Influence of Liquid Crystallinity and Mechanical Deformation on the Molecular Relaxations of an Auxetic Liquid Crystal Elastomer

Liquid Crystal Elastomers (LCEs) combine the anisotropic ordering of liquid crystals with the elastic properties of elastomers, providing unique physical properties, such as stimuli responsiveness and a recently discovered molecular auxetic response. Here, we determine how the molecular relaxation dynamics in an acrylate LCE are affected by its phase using broadband dielectric relaxation spectroscopy, calorimetry and rheology. Our LCE is an excellent model system since it exhibits a molecular auxetic response in its nematic state, and chemically identical nematic or isotropic samples can be prepared by cross-linking. We find that the glass transition temperatures (Tg) and dynamic fragilities are similar in both phases, and the T-dependence of the α relaxation shows a crossover at the same T* for both phases. However, for T>T*, the behavior becomes Arrhenius for the nematic LCE, but only more Arrhenius-like for the isotropic sample. We provide evidence that the latter behavior is related to the existence of pre-transitional nematic fluctuations in the isotropic LCE, which are locked in by polymerization. The role of applied strain on the relaxation dynamics and mechanical response of the LCE is investigated; this is particularly important since the molecular auxetic response is linked to a mechanical Fréedericksz transition that is not fully understood. We demonstrate that the complex Young’s modulus and the α relaxation time remain relatively unchanged for small deformations, whereas for strains for which the auxetic response is achieved, significant increases are observed. We suggest that the observed molecular auxetic response is coupled to the strain-induced out-of-plane rotation of the mesogen units, in turn driven by the increasing constraints on polymer configurations, as reflected in increasing elastic moduli and α relaxation times; this is consistent with our recent results showing that the auxetic response coincides with the emergence of biaxial order.

Preparation by solution mixing and characterization of condensation type poly(dimethyl siloxane)/graphene nanoplatelets composites

The impact of the incorporation of graphene nanoplatelets (GN) on the properties of hydroxyl-terminated poly(dimethylsiloxane) (PDMS) matrices was investigated. The composites were prepared by solution mixing, using tetrahydrofuran (THF) as a solvent. Brookfield viscosimetry, implemented during the vulcanization process, revealed that GN increases the viscosity of the system, compared to pristine PDMS, proportionally to its concentration. X-ray diffraction patterns suggested an efficient dispersion of GN in the polysiloxane matrix. The D and G bands ratio (ID/IG) calculation, based on RAMAN spectra of GN/PDMS specimens, revealed more defects in graphene nanoplatelets when incorporated in the PDMS matrix. By differential scanning calorimetry (DSC), a marginal increase in crystallization, glass transition and melting temperatures of PDMS in GN/PDMS composites was observed. Improvement of the thermal stability of LMW PDMS composites, especially for higher GN concentrations (3 and 5 phr), was noticed by thermogravimetric analysis (TGA). Additionally, GN enhanced the tensile strength of composites, up to 73% for the 3 phr GN/LMW PDMS composite. A significant increase in the elongation at break was recorded, whereas no effect on the modulus of elasticity was recorded. The decrease in toluene-swelling, for the LMW PDMS matrix composites, was attributed to the increase in the tortuosity path because of the efficient dispersion of GN. A decrease in oxygen permeability of 55–65% and 44–58% was measured in membranes made of PDMS composites containing 0.5 phr and 1 phr GN, respectively. Dielectric relaxation spectroscopy (DRS) measurements recorded a significant increase in the conductivity of the higher graphene content composites.

Temperature dependence of the microwave dielectric properties of $$\gamma$$-aminobutyric acid

The GABA molecule is the major inhibitory neurotransmitter in the mammalian central nervous system. Through binding to post-synaptic neurons, GABA reduces the neuronal excitability by hyperpolarization. Correct binding between the GABA molecules and its receptors relies on molecular recognition. Earlier studies suggest that recognition is determined by the geometries of the molecule and its receptor. We employed dielectric relaxation spectroscopy (DRS) to study the conformation and dielectric properties of the GABA molecule under physiologically relevant laboratory conditions. The dielectric properties of GABA investigated have given us new insights about the GABA molecule, such as how they interact with each other and with water molecules at different temperatures (22°C and 37.5°C). Higher temperature leads to lower viscosity, thus lower relaxation time. The change in the GABA relaxation time due to concentration change is more associated with the solution viscosity than with the GABA dipole moment. A resonance behavior was observed with high GABA concentrations at physiological temperature, where there might be a phase transition at a certain temperature for a given GABA concentration that leads to a sudden change of the dielectric properties.