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CN112479717B - 一种自愈合基体改性SiC/SiC复合材料及其制备方法 - Google Patents

一种自愈合基体改性SiC/SiC复合材料及其制备方法 Download PDF

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CN112479717B
CN112479717B CN202011306589.XA CN202011306589A CN112479717B CN 112479717 B CN112479717 B CN 112479717B CN 202011306589 A CN202011306589 A CN 202011306589A CN 112479717 B CN112479717 B CN 112479717B
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宋环君
于艺
刘伟
金鑫
王鹏
李晓东
于新民
刘俊鹏
裴雨辰
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Aerospace Research Institute of Materials and Processing Technology
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Abstract

本发明涉及一种自愈合基体改性SiC/SiC复合材料及其制备方法，属于航空航天材料制备工艺领域，所述制备方法包括如下步骤：选用SiC纤维编织成预制体，通过化学气相沉积工艺在纤维表面沉积一层BN界面层，厚度为200～1000nm，然后在BN界面层外层沉积一层SiC层，厚度为2～5μm。最后再配制特定料浆，经过8～12个周期的浸渍‑固化‑烧结循环操作，得到目标SiC/SiC复合材料。相比于具有传统的陶瓷前驱体烧结基体，新型自愈合基体将有效提高SiC/SiC循环应力氧化性能。

Description

一种自愈合基体改性SiC/SiC复合材料及其制备方法
技术领域
本发明涉及航空航天材料制备工艺技术领域，尤其涉及一种自愈合基体改性SiC/SiC复合材料制备方法。
背景技术
SiC/SiC复合材料具有轻质、高强度、高模量和优异的高温抗氧化性能，是未来航空发动机取代镍基高温合金提高推重比的关键材料。从二十世纪八十年代开始，美国和法国等西方发达国家对SiC/SiC复合材料进行了大量研究，已经打通了材料攻关、构件验证和装备应用完整的产业链。与国外发达国家相比，我国对于SiC/SiC复合材料的研究仍处于材料攻关阶段。
SiC/SiC复合材料通常由纤维预制体、界面层和陶瓷基体等部分组成。其中纤维是复合材料的骨架，对于力学性能至关重要，通常根据不同的应用环境，可选择2D、2.5D和3D等多种编织方法。陶瓷基体是SiC/SiC复合材料抗热冲击和高温抗氧化部分，其在应力条件下，尤其是高温氧化应力条件下的失效机理是基体微裂纹的产生，氧化气氛通过裂纹进入复合材料内部，腐蚀界面和纤维，导致复合材料破坏。
前驱体浸渍裂解是制备SiC/SiC复合材料常用工艺，其具有工艺简单、稳定的优点。传统的SiC前驱体制备的SiC/SiC复合材料基体内部微孔较多，在高温氧化应力条件下容易产生微裂纹，影响复合材料的力学性能和抗氧化性能。而传统的SiC前驱体制备的SiC陶瓷基体不具有自愈合能力，因此急需对基体进行改性，使基体具备修复裂纹的能力，提高SiC/SiC复合材料在高温应力氧化环境下的使用寿命。
因此，针对以上不足，需要提供一种自愈合基体改性SiC/SiC复合材料的制备方法。
发明内容
(一)要解决的技术问题
本发明要解决的技术问题是现有SiC/SiC复合材料基体在高温应力氧化环境使用寿命不足的问题。
(二)技术方案
为了解决上述技术问题，本发明在第一方面提供了一种自愈合基体改性SiC/SiC复合材料的制备方法，所述制备方法包括如下步骤：
(1)采用SiC纤维制备SiC纤维预制体，得到第一试样；
(2)采用化学气相沉积法，在第一试样的SiC纤维表面沉积BN界面层，得到第二试样；
(3)采用化学气相沉积法，在第二试样外侧沉积SiC界面层，得到第三试样；
(4)配制料浆；
(5)将第三试样放入料浆中浸渍，得到第四试样；
(6)对第四试样进行固化反应，得到第五试样；
(7)对第五试样进行烧结反应，得到第六试样；
(8)重复步骤(4)至步骤(7)至少一次，得到自愈合基体改性SiC/SiC复合材料。
本发明在第二方面提供了一种自愈合基体改性SiC/SiC复合材料，所述复合材料按照本发明第一方面所述的制备方法制备得到。
(三)有益效果
本发明的上述技术方案具有如下优点：
(1)本发明采用了宽温域范围具有高温应力氧化环境使用寿命的陶瓷基体。
(2)本发明所述自愈合基体能实现700～1400℃基体自愈合能力，其原因是在传统SiC/SiC复合材料中引入了多种粉体，粉体自身或其氧化产物分别在700～1100℃、1100～1250℃、1250～1400℃宽温度范围内变为流动相，能良好填充基体裂纹，实现700～1400℃宽温域基体自愈合。
(3)本发明所述自愈合基体能明显提高复合材料氧化环境中高温力学性能，也能明显提高SiC/SiC复合材料循环应力氧化性能。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明在第一方面提供了一种自愈合基体改性SiC/SiC复合材料的制备方法，所述制备方法包括如下步骤：
(1)采用SiC纤维制备SiC纤维预制体，得到第一试样；
(2)采用化学气相沉积法，在第一试样的SiC纤维表面沉积BN界面层，得到第二试样；
(3)采用化学气相沉积法，在第二试样外侧沉积SiC界面层，得到第三试样；
(4)配制料浆；
(5)将第三试样放入料浆中浸渍，得到第四试样；
(6)对第四试样进行固化反应，得到第五试样；
(7)对第五试样进行烧结反应，得到第六试样；
(8)重复步骤(4)至步骤(7)至少一次，得到自愈合基体改性SiC/SiC复合材料。
根据一些优选的实施方式，在步骤(1)中，所述SiC纤维为一代纤维或二代纤维；
所述制备SiC纤维预制体的方式为编织方式；
优选的是，所述编织方式为缝合、2.5D和三维四向编织；和/或
所述SiC纤维预制体的纤维体积分数为25％～45％，例如，25％，27％，30％，32％，35％，37％，40％，42％，45％。
根据一些优选的实施方式，在步骤(2)中，所述化学沉积法在化学气相沉积炉中进行；
所述化学沉积法采用的前驱体气体包含硼源、氮气和氢气，所述硼源选自由三氯化硼、三氟化硼和硼吖嗪组成的组的一种或多种；
所述化学沉积法的沉积温度为800℃～1200℃(例如，800℃，900℃，1000℃，1100℃，1200℃)，真空度为-0.1～0MPa，沉积时间为0.5h～10h(例如，0.5h，1h，2h，3h，4h，5h，6h，7h，8h，9h，10h)；和/或
所述BN界面层的厚度为200～1000nm(例如，200nm，250nm，300nm，350nm，400nm，450nm，500nm，550nm，600nm，700nm，800nm，900nm，1000nm)。
根据一些优选的实施方式，在步骤(3)中，所述化学气相沉积法采用的前驱体可以选择氯代甲基硅烷、氟代甲基硅烷、硅烷、甲基硅烷等；
所述化学气相沉积法采用的沉积温度为800～1200℃(例如，800℃，900℃，1000℃，1100℃，1200℃)，真空度-0.09～-0.01MPa，沉积时间为10-20h(例如为10h、11h、12h、13h、14h、15h、16h、17h、18h、19h、20h)；
所述SiC界面层厚度为2～5μm。
根据一些优选的实施方式，在步骤(4)中，所述料浆由粉末材料和前驱体溶液配制；
优选的是，所述粉末材料包含选自由碳化锗(GeC)、氧化锗(GeO2)、SiC、SiO2、BN、B2O3、CuO组成的组的两种或者三种；和/或
所述前驱体溶液的溶质可以选择聚碳硅烷(PCS)、全氢聚碳硅烷(AHPCS)、液态聚碳硅烷(LPCS)等；所述前驱体溶液的溶剂可以选择丁酮、二甲苯、甲苯等。
根据一些优选的实施方式，在步骤(5)中，所述浸渍的浸渍温度为60～130℃(例如，60℃，70℃，80℃，90℃，100℃，110℃，120℃，130℃)，浸渍压力为1～5MPa(例如，1MPa，2MPa，3MPa，4MPa，5MPa)，浸渍时间为0.5～4h(例如，0.5h，1h，1.5h，2h，2.5h，3h，3.5h，4h)。
根据一些优选的实施方式，在步骤(6)中，所述固化反应在高压罐中进行；
所述固化反应的固化温度为100～320℃(例如100℃，150℃，200℃，250℃，300℃，320℃)，固化时间为1～5h，固化压力为3～5MPa。
根据一些优选的实施方式，在步骤(7)中，所述烧结反应在高温烧结炉中进行；
优选的是，所述烧结反应的烧结温度为700～1400℃(例如，700℃，800℃，900℃，1000℃，1100℃，1200℃，1300℃，1400℃)，烧结真空为-0.09～-0.1MPa，烧结时间为2～4h。
根据一些优选的实施方式，在步骤(8)中，所述重复的次数为8到12次。
本发明在第二方面提供了一种自愈合基体改性SiC/SiC复合材料，所述复合材料按照本发明第一方面所述的制备方法制备得到。
实施例1
(1)将二代SiC纤维编织为2.5D预制体，得到纤维体积分数为32％的第一试样，经线密度7根/cm，纬线密度3根/cm；
(2)选取等摩尔比的三氯化硼、氮气和氢气为前驱体，在1000℃、-0.04MPa的条件下，用化学气相沉积炉在第一试样的纤维表面沉积1h，得到500nm厚的BN界面层；
(3)将第二试样移动至化学气相沉积炉子中，采用三氯甲基硅烷为前驱体，在1200℃、-0.05MPa真空度条件下沉积20h，得到含有厚度为2μm SiC界面层的第三试样；
(4)选取等摩尔比的GeC、BN和SiC粉体与聚碳硅烷二甲苯溶液配制成固含量为30％的前驱体料浆，在70℃、2MPa高压下，将第三试样放入前驱体中浸渍2h，得到第四试样；
(5)在150℃、3MPa压力条件下，将第四试样放入高压罐中进行固化3h，得到第五试样；
(6)在850℃、-0.04MPa真空条件下，将第五试样放入高温烧结炉中烧结3h，取出得到第六试样；
(7)重复步骤(4)至步骤(6)，重复次数为8次；
将步骤(7)所得样件加工弯曲测试样条，测得空气气氛1300℃条件下弯曲强度为274MPa，拉伸强度为159MPa。1200℃、100MPa、1h循环拉伸次数为9次；具体见表1。
实施例2
本实施例2与实施例1基本相同，不同之处在于：在步骤(4)中，所述配制料浆的粉末材料为等摩尔比的SiO2、B2O3和CuO。
将制备得到的样件加工弯曲测试样条，测得空气气氛1300℃条件下弯曲强度为293MPa，拉伸强度为170MPa。1200℃、100MPa、1h循环拉伸次数为13次；具体见表1。
实施例3
本实施例3与实施例1基本相同，不同之处在于：在步骤(4)中，所述配制料浆的粉末材料为等摩尔比的BN和GeC。
将制备得到的样件加工弯曲测试样条，测得空气气氛1300℃条件下弯曲强度为295MPa，拉伸强度为168MPa。1200℃、100MPa、1h循环拉伸次数为16次；具体见表1。
实施例4
本实施例4与实施例1基本相同，不同之处在于：在步骤(4)中，所述配制料浆的粉末材料为等摩尔比的GeC和SiC。
将制备得到的样件加工弯曲测试样条，测得空气气氛1300℃条件下弯曲强度为287MPa，拉伸强度为154MPa。1200℃、100MPa、1h循环拉伸次数为12次；具体见表1。
实施例5
(1)将一代SiC纤维通过三维四向编织制备为预制体，得到纤维体积分数为45％的第一试样，经线密度7根/cm，纬线密度3根/cm；
(2)选取等摩尔比的三氯化硼、氮气和氢气为前驱体，在800℃、-0.04MPa的条件下，用化学气相沉积炉在第一试样的纤维表面沉积10h，得到1000nm厚的BN界面层；
(3)将第二试样移动至化学气相沉积炉子中，采用三氯甲基硅烷为前驱体，在800℃、-0.05MPa真空度条件下沉积10h，得到含有厚度为5μm SiC界面层的第三试样；
(4)选取等摩尔比的GeC、CuO、SiC粉体与全氢聚碳硅烷甲苯溶液配制成固含量为30％的前驱体料浆，在70℃、2MPa高压下，将第三试样放入前驱体中浸渍2h，得到第四试样；
(5)在320℃、3MPa压力条件下，将第四试样放入高压罐中进行固化5h，得到第五试样；
(6)在1400℃、-0.04MPa真空条件下，将第五试样放入高温烧结炉中烧结4h，取出得到第六试样；
(7)重复步骤4至步骤6，重复次数为8次。
将制备得到的样件加工弯曲测试样条，测得空气气氛1300℃条件下弯曲强度为151MPa，拉伸强度为107MPa。1200℃、100MPa、1h循环拉伸次数为3次；具体见表1。
实施例6
(1)将二代SiC纤维编织为2.5D预制体，得到纤维体积分数为32％的第一试样，经线密度7根/cm，纬线密度3根/cm；
(2)选取等摩尔比的三氯化硼、氮气和氢气为前驱体，在1000℃、-0.04MPa的条件下，用化学气相沉积炉在第一试样的纤维表面沉积1h，得到500nm厚的BN界面层；
(3)将第二试样移动至化学气相沉积炉子中，采用三氯甲基硅烷为前驱体，在1200℃、-0.05MPa真空度条件下沉积20h，得到含有厚度为2μm SiC界面层的第三试样；
(4)选取聚碳硅烷二甲苯溶液配制成前驱体溶液，在70℃、2MPa高压下，将第三试样放入前驱体中浸渍2h，得到第四试样；
(5)在150℃、3MPa压力条件下，将第四试样放入高压罐中进行固化3h，得到第五试样；
(6)在850℃、-0.04MPa真空条件下，将第五试样放入高温烧结炉中烧结3h，取出得到第六试样；
(7)重复步骤4至步骤6，重复次数为8次。
将制备得到的样件加工弯曲测试样条，测得空气气氛1300℃条件下弯曲强度为257MPa，拉伸强度为131MPa。1200℃、100MPa、1h循环拉伸次数为1次；具体见表1。
Figure BDA0002788033660000101
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。

Claims (10)

1.一种自愈合基体改性SiC/SiC复合材料的制备方法，其特征在于，所述制备方法包括如下步骤：
（1）采用SiC纤维制备SiC纤维预制体，得到第一试样；所述SiC纤维预制体的纤维体积分数为25%~45%；
（2）采用化学气相沉积法，在第一试样的SiC纤维表面沉积BN界面层，得到第二试样；所述BN界面层的厚度为500nm；
（3）采用化学气相沉积法，在第二试样外侧沉积SiC界面层，得到第三试样；所述SiC界面层的厚度为2μm；所述化学气相沉积法采用的前驱体为氯代甲基硅烷；所述化学气相沉积法采用的沉积温度为1200℃，真空度-0.05MPa，沉积时间为20h；
（4）配制料浆；选取等摩尔比的GeC、BN粉体与前驱体溶液配制成固含量为30％的前驱体料浆；所述前驱体溶液的溶质选自由聚碳硅烷PCS、全氢聚碳硅烷AHPCS、液态聚碳硅烷LPCS组成的组的一种或多种；
（5）将第三试样放入料浆中浸渍，得到第四试样；
（6）对第四试样进行固化反应，得到第五试样；
（7）对第五试样进行烧结反应，得到第六试样；所述烧结反应的烧结温度为700~1400℃，烧结真空度为-0.09~-0.1MPa，烧结时间为2~4h；
（8）重复步骤（4）至步骤（7）至少一次，得到自愈合基体改性SiC/SiC复合材料。
2.根据权利要求1所述的制备方法，其特征在于：
在步骤（1）中，所述SiC纤维为一代纤维或二代纤维；
所述制备SiC纤维预制体的方式为编织方式；所述编织方式为缝合、2.5D和三维四向编织。
3.根据权利要求1所述的制备方法，其特征在于：
在步骤（2）中，所述化学气相沉积法在化学气相沉积炉中进行；
所述化学气相沉积法采用的前驱体气体包含硼源、氮气和氢气，所述硼源选自由三氯化硼、三氟化硼和硼吖嗪组成的组的一种或多种；
所述化学气相沉积法的沉积温度为800℃~1200℃，真空度为-0.1~0MPa，沉积时间为0.5h~10h。
4.根据权利要求1所述的制备方法，其特征在于：
在步骤（4）中，所述前驱体溶液的溶剂选自由丁酮、二甲苯、甲苯组成的组一种或多种。
5.根据权利要求1所述的制备方法，其特征在于：
在步骤（5）中，所述浸渍的浸渍温度为60~130℃，浸渍压力为1~5MPa，浸渍时间为0.5~4h。
6.根据权利要求1所述的制备方法，其特征在于：
在步骤（6）中，所述固化反应在高压罐中进行。
7.根据权利要求6所述的制备方法，其特征在于：
在步骤（6）中，所述固化反应的固化温度为100~320℃，固化时间为1~5h，固化压力为3~5MPa。
8.根据权利要求1所述的制备方法，其特征在于：
在步骤（7）中，所述烧结反应在高温烧结炉中进行。
9.根据权利要求1所述的制备方法，其特征在于：
在步骤（8）中，所述重复的次数为8到12次。
10.一种自愈合基体改性SiC/SiC复合材料，其特征在于：
所述复合材料按照权利要求1-9任一项所述的制备方法制备得到。
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