Characterization of cross-linking structures in UV-cured acrylic ester resin by MALDI-MS combined with supercritical methanolysis.

The cross-linking structure of the ultra violet (UV)-cured resin prepared from dipentaerithritol hexacrylate (DPHA) was characterized by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) combined with supercritical methanolysis. The MALDI-mass spectrum of the decomposition products obtained by supercritical methanolysis contained a series of peaks of sodium-cationized methyl acrylate (MA) oligomers up to around m/z = 4000 formed through selective cleavage and methylation occurred at ester linkages in UV-cured DPHA. Furthermore, in order to observe widely distributed sequence lengths in the cross-linking junctions, the decomposed products of the cured resin were then fractionated using size exclusion chromatography followed by the MALDI-MS measurements of the individual fractions. The MALDI-mass spectra of the lower molar mass fractions mainly consisted of a series of peaks of MA oligomers around m/z values of several thousands, whereas those of higher molecular weight showed a broad peak up to m/z ca. 180000. The observed distributions of the supercritical methanolysis products suggested that the network junctions in the given UV-cured resin were composed of up to around 2000 acrylate units.     

Solution growth of CuGaS2 and CuGaSe2 using CuI solvent

The phase diagrams of the CuGaS₂-CuI and CuGaSe₂-CuI pseudobinary systems are investigated. Both systems show eutectic behavior; liquids along the liquids curves for solute concentrations of more than 15 mol% are shown to be single phase and solids in equilibrium with the liquids are demonstrated to be CuGaS₂ and CuGaSe₂ chalcopyrite compounds. On the basis of the results, bulk crystals of CuGaS₂ and CuGaSe₂ are prepared from CuI solutions using the Bridgman technique. The photoluminescence spectra of these crystals are nearly the same as those of the crystals grown by iodine transport method.     

Spatial frequency selective reconstruction using Fourier transform holograms generated in functionalized mesogenic composites

We have demonstrated spatial frequency selective reconstruction (SFSR) of two-dimensional optical images by using functionalized mesogenic composites possessing real-time holographic capability. The two-dimensional optical image was Fourier transformed by a lens and part of the spatial frequency was brought into interference with the reference beam in the Raman-Nath regime. The SFSR images were observed in the self-diffraction patterns and we calculated the expected reconstructed images which were in good agreement with the observed images.     

Phase grating generation and optical phase conjugation in photorefractive polymer/dissolved liquid crystal composites

The orientational photorefractive properties of photorefractive mesogenic composites have been investigated by means of two-beam coupling and degenerate four-wave mixing. Photorefractive mesogenic composites, consisting of low molar mass liquid crystals, polymer, and photoconductive sensitizer, constitute novel organic materials possessing high performance photoreractivity. The refractive index change was estimated on the basis of the theory of two-beam coupling and four-wave mixing, and large index modulation of over 0.01 was obtained.     

Thermally enhanced photoinduced in‐plane reorientation in photo‐cross‐linkable polymer liquid crystalline films and its application to linear polarizer

Thermally enhanced photoinduced in‐plane molecular reorientation in new photo‐cross‐linkable polymer liquid crystalline (PPLC) films comprising 4‐[ω‐(4‐methoxycinnamoyloxy)alkyloxy]biphenyl side groups is explored using linearly polarized ultraviolet (LPUV) light exposure and subsequent annealing. The influence of the alkylene spacer length between the photo‐cross‐linkable group and the biphenyl mesogenic moiety is investigated. The straight‐line characteristics of the photoreactive mesogenic side group and the 4‐methoxycinnamoyl group play important roles in the high photoreactivity and the large thermally enhanced molecular reorientation, where the in‐plane order and the birefringence of the reoriented film are 0.61 and 0.18 are obtained. Finally, cooperative molecular reorientation of dichroic dyes doped in PPLC films is also achieved to fabricate a linear polarizer. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4712–4718, 2008     

An X-ray diffraction study of anharmonic thermal vibrations in the ionic conductor,barium chloride fluoride (BaClF)

Integrated intensities of X-ray reflections from a barium chloride fluoride single crystal were measured at 24, 180, 289, 402, 467 and 610°C. The intensities were used for the determination of the anharmonic potential parameters up to the third order. Harmonic potential parameters for each ion were obtained from the temperature dependence of thermal parameters, and anharmonic potential parameters were determined by the least-squares procedures, utilizing the temperature factor formalism based on the cumulant expansion. As a result, it has been found that the Ba²⁺ and Cl^? ions show an anharmonicity, while no significant anharmonic effect was detected for the F^? ion. From the potential calculated around the Cl^? and F^? ions, it was found that both Cl^? and F^? ions diffuse more easily within the (001) plane than along the c axis.     

Acousto-induced structural change in amorphous As2S3

The acoustic flux injection method was applied to amorphous As₂S₃. The velocity and the attenuation constant for shear wave at ～ 100MHz were measured through the observation of the Brillouin scattering of the light beam from a He-Ne laser. The optical transmission around absorption edge was found to change after the injection of acoustic fluxes. It was also found that the sound velocity decreased with increasing injection time of acoustic fluxes and the amount of the change of the sound velocity reached ～ 20% after 10⁵ injections. The changes in the optical transmission and the sound velocity tended to be erased by annealing below the glass transition temperature. These phenomena are considered to be due to structural changes caused by the injection of strong acoustic fluxes.     

Studies on pyrazines. 31 Alkylation of chloropyrazine N-oxides by nickel-catalyzed cross-coupling reaction with dialkylzincs

3-Chloro-2,5-dimethylpyrazine 1-oxide underwent cross-coupling with dialkylzinc reagents forming 3-alkyl-2,5-dimethylpyrazine 1-oxides. The reaction was realized by catalytic 1,3-bis(diphenylphosphino)-propane nickel(II) chloride and the optimum results were examined.