我国锆材料现状及江西锆业发展思路

简要介绍了锆铪资源的分布、特点，在国民经济和国防建设中的意义；重点叙述了我国锆铪工业的发展历史、锆材料现状以及锆铪产品与锆铪产品的生产工艺、技术水平，锆铪材料贸易及应用前景，同时，介绍江西锆业状况与今后的发展思路。     

第二届全国锆铪行业大会暨锆铪发展论坛在京召开

11月2日-3日,由中国有色金属工业协会钛锆铪分会主办的第二届全国锆铪行业大会暨锆铪发展论坛在京召开。这也是钛锆铪分会成立来的第一次探讨我国锆铪发展的大会。近两年来,我国钛工业取得跳跃式进步,2005年海绵钛生产了9511吨,同比年增长97.8%;钛加工材生产了9963吨,同比年增长17.0%;锆铪工业随着我国有色金属工业的高速增长,也取得了重大进步。普通金属锆的产能达到200吨/年,2005年实际生产170吨,同比年增长90%;以氯氧化锆、碳酸锆、硫酸锆、二氧化锆、电熔锆、硅酸锆等产品为主的化学锆制品的年产量已超过16万吨,我国已是一个化学锆制品…     

第二届全国锆铪行业大会暨中国锆铪发展论坛会议纪要

由中国有色金属工业协会钛锆铪分会主办，第二届全国锆铪行业大会暨中国锆铪发展论坛于2006年11月1日至3日在北京召开。来自国内外从事锆铪采选、锆砂加工应用、化学制品生产、锆铪冶炼、锆铪加工、锆铪科研及新材料研发的企业、院所、高校和新闻媒体的代表共170人参加了会议。中国有色金属工业协会党委副书记、副秘书长赵家生，国家科技部黄世兴处长，钛锆铪分会顾问曹春晓院士，中国有色金属学会稀有金属学委会主任张国成院士出席了会议。     

P204—H2SO4体系中萃取富集铪的研究

介绍了用酸性萃取剂Ｐ２０４在Ｈ２ＳＯ４溶液介质中对锆铪萃取分离性能的研究。以Ｎ２３５－Ｈ２ＳＯ４体系萃取分离锆铪制备原子能级氧化锆流程中锆萃余液为料液，研究了Ｐ２０４浓度，平衡时间，洗涤液酸度及草酸浓度对锆铪在有机相中分配比的影响，确定了在Ｐ２０４－Ｈ２ＳＯ４体系中锆铪分离以富集铪的工艺条件。     

五颜六色的添加剂—锆和铪

五颜六色的添加剂—锆和铪金属锆和铪都是高熔点稀有金属，它们象一对“孪生兄弟”，在自然界中经常伴生在一起，二者的化学性质极其相似。直到１９４９年科学家们才成功地将锆和铪分离，这一重大突破，使锆和铪如鱼得水，大显神通。在冶金工业中，锆和铪广泛地用作合金添...     

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。     

紫外级氧化铪的生产工艺研究

紫外级氧化铪具有优异的光学性能和抗激光损伤性能,是制备高功率激光薄膜、高折射率紫外薄膜以及其他光学薄膜的重要材料.锆铪分离足制备紫外级氧化铪的关键.本实验研究了 N235-H2SO4萃取分离锆铪体系的影响因素,并得到用N235-H2SO4萃取分离体系制备低锆氧化铪的最佳工艺.经过4级萃取,制备出含锆量低于0.1%的紫外级氧化铪.     

锆铪材料的性质、应用、生产技术与发展前景

综述锆铪材料的性质、应用领域,介绍国内外锆铪工业现状、锆铪分离与金属制备工艺及材料加工难点;叙述锆铪材料的市场与技术发展前景。     

中国锆业：十年回顾 十年前瞻

中国锆业和中国国民经济的发展同步，我国已建成从锆砂采选生产、锆铪化合物制备、采用冶炼新技术、拥有国际先进水平的锆铪加工工艺和设备完整配套的锆铪工业体系。科技创新将作为重要的发展动力大幅提升中国锆业的水平。     

阴离子交换法分离铪（Ⅳ）中锆（Ⅳ）的研究

了三种强碱笥阴离子交换树脂（Ｄ２９６＊７，Ｄ２９０＊７，２０１＊７）在盐酸、硫酸、硝酸体系中对锆和铪的吸附行为。讨论了在不同浓度的盐酸或硫酸介质中，前述三种树脂对锆和铪吸附的最佳条件。结果表明，在盐酸或硫酸介质中，阴离子交换树脂对锆和铪络阴离子有明显的吸附作用，而在硝酸中基本上无吸附。且Ｄ２９６＊７型树脂对锆和铪吸附效果最好，吸附率最高，实用性好。利用锆和铪中不同浓度盐酸或硫酸中吸附能力的较在磋异     

Effect of Hf and Zr Contents on Stress-rupture and Fatigue Crack Growth Rate Performances in FGH96PM Superalloy

Four experimental FGH96alloys with various contents of Hf and Zr(0and 0.04%,0.3% and 0.04%,0.6% and 0.04%,0.3%and 0.06%,respectively)were produced using PREP(plasma rotating electrode process)+HIP(hot isostatic pressing)route.The unnotched and notched stress-rupture properties and fatigue crack growth rate(FCGR)of all the experimental alloys were investigated to study the effect of Hf and Zr.Relevant fracture morphology and microstructure were observed by scanning electron microscopy and transmission electron microscopy.The results revealed that appropriate content of Hf could lengthen stress-rupture life,eliminate notch sensitivity and slower FCGR.Microstructure analysis showed that the amount ofγ′phase should be increased or decreased by adjusting Hf and Zr contents,and MC carbide and oxide coupled growth should be increased by adding Hf content,which caused oxycarbide to precipitate along grain boundary and strengthen the alloy.It was found that excessive Zr in Hfcontaining FGH96alloy had certain deleterious effects on stress-rupture property because there was strong Zr segregation at prior particle boundary,leaving a long chain of large-size oxides along the boundary.The optimal content of Hf and Zr in FGH96alloy was 0.6%and 0.04%,respectively.     

溴邻苯三酚红—氯化十六烷基三甲铵光度法同时测定锆和铪

本文对Zr(Hf)—BPR—CTMAC体系的多元配合物进行了研究.发现在锆、铪共存时,可利用试剂加入顺序的不同,其锆、铪配合物之吸光度直有极大差异,则可分别测出锆、铪的含量,适用范围为锆(铪)0～37μg/25ml.     

改进的P507在H_2SO_4体系中对锆铪的静态吸附实验

对P507萃淋树脂合成条件进行了改进,并用此合成的P507树脂在H2SO4体系中进行锆铪吸附分离性能的研究。研究了在不同温度与不同酸度下P507树脂对锆铪吸附性能,并求出了分离系数;研究了最佳吸附平衡时间,Hf的不同百分含量时的分离系数以及锆铪洗脱条件。     

Mechanical behavior of zirconium and hafnium in tension and compression

The mechanical behavior and substructural evolution of highly textured hafnium (Hf) has been examined in tension and compression and compared to the mechanical response of zirconium (Zr). The quasi-static work-hardening rate as a function of strain for both metals exhibits a compression-tension asymmetry. Both Zr and Hf exhibit a downward work-hardening response in tension, while each displays a parabolic and then concave upward work-hardening behavior in compression. Additionally, Hf displays higher flow stresses than Zr both in tension and compression. The stress-strain and strain-hardening curves for Zr and Hf have been characterized in terms of their propensity for deformation twinning and evolution of substructure with strain. Differences in the work-hardening rates and flow stresses as a function of the sense of the applied load and material are discussed in terms of slip-twin interactions during deformation.     

Ab-initio analysis of stability of ω-phase in Ti, Zr and Hf under high pressure

The unusual occurrence of ω phase (a three atom simple hexagonal structure) prior to β (bcc) phase under high pressure in group IV transition metals Ti, Zr and Hf has been analyzed through first principles electronic band structure calculations. The analysis of band structure of ω and β phases in the w stability regime suggest that the opening of band gap at the Fermi level in ω phase lowers the total energy of this phase relative to β, and stabilizes the ω phase. Additionally, the extension of band gap near Fermi level is largest in Ti followed by Hf and then Zr suggesting that ω phase is most stable in Ti and least in Zr, in line with the experimental observations. Further, the density of states of ～ 0.33, 0.4 and 0.5, respectively at Fermi energy for ω phase relative to β phase in Ti, Hf and Zr indicates that the lowering in energy for ω is highest in Ti and lowest in Zr.     

Giant Magnetoimpedance Effect in Fe89Zr7-xHfxB4 Ribbon

The giant magnetoimpedance (GMI) effect in Fe89Zr7-xHfxB4 (x=0.5 or 1.0) ribbon annealed at different temperatures was investigated. The results show that some addition of hafnium to Fe-Zr-B raises the GMI effect. There is an optimum annealing temperature about 570℃ for obtaining large GMI behavior in Fe89 Zr7-xHfxB4 (x=0.5 or 1.0) nanocrystalline ribbons. At 900 kHz, the magnetoimpedance for Fe89 Zr6Hf1B4 nanocrystalline ribbon monotonically changes with applied DC field, and reaches-33.4 % at 7 162 A/m. Meanwhile, the results show that the transverse anisotropy field of Fe89 Zr6 Hf1 B4 ribbons decreases with increasing annealing temperature from 520℃ to 620℃.     

Statistical Modeling of Zr/Hf Extraction using TBP–D2EHPA Mixtures

In the present work, response surface methodology was employed for the study and prediction of Zr/Hf extraction curves in a solvent extraction system using D2EHPA-TBP mixtures. The effect of change in the levels of temperature, nitric acid concentration, and TBP/D2EHPA ratio (T/D) on the Zr/Hf extraction/separation was studied by the use of central composite design. The results showed a statistically significant effect of T/D, nitric acid concentration, and temperature on the extraction percentage of Zr and Hf. In the case of Zr, a statistically significant interaction was found between T/D and nitric acid, whereas for Hf, both interactive terms between temperature and T/D and nitric acid were significant. Additionally, the extraction curves were profitably predicted applying the developed statistical regression equations; this approach is faster and more economical compared with experimentally obtained curves.     

偏硼酸锂熔融-电感耦合等离子体原子发射光谱法测定锆矿石中10种元素

锆矿石作为一种重要的战略性矿产,准确分析锆及其共伴生有用有害元素含量对综合评价锆矿资源具有重要意义。然而锆矿石是一种难溶矿石,且在制样过程中Zr、Hf容易水解沉淀。实验通过样品前处理方法的选择和仪器工作条件的优化,建立了偏硼酸锂熔融,稀硫酸+酒石酸提取后电感耦合等离子体原子发射光谱法(ICP-AES)测定锆矿石中Zr、Hf、K、Na、Ca、Mg、Al、Fe、Ti、Mn等10种元素(以氧化物计)含量的方法。利用偏硼酸锂的熔融分解特性制样,熔剂质量为样品质量5倍时可取得较好的处理效果;稀硫酸提取液中加入酒石酸可以抑制Zr、Hf水解;设定仪器工作条件为发生器功率1.3kW、进样速度1.0mL/min、雾化气流量0.7L/min;选择Zr 343.823nm、Hf 277.336nm、K 766.490nm、Na 589.592nm、Ca 317.933nm、Mg 285.213nm、Al 396.153nm、Fe 238.204nm、Ti 334.940nm、Mn 257.610nm为分析谱线进行测定,采用基体匹配法绘制校准曲线消除基体效应的影响。方法中各元素校准曲线的线性相关系数均大于0.9990;各元素的检出限为1.57~58.8μg/g。方法用于测定锆矿石成分分析标准物质GBW07156、GBW07157中Zr、Hf、K、Na、Ca、Mg、Al、Fe、Ti、Mn(以氧化物计),结果的相对标准偏差(RSD,n=10)为0.67%~4.1%,相对误差(RE)为0.13%~4.8%。按照实验方法测定实际样品中各元素(以氧化物计),结果的相对标准偏差(RSD,n=5)为0.27%~4.4%。方法能快速、完全地分解锆矿石,并有效避免Zr、Hf元素的水解,适用于锆矿石中10种元素的准确分析。     

Diffusion Interaction in Fiber-Reinforced Composites of the Chromium Alloy – Silicon Carbide System

Diffusion interaction in the Cr – ZrC and Cr – HfC systems has been studied in the temperature range 1200-1400°C. The impurities contained in chromium or carbides were found to affect the interaction in the systems. Almost no interaction was observed when the systems were held at temperatures up to 1300°C for 100 h. At higher temperatures the carbides were reduced to ZrO₂, HfO₂, and Cr₂₃C₆ because of the presence of a slight amount of oxygen. Thermodynamic calculations indicated no interaction in these systems at temperatures up to 1600°C. A study of the interaction in the systems SiC – ZrC and SiC – HfC showed that a transition zone formed already in the stage of sample preparation by diffusion welding in vacuum (1300°C, vacuum of 10^_3 Pa, with a load applied for 20 min). During annealing (1300°C, 50 h) the transition zone stratified, forming a solid solution of silicon in Zr(Hf)C and SiC inclusions in the SiC – Zr(Hf)C solid solution. A transition zone formed on the zirconium carbide side when SiC interacted with Zr(Hf)C. The interaction in SiC – Zr(Hf)C casts doubt on the use of them as a barrier without antidiffusion layers.