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It has been widely recognized that the combination of carbon nanotube (CNT) and liquid crystals (LCs) not only provides a useful way to align CNTs, but also dramatically enhances the order in the LC phases, which is especially useful in liquid crystal display (LCD) technology. As the measure of this phase behavior, the complex specific heat is presented over a wide temperature range for a negative dielectric anisotropy alkoxyphenylbenzoate liquid crystal (9OO4) and CNT composites as a function of CNT concentration. The calorimetric scans were performed under near-equilibrium conditions between 25 and 95°C, first cooling and then followed by heating for CNT weight percent ranging from ɸw = 0 to 0.2. All 9OO4/CNT mesophases have transition temperatures ~1 K higher and a crystallization temperature 4 K higher than that of the pure 9OO4. The crystal phase superheats until a strongly first-order specific heat feature is observed, 0.5 K higher than in the pure 9OO4. The transition enthalpy for the nanocomposite mesophases is 10% lower than that observed in the pure 9OO4. The strongly first-order crystallization and melting transition enthalpies are essentially constant over this range of ɸw. Complementary electroclinic measurement on a 0.05 wt. % sample, cooling towards the smectic-C phase from the smectic-A, indicates that the SmA-SmC transition remains mean-field-like in the presence of the CNTs. Given the homogeneous and random distribution of CNTs in these nanocomposites, we interpret these results as arising from the LC-CNT surface interaction pinning the orientational order uniformly along the CNT, without pinning the position of the 9OO4 molecule, leading to a net ordering effect for all phases. These effects of incorporating CNTs into LCs are likely due to "anisotropic orientational" coupling between CNT and LC, the change in the elastic properties of composites and thermal anisotropic properties of the CNTs. [ABSTRACT FROM AUTHOR]

High-resolution calorimetry has been performed to study the effect of dilution by a nonmesogenic, low-molecular weight solvent (linear n-hexane) on the isotropic-nematic (I-N) phase transition in the liquid crystal (LC) octylcyanobiphenyl (8CB) as a function of n-hexane concentration. Numerous temperature scans were performed without continuous mixing for pure 8CB and all mixture samples of n-hexane mole fraction ranging from xhex=0.02 to 0.12. The I-N specific heat peak remains first-order for all samples and shifts toward lower temperature nonlinearly while the two-phase I+N coexistence width broadens linearly with increasing xhex. Multiple heating and cooling scans are reproducible and indicate phase separation, if it occurs, must be on very short length scales and is reversible. These results may be a consequence of a competition between random dilution effects and the tendency to phase separate. It is shown that solvent dilution of a LC, if miscible and depending on solvent structure, can lead to a controlled altering of the intermolecular potentials and softening of the LC viscoelastic properties. [ABSTRACT FROM AUTHOR]

The microscopic properties of the inner surface of the cavities of Anopore and Nuclepore membranes are investigated with scanning electron microscopy (SEM), nitrogen adsorption isotherms, and deuterium nuclear magnetic resonance (2H-NMR). Useful information about the cavity orientation and morphology, and internal surface area is obtained. Analysis of SEM photographs yields estimates of the surface area and the porosity of these membranes which complements the adsorption results. The orientation of liquid crystals permeated in the cavities of Anopore and Nuclepore membranes is probed with the 2H-NMR technique. It is found that the orientation of the liquid crystal molecules is governed by the confining volume and surface conditions. The 2H-NMR spectral line shape of the confined liquid crystal also provides information on the substrate morphology and roughness that is consistent with SEM and adsorption experiments. [ABSTRACT FROM AUTHOR]

There is a well-known de Gennes coupling between the scalar nematic order parameter S and the smectic density-wave amplitude /Psi/, which causes the nematic-smectic-A phase transition to cross over from second order to first order via a tricritical point. This sort of crossover is observed for numerous liquid crystals (LCs) with small to moderate nematic ranges. Recent studies of LC+aerosil systems, where the aerosil particles form a soft thixotropic gel, have shown that such aerosil gels can greatly reduce or completely suppress this coupling. The underlying LC critical exponents once de Gennes coupling is absent are discussed and compared with theory.

High-resolution ac calorimetry has been used to study the nematic to smectic- A (N-SmA) phase transition in the liquid crystal octylcyanobiphenyl (8CB) confined in aligned colloidal aerosil gels. A stable and robust nematic alignment was achieved by repeated thermal cycling of the samples in the presence of a strong uniform magnetic field. In some ways (such as transition temperature and integrated enthalpy), the dependence of the specific heat peak associated with the N-SmA transition on the aerosil density for aligned gels is consistent with that observed in unaligned (random) gel samples. However, a power-law analysis reveals that the behavior of the critical exponent alpha is quite different. For random gels, alpha varies gradually with aerosil density, whereas we find that alpha for aligned gels shifts abruptly to an XY -like value for the lowest aerosil density studied and remains essentially constant as the sil density increases. This aerosil density independence of alpha is consistent with the critical behavior of the smectic correlation lengths obtained from an x-ray scattering study of 8CB in aligned aerosil gels. The combined calorimetric and x-ray results indicate that the role of quenched randomness in aligned gels of 8CB+sils differs significantly from that in random gels.

Recent high-resolution x-ray investigations of the smectic- A (SmA) phase near the nematic-to-SmA transition provide information about the critical behavior of the linear thermal expansion coefficient alpha// parallel to the director. Combining such data with available volume thermal expansion alpha(V) data yields the in-plane linear expansion coefficient alpha(perpendicular) . The critical behaviors of alpha// and alpha(perpendicular) are the same as those for alpha(V) and the heat capacity Cp. However, for any given liquid crystal, alpha//(crit) and alpha(perpendicular)(crit) differ in sign. Furthermore, the quantity alpha// (crit) is positive for SmAd partial bilayer smectics, while it is negative for nonpolar SmAm monomeric smectics. This feature is discussed in terms of the molecular structural aspects of these smectic phases.

High-resolution x-ray diffraction and ac-calorimetric experiments have been carried out on the liquid-crystal octyloxycyanobiphenyl in which aerosil particles are dispersed. The measurements were made over a temperature range around the bulk nematic to smectic-A transition temperature. At this transition the liquid crystal breaks translational symmetry in a single direction. The silica particles, which hydrogen bond together to form a very low density gel, provide the quenched disorder. The random gel leads to observable broadening of the x-ray reflection from the smectic layers. The structure factor is well described by modeling the effect of the aerosils as a quenched random field. Dispersed aerosils are thought to pin both the direction of the translational ordering and the position of the layers. The latter appears to have the greatest effect on the x-ray line shape. We show that the aerosil surface area, as verified by small-angle scattering, equates to the variance of the random field. Calorimetric results reveal substantial change in the specific heat peak associated with the nematic to smectic-A transition. As the concentration of aerosil increases, the specific heat peak remains sharp yet decreases in magnitude and shifts in temperature in a nonmonotonic fashion. In this regime, the critical exponent alpha becomes progressively smaller. For the samples with the largest concentrations of aerosil particles the C(p)(N-A) peak becomes highly smeared and shifts smoothly to lower temperatures.

Deuteron NMR (DNMR) measurements were performed with high-temperature and spectral resolution on the octylcyanobiphenyl (8CB) liquid crystal confined to the randomly interconnected pores of silica aerogel as a function of temperature and silica density. The aerogel density was varied by one order of magnitude and the temperature spanned the isotropic (I), nematic (N), and smectic-A (SmA) phases of 8CB. For all samples, the liquid crystal was confined to pores smaller than the micron-sized magnetic coherence length. Thus the observed line shapes reflect the director pattern, n(r-->), and the orientational order, Q, as dictated by the porous host. The DNMR spectral patterns are consistent with powder line shapes representative of a randomized n(r-->) characterized by a single Q. The nematic domains formed are of finite dimension that likely exceeds the confining size. The weakly first-order nematic-to-isotropic phase transition becomes less discontinuous with decreasing pore size, eventually becoming continuous at an aerogel density between 0.36 and 0.5 g/cm(3). In the most severe confinement, no phase transitions are observed with only a continuous evolution of Q present. The orientational order is suppressed from the bulk's with no enhancement upon the onset of the SmA phase. This indicates a decoupling of nematic and smectic order parameters and a severe suppression of the SmA phase by this porous media.