The Miesowicz viscosities ηc and ηb of
dilute nematic solutions of the main-chain liquid
crystal polymer (LCP) TPBx, in
4‘-(pentyloxy)-4-cyanobiphenyl (5OCB) or 4‘-pentyl-4-cyanobiphenyl
(5CB)
as nematic solvents, were measured by cone-and-plate rheometry in the
presence and absence, respectively,
of an external electric field. TPBx has a mesogenic
group, 1-(4-hydroxy-4‘-biphenyl)-2-(4-hydroxyphenyl)butane, separated by flexible n-alkyl spacers of variable
length x. Since for these solutions ηc
≫ ηb, a
pronounced electrorheological effect is observed, the viscosity with
the field on being an order of magnitude
larger than that with the field off. The intrinsic viscosity,
[ηc], of TPB10 in 5OCB, was found to
follow
a Mark−Houwink−Sakurada relationship, [ηc] =
KMα, with α ≈ 1.0. Applying a theoretical
description
by Brochard, this result suggests that TPB10 behaves hydrodynamically
in 5OCB like a free-draining
random coil stretched along the director. Comparisons were made of
[ηc] and [ηb] for TPBx and
a
hyperbranched LCP, TPD-b-8, based on a similar mesogen. From the
ratio [ηc]/[ηb], via the
Brochard
model, the ratio
(R
∥/R
⊥) of the
end-to-end distances of the LCP measured parallel and perpendicular
to
the nematic director were found to be ∼2−2.5 for TPBx
and ∼1.45 for TPD-b-8, consistent with the
expectation that the chain anisotropy of the branched species in the
nematic state is smaller.
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