CN108504096B - 一种碳纳米管/聚合物复合材料的制备方法 - Google Patents

一种碳纳米管/聚合物复合材料的制备方法 Download PDF

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CN108504096B
CN108504096B CN201810355067.5A CN201810355067A CN108504096B CN 108504096 B CN108504096 B CN 108504096B CN 201810355067 A CN201810355067 A CN 201810355067A CN 108504096 B CN108504096 B CN 108504096B
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polymer
carbon
composite material
porous
carbon nano
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CN108504096A (zh
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封伟
张飞
冯奕钰
秦盟盟
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Tianjin University
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Abstract

本发明提供了一种碳纳米管/聚合物复合材料的制备方法，包括以下步骤：将多孔聚合物，通过真空镀膜技术，在表面镀纳米硅氧化膜；通过真空溅射在纳米硅氧化膜上沉积纳米金属催化剂薄膜；通过等离子体增强化学气相沉积法在聚合物表面原位生长阵列碳纳米管，得到碳纳米管/聚合物多孔复合材料；将碳纳米管/聚合物多孔复合材料浸渍聚合物、固化，得到碳纳米管/聚合物复合材料。本发明利用耐热高分子具有高的耐热温度和PECVD技术，低温下直接在聚合物的表面原位生长碳纳米管制备复合材料，克服了以往制备复合材料碳管难以分散均匀和材料界面结合力弱的缺陷，开创了利用有序复合结构提升材料定向导热和力学强度性能的新技术。

Description

一种碳纳米管/聚合物复合材料的制备方法
技术领域
本发明涉及碳纳米管材料技术领域，尤其涉及一种碳纳米管/聚合物复合材料的制备方法。
背景技术
碳纳米管自1991年发现以来，其特有的力学、电学、热学等性质及独特的准一维管状分子结构，使其在纳米电子器件、储氢燃料电池等未来高科技领域具有诸多潜在的应用价值。碳纳米管可以看作是由二维石墨烯卷曲封闭而得到的，其理想结构是六边形碳原子网格围成的无缝、中空管体，两端由半球形的大富勒烯分子罩住。纳米碳管的管壁由碳的六元环构成，每个六元环中的碳原子都以SP2杂化为主，每一碳原子又都以SP2杂化轨道与相邻六元环上的碳原子的SP2杂化轨道相互重叠形成碳-碳σ键，由于形成空间结构，SP2杂化轨道发生变形，形成介于SP2和SP3之间的杂化结构。
碳纳米管具有超强的力学性能、极大的长径比、良好的电学性能、很高的化学和热稳定性等，理论和实验研究都表明碳纳米管可以用来制备性能优良的聚合物基复合材料，可以使复合材料具有良好的强度、弹性、抗疲劳性及各向同性，给复合材料的力学性能带来极大的改善。同时碳纳米管具有良好的传热性能，其轴向的热传导率极高，实验测定结果表明，单根SWCNTs的导热率高达6000W/(wK)，因此碳纳米管广泛地用于制备导热复合材料。聚合物具有质量轻、耐腐蚀、耐辐射等优点，使其可以应用于新型航天器上，但其力学性能及导热性能差的特点制约了其应用范围，很多研究者通过添加石墨烯、碳纳米管等纳米碳材料来提高聚合物的力学性能和导热性能。现有的聚合物与碳纳米管复合材料都是将碳纳米管作为填料，与聚合物前驱体混合，以此制备碳纳米管/聚合物复合材料，这种方法虽然简单但存在一些缺点，比如碳纳米管在聚合物中的分散性不好，容易团聚；碳纳米管与聚合物界面结合方面需要改善等。同时，为了使聚合物与碳纳米管形成良好结合，经常需要对碳纳米管表面进行修饰和改性，改善其加工性，增强碳纳米管与聚合物之间的相容性，并提高其分散性。但是，碳纳米管的表面修饰和改性会增加碳管的缺陷，造成其导热性能及力学性能的大幅度降低，从而严重影响复合材料的综合性能。因此现有的技术无法满足制备高质量、高分散、高界面结合的碳纳米管与聚合物复合材料。
发明内容
有鉴于此，本发明要解决的技术问题在于提供一种碳纳米管/聚合物复合材料的制备方法，具有较高的强度和导热性能。
本发明提供了一种碳纳米管/聚合物复合材料的制备方法，包括以下步骤：
将多孔聚合物，通过真空镀膜技术，在表面镀纳米硅氧化膜；
通过真空溅射在纳米硅氧化膜上沉积纳米金属催化剂薄膜；
通过等离子体增强化学气相沉积法在多孔聚合物表面原位生长阵列碳纳米管，得到碳纳米管/聚合物多孔复合材料；
将碳纳米管/聚合物多孔复合材料浸渍聚合物、固化，得到碳纳米管/聚合物复合材料。
优选的，所述多孔聚合物按照以下方法制备：
将聚合物单体溶液，通过静电纺丝技术或冷冻干燥技术，制备得到多孔聚合物。
优选的，所述聚合物为聚酰亚胺、酚醛树脂、环氧树脂、聚苯并咪唑和聚酰胺中的一种或多种。
优选的，所述纳米硅氧化膜的厚度为5～50nm，所述纳米金属催化剂薄膜的厚度为1～10nm。
优选的，所述金属催化剂薄膜为镍、铁和钴中的一种或多种。
优选的，所述原位生长阵列碳纳米管的温度为200～450℃，压强为5～20Pa。
优选的，所述原位生长阵列碳纳米管以H2为载气，乙炔或甲烷为碳源，等离子体功率为10～500W，生长时间为5～60min。
优选的，所述浸渍聚合物在真空条件下进行。
本发明通过静电纺丝和冷冻干燥技术将聚合物制备成多孔的块体材料，以真空镀膜和真空溅射技术在聚合物表面沉积基体和催化剂，再利用PECVD技术，在低温和负压条件下通过等离子体加强沉积技术在聚合物表面原位生长碳纳米管，最后通过封装及致密化处理，制备得到高强度、高导热的碳纳米管/聚合物复合材料。得到的材料中，碳纳米管均匀生长在聚合物多孔结构表面，使碳纳米管与聚合物很好的结合在一起，同时阵列碳纳米管的原位生长技术使其均匀分布在材料孔隙内部，不存在分散不均匀及团聚的问题，使得复合材料具有优良的力学性能和导热性能。
附图说明
图1为本发明的制备方法步骤示意图；
图2为本发明制备的多孔聚酰亚胺的扫描电子显微镜图；
图3为本发明制备的负载催化剂聚酰亚胺的扫描电子显微镜图；
图4为本发明制备的原位生长有碳纳米管的复合材料的扫描电子显微镜图；
图5为本发明制备的封装后复合材料的扫描电子显微镜图。
具体实施方式
本发明提供了一种碳纳米管/聚合物复合材料的制备方法，包括以下步骤：
将多孔聚合物，通过真空镀膜技术，在表面镀纳米硅氧化膜；
通过真空溅射在纳米硅氧化膜上沉积纳米金属催化剂薄膜；
通过等离子体增强化学气相沉积法在多孔聚合物表面原位生长阵列碳纳米管，得到碳纳米管/聚合物多孔复合材料；
将碳纳米管/聚合物多孔复合材料浸渍聚合物、固化，得到碳纳米管/聚合物复合材料。
所述多孔聚合物材料的聚合物优选为聚酰亚胺、酚醛树脂、环氧树脂、聚苯并咪唑和聚酰胺等耐高温聚合物中的一种或多种。
上述多孔聚合物材料优选按照以下方法制备：
将聚合物单体溶液，通过静电纺丝技术或冷冻干燥技术，制备得到多孔聚合物。
所述聚合物单体溶液的溶剂可以根据聚合物种类自行选择，优选为二甲基乙酰胺(DMAC)或N-甲基吡咯烷酮(NMP)。
当聚合物聚合固化困难时，可以在聚合物溶液中添加固化剂和/或促进剂，所述固化剂、促进剂的种类可以为本领域技术人员熟知的适用的固化剂、促进剂。
所述聚合物单体溶液的固含量优选为10％～30％。
然后可以利用静电纺丝技术，制备出多孔的聚合物纤维毡；或利用冷冻干燥技术，将制备的聚合物浆料在液氮中冷冻，并通过冷冻干燥技术去除溶剂，最后再固化得到多孔的聚合物材料，作为复合材料的骨架结构。
然后通过真空镀膜技术，在所述多孔聚合物材料表面镀一层纳米级厚度的硅氧化物膜，称为纳米硅氧化膜，作为生长碳纳米管的基体。所述硅氧化膜负载于聚合物及其孔洞的表面。
所述纳米硅氧化膜的厚度优选为5～50nm。
再通过真空溅射技术在纳米硅氧化膜上溅射沉积一层纳米级厚度的金属催化剂薄膜，称为纳米金属催化剂薄膜，作为生长阵列碳纳米管的催化剂。
所述金属催化剂薄膜优选为镍、铁和钴等金属中的一种或多种。
所述纳米金属催化剂薄膜的厚度优选为1～10nm。
然后通过等离子体增强化学气相沉积法(PECVD)在纳米金属催化剂薄膜表面原位生长阵列碳纳米管，得到碳纳米管/聚合物多孔复合材料。
具体的，将负载有金属催化剂的多孔聚合物材料置于PECVD炉中；抽真空使炉管中形成负压，压强优选为5～20Pa，然后通入H2作为载气，流量优选为10～100sccm，优选当温度升至200～450℃，打开射频等离子体发射器，优选设置射频功率为10～500W，射频信号频率13.56MHz，优选在H2的等离子体环境下处理5～30min后，通入乙炔或甲烷作为生长碳管的碳源，优选流量为10～80sccm，调整不同的H2和乙炔或甲烷的流量比，生长时间优选为5～60min。反应结束后关闭等离子体，在H2气氛环境下随炉冷却至室温。
上述温度低于聚合物的最高使用温度，聚合物不会发生高温热解。
最后将生长后的碳纳米管/聚合物多孔复合材料在真空辅助下浸渍相应的聚合物单体，再通过聚合固化过程，固定碳管并填充孔隙，对碳纳米管孔隙进行封装，通过多次浸渍和固化过程，得到致密的碳纳米管/聚合物复合材料。
与目前普遍采用的共混法制备的复合材料不同，本发明在聚合物表面原位生长阵列碳纳米管，制备的微观有序复合材料，能实现定向的高效热传导和力学增强，开创了制备有序碳/聚合物复合材料的新方法。利用耐热高分子具有高的耐热温度和PECVD技术可以低温下生长阵列碳纳米管，直接在聚合物的表面原位生长碳纳米管制备复合材料，克服了以往制备复合材料碳管难以分散均匀和材料界面结合力弱的缺陷，开创了利用有序复合结构提升材料定向导热和强度性能的新技术。
为了进一步说明本发明，下面结合实施例对本发明提供的碳纳米管/聚合物复合材料的制备方法进行详细描述。
实施例1：
(1)按照摩尔比1:1称取3,3,4,4-联苯二酐(BPDA)和4,4'-二氨基二苯醚(ODA)溶于二甲基乙酰胺(DMAC)，在0℃以下反应5小时，然后加入1,3,5-三氨基苯氧基苯(TAB)进行化学交联，制备得到固含量为15％的聚酰胺酸(PAA)原液。然后利用静电纺丝技术制备出低聚物的纤维毡，最后在350℃下亚胺化得到多孔的聚酰亚胺纤维毡。多孔聚酰亚胺的扫描电子显微镜图如图2所示。
(2)将制备的多孔聚酰亚胺材料通过真空镀膜技术，在其表面镀一层10nm厚的硅氧化物膜，然后再通过真空溅射在聚酰亚胺上溅射一层2nm厚的镍(或铁、钴)薄膜，作为生长碳纳米管的催化剂。制备的负载催化剂的聚酰亚胺材料的扫描电子显微镜图如图3所示。
(3)将负载有催化剂的多孔聚酰亚胺置于PECVD炉中；抽真空使炉管中的压强为5～20Pa，然后通入H2作为载气，流量为100sccm，当温度升至300℃，打开射频等离子体发射器，设置射频功率为200W，射频信号频率13.56MHz，在H2的等离子体环境下处理30min后，通入乙炔作为生长碳管的碳源，流量为20sccm，生长碳纳米管时间为15min，反应结束后关闭等离子体，在H2气氛环境下随炉冷却至室温，得到生长有阵列碳纳米管的聚酰亚胺。上述原位生长了碳纳米管的复合材料的扫描电子显微镜图如图4所示。
(4)将生长了碳管后的多孔材料浸渍聚酰胺酸溶液，在350℃下热胺化处理。重复多次，使材料致密化。最后得到致密的碳纳米管/聚酰亚胺复合材料，封装后的复合材料的扫描电子显微镜图如图5所示。
得到的聚酰亚胺/碳管复合材料碳纳米管质量分数为6.5wt％，具有优良的力学性能和导热性能，其拉伸断裂强度高达410MPa，拉伸模量3.2GPa，导热系数为13W/mK。
实施例2：
(1)按照摩尔比1:1称取3,3,4,4-联苯二酐(BPDA)和4,4'-二氨基二苯醚(ODA)溶于二甲基乙酰胺(DMAC)，在0℃以下反应5小时，然后加入1,3,5-三氨基苯氧基苯(TAB)进行化学交联，制备得到固含量为15％的聚酰胺酸(PAA)原液。然后利用冷冻干燥技术，将制备的凝胶在液氮中冷冻，通过冷冻干燥技术去除溶剂，最后在350℃下亚胺化得到多孔的聚酰亚胺材料。
(2)将制备的多孔聚酰亚胺材料通过真空镀膜技术，在其表面镀一层20nm厚的硅氧化物膜，然后再通过真空溅射在聚酰亚胺上溅射一层10nm厚的镍(或铁、钴)薄膜，作为生长碳纳米管的催化剂。
(3)将附有催化剂的多孔聚酰亚胺置于PECVD炉中；抽真空使炉管中的压强为5～20Pa，然后通入H2作为载气，流量为50sccm，当温度升至450℃，打开射频等离子体发射器，设置射频功率为100W，射频信号频率13.56MHz，在H2的等离子体环境下处理30min后，通入乙炔作为生长碳管的碳源，流量为50sccm，生长碳纳米管时间为30min，反应结束后关闭等离子体，在H2气氛环境下随炉冷却至室温。
(4)将生长了碳管后的多孔材料浸渍聚酰胺酸溶液，在350℃下热胺化处理。重复多次，使材料致密化。最后得到致密的碳纳米管/聚酰亚胺复合材料。
得到的聚酰亚胺/碳管复合材料碳纳米管质量分数为8.2wt％，具有优良的力学性能和导热性能，其拉伸断裂强度高达479MPa，拉伸模量4.13GPa，导热系数为17.3W/mK。
实施例3：
(1)在室温下将环氧树脂(E-03，环氧值0.00～0.04)溶于1-甲氧基-2-丙醇(MP)中，搅拌30分钟使环氧树脂充分溶解，配置出浓度为30％的环氧树脂溶液。然后利用静电纺丝技术制备出环氧树脂的纤维毡。
(2)将制备的多孔环氧树脂材料通过真空镀膜技术，在其表面镀一层10nm厚的硅氧化物膜，然后再通过真空溅射在环氧树脂上溅射一层10nm厚的镍(或铁、钴)薄膜，作为生长碳纳米管的催化剂。
(3)将附有催化剂的多孔环氧树脂置于PECVD炉中；抽真空使炉管中的压强为5～20Pa，然后通入H2作为载气，流量为100sccm，当温度升至200℃，打开射频等离子体发射器，设置射频功率为300W，射频信号频率13.56MHz，在H2的等离子体环境下处理10min后，通入乙炔作为生长碳管的碳源，流量为10sccm，生长碳纳米管时间为20min，反应结束后关闭等离子体，在H2气氛环境下随炉冷却至室温。
(4)将生长了碳管后的多孔材料浸渍环氧树脂溶液，再在100℃真空烘箱中固化。重复多次，使材料致密化。最后得到致密的碳纳米管/环氧树脂复合材料。
得到的碳纳米管/环氧树脂复合材料碳纳米管质量分数为5.5wt％，具有优良的力学性能和导热性能，其拉伸断裂强度高达32.2MPa，拉伸模量3.1GPa，同时，导热系数为9.8W/mK。
实施例4：
(1)在室温下将环氧树脂(E-03，环氧值0.00～0.04)溶于1-甲氧基-2-丙醇(MP)中，搅拌30分钟使环氧树脂充分溶解，配置出浓度为20％的环氧树脂溶液。然后利用静电纺丝技术制备出环氧树脂的纤维毡。
(2)将制备的多孔环氧树脂材料通过真空镀膜技术，在其表面镀一层10nm厚的硅氧化物膜，然后再通过真空溅射在环氧树脂上溅射一层5nm厚的镍(或铁、钴)薄膜，作为生长碳纳米管的催化剂。
(3)将附有催化剂的多孔环氧树脂置于PECVD炉中；抽真空使炉管中的压强为5～20Pa，然后通入H2作为载气，流量为100sccm，当温度升至150℃，打开射频等离子体发射器，设置射频功率为300W，射频信号频率13.56MHz，在H2的等离子体环境下处理10min后，通入乙炔作为生长碳管的碳源，流量为20sccm，生长碳纳米管时间为30min，反应结束后关闭等离子体，在H2气氛环境下随炉冷却至室温。
(4)将生长了碳管后的多孔材料浸渍环氧树脂溶液，再在100℃真空烘箱中固化。重复多次，使材料致密化。最后得到致密的碳纳米管/环氧树脂复合材料。
得到的碳纳米管/环氧树脂复合材料碳纳米管质量分数为6.2wt％，具有优良的力学性能和导热性能，其拉伸断裂强度高达35.1MPa，拉伸模量3.5GPa，同时，导热系数为10.2W/mK。
实施例5：
(1)将酚醛树脂与聚乙烯醇缩丁醛(PVB)溶于乙醇中，酚醛树脂、PVB和乙醇的质量比为40：0.5：55.5，搅拌2h，混合均匀后得到酚醛树脂的溶液。然后利用静电纺丝技术制备出酚醛树脂的初纺纤维毡，最后在180℃下固化得到多孔的酚醛树脂纤维毡。
(2)将制备的多孔酚醛树脂材料通过真空镀膜技术，在其表面镀一层20nm厚的硅氧化物膜，然后再通过真空溅射在酚醛树脂上溅射一层2nm厚的镍(或铁、钴)薄膜，作为生长碳纳米管的催化剂。
(3)将附有催化剂的多孔酚醛树脂置于PECVD炉中；抽真空使炉管中的压强为5～20Pa，然后通入H2作为载气，流量为10sccm，当温度升至200℃，打开射频等离子体发射器，设置射频功率为500W，射频信号频率13.56MHz，在H2的等离子体环境下处理30min后，通入乙炔作为生长碳管的碳源，流量为20sccm，生长碳纳米管时间为60min，反应结束后关闭等离子体，在H2气氛环境下随炉冷却至室温。
(4)将生长了碳管后的多孔材料浸渍酚醛树脂溶液，在180℃下固化。重复多次，使材料致密化。最后得到致密的碳纳米管/酚醛树脂复合材料。
得到的碳纳米管/酚醛树脂复合材料碳纳米管质量分数为8.1wt％，具有优良的力学性能和导热性能，其拉伸断裂强度高达235.1MPa，拉伸模量7.5GPa，导热系数为19.8W/mK。
实施例6：
(1)将酚醛树脂与聚乙烯醇缩丁醛(PVB)溶于乙醇中，酚醛树脂、PVB和乙醇的质量比为40：0.5：55.5，搅拌2h，混合均匀后得到酚醛树脂的溶液。然后利用静电纺丝技术制备出酚醛树脂的初纺纤维毡，最后在180℃下固化得到多孔的酚醛树脂纤维毡。
(2)将制备的多孔酚醛树脂材料通过真空镀膜技术，在其表面镀一层50nm厚的硅氧化物膜，然后再通过真空溅射在酚醛树脂上溅射一层1nm厚的镍(或铁、钴)薄膜，作为生长碳纳米管的催化剂。
(3)将附有催化剂的多孔酚醛树脂置于PECVD炉中；抽真空使炉管中的压强为5～20Pa，然后通入H2作为载气，流量为10sccm，当温度升至150℃，打开射频等离子体发射器，设置射频功率为300W，射频信号频率13.56MHz，在H2的等离子体环境下处理30min后，通入乙炔作为生长碳管的碳源，流量为20sccm，生长碳纳米管时间为30min，反应结束后关闭等离子体，在H2气氛环境下随炉冷却至室温。
(4)将生长了碳管后的多孔材料浸渍酚醛树脂溶液，在180℃下固化。重复多次，使材料致密化。最后得到致密的碳纳米管/酚醛树脂复合材料。
得到的碳纳米管/酚醛树脂复合材料碳纳米管质量分数为7.2wt％，具有优良的力学性能和导热性能，其拉伸断裂强度高达185.8MPa，拉伸模量6.1GPa，导热系数为18.2W/mK。
由上述实施例可知，本发明制备得到了碳纳米管/聚合物复合材料，且具有优良的力学性能和导热性能。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。

Claims (8)

1.一种碳纳米管/聚合物复合材料的制备方法，包括以下步骤：
将多孔聚合物，通过真空镀膜技术，在表面镀纳米硅氧化膜；
通过真空溅射在纳米硅氧化膜上沉积纳米金属催化剂薄膜；
通过等离子体增强化学气相沉积法在所述纳米金属催化剂薄膜表面原位生长阵列碳纳米管，得到碳纳米管/聚合物多孔复合材料；
将碳纳米管/聚合物多孔复合材料浸渍聚合物、固化，得到碳纳米管/聚合物复合材料。
2.根据权利要求1所述的制备方法，其特征在于，所述多孔聚合物按照以下方法制备：
将聚合物单体溶液，通过静电纺丝技术或冷冻干燥技术，制备得到多孔聚合物。
3.根据权利要求1所述的制备方法，其特征在于，所述聚合物为聚酰亚胺、酚醛树脂、环氧树脂、聚苯并咪唑和聚酰胺中的一种或多种。
4.根据权利要求1所述的制备方法，其特征在于，所述纳米硅氧化膜的厚度为5～50nm，所述纳米金属催化剂薄膜的厚度为1～10nm。
5.根据权利要求1所述的制备方法，其特征在于，所述金属催化剂薄膜为镍、铁和钴中的一种或多种。
6.根据权利要求1所述的制备方法，其特征在于，所述原位生长阵列碳纳米管的温度为200～450℃，压强为5～20Pa。
7.根据权利要求1所述的制备方法，其特征在于，所述原位生长阵列碳纳米管以H2为载气，乙炔或甲烷为碳源，等离子体功率为10～500W，生长时间为5～60min。
8.根据权利要求1所述的制备方法，其特征在于，所述浸渍聚合物在真空条件下进行。
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