铝、硅、碳还原剂对合成矾土基Sialon的作用及机理探讨
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摘要
本论文采用我国丰富的高铝矾土，分别以碳黑、Si粉和Al粉为还原剂利用综合差热分析(TG-DTA)、热天平、X-ray衍射(XRD)和扫描电子显微镜(SEM)来探讨铝、硅、碳三种还原剂对合成矾土基Sialon的作用及其合成机理；同时简单探讨了矾土原料中结晶水对合成Sialon的影响和三种还原剂对合成矾土基Sialon的过程的对比。
论文较全面地探讨了铝、硅、碳三种还原剂合成矾土基Sialon的反应过程，实验数据表明：铝热还原氮化合成矾土基Sialon的过程可分为以下5个阶段：(1)AlN的形成(600-800℃)；(2)SiO_2被还原并形成Si_3N_4(900-1200℃)；(3)β-Sialon开始形成(1300-1350℃)；(4)形成Si_2N_2O和过渡态Sialon(1400℃左右)；(5)最终形成z=3的β-Sialon(1450-1500℃)。得到的β-Sialon相大部分为短柱状，尺寸为10um左右。
硅热还原氮化合成矾土基Sialon的过程如下：(1)Si粉的氮化(900-1200℃)；(2)Si_3N_4从1200℃左右与SiO_2反应生成Si_2N_2O，从1300℃左右开始Si_2N_2O与Al_2O_3反应生成O′-Sialon；(3)1300℃左右开始，Si还原原料中的SiO_2生成SiO，在N_2下SiO与N_2反应生成Si_2N_2O，从而从1400℃开始β-Sialon生成；(4)在1450-1500℃，还原氮化反应完成，最终主要产物为β-Sialon和O′-Sialon。得到的Sialon相主要为晶须状。
碳热还原氮化合成矾土基Sialon的过程如下：(1)碳还原原料中SiO_2和莫来石生成SiO，SiO与N_2反应生成Si_2N_2O，Si_2N_2O与Al_2O_3反应生成X相(1300-1350℃)；(2)β-Sialon开始生成，X相为中间产物(1400-1450℃)；(3)一部分β-Sialon分解生成15R，最终物相为z=3的β-Sialon和少量的15R(1500-1550℃)。得到的β-Sialon相大多为长柱状，尺寸为10um左右。
This paper studies the process of synthesizing Sialon based on bauxite by aluminum thermal reduction-nitridation, silicon thermal reduction-nitridation and carbonthermal reduction-nitridation methods, using DTA-TG, thermal balance, XRD analysis and SEM with ED AX. The effect of crystal water on synthesization of Sialon and the influnces of the three reduction agents on the reaction processes are also compared.
The aluminum thermal reduction-nitridation reactions involved are found to proceed in five stages as follows: (1) Formation of A1N(600-800); (2) Reduction of SiO2 and formation of Si3N4(900-1200癈); (3) Initial formation of P -Sialon(1300-1350癈); (4) Formation of Si2N2O and transitory Sialon phase(1400or so); (5) Ultimate formation of P -Sialon(Z=3) (1450-1500 癈).The ultimate microstructure of P -Sialon crystals are regular short and long column with crystal size about 1 Oum.
The silicon thermal reduction-nitridation reactions involved are found to proceed in four
stages as follows: (1) Formation of Si3N4 (900-1200 );(2)Initial formation of Si2N2O and
further formation of O'-Sialon (1200-1300);(3) Reduction of SiO2 and initial formation of
P-Sialon(l 300-1400 );(4) Ultimate formation of 逽ialon and O'-Sialon (1450-1500
).Most of the Sialon crystals formed are whiskers.
The carbonthermal reduction-nitridation reactions involved are found to proceed in three stages as follows: (1) Reduction of mullite and cristobalite(1300-1350);(2) Formation of P -Sialon from X-phase as the intermediate product(1400-1450癈);(3) Partially formation of 15R from P -Sialon(1500-1550).The ultimate microstructure of P -Sialon crystals are long column with crystal size about lOum.
论文较全面地探讨了铝、硅、碳三种还原剂合成矾土基Sialon的反应过程，实验数据表明：铝热还原氮化合成矾土基Sialon的过程可分为以下5个阶段：(1)AlN的形成(600-800℃)；(2)SiO_2被还原并形成Si_3N_4(900-1200℃)；(3)β-Sialon开始形成(1300-1350℃)；(4)形成Si_2N_2O和过渡态Sialon(1400℃左右)；(5)最终形成z=3的β-Sialon(1450-1500℃)。得到的β-Sialon相大部分为短柱状，尺寸为10um左右。
硅热还原氮化合成矾土基Sialon的过程如下：(1)Si粉的氮化(900-1200℃)；(2)Si_3N_4从1200℃左右与SiO_2反应生成Si_2N_2O，从1300℃左右开始Si_2N_2O与Al_2O_3反应生成O′-Sialon；(3)1300℃左右开始，Si还原原料中的SiO_2生成SiO，在N_2下SiO与N_2反应生成Si_2N_2O，从而从1400℃开始β-Sialon生成；(4)在1450-1500℃，还原氮化反应完成，最终主要产物为β-Sialon和O′-Sialon。得到的Sialon相主要为晶须状。
碳热还原氮化合成矾土基Sialon的过程如下：(1)碳还原原料中SiO_2和莫来石生成SiO，SiO与N_2反应生成Si_2N_2O，Si_2N_2O与Al_2O_3反应生成X相(1300-1350℃)；(2)β-Sialon开始生成，X相为中间产物(1400-1450℃)；(3)一部分β-Sialon分解生成15R，最终物相为z=3的β-Sialon和少量的15R(1500-1550℃)。得到的β-Sialon相大多为长柱状，尺寸为10um左右。
This paper studies the process of synthesizing Sialon based on bauxite by aluminum thermal reduction-nitridation, silicon thermal reduction-nitridation and carbonthermal reduction-nitridation methods, using DTA-TG, thermal balance, XRD analysis and SEM with ED AX. The effect of crystal water on synthesization of Sialon and the influnces of the three reduction agents on the reaction processes are also compared.
The aluminum thermal reduction-nitridation reactions involved are found to proceed in five stages as follows: (1) Formation of A1N(600-800); (2) Reduction of SiO2 and formation of Si3N4(900-1200癈); (3) Initial formation of P -Sialon(1300-1350癈); (4) Formation of Si2N2O and transitory Sialon phase(1400or so); (5) Ultimate formation of P -Sialon(Z=3) (1450-1500 癈).The ultimate microstructure of P -Sialon crystals are regular short and long column with crystal size about 1 Oum.
The silicon thermal reduction-nitridation reactions involved are found to proceed in four
stages as follows: (1) Formation of Si3N4 (900-1200 );(2)Initial formation of Si2N2O and
further formation of O'-Sialon (1200-1300);(3) Reduction of SiO2 and initial formation of
P-Sialon(l 300-1400 );(4) Ultimate formation of 逽ialon and O'-Sialon (1450-1500
).Most of the Sialon crystals formed are whiskers.
The carbonthermal reduction-nitridation reactions involved are found to proceed in three stages as follows: (1) Reduction of mullite and cristobalite(1300-1350);(2) Formation of P -Sialon from X-phase as the intermediate product(1400-1450癈);(3) Partially formation of 15R from P -Sialon(1500-1550).The ultimate microstructure of P -Sialon crystals are long column with crystal size about lOum.
引文
[1] Jack K.H. Sialons and related nitrogen ceramics. J. Mater. Sci., 1976, 11(3): 1135-1158
[2] 文红杰．红柱石的应用基础研究．[博士学位论文]．北京．北京科技大学，1997：128
[3] 钟香崇．矾土基耐火材料的研究与发展．耐火材料，1997(3)：125-130
[4] 钟香崇．中国耐火原料的发展．耐火材料，1999(6)：307-309
[5] Zhong X.C.,Li G.P. Sintering Characteristics of Chinese Bauxites. Ceramics International,1981,7(2):65-68
[6] 孙庚辰，钟香崇．我国DK型烧结高铝矾土材料的应力．应变特征．硅酸盐学报，1984，12(3)：355-362
[7] Zhong X.C. et al.. The Effect of some Oxide Additions on the Microstrure and Thermomechanical properties of Sintered Chinese Bauxites. Ceramics. Inter. 1988:108-122
[8] Zhong X.C., Sun G.C., Yin R. S. High Temperature Mechanical Properties of Bauxite Refractories in Microstructure and Properties of Ceramic Materials. Eds. Yan T.S. Pask J.A. 1984:254-261
[9] O'yama y. and Kamigaito. K.. Solid solubility of some oxides in Si_3N_4. Jpn. J. Appl. Phys, 1971,10:1637-1642
[10] Jack, K. H. and Wilson, W.I. Ceramics based on the Si-Al-O-N and related systems. Nature Phys.Sci.(London), 1972,23 8:28-29
[11] Jack K. H., WI. Nature(London), Phys. Sci., 1997,238:28-29
[12] 陈卫武，孙维莹，严东生．Ln-a-Sialon-AlN多型体(Ln=Y，Y+Sm，Sm)复相陶瓷微观结构的研究．无机材料学报，2000，6，15(3)：441-446
[13] T. Ekstrom, P.O. Kall, M. Nygren and P.O. Olson. Dense Single-phase β -Sialon Ceramics by glass-wmcapsulated hot isostatic pressing. J.Mater. Sci.1989 (24): 1853-1861
[14] A. Zangvil, L.J. Gauchkler, M. Ruhle. Indexed X-ray diffraction data for the sialon X-phase. J.Mat. Sci. Letters 15(1980)
[15] 李世普主编 《特种陶瓷工艺学》 武汉．武汉工业大学出版社，1990
[16] M. B. Trigg, et al. J. Mater. Sci., 23,1981,481
[17] XU Y. HUANG C M KRIVEN W Met al. Residual a -Si3N4 in o'-Crystals in CeO_2-Doped o'+β'-Sialon Ceramics. J. Am. Ceram soc. 1994 77(8)
[18] 仲维斌，李文超，王俭．塞隆陶瓷的发展概况．耐火材料，1994，28(4)：233-236
[19] Jack, K.H. Sialons and related nitrogen ceramics. J. Mater. Sci. 1976(11): 1135-1158
[20] 陈祖熊．材料导报，1993，71(1)：29
[21] 都兴红，张广荣，隋智通，Sialon陶瓷的性质．中国陶瓷1998，34(2)：42-44
[22] 张宏泉，戴英，李凝芳 Sialon的合成技术与应用，陶瓷研究，1996，11(2)：83-87
[23] J. Vleugels, T. Laoui, Kvercam men, J.P. Ceils and O. Ven Der Biest, Mater. Sci. Eng.,1994(A187):177
[24] Hoggard, D. B. etal. Refractories'87 2~(nd) International Conference on Refractory. Tokyo, Japan, Nov.1987
[25] Hoggard, Dale. B. etal. Prevention of Al_2O_3 formation in pouting nozzles and the like. Us. 4870037,Spt. 1989
[26] 黄莉萍，徐友仁，唐铮等．以高岭土制备β'-Sialon粉料．硅酸盐学报．1991，19(1)：11-18
[27] 都兴红 博士论文(1998) 东北大学
[28] 王军李楠 硕士学位论文(1996) 武汉冶金科技大学
[29] A.D. Mazzoni, E.F. Aglietti. Phase evolution ofandulusite (Al_2O_3-2SiO_2)-Al system in nitrogen atmosphere. Materials Chemistry and Physics. 1997, 48,41-47
[30] 曹林洪，蒋明学．氮化反应合成β'-Sialon材料的工艺研究．耐火材料，2002，36(3)，333-335
[31] 王世铭．β-Sialon新材料的合成．福建师范大学学报，1996，12(3)：42-47
[32] 张宏泉，杨中民．用不同粘土矿物合成Sialon粉末的研究．中国陶瓷，1998，34(1)：16-19
[33] H. Higgins, A. Hendery, Br. Ceram. Trans. J. 1986(85):161-166
[34] A.D. Mazzoni, E.F. Aglietti. Mechanism of the carbonitriding reactions of SiO_2-Al_2O_3 minerals in the Si-Al-O-N system. Applied Clay Science 12(1998):447-461
[35] 叶国田，贺可音．碳热还原法合成β-Sialon．西南工学院学报，1995(3)，10(1)
[36] Lee, June Gunn and Cutler, Ivan B., Sinterable Sialon powder by reaction of clay with carbon and nitrogen. Am. Ceram. Soc. Bull. 58(9):869-871(1979)
[37] 丘克辉，曹爱红．由高岭土合成高纯β-Sialon粉料的探讨．材料科学与工程，1996，14(3)：40-44
[38] 张宏泉，戴英，李晔，李凝芳．碳热还原氮化高岭土合成Sialon粉末．中国有色金属学报，1998，3，8(1)
[39] 张宏泉，张起民等．粘土合成sialon的研究进展及其添加剂的研究．硅酸盐通报，1998(4)：28-31
[40] Yuonne Menke, Valerie Peltier-Baron, Stuart Hampshire. Effect of rare-earth cations on properties of sialon glasses. Jounal of Non-Crystalline Solids 276(2000):145-150
[41] W. Y. Sun, D.S. Yan, L.Gao, K.Liddeli and D.P. Thompsion. Subsolidus Phase Relationships in the System Ln_2O_3-Si_3N_4-AlN-Al_2O-3(Ln=Nd,Sm)．第二届复相陶瓷的优化设计与性能的研究学术交流会论文集(二)，上海，1995，5：117-138
[42] J.B. Baldo, V.C. Pandolfelli, J.R. Casarini, Relevant parameters in the production of β-Sialon from natural raw materials via carbothermic reduction, Ceramic Powders, ed. P. Vincenzini, Elsevier, Amsterdam, The Netherlands(1983):437-444
[43] J.B. Baldo, V.C. Pandolfelli, J.R. Casarini, Relevant parameters in the production of β-Sialon from natural raw materials via carbothermic reduction, Ceramic Powders, ed. P. Vincenzini, Elsevier,Amsterdam, The Netherlands(1983):437-444
[44] Kokmeiger, B. etal., Influnce of process parameters and starting compositon on the carbothermal production Sialon. J. Mater. Sci. 25(2B) 1261-1267(1990)
[45] Jie Zheng and Bertil Forslund. Carbothermal Preparation of β-Sialon Powder at Elevated Nitrogen
[2] 文红杰．红柱石的应用基础研究．[博士学位论文]．北京．北京科技大学，1997：128
[3] 钟香崇．矾土基耐火材料的研究与发展．耐火材料，1997(3)：125-130
[4] 钟香崇．中国耐火原料的发展．耐火材料，1999(6)：307-309
[5] Zhong X.C.,Li G.P. Sintering Characteristics of Chinese Bauxites. Ceramics International,1981,7(2):65-68
[6] 孙庚辰，钟香崇．我国DK型烧结高铝矾土材料的应力．应变特征．硅酸盐学报，1984，12(3)：355-362
[7] Zhong X.C. et al.. The Effect of some Oxide Additions on the Microstrure and Thermomechanical properties of Sintered Chinese Bauxites. Ceramics. Inter. 1988:108-122
[8] Zhong X.C., Sun G.C., Yin R. S. High Temperature Mechanical Properties of Bauxite Refractories in Microstructure and Properties of Ceramic Materials. Eds. Yan T.S. Pask J.A. 1984:254-261
[9] O'yama y. and Kamigaito. K.. Solid solubility of some oxides in Si_3N_4. Jpn. J. Appl. Phys, 1971,10:1637-1642
[10] Jack, K. H. and Wilson, W.I. Ceramics based on the Si-Al-O-N and related systems. Nature Phys.Sci.(London), 1972,23 8:28-29
[11] Jack K. H., WI. Nature(London), Phys. Sci., 1997,238:28-29
[12] 陈卫武，孙维莹，严东生．Ln-a-Sialon-AlN多型体(Ln=Y，Y+Sm，Sm)复相陶瓷微观结构的研究．无机材料学报，2000，6，15(3)：441-446
[13] T. Ekstrom, P.O. Kall, M. Nygren and P.O. Olson. Dense Single-phase β -Sialon Ceramics by glass-wmcapsulated hot isostatic pressing. J.Mater. Sci.1989 (24): 1853-1861
[14] A. Zangvil, L.J. Gauchkler, M. Ruhle. Indexed X-ray diffraction data for the sialon X-phase. J.Mat. Sci. Letters 15(1980)
[15] 李世普主编 《特种陶瓷工艺学》 武汉．武汉工业大学出版社，1990
[16] M. B. Trigg, et al. J. Mater. Sci., 23,1981,481
[17] XU Y. HUANG C M KRIVEN W Met al. Residual a -Si3N4 in o'-Crystals in CeO_2-Doped o'+β'-Sialon Ceramics. J. Am. Ceram soc. 1994 77(8)
[18] 仲维斌，李文超，王俭．塞隆陶瓷的发展概况．耐火材料，1994，28(4)：233-236
[19] Jack, K.H. Sialons and related nitrogen ceramics. J. Mater. Sci. 1976(11): 1135-1158
[20] 陈祖熊．材料导报，1993，71(1)：29
[21] 都兴红，张广荣，隋智通，Sialon陶瓷的性质．中国陶瓷1998，34(2)：42-44
[22] 张宏泉，戴英，李凝芳 Sialon的合成技术与应用，陶瓷研究，1996，11(2)：83-87
[23] J. Vleugels, T. Laoui, Kvercam men, J.P. Ceils and O. Ven Der Biest, Mater. Sci. Eng.,1994(A187):177
[24] Hoggard, D. B. etal. Refractories'87 2~(nd) International Conference on Refractory. Tokyo, Japan, Nov.1987
[25] Hoggard, Dale. B. etal. Prevention of Al_2O_3 formation in pouting nozzles and the like. Us. 4870037,Spt. 1989
[26] 黄莉萍，徐友仁，唐铮等．以高岭土制备β'-Sialon粉料．硅酸盐学报．1991，19(1)：11-18
[27] 都兴红 博士论文(1998) 东北大学
[28] 王军李楠 硕士学位论文(1996) 武汉冶金科技大学
[29] A.D. Mazzoni, E.F. Aglietti. Phase evolution ofandulusite (Al_2O_3-2SiO_2)-Al system in nitrogen atmosphere. Materials Chemistry and Physics. 1997, 48,41-47
[30] 曹林洪，蒋明学．氮化反应合成β'-Sialon材料的工艺研究．耐火材料，2002，36(3)，333-335
[31] 王世铭．β-Sialon新材料的合成．福建师范大学学报，1996，12(3)：42-47
[32] 张宏泉，杨中民．用不同粘土矿物合成Sialon粉末的研究．中国陶瓷，1998，34(1)：16-19
[33] H. Higgins, A. Hendery, Br. Ceram. Trans. J. 1986(85):161-166
[34] A.D. Mazzoni, E.F. Aglietti. Mechanism of the carbonitriding reactions of SiO_2-Al_2O_3 minerals in the Si-Al-O-N system. Applied Clay Science 12(1998):447-461
[35] 叶国田，贺可音．碳热还原法合成β-Sialon．西南工学院学报，1995(3)，10(1)
[36] Lee, June Gunn and Cutler, Ivan B., Sinterable Sialon powder by reaction of clay with carbon and nitrogen. Am. Ceram. Soc. Bull. 58(9):869-871(1979)
[37] 丘克辉，曹爱红．由高岭土合成高纯β-Sialon粉料的探讨．材料科学与工程，1996，14(3)：40-44
[38] 张宏泉，戴英，李晔，李凝芳．碳热还原氮化高岭土合成Sialon粉末．中国有色金属学报，1998，3，8(1)
[39] 张宏泉，张起民等．粘土合成sialon的研究进展及其添加剂的研究．硅酸盐通报，1998(4)：28-31
[40] Yuonne Menke, Valerie Peltier-Baron, Stuart Hampshire. Effect of rare-earth cations on properties of sialon glasses. Jounal of Non-Crystalline Solids 276(2000):145-150
[41] W. Y. Sun, D.S. Yan, L.Gao, K.Liddeli and D.P. Thompsion. Subsolidus Phase Relationships in the System Ln_2O_3-Si_3N_4-AlN-Al_2O-3(Ln=Nd,Sm)．第二届复相陶瓷的优化设计与性能的研究学术交流会论文集(二)，上海，1995，5：117-138
[42] J.B. Baldo, V.C. Pandolfelli, J.R. Casarini, Relevant parameters in the production of β-Sialon from natural raw materials via carbothermic reduction, Ceramic Powders, ed. P. Vincenzini, Elsevier, Amsterdam, The Netherlands(1983):437-444
[43] J.B. Baldo, V.C. Pandolfelli, J.R. Casarini, Relevant parameters in the production of β-Sialon from natural raw materials via carbothermic reduction, Ceramic Powders, ed. P. Vincenzini, Elsevier,Amsterdam, The Netherlands(1983):437-444
[44] Kokmeiger, B. etal., Influnce of process parameters and starting compositon on the carbothermal production Sialon. J. Mater. Sci. 25(2B) 1261-1267(1990)
[45] Jie Zheng and Bertil Forslund. Carbothermal Preparation of β-Sialon Powder at Elevated Nitrogen
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