Pseudo-Casimir force in confined nematic polymers

We investigate the pseudo-Casimir force in a slab of material composed of nematically ordered long polymers. We write the total mesoscopic energy together with the constraint connecting the local density and director fluctuations and evaluate the corresponding fluctuation free energy by standard methods. It leads to a pseudo-Casimir force of a different type than in the case of standard, short molecule nematic. We investigate its separation dependence and its magnitude and explicitly derive the relevant limiting cases.Comment: 7 pages, 2 figure

Untwisting of a cholesteric elastomer by a mechanical field

A mechanical strain field applied to a monodomain cholesteric elastomer will unwind the helical director distribution. There is an analogy with the classical problem of an electric field applied to a cholesteric liquid crystal, but with important differences. Frank elasticity is of minor importance unless the gel is very weak. The interplay is between director anchoring to the rubber elastic matrix and the external mechanical field. Stretching perpendicular to the helix axis induces the uniform unwound state via the elimination of sharp, pinned twist walls above a critical strain. Unwinding through conical director states occurs when the elastomer is stretched along the helical axis.Comment: 4 pages, RevTeX 3 style, 3 EPS figure

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

Chirality transfer and stereo-selectivity of imprinted cholesteric networks

Imprinting of cholesteric textures in a polymer network is a method of preserving a macroscopically chiral phase in a system with no molecular chirality. By modifying the elastics properties of the network, the resulting stored helical twist can be manipulated within a wide range since the imprinting efficiency depends on the balance between the elastics constants and twisting power at network formation. One spectacular property of phase chirality imprinting is the created ability of the network to adsorb preferentially one stereo-component from a racemic mixture. In this paper we explore this property of chirality transfer from a macroscopic to the molecular scale. In particular, we focus on the competition between the phase chirality and the local nematic order. We demonstrate that it is possible to control the subsequent release of chiral solvent component from the imprinting network and the reversibility of the stereo-selective swelling by racemic solvents

Adsorption of Multi-block and Random Copolymer on a Solid Surface: Critical Behavior and Phase Diagram

The adsorption of a single multi-block $AB$-copolymer on a solid planar substrate is investigated by means of computer simulations and scaling analysis. It is shown that the problem can be mapped onto an effective homopolymer adsorption problem. In particular we discuss how the critical adsorption energy and the fraction of adsorbed monomers depend on the block length $M$ of sticking monomers $A$, and on the total length $N$ of the polymer chains. Also the adsorption of the random copolymers is considered and found to be well described within the framework of the annealed approximation. For a better test of our theoretical prediction, two different Monte Carlo (MC) simulation methods were employed: a) off-lattice dynamic bead-spring model, based on the standard Metropolis algorithm (MA), and b) coarse-grained lattice model using the Pruned-enriched Rosenbluth method (PERM) which enables tests for very long chains. The findings of both methods are fully consistent and in good agreement with theoretical predictions.Comment: 27 pages, 12 figure

Imprinted Networks as Chiral Pumps

We investigate the interaction between a chirally imprinted network and a solvent of chiral molecules. We find, a liquid crystalline polymer network is preferentially swollen by one component of a racemic solvent. This ability to separate is linked to the chiral order parameter of the network, and can be reversibly controlled via temperature or a mechanical deformation. It is maximal near the point at which the network loses its imprinted structure. One possible practical application of this effect would be a mechanical device for sorting mixed chiral molecules.Comment: 4 pages, 5 figure

Universal properties of knotted polymer rings

By performing Monte Carlo sampling of $N$-steps self-avoiding polygons embedded on different Bravais lattices we explore the robustness of universality in the entropic, metric and geometrical properties of knotted polymer rings. In particular, by simulating polygons with $N$ up to $10^5$ we furnish a sharp estimate of the asymptotic values of the knot probability ratios and show their independence on the lattice type. This universal feature was previously suggested although with different estimates of the asymptotic values. In addition we show that the scaling behavior of the mean squared radius of gyration of polygons depends on their knot type only through its correction to scaling. Finally, as a measure of the geometrical self-entanglement of the SAPs we consider the standard deviation of the writhe distribution and estimate its power-law behavior in the large $N$ limit. The estimates of the power exponent do depend neither on the lattice nor on the knot type, strongly supporting an extension of the universality property to some features of the geometrical entanglement.Comment: submitted to Phys.Rev.

Nematic liquid crystal dynamics under applied electric fields

In this paper we investigate the dynamics of liquid crystal textures in a two-dimensional nematic under applied electric fields, using numerical simulations performed using a publicly available LIquid CRystal Algorithm (LICRA) developed by the authors. We consider both positive and negative dielectric anisotropies and two different possibilities for the orientation of the electric field (parallel and perpendicular to the two-dimensional lattice). We determine the effect of an applied electric field pulse on the evolution of the characteristic length scale and other properties of the liquid crystal texture network. In particular, we show that different types of defects are produced after the electric field is switched on, depending on the orientation of the electric field and the sign of the dielectric anisotropy.Comment: 7 pages, 12 figure

Variational bounds for the shear viscosity of gelling melts

We study shear stress relaxation for a gelling melt of randomly crosslinked, interacting monomers. We derive a lower bound for the static shear viscosity $\eta$, which implies that it diverges algebraically with a critical exponent $k\ge 2\nu-\beta$. Here, $\nu$ and $\beta$ are the critical exponents of percolation theory for the correlation length and the gel fraction. In particular, the divergence is stronger than in the Rouse model, proving the relevance of excluded-volume interactions for the dynamic critical behaviour at the gel transition. Precisely at the critical point, our exact results imply a Mark-Houwink relation for the shear viscosity of isolated clusters of fixed size.Comment: 5 pages; CHANGES: typos corrected, some references added; version as publishe

Bethe approximation for self-interacting lattice trees

In this paper we develop a Bethe approximation, based on the cluster variation method, which is apt to study lattice models of branched polymers. We show that the method is extremely accurate in cases where exact results are known as, for instance, in the enumeration of spanning trees. Moreover, the expressions we obtain for the asymptotic number of spanning trees and lattice trees on a graph coincide with analogous expressions derived through different approaches. We study the phase diagram of lattice trees with nearest-neighbour attraction and branching energies. We find a collapse transition at a tricritical theta point, which separates an expanded phase from a compact phase. We compare our results for the theta transition in two and three dimensions with available numerical estimates.Comment: 10 pages, 3 figures, to be published in Europhysics Letter