CN106966699B - 一种高温复合材料全温度段热匹配涂层的制备方法 - Google Patents
一种高温复合材料全温度段热匹配涂层的制备方法 Download PDFInfo
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Abstract
本发明提供了一种高温复合材料全温度段热匹配涂层的制备方法,包括:制备自密封粘接层步骤;制备热匹配功能层步骤和制备高温阻挡层步骤。本发明引入与高温复合材料基体物理及化学相容性好的具有机械互锁的自密封粘接层,再采用负热膨胀效应优异的材料作为热匹配功能层,采用耐高温烧蚀的材料作为高温阻挡层,使其与高温复合材料的热膨胀系数从室温到高温完全匹配,制备出了高温复合材料全温度段热匹配涂层,该涂层制备成本低,制备工艺简单,是一种能够适用于全温度段的高温涂层,能够使高温复合材料的涂层与基体之间在较低温度时也不会产生裂纹,增加涂层的使用寿命。
Description
技术领域
本发明涉及无机功能涂层材料技术领域,特别是涉及一种高温复合材料全温度段热匹配涂层的制备方法。
背景技术
高温复合材料是一种新型高温材料,具有模量高、比强度大、热导率高、抗热震性好、耐高温、耐磨擦磨损等一系列优异性能,使得其成为最有发展前途的航空高温部件之一。然而在高温有氧环境下,高温复合材料会发生氧化,大大地限制了高温复合材料的应用范围,因此抗氧化成为高温复合材料在高温有氧气氛下应用的前提条件。而目前所制备的防护涂层无法满足全温度段长寿命的要求,大多数高温抗氧化涂层体系只能在1300℃以上实现有效的氧化防护。由于涂层与基体之间的热膨胀系数存在差异,因此在涂层制备过程中从高温降低到室温时会产生微裂纹,且不易愈合,这样就会给氧气的渗透提供通道,加快氧化进程,降低涂层使用寿命。因此,如何使高温复合材料的涂层与基体之间在较低温度时也不会产生裂纹,增加涂层的使用寿命成为本领域亟需解决的技术问题。
发明内容
为此,本发明的一个目的在于提出一种制备成本较低,制备工艺较简单的新型全温度段热匹配涂层的制备方法。
本发明提供了一种高温复合材料全温度段热匹配涂层的制备方法,包括:
制备自密封粘接层:
对高温复合材料基体进行表面打磨,将表面打磨后的高温复合材料基体放入清洗液中超声清洗,清洗后的所述高温复合材料基体放入烘箱中在90-100℃条件下烘干2-6h;将一定质量配比的硅粉、氧化钽粉、碳化硼粉、碳化硅粉混合,球磨8-10h,制得所述自密封粘结层的混合粉料,将所述混合粉料放入石墨坩埚内,将所述高温复合材料基体包埋于所述混合粉料中;将所述石墨坩埚放入高温炉中,抽真空并通入保护气体,以20-30℃/min的升温速率将所述高温炉的炉温升至1700-2000℃,保温3-6h,随后以20-30℃/min的降温速率将所述高温炉的炉温降至200-400℃,而后关闭所述高温炉的电源使所述石墨坩埚自然降温至室温;将处理后的所述高温复合材料基体取出,放入清洗液中超声清洗,清洗后放入烘箱中在90-100℃条件下烘干2-6h,在所述高温复合材料基体的表面制备出自密封粘接层。
制备热匹配功能层:
将表面有自密封粘接层的高温复合材料基体放入化学气相沉积炉中,抽真空至-0.1Mpa;将所述化学气相沉积炉升温至900-1100℃,通入硅酸乙酯和高纯氩气的混合气体,炉内压力为500Pa-1000Pa,气流量为20-40sccm,沉积时间为25-40h,得到热匹配功能层。
制备高温阻挡层:
取出一定的质量配比的硅溶胶、氧化钇粉、硼化锆粉和氧化锆粉,将取出的氧化钇粉、硼化锆粉和氧化锆粉混合,球磨5-10h,再与取出的硅溶胶混合,搅拌6-10h,得到高温阻挡层的硅溶胶料浆;将表面有自密封粘接层和热匹配功能层的高温复合材料基体放入浸渍罐中,抽真空至-0.1MPa,注入搅拌均匀的所述高温阻挡层的料浆,浸渍完全后,取出自然晾干;将表面浸有高温阻挡层的料浆的高温复合材料基体放入高温炉中,抽真空,通入保护气体,以10-20℃/min的升温速率将炉温升至1400-1800℃,保温1-2h,随后以20-40℃/min的降温速率将炉温降至200-400℃,关闭所述高温炉的电源,自然降温至室温,制备出高温阻挡层。
本发明引入与高温复合材料基体物理及化学相容性好的具有机械互锁的自密封粘接层,再采用负热膨胀效应优异的材料作为热匹配功能层,采用耐高温烧蚀的材料作为高温阻挡层,使其与高温复合材料的热膨胀系数从室温到高温完全匹配,制备出了高温复合材料全温度段热匹配涂层,该涂层制备成本低,制备工艺简单,是一种能够适用于全温度段的高温涂层,能够使高温复合材料的涂层与基体之间在较低温度时也不会产生裂纹,增加涂层的使用寿命。
进一步地,所述清洗液为无水乙醇。
进一步地,所述制备自密封粘接层步骤中硅粉、氧化钽粉、碳化硼粉和碳化硅粉的质量配比如下:35-50wt%硅粉,15-30wt%氧化钽粉,20-30wt%碳化硼粉,10-20wt%碳化硅粉。
进一步地,所述保护气体为高纯氩气。
进一步地,所述制备热匹配功能层步骤中硅酸乙酯和高纯氩气的摩尔比的范围为1-10。
进一步地,所述制备高温阻挡层步骤中硅溶胶、氧化钇粉、硼化锆粉和氧化锆粉的质量配比如下:20-40wt%硅溶胶,10-20wt%氧化钇粉,20-30wt%硼化锆粉和20-40wt%氧化锆粉。
进一步地,所述制备高温阻挡层步骤中,将表面有自密封粘接层和热匹配功能层的高温复合材料基体放入浸渍罐中抽真空至-0.1MPa,注入搅拌均匀的所述高温阻挡层的料浆,浸渍完全后,取出自然晾干的操作重复4-6次。
本发明的附加方面和优点将在下面的描述中部分给出,部分将从下面的描述中变得明显,或通过本发明的实践了解到。
附图说明
图1示出了本发明实施例的一种高温复合材料全温度段热匹配涂层的制备方法的流程图;
图2示出了本发明实施例制备的一种高温复合材料全温度段热匹配涂层的结构示意图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,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。
实施例一
如图1所示,本发明提供了一种高温复合材料全温度段热匹配涂层的制备方法,包括:
步骤S1,制备自密封粘结层;
对高温复合材料基体进行表面打磨,将表面打磨后的高温复合材料基体放入无水乙醇中超声清洗,清洗后的所述高温复合材料基体放入烘箱中在100℃条件下烘干2h。此处使用无水乙醇作为清洗溶剂,由于乙醇易挥发,容易去除,同时乙醇比较便宜,可以降低制备成本。
将质量配比为50wt%的硅粉,20wt%的氧化钽粉,20wt%的碳化硼粉,10wt%的碳化硅粉混合,球磨10h,制得所述自密封粘结层的混合粉料,将所述混合粉料放入石墨坩埚内,将所述高温复合材料基体包埋于所述混合粉料中。
将所述石墨坩埚放入高温炉中,抽真空并通入保护气体,以30℃/min的升温速率将所述高温炉的炉温升至2000℃,保温4h,随后以30℃/min的降温速率将所述高温炉的炉温降至400℃,而后关闭所述高温炉的电源使所述石墨坩埚自然降温至室温。
将处理后的所述高温复合材料基体取出,放入清洗液中超声清洗,清洗后放入烘箱中在100℃条件下烘干6h,在所述高温复合材料基体的表面制备出自密封粘接层。
步骤S2,制备热匹配功能层;
将表面有自密封粘接层的高温复合材料基体放入化学气相沉积炉中,抽真空至-0.1Mpa。
将所述化学气相沉积炉升温至1100℃,通入硅酸乙酯和高纯氩气的摩尔比为5的混合气体,炉内压力为1000Pa,气流量为40sccm,沉积时间为40h,得到热匹配功能层。
步骤S3,制备高温阻挡层;
取出质量配比为40wt%的硅溶胶,10wt%的氧化钇粉,30wt%的硼化锆粉和20wt%的氧化锆粉,将取出的氧化钇粉、硼化锆粉和氧化锆粉混合,球磨10h,再与取出的硅溶胶混合,搅拌10h,得到高温阻挡层的硅溶胶料浆。
将表面有自密封粘接层和热匹配功能层的高温复合材料基体放入浸渍罐中,抽真空至-0.1MPa,注入搅拌均匀的所述高温阻挡层的料浆,浸渍完全后,取出自然晾干,如此重复6次。
将表面浸有高温阻挡层的料浆的高温复合材料基体放入高温炉中,抽真空,通入保护气体,以20℃/min的升温速率将炉温升至1800℃,保温2h,随后以40℃/min的降温速率将炉温降至400℃,关闭所述高温炉的电源,自然降温至室温,制备出高温阻挡层。
本发明引入与高温复合材料基体物理及化学相容性好的具有机械互锁的自密封粘接层,再采用负热膨胀效应优异的材料作为热匹配功能层,采用耐高温烧蚀的材料作为高温阻挡层,使其与高温复合材料的热膨胀系数从室温到高温完全匹配,制备出了高温复合材料全温度段热匹配涂层,该涂层制备成本低,制备工艺简单,是一种能够适用于全温度段的高温涂层,能够使高温复合材料的涂层与基体之间在较低温度时也不会产生裂纹,增加涂层的使用寿命。
在本发明实施例的一个方面,制得的高温复合材料全温度段热匹配涂层如图2所示,从内到外依次为自密封粘结层,热匹配功能层和高温阻挡层。经过涂层测试,本实施例方法制备的高温复合材料全温度段热匹配涂层在1650℃的氧化环境中,200小时后氧化失重为3.45wt%,在较低温度时未产生裂纹,能够在全温度段具有较好的抗氧化效果。
在本发明实施例的一个方面,所述保护气体为氩气,由于氩气为惰性气体,不易发生化学反应,常用作化学反应中的保护气体。
实施例二
如图1所示,本发明提供了一种高温复合材料全温度段热匹配涂层的制备方法,包括:
步骤S1,制备自密封粘结层;
对高温复合材料基体进行表面打磨,将表面打磨后的高温复合材料基体放入无水乙醇中超声清洗,清洗后的所述高温复合材料基体放入烘箱中在90℃条件下烘干6h。此处使用无水乙醇作为清洗溶剂,由于乙醇易挥发,容易去除,同时乙醇比较便宜,可以降低制备成本。
将质量配比为35wt%的硅粉,15wt%的氧化钽粉,30wt%的碳化硼粉,20wt%的碳化硅粉混合,球磨8h,制得所述自密封粘结层的混合粉料,将所述混合粉料放入石墨坩埚内,将所述高温复合材料基体包埋于所述混合粉料中。
将所述石墨坩埚放入高温炉中,抽真空并通入保护气体,以20℃/min的升温速率将所述高温炉的炉温升至1700℃,保温3h,随后以20℃/min的降温速率将所述高温炉的炉温降至200℃,而后关闭所述高温炉的电源使所述石墨坩埚自然降温至室温。
将处理后的所述高温复合材料基体取出,放入清洗液中超声清洗,清洗后放入烘箱中在90℃条件下烘干2h,在所述高温复合材料基体的表面制备出自密封粘接层。
步骤S2,制备热匹配功能层;
将表面有自密封粘接层的高温复合材料基体放入化学气相沉积炉中,抽真空至-0.1Mpa。
将所述化学气相沉积炉升温至900℃,通入硅酸乙酯和高纯氩气的摩尔比为1的混合气体,炉内压力为500Pa,气流量为20sccm,沉积时间为25h,得到热匹配功能层。
步骤S3,制备高温阻挡层;
取出质量配比为20wt%的硅溶胶,20wt%的氧化钇粉,20wt%的硼化锆粉和40wt%的氧化锆粉,将取出的氧化钇粉、硼化锆粉和氧化锆粉混合,球磨5h,再与取出的硅溶胶混合,搅拌6h,得到高温阻挡层的硅溶胶料浆。
将表面有自密封粘接层和热匹配功能层的高温复合材料基体放入浸渍罐中,抽真空至-0.1MPa,注入搅拌均匀的所述高温阻挡层的料浆,浸渍完全后,取出自然晾干,如此重复4次。
将表面浸有高温阻挡层的料浆的高温复合材料基体放入高温炉中,抽真空,通入保护气体,以10℃/min的升温速率将炉温升至1400℃,保温1h,随后以20℃/min的降温速率将炉温降至200℃,关闭所述高温炉的电源,自然降温至室温,制备出高温阻挡层。
本发明引入与高温复合材料基体物理及化学相容性好的具有机械互锁的自密封粘接层,再采用负热膨胀效应优异的材料作为热匹配功能层,采用耐高温烧蚀的材料作为高温阻挡层,使其与高温复合材料的热膨胀系数从室温到高温完全匹配,制备出了高温复合材料全温度段热匹配涂层,该涂层制备成本低,制备工艺简单,是一种能够适用于全温度段的高温涂层,能够使高温复合材料的涂层与基体之间在较低温度时也不会产生裂纹,增加涂层的使用寿命。
在本发明实施例的一个方面,制得的高温复合材料全温度段热匹配涂层如图2所示,从内到外依次为自密封粘结层,热匹配功能层和高温阻挡层。经过涂层测试,本实施例方法制备的高温复合材料全温度段热匹配涂层在1650℃的氧化环境中,200小时后氧化失重为4.52wt%,在较低温度时未产生裂纹,能够在全温度段具有较好的抗氧化效果。
在本发明实施例的一个方面,所述保护气体为氩气,由于氩气为惰性气体,不易发生化学反应,常用作化学反应中的保护气体。
实施例三
如图1所示,本发明提供了一种高温复合材料全温度段热匹配涂层的制备方法,包括:
步骤S1,制备自密封粘结层;
对高温复合材料基体进行表面打磨,将表面打磨后的高温复合材料基体放入无水乙醇中超声清洗,清洗后的所述高温复合材料基体放入烘箱中在100℃条件下烘干4h。此处使用无水乙醇作为清洗溶剂,由于乙醇易挥发,容易去除,同时乙醇比较便宜,可以降低制备成本。
将质量配比为35wt%的硅粉,30wt%的氧化钽粉,25wt%的碳化硼粉,10wt%的碳化硅粉混合,球磨8h,制得所述自密封粘结层的混合粉料,将所述混合粉料放入石墨坩埚内,将所述高温复合材料基体包埋于所述混合粉料中。
将所述石墨坩埚放入高温炉中,抽真空并通入保护气体,以25℃/min的升温速率将所述高温炉的炉温升至1800℃,保温4h,随后以20℃/min的降温速率将所述高温炉的炉温降至300℃,而后关闭所述高温炉的电源使所述石墨坩埚自然降温至室温。
将处理后的所述高温复合材料基体取出,放入清洗液中超声清洗,清洗后放入烘箱中在100℃条件下烘干4h,在所述高温复合材料基体的表面制备出自密封粘接层。
步骤S2,制备热匹配功能层;
将表面有自密封粘接层的高温复合材料基体放入化学气相沉积炉中,抽真空至-0.1Mpa。
将所述化学气相沉积炉升温至1000℃,通入硅酸乙酯和高纯氩气的摩尔比为10的混合气体,炉内压力为800Pa,气流量为30sccm,沉积时间为30h,得到热匹配功能层。
步骤S3,制备高温阻挡层;
取出质量配比为30wt%的硅溶胶,10wt%的氧化钇粉,30wt%的硼化锆粉和30wt%的氧化锆粉,将取出的氧化钇粉、硼化锆粉和氧化锆粉混合,球磨8h,再与取出的硅溶胶混合,搅拌8h,得到高温阻挡层的硅溶胶料浆。
将表面有自密封粘接层和热匹配功能层的高温复合材料基体放入浸渍罐中,抽真空至-0.1MPa,注入搅拌均匀的所述高温阻挡层的料浆,浸渍完全后,取出自然晾干,如此重复5次。
将表面浸有高温阻挡层的料浆的高温复合材料基体放入高温炉中,抽真空,通入保护气体,以10℃/min的升温速率将炉温升至1600℃,保温2h,随后以30℃/min的降温速率将炉温降至400℃,关闭所述高温炉的电源,自然降温至室温,制备出高温阻挡层。
本发明引入与高温复合材料基体物理及化学相容性好的具有机械互锁的自密封粘接层,再采用负热膨胀效应优异的材料作为热匹配功能层,采用耐高温烧蚀的材料作为高温阻挡层,使其与高温复合材料的热膨胀系数从室温到高温完全匹配,制备出了高温复合材料全温度段热匹配涂层,该涂层制备成本低,制备工艺简单,是一种能够适用于全温度段的高温涂层,能够使高温复合材料的涂层与基体之间在较低温度时也不会产生裂纹,增加涂层的使用寿命。
在本发明实施例的一个方面,制得的高温复合材料全温度段热匹配涂层如图2所示,从内到外依次为自密封粘结层,热匹配功能层和高温阻挡层。经过涂层测试,本实施例方法制备的高温复合材料全温度段热匹配涂层在1650℃的氧化环境中,200小时后氧化失重为3.99wt%,在较低温度时未产生裂纹,能够在全温度段具有较好的抗氧化效果。
在本发明实施例的一个方面,所述保护气体为氩气,由于氩气为惰性气体,不易发生化学反应,常用作化学反应中的保护气体。
以上对本发明的一个或几个实施例进行了详细说明,但所述内容仅为本发明的较佳实施例,不能被认为用于限定本发明的实施范围。凡依本发明申请范围所作的均等变化与改进,均应归属于本发明的专利涵盖范围之内。
Claims (5)
1.一种高温复合材料全温度段热匹配涂层的制备方法,其特征在于,包括:
制备自密封粘接层:
对高温复合材料基体进行表面打磨,将表面打磨后的高温复合材料基体放入清洗液中超声清洗,清洗后的所述高温复合材料基体放入烘箱中在90-100℃条件下烘干2-6h;
将一定质量配比的硅粉、氧化钽粉、碳化硼粉、碳化硅粉混合,球磨8-10h,制得所述自密封粘结层的混合粉料,将所述混合粉料放入石墨坩埚内,将所述高温复合材料基体包埋于所述混合粉料中;
将所述石墨坩埚放入高温炉中,抽真空并通入保护气体,以20-30℃/min的升温速率将所述高温炉的炉温升至1700-2000℃,保温3-6h,随后以20-30℃/min的降温速率将所述高温炉的炉温降至200-400℃,而后关闭所述高温炉的电源使所述石墨坩埚自然降温至室温;
将处理后的所述高温复合材料基体取出,放入清洗液中超声清洗,清洗后放入烘箱中在90-100℃条件下烘干2-6h,在所述高温复合材料基体的表面制备出自密封粘接层;
制备热匹配功能层:
将表面有自密封粘接层的高温复合材料基体放入化学气相沉积炉中,抽真空至-0.1Mpa;
将所述化学气相沉积炉升温至900-1100℃,通入硅酸乙酯和高纯氩气的混合气体,炉内压力为500Pa-1000Pa,气流量为20-40sccm,沉积时间为25-40h,得到热匹配功能层;
制备高温阻挡层:
取出一定的质量配比的硅溶胶、氧化钇粉、硼化锆粉和氧化锆粉,将取出的氧化钇粉、硼化锆粉和氧化锆粉混合,球磨5-10h,再与取出的硅溶胶混合,搅拌6-10h,得到高温阻挡层的硅溶胶料浆;
将表面有自密封粘接层和热匹配功能层的高温复合材料基体放入浸渍罐中,抽真空至-0.1MPa,注入搅拌均匀的所述高温阻挡层的料浆,浸渍完全后,取出自然晾干;
将表面浸有高温阻挡层的料浆的高温复合材料基体放入高温炉中,抽真空,通入保护气体,以10-20℃/min的升温速率将炉温升至1400-1800℃,保温1-2h,随后以20-40℃/min的降温速率将炉温降至200-400℃,关闭所述高温炉的电源,自然降温至室温,制备出高温阻挡层;
所述制备自密封粘接层步骤中硅粉、氧化钽粉、碳化硼粉和碳化硅粉的质量配比如下:35-50wt%硅粉,15-30wt%氧化钽粉,20-30wt%碳化硼粉,10-20wt%碳化硅粉;
所述制备高温阻挡层步骤中硅溶胶、氧化钇粉、硼化锆粉和氧化锆粉的质量配比如下:20-40wt%硅溶胶,10-20wt%氧化钇粉,20-30wt%硼化锆粉和20-40wt%氧化锆粉。
2.根据权利要求1所述的一种高温复合材料全温度段热匹配涂层的制备方法,其特征在于,所述清洗液为无水乙醇。
3.根据权利要求1所述的一种高温复合材料全温度段热匹配涂层的制备方法,其特征在于,所述保护气体为高纯氩气。
4.根据权利要求1所述的一种高温复合材料全温度段热匹配涂层的制备方法,其特征在于,所述制备热匹配功能层步骤中硅酸乙酯和高纯氩气的摩尔比的范围为1-10。
5.根据权利要求1所述的一种高温复合材料全温度段热匹配涂层的制备方法,其特征在于,所述制备高温阻挡层步骤中,将表面有自密封粘接层和热匹配功能层的高温复合材料基体放入浸渍罐中抽真空至-0.1MPa,注入搅拌均匀的所述高温阻挡层的料浆,浸渍完全后,取出自然晾干的操作重复4-6次。
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