还原氧化钽制备钽粉工艺研究进展

评述了几种由氧化钽还原制取钽粉的新工艺。并阐述了不同方法的工艺原理、特点和产品特性。钠还原法反应时间短,还原温度范围广,能过得到高纯度高比表面的钽粉。FFC法具有工艺简单,污染小,成本低的特点,可以用来制备电容器级粉末。SOM法电解速度快,具有很好的发展前景。采用镁蒸汽还原能够得到性能好的钽粉,但是还原时间长,还原装置复杂。     

电容器用铌粉和钽粉制备技术的进展

综述了铌粉和钽粉的现行生产工艺及几种新的还原方法,介绍了金属热还原反应中的电化学反应机理.钽粉的现行生产工艺几乎都用亨特法,铌粉则大部分采用铝热还原法生产.通过对亨特法还原条件、稀释剂组成等各种工艺参数的改进,已经可以制备纯度高、形态可控的金属钽粉.铌粉新还原方法的研究主要包括金属预成形热还原法、镁等蒸气还原预成形氧化物粉末的方法、镁或钠的蒸气还原氯化物蒸气的气相还原法、以液氨为介质在低温液相中均相还原铌或钽的氯化物的方法、反应媒介熔盐在强搅拌条件下的液体镁热还原金属氧化物的方法等.     

钽铌电子材料新进展(Ⅰ)

代表中国钽铌工业整体水平的宁夏东方有色金属集团有限公司,近年来,研究了钽粉的微观结构,开发出降低杂质含量,改善物理性能等新技术以及Ta2O5钠还原制取高比容钽粉、TaCl5低温钠还原制取纳米级钽粉的新工艺方法;研制并生产出性能优良的、适用于钽电容器的高比容钽粉,同时也开发了高比容铌粉、一氧化铌粉的制造新技术,制得高性能的电容器级铌粉和一氧化铌粉,为铌电容器作为一种新型电容器产业参与竞争提供了优质的基础材料.     

钽铌电子材料新进展(Ⅱ)

代表中国钽铌工业整体水平的宁夏东方有色金属集团有限公司,近年来,研究了钽粉的微观结构,开发出降低杂质含量、改善物理性能等新技术以及钠还原Ta2O5制取高比容钽粉、低温钠TaCl5还原制取纳米级钽粉的新工艺方法;研制并生产出性能优良的、适用于钽电容器的高比容钽粉,同时也开发了高比容铌粉、一氧化铌粉的制造新技术,制得高性能的电容器级铌粉和一氧化铌粉,为铌电容器作为一种新型电容器产业参与竞争提供了优质的基础材料.     

电容器用钽铌粉的研究进展

概括介绍了电容器用钽铌粉的研究进展,介绍了钽粉的3种钠还原制备方法的化学反应机理并进行了比较,同时还介绍了铌粉的制备方法,包括铝热还原法、电解还原法、蒸气还原法、钠还原法和金属热还原法;阐述了钽铌粉中杂质的测定方法以及有关钽铌粉的其它研究进展.     

钙热还原法制备钛粉过程的研究

以颜料级TiO2、分析纯无水CaCl2和金属钙为原料,探索一种真空钙热还原制备金属钛粉的新方法,并借助XRD,SEM/EDS等设备对产物成分和钛粉进行表征。结果表明,添加的CaCl2可有效地减弱烧结影响并增大了气-固反应界面有助于还原反应。当CaCl2与TiO2比例为1∶4时,片状原料在1000℃下和钙蒸气充分反应6h,还原产物酸洗干燥后制备出低杂质含量的钛粉。粒度分布在10～20μm之间,粉末颗粒呈不规则形状,分布均匀且无大块团聚现象。     

真空钙热还原法制备金属钛粉的研究

在真空炉中(30~40 Pa)1273 K下,将物料放入螺纹密封的石墨坩埚中进行不同时间下的还原反应。本文采用热力学分析及X射线衍射、扫描电子显微镜及能量弥散X射线谱等方法与手段,系统研究了金属钙(Ca)与反应器中的氧气(O2)、氮气(N2)、二氧化钛(TiO2)的反应和还原时间及还原产物的预处理对得到金属钛粉(Ti)的影响。通过热力学研究,在温度低于钙的熔点(1115 K)时,密封容器内的O2与Ca的反应及N2与Ca的反应满足反应发生的热力学条件。当温度达到1273K时,Ca的饱和蒸气压p*≈p系,有利于整个气固反应进行。实验研究表明,在还原反应发生前,反应器内的O2,N2与Ca反应完全。将在1273 K下还原时间为4 h得到的还原产物在酸洗前真空挥发处理还原产物表面大量的Ca时,金属单质Ti再次被氧化成低价氧化物,最终得不到金属Ti粉。将反应时间延长至6 h时,酸洗过滤后得到形状不规则、纯度达到98.64%的Ti粉。     

球形Ta2O5/Nb2O5制备方法的研究

研究了用氨沉淀氟钽(或铌)酸溶液制备球形Ta2O5/Na2O5工艺.通过实验探讨了沉淀条件、溶液浓度、沉淀时间、焙烧温度等工艺参数的最佳组合.结果表明,用氨沉淀氟钽(或铌)酸溶液制备球形的Ta2O5/Nb2O5,必须首先得到不规则的Ta(OH)5/Nb(OH)5.要得到不规则Ta(OH)5/Nb(OH)5,反应时搅拌强度要大,搅拌速率应控制在800～1 200 r/min,反应结束后继续搅拌10～20 min,终点pH值控制为8.5;氟钽(或铌)酸溶液浓度为60～80 g/L沉淀10 min,浓度为120～140 g/L沉淀15 min,之后可得到不规则Ta(OH)5/Nb(OH)5.再在800～850℃,焙烧6 h可得到球形Ta2O5/Nb2O5.     

钽粉制备工艺研究进展

介绍了制备金属钽粉的传统工艺氟钽酸钾钠热还原工艺及其发展状况,评述了几种制备金属钽粉的最新工艺,包括均相还原法、电子间接还原法、氧化钽加氯化钙钠还原法及FFC法,阐明了新方法的原理及特点,并提出了钽粉生产今后的发展方向.     

热处理温度对钽粉性能的影响

用钠还原氟钽酸钾得到的原粉分别在1 350,1 400,1 450℃温度下进行热处理,得到的3种钽粉按照相同的条件进行镁还原脱氧处理,测试钽粉的化学成分、物理性能和电性能.表明提高热处理温度:可降低钽粉氧,钾,钠杂质含量,平均粒径和松装密度增大,细粉比例和收缩率降低,颗粒强度和坯块强度提高;在条件I下赋能的钽粉比容、漏电流、损耗降低;在条件Ⅱ下赋能的钽粉漏电流和损耗降低,比容提高.因此,热处理温度低的钽粉适合在较低温度下烧结、低压赋能制作电容器;而热处理温度高的钽粉适合于较高温度烧结和较高电压赋能制作电容器.     

Some phase relationships within the system Na2O/B2O3/Nb2O5

Phase behaviour over regions of the ternary system Na₂O/B₂O₃/Nb₂O₅ has been explored.Liquidus temperatures and the stability regions of primary phases have been determined over selected composition ranges by high temperature microscopy. Crystallisation processes in melts and corresponding glasses have been followed using both conventional methods of thermal analysis and newly developed micro techniques combined with hot stage microscopy.An electron microscope has been employed to follow changes in the microstructure of quenched glasses after controlled heat treatments.It has been shown that the system contains a liquid immiscibility gap, and some attention is given in the discussions to the influence that can be assigned to cations in determining the extent of such gaps and general structural relationships in borate/oxide systems.     

去除Ta2O5/Nb2O5中杂质S的工艺研究

从理论和实际应用方面,研究了去除Ta2O5/Nb2O5中杂质S的方法.通过对制取高纯Ta2O5和Nb2O5的中间产品高纯Ta(OH)5/Nb(OH)3进行过氧化处理,改变Ta,Nb,S等元素在物料中的存在方式,增大了含S杂质的溶解性,降低了物料对含S离子的吸附能力及硫酸盐的分解温度,通过洗涤、焙烧达到有效去除产品中杂质元素S的目的.该方法可在不影响Ta2O5/Nb2O5产品质量的情况下,使杂质S降低到0.0001%以下.     

Optical absorption spectra of evaporated V2O5 and co-evaporated V2O5/B2O3 thin films

The optical absorption spectra of evaporated V₂O₅ and co-evaporated V₂O₅/B₂O₃ thin films have been studied. For higher photon energies, the absorption is found to be due to a direct forbidden electronic transition process from the oxygen 2p band to the vanadium 3d band in a similar way to that observed in crystalline V₂O₅. The exponential behaviour of absorption edge for lower photon energies is attributed to the electronic transitions between the tailed-off d-d states corresponding to V⁴⁺ ions. For co-evaporated V₂O₅/B₂O₃ films the optical energy gap is observed to increase with the increase in V₂O₅ content of the composite films.     

V2O5/polypyrrole core-shell nanotubes for gas sensor

V2O5/polypyrrole core-shell nanotubes have been synthesized through an in situ polymerization of pyrrole monomers in the presence of prepared vanadium oxide nanotubes. Formation of polypyrrole in core-shell structure was endorsed by FTIR spectral analyses. Transmission electron microscopy images revealed that one dimensional morphology of vanadium oxide nanotubes remained undisturbed upon coating of polypyrrole, and polypyrrole was uniformly coated on the surface of vanadium oxide nanotubes, with a thickness of 30 nm. XRD suggested certain synergetic interaction existed in the core-shell structure, probably resulting in the enhanced thermal stability of polypyrrole coatings. The gas tests showed that the core-shell structure exhibited a high response, good stability and a short response/recovery time in the detection of different concentrations of ethanol at room temperature, implying its potential application for gas sensors. The enhanced gas sensing properties due to the synergic interaction between intimately contacted polypyrrole and vanadium oxide nanotubes lead to the formation of a hetero p-n junction with a depletion region, which is similar to a field effect transistor. The gas effects a change of the depletion region and thus modulates the conductivity of the junction.     

Infrared absorption spectra of evaporated V2O5 and co-evaporated V2O5/B2O3 thin films

The Fourier transform infrared spectra of different compositions of evaporated V₂O₅/B₂O₃ thin films have been investigated. Most of the absorption bands corresponding to V₂O₅ and B₂O₃ films coincide with those reported by other authors. The short-range order in amorphous V₂O₅ films is found to be conserved. The absorption spectra indicate a boroxol ring structure for B₂O₃ films. In co-evaporated V₂O₅/B₂O₃ films the boron is observed to substitute in the V₂O₅ network such that the coordination number of vanadium ion remains unchanged. The presence of a number of bands corresponding to -OH groups indicates the hygroscopic character of the films.     

Optical absorption studies for TeO2-P2O5 and Bi2O3-TeO2-P2O5 glasses

A range of TeO₂-P₂O₅ and Bi₂O₃-TeO₂-P₂O₅ glass systems were prepared. The optical absorption spectra were measured in the spectral range 300–800 nm and it was found that the fundamental absorption of these glasses is dependent on the glass composition. The optical energy gap of binary glasses increases with increasing TeO₂ content while the addition of Bi₂O₃ to TeO₂-P₂O₅ decreases the optical energy gap. The absorption edges of these glasses arise from direct forbidden transitions and occur at photon energies in the range of 2.17 to 2.97 eV for TeO₂-P₂O₅ glasses and 2.63 to 2.32 eV for Bi₂O₃-TeO₂-P₂O₅ glasses depending on their composition.     

Electron spin resonance studies of evaporated V2O5 and co-evaporated V2O5/B2O3 thin films

Electron spin resonance studies of evaporated V₂O₅ and co-evaporated V₂O₅/B₂O₃ amorphous thin films have been made. For lower molar contents of B₂O₃, the co-evaporated V₂O₅/B₂O₃ films show poorly resolved hyperfine structure, whereas for higher content of B₂O₃ the hyperfine spectra are well resolved. This behaviour of films is attributed to the increase in the lifetime of a particular V⁴⁺ ion due to Anderson localization of charge, as the degree of disorder increases with increase in the molar content of B₂O₃. The unpaired electron at a given time is localized on a single ⁵¹V nucleus. The low intensity of ESR signal for higher concentration of V₂O₅ in the co-evaporated V₂O₅/B₂O₃ films has been related to the less effective concentration of V⁴⁺ ions due to antiferromagnetic coupling of the V⁴⁺ ions.     

Electrical conduction through MIM structures of evaporated V2O5 and V2O5/B2O3 amorphous thin films

The electrical conduction through vacuum-evaporated thin films of V₂O₅ and V₂O₅/B₂O₃ in MIM structures has been investigated. The high-field behaviour of both types of film is in accordance with the Poole-Frenkel type of mechanism. The increase in B₂O₃ content in co-evaporated V₂O₅/B₂03 films results in a decrease in the conductivity of the composite films. This is attributed to the expansion of the resultant film structure due to the network-forming effect of B₂O₃. The covaporated thin films of V₂O₅/B₂O₃ with a molar content of B₂O₃ larger than 40% are observed to be unstable because of their hygroscopic nature.