二硼化锆基超高温陶瓷的制备及性能

用碳化硅(SiC)颗粒增韧二硼化锆(ZrB2)陶瓷,在氩气流中热压烧结温度为1 950℃、保温1 h,20 MPa压力下成功制备出了致密的ZrB2/SiCp复合材料.ZrB2/SiCp复合材料的致密度随着SiC颗粒添加量的增加而增加.当SiC颗粒的体积分数(下同)为15%时,相对致密度达到100%.ZrB2/SiCp复合材料的抗弯强度和断裂韧性都随着SiC添加量的增加成上升趋势,当SiC颗粒的添加量在15%时同时达得最大值,分别为646 MPa和8.52 MPam·m1/2.SiCp的添加还提高了ZrB2/SiCp复合材料的耐氧化烧蚀性能.     

Synthesis of High-Purity Zirconium Fluoride for Fluoride Glass Fibers by Chemical Vapor Deposition

A technique for synthesizing ultra-high-purity ZrF₄ using chemical vapor deposition in a ZrBr₄–HF system is developed and a purification mechanism is clarified. The Fe concentration in ZrF₄ is evaluated at less than 10 ppb based on analysis of the transmission loss spectrum of a fiber prepared using synthesized ZrF₄. Purification is achieved mainly in a sublimation process of ZrBr₄, and purification efficiency is determined by sublimation temperature and activity of impurities in ZrBr₄. The concentration of transition-metal impurities in ZrF₄, synthesized by chemical vapor deposition in the ZrBr₄–HF system, is expected to be less than 1 ppb.     

氧氯化锆的生产及其在现代新能源中的应用

介绍了氧氯化锆（氧化锆）的生产原理和生产工艺，一酸一碱法是国内外普遍采用的方法，沸腾氯化法是国际上较为先进的锆英石分解方法，阐述了氧氯化锆（氧化锆）产品在镍氢动力电池负极材料（贮氢材料AB2）、燃料电池（特别是高温固体氧化物燃料电池），电池隔膜纸中的应用前景。     

Preparation of superacid of iron-supported zirconia for reaction of butane to isobutane

A highly active superacid of 2 wt% Fe-supported ZrO₂ for the skeletal isomerization of butane to isobutane was obtained by sfexposing Fe₂O₃/ZrO₂ to 1 N H₂SO₄ followed by calcining in air at 700°C for more than 24 h; the Fe₂O₃/ZrO₂ was prepared by impregnating zirconia gel with a solution of Fe(NO₃)₃ followed by drying at 300°C (2 wt% Fe). A much lower activity was observed with the opposite procedure, where the first impregnation was sulfation of the gel, followed by a second impregnation with the iron compound. It was proved from analysis of the sulfur content in the catalysts that residual sulfur species were not related with generation of the superacidic sites. XPS showed the catalyst to be Fe₂O₃ supported on ZrO₂.Superacids by metal oxides, VIII. For previous publications VI and VII in this series see refs. [10,11].     

氯氧化锆生产中除钠工艺的研究

概述烧碱生产氯氧化锆工艺的传统方法，介绍新的除钠方法，该法比传统方法具有明显的优势。     

水热法制备ZrO_2纳米微晶及对乙醇和丁烷气敏性研究

用水热法制备 Zr O2 纳米微晶的平均尺寸为直径 5 nm,长 7.5 nm。由 X射线衍射确认晶相为单斜相。并对其形状和大小进行了透射电镜和激光散射分析 ,结果表明 Zr O2 纳米粒子在水溶液中存在软团聚 ,团聚体平均尺寸约 90 nm。着重研究了 Zr O2 纳米微晶对乙醇及丁烷的气敏性能 ,结果表明用纳米级 Zr O2 粒子制备的气敏元件对乙醇和丁烷有好的气敏性。并且随着纳米粒子尺寸降低 ,对气体敏感性增强     

EDTA络合滴定法快速测定碳酸锆中锆铪含量

锆铪氧化物含量的测定通常采用苦杏仁酸[C6H5CH（OH）COOH]重量法。该法经典、准确,但操作烦琐,分析时间长,对日常生产、入库或销售不利。乙二胺四乙酸二钠（EDTA）络合滴定法（容量法）操作简便、快速、准确,适合日常检验。但用基准氧化锌、高纯二氧化锆或氯氧化锆来标定EDTA时,测定结果偏低。采用重量法和容量法相结合,先用重量法测定锆铪氧化物含量,以已知锆铪氧化物含量的碳酸锆作标定物,再标定EDTA标准溶液的滴定度,用此EDTA标准溶液测定相同原料生产的碳酸锆。该法简便、快速、准确,试剂安全性好。     

Thermal Expansion of Solid Solutions in the ZrTiO4—In2O3—M2O5 (M = Sb, Ta) System

Axial and dilatometric thermal expansions and phase transformations were studied for solid solutions having the α-PbO₂ structure in the ZrTiO₄—In₂O₃—M₂O₅ (M = Sb, Ta) system with nominal formulas of Zr _x Ti _y In _z Sb _z O₄ and Zr _x Ti _y In _z Ta _z O₄ where x + y + 2 z = 2. With increased substitution of z , the cell volume increased, the difference in the b parameters at room temperature between those quenched from 1400° and 1000°C decreased, and the thermal expansion decreased. The axial thermal expansion of ZrTi _y In _z · Ta _z O₄ with z = 0.3 was almost identical with that of HfTiO₄, and those with z = 0.4 and z = 0.45 were smaller than that of HfTiO₄. Unit-cell volumes of these compound were compared with those of single oxides to make it clear that the unit-cell volume of ZrTiO₄ was small anomalously and to distinguish the normal and abnormal substitution systems. These results were explained by the working hypothesis proposed for these compounds.     

Hydrogenolysis of alkanes and olefin polymerization on the silica-supported zirconium hydrides: A comparative DFT study

The model reactions of ethylene polymerization and hydrogenolysis of linear alkanes (propane, n-butane, and n-pentane) on the silica-supported zirconium hydrides (Si–O)₃Zr^IVH, (Si–O)₂Zr^IVH₂, and (Si–O)₂Zr^IIIH were studied using the DFT approach. Catalytic processes under study were shown to occur involving different surface hydrides. The ethylene polymerization was found to proceed at comparable rates on the zirconium monohydrides, (Si–O)₃ZrH, and dihydrides, (Si–O)₂ZrH₂. Cleavage of linear alkanes on the monohydrides (Si–O)₃ZrH is thermodynamically unfavorable; however, the dihydrides (Si–O)₂ZrH₂ can act as catalysts of the process under mild conditions. Hydrides of the trivalent zirconium, (Si–O)₂Zr^IIIH, can also contribute to the hydrogenolysis reaction. A feature of all the systems studied is low regioselectivity of the corresponding processes.     

层状磷酸锆的制备及插层研究

具有层状结构的磷酸锆α-Zr（HPO4）2·H2O通过粉末X-射线衍射（XRD）,振动光谱（红外IR和拉曼光谱Raman）,热分析仪（TG）,透射电子显微镜（TEM）,扫描电子显微镜（SEM）和BET氮气吸附等手段进行了表征.所制备的α-Zr（HPO4）2·H2O的BET表面积为12.29 m^2/g.研究了α-Zr（HPO4）2·H2O的插入行为,与四甲基溴化铵和十六烷基三甲基溴化铵的插入反应表明插入是完全的,层间距分别增加了0.46 nm和1.68 nm,且插入化合物的荧光性质在室温被检测.