Critical anomalies in thermal diffusivity of liquid-crystalline terephthal-bis-(4-n-butylaniline).

A temperature wave method has been applied to observe the thermal diffusivity through the isotropic (Iso)-nematic (N)-smectic Sm-A-Sm-C-Sm-B-crystals VI-VII-VIII phase transitions of terephthal-bis-(4-n-butylaniline) (TBBA). Critical anomalies have been found in the N-Sm-A and Sm-C-Sm-B phase transitions as diplike shaped, consistent with the predictions based on the dissipative couplings between the order parameter and the conserved free-energy density. Singular points with a gap have been observed at the Sm-B-crystal VI, crystals VI-VII, and crystals VII-VIII phase transitions, which show polymorphic behaviors on heating and cooling. The second-order Sm-A-Sm-C phase transition emerged as a singular temperature dependence. In all the phases thermal diffusivity decreases with increasing temperature except for Sm-C, where thermal diffusivity increases with increasing temperature. The origin of the anomaly in the thermal diffusivity in Sm-C is discussed based on the parametric analysis of dynamic critical behavior in the Sm-A-Sm-C phase transitions together with the tilt angle change obtained by use of simultaneous measurements of x-ray diffraction and differential scanning calorimetry.

De- and rehydration behavior of alpha,alpha-trehalose dihydrate under humidity-controlled atmospheres.

Effects of humidity were investigated on de- and rehydration behavior of alpha,alpha-trehalose dihydrate (T(h)) throughout simultaneous measurements of differential scanning calorimetry and X-ray diffractometry (DSC-XRD) and simultaneous thermogravimetry and differential thermal analysis (TG-DTA). When T(h) was heated from room temperature under dry nitrogen atmosphere, a metastable anhydrous crystal (T(alpha)) was formed at 105 degrees C after dehydration of T(h). The resulting T(alpha) melted at 125 degrees C and became amorphous, followed by cold crystallization from 150 degrees C giving rise to a stable anhydrous crystal T(beta). Under a highly humid atmosphere, on the other hand, T(beta) was formed at 90 degrees C directly as a result of T(h) dehydration. T(alpha) was readily rehydrated and turned back to T(h) when nitrogen gas with low water vapor pressure of 2.1kPa was admitted, whereas high water vapor pressure up to 7.4kPa was required for rehydration of T(beta) into T(h). This study provided a picture of pathways that link various solid forms of trehalose, taking into account the effects of a humid environment.

Simultaneous XRD-DSC measurements of water-2-propanol at sub-zero temperatures.

A simultaneous low-temperature X-ray powder-diffractometric (XRD)-DSC technique was applied to the solid state and melting process of frozen aqueous solutions of 2-propanol. 1H NMR spectra were also obtained at low temperatures. The chemical shifts of the CH3 proton and the CH proton can be classified into four temperature regions: higher than -20 degrees C, around -20 degrees C, -50 to -20 degrees C, and lower than -50 degrees C. In the XRD data, five small diffraction peaks for 2 theta at 21.0 degrees, 25.2 degrees, 27.8 degrees, 31.1 degrees and 32.1 degrees can be attributed to the peritectic, while five diffraction peaks at 22.5 degrees, 24 degrees, 25.6 degrees, 33.4 degrees and 39.8 degrees can be attributed to ice; these peaks are due to the hexagonal form of ice, which disappears upon melting. However, the diffraction peak at 33.4 degrees showed a different pattern than the other peaks due to hexagonal ice. These results indicate that the temperature dependence of the diffraction peak at 33.4 degrees for 2 theta is related to the formation of hydrogen bonds between 2-propanol and water. The simultaneous XRD-DSC technique was effective for investigating this water-alcohol mixture at low temperatures.