纯氮、氮—氨离子渗氮工艺和机理研究
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摘要
本文采用高电压低气压、闭炉保温的渗氮工艺对合金钢在纯氮气氛下离子渗氮和采用氨气以及不同氮氨比混合气进行普通离子渗氮。利用显微硬度计、金相显微镜和X射线衍射仪测定了渗氮层的硬度梯度、层深、显微组织和相组成。结果表明在相同的渗氮时间里，纯氮离子渗氮获得了比以氨气作为渗氮气源进行离子渗氮更好的效果。而且克服了氨气渗氮容易产生环境污染的缺点。
通过对实验中纯氮离子渗氮系统的研究，发现只有在足够高的电压下才有明显的渗氮效果。分析了纯氮离子渗氮和氮氨混合气体离子渗氮过程中阴极位降区内粒子的行为，计算正离子在电场力作用下一个平均自由程内与中性氮分子发生非弹性碰撞传递给氮分子的能量，找出离子渗氮时氮分子产生活性氮原子的电压临界值，导出了离子渗氮中电压、气压、阴极位降区厚度和离子平均自由程的关系式。从理论上推测了几种混合气体离子渗氮活性氮原子产生的能量要求，理论计算与文献报导的实验结果基本一致。探讨了氮氢、氮氩混合气体离子渗氮中氢和氩的作用，提出了渗氮的机理。
In this paper, alloy steel was nitrided under the atmosphere of pure nitrogen, using the ion nitriding technique by high voltage, low air pressure and holding heat with closed furnace, and alloy steel was also nitrided by normal techniques under the atmosphere of the different rate of N2 and NH3 . The hardness gradient, depth , microstructure and phases of nitrided layers were measured with Microhardness Apparatus, Microcopy and X-ray diffractometer . The result shows that under the same nitriding time, better experiment effects was achieved by using pure nitrogen than NH3, and the former technique overcomes the disadvantage of NH3 which is inclined to produce environmental pollutions.
After the contrast studies of various techniques of pure nitrogen ion-nitriding , it is found that obvious ion-nitriding effects were achieved only on the condition of sufficiently high voltage. The behavior of molecule or ion around cathode zone on the process of ion nitriding was analyzed, In a mean free path, under the effect of the electric field, positive ion nitrogen has a inelastic collision with neutral nitrogen molecule and releases certain energy that received by the neutral nitrogen molecule, we quantitate this energy. Also we have found out the critical voltage needed in the production of active nitrogen atoms in ion-nitriding. Deduce the relation among the voltage, air pressure and the thickness of cathe zone. It presume the requirement of energy which produce the active nitrogen under some certain mixtured gases in theory, the theoretical quantitation is consistent weith the trial result of literature reports. Meanwhile, the effect of hydrogen and argon in the N2-H2 and N2-Ar ion-nitriding, and
the mechanism of pure nitrogen ion nitriding was discussed .
通过对实验中纯氮离子渗氮系统的研究，发现只有在足够高的电压下才有明显的渗氮效果。分析了纯氮离子渗氮和氮氨混合气体离子渗氮过程中阴极位降区内粒子的行为，计算正离子在电场力作用下一个平均自由程内与中性氮分子发生非弹性碰撞传递给氮分子的能量，找出离子渗氮时氮分子产生活性氮原子的电压临界值，导出了离子渗氮中电压、气压、阴极位降区厚度和离子平均自由程的关系式。从理论上推测了几种混合气体离子渗氮活性氮原子产生的能量要求，理论计算与文献报导的实验结果基本一致。探讨了氮氢、氮氩混合气体离子渗氮中氢和氩的作用，提出了渗氮的机理。
In this paper, alloy steel was nitrided under the atmosphere of pure nitrogen, using the ion nitriding technique by high voltage, low air pressure and holding heat with closed furnace, and alloy steel was also nitrided by normal techniques under the atmosphere of the different rate of N2 and NH3 . The hardness gradient, depth , microstructure and phases of nitrided layers were measured with Microhardness Apparatus, Microcopy and X-ray diffractometer . The result shows that under the same nitriding time, better experiment effects was achieved by using pure nitrogen than NH3, and the former technique overcomes the disadvantage of NH3 which is inclined to produce environmental pollutions.
After the contrast studies of various techniques of pure nitrogen ion-nitriding , it is found that obvious ion-nitriding effects were achieved only on the condition of sufficiently high voltage. The behavior of molecule or ion around cathode zone on the process of ion nitriding was analyzed, In a mean free path, under the effect of the electric field, positive ion nitrogen has a inelastic collision with neutral nitrogen molecule and releases certain energy that received by the neutral nitrogen molecule, we quantitate this energy. Also we have found out the critical voltage needed in the production of active nitrogen atoms in ion-nitriding. Deduce the relation among the voltage, air pressure and the thickness of cathe zone. It presume the requirement of energy which produce the active nitrogen under some certain mixtured gases in theory, the theoretical quantitation is consistent weith the trial result of literature reports. Meanwhile, the effect of hydrogen and argon in the N2-H2 and N2-Ar ion-nitriding, and
the mechanism of pure nitrogen ion nitriding was discussed .
引文
[1] 杨烈宇．离子轰击渗扩技术．北京．人民交通出版．1990．3
[2] [日]山中久彦．李贻锦．朱雅年译．离子渗氮．机械工业出版社．1985．4
[3] Freidrich Hombeck. Ion nitriding. International Conference and Exhibition. 1986.9
[4] B.Berghaus German patant DRP 375.235.1930.
[5] B.Berghaus German patant DRP 668.639.1932.
[6] B.Berghaus German patant DRP 851.540.1939.
[7] B.Berghaus us patant 3318409.1956.
[8] B.Berghaususpatant 3345280.1961.
[9] G.waidman Fersching sberichte des lands NRW. 944.1961.
[10] J.Kbel ibid. 1955.1965.
[11] A.F steinegger and S.Jentzch Ibid. 1548.1965.
[12] A.F steingg and J.Klanusler Ibid. 1743.1966.
[13] A.F steinegger and J.Klausler Ibid. 1617.1966.
[14] V.A Phillips and A.V Seybolt.Met prog. 242.1968.
[15] A.V Seybolt.Met prog. 245.1969.
[16] 浙江大学．离子氮化．《新技术译丛》编译组．1978．6
[17] 周上祺．离子氮化及离子轰击热处理．重庆大学冶金及材料工程系．1983．2
[18] 徐重．兵器工艺技术．北京．北京出版社．1979．2
[19] 齐见新．微型计算机在离子氮化炉中的应用．鞍山．鞍山钢铁学报．2001．6．Vol．24．No．3．P164-167
[20] 唐红文．离子渗氮自动控制系统的设计．中南民族学院学报．2001．3．Vol．20．No．1．P6-9
[21] 周孝重．陈大凯．等离子体热处理技术．北京．机械工业出版社．1990．4
[22] J.Klbel The formation of nitride layers in glow discharge nitriding. German. Ibids. 1555.1965.
[23] Martin Hudis J.Appl.phys. 1977.Vol44. No.4 1489-1496
[24] Cary G Tibbetts J.Appl.phys. Vol45(1978) No.11 95072
[25] 徐冰仲．张颖智．离子氮化氮的渗入机理．金属热处理 1983．No．10．P29—41
[26] 徐冰仲．张颖智．离子氮化离解模型．中国铁道化学研究所．1986．Vol．7 No．2
[27] 拉赫金著．郭铮匀译．钢的氮化．北京．国防工业出版社．1979．10
[28] 洪班德．姚忠凯．化学热处理．哈尔滨．黑龙江人民出版社．1981．12
[29] 牧村．夏立芳译．《热处理》．1979．Vol．19 No．6
[30] F．Homebeck等．离子体的技术与经济特点．巴黎．第三届国际材料热处理大会论文选集．1983．11
[31] H．J．spies．钢渗氮层的韧性及其特征．布达佩斯．第四届国际材料热处理大会论文选集．1985．6
[32] 夏立芳．高彩桥．钢的滲氮．北京．机械工业出版社．1989．6
[33] 杜树芳．黄辉．氮化钢离子氮化化合物形成过程的研究．金属热处理．1984．No．3
[34] 孟繁杰．黄国靖．十年来离子渗氮技术的发展．金属热处理．1986．10
[35] 谢黎雄．氮势控制技术及其应用．金属热处理．2002．No．5．Vol．27．P25—27
[36] 陈秀玉．陈俭康．渗氮钢高韧性层离子渗氮相成分控制及性能的研究．郑州机械研究所．1988．7
[37] 钟厉．周上祺．氮化层的形成与工艺参数的关系．全国第三届低温化学热处理学术论文讨论会论文．1992．9
[38] Matrin Hudis．离子氮化的研究．J．Appl．phys Vol．44 No．4 April 1973
[39] 周上棋．辉光离子氮化机理的初步探讨(二)重庆大学学报．1980．No．2
[40] 王丽莲．渗氮技术及其发展．热处理2001．No．2．P6—9
[41] 北京第二通用机械厂．法净氮化法．一机所情报活页技术资料．第二号．机械工业出版社．1974
[42] 余宗森．钢中稀土．北京．冶金工业出版社．1982
[43] 王成国．王世清．稀土催渗离子渗氮的研究．金属热处理 1991．No．3．P12—14
[44] 程先华．丁定远．稀土对渗氮过程的影响．金属热处理．1990．No．12．P3-8
[45] 胡以正．现代低温化学热处理．工艺概况及其技术覆盖面会议．武汉材料保护研究所．1987．4
[46] Ю．М．ЛахтлИ．渗氮技术的发展前景．金属热处理 1981．No．12．P7—13
[47] B．Grellet．渗层的表明特性和处理后零件的摩擦性能的研究．巴黎．第三届国际材料热处理大会论文选集1983．11
[48] 陈秀玉．离子深层可控渗氮在低速重载齿轮上的应用．北京．离子轰击热处理学术论文会论文．1986．5
[49] 荣国器．胡治流．氮化技术发展动向．北京．全国第二届低温化学热处理学术论文交流论文．1990．9
[50] 詹锡思．气体快速氮化经验介绍．四川自贡高压阀门总厂内部资料．1976
[51] K．H．Jack．氮化．北京．国外热处理．1981．No．9
[52] 周上祺．40Cr钢离子氮化后的时效的初步研究．北京．全国离子轰击热处理会议论文．1986
[53] 张津．工业纯铁与碳钢离子氮化缓冷时效研究．重庆大学硕士研究生论文．1989
[54] 范秋林．快速深层离子氮化处理工艺及机理研究．重庆大学硕士研究生论文．1992．7
[55] 李崇谟．氮势、气氛的供氮能力及其他．金属热处理．1988．9．P33—34
[56] 章子元．渗氮热力学．金属热处理．1988．5．P23—25
[57] 潘建生．胡明娟．钢铁化学热处理原理．上海．上海交通大学出版社．1988．8
[58] 机械工业部机电研究所主编．钢铁材料渗氮层金相组织图谱．北京．机械工业出版社．1986．10
[59] 周上褀．X射线衍射分析．重庆．重庆大学出版社．1991．12
[60] 杨承岳．块状试样的X射线定量金相分析技术．理学X射线衍射仪用户协会论文选集．1989．No．2
[61] 孟繁杰．黄国靖．氮化疏松的影响因素及形成过程．金属热处理．1987．No．3
[62] 朱联锡．等离子射流法制取氮化钛．国外稀有金属．1985．No．4
[63] 林化春．李凤照．离子渗氮层的磨损及磨损机理的探讨．金属热处理．1982．No．11
[64] 周一志．杨明忠．45钢离子渗氮层的微量磨损特性．金属热处理．1986．No．8
[65] J.GEORGES.TC Plasma Nitriding. Heat Treament of Metals .2001.2.P33-37
[66] Edenhofer B.Physical and metallurgical aspects of nitriding.Heat Treatment of Metals. 1974.1. Vol. 1. P23-28 and 1974.2.P59-67
[67] Marchiniak T.A and Karpinski T.comparative studines on energy consumption in installations fou ion and gas nitriding .Industrial Heating. 1980.4. Vol.47.P42-44
[68] Du.H.and Agren J.Theoretical treatment of nitriding and nitrocarburizing of ion. Metall. Trans. A. 1996.Vol.27.P 1073-1080
[69] Torchans L.,Bilger P.,Dulcy J.and Gantois M.Control of the compound layergreowth kinetics in the binary Fe-N system.Metall.Mater.Trans.A. 1996.Vol.27.P 1823-1835
[70] Du H.and Agren J.Gaseous nitriding of iron:evalution of diffusion data of N inγ and ε phases. Z. Metallkde. 1995.Vol.86.P522-529
[71] Jack K.H. The iron-nitrogen system:the crystal structures ofεphase iron nitrides. Acta Cryst. 1952.Vol.5.P404-401
[72] Jack K.H.Binary and ternary interstitial alloys:I.The iron-nitrogen system:the structures of Fe_2N and Fe_4N.Proc.Roy.Soc.London 1948. Vol.A195.P34-40
[73] Wells A.and Bell T.Structural control of the compound layers formed during ferrtic nitrocarburising in methanol/ammonia atmospheres.HEAT TREATMENT OF METALS. 1983.2. Vol. 10.P39-44
[74] 胡光立．谢希文．钢的热处理[M]．西安：西工大出版社．1993．P251．
[75] 杨津基．气体放电[M]．北京．科学出版社．1983．P18-20．
[76] 陈宗柱．高树香．气体导电(上册)[M]．南京．南京工学院出版社．1988．P54．
[77] 陈宗柱．高树香．气体导电(下册)[M]．南京．南京工学院出版社．1988．P14-16．
[78] 顾彩香．朱雅年．沈兆荃．加氩离子滲氮工艺研究．金属热处理．2000．No．2．P17-19
[2] [日]山中久彦．李贻锦．朱雅年译．离子渗氮．机械工业出版社．1985．4
[3] Freidrich Hombeck. Ion nitriding. International Conference and Exhibition. 1986.9
[4] B.Berghaus German patant DRP 375.235.1930.
[5] B.Berghaus German patant DRP 668.639.1932.
[6] B.Berghaus German patant DRP 851.540.1939.
[7] B.Berghaus us patant 3318409.1956.
[8] B.Berghaususpatant 3345280.1961.
[9] G.waidman Fersching sberichte des lands NRW. 944.1961.
[10] J.Kbel ibid. 1955.1965.
[11] A.F steinegger and S.Jentzch Ibid. 1548.1965.
[12] A.F steingg and J.Klanusler Ibid. 1743.1966.
[13] A.F steinegger and J.Klausler Ibid. 1617.1966.
[14] V.A Phillips and A.V Seybolt.Met prog. 242.1968.
[15] A.V Seybolt.Met prog. 245.1969.
[16] 浙江大学．离子氮化．《新技术译丛》编译组．1978．6
[17] 周上祺．离子氮化及离子轰击热处理．重庆大学冶金及材料工程系．1983．2
[18] 徐重．兵器工艺技术．北京．北京出版社．1979．2
[19] 齐见新．微型计算机在离子氮化炉中的应用．鞍山．鞍山钢铁学报．2001．6．Vol．24．No．3．P164-167
[20] 唐红文．离子渗氮自动控制系统的设计．中南民族学院学报．2001．3．Vol．20．No．1．P6-9
[21] 周孝重．陈大凯．等离子体热处理技术．北京．机械工业出版社．1990．4
[22] J.Klbel The formation of nitride layers in glow discharge nitriding. German. Ibids. 1555.1965.
[23] Martin Hudis J.Appl.phys. 1977.Vol44. No.4 1489-1496
[24] Cary G Tibbetts J.Appl.phys. Vol45(1978) No.11 95072
[25] 徐冰仲．张颖智．离子氮化氮的渗入机理．金属热处理 1983．No．10．P29—41
[26] 徐冰仲．张颖智．离子氮化离解模型．中国铁道化学研究所．1986．Vol．7 No．2
[27] 拉赫金著．郭铮匀译．钢的氮化．北京．国防工业出版社．1979．10
[28] 洪班德．姚忠凯．化学热处理．哈尔滨．黑龙江人民出版社．1981．12
[29] 牧村．夏立芳译．《热处理》．1979．Vol．19 No．6
[30] F．Homebeck等．离子体的技术与经济特点．巴黎．第三届国际材料热处理大会论文选集．1983．11
[31] H．J．spies．钢渗氮层的韧性及其特征．布达佩斯．第四届国际材料热处理大会论文选集．1985．6
[32] 夏立芳．高彩桥．钢的滲氮．北京．机械工业出版社．1989．6
[33] 杜树芳．黄辉．氮化钢离子氮化化合物形成过程的研究．金属热处理．1984．No．3
[34] 孟繁杰．黄国靖．十年来离子渗氮技术的发展．金属热处理．1986．10
[35] 谢黎雄．氮势控制技术及其应用．金属热处理．2002．No．5．Vol．27．P25—27
[36] 陈秀玉．陈俭康．渗氮钢高韧性层离子渗氮相成分控制及性能的研究．郑州机械研究所．1988．7
[37] 钟厉．周上祺．氮化层的形成与工艺参数的关系．全国第三届低温化学热处理学术论文讨论会论文．1992．9
[38] Matrin Hudis．离子氮化的研究．J．Appl．phys Vol．44 No．4 April 1973
[39] 周上棋．辉光离子氮化机理的初步探讨(二)重庆大学学报．1980．No．2
[40] 王丽莲．渗氮技术及其发展．热处理2001．No．2．P6—9
[41] 北京第二通用机械厂．法净氮化法．一机所情报活页技术资料．第二号．机械工业出版社．1974
[42] 余宗森．钢中稀土．北京．冶金工业出版社．1982
[43] 王成国．王世清．稀土催渗离子渗氮的研究．金属热处理 1991．No．3．P12—14
[44] 程先华．丁定远．稀土对渗氮过程的影响．金属热处理．1990．No．12．P3-8
[45] 胡以正．现代低温化学热处理．工艺概况及其技术覆盖面会议．武汉材料保护研究所．1987．4
[46] Ю．М．ЛахтлИ．渗氮技术的发展前景．金属热处理 1981．No．12．P7—13
[47] B．Grellet．渗层的表明特性和处理后零件的摩擦性能的研究．巴黎．第三届国际材料热处理大会论文选集1983．11
[48] 陈秀玉．离子深层可控渗氮在低速重载齿轮上的应用．北京．离子轰击热处理学术论文会论文．1986．5
[49] 荣国器．胡治流．氮化技术发展动向．北京．全国第二届低温化学热处理学术论文交流论文．1990．9
[50] 詹锡思．气体快速氮化经验介绍．四川自贡高压阀门总厂内部资料．1976
[51] K．H．Jack．氮化．北京．国外热处理．1981．No．9
[52] 周上祺．40Cr钢离子氮化后的时效的初步研究．北京．全国离子轰击热处理会议论文．1986
[53] 张津．工业纯铁与碳钢离子氮化缓冷时效研究．重庆大学硕士研究生论文．1989
[54] 范秋林．快速深层离子氮化处理工艺及机理研究．重庆大学硕士研究生论文．1992．7
[55] 李崇谟．氮势、气氛的供氮能力及其他．金属热处理．1988．9．P33—34
[56] 章子元．渗氮热力学．金属热处理．1988．5．P23—25
[57] 潘建生．胡明娟．钢铁化学热处理原理．上海．上海交通大学出版社．1988．8
[58] 机械工业部机电研究所主编．钢铁材料渗氮层金相组织图谱．北京．机械工业出版社．1986．10
[59] 周上褀．X射线衍射分析．重庆．重庆大学出版社．1991．12
[60] 杨承岳．块状试样的X射线定量金相分析技术．理学X射线衍射仪用户协会论文选集．1989．No．2
[61] 孟繁杰．黄国靖．氮化疏松的影响因素及形成过程．金属热处理．1987．No．3
[62] 朱联锡．等离子射流法制取氮化钛．国外稀有金属．1985．No．4
[63] 林化春．李凤照．离子渗氮层的磨损及磨损机理的探讨．金属热处理．1982．No．11
[64] 周一志．杨明忠．45钢离子渗氮层的微量磨损特性．金属热处理．1986．No．8
[65] J.GEORGES.TC Plasma Nitriding. Heat Treament of Metals .2001.2.P33-37
[66] Edenhofer B.Physical and metallurgical aspects of nitriding.Heat Treatment of Metals. 1974.1. Vol. 1. P23-28 and 1974.2.P59-67
[67] Marchiniak T.A and Karpinski T.comparative studines on energy consumption in installations fou ion and gas nitriding .Industrial Heating. 1980.4. Vol.47.P42-44
[68] Du.H.and Agren J.Theoretical treatment of nitriding and nitrocarburizing of ion. Metall. Trans. A. 1996.Vol.27.P 1073-1080
[69] Torchans L.,Bilger P.,Dulcy J.and Gantois M.Control of the compound layergreowth kinetics in the binary Fe-N system.Metall.Mater.Trans.A. 1996.Vol.27.P 1823-1835
[70] Du H.and Agren J.Gaseous nitriding of iron:evalution of diffusion data of N inγ and ε phases. Z. Metallkde. 1995.Vol.86.P522-529
[71] Jack K.H. The iron-nitrogen system:the crystal structures ofεphase iron nitrides. Acta Cryst. 1952.Vol.5.P404-401
[72] Jack K.H.Binary and ternary interstitial alloys:I.The iron-nitrogen system:the structures of Fe_2N and Fe_4N.Proc.Roy.Soc.London 1948. Vol.A195.P34-40
[73] Wells A.and Bell T.Structural control of the compound layers formed during ferrtic nitrocarburising in methanol/ammonia atmospheres.HEAT TREATMENT OF METALS. 1983.2. Vol. 10.P39-44
[74] 胡光立．谢希文．钢的热处理[M]．西安：西工大出版社．1993．P251．
[75] 杨津基．气体放电[M]．北京．科学出版社．1983．P18-20．
[76] 陈宗柱．高树香．气体导电(上册)[M]．南京．南京工学院出版社．1988．P54．
[77] 陈宗柱．高树香．气体导电(下册)[M]．南京．南京工学院出版社．1988．P14-16．
[78] 顾彩香．朱雅年．沈兆荃．加氩离子滲氮工艺研究．金属热处理．2000．No．2．P17-19
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