Tunability of the elastocaloric response in main-chain liquid crystalline elastomers

Materials exhibiting a large caloric effect could lead to the development of a new generation of heat-management technologies that will have better energy efficiency and be potentially more environmentally friendly. The focus of caloric materials investigations has shifted recently from solid-state materials towards soft materials, such as liquid crystals and liquid crystalline elastomers. It has been shown recently that a large electrocaloric effect exceeding 6 K can be observed in smectic liquid crystals. Here, we report on a significant elastocaloric response observed by direct elastocaloric measurements in main-chain liquid crystal elastomers. It is demonstrated that the character of the nematic to paranematic/isotropic transition can be tuned from the supercritical regime towards the first-order regime, by decreasing the density of crosslinkers. In the latter case, the latent heat additionally enhances the elastocaloric response. Our results indicate that a significant elastocaloric response is present in main-chain liquid crystalline elastomers, driven by stress fields much smaller than in solid elastocaloric materials. Therefore, elastocaloric soft materials can potentially play a significant role as active cooling/heating elements in the development of new heat-management devices

Deuteron NMR resolved mesogen vs. crosslinker molecular order and reorientational exchange in liquid single crystal elastomers

Differences in the temperature behaviour of orientational ordering of structurally equivalent side-chain liquid single crystal elastomers (LSCEs) with 2H-labelled crosslinker and mesogen have been studied by deuteron quadrupole-perturbed NMR. The impact of nematic director reorientations on the deuteron NMR spectral shapes was analyzed in terms of a discrete reorientational exchange model. This provided for the determination of the degree of nematic director alignment and for the quantification of the influence of the reorientational exchange on the 2H NMR spectra in terms of two parameters, the nematic director orientational dispersion parameter σθ and the motional effectiveness parameter α. A comparative analysis of model simulations and experimental spectra reveals that mesogenic molecules in LSCEs exhibit faster reorientational dynamics as compared to crosslinker molecules and that mesogens and crosslinkers exhibit a similar and rather substantial static director orientational disorder

Effect of co-monomers' relative concentration on self-assembling behaviour of side-chain liquid crystalline elastomers

This work deals with the design and characterization of a new series of liquid crystalline elastomers in the form of monodomain films, showing self-assembling behaviour, namely the nematic and the orthogonal smectic A phases. The procedure for the design and preparation of monodomain and polydomain polysiloxane-based side-chain liquid crystalline elastomers containing different concentrations of two mesogenic monomers and a constant density (about 15 mol%) of the crosslinker is reported. The phase diagram and mesomorphic behaviour of the new resulting liquid crystalline elastomers were determined by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and especially X-ray diffraction studies, which helped to clearly identify the smectic A phase. Among new liquid crystalline elastomer films, a specific concentration of co-mesogens gives an unconventional and fascinating system with a direct transition from the isotropic to smectic A phase. Results of the thermo-mechanic studies confirmed the shape-memory properties of these films, which have elastic properties optimal for applications as thermo-mechanic actuators