Influence of the nematic order on the rheology and conformation of stretched comb-like liquid crystalline polymers
V. Fourmaux-Demange1 - A. Brûlet1 - F. Boué1 - P. Davidson2 - P. Keller3 - J.P. Cotton1
1 Laboratoire Léon Brillouin (CEA-CNRS), CEA Saclay, 91191
Gif/Yvette, France - Laboratoire de Physique des Solides,
Bât. 510, Université Paris XI, 91405 Orsay, France
2 Institut Curie, Section de Recherche, 75231 Paris Cedex 5,
France
brulet@llb.saclay.cea.fr
Received 5 May 1999 and Received in final form 18 October 1999
Abstract
We have studied the rheology and the conformation of stretched
comb-like liquid-crystalline polymers. Both the influence of the
comb-like structure and the specific effect of the nematic
interaction on the dynamics are investigated. For this purpose,
two isomers of a comb-like polymetacrylate polymer, of
well-defined molecular weights, were synthesized: one displays a
nematic phase over a wide range of temperature, the other one has
only an isotropic phase. Even with high degrees of polymerization
N, between 40 and 1000, the polymer chains studied were not
entangled. The stress-strain curves during the stretching and
relaxation processes show differences between the isotropic and
nematic comb-like polymers. They suggest that, in the nematic
phase, the chain dynamics is more cooperative than for a usual
linear polymer. Small-angle neutron scattering has been used in
order to determine the evolution of the chain conformation after
stretching, as a function of the duration of relaxation
t/Ir. The conformation can be described with two
parameters only:
,
the global deformation of the
polymer chain, and p, the number of statistical units of locally
relaxed sub-chains. For the comb-like polymer, the chain
deformation is pseudo-affine:
is always smaller
than 
(the deformation ratio of the whole sample). In the
isotropic phase,
has a constant value, while pincreases as
t/Ir. This latter behavior is not that expected for
non-entangled chains, in which p varies as
t/Ir1/2 (Rouse model).
In the nematic phase,
decreases as a stretched
exponential function of
t/Ir, while p remains constant.
The dynamics of the comb-like polymers is discussed in terms of
living clusters from which junctions are produced by interactions
between side chains. The nematic interaction increases the
lifetime of these junctions and, strikingly, the relaxation is the
same at all scales of the whole polymer chain.
PACS
61.30.-v Liquid crystals -
83.10.Nm Polymer dynamics -
61.12.Ex Neutron scattering techniques (including small-angle scattering) -
83.50.-v Deformation; material flow
Copyright EDP Sciences, Società Italiana di Fisica, Springer-Verlag
