Preparation and performance of anti-oxidation MoSi2-CrB2-SiC-Si composite coating for graphite materials

doi:10.3969/j.issn.1001-1935.2025.05.006

Abstract

Abstract: To enhance the oxidation resistance of graphite materials,a graphite substrate was used,with MoSi₂,CrB₂,and SiC powders as raw materials,anhydrous ethanol as the solvent,and phenolic resin as both the carbon source and binder to prepare the inner and outer coating slurry.The graphite substrate was first reacted,impregnated,and cured,followed by vacuum-assisted gas-phase silicon diffusion at 1 625 ℃ for 40 min,resulting in a MoSi₂-CrB₂-SiC-Si anti-oxidation composite coating on the graphite surface.The phase composition,microstructure,and oxidation resistance at 1 400 and 1 700 ℃ of the coating were investigated.The results indicate that:(1)the coating consists of MoSi₂,CrB₂,SiC,and Si,of dense structure without through cracks,exhibiting good adhesion to the substrate;(2)after 250 h of oxidation at 1 400 ℃,the coating retains intact with a mass gain of 0.36%,due to the formation of a dense Cr-Si-Mo-O multi-phase glass anti-oxidation layer on the coating surface,providing effective protection;(3)after the oxidation at 1 700 ℃ for 40 min,the mass of the coating increases by 1.51%,also due to the formation of a Cr-Si-Mo-O multi-phase glass anti-oxidation layer on the coating surface.However,after 60 min of oxidation,the mass decreases by 0.23% due to the volatilisation of gaseous by-products and the spalling of part of the oxide layer.

Key words: multi-phase ceramic coatings, graphite, anti-oxidation, multi-phase glass layer, in situ reaction

摘要： 为了提高石墨材料的抗氧化性能,以石墨为基体,以MoSi₂、CrB₂、SiC粉体为原料,以无水乙醇为溶剂,酚醛树脂为碳源和黏结剂,制备内外涂层浆料;将石墨基体先反应浸渍固化,再在 1 625 ℃保温40 min的真空环境下进行气相渗硅,在石墨表面获得MoSi₂-CrB₂-SiC-Si抗氧化复合涂层。研究了涂层的物相组成和显微结构,分析了涂层试样在1 400、1 700 ℃下的抗氧化性。结果表明:1)涂层的物相有MoSi₂、CrB₂、SiC、Si,结构致密且无贯穿性裂纹,与基体结合良好。2)涂层试样在1 400 ℃氧化250 h后,表面保持完好,质量增加了0.36%,因为涂层表面生成了致密的Cr-Si-Mo-O复相玻璃抗氧化膜,起到了良好的防护作用。3)涂层试样在1 700 ℃氧化40 min后质量增加了1.51%,也是因为涂层表面生成了含有Cr-Si-Mo-O复相玻璃抗氧化膜,而氧化 60 min 后质量损失了0.23%,因为气体副产物等挥发及部分氧化层的剥落。

关键词: 多相陶瓷涂层, 石墨, 抗氧化, 复相玻璃层, 原位反应

CLC Number:

TQ174.79

Yang Jiani, Guo Xiaoyang, Jiang Yan. Preparation and performance of anti-oxidation MoSi₂-CrB₂-SiC-Si composite coating for graphite materials[J]. Refractories, 2025, 59(5): 398-405.

杨佳妮, 郭晓阳, 姜岩. 石墨材料抗氧化MoSi₂-CrB₂-SiC-Si复合涂层的制备及性能研究[J]. 耐火材料, 2025, 59(5): 398-405.

References

[1] HE Q C,LI H J,TAN Q,et al.Influence of carbon preform density on the microstructure and ablation resistance of CLVD-C/C-ZrC-SiC composites[J].Corrosion Science,2021,190:109648.
[2] ZHOU L,FU Q G,HU D,et al.A dense ZrB₂-SiC-Si/SiC-Si coating to protect carbon/carbon composites against oxidation at 1 773 K and 1 973 K[J].Corrosion Science,2021,183:109331.
[3] ZHUANG L,FU Q G,TAN B Y,et al.Ablation behaviour of C/C and C/C-ZrC-SiC composites with cone-shaped holes under an oxyacetylene flame[J].Corrosion Science,2016,102:84-92.
[4] FU Q G,ZHANG P,ZHUANG L,et al.Micro/nano multiscale reinforcing strategies toward extreme high-temperature applications:Take carbon/carbon composites and their coatings as the examples[J].Journal of Materials Science & Technology,2022,96:31-68.
[5] 李翠云,李辅安.碳/碳复合材料的应用研究进展[J].化工新型材料,2006(3):18-20.
[6] 任岩.石墨材料表面ZrB₂-SiC基抗高温/超高温氧化防护涂层的制备与性能研究[D].合肥:中国科学技术大学,2021.
[7] WANG P P,LI H J,REN X R,et al.HfB₂-SiC-MoSi₂ oxidation resistance coating fabricated through in-situ synthesis for SiC coated C/C composites[J].Journal of Alloys and Compounds,2017,722:69-76.
[8] GHADAMI S,TAHERI-NASSAJ E,BAHARVANDI H R,et al.Effect of in situ SiC and MoSi₂ phases on the oxidation behavior of HfB₂-based composites[J].Ceramics International,2020,46(12):20299-20305.
[9] WANG C C,LI K Z,HE D Y,et al.Evolution behavior of rare-earth yttria modified silicide oxidation-resistant coating at 1 700 ℃[J].Journal of the European Ceramic Society,2020,40(13):4419-4427.
[10] 刘保侠,张盟,周绪强,等.高能等离子喷涂垂直裂纹氧化锆热障涂层工艺及结合性能研究[J].耐火材料,2024,58(4):284-289..
[11] LIU Y,SHAO G,TSAKIROPOULOS P.Thermodynamic reassessment of the Mo-Si and Al-Mo-Si systems[J].Intermetallics,2000,8(8):953-962.
[12] 殷玲,郭顺,张武装,等.包埋法制备SiC涂层内残留Si的高温抗氧化作用机制[J].复合材料学报,2012,29(1):91-97.
[13] 焦更生,李贺军,李克智,等.包埋法制备碳/碳复合材料碳化硅涂层缺陷的形成机制及控制[J].硅酸盐学报,2007(6):721-724.
[14] 张武装,熊翔,曾毅.包埋法制备SiC涂层C/C复合材料及真空热处理对涂层的影响[J].粉末冶金材料科学与工程,2011,16(2):231-236.
[15] 王标,李克智,李贺军,等.包埋浸渗/气相沉积二步法在C/C复合材料表面制备SiC涂层[J].无机材料学报,2007(4):737-741.
[16] FENG G H,LI H J,YANG L,et al.Investigation on the ablation performance and mechanism of HfC coating modified with TaC[J].Corrosion Science,2020,170:108649.
[17] PAN X H,NIU Y R,LIU T,et al.Ablation behaviors of ZrC-TiC coatings prepared by vacuum plasma spray:above 2 000 ℃[J].Journal of the European Ceramic Society,2019,39(11):3292-3300.
[18] ZHANG Y L,WANG H H,LI T,et al.Ultra-high temperature ceramic coating for carbon/carbon composites against ablation above 2 000 K[J].Ceramics International,2018,44(3):3056-3063.
[19] ZHANG Y L,HU H,REN J C,et al.Effect of the surface microstructure of SiC inner coating on the bonding strength and ablation resistance of ZrB₂-SiC coating for C/C composites[J].Ceramics International,2016,42(16):18657-18665.
[20] 刘兴昉,黄启忠,苏哲安,等.化学气相反应法制备SiC涂层[J].硅酸盐学报,2004(7):906-910.
[21] YAO X Y,LI H J,ZHANG Y L,et al.A SiC/ZrB₂-SiC/SiC oxidation resistance multilayer coating for carbon/carbon composites[J].Corrosion Science,2012,57:148-153.
[22] WANG Y L,XIONG X,LI G D,et al.Preparation and ablation properties of Hf (Ta) C co-deposition coating for carbon/carbon composites[J].Corrosion Science,2013,66:177-182.
[23] 王博,庄辛鹏,李归,等.SiC纳米线对大气等离子喷涂硅涂层性能的影响[J].耐火材料,2024,58(5):369-375.
[24] XIONG X,WANG Y L,LI G D,et al.HfC/ZrC ablation protective coating for carbon/carbon composites[J].Corrosion Science,2013,77:25-30.
[25] 曾毅,张武装,熊翔.C/C复合材料SiC/ZrB₂-MoSi₂复合涂层的抗氧化机制[J].复合材料学报,2010,27(3):50-55.
[26] 窦如令.碳碳复合材料SiC/Cr-Al-Si复合涂层的抗氧化性能研究[J].中国陶瓷,2018,54(09):54-60.
[27] WANG K T,CAO L Y,HUANG J F,et al.A mullite/SiC oxidation protective coating for carbon/carbon composites[J].Journal of the European Ceramic Society,2013,33(1):191-198.
[28] 姜岩,冯东,茹红强,等.石墨表面Si-SiC-ZrB₂抗氧化复合涂层的制备及性能表征[J].耐火材料,2018,52(4):241-245.
[29] 田原,姜岩,付琬璐.石墨表面Si-SiC-TaB₂抗烧蚀复合涂层的制备及性能研究[J].耐火材料,2023,57(1):35-40.
[30] JIANG Y,RU H Q,YE C C,et al.A dense structure Si-SiC coating for oxidation and ablation protection of graphite fabricated by impregnation-pyrolysis and gaseous silicon infiltration[J].Ceramics International,2018,44(14):17369-17376.
[31] ZHU X F,ZHANG Y L,QIANG X F,et al.An oxidation protective coating prepared by SiC densifying HfB₂-SiC skeleton for SiC-coated C/C composites at 1473,1773,and 1973 K[J].Corrosion Science,2022,207:110559.
[32] ZHU C Z,JI X,CHEN Y X,et al.Enhanced oxidation resistance of LaB₆-modified HfB₂-SiC coating at 1 700 ℃ by low-loss film-forming treatment[J].Applied Surface Science,2025,688:162397.
[33] WANG P P,LI H J,YUAN R M,et al.A CrSi₂-HfB₂-SiC coating providing oxidation and ablation protection over 1 973 K for SiC coated C/C composites[J].Corrosion Science,2020,167:108536.

Preparation and performance of anti-oxidation MoSi₂-CrB₂-SiC-Si composite coating for graphite materials

石墨材料抗氧化MoSi₂-CrB₂-SiC-Si复合涂层的制备及性能研究

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