TSD Current Spectroscopy of NCO Terminated Liquid

Crystalline Polyurethane

J.K. Quamara, Sohan Lal, S.K. Mahana and Pushkar Raj*

Department of physics
National institute of Technology, Kurukshetra-136119
*DRDO,Delhi
Email: jkquamara@yahoo.com

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INTRODUCTION was added followed by another stirring for 5 minutes.

The unique properties of liquid crystal polymers
i.e. pol ym ers exhi bi t i ng li qui d crys t al l i ne
s t at e have led to the increasing interest of
researchers. Though these polymers are still in the
research stage but some of them have found
significant applications in science as well as in
technology. Thermotropic liquid crystalline
polyurethanes are an important class of polymers
owing to their widespread commercial applications in
high-strength fibers, thermoplastics displays and
optical storage devices. In the present paper we are
reporting on the multiple dielectric relaxation
processes in side chain liquid crystalline
polyurethane (LCPU) based on NCO- terminated
polybutadiene and Bi-Phenol using thermally
stimulated depolarization current (TSDC) technique.
SYNTHESIS OF LIQUID
CRYSTALLINE
POLYURETHANE
In order to synthesize liquid crystal
polyurethane 5 grams of NCO terminated
Polybutadine was taken in a 100 ml conical flask, to
this 25ml of tetrahydofuron (THF) was added, in
order to dissolve the NCO terminated Polybutadine in
THF the solution was stirred continuously for 5
minutes. In the solution so obtained, 4-4 Bi-Phenol
In this solution small quantity of Di-Butyl Tin
DiLaurate (DBTDL C32H6404Sn) was added as
catalyst. This solution was stirred continuously for
two hours at room temperature in nitrogen
atmosphere then the temperature was raised to 50
degree Celsius and again stirring was continued for
two hours, the viscous fluid so obtained was poured
on a Teflon mould to obtained the film once the
solvent got evaporated. The film so obtained was
kept in desicator for a day to remove traces of
solvent.
EXPERIMENTAL
The experimental arrangement for TSDC
measurements was the conventional one as described
by the authors elsewhere. The samples were
polarized by subjecting them to the desired dc field
(Ep) at a constant temperature (Tp) for 1h. The
samples were then cooled to the room temperature
within fixed time (1/2h) in the presence of Ep. The
depolarization currents were measured with the help
of Keithley electrometer (610C) at a linear heating
0
rate of 2 C/minute. Activation energies were
calculated using Bucci- Plot method.
RESULTS AND DISCUSSION
The TSD current spectra of pristine LCPU
samples in the temperature range 300 to 2500C for
various polarization conditions have been illustrated
in Figures 1 and 2 respectively.
Polarizing Field (Ep) Effect
The TSDC characteristics for LCPU samples
polarized at different polarizing fields (Ep) ranging
from 27.0 to 82.0 kV/cm for T p: 800C are shown in
Fig.1. These TSD spectra consist of a well defined
peak around 800C denoted as β - peak. The peak
magnitude increases with Ep. In high temperature
region we observe abnormal TSDC (i.e. same current
direction as that of charging current). The
temperature at which the current reversal takes place
increases with increasing Ep.
FIGURE 1. The TSDC spectrum of pristine LCPU sample
polarized at different field: ■50kV/cm, ▲60kV/cm and
× 75kV/cm.
Polarization Temperature
(Tp) Effect
The effect of polarizing temperature (Tp) on the
TSDC spectrum of LCPU samples polarized at Ep:
55.0 kV/cm has been shown in Fig.2. The β - peak is
very broad at low Tp and becomes sharp at high Tp. A
significant enhancement in peak magnitude occurs
with a shift towards higher temperature with
increasing Tp. The abnormal TSDC is also observed
in low Tp samples. Tp.
The dielectric relaxation processes in liquid
crystalline polymers are quite complex and results
from several different competitive mechanisms
involving various physical states associated with
crystalline and amorphous phase. The liquid
crystalline polyurethane structure contains large
number of carbonyl [>C=O] groups, which provide
polar nature to this polymer. The TSDC current peak
(β - peak) appearing around 800C has been assigned
to dipole orientation polarization. This observation is
confirmed by the fact that the average activation
energy (~0.31eV) corresponding to this relaxation
does not appreciably differ from the theoretical
predicted value (~0.24eV) assigned to the dipolar
polarization. Emergence of this peak is also
consistent with the glass transition temperature of this
PLC which is around 700C. The broad nature of this
peak shows a distributed dipolar polarization
associated with β - relaxation owing to unidentical
environment around the different >C=O groups. The
LCPU has rigid liquid crystal (LC) groups (biphenyl
groups) connected together by either rigid or flexible
non - LC spacers. The type and length of the spacers
can determine whether a nematic, cholesteric or
smectic phase is formed. For these longitudinal
polymers the viscosity in the isotropic phase is higher
than in the nematic phase. At elevated temperature
and under the influence of field, reduction in the
length of the spacer results in the increase of rigidity
of molecules, thereby shifting Tg to higher
temperature, which explains the occurrence of β -
peak at higher temperature than the reported Tg value.
The peak (α - peak) appearing around 1600C
(Fig.2) has been associated to the space charge
trapping mechanism. In LCPU the charge trapping is
possible due to various mechanisms The flexible
segment but-2-ene in LCPU and the unsaturated
carbonyl groups may act to a significant extent as
traps for charge carriers contributing to their transport
and trapping. If the charges are in the form of ions,
their transport in the polymer takes place trough
hopping from one trap site to another while the
electrons or holes remain immobile in the local traps.
Further the cold crystallization of biphenyl phase
may also be held responsible for α - relaxation.
FIGURE 2. The TSDC spectrum of pristine LCPU sample
polarized at different temperature: ▲800C, × 1500C,
♦1800C
Acknowledgments
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