CN106192371A - 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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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HCI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HCI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HCI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HCI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HCI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HCI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HCI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陶瓷粉末的固含量为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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| CN110318253A (zh) * | 2019-08-11 | 2019-10-11 | 西南石油大学 | 一种碳纤维表面改性抗氧化复合涂层的制备方法 |
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