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.     

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.     

Mechanical behavior and interphase structure in a silica-polystyrene nanocomposite under uniaxial deformation

The mechanical behavior of polystyrene and a silica-polystyrene nanocomposite under uniaxial elongation has been studied using a coarse-grained molecular dynamics technique. The Young's modulus, the Poisson ratio and the stress-strain curve of polystyrene have been computed for a range of temperatures, below and above the glass transition temperature. The predicted temperature dependence of the Young's modulus of polystyrene is compared to experimental data and predictions from atomistic simulations. The observed mechanical behavior of the nanocomposite is related to the local structure of the polymer matrix around the nanoparticles. Local segmental orientational and structural parameters of the deforming matrix have been calculated as a function of distance from nanoparticle's surface. A thorough analysis of these parameters reveals that the segments close to the silica nanoparticle's surface are stiffer than those in the bulk. The thickness of the nanoparticle-matrix interphase layer is estimated. The Young's modulus of the nanocomposite has been obtained for several nanoparticle volume fractions. The addition of nanoparticles results in an enhanced Young's modulus. A linear relation describes adequately the dependence of Young's modulus on the nanoparticle volume fraction.     

Increased permittivity nanocomposite dielectrics by controlled interfacial interactions

The use of nanoparticles in polymer composite dielectrics has promised great improvements, but useful results have been elusive. Here, the importance of the interfacial interactions between the nanoparticles and the polymer matrix are investigated in TiO₂ nanocomposites for dielectric materials using surface functionalisation. The interface is observed to dominate the nanocomposite properties and leads to a threefold increase in permittivity at volume fractions as low as 10%. Surface functionalisation of the filler nanoparticles with silanes allows control of this interface, avoiding significant degradation of the other important material properties, particularly electrical breakdown strength, and resulting in a material that is demonstrated successfully as an active material in a dielectric elastomer actuator application with increased work output compared to the pure polymer. Although further permittivity increases are observed when the interface regions have formed a percolation network, the other material properties deteriorate. The observation of percolation behaviour allows the interface thickness to be estimated.     

Dynamic mechanical analysis of fumed silica/cyanate ester nanocomposites

Fumed silica particles with average primary particle diameters of 12 and 40 nm were combined with a low viscosity bisphenol E cyanate ester resin to form composite materials with enhanced storage modulus and reduced damping behavior, as evidenced by dynamic mechanical analysis (DMA). The storage modulus increased with volume fraction of fumed silica in both the glassy and rubbery regions, but the increase was more pronounced in the rubbery region. The maximum increase in storage modulus in the glassy region was 75% for 20.7 vol% of 40 nm fumed silica, while the same composition showed a 231% increase in the rubbery storage modulus. Furthermore, decreases in damping behavior were used to estimate the effective polymer-particle interphase thickness. The glass transition temperature of the nanocomposites was not changed significantly with increasing volume fraction.     

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。     

Intercalation/Exfoliation mechanism of hybrid formation in polypropylene/lamellar mesostructured silica nanocomposites

Understanding the optimal processing conditions for the fabrication of polymer nanocomposites is of fundamental importance in designing materials with balance of properties. To understand these conditions in the case of maleic anhydride grafted polypropylene (PP-g-MA)/layered mesostructured silica (LMS) nanocomposites, the effect of temperature, shear rate, and residence time during processing on the structure of the nanocomposites were studied. The results showed that the combination of temperature, residence time, and mechanical shears have strong effect on the structure of the nanocomposites, rather than just interfacial interactions between the polymer matrix and silicate layers. However, interfacial interactions between the polymer matrix and silicate layers primarily play an important role to the intercalation of polymer chains into the silicate galleries. On the basis of our experimental results, a first explanation of the formulation mechanism of PP-g-MA/LMS nanocomposites is proposed. Finally, a general concept of processing conditions for manufacturing of polymer nanocomposites by melt-compounding process in a batch-mixer is described.     

Thermomechanical modeling of polymer nanocomposites by the asymptotic homogenization method

There is much current interest to incorporate nano-scale fillers into polymer matrices to achieve potentially unique properties. Compared with traditional microcomposites, a nanocomposite has a significant large ratio of interface area to volume that results in improved thermomechanical properties. Desired thermomechanical properties of polymer nanocomposites, to achieve the ever-increasing performance requirements, can be obtained by tailoring their microstructures. To this end, computational analyses of the relations between the thermomechanical properties, e.g., Young’s modulus, shear modulus, Poisson’s ratio, yield strength, coefficient of thermal expansion and coefficient of thermal conductivity, in different directions and the microstructures of polymer nanocomposites are performed. The asymptotic homogenization method based on the finite element analysis is used to model the thermomechanical behaviors of different polymer nanocomposites with periodic microstructures. The effects of adding silica, rubber, and clay nanoparticles to epoxy resin as a polymer matrix are analyzed. Mixtures of the nano-particles which differ in volume fraction, material type, size and/or geometry are considered. Some predictions of the thermomechanical properties are compared with experimental data in order to verify the applied modeling technique as an effective design tool to tailor optimal microstructures of polymer nanocomposites.     

Structure evolution of conductive polymer composites revealed by solvent vapor induced time-dependent percolation

The authors of this paper synthesized a series of amphiphilic triblock copolymers of polystyrene-b-poly(ethylene glycol)-b-polystyrene (PS-PEG-PS) having different PEG/PS ratios with nearly identical molecular weights of the entire copolymers. The interfacial interactions in the composites consisting of carbon black and the copolymers can thus be tailored. When these conducting composites are exposed to certain solvent vapors, their electrical resistances greatly increase, showing the gas sensitivity. The present work indicated that this switching behavior is controlled by the structural relaxation of the composites because matrix swelling acts as the main mechanism. The response time has been correlated with absolute temperature by Arrhenius equation, and the estimated activation energy reflects mobility of the fillers involved in the solvent induced expansion of the surrounding polymer. Therefore, by using the gas sensibility of the conductive composites, the structure evolution of the composite materials in solid state and the effect of filler/matrix interfacial interaction on the relaxation property of the matrix polymer has been inspected. It was found that lower activation energy represents stronger interfacial interaction in case good solvent of the matrix was used for the test.     

Stochastic analysis of the fracture toughness of polymeric nanoparticle composites using polynomial chaos expansions

The fracture energy is a substantial material property that measures the ability of materials to resist crack growth. The reinforcement of the epoxy polymers by nanosize fillers improves significantly their toughness. The fracture mechanism of the produced polymeric nanocomposites is influenced by different parameters. This paper presents a methodology for stochastic modelling of the fracture in polymer/particle nanocomposites. For this purpose, we generated a 2D finite element model containing an epoxy matrix and rigid nanoparticles surrounded by an interphase zone. The crack propagation was modelled by the phantom node method. The stochastic model is based on six uncertain parameters: the volume fraction and the diameter of the nanoparticles, Young’s modulus and the maximum allowable principal stress of the epoxy matrix, the interphase zone thickness and its Young’s modulus. Considering the uncertainties in input parameters, a polynomial chaos expansion surrogate model is constructed followed by a sensitivity analysis. The variance in the fracture energy was mostly influenced by the maximum allowable principal stress and Young’s modulus of the epoxy matrix.     

纤维增强聚合物复合材料的三相动态粘弹模型及其界面结构参数

本文以复合材料界面作为中间相(界面相),借助Takayanagi的两相共混模型及Ziege的修正公式,导出了单向纤维增强聚合物复合材料的三相动态粘弹共混模型,得到了界面层的几何结构混合参数(r_i、V_i、λ_L及中间参数B)及界面相的各个动态粘弹性参数.这些参数可以根据复合材料的动态粘弹性实验结果求得,利用上述导出的模型,对玻璃纤维单向增强不饱和聚酯的动态粘弹性进行了试验,结果表明,随着温度的变化,界面相的厚度r_i、体积分数V_i及动态粘弹参数也会发生一定的变化,存在着界面相与基体相之间的相互转变.      

Highly loaded silicone nanocomposite exhibiting quick thermoresponsive optical behavior

Bulk silicone nanocomposites with thermoresponsive optical behavior were fabricated using silica nanoparticle fillers within a cross-linked silicone matrix. Silica nanoparticles (25 nm diameter) were surface-modified, allowing for even distribution at 6-24 wt % within and covalent bonding to the silicone matrix. Utilizing the temperature-dependent match/mismatching of the refractive indices of the silica nanoparticle filler and the silicone matrix, bulk nanocomposites are highly transparent at room temperature and demonstrate significant increases in opacity with increasing temperature up to 100-150 °C. Such a response could be cycled quickly and repeatedly with no detrimental effect on the material.     

Composites of polypropylene melt blended with synthesized silica nanoparticles

Spherical and layered silica nanoparticles synthesized by the sol-gel method were melt blended with a polypropylene matrix in order to quantify their effect on thermal and mechanical behaviours of the resulting polymer composites. Transmission electron microscopy images showed that spherical nanoparticles were dispersed in the polymer matrix whereas layered particles display tactoid and agglomerated structures. By thermogravimetric analysis, it was observed that independent of the particle aspect ratio, the nanofillers render larger thermal degradation stabilization to the polymer matrix under oxidative conditions than under inert atmosphere. Noteworthy, the largest improvements were found by using spherical nanoparticles in presence of a compatibilizer. These results allow the conclusion that the physical/chemical adsorption of the volatile products on the particle surface during the oxidative degradation is the plausible mechanism behind the thermal stabilization. Tensile stress-strain tests otherwise showed that composites with spherical nanoparticles can display similar or even larger elastic modulus than composites with layered particles showing that the polymer/particle entanglement could be the mechanism for the load transfer in these nanocomposites.     

Molecular theories of polymer nanocomposites

Significant progress towards the development of microscopic predictive theories of the equilibrium structure, polymer-mediated interactions, and phase behavior of polymer nanocomposites has been made recently based on liquid state integral equation, density functional, and self-consistent mean field approaches. The basics of these three theoretical frameworks are summarized, and selected highlights of their recent applications discussed for spherical, nonspherical, and polymer-grafted nanoparticles dissolved in athermal and adsorbing concentrated solutions and homopolymer melts. The role of nanoparticle size, volume fraction, and interfacial cohesive interactions is emphasized, especially with regards to their influence on filler dispersion and spatial ordering via entropic depletion attraction, polymer adsorption-mediated steric stabilization, and local bridging of nanoparticles. Some of the many remaining theoretical challenges and open fundamental questions are summarized.     

碳纳米管/聚苯乙烯复合材料的制备及流变行为

强酸氧化法对多壁碳纳米管(CNTs)进行了纯化,用FT-IR和TEM对CNTs的纯化效果和形态进行了表征。制备了CNTs/PS纳米复合材料,在ARES-RFS型旋转流变仪上对复合材料的动态流变行为进行了研究。结果表明,与纯聚合物相比,CNTs的加入使复合材料熔体呈现出由类液体粘弹行为向类固体粘弹行为的转变,表现为在低剪切速率作用下,纳米复合材料的黏度和储存模量对频率的依赖性变小。     

Pseudo-percolation: Critical volume fractions and mechanical percolation in polymer nanocomposites

Polymer nanocomposites offer a basis for the design and manufacture composite materials with greatly enhanced properties at relatively low volume fractions of the included phase. One underlying mechanism, thought to contribute to these properties is the presence of an interfacial region, ∼15 nm thick, between the polymer matrix and included particles. The size of the interface makes relatively little contribution to the effective properties of composites with micro-sized particles but, because its thickness is comparable to the size of the nanoscaled included phase, its potential impact within nanocomposites is much greater. In particular, percolated nano-microstructures may result at volume fractions below theoretical thresholds, due to connectivity achieved through rod-interface-rod, or ‘pseudo-percolation’, contact. In this work the influence of the interface layer is incorporated into estimates of critical volume fraction through an excluded volume model. Results show a significant reduction in the range of critical volume fractions. These values are incorporated into a mean-field micromechanics model to illustrate mechanical percolation through changes in predicted effective elastic composite properties.     

Enhancing the thermomechanical behaviour of poly(phenylene sulphide) based composites via incorporation of covalently grafted carbon nanotubes

The thermal and thermomechanical properties of poly(phenylene sulphide) (PPS) based nanocomposites incorporating a polymer derivative covalently anchored onto single-walled carbon nanotubes (SWCNTs) were investigated. The grafted fillers acted as nucleating agents, increasing the crystallization temperature and degree of crystallinity of the matrix. They also enhanced its thermal stability, flame retardancy, glass transition (T_g) and heat deflection temperatures while reduced the coefficient of thermal expansion at temperatures below T_g. A strong rise in the thermal conductivity, Young’s modulus and tensile strength was found with increasing filler loading both in the glassy and rubbery states. All these outstanding improvements are ascribed to strong matrix-filler interfacial interactions combined with a compatibilization effect that results in very homogeneous SWCNT dispersion. The results herein offer useful insights towards the development of engineering thermoplastic/CNT nanocomposites for high-temperature applications.     

Zirconium tungstate/cyanate ester nanocomposites with tailored thermal expansivity

The dimensional stability of polymer matrix composites can be enhanced by reducing the mismatch in the coefficient of thermal expansion (CTE) between the high CTE polymer matrix and low CTE fiber reinforcements, which leads to development of residual stresses and matrix microcracking. A potential strategy to diminish these residual stresses involves development of polymer nanocomposites with well dispersed nanoparticles that reduce the extent of mismatch in CTE. In this work, we explore the potential for development of bulk polymer nanocomposites with tailored thermal expansivity through incorporation of zirconium tungstate nanoparticles that are characterized by a negative CTE in a unique low viscosity bisphenol E cyanate ester (BECy) thermosetting polymer matrix. Incorporation of up to 10 vol.% whisker-like nanoparticles, synthesized by a hydrothermal method, results in a 20% reduction in the CTE of the polymer matrix. However, the nanoparticles exert a dramatic catalytic effect on the cure reaction of BECy resin and subsequently decrease the onset temperature of the glass transition for the cured polymer network, at high filler loadings.     

Effects of organic chain length of layered zirconium phosphonate on the structure and properties of castor oil-based polyurethane nanocomposites

Three novel organic–inorganic hybrid molecules, layered zirconium phosphates or phosphonates, were synthesized. To study the effects of organic chain length of them on the structure and properties of polymer nanocomposites, the polyurethane/α-zirconium phosphate (PU/ZrP), polyurethane/zirconium 2-aminoethylphosphonate (PU/ZrAEP) and polyurethane/zirconium 2-(2-(2-(2-aminoethylamino)ethylamino)ethylamino) ethylphosphonate (PU/Zr(AE)₄P) nanocomposites were prepared, and characterized by Fourier Transform Infrared (FT-IR) spectroscopy, wide-angle X-ray diffraction (XRD), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC) and tensile testing. It was revealed that morphological, mechanical, and thermal properties of these nanocomposites were strongly dependent on the organic chain length of the layered zirconium phosphonates. The results showed that the fillers with longer chain length exhibited better dispersion in the PU matrix. As expected, the mechanical properties and water resistance were improved with the increasing of organic chain length of fillers, which attributed to better interfacial adhesion between fillers and PU matrix.