CN115286390A - C/C复合材料表面ZrC-SiC抗烧蚀涂层及涂刷法结合气相反应复合制备方法 - Google Patents
C/C复合材料表面ZrC-SiC抗烧蚀涂层及涂刷法结合气相反应复合制备方法 Download PDFInfo
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Abstract
本发明涉及一种C/C复合材料表面ZrC‑SiC抗烧蚀涂层及涂刷法结合气相反应复合制备方法，首先采用料浆涂刷结合高温碳化工艺在C/C复合材料表面制备SiC‑树脂碳多孔预涂层，通过控制涂刷次数以及每次涂刷的SiC‑树脂的相对含量，实现SiC‑树脂碳多孔预涂层厚度与孔隙结构的有效控制。在此基础上，结合SiC‑树脂碳多孔预涂层的结构特征以及Zr‑Si合金的渗入与反应过程，通过调控反应渗Zr‑Si合金的温度、试样与粉体的距离、升降温速率和保温时间等参数，实现了涂层内各组元的均匀分布。该方法工艺简单，制备的涂层厚度可设计，且与C/C基体结合良好。
Description
技术领域
本发明属于C/C复合材料表面涂层及制备方法，涉及一种C/C复合材料表面ZrC-SiC抗烧蚀涂层及涂刷法结合气相反应复合制备方法。
背景技术
碳/碳(C/C)复合材料具有密度低、比强度和模量高、抗热震等优异性能，被认为是航空航天高温热结构件的最佳材料之一。然而C/C复合材料在静态空气条件下370℃开始氧化，超过400℃后氧化速度会迅速增加，最终使材料失效。此外，航空航天高温服役环境下，C/C复合材料除了经受氧化外，还要承受高速气流和高速粒子的冲刷和撞击，进一步制约了该材料在高温含氧环境下的可靠应用。
抗烧蚀涂层技术是在C/C复合材料表面制备一层保护涂层，隔绝其与外界环境的直接接触，是目前实现C/C复合材料高温长时抗烧蚀的有效方法之一。ZrC具有高熔点(3540℃)、高强度、高硬度，且其氧化后形成的ZrO2不但熔点高(2700℃)而且具有低的蒸气压和热导率，有优异的髙温抗氧化烧蚀能力；而SiC具有高比强度和比模量，并且与C/C复合材料有良好的物理化学相容性。此外，SiC-ZrC复相陶瓷高温烧蚀下会形成熔融态的ZrO2-SiO2二元相化合物氧化膜，可以有效抵御燃气冲刷和减少氧气扩散。因此，ZrC-SiC可以作为C/C复合材料的抗烧蚀涂层的理想体系。
目前，已报道的ZrC-SiC涂层制备方法主要有化学气相沉积(CVD)、等离子喷涂法、涂刷法、固相浸渗等。文献一“Q.M.Liu,J.Liu,X.G.Luan.Preparation of ZrC-SiCcomposite coatings by chemical vapor deposition and study of co-depositionmechanism[J].Journal of Materials Science&Technology.2019,35(12):2942-2949”采用三氯甲基硅烷(MTS)-ZrCl4-CH4-H2体系通过CVD共沉积制备了ZrC-SiC复合涂层，该涂层致密且成分厚度均匀。但CVD法沉积过程易产生含氯有害气体，且成本较高。文献二“H.Wu,H.J.Li,Q.G.Fu,D.J.Yao,Y.J.Wang,C.Ma,J.F.Wei,Z.H.Han.Microstructures andablation resistance of ZrC coating for SiC-coated carbon/carbon compositesprepared by supersonic plasma spraying[J].Journal of Thermal SprayTechnology.2011,20(6):1286-1291”采用包埋法制备SiC内涂层和等离子喷涂制备ZrC外涂层相结合的方法，在C/C复合材料表面制备了SiC-ZrC涂层，该涂层在氧乙炔焰烧蚀30s后，线烧蚀率为0.9×10-3mm/s，质量烧蚀率为2.0×10-3g/s。但包埋法制备的SiC内涂层的厚度和均匀性较难控制；等离子喷涂法制备的ZrC外涂层孔隙率较高，与SiC内涂层的结合力有待进一步提升。文献三“Z.Q.Li,H.J.Li,W.Li,J.Wang,S.Y.Zhang,J.Guo,Preparationand ablation properties of ZrC-SiC coating for carbon/carbon composites bysolid phase infiltration[J],Applied Surfure Science.2011,258(1):565-571”采用固相浸渍的方法：首先将Zr，ZrO2，Si粉体和碳粉以2：0.1：5：2摩尔比混合均匀后得到混合涂层粉体，再将C/C复合材料埋入粉料中，在2300℃热处理2h后得到ZrC-SiC复合涂层。该涂层在氧乙炔焰烧蚀20s后质量烧蚀率为2.36×10-3g/s，与未处理的C/C复合材料相比降低了37.1％，但该方法制备的ZrC-SiC涂层的厚度和均匀性较难控制。
发明内容
要解决的技术问题
为了避免现有技术的不足之处，本发明提出一种C/C复合材料表面ZrC-SiC抗烧蚀涂层及涂刷法结合气相反应复合制备方法，该方法工艺简单，制备的涂层厚度可设计，且与C/C基体结合良好。其制备方法特征在于：首先采用料浆涂刷结合高温碳化工艺在C/C复合材料表面制备SiC-树脂碳多孔预涂层，通过控制涂刷次数以及每次涂刷的SiC-树脂的相对含量，实现SiC-树脂碳多孔预涂层厚度与孔隙结构的有效控制。在此基础上，结合SiC-树脂碳多孔预涂层的结构特征以及Zr-Si合金的渗入与反应过程，通过调控反应渗Zr-Si合金的温度、试样与粉体的距离、升降温速率和保温时间等参数，实现了涂层内各组元的均匀分布。
技术方案
一种C/C复合材料表面ZrC-SiC抗烧蚀涂层，其特征在于涂层结构为：SiC-树脂碳多孔预涂层和预涂层中渗入的Zr-Si合金，孔隙内填充ZrC，形成均匀分布的ZrC物相和SiC物相。
所述SiC-树脂预涂层厚度为100-200μm。
一种采用涂刷法结合气相反应复合所述C/C复合材料表面ZrC-SiC抗烧蚀涂层的方法，其特征在于步骤如下：
步骤1、C/C复合材料表面SiC-树脂预涂层制备：将SiC粉末，酚醛树脂，无水乙醇混合，配制的含有SiC和树脂的混合料浆涂刷在C/C复合材料表面，70-90℃烘干，重复涂刷和烘干多次，在C/C复合材料表面获得厚度为100-200μm的SiC-树脂预涂层；
步骤2、SiC-树脂预涂层的碳化：将带有SiC-树脂预涂层的C/C复合材料放入热处理炉，在Ar环境下以4-8℃/min速率升温到800-1000℃保温1-2h后，冷却到室温取出，得到带有SiC-树脂碳预涂层的C/C复合材料；
步骤3、气相反应制备ZrC-SiC涂层：将ZrSi2粉体与C粉混合均匀后置于石墨坩埚中，将步骤2得到的带SiC-树脂碳预涂层的C/C复合材料放于石墨支架上，一并置于高温炉中，通入氩气以4-8℃/min的升温速率升温到2000-2200℃，保温2-5h，冷却到室温后取出，得到带ZrC-SiC涂层的C/C复合材料；
所述步骤2中SiC-树脂预涂层中SiC粉末与酚醛树脂的质量比为3﹕1～6﹕1。
所述步骤3中ZrSi2粉体与C粉的质量比为8﹕1～10﹕1。
所述ZrSi2合金由βZrSi相和Zr-Si共熔体组成。
有益效果
本发明提出的一种C/C复合材料表面ZrC-SiC抗烧蚀涂层及涂刷法结合气相反应复合制备方法，基于料浆涂刷和气相反应的复合工艺，本发明提出一种在C/C复合材料表面制备ZrC-SiC抗烧蚀涂层的方法，通过改变涂刷次数以及每次涂刷的SiC-树脂的相对含量来控制预涂层的厚度与孔隙结构。图2(a-b)为步骤2所得典型的SiC-树脂碳预涂层表面及截面形貌，可以看出预涂层表面没有明显裂纹缺陷，且与基体结合良好。由于采用料浆涂刷和气相反应结合这一新的工艺组合，ZrC-SiC涂层的形成过程如下：1.由于涂刷法制备的预涂层具有多孔结构，ZrSi2的起始熔点为1620℃，在这一温度下，ZrSi2合金主要由βZrSi相和Zr-Si共熔体组成。随着温度升高，ZrSi2中的Zr-Si共熔体占主体，Zr-Si共熔体将通过毛细管力渗透到涂层内部进行反应：2.随着Zr-Si共熔体不断渗入，由于Zr的活性高于Si，因此此时涂层中主要反应生成ZrC，ZrC的生成导致孔隙直径不断减少：随着合金的不断渗入和反应的不断进行，ZrC逐渐饱和，残余的Si与C发生反应生成SiC，最终形成较为致密的ZrC-SiC涂层。本发明结合Zr-Si合金渗入与原位反应生成涂层的过程特点，通过控制涂刷次数以及每次涂刷的SiC-树脂相对含量，可为上述反应过程提供孔隙与厚度可控的预涂层，从而实现物相的分布控制，如图3所示，结合其能谱分析和XRD可知，涂层表面白色相为ZrC，灰色相为SiC，物相分布较为均匀。
氧乙炔烧蚀环境下，通过ZrC-SiC氧化烧蚀产物(ZrO2、SiO2)的协同抗氧化，可以有效抵御燃气冲刷和减少氧气扩散，进而保护C/C复合材料基体。相比于无SiC-树脂碳预涂层仅步骤3所得试样，SiC-树脂预涂层优化设计后所得的ZrC-SiC复合涂层可以实现C/C复合材料的有效烧蚀防护，氧乙炔烧蚀30s后，复合材料的质量烧蚀率降低了90％，线烧蚀率降低了40％。
附图说明
图1是本发明工艺流程图
图2是本发明所制备SiC-树脂碳预涂层表面及截面形貌照片
图3是本发明所制备ZrC-SiC涂层表面及截面微观照片、能谱及XRD。
具体实施方式
现结合实施例、附图对本发明作进一步描述：
实施例1
步骤一涂刷法制备SiC-树脂碳预涂层：
1)将C/C复合材料用砂纸打磨抛光，无水乙醇超声清洗30min，然后放在烘箱中120℃下干燥1h；
2)将SiC粉末(6-10g)，酚醛树脂(1-3g)，无水乙醇(12-20ml)配制不同SiC、树脂含量的混合料浆，涂刷在C/C复合材料表面，70-90℃烘干，重复多次，在C/C复合材料表面获得厚度为150μm的SiC-树脂预涂层；
3)将得到的带有SiC-树脂预涂层的C/C试样放入热处理炉，在Ar环境下以4-8℃/min速率升温到800-1000℃保温1-2h后，冷却到室温取出，得到带有SiC-树脂碳预涂层的C/C复合材料。
步骤二气相反应：
将30-50g ZrSi2粉，3-6g C粉混合放置于树脂球磨罐中，混合3-5h得到均匀粉料，再将步骤一得到的带SiC-树脂碳预涂层C/C试样放于石墨支架上，一并置于高温炉中，通入氩气以4-8℃/min的升温速率将高温炉升温到2000-2200℃，保温2-5h，冷却到室温后取出，得到带ZrC-SiC涂层的C/C复合材料。
本实施例制备的ZrC-SiC复合陶瓷涂层厚度约为170μm，对其高温抗烧蚀进行了测试，氧乙炔烧蚀90s后质量烧蚀率为-0.35mg/s，线烧蚀率为0.94μm/s。所引文献二中包埋法结合喷涂法制备的ZrC-SiC涂层，在氧乙炔烧蚀30s后线烧蚀率达到0.9×10-3mm/s，相比之下本实验制备的涂层稳定性更好。
实施例2
步骤一涂刷法制备SiC-树脂碳预涂层：
1)将C/C复合材料用砂纸打磨抛光，无水乙醇超声清洗30min，然后放在烘箱中120℃下干燥1h；
2)将SiC粉末(6-10g)，酚醛树脂(1-5g)，无水乙醇(12-20ml)配制不同SiC、树脂含量的混合料浆，涂刷在C/C复合材料表面，70-90℃烘干，重复多次，在C/C复合材料表面获得厚度为200μm的SiC-树脂预涂层；
3)将得到的带有SiC-树脂预涂层的C/C试样放入热处理炉，在Ar环境下以4-8℃/min速率升温到800-1000℃保温1-2h后，冷却到室温取出，得到带有SiC-树脂碳预涂层的C/C复合材料。
步骤二气相反应：
将30-50g ZrSi2粉，3-5g C粉混合放置于树脂球磨罐中，混合3-6h得到均匀粉料，再将步骤一得到的带SiC-树脂碳预涂层C/C试样放于石墨支架上，一并置于高温炉中，通入氩气以4-8℃/min的升温速率将高温炉升温到2000-2200℃，保温2-5h，冷却到室温后取出，得到带ZrC-SiC涂层的C/C复合材料。
本实施例制备的ZrC-SiC复合陶瓷涂层厚度约为220μm，对其高温抗烧蚀进行了测试，氧乙炔烧蚀90s后质量烧蚀率为2.83mg/s，线烧蚀率为-2.28μm/s。
Claims (6)
1.一种C/C复合材料表面ZrC-SiC抗烧蚀涂层，其特征在于涂层结构为：SiC-树脂碳多孔预涂层和预涂层中渗入的Zr-Si合金，孔隙内填充ZrC，形成均匀分布的ZrC物相和SiC物相。
2.根据权利要求1所述C/C复合材料表面ZrC-SiC抗烧蚀涂层，其特征在于：所述SiC-树脂预涂层厚度为100-200μm。
3.一种采用涂刷法结合气相反应复合制备权利要求1或2所述C/C复合材料表面ZrC-SiC抗烧蚀涂层的方法，其特征在于步骤如下：
步骤1、C/C复合材料表面SiC-树脂预涂层制备：将SiC粉末，酚醛树脂，无水乙醇混合，配制的含有SiC和树脂的混合料浆涂刷在C/C复合材料表面，70-90℃烘干，重复涂刷和烘干多次，在C/C复合材料表面获得厚度为100-200μm的SiC-树脂预涂层；
步骤2、SiC-树脂预涂层的碳化：将带有SiC-树脂预涂层的C/C复合材料放入热处理炉，在Ar环境下以4-8℃/min速率升温到800-1000℃保温1-2h后，冷却到室温取出，得到带有SiC-树脂碳预涂层的C/C复合材料；
步骤3、气相反应制备ZrC-SiC涂层：将ZrSi2粉体与C粉混合均匀后置于石墨坩埚中，将步骤2得到的带SiC-树脂碳预涂层的C/C复合材料放于石墨支架上，一并置于高温炉中，通入氩气以4-8℃/min的升温速率升温到2000-2200℃，保温2-5h，冷却到室温后取出，得到带ZrC-SiC涂层的C/C复合材料。
4.根据权利要求3所述的方法，其特征在于：所述步骤2中SiC-树脂预涂层中SiC粉末与酚醛树脂的质量比为3﹕1～6﹕1。
5.根据权利要求3所述的方法，其特征在于：所述步骤3中ZrSi2粉体与C粉的质量比为8﹕1～10﹕1。
6.根据权利要求3所述的方法，其特征在于：所述ZrSi2合金由βZrSi相和Zr-Si共熔体组成。
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