聚合物/热塑性弹性体/纳米无机粒子三元复合材料的增韧增强研究进展

介绍了聚合物/热塑性弹性体/纳米无机粒子三元复合材料的形态结构及增韧机理,分析了热塑性弹性体、纳米无机粒子、加工工艺、界面性能4个方面对聚合物/热塑性弹性体/纳米无机粒子三元复合材料形态和性能的影响。热塑性弹性体和纳米无机粒子对聚合物有协同增韧增强作用,加料顺序是形态结构的最主要影响因素,聚合物的力学性能非常依赖热塑性弹性体和纳米无机粒子在聚合物中的存在形态。最后,展望了该体系未来的研究方向。     

聚合物纳米复合材料界面结构的表征

聚合物中加入纳米粒子可以制得性能更加优异的纳米复合材料,其中纳米粒子和聚合物基体间的界面结构对纳米复合材料的性能起着重要作用。综述了近些年来聚合物纳米复合材料中界面结构的表征手段,如红外光谱(FTIR)、核磁共振技术(NMR)、热重(TGA)、电子显微镜、原子力显微镜(AFM)、X射线光电子能谱(XPS)、小角中子散射(SANS)及小角X射线散射(SAXS)等,并对这一领域的研究进行了展望。     

SiO2的功能化改性及其与聚合物基体的界面研究进展

纳米二氧化硅(SiO_2)作为一种最常用的无机纳米材料,受到了各个领域研究者的广泛关注且已得到实际应用。以纳米SiO_2作为改性填料,得到的聚合物纳米复合材料兼具了聚合物基体和纳米SiO_2二者的优点,因而表现出优异的力学性能、热学性能、光学性能以及化学稳定性等。但是纳米SiO_2表面富含大量活性硅羟基,极易团聚,用一般方法难以实现其在纳米尺度上的均匀分散以及与高分子基体材料间良好的界面粘结。因此,在制备纳米SiO_2改性的聚合物基纳米复合材料前,研究者们常通过对SiO_2进行表面改性,以改善其与聚合物基体的界面相容性及其在聚合物基体中的分散性,并赋予其一定的功能性。目前,纳米SiO_2的改性方法有很多,总的来说主要为物理改性和化学改性,而根据改性剂的种类不同,又可以分为有机改性、无机改性和杂化改性三种。聚合物/纳米SiO_2复合材料的优异性能不仅取决于有机聚合物和无机纳米SiO_2两组分的性能,还取决于两者间的界面结构和形态特征。尽管界面相的体积含量只占总体积含量中很少的一部分,但是界面间的相互作用、界面处聚合物结构与基体结构的差异、界面相微观形貌的变化等都会使整个复合体系的宏观性能发生明显的改变。因而针对有机聚合物与无机纳米SiO_2间的界面研究对于纳米复合材料性能的优化设计具有重要的科学意义。近年来,关于聚合物与无机纳米粒子之间的界面研究主要集中在两个方面:一方面是聚合物及无机纳米粒子表面的物理、化学性质对界面处性能的影响;另一方面是聚合物基体与无机纳米粒子之间的界面相互作用对复合材料性能的影响。目前,常通过现代仪器分析技术测试界面相的微观形貌(如粗糙程度、厚度等)及化学结构(如化学键合方式、键能等),或结合分子动力学模拟阐明分子集合体结构以及相互间的微观作用机理,从理论角度更准确地解释界面性能和界面行为,为复合材料的优化设计提供理论基础和新方法。本文归纳了有机改性、无机改性和杂化改性三种方法在纳米SiO_2的功能化方面的研究进展,讨论并对比了不同改性方法的优势和缺点,较全面地综述了当前现代仪器分析表征和分子动力学模拟在聚合物/SiO_2界面作用研究方面的最新进展,最后展望了纳米SiO_2与聚合物基体界面作用未来研究的工作重点。     

Characterization of Interracial Structure of Polymer Nanocomposites

聚合物中加入纳米粒子可以制得性能更加优异的纳米复合材料,其中纳米粒子和聚合物基体间的界面结构对纳米复合材料的性能起着重要作用.综述了近些年来聚合物纳米复合材料中界面结构的表征手段,如红外光谱(FTIR)、核磁共振技术(NMR)、热重(TGA)、电子显微镜、原子力显微镜(AFM)、X射线光电子能谱(XPS)、小角中子散射(SANS)及小角X射线散射(SAXS)等,并对这一领域的研究进行了展望.     

环氧树脂及其复合材料交联结构和宏观性能的分子模拟研究与进展

分子模拟技术能够从原子尺度探究聚合物体系的反应机制和内部结构的微观参数,从而讨论对聚合物基复合材料的宏观性能等方面的影响因素。本文围绕环氧树脂基复合材料的材料体系设计和结构-性能的关联性研究,总结了当前国内外应用分子模拟技术针对环氧树脂基体交联网络结构、纳米粒子增强环氧树脂机制的研究结果。同时,介绍了国内外运用分子模拟方法,针对碳纤维/环氧树脂复合材料的微观界面及结构设计等科学问题开展研究的最新成果,并提出了分子模拟方法在高性能聚合物基复合材料未来发展中的指导意义和研究策略。      

修饰纳米CdS/聚合物的界面相互作用与光学性能

采用微乳液法结合原位表面修饰合成了纳米尺度的硫化镉粒子,采用溶液共混和静态铺膜方法制备了纳米粒子/聚合物复合体系,以研究纳米粒子与聚合物间的界面作用.结果表明,经修饰的纳米CdS粒子比较均匀地分散于聚合物基体内,纳米粒子与聚合物基体间存在较强的相互作用.根据复合体系的紫外-可见吸收光谱和荧光光谱,分析了表面修饰(表面修饰剂种类、表面修饰剂用量等)对纳米粒子的分散以及复合体系界面特性的影响,证实了表面修饰剂具有促进纳米粒子分散和消除粒子表面缺陷的作用.     

PMMA/纳米SiO2纳米复合材料的制备和界面研究

用硅烷偶联剂KH570对纳米SiO2进行修饰改性,采用原位分散聚合法制备了PMMA/纳米SiO2纳米复合材料,用溶解实验、力学性能、SEM和DMA等方法对纳米SiO2粒子和PMMA基体之间的界面相容性进行了表征和研究,由拉伸强度计算出来界面相互作用参数B.结果表明:SiO2在基体中可能起到了交联点的作用;改性后的氧化硅与聚合物基体形成强的界面结合;随着纳米粒子含量的增加,粒子和聚合物基体之间有效的界面相互作用越强.     

核-壳式纳米Al2O3 / PS 复合粒子改性聚苯乙烯的选区激光烧结实验研究

针对纳米粒子易团聚的特点, 利用乳液聚合方法制备纳米Al₂O₃ / PS 复合粒子。用TEM、FTIR 对复合粒子结构进行了表征。结果表明, 所制备的复合粒子具备以纳米氧化铝为核、以聚苯乙烯为壳的核2壳式结构, 而且包覆层厚度大约为10～20 nm。用复合粒子改性选区激光烧结制备聚苯乙烯基纳米复合材料, 通过SEM 和FE2SEM 研究纳米复合材料烧结体的显微结构, 发现纳米粒子较好地分散在聚合物基体中, 且纳米氧化铝与聚合物基体之间的界面相容性和粘结性较好, 烧结体结构较致密。      

石墨烯基磁性纳米复合材料的制备与微波吸收性能研究进展

本文首先概述了石墨烯独特的物理结构和优异的力学、热学、电磁学性能,然后综述了石墨烯基磁性纳米复合材料的制备方法,并分析了其微波吸收机理,最后结合国内外研究现状展望了石墨烯基磁性纳米复合材料制备与微波吸收性能研究的发展方向,指出揭示复合材料的界面结合机制,调控复合材料的微观形貌,探索石墨烯与磁性纳米粒子微波吸收的协同效应将成为今后研究的重点和热点。     

纳米粒子在润滑材料中的应用进展

介绍了纳米润滑粒子的制备方法,探讨了纳米粒子的润滑机理,包括膜作用机理、类滚珠作用机理和表面优化作用机理.着重综述了纳米粒子在润滑材料中的应用,具体包括:纳米无机粒子可作为添加剂在润滑油、聚合物基复合材料中起抗磨、减摩作用;纳米粒子应用于非聚合物基复合涂层,可形成一种根据环境自我调节的活泼纳米复合涂层,此涂层具有广泛的应用前景.     

Candidate mechanisms controlling the electrical characteristics of silica/XLPE nanodielectrics

The incorporation of silica nanoparticles into polyethylene has been shown to increase the breakdown strength significantly compared to composites with micron scale fillers. Additionally, the voltage endurance of the nanocomposites is two orders of magnitude higher than that of the base polymer. The most significant difference between micron-scale and nano-scale fillers is the large interfacial area in nanocomposites. Because the interfacial region (interaction zone) is likely to be pivotal in controlling properties, this paper compares the behavior of nanoscale silica/cross-linked low density polyethylene nanocomposites with several silica surface treatments. In addition to breakdown strength and voltage endurance, dielectric spectroscopy, absorption current measurements, and thermally stimulated current determinations (TSC) were performed to elucidate the role of the interface. It was found that a reduction in the mobility in nanocomposites as well as a change in the defect size may be key to explaining the improvement in the properties.     

The role of interfacial interactions on the glass-transition and viscoelastic properties of silica/polystyrene nanocomposite

Filler surface properties and polymer-filler interactions have dominate influence on viscoelastic behavior of polymeric matrix composites. When the filler-filler spacing is on the order of the polymeric matrix molecular size, fillers may agglomerate through direct short-range interactions, also by overlapping of interfacial layers of neighboring fillers. In this work the effect of interfacial layer on the viscoelastic properties of silica/polystyrene composite was investigated.The Si/Ps nanocomposites were prepared by solution mixing method, and dynamic rheometry was employed to determine the viscoelastic behavior in the melt state. Experimental results show that, addition of silica nanoparticles to polystyrene matrix would increase the glass-transition temperature of polymer. This increasing will be accelerated by presence of nanoparticles with more filler-polymer adhesion energy, because of more interfacial layer volume fraction. It is helpful in evaluating the volume fraction and equivalent thickness of interfacial layer in polymer nanocomposites. Likewise it is shown that, the dynamic moduli of nanocomposite is enhanced associated with the increase in the glass-transition temperature. This study implies that the main source of increment in both dynamic modulus and glass-transition temperature of polymer nanocomposites is the presence of the immobilized interfacial layer and the secondary filler network.     

Model polymer nanocomposites provide an understanding of confinement effects in real nanocomposites

Owing to the improvement of properties including conductivity, toughness and permeability, polymer nanocomposites are slated for applications ranging from membranes to fuel cells. The enhancement of polymer properties by the addition of inorganic nanoparticles is a complex function of interfacial interactions, interfacial area and the distribution of inter-nanofiller distances. The latter two factors depend on nanofiller dispersion, making it difficult to develop a fundamental understanding of their effects on nanocomposite properties. Here, we design model poly(methyl methacrylate)-silica and poly(2-vinyl pyridine)-silica nanocomposites consisting of polymer films confined between silica slides. We compare the dependence of the glass-transition temperature (Tg) and physical ageing on the interlayer distance in model nanocomposites with the dependence of silica nanoparticle content in real nanocomposites. We show that model nanocomposites provide a simple way to gain insight into the effect of interparticle spacing on Tg and to predict the approximate ageing response of real nanocomposites.     

橡胶纳米复合材料计算机模拟研究进展与挑战

总结了作者课题组采用分子动力学模拟研究橡胶纳米复合材料目前取得的主要进展,包括不同几何形状的纳米颗粒在橡胶基体中的分散机理、颗粒与橡胶分子链间的界面结合(聚合物玻璃化层是否存在)、颗粒对应力应变增强机理、碳纳米弹簧的引入对橡胶粘弹性的调控以及橡胶纳米复合材料非线性行为(Payne效应)产生的机理。模拟结果表明,存在一个最佳界面相互作用与接枝密度以实现纳米颗粒均匀分散;对于片状颗粒,在类似氢键界面相互作用时,存在聚合物玻璃化层。静态力学增强来自于两个方面:一是颗粒诱导分子链取向与排列,二是分子链吸附临近颗粒形成桥链在大变形下的有限链伸长。同时发现,碳纳米弹簧的加入会明显降低复合材料的滞后损失,并且得出纳米颗粒直接接触聚集与由分子链同时吸附多个颗粒成网对Payne效应非线性行为均有贡献。这些基础问题的澄清,将为制备动静态力学性能兼顾的橡胶纳米复合材料提供重要科学依据与理论指导,进而实现我国轮胎制品的高性能化与绿色化。最后针对橡胶纳米复合材料多层次多尺度结构与性能关系,简要评述了计算机模拟研究存在的挑战。     

纳米SiO2增韧增强聚丙烯的界面效应与逾渗行为

报道了聚苯乙烯辐射接枝纳米二氧化硅微粒(SiO₂-g-PS)填充聚丙烯(PP)的增强增韧作用,并从界面效应和逾渗行为的角度对此类复合材料的力学行为进行了分析。结果表明,接枝纳米微粒填充入聚合物时所形成的微粒/聚合物复合颗粒可以整体发挥协同作用,带来较强的界面效应,并有可能导致双逾渗行为,从而有利于发挥纳米微粒的特殊性能。     

Electrical transport behaviour of silver–PMMA nanocomposite films at low temperature

In this study, the silver nanoparticles, capped with oleylamine, were embedded in polymethylmethacrylate (PMMA) using sonication to fabricate Ag–PMMA nanocomposites. The well-dispersed nanocomposite samples are analysed using UV-Vis absorption spectroscopy, atomic force microscopy and small angle X-ray scattering. The interfacial interaction of Ag nanoparticles and PMMA polymer is investigated using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. It is concluded that a ligand-exchange process occurs when capped silver nanoparticles are incorporated in PMMA polymer. Electrical resistivity of nanocomposite samples was measured by a four-probe technique in the 70–300?K range. The nanocomposites showed a transition with onsets at ～230 and ～160?K. They exhibited a semiconductor-like conductivity at higher temperatures, a rapid metallic conductivity at middle range and nearly temperature independent conductivity at lower temperatures.     

Thermally assisted semiconductor-like to insulator transition in gold-poly(methyl methacrylate) nanocomposites

Gold-polymethylmethacrylate (PMMA) nanocomposites were fabricated by mixing gold nanoparticles capped with oleylamine in polymethylmethacrylate. The samples were analysed using UV-vis absorption spectroscopy, transmission electron microscopy, small angle x-ray scattering, Fourier transform infrared spectrometry (FTIR) and x-ray photoelectron spectroscopy (XPS). Electrical resistivity of nanocomposite samples was measured by a four-probe technique in the 70-300?K range. The nanocomposites showed a transition with an onset at ～160-165?K. They exhibited a semiconductor-like conductivity at higher temperatures and nearly temperature independent conductivity at lower temperatures. The interfacial interaction of Au nanoparticles and PMMA polymer is investigated using FTIR and XPS. A ligand-exchange process occurs when capped gold nanoparticles are incorporated in PMMA polymer.     

Direct Detection of Local Electric Polarization in the Interfacial Region in Ferroelectric Polymer Nanocomposites

Ferroelectric polymer nanocomposites are widely used in capacitive energy storage, electrocaloric refrigeration, and mechanical energy harvesting due to their exceptional electric polarization property and ease of fabrication. It is generally considered that the abnormal performance of ferroelectric nanocomposites stems from the interfacial region between the polymer matrix and embedded nanoparticles. However, direct evidence of the distinct local electric polarization property at the interfacial region is not yet accessible. Herein, a modified Kelvin probe force microscopy (KPFM) method with nanoscale spatial resolution is reported for direct detection of local polarization property at the matrix/particle interface in ferroelectric nanocomposites. Typical ferroelectric nanocomposites are studied using the present method. It is quantitatively probed that the electric polarization at matrix/particle interfacial region is higher than the polymer matrix under applied electric fields. Taking into account the enhanced local electric polarization gauged by the modified KPFM, the dielectric property of ferroelectric polymer nanocomposites matches with bulk experimental characterizations, indicating that the established method is reliable. It is anticipated that the present method, opening up new possibilities in understanding the matrix/particle interfacial region, may help with judicious design and engineering of high‐performance ferroelectric polymer nanocomposites.