170 research outputs found
Stereo-selective swelling of imprinted cholesteric networks
Molecular chirality, and the chiral symmetry breaking of resulting
macroscopic phases, can be topologically imprinted and manipulated by
crosslinking and swelling of polymer networks. We present a new experimental
approach to stereo-specific separation of chiral isomers by using a cholesteric
elastomer in which a helical director distribution has been topological
imprinted by crosslinking. This makes the material unusual in that is has a
strong phase chirality, but no molecular chirality at all; we study the nature
and parameters controlling the twist-untwist transition. Adding a racemic
mixture to the imprinted network results in selective swelling by only the
component of ``correct'' handedness. We investigate the capacity of demixing in
a racemic environment, which depends on network parameters and the underlying
nematic order
Symmetries and Elasticity of Nematic Gels
A nematic liquid-crystal gel is a macroscopically homogeneous elastic medium
with the rotational symmetry of a nematic liquid crystal. In this paper, we
develop a general approach to the study of these gels that incorporates all
underlying symmetries. After reviewing traditional elasticity and clarifying
the role of broken rotational symmetries in both the reference space of points
in the undistorted medium and the target space into which these points are
mapped, we explore the unusual properties of nematic gels from a number of
perspectives. We show how symmetries of nematic gels formed via spontaneous
symmetry breaking from an isotropic gel enforce soft elastic response
characterized by the vanishing of a shear modulus and the vanishing of stress
up to a critical value of strain along certain directions. We also study the
phase transition from isotropic to nematic gels. In addition to being fully
consistent with approaches to nematic gels based on rubber elasticity, our
description has the important advantages of being independent of a microscopic
model, of emphasizing and clarifying the role of broken symmetries in
determining elastic response, and of permitting easy incorporation of spatial
variations, thermal fluctuations, and gel heterogeneity, thereby allowing a
full statistical-mechanical treatment of these novel materials.Comment: 21 pages, 4 eps figure
Electro-Mechanical Fredericks Effects in Nematic Gels
The solid nematic equivalent of the Fredericks transition is found to depend
on a critical field rather than a critical voltage as in the classical case.
This arises because director anchoring is principally to the solid rubbery
matrix of the nematic gel rather than to the sample surfaces. Moreover, above
the threshold field, we find a competition between quartic (soft) and
conventional harmonic elasticity which dictates the director response. By
including a small degree of initial director misorientation, the calculated
field variation of optical anisotropy agrees well with the conoscopy
measurements of Chang et al (Phys.Rev.E56, 595, 1997) of the electro-optical
response of nematic gels.Comment: Latex (revtex style), 5 EPS figures, submitted to PRE, corrections to
discussion of fig.3, cosmetic change
Oscillatory Shear Flow-Induced Alignment of Lamellar Melts of Hydrogen-Bonded Comb Copolymer Supramolecules
In this work we present the orientational behavior of comb copolymer-like supramolecules P4VP(PDP)1.0, obtained by hydrogen bonding between poly(4-vinylpyridine) and pentadecylphenol, during large-amplitude oscillatory shear flow experiments over a broad range of frequencies (0.001-10 Hz). The alignment diagram, presenting the macroscopic alignment in T/TODT vs ω/ωc, contains three regions of parallel alignment separated by a region of perpendicular alignment. For our material, the order-disorder temperature TODT = 67 °C and ωc, the frequency above which the distortion of the chain conformation dominates the materials’ viscoelasticity, is around 0.1 Hz at 61 °C. For the first time flipping from a pure transverse alignment via biaxial transverse/perpendicular alignment to a perpendicular alignment as a function of the strain amplitude was found.
Coincident molecular auxeticity and negative order parameter in a liquid crystal elastomer
Auxetic materials have negative Poisson's ratios and so expand rather than contract in one or several direction(s) perpendicular to applied extensions. The auxetics community has long sought synthetic molecular auxetics - non-porous, inherently auxetic materials which are simple to fabricate and avoid porosity-related weakening. Here, we report, synthetic molecular auxeticity for a non-porous liquid crystal elastomer. For strains above ~0.8 applied perpendicular to the liquid crystal director, the liquid crystal elastomer becomes auxetic with the maximum negative Poisson's ratio measured to date being -0.74 ± 0.03 - larger than most values seen in naturally occurring molecular auxetics. The emergence of auxeticity coincides with the liquid crystal elastomer backbone adopting a negative order parameter, QB = -0.41 ± 0.01 - further implying negative liquid crystal ordering. The reported behaviours consistently agree with theoretical predictions from Warner and Terentjev liquid crystal elastomer theory. Our results open the door for the design of synthetic molecular auxetics
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