CN106192371B - 一种耐高温3Al2O3-2SiO2-SiBNC碳纤维复合涂层的制备方法 - Google Patents
一种耐高温3Al2O3-2SiO2-SiBNC碳纤维复合涂层的制备方法 Download PDFInfo
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种耐高温3Al2O3‑2SiO2‑SiBNC碳纤维复合涂层的制备方法,其特征在于,依次包括碳纤维的预处理、3Al2O3‑2SiO2溶胶的制备、SiBNC陶瓷粉在3Al2O3‑2SiO2溶胶中的均匀分散、碳纤维的浸渍涂层、碳纤维涂层的高温裂解等步骤,即得耐高温的3Al2O3‑2SiO2‑SiBNC碳纤维复合涂层。本发明工艺简单,可实施性强,得到的3Al2O3‑2SiO2‑SiBNC碳纤维涂层表面均匀致密,不仅保持了碳纤维原有的力学性能,而且提高了其高温抗氧化性能。
Description
技术领域
本发明属于改性碳纤维领域,特别涉及一种耐高温3Al2O3-2SiO2-SiBNC碳纤维涂层的制备方法。
背景技术
碳纤维(以下简称CF)以其高比强度、比模量,优良的导热、导电性、以及在惰性气氛中的良好热稳定性,对酸、碱化学侵蚀的强稳定性,引起人们的广泛关注并迅速将其应用于航空、航天等高技术领域以及民用工业的许多领域。但是,碳纤维的高温抗氧化能力差,在400℃空气气氛下发生明显失重,强度大幅度降低,这个缺点限制了碳纤维在高温有氧环境下的应用。目前提高碳纤维抗氧性能的方法主要包括:提高碳纤维自身的抗氧化性能,如石墨化;二是通过对碳纤维表面进行涂层改性提高其抗氧化性能。
中国专利CN 104611916 A(公开日为2015年05月13日)公开了一种外表沉积SiBNC涂层的碳纤维及其制备方法,该方法是采用气相沉积法,在沉积炉炉膛中导入载气和稀释气,通过鼓泡方式将硼吖嗪和液态聚碳硅烷载入,经稀释气稀释后通入沉积炉内,在沉积炉内分解出的SiBNC逐步沉积于碳纤维表面,形成SiBNC涂层。该方法的优点是涂层均匀、致密、高温稳定性好;缺点是化学气相沉积法需要特殊的仪器设备、成本昂贵、操作复杂,很难实现工业化生产,且该方法的反应物多为有毒气体,在高温高压的环境下实验大大地增加了危险性。
中国专利CN 103266470 A(公开日为2013年08月28日)公开了一种碳纤维抗氧化涂层及其制备方法,该方法是采用先驱体浸渍法,以二甲苯为溶剂,正硅酸乙酯掺杂聚硅碳烷为先驱体,经过压力浸渍,固化处理及高温裂解制备得到的SiO2掺杂的SiC涂层。该方法的优点是溶液浸渍法原料价格低廉、设备简单、操作方便、易于实现工业化;缺点是SiC陶瓷涂层的高温稳定极限温度为1400℃左右,不能应用于更高的使用温度。
发明内容
本发明所要解决的技术问题是现有3Al2O3-2SiO2-SiBNC碳纤维复合涂层不能耐1400℃以上高温。
为了解决上述技术问题,本发明提供了一种耐高温3Al2O3-2SiO2-SiBNC碳纤维复合涂层的制备方法,其特征在于,包括以下步骤:
步骤1):预处理碳纤维:首先将碳纤维在氮气气氛的管式炉中热处理,然后将热处理后的碳纤维在硝酸中浸泡刻蚀,将刻蚀后的碳纤维在偶联剂中浸泡备用;
步骤2):制备溶胶:用HCl调节蒸馏水的pH,剧烈搅拌下缓慢滴入正硅酸乙酯和无水乙醇的混合溶液,得到稳定透明的SiO2溶胶;再向SiO2溶胶中缓慢滴加硝酸铝和浓硝酸的混合溶液,得到稳定透明的3Al2O3-2SiO2溶胶;
步骤3):将SiBNC陶瓷粉末通过磁力搅拌均匀的分散在3Al2O3-2SiO2溶胶中;
步骤4):碳纤维浸渍涂层:将预处理后的碳纤维在步骤3)所得的溶胶中超声波振动浸渍后静置,取出碳纤维在干燥烘箱中干燥,反复操作得到涂层后的碳纤维;
步骤5):碳纤维涂层的高温裂解:在氮气氛围中,将涂层后的碳纤维在管式炉中高温裂解,最后得到耐高温的3Al2O3-2SiO2-SiBNC碳纤维复合涂层。
优选地,所述步骤1)中碳纤维热处理条件是在400-600℃的管式炉中处理2-6h;碳纤维刻蚀是在浓度为30-70%的硝酸中浸泡2-6h;碳纤维偶联是在浓度为1-3wt%的偶联剂中,在20-80℃的条件下处理2-6h,偶联剂采用硅烷偶联剂KH550。
优选地,所述步骤2)中用HCl调节蒸馏水的pH,是将蒸馏水的pH调节至2-4;所述浓硝酸采用摩尔浓度为1-3%的浓硝酸;制备SiO2溶胶所需的搅拌时间为12-24h,制备3Al2O3-2SiO2溶胶所需的搅拌时间为8-24h。
优选地,所述步骤3)中SiBNC陶瓷粉末使用前经球磨,其颗粒尺寸为50-100nm,所配置溶胶中SiBNC陶瓷粉末的固含量为5-30%。
优选地,所述步骤4)中在超声波振动中浸渍涂层是在30-90℃的水浴中浸渍涂层0.5-1.5h;在烘箱中干燥是在30-90℃的烘箱中干燥20-60min。
优选地,所述步骤5)中涂层的高温裂解是在温度为800-1200℃的管式炉中高温裂解2-6h,所得到的复合涂层的厚度为400nm-1000nm。
莫来石(Al2O3-SiO2)具有较高的热稳定性和抗氧化性能,其熔点在1800℃以上;此外,在高温下可以生成渗氧率低的SiO2相层和高温稳定性良好的Al2O3,能够明显提高材料的高温抗氧化性能。SiBNC具有抗氧化性能强,抗结晶温度高,热膨胀系数小等优异特性,即使在高温下其结构和力学性能也基本保持不变,SiBNC在1700℃以下不晶化,力学性能和抗结晶性能均比SiNC、SiC、SiO2要优良。在1700℃下空气中的抗氧化性能远好于SiC和Si3N4陶瓷。
与现有技术相比,本发明的有益效果在于:
(1)本发明的制备工艺简单,无特殊设备要求,可操作性强,适合工业化生产;
(2)本发明得到的碳纤维表面的3Al2O3-2SiO2-SiBNC涂层均匀致密,无微裂纹,高温抗氧化性能优异。通过检测,本发明得到的复合涂层的厚度为400nm-1000nm,涂层在1400℃下保温2h,涂层未出现脱落、开裂现象。
附图说明
图1为未涂层的碳纤维SEM图;
图2为3Al2O3-2SiO2-SiBNC涂层碳纤维的SEM图。
具体实施方式
为使本发明更明显易懂,兹以优选实施例,并配合附图作详细说明如下。
实施例1
一种耐高温3Al2O3-2SiO2-SiBNC碳纤维复合涂层的制备方法:
首先对碳纤维进行预处理,将碳纤维在400℃氮气氛围的管式炉中去胶处理6h,将去胶后的碳纤维在浓度为30%的硝酸中浸泡刻蚀6h,再将刻蚀后的碳纤维在浓度为1wt%的KH550中浸泡偶联6h;
制备3Al2O3-2SiO2溶胶,用HCl调节蒸馏水的pH至2,剧烈搅拌下缓慢滴入正硅酸乙酯和无水乙醇的混合溶液,持续搅拌12h后得到稳定透明的SiO2溶胶,再向SiO2溶胶中缓慢滴加硝酸铝和浓硝酸的混合溶液,其中浓硝酸的摩尔含量为1%,搅拌8h后得到稳定透明的3Al2O3-2SiO2溶胶;
将颗粒尺寸为50nm的SiBNC陶瓷粉末通过磁力搅拌均匀分散在3Al2O3-2SiO2溶胶中,使SiBNC陶瓷粉末的体积含量为5%;
将处理后的碳纤维在30℃的混合溶胶中超声波振动浸渍90min,静置10min,取出碳纤维在30℃的干燥烘箱中干燥60min,反复操作得到涂层后的碳纤维;
将涂层后的碳纤维在800℃氮气氛围的管式炉中高温裂解6h,即得到耐高温的3Al2O3-2SiO2-SiBNC碳纤维复合涂层。通过检测,该实施例中得到的复合涂层的耐最高温度为1200℃。
实施例2
一种耐高温3Al2O3-2SiO2-SiBNC碳纤维复合涂层的制备方法:
首先对碳纤维进行预处理,将碳纤维在500℃氮气氛围的管式炉中去胶处理4h,将去胶后的碳纤维在浓度为50%的硝酸中浸泡刻蚀4h,再将刻蚀后的碳纤维在浓度为2wt%的KH550中浸泡偶联4h;
制备3Al2O3-2SiO2溶胶,用HCl调节蒸馏水的pH至3,剧烈搅拌下缓慢滴入正硅酸乙酯和无水乙醇的混合溶液,持续搅拌18h后得到稳定透明的SiO2溶胶,再向SiO2溶胶中缓慢滴加硝酸铝和浓硝酸的混合溶液,其中浓硝酸的摩尔含量为1%,搅拌16h后得到稳定透明的3Al2O3-2SiO2溶胶;
将颗粒尺寸为80nm的SiBNC陶瓷粉末通过磁力搅拌均匀分散在3Al2O3-2SiO2溶胶中,使SiBNC陶瓷粉末的体积含量为15%;
将处理后的碳纤维在60℃的混合溶胶中超声波振动浸渍60min,静置20min,取出碳纤维在60℃的干燥烘箱中干燥40min,反复操作得到涂层后的碳纤维;
将涂层后的碳纤维在1000℃氮气氛围的管式炉中高温裂解4h,即得到耐高温的3Al2O3-2SiO2-SiBNC碳纤维复合涂层。通过检测,该实施例中得到的复合涂层的耐最高温度为1400℃。
实施例3
一种耐高温3Al2O3-2SiO2-SiBNC碳纤维复合涂层的制备方法:
首先对碳纤维进行预处理,将碳纤维在600℃氮气氛围的管式炉中去胶处理2h,将去胶后的碳纤维在浓度为70%的硝酸中浸泡刻蚀2h,再将刻蚀后的碳纤维在浓度为3wt%的KH550中浸泡偶联2h;
制备3Al2O3-2SiO2溶胶,用HCl调节蒸馏水的pH至4,剧烈搅拌下缓慢滴入正硅酸乙酯和无水乙醇的混合溶液,持续搅拌24h后得到稳定透明的SiO2溶胶,再向SiO2溶胶中缓慢滴加硝酸铝和浓硝酸的混合溶液,其中浓硝酸的摩尔含量为3%,搅拌24h后得到稳定透明的3Al2O3-2SiO2溶胶;
将颗粒尺寸为100nm的SiBNC陶瓷粉末通过磁力搅拌均匀分散在3Al2O3-2SiO2溶胶中,使SiBNC陶瓷粉末的体积含量为30%;
将处理后的碳纤维在90℃的混合溶胶中超声波振动浸渍30min,静置30min,取出碳纤维在90℃的干燥烘箱中干燥20min,反复操作得到涂层后的碳纤维;
将涂层后的碳纤维在1200℃氮气氛围的管式炉中高温裂解2h,即得到耐高温的3Al2O3-2SiO2-SiBNC碳纤维复合涂层。通过检测,该实施例中得到的复合涂层的耐最高温度为1400℃。
图1、图2分别为涂层前后的碳纤维表面形貌图,由图可以看出,涂层前的碳纤维表面有很多沟壑,涂层后的碳纤维表面沟壑被填充,且表面涂层均匀致密,无明显缺陷。
Claims (6)
1.一种耐高温3Al2O3-2SiO2-SiBNC碳纤维复合涂层的制备方法,其特征在于,包括以下步骤:
步骤1):预处理碳纤维:首先将碳纤维在氮气气氛的管式炉中热处理,然后将热处理后的碳纤维在硝酸中浸泡刻蚀,将刻蚀后的碳纤维在偶联剂中浸泡备用;
步骤2):制备溶胶:用HCl调节蒸馏水的pH,剧烈搅拌下缓慢滴入正硅酸乙酯和无水乙醇的混合溶液,得到稳定透明的SiO2溶胶;再向SiO2溶胶中缓慢滴加硝酸铝和浓硝酸的混合溶液,得到稳定透明的3Al2O3-2SiO2溶胶;
步骤3):将SiBNC陶瓷粉末通过磁力搅拌均匀的分散在3Al2O3-2SiO2溶胶中;
步骤4):碳纤维浸渍涂层:将预处理后的碳纤维在步骤3)所得的溶胶中超声波振动浸渍后静置,取出碳纤维在干燥烘箱中干燥,反复操作得到涂层后的碳纤维;
步骤5):碳纤维涂层的高温裂解:在氮气氛围中,将涂层后的碳纤维在管式炉中高温裂解,最后得到耐高温的3Al2O3-2SiO2-SiBNC碳纤维复合涂层。
2.如权利要求1所述的耐高温3Al2O3-2SiO2-SiBNC碳纤维复合涂层的制备方法,其特征在于,所述步骤1)中碳纤维热处理条件是在400-600℃的管式炉中处理2-6h;碳纤维刻蚀是在浓度为30-70%的硝酸中浸泡2-6h;碳纤维偶联是在浓度为1-3wt%的偶联剂中,在20-80℃的条件下处理2-6h,偶联剂采用硅烷偶联剂KH550。
3.如权利要求1所述的耐高温3Al2O3-2SiO2-SiBNC碳纤维复合涂层的制备方法,其特征在于,所述步骤2)中用HCl调节蒸馏水的pH,是将蒸馏水的pH调节至2-4;所述浓硝酸采用摩尔浓度为1-3%的浓硝酸;制备SiO2溶胶所需的搅拌时间为12-24h,制备3Al2O3-2SiO2溶胶所需的搅拌时间为8-24h。
4.如权利要求1所述的耐高温3Al2O3-2SiO2-SiBNC碳纤维复合涂层的制备方法,其特征在于,所述步骤3)中SiBNC陶瓷粉末使用前经球磨,其颗粒尺寸为50-100nm,所配置溶胶中SiBNC陶瓷粉末的体积含量为5-30%。
5.如权利要求1所述的耐高温3Al2O3-2SiO2-SiBNC碳纤维复合涂层的制备方法,其特征在于,所述步骤4)中在超声波振动中浸渍涂层是在30-90℃的水浴中浸渍涂层0.5-1.5h;在烘箱中干燥是在30-90℃的烘箱中干燥20-60min。
6.如权利要求1所述的耐高温3Al2O3-2SiO2-SiBNC碳纤维复合涂层的制备方法,其特征在于,所述步骤5)中涂层的高温裂解是在温度为800-1200℃的管式炉中高温裂解2-6h,所得到的复合涂层的厚度为400nm-1000nm。
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