高性能抗震掺杂钨丝的制备研究
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摘要
随着国家经济的发展,交通运输、国防等工业需大量从国外进口工作环境恶劣条件下不易下垂和震断的高性能抗震钨丝。本文探索并明确了在普通掺杂钨丝的工艺生产基础上制备出具有良好高温抗下垂性能和抗震性能的高掺杂钨丝的生产技术。
本论文认为在掺杂钨丝制备的粉末冶金阶段对钨丝的高温性能与抗震性能有关键的影响:
1)选用各种杂质含量小于50ppm,晶粒形貌为单斜晶六方形结构,流动性能良好的仲钨酸铵在温度260～460℃、氢气流量:0.3～0.5m~3/h条件下还原获得粒度为9.1μm的蓝色氧化钨。
2)往蓝色氧化钨中添加K、Si、Al、Co元素在550～870℃下经过两阶段还原获得不同粒度的钨粉,认为B:D粉末为4:6的比例搭配使钨粉粒度呈正态分布,最有利于钨丝获得好的高温抗下垂性能和抗震性能。3)在85%FC电流下用二阶段慢速升温烧结能获得外形尺寸为15×15×400mm、比重在17.2g/cm~3、晶粒度为7～8级的烧结钨条能获得具有优良高温性能的钨丝,分析认为要获得具有好的加工性和抗震性掺钴钨丝最好采用中温慢速升温最好。
同时本文对鈷改善钨丝抗震性能的机理和掺钴钨坯条在塑性加工的过程中(旋锻、拉伸)组织和性能的变化规律进行了研究,认为鈷能改善金属K对钨基体的渗入降低钨晶粒中的氧含量,提高钨丝的抗震性能;随着塑性加工的深入钨丝的密度增加,抗拉强度和加工硬化提高,得具有加工成品率高、高温性能好的钨丝。
Along with the development of national economy, transportation and national defense industries need a large number of imported from abroad high-performance anti-seismic tungsten filament, which not easy prolapse and breathe in working environment harsh conditions. This article explores and explicits to preparative well craft tungsten filament that high resistance of prolapse and shake production techniques base on ordiuary technology.
This paper holds that in the preparation of doping tungsten powder metallurgical stage to the high temperature performance and tungsten filament seismic performance have key effect::
1) This article thinks that chooses various impurities content less 50 ppm and grain feature of a single oblique crystal hexagon structure and good flowing performance of APT, which can obtain crystal size of 9.1um blue tungstic oxide in temperature of 260℃-460℃and hydrogen flowing of 0.3-0.5m3 /h conditions.
2) The blue tungsten oxide that adding K, Al, Co, Si elements can get different partied sizes of tungsten powder, which need to pass two deoxidation phases in temperature 550℃-870℃. This article think B:D powder the best proportion of 4:6. Because tungsten powder size can appear normal distribution and tungsten filament resistance of prolapse and shake performance greatly improved in high temperature.
3) Sintering tungsten bars of shape dimension for 15×15×400mm and specific gravity in 17.2g/cm and crystallite size for 7—8 levels obtain to pass two slowly temperature rising sintering phases. This sintering tungsten bar can get excellent temperature performance tungsten filament. It is analyzed that crafe co tungsten filament obtain good workability and resistance of shake performance best technology which need to use mesotherm slowly speed rising.
This article analyzes the mixed cobalt tungsten billet organization and performance the change of the law in plastic processing process (rotary swaging, stretching). Because of plastic processing in depth, tungsten filament density increase and work hardening improve in promptly intermediation annealing condition. To phi 10.0mm annealing tungsten filament analyzes performance of influence in high temperature. Good high temperature and high processing yield tungsten filament need 1900℃recrystallization annealing ,because this condition potassium bubble easily split, annealing speed on tungsten performance little impact.
本论文认为在掺杂钨丝制备的粉末冶金阶段对钨丝的高温性能与抗震性能有关键的影响:
1)选用各种杂质含量小于50ppm,晶粒形貌为单斜晶六方形结构,流动性能良好的仲钨酸铵在温度260～460℃、氢气流量:0.3～0.5m~3/h条件下还原获得粒度为9.1μm的蓝色氧化钨。
2)往蓝色氧化钨中添加K、Si、Al、Co元素在550～870℃下经过两阶段还原获得不同粒度的钨粉,认为B:D粉末为4:6的比例搭配使钨粉粒度呈正态分布,最有利于钨丝获得好的高温抗下垂性能和抗震性能。3)在85%FC电流下用二阶段慢速升温烧结能获得外形尺寸为15×15×400mm、比重在17.2g/cm~3、晶粒度为7～8级的烧结钨条能获得具有优良高温性能的钨丝,分析认为要获得具有好的加工性和抗震性掺钴钨丝最好采用中温慢速升温最好。
同时本文对鈷改善钨丝抗震性能的机理和掺钴钨坯条在塑性加工的过程中(旋锻、拉伸)组织和性能的变化规律进行了研究,认为鈷能改善金属K对钨基体的渗入降低钨晶粒中的氧含量,提高钨丝的抗震性能;随着塑性加工的深入钨丝的密度增加,抗拉强度和加工硬化提高,得具有加工成品率高、高温性能好的钨丝。
Along with the development of national economy, transportation and national defense industries need a large number of imported from abroad high-performance anti-seismic tungsten filament, which not easy prolapse and breathe in working environment harsh conditions. This article explores and explicits to preparative well craft tungsten filament that high resistance of prolapse and shake production techniques base on ordiuary technology.
This paper holds that in the preparation of doping tungsten powder metallurgical stage to the high temperature performance and tungsten filament seismic performance have key effect::
1) This article thinks that chooses various impurities content less 50 ppm and grain feature of a single oblique crystal hexagon structure and good flowing performance of APT, which can obtain crystal size of 9.1um blue tungstic oxide in temperature of 260℃-460℃and hydrogen flowing of 0.3-0.5m3 /h conditions.
2) The blue tungsten oxide that adding K, Al, Co, Si elements can get different partied sizes of tungsten powder, which need to pass two deoxidation phases in temperature 550℃-870℃. This article think B:D powder the best proportion of 4:6. Because tungsten powder size can appear normal distribution and tungsten filament resistance of prolapse and shake performance greatly improved in high temperature.
3) Sintering tungsten bars of shape dimension for 15×15×400mm and specific gravity in 17.2g/cm and crystallite size for 7—8 levels obtain to pass two slowly temperature rising sintering phases. This sintering tungsten bar can get excellent temperature performance tungsten filament. It is analyzed that crafe co tungsten filament obtain good workability and resistance of shake performance best technology which need to use mesotherm slowly speed rising.
This article analyzes the mixed cobalt tungsten billet organization and performance the change of the law in plastic processing process (rotary swaging, stretching). Because of plastic processing in depth, tungsten filament density increase and work hardening improve in promptly intermediation annealing condition. To phi 10.0mm annealing tungsten filament analyzes performance of influence in high temperature. Good high temperature and high processing yield tungsten filament need 1900℃recrystallization annealing ,because this condition potassium bubble easily split, annealing speed on tungsten performance little impact.
引文
[1]张启修,赵秦生.钨钼冶金[M].北京:冶金工业出版社,2005
[2]赵暮岳,王伏生,范竞莲.我国钨基高比重合金的发展和现状[J].粉末冶金材料科学与工程. 2000,3(1):27-32
[3]印协世.钨丝生产原理、工艺及其性能[M].北京:冶金工业出版社,1998
[4]鲁利国,夏耀勤.钨合金的开发和应用现状[J].中国钨业.2008, 6(3):37-39
[5]闵邦平.浅谈掺杂钨丝的多牌号技术[J].中国钨业.2002,10(5): 43 -44
[6]杨宇锋,中国钨材钨丝加工业现状及发展趋势[J].中国照明电器. 2003,18(1):30-34
[7]付洁,李中奎,郑欣等.钨及钨合金的研发及应用现状[J].稀有金属快报.2005,24(7):11-15
[8]冯沛卿,朱宪忠,马晓蓉等.耐震钨丝特性及应用[J].中国钨业.2002,12(6):34-36
[9]傅小明,吴晓东.抗震钨丝的现状与展望[J].上海有色金属. 2004,3(1):18-21
[10]杨晓青,罗震中,郭荣辉等.钨电极材料研究进展[J].稀有金属与硬质合金.2005,12(4):52-54
[11]周美玲,张久兴,聂祚仁等.稀土钨、钼电极电子发射性能研究与应用开发[J].中国钨业. 2001,16(5):52-56
[12]王发展,诸葛飞,张晖等.旋锻法制备高掺杂ThO2纳米颗粒的W热阴极材料的结构与性能[J].稀有金属材料与工程.2004,5(5): 468-472
[13]黄启华.抗震钨丝研发有所突破[N].中国有色金属报.2002.l2
[14]聂祚仁,周美玲等.复合钨电极材料的性能[J].金属学报.1999,3.35
[15]王发展,张晖,丁秉钧.W-ThO2电极材料的研究进展[J].兵器材料科学与工程.2001,24(4):61-64
[16]聂祚仁,周美玲,张久兴等.稀土W电极材料及稀土氧化物的作用[J].稀有金属材料与工程.1997,26(6):1-6
[17]贾佐诚等.新型稀土电极材料[J].粉末冶金技术.1993,11(3): 196-201
[18] Nie Z R , Zhou M L , Zhang J X et al. Rare Metal Mater Eng, 1997,26:1
[19] Nie Z R , Zhou M L , Zhang J X et al. Beijing Polytechnic Univ, 1998,24:28
[20] Nie Z R , Zhou M L , Chen Y, et al. Acta Metal Sin ,1999, (35): 334
[21] Sadek A A , Ushio M , Matesuda F. Effect of rare earth metal oxide additions to tungsten electrodes[J]. Metallurgical Transactions A , 1990 , 21A:3221-3236.
[22]印协世.钨铼合金和钨铼热电偶[M].北京:冶金工业出版社, 1992
[23]张太全,王玉金,松桂明.钨及钨合金的变形、断裂及强化机制研究综述[J].有色金属.2004,56(1):7-12
[24]彭鹰,胡福成,李炳山等.多元复合稀土钨电极研究[J].中国钨业.2007,2(1):42-45
[25]向铁根.液-液掺杂钨粉的工艺研究[J].硬质合金.1996,11(4): 216-220
[26] Zeiler B.Schubert W D,Lux B.Tungsten Blue Oxide[J]. Int J Refr Metals&Hard Mater.1991,10:91-105
[27] Zeiler B.Schubert W D,LuxB.Tungsten and Tungsten Alloys- Recent Advances [J].Int J Refr Metals&Hard Mster. 1993~1994, 12:9-16
[28]周海红,余永峰.掺杂蓝钨不酸洗工艺的研究[J].粉末冶金工业. 2002,12 (4):32-36
[29]刘光耀.掺杂钨APT研究[J] .钨钼材料.992,(3):1-4
[30] Haubner R.The Reduction Mechanision of Doped Tungsten[J].Internationnal Journal of Refractory s&Hard Metals.1983,(3):08-115
[31]杨宇锋,中国钨丝工业[J].中国钨业. 1994,14:5-6
[32] Luo Anhua,Skin K S, JacobsonD L.Hight temperature tensile properties of W-Re-ThO2 alloys[J].Materials Science andEngineering. 1991, A 148:219-229
[33] G.L. Davis. Netaiiurgia [J].1958.vol.58.9:177-228
[34] Lux B.Zeiler B.Schubert W D.Formation and Incorporation of Dopant Phases during Technical Reduction of NS-Doped Tungster Blue[J]. Int J of Refr Metals & Hard Mater.1991,10:83-90
[35] Bewlay B P.Briant C L.The Formation and the Role of Potassium Bubbles in NS-Doped Tungsten [J].Int J. of Refr Metals & Hard Mater. 1995,13:127-143
[36]范景莲.钨合金及其备新技术[M].北京:冶金工业出版社,2006
[37] Bartha L.h∞ner E . The Chemistry of Non.sag Tungsten [M].自贡硬质合金有限责任公司译.2001:126-147
[38] B.P.Bewlay C.L.Briant.抗下垂掺杂钨中钾泡的形成及其作用.[J].中国钨业. 1997,11
[39]白淑文,张胜华.钨钼丝加工原理[M].1988.轻工业出版社.北京.261
[40]周美玲,左铁镛.旋锻加工过程中钨的形变与组织的研究[J].中南矿冶学院学报.1984,42(4):111-17
[41] Pink.E.BARTHA,L.TheMetallurgy of Doped/Non-sag Tungsten [M]. London.Elsevier.1989:209-233.
[42]陈中春.掺杂钨丝特异再结晶行为的研究[G].中国有色金属学会.中国金属学会第六届难熔金属学会交流会.1988:31-34
[43] Snow,D.B.The Recystallization of commercially Pure and Doped Tungsten Wire to High Strain [J].Metal Trans.1979,10(7):815
[44]殷为宏.钨和钨合金的新发展[J].钨粉末和掺杂钨丝.1990,(2): 2-10
[45]张存信,张树格,田华等.加热温度对掺杂钨丝再结晶组织及性能的影响[J].热处理技术与装备.2007,(1):15-17
[46]杨宇锋,唐元春,中国钨丝行业的现状及发展趋势[J].中国照明电器. 2008,4:1-3
[47]闵邦平.中国钨丝加工的技术现状及发展趋势[J].中国钨业. 2002,6(3):21-23
[48]石明柱.粒度组成对掺杂钨某些性能的影响[J].稀有金属材料与工程.1987,5:27-33
[49]李葵初.论旋锤加工对钨丝质量的影响(一)[J].稀有金属与硬质合金.1990,2:22-24
[2]赵暮岳,王伏生,范竞莲.我国钨基高比重合金的发展和现状[J].粉末冶金材料科学与工程. 2000,3(1):27-32
[3]印协世.钨丝生产原理、工艺及其性能[M].北京:冶金工业出版社,1998
[4]鲁利国,夏耀勤.钨合金的开发和应用现状[J].中国钨业.2008, 6(3):37-39
[5]闵邦平.浅谈掺杂钨丝的多牌号技术[J].中国钨业.2002,10(5): 43 -44
[6]杨宇锋,中国钨材钨丝加工业现状及发展趋势[J].中国照明电器. 2003,18(1):30-34
[7]付洁,李中奎,郑欣等.钨及钨合金的研发及应用现状[J].稀有金属快报.2005,24(7):11-15
[8]冯沛卿,朱宪忠,马晓蓉等.耐震钨丝特性及应用[J].中国钨业.2002,12(6):34-36
[9]傅小明,吴晓东.抗震钨丝的现状与展望[J].上海有色金属. 2004,3(1):18-21
[10]杨晓青,罗震中,郭荣辉等.钨电极材料研究进展[J].稀有金属与硬质合金.2005,12(4):52-54
[11]周美玲,张久兴,聂祚仁等.稀土钨、钼电极电子发射性能研究与应用开发[J].中国钨业. 2001,16(5):52-56
[12]王发展,诸葛飞,张晖等.旋锻法制备高掺杂ThO2纳米颗粒的W热阴极材料的结构与性能[J].稀有金属材料与工程.2004,5(5): 468-472
[13]黄启华.抗震钨丝研发有所突破[N].中国有色金属报.2002.l2
[14]聂祚仁,周美玲等.复合钨电极材料的性能[J].金属学报.1999,3.35
[15]王发展,张晖,丁秉钧.W-ThO2电极材料的研究进展[J].兵器材料科学与工程.2001,24(4):61-64
[16]聂祚仁,周美玲,张久兴等.稀土W电极材料及稀土氧化物的作用[J].稀有金属材料与工程.1997,26(6):1-6
[17]贾佐诚等.新型稀土电极材料[J].粉末冶金技术.1993,11(3): 196-201
[18] Nie Z R , Zhou M L , Zhang J X et al. Rare Metal Mater Eng, 1997,26:1
[19] Nie Z R , Zhou M L , Zhang J X et al. Beijing Polytechnic Univ, 1998,24:28
[20] Nie Z R , Zhou M L , Chen Y, et al. Acta Metal Sin ,1999, (35): 334
[21] Sadek A A , Ushio M , Matesuda F. Effect of rare earth metal oxide additions to tungsten electrodes[J]. Metallurgical Transactions A , 1990 , 21A:3221-3236.
[22]印协世.钨铼合金和钨铼热电偶[M].北京:冶金工业出版社, 1992
[23]张太全,王玉金,松桂明.钨及钨合金的变形、断裂及强化机制研究综述[J].有色金属.2004,56(1):7-12
[24]彭鹰,胡福成,李炳山等.多元复合稀土钨电极研究[J].中国钨业.2007,2(1):42-45
[25]向铁根.液-液掺杂钨粉的工艺研究[J].硬质合金.1996,11(4): 216-220
[26] Zeiler B.Schubert W D,Lux B.Tungsten Blue Oxide[J]. Int J Refr Metals&Hard Mater.1991,10:91-105
[27] Zeiler B.Schubert W D,LuxB.Tungsten and Tungsten Alloys- Recent Advances [J].Int J Refr Metals&Hard Mster. 1993~1994, 12:9-16
[28]周海红,余永峰.掺杂蓝钨不酸洗工艺的研究[J].粉末冶金工业. 2002,12 (4):32-36
[29]刘光耀.掺杂钨APT研究[J] .钨钼材料.992,(3):1-4
[30] Haubner R.The Reduction Mechanision of Doped Tungsten[J].Internationnal Journal of Refractory s&Hard Metals.1983,(3):08-115
[31]杨宇锋,中国钨丝工业[J].中国钨业. 1994,14:5-6
[32] Luo Anhua,Skin K S, JacobsonD L.Hight temperature tensile properties of W-Re-ThO2 alloys[J].Materials Science andEngineering. 1991, A 148:219-229
[33] G.L. Davis. Netaiiurgia [J].1958.vol.58.9:177-228
[34] Lux B.Zeiler B.Schubert W D.Formation and Incorporation of Dopant Phases during Technical Reduction of NS-Doped Tungster Blue[J]. Int J of Refr Metals & Hard Mater.1991,10:83-90
[35] Bewlay B P.Briant C L.The Formation and the Role of Potassium Bubbles in NS-Doped Tungsten [J].Int J. of Refr Metals & Hard Mater. 1995,13:127-143
[36]范景莲.钨合金及其备新技术[M].北京:冶金工业出版社,2006
[37] Bartha L.h∞ner E . The Chemistry of Non.sag Tungsten [M].自贡硬质合金有限责任公司译.2001:126-147
[38] B.P.Bewlay C.L.Briant.抗下垂掺杂钨中钾泡的形成及其作用.[J].中国钨业. 1997,11
[39]白淑文,张胜华.钨钼丝加工原理[M].1988.轻工业出版社.北京.261
[40]周美玲,左铁镛.旋锻加工过程中钨的形变与组织的研究[J].中南矿冶学院学报.1984,42(4):111-17
[41] Pink.E.BARTHA,L.TheMetallurgy of Doped/Non-sag Tungsten [M]. London.Elsevier.1989:209-233.
[42]陈中春.掺杂钨丝特异再结晶行为的研究[G].中国有色金属学会.中国金属学会第六届难熔金属学会交流会.1988:31-34
[43] Snow,D.B.The Recystallization of commercially Pure and Doped Tungsten Wire to High Strain [J].Metal Trans.1979,10(7):815
[44]殷为宏.钨和钨合金的新发展[J].钨粉末和掺杂钨丝.1990,(2): 2-10
[45]张存信,张树格,田华等.加热温度对掺杂钨丝再结晶组织及性能的影响[J].热处理技术与装备.2007,(1):15-17
[46]杨宇锋,唐元春,中国钨丝行业的现状及发展趋势[J].中国照明电器. 2008,4:1-3
[47]闵邦平.中国钨丝加工的技术现状及发展趋势[J].中国钨业. 2002,6(3):21-23
[48]石明柱.粒度组成对掺杂钨某些性能的影响[J].稀有金属材料与工程.1987,5:27-33
[49]李葵初.论旋锤加工对钨丝质量的影响(一)[J].稀有金属与硬质合金.1990,2:22-24