CN114853506A - 碳/碳复合材料表面(HfZrTi)C3中熵碳化物抗烧蚀涂层及制备方法 - Google Patents
碳/碳复合材料表面(HfZrTi)C3中熵碳化物抗烧蚀涂层及制备方法 Download PDFInfo
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Abstract
本发明涉及一种碳/碳复合材料表面(HfZrTi)C3中熵碳化物抗烧蚀涂层及制备方法，首先在高温热处理炉中将HfO2粉、ZrO2粉、TiO2粉和碳粉混合烧结，利用碳热还原反应制备出(HfZrTi)C3中熵陶瓷粉体，该合成工艺简单、成分均匀、成本低、制备周期短；然后研磨并造粒，采用超音速等离子喷涂技术在包覆有SiC内涂层的C/C复合材料表面制备了(HfZrTi)C3中熵陶瓷涂层，该涂层具有优异抗烧蚀能力。该发明为高性能中熵碳化物抗烧蚀涂层C/C复合材料在空天飞行器热端部件的应用奠定基础。
Description
技术领域
本发明属于超高温抗烧蚀涂层领域，涉及一种碳/碳复合材料表面(HfZrTi)C3中熵碳化物抗烧蚀涂层及制备方法。
背景技术
碳/碳(C/C)复合材料具有密度低、导热系数高、机械性能好、高温热膨胀系数低等优异性能，已被应用于飞机和航空航天领域。然而C/C复合材料在高于450℃的氧化环境中会因为C/C发生氧化而导致其力学性能降低。甚至在超高温(2000℃以上)和富氧环境条件下，在外部高压和高速燃烧气流作用下，C/C复合材料将发生烧蚀，力学性能急剧降低。制备难熔碳化物涂层被认为是避免C/C复合材料快速烧蚀的有效方法。
文献1“Jincui Ren,Errong Feng,Yulei Zhang,et al.Influences ofdeposition temperature,gas flow rate and ZrC content on the microstructureand anti-ablation performance of CVD-HfC-ZrC coating[J].CeramicsInternational,2021,47:556-566.”用化学气相沉积法制备了HfC-ZrC双相涂层，在烧蚀过程中，涂层表面形成疏松的氧化物骨架，可以一定程度上保护C/C复合材料。但是这种结构不利于阻氧，氧气会向内涂层扩散并发生反应，导致涂层失效，该涂层不利于C/C复合材料长时间抗烧蚀。
考虑到TiO2具有比HfO2和ZrO2更低熔点温度的特点，容易在烧蚀过程中形成低熔点液相，从而填补疏松骨架。因此可以在HfC-ZrC涂层基础上添加TiC，从而提高HfC-ZrC涂层抗烧蚀性能。此外，中熵碳化物可以整合多种碳化物优异特性，并且具有较大晶格畸变效应特点，这使得它们比传统的单相碳化物具有更高的硬度和强度、良好的耐磨性和优异的耐腐蚀性。因此可以考虑在C/C复合材料表面制备(ZrHfTi)C3中熵碳化物抗烧蚀涂层，从而提高C/C复合材料涂层抗烧蚀性能。
文献2“Huilin Lun,Yi Zeng,Xiang Xiong,et al.Oxidation behavior of non-stoichiometric(Zr,Hf,Ti)Cx carbide solid solution powders in air[J].Journalof Advanced Ceramics,2021,10:741-757.”报道了一种非等比例HfxZryTizC中熵粉体的制备方法。具体方法是将铪粉、锆粉、钛粉和碳粉在真空(<5Pa)下以100℃/min的加热速率升温至1600℃，并进行15min的无压等离子烧结。实验结果发现HfxZryTizC具有比单相碳化物HfC和ZrC更好的抗氧化性能。然而这种方法并不能直接在C/C复合材料表面将HfxZryTizC粉体制备成涂层。
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，本发明提出一种碳/碳复合材料表面(HfZrTi)C3中熵碳化物抗烧蚀涂层及制备方法，获得具有优异抗烧蚀性能的C/C复合材料涂层。首先采用碳热还原反应直接制备出(ZrHfTi)C3中熵陶瓷粉体，然后将造粒后的(ZrHfTi)C3中熵陶瓷粉体，采用超音速等离子喷涂技术在包覆有SiC内涂层的C/C复合材料表面得到(HfZrTi)C3中熵陶瓷涂层。
技术方案
一种碳/碳复合材料表面(HfZrTi)C3中熵碳化物抗烧蚀涂层，其特征在于内涂层为SiC涂层，外涂层为(HfZrTi)C3。
一种制备所述碳/碳复合材料表面(HfZrTi)C3中熵碳化物抗烧蚀涂层的方法，其特征在于步骤如下：
步骤1：HfO2粉、ZrO2粉、TiO2粉以及C粉混合作为原料得到混合粉末；
所述HfO2粉﹕ZrO2粉﹕TiO2粉﹕C粉摩尔比为1﹕1﹕1﹕3；
步骤2：将石墨纸包裹混合粉体，放置于石墨坩埚内，然后在石墨纸上施加5-10MPa载荷；将石墨坩埚放入高温热处理炉底部；采用惰性气体保护，随炉冷却到室温，利用碳热还原反应制备(HfZrTi)C3中熵陶瓷粉体；
步骤3：将(HfZrTi)C3中熵陶瓷粉体放入球磨罐中研磨；将研磨后粉体采用喷雾干燥法进行造粒；
步骤4：将造粒后(HfZrTi)C3中熵陶瓷粉体装入超音速等离子喷涂送粉器，在包覆有SiC内涂层的C/C复合材料表面制备(HfZrTi)C3中熵涂层；
所述等离子喷涂工艺参数：喷涂直流电流：350～450A；喷涂直流电压：80～150V；主气流量：70～90L/min；辅气流量：4～6L/min；送粉速率：15～35g/min；喷涂距离：70～120mm；喷涂过程为6～10次喷涂。
所述混合粉末中的Hf﹕Zr﹕Ti摩尔比为1﹕1﹕1。
所述混合粉末通过行星式球磨罐研磨原料得到。
所述HfO2粉、ZrO2粉、TiO2粉的纯度均≥99.5％，粒径均为1～3μm。
所述C粉的纯度≥99.9％，粒径为1～3μm。
所述球磨机的转速为200-300r/min，球磨时间为6～10h。
所述步骤2中，惰性气体为Ar气；热处理炉以3～6℃/min升温到2000～2200℃。
所述步骤3中，(HfZrTi)C3中熵陶瓷粉体造粒粒径为40～70μm；所述喷雾干燥法造粒时：干燥器进口温度310～330℃，出口温度100～150℃，喷头转速25～35rpm，进料速度70～80ml/min。
所述步骤4中，喷涂直流电流：350～450A；喷涂直流电压：80～150V；喷涂过程为6～10次喷涂。
有益效果
本发明提出的一种碳/碳复合材料表面(HfZrTi)C3中熵碳化物抗烧蚀涂层及制备方法，首先在高温热处理炉中将HfO2粉、ZrO2粉、TiO2粉和碳粉混合烧结，利用碳热还原反应制备出(HfZrTi)C3中熵陶瓷粉体，该合成工艺简单、成分均匀、成本低、制备周期短；然后研磨并造粒，采用超音速等离子喷涂技术在包覆有SiC内涂层的C/C复合材料表面制备了(HfZrTi)C3中熵陶瓷涂层，该涂层具有优异抗烧蚀能力。该发明为高性能中熵碳化物抗烧蚀涂层C/C复合材料在空天飞行器热端部件的应用奠定基础。
对于涂层的改变：传统的HfC和ZrC涂层由于其氧化物(HfO2和ZrO2)骨架疏松，在2100℃下烧蚀90s时涂层完全失效，无法抵御长期烧蚀。本发明所用中熵碳化物(ZrHfTi)C3涂层相对传统单相碳化物而言，中熵碳化物具有较大晶格畸变效应，可以提高峰值氧化温度以及高温条件下氧化物相稳定性，所形成的氧化层(Hf,Zr,Ti)O2致密，有效阻隔氧气渗入，在烧蚀120s以后，依旧能够有效保护C/C复合材料。因此中熵碳化物(ZrHfTi)C3涂层具有更优异的烧蚀性能。
对于工艺的改变：首先在包裹混合粉体的石墨纸上施加5-10MPa载荷，然后将其放入高温热处理炉底部，采用碳热还原反应制备出(ZrHfTi)C3中熵陶瓷粉体，该过程工艺简单、成本低、制备周期短，施加一定载荷可以制备出成分均匀的中熵粉体，有助于(ZrHfTi)C3中熵陶瓷粉体合成技术的推广。然后采用超音速等离子喷涂技术获得(ZrHfTi)C3中熵涂层，成功将中熵粉体制备于C/C复合材料表面，这为高性能中熵碳化物抗烧蚀涂层C/C复合材料在空天飞行器热端部件的应用奠定基础。
附图说明
图1是超高温陶瓷(HfZrTi)C3中熵粉末的X射线衍射图谱；
经过步骤1和步骤2所得粉体的X射线衍射图谱，可看到图中所有的峰都位于对应HfC、ZrC和TiC峰中间，没有氧化物存在，说明该(HfZrTi)C3中熵粉末成功制备。
图2是超高温陶瓷(HfZrTi)C3中熵涂层表面的宏观照片；
图3是超高温陶瓷(HfZrTi)C3中熵涂层截面的宏观照片
图4是超高温陶瓷(HfZrTi)C3中熵涂层X射线衍射图谱
图2和图3分别是(HfZrTi)C3中熵涂层的表面和截面图片，图4是(HfZrTi)C3中熵涂层X射线衍射图谱。由于超音速等离子喷涂设备温度较高，喷涂过程中出现少量氧化，这是不可避免的。但是XRD结果显示不存在碳化物分相现象，(HfZrTi)C3依旧是主要峰形，并且喷涂以后涂层致密，因此该方法能成功制备出(HfZrTi)C3中熵涂层。
图5是超高温陶瓷(HfZrTi)C3中熵涂层的宏观烧蚀照片
图6是超高温陶瓷(HfZrTi)C3中熵涂层烧蚀60s后氧化物层扫描电镜图
图5和图6分别是超高温陶瓷(HfZrTi)C3中熵涂层烧蚀60s后的宏观烧蚀照片和氧化物层扫描电镜图，可以看到涂层经过烧蚀以后，表面没有任何缺陷，烧蚀性能优异。
图7是本发明实施反例1所制备粉体X射线衍射图谱
是本发明实施反例1所制备粉体X射线衍射图谱，这是通过将1:1:1:3的HfO2粉、ZrO2粉、TiO2粉和C粉在1700℃下烧结，XRD结果显示粉体中含有少量TiC粉末的存在，说明在碳热还原反应过程中，TiO2粉与C粉反应生成TiC，然而在此温度条件下，并不能成功制备出(HfZrTi)C3中熵陶瓷粉体。
图8是本发明实施反例2所制备涂层X射线衍射图谱
是本发明实施反例2所制备涂层的X射线衍射图谱。这是将摩尔比为1:1:1的HfC粉、ZrC粉和TiC粉混合并造粒，然后直接喷涂于SiC内涂层的C/C复合材料表面。喷涂后涂层XRD数据显示涂层中依旧有HfC、ZrC和TiC峰的存在。因此直接用该方式无法制备出(HfZrTi)C3中熵涂层。
图9是本发明实施反例2所制备涂层烧蚀60s后氧化物层扫描电镜图
是本发明实施反例2所制备涂层烧蚀60s后后氧化物层扫描电镜图。该方法所制备涂层烧蚀以后，出现烧蚀坑，烧蚀性能差。
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1：称取摩尔比为1:1:1:3的HfO2粉、ZrO2粉、TiO2粉以及C粉混合作为原料放入行星式球磨罐，以240r/min的转速球磨6h得到混合粉末。
步骤2：将石墨纸包裹步骤1中得到的混合粉体，放置于石墨坩埚内，然后在石墨纸上施加5MPa载荷；将石墨坩埚放入高温热处理炉底部；在Ar气保护下，以5℃/min升温速度将炉温升到2100℃，保温3h；随炉冷却到室温，利用碳热还原反应制备得到(HfZrTi)C3中熵陶瓷粉体。
步骤3：将步骤2中所得(HfZrTi)C3中熵陶瓷粉体放入球磨罐中研磨；将研磨后粉体采用喷雾干燥法进行造粒。
干燥器进口温度为330℃，出口温度120℃，喷头转速30rpm，进料速度75ml/min。
步骤4：将步骤3中造粒后(HfZrTi)C3中熵陶瓷粉体装入超音速等离子喷涂送粉器，在包覆有SiC内涂层的C/C复合材料表面制备(HfZrTi)C3中熵涂层；
等离子喷涂工艺参数：喷涂直流电流：450A；喷涂直流电压：120V；主气流量：75L/min；辅气流量：4.5L/min；送粉速率：20g/min；喷涂距离：80mm；喷涂过程为8次喷涂，即得到中熵超高温陶瓷(HfZrTi)C3中熵涂层。
实施例2：
步骤1：称取摩尔比为1:1:1:3的HfO2粉、ZrO2粉、TiO2粉以及C粉混合作为原料放入行星式球磨罐，以300r/min的转速球磨8h得到混合粉末。
步骤2：将石墨纸包裹步骤1中得到的混合粉体，放置于石墨坩埚内，然后在石墨纸上施加6MPa载荷；将石墨坩埚放入高温热处理炉底部；在Ar气保护下，以5℃/min升温速度将炉温升到2200℃，保温4h；随炉冷却到室温，利用碳热还原反应制备得到(HfZrTi)C3中熵陶瓷粉体。
步骤3：将步骤2中所得(HfZrTi)C3中熵陶瓷粉体放入球磨罐中研磨；将研磨后粉体采用喷雾干燥法进行造粒。
干燥器进口温度为350℃，出口温度130℃，喷头转速30rpm，进料速度80ml/min。
步骤4：将步骤3中造粒后(HfZrTi)C3中熵陶瓷粉体装入超音速等离子喷涂送粉器，在包覆有SiC内涂层的C/C复合材料表面制备(HfZrTi)C3中熵涂层；
等离子喷涂工艺参数：喷涂直流电流：420A；喷涂直流电压：120V；主气流量：75L/min；辅气流量：4.5L/min；送粉速率：20g/min；喷涂距离：80mm；喷涂过程为6次喷涂，即得到中熵超高温陶瓷(HfZrTi)C3中熵涂层。
实施例3：
步骤1：称取摩尔比为1:1:1:3的HfO2粉、ZrO2粉、TiO2粉以及C粉混合作为原料放入行星式球磨罐，以200r/min的转速球磨8h得到混合粉末。
步骤2：将石墨纸包裹步骤1中得到的混合粉体，放置于石墨坩埚内，然后在石墨纸上施加5MPa载荷；将石墨坩埚放入高温热处理炉底部；在Ar气保护下，以5℃/min升温速度将炉温升到2100℃，保温3h；随炉冷却到室温，利用碳热还原反应制备得到(HfZrTi)C3中熵陶瓷粉体。
步骤3：将步骤2中所得(HfZrTi)C3中熵陶瓷粉体放入球磨罐中研磨；将研磨后粉体采用喷雾干燥法进行造粒。
干燥器进口温度为350℃，出口温度120℃，喷头转速25rpm，进料速度75ml/min。
步骤4：将步骤3中造粒后(HfZrTi)C3中熵陶瓷粉体装入超音速等离子喷涂送粉器，在包覆有SiC内涂层的C/C复合材料表面制备(HfZrTi)C3中熵涂层；
等离子喷涂工艺参数：喷涂直流电流：400A；喷涂直流电压：140V；主气流量：75L/min；辅气流量：5L/min；送粉速率：25g/min；喷涂距离：100mm；喷涂过程为10次喷涂，即得到中熵超高温陶瓷(HfZrTi)C3中熵涂层。
实施反例1：
步骤1：称取摩尔比为1:1:1:3的HfO2粉、ZrO2粉、TiO2粉以及C粉混合作为原料放入行星式球磨罐，以240r/min的转速球磨6h得到混合粉末。
步骤2：将石墨纸包裹步骤1中得到的混合粉体，放置于石墨坩埚内，然后在石墨纸上施加5MPa载荷；将石墨坩埚放入高温热处理炉底部；在Ar气保护下，以5℃/min升温速度将炉温升到1700℃，保温3h；随炉冷却到室温，利用碳热还原反应制备得到陶瓷粉体。
从图7该实施反例的XRD结果中可以看到，合成的粉体中含有少量TiC粉末的存在，说明在碳热还原反应过程中，TiO2粉与C粉反应生成TiC，然而在此温度条件下，并不能成功制备出(HfZrTi)C3中熵陶瓷粉体。
实施反例2：
步骤1：称取摩尔比为1:1:1的HfC粉、ZrC粉、TiC粉混合作为原料放入行星式球磨罐，以240r/min的转速球磨6h得到混合粉末。
步骤2：将步骤1中所得混合粉体放入球磨罐中研磨；将研磨后粉体采用喷雾干燥法进行造粒。干燥器进口温度为350℃，出口温度120℃，喷头转速25rpm，进料速度75ml/min。
步骤4：将步骤3中造粒后陶瓷粉体装入超音速等离子喷涂送粉器，在包覆有SiC内涂层的C/C复合材料表面制备涂层；
等离子喷涂工艺参数：喷涂直流电流：400A；喷涂直流电压：130V；主气流量：75L/min；辅气流量：5L/min；送粉速率：25g/min；喷涂距离：100mm；喷涂过程为10次喷涂。
该反例直接采用HfC粉、ZrC粉和TiC粉混合并造粒，然后喷涂在SiC内涂层的C/C复合材料表面制备涂层。图8为该实施反例喷涂后涂层XRD数据，可以看到依旧有HfC、ZrC和TiC峰的存在。因此直接用该方法喷涂无法制备出(HfZrTi)C3中熵涂层。然后图9显示该方法所制备涂层烧蚀以后，出现烧蚀坑，烧蚀性能差。
Claims (10)
1.一种碳/碳复合材料表面(HfZrTi)C3中熵碳化物抗烧蚀涂层，其特征在于内涂层为SiC涂层，外涂层为(HfZrTi)C3。
2.一种制备权利要求1所述碳/碳复合材料表面(HfZrTi)C3中熵碳化物抗烧蚀涂层的方法，其特征在于步骤如下：
步骤1：HfO2粉、ZrO2粉、TiO2粉以及C粉混合作为原料得到混合粉末；
所述HfO2粉﹕ZrO2粉﹕TiO2粉﹕C粉摩尔比为1﹕1﹕1﹕3；
步骤2：将石墨纸包裹混合粉体，放置于石墨坩埚内，然后在石墨纸上施加5-10MPa载荷；将石墨坩埚放入高温热处理炉底部；采用惰性气体保护，随炉冷却到室温，利用碳热还原反应制备(HfZrTi)C3中熵陶瓷粉体；
步骤3：将(HfZrTi)C3中熵陶瓷粉体放入球磨罐中研磨；将研磨后粉体采用喷雾干燥法进行造粒；
步骤4：将造粒后(HfZrTi)C3中熵陶瓷粉体装入超音速等离子喷涂送粉器，在包覆有SiC内涂层的C/C复合材料表面制备(HfZrTi)C3中熵涂层；
所述等离子喷涂工艺参数：喷涂直流电流：350～450A；喷涂直流电压：80～150V；主气流量：70～90L/min；辅气流量：4～6L/min；送粉速率：15～35g/min；喷涂距离：70～120mm；喷涂过程为6～10次喷涂。
3.根据权利要求2所述的方法，其特征在于：所述混合粉末中的Hf﹕Zr﹕Ti摩尔比为1﹕1﹕1。
4.根据权利要求2所述的方法，其特征在于：所述混合粉末通过行星式球磨罐研磨原料得到。
5.根据权利要求2所述的方法，其特征在于：所述HfO2粉、ZrO2粉、TiO2粉的纯度均≥99.5％，粒径均为1～3μm。
6.根据权利要求2所述的方法，其特征在于：所述C粉的纯度≥99.9％，粒径为1～3μm。
7.根据权利要求4所述的方法，其特征在于：所述球磨机的转速为200-300r/min，球磨时间为6～10h。
8.根据权利要求2所述的方法，其特征在于：所述步骤2中，惰性气体为Ar气；热处理炉以3～6℃/min升温到2000～2200℃。
9.根据权利要求2所述的方法，其特征在于：所述步骤3中，(HfZrTi)C3中熵陶瓷粉体造粒粒径为40～70μm；所述喷雾干燥法造粒时：干燥器进口温度310～330℃，出口温度100～150℃，喷头转速25～35rpm，进料速度70～80ml/min。
10.根据权利要求2所述的方法，其特征在于：所述步骤4中，喷涂直流电流：350～450A；喷涂直流电压：80～150V；喷涂过程为6～10次喷涂。
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