Organo-zincate molten salts as immobilising agents for organometallic catalysis

The combination of 1-n-butyl-3-methylimidazolium chloride with ZnCl₂ affords ionic mixtures with different melting point temperatures depending on the zinc molar fraction. RuCl₂(PPh₃)₃ immobilised in the low melting mixture (60°C) promotes the 1-hexene hydrogenation (turnover frequencies up to 44 min^–1) and the recovered solid catalyst phase can be reused several times.     

Polymer electrolytes from PEO and novel quaternary ammonium iodides for dye-sensitized solar cells

Polymer electrolytes were prepared by blending high molecular weight poly(ethylene oxide) (PEO) and a series of novel quaternary ammonium iodides, the polysiloxanes with oligo(oxyethylene) side chains and quaternary ammonium groups. X-ray diffraction (XRD) measurements ensured relatively low crystallinity when the quaternary ammonium iodides were incorporated into the PEO host. The ionic conductivity of these complexes was improved with the addition of plasticizers. The improvement in the ionic conductivity was determined by the polarity, viscosity and amounts of plasticizers. A plasticized electrolyte containing the novel quaternary ammonium iodide was successfully used in fabricating a quasi-solid-state dye-sensitized solar cell for the first time. The fill factor and energy conversion efficiency of the cell were calculated to be 0.68 and 1.39%, respectively.     

Thermal analysis of montmorillonites modified with quaternary phosphonium and ammonium surfactants

The thermal stability of seven organically modified montmorillonites (‘organoclays’) has been investigated using differential thermal analysis, differential scanning calorimetry, and thermogravimetry in conjunction with X-ray diffractometry. Six organoclays were synthesised by replacing the interlayer inorganic cations, initially present, with quaternary phosphonium and ammonium surfactant cations. The samples modified with tetrabutylphosphonium (TBP), and butyltriphenylphosphonium (BTPP) ions have an appreciably higher thermal stability than the octadecyltrimethylammonium (ODTMA)-modified clays. Thus, in the case of TBP- and BTPP-modified montmorillonites, the onset temperature of decomposition is close to 300 °C. Samples modified with hexadecyltributylphosphonium (HDTBP) ions have a lower onset temperature of decomposition of 225 °C. In comparison, the onset temperature for ODTMA-montmorillonites (obtained at different concentrations of ODTMA-bromide) ranges from 158 to 222 °C, being highest where the concentration of intercalated surfactant is lowest. The onset temperature for a commercial alkylsilane-treated quaternary ammonium-modified organoclay (S-BEN N-400FP) is 207 °C. The basal spacing of the TBP- and BTPP-modified clays is 1.7–1.8 nm, indicating a monolayer arrangement of quaternary phosphonium ions in the interlayer space, while the value of 2.5 nm for HDTBP-montmorillonite indicates a more open structure. The ODTMA-modified samples have basal spacings ranging from 1.9 to 2.1 nm, indicative of a bilayer to pseudo-trilayer arrangement. The exceptionally high basal spacing of 3.4 nm for the S-BEN N-400FP organoclay might be due to interlayer penetration of organosilane hydrolysis products during synthesis. The thermal properties of organoclays are apparently related to the nature of the surfactants and their arrangement in the interlayer space of montmorillonite.     

Water vapor adsorption in activated carbon modified with hydrophilic organic salts

Five different kinds of hydrophilic organic salts were used to modify commercial activated carbon in order to prepare hydrophilic carbon materials. Properties of the samples were analyzed by surface area analyzer and SEM-EDX. The hydrophilic organic salts with different properties were introduced into activated carbon and significantly affected the properties of the samples.During adsorption experiments, the water vapor adsorption amount in modified samples increases by 0.57-17.12 times in temperature range from 303 to 323 K and at relative pressure below 0.50. Water molecules combined with surface hydrophilic groups through H-bonding exhibit good thermo stability. The effects of temperature, oxygen content and properties of the hydrophilic organic salts on water vapor adsorption were studied. It is indicated that water vapor adsorption in modified samples is mainly affected by the surface oxygen content. The carboxylate radicals in the hydrophilic organic salts greatly affect the micropore structure of the modified samples, while the metal ions in them exhibit limited influence. Different adsorption capacity of modified samples can be explained with the electronegativity of elements presented by Pauling.     

柴达木盆地涩北地区第四系泥岩型生物气储层孔隙有效性评价

通过低场核磁共振实验分析了柴达木盆地涩北地区第四系泥岩型生物气储层在饱和水状态及渐变烘干温度状态下的T₂谱,明确了孔隙流体的核磁响应特征,以评价孔隙的有效性。研究结果表明： ①核磁共振实验是以饱和水状态T₂谱为基础,采用正态分布函数拟合构建了离心束缚水T₂谱,确定了可动流体和毛管束缚流体T₂截止值,用于划分出流体类型并开展了孔隙有效性评价。②研究区岩样饱和水状态T₂谱谱峰呈左小右大的形态,右峰幅度值远大于左峰,占T₂谱幅度值90%以上;随着烘干温度的升高,T₂谱幅度减小且左移趋势明显;束缚水T₂谱形态近似于正态分布,起始位置与饱和水状态的T₂谱基本重合。③研究区可动流体T₂截止值T_{2 C1}平均为3.3 ms,毛管束缚流体T₂截止值T_{2 C2}平均为1.8 ms;孔隙流体包括可动水、毛管束缚水和黏土束缚水,黏土束缚水T₂小于T_{2 C2},毛管束缚水T₂大于T_{2 C2}且小于T_{2 C1},可动流体T₂大于T_{2 C1};毛管束缚水含量最高,黏土束缚水其次,两者占总孔隙流体的84.43%～95.06%,可动水含量低。④研究区储层有效孔隙占总孔隙的54.99%,主要为毛管束缚孔,黏土束缚孔为无效孔隙;黏土含量越高,有效孔隙度越小。     

Electrochemical production of Sn-filled carbon nanotubes in molten salts

Sn-filled carbon nanotubes(CNTs) were prepared in situ by electrolysis of graphite in molten LiCl/SnCl2 mixtures. Transmission electron microscopy(TEM) investigation shows that the as-made products contain abun-dance of carbon nanotubes and most of them are filled with metal nanoparticles or nanorods. Some nanotubes are e-ven inserted with long continuous nanowires more than several micrometers in length. Selected area electron diffrac-tion(SAED) patterns and energy dispersive X-ray spectroscopy(EDS) of the filled nanotubes confirm the presence of Sn inside the nanotubes. The encapsulated Sn was further identified as β-Sn with tetragonal structure. Based on the experimental results, a possible growth mechanism of the Sn-filled nanotubes was also discussed.     

熔盐电解法制备钛的进展和发展趋势

介绍了熔盐电解法制备金属钛的研究进展,对比传统熔盐电解法和新熔盐电解法的基本原理以及发展状态,指出二氧化钛的直接电化学还原法是一种低能耗、无污染的绿色生产新工艺,最有希望取代传统的Kroll法。     

High temperature corrosion mechanisms and effect of alloying elements for materials used in waste incineration environment

Corrosion products on two typical materials, SA213-T12 steel and alloy 625 exposed to the actual combustion gas, were analyzed in addition to laboratory tests for penetration of corrosive matter. It has been clarified that corrosion products of oxides containing a little chlorides and sulphides show lamellar structures and that at the alloy-scale interface, chlorination, sulphidation, and oxidation occur under a low P_O2-high P_Cl2 condition. The formation of scale structures and the effect of corrosion-resistant alloying elements can be explained according to the stability tendencies of metals, chlorides, and oxides in the M-Cl-O equilibrium diagrams. The severity of corrosion environments at the interface is influenced by the penetration extent of corrosive matters through deposits and scales, and the protective effects of oxide films derived from alloying elements play an important role in preventing the corrosion. On the other hand, it has been shown that thermal fluctuation characterized in this kind of environment makes the lamellar scale structures and sometimes breaks and peels off the scale, and thus accelerates the corrosion. On the basis of the above mentioned knowledge, a new corrosion model is presented.     

Nacl—Bacl2—Srcl2三元熔盐相图的计算

本文运用作者提出的从三个对应的二元系的热力学性质预示三元溶液的热力学性质的新对称几何模型,推导得到三元溶液中三个组元的偏摩尔热力学性质的数学表达式。进而将这一结果应用于NaCl-BaCl_2-SrCl_2三元熔盐相图的计算中,得到此三元系的液相析出面及若干等温截面。计算所得结果与实测结果偏差小于5℃,说明此模型在一些熔盐体系中有较好的适用性。