Photoacoustic evaluation of the thermal effusivity in the isotropic phase of certain comb-shaped polymers

The thermal effusivity values in the isotropic phase of certain comb-shaped polymers have been evaluated for the first time using an open photoacoustic cell configuration. The compounds investigated have siloxane and acrylate backbone and they carry mesogenic groups in their side chain. The results indicate that the polymer chain length as well as the side chain length have pronounced influence on the thermal effusivity values in liquid crystalline polymers

Enhancement of the Nonlinear Optical Absorption of the E7 Liquid Crystal at the Nematic-Isotropic Transition

We present an experimental study of the nonlinear optical absorption of the eutectic mixture E7 at the nematic-isotropic phase transition by the Z-scan technique, under continuous-wave excitation at 532 nm. In the nematic region, the effective nonlinear optical coefficient beta, which vanishes in the isotropic phase, is negative for the extraordinary beam and positive for an ordinary beam. The parameter , whose definition in terms of the nonlinear absorption coefficient follows the definition of the optical-order parameter in terms of the linear dichroic ratio, behaves like an order parameter with critical exponent 0.22 +/- 0.05, in good agreement with the tricritical hypothesis for the nematic-isotropic transition.

Tricritical-like behavior of the nonlinear optical refraction at the nematic-isotropic transition in the E7 thermotropic liquid crystal

We use Z-scan technique to investigate the nonlinear optical response of the thermotropic liquid crystal E7 in the neighborhood of the nematic-isotropic phase transition. The analysis of the data for the nonlinear optical birefringence is compatible with an effective critical exponent of the order parameter, beta = 0.28 +/- 0.03, which is close to the classical value, beta = 0.25, for a tricritical point. The nonlinear optical absorption in the nematic range depends on the geometrical configuration of the nematic director with respect to the polarization beam, and vanishes in the isotropic phase.

Infiltration of a photonic crystal fiber with cholesteric liquid crystal and blue phase

Photonic crystal fibers (PCF) have been selectively filled with a cholesteric liquid crystal (ChLC) with special interest in the blue phase (BP) of the liquid crystal. It has been observed thermal tuning of the guided light in the visible region. A dramatically enhance appears when the phase of the liquid crystal changes from cholesteric to blue phase I (BPI). When a thermal range of the blue phase I is achieved, no changes are observed while increasing temperature from BPI through BPII and to the isotropic phase.

Magnetic behavior of 10 nm-magnetite particles diluted in lyotropic liquid crystals

A magnetic study of 10 nm magnetite nanoparticles diluted in lyotropic liquid crystal and common liquids was carried out. In the liquid crystal the ZFC-FC curves showed a clear irreversible behavior, and it was possible to distinguish the nematic from the isotropic phase since the magnetization followed the dependence of the nematic order parameter with the temperature. This behavior could be mimicked by Monte Carlo simulation. (C) 2011 American Institute of Physics. [doi:10.1063/1.3549616]

Complex fluids at complex surfaces simply complicated

We study wetting and filling of patterned surfaces by a nematic liquid crystal. We focus on three important classes of periodic surfaces: triangular, sinusoidal and rectangular. The results highlight the similarities and differences of nematic wetting of these surfaces and wetting by simple fluids. The interplay of geometry, surface and elastic energies can lead to the suppression of either filling or wetting. The periodic rectangular surface displays re-entrant transitions, with a sequence dry-filled-wet-filled, in the relevant region of parameter space.

Microscopic Theory of Anchoring Transitions at the Surfaces of Pure Liquid-Crystals and their Mixtures .1. The Fowler Approximation

We have generalized earlier work on anchoring of nematic liquid crystals by Sullivan, and Sluckin and Poniewierski, in order to study transitions which may occur in binary mixtures of nematic liquid crystals as a function of composition. Microscopic expressions have been obtained for the anchoring energy of (i) a liquid crystal in contact with a solid aligning surface; (ii) a liquid crystal in contact with an immiscible isotropic medium; (iii) a liquid crystal mixture in contact with a solid aligning surface. For (iii), possible phase diagrams of anchoring angle versus dopant concentration have been calculated using a simple liquid crystal model. These exhibit some interesting features including re-entrant conical anchoring, for what are believed to be realistic values of the molecular parameters. A way of relaxing the most drastic approximation implicit in the above approach is also briefly discussed.

Influence of constraining and confinement in the molecular mobility of low molecular weight materials

Dissertation presented to obtain a Ph.D. Degree in Chemical Physics

Liquid crystal mobility and PDLC memory effects

Dissertation presented at Faculdade de Ciências e Tecnologia of Universidade Nova de Lisboa to obtain the Degree of Master in Chemical and Biochemical Engineering

Pressure effects revealed by small angle neutron scattering on block copolymer gels

We study the effects of hydrostatic pressure (P) on aqueous solutions and gels of the block copolymer B20E610 (E, oxyethylene; B, oxybutylene; subscripts, number of repeats), by performing simultaneous small angle neutron scattering/pressure experiments. Micellar cubic gels were studied for 9.5 and 4.5 wt% B20E610 at T = 20-80 and 35-55 degrees C, respectively, while micellar isotropic solutions where Studied for 4.5 wt% B20E610 at T > 55 degrees C. We observed that the interplanar distance d(110) (cubic unit cell parameter a = root 2d(110)) decreases while the correlation length of the Cubic order (delta) increases, upon increasing P at a fixed T for 9.5 wt% B20E610. The construction of master Curves for d(110) and delta corresponding to 9.5 wt% B20E610 proved the correlation between changes in T and P. Neither d(110) and delta nor the cubic-isotropic phase transition temperature was affected by the applied pressure for 4.5 wt% B20E610. The dramatic contrast between the pressure-induced behavior observed for 9.5 and 4.5 wt% B20E610 suggests that pressure induced effects might be more effectively transmitted through samples that present wider domains of cubic structure order (9.5 wt% compared to 4.5 wt% B20E610).

Small-angle x-ray scattering study of flow alignment of a thermotropic liquid crystal in the nematic and smectic phases

WThe capillary flow alignment of the thermotropic liquid crystal 4-n-octyl-4′-cyanobiphenyl in the nematic and smectic phases is investigated using time-resolved synchrotron small-angle x-ray scattering. Samples were cooled from the isotropic phase to erase prior orientation. Upon cooling through the nematic phase under Poiseuille flow in a circular capillary, a transition from the alignment of mesogens along the flow direction to the alignment of layers along the flow direction (mesogens perpendicular to flow) appears to occur continuously at the cooling rate applied. The transition is centered on a temperature at which the Leslie viscosity coefficient α3 changes sign. The configuration with layers aligned along the flow direction is also observed in the smectic phase. The transition in the nematic phase on cooling has previously been ascribed to an aligning-nonaligning or tumbling transition. At high flow rates there is evidence for tumbling around an average alignment of layers along the flow direction. At lower flow rates this orientation is more clearly defined. The layer alignment is ascribed to surface-induced ordering propagating into the bulk of the capillary, an observation supported by the parallel alignment of layers observed for a static sample at low temperatures in the nematic phase.

Memory effects in liquid crystal elastomers

Free-standing monodomain liquid crystal elastomer samples are shown to have a complete memory of the orientational configuration at the time of cross-linking. This memory is demonstrated through samples in which the parent polymer system is first aligned in a magnetic field prior to cross-linking. These films show reversible nematic-isotropic phase transitions and x-ray scattering patterns characteristic of nematic phases. The liquid crystal elastomer films exhibit a remarkable memory effect, in that the sample may be held at temperatures well above the nematic-isotropic transition for extended periods ( > 2 weeks), but on cooling into the liquid crystal phase region, both the original director alignment and the degree of preferred orientation are recovered. It is demonstrated that these novel memory effects are equilibrium in nature. The origins of this phenomena in terms of coupling between the mesogenic side-chains and the polymer network are discussed.

Side-chain liquid crystalline elastomers: the relationship between the orientational ordering of the polymer backbone and the length of the coupling chain

The influence of cross-linking on the phase behaviour of a series of side-chain liquid crystalline elastomers has been studied. For samples cross-linked in the temperature range corresponding to the nematic phase, the phase transition was shifted compared to that observed when an identical sample was cross-linked in the isotropic phase. This shift represented a stabilisation of the nematic phase in the former case, in line with theoretical expectations. By utilising a novel, slow cross-linking method, which allows the polymer backbone to take up an equilibrium conformation prior to network formation, it proved possible to monitor the shifts in phase transition temperature as a function of the length of the methylene chain coupling the mesogenic units to the polymer backbone. The results obtained are related to the backbone anisotropy and indicate that the level of orientational order of the polymer in the nematic phase backbone increases with a reduction in the length of the coupling chain.

Room Temperature Ionic Liquid-Lithium Salt Mixtures: Optical Kerr Effect Dynamical Measurements

The addition of lithium salts to ionic liquids causes an increase in viscosity and a decrease in ionic mobility that hinders their possible application as an alternative solvent in lithium ion batteries. Optically heterodyne-detected optical Kerr effect spectroscopy was used to study the change in dynamics, principally orientational relaxation, caused by the addition of lithium bis(trifluoromethylsulfonyl)imide to the ionic liquid 1-buty1-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Over the time scales studied (1 ps-16 ns) for the pure ionic liquid, two temperature-independent power laws were observed: the intermediate power law (1 ps to similar to 1 ns), followed by the von Schweidler power law. The von Schweidler power law is followed by the final complete exponential relaxation, which is highly sensitive to temperature. The lithium salt concentration, however, was found to affect both power laws, and a discontinuity could be found in the trend observed for the intermediate power law when the concentration (mole fraction) of lithium salt is close to chi(LiTf(2)N) = 0.2. A mode coupling theory (MCT) schematic model was also used to fit the data for both the pure ionic liquid and the different salt concentration mixtures. It was found that dynamics in both types of liquids are described very well by MCT.

Formation and characterization of soy bean oil/surfactant/water microemulsions

Pseudoternary phase diagrams, at 25 degrees C, were constructed for the systems soy bean oil (SBO)/surfactant/water, with single anionic sodium bis(2-ethylhexyl)sulfosuccinate (AOT), nonionic monoolein (MO) and mixtures of these surfactants, showing the isotropic phase of W/O microemulsions (MEs). The area of ME formation in the phase diagrams was shown to be dependent of the relative amount of surfactants, being larger for MO:AOT equals to 2:1. Rheological and dynamic light scattering (DLS) studies indicated that the viscosity of the isotropic ME phase exhibited two different behaviors depending on composition. The viscosity of dry MEs initially decreased with increasing amount of water following a dilution line in the phase diagram, i.e., a constant surfactant:SBO percentage ratio. As the water content increased the relative viscosity attained a minimum and then increased. This minimum could be related to the transition between two ME regions, L-2 and L'(2), having different characteristics. DLS measurements confirm the existence of ordinary W/O ME droplets in the L-2 region and suggest the existence of another structure in the L'(2) region. The size of the MEs droplets in L-2 phase ranges from 3.6 to 16.5 nm, depending on composition of SBO, surfactant and water. Small angle X-ray scattering (SAXS) also indicates the existence of structures with different characteristics, for the SAXS curves exhibit a typical micelle asymmetrical peak at low scattering vector q for MEs in L-2 but a symmetrical correlation peak at higher q vector in L'(2). (c) 2006 Elsevier B.V. All rights reserved.