CN115304391A - 石墨毡基复合材料及其制备方法 - Google Patents
石墨毡基复合材料及其制备方法 Download PDFInfo
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- CN115304391A CN115304391A CN202210982038.8A CN202210982038A CN115304391A CN 115304391 A CN115304391 A CN 115304391A CN 202210982038 A CN202210982038 A CN 202210982038A CN 115304391 A CN115304391 A CN 115304391A
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- graphite felt
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- ceramic
- carbon
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- FMNFAXVBAQEWCV-UHFFFAOYSA-N aminooxyboronic acid Chemical compound NOB(O)O FMNFAXVBAQEWCV-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及碳纤维材料技术领域,尤其涉及石墨毡基复合材料及其制备方法。石墨毡基复合材料包括:石墨毡,以及依次包覆于石墨毡表面的过渡层及两层以上的陶瓷涂层;在陶瓷涂层中,陶瓷前驱体的重量含量为1%~80%,且沿着远离石墨毡的方向,陶瓷涂层中陶瓷前驱体的含量递增;过渡层中含有碳纳米材料。本发明提供的石墨毡基复合材料,石墨毡与陶瓷涂层的结合力强,通过设置陶瓷前驱体浓度逐渐增大的陶瓷涂层,使热膨胀系数的差异性缓慢过渡,有效防止热失配造成的陶瓷涂层剥脱失效。
Description
技术领域
本发明涉及碳纤维材料技术领域,尤其涉及石墨毡基复合材料及其制备方法。
背景技术
石墨毡具有低体积密度、耐高温、绝热性好、碳含量高且易加工等优点,被广泛应用于太阳能、半导体硅等行业,其中主要是用作高温炉体内的保温隔热材料。随着单晶的尺寸需求逐年增大,单晶硅行业对热场尺寸和热场部件的安全性也提出了更高的要求。单晶制备过程中,石英坩埚在高温环境中与硅熔体长时间接触会产生SiO气体,并随氩气传递到单晶炉底部,此过程对用作保温材料的石墨毡会产生冲刷腐蚀。因此,为了延长石墨毡的高温使用寿命,通常在其表面构建防腐蚀层,以满足当前大尺寸热场、长时间高温运行的安全性需求。
目前,碳纤维及其复合材料的涂层主要为陶瓷类涂层和复合涂层,陶瓷类材料具有抗氧化、耐高温、高化学稳定性等特点,可提高碳/石墨材料的耐腐蚀性,也适用于保温石墨毡表面防腐蚀层的构建。但陶瓷材料的热膨胀系数和石墨严重不匹配,导致在高温-冷却循环过程中容易发生涂层剥离、脱落现象,这不仅造成涂层失效,脱落层还将污染单晶炉体。因此,构建合适、有效且使用寿命长的涂层首先需要解决陶瓷与石墨层的热失配问题。
综上所述,如何提供一种石墨毡与陶瓷涂层结合力强的石墨毡基复合材料,使其在大热场、长时间高温运行的环境下具有较好的稳定性,成为本领域亟待解决的技术难题。
发明内容
本发明提供一种石墨毡基复合材料及其制备方法,用以解决现有技术中的以下缺陷,包括:(1)热场石墨毡经受SiO气体冲刷腐蚀而难以满足大热场、长时间高温运行的需求;(2)陶瓷类耐腐蚀涂层与石墨材料存在严重热失配,易在使用中与基体剥离脱落造成失效。
本发明提供了一种石墨毡基复合材料,其包括:石墨毡,以及依次包覆于石墨毡表面的过渡层及两层以上的陶瓷涂层;
在所述陶瓷涂层中,陶瓷前驱体的重量含量为1%~80%,且沿着远离石墨毡的方向,所述陶瓷涂层中陶瓷前驱体的含量递增;
所述过渡层中含有碳纳米材料。
根据本发明提供的一种优选的实施方案,与所述过渡层接触的陶瓷涂层中陶瓷前驱体的重量含量为5%~30%,且沿着远离石墨毡的方向,陶瓷涂层中陶瓷前驱体含量的增量为5%~30%。
根据本发明提供的一种优选的实施方案,所述碳纳米材料为氧化石墨烯、磺化石墨烯、碳纳米管、碳纳米纤维及其改性碳纳米产物中的至少一种。
根据本发明提供的一种优选的实施方案,在所述陶瓷涂层中,不同层的陶瓷前驱体相同或不同,各自独立选自金属无机盐、有机金属醇盐或氮硼化合物中的至少一种。
进一步,本发明提供了上述任一实施方案中石墨毡基复合材料的制备方法,包括如下步骤:
(1)将石墨毡与碳纳米材料浸渍液混合,经固化后制得包覆碳纳米材料的石墨毡;
(2)将所述包覆碳纳米材料的石墨毡与陶瓷前驱体溶胶混合后固化,制得半成品石墨毡;
(3)将半成品石墨毡与陶瓷前驱体含量高于上一步骤的陶瓷前驱体溶胶混合,然后固化;
(4)进行1次以上步骤(3)后,烧结制得所述石墨毡基复合材料。
根据本发明提供的一种优选的实施方案,所述碳纳米材料浸渍液中含有碳纳米材料和粘稠溶液,所述粘稠溶液中含有水溶性稳定剂和水溶性胶黏剂,所述碳纳米材料占所述粘稠溶液的重量百分比为0.1~5wt.%。
根据本发明提供的一种优选的实施方案,所述水溶性稳定剂为羧甲基纤维素钠、羧甲基纤维素、海藻酸钠、明胶中的至少一种;
和/或,所述水溶性胶黏剂为聚乙烯醇、水性环氧树脂、甲阶酚醛树脂、聚丙烯酸酯乳液中的至少一种。
根据本发明提供的一种优选的实施方案,所述陶瓷前驱体溶胶中包含有陶瓷前驱体、石墨烯水分散液、催化剂和胶黏剂。
根据本发明提供的一种优选的实施方案,所述胶黏剂为聚乙烯醇、聚乙二醇、环氧树脂、酚醛树脂中的至少一种;
和/或,所述石墨烯水分散液中石墨烯的质量分数为0.5~2wt.%;
和/或,所述催化剂为NH3·H2O、六次甲基四胺、NaOH、硝酸、醋酸中的至少一种。
根据本发明提供的一种优选的实施方案,所述陶瓷前驱体溶胶的制备方法包括:先将陶瓷前驱体与溶剂、石墨烯水分散液、催化剂混合后反应,制得溶胶;而后将所述溶胶与胶黏剂溶液混合,制得所述陶瓷前驱体溶胶。
此外,本发明还提供了由上述任一实施方案制得的石墨毡基复合材料。
进一步,本发明还提供了一种保温隔热材料,其含有上述任一实施方案中的石墨毡基复合材料。
更进一步,本发明还提供了一种高温炉,其中含有上述保温隔热材料。
本发明提供的石墨毡基复合材料,其中具有的含有碳纳米材料的过渡层能够提高石墨毡的比表面积,为陶瓷涂层的制备提供更多的反应点,增大石墨毡与陶瓷涂层的结合力;同时通过设置陶瓷前驱体浓度逐渐增大的陶瓷涂层,进一步缓解陶瓷涂层与石墨毡结合界面处的热膨胀系数骤变,使热膨胀系数的差异性缓慢过渡,从而防止热失配造成的陶瓷涂层剥脱失效。
附图说明
图1是本发明试验例的氧化失重量变化折线图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面将对本发明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作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。
首先,作为本发明的一个实施例,本实施例提供了一种石墨毡基复合材料,其包括:石墨毡,以及依次包覆于石墨毡表面的过渡层及两层以上的陶瓷涂层;在所述陶瓷涂层中,陶瓷前驱体的重量含量为1%~80%,且沿着远离石墨毡的方向,所述陶瓷涂层中陶瓷前驱体的含量递增;所述过渡层中含有碳纳米材料。
本发明通过在石墨毡表面包覆石墨烯、碳纳米管或纳米纤维等纳米碳过渡层,在不改变石墨毡本身晶体结构的同时,可提高石墨毡比表面积,为陶瓷涂层提供更多的反应点,增大石墨毡与陶瓷涂层的结合力,且纳米碳过渡层具有良好的韧性,可改善陶瓷涂层的力学性能。与此同时,通过设置陶瓷前驱体浓度逐渐增大的陶瓷涂层,能够有效缓解陶瓷涂层与石墨毡结合界面处的热膨胀系数骤变,使热膨胀系数的差异性缓慢过渡,减少温度改变时明显热失配造成的应力集中,显著降低热失配造成的涂层剥脱失效。
作为本发明的一个优选的实施例,与所述过渡层接触的陶瓷涂层中陶瓷前驱体的重量含量为5%~30%,且沿着远离石墨毡的方向,陶瓷涂层中陶瓷前驱体含量的增量为5%~30%。
作为本发明的一个优选的实施例,石墨毡基复合材料中的碳纳米材料为氧化石墨烯、磺化石墨烯、碳纳米管、碳纳米纤维及其改性碳纳米产物中的至少一种。
在具体实施过程中,上述碳纳米材料仅是举例,其它的碳纳米材料也可用于制备所述过渡层。
本发明发现碳纳米材料与石墨毡基体均属于碳材料,亲和性好,而且碳纳米材料比表面积大且具有良好的韧性,因此可以减少陶瓷材料脆性导致的易和石墨毡剥离的现象。
作为本发明的一个优选的实施例,在所述陶瓷涂层中,不同层的陶瓷前驱体相同或不同,各自独立选自金属无机盐、有机金属醇盐或氮硼化合物中的至少一种。
在具体实施过程中,每层陶瓷涂层的陶瓷前驱体可选自包括但不限于上述前驱体中的至少一种。例如,所述陶瓷前驱体包括但不限于Zr(NO3)2·2H2O、Al(NO3)3·9H2O、ZrOCl2·8H2O、硼酸氨基三乙酯、正硅酸乙酯、四乙氧基硅烷、钛酸四丁酯等。
作为本发明的一个优选的实施例,石墨毡基复合材料的制备方法包括如下步骤:
(1)将石墨毡与碳纳米材料浸渍液混合,经固化后制得包覆碳纳米材料的石墨毡;
(2)将所述包覆碳纳米材料的石墨毡与陶瓷前驱体溶胶混合后固化,制得半成品石墨毡;
(3)将半成品石墨毡与陶瓷前驱体含量高于上一步骤的陶瓷前驱体溶胶混合,然后固化;
(4)进行1次以上步骤(3)后,烧结制得所述石墨毡基复合材料。
在具体实施过程中,步骤(1)也可进行1次以上,优选1~5次。
通过循环“浸渍-沉积-固化”的温和包覆方式,将碳纳米材料有效快速地沉积于石墨毡表面,经过固化后形成过渡层。而后通过循环“沉积-原位聚合-固化”的方式,使陶瓷前驱体溶胶充分附着在石墨毡的碳纳米材料过渡层表面并使其原位聚合增大分子链,依次在过渡层表面构建具有浓度梯度陶瓷前驱体的陶瓷涂层。本发明的制备工艺操作简单,工艺周期短,无需使用化学沉积设备等仪器,能耗低、成本低,可行性高。而现有技术中,涂层的制备方法包括化学气相沉积法、电镀法和涂覆法等。相比涂覆法,前两种方法制备的涂层均匀性较高,但化学沉积法沉积速度慢、成本较高,而电镀法工艺复杂、能耗较高。由此可见,相比现有技术,本发明提供了一种高效、低成本的均匀涂层的制备方式,可解决目前涂层制备工艺较为复杂、成本高、效率低的缺陷。
在具体实施过程中,固化的方式包括但不限于烘干。
在具体实施过程中,包括但不限于采用超声辅助混合过程。
在具体实施过程中,步骤(1)和步骤(3)的混合过程中,将石墨毡或半成品石墨毡浸渍于碳纳米材料浸渍液或陶瓷前驱体溶胶中;浸渍液量以可完全浸没石墨毡为宜。优选浸渍60~180min。浸渍过程温度可保持在室温~90℃。
优选地,将石墨毡与碳纳米材料浸渍液混合后,超声浸渍0.5h~24h,而后在50~110℃下烘干固化30~120min,制得包覆碳纳米材料的石墨毡。
在具体实施过程中,包括但不限于采用超声清洗后的石墨毡。
优选地,采用乙醇和水分别清洗石墨毡3次以上,每次清洗10~30min。
优选地,步骤(3)中每次包覆陶瓷前驱体溶胶后,烘干固化的温度为60~120℃,和/或,固化时间为1~5h。
在具体实施过程中,包括但不限于采用抽滤的方式将石墨毡表面多余的碳纳米材料浸渍液、陶瓷前驱体溶胶去除。
在具体实施过程中,包括但不限于采用气氛炉进行烧结。
优选地,所述烧结的气氛为氮气或氩气;和/或,升温速度为1~10℃/min。
在具体实施过程中,烧结温度需按陶瓷种类设定,主要为400~1800℃,保温时间为0.5~5h。
作为本发明的一个优选的实施例,所述碳纳米材料浸渍液中含有碳纳米材料和粘稠溶液,所述粘稠溶液中含有水溶性稳定剂和水溶性胶黏剂,所述碳纳米材料占所述粘稠溶液的重量百分比为0.1~5wt.%
作为本发明的一个优选的实施例,所述碳纳米材料浸渍液的制备方法包括:先将水溶性稳定剂和水溶性胶黏剂分散于水中,制得粘稠溶液,而后将碳纳米材料分散于所述粘稠溶液中,控制碳纳米材料占所述粘稠溶液的重量百分比为0.1~5wt.%,制得所述碳纳米材料浸渍液。
在具体实施过程中,包括但不限于采用加热的方式,和/或超声的方式将水溶性稳定剂和水溶性胶黏剂分散于水中,制成具有一定粘稠度的粘稠溶液。
优选地,在30~90℃下将水溶性稳定剂和胶黏剂加热溶解在纯水中,而后剧烈搅拌、超声振荡20~60min,制得所述粘稠溶液。
在具体实施过程中,包括但不限于采用超声的方式将碳纳米材料分散于所述粘稠溶液中。
作为本发明的一个优选的实施例,所述水溶性稳定剂为羧甲基纤维素钠、羧甲基纤维素、海藻酸钠、明胶中的至少一种;
和/或,所述水溶性胶黏剂为聚乙烯醇、水性环氧树脂、甲阶酚醛树脂、聚丙烯酸酯乳液中的至少一种。
在具体实施过程中,上述水溶性稳定剂和水溶性胶黏剂仅是举例,其它的水溶性稳定剂和水溶性胶黏剂也可用于制备所述碳纳米材料浸渍液。
优选地,所述水溶性稳定剂的质量分数为0.1wt.%~3wt.%;和/或,所述水溶性胶黏剂的质量分数为0.1wt.%~20wt.%。
作为本发明的一个较优选的实施例,所述碳纳米材料浸渍液的制备方法包括:
(1)在30~90℃下将水溶性稳定剂和胶黏剂加热溶解在纯水中,而后剧烈搅拌、超声振荡20~60min,制得粘稠溶液;
(2)将碳纳米材料分散于所述粘稠溶液中,超声振荡30~90min,控制碳纳米材料占所述粘稠溶液的重量百分比为0.1~5wt.%,制得碳纳米材料浸渍液。
作为本发明的一个优选的实施例,所述陶瓷前驱体溶胶中包含有陶瓷前驱体、石墨烯水分散液、催化剂和胶黏剂。
作为本发明的一个优选的实施例,所述胶黏剂为聚乙烯醇、聚乙二醇、环氧树脂、酚醛树脂中的至少一种;
和/或,所述石墨烯水分散液中石墨烯的质量分数为0.5~2wt.%;
和/或,所述催化剂为NH3·H2O、六次甲基四胺、NaOH、硝酸、醋酸中的至少一种。
作为本发明的一个优选的实施例,所述陶瓷前驱体溶胶的制备方法包括:先将陶瓷前驱体与溶剂、石墨烯水分散液、催化剂混合后反应,制得溶胶;而后将所述溶胶与胶黏剂溶液混合,制得所述陶瓷前驱体溶胶。
在本发明中,优选采用石墨烯水分散液作为稀释剂。
通过调整陶瓷前驱体的添加量为1~80wt.%,制备不同陶瓷前驱体含量的陶瓷前驱体溶胶。
优选地,所述胶黏剂溶液中胶黏剂的重量百分比为10wt.%以下。
在具体实施过程中,胶黏剂、催化剂可选择的物质包括但不限于上述成分。
在具体实施过程中,所述溶剂包括但不限于水、乙醇、甲醇、异丙醇等。
在具体实施过程中,反应温度按照前驱体成分而定,一般为室温~90℃,反应时间为30~180min。
在具体实施过程中,包括但不限于采用超声、振荡的方式将所述溶胶与胶黏剂溶液混合,制得具有一定黏度的陶瓷前驱体溶胶。
优选地,超声时间为30~120min。
作为本发明的一个较优选的实施例,陶瓷前驱体溶胶的制备方法包括:
(1)将胶黏剂与溶剂混合,配制成质量分数为10wt.%以下的胶黏剂溶液;
(2)将陶瓷前驱体与溶剂、石墨烯水分散液、催化剂混合,搅拌并反应后制得溶胶;
(3)将所述胶黏剂溶液和所述溶胶混合,超声振荡后制得陶瓷前驱体溶胶。
本发明还提供了由上述任一实施例制得的石墨毡基复合材料。
进一步,本发明的实施例提供了一种保温隔热材料,其含有上述任一实施方案中的石墨毡基复合材料。由于本发明的石墨毡基复合材料中石墨毡与陶瓷涂层结合力强,因此,含有本发明石墨毡基复合材料的保温隔热材料也具有本发明的优异效果。
更进一步,本发明的实施例提供了一种高温炉,其中含有上述保温隔热材料,因此,其可应用在太阳能、半导体硅等行业中的大热场、长时间高温运行的环境中。
下面将结合更为具体的实施例阐述本发明的石墨毡基复合材料及其制备方法。
实施例中未注明具体技术或条件者,均为常规方法或者按照本领域的文献所描述的技术或条件进行,或者按照产品说明书进行。所用试剂和仪器等未注明生产厂商者,均为可通过正规渠道商购买得到的常规产品。
实施例1
本实施例提供了一种石墨毡基复合材料,其制备方法包括如下步骤:
(1)取小块石墨毡用无水乙醇和蒸馏水先后超声清洗3次,每次清洗10min,置于鼓风干燥箱中80℃烘干备用。
(2)将1g聚乙烯醇、0.5g羧甲基纤维素钠在90℃水浴加热溶于100g纯水中,搅拌均匀后,加入0.5g氧化石墨烯粉末,超声振荡30min制得均匀分散的碳纳米材料浸渍液。石墨毡在浸渍液中超声浸没30min,抽滤去除浸渍液后于80℃烘干固化,循环此浸渍-烘干过程一次。
(3)配制质量分数分别为20wt.%和40wt.%的ZrO2陶瓷前驱体溶胶:取20g Zr(NO3)2·2H2O溶于80g纯水中,80℃水浴并开启磁力搅拌,缓慢滴加10mL 1mol/L的NH3·H2O,反应30min后先后加入10g质量分数为5wt.%的聚乙烯醇水溶液和10g质量分数为1wt.%的石墨烯水分散液,经过超声振荡30min后继续水浴加热、磁力搅拌反应60min后制得质量分数为20wt.%的ZrO2前驱体溶胶。40wt.%的ZrO2前驱体溶胶则将Zr(NO3)2·2H2O的质量增大为40g,NH3·H2O加入量增加为20mL,其余过程不变。
将(2)中获得的石墨毡首先浸渍在20wt.%的前驱体溶胶中,超声浸渍60min后抽滤、90℃烘干固化,再浸渍入40wt.%的前驱体溶胶中60min后再次抽滤、烘干固化,获得ZrO2前驱体包覆的石墨毡。
(4)将(3)中获得的石墨毡在N2气氛炉中3℃/min升温至600℃烧结,保温60min,最终获得具有梯度浓度的ZrO2涂层的石墨毡基复合材料。
实施例2
本实施例提供了一种石墨毡基复合材料,其制备方法包括如下步骤:
(1)取小块石墨毡用无水乙醇和蒸馏水先后超声清洗3次,每次清洗10min,置于鼓风干燥箱中80℃烘干备用。
(2)将2g水性环氧树脂、0.5g羧甲基纤维素钠在80℃水浴加热溶于100g纯水中,搅拌均匀后,加入0.5g碳纳米管,超声振荡30min制得均匀分散的碳纳米材料浸渍液。石墨毡在浸渍液中超声浸没30min,抽滤去除浸渍液后80℃烘干固化,循环此浸渍-烘干过程一次。
(3)配制质量分数分别为15wt%和质量分数为30wt%的SiC陶瓷前驱体溶胶:取15g正硅酸乙酯溶于80g乙醇中,40℃水浴并开启磁力搅拌,缓慢滴加1mol/L的NH3·H2O调节pH值至7,反应30min后先后加入20g质量分数为15wt.%的甲阶酚醛树脂液和5g炭黑粉末,经超声振荡30min后继续水浴加热、磁力搅拌反应60min后制得质量分数为15wt%的SiC前驱体溶胶。30wt%的SiC前驱体溶胶则将正硅酸乙酯的质量增大为30g,NH3·H2O加入量增加为20mL,其余过程不变。
将(2)中获得石墨毡首先浸渍在15wt%的前驱体溶胶中,超声浸渍60min后抽滤、90℃烘干固化,再浸渍入30wt%的前驱体溶胶中60min后再次抽滤、烘干固化,获得SiC前驱体包覆的石墨毡。
(4)将(3)获得的石墨毡在N2气氛炉中3℃/min升温至1600℃烧结,保温120min,最终获得具有梯度浓度的SiC涂层的石墨毡基复合材料。
实施例3
本实施例提供了一种石墨毡基复合材料,其制备方法包括如下步骤:
(1)取小块石墨毡用无水乙醇和蒸馏水先后超声清洗3次,每次清洗10min,置于鼓风干燥箱中80℃烘干备用。
(2)将2g聚乙烯醇、0.5g羧甲基纤维素钠在80℃水浴加热溶于100g纯水中,搅拌均匀后,加入1g氧化石墨烯,超声振荡30min制得均匀分散的碳纳米材料浸渍液。石墨毡在浸渍液中超声浸没30min,抽滤去除浸渍液后80℃烘干固化,循环此浸渍-烘干过程一次。
(3)配制质量分数分别为10wt.%、20wt.%和30wt.%的一系列BN陶瓷前驱体溶胶:取5g三聚氰胺、5g硼酸溶于80g纯水中,40℃水浴并开启磁力搅拌,反应30min后先后加入10g质量分数为5wt.%的聚乙烯醇水溶液和10g质量分数为1wt.%的石墨烯水分散液,经超声振荡30min后继续水浴加热、磁力搅拌反应60min后制得质量分数为10wt.%的BN前驱体溶胶。20wt.%和30wt.%的BN前驱体溶胶则将三聚氰胺和硼酸总质量分别增大20g和30g,保持三聚氰胺与硼酸质量比为1:1,其余过程不变。
将(2)中获得石墨毡首先浸渍入10wt.%的前驱体溶胶中,超声浸渍60min后抽滤、90℃烘干固化,再分别浸渍入20wt.%和30wt.%的前驱体溶胶中60min后抽滤、烘干固化,获得BN前驱体包覆的石墨毡。
(4)将(3)获得的石墨毡在N2气氛炉中5℃/min升温至700℃烧结,保温120min,最终获得具有梯度浓度的BN涂层的石墨毡基复合材料。
对比例
本对比例提供了一种石墨毡基复合材料,其制备方法仅与实施例2不同的是:不进行步骤(2),步骤(3)中直接将步骤(1)清洗干燥后的石墨毡浸渍SiC前驱体溶胶。
试验例
对上述实施例2、对比例制备的石墨毡基复合材料及未进行任何处理的空白对照组(石墨毡)进行剪切强度测试和抗氧化性能评估。
(1)剪切强度采用万能材料试验机测试,并参照HB-5476-91标准制备样品。具体步骤为:将三种样品与对偶件用高温胶片粘结并在180℃固化后(粘结强度约80MPa),在万能试验机上进行拉伸试验,拉伸速度为1mm·min-1。每组样品进行4个平行试样测试取平均值,结果如表1所示。
表1抗拉强度测试结果
样品 | 抗拉强度/MPa |
石墨毡空白对照组 | 0.32±0.02 |
实施例2 | 0.41±0.04 |
对比例 | 0.35±0.03 |
需注意,此试验设计中复合材料的整体拉伸强度值会受石墨纤维径向强度、石墨毡本身抗拉强度、高温粘结剂对石墨毡的粘结力、陶瓷涂层强度及涂层结合强度共同作用。但是,由于本试验中所使用高温胶的抗拉强度约80MPa,单根石墨纤维的抗拉强度约为1.8GPa,均远高于石墨毡和涂层结合力,因此石墨毡基复合材料的抗拉强度仅受到涂层强度与石墨毡自身剪切强度限制。
由表中可知,石墨毡自身强度为0.32MPa,实施例2和对比例的抗拉强度相对空白组均有一定提升,这是由于陶瓷涂层具有一定强度,引入可提高石墨毡的抗拉强度。实施例2的抗拉强度达到0.41MPa,表明构建碳纳米材料过渡层后,陶瓷涂层与石墨毡结合更为牢固。
(2)抗氧化性能通过样品在大气条件下,800℃时在不同保持时间时的氧化失重量来表征。结果如图1所示。由图1可知,石墨毡空白对照组在800℃时,随着时间延长,残留量迅速降低,表明石墨毡的氧化反应极为剧烈,在40min后仅残留3%。而实施例2和对比例由于陶瓷涂层的保护,氧化速率明显降低,在40min时分别残留68%和60%,极大延长了石墨毡的使用寿命。且由于实施例2中存在碳纳米过渡层,比表面积较大使陶瓷涂层与石墨毡基体的结合力更大,涂层对基体的包覆作用有较好改善,因此实施例2的抗氧化性能优于对比例。
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)
1.一种石墨毡基复合材料,其特征在于,其包括:石墨毡,以及依次包覆于石墨毡表面的过渡层及两层以上的陶瓷涂层;
在所述陶瓷涂层中,陶瓷前驱体的重量含量为1%~80%,且沿着远离石墨毡的方向,所述陶瓷涂层中陶瓷前驱体的含量递增;
所述过渡层中含有碳纳米材料。
2.根据权利要求1所述的石墨毡基复合材料,其特征在于,所述碳纳米材料为氧化石墨烯、磺化石墨烯、碳纳米管、碳纳米纤维及其改性碳纳米产物中的至少一种。
3.根据权利要求1或2所述的石墨毡基复合材料,其特征在于,在所述陶瓷涂层中,不同层的陶瓷前驱体相同或不同,各自独立选自金属无机盐、有机金属醇盐或氮硼化合物中的至少一种。
4.权利要求1~3中任一项所述的石墨毡基复合材料的制备方法,其特征在于,包括如下步骤:
(1)将石墨毡与碳纳米材料浸渍液混合,经固化后制得包覆碳纳米材料的石墨毡;
(2)将所述包覆碳纳米材料的石墨毡与陶瓷前驱体溶胶混合后固化,制得半成品石墨毡;
(3)将半成品石墨毡与陶瓷前驱体含量高于上一步骤的陶瓷前驱体溶胶混合,然后固化;
(4)进行1次以上步骤(3)后,烧结制得所述石墨毡基复合材料。
5.根据权利要求4所述的石墨毡基复合材料的制备方法,其特征在于,所述碳纳米材料浸渍液中含有碳纳米材料和粘稠溶液,所述粘稠溶液中含有水溶性稳定剂和水溶性胶黏剂,所述碳纳米材料占所述粘稠溶液的重量百分比为0.1~5wt.%。
6.根据权利要求5所述的石墨毡基复合材料的制备方法,其特征在于,所述水溶性稳定剂为羧甲基纤维素钠、羧甲基纤维素、海藻酸钠、明胶中的至少一种;
和/或,所述水溶性胶黏剂为聚乙烯醇、水性环氧树脂、甲阶酚醛树脂、聚丙烯酸酯乳液中的至少一种。
7.根据权利要求4~6中任一项所述的石墨毡基复合材料的制备方法,其特征在于,所述陶瓷前驱体溶胶中包含有陶瓷前驱体、石墨烯水分散液、催化剂和胶黏剂。
8.根据权利要求7所述的石墨毡基复合材料的制备方法,其特征在于,所述胶黏剂为聚乙烯醇、聚乙二醇、环氧树脂、酚醛树脂中的至少一种;
和/或,所述石墨烯水分散液中石墨烯的质量分数为0.5~2wt.%;
和/或,所述催化剂为NH3·H2O、六次甲基四胺、NaOH、硝酸、醋酸中的至少一种。
9.一种保温隔热材料,其特征在于,其含有权利要求1~3中任一项所述的石墨毡基复合材料或权利要求4~8中任一项所述制备方法制得的石墨毡基复合材料。
10.一种高温炉,其特征在于,其含有权利要求9所述的保温隔热材料。
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CN107740097A (zh) * | 2017-09-30 | 2018-02-27 | 中国科学院合肥物质科学研究院 | 一种含碳纳米管涂层材料及其制备方法 |
CN108117811A (zh) * | 2018-01-25 | 2018-06-05 | 惠州市栢诗新材料有限公司 | 一种石墨烯-硅电磁屏蔽填料及电磁屏蔽涂料 |
CN111113946A (zh) * | 2019-12-17 | 2020-05-08 | 江苏理工学院 | 一种混杂复合材料层合板及其制备工艺 |
CN113788684A (zh) * | 2021-09-22 | 2021-12-14 | 航天特种材料及工艺技术研究所 | 一种梯度密度碳-陶瓷复合材料及其制备方法 |
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