Reaction of Iradium with Metal Carbides in the Temperature Range of 1923 to 2400 K

The reactions of titanium carbide and hafnium carbide with iridium have been studied in thin film couples fabricated by vapor deposition processes. The reaction product layers after exposure in the temperature range of 1923 to 2400 K are dependent on the stoichiometry of the metal carbide layers and range from simple solid solutions to MIr_x compounds. The observed microstructures are predictable from available thermochemical data. The morphology of residual carbon in the reacted metal carbide-iridium product layer varies from interfacial deposits to uniform carbon dispersion and depends upon exposure temperature and metal carbide stoichiometry.     

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.     

Application of a counter-current gaseous diffusion model to the oxidation of hafnium carbide at 1200 to 1530°C

A counter-current gaseous diffusion model is presented to describe the oxidation of hafnium carbide between 1200 and 1530°C. The model separates the porous hafnia scale into two gas diffusion regions separated by a flame front, where O ₂ and CO react to form CO ₂.In the outer region, O ₂ and CO ₂ counter-diffuse; in the inner region, CO ₂ and CO counter-diffuse. The concentration gradients of each gaseous specie in the pores of the hafnia are determined and the rate of oxidation is calculated. A porosity of 2% and a pore radius of 0.01 m are representative of the values observed in hafnia during the early stages of HfC oxidation. These values lead to predictions of parabolic rate constants that are close to those measured by thermogravimetric analysis. In addition, the predicted and measured parabolic rate constants are shown to have the same dependence upon temperature and oxygen partial pressure.     

Experimental Validation of Reaction Rate Distributions for a SVEA-96+ BWR Assembly with Hafnium Control Blades

The accurate estimation of reactor physics parameters related to the presence of cruciform absorber blades in boiling water reactors (BWRs) is important for safety assessment and for achieving flexible operation during the cycle. Characteristics that are affected significantly include distributions of the total fission (F_tot) and ²³⁸Ucapture (C₈) rates for controlled regions. Representative experimental investigations have been performed in the framework of the LWR-PROTEUS programme. In particular, the LWRPROTEUS I-2A experiments concerned the neutronics characterisation of a SVEA-96+ BWR assembly controlled with a hafnium (Hf) blade under full-density water moderation conditions. The current paper presents the comparisons of the measured F_tot and C₈ pin-wise distributions with a variety of stochastic and deterministic calculations: (a) MCNPX2.5 using recent nuclear data libraries (JEFF-3.1, ENDF/BVI. 8, and JENDL-3.3), (b) PHOENIX4 using ENDF/B-VI.3, (c) BOXER using JEF-1, (d) CASMO₄ using JEF-2.2, and (e) HELIOS1.6 using ENDF/B-VI.1. The calculation/experiment comparisons show standard deviations from 1.2% (MCNPX2.5) up to 1.9% (BOXER) for the prediction of the F_tot distribution, the highest individual discrepancy (7.6% with BOXER) being seen close to the “Hf-vertex.” The C₈ comparisons show systematically better agreement than those of F_tot, the lowest standard deviations being 1.0% (BOXER) and the highest only 1.4% (HELIOS). In addition, sensitivity studies highlight the greater importance of modelling aspects, compared with that of nuclear data libraries, for the achievement of satisfactory and validated F_tot and C₈ predictions.     

Solvent extraction reaction of hafnium(IV) from strong sulfuric acid solutions with D2EHPA and PC 88A

Hafnium can be selectively extracted over zirconium from strong sulfuric acid solutions by D2EHPA or PC 88A. Solvent extraction experiments have been performed to identify the reaction of Hf from strong sulfuric acid solutions (1 to 7 M) by these two extractants. Hafnium extraction was gradually decreased and then increased again with the increase of sulfuric acid concentration. By applying a slope method, the extracted Hf species was proposed to be HfA₄·(HA)₂ by D2EHPA and Hf(HSO₄)₂A₂·(HA)₂ by PC 88A, respectively. This difference in the nature of the extracted species was verified by FT-IR spectra.     

Phase Relations and Volume Changes of Hafnia under High Pressure and High Temperature

Using multi-anvil high-pressure devices and synchrotron radiation, X-ray in situ observations of HfO₂ under high pressure and high temperature have been performed to investigate its phase relations and compression behavior. An orthorhombic phase (orthoI) is stable from 4 to 14.5 GPa below 1250°–1400°C and transforms to a tetragonal phase, which is one of the high-temperature forms of HfO₂, above these temperatures. Another orthorhombic phase (orthoII) with a cotunnite-type structure appears above 14.5 GPa. OrthoII is stable up to 1800°C at 21 GPa. OrthoII is quenchable to ambient conditions. The orthoI-to-orthoII transition is accompanied by ∼8 vol% decrease. The bulk moduli of orthoI and orthoII at room temperature are 220 and 312 GPa, respectively. This low compressibility of orthoII indicates that it is a potential candidate for very hard materials.     

钽铪在硫酸体系下的浸出分离研究

针对钽、铪分离多采用HF体系,易造成环境污染这一现状,以某牌号含钽、铪合金渣为原料,采用焙烧+浓硫酸浸出工艺对钽、铪的分离进行研究。试验表明,当合金渣与碳酸钠质量比为1∶1、焙烧温度1 000℃、浓硫酸与合金渣体积质量为1∶1、浸出时间1h时,钽、铪的分离效率最高,可实现钽与铪的有效分离。     

富集渣中铪的TBP萃取分离研究

以铪钛富集渣为原料,经硝酸溶解后采用TBP进行铪的萃取分离试验,主要考察铪钛质量浓度、有机相初始酸度、萃取时间、水相初始酸度、相比等对铪钛分离的影响,同时进行了不同浓度硝酸洗涤试验,以萃取和洗涤得到数据为基础进行了分馏萃取理论级数的计算。结果表明,最优萃取条件为:铪钛总质量浓度2.8g/L、有机相初始酸度3.1mol/L、萃取时间6min、水相初始酸度6.5mol/L、相比1∶1,铪、钛萃取率分别为84.8%和5.1%,铪、钛分配比分别为5.6和0.054,萃取分离系数β_(Hf/Ti)=104。选用10mol/L硝酸洗涤TBP载铪有机相,得到洗涤β_(Hf/Ti)=105,基本与β_(Hf/Ti)保持一致,经计算分馏萃取分离铪钛需要萃取级数3级,洗涤级数4级。     

硫化锌衬底上氧化铪保护膜制备及性能研究

采用磁控溅射法在硫化锌衬底上制备了氧化铪薄膜,并对氧化铪薄膜的结构和性能进行了分析和测试.结果表明,制备的氧化铪薄膜结构为单斜相,膜层致密,在8～12 μm波段对硫化锌衬底的透过率没有明显影响,硬度显著高于衬底的硬度,且与衬底结合良好,适合用作硫化锌的红外保护膜.