Smectic-A and smectic-C phases and phase transitions in 8S5 liquid-crystal-aerosil gels.

High-resolution x-ray scattering studies of the nonpolar thermotropic liquid crystal 4-n-pentylphenylthiol-4'-n-octyloxybenzoate (8S5) in aerosil gel nanonetworks reveal that the aerosil-induced disorder significantly alters both the nematic to smectic-A and smectic-A to smectic-C phase transitions. The limiting 8S5 smectic-A correlation length follows a power-law dependence on the aerosil density in quantitative agreement with the limiting lengths measured previously in other smectic-A liquid crystal gels. The smectic-A to smectic-C liquid crystalline phase transition is altered fundamentally by the presence of the aerosil gel. The onset of the smectic-C phase remains relatively sharp but there is an extended coexistence region where smectic-A and smectic-C domains can exist.

High-resolution calorimetric study of the nematic to smectic-A transition in aligned liquid crystal-aerosil gels.

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.

Effect of aerosil gels on de Gennes nematic-smectic coupling.

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 x-ray study of nematic-smectic-A and smectic-A-reentrant-nematic transitions in liquid-crystal-aerosil gels.

We have studied the effects of quenched random disorder created by dispersed aerosil nanoparticle gels on the nematic to smectic- A (N- SmA ) and smectic- A to reentrant nematic ( SmA -RN) phase transitions of thermotropic liquid-crystal mixtures of hexyloxycyanobiphenyl (6OCB) and octyloxycyanobiphenyl (8OCB). These effects are probed using high-resolution synchrotron x-ray diffraction techniques. We find that the reentrant characteristics of the system are largely unchanged by the presence of the aerosil gel network. By comparing measurements of the smectic static structure amplitude for this 8OCB- 6OCB+aerosil system with those for butyloxybenzilidene-octylaniline (4O.8)+aerosil gels, we find that the short-range smectic order in the smectic- A phase is significantly weaker in the reentrant system. This result is consistent with the behavior seen in pure 8OCB-6OCB mixtures. The strength of the smectic ordering decreases progressively as the 6OCB concentration is increased. Detailed line shape analysis shows that the high- and low-temperature nematic phases (N and RN) are similar to each other.

High-resolution x-ray scattering study of the effect of quenched random disorder on the nematic-smectic-A transition.

Using high-resolution x-ray scattering, the effect of quenched random disorder (QRD) on the second-order nematic-smectic-A (N-SmA) phase transition in butyloxybenzilidene-octylaniline (4O.8) has been studied. 4O.8 is a nonpolar liquid crystal (LC) with a monomeric smectic-A phase. The QRD is created by aerosil nanoparticles which gelate to form a three-dimensional network, confining the LC. The QRD caused by the aerosil gel generates quenched random fields acting on both the nematic and smectic-A order parameters. This results in the destruction of the quasi-long-range order of the smectic-A phase. The x-ray scattering data are modeled with a structure factor composed of two terms, one thermal and one static, corresponding to the connected and disconnected susceptibilities, respectively. Unlike previous studies, the two parts of the structure factor are decoupled by allowing different thermal and static correlation lengths. Our fitting procedure involves temperature-dependent and temperature-independent (global) variables. The amplitude and the parallel correlation length for the thermal part of the line-shape show critical-like behavior both above and below the transition temperature. Detailed analysis reveals that the thermal correlation length does not truly diverge at the phase transition. This effect is discussed on the basis of a cutoff for the divergence caused by the random fields generated by the aerosil network confining the liquid crystal. The intensity of the static term in the line-shape behaves like the order parameter squared at a conventional second-order phase transition. The effective order parameter critical exponent shows an evolution with increasing aerosil gel density ranging from the Gaussian tricritical value to the 3D- XY value. The results of a pseudocritical scaling analysis are compared to an analysis of 4O.8+aerosil heat capacity data and discussed using a phenomenological correlation between the nematic range of pure liquid crystals and the aerosil mass density, rho{s}.

Critical linear thermal expansion in the smectic-A phase near the nematic-smectic phase transition.

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.

First-order isotropic-smectic-A transition in liquid-crystal-aerosil gels.

The short-range order which remains when the isotropic to smectic- A transition is perturbed by a gel of silica nanoparticles (aerosils) has been studied using high-resolution synchrotron x-ray diffraction. The gels have been created in situ in decylcyanobiphenyl, which has a strongly first-order isotropic to smectic- A transition. The effects are determined by detailed analysis of the temperature and gel density dependence of the smectic structure factor. In previous studies of the continuous nematic to smectic- A transition in a variety of thermotropic liquid crystals the aerosil gel appeared to pin, at random, the phase of the smectic density modulation. For the isotropic to smectic- A transition the same gel perturbation yields different results. The smectic correlation length decreases more slowly with increasing random-field variance in good quantitative agreement with the effect of a random pinning field at a transition from a uniform phase directly to a phase with one-dimensional translational order. We thus compare the influence of random fields on a freezing transition with and without an intervening orientationally ordered phase.

High-resolution x-ray study of the nematic-smectic-A and smectic-A-smectic-C transitions in liquid-crystal-aerosil gels.

The effects of dispersed aerosil nanoparticles on two of the phase transitions of the thermotropic liquid-crystal material 4-n-pentylphenylthiol-4(')-n-octyloxybenzoate (8;S5) have been studied using high-resolution x-ray diffraction techniques. The aerosils hydrogen bond together to form a gel which imposes a weak quenched disorder on the liquid crystal. The smectic-A fluctuations are well characterized by a two-component line shape representing thermal and random-field contributions. An elaboration on this line shape is required to describe the fluctuations in the smectic-C phase; specifically the effect of the tilt on the wave-vector dependence of the thermal fluctuations must be explicitly taken into account. Both the magnitude and the temperature dependence of the smectic-C tilt order parameter are observed to be unaffected by the disorder. This may be a consequence of the large bare smectic correlation length in the direction of modulation for this transition. These results show that the understanding developed for the nematic to smectic-A transition for octylcyanobiphenyl and octyloxycyanobiphenyl liquid crystals with quenched disorder can be extended to quite different materials and transitions.

Smectic ordering in liquid-crystal-aerosil dispersions. I. X-ray scattering.

Comprehensive x-ray scattering studies have characterized the smectic ordering of octylcyanobiphenyl (8CB) confined in the hydrogen-bonded silica gels formed by aerosil dispersions. For all densities of aerosil and all measurement temperatures, the correlations remain short range, demonstrating that the disorder imposed by the gels destroys the nematic (N) to smectic-A (SmA) transition. The smectic correlation function contains two distinct contributions. The first has a form identical to that describing the critical thermal fluctuations in pure 8CB near the N-SmA transition, and this term displays a temperature dependence at high temperatures similar to that of the pure liquid crystal. The second term, which is negligible at high temperatures but dominates at low temperatures, has a shape given by the thermal term squared and describes the static fluctuations due to random fields induced by confinement in the gel. The correlation lengths appearing in the thermal and disorder terms are the same and show a strong variation with gel density at low temperatures. The temperature dependence of the amplitude of the static fluctuations further suggests that nematic susceptibility becomes suppressed with increasing quenched disorder. The results overall are well described by a mapping of the liquid-crystal-aerosil system onto a three-dimensional XY model in a random field with disorder strength varying linearly with the aerosil density.

Effect of a quenched random field on a continuous symmetry breaking transition: nematic to smectic-A transition in octyloxycyanobiphenyl-aerosil dispersions.

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.

Hydrogen-bonded silica gels dispersed in a smectic liquid crystal: a random field XY system.

The effect on the nematic to smectic-A transition in octylcyanobiphenyl (8CB) due to dispersions of hydrogen-bonded silica (aerosil) particles is characterized with high-resolution x-ray scattering. The particles form weak gels in 8CB creating a quenched disorder that replaces the transition with the growth of short-range smectic correlations. The correlations include thermal critical fluctuations that dominate at high temperatures and a second contribution that quantitatively matches the static fluctuations of a random field system and becomes important at low temperatures.