab. 1. Thermodynamic properties of EBBA and MBBA

EBBA

q (40 8C) = 0.9881g/cm3 a = 8.22 N 10–4 K–1 V* = 229.3 cm3/mol

Tni = 76.4 8C ~ at Tni = 1.242
V T* = 351.2 K
xr = 3.7

MBBA

q (40 8C) = 1.0332 g/cm3 a = 8.5 N 10–4 K–1 V* = 211.2 cm3/mol

Tni = 43.6 8C ~ at Tni = 1.225
V T* = 351.7 K
xr = 3.4

Tab. 2. Values of adjustable model parameters for EBBA/PS

systems
—
Mw of PS d0 d1 b
Fig. 2. Phase diagram of the EBBA/PS (39 000) system. The
22 000 0.2635 –91.8928 1.000 solid line is the proposed model. Dotted line and dashed line are
39 000 0.4680 –163.0714 1.000 Dorgan’s model for T*iso = 45.0 K and T*iso = 47.0 K, respectively
56 000 0.8466 –295.5345 1.000
60 000 0.3551 –123.8528 1.000
71 000 0.5717 –199.2945 1.000
113 000 0.5013 –174.8887 1.000

Tab. 3. Values of adjustable model parameters for MBBA/PS

systems
—
Mw of PS d0 d1 b

25 000 0.4315 –136.7206 1.000

56 000 0.5577 –176.8051 1.000

Fig. 3. Phase diagram of the EBBA/PS (56 000) system. The

solid line is the proposed model. Dotted line and dashed line are
Dorgan’s model for T*iso = 55.0 K and T*iso = 60.0 K, respectively

Fig. 1. Phase diagram of the EBBA/PS (22 000) system. The

solid line is the proposed model. The dotted line is Dorgan’s
model for T*iso = 42.0 K

sition temperatures calculated by using our model.

Dashed line and dotted line are those of Dorgan et al.11)
As shown in Fig. 1, in the lower molecular weight
range of PS, Dorgan’s model shows slightly better agree-
ment with experimental data than the model presented in
this work. However, in the higher molecular weight range Fig. 4. Phase diagram of the EBBA/PS (60 000) system. The
of PS (Fig. 2 – 6), our model describes very well phase solid line is the proposed model. Dotted line and dashed line are
behaviours of the given systems compared to that of Dor- Dorgan’s model for T*iso = 25.0 K and T*iso = 42.0 K, respectively
Phase behaviour of nematic liquid crystal/linear polymer systems: ... 549

Fig. 5. Phase diagram of the EBBA/PS (71 000) system. The Fig. 8. Phase diagram of the MBBA/PS (56 000) system. The
solid line is the proposed model. Dotted line and dashed line are solid line is the proposed model. Dotted line and dashed line are
Dorgan’s model for T*iso = 40.0 K and T*iso = 45.0 K, respectively Dorgan’s model for T*iso = 42.0 K and T*iso = 47.0 K, respectively

gan. Further, Dorgan’s model predicts narrower phase

diagrams with increasing T*iso value. For systems of
MBBA/PS shown in Fig. 7 and Fig. 8, the model pro-
posed in this study also gives slightly better agreement
with experimental data than that of Dorgan.
In this work, we showed that the extended Flory-Hug-
gins equation is well adapted for LC/PS systems both
quantitatively and qualitatively. A slight deviation from
experimental results appears in the calculation of phase
behaviours of the given systems. It might be that we did
not consider all interactions that exist in the given sys-
tems, especially specific interactions between molecules.
It is likely that this deficiency is basically responsible for
the remaining discrepancy between the proposed model
Fig. 6. Phase diagram of the EBBA/PS (113 000) system. The
and experimental data.
solid line is the proposed model. Dotted line and dashed line are
Dorgan’s model for T*iso = 40.0 K and T*iso = 45.0 K, respectively

Nomenclature
Eorient – orientational energy of the system as a whole
HM – enthalpy of mixing
n0 – number of vacancies on the lattice
nc – number of coil-like molecules
nr – number of rod-like molecules
R – gas constant
T – absolute temperature
Tni – nematic-isotropic transition temperature
V* – molar hardcore volume
~c
V – reduced volume of the coil-like molecules
~r
V – reduced volume of the rod-like molecules
vc – volume fraction of coil-like molecules
vr – volume fraction of rod-like molecules
xc – contour length of the polymer chain
Fig. 7. Phase diagram of the MBBA/PS (25 000) system. The xr – aspect ratio of rod-like component
solid line is the proposed model. Dotted line and dashed line are w – angle between rod axis and preferred axis
Dorgan’s model for T*iso = 42.0 K and T*iso = 45.0 K, respectively h – reduced temperature (T/T*)
550 Y. S. Lee, Y. C. Bae

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