钙钛矿型CaSiO_3解压缩和重压缩过程的分子动力学模拟

用分子动力学模拟方法 (MD)研究了 3 0 0K时钙钛矿型CaSiO3 ,从高压到负压的解压缩过程 .MD模拟获得的P V关系与实验数据相近 ,与已报道的MD模拟数据基本一致 ,所得体积模量也在实验数据分布范围内 .减压缩和重压缩的MD模拟数据与实验结果相似 .钙钛矿型CaSiO3 解压缩成非晶态时 ,存在两个结构破坏阶段 :破坏硅氧八面体和破坏钙氧二十面体 .当钙氧二十面体被破坏后 ,重压缩不能得到钙钛矿型结构 .只要钙氧二十面体未被破坏 ,重压缩可恢复钙钛矿型结构 .本研究得到的结果尚未见相关报道 .由MD模拟数据计算了CaSiO3 系统的红外光谱 ,分析这些数据可知钙钛矿型CaSiO3 解压缩非晶化是一个二阶软模相变 .研究表明钙钛矿型CaSiO3 结构存在一个等容的亚稳极限 ,其解压缩非晶化是一个受动力学控制的亚稳状态 .     

FOURIER TRANSFORM FAR INFRARED SPECTRA AND NORMAL COORDINATE ANALYSIS OF FIFTEEN RARE-EARTH OXALATE HYDRATES

The Fourier transform far infrared spectra of oxalate hydrates of whole rare-earth series except Pm and Sc are investigated in the range of 100-400 cm~(-1). The assignment of vibrational frequencies is made on the basis of normal coordinate analysis using our NORVIB program. The model used for the hghter elements of the lanthanide series (La to Eu) is based on the crystal structure of Nd_2(C_2O_4)_3. 10H_2O, in which each lanthanide ion is surrounded by nine O atoms, six from three oxalate ions and three from Water molecules.The model adopted for the heavier elements of the lanthanide series (Gd to Lu) and Ytterbium is based on the crystal structure of Yb_2(C_2O_4)_3· 6H_2O, in which each ion is surrounded by eight atoms, six from three oxalate ions and two from water molecules. The variation of the metal-ligand frequencies and force constants with the atomic numbers of lanthanides is plotted and discussed.     

Identification of a chemical indicator of the rupture of 1,4-β-glycosidic bonds of cellulose in an oil-impregnated insulating paper system

In this study, headspace gas chromatography/mass spectrometry has been used to assess the volatile by-products generated by the ageing of oil-impregnated paper insulation of power transformers. Sealed-glass ampoules were used to age under oxidative conditions 0.5-g specimens of insulating paper in 9 mL of inhibited mineral oil in a temperature range of 60–120 °C and moisture of 0.5, 1 and 2% (w/w). A linear relationship between one of the oil-soluble degradation by-products, i.e. methanol, and the number of ruptured 1,4-β-glycosidic bonds of cellulose, regardless of the type of paper (ordinary Kraft or thermally-upgraded (TU) Kraft paper), was established for the first time in this field. Ageing at 130 °C of model compounds of the Kraft paper constituents (α-cellulose, hemicellulose and lignin) and two cellulosic breakdown by-products (D-(+)-glucose and 1,6-anhydro-β-d-glucopyranose) confirmed that the α-cellulose degradation was mostly responsible for the presence of this molecule in the system. Furthermore, additional 130 °C-tests with six different papers and pressboard samples under a tight control of initial moisture indicated that at least one molecule of methanol is formed for each rupture of 1,4-β-glucosidic bond of the molecular chains. Stability tests showed that the ageing indicator is stable under the oxygen and temperature conditions of open-breathing transformers. The presence of methanol was detected in 94% of oil samples collected from over than 900 in-service pieces of equipment, confirming the potential for this application. Lastly, the tests have shown that oil-oxidation by-products and TU-nitrogenous agents modify the methanol partitioning coefficients in the paper/oil/air system, which makes their study essential over a range of field conditions encountered by power transformers. Results are presented and discussed in comparison with 2-furfuraldehyde, which is the current reference in the domain.     

Photovoltaic effect and carrier transport mechanisms in Hg1-Mnxtdiodes

Hg_1-xMn_xTe semiconducting semimagnetic alloy has been examined in the context of its possible applications in infrared detectors. For analysis of detector properties the intrinsic carrier concentration has been calculated as a function of temperature and crystal composition. The starting material was In-doped Hg_1-xMn_xTe grown by the modified Bridgman method. The as-grown crystals with manganese content of 12-19% were p-type with carrier concentration and mobility of 100 cm²/ Vs at 77 K. An-type layer was formed on the surface by the annealing process in saturated Hg-vapour at 270-320° for 2 hrs. Capacitance-voltage curves have C^-3 dependence on applied voltage indicating that the junction is linearly graded. From standard electrical measurements and spectral characteristics the main detector parameters were determined and compared to those of Hg_1-xCd_xTe devices. The influence of material properties on detector parameters was analyzed. In order to estimate the carrier transport mechanisms, differential resistivities and current-voltage curves were measured over a wide range of temperaturesi.e. 25 to 300 K. From the temperature dependence of the R₀A product, it was established that at high temperatures (150-300 K) the carrier transport is dominated by a recombination-generation mechanism. In low temperature region the excess current at forward bias is probably attributed to carrier tunneling via energy states distributed randomly within the forbidden gap. At reverse bias the leakage surface or volume currents dominate in the carrier transport.     

Applications of chalcogenide glass optical fibers

Chalcogenide-glass fibers based on sulfide, selenide, telluride and their rare-earth-doped compositions are being actively pursued worldwide. Great strides have been made in reducing optical losses using improved chemical purification techniques, but further improvements are needed in both purification and fiberization technology to attain the theoretical optical losses. Despite this, chalcogenide-glass fibers are enabling numerous applications that include laser power delivery, chemical sensing, and imaging, scanning near field microscopy/spectroscopy, IR sources/lasers, amplifiers and optical switches.     

Infrared Evidence for Hoffman Reaction During Calcination of Surfactant-Templated Silica Films and Analysis of the Resulting Surface Sites

Fourier Transform Infrared transmission spectroscopy is used to characterize surfactant-templated silica films on glass. The calcination process is followed in situ and evidence for the removal of the surfactant along the Hoffman reaction is given. Once calcined, the surface of the pores of the mesoporous films is proven by deuteration experiment to be hydroxylated. Bands are attributed to isolated and hydrogen-bonded silanols. Silylation reaction with hexamethyldisilazane only occurs with isolated silanol groups.     

Occurrence and distribution of metals and porphyrins in Nigerian coal minerals

The metal contents of Nigerian coal minerals were analyzed using an atomic absorption spectrophotometer. Calcium, Na, and Fe occurred as the major elements with concentrations ranging from 9 782 μg/g for Ca to 432 μg/g for Na whereas K, Mg, Mn, Ni, Cr, Zn, Pb, and Cu, which occurred at trace levels ranged from 673.73 μg/g for Mg to 2.97 μg/g for Mn. The results of the quantitative analysis of porphyrins extracted from the coal minerals showed that Onyeama coal has the highest amount of porphyrins (ca～0.96 μg/g) while Okpara has the lowest (ca～0.30 μg/g). The porphyrins were qualitatively characterized by a combination of thin layer chromatography (TLC), infrared, and ultraviolet-visible spectrophotometers. The results of the mid infrared analysis (MIR) showed the presence of absorption bands at 3 440 cm～1～3 450 cm-1 and 1 640 cm-1～1 680 cm-1 , which are owing to the stretching vibrations of N - H and C = C of aromatics, with C- H out of plane (oop) bending vibrations at wavenumbers less than 900 cm-1, all of which are characteristic absorptions of porphyrin free base. The ultraviolet-visible data showed prominent peaks at ～400 nm(Soret band) and at wavelength ranges of 535 nm～550 nm(β-band) and 565 nm～ 600 nm (α-band) for the coal porphyrins analyzed. The geochemical significance of the metals and porphyrins in coal minerals are discussed.     

中药配方颗粒红外光谱法的快速鉴别

采用红外光谱法对中药配方颗粒及其辅料进行了鉴别研究。结果表明：不同生产厂商的配方颗粒中所添加的辅料类型及用量有较大差别；不同种的配方颗粒在辅料含量较低的情况下有较明显的指纹性，而辅料含量较高时，采用差谱技术可以提高谱图的指纹性，达到中药配方颗粒--鉴别的目的。该法简便、快速、可靠，是中药配方颗粒宏观质控的一个强有力的手段。     

GC-MS法测定焦化厂气溶胶中多环芳烃

利用气相色谱-质谱(GC-MS),电子轰击离子化(EI)法测定焦化厂气溶胶中多环芳烃的含量。超声波抽提气溶胶样品,用GC-MS的选择离子监测(SIM)方式测定EPA提出的优先监测的16种多环芳烃的含量。该法的检出限为0.167pg·m~(-3),PAHs的回收率为85.1％～110.5％,相对标准偏差为4.62％～19.4％。应用该法测定气溶胶中PAHs获得满意的结果。