C/C复合材料ZrB_2-SiC基陶瓷涂层的微观结构及氧化机理
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摘要
为提高C/C复合材料在高温富氧环境中的抗氧化性能,采用两步刷涂+化学气相沉积法在C/C复合材料表面制备含Si_3N_4、MoSi_2、TaC等添加剂的ZrB_2-SiC基多层复合陶瓷涂层。利用XRD和SEM等分析测试手段研究涂层的物相组成和微观结构,并分析讨论涂层在900和1500℃的等温抗氧化机理。结果表明:利用两步刷涂+化学气相沉积法制备的ZrB_2-SiC基复合陶瓷涂层整体厚度约为200μm。Si3N4、MoSi_2可很好地促进ZrB_2-SiC基氧阻挡层的高温烧结,使涂层致密化,并提高涂层在900℃的抗氧化性能;与之相比,TaC则不能很好地发挥致密化作用,对涂层在900℃时抗氧化性能的提高有限。在900℃时,ZrB_2-SiC基陶瓷涂层的氧化过程主要受氧在涂层孔隙等缺陷中的扩散所控制,添加剂主要通过改变涂层的致密化程度来影响涂层的抗氧化性能。在1500℃氧化过程中,涂层抗氧化性能恶化,但致密的化学气相沉积SiC封填层的引入可显著改善涂层在1500℃时的抗氧化性能,涂层表面生成了完整的含有ZrO_2和ZrSiO_4等高熔点颗粒的SiO_2玻璃态氧化膜,为基体提供有效的氧化防护。
To improve the anti-oxidation performance of C/C composites under high temperature and oxygen enriched environment,ZrB_2-SiC based ceramic coatings with Si_3N_4,MoSi_2 and TaC addition were prepared by two-step slurry painting+chemical vapor deposition(CVD).Phase composition and microstructure of the as-prepared coating were investigated by using X-ray diffractometry and scan electron microscopy,and the isothermal anti-oxidation mechanism at 900 ℃ and 1500 ℃ were also analyzed and discussed.The conclusions are as follows,the thickness of the as-prepared ZrB_2-SiC based composite ceramic coating is about 200 μm.The densification and the anti-oxidation properties of the coating can be improved by the addition of Si_3N_4 and Mo Si_2,effectively.While the anti-oxidation properties of the coating can not be improved by the addition of Ta C effectively at 900 ℃.At 900 ℃,the oxidation process of ZrB_2-SiC ceramic coating was mainly controlled by the diffusion of oxygen in pore and other defects in the coating.The anti-oxidation property of coating can be improved by the addition by affecting the density of coating.In the oxidation process of 1500 ℃,the oxidation resistance of the coating decreases.The introduction of the compact structure of CVD SiC sealing layer can improve the oxidation resistance significantly.At 1500 ℃,in oxidation process,SiO_2 glassy oxide film with Zr O_2 and ZrSiO_4 on the coating is generated,this can provide effective oxidation protection for the substrate.
To improve the anti-oxidation performance of C/C composites under high temperature and oxygen enriched environment,ZrB_2-SiC based ceramic coatings with Si_3N_4,MoSi_2 and TaC addition were prepared by two-step slurry painting+chemical vapor deposition(CVD).Phase composition and microstructure of the as-prepared coating were investigated by using X-ray diffractometry and scan electron microscopy,and the isothermal anti-oxidation mechanism at 900 ℃ and 1500 ℃ were also analyzed and discussed.The conclusions are as follows,the thickness of the as-prepared ZrB_2-SiC based composite ceramic coating is about 200 μm.The densification and the anti-oxidation properties of the coating can be improved by the addition of Si_3N_4 and Mo Si_2,effectively.While the anti-oxidation properties of the coating can not be improved by the addition of Ta C effectively at 900 ℃.At 900 ℃,the oxidation process of ZrB_2-SiC ceramic coating was mainly controlled by the diffusion of oxygen in pore and other defects in the coating.The anti-oxidation property of coating can be improved by the addition by affecting the density of coating.In the oxidation process of 1500 ℃,the oxidation resistance of the coating decreases.The introduction of the compact structure of CVD SiC sealing layer can improve the oxidation resistance significantly.At 1500 ℃,in oxidation process,SiO_2 glassy oxide film with Zr O_2 and ZrSiO_4 on the coating is generated,this can provide effective oxidation protection for the substrate.
引文
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[2]李斌.Ta C陶瓷改性C/C复合材料的设计、制备及其性能[D].长沙:中南大学,2013:1-80.LI Bin.Design,preparation and properties of Ta C ceramic modified C/C Composites[D].Changsha:Central South University,2013:1-80.
[3]李军,杨鑫,刘红卫,黄启忠,苏哲安.耐烧蚀超高温陶瓷改性C/C复合材料的研究进展[J].中国有色金属学报,2015,25(7):1731-1743.LI Jun,YANG Xin,LIU Hong-wei,HUANG Qi-zhong,SU Zhe-an.Research process of ultra high temperature ceramics modified carbon/carbon composites for ablation resistance[J].The Chinese Journal of Nonferrous Metals,2015,25(7):1731-1743.
[4]李斌,陈招科,熊翔.热处理对含C-Si C-Ta C-C界面C/C复合材料力学性能的影响[J].复合材料学报,2012,29(1):98-103.LI Bin,CHEN Zhao-ke,XIONG Xiang.Effect of heat treatment on mechanical properties of C/C composites with C-Si C-Ta C-C multi-innterlayers[J].Acta Materiae Compositae Sinca,2012,29(1):98-103.
[5]ZHANG Yu-lei,LI He-jun,LI Ke-zhi,FEI Jie,ZENG Xie-rong.C/Si C/Si-Mo-Cr multilayer coating for carbon/carbon composites for oxidation protection[J].New Carbon Materials,2012,27(2):105-110.
[6]胡兴华,吴明铂,查庆芳.炭/炭复合材料抗氧化研究进展[J].炭素,2006(3):38-45.HU Xing-hua,WU Ming-bo,ZHA Qing-fang.Development of oxidation resistance of carbon/carbon composites at high temperature[J].Carbon,2006(3):38-45.
[7]任富建,刘红娟,沈毅.C/C复合材料高温抗氧化性的研究进展[J].中国陶瓷工业,2008,14(5):28-31.REN Fu-qiang,LIU Hong-juan,SHEN Yi.Progress in the study on oxidation resistance of carbon/carbon composites at high temperature[J].China Ceramic Industry,2008,14(5):28-31.
[8]韩立军,李铁虎,郭恩明,刘方军,武洪臣,邱海鹏.碳/碳复合材料抗氧化方法及发展趋势[J].航空制造技术,2003,5(12):26-30.HAN Li-jun,LI Tie-hu,GUO En-ming,LIU Fng-jun,WU Hong-chen,QIU Hai-peng.Oxidation protection development trend for carbon-carbon composites[J].Aeronautucal Manufacturing Technology,2003,5(12):26-30.
[9]ZHU Y C,OHTANI S,SATO Y,IWAMOTO N.Formation of a functionally gradient(Si3N4+Si C)/C layer for the oxidation protection of carbon–carbon composites[J].Carbon,1999,37(9):1417-1423.
[10]PI H,FAN S,WANG Y.C/Si C-Zr B2-Zr C composites fabricated by reactive melt infiltration with Zr Si2 alloy[J].Ceramics International,2012,38(8):6541-6548.
[11]刘国玺,郭在在,燕东明,牟晓明,常永威,傅宇东.二硼化锆超高温陶瓷的研究进展[J].兵器材料科学与工程,2012,35(1):102-106.LIU Guo-xi,GUO Zai-zai,YAN Dong-ming,MU Xiao-ming,CHANG Yong-wei,FU Yu-dong.Research and development of Zr B2 ultra-high temperature ceramics[J].Ordnance Material Science and Engineering,2012,35(1):102-106.
[12]YAN Y,ZHANG H,HUANG Z,LIU J,JIANG D,HUANG Z.In situ synthesis of ultrafine Zr B2-Si C composite powders and the pressureless sintering behaviors[J].Journal of the American Ceramic Society,2008,91(4):1372-1376.
[13]ZOU X,FU Q,LIU L,LI H,WANG Y,YAO X,HE Z.Zr B2-Si C coating to protect carbon/carbon composites against ablation[J].Surface and Coatings Technology,2013,226:17-21.
[14]ZHANG W Z,ZENG Y,GBOLOGAH L,XIONG X,HUANG B Y.Preparation and oxidation property of Zr B2-Mo Si2/Si C coating on carbon/carbon composites[J].Transactions of Nonferrous Metals Society of China,2011,21(7):1538-1544.
[15]ZHANG Yu-lei,LI He-jun,HU Zhi-xiong,LI Ke-zhi,ZHANG Lei-lei.C/Si C/Mo Si2-Si C-Si multilayer coating for oxidation protection of carbon/carbon composites[J].Transactions of Nonferrous Metals Society of China,2013,23(7):2118-2122.
[16]WANG Y,MA B,LI L,AN L.Oxidation behavior of Zr B2-Si C-Ta C ceramics[J].Journal of the American Ceramic Society,2012,95(1):374-378.
[17]REZAIE A,FAHRENHOLTZ W G,HILMAS G E.Evolution of structure during the oxidation of zirconium diboride-silicon carbide in air up to 1500℃[J].Journal of the European Ceramic Society,2007,27(6):2495-2501.
[18]王超.Zr B2-Si C基超高温陶瓷复合材料失效机制的表征与评价[D].哈尔滨:哈尔滨工业大学,2009.WANG Chao.Characterization and evaluation of failure mechanism of Zr B2-Si C ultra high temperature ceramic composites[D].Harbin:Harbin Institute of Technology,2009.
[19]曾毅,张武装,熊翔.C/C复合材料Si C/Zr B2-Mo Si2复合涂层的抗氧化机制[J].复合材料学报,2010(3):50-55.ZENG Yi,ZHANG Wu-zhuang,XIONG Xiang.Anti-oxidation mechanisms of the Si C/Zr B2-Mo Si2 coating on the carbon/carbon composites[J].Acta Materiae Compositae Sinca,2010(3):50-55.
[20]周庭,谢征芳.Zr B2陶瓷制备研究进展[J].化工进展,2013,32(10):2434-2439.ZHOU Ting,XIE Zheng-fang.Research progress of preparation of zirconium boride ceramics[J].Chemical Industry and Engineering Progress,2013,32(10):2434-2439.