CN113387724B - 一种碳/碳复合材料表面耐高温长寿命复合涂层及制备方法 - Google Patents
一种碳/碳复合材料表面耐高温长寿命复合涂层及制备方法 Download PDFInfo
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Abstract
本发明涉及一种碳/碳复合材料表面耐高温长寿命复合涂层及制备方法，采用料浆浸涂结合气相渗硅工艺制备了一种(Hf0.25Ta0.25Zr0.25Ti0.25)B2‑SiC‑Si/SiC‑Si复合抗氧化涂层，SiC‑Si内涂层用于缓解涂层与基体之间的热失配，外层为(Hf0.25Ta0.25Zr0.25Ti0.25)B2‑SiC‑Si，通过在外涂层中引入高熵陶瓷，氧化后生成多元金属氧化物，进而提高SiO2在高温下的稳定性，最终实现涂层在高温下对C/C复合材料的长时有效防护。本发明所制备的(Hf0.25Ta0.25Zr0.25Ti0.25)B2‑SiC‑Si/SiC‑Si复合抗氧化涂层试样在1500℃下氧化2000h后涂层试样增重1.12％，在1700℃下500h后涂层试样增重1.05％。
Description
技术领域
本发明属于抗氧化涂层制备技术领域，涉及一种碳/碳复合材料表面耐高温长寿命复合涂层及制备方法，具体涉及一种(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si复合抗氧化涂层及其制备方法。
背景技术
碳/碳(C/C)复合材料具有比强度高、热膨胀系数低、耐高温等优异性能，特别是在超高温下仍能保持高强度的特性，使其广泛应用于航空航天领域中的高温结构部件。然而，C/C复合材料在超过370℃有氧环境中易氧化会导致其力学性能及各项物理化学性能迅速下降，稳定持久的抗氧化防护已成为保证C/C复合材料应用于新一代尖端武器装备及严酷环境工程化应用的关键。
抗氧化涂层被认为是解决C/C复合材料高温氧化防护问题的有效方法。为防止C/C复合材料在高温下氧化，国内外研究人员进行了大量的理论和试验研究，开发出多种抗氧化涂层体系。
在众多涂层体系中，陶瓷涂层是目前研究的热点。在陶瓷涂层体系里，一般采用SiC为内涂层的复合涂层结构，复合涂层的外涂层则采用不同种类的高温陶瓷。目前研究较多的一类是硅基陶瓷涂层，如SiCn[J.F.Huang,M.Liu,B.Wang,L.Y.Cao,C.K.Xia,J.P.Wu,SiCn/SiC oxidation protective coating for carbon/carbon composites,Carbon47(2009)1198-1201.]、Si-Mo-Cr/SiC[J.C.Ren,Y.L.Zhang,H.Hu,P.F.Zhang,T.Fei,L.L.Zhang,HfC nanowires to improve the toughness and oxidation resistance ofSi-Mo-Cr/SiC coating for C/C composites,Ceram.Int.42(2016)14518-14525]等硅基陶瓷涂层。其主要的氧化防护机理是利用高温下涂层氧化所产生的SiO2来愈合涂层中的裂纹等缺陷，利用其低的氧渗透率来阻止氧气的扩散，进而实现对C/C复合材料的氧化防护。但是，在高温氧化气氛或烧蚀环境中长期使用后，SiO2玻璃不可避免地大量挥发，从而在涂层中产生许多缺陷，从而失去了对C/C复合材料的保护能力。此外，一旦氧化温度超过1650℃，SiC就会发生主动氧化，这也会加速涂层的消耗。随着氧化时间的延长会逐渐挥发，使得玻璃层下面的涂层材料暴露在空气中。由于涂层材料的高透氧率，氧气在涂层中迅速扩散，导致C/C复合材料基体呈现快速氧化失重。此外，非晶态SiO2会在1700℃快速晶化，且伴随着体积收缩，导致玻璃层开裂和剥落。因此，设计出满足1700℃以上长寿命服役的涂层成分，并实现裂纹和孔隙的快速修复，是硅基陶瓷涂层成功应用于C/C复合材料1700℃长时间防氧化的前提，也是该方向研究需要突破的关键。
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/碳复合材料表面耐高温长寿命复合涂层及制备方法，首先采用料浆浸涂法在C/C复合材料表面制备SiC内涂层和(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si外涂层，随后采用气相渗硅工艺制得(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si复合涂层。
技术方案
一种碳/碳复合材料表面耐高温长寿命复合涂层，其特征在于C/C复合材料表面涂层为内涂层和外涂层组成，其中内涂层组份为SiC-Si涂层，外涂层组份为(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si。
一种制备所述碳/碳复合材料表面耐高温长寿命复合涂层的方法，其特征在于步骤如下：
步骤1：将酚醛树脂与无水乙醇超声处理后搅拌均匀得到酚醛树脂溶液A，其中乙醇的质量分数为70-90wt％，酚醛树脂的质量分数为10-30wt％；
步骤2：向酚醛树脂溶液A中加入SiC粉体，搅拌均匀后得料浆B，其中SiC的质量分数为30-40wt％；
向酚醛树脂溶液A中加入(Hf0.25Ta0.25Zr0.25Ti0.25)B2和SiC粉体，搅拌均匀后得料浆C，其中SiC的质量分数为10-20wt％，(Hf0.25Ta0.25Zr0.25Ti0.25)B2的质量分数为30-40wt％；
步骤3：将C/C复合材料浸到料浆B中进行预涂层浸涂，取出后在烘箱中干燥，该过程重复多次后，得到SiC内涂层；将带有SiC内涂层的C/C复合材料浸到料浆C中进行浸涂，取出后在烘箱中干燥，该过程重复多次后，得到(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC/SiC涂层；
步骤4：再置于管式气氛炉中温度为150-200℃，固化时间为2-4h进行固化；然后在温度为900-1100℃，碳化时间为2-4h进行碳化后得到预涂层；
步骤5：置于石墨坩埚中，坩埚底部放置一定量的硅块，得到预涂层的材料与硅块之间采用多孔石墨板隔开；密封坩埚后将石墨坩埚放入高温石墨化炉中在氩气保护下，温度为1800-2000℃，时间为15-30min进行气相渗硅，之后随炉冷却，在碳/碳复合材料表面得到耐高温长寿命复合涂层：(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si。
所述步骤3的重复多次为3次。
所述步骤3的浸涂时间为3-5s。
所述步骤3的干燥温度为50-80℃，干燥时间为10-30min。
有益效果
本发明提出的一种碳/碳复合材料表面耐高温长寿命复合涂层及制备方法，C/C复合材料表面涂层为内涂层和外涂层组成，其中内涂层组份为SiC-Si涂层，外涂层组份为(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si。本发明采用料浆浸涂结合气相渗硅工艺制备了一种(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si复合抗氧化涂层，SiC-Si内涂层用于缓解涂层与基体之间的热失配，外层为(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si，通过在外涂层中引入高熵陶瓷，氧化后生成多元金属氧化物，进而提高SiO2在高温下的稳定性，最终实现涂层在高温下对C/C复合材料的长时有效防护。本发明所制备的(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si复合抗氧化涂层试样在1500℃下氧化2000h后涂层试样增重1.12％，在1700℃下500h后涂层试样增重1.05％。
本发明的涂层避免了在高温氧化气氛或烧蚀环境中长期使用后，SiO2玻璃不可避免地大量挥发，从而在涂层中产生许多缺陷，从而失去了对C/C复合材料的保护能力的缺陷。同时，在一旦氧化温度超过1650℃，SiC就会发生主动氧化，这也会加速涂层的消耗。随着氧化时间的延长会逐渐挥发，使得玻璃层下面的涂层材料暴露在空气中的问题。以及由于涂层材料的高透氧率，氧气在涂层中迅速扩散，导致C/C复合材料基体呈现快速氧化失重，非晶态SiO2会在1700℃快速晶化，且伴随着体积收缩，导致玻璃层开裂和剥落的问题。本发明满足1700℃以上长寿命服役的涂层成分，并实现裂纹和孔隙的快速修复，是硅基陶瓷涂层成功应用于C/C复合材料1700℃长时间防氧化的前提，也是该方向研究需要突破的关键。
附图说明
图1(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si涂层试样的SEM照片：(a)表面SEM照片，(b)截面SEM照片
图2(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si涂层试样在不同温度下的的氧化质量变化曲线：(a)1500℃,(b)1700℃
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：
(1)称取一定量的酚醛树脂于烧杯中，向其中加入一定量的无水乙醇，其中酚醛树脂与无水乙醇的质量比为2:8，将其超声处理后搅拌均匀得到酚醛树脂溶液A；
(2)向酚醛树脂溶液A中加入SiC粉体，搅拌均匀后得料浆B，其中SiC的质量分数为40wt％；向酚醛树脂溶液A中加入(Hf0.25Ta0.25Zr0.25Ti0.25)B2和SiC粉体，其中SiC的质量分数为10wt％，(Hf0.25Ta0.25Zr0.25Ti0.25)B2的质量分数为30wt％，搅拌均匀后得料浆C；
(3)将C/C复合材料浸到料浆B中浸涂3s，取出后在烘箱中于50℃干燥30min，该过程重复3次后，得到SiC内涂层；将带有SiC内涂层的C/C复合材料浸到料浆C中浸涂3s，取出后在烘箱中于50℃干燥30min，该过程重复3次后，得到(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC外涂层；
(4)将(3)所得试样在管式气氛炉中于氩气气氛保护下在150℃中保温4h，随即升温至900℃，热处理4h后得到预涂层试样；
(5)将(4)所得的预涂层试样置于自制的石墨坩埚中，坩埚底部放置一定量的硅块，试样与硅块通过多孔石墨板隔开，密封坩埚后将其放入高温石墨化炉中在氩气保护下进行气相渗硅，渗硅温度为1900℃，保温时间20min，之后随炉冷却，即得(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si涂层试样。
实施例2：
(1)称取一定量的酚醛树脂于烧杯中，向其中加入一定量的无水乙醇，其中酚醛树脂与无水乙醇的质量比为1:9，将其超声处理后搅拌均匀得到酚醛树脂溶液A；
(2)向酚醛树脂溶液A中加入SiC粉体，搅拌均匀后得料浆B，其中SiC的质量分数为35wt％；向酚醛树脂溶液A中加入(Hf0.25Ta0.25Zr0.25Ti0.25)B2和SiC粉体，其中SiC的质量分数为15wt％，(Hf0.25Ta0.25Zr0.25Ti0.25)B2的质量分数为35wt％，搅拌均匀后得料浆C；
(3)将C/C复合材料浸到料浆B中浸涂4s，取出后在烘箱中于70℃干燥15min，该过程重复3次后，得到SiC内涂层；将带有SiC内涂层的C/C复合材料浸到料浆C中浸涂4s，取出后在烘箱中于70℃干燥15min，该过程重复3次后，得到(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC外涂层；
(4)将(3)所得试样在管式气氛炉中于氩气气氛保护下在200℃中保温2h，随即升温至1200℃，热处理2h后得到预涂层试样；
(5)将(4)所得的预涂层试样置于自制的石墨坩埚中，坩埚底部放置一定量的硅块，试样与硅块通过多孔石墨板隔开，密封坩埚后将其放入高温石墨化炉中在氩气保护下进行气相渗硅，渗硅温度为1800℃，保温时间30min，之后随炉冷却即得(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si涂层试样。
实施例3：
(1)称取一定量的酚醛树脂于烧杯中，向其中加入一定量的无水乙醇，其中酚醛树脂与无水乙醇的质量比为2:8，将其超声处理后搅拌均匀得到酚醛树脂溶液A；
(2)向酚醛树脂溶液A中加入SiC粉体，搅拌均匀后得料浆B，其中SiC的质量分数为30wt％；向酚醛树脂溶液A中加入(Hf0.25Ta0.25Zr0.25Ti0.25)B2和SiC粉体，其中SiC的质量分数为20wt％，(Hf0.25Ta0.25Zr0.25Ti0.25)B2的质量分数为40wt％，搅拌均匀后得料浆C；
(3)将C/C复合材料浸到料浆B中浸涂5s，取出后在烘箱中于80℃干燥10min，该过程重复3次后，得到SiC内涂层；将带有SiC内涂层的C/C复合材料浸到料浆C中浸涂5s，取出后在烘箱中于80℃干燥10min，该过程重复3次后，得到(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC外涂层；
(4)将(3)所得试样在管式气氛炉中于氩气气氛保护下在180℃中保温3h，随即升温至1000℃，热处理3h后得到预涂层试样；
将(4)所得的预涂层试样置于自制的石墨坩埚中，坩埚底部放置一定量的硅块，试样与硅块通过多孔石墨板隔开，密封坩埚后将其放入高温石墨化炉中在氩气保护下进行气相渗硅，渗硅温度为2000℃，保温时间15min，之后随炉冷却，即得(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si涂层试样。
Claims (5)
1.一种碳/碳复合材料表面耐高温长寿命复合涂层，其特征在于C/C复合材料表面涂层为内涂层和外涂层组成，其中内涂层组份为SiC-Si涂层，外涂层组份为(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si。
2.一种制备权利要求1所述碳/碳复合材料表面耐高温长寿命复合涂层的方法，其特征在于步骤如下：
步骤1：将酚醛树脂与无水乙醇超声处理后搅拌均匀得到酚醛树脂溶液A，其中乙醇的质量分数为70-90wt％，酚醛树脂的质量分数为10-30wt％；
步骤2：向酚醛树脂溶液A中加入SiC粉体，搅拌均匀后得料浆B，其中SiC的质量分数为30-40wt％；
向酚醛树脂溶液A中加入(Hf0.25Ta0.25Zr0.25Ti0.25)B2和SiC粉体，搅拌均匀后得料浆C，其中SiC的质量分数为10-20wt％，(Hf0.25Ta0.25Zr0.25Ti0.25)B2的质量分数为30-40wt％；
步骤3：将C/C复合材料浸到料浆B中进行预涂层浸涂，取出后在烘箱中干燥，该过程重复多次后，得到SiC内涂层；将带有SiC内涂层的C/C复合材料浸到料浆C中进行浸涂，取出后在烘箱中干燥，该过程重复多次后，得到(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC/SiC涂层；
步骤4：再置于管式气氛炉中温度为150-200℃，固化时间为2-4h进行固化；然后在温度为900-1100℃，碳化时间为2-4h进行碳化后得到预涂层；
步骤5：置于石墨坩埚中，坩埚底部放置一定量的硅块，得到预涂层的材料与硅块之间采用多孔石墨板隔开；密封坩埚后将石墨坩埚放入高温石墨化炉中在氩气保护下，温度为1800-2000℃，时间为15-30min进行气相渗硅，之后随炉冷却，在碳/碳复合材料表面得到耐高温长寿命复合涂层：(Hf0.25Ta0.25Zr0.25Ti0.25)B2-SiC-Si/SiC-Si。
3.根据权利要求2所述的方法，其特征在于：所述步骤3的重复多次为3次。
4.根据权利要求2所述的方法，其特征在于：所述步骤3的浸涂时间为3-5s。
5.根据权利要求2所述的方法，其特征在于：所述步骤3的干燥温度为50-80℃，干燥时间为10-30min。
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02129366A (ja) * | 1988-11-08 | 1990-05-17 | Sumitomo Electric Ind Ltd | 被覆構造材料 |
| CN1903790A (zh) * | 2005-07-28 | 2007-01-31 | 西北工业大学 | 碳/碳复合材料基二硅化钽/碳化硅涂层及其制备方法 |
| CN106242642A (zh) * | 2016-07-28 | 2016-12-21 | 航天材料及工艺研究所 | 一种耐1700℃低密度碳瓦表面抗氧化涂层及其制备方法 |
| CN108530109A (zh) * | 2018-03-23 | 2018-09-14 | 西北工业大学 | 一种碳/碳复合材料表面1500~1700℃抗氧化涂层及制备方法 |
| CN109735789A (zh) * | 2019-01-25 | 2019-05-10 | 航天材料及工艺研究所 | 一种多元Zr/Hf基超高熔点碳化物抗氧化涂层及其制备方法 |
| CN110078512A (zh) * | 2019-05-17 | 2019-08-02 | 淄博星澳新材料研究院有限公司 | 超高温高熵碳化物粉体及其制备方法 |
| CN110903107A (zh) * | 2018-09-18 | 2020-03-24 | 付红 | 一种提高碳/碳复合材料抗氧化性能的复合涂层 |
-
2021
- 2021-06-10 CN CN202110648462.4A patent/CN113387724B/zh active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02129366A (ja) * | 1988-11-08 | 1990-05-17 | Sumitomo Electric Ind Ltd | 被覆構造材料 |
| CN1903790A (zh) * | 2005-07-28 | 2007-01-31 | 西北工业大学 | 碳/碳复合材料基二硅化钽/碳化硅涂层及其制备方法 |
| CN106242642A (zh) * | 2016-07-28 | 2016-12-21 | 航天材料及工艺研究所 | 一种耐1700℃低密度碳瓦表面抗氧化涂层及其制备方法 |
| CN108530109A (zh) * | 2018-03-23 | 2018-09-14 | 西北工业大学 | 一种碳/碳复合材料表面1500~1700℃抗氧化涂层及制备方法 |
| CN110903107A (zh) * | 2018-09-18 | 2020-03-24 | 付红 | 一种提高碳/碳复合材料抗氧化性能的复合涂层 |
| CN109735789A (zh) * | 2019-01-25 | 2019-05-10 | 航天材料及工艺研究所 | 一种多元Zr/Hf基超高熔点碳化物抗氧化涂层及其制备方法 |
| CN110078512A (zh) * | 2019-05-17 | 2019-08-02 | 淄博星澳新材料研究院有限公司 | 超高温高熵碳化物粉体及其制备方法 |
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