Formation of GaAsP interface layers monitored by reflectance anisotropy spectroscopy

Reflectance anisotropy spectroscopy (RAS) has been used to study As-by-P exchange during metalorganic vapor phase epitaxy. The study focuses on the processes occurring during switching from GaAs to GaInP, especially the effect of purging PH₃ over a GaAs surface. GaAsP/GaAs superlattices of different periodicity were grown and the P-content was determined by high-resolution x-ray diffraction and correlated to the RAS spectra. From the temperature dependence of the P-content, an activation energy of 0.56 eV was estimated for the incorporation mechanism. In addition to the insights into the processes at mixed group-V heterointerfaces, our study demonstrates the reproducibility of RAS transients that thus can be used for process monitoring.     

Electrical characterization of porous BaTiO3 using impedance spectroscopy in humid condition

The humidity response characteristics of La doped BaTiO₃ with different sintered densities and room temperature electrical conductivities were investigated using complex impedance measurement. The samples with low density and high resistivity showed the large and nearly linear sensitivity to the change of humidity. The impedance spectra of samples, when exposed to high humidity, can exhibit microstructure-related features, even though they do not give rise to a noticeable characteristic change when exposed to low humidity. The observed impedance patterns were dependent upon the density, and hence the oxidation kinetics of BaTiO₃.     

Evolution of the capillary network in a reactive powder concrete during hydration process

Ultrasonic waves in echographic mode, combined with autogenous shrinkage measurements, were used to study the evolution of the capillary network of reactive powder concrete (RPC) from the time after the mixing. Two characteristic porous classes have been identified: the first, between 10 and 20 nm, begins when the material reaches its solid hyperstatic state, and the second about 1 or 2 nm. The first class is associated with the porous space between the C-S-H hydrate clusters and the second with the internal porosity of the hydrate. The evolution of the active capillary radius as a function of the degree of hydration allows us to understand the strong interaction between the capillary network size and the chemical activity given by the dissipated calorimetric power curve. Indeed, the maximum point of the chemical activity marks the transition of the first class of pores to the second one. Finally, measurements of electrical conductivity through RPC samples show that after the maximum of the dissipated power, the curve of this electrical conductivity presents the same evolution as the capillary radius. As the electrical conductivity clearly depends on the evolution of the capillary network, the similarity between the results confirms our analysis in pore classes.     

含氟聚酰亚胺的辐射交联及其交联度的XPS表征

含氟聚酰亚胺(FPI)是一种耐高温、耐水解的新型聚酰亚胺。到目前为止,尚未见文献报道它的辐射交联。本文发现它能在高温辐射下交联,交联后的含氟聚酰亚胺的玻璃化转变温度以及高温力学性能有明显提高。本文还首次用XPS方法做了它的交联度表征。用XPS方法求得FPI的凝胶化剂量为50Mrad。     

On-line H NMR spectroscopic investigation of hydrogen bonding in supercritical and near critical CO2–methanol up to 35 MPa and 403 K

On-line NMR spectroscopy can beneficially be applied to studies of supercritical and near-critical fluids as an alternative to optical spectroscopy. Up to now high pressure NMR experiments are predominantly accomplished using custom made NMR batch reactors. The authors present a novel high pressure cell with displacement plunger for on-line NMR experiments on compressible fluids which can be used in conjunction with commercially available SCF NMR flow probes. The on-line technique offers advantages compared to stopped flow techniques such as enhanced control of mixture composition and reaction parameters as well as the facility of engagement into the reaction. The new apparatus is used for NMR studies on hydrogen bonding of methanol in near critical and supercritical carbon dioxide up to 403 K and 35 MPa for which data on the chemical shift of the hydroxyl group and methyl group are reported and interpreted.     

CARS光谱测温及仪器狭缝函数对测量的影响

设计了一种利用光参量振荡器(OPO)来代替染料激光器的宽带相干反斯托克斯喇曼散射(CARS)光谱测温实验装置。为了提高CARS测量温度的精度,测量和分析了检测系统中狭缝函数对测量结果的影响,确定了狭缝函数的具体形式。将测量结果与热电偶读数比较,发现在温度范围300K～1200K内,温度测量的不确定度小于2%。     

Dynamics of hydrated iron(II) cations in nafion polymer membranes

Mössbauer studies of Fe²⁺ in water-soaked nafion polymer membranes in the temperature range between 90 K and 250 K have been performed. Above a critical temperature (～ 180 K) the spectra exhibit both elastic narrow absorption lines and quasielastic broad lines. These spectra are typical of bounded diffusion phenomena observed by Mössbauer spectroscopy in macromolecular systems like haemoglobin, myoglobin and ferritin. Similar spectral shapes have been observed by quasielastic neutron scattering from water in nafion membranes. Within 50 K above the critical temperature the total Mössbauer absorption area decreases by an order of magnitude whereas the narrow absorption line decreases by two orders of magnitude. The results are interpreted in terms of bounded diffusive motion of the iron. Using a model based on overdamped harmonically bound Brownian motion, the essential parameters of the iron motion can be derived as a function of temperature. The iron motion most probably reflects the motion of a large Fe²⁺ complex, e.g. Fe(H₂O)²⁺₆, which is attached to the polymer side chains via the sulphonic group.     

从头算法对甲基磺酸拉曼光谱振动频率指认

对液态的甲基磺酸进行了拉曼光谱测定。采取从头算法用各种不同的基组 (最大的基组为MP2 / 6 -311+G( 2d ,2 p) )对甲基磺酸的结构和光谱进行了计算 ,得到了甲基磺酸的结构参数及稳定构象信息。采用一个具有Ci 对称的二聚体模型解释了甲基磺酸的液态光谱。对单体和二聚体的甲基磺酸进行了简正坐标计算 ,结果表明二聚体结构是液态甲基磺酸聚积态分子的合理模型。