取向硅钢氮化与AlN形成的模拟计算
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摘要
本世纪30年代初Goss.N.P发现冷轧变压器硅钢片具有{110}<001>晶粒取向后,磁性能可大幅上升,立即引起人们的注意并开始广泛研究。因此,如何在取向硅钢中获得更多{110}<001>取向便成为研究热点。
研究中发现{110}<001>织构是一个利用析出的第二相质点二次再结晶的问题。也就是说二次再结晶过程中,由于硅钢中沉淀析出弥散分布的第二相夹杂物有效抑制了初次再结晶的正常晶粒的生长,为{110}<001>取向晶粒的迅速长大提供了条件。因此,如何提高细小弥散的抑制剂数量便成为核心问题之一,而对于生产高牌号的取向硅钢,多数使用AlN+MnS抑制剂方案,如何提高取向硅钢二次再结晶之前抑制剂的数量便成为一个问题,近年来研究发现二次再结晶之前进行渗氮处理可以有效提高AlN生成量,因此本工作主要通过对各种国内外渗氮模型进行分析,建立适于取向硅钢渗氮过程的扩散及动力学模型。从气氛分解、吸附、扩散、渗入,形核几部分模型入手,辅以Fe-Al-Mn三元系合金参数、平衡状态的固溶积和经典形核理论,建立出计算结果与实验相吻合的模型。并对其进行简要误差分析(误差小于7.5×10-7g)。导出了不同温度下氮原子的有效扩散系数,建立了适用于取向硅钢渗氮计算的有效的扩散系数与温度间的关系及氮原子的扩散激活能。渗氮气氛一定的情况下,渗入氮含量随温度增加而增大。温度升高时,氮浓度梯度增加。利用所建模型可以有效对取向硅钢氮化过程中AlN扩散形核进行计算。
The finding of great enhancement in magnetic property of Cold-Rolling Orientated Silicon Sheet quickly allured flourish abroad research enthusiasm since there would be benefit to render{110}<001>texture in silicon steel sheet. So how to acquire more{110}<001>texture in silicon sheet is currently under academic spotlight.
Recent research discover that the{110}<001>texture is a problem which should utilize second phase particles to control secondary recrystallization; to be in short, the key factor to restrain recrystallization is particles which precipitated from dispersion distribution inhibitors, the driving force coming along with this procedure. By consideration of the critical factor of inhibitor in manufacturing of silicon sheets, how to increase amount of inhibitor of AIN in fabrication of grain-oriented steel is coming as a crux. Many references state that nitrding process may enhance amount of AIN, but there are still too few relevant references to browse specific discussion in this affairs with numerical calculation. So the major in this thesis is taking analysis about nitrding models all round, construct proper model to cater our demand in diffusion kinetic, atmosphere decomposition, adsorption and nucleation interdisciplinary, getting a company with phrase diagram of the Fe-Al-Mn, decholesterinization volume and classic nucleation theory, by using above mentioned, we can induct agreeable model, testing and rejoining its error (error parameter less than 7.5×10-7g). It is also a convenient for us to inducing the effective diffusion coefficient in nitrogen and its connection between nitrogen coefficient and temperature along with the relation in diffusion activation energy. From that we concluded that with finite temperature, the amount of nitrogen increased with enhancing of temperature, the concentration gradient will be aggrandizing with slope. It would be very effective, if these models which were established in this thesis could be utilized and applied in manufacturing process due to nitrding process for silicon sheet.
研究中发现{110}<001>织构是一个利用析出的第二相质点二次再结晶的问题。也就是说二次再结晶过程中,由于硅钢中沉淀析出弥散分布的第二相夹杂物有效抑制了初次再结晶的正常晶粒的生长,为{110}<001>取向晶粒的迅速长大提供了条件。因此,如何提高细小弥散的抑制剂数量便成为核心问题之一,而对于生产高牌号的取向硅钢,多数使用AlN+MnS抑制剂方案,如何提高取向硅钢二次再结晶之前抑制剂的数量便成为一个问题,近年来研究发现二次再结晶之前进行渗氮处理可以有效提高AlN生成量,因此本工作主要通过对各种国内外渗氮模型进行分析,建立适于取向硅钢渗氮过程的扩散及动力学模型。从气氛分解、吸附、扩散、渗入,形核几部分模型入手,辅以Fe-Al-Mn三元系合金参数、平衡状态的固溶积和经典形核理论,建立出计算结果与实验相吻合的模型。并对其进行简要误差分析(误差小于7.5×10-7g)。导出了不同温度下氮原子的有效扩散系数,建立了适用于取向硅钢渗氮计算的有效的扩散系数与温度间的关系及氮原子的扩散激活能。渗氮气氛一定的情况下,渗入氮含量随温度增加而增大。温度升高时,氮浓度梯度增加。利用所建模型可以有效对取向硅钢氮化过程中AlN扩散形核进行计算。
The finding of great enhancement in magnetic property of Cold-Rolling Orientated Silicon Sheet quickly allured flourish abroad research enthusiasm since there would be benefit to render{110}<001>texture in silicon steel sheet. So how to acquire more{110}<001>texture in silicon sheet is currently under academic spotlight.
Recent research discover that the{110}<001>texture is a problem which should utilize second phase particles to control secondary recrystallization; to be in short, the key factor to restrain recrystallization is particles which precipitated from dispersion distribution inhibitors, the driving force coming along with this procedure. By consideration of the critical factor of inhibitor in manufacturing of silicon sheets, how to increase amount of inhibitor of AIN in fabrication of grain-oriented steel is coming as a crux. Many references state that nitrding process may enhance amount of AIN, but there are still too few relevant references to browse specific discussion in this affairs with numerical calculation. So the major in this thesis is taking analysis about nitrding models all round, construct proper model to cater our demand in diffusion kinetic, atmosphere decomposition, adsorption and nucleation interdisciplinary, getting a company with phrase diagram of the Fe-Al-Mn, decholesterinization volume and classic nucleation theory, by using above mentioned, we can induct agreeable model, testing and rejoining its error (error parameter less than 7.5×10-7g). It is also a convenient for us to inducing the effective diffusion coefficient in nitrogen and its connection between nitrogen coefficient and temperature along with the relation in diffusion activation energy. From that we concluded that with finite temperature, the amount of nitrogen increased with enhancing of temperature, the concentration gradient will be aggrandizing with slope. It would be very effective, if these models which were established in this thesis could be utilized and applied in manufacturing process due to nitrding process for silicon sheet.
引文
[1]何忠治．电工钢[M]，北京：冶金工业出版社，1996
[2]潘邻．化学热处理应用技术[M]，北京：机械工业出版社，2004
[3]徐瑞．材料中的数值模拟与计算[M]，哈尔滨：哈尔滨工业大学出版社，2005．4．
[4]魏天斌．国内外冷轧硅钢片供需现状及发展趋势[J]，武汉，武钢技术，2006
[5]Goss．N．P．U．S．Patent，No．1 965559，1934．
[6]田中悟．电磁钢板[M]，新日本制铁株式会社，1979．中岗一秀，高田芳一ほ高磁率磁性薄钢板の制造方法，日本公开特许公报，昭61-80806,1986．
[7] #12
[8] #12
[9]荒井贤一，石山和志．薄硅素钢板の三次再结晶上磁气特性[J]，日本金属学会会报[J]，1992，31(5)：429-435．
[10]石山和志，荒井贤一，本田崇，中野正基．薄硅素钢板の含有不纯物と三次再结晶举动[J]，日本金属学会誌，1993，57(1)：114-118．
[11]荒井贤一，上野雅郎ほか．低铁损方向性硅素钢板の制造方法[J]，日本公开特许公报，平3-100123，1991．
[12]荒齿有浩，吉刚进，上野雅郎ほか．方向性硅素钢板の热处理方法[J]，日本公开特许公报，平2-149623，1990．
[13]赵宇．电工钢中的晶界偏聚[J]，钢铁研究学报，1995，7(1)：66-72．
[14]梁志德，徐家桢，王福．织构材料的三维取向分析术-ODF[M]，沈阳：东北工学院，1986．
[15]何忠治．电工钢的现状与展望[J]，北京：中国冶金，2001，12(3)．
[16]王振清，张建华．炉内气氛及计算机测控应用[M]，北京：航空航天大学，1996，135．
[17]Heo.N.H, Kim.S.B.Interfacial Segregation, Nucleation and Texture and Texture Development in 3%Silicon steel[J], Acta Mater, 2003, 51, 43-49.
[18]Dimitrov.V.I. Jekov.K. Prediction of the Solubility of Nitrogrn in Steels by High Pressure, Comput Mater Sci[J], 1999,15,400-410.
[19]卢凤喜，姚成军．日本高磁感取向硅钢最新进展[M]，金属功能材料，2006,Vol．13．
[20]Toshito.T,Mitsumasa.K. Effect of Hydrogen in the Final Annealing Atmosphere on the Secondary Recrystallization of Grain-oriented Si Steel[J]. Jul of Magnetic Mater,2003,254-252.
[21]蒙肇斌,赵宇,何忠治.高磁感取向硅钢中抑制剂质点硫化物与A1N析出形态的研究[J],金属功能材料,1997,34(2)：38.
[22]蒙肇斌,赵宇,何忠治.高磁感取向硅钢常化处理过程中氮化物沉淀[J],特殊钢,Vol.20：51.
[23]Dimitrov.I, Jekov.K, Avinc.A. Modeling of Nitride Layer Formation during Nitrding of Iron[J]. Comput Mater Sci,1999,(15):22-54.
[24]Goune.T,Belmonte.J, Fiiorani.M.Modeling of Diffusion-precipitation in Nitrded Alloyed Iron[J].Thin Solid Films,2000,377-387.
[25]Eidel.M.O.Applications and Services[A].High Nitrogen Steels and Stainless Steels, Properties and Application[C].Alpha Sci Inter Ltd, Pangbourne U.K,2004:243-255.
[26]文凡.钢的高压氮气合金化[C],国外金属材料,1991,(1)：4-7.
[27]Takahashi.I,Tanaka.K. Deoxidation and Desulfurization Steels with Calcium[J]. Inter,1990,30(3):192-198.
[28]沈小军等.冷塑性变形对渗氮过程的影响[J],金属材料,2001,(4)：60-37.
[29]Tsuchiyama.L.Nitrogen in Austenitic Stainless Steels [J]. JOM,1989(3):16-21.
[30]Aldev.J,Kachami M. Historical Evolution of HNS Alloys[A]. High Nitrogen Steels Stainless Steels-Manufacturing, Properties and Applications[C]. Alpha Science, International Ltd., Pangbourne U. K.,2004,(6):1-9.
[31]Frisk.K.氮在钢中的某些有益作用[J].许嘉龙,葛红林译.高氮钢译文集[C].上海：上海钢铁研究所,1990,3(28)：1-21.
[32]陆利明,李宏,壮云乾等.氮气加压熔炼高氮钢若干理论问题探讨[[J].钢铁研究学报,1996,8(6)：6-10.
[33]铮匀译.钢的氮化[M].北京：国防工业出版社,1979,136-139.
[34]Oct.J.High Nitrogen Steel:From Science to Technology. High Nitrogen Steel HNS-90Con, Achen, Germany,1990,3(9):13-16.
[35]志远,吴光英.氮基气氛热处理[M].北京：机械工业出版社,1988：143-152.
[36]Schiptschin.A.P.Thermodynamics[M].U.S:Springer,2000,43-50.
[37]Tanaka.H. Thermal Analysis and Kinetics of Solid State Reactions[J]. Thermochim. Acta,1998,267:29-44
[38]Marick.T.P.Making Silicon Nitride Film a Viable Gate Dielectric, IEEE Trans. Electron [J]. Dev,1998,680-690.
[39]雷声,黄已立.临界氮势及影响因素[J].安徽大学学报(自然科学版),Vol.28,No.2.
[40]Tomoji.K.渗氮对含硅晶粒取向硅钢的影响[M],ISIJ,2005,(2)：72.
[41]吴季询等译.钢的氮化文集[M].北京：机械工业出版社,1975.
[42]Gokhsier.N.A.The Al-N System[A]. Bulletin of Alloy Phase Diagrams,1990,11(1): 33-42.
[43]张显鹏等编.铁合金辞典[M].沈阳：辽宁科学技术出版社,1996.
[44]郝士明等编.材料热力学[M].东北大学出版社,2002,(2)：38-44.
[45]Udielka.H, Grabke.H.J.Investigation of the Aluminum-Nitrogen Phase Diagram by X-ray Diffraction at High Temperatures [J]. Z Metallkd,1975,66(6):469-471.
[46]Chenck.V.H, Frohberg.M.G, Reinders.F. The Solubility of Nitrogen in Iron Alloys in the Temperature Range 7000-12000C [J]. Stahl and Eisen,1963,83(2):93-99.
[47]Ompe.R,.A Theory to Analysis of the Solubility of Nitrogen Gas in Aluminuim in the13-25at [N]%[J], J Less-Common Metals,1979, (65):237-252.
[48]Hiterpuer.A.Reevaluation of the Fe-N and Fe-C-N Systems[J]. J Phase Equilibria, 1993,14(6):682-693.
[49]Yonglin.K, Hao.Y, Jie.F, Kelu.W, Zhongbing.W. Morphology and Precipitation Kinetic of AlN in Hot strip of Low Carbon Steel Produced by the Compact Strip Production[J], Mater Sci& Engr,2003,265-271.
[50]Illert.M,Jarl.M. A Thermodynamic Analysis of the Iron-nitrogen System[J]. Metall Trans,1975,6A (3):553-559.
[51]清斌,土晓春编译.合金中的扩散性相变与合金热力学[M].沈阳：辽宁科学技术出版社.1984,(2)：23-27.
[2]潘邻．化学热处理应用技术[M]，北京：机械工业出版社，2004
[3]徐瑞．材料中的数值模拟与计算[M]，哈尔滨：哈尔滨工业大学出版社，2005．4．
[4]魏天斌．国内外冷轧硅钢片供需现状及发展趋势[J]，武汉，武钢技术，2006
[5]Goss．N．P．U．S．Patent，No．1 965559，1934．
[6]田中悟．电磁钢板[M]，新日本制铁株式会社，1979．中岗一秀，高田芳一ほ高磁率磁性薄钢板の制造方法，日本公开特许公报，昭61-80806,1986．
[7] #12
[8] #12
[9]荒井贤一，石山和志．薄硅素钢板の三次再结晶上磁气特性[J]，日本金属学会会报[J]，1992，31(5)：429-435．
[10]石山和志，荒井贤一，本田崇，中野正基．薄硅素钢板の含有不纯物と三次再结晶举动[J]，日本金属学会誌，1993，57(1)：114-118．
[11]荒井贤一，上野雅郎ほか．低铁损方向性硅素钢板の制造方法[J]，日本公开特许公报，平3-100123，1991．
[12]荒齿有浩，吉刚进，上野雅郎ほか．方向性硅素钢板の热处理方法[J]，日本公开特许公报，平2-149623，1990．
[13]赵宇．电工钢中的晶界偏聚[J]，钢铁研究学报，1995，7(1)：66-72．
[14]梁志德，徐家桢，王福．织构材料的三维取向分析术-ODF[M]，沈阳：东北工学院，1986．
[15]何忠治．电工钢的现状与展望[J]，北京：中国冶金，2001，12(3)．
[16]王振清，张建华．炉内气氛及计算机测控应用[M]，北京：航空航天大学，1996，135．
[17]Heo.N.H, Kim.S.B.Interfacial Segregation, Nucleation and Texture and Texture Development in 3%Silicon steel[J], Acta Mater, 2003, 51, 43-49.
[18]Dimitrov.V.I. Jekov.K. Prediction of the Solubility of Nitrogrn in Steels by High Pressure, Comput Mater Sci[J], 1999,15,400-410.
[19]卢凤喜，姚成军．日本高磁感取向硅钢最新进展[M]，金属功能材料，2006,Vol．13．
[20]Toshito.T,Mitsumasa.K. Effect of Hydrogen in the Final Annealing Atmosphere on the Secondary Recrystallization of Grain-oriented Si Steel[J]. Jul of Magnetic Mater,2003,254-252.
[21]蒙肇斌,赵宇,何忠治.高磁感取向硅钢中抑制剂质点硫化物与A1N析出形态的研究[J],金属功能材料,1997,34(2)：38.
[22]蒙肇斌,赵宇,何忠治.高磁感取向硅钢常化处理过程中氮化物沉淀[J],特殊钢,Vol.20：51.
[23]Dimitrov.I, Jekov.K, Avinc.A. Modeling of Nitride Layer Formation during Nitrding of Iron[J]. Comput Mater Sci,1999,(15):22-54.
[24]Goune.T,Belmonte.J, Fiiorani.M.Modeling of Diffusion-precipitation in Nitrded Alloyed Iron[J].Thin Solid Films,2000,377-387.
[25]Eidel.M.O.Applications and Services[A].High Nitrogen Steels and Stainless Steels, Properties and Application[C].Alpha Sci Inter Ltd, Pangbourne U.K,2004:243-255.
[26]文凡.钢的高压氮气合金化[C],国外金属材料,1991,(1)：4-7.
[27]Takahashi.I,Tanaka.K. Deoxidation and Desulfurization Steels with Calcium[J]. Inter,1990,30(3):192-198.
[28]沈小军等.冷塑性变形对渗氮过程的影响[J],金属材料,2001,(4)：60-37.
[29]Tsuchiyama.L.Nitrogen in Austenitic Stainless Steels [J]. JOM,1989(3):16-21.
[30]Aldev.J,Kachami M. Historical Evolution of HNS Alloys[A]. High Nitrogen Steels Stainless Steels-Manufacturing, Properties and Applications[C]. Alpha Science, International Ltd., Pangbourne U. K.,2004,(6):1-9.
[31]Frisk.K.氮在钢中的某些有益作用[J].许嘉龙,葛红林译.高氮钢译文集[C].上海：上海钢铁研究所,1990,3(28)：1-21.
[32]陆利明,李宏,壮云乾等.氮气加压熔炼高氮钢若干理论问题探讨[[J].钢铁研究学报,1996,8(6)：6-10.
[33]铮匀译.钢的氮化[M].北京：国防工业出版社,1979,136-139.
[34]Oct.J.High Nitrogen Steel:From Science to Technology. High Nitrogen Steel HNS-90Con, Achen, Germany,1990,3(9):13-16.
[35]志远,吴光英.氮基气氛热处理[M].北京：机械工业出版社,1988：143-152.
[36]Schiptschin.A.P.Thermodynamics[M].U.S:Springer,2000,43-50.
[37]Tanaka.H. Thermal Analysis and Kinetics of Solid State Reactions[J]. Thermochim. Acta,1998,267:29-44
[38]Marick.T.P.Making Silicon Nitride Film a Viable Gate Dielectric, IEEE Trans. Electron [J]. Dev,1998,680-690.
[39]雷声,黄已立.临界氮势及影响因素[J].安徽大学学报(自然科学版),Vol.28,No.2.
[40]Tomoji.K.渗氮对含硅晶粒取向硅钢的影响[M],ISIJ,2005,(2)：72.
[41]吴季询等译.钢的氮化文集[M].北京：机械工业出版社,1975.
[42]Gokhsier.N.A.The Al-N System[A]. Bulletin of Alloy Phase Diagrams,1990,11(1): 33-42.
[43]张显鹏等编.铁合金辞典[M].沈阳：辽宁科学技术出版社,1996.
[44]郝士明等编.材料热力学[M].东北大学出版社,2002,(2)：38-44.
[45]Udielka.H, Grabke.H.J.Investigation of the Aluminum-Nitrogen Phase Diagram by X-ray Diffraction at High Temperatures [J]. Z Metallkd,1975,66(6):469-471.
[46]Chenck.V.H, Frohberg.M.G, Reinders.F. The Solubility of Nitrogen in Iron Alloys in the Temperature Range 7000-12000C [J]. Stahl and Eisen,1963,83(2):93-99.
[47]Ompe.R,.A Theory to Analysis of the Solubility of Nitrogen Gas in Aluminuim in the13-25at [N]%[J], J Less-Common Metals,1979, (65):237-252.
[48]Hiterpuer.A.Reevaluation of the Fe-N and Fe-C-N Systems[J]. J Phase Equilibria, 1993,14(6):682-693.
[49]Yonglin.K, Hao.Y, Jie.F, Kelu.W, Zhongbing.W. Morphology and Precipitation Kinetic of AlN in Hot strip of Low Carbon Steel Produced by the Compact Strip Production[J], Mater Sci& Engr,2003,265-271.
[50]Illert.M,Jarl.M. A Thermodynamic Analysis of the Iron-nitrogen System[J]. Metall Trans,1975,6A (3):553-559.
[51]清斌,土晓春编译.合金中的扩散性相变与合金热力学[M].沈阳：辽宁科学技术出版社.1984,(2)：23-27.