六铝酸钙轻质耐火材料的研究
|
摘要
六铝酸钙材料具有诸多优异的耐火性能,可制备成新型耐高温轻质耐火材料。本文首先采用工业氢氧化铝、工业氧化铝、氢氧化钙、氧化钙、碳酸钙为原材料,铝酸钙水泥为结合剂,进行六铝酸钙的合成研究,研究了合成温度、保温时间、球磨混合时间对反应形成六铝酸钙的影响。其次在前面实验的基础上,采用发泡法制取六铝酸钙轻质材料,研究了不同发泡剂的发泡性能;外加剂对制备轻质六铝酸钙材料的影响。
研究表明:CA_6的开始生成温度为1200℃,大量生成CA_6的温度为1400℃;相比工业氢氧化铝,以工业氧化铝为原料,更有利于CA_6的合成;CA_6晶粒发育良好,为典型的CA_6片状晶体;降低原料粒度,延长保温时间有利于CA_6片状晶体的发育。
影响轻质CA_6材料性能的因素较多,首先,发泡剂种类对材料的性能有显著影响,其中十二烷基苯磺酸钠发泡量最大,发泡性能较好;其次糊精的加入可明显提高气泡的稳定性;此外加水量、搅拌时间等工艺因素对轻质CA_6的性能亦有较大影响。增加水泥含量,或引进活性α-Al_2O_3,都可明显提高试样的耐压强度。
Calcium-hexaluminate materials have many excellent performances, which could be used as a new type of light high temperature refractory. Firstly, Using industrial aluminum hydroxide, industrial alumina, calcium hydroxide, calcium oxide and calcium carbonate as raw materials, cement as bonding agent, the synthesis of Calcium-hexaluminate was studied in the paper. The effect of synthesis temperature, holding time, mixing crushed time on synthesis of calcium-hexaluminate are investigated. And on the basic of the previous experiments, the lightweight calcium hexaluminate refractories were prepared by the foaming way. The influences of different foaming agents and adding agents on properties of lightweight CA_6 refractory were studied.
The results showed that CA_6 could be observed from 1200℃, and a lot of CA_6 crystals presented at 1400℃. Comparing with industrial aluminum hydroxide, using industrial alumina as raw material, it was better to synthesize CA_6. The crystals of CA_6 are the typical platelet shape. Discreasing the particle size and prolonging the sorking time were favor to the morphology development of CA_6 crystal grains.
Many factors influenced the properties of lightweight CA_6 materials. Firstly, the types of foaming agents remarkably affect the performances of materials, and the SDBS is suitble, because of it’s the better foaming performance and lots of air bubbles. Secondly, the stability of air bubble was markedly improved by adding the dextrin. And the water content and mixing time also affect the properties of lightweight CA_6. When cement content was increased and activeα-Al_2O_3 was added, the crushing strength of the material increases obviously.
研究表明:CA_6的开始生成温度为1200℃,大量生成CA_6的温度为1400℃;相比工业氢氧化铝,以工业氧化铝为原料,更有利于CA_6的合成;CA_6晶粒发育良好,为典型的CA_6片状晶体;降低原料粒度,延长保温时间有利于CA_6片状晶体的发育。
影响轻质CA_6材料性能的因素较多,首先,发泡剂种类对材料的性能有显著影响,其中十二烷基苯磺酸钠发泡量最大,发泡性能较好;其次糊精的加入可明显提高气泡的稳定性;此外加水量、搅拌时间等工艺因素对轻质CA_6的性能亦有较大影响。增加水泥含量,或引进活性α-Al_2O_3,都可明显提高试样的耐压强度。
Calcium-hexaluminate materials have many excellent performances, which could be used as a new type of light high temperature refractory. Firstly, Using industrial aluminum hydroxide, industrial alumina, calcium hydroxide, calcium oxide and calcium carbonate as raw materials, cement as bonding agent, the synthesis of Calcium-hexaluminate was studied in the paper. The effect of synthesis temperature, holding time, mixing crushed time on synthesis of calcium-hexaluminate are investigated. And on the basic of the previous experiments, the lightweight calcium hexaluminate refractories were prepared by the foaming way. The influences of different foaming agents and adding agents on properties of lightweight CA_6 refractory were studied.
The results showed that CA_6 could be observed from 1200℃, and a lot of CA_6 crystals presented at 1400℃. Comparing with industrial aluminum hydroxide, using industrial alumina as raw material, it was better to synthesize CA_6. The crystals of CA_6 are the typical platelet shape. Discreasing the particle size and prolonging the sorking time were favor to the morphology development of CA_6 crystal grains.
Many factors influenced the properties of lightweight CA_6 materials. Firstly, the types of foaming agents remarkably affect the performances of materials, and the SDBS is suitble, because of it’s the better foaming performance and lots of air bubbles. Secondly, the stability of air bubble was markedly improved by adding the dextrin. And the water content and mixing time also affect the properties of lightweight CA_6. When cement content was increased and activeα-Al_2O_3 was added, the crushing strength of the material increases obviously.
引文
[1] 徐惠忠,周明. 绝热耐火材料生产及应用[M].北京:中国建材工业出版社,2001,8:7~9
[2] 徐维忠.耐火材料[M].北京:冶金工业出版社,1992,5:85~89
[3] 王维邦.耐火材料工艺学[M].(第2版). 北京:冶金工业出版社,1994,5:7~8 [4] 高振听.烧矾土中的六铝酸钙.硅酸盐学报.1982,10(2):216-220
[5] Asmi D and Low I.M,Self-reinforced Ca-hexaluminate/alumina composites with graded microstructures[M]. Ceramics International,2006,71~73
[6] 高振昕,周宁生.论不定形耐火材料的热反应与显微结构的形成与演变[C].2003年全国不定形耐火材料学术会议论文集,2003, 20~37
[7] Linan An and Helen M. chan. R -Curve behavior of in-situ-toughened A12O3: CaA112O19 caramic composites[J]. Journal of American Ceramic Society,1996, 12(79):3142~3148
[8] Cristina Dominguez,Jdrome Chevalier etl. Thermomechanical properties and fracture mechanisms of calcium hexaluminate[J]. Journal of European Ceramic Society, 2001, (21):907~917
[9] E .Cr iado(西班牙).国外耐火材料.1992,10:58-62
[10] Curien, H., Guillemin, C. and Orcel ,et al.L Hibonite,nouvelle espece minerale. Compt.Rend.Hebd.Seances Acad,Sci,1958,242,2845~2847
[11] 李北星,于其俊,冯修吉.CaO-A12O3系统铝酸钙矿物水化活性差异SCC-DV-Xα方法研究[J].硅酸盐学报,1998,26(4):411~415
[12] Michael P. Mallamaci, Kevin B. Sartain, etl. Crystallization of calcium hexaluminate on basal alumina[J].Philosophical Magazine A ,1998, 77(3 ):561~575.
[13] Cristina Dominguez, Jerome Chevalier, Ramon Torrecillas. Microstructure development in calcium hexaluminate[J].Journal of the European Ceramic Society,2001,21:381~387
[14] 武鹏.稀土六铝酸盐的结构及在高温催化材料中的应用[J].稀土.2003, 24(3):42~46
[15] 梁英教,车荫昌.无机物热力学数据手册[M].沈阳:东北工学院出版社,1993,8:85~86
[16] Jose Luis Mendoza,Aaron Freese and Robert E .Moore.Thermalmechanical behavior of calcium aluminate composites[J]. Ceramic Transactions Advanced in Refractories Technology,1990,10:162~167
[17] 李有奇,李亚伟,李 楠. 六铝酸钙材料的合成及其显微结构研究[J].耐火材料,2004,38(5):318~323
[18] M.A.Serry, N.M.Kalil and M.F.Zaaweah.Phase Evolution and Hydraulic Properties of Cement Castables Matrixes.Trans.Brit.Cer.Soc.,2001,4:171-176
[19] Vipin Kant Singh and Krishna Kumar Sharma, Low-Temperature Synthesis of Calcium Hexa-aluminate[J].Journal of American Ceramic Society, 2002, 4 (4):769~772
[20] J.M.Tulliani, G.Pages, G.Fantozzi and L.Montanaro.Journal of Thermal Analysis and Calorimetry. Vol.72 ( 2003)1135-1140
[21] D.Asmi, I M. Low, B H O’Connor.Phase compositions and depth-profiling of calcium aluminates in a functionally-grade alumina/calcium-hexaluminate composite[J]. Joumal of Matcrials Processing Technology, 2001,(118):219~224
[22]Vladimir V. Pimachenko and Valery V Martynenko etl. Super Low Thermal Conductivity Heat Insulating Lightweight Material on the Basis of Calcium Hexaluminate.Proceedings of the Second International Symposium on Refractories[J]. 2002:1188-1192
[23] L.An, H. M. Chan. Control of calcium hexaluminate grain morphology in in-situ toughened ceramic composites[J].Journal of Material Science,1996,(31):3223~3229
[24] Asmi D and Low I.M, Processing of an in-situ layered and graded alumina/calcium hexaluminate composite: Physical characteristics[M] .J E tu Ceram Soc,1998,18 , 2019~2024.
[25]Webb Janich, Maria, Suszczynski, et al. high temperature insulating refractory monolithics based on microporous aggregates[J].UNITECR.1999:177-18
[26] 翟彦青,李永丹,孟明.高温燃烧催化剂—六铝酸盐的结构、性质及制备[J].稀土.2004, 25(5):58~61
[27] 李天清,李楠. 反应烧结法制备六铝酸钙多孔材料[J]. 耐火材料 2004,38(5):309~311
[28] Y C Ko , C F Chan. Effect of spinel content on hot strength of alumina-spinel castables in the temperature range 1000–1500 ℃[ J]. Journal of the European Ceramic Society, 1999 (19) :2633~2639
[29] 裴春秋,石 干,徐建峰.六铝酸钙新型隔热耐火材料的性能及应用[J].工业炉.2007,29(1):45～49
[30] 刘新彧，Andreas Bhur.博耐特(Bonite)———一种新型的合成致密 CA6 耐火原料[J]. /耐火材料 2006,40(1):60～64
[31]Van Garsel, etl. Long term high temperature stability of microstructure calcium hexaluminate based insulating materials[J]. UNITECR.1999:18118
[32] 雷永泉.新能源材料[M].天津:天津大学出版社.2000,12:85~87
[33] 张玉祥.中国保温隔热材料发展现状及迈入21世纪的对策 [J],江西建材,1998,(1):15~20
[34] 郭利芳,管红梅.铝酸盐水泥在耐火材料中的应用.包钢科技,2003,1(2):26-29
[35] Cristina Dominguez, Ramon Torrecillas. Influence of Fe3+ on sintering and microstructural evolution of reaction sintered calcium hexaluminate. Journal of European Ceramic Society,1998,18(9):1373-1379
[36] Tulliani J M, Pages G, Fantozzi G, et al. Dilatometry as a tool to study a new synthesis forcalcium hexaluminate.Journal of Thermal Analysis and Calorimetry,2003,72(3):1135-1140
[37] 王捷.氧化铝生产工艺[M]. 冶金工业出版社 2006
[38] 顾培基.偶氮二甲酰胺的生产现状、合成及用途[J].上海化工,2002,6(23):40～42
[39] 陈海群,李英勇,朱俊武.十二烷基磺酸钠改性蒙脱土的制备与表征[J].无机化学学报,2004,3(20):251～255
[40] 陆佩文. 硅酸盐物理化学[M].武汉工业大学出版社,2000
[41] 孙红杰,赵明举,张志群. 超声降解十二烷基苯磺酸钠的实验研究[J].环境科学学报,2003,3(23):386～390
[42] 李楠. 保温保冷材料及其应用[M].上海科学技术出版社,1985
[43] 黄立新,陈玲.麦芽糊精在食品中的应用[J].食品工业,1999,3:32
[44] Vania Regina Salvini et al. Direct foaming porous alumina ceramics. Unitecr 2007,23(5):134~137
[45] 尹正刚,王坚.聚丙烯纤维增强水泥基材料性能技术应用及研究的现状[J].建筑材料,2007,48(10):43～44
[2] 徐维忠.耐火材料[M].北京:冶金工业出版社,1992,5:85~89
[3] 王维邦.耐火材料工艺学[M].(第2版). 北京:冶金工业出版社,1994,5:7~8 [4] 高振听.烧矾土中的六铝酸钙.硅酸盐学报.1982,10(2):216-220
[5] Asmi D and Low I.M,Self-reinforced Ca-hexaluminate/alumina composites with graded microstructures[M]. Ceramics International,2006,71~73
[6] 高振昕,周宁生.论不定形耐火材料的热反应与显微结构的形成与演变[C].2003年全国不定形耐火材料学术会议论文集,2003, 20~37
[7] Linan An and Helen M. chan. R -Curve behavior of in-situ-toughened A12O3: CaA112O19 caramic composites[J]. Journal of American Ceramic Society,1996, 12(79):3142~3148
[8] Cristina Dominguez,Jdrome Chevalier etl. Thermomechanical properties and fracture mechanisms of calcium hexaluminate[J]. Journal of European Ceramic Society, 2001, (21):907~917
[9] E .Cr iado(西班牙).国外耐火材料.1992,10:58-62
[10] Curien, H., Guillemin, C. and Orcel ,et al.L Hibonite,nouvelle espece minerale. Compt.Rend.Hebd.Seances Acad,Sci,1958,242,2845~2847
[11] 李北星,于其俊,冯修吉.CaO-A12O3系统铝酸钙矿物水化活性差异SCC-DV-Xα方法研究[J].硅酸盐学报,1998,26(4):411~415
[12] Michael P. Mallamaci, Kevin B. Sartain, etl. Crystallization of calcium hexaluminate on basal alumina[J].Philosophical Magazine A ,1998, 77(3 ):561~575.
[13] Cristina Dominguez, Jerome Chevalier, Ramon Torrecillas. Microstructure development in calcium hexaluminate[J].Journal of the European Ceramic Society,2001,21:381~387
[14] 武鹏.稀土六铝酸盐的结构及在高温催化材料中的应用[J].稀土.2003, 24(3):42~46
[15] 梁英教,车荫昌.无机物热力学数据手册[M].沈阳:东北工学院出版社,1993,8:85~86
[16] Jose Luis Mendoza,Aaron Freese and Robert E .Moore.Thermalmechanical behavior of calcium aluminate composites[J]. Ceramic Transactions Advanced in Refractories Technology,1990,10:162~167
[17] 李有奇,李亚伟,李 楠. 六铝酸钙材料的合成及其显微结构研究[J].耐火材料,2004,38(5):318~323
[18] M.A.Serry, N.M.Kalil and M.F.Zaaweah.Phase Evolution and Hydraulic Properties of Cement Castables Matrixes.Trans.Brit.Cer.Soc.,2001,4:171-176
[19] Vipin Kant Singh and Krishna Kumar Sharma, Low-Temperature Synthesis of Calcium Hexa-aluminate[J].Journal of American Ceramic Society, 2002, 4 (4):769~772
[20] J.M.Tulliani, G.Pages, G.Fantozzi and L.Montanaro.Journal of Thermal Analysis and Calorimetry. Vol.72 ( 2003)1135-1140
[21] D.Asmi, I M. Low, B H O’Connor.Phase compositions and depth-profiling of calcium aluminates in a functionally-grade alumina/calcium-hexaluminate composite[J]. Joumal of Matcrials Processing Technology, 2001,(118):219~224
[22]Vladimir V. Pimachenko and Valery V Martynenko etl. Super Low Thermal Conductivity Heat Insulating Lightweight Material on the Basis of Calcium Hexaluminate.Proceedings of the Second International Symposium on Refractories[J]. 2002:1188-1192
[23] L.An, H. M. Chan. Control of calcium hexaluminate grain morphology in in-situ toughened ceramic composites[J].Journal of Material Science,1996,(31):3223~3229
[24] Asmi D and Low I.M, Processing of an in-situ layered and graded alumina/calcium hexaluminate composite: Physical characteristics[M] .J E tu Ceram Soc,1998,18 , 2019~2024.
[25]Webb Janich, Maria, Suszczynski, et al. high temperature insulating refractory monolithics based on microporous aggregates[J].UNITECR.1999:177-18
[26] 翟彦青,李永丹,孟明.高温燃烧催化剂—六铝酸盐的结构、性质及制备[J].稀土.2004, 25(5):58~61
[27] 李天清,李楠. 反应烧结法制备六铝酸钙多孔材料[J]. 耐火材料 2004,38(5):309~311
[28] Y C Ko , C F Chan. Effect of spinel content on hot strength of alumina-spinel castables in the temperature range 1000–1500 ℃[ J]. Journal of the European Ceramic Society, 1999 (19) :2633~2639
[29] 裴春秋,石 干,徐建峰.六铝酸钙新型隔热耐火材料的性能及应用[J].工业炉.2007,29(1):45～49
[30] 刘新彧，Andreas Bhur.博耐特(Bonite)———一种新型的合成致密 CA6 耐火原料[J]. /耐火材料 2006,40(1):60～64
[31]Van Garsel, etl. Long term high temperature stability of microstructure calcium hexaluminate based insulating materials[J]. UNITECR.1999:18118
[32] 雷永泉.新能源材料[M].天津:天津大学出版社.2000,12:85~87
[33] 张玉祥.中国保温隔热材料发展现状及迈入21世纪的对策 [J],江西建材,1998,(1):15~20
[34] 郭利芳,管红梅.铝酸盐水泥在耐火材料中的应用.包钢科技,2003,1(2):26-29
[35] Cristina Dominguez, Ramon Torrecillas. Influence of Fe3+ on sintering and microstructural evolution of reaction sintered calcium hexaluminate. Journal of European Ceramic Society,1998,18(9):1373-1379
[36] Tulliani J M, Pages G, Fantozzi G, et al. Dilatometry as a tool to study a new synthesis forcalcium hexaluminate.Journal of Thermal Analysis and Calorimetry,2003,72(3):1135-1140
[37] 王捷.氧化铝生产工艺[M]. 冶金工业出版社 2006
[38] 顾培基.偶氮二甲酰胺的生产现状、合成及用途[J].上海化工,2002,6(23):40～42
[39] 陈海群,李英勇,朱俊武.十二烷基磺酸钠改性蒙脱土的制备与表征[J].无机化学学报,2004,3(20):251～255
[40] 陆佩文. 硅酸盐物理化学[M].武汉工业大学出版社,2000
[41] 孙红杰,赵明举,张志群. 超声降解十二烷基苯磺酸钠的实验研究[J].环境科学学报,2003,3(23):386～390
[42] 李楠. 保温保冷材料及其应用[M].上海科学技术出版社,1985
[43] 黄立新,陈玲.麦芽糊精在食品中的应用[J].食品工业,1999,3:32
[44] Vania Regina Salvini et al. Direct foaming porous alumina ceramics. Unitecr 2007,23(5):134~137
[45] 尹正刚,王坚.聚丙烯纤维增强水泥基材料性能技术应用及研究的现状[J].建筑材料,2007,48(10):43～44