LaCl3—SrCl2—MgCl2三元体系相图

本文借助于ＤＴＡ和Ｘ射线结构分析测定了ＬａＣｌ３－ＳｒＣｌ２－ＭｇＣｌ２三元体系相图，发现它属简单低共熔型，体系内有对应于ＬａＣｌ３，ＳｒＣｌ２和ＭｇＣｌ２的３个液相面、３条２次结晶线和１个三元低共熔点Ｅ（１５．０ｗｔ％ＬａＣｌ３，４９．５ｗｔ％ＳｒＣｌ２，３５．５ｗｔ％ＭｇＣｌ２；５４５℃），并且在固相下有一个不稳定的化合物生成，在约５００℃时分解。     

四元体系CsCl—PrCl3—13%HCl—H2O（25℃）和CsCl—PrCl3—42%H…

测定了四元体系ＣｓＣｌ－ＰｒＣｌ３－１３％ＨＣｌ－Ｈ２Ｏ（２５℃）和ＣｓＣｌ－ＰｒＣｌ３－４２％ＨＡｃ－Ｈ２Ｏ（３０℃）的稳定平衡态的溶液数据，绘制了相应的溶度图，两个体系的皆中有４种固相，ＣｓＣｌ，ＰｒＣｌ３．６Ｈ２Ｏ２种原始盐和ＣｓＣｌ．ＰｒＣｌ３．６Ｈ２Ｏ，３ＣｓＣｌ．ＰｒＣｌ３．７Ｈ２Ｏ２种复盐，证实了文献中对Ｍｅｙｅｒ反应１机理的解释，并对新相进行了热分析，Ｘ射线粉末衍射及偏光显微镜测定     

希土化合物对离体巨噬细胞的影响

本文应用细胞培养法和单细胞阳离子测定系统研究了希土化合物以地巨噬细胞的影响，结果表明，在培养介质中ＳｍＣｌ３和Ｙｃｌ３的浓度大于１ｍｍｏｌ．ｄｍ＾－３时，有明显的细胞毒性，Ｙｃｌ３的细胞毒性大于ＳｍＣｌ３，ＳｍＣｌ３和ＹＣｌ３的细胞毒性明显大于Ｓｍ（Ａｌａ）３Ｃｌ３和Ｙ（Ａｌａ）２Ｃｌ３。希土化合物的作用使细胞（Ｃａ＾２＋ｉ）升高；毒性越大，Ｃａ＾２＋ｉ升高越甚。低浓度Ｓｍ＾３＋和Ｙ６３＋对细胞膜     

四元交互体系Li^＋,k^＋／Cl,SO^2—4—H2O50,75℃相平衡研究

采用等温溶解平衡法测了四元交互体系Ｌｉ＾＋，Ｋ＾＋／Ｃｌ，ＳＯ＾２－４－Ｈ２Ｏ５０，７５℃平衡溶液的物化物质（密度，粘度，折光率），该四元交互体系５０，７５℃的溶解度等温图有５个相区：即Ｌｉ２ＳＯ４．Ｈ２Ｏ，ＫＬｉＳＯ４，ｋｃｌ，ｋ２ｓｏ４，ｌＩｃＬ．Ｈ２Ｏ，７条单变量曲线，３个共饱点，其中ＬｉＳＯ４．Ｈ２Ｏ＋ＫＣＬ＋ＬｉＣｌ．Ｈ２Ｏ为一致零变量点，用我们以往提出的经验公式处理了平衡溶液的密度和折     

氯化铯和氯化镧溶剂体系及四类新化合物的合成

研究了四元体系ＣｓＣｌ－ＬａＣｌ３－ＨＣｌ－Ｈ２Ｏ（２５℃、「ＨＣｌ」＝１３％（ｗｔ），２３％（ｗｔ）和ＣｓＣｌ－ＬａＣｌ３－ＨＡｃ－Ｈ２Ｏ（３０℃，「ＨＡｃ」＝４２％（ｗｔ））的平衡态的溶度数据，并给出制了相应的溶度图，共得到了ＣｓＣｌ．ＬａＣｌ３．４Ｈ２Ｏ、２ＣｓＣｌ．ＬａＣｌ３．２Ｈ２Ｏ和３ＣｓＣｌ．ＬａＣｌ３．３Ｈ２Ｏ３种化合物。对得到的新相进行了热分析，Ｘ射线粉末衍射及偏光性质的测定，依     

复合催化剂AlCl3／SbCl3的α—蒎烯／苯乙烯阳离子聚合反…

用微臭氧化－薄层层析法分析测定了复合催化剂ＡｌＣｌ３／ＳｂＣｌ３在不同Ｓｂ比、投料比、溶剂和温度等条件下的α－蒎烯（Ｍ１）／苯乙烯（Ｍ２）共聚产物的构成。表明该复合催化剂可获得￣１００％共聚体，其中α－蒎烯链节含量Ｆ１可在３０％￣５６％之间调控。在仅生成共聚体的条件下由Ｍａｙｏ－Ｌｅｗｉｓ积分式首次测定了竞聚率。ＡｌＣｌ３／ＳｂＣｌ３和单独ＡｌＣｌ３相比，ｒ１增大，ｒ２减小，ｒ２／ｒ１值降低了５￣     

两相体系中钌膦配合物催化4—苯基—3—丁烯—2—酮加氢反应的研究

研究了水和有机物组成的两相催化体系中,由ＲｕＣｌ３－ＴＰＰＴＳ（ＴＰＰＴＳ：Ｐ（ｍ－Ｃ６Ｈ４ＳＯ３Ｎａ）３）原位反应生成的催化活性物种对４－苯基－３－丁烯－２－酮（又名苄叉丙酮）的催化加氢反应．考察了钌浓度（１．０×１０－３～６．０×１０－３ｍｏｌ／Ｌ）、氢压（１．０～６．０ＭＰａ）、反应温度（３０～７０℃）、配体浓度（１．２～７．２×１０－２ｍｏｌ／Ｌ）、阳离子表面活性剂（ＣＴＡＢ：十六烷基三甲基溴化铵）及反应时间等对加氢反应活性和选择性的影响,并与以配合物ＲｕＣｌ２（ＴＰＰＴＳ）３为催化剂前体生成的催化活性物种对加氢反应的活性及选择性进行了比较．结果表明,分别由配合物ＲｕＣｌ２（ＴＰＰＴＳ）３及ＲｕＣｌ３－ＴＰＰＴＳ原位反应生成的催化活性物种,都只催化４－苯基－３－丁烯－２－酮的Ｃ＝Ｃ键选择加氢．由配合物ＲｕＣｌ２（ＴＰＰＴＳ）３形成的催化体系的加氢活性及选择性均优于ＲｕＣｌ３－ＴＰＰＴＳ原位反应生成的催化活性物种．阳离子表面活性剂的加入,使加氢反应活性下降,选择性略有提高     

Selective Reduction of α,β-Unsaturated Amides with NaBH_4/BiCl_3 System

ＳｅｌｅｃｔｉｖｅＲｅｄｕｃｔｉｏｎｏｆα，β－ＵｎｓａｔｕｒａｔｅｄＡｍｉｄｅｓｗｉｔｈＮａＢＨ_４／ＢｉＣｌ_３ＳｙｓｔｅｍＳｅｌｅｃｔｉｖｅＲｅｄｕｃｔｉｏｎｏｆα，β－ＵｎｓａｔｕｒａｔｅｄＡｍｉｄｅｓｗｉｔｈＮａＢＨ_４／ＢｉＣｌ_３Ｓｙｓｔｅ...     

The Effect of CaAl_2O_4 Spinel on Ni/Al_2O_3 Catalyst for CH_4/O_2-to-Syngas Reaction

ＴｈｅＥｆｅｃｔｏｆＣａＡｌ２Ｏ４ＳｐｉｎｅｌｏｎＮｉ／Ａｌ２Ｏ３ＣａｔａｌｙｓｔｆｏｒＣＨ４／Ｏ２－ｔｏ－ＳｙｎｇａｓＲｅａｃｔｉｏｎ１）ＬＵＹｏｎｇＬＩＵＹｕＳＨＥＮＳｈｉｋｏｎｇ（ＬａｎｚｈｏｕＩｎｓｔｉｔｕｔｅｏｆＣｈｅｍｉｃａｌＰｈｙｓｉｃ...     

YbCl3—CaCl2—NaCl三元体系相图的研究

借助ＤＴＡ研究了ＹｂＣｌ３－ＣａＣｌ２－ＮａＣｌ三元体系相图，发现该体系有对应于ＹｂＣｌ３、ＣａＣｌ２，Ｎａ３ＹｂＣｌ６的４个液相面，５条二次结晶线，１个三元低共熔点Ｅ（８７．０％ＹｂＣｌ３，１．０％ＣａＣＬ２，１２．０％ＮａＣＬ；４５０℃）和三元转熔点Ｐ（６１．０％ＹｂＣｌ３，１９．０％ＣａＣｌ２，２０．０％ＮａＣｌ；４７４℃）。     

Equation-of-state properties and surface tension of ethylene-vinyl alcohol random copolymers

Pressure-volume-temperature (PVT) data were studied for ethylene-vinyl alcohol random copolymers (EVOH) and served to determine bulk reduction parameters for the equation-of-state by Flory-Orwoll-Vrij. The compressibility factor as a function of copolymer composition displays positive deviation from additivity. Sessile drop method yielded surface tensions of EVOH melts at different temperatures. To a good approximation linear variation of surface tension with respect to copolymer composition was observed. It indicates that conformational restrictions prevent surface excess of the low-energy units. Results on surface tensions are discussed in terms of different theoretical approaches. It turns out that the parachor approach is in excellent agreement with experimental data. The corresponding state approximation revealed decreasing surface energy with ascending ethylene content whereas the surface entropy remains approximately constant as long as vinyl alcohol units are in excess.     

Surface tension and density measurements of the molten YCl3-KCl binary system

The surface tension and the density of the YCl₃-KCl system were determined as a function of temperature (1073–1248 K) by the maximum bubble pressure technique. These results are represented by linear empirical equations as functions of temperature. At a constant temperature, the surface tensions of YCl₃-KCl melts show a negative deviation from Guggenheim's equation for ideal solutions.     

Density of lithium fluoride—lithium carbonate-based molten salts

The density of the LiF-Li₂CO₃ melts system was measured using the Archimedean method. Using the quadratic regression orthogonal design with two factors, a regression equation for the density of LiF-Li₂CO₃ melts was obtained in which the concentration of LiF and temperature were considered. The results indicated that the density of the LiF-Li₂CO₃ melts decreased with either increasing the concentration of LiF or increasing temperature; a linear relation was observed between density and temperature. In addition, the influences of NaF, KF, NaCl, and KCl additives on the densities of the given systems were studied. The addition of NaF and KF increased the density of the melts, whereas NaCl and KCl resulted in an initial increase and subsequent decrease with an increasing additive concentration. The density attained a maximum at NaCl and KCl mass fraction of approximately 15%.     

Surface tension of CaO-Al2O3, CaO-SiO2, and CaO-Al2O3-SiO2 melts

A method for the approximation of the temperature-concentration dependence of the surface tension of CaO-Al₂O₃, CaO-SiO₂, and CaO-Al₂O₃-SiO₂ melts was suggested. The method was based on the statistical-thermodynamic model of associated solutions. A comparison of the calculated surface tensions of the melts with the available literature data showed that the suggested approach allowed the surface tension of liquid slags to be correctly predicted as a function of temperature and composition.     

Effect of water on glass transition in starch/sucrose matrices investigated through positron annihilation lifetime spectroscopy: a new approach

Glass transition is studied through positron annihilation lifetime spectroscopy (PALS) in maize starch matrices containing 10 (batch STS10) and 20 (STS20) w/w% sucrose, as a function of temperature (T) and water content (c(w)). To circumvent important losses of water upon heating while recording the PALS spectra, a new method is developed: instead of a series of measurements of τ(3), the triplet positronium lifetime, at different T, the latter is kept constant and the series relates to c(w), which is left to decrease at a constant rate. Similarly to the changes in τ(3) with T, the τ(3)vs. c(w) plots obtained show a smooth linear increase until a break, denoting the occurrence of glass transition, followed by a sharper increase. The gradients appear to be independent of T. The variation of the glass transition temperature, T(g), with c(w) shows a broad sigmoid with a large linear central part; as expected from the plasticising effect of sucrose, the plot for STS20 lies some 10 K below that for STS10. Results from differential scanning calorimetry for STS20 yield T(g) values some 15 K higher than from PALS. On the basis of the general shape of the τ(3)vs. T variations, a general equation is set for τ(3)(T, c(w)), leading one to expect a similar shape for τ(3)vs. c(w), as experimentally observed.     

Improved dielectric and mechanical properties of polystyrene-hybrid silica sphere composite induced through bifunctionalization at the interface

Hybrid silica spheres (HS) of size 270-350 nm with vinyl and aminopropyl surface groups were incorporated in polystyrene (PS), and its effect on dielectric properties, coefficient of thermal expansion (CTE), and strength of PS-HS composite was studied. Incorporation of HS in PS followed a decrease in the dielectric constant from 3.2 for PS to 2.6 for composite with 7.5 vol % HS. The decrease in the dielectric constant was attributed to (i) increased interfacial porosity, (ii) formation of anhydrous HS having low dielectric constant, during hot processing of the composites, and (iii) dispersion and preservation of the anhydrous HS in the hydrophobic matrix. The dielectric constant of the composites with HS content up to 7.5 vol % does not vary much with temperature in the range from -20 to 65 °C. These composites also exhibited reduced CTE and improved flexural strength/stiffness due to good interfacial bonding through HS vinyl groups and dispersion of the filler in the matrix. The dielectric loss increased with HS content, and the loss measured for 7.5 vol % PS-HS composite was 6 × 10(-3), as compared to 10(-4) for PS. At HS loading above 7.5 vol %, the tendency of HS to agglomerate and form percolated structure lead to an increase in the dielectric constant and decrease in the mechanical properties of the composites.     

含氟丙烯酸酯聚合物乳胶膜表面性质

采用XPS和界面张力仪分别测定了含氟丙烯酸酯聚合物乳胶膜表面的组成及水在其表面的动态接触角, 并用状态逼近方程模型计算了含氟聚合物乳胶膜的表面张力, 考察了温度对乳胶膜润湿性的影响. 结果表明, 含氟聚合物乳胶膜表层较深处的F 1s信号强度比近表面要弱, 乳胶膜表面张力随表面氟原子浓度增加在一定程度上呈现线性下降；含氟侧链(Rf)较长(碳原子数n＞6)的含氟聚合物, 其表面张力随Rf单元含量增加而下降的趋势显著高于Rf较短(n≤6)的含氟聚合物, 而水在含氟聚合物乳胶膜表面上的后退接触角θr随n增大出现急剧上升, n≥10 时, θr值几乎恒定不再随n增大而改变. 此外, 参与共聚的非氟丙烯酸酯酯基碳链较短时, 水在共聚物乳胶膜表面的θr随氟单元含量增加而增加的趋势更显著；温度超过40 ℃后, 水对聚合物乳胶膜的润湿性随温度上升略有改善.     

The Wolf method applied to the liquid-vapor interface of water

The Wolf method for the calculation of electrostatic interactions is applied in a liquid phase and at the liquid-vapor interface of water and its results are compared with those from the Ewald sums method. Molecular dynamics simulations are performed to calculate the radial distribution functions at room temperature. The interface simulations are used to obtain the coexisting densities and surface tension along the coexistence curve. The water model is a flexible version of the extended simple point charge model. The Wolf method gives good structural results, fair coexistence densities, and poor surface tensions as compared with those obtained using the Ewald sums method.     

Aluminium anodising in ultra-dense sulfate baths: discovery by overall kinetic and potentiometric studies of the critical role of interface colloidal Al2(SO4)3 nanoparticles in the mechanism of growth and nanostructure of porous oxide coatings

The solubility of Al₂(SO₄)₃ in H₂SO₄ at different concentrations was determined and showed a minimum at 95% w/v. Overall kinetic and potentiometric studies of Al anodising were performed in large ranges of concentrations of saturated H₂SO₄ solutions and current densities. During anodising quasi-steady-state supersaturation and unsaturation conditions for concentrations below and above 95% w/v dominate in the pore-filling solution affecting those in the oxide–electrolyte interface. Interface colloidal Al₂(SO₄)₃ nanoparticles form occupying surface fractions increasing with salt concentration, supersaturation, field strength in the pore base surface and current density increase and temperature decrease. These control the mechanism and kinetics of growth and structural parameters of films and impose the growth of non-pitted uniform films up to current densities higher than in unsaturated baths, more effectively under supersaturation conditions. Well-defined peaks of structural parameters appear depending on thickness and current. Thus optimal regularly grown films of desired nanostructure and the introduction of new anodising technologies can be achieved.     

高温下煤中矿物质对气化反应的影响

利用XRD对1100℃~1500℃高温下矿物质在弱还原气氛中的变化进行考察,并利用RIR对矿物质进行半定量分析,发现随着温度的升高莫来石含量增大,而SiO₂含量下降,符合SiO₂-Al₂O₃二元相图的变化。高温下部分无定形矿物质发生熔融,主要为硅铝酸盐。在煤焦二氧化碳气化过程中,熔融的硅铝酸盐与煤焦表面接触阻碍气化反应进行。利用FT-IR测定了硅铝酸盐结构的变化,说明高温下矿物质对气化反应的影响与硅铝酸盐的聚合程度存在一定的关系。