摘要
碳纳米管(CNTs)由于其独特的准一维结构和优越的物理化学特性,在很多方面都有着巨大的潜在应用。在碳纳米管的诸多应用中,将其用于加强复合材料的性能或制备多功能复合材料方面具有很大的优势,并且可以很快的实现工业化应用。但在制备碳纳米管基聚合物复合材料时,由于碳纳米管纳米级的表面特征和易于弯曲缠绕的特点,使得碳管在聚合物中不易分散,这大大影响了复合材料的性能。为了解决碳管的分散性问题同时又不破坏其本身结构,我们设计了一种基于碳纳米管的多维多尺度复合杂化结构,这种复合杂化结构不但可以在微米尺度自组装碳管,解决其分散性的问题,而且还具有很多其它的优点。多维多尺度杂化结构中碳管的形貌和结构对其改性的复合材料性能有着重要影响,因此,我们对反应条件和载体性质共同塑造杂化结构的机理进行了研究,实现了多维多尺度杂化结构中碳管形貌和组织模式的可控制备。此外,我们还将几种特殊结构杂化粒子用于复合材料中,研究了杂化粒子的引入对复合材料性能的影响以及相应的结构-性能关系。本论文的主要工作如下：
(1)对制备杂化结构过程中涉及到的几种碳氢化合物的化学气相沉积过程进行了实验研究。分别研究了反应条件对碳氢化合物热裂解以及催化剂与载体的相互作用对碳氢化合物催化裂解过程的影响。结果表明：H2对不同碳氢化合物热裂解有着不同的作用,而且几种碳氢化合物的成碳机理也不尽相同,但其成碳过程中都会有C6H6产生。
(2)对基于A1203微球颗粒的CNTs/Al2O3多尺度杂化粒子的可控制备和形成机理进行了研究。制备了三种不同结构的杂化粒子,研究了反应条件和微球颗粒的表面性质对杂化粒子形貌和结构的影响以及各种结构的形成机理。制备了堆栈结构的CNTs/Al2O3纳微米杂化粒子,准原位的研究碳管的生长过程以及堆栈结构中界面的形成机理。将制备的CNTs/Al2O3杂化粒子用于改性水性聚氨酯/丙烯酸酯涂料(PUs)涂料,可使PUs涂料的导电、导热和硬度等多方面的性能得到加强,这种CNTs/Al2O3-PUs复合涂料在航空航天等领域有着重要的应用前景。
(3)对基于板状SiC颗粒的CNTs/SiC多尺度杂化粒子的可控制备和形成机理进行了研究。制备了两种不同结构的杂化粒子,研究了反应条件和板状颗粒的表面性质对杂化粒子形貌和结构的影响以及各种结构的形成机理。将制备的杂化粒子用于改性聚偏氟乙烯(PVDF)聚合物复合材料,研究CNTs/SiC-PVDF复合材料的电学和热学性能,结果表明：杂化粒子的引入可有效的提高复合材料的电学和热学性能,并使其性能具有各向异性的特点,通过改变杂化粒子的含量可以调节此各向异性的差异。对复合材料结构性能关系进行研究表明：在微米范围自组织的CNTs/SiC杂化粒子,可以通过特殊制备的过程,使其在复合材料里宏观取向排列,在水平和垂直方向上形成了不同类型的导通网络,这种导通网络的差异决定了不同方向上性能的差异。
(4)对基于石墨烯(GNs)的CNTs/GNs多维杂化结构的可控制备和形成机理进行了研究。研究了石墨烯的比表面积和反应条件对此多维杂化结构的影响,得到了制备CNTs/GNs多维杂化结构的最佳实验条件。这种CNTs/GNs多维杂化结构可以有效的防止GNs在复合材料里的聚集和堆栈,使得其在改性锂离子电池负极材料和多功能复合材料领域有着潜在的应用前景。
Since their discovery by detailed observations, carbon nanotubes (CNTs) attracted worldwide attention due to unique structure, excellent physical and chemical properties, and many potential applications. In particular, using CNT as an advanced filler material in composites is one of the most realizable industry applications in the short term. The composites prepared by adding CNTs usually exhibit reinforced and multifunctional properties. However, it is difficult to well disperse and distribute CNTs in polymer matrix when fabricating CNTs-based composites, because CNTs are usually entangled and aggregated due to high aspect ratio and nanoscale interface. To well disperse CNTs in composites and retain intrinsic properties of CNTs, we designed some multi-scale and multi-dimension hybrid structures based on self-assembly CNTs, which can significantly improve CNT dispersion in composites and had many other advantages. The morphology and organization mode of CNTs in hybrid structures greatly influenced the properties of composites. Therefore, we studied the effect of experimental parameters and substrate nature on hybrid structures, and the formation mechanism of multi-form hybrid structures was also investigated in detail.In addition, some hybrid structures with special CNT organization were applied to enforce the properties of composites and the corresponding relationship of structure and property was discussed. The main contents of this paper are presented as follows:
(a) The chemical vapor deposition (CVD) process of several hydrocarbons involved was investigated experimentally. The effect of experimental parameters on thermal decomposition and the function of catalyst and substrate in catalytic decomposition of hydrocarbons were studied, respectively. The results indicated that the effect of H2 and the formation mechanism of carbon for these hydrocarbons were different. However, the bezene ring (C6H6) seemed to be a necessary intermediate for carbon formation from hydrocarbons.
(b) The controllable preparation and formation mechanism of multi-scale hybrid structures based on CNTs and Al2O3 spherical particles were studied. The influence of reaction conditions and surface properties of Al2O3 spherical particles on hybrid structures were investigated, respectively. Three special forms of CNTs/Al2O3 hybrid structures were prepared, and the formation mechanism for different hybrid structures was discussed. Stacked CNTs/Al2O3 hybrid structures were prepared to monitor the CNT growth quasi-in situ, and the formation process of the boundary between stacks was discussed. Hybrid structures were used in waterborne acrylic polyurethane (PU) paint to improve its properties (hardness, thermal and electrical conductivity, etc.), and this CNTs/Al2O3-PUS composite shows great potential in the field of aerospace.
(c) The controllable preparation and formation mechanism of multi-scale hybrid structures based on CNTs and SiC plate-like particles were studied. The co-effect of experimental conditions and SiC surface nature on the CNTs/SiC hybrid structures was researched in detail. Two special forms of CNTs/SiC hybrid structures were prepared and the related formation mechanism was discussed. The prepared CNTs/SiC was used in Polyvinylidene Fluoride (PVDF) polymer matrix to fabricate CNTs/SiC-PVDF composites. The results showed that the thermal and electrical conductivities of composites were greatly reinforced and the conductivity was asymmetric in different directions. The direction-related difference can be tuned by the content of hybrid structures in composites. The corresponding the structure-property relationship was analyzed. Perfectly self-assembly CNT array on micro-particles can be arranged directionally in composites by facile fabrication process. As a result, different types of conductive networks were formed in parallel and perpendicular directions, which led to the direction-related property difference.
(d) The controllable preparation and formation mechanism of multi-dimension hybrid structures based on CNTs and graphene nanosheets (GNs) were studied. The effects of surface area of GNs and experimental conditions on hybrid structures were investigated, and the optimal experimental parameters were acquired. This multi-dimension hybrid structure can effectively prevent GNs aggregating and restacking in composites and can be used in the fields of lithium-ion battery and multifunctional composites.
引文
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