Zirconium Dodecaboride-based cutting material

Samples of zirconium dodecaboride are obtained by means of arc and induction melting of a mixture of zirconium and boron powders. A solder for binding the zirconium dodecaboride to the steel holder of the tool is selected. It is established that cutting tools supplied with zirconium dodecaboride may be used in operations of finish turning of adhesive-active titanium alloys.     

The mechanism of shrinkage of zirconium diboride during sintering

Summary The sintering shrinkage of zirconium diboride, like that of other brittle materials, is the same in the direction of application of the compacting force and in the radial direction.At temperatures of up to 1700° C, there is a slight, practically linear dependence of shrinkage on holding time, which is due solely to the ordering of the grain boundaries. At sintering temperatures of 1800–2200° C and holding periods of up to 30 min, a pronounced shrinkage is observed, which is probably due to slip processes taking place at the grain boundaries under the influence of surface tension forces. At slight grain coarsening takes place at the same time.At high temperatures and holding periods greater than 30 min, shrinkage is brought about by viscous flow, which is due to a directional diffusional displacement of the atoms.The presence of dodecaboride in zirconium diboride activates shrinkage by accelerating diffusional processes along the grain boundaries.     

SPD技术对锆及锆合金力学行为影响研究现状

综述了锆及锆合金剧烈塑性变形(SPD)后性能变化的研究进展,系统阐述了锆及锆合金经剧烈塑性变形后显微硬度、拉伸/压缩性能、高低周疲劳性能,重点介绍了SPD技术在纯锆、Zr-Nb系合金中的应用.经过剧烈塑性变形后,锆及锆合金的抗拉强度及屈服强度均显著提升,但依据剧烈塑性成形轨迹、合金成分、第二相分布、热处理制度不同,其提...     

碘化法提纯金属锆的热力学分析

对碘化法提纯金属锆进行了热力学计算,并结合试验分析了碘化反应气氛的组成。结果表明,粗锆原料在低温区被碘化,生成的碘化物在高温区分解。反应物在低温区生成ZrI4和少量的低价碘化物,ZrI4气体向高温区进行扩散,在高温区ZrI4气体受热易解离生成Zr和碘原子气体,碘原子向原料扩散,到低温区后反应生成ZrI4。经过碘化处理后,金属锆纯度有明显提高。     

2012年中国锆工业年评

统计了2012年中国锆产业的生产状况,重点分析了生产和进口情况。2012年中国共生产锆英砂约4.0×104t,进口锆英砂总量(折合成精矿)为5.89×105t,总需求量为6.29×105t;生产氧氯化锆197 250 t,生产二氧化锆17 972t,生产硫酸锆6 844 t,生产碳酸锆20 541 t,生产硅酸锆255 000 t,生产电熔锆44 300 t。与2011年相比,中国锆英砂、化学锆及金属锆产量均出现不同程度下降。2012年中国锆企业在需求下降和原料高涨的双重压力下,效益普遍不好。因此,建议我国锆企业大力发展高技术产品,实现产业升级,并能够主动走出去,开发利用国外锆资源。     

ICP-AES测定金红石中的锆

采用全谱直读电感耦合等离子体发射光谱法测定金红石中锆的含量,方法的检出限为0.02μg/mL,回收率为96.50%~101.00%,相对标准偏差锆为2.62%,测定结果令人满意,方法简捷、快速、可信。     

Effect of zirconium on the oxygen solubility in liquid nickel and Ni–Fe melts

The oxygen solubility in liquid nickel containing zirconium is studied experimentally for the first time at 1873 K. The equilibrium constants of the reaction of interaction between zirconium and oxygen dissolved in liquid nickel, the interaction parameters characterizing these solutions, and the zirconium activity coefficient in nickel at infinite dilution are found. The equilibrium constants of the reaction of interaction between zirconium and oxygen dissolved in the melt, the Gibbs energy of the reaction of interaction between zirconium and oxygen, and the interaction parameters characterizing these solutions are calculated at 1873 K for a wide composition range of Ni–Fe alloys. The oxygen solubility in various Ni–Fe melts containing zirconium is found at 1873 K. The deoxidizing capacity of zirconium increases as the iron content increases to 30% and decreases at higher iron content in the melt. This can be explained by the fact that an increase in the iron content lead to, on the one hand, a strengthening of the bonding forces of oxygen atoms in a melt and, on the other hand, to a significant weakening of the bonding forces of zirconium atoms with the base metal.     

DIBK-P204体系萃取锆和铪的动力学

研究了DIBK-P204体系萃取锆和铪的动力学,采用恒界面池法考察搅拌速度、界面积和温度对锆和铪萃取速率的影响。结果表明,DIBK-P204体系对锆和铪萃取速率符合准一级反应,萃取反应的控制类型分别为相内反应控制和混合控制,对锆和铪萃取的表观活化能分别为-32.193kJ/mol和-18.984kJ/mol,升高温度不利于萃取反应的进行。     

碳酸锆生产废水综合利用技术研究

阐述国内碳酸锆生产废水综合利用状况;对利用氢氧化钠水溶液处理技术进行了研究,回收得到氢氧化锆酰,二次废水可达到国家一级排放标准;氢氧化锆酰可返回碳酸锆生产或制备硫酸锆。     

Separation of zirconium from hafnium in nitric acid solutions by solvent extraction using dibutyl butylphosphonate: Part 2. Mixer-settler runs

A process for zirconium/hafnium separation based on the distribution data given in Part 1 (Brown and Healy, 1978) has been successfully tested in a 10-stage Croda mixer-settler. The hafnium content of the zirconium could be reduced below the specification for nuclear grade zirconium. Purification of the zirconium from uranium could be achieved, and the hafnium could be recovered if desired. A flowsheet is presented.     

管道中锆粉云火焰传播的温度与速度特性

粉末状的锆金属不仅燃烧速度快,而且燃烧释放出的热量非常高,作为高能燃料被广泛应用在航天和军工领域.锆金属以粉尘云的形态燃烧时,大量微小悬浮锆颗粒燃烧会形成具有一定面积的火焰,采用实验方法研究锆粉云火焰在竖直管道中的温度和速度特性.研究结果表明,热电偶处的锆粉云最高火焰温度与瞬间火焰传播速度有相同变化趋势,都随锆粉云质量浓度增加先增大后减小.当锆粉云质量浓度为0.625 kg·m-3时,出现最高火焰温度,可达1777.81℃,在此条件下管道中最快火焰传播速度可达39.7 m·s-1.当质量浓度超过0.625 kg·m-3后,热电偶处的锆粉云最高火焰温度与瞬间火焰传播速度都会降低,主要是由于富燃料燃烧、管道中氧气不足而导致颗粒不能完全燃烧.实验得到了不同质量浓度锆粉云的最高火焰温度值与最快火焰传播速度.      

DIBK溶剂萃取法分离锆铪

以二异丁基甲酮(DIBK)作萃取剂,以TBP或P204作改质剂,从不同酸性介质中萃取分离锆铪。考察酸性介质、TBP加入量、P204加入量和盐析剂(NH4)2SO4等对萃取分离锆铪效果的影响。结果表明:DIBK只有在HSCN介质中优先萃取铪,改质剂TBP或P204的加入能显著增加铪的萃取率和锆铪的分离系数。锆铪的分离系数可达到9,与MIBK萃取分离锆铪的性能相似。     

惰气熔融-红外/热导法同时测定锆合金中氧和氮

测定锆合金中氧和氮的方法多为单独测定,操作繁琐,故实验提出了锆合金中氧和氮同时测定的方法。称取0.06g锆合金样品,放入镍篮,投入脱气后的石墨套坩埚中,控制分析功率为5.0kW,氧和氮积分时间分别为40s和60s,以锆合金标样AR640建立校准曲线,实现了惰气熔融-红外/热导法对锆合金中氧和氮含量的同时测定。氧和氮的方法测定下限分别为0.000 7%和0.000 2%。采用实验方法对2个锆合金实际样品中氧和氮进行测定,氧和氮测定结果的相对标准偏差(RSD,n=11)分别为1.5%~4.4%和7.6%~8.6%。按照实验方法测定锆合金标样BCR-276中氧和氮,测定结果与认定值基本一致。     

湿法球磨工艺参数对硅酸锆平均粒度的影响

对锆英砂湿法球磨加工中存在的问题进行了概述和分析,研究了湿法球磨中的球磨机转速、研磨时间、浆料浓度、填充率、球料比等工艺参数对硅酸锆的平均粒度的影响规律。研究结果表明,增加球磨机的转速,延长球磨时间,都会使研磨出的硅酸锆粒度变得更小,且硅酸锆平均粒度变化曲线都呈初期变化大,超过拐点后变化减缓的趋势。填充率和浆料浓度对硅酸锆平均粒度的影响类似,随着填充率或浆料浓度的不断增加,研磨出来的硅酸锆粒度越小,但总体上下降幅度不大,其变化幅度的差别主要来自于罐中水和空气的比例不同。球料比对硅酸锆的平均粒度影响显著,当球料比在2∶1到6∶1的范围内变化时,随着球料比增大,研磨出来的硅酸锆的平均粒度由6.55μm下降到1.82μm。     

Thermodynamics of the oxygen solutions in zirconium-containing iron-nickel melts

Thermodynamic analysis of the oxygen solutions in zirconium-containing iron-nickel melts is carried out. The equilibrium deoxidation constants of the melts by zirconium, the activity coefficients at infinite dilution, and the interaction parameters in melts of various compositions are determined. The dependences of the oxygen solubility in the melts on the nickel or zirconium content are calculated. Zirconium is shown to possess a very high deoxidizing capacity in iron-nickel alloys. The zirconium contents at the minima in oxygen solubility curves and the corresponding minimum oxygen concentrations are determined. As the nickel content in a melt increases to ∼45%, the deoxidizing capacity of zirconium decreases and, then, increases. The deoxidizing capacity of zirconium in pure nickel is noticeably higher than that in pure iron.     

氢化物发生-原子荧光光谱法测定纯锆中微量铋

纯锆被广泛应用于航空航天、航海和核反应堆等领域。铋元素对锆的耐腐蚀性有重要影响,准确测定纯锆中铋含量非常重要。实验建立了氢化物发生-原子荧光光谱法(HG-AFS)测定纯锆中微量铋元素的分析方法。采用HCl-HNO₃-HF可将纯锆完全溶解;以硫脲-抗坏血酸为预还原剂,12g/L硼氢化钾溶液为还原剂,20%(体积分数)盐酸为测定介质,光电倍增管负高压为300V,灯电流为80mA,实现了HG-AFS对纯锆中铋的测定。实验表明锆基体对铋元素测定的干扰可忽略,因此配制标准溶液系列时不需要进行锆基体的匹配。铋校准曲线的线性范围为0.00005%~0.0010%,校准曲线线性相关系数r=0.9998;方法检出限为0.000002%。按照实验方法分析3个纯锆样品中铋,结果的相对标准偏差(RSD,n=10)为0.29%~0.75%;测定结果与电感耦合等离子体质谱法(ICP-MS)基本一致。     

Na2EDTA返滴定法测定铜冶炼烟尘中镉

铜冶炼烟尘中含有较高含量的铅、铜、砷、铝、铁、锑、铋等元素,对滴定法测镉产生干扰。采用氟化铵-盐酸-硝酸-高氯酸分解试样,用氢溴酸除去砷、锑、锡等干扰元素。硫酸铅沉淀分离铅,氨水沉淀分离铁、铋、部分铝等共存元素,在稀硫酸介质中加入硫代硫酸钠使铜离子以硫化亚铜状态从溶液中分离,滤液中加入过量的Na₂EDTA标准滴定溶液,加入氟化钾掩蔽剩余铝,在pH 5.5~5.6的盐酸-六次甲基四胺缓冲溶液中,以二甲酚橙为指示剂,用锌标准滴定溶液返滴定。测得结果为锌、镉合量,扣除锌量,即为镉量。优化了氨水用量、氟化钾用量等实验条件,建立了Na₂EDTA返滴定法测定铜冶炼烟尘中镉含量的方法。方法用于测定铜冶炼烟尘中镉,结果与电感耦合等离子体原子发射光谱法(ICP-AES)一致,结果的相对标准偏差(RSD,n=11)为0.56%~0.92%。按照实验方法对铜冶炼烟尘样品进行加标回收试验,回收率为99.6%～100.2%。     

Effects of ammonia concentration in hydrothermal treatment on structure and redox properties of cerium zirconium solid solution

Cerium zirconium solid solution is a key washcoat material for automotive three-way catalysts(TWCs).However,improving the redox ability and high temperature thermal stability of cerium zirconium solid solution is still a challenge.In this paper,the cerium zirconium solid solution was prepared by a coprecipitation-hydrothermal method,and the effects of the ammonia concentration on their structures and redox properties were investigated.The results show that when the ammonia concentration is 0.8 mol/L,the aged sample(1100℃/10 h)of cerium zirconium solid solution has the highest specific surface area of 23.01 m²/g.Additionally,the increase of ammonia concentration improves the uniformity of phase compositions and increases the oxygen vacancies.When the ammonia concentration reaches 0.4 mol/L,the cerium zirconium solid solution exhibits the best redox activity,with the lowest reduction temperature of 565℃.Therefore,increasing ammonia concentration in the hydrothermal treatment is beneficial to the thermal stability and redox performance of cerium zirconium solid solution.     

铌对氢化锆裂纹行为和氢含量的影响

氢化锫是一种理想的固体中子慢化材料,尤其适用于空间核电源的反应堆,但是高氢含量的氢化锫在制备过程中很容易形成裂纹.Nb是氢化锆中的主要添加元素,对氢化锆的裂纹形成和氢含量有一定影响,这是由Nb在氢化锆中的存在形式决定的,对此进行了研究.结果表明,在吸氢充分的情况下,不同Nb含量的Zr - Nb合金氢化后产物的主要组成都是ZrH2,ZrH1.950和ZrH1.801的ε相氢化锆混合物,Nb的添加对氢化锫的晶格常数和晶胞大小影响不大.Nb改善了氢化锫的多缺陷状态,减少了氢富集的位置,从而起到抑制裂纹产生的作用.常压下,Nb的添加会影响合金的最大吸氢量,尤其当Nb含量在10％以上时,会生成低氢含量的NbHx固溶体,影响锆合金的整体吸氢量.Nb在氢化锆中的固溶度较小,Nb含量较低时,大部分Nb以白色含H锫铌固溶体小颗粒的形式弥散分布在氢化锫表面.     

Settling of undissolved zirconium particles in pure magnesium melts

Zirconium is a remarkable grain refiner for magnesium alloys and is currently introduced into magnesium alloys primarily in the form of a Mg–Zr master alloy (Zirmax^® a Mg–33.3Zr alloy supplied by Magnesium Elektron). Owing to the difficulties of attaining complete dissolution, undissolved zirconium particles are often observed in Zirmax^® alloyed magnesium microstructures in the form of both isolated individual particles varying from submicrometre to greater than 10 μm, and various sizes of clusters that contain a number of zirconium particles. Aimed at improving the alloying efficiency with Zirmax^® and eliminating these undesirable large zirconium inclusions prior to pouring, this paper provides a detailed theoretical and experimental study of the settling behaviour of undissolved zirconium particles in pure magnesium melts. Various characteristics of the settling behaviour of zirconium particles are clarified based on the good agreement achieved between the experimental observations and theoretical predictions. In addition, it is also shown that wet chemical analysis of the total zirconium content in samples taken after different settling times at temperature can be an effective approach for evaluating the settling behaviour of undissolved zirconium particles in pure magnesium melts.