Al_2O_3-ZrB_2-C质复合材料的
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摘要
本工作旨在研制A12O3-ZrB2-C复合材料,应用于中间包钢水连续测温用热电偶保护套管。对复合材料的制备、添加剂的加入及其与复合材料性能的关系进行了研究,同时研究了复合材料的抗热震性能、抗氧化性能和抗渣性能。
研究表明:ZrB2的引入可以提高复合材料的机械性能,改善材料的导热性能和抗热震性能;添加剂的(Si、SiC、Al)引入,可以促进复合材料的烧结,降低材料的气孔率,促使材料的致密化,改善材料的机械性能,最主要的是能够起到抗氧化作用,保护材料中ZrB2不被氧化。
对复合材料的抗热震性能的研究表明:在ZrB2和石墨(C)的共同作用下,复合材料有较好的抗热震性能。
抗氧化研究表明:抗氧剂和部分ZrB2氧化后形成的氧化层能够很好的阻止复合材料的进一步氧化。对复合材料的氧化动力学研究表明:复合材料的氧化可分为三个阶段,第一阶段氧化前期,第二阶段氧化中期,时间很短,实验中无法读取数据,第三阶段氧化后期。
对抗渣试样的SEM显微结构研究表明:ZrB2的引入能够提高复合材料的抗渣性能。
In the present paper, the development of A12O3-ZrB2-C composite is introduced. The composite will be applied to thermocouple’s protection tubes which are a kind of measuring system for temperature of molten steel in ladle of continuous casting. The preparation of the composite, theaddition of additives and the relationship between the amount of additives and properties of the composite have been studied. Meanwhile, the behaviors of the thermal-shock resistance, the oxidation resistance and the slag resistance of the composite have also been revealed.
The results indicate that the addition of ZrB2 can improve the mechanical properties, the thermal conductivity and the thermal-shock resistance of the composite; the addition of additives can promote the sintering and increase the density of the composite and reduce the apparent porosity of the composite. The most of all, additives can improve the behavior of the oxidation resistance and protect ZrB2.
The experiment of the thermal-shock resistance indicates that the composite has good thermal-shock resistance with the cooperation of ZrB2 and C.
The experiment of the oxidation resistance indicates that the oxidation’s layer of additives and portion of ZrB2 can stop the further oxidation. The oxidation kinetic study for A12O3-ZrB2-C composite indicates that the oxidation process can be divided into three stages: the first stage is the prophase of oxidation, the second stage is the metaphase of oxidation, the time of the stage is so short that the data of the stage is not been got, the third stage is the anaphase of oxidation. The experiment of the slag resistance indicates that the addition of ZrB2 can improve the slag resistance of composite.
研究表明:ZrB2的引入可以提高复合材料的机械性能,改善材料的导热性能和抗热震性能;添加剂的(Si、SiC、Al)引入,可以促进复合材料的烧结,降低材料的气孔率,促使材料的致密化,改善材料的机械性能,最主要的是能够起到抗氧化作用,保护材料中ZrB2不被氧化。
对复合材料的抗热震性能的研究表明:在ZrB2和石墨(C)的共同作用下,复合材料有较好的抗热震性能。
抗氧化研究表明:抗氧剂和部分ZrB2氧化后形成的氧化层能够很好的阻止复合材料的进一步氧化。对复合材料的氧化动力学研究表明:复合材料的氧化可分为三个阶段,第一阶段氧化前期,第二阶段氧化中期,时间很短,实验中无法读取数据,第三阶段氧化后期。
对抗渣试样的SEM显微结构研究表明:ZrB2的引入能够提高复合材料的抗渣性能。
In the present paper, the development of A12O3-ZrB2-C composite is introduced. The composite will be applied to thermocouple’s protection tubes which are a kind of measuring system for temperature of molten steel in ladle of continuous casting. The preparation of the composite, theaddition of additives and the relationship between the amount of additives and properties of the composite have been studied. Meanwhile, the behaviors of the thermal-shock resistance, the oxidation resistance and the slag resistance of the composite have also been revealed.
The results indicate that the addition of ZrB2 can improve the mechanical properties, the thermal conductivity and the thermal-shock resistance of the composite; the addition of additives can promote the sintering and increase the density of the composite and reduce the apparent porosity of the composite. The most of all, additives can improve the behavior of the oxidation resistance and protect ZrB2.
The experiment of the thermal-shock resistance indicates that the composite has good thermal-shock resistance with the cooperation of ZrB2 and C.
The experiment of the oxidation resistance indicates that the oxidation’s layer of additives and portion of ZrB2 can stop the further oxidation. The oxidation kinetic study for A12O3-ZrB2-C composite indicates that the oxidation process can be divided into three stages: the first stage is the prophase of oxidation, the second stage is the metaphase of oxidation, the time of the stage is so short that the data of the stage is not been got, the third stage is the anaphase of oxidation. The experiment of the slag resistance indicates that the addition of ZrB2 can improve the slag resistance of composite.
引文
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[5] 张 琛,译.性能优良的A12O3-C质滑板[J].国外耐火材料,1994 (5):33
[6] 李晓明.铝碳滑板在高温使用后莫来石分解的热力学分析[J].耐火材料,1987(4):57
[7] 王天仇.铝碳锆质滑板的生产工艺和应用[J].耐火材料,1992 (4):207
[8] 成 濑,余 市等.含氧化锆碳结合滑动水口的性质及使用性能[J].国外耐火材料,1985 (10):47
[9] 杨开保,张文杰,皮 波.加入锆莫来石及特殊碳对烧成铝碳滑板性能的影响[J].耐火材料,1994 (1):38
[10] 张文杰,汪厚植等.结合剂及工艺条件对铝锆碳滑板性能的影响[J].耐火材料,1992 (3):135
[11] 刘新域,孙庚辰,钟香崇.炉渣对Al2O3-SiO2-ZrO2-C系材料的侵蚀[J].耐火材料,1989 (5):1
[12] 张国栋,尤 丽,译.铝碳质耐火材料的发展状况[J].国外耐火材料,1999(1):7
[13] 王玺堂,齐景娥,符汉道.Al2O3-SiC-C 质高炉出铁沟自流浇注料的开发及其应用[J].钢铁研究,1999(2):3
[14] 顾立德.特种耐火材料[M] .北京:冶金工业出版社,1982,8
[15] 辜 萍.助燃剂对二硼化钛陶瓷烧结行为、结构与性能的影响[硕士论文].武汉工业大学,1999.6
[16] Radev D D,Klissurski D.Mechanochemical and SHS of diboride of titanium and zirconium[J] .Journal of Material synthesis and processing ,2001,9(3)page:131
[17] Andrievskii Ra,Kravchenkose, Shikin SP.Preparation and some properties of ultra fine zirconium boride and titanium boride powders [J].Inorganic Material,1995,31(8)page:965
[18] Klaus Hunold.Boron compounds ini carbon-bonded refractories[J].Ceramic industry,1995(2)page:47-50
[19] Kobayashi H, Katoh M.Preparation of ZrB2 fine powders using thermite method by reduction with Mg [J].Ceramic Soc J ap,1992,100(2)page:172-177
[20] 刘国齐,李红霞, 杨 彬,三金相等.铝碳材料中 ZrB2 的原位合成[J].洛阳耐火材料研究院建院四十周年院庆科技文集,Page:110-113
[21] Hong Zhao,Yu He,Zongzhe Jin.Preparation of zirconium boride powder[J].Journal of American Ceramic Society,1999,78(9)page:2534
[22] MERZHANOV A G.Fluid dynamics phenomena in the processes of self propagating high temperature synthesis[J].Combus Sci Technol,1995,105(4-6):295-325
[23] 袁润章.自蔓延高温合成技术研究进展[M].武汉:武汉工业大学出版社,1994,序
[24] MERZHANOV A G.History and new developments in SHS[J].Ceramic Trans,1995,56:3-25
[25] 方 舟,王 皓,傅正义.Zr-B2O3-Mg 体系自蔓延高温合成 ZrB2 陶瓷粉末[J].硅酸盐学报,2004,32(6):755-757
[26] Devyakin S V.Electro synthesis of zirconium boride from cryolite-alumina melts containing zirconium and boron oxide[J].Russian Journal of Electro chemistry,2001,37(12):1499
[27] Pierson J F, Belmonte T, Czerwied T,et al.Low temperature ZrB2 remote plasma enhanced chemical vapor deposition[J].Thin Solid Films,2000,359:67
[28] Berthon S,Male G.Infiltration of zirconium diboride by ICVI in porous materials[J].Composites Science and Technology,1997,57:217
[29] Pierson J F, Belmonte T, Michel H.Effect of ZrCl4 addition on ZrB2 film synthesis in flowing Ar-BCl3 post-dischrges[J].Surface and Coatings Technology, 2000,12:133-134
[30] Millet P,Hwang T.Preparation of TiB2 and ZrB2 influence of a mechano-chemical treatment on the carbon-thermic reduction of titania and zirconia[J].Master Sci,1996,31:351
[31] F Monteverde,A Bellosi.Processing and properties of zirconium diboride-based composites [J].Journal of the European Ceramic Society,2002,22 (3 ):279-288
[32] B Basu,J Vlegugels,O Van Der Biest.Development of ZrB2-ZrO2 composites[J].Alloys and Composites,2002,334:200
[33] 赵 宏,金宗哲.ZrO2 相变对 ZrB2 陶瓷的增强和增韧效应[J].硅酸盐学报,1990,18(1):54
[34] Stefan Postrach,Jurgen potschke. Pressureless sintering of Al2O3 containing up to 20vol% zirconium diboride [J].EurOpean Ceramic Society,2000,20:1459
[35] 殷 明, 赵海雷,成丽丽,冯 涤等.刚玉/莫来石-硼化锆陶瓷复合材料的烧结工艺及显微结构[J].钢铁研究学报,1998,10 (5):53-56
[36] 赵海雷, 王 俭,李文超.ZrB2-刚玉/莫来石复合材料氧化动力学的研究[J].耐火材料,1998, 32 (6): 322-325
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