Long-Time Relaxation of Stress-Induced Birefringence of Microcrystalline Alkali Halide Crystals.

Alkali halide single crystals are most commonly used as the diluent matrix in the tablet method or disk technique for spectroscopic measurements. However, stress-induced birefringence (SIB) of alkali halides as well as intrinsic birefringence manifest during the disk formation process. Thus, the true chiroptical measurement is disturbed by optical anisotropies (OA) containing SIB and intrinsic birefringence, except in the case of optical homogeneity. SIB is generally larger than intrinsic birefringence and has a value of several thousand millidegrees in the ultraviolet-visible wavelength range, although this varies with disk type. Here, to investigate the SIB origin, alkali halide crystals were examined using polarized light, X-ray diffraction, Fourier-transform infrared, and electron backscattering diffraction spectroscopic measurements. It was found that, after stress release, the SIB exhibited nonlinear long-time relaxation, which roughly converged within several hours, with the only time-invariant intrinsic birefringence remaining being due to OA. This behavior was strongly related to an increase in the quasi-amorphous domain and the generation of an air gap between the crystallite boundaries and their pellets. Further, a straightforward correlation was found between amorphization and an increase in the disk water content caused by deliquescence. Thus, the OA of alkali halide single crystals was found to have two different origins yielding intrinsic birefringence and SIB.

Structure and photoactivity of titania derived from nanotubes and nanofibers.

Photoactivity under UV irradiation for the decomposition of methylene blue in water and for the oxidation of NO gas was studied on titania powders derived from titanate nanotube (TNT) and nanofiber (TNF) by annealing at high temperatures, comparing with granular titania (ST-01). Rate constant for methylene blue decomposition k(MB) increased with increasing annealing temperature above 300 degrees C after the conversion from titanate to tinania. It tended to decrease above 700 degrees C, mainly due to the phase transformation from anatase to rutile. The dependences of k(MB) on full width at half maximum intensity (FWHM) were common for three samples, a sharp maximum at around 0.4 degrees in FWHM, but TNF-derived sample gave much higher maximum than ST-01. Change in fraction of oxidized NO with annealing temperature showed a plateau at around 50% and then decreased abruptly by high temperature annealing. Starting from TNT and TNF has an advantage to form fine particles by annealing above 300 degrees C, giving high photoactivity due to high crystallinity and high adsorptivity particularly for methylene blue.