Deuterium NMR study of mobility and fluctuations in nematic and isotropic elastomers.

Orientational ordering in polydomain nematic and isotropic elastomers with identical polysiloxane backbone and different deuterium-labeled side groups is studied by D-NMR. In the nematic elastomer the orientational order parameter grows in a critical fashion on crossing the I-N transition implying a continuous phase transition driven by critical fluctuations of local director. The orientational (nematic) ordering occurs on the background of the polymer dynamics exhibited by the backbone, which is similar in the nematic and the analogous isotropic elastomers. The temperature dependence of NMR linewidths is compatible with a Vogel-Fulcher glassy dynamics.

Chirality transfer and stereoselectivity 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 elastic 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 elastic 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 a 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 a chiral solvent component from the imprinting network and the reversibility of the stereo-selective swelling by racemic solvents.

Photonic gaps in cholesteric elastomers under deformation.

Cholesteric liquid crystal elastomers have interesting and potentially very useful photonic properties. In an ideal monodomain configuration of these materials, one finds a Bragg reflection of light in a narrow wavelength range and a particular circular polarization. This is due to the periodic structure of the material along one dimension. In many practical cases, the cholesteric rubber possesses a sufficient degree of quenched disorder, which makes the selective reflection broadband. We investigate experimentally the problem of how the transmittance of light is affected by mechanical deformation of the elastomer, and the relation to changes in liquid crystalline structure. We explore a series of samples which have been synthesized with photonic stop gaps across the visible range. This allows us to compare results with detailed theoretical predictions regarding the evolution of stop gaps in cholesteric elastomers.

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 cross-linking 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 topologically imprinted by cross-linking. 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.

Phase chirality and stereo-selective swelling of cholesteric elastomers.

Cholesteric elastomers possess a macroscopic "phase chirality" as the director n rotates in a helical fashion along an optical axis z and can be described by a chiral order parameter alpha. This parameter can be tuned by changing the helix pitch p and the elastic properties of the network at formation. The cholesterics also possess a local nematic order, changing with temperature or during solvent swelling. In this paper, by measuring the power of optical rotation d upsilon /dz , we discover how these two parameters vary as functions of temperature or solvent adsorbed by the network. The main result is a finding of pronounced stereo-selectivity of cholesteric elastomers, demonstrating itself in the retention of the "correct" chirality component of a racemic solvent. It has been possible to quantify the amount of such stereo-separation, and the basic dynamics of the effect.

Evolution of photonic structure on deformation of cholesteric elastomers.

We subject a monodomain cholesteric liquid crystal elastomer to uniaxial strain perpendicular to its helical axis and study the response of its texture to deformation. A combination of mechanical, optical, and x-ray scattering measurements confirms the prediction for the director rotation, coarsening, and then unwinding the cholesteric helix. The study of optical absorption of circularly polarized light quantifies the complex dependence of the photonic band-gap structure on strain and directly relates to the microscopic deformation of elastomer. Agreement is found with the recently proposed theoretical prediction of the photonic structure of cholesteric elastomers.

UV manipulation of order and macroscopic shape in nematic elastomers.

A range of monodomain nematic liquid-crystal elastomers containing differing proportions of photoisomerizable mesogenic moieties, which turn from a rodlike to a kinked shape upon ultraviolet (uv) irradiation, was studied. Depending on the proportion and positional role of the photosensitive groups in the crosslinked polymer network, different types and magnitudes of response were found. The principle consequence of such photoisomerization is the destabilization of the nematic phase, whose order parameter depends on temperature in a near-critical fashion. Accordingly, the effect of uv irradiation is dramatically enhanced near the critical temperature, with the associated reduction in the nematic order parameter manifesting as a change in the macroscopic shape of the elastomer samples, producing a large uniaxial contraction. Theoretical analysis of this phenomenon gives a good quantitative agreement with experiment.

Effect of cross-linker geometry on dynamic mechanical properties of nematic elastomers.

We study three monodomain (single-crystal) nematic elastomer materials, all side-chain siloxane polymers with the same mesogenic groups but with different types of cross linking: (i) short flexible siloxane linkage affine to the network backbone, (ii) short flexible aliphatic cross links miscible with mesogenic side-chain groups, and (iii) long segments of main-chain nematic polymer. The dynamic mechanical response of these three systems shows a characteristically universal decrease of storage modulus and a corresponding increase of loss factor. This effect of "dynamic soft elasticity" is strongly anisotropic, depending on the nematic director orientation. We examine the important role of the average backbone chain anisotropy r(T)=l(parallel)/l(perpendicular), which is affected by the cross-linking geometry and contributes to the magnitude and frequency dependence of the dynamic anomaly, and discuss possible applications in mechanical damping and polarized acoustic technology.

UV isomerisation in nematic elastomers as a route to photo-mechanical transducer.

The macroscopic shape of liquid-crystalline elastomers strongly depends on the order parameter of the mesogenic groups. This order can be manipulated if photo-isomerisable groups, e.g. containing N=N bonds, are introduced into the material. We have explored the large photo-mechanical response of such an azobenzene-containing nematic elastomer at different temperatures, using force and optical birefringence measurements, and focusing on fundamental aspects of population dynamics and the related speed and repeatability of the response. The characteristic time of "on" and "off" regimes strongly depends on temperature, but is generally found to be very long. We were able to verify that the macroscopic relaxation of the elastomer is determined by the nematic order dynamics and not, for instance, by the polymer network relaxation.

Effect of crosslinker geometry on equilibrium thermal and mechanical properties of nematic elastomers.

We study three monodomain (single-crystal) nematic elastomer materials, all side-chain siloxane polymers with the same mesogenic groups but with different types of crosslinking: (i) short flexible siloxane linkage affine to the network backbone, (ii) short flexible aliphatic crosslinks miscible with mesogenic side chain groups, and (iii) long segments of main-chain nematic polymer. Equilibrium physical properties of these three systems are very different, especially the spontaneous thermal expansion and anisotropic stress-strain response along and perpendicular to the uniform nematic director. In the latter case, we examine the soft elastic plateau during the director reorientation. We compare the nematic order-parameter Q(T), provided primarily by the side mesogenic groups and relatively constant between the samples, and the average backbone chain anisotropy r(T)=l( parallel)/l( perpendicular), which is strongly affected by the crosslinking geometry. The experimental data is compared quantitatively with theoretical models of nematic elastomers.

Anomalous viscoelastic response of nematic elastomers.

We report a combined theoretical and experimental study of linear viscoelastic response in oriented monodomain nematic elastomers. The model predicts a dramatic decrease in the dynamic modulus in certain deformation geometries in an elastic medium with an independently mobile internal degree of freedom, the nematic director with its own relaxation dynamics. Dynamic mechanical measurements on monodomain nematic elastomers confirm our predictions of dependence on shear geometry and on nematic order, and also show a very substantial mechanical loss clearly associated with director relaxation.