摘要
本论文利用低熔点金属（Low Melting Point Metal, LMPM）、碳纳米管等导电填料制备得到导电/抗静电聚合物复合材料及纤维。通过四种不同的物理或化学的方法改性控制导电填料在聚合物中的形貌，研究聚合物纳米复合材料微观形貌与性能之间的关系。主要工作如下：
1、提出了导电/抗静电聚合物复合纤维制备的新方法和新原理。采用电导率高、易加工的LMPM作为导电填料，通过熔融混合以及固相拉伸等方法，制备聚丙烯/LMPM和聚丙烯/纳米颗粒/LMPM导电/抗静电复合纤维。
在合适的温度区间内，通过聚合物纤维固相拉伸，金属颗粒在聚合物纤维内部原位发生微纤化形变。通过微观结构的表征发现，随着拉伸倍率的提高，金属纤维直径减小、长径比增加，相邻金属纤维间距不断减小，并且金属纤维沿着纤维拉伸方向平行分布。聚合物/LMPM复合纤维具有其电阻率随着拉伸倍率的提高而降低的性质。与未含有LMPM纤维的复合纤维比较，含有超细金属纤维的复合纤维的强度和断裂伸长率都有所提高。而传统导电/抗静电聚合物纤维由于拉伸过程中导电填料间距增大，导电网络受到破坏，导致纤维中导电填料含量高，聚合物纤维断裂伸长率极低，并且不能通过拉伸取向提高纤维强度。
通过在复合纤维中添加碳纳米管和纳米蒙脱土显著降低了金属颗粒粒径。制备了含有粒径更细、分布更均匀的超细金属纤维的聚合物/纳米颗粒/金属复合纤维，并且该纤维获得了更加优异的电性能和力学性能。
2、提出了纳米粒子阻碍金属液滴凝并理论，制备了含有超细金属颗粒的超低逾渗值导电复合材料。利用超细粉末橡胶和碳纳米管，将平均粒径为30μm的金属颗粒原位转化为平均粒径为0.93μm的超细金属颗粒。由于碳纳米管与金属颗粒之间较低的接触电阻以及协同导电效应，显著的降低了复合材料的导电逾渗值。与普通导电复合材料相比，含有超细金属颗粒的导电复合材料的导电逾渗值仅为0.25vol%。并且当碳管和金属含量仅为1vol%和1.96vol%时，复合材料的体积电阻率降为89cm。通过进一步研究材料拉伸形变-电性能发现，在大拉伸形变时，含有超细金属颗粒的复合材料具有优良的电学稳定性能。
3、本章利用传统的熔融加工方法，通过控制碳纳米管在二元全硫化热塑性弹性体中选择性分布，制备出具有三种不同微观结构的导电全硫化热塑性弹性体，即碳纳米管分布于两相界面处的全硫化热塑性弹性体、碳纳米管分布于基体中的全硫化热塑性弹性体和碳纳米管分布于分散相中的全硫化热塑性弹性体。通过比较三种导电全硫化热塑性弹性体的性能发现，在保持优良的回弹性条件下，碳纳米管分布于两相界面处的全硫化热塑性弹性体具有最低的逾渗值和最为优异的电性能。通过微观结构的详细分析，推论出二元全硫化热塑性弹性体的理想导电模型：导电粒子优先包裹橡胶相形成导电壳层；随着导电粒子含量的增加，导电粒子逐渐分散于基体中，起到连接各个导电壳层的作用；当导电粒子的含量进一步增加，整个体系中开始形成导电网络。
4、为了增强聚合物材料，采用改性碳纳米管填充聚乙烯醇并制备聚乙烯醇/聚乙烯醇接枝碳纳米管复合材料。为了改善碳纳米管与聚乙烯醇界面作用力，在酸化碳纳米管表面，利用二元异氰酸酯作为桥接试剂接枝聚乙烯醇分子，并制备得到聚乙烯醇接枝碳纳米管。通过分析材料结晶行为和偏振拉曼光谱证明聚乙烯醇接枝碳纳米管与基体之间产生了强相互作用，提高了基体与碳纳米管之间应力传递的效率。力学性能测试表明，相对于未改性碳纳米管，当仅含有0.9wt%改性碳纳米管的聚乙烯醇/聚乙烯醇接枝碳纳米管复合材料的拉伸强度和杨氏模量分别提高了160.7%和109.2%。
In this thesis, the Low melting point metal (LMPM) and Carbonnanotubes (CNT) as conductive fillers had been used to prepareconductive/anti-static polymer composites and fibers. Four physical/Chemicalmethods were designed to control the morphology of composites. Therelationship between morphology and properties in the composite was studiedin detail.
The main results of the thesis were as follows:
(1) A new method and theory for preparing conductive/anti-staticpolymer fiber had been proposed. LMPM, due to its high electricalconductivity and easy processability, was employed as the conductive filler toprepare an anti-static polypropylene (PP)/in-situ Ultra-fine metal fibers(UFMF) and/or PP/CNT/UFMF composite fiber via melt blending and thensolid phase drawing processes. In appropriate temperature range, LMPMpowders were in-situ converted into UFMF without aggregation or oxidationin anti-static polymer fibers. The axes of UFMF and polymer fiber were inparallel and the interval of UFMFs decreased obviously, which promoted thepercolated network. In addition, the PP/UFMF fibers showed an increase inconductivity after solid phase drawing, in contrast to PP/CNTs fiber. Thepolymer fiber containing UFMF obtained the better mechanical propertiesthan the fiber without UFMF. Surprisingly, the diameter of UFMF decreasedwith incorporation of nano-filler, such as CNT and Montmorillonoid (MMT).The conductivity and mechanical properties of PP/nano-filler/UFMF composite fiber containing smaller and more uniform UFMF were better thanthat of the PP/UFMF composite fiber.
(2) Theory for nanoparticles-hindering coalescence of LMPM drops wasproposed. A conductive polymer/Ultra-fine full-vulcanized powdered rubber(UFPR)/CNT/in-situ ultra-fine metal particles (UFMP) composite withultra-low percolation threshold was prepared via melt blending. Incorporationof UFPR and CNT hindered the coalescing of metal particles and caused ashift to the breakup direction in the breakup/coalescence equilibrium of metalparticles. The prime metal particles with a diameter of about26.4μm werein-situ converted into the UFMPs with a diameter of about932nm. Theconductive network of carbon nanotubes had been perfected and thepercolated threshold decreased due to in-situ formation of UFMPs anddecrease of contact resistance between CNTs and UFMPs. The percolatedthreshold of this composite was only0.25vol%CNT and the volumeresistance of this composite with only1vol%carbon nanotubes and1.96vol%ultra-fine metal particles can reached to89cm. Moreover, the conductivecomposites with UFMP kept more stable electrical response under stretchablestrain than the conductive composite without UFMP.
(3) Three types of conductive thermoplastic vulcanizates (TPVs) wereprepared by blending PP, CNT, and UFPR. The CNT locations were differentin these three types of TPVs, i.e., CNT were localized in polymer matrix, inUFPR dispersed-phase, or mainly in the interface. It had been found that TPVwith CNT localized mainly in the interface had the lowest conductivepercolation threshold among these three types of TPVs. Moreover, theconductive TPV possessed good mechanical properties. An ideal morphologyfor the conductive TPV had been found, i.e., most of CNT were localized inthe interface to form a conductive shell covered the rubber particle and a fewof CNTs were dispersed in polymer matrix as bridges to connect theconductive rubber particles to form conductive pathway.
(4) The poly (vinyl alcohol)(PVA)-based composite embedded withmodified CNT were prepared. To enhanced the interfacial interaction between CNT and PVA, acid-treated CNTs were grafted with PVA chains,compatibilizing CNTs and the matrix. The better dispersion of CNTs in PVAmatrix was obtained by the introduction of Diphenylmethane4,4’-diisocyanate (MDI) reaction bridges and then PVA molecules onto thesurface of CNTs. Moreover, strong interaction between CNTs and PVA matrixwas evidenced through the measurement results of the melting behavior,polarized Raman measurement, and non-isothermal crystallization behavior ofthe composites. Owing to the reinforcement of CNTs, the tensile strength andmodulus of PVA composite containing0.9wt%CNT were increased by160.7and109.2%, respectively, compared to neat PVA.
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