J.

Phys.

II

France

(1992)

209-218

FEBRUARY

1992,

PAGE

209

Classification

Physics
61.30

Abstracts

61.40K

64.70M

Kerr

effect

in

the

isotropic

phase

of

side-chain

polymeric

liquid crystal
V.

Reys (I),

Y.

Dorrnoy (I),
d'Ultrasons
et

D.
de

Collin

(I),

P.
des

Keller
Fluides

(~)

and

P.

Martinoty (')
(*),
Universit6
Louis

Laboratoire (1) Pasteur, 4 rile

Dynalnique

Complexes

Blaise Lon

(~)

Laboratoire

Pascal, 67070 Strasbourg Brillouin, C.E.N. Saclay,

revised
lo

Cedex,
91191

France

Gif-sun-Yvette

Cedex,
7November

France

(Received

21

December1990,

October

1991,

accepted

1991)

R4sum4.
studier Ies

La effets

bitflingence induite prtransitionnels

obtenus
et
une

par un assoc16s

champ Iectrique impulsionnel a t6 polysiloxane la phase isotrope d'un

effets
de

utilis6e h

pour chaines

lat6raIes.
de

Les

l'exposant
que
au

montre

applicable
les
moments

classique caract6ris6s valeur sont par une l'exposant dynalnique. Ce demier r6sultat dynalnique des cristaux liquides de bas poids mo16culaire n'est la th60rie pas 6galement en Evidence competition entre present. Les experiences mettent cas une dipolaires induits par le champ 61ectrique et les moments molecules des permanents
r6sultats
montrent

statique

valeur

que ces anormale

m6sogbnes.
Abstract. obtained
and
an

pretransitional

molecular

dipolar
molecules.

by a pulsed electrical field study the used to was isotropic phase of a side-chain polysiloxane. The results that these effects characterised by a conventional show value of the static exponent are abnormal which that the dynamic theory of low value of the dynamic shows exponent, weight liquid crystals does not apply. The results also reveal competition between the field and the of the mesogenic induced by the electrical moments permanent moments
The

bireflingence
associated

induced

effects

with

the

1.

Introduction.

composed of a principal chain onto the sides of which mesogenic groups have been grafted, by means of a These compounds are spacer. new with since they have special properties associated presently the object of intense research, competition the tendency order, imposed by mesogenic elements, and the between the to imposed by the polymer skeleton [Ii. tendency to disorder, poly[(acryloxy-6-hexyloxy)We have recently studied the isotropic phase of a polyacrylate, PA60CB, 4-cyano-4'-biphenyl], abbreviated with molecular Mw of 62 000, and to mass
Side-chain
are

liquid crystal polymers

(*)

Unit6

de

Recherche

Associe

au

CNRS

851.

210

JOURNAL

DE

PHYSIQUE
shown

II

polydispersity
orientational
molecular
elements
are

of

3.38

[2].

This

study

has

that
formula

the

static

properties
(PCB),
to

of

the

local
a

comparable to those are weight liquid crystal (LMWLC)

order
the

of
with

pentylcyanobiphenyl
a

which
of the

is

low

similar
of the

that

mesogenic
order

of

polymer.
from those

However,
of PCB.

the

dynamic
difference

properties
is

local

orientational
time
and

very

different
order

This

orientational

diverges
In
order

with
to

which is about 500 times parameter, of the order of 1.5 than I. rather exponent an effects, have whether these general check we are

relaxation apparent on the greater than that of PCB, studied another

of the which

side-chain
a

polymer. The polymerisation

obtained
confirm

compound in question and mesogenic groups

the abnormal
value

was

a
are

polysiloxane
different
from

characterised
those of

by
PA60CB.

degree
The

of

which the

results

conventional value of dynamic exponent and the induced the dipolar by static competition between They also reveal the moments exponent. presenting of the mesogenic molecules. Before electric field and the the permanent moments (Sect. 4), we shall first of all describe the polymer studied and the and discussing results our Landau-de Gennes review the theory of the technique (Sect. 2), and then briefly used molecular weight liquid crystals (Sect. 3). isotropic phase of low
of

2.

Materials

and

methods.

The

formula
mass

and

molecular

phase diagram Mw is 31 000, and

and

of
its
the

P(o, as degree
local

where

80

represent
have

studied shown in figure I. the polysiloxane are polydispersity is I. I. It shall subsequently be referred in the and of methylene number spacer, groups
In also

Its
to

the

of

polymerisation,
order,
is of
a

respectively.
we

order

to

ascertain

the

influence

of the

chain

on

the

orientational which
to

studied

benzoate,
identical MPHOB.

that

liquid crystal mesogenic the

of

low

elements

4-methoxyphenyle weight, with molecular of P(o. This compound

4'-((5-hexenyl) oxy) (cf. Fig, I) formula

be

shall

referred

to

as

1~~80

CH~

(CH~)~-Si-O-[Si-O[o-Si-(CH~b

(cH~)~-o-~g-coz-~g-o-cH~
T~j=
108C

T~smc"

46C

T~s~c"

3C

MPHOB
CH~=CH-(CH~)~-O-~9-CO~-~9-O-CH~

TNT" 59C

Fig.

1.

Chemical

formulas

and

transition

temperatures

for P(o and

MPHOB.

N 2

KERR

EFFECT

IN

THE

ISOTROPIC

PHASE

OF P~o

211

determine birefringence induced by a pulsed electric field was used to simultaneously intensity and the characteristic orientational time of the local order, which appears in the vicinity of the Nematic-Isotropic transition. The birefringence measured at 6 328 A, with was He-Ne and a 10 mm long Kerr cell with an inter-electrode laser as a light-source, a 5 mW length of 2.2 mm, the cell-temperature being kept constant to within 0.05 C. The electrical rectangular in shape, with a amplitude of 500V, for pulses maximum and each were their duration adjusted in such a way as to ensure stationary birefringence. temperature, was
The

the

The

rise

and

decay
of
The

times the

of the

electric orientational

field

were

less of the

than

0.2 ~Ls.

This which

is

much could

less

than

the

relaxation

time

local

order

polymer,

therefore

be

determined.
weaker than

induced

in

PA60CB),
transition
be
to

nematic-isotropic
E~
was

birefringence in the P(o is very weak (approximately and only the taken in the first 8 degrees measurements signal-to-noise ratio. The variation of have j good
for all the

100
above
An

times
the with

found

linear

electric
were were

fields also

used. carried
out
one on

Scattered-light practical reasons,

as

intensity
these
to

measurements measurements

the

same

set-up.
chosen

For
so

only

taken

for
the

observation

angle,
which
inert

to

correspond

90
were

to

the

incident
and

beam.
on

An/E~, r and I degassed prior to

measured

simultaneously
the

same

sample,
under
an

had

been

the

experiments,

measurements

taken

atmosphere.

3. For

Review
a

of

the

Landau-de the

Gennes order

model

[3].
is
a

uniaxial
as :

nematic,

parameter

symmetrical

tensor

of

zero

trace

which

can

be

written

Qp
where of the
n~,

"

S(3
unit

n~ np

8~p)
which
indicates
rate

(1)
the

np

are

the

components

of

vector

(the director)
the molecular

direction
relation
of
to

optical axis, and S is a scalar which fixes the optical axis. In the isotropic phase, the free energy per unit development of Q~p in the following way :
F
=

orientational
be

in

volume

can

expressed

as

function

Fo

jAQ
also

up

Qpa
written

jBoap
as :

Qfly Qya

(Qp Qp)~

(2)

which,

using (I),

can

be

=Fo+(AS~-(BS~+ (CS~+.

(3)

If

coefficient
at

transition

order,
and

and that

B then the system involve a would second-order Nematic-Isotropic were zero, indicates that the transition is of the first temperature Tf. That this is not the case Tf. The Landau Tf), model that A temperature T~ at occurs assumes a (T
~
=

coefficients
of
to

and

are

only

very
us

slightly
show

development (proportional

the

free

(Q~) )

energy scales as

enables
:

to

dependent This temperature. on that the scattered-light intensity I

~
~

~Tf

~~~

which

shows

that

diverges

when

T-

Tf.

212

JOURNAL

DE

PHYSIQUE

II

In

the

presence the

of

dc

electric

field

E, the
and
:

term

(1/2)
dc

where

so is order

vacuum

permittivity,
by
the

e(j

so

e(j

E~ Ep
tensor.

must

be

added linked

to
to

(2)
the

the

dielectric

e(j

is

Qp

parameter

relation

(Sap )~~
where
=

"

(P)~~ 8p

(A8~ax)~~ Qfl
of the
we

(5)
oriented
can

Ae~~~

ejj
+

e~

represents
The

(1/3)(2 P minimizing

e~
the

ejj).

order
With

the anisotropy produced by

E

for electric

perfectly
field E

nematic,
calculated

and

be

by

free

energy.

along
~
=

Oz,

find

~~~~~~~
Tf)

E~

(6)

9 a(T

This

leads

to

an

electrically
~~

induced

birefringence

given by
(AS )f~~
~
~

A~maK S

~ ~ ~~maK
=

~~~
is the

~l)

~~

where

An
=

oriented

nematic

(e~~)~/~- (e~,)~/~, and An~~~ phase (S I).

=

anisotropy
[4], taking

of

the

refractive

index

in

the

(As )$~~ has

the

been
and

calculated

induced

permanent

by Maier and dipoles. Based

4 MN
=

Meier
on

account

of the
this

contributions

of

the

Onsager

model,

calculation

gives
(8)

(he )$~~
where N

Au
+

~'

"~~~ ~~ ~
2 kB T

hF'

is

the

number

of

molecules

per

unit
mean

anisotropy, v the permanent dipole, and p the if the long axis of the molecule. F' I/(I with f 8 MN (P 1)/3(2 P + I) and & the factor describes the cavity field. In which a
= =

volume, angle
factor
molecular

Au

the
the

molecular

between
which

permanent
the h
=

polarisability dipole and

reactive
field
P +

is
mean

the

describes

these

polarisability. An/E~ is conditions,

p
I

3/(2
:

I) is

written

An

80(An)max
a(T
electrical

7TN
~"
~

F'

v~(3 cos~
2 kB T of the

E~
In the presence
:

Tf
field,
the

~~

~~~

of

an

behavior

order

parameter

is

govemed by

the

equation

fi ~"~

~~

so
"~

(Ae)$~~
3
is

~" ~~

~~~~
that there is and the

where

is

local
to

friction
enables field
:

coefficient.
of the the be transient determined.

I-eof

no

This
the

coupling equation
electrical

gradients
to

Equation (10) velocity field. birefringence

For
a

obtained

assuming
with
one

no

flow,
cut-off

associated

the

switch-on for

rectangular
e~~/~)
~/~

field,

obtains

rise-and-

decay

birefringence

AnR(t)
An~ (t )
where
r

Ano(I
Ano
e~

(l la)
( l16)

VIA is
=

the

order

parameter

relaxation

time

and

Ano the

stationary

birefringence,

given by equation (7).

KERR

EFFECT

IN

THE

ISOTROPIC

PHASE

OF P~o

213

4.

Results STATIC

and

discussion.
INVESTIGATIONS.

4,I.

We taken

shall

begin by
2

induced the results

birefringence
obtained
the whole

data for of
the

from

MPHOB,

polymer.
Such

Figure
has

virtually To of the
reflects the

the

temperature-range
behavior between

order
the

of

80 C.
of

existence
moment
can

competition

electricallyto interpret that birefringence is negative throughout shows studied, and changes sign at a temperature in other been encountered compounds [5], and the electrical induced by the field and moment
the which will be necessary

presenting

stationary
in

order

permanent

birefringence

be

the to proper written according

molecules.
to

It

should,
as :

indeed,

be

remembered

that

equation (9)
~~

~(
~
where F'
=

~2

F'v2(3 cos~
Tl)
and
Au
~

1)

(T

k~

(12)

v~(3 cos~
induced

1)/2 k~ T
the

are

the fl is An

contributions

of

the

permanent

dipoles

and

the

dipoles

by

field

respectively
fl
=

given by
MN

8 hF

'

eo(

)~~,

(13)
is
cancelled

If

To

is

called
:

the

temperature

at

which

birefringence

out,

equation

(12)

can

be

rewritten

~~

E~

(T

Tf)
=

~
fl
Au

(14)

,Ta"7g.56c

~i

MPHOB

~fl

~~

~
~

=
w

-100

~
~
~

g
O
~

-150

T(
-200
2.80 2.85 2.90

2.95

3.00

10~/T
Fig.
2.

(K~~)
of

Variation order show

of

(An/E~)(T
temperature
at

Tf)
and

ratio An

as

function

I/T for
induced
line

MPHOB

where

Tf
with

is

the

virtual E.

second
results

transition
that
An

the

birefringence
To.
The

by

an

electrical
the

field

The

changes sign

temperature

solid

represents

fit

equation (14)

(see text).

214

JOURNAL

DE

PHYSIQUE

II

N 2

where

temperature

To is given by

~
The

F'(3 cos~ p
2

1)

/~

k~

(15)

Au

implies either that F'(3 cos~ p -1) < 0 and Au ~0, or that that To is positive cost nematic molecules, positive F'(3 p -1) ~ 0 and Au < 0. For elongated Au is always I) must therefore be negative. [5] ; F'(3 cos~ p analysed with equation (14) which indicates that variation of The experimental points were (An/E~)(T Tf ) as a function of I IT must be linear, and the results in figure 2 show that this
fact
is indeed the
case.

The

parameters

corresponding

to

this C C

analysis

are

Tf
To
fl
Au
=

58.93
=

0.01

79.56
=

0.02 10

(2 758

Ii

~m~ V~~ by

K.
the in

Competition
permanent
We have the

between of the

the

moments

dipolar mesogenic
the

moments

induced
must

electrical
the
case

field of
the

and

the shows line

molecules

also

exist

polymer.
3 solid

that

therefore analyzed experimental results

the

results
are

obtained
well

for

obtained
and

accounted
to

represents

calculated

curve,

corresponds
107.79
=

P(o, using equation (14). Figure for by this equation. The the following parameters :
C

Tf
To
flu
=

0.04

104.48
=

0.3 C
10
~

(5 744
160

196~

m~

V~

q
c~

140

p6~~

120

I
g

loo

80

T(
60 2.58

2.59

2.60

2.61

2.62

2.63

10~/T (K~~)
Fig.
3.

Same
the the

as

for fit
of

represents
outside

best

range

figure 2, but for P(o. The data show with equation (14). The temperature of the isotropic phase. occurrence

that

the
at

To

which

birefringence is positive. The solid line the birefringence changes sign is

N 2

KERR

EFFECT

IN

THE

ISOTROPIC
the P(o is representing

PHASE

OF P(o

215

It also T~
the In
~.

must

be
to

noted
the

that

the

temperature

To of
line

not

identical
variation

to

that of

of

MPHOB.

This with

applies
These

slope

of the
are
a

straight
reflection
moments

the

An/E~(T
on

Tf)
the ratio

differences
and
to

of the of
in the

influence

of the

polymer

skeleton

of

induced
order

permanent
the value

mesogenic
to

molecules.

confirm

of
The

Tf

relation

the
are

light intensity measurements. using the following law :

results

obtained

polymer, we have also given in figure 4. They

taken
were

scattered-

analyzed

1
=

Io

~~
+

T-Tc
a

(16)
~

and

the

fit to

the

experimental plot,
:

shown

as

solid

line

in

this

same

figure,

corresponds

to

the

following

parameters

lo
M T~* Constant

0.648
=

0.042 (a.

u.

)
u.

(5.30
=

0.63)
0.13

10~~ (a.

107.86
=

parasitic effects which could be due to for temperature-independent example the catalyst). This fit shows that the intensity of the light scattered by the local orientational diverges as (T- Tf)~ ~, which with the order agrees predictions. Note that, to within experimental error, the value of Tf is the same as theoretical from analysis of the An/E~-curve. that deduced lo
accounts

synthesis

residues

(for

3.5

~'~

80

z.5
-

z-o

'
l

~
.5

0.0

106
T(c)

Fig.

4.2.

DYNAMIC

INVESTIGATIONS.

These

measurements

only
short
to

concem

the

polymer,

as

the

characteristic

time

associated

with

MPHOB

is

too

be

determined

with

the

experimental set-up in use. for The recordings obtained tial, as suggested in equations

each

temperature
and

were

(lla)

(llb).

These

analysed using a single-time exponenanalyses show that, for each of the

216

JOURNAL

DE

PHYSIQUE
associated of
these

II

temperatures
similar
does
to

considered,
associated
of

the
with

characteristic the
or a

time

with
same

the

switch-on

of the
a

field

is

that

cut-off.

Analysis

recordings, using
that the
moment

Gaussian

distribution
indeed

exponentials, correspond to a
of the field
written is the the

stretched
of

single-time
order
cut

confirms exponential, (single-order exponential The values of of

r

transient
close
to

regime
zero,
to
or

stretching
determined
In Gennes order

coefficient when
to

one).

shown

below

correspond
to

those

off.

determine

critical

behavior
it is

r~~,

which
to

according
the

the
of

Landau-de
v

model

is

r~~L

Alp,

necessary of the
wfi~

know

variation

with

temperature.
We first of all

conventional

supposed the thermal liquid crystals [6]. If this

variation
were

to

be
r

arrhenian would
be

in
:

nature,

as

in the

case

of

case,
T

b
=

T-

~ Tc.

(17)

Figure 5 equation.

shows
The

that

it

is,

indeed,
with

fit is

obtained
b

the

possible to analyze the following parameters

(1.04

experimental

results

using

this

0.63)
223 K

llJ~

~~

SK

w/k~
=

5 652

T~
It

108.48
=

0.02 C

incompatible with the value of Tf is that intensity). It is birefringence or scattered-light from the static value of Tf obtained therefore measurements, to apply to the fit the necessary from figure 6. but when this is done, it is no longer possible to obtain a good fit, as can be seen Equation (17) is not therefore a satisfactory description, of the divergence of r. Williams-Landel-Ferry free-volume theory Another consists in using the possibility according to (W.L.F.) [7] which predicts that viscosity will vary as a function of temperature,
should, however,
the be

pointed
data

out

that

determined

from

static

(induced

the

law

~~
v
=

v~ exp

~~
2

~f
~)
temperature
time
r

I(18)
and
be

(T

where

Ci

and

C~

are

T~.

With

this

thermal

constants, variation

T~ the glass
of
v,

transition

v~ the

viscosity

at

the

characteristic

would

C~
r
=

Ci(T-T~)
exp

Tc~

C2
in
not

(T

T~)
the values
for the

(19)
of

The

analyses
107.8
=

carried

out

with

this
show

equation,
that it

which

Tf

(Tf
the

C,
case.

lj

3
=

C),

does of
we

account

critical

and Tg behavior
of

are

imposed
of
r,
as

in

previous
Since
none

of the

conventional
de

behaviors

gives

satisfactory
that
r

account

our

data
to
a

within

the
law.
In

framework

of

the

Gennes

model,

have

assumed

varies

according

power should

this
a

give

eventuality, straight line,

of
r

representing
and
well

as

function

of T

Tf
that

in

the

results
for

in

figure
the

7
law
:

show

this

coordinates logarithmic is, indeed, the case.

The

divergence

is

accounted

by

~
r
=

(20)

(T

Tf ) ~

KERR

EFFECT

IN

THE

ISOTROPIC

PHASE

OF

P(o

217

50

50

40

p6~~

40
.
-

p6
~

~
~

30

'o

zo
lo

lo
e

ig.

5.

ig.

6.

218

JOURNAL

DE

PHYSIQUE

II

N 2

with

p
C
=

1.49
=

0.15
x

(57.50
107.87

15.8)
0.18

10~~ S K

Tf
=

The
makes

transition
the

temperature
credible.
and

Tf
The

is

identical
value of

to

that

determined

by
to

the confirms

static the

data,
value

and

this

analysis
for

exponent
to

p(=1.5)
be

found

previously polymers.
5. In

PA60CB,

would

thus

appear

intrinsic

side-chain

liquid-crystal

Conclusions.

nematic-isotropic transition of P(o is (I), and abnormal of the value a an confirm dynamic (1.5). These results those obtained previously on another sideexponent chain polymer, PA60CB, with different physico-chemical characteristics. They suggest that the static behavior of liquid-crystal polymers is identical molecular-weight liquid to that of low crystals, but that their dynamic behavior is completely different, indicating that the classical dynamic description of low molecular-weight liquid crystals does not apply to them. We have also shown the existence of competition the dipolar induced by the between electrical moment field and the of the molecules. This competition does not exist for permanent moments
this

article,

we

have

demonstrated value

that

the

characterised

by

conventional

of the

static

exponent

PA60CB.

References

[Ii [2] [3] [4] [5] [6] [7]

Intemational Conference Liquid-Crystal Polymers, Mol. example, Proceedings of the on Cryst. Liq. Cryst. (1987) 153 and 155. REYS V., DORMOY Y., GALLANT J. L. and MARTINOTY P., Phys., Rev. Lett. 61 (1988) 2340. DE GENNES P. G., Mol. Cryst. Liq. Cryst. 12 (1971) 193. MATER W. and METER G., Z. Nattl~fiorsch. 16a (1961) 262. BISCHOmERGER T., Yu R. and SHEN Y. R., Mot Cryst. Liq. Cryst. 43 (1977) 287.

See,

for

STINSON
See for
5

T.

W.

and

LITSTER
G. C.

J. D., and

Phys.
FOX

Rev.

Lett.

25

example BERRY 1968) p. 261;

J. D.,

T. G.,

Advances

(1970) 503. in Polymer

N-Y-,

Science

(Springer-Verlag

N-Y-

FERRY

Viscoelastic

Properties

of

Polymers

(Wiley,

1980).