高熔点金属氢氩等离子弧纯化研究
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摘要
高熔点金属在电子、化工、原子能、航空航天、武器装备等领域具有广泛应用,但是都含有一定量的气体杂质元素、金属和非金属杂质元素,以及各类物理"杂质"(晶体缺陷)等,这些杂质含量在达到一定浓度时对材料的物理与化学性能会产生很大的影响,因此需要对高熔点金属进行有效提纯。采用Ar-H_2等离子体电弧熔炼纯化高熔点金属Zr,利用氢气较高的还原性以及电离态的氢原子具有极高的热导率来增强提纯效果,并进行了成分和含量测定、元素蒸气压分析和硬度测量。结果表明, Ar-H_2等离子体电弧熔炼能够有效提高高熔点金属Zr的纯度,明显降低杂质元素的含量,并且随着纯度的提高,硬度逐渐降低,符合金属越纯其硬度越小的原理。与未提纯金属Zr(纯度96.4%)相比,在熔炼10 min时,纯氩气条件下样品纯度达到98.09%;通入5%氢气时,样品最终纯度为98.18%;通入10%氢气时,样品最终纯度为98.22%。在30 min时,纯氩气条件下样品纯度达到98.12%; 5%氢气的样品纯度为98.21%; 10%氢气的样品纯度为98.23%。
High melting point metals are widely used in the fields of electronics, chemical industry, atomic energy, aerospace, weaponry, but they all contain a certain amount of gas impurity elements, metal and non-metallic impurity elements, as well as various physical "impurities"(crystal defects), the content of these impurities in a certain concentration will have a great impact on the physical and chemical properties of the material, so it is necessary to effectively purify high melting point metals. In this paper, Ar-H_2 plasma arc melting was used to purify the high melting point metal Zr. The purification effect was enhanced by the high reduction of hydrogen and the extremely high thermal conductivity of the hydrogen atoms in the ionization state, and the composition and content were determined. Element vapor pressure analysis and hardness measurement were completed. The results showed that Ar-H_2 plasma arc melting could effectively improve the purity of high melting point metal Zr and decrease the content of impurity elements, and with the increase of purity, the hardness decreased gradually, which accorded with the principle that the more pure metal was, the smaller the hardness was. Compared with the unpurified metal Zr(96.4%), the purity of the sample was 98.09% in pure argon, 98.18% in 5% hydrogen and 98.22% in 10% hydrogen, respectively. At 30 min, the purity of the sample reached 98.12% in pure argon gas. The purity of the sample in10% hydrogen was 98.21% and the purity of that in 5% hydrogen was 98.23%.
High melting point metals are widely used in the fields of electronics, chemical industry, atomic energy, aerospace, weaponry, but they all contain a certain amount of gas impurity elements, metal and non-metallic impurity elements, as well as various physical "impurities"(crystal defects), the content of these impurities in a certain concentration will have a great impact on the physical and chemical properties of the material, so it is necessary to effectively purify high melting point metals. In this paper, Ar-H_2 plasma arc melting was used to purify the high melting point metal Zr. The purification effect was enhanced by the high reduction of hydrogen and the extremely high thermal conductivity of the hydrogen atoms in the ionization state, and the composition and content were determined. Element vapor pressure analysis and hardness measurement were completed. The results showed that Ar-H_2 plasma arc melting could effectively improve the purity of high melting point metal Zr and decrease the content of impurity elements, and with the increase of purity, the hardness decreased gradually, which accorded with the principle that the more pure metal was, the smaller the hardness was. Compared with the unpurified metal Zr(96.4%), the purity of the sample was 98.09% in pure argon, 98.18% in 5% hydrogen and 98.22% in 10% hydrogen, respectively. At 30 min, the purity of the sample reached 98.12% in pure argon gas. The purity of the sample in10% hydrogen was 98.21% and the purity of that in 5% hydrogen was 98.23%.
引文
[1] Liu W,Ding L L,Li J W,Wei S Z.Recovery of rhenium and molybdenum from dust of roasted molybdenum concentrate by oxidized alkali fusion followed by water leaching [J].Chinese Journal of Rare Metals,2018,42(9):959.(刘伟,丁留亮,李继文,魏世忠.碱熔-水浸法从钼精矿焙烧烟灰中回收铼和钼 [J].稀有金属,2018,42(9):959.)
[2] Takada J,Nagae M,Hiraoka Y,Takemoto Y.High melting point metal based alloy material having high toughness and strength [P].US:US 6589368 B1.2003.
[3] Katoh M,Nakazuka H.A simple vacuum evaporation method of high melting-point metals and its application [J].Journal of Electron Microscopy,1977,26(3):219.
[4] Andrievski R A.High-melting-point compounds:new approaches and new results [J].Physics Uspekhi,2017,60(3).
[5] Zee R H,Xiao Z,Chin B A,Liu J.Processing of single crystals for high temperature applications [J].Journal of Materials Processing Technolgy,2001,113(1-3):75.
[6] Feng Z Y,Huang X W,Wang M,Zhang G C.Progress and trend of green chemistry in extraction and separation of typical rare earth resources [J].Chinese Journal of Rare Metals,2017,41(5):604.(冯宗玉,黄小卫,王猛,张国成.典型稀土资源提取分离过程的绿色化学进展及趋势 [J].稀有金属,2017,41(5):604.)
[7] Waseda Y,Isshiki M.Purification Process and Characterization of Ultra High Purity Metals:Application of Basic Science to Metallurgical Processing [M].Springer Berlin Heidelberg,2002.1.
[8] Eerden J P V D,Bruinsma O S L.Science and Technology of Crystal Growth [M].Springer Netherlands,1995,103(2):259.
[9] Li L P,Hu Z W,Yin T,Zhang W,Gao X Q,Guo L J.Development of single crystals of high-purity refractory metals and alloys [J].Materials China,2014,(z1):560.(李来平,胡忠武,殷涛,张文,高选乔,郭林江.高纯难熔金属及其合金单晶的发展 [J].中国材料进展,2014,(z1):560.)
[10] Zhang X Q,Jiang Y J,Dai Q.Preparation of high purity gadolinium by vacuum distillation [J].Baotou Steel Technology,2007,33(3):17.(张小琴,姜银举,代清.真空蒸馏法制备高纯金属钆 [J].包钢科技,2007,33(3):17.)
[11] Zhang Y W,Ding W Z,Guo S Q,Xu K D.Reduction of metal oxide in nonequilibrium hydrogen plasma [J].Chinese Journal of Nonferrous Metals,2004,14(2):317.(张玉文,丁伟中,郭曙强,徐匡迪.等离子态氢还原金属氧化物初探 [J].中国有色金属学报,2004,14(2):317.)
[12] Zheng S B.Basic research on hydrogen metallurgyand new ironmaking idea-process [J].China Metallurgy,2012,22(7):1.(郑少波.氢冶金基础研究及新工艺探索 [J].中国冶金,2012,22(7):1.)
[13] Cao C Z,Guo P M,Zhao P,Pang J M.Technology analysis on fluidized bed hydrogen metallurgy at low temperature [J].Iron Steel Vanadium Titanium,2008,29(4):1.(曹朝真,郭培民,赵沛,庞建明.流化床低温氢冶金技术分析 [J].钢铁钒钛,2008,29(4):1.)
[14] Cao C Z,Guo P M,Zhao P,Pang J M.Study on high temperature smelting hydrogen metallurgy [J].Iron Steel Vanadium Titanium,2009,30(1):1.(曹朝真,郭培民,赵沛,庞建明.高温熔态氢冶金技术研究 [J].钢铁钒钛,2009,30(1):1.)
[15] Xu K D,Jiang G C,Xu J L.Theoretical Analysis of Iron and Steel Production Process in the 21st Century [M].Beijing:National Natural Science Foundation,1999.45.(徐匡迪,蒋国昌,徐建伦.21世纪钢铁生产流程的理论解析 [M].北京:国家自然科学基金委员会,1999.45.)
[16] Li G L,Tian F,Li L,Tian W H,Li X G.Application of hydrogen plasma arc melting technique on refining refractory metals [J].Rare Metal Materials and Engineering,2015,44(3):775.(李国玲,田丰,李里,田文怀,李星国.氢等离子体电弧熔炼技术在难熔金属提纯中的应用 [J].稀有金属材料与工程,2015,44(3):775.)
[17] Gracianov.Precision Alloy Metallurgy [M].Beijing:Beijing Metallurgical Research Press,1976.94.(格兰基阿诺夫.精密合金冶金学 [M].北京:北京冶金研究出版社,1976.94.)
[18] Elanski D,Lim J W,Mimura K,Isshiki M.Impurity removal from Zr,Nb and Ta metals by hydrogen plasma arc melting and thermodynamic estimation of hydride formation [J].Journal of Alloys & Compounds,2006,413(1-2):251.
[19] Li G L,Guo H,Li L,Wang C Y,Zheng J,Tian W H,Li H P,Li X G.Purification of terbium by means of argon and hydrogen plasma arc melting [J].Journal of Alloys & Compounds,2016,659:1.
[20] Mimura K,Lim J W,Oh J M,Choi G S,Cho S W,Uchikoshi M,Isshiki M.Refining effect of hydrogen plasma arc melting on titanium sponges [J].Materials Letters,2010,64(3):411.
[21] Lalev G M,Lim J W,Munirathnam N R,Choi G S,Uchikoshi M,Mimura M,Isshiki M.Concentration behavior of non-metallic Impurities in Cu rods refined by argon and hydrogen plasma-arc zone melting [J].Materials Transactions,2009,50(3):618.
[22] Li G L.Study on High Purification Process and Mechanism of Rare Earth Metal Gadolinium and Terbium [D].Beijing:University of Science and Technology Beijing,2016.130.(李国玲.稀土金属钆铽高纯化过程与机理研究 [D].北京:北京科技大学,2016.130.)
[23] Elanski D,Mimura K,Ito T,Isshiki M.Purification of tantalum by means of hydrogen plasma arc melting [J].Materials Letters,1997,30(1):1.
[24] Li G L,Li L,Miao R Y,Tian W H,Yan S H,Li X G.Research on the removal of impurity elements during ultra-high purification process of terbium [J].Vacuum,2016,125:21.
[25] Lim J W,Mimura K,Miyawaki D,Oh J M,Choi G S,Kim S B,Uchikoshi M,Isshiki M.Hydrogen effect on refining of Mo metal by Ar-H2,plasma arc melting [J].Materials Letters,2010,64(21):2290.
[2] Takada J,Nagae M,Hiraoka Y,Takemoto Y.High melting point metal based alloy material having high toughness and strength [P].US:US 6589368 B1.2003.
[3] Katoh M,Nakazuka H.A simple vacuum evaporation method of high melting-point metals and its application [J].Journal of Electron Microscopy,1977,26(3):219.
[4] Andrievski R A.High-melting-point compounds:new approaches and new results [J].Physics Uspekhi,2017,60(3).
[5] Zee R H,Xiao Z,Chin B A,Liu J.Processing of single crystals for high temperature applications [J].Journal of Materials Processing Technolgy,2001,113(1-3):75.
[6] Feng Z Y,Huang X W,Wang M,Zhang G C.Progress and trend of green chemistry in extraction and separation of typical rare earth resources [J].Chinese Journal of Rare Metals,2017,41(5):604.(冯宗玉,黄小卫,王猛,张国成.典型稀土资源提取分离过程的绿色化学进展及趋势 [J].稀有金属,2017,41(5):604.)
[7] Waseda Y,Isshiki M.Purification Process and Characterization of Ultra High Purity Metals:Application of Basic Science to Metallurgical Processing [M].Springer Berlin Heidelberg,2002.1.
[8] Eerden J P V D,Bruinsma O S L.Science and Technology of Crystal Growth [M].Springer Netherlands,1995,103(2):259.
[9] Li L P,Hu Z W,Yin T,Zhang W,Gao X Q,Guo L J.Development of single crystals of high-purity refractory metals and alloys [J].Materials China,2014,(z1):560.(李来平,胡忠武,殷涛,张文,高选乔,郭林江.高纯难熔金属及其合金单晶的发展 [J].中国材料进展,2014,(z1):560.)
[10] Zhang X Q,Jiang Y J,Dai Q.Preparation of high purity gadolinium by vacuum distillation [J].Baotou Steel Technology,2007,33(3):17.(张小琴,姜银举,代清.真空蒸馏法制备高纯金属钆 [J].包钢科技,2007,33(3):17.)
[11] Zhang Y W,Ding W Z,Guo S Q,Xu K D.Reduction of metal oxide in nonequilibrium hydrogen plasma [J].Chinese Journal of Nonferrous Metals,2004,14(2):317.(张玉文,丁伟中,郭曙强,徐匡迪.等离子态氢还原金属氧化物初探 [J].中国有色金属学报,2004,14(2):317.)
[12] Zheng S B.Basic research on hydrogen metallurgyand new ironmaking idea-process [J].China Metallurgy,2012,22(7):1.(郑少波.氢冶金基础研究及新工艺探索 [J].中国冶金,2012,22(7):1.)
[13] Cao C Z,Guo P M,Zhao P,Pang J M.Technology analysis on fluidized bed hydrogen metallurgy at low temperature [J].Iron Steel Vanadium Titanium,2008,29(4):1.(曹朝真,郭培民,赵沛,庞建明.流化床低温氢冶金技术分析 [J].钢铁钒钛,2008,29(4):1.)
[14] Cao C Z,Guo P M,Zhao P,Pang J M.Study on high temperature smelting hydrogen metallurgy [J].Iron Steel Vanadium Titanium,2009,30(1):1.(曹朝真,郭培民,赵沛,庞建明.高温熔态氢冶金技术研究 [J].钢铁钒钛,2009,30(1):1.)
[15] Xu K D,Jiang G C,Xu J L.Theoretical Analysis of Iron and Steel Production Process in the 21st Century [M].Beijing:National Natural Science Foundation,1999.45.(徐匡迪,蒋国昌,徐建伦.21世纪钢铁生产流程的理论解析 [M].北京:国家自然科学基金委员会,1999.45.)
[16] Li G L,Tian F,Li L,Tian W H,Li X G.Application of hydrogen plasma arc melting technique on refining refractory metals [J].Rare Metal Materials and Engineering,2015,44(3):775.(李国玲,田丰,李里,田文怀,李星国.氢等离子体电弧熔炼技术在难熔金属提纯中的应用 [J].稀有金属材料与工程,2015,44(3):775.)
[17] Gracianov.Precision Alloy Metallurgy [M].Beijing:Beijing Metallurgical Research Press,1976.94.(格兰基阿诺夫.精密合金冶金学 [M].北京:北京冶金研究出版社,1976.94.)
[18] Elanski D,Lim J W,Mimura K,Isshiki M.Impurity removal from Zr,Nb and Ta metals by hydrogen plasma arc melting and thermodynamic estimation of hydride formation [J].Journal of Alloys & Compounds,2006,413(1-2):251.
[19] Li G L,Guo H,Li L,Wang C Y,Zheng J,Tian W H,Li H P,Li X G.Purification of terbium by means of argon and hydrogen plasma arc melting [J].Journal of Alloys & Compounds,2016,659:1.
[20] Mimura K,Lim J W,Oh J M,Choi G S,Cho S W,Uchikoshi M,Isshiki M.Refining effect of hydrogen plasma arc melting on titanium sponges [J].Materials Letters,2010,64(3):411.
[21] Lalev G M,Lim J W,Munirathnam N R,Choi G S,Uchikoshi M,Mimura M,Isshiki M.Concentration behavior of non-metallic Impurities in Cu rods refined by argon and hydrogen plasma-arc zone melting [J].Materials Transactions,2009,50(3):618.
[22] Li G L.Study on High Purification Process and Mechanism of Rare Earth Metal Gadolinium and Terbium [D].Beijing:University of Science and Technology Beijing,2016.130.(李国玲.稀土金属钆铽高纯化过程与机理研究 [D].北京:北京科技大学,2016.130.)
[23] Elanski D,Mimura K,Ito T,Isshiki M.Purification of tantalum by means of hydrogen plasma arc melting [J].Materials Letters,1997,30(1):1.
[24] Li G L,Li L,Miao R Y,Tian W H,Yan S H,Li X G.Research on the removal of impurity elements during ultra-high purification process of terbium [J].Vacuum,2016,125:21.
[25] Lim J W,Mimura K,Miyawaki D,Oh J M,Choi G S,Kim S B,Uchikoshi M,Isshiki M.Hydrogen effect on refining of Mo metal by Ar-H2,plasma arc melting [J].Materials Letters,2010,64(21):2290.