钼及钼合金烧结技术研究及发展
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摘要
从粉末冶金烧结理论、烧结设备、烧结工艺参数及新型烧结技术等方面概述了钼及钼合金烧结技术的研究现状及进展。结论指出,钼及钼合金烧结理论仍集中在传统粉末冶金理论体系;烧结技术发展方向是获得全致密化、细晶、均质化的烧结坯体;发展趋势是烧结设备及工装与粉末冶金新技术结合更为紧密,出现更多交叉研究;研究热点和难点是大型钼及钼合金坯件烧结致密化、微观组织均质化、细晶化及复杂烧结态异型坯件烧结过程中形状精确控制等。
The progress and prospect on the sintering techniques of molybdenum and molybdenum alloys were summarized in this paper, including sintering theory, sintering equipment, and sintering processing parameters, and new sintering techniques. In the results, the sintering theory of molybdenum and molybdenum alloys still focuses on the traditional theory of powder metallurgy. The development of sintering technology is to obtain the fully densified, fine crystal, and homogenized sintered billets. The tendency of sintering technology is the closely combination of sintering equipment and tooling with new powder metallurgy technology, resulting in more cross-research. Fully densification, microstructure homogenization, fine crystallization, and precise shapes controlling of sintered complex shapes molybdenum products during the sintering processing of large molybdenum and molybdenum alloys billets will be the hot and difficult points on the studies of molybdenum and molybdenum alloys sintering techniques.
The progress and prospect on the sintering techniques of molybdenum and molybdenum alloys were summarized in this paper, including sintering theory, sintering equipment, and sintering processing parameters, and new sintering techniques. In the results, the sintering theory of molybdenum and molybdenum alloys still focuses on the traditional theory of powder metallurgy. The development of sintering technology is to obtain the fully densified, fine crystal, and homogenized sintered billets. The tendency of sintering technology is the closely combination of sintering equipment and tooling with new powder metallurgy technology, resulting in more cross-research. Fully densification, microstructure homogenization, fine crystallization, and precise shapes controlling of sintered complex shapes molybdenum products during the sintering processing of large molybdenum and molybdenum alloys billets will be the hot and difficult points on the studies of molybdenum and molybdenum alloys sintering techniques.
引文
[1] Huang P Y. Theory of Power Metallurgy. 2nd Ed. Beijing:Metallurgical Industry Press, 2004(黄培云.粉末冶金原理. 2版.北京:冶金工业出版社,2004)
[2] Xu K D. Science and Engineering of Molybdenum Material. Beijing:Metallurgical Industry Press, 2014(徐克玷.钼的材料科学与工程.北京:冶金工业出版社, 2014)
[3] Edtmaier C, Schubert W D, Gierl C, et al. Pre-sintering behaviour of Mo-powder//18th Plansee Seminar. Reutte,2013:RM 97/1
[4] Kim S H, Kim D G, Park M S, et al. Sintering kinetics analysis of molybdenum nanopowder in a non-isothermal process. Met Mater Int, 2011, 17(1):63
[5] Garg P, Park S J, German R M. Effect of die compaction pressure on densification behavior of molybdenum powders. Int J Refract Met Hard Mater, 2007, 25(1):16
[6] Xie H, Sun J, Yang L X, et al. Phase field simulation of Mo powder during sintering process. Foundry Technol,2006, 27(12):1366(谢辉,孙军,杨刘晓,等. Mo粉末烧结过程的相场模拟.铸造技术, 2006, 27(12):1366)
[7] Jia L, Xie H, LüZ L. Expert system for density prediction of Mo sintered bodies. China Molybd Ind, 2008, 32(5):30(贾磊,谢辉,吕振林. Mo粉末压坯烧结密度预测专家系统.中国钼业, 2008, 32(5):30)
[8] Blaine D C, Gurosik J D, Park S J, et al. Master sintering curve concepts as applied to the sintering of molybdenum.Metall Mater Trans A, 2006, 37(3):715
[9] Xie H, Yang L X, Zhao B H, et al. Influence of sintering modes on sintering quality of Mo products. Foundry Technol, 2007, 28(5):642(谢辉,杨刘晓,赵宝华,等.烧结方式对Mo烧结品质的影响.铸造技术, 2007, 28(5):642)
[10] Wu Z, Sun Y J, Comparison of sintering quality of molybdenum products from mid-frequency furnace and electric resistance furnace. China Molybd Ind, 2008, 32(3):50(武洲,孙院军.钼制品在中频炉与电阻炉中烧结品质的比较.中国钼业, 2008, 32(3):50)
[11] Zhang C L. Fast cooling technique of intermediate frequency furnace for molybdenum products. Mater China, 2012, 31(4):55(张常乐,钼产品的中频炉快冷技术.中国材料进展,2012, 31(4):55)
[12] Feng P F, Fu J B, Liu R Z, et al. Analysis on time sequence characteristics of occurrence status of lanthanum in Mo alloy wires. Chin J Rare Met, 2011, 35(4):486(冯鹏发,付静波,刘仁智,等. La元素在钼合金丝中赋存形式的时序性分析.稀有金属, 2011, 35(4):486)
[13] Yang Q L, Meng Q L, Feng P F, et al. Effect of rare-earth Y and Ce on the mechanical properties of Mo alloy. China Molybd Ind, 2012, 36(5):51(杨秦莉,孟庆乐,冯鹏发,等.稀土Y、Ce对钼合金力学性能的影响.中国钼业, 2012, 36(5):51)
[14] Dong D, Huang H T, Xiong N, et al. Application of molybdenum and molybdenum alloys in nuclear reactors.China Molybd Ind, 2018, 42(4):6(董帝,黄洪涛,熊宁,等.钼及钼合金在核反应堆中的应用.中国钼业, 2018, 42(4):6)
[15] Yu Z T, Wang K S, Hu P, et al. Progress of low oxygen TZM molybdenum alloy. Mater Rev, 2015, 29(1):92(于志涛,王快社,胡平,等.低氧TZM合金研究进展.材料导报, 2015, 29(1):92)
[16] Zheng X, Bai R, Wang D H, et al. Research development of refractory metal materials used in the field of aerospace.Rare Met Mater Eng, 2011, 40(10):1871(郑欣,白润,王东辉,等.航天航空用难熔金属材料的研究进展.稀有金属材料与工程, 2011, 40(10):1871)
[17] Shi Z Q, Huang X L, Yi Y P. Aanlysis on the influencing factors of molybdenum anvil service life. China Molybd Ind, 2014, 38(5):57(史振琦,黄晓玲,易永鹏.影响钼合金顶头使用寿命因素浅析.中国钼业, 2014, 38(5):57)
[18] Chen Q, Li D C, Bu C Y. Effect of aluminum-potassium-silicon on properties and microstructure of molybdenum powder and sintered ingots. Chin J Rare Met, 2007, 31(3):300(陈强,李大成,卜春阳.掺杂Si–Al–K对钼粉及其烧结制品组织、性能的影响.稀有金属, 2007, 31(3):300)
[19] Iorio L E, Bewlay B P, Larsen M. Dopant particle characterization and bubble evolution in aluminumpotassium-silicon-doped molybdenum wire. Metall Mater Trans A, 2002, 33(11):3349
[20] Tang R Z, Tian R Z. Binary Alloy Phase Diagram and Crystal Structure of Intermediate Phase. Changsha:Central South University Press, 2009(唐仁政,田荣璋.二元合金相图及中间相晶体结构.长沙:中南大学出版社, 2009)
[21] Chen C, Wang M P, Tan W, et al. Study on preparation of molybdenum-rhenium alloys by powder metallurgy methods. Mater Rev, 2008, 22(5):74(陈畅,汪明朴,谭望,等.粉末冶金方法制备钼铼合金的研究.材料导报, 2008, 22(5):74)
[22] Zhao H, Shi Z Q, Fu J B, et al. Densification method of Mo15Ta alloy and its microstructure&properties.Foundry Technol, 2017, 38(9):2108(赵虎,史振琦,付静波,等. Mo15Ta合金致密化方法及其组织和性能研究.铸造技术, 2017, 38(9):2108)
[23] Dang X M, An G, Li J, et al. Effect of niobium powder granularity and sintering method on Mo–Nb alloy. Powder Metall Technol, 2016, 34(4):272(党晓明,安耿,李晶,等.铌粉粒度和烧结方法对钼铌合金的影响.粉末冶金技术, 2016, 34(4):272)
[24] Xi J J. Preparation and applications of MoSi2 materials.Powder Metall Technol, 2010, 28(1):61(席俊杰. MoSi2材料的制备及其应用.粉末冶金技术,2010, 28(1):61)
[25] Huang W J, Zhou Y, Li S, et al. Study on phase composition and microstructure of typical Mo Si2 heating elements. J Zhengzhou Univ Eng Sci, 2017, 38(6):88(黄文江,周颖,李斯,等.典型Mo Si2发热元件物相与显微结构分析.郑州大学学报(工学版), 2017, 38(6):88)
[26] Lin Y C, Tu Y Y, Shen C H. Na-doped Mo target sputtering for Cu(In, Ga)Se2 thin film solar cells. J Mater Sci Mate Electron, 2013, 24(2):514
[27] Zhu Q, Chen L B, Wang N, et al. Preparation of Mo–Na targets by vacuum hot pressing technique. China Molybd Ind, 2015, 39(6):55(朱琦,陈良斌,王娜,等.真空热压烧结制备Mo–Na合金靶材的研究.中国钼业, 2015, 39(6):55)
[28] Segurado J, Parteder E, Plankensteiner A F, et al.Micromechanical studies of the densification of porous molybdenum. Mater Sci Eng A, 2002, 333(1-2):270
[29] Gong W P, Chen T F, Gong Y P. Thermodynamic investigation on the liquid sintering of the refractory Mo alloys. Min Metall Eng, 2006, 26(3):65(龚伟平,陈腾飞,龚育平.钼合金耐火材料液相烧结性能热力学研究.矿冶工程, 2006, 26(3):65)
[30] Zhang J P, Hui J S, Zhao H. The effect of sintering method on molybdenum microstructure and performance. China Molybd Ind, 2015, 39(3):41(张菊平,惠军胜,赵虎.烧结方式对钼制品组织性能的影响研究.中国钼业, 2015, 39(3):41)
[31] Yang Q L, Zhao H, Zhuang F, et al. Study on the influencing factors of oxygen content in the preparation of Mo plate with ultrafine power. Foundry Technol, 2018,39(9):1916(杨秦莉,赵虎,庄飞,等.超细钼粉制备钼板过程中O含量影响因素研究.铸造技术, 2018, 39(9):1916)
[32] Wang Q F, Zhang Y M, Guo X H, et al. The latest development and research progress of spark plasma sintering process. Rare Met Cemented Carbides, 2014,42(3):44(王庆福,张彦敏,国秀花,等.放电等离子烧结技术的研究现状及进展.稀有金属与硬质合金, 2014, 42(3):44)
[33] Sakamoto T. Sintering of molybdenum powder compacts by spark plasma sintering. J Jpn Soc Powder Powder Metall, 1997, 44(9):845
[34] Madigan J, Gigl P, Agrawal D. Continuous microwave sintering of tungsten carbide products. Sintering Powder Metall, 2005,(9):109
[35] Zhang C L. Performance analysis and comparison of molybdenum plates from different sintering ways. China Molybd Ind, 2012, 36(5):55(张常乐.不同烧结方式的钼板坯性能比较分析.中国钼业, 2012, 36(5):55)
[36] Lin X H, Li L P, Li B, et al. Application of hot isostatic pressing in preparation of rare and refractory metal products. Powder Metall Ind, 2017, 27(3):63(林小辉,李来平,李斌,等.热等静压在稀有难熔金属产品制备中的应用.粉末冶金工业, 2017, 27(3):63)
[2] Xu K D. Science and Engineering of Molybdenum Material. Beijing:Metallurgical Industry Press, 2014(徐克玷.钼的材料科学与工程.北京:冶金工业出版社, 2014)
[3] Edtmaier C, Schubert W D, Gierl C, et al. Pre-sintering behaviour of Mo-powder//18th Plansee Seminar. Reutte,2013:RM 97/1
[4] Kim S H, Kim D G, Park M S, et al. Sintering kinetics analysis of molybdenum nanopowder in a non-isothermal process. Met Mater Int, 2011, 17(1):63
[5] Garg P, Park S J, German R M. Effect of die compaction pressure on densification behavior of molybdenum powders. Int J Refract Met Hard Mater, 2007, 25(1):16
[6] Xie H, Sun J, Yang L X, et al. Phase field simulation of Mo powder during sintering process. Foundry Technol,2006, 27(12):1366(谢辉,孙军,杨刘晓,等. Mo粉末烧结过程的相场模拟.铸造技术, 2006, 27(12):1366)
[7] Jia L, Xie H, LüZ L. Expert system for density prediction of Mo sintered bodies. China Molybd Ind, 2008, 32(5):30(贾磊,谢辉,吕振林. Mo粉末压坯烧结密度预测专家系统.中国钼业, 2008, 32(5):30)
[8] Blaine D C, Gurosik J D, Park S J, et al. Master sintering curve concepts as applied to the sintering of molybdenum.Metall Mater Trans A, 2006, 37(3):715
[9] Xie H, Yang L X, Zhao B H, et al. Influence of sintering modes on sintering quality of Mo products. Foundry Technol, 2007, 28(5):642(谢辉,杨刘晓,赵宝华,等.烧结方式对Mo烧结品质的影响.铸造技术, 2007, 28(5):642)
[10] Wu Z, Sun Y J, Comparison of sintering quality of molybdenum products from mid-frequency furnace and electric resistance furnace. China Molybd Ind, 2008, 32(3):50(武洲,孙院军.钼制品在中频炉与电阻炉中烧结品质的比较.中国钼业, 2008, 32(3):50)
[11] Zhang C L. Fast cooling technique of intermediate frequency furnace for molybdenum products. Mater China, 2012, 31(4):55(张常乐,钼产品的中频炉快冷技术.中国材料进展,2012, 31(4):55)
[12] Feng P F, Fu J B, Liu R Z, et al. Analysis on time sequence characteristics of occurrence status of lanthanum in Mo alloy wires. Chin J Rare Met, 2011, 35(4):486(冯鹏发,付静波,刘仁智,等. La元素在钼合金丝中赋存形式的时序性分析.稀有金属, 2011, 35(4):486)
[13] Yang Q L, Meng Q L, Feng P F, et al. Effect of rare-earth Y and Ce on the mechanical properties of Mo alloy. China Molybd Ind, 2012, 36(5):51(杨秦莉,孟庆乐,冯鹏发,等.稀土Y、Ce对钼合金力学性能的影响.中国钼业, 2012, 36(5):51)
[14] Dong D, Huang H T, Xiong N, et al. Application of molybdenum and molybdenum alloys in nuclear reactors.China Molybd Ind, 2018, 42(4):6(董帝,黄洪涛,熊宁,等.钼及钼合金在核反应堆中的应用.中国钼业, 2018, 42(4):6)
[15] Yu Z T, Wang K S, Hu P, et al. Progress of low oxygen TZM molybdenum alloy. Mater Rev, 2015, 29(1):92(于志涛,王快社,胡平,等.低氧TZM合金研究进展.材料导报, 2015, 29(1):92)
[16] Zheng X, Bai R, Wang D H, et al. Research development of refractory metal materials used in the field of aerospace.Rare Met Mater Eng, 2011, 40(10):1871(郑欣,白润,王东辉,等.航天航空用难熔金属材料的研究进展.稀有金属材料与工程, 2011, 40(10):1871)
[17] Shi Z Q, Huang X L, Yi Y P. Aanlysis on the influencing factors of molybdenum anvil service life. China Molybd Ind, 2014, 38(5):57(史振琦,黄晓玲,易永鹏.影响钼合金顶头使用寿命因素浅析.中国钼业, 2014, 38(5):57)
[18] Chen Q, Li D C, Bu C Y. Effect of aluminum-potassium-silicon on properties and microstructure of molybdenum powder and sintered ingots. Chin J Rare Met, 2007, 31(3):300(陈强,李大成,卜春阳.掺杂Si–Al–K对钼粉及其烧结制品组织、性能的影响.稀有金属, 2007, 31(3):300)
[19] Iorio L E, Bewlay B P, Larsen M. Dopant particle characterization and bubble evolution in aluminumpotassium-silicon-doped molybdenum wire. Metall Mater Trans A, 2002, 33(11):3349
[20] Tang R Z, Tian R Z. Binary Alloy Phase Diagram and Crystal Structure of Intermediate Phase. Changsha:Central South University Press, 2009(唐仁政,田荣璋.二元合金相图及中间相晶体结构.长沙:中南大学出版社, 2009)
[21] Chen C, Wang M P, Tan W, et al. Study on preparation of molybdenum-rhenium alloys by powder metallurgy methods. Mater Rev, 2008, 22(5):74(陈畅,汪明朴,谭望,等.粉末冶金方法制备钼铼合金的研究.材料导报, 2008, 22(5):74)
[22] Zhao H, Shi Z Q, Fu J B, et al. Densification method of Mo15Ta alloy and its microstructure&properties.Foundry Technol, 2017, 38(9):2108(赵虎,史振琦,付静波,等. Mo15Ta合金致密化方法及其组织和性能研究.铸造技术, 2017, 38(9):2108)
[23] Dang X M, An G, Li J, et al. Effect of niobium powder granularity and sintering method on Mo–Nb alloy. Powder Metall Technol, 2016, 34(4):272(党晓明,安耿,李晶,等.铌粉粒度和烧结方法对钼铌合金的影响.粉末冶金技术, 2016, 34(4):272)
[24] Xi J J. Preparation and applications of MoSi2 materials.Powder Metall Technol, 2010, 28(1):61(席俊杰. MoSi2材料的制备及其应用.粉末冶金技术,2010, 28(1):61)
[25] Huang W J, Zhou Y, Li S, et al. Study on phase composition and microstructure of typical Mo Si2 heating elements. J Zhengzhou Univ Eng Sci, 2017, 38(6):88(黄文江,周颖,李斯,等.典型Mo Si2发热元件物相与显微结构分析.郑州大学学报(工学版), 2017, 38(6):88)
[26] Lin Y C, Tu Y Y, Shen C H. Na-doped Mo target sputtering for Cu(In, Ga)Se2 thin film solar cells. J Mater Sci Mate Electron, 2013, 24(2):514
[27] Zhu Q, Chen L B, Wang N, et al. Preparation of Mo–Na targets by vacuum hot pressing technique. China Molybd Ind, 2015, 39(6):55(朱琦,陈良斌,王娜,等.真空热压烧结制备Mo–Na合金靶材的研究.中国钼业, 2015, 39(6):55)
[28] Segurado J, Parteder E, Plankensteiner A F, et al.Micromechanical studies of the densification of porous molybdenum. Mater Sci Eng A, 2002, 333(1-2):270
[29] Gong W P, Chen T F, Gong Y P. Thermodynamic investigation on the liquid sintering of the refractory Mo alloys. Min Metall Eng, 2006, 26(3):65(龚伟平,陈腾飞,龚育平.钼合金耐火材料液相烧结性能热力学研究.矿冶工程, 2006, 26(3):65)
[30] Zhang J P, Hui J S, Zhao H. The effect of sintering method on molybdenum microstructure and performance. China Molybd Ind, 2015, 39(3):41(张菊平,惠军胜,赵虎.烧结方式对钼制品组织性能的影响研究.中国钼业, 2015, 39(3):41)
[31] Yang Q L, Zhao H, Zhuang F, et al. Study on the influencing factors of oxygen content in the preparation of Mo plate with ultrafine power. Foundry Technol, 2018,39(9):1916(杨秦莉,赵虎,庄飞,等.超细钼粉制备钼板过程中O含量影响因素研究.铸造技术, 2018, 39(9):1916)
[32] Wang Q F, Zhang Y M, Guo X H, et al. The latest development and research progress of spark plasma sintering process. Rare Met Cemented Carbides, 2014,42(3):44(王庆福,张彦敏,国秀花,等.放电等离子烧结技术的研究现状及进展.稀有金属与硬质合金, 2014, 42(3):44)
[33] Sakamoto T. Sintering of molybdenum powder compacts by spark plasma sintering. J Jpn Soc Powder Powder Metall, 1997, 44(9):845
[34] Madigan J, Gigl P, Agrawal D. Continuous microwave sintering of tungsten carbide products. Sintering Powder Metall, 2005,(9):109
[35] Zhang C L. Performance analysis and comparison of molybdenum plates from different sintering ways. China Molybd Ind, 2012, 36(5):55(张常乐.不同烧结方式的钼板坯性能比较分析.中国钼业, 2012, 36(5):55)
[36] Lin X H, Li L P, Li B, et al. Application of hot isostatic pressing in preparation of rare and refractory metal products. Powder Metall Ind, 2017, 27(3):63(林小辉,李来平,李斌,等.热等静压在稀有难熔金属产品制备中的应用.粉末冶金工业, 2017, 27(3):63)
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