Automated procedure to determine the thermodynamic stability of a material and the range of chemical potentials necessary for its formation relative to competing phases and compounds

We present a simple and fast algorithm to test the thermodynamic stability and determine the necessary chemical environment for the production of a multiternary material, relative to competing phases and compounds formed from the constituent elements. If the material is found to be stable, the region of stability, in terms of the constituent elemental chemical potentials, is determined from the intersection points of hypersurfaces in an (n−1)$(n-1)$-dimensional chemical potential space, where n$n$ is the number of atomic species in the material. The input required is the free energy of formation of the material itself, and that of all competing phases. Output consists of the result of the test of stability, the intersection points in the chemical potential space and the competing phase to which they relate, and, for two- and three-dimensional spaces, a file which may be used for visualization of the stability region. We specify the use of the program by applying it both to a ternary system and to a quaternary system. The algorithm automates essential analysis of the thermodynamic stability of a material. This analysis consists of a process which is lengthy for ternary materials, and becomes much more complicated when studying materials of four or more constituent elements, which have become of increased interest in recent years for technological applications such as energy harvesting and optoelectronics. The algorithm will therefore be of great benefit to the theoretical and computational study of such materials.     

Homogeneous Catalysis for the Production of Fine Chemicals. Palladium- and Nickel-Catalysed Aromatic Carbon–Carbon Bond Formation

In this article we describe our recent efforts in the area of palladium- and nickel-catalysed aromatic substitution reactions. Main focus is on low cost and low waste production methods. The use of aromatic carboxylic anhydrides in the Heck reaction leads to a waste-free protocol. In addition these reactions are easy to work up as no ligands or bases are used. For Heck reactions where substrates or products do not tolerate high temperatures we found that use of a bulky phosphoramidite (13b) as ligand for palladium leads to a very fast reaction at low temperatures. Recycle of palladium in ligand-free Heck and Suzuki reactions is easily accomplished by treating the palladium black that precipitates at the end of the reaction on a carrier material with a small excess of I₂ prior to its re-use in the next run. Use of aryl chlorides in the palladium- and nickel-catalysed formation of biaryls can be accomplished by using the nickel-catalysed coupling with arylzinc chlorides. Better still, it was possible to make use of the arylgrignard and use a catalytic amount of ZnCl₂. Whereas the strength of these aromatic substitution reactions lies in their broad tolerance of functional groups, one exception was the Sonogashira reaction on 3-bromoaniline. The problem was solved by making use of in situ catalytic protection of the NH₂ group with benzaldehyde.     

云母钛珠光颜料的形成机理研究

阐述了云母钛的形成机理，即云母依靠静电引力吸附[Ti(H2O)6]^4 形成双电层，双电层上的[Ti(H2O)6]^4 发生水解引起多核络合物生长为水合二氧化钛，水解的水合二氧化钛与云母产生异质颗粒间的互凝而形成云母钛。     

Hygrothermal aging of rubber‐modified and mineral‐filled dicyandiamide‐cured DGEBA epoxy resin. III. Dielectric spectroscopy investigation

The effects of moisture absorption on the dielectric properties of a rubber‐modified, mineral‐filled, epoxy resin based on the diglycidyl ether of bisphenol A cured with dicyandiamide are reported. Samples of the resin were aged by immersing in deionized water, or 5% w/w NaCl solution, at elevated temperatures. Dielectric measurements were carried out over the frequency range 10^?1 to 6 × 10⁵ Hz. A featureless dielectric spectrum was observed with both real and imaginary dielectric permittivity increasing with the amount of absorbed water. The change in the dielectric properties with absorption of water was independent of presence of salt, temperature of exposure, and aging history, although a hysteresis of the hydration–dehydration process was observed at low frequencies. Two types of absorbed water were observed—water molecularly dispersed within the epoxy matrix and clustered water in spherical microcavities. The time dependence of the real dielectric permittivity measured at 10 kHz was found to closely resemble that of the water absorption, which allowed the activation energy of diffusion to be calculated from both dielectric and gravimetric data. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1011–1024, 2002; DOI 10.1002/app.10368     

The effect of reaction conditions on montmorillonite-catalysed peptide formation

Oligomerization of glycine (gly) and diglycine (gly₂) on montmorillonite was performed as cyclic, drying-wetting process at temperatures below 100°C, under varying reaction conditions. The influence of substrate/clay ratio, temperature and pH was found to be different for amino acid (AA) dimerization, cyclic anhydride (CA) formation and peptide chain elongation. High temperatures and neutral pH favour CA formation over diglycine production. An AA/catalyst ratio of 0.2 mmol/g leads to optimal yields. This supports the assumption that amino acid dimerization and CA formation take place at the edges of clay particles. Peptide chain elongation, starting from gly₂, produces higher yields at higher temperatures and neutral pH.     

球形氧化锆的湿法制备过程研究

以氯氧化锆和碳酸氢铵为原料，采用连续反应沉淀法制备了微米级球形氧化锆前驱体，此前驱体在500℃下于空气气氛中煅烧2h得到球形氧化锆粉体。探讨了锆盐溶液浓度、加料速度、pH、反应时间对粉体颗粒粒径大小及其分布的影响。经SEN，XRD，TG—DSC和激光粒度测试仪分析，结果表明在最佳工艺条件下制备的氧化锆前驱体颗粒呈球形，分散性好，粒径分布在8—18μm。     

烧成系统NOx的形成及排放控制技术介绍

煤燃烧过程中污染物的形成、迁徙、排放和抑制规律、NOx污染控制技术等是煤燃烧领域重点研究的内容。文章分析了水泥工业回转窑中煤粉燃烧过程中NOx的形成机理，并针对NOx的形成机理和影响因素，探讨了水泥工业相关的低NOx燃烧技术。目前，较为实际的方法是采取空气分级燃烧技术和设计出科学的燃烧器二种。     

聚乙烯吡咯烷酮在天然气水合物生成中的作用

研究了聚乙烯吡咯烷酮(PVP)在天然气水合物生成中的促进和抑制作用,结果表明PVP作为促进剂时,在确定的反应温度和压力下有一个最佳的浓度,在确定的使用浓度和温度时则有一个最佳反应压力,否则PVP的加入将抑制水合物的生成。认为PVP在低浓度时作为高分子表面活性剂,降低了溶液的表面张力,加速了水合物生成。在高浓度时,其长链上的五元环吸附水合物表面未完成的孔穴,阻止了水合物晶核的增长。     

Chaos in bubbling—nonlinear analysis and modelling

In the present paper, nonlinear features and analytical results for the chaotic bubbling from a submerged orifice are described. A chain of air bubbles was produced from the single orifice of in diameter and micro-convection induced by the bubble generation was recorded using hot-probe anemometer located close to the orifice. The air flow rate was varied widely from q=100 to and the aspects of bubbling were observed by high-speed video. The nonlinear analysis is performed for the time series data of hot-probe anemometer especially in the range of q=435-. The calculated largest Lyapunov exponent shows that with increase of air volume flow rate, the time period for the process of liquid flow to lose stability becomes shorter and at high air flow rate such as , it is shorter than the time period between subsequent bubbles. To explain such chaotic behaviors of bubbling, a simple model has been proposed. The model simulates the process of interaction between the elastic bubble wall and liquid. Simulation results compared well with the analytical results of experimental data. Summarizing, it is concluded that one of the reasons for chaos appearance is the nonlinear character of interaction between an elastic bubble wall and the liquid stream.     

纳米二氧化硅模板的制备

以微乳液法制备纳米二氧化硅（SiO2）粒子，经压制、烧结制备SiO2模板。通过红外（IR）、热分析（TGDTA）、扫描电镜（SEM）等方法对SiO2模板进行表征，结果表明所得SiO2粒度在100nm左右．烧结温度在800℃时，SiO2粒子之间将实现颈长，有利于有机／无机杂化多孔材料的制备。