Internal displacement reactions in multicomponent oxides. Part I. Line compounds with narrow homogeneity range

As a model of an internal displacement reaction involving a ternary oxide “line” compound, the following reaction was studied at 1273 K as a function of time, t: Both polycrystalline and single-crystal materials were used as the starting NiTiO₃ oxide. During the reaction, the Ni in the oxide compound is displaced by Fe and it precipitates as a γ-(Ni-Fe) alloy. The reaction preserves the starting ilmenite structure. The product oxide has a constant Ti concentration across the reaction zone, with variation in the concentration of Fe and Ni, consistent with ilmenite composition. In the case of single-crystal NiTiO₃ as the starting oxide, the γ alloy has a “layered” structure and the layer separation is suggestive of Liesegang-type precipitation. In the case of polycrystalline NiTiO₃ as the starting oxide, the alloy precipitates mainly along grain boundaries, with some particles inside the grains. A concentration gradient exists in the alloy across the reaction zone and the composition is >95 at. pct Ni at the reaction front. The parabolic rate constant for the reaction is k _p =1.3 × 10⁻¹² m² s⁻¹ and is nearly the same for both single-crystal and polycrystalline oxides.     

钙锶氯化物体系中钙和锶的重量法分析

针对氯化钙氯化锶混合体系,探索出能够准确分析该体系中钙和锶含量的分析方法。首先,用碳酸盐重量法分别对氯化钙和氯化锶单盐溶液进行分析,能够获得比较准确的测定结果且确定了碳酸盐沉淀适宜的烘干温度和烘干时间分别为200 ℃和20 h。在此基础上,结合碳酸盐重量法和经典的氯化银重量法对氯化钙和氯化锶的混合溶液进行准确地分析,分别获得碳酸盐沉淀的总质量和总氯的物质的量,再通过联立方程组求解得到钙锶氯化物共存体系中各组分的含量。最后,将实验方法用于分析钙和锶物质的量之比YB(YB=nCa∶nSr)为49、9.4、0.98、0.10和0.030的氯化物体系中氯化钙和氯化锶的组分含量时,测定结果比较准确,绝对误差小于0.5%。     

Solubility of magnesium oxide in calcium oxide-calcium chloride mixtures

Measurements and theoretical calculations of the solubility product of magnesium oxide in calcium chloride-calcium oxide mixtures at 1133 K are reported. A filtration technique in an inert atmosphere was used to obtain samples for analysis by atomic absorption for magnesium content. At low concentrations of O^-2, the data are in consonance with the very low solubility product of 10^-6.2 predicted by a simple thermodynamic cycle first proposed by Flood, Fϕrland and Grjotheim. Work performed under the auspices of the U.S. Energy Research and Development Administration.