掺杂稀土钼热阴极材料的制备及性能研究
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摘要
本文采用粉末冶金和塑性加工方法成功制备出六种高含量(4-4.5wt％)稀土钼热阴极材料，确定了其优良的制备工艺。采用了SEM，X-Ray衍射等分析手段对稀土钼热阴极材料在制备过程中的性能进行了测试和研究，借助了拉伸等实验方法对退火态的稀土钼热阴极材料的力学性能进行了检测与研究，研究了稀土氧化物对钼阴极丝材再结晶过程的影响，最后测量分析了几种碳化后的稀土钼热阴极的热电子发射性能。
掺杂复合稀土元素的钼粉，经过二次氢还原后，粉末颗粒细小而且均匀。稀土氧化物的加入明显提高了烧结钼坯的密度。采用低温长时的中频烧结工艺烧结的稀土钼坯性能较好，烧结的材料中稀土损失较少。
4 wt％左右稀土氧化物的加入，能显著提高钼热阴极丝材的再结晶温度和室温抗拉强度。含量为4wt％左右稀土氧化物的钼热阴极丝材在经过1700℃左右热处理后，其延伸率能够达到电子管热阴极用丝材的塑性要求。
对于采用渗透碳化方式的稀土钼热阴极而言，镧钼阴极，镧铈-钼阴极，铈-钼阴极，镧钇-钼阴极具有良好的热电子发射性能，镧钇铼-钼阴极的热电子发射性能一般。采用流动碳化方式的镧铼-钼阴极的热电子发射性能最差。
Six kinds of molybdenum thermionic cathode materials doped with different weight content of rare earth oxides were successfully prepared by powder metallurgy method and metal processing technology, and the fine technics of preparation was confirmed.The properties of the materials during preparation were studied by means of SEM,X-Ray and XRD, the effect of rare earth oxides on the recrystallization and mechanical properties of molybdenum wires were studied by means of experimental method of tension and OM method, thermoinic electron emission character of several kinds of carbonized molybdenum thermionic cathode doped with rare earth oxides were studied.
The granules of the reverted molybdenum powder doped with rare earth oxides are fine and uniformity. Density of molybdenum compact is greatly improved by addition of rare earth.The sintering technics by low temperature and long hours can prepare molybdenum compact of fine properties.
The recrystallization temperature and the strenth of molybdenum thermionic cathode wires are increased greatly by addition of about 4wt% content of rare earth oxides .The elongation of molybdenum wires after heat treatment at 1700C can reach the needs of the application in vacuum tube.
La-Mo, La-Y-Mo, La-Ce-Mo and Ce-Mo thermionic cathode which were infiltrative carbonized show excellent thermoinic electron emission character, La-Y-Re-Mo thermionic cathode which was infiltrative carbonized shows common thermoinic electron emission character,La-Re-Mo thermionic cathode which was flowing carbonized shows poor thermoinic electron emission character.
掺杂复合稀土元素的钼粉，经过二次氢还原后，粉末颗粒细小而且均匀。稀土氧化物的加入明显提高了烧结钼坯的密度。采用低温长时的中频烧结工艺烧结的稀土钼坯性能较好，烧结的材料中稀土损失较少。
4 wt％左右稀土氧化物的加入，能显著提高钼热阴极丝材的再结晶温度和室温抗拉强度。含量为4wt％左右稀土氧化物的钼热阴极丝材在经过1700℃左右热处理后，其延伸率能够达到电子管热阴极用丝材的塑性要求。
对于采用渗透碳化方式的稀土钼热阴极而言，镧钼阴极，镧铈-钼阴极，铈-钼阴极，镧钇-钼阴极具有良好的热电子发射性能，镧钇铼-钼阴极的热电子发射性能一般。采用流动碳化方式的镧铼-钼阴极的热电子发射性能最差。
Six kinds of molybdenum thermionic cathode materials doped with different weight content of rare earth oxides were successfully prepared by powder metallurgy method and metal processing technology, and the fine technics of preparation was confirmed.The properties of the materials during preparation were studied by means of SEM,X-Ray and XRD, the effect of rare earth oxides on the recrystallization and mechanical properties of molybdenum wires were studied by means of experimental method of tension and OM method, thermoinic electron emission character of several kinds of carbonized molybdenum thermionic cathode doped with rare earth oxides were studied.
The granules of the reverted molybdenum powder doped with rare earth oxides are fine and uniformity. Density of molybdenum compact is greatly improved by addition of rare earth.The sintering technics by low temperature and long hours can prepare molybdenum compact of fine properties.
The recrystallization temperature and the strenth of molybdenum thermionic cathode wires are increased greatly by addition of about 4wt% content of rare earth oxides .The elongation of molybdenum wires after heat treatment at 1700C can reach the needs of the application in vacuum tube.
La-Mo, La-Y-Mo, La-Ce-Mo and Ce-Mo thermionic cathode which were infiltrative carbonized show excellent thermoinic electron emission character, La-Y-Re-Mo thermionic cathode which was infiltrative carbonized shows common thermoinic electron emission character,La-Re-Mo thermionic cathode which was flowing carbonized shows poor thermoinic electron emission character.
引文
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2．钟培全．钼与钼合金的应用及其加工方法．中国钼业．2000，10，Vol．24．No．5
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5．周美玲等．稀有金属材料与工程．1989，No．6：11-15
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8．江剑平．翁甲辉等．阴极电子学与气体放电原理[M]．北京：国防工业出版社，1980
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11．薛增泉．吴泉德．电子发射与光电子能谱．北京大学出版社，1992
12. J.M. Lafferty, J. Appl. Phys.,1951,22,229
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14. M.J. Albert, Brit. J. appl. Phys.,167,18,627.
15. H.E. Gallagher, IEEE Conf. Record of 1968 9th conf. On Tube Techniq. New York, 1968
16．徐光宪主编．《稀土》(第2版)．北京，冶金工业出版社，1995，315-329
17．李小琼．廖显恒．刘桂全．稀土金属化合物阴极．电子学报．1965，3，48-56
18. Buxbaum C.,Gessinger G.U.S.,4019081,1977, 4, 19
19. Buxbaum C.U.S.,4274030,1981.6.16
20. Buxbaum C. NTG Fachber, 1983,85:223-227
21. Buxbaum C.,Baden. Brown Boveri Rev. 1-79.43-45
22. D.M. Goebel etal, Rev Sci Instrum, 1980,51(11):1468
23. Goebel. D.M.,Hirooka. Y.&.Campbell. G.A. Rev. Sci. Instrum. 56(10),1985.10.1888
24. Frank B.,Oartuer G. U.S.,4533852,1985.8.6
25. M. Endo, etal., Proc. 12th. int. Plansee. Seminar, Vol.1,1989:37—52
26．王永树．邓耀得．王奇．一种抗中毒的阴极．电子科学学刊．1983，5(1)：64-65
27．王永树．邓耀得．王奇．对镧-碳化钨阴极发射大和抗油蒸汽中毒的探讨．电子科学学刊．1986，8(4)：287-292
28．冯辅义．La-Mo阴极及其应用．真空电子材料与器件第九届学术年会论文集．1992，1-6
29．冯辅义．真空电子技术．1993，No．4：6-9
30. Zhou. Meiling, Cheng. Zhongchun, Zhang. Jiuxin, etal., High. Temperature-High. Pressures, 1994,Vol.26:145-149
31．聂祚仁等．中国稀土学报．1998，3，Vol．16．No．1
32．张久兴等．北京工业大学学报．1998，9，Vol．24．No．3
33．聂祚仁．中南工业大学博士论文．北京：北京图书馆，1997．11
34．张久兴．中南工业大学博士论文．北京：北京图书馆，1993．7
35．王金淑．北京工业大学博士论文．北京：北京图书馆，1999．2
36．武志敏．钼条生产及深加工工艺浅探．中国钼业．2001，8，Vol．25．No．4
37．姚草根．北京工业大学硕士学位论文．北京：北京工业大学档案馆，1999
38．张久兴．稀土氧化物对钼材力学性能的影响．北京工业大学学报．1998，6，Vol．24．No．2
39. Zhou Meiling etal, High Temperature-High Pressure, 1994, 26:145
40．张久兴等．96中国材料研讨会．VI：586
41．魏勇．刘心宇等．钼还原过程相变化研究．1996，9，Vol．126．No．13
42．刘心宇．王德志．La_2O_3，对钼还原和烧结过程的影响．第八届全国难熔金属学术交流会文集．1994．11．3-6
43．廖复疆．吴固基．真空电子技术．国防工业出版社．1999
44．刘冬梅．国际阴极发展概述．军用阴极电子源技术研讨会．2002．9．37-41
45．杨宇锋．钼和钼合金深加工技术进展．中国钼业．2001，8，Vol．25．No．4
46．周美玲．张久兴等．稀土钨．钼电极电子发射性能研究与应用开发．中国钨业．2001，11，VOL。16，,NO。5-6
47．白淑文．张胜华．钨钼丝加工原理．轻工业出版社．1983
48．印协世．钨丝生产原理、工艺及其性能．冶金工业出版社．1997
49．黄培云．粉末冶金原理(第2版)．冶金工业出版社．1997
50．唐仁正．物理冶金基础．冶金工业出版社．1997
2．钟培全．钼与钼合金的应用及其加工方法．中国钼业．2000，10，Vol．24．No．5
3. R. Eck, Proc. 12th, Int, Plansee Seminar, VoL. 1,1989:1047
4. G. Leichtfried, etal, Proc. 12th, Int, Plansee Seminar, VoL. 1, 1989
5．周美玲等．稀有金属材料与工程．1989，No．6：11-15
6．周美玲．李俊．左铁镛，中国有色金属学报．1994．6，VoL．4，No．2：45-50
7．王金淑等．钨钼热阴极材料的进展．稀有金属．2001，1，Vol．25．No．1
8．江剑平．翁甲辉等．阴极电子学与气体放电原理[M]．北京：国防工业出版社，1980
9. G. Gessinger, C. Buxbaum. High. Temperature[J],1978,10:325-330
10. C. Buxbaum, G. Gessinger. Lanthanated. Thermionic Cathode[P].U.S.Patent 4083811,1978-04-11
11．薛增泉．吴泉德．电子发射与光电子能谱．北京大学出版社，1992
12. J.M. Lafferty, J. Appl. Phys.,1951,22,229
13. Yada Keiji etal.,J. Electron Mocrosc Tech 12(3),1989,252
14. M.J. Albert, Brit. J. appl. Phys.,167,18,627.
15. H.E. Gallagher, IEEE Conf. Record of 1968 9th conf. On Tube Techniq. New York, 1968
16．徐光宪主编．《稀土》(第2版)．北京，冶金工业出版社，1995，315-329
17．李小琼．廖显恒．刘桂全．稀土金属化合物阴极．电子学报．1965，3，48-56
18. Buxbaum C.,Gessinger G.U.S.,4019081,1977, 4, 19
19. Buxbaum C.U.S.,4274030,1981.6.16
20. Buxbaum C. NTG Fachber, 1983,85:223-227
21. Buxbaum C.,Baden. Brown Boveri Rev. 1-79.43-45
22. D.M. Goebel etal, Rev Sci Instrum, 1980,51(11):1468
23. Goebel. D.M.,Hirooka. Y.&.Campbell. G.A. Rev. Sci. Instrum. 56(10),1985.10.1888
24. Frank B.,Oartuer G. U.S.,4533852,1985.8.6
25. M. Endo, etal., Proc. 12th. int. Plansee. Seminar, Vol.1,1989:37—52
26．王永树．邓耀得．王奇．一种抗中毒的阴极．电子科学学刊．1983，5(1)：64-65
27．王永树．邓耀得．王奇．对镧-碳化钨阴极发射大和抗油蒸汽中毒的探讨．电子科学学刊．1986，8(4)：287-292
28．冯辅义．La-Mo阴极及其应用．真空电子材料与器件第九届学术年会论文集．1992，1-6
29．冯辅义．真空电子技术．1993，No．4：6-9
30. Zhou. Meiling, Cheng. Zhongchun, Zhang. Jiuxin, etal., High. Temperature-High. Pressures, 1994,Vol.26:145-149
31．聂祚仁等．中国稀土学报．1998，3，Vol．16．No．1
32．张久兴等．北京工业大学学报．1998，9，Vol．24．No．3
33．聂祚仁．中南工业大学博士论文．北京：北京图书馆，1997．11
34．张久兴．中南工业大学博士论文．北京：北京图书馆，1993．7
35．王金淑．北京工业大学博士论文．北京：北京图书馆，1999．2
36．武志敏．钼条生产及深加工工艺浅探．中国钼业．2001，8，Vol．25．No．4
37．姚草根．北京工业大学硕士学位论文．北京：北京工业大学档案馆，1999
38．张久兴．稀土氧化物对钼材力学性能的影响．北京工业大学学报．1998，6，Vol．24．No．2
39. Zhou Meiling etal, High Temperature-High Pressure, 1994, 26:145
40．张久兴等．96中国材料研讨会．VI：586
41．魏勇．刘心宇等．钼还原过程相变化研究．1996，9，Vol．126．No．13
42．刘心宇．王德志．La_2O_3，对钼还原和烧结过程的影响．第八届全国难熔金属学术交流会文集．1994．11．3-6
43．廖复疆．吴固基．真空电子技术．国防工业出版社．1999
44．刘冬梅．国际阴极发展概述．军用阴极电子源技术研讨会．2002．9．37-41
45．杨宇锋．钼和钼合金深加工技术进展．中国钼业．2001，8，Vol．25．No．4
46．周美玲．张久兴等．稀土钨．钼电极电子发射性能研究与应用开发．中国钨业．2001，11，VOL。16，,NO。5-6
47．白淑文．张胜华．钨钼丝加工原理．轻工业出版社．1983
48．印协世．钨丝生产原理、工艺及其性能．冶金工业出版社．1997
49．黄培云．粉末冶金原理(第2版)．冶金工业出版社．1997
50．唐仁正．物理冶金基础．冶金工业出版社．1997