MgAlON复合材料的研制及应用
摘要
采用传统烧结法开展了单相MgAlON材料的合成与性能分析的研究工作,研究了矾土基合成单相MgAlON材料的工艺参数对材料的微观组织结构的影响。以降低生产成本和降低烧成温度为目的,在原料中引入MgO粉,以使其烧成温度降低,所得产物应为MgAlON;分别进行了以Al粉代替AlN再进行氮化,矾土代替Al_2O_3粉,纳米Al_2O_3粉代替Al_2O_3粉等工艺实验,研究了合成产物的组织结构特征;实施了以Air代替N_2,以及用碳黑代Al粉进行埋碳烧结的实验,得到了合成MgAlON的最佳方案,同时也对其性能进行了检测。
在耐火材料领域探索AlON材料的应用潜力,其中MgO的固溶掺杂对AlON影响的研究是本文的创新性工作之一。研究表明,只有MgO含量为8%(wt)时,N的相对含量、Al的相对含量以及AlN的相对含量同时达最大值,此时MgAlON的合成效果被认为最好;从经济效果来说,矾土在空气中C化这一方案更适合工业生产;采用纳米Al_2O_3粉合成MgAlON材料时,在相对较低的温度下,结合埋碳并通氮气的条件,能够合成单相的MgAlON。
MgAlON材料防氧化措施的研究结果表明,抗氧化剂的种类和加入方式对防氧化效果有显著的影响。当抗氧化剂以单一形式加入时,B_4C的防氧化效果最好,金属Si粉次之,SiC基本上起不到防氧化作用。金属Si粉和B4C组成的复合抗氧化剂的防氧化效果明显优于单一抗氧化剂。
在Al_2O_3-SiC-C质铁沟浇注料中加MgAlON合成料的研究表明,MgAlON加入量控制在15%以内时,所得制品的显气孔率、耐压强度、抗折强度以及抗渣性能都有所改善,但施工性能没有显著变化。
Single-phase synthesis and properties of MgAlON materials are researched by using the traditional sintering methods, and the impact of parameters for the synthesis of bauxite-based single-phase MgAlON on the microstructure of the material is also studied. To reduce production costs and decrease firing temperature, MgO powder is added in raw material to reduce its sintering temperature, and the products was MgAlON. To study the microstructure of products, AlN was substituted by Al to further nitridate, bauxite by Al_2O_3 powder and Al_2O_3 powder by nano-Al_2O_3 powder. Air was introduced to replace the N_2 atmosphere and the carbon black was introduced to replace Al to conduct experiment of burying carbon powder sintering. At last the best plan for MgAlON synthesis is got. Meanwhile its performance is detected.
The aim of this paper is to explore the potential applications of AlON in the field of refractory materials. The influence of solid solution of MgO on ALON is one of the innovative work. The investigation shows that only when the addition amout of MgO was 8%(wt), the relative content of N, Al and AlN reach max content at the same time, and the effect for synthesis of MgAlON was the best. From the economic effect, the program of bauxite carbonizing in the air is more suitable for industrial production. Combining the condition of buried carbon and nitrogen, the single-phase MgAlON can be synthesised at a relatively low temperatures when nano-Al_2O_3 powder was used in MgAlON synthesis.
The results of anti-oxidation measures for MgAlON materials show that the type and addition methods of the antioxidant have a marked influence on the anti-oxidation effect. When the antioxidants is addde in a single form, the anti-oxidation effect of B4C is the best, followed by metal powder Si. SiC played an ineffective role. The composition of antioxidant effect with B4C and metal Si is better than a single antioxidant.
The addition of MgAlON in Al_2O_3-SiC-C iron ditch castable was studied. When the adding amount of MgAlON is less than 15 percent, apparent bulk porosity, compressive strength, modulus of rapture and the performance of slag resistance are improved, but construction performance did not changed significantly.
在耐火材料领域探索AlON材料的应用潜力,其中MgO的固溶掺杂对AlON影响的研究是本文的创新性工作之一。研究表明,只有MgO含量为8%(wt)时,N的相对含量、Al的相对含量以及AlN的相对含量同时达最大值,此时MgAlON的合成效果被认为最好;从经济效果来说,矾土在空气中C化这一方案更适合工业生产;采用纳米Al_2O_3粉合成MgAlON材料时,在相对较低的温度下,结合埋碳并通氮气的条件,能够合成单相的MgAlON。
MgAlON材料防氧化措施的研究结果表明,抗氧化剂的种类和加入方式对防氧化效果有显著的影响。当抗氧化剂以单一形式加入时,B_4C的防氧化效果最好,金属Si粉次之,SiC基本上起不到防氧化作用。金属Si粉和B4C组成的复合抗氧化剂的防氧化效果明显优于单一抗氧化剂。
在Al_2O_3-SiC-C质铁沟浇注料中加MgAlON合成料的研究表明,MgAlON加入量控制在15%以内时,所得制品的显气孔率、耐压强度、抗折强度以及抗渣性能都有所改善,但施工性能没有显著变化。
Single-phase synthesis and properties of MgAlON materials are researched by using the traditional sintering methods, and the impact of parameters for the synthesis of bauxite-based single-phase MgAlON on the microstructure of the material is also studied. To reduce production costs and decrease firing temperature, MgO powder is added in raw material to reduce its sintering temperature, and the products was MgAlON. To study the microstructure of products, AlN was substituted by Al to further nitridate, bauxite by Al_2O_3 powder and Al_2O_3 powder by nano-Al_2O_3 powder. Air was introduced to replace the N_2 atmosphere and the carbon black was introduced to replace Al to conduct experiment of burying carbon powder sintering. At last the best plan for MgAlON synthesis is got. Meanwhile its performance is detected.
The aim of this paper is to explore the potential applications of AlON in the field of refractory materials. The influence of solid solution of MgO on ALON is one of the innovative work. The investigation shows that only when the addition amout of MgO was 8%(wt), the relative content of N, Al and AlN reach max content at the same time, and the effect for synthesis of MgAlON was the best. From the economic effect, the program of bauxite carbonizing in the air is more suitable for industrial production. Combining the condition of buried carbon and nitrogen, the single-phase MgAlON can be synthesised at a relatively low temperatures when nano-Al_2O_3 powder was used in MgAlON synthesis.
The results of anti-oxidation measures for MgAlON materials show that the type and addition methods of the antioxidant have a marked influence on the anti-oxidation effect. When the antioxidants is addde in a single form, the anti-oxidation effect of B4C is the best, followed by metal powder Si. SiC played an ineffective role. The composition of antioxidant effect with B4C and metal Si is better than a single antioxidant.
The addition of MgAlON in Al_2O_3-SiC-C iron ditch castable was studied. When the adding amount of MgAlON is less than 15 percent, apparent bulk porosity, compressive strength, modulus of rapture and the performance of slag resistance are improved, but construction performance did not changed significantly.
引文
[1]李亚伟.氧氮化铝(AlON)的合成及AlON结合刚玉材料的制备、结构与性能研究,博士论文,武汉工业大学,1996.
[2] Yamaguchi G., Yanagida. H. Study on the reductive spinel-A new spinel formula AlN-Al2O3 instead of the previous one Al2O3. Chem. Soc. of Japan bull., 1959, 32(11):1264
[3] McCauley J W.,A Simple model for aluminum oxynitride spinels. J. Am. Ceram. Soc.,1978, 61(7-8): 372
[4] Goursat P, Billey M, Goeuriot P, Labbe J C, Villechenoux J M, Roult G. and Bardolle J.,Contribution a l’etude du systeme Al/O/N II-retention d’azote dansles products d’oxynitride d’aluminum-γ. Mat. Chem., 1981, 6: 81
[5] Goursat P, Goeuriot P, Billey M. Contribution a l’etude du systeme Al/O/N I-reactivitede. I’oxynitrue d’aluminum-γ. Mat. Chem., 1976, 1: 131
[6] Michel D. Contribution a l’etude de phenomenes d’or donnancement de defaouts daus des monocristaux de materiaux refractaies a base d’alumine et dezircone. Rev. Int. HautesTempr. Et refrac., 1972, 9: 225
[7] Lefebvre P A. Structureáantiphases periodiques de I’oxynitride d’aluminum-δnon-stoechiometrique de composition 9 Al2O3-AlN. J. Appl. Cryst., 1975: 235
[8] Lejus A M. Sur La formationáhaute température de spinelles non stoetchiométriqueset de phase dérivées. Rev. Hautes Tempr. et Refrac., 1964, 1: 53
[9] McCauley J W and Corbin N D. High temperaure reactions and microstructures in theAl2O3-AlN system. In progress In Nitrogen ceramics. ed. F. L. Riley. Martinus Nijhoff.Boston. MA. 1983: 111
[10] Qiu C and Metselaar R. Phase relations in aluminum carbide-aluminum nitride-aluminum oxide system. J. Am. Ceram. Soc., 1997, 80(8): 2013～2020
[11] Takebe H, Kameda T, Komatsu M., Komega K and Morinage K. Fabrication of translucent sntered aluminum oxynitride spinel(AlON). J. Ceram. Soc. Jpn. Inter. Edn.,1989, 97: 163～169
[12] Li Yawei, Li Nan and Yuan Runzhang. The Formation and Stability ofγ- Aluminum Oxynitride Spinel in the Carbothermal Reduction and Reaction SinteringProcess. J. Mater. Sci., 1997, 32: 979～982
[13] Willems H X, Hendrix M M R M, de With G. and Metselaar R. Thermodynamics of AlON I: Stability at Lower Temperatures. J. Eur. Ceram. Soc., 1992, 10: 327～337
[14] Ish-shalon M. Formation of Aluminum Oxynitride by Carbothermal Reaction of Aluminum Oxide in Nitroges. J. Mater. Sci. Lett., 1982: 147～149
[15] Lefort P, Michel Billy. Mechanism of AlN Formation through the Carbothermalic Reduction of Al2O3 in a Flowing Nitrogen Atmosphere. J. Am. Ceram. Soc., 1993, 76(9): 2295～2299
[16] Li Yawei, Li Nan, et al. Preparation of Aluminum Oxynitride by Carbothermal Reduction of Aluminum Oxide in a Flowing N2 Atmosphere. China’s Refractories, 1996, 5(1): 24～29
[17] Zheng J and Forslund B. Carbothermal Synthesis of Aluminum Oxynitride (AlON) Powder. Influence of Starting Materials and Synthesis Parameters, J. Eur. Ceram. Soc.,1995, 15: 1087～1100
[18] Michel D and Huler M. Etude Sur monocristaux de I’ordonnancement des defauts dans I’oxynitrure d’aluminum-γ. Rev. Int. Hautes. Temper. et Refaract., 1970, 7: 145
[19] Irene E A, Silvestri V J and Woolhouse G. R. Some properties of chemically vapor deposited films of AlXOYNZ on silicon. J. Electronic. Mat., 1975, 4: 409
[20] Jiping Cheng, Agrawal D, Roy R. Microwave Synthesis of Aluminum Oxynitride(AlON). J. Mater. Sci. Lett., 1999,18: 1989～1990
[21] Hiroyuki Fukuyama et al. New Synthetic Method of Forming Aluminum Oxynitride by Plasma Arc Melting. J. Am. Ceram. Soc. 1999, 82(6): 1381～1387
[22] Takeda K, Hosaka T. Characteristic of new raw material“AlON”for refractories. Interceram, 1989,1: 18～22
[23]王玺堂.MgAlON及其复合耐火材料的制备、机理和性能研究,博士论文,北京科技大学,2002
[24] Hosaka T, Kato M. A study of Compositional Modification of Trough Mixture by using Aluminum oxynitride. Japn. Refractories, 1985, 37(10): 22～26
[25]李亚伟等.添加MgO对碳热还原法合成尖晶石型氮氧化铝粉末的影响.硅酸盐学报,1997,25(6):669～674
[26] Weiss J, Greil P, Gauckler L J. The system Al-Mg-O-N. J. Am. Ceram. Soc. 1982, 65:68～69
[27]孙维莹,马利泰,严东生.Mg-Al-O-N系统的相关系.科学通报,1990,3:200
[28] Granon A, Goeuriot P and Thevenot F, Reactivity in the Al2O3-AlN-MgO System. The MgAlON Spinel Phase. J. Eur. Ceram. Soc.,1994, 13: 365～370
[29]邓承继.MgAlON材料的合成机理、性能及应用的研究:博士论文.北京科技大学,1999
[2] Yamaguchi G., Yanagida. H. Study on the reductive spinel-A new spinel formula AlN-Al2O3 instead of the previous one Al2O3. Chem. Soc. of Japan bull., 1959, 32(11):1264
[3] McCauley J W.,A Simple model for aluminum oxynitride spinels. J. Am. Ceram. Soc.,1978, 61(7-8): 372
[4] Goursat P, Billey M, Goeuriot P, Labbe J C, Villechenoux J M, Roult G. and Bardolle J.,Contribution a l’etude du systeme Al/O/N II-retention d’azote dansles products d’oxynitride d’aluminum-γ. Mat. Chem., 1981, 6: 81
[5] Goursat P, Goeuriot P, Billey M. Contribution a l’etude du systeme Al/O/N I-reactivitede. I’oxynitrue d’aluminum-γ. Mat. Chem., 1976, 1: 131
[6] Michel D. Contribution a l’etude de phenomenes d’or donnancement de defaouts daus des monocristaux de materiaux refractaies a base d’alumine et dezircone. Rev. Int. HautesTempr. Et refrac., 1972, 9: 225
[7] Lefebvre P A. Structureáantiphases periodiques de I’oxynitride d’aluminum-δnon-stoechiometrique de composition 9 Al2O3-AlN. J. Appl. Cryst., 1975: 235
[8] Lejus A M. Sur La formationáhaute température de spinelles non stoetchiométriqueset de phase dérivées. Rev. Hautes Tempr. et Refrac., 1964, 1: 53
[9] McCauley J W and Corbin N D. High temperaure reactions and microstructures in theAl2O3-AlN system. In progress In Nitrogen ceramics. ed. F. L. Riley. Martinus Nijhoff.Boston. MA. 1983: 111
[10] Qiu C and Metselaar R. Phase relations in aluminum carbide-aluminum nitride-aluminum oxide system. J. Am. Ceram. Soc., 1997, 80(8): 2013～2020
[11] Takebe H, Kameda T, Komatsu M., Komega K and Morinage K. Fabrication of translucent sntered aluminum oxynitride spinel(AlON). J. Ceram. Soc. Jpn. Inter. Edn.,1989, 97: 163～169
[12] Li Yawei, Li Nan and Yuan Runzhang. The Formation and Stability ofγ- Aluminum Oxynitride Spinel in the Carbothermal Reduction and Reaction SinteringProcess. J. Mater. Sci., 1997, 32: 979～982
[13] Willems H X, Hendrix M M R M, de With G. and Metselaar R. Thermodynamics of AlON I: Stability at Lower Temperatures. J. Eur. Ceram. Soc., 1992, 10: 327～337
[14] Ish-shalon M. Formation of Aluminum Oxynitride by Carbothermal Reaction of Aluminum Oxide in Nitroges. J. Mater. Sci. Lett., 1982: 147～149
[15] Lefort P, Michel Billy. Mechanism of AlN Formation through the Carbothermalic Reduction of Al2O3 in a Flowing Nitrogen Atmosphere. J. Am. Ceram. Soc., 1993, 76(9): 2295～2299
[16] Li Yawei, Li Nan, et al. Preparation of Aluminum Oxynitride by Carbothermal Reduction of Aluminum Oxide in a Flowing N2 Atmosphere. China’s Refractories, 1996, 5(1): 24～29
[17] Zheng J and Forslund B. Carbothermal Synthesis of Aluminum Oxynitride (AlON) Powder. Influence of Starting Materials and Synthesis Parameters, J. Eur. Ceram. Soc.,1995, 15: 1087～1100
[18] Michel D and Huler M. Etude Sur monocristaux de I’ordonnancement des defauts dans I’oxynitrure d’aluminum-γ. Rev. Int. Hautes. Temper. et Refaract., 1970, 7: 145
[19] Irene E A, Silvestri V J and Woolhouse G. R. Some properties of chemically vapor deposited films of AlXOYNZ on silicon. J. Electronic. Mat., 1975, 4: 409
[20] Jiping Cheng, Agrawal D, Roy R. Microwave Synthesis of Aluminum Oxynitride(AlON). J. Mater. Sci. Lett., 1999,18: 1989～1990
[21] Hiroyuki Fukuyama et al. New Synthetic Method of Forming Aluminum Oxynitride by Plasma Arc Melting. J. Am. Ceram. Soc. 1999, 82(6): 1381～1387
[22] Takeda K, Hosaka T. Characteristic of new raw material“AlON”for refractories. Interceram, 1989,1: 18～22
[23]王玺堂.MgAlON及其复合耐火材料的制备、机理和性能研究,博士论文,北京科技大学,2002
[24] Hosaka T, Kato M. A study of Compositional Modification of Trough Mixture by using Aluminum oxynitride. Japn. Refractories, 1985, 37(10): 22～26
[25]李亚伟等.添加MgO对碳热还原法合成尖晶石型氮氧化铝粉末的影响.硅酸盐学报,1997,25(6):669～674
[26] Weiss J, Greil P, Gauckler L J. The system Al-Mg-O-N. J. Am. Ceram. Soc. 1982, 65:68～69
[27]孙维莹,马利泰,严东生.Mg-Al-O-N系统的相关系.科学通报,1990,3:200
[28] Granon A, Goeuriot P and Thevenot F, Reactivity in the Al2O3-AlN-MgO System. The MgAlON Spinel Phase. J. Eur. Ceram. Soc.,1994, 13: 365～370
[29]邓承继.MgAlON材料的合成机理、性能及应用的研究:博士论文.北京科技大学,1999