D296树脂吸附分离锆铪试验研究

研究了用D296树脂从硫酸体系中吸附锆、铪,考察了吸附时间、初始料液质量浓度、温度、硫酸浓度对树脂吸附锆、铪及锆、铪分离系数的影响及吸附反应动力学。结果表明:溶液中锆离子质量浓度为120g/L、温度1℃、硫酸浓度1.6mol/L条件下,D296树脂对锆、铪的静态吸附分离系数最大,为1.19。动力学研究结果表明,D296树脂吸附锆离子的控制步骤为液膜扩散,D296树脂吸附锆离子的活化能E=158.639kJ/mol。     

阴离子交换法分离铪(IV)中锆(IV)的研究

研究了三种强碱性阴离子交换树脂 (D2 96 7,D2 90 7,2 0 1 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D2 96 7型树脂对锆和铪吸附效果最好 ,吸附率最高 ,实用性好。利用锆和铪在不同浓度盐酸或硫酸中吸附能力的较大差异 ,可望做到锆和铪的成功分离。     

P507萃取锆和铪及分离性能

以氯氧化锆(铪)溶液为料液, 用2-乙基己基膦酸单2-乙基己基酯(P507)萃取剂在盐酸介质中萃取锆铪.研究了P507浓度、料液浓度、萃取温度和时间、盐酸或氯离子浓度、添加剂浓度等因素对锆铪萃取率、分配比和分离系数的影响.结果表明: P507萃取锆铪的反应为吸热反应; 萃取速率较慢, 平衡时间≥40 min, 改变金属离子和萃取剂浓度, 以及在有机相中添加仲辛醇等均难以使萃取速率得到有效提高; 饱和法测得有机相中萃取剂与金属离子的物质的量之比为3左右; 锆、铪的分配比随着P507浓度的增加而增加, 但增加的幅度在低浓度区域和高浓度区域各不相同.锆铪之间的分离系数在萃取剂浓度0.9 mol·L-1附近呈极小值; 盐酸和氯离子浓度的影响较复杂, 呈波浪式变化.     

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     

强碱性阴离子树脂分离富集光度法测定锆和铪的研究

研究了 2 0 1× 7型强碱性阴离子树脂在硫酸和高氯酸介质中对锆和铪的吸附行为 ,讨论了 2 0 1× 7型强碱性阴离子树脂对锆和铪的吸附和洗脱的最佳条件 ,分离后用分光光度法进行测定 ,方法灵敏、准确。用于多种样品的测定结果令人满意。     

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。     

合金渣中铪的MIBK萃取分离试验

采用MIBK作为萃取剂,在盐酸体系下,对含铪合金渣中的铪进行萃取分离试验,主要考察合金渣中含量较高的锆、钛、铬和铪在萃前液不同氢离子浓度、NH4SCN浓度、有机相HSCN浓度及相比下的分离性能。结果表明,铪和锆钛分离难度较大、和铬分离较易,铪的最优分离条件为:萃前液氢离子浓度0.96mol/L、萃前液NH4SCN浓度2.56mol/L、有机相HSCN浓度2.73 mol/L、相比1。在最优条件下,铪和锆的相对分离系数为6.63,铪的分配比为1.79,对于锆含量较低的合金渣,可以有效提升锆铪分离效率,钛最好于萃取分离前进行分离。     

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。     

湿法分离锆铪的研究进展

锆铪分离是制备核级锆和铪的技术关键。简单综述了工业上生产核级锆铪的主要溶剂萃取分离工艺,即甲基异丁基酮(MIBK)法、磷酸三丁酯(TBP)法、三辛胺或三烷基叔胺(TOA或N235)法,并对各种工艺流程的优劣进行了技术分析,重点介绍了中性萃取体系、酸性萃取体系、螯合萃取体系、碱性萃取体系和协同萃取体系等溶剂萃取分离锆铪技术的新进展。另外,还阐述了其他锆铪湿法分离的方法如分步结晶和沉淀法、吸附分离法、膜分离法、微溶剂萃取法、双水相萃取法和液膜萃取法对锆铪进行富集和分离的现状。可以发现,新开发的锆铪湿法分离技术大都是优先分离锆铪原料中含量较多的锆,且大多仅进行了分离工艺的研究,而对锆铪分离的机制、热力学和动力学的相关研究较少。为了提高分离效率和保护环境,开发优先萃取铪且环境友好型的绿色分离体系显得尤为必要。     

P507/HZ818浸渍树脂在硫酸体系中选择性吸附铟(Ⅲ)的性能

以苯乙烯-二乙烯基苯大孔树脂(HZ818)为载体、2-乙基己基磷酸单(2-乙基己基)酯(P507)为萃取剂制备了P507/HZ818浸渍树脂,并用扫描电镜(SEM)和红外光谱(IR)对其进行了表征。研究了该浸渍树脂在硫酸体系中选择性吸附In(Ⅲ)的性能。静态吸附实验表明:在In、Ga二元体系中,P507/HZ818浸渍树脂能够较好地选择性吸附In,In/Ga分离系数在溶液pH=1.2时达到最大;在In、Ga、Zn、Fe、Cu多元混合体系中,浸渍树脂对In的选择性吸附在溶液pH=0.9时效果最好。动态吸附实验表明:控制In、Ga二元体系溶液pH=1.2,浸渍树脂柱对Ga(Ⅲ)没有吸附作用,仅选择性吸附了In(Ⅲ),实现了In、Ga的分离;控制In、Ga、Zn、Fe、Cu多元体系溶液pH=0.9,可以较好地实现In的富集。     

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、Mg285.213nm、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0.9...     

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.     

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.     

锆铪丝材加工及其在等离子切割电极中的应用

简要介绍了锆铪丝材加工水平及其在等离子切割用电极中的应用现状，分析了等离子切割电极的结构原理及其寿命的影响因素，探讨了锆铪丝材质量对电极寿命的影响作用，从而指出提高锆铪丝材质量、改进电极加工方法对延长电极寿命、促进等离子切割技术的发展具有重要意义。     

改性三钛酸钠晶须对钼(Ⅵ)吸附行为的研究

利用浸渍法对三钛酸钠晶须进行表面改性,制备出改性三钛酸钠晶须,并用扫描电镜(SEM)等手段对其进行了表征。以其为吸附剂,电感耦合等离子体原子发射光谱(ICP-AES)为分析手段,探讨了改性三钛酸钠晶须在静态吸附条件下对Mo(Ⅵ)的吸附性能;考察了影响其吸附和解脱的主要因素及在优化条件下Mo(Ⅵ)的吸附容量;研究了常见共存离子的影响,并做了选择性比较实验。结果表明:在pH 2.0下,0.300 0 g改性三钛酸钠晶须对Mo(Ⅵ)的吸附率可达到99%以上;10 mL 0.1 mol/L NH3.H2O作为解脱剂可使Mo(Ⅵ)定量解脱;优化条件下Mo(Ⅵ)的吸附容量为8.3 mg/g;与改性前相比,改性三钛酸钠晶须对Mo(Ⅵ)的吸附性和选择性更好;将其用于水样测定,结果满意。     

CTS凝胶球表面印迹钼酸根吸附材料的制备

以壳聚糖(CTS)为基材,钼酸根离子为印迹离子,制备了一种新的CTS表面阴离子印迹凝胶球。以Mo(Ⅵ)的吸附量作为评价指标,对凝胶球的制备条件进行了优化。结果表明,当CTS质量分数为2%,凝固浴温度为20℃,钼酸铵和三乙醇胺的质量分数分别为2%和11%,热处理温度为60℃,洗脱剂NaOH的浓度为8.0g/L时,所制备的凝胶球吸附性能较佳。与不添加印迹阴离子的壳聚糖凝胶球相比,这种CTS表面阴离子印迹凝胶球吸附容量有了大幅度提升。     

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.     

Transition metal alloys of extraordinary stability; An example of generalized Lewis-acid-base interactions in metallic systems

The Engel theory of metals predicts unusually high thermodynamic stability for certain classes of alloys of transition metals for which generalized Lewis-acid-base interactions are possible. To test these predictions, phase equilibria were studied for ternary systems of Zr, C, and the transition metals Re, Ru, Os, Rh, Ir, Pd, Pt, Ag, and Au. Similar literature data for Nb, Ta, Hf, Th, Y, Ce, Er, and Pu with Re, Ru, Rh, Ir, Pt, and Au were evaluated. Thermodynamic data for the carbides of Zr, Hf, Th, Nb, Ta, U, and Y were critically evaluated, tabulated for 1200 to 2300 K, and used to fix the Gibbs energies of formation in kcal/g-atom of alloy, or their limits, for the binary phases of the above metals. In addition, for Zr, activity coefficients and excess Gibbs energies are tabulated. The predicted high stabilities for alloys of Rh, Ir, Pd, and Pt are confirmed with excess Gibbs energies ranging to —100 kcal/g-atom and activity coefficients as low as 10^-12 for zirconium or hafnium in dilute solutions of platinum at 1800 K. Some of the properties of these unusually stable compounds have been measured. An erratum to this article is available at .     

几种螯合树脂在模拟的钴电解液中吸附铜的性能研究

对比研究了三种亚胺二乙酸螯合树脂D850、D463、D751、一种氨膦酸基螯合树脂D860及一种氨甲基吡啶树脂CuWRAM在模拟的钴电解液的硫酸盐体系、氯盐体系及硫酸盐-氯盐混合体系中吸附铜的性能.结果表明:五种树脂均在料液pH较高的条件下对铜的吸附容量最大,其中以D860的对铜的交换容量最大,以CuWRAM对铜的交换...