活性填料在先驱体转化法纤维增强陶瓷基复合材料中的应用 Ⅰ.复合材料的致密化模型

在先驱体转化陶瓷基复合材料的制备中,坯体在裂解前后的体积发生变化。引入体系体积收缩率参数,对单一先驱体转化纤维增强陶瓷基复合材料致密化模型进行了修正。同时,分别对含惰性填料和/或活性填料的先驱体浆料浸渍-裂解纤维增强陶瓷基复合材料致密化进行了模型分析。从理论上揭示了复合材料的浸渍-裂解周期与材料的理论密度和理论孔隙率之间的关系。当先驱体浆料中含有活性填料时,复合材料的理论密度和理论孔隙率与活性填料的反应陶瓷产率、反应密度比、体积收缩率有密切的数学关系。在先驱体中引入活性填料比引入惰性填料能更为有效地提高材料的密度,降低材料的孔隙率。     

Work of adhesion influence on the rheological properties of silica filled polymer composites

As the work of adhesion, W _a, increases between a silica filler surface and a polymer matrix, the dynamic viscosity and the shear modulus of the composite material increase. The logarithms of these properties decrease linearly as W _a decreases. At lower dynamic test frequencies, a change in W _a has a more dramatic impact on these properties than at higher frequencies. An “effective silica particle size” model can be used to explain why W _a affects the viscosity and the shear modulus of a composite. According to that model, the thickness of the interphase layer increases as the W _a increases. An increase in effective particle size decreases the “free” polymer volume, and the decrease free volume polymer causes both the viscosity and the shear modulus to increase. Increasing the dynamic test frequency releases some of the immobilized polymer from the filler surface which causes the effective particle size to decrease. As the effective particle size decreases because of the increased testing frequency and approaches the mean size of the original filler, the impact of the W _a value on viscosity and shear modulus should decrease. However, the friction experienced between the filler interphase and the polymer, the so called “skin friction”, depends on the magnitude of W _a and the more general term, bond energy density (BED). The skin friction determines the viscosity of the composite, particularly at lower frequencies. Higher W _a values induce higher skin friction and thereby higher flow resistance (viscosity) as polymer chains move along the filler surface.     

Failure processes in particulate filled polypropylene

In this paper the common degradation effect of silicon oxide filler on fracture strain and fracture toughness of isotactic polypropylene is investigated by analysing the failure processes in the composite material by microscopic methods. Experiments demonstrate that, although fracture of the polymer regions absorbs considerable energy by plastic deformation, void formation and cracking of the interface between the polymer and the filler usually requires very little energy. These weak interfaces do not resist cracking and are the cause of brittleness in particulate filled systems. The crucial parameters influencing the fracture data of the composite were found to be the volume fraction of the filler and the interfacial adhesion between polymer matrix and particles. As the interfacial fracture energy is usually much smaller than the polymer fracture energy, the composite toughness drops when filler is added. Using a model which describes the individual steps of crack formation and final fracture, an attempt is made to explain the decrease of crack resistance of the polymer matrix with increasing filler fraction and to calculate the fracture energy of the composite by introducing partial values of crack resistance of the matrix and the interface, respectively. In addition, it is discussed how a coarse spherulitic morphology of the matrix, as produced by isothermal crystallization from the melt, can modify this behaviour.     

Enhanced dielectric properties and energy storage density of surface engineered BCZT/PVDF-HFP nanodielectrics

Polymer nanocomposites have proved to be promising energy storage devices for modern power electronic systems. In this work we have studied the dielectric properties and dielectric energy storage densities of 0–3 type BCZT/PVDF-HFP polymer nanocomposites with different filler volume concentrations. BCZT nanopowder was synthesized by solgel method through citrate precursor method. The structural and morphological features of the BCZT nanopowder were examined by X-ray diffraction and transmission electron microscopy. For better polymer ceramic interface coupling, BCZT was surface functionalized with extended aromatic ligand, naphthyl phosphate (NPh). The surface functionalization was validated and quantified by thermogravimetric analysis and X-ray photoelectron spectroscopy. The dielectric constant of surface passivated BCZT nanoparticles was estimated to be ~?155 using slurry technique, while the dielectric permittivity of pristine BCZT nanopowder could not be assessed due to high innate surface conductivity. BCZT/PVDF-HFP polymer nanocomposite thin films were fabricated using solution casting technique. The dispersion quality of the ceramic fillers in the polymer matrix was examined by scanning electron microscopy. Due to better polymer ceramic interface, At 5 vol% filler concentration, NPh modified nanoBCZT/PVDF-HFP films showed enhanced dielectric breakdown strength and energy storage density than untreated nanoBCZT/PVDF-HFP and even pure polymer films. Maximum energy storage density of 8.5 J cm^?3 was obtained at an optimum filler concentration of 10 vol% for surface functionalized BCZT/PVDF-HFP composite films of 10 μm thickness.     

Acoustic properties of particle/polymer composites for ultrasonic transducer backing applications

The acoustic impedance and attenuation in composites made of particle fillers loaded in polymer matrices for transducer backing applications is investigated. The acoustic impedance of tungsten/vinyl composites was modeled, and an experimental matrix identifying variables that contribute to composite attenuation was established. The variable included the particle type, the particle size and volume fraction of a filler, the physical characteristics of the polymer matrix, and the processing route that determined the composite connectivity. Experimental results showed that with an increase in filler particle size or a decrease in volume fraction of filler, there is an increase in composite attenuation. Overall, the various types of filler, the polymer matrix, and the interface between the two contribute to attenuation in the composite, as confirmed by the acoustic properties and the microstructural analysis.     

Improved polymer nanocomposite dielectric breakdown performance through barium titanate to epoxy interface control

A composite approach to dielectric design has the potential to provide improved permittivity as well as high breakdown strength and thus afford greater electrical energy storage density. Interfacial coupling is an effective approach to improve the polymer-particle composite dielectric film resistance to charge flow and dielectric breakdown. A bi-functional interfacial coupling agent added to the inorganic oxide particles’ surface assists dispersion into the thermosetting epoxy polymer matrix and upon composite cure reacts covalently with the polymer matrix. The composite then retains the glass transition temperature of pure polymer, provides a reduced Maxwell-Wagner relaxation of the polymer-particle composite, and attains a reduced sensitivity to dielectric breakdown compared to particle epoxy composites that lack interfacial coupling between the composite filler and polymer matrix. Besides an improved permittivity, the breakdown strength and thus energy density of a covalent interface nanoparticle barium titanate in epoxy composite dielectric film, at a 5 vol.% particle concentration, was significantly improved compared to a pure polymer dielectric film. The interfacially bonded, dielectric composite film had a permittivity ∼6.3 and at a 30 μm thickness achieved a calculated energy density of 4.6 J/cm³.     

A fundamental model for prediction of optimal particulate composite properties

Particulate composite systems comprising a high content of granular filler (over 60% by weight) in a polymer matrix are greatly influenced by the filler-to-binder ratio, the size distribution of the filler particles and the amount of wetting and adhesion between the filler and the matrix. Relative density and mechanical compressive properties present sensitive variables for studying these effects. Two principal models are presented, one for evaluating the optimal filler size distribution (gradation) and the other to determine the optimal matrix content for this evaluated gradation. Adopting both models provides a prediction of a composite system with enhanced mechanical properties and optimal compaction. The constants of both models are derived experimentally using an epoxy/SiC mixture. The optimal distribution of the matrix between the various filler components and the optimal filler gradation of the composite system are thus obtained. Results show that, despite its low content, the fine filler plays a major role in determining the total optimal composite mixture. Slightly different constants are determined for the various properties tested. Optimal formulation can thus be specified for either a critical property desired or a mean optimum for all relevant properties. Experimental verification of both models proves their efficiency in predicting optimal mixture parameters in order to achieve the best performance of the polymerized composite system.     

Enhanced Dielectric Performance in Polymer Composite Films with Carbon Nanotube‐Reduced Graphene Oxide Hybrid Filler

The electrical conductivity and the specific surface area of conductive fillers in conductor‐insulator composite films can drastically improve the dielectric performance of those films through changing their polarization density by interfacial polarization. We have made a polymer composite film with a hybrid conductive filler material made of carbon nanotubes grown onto reduced graphene oxide platelets (rG‐O/CNT). We report the effect of the rG‐O/CNT hybrid filler on the dielectric performance of the composite film. The composite film had a dielectric constant of 32 with a dielectric loss of 0.051 at 0.062 wt% rG‐O/CNT filler and 100 Hz, while the neat polymer film gave a dielectric constant of 15 with a dielectric loss of 0.036. This is attributed to the increased electrical conductivity and specific surface area of the rG‐O/CNT hybrid filler, which results in an increase in interfacial polarization density between the hybrid filler and the polymer.     

Effect of the microstructure of a filled rubber on its overall mechanical properties

Mechanical behavior of filled rubber is very different from the corresponding unfilled gum rubber. To understand such difference, a multiscale material model of a filled rubber, which combines molecular mechanics, statistical mechanics and micromechanics, has been developed. The model has been used to explore how filler particles and filler–elastomer bond strength influence the overall elastic properties of a filled rubber. The model confirmed the well-established phenomena such as non-uniform strain amplification, but now, the model added much more detailed molecular information such as cross-linking density, bond strength at filler–elastomer interface, etc. to the whole phenomena. This capability enables us to investigate the influences of the factors on the overall mechanical properties of filled rubber. The results revealed that the degree of stretching is significantly amplified in elastomer chains that locate in between the filler particles along the loading direction. The degree of non-uniform stretching increases with filler volume fraction. The fully stretched elastomer chains contribute significantly greater force and stiffness than those that are stretched less. Both the Mullins effect and the Payne effect come from the non-uniform filler size and/or spatial distribution. Reducing non-uniformity of filler size and spatial distribution can decrease the degree of the Mullins effect and the Payne effect. Improving bond strength at filler–elastomer interface can delay the Mullins effect and the Payne effect but cannot eliminate them.     

Mechanical analysis of bi-component-fibre nonwovens: Finite-element strategy

In thermally bonded bi-component fibre nonwovens, a significant contribution is made by bond points in defining their mechanical behaviour formed as a result of their manufacture. Bond points are composite regions with a sheath material reinforced by a network of fibres’ cores. These composite regions are connected by bi-component fibres — a discontinuous domain of the material. Microstructural and mechanical characterization of this material was carried out with experimental and numerical modelling techniques. Two numerical modelling strategies were implemented: (i) traditional finite element (FE) and (ii) a new parametric discrete phase FE model to elucidate the mechanical behaviour and underlying mechanisms involved in deformation of these materials. In FE models the studied nonwoven material was treated as an assembly of two regions having distinct microstructure and mechanical properties: fibre matrix and bond points. The former is composed of randomly oriented core/sheath fibres acting as load-transfer link between composite bond points. Randomness of material’s microstructure was introduced in terms of orientation distribution function (ODF). The ODF was obtained by analysing the data acquired with scanning electron microscopy (SEM) and X-ray micro computed tomography (CT). Bond points were treated as a deformable two-phase composite. An in-house algorithm was used to calculate anisotropic material properties of composite bond points based on properties of constituent fibres and manufacturing parameters such as the planar density, core/sheath ratio and fibre diameter. Individual fibres connecting the composite bond points were modelled in the discrete phase model directly according to their orientation distribution. The developed models were validated by comparing numerical results with experimental tensile test data, demonstrating that the proposed approach is highly suitable for prediction of complex deformation mechanisms, mechanical performance and structure-properties relationships of composites.     

Fatigue behaviour characterization of the fibre-matrix interface

The fracture behaviour of FRP composite materials is significantly influenced by the behaviour of the fibre-matrix interfacial bond. Thus far interfacial bond mechanical characterization has been based upon the critical strength and critical fracture energy of debonding. Characterization of the fatigue behaviour of the interfacial debonding process, however, may be more valuable for composite design and fibre-matrix selection. A fracture mechanics model of interfacial bond fatigue based on the mode II strain energy release rate (G _II) is presented. An expression forG _II is derived for a single fibre in matrix cylinder model. By fitting the model to single fibre pull-out fatigue test data, fatigue crack propagation plots for specific fibre-matrix combinations can be drawn. These should prove useful for the development of fatigue resistant FRP composite materials.     

Layer-Controlled Perovskite 2D Nanosheet Interlayer for the Energy Storage Performance of Nanocomposites

Polymer-based nanocomposites are desirable materials for next-generation dielectric capacitors. 2D dielectric nanosheets have received significant attention as a filler. However, randomly spreading the 2D filler causes residual stresses and agglomerated defect sites in the polymer matrix, which leads to the growth of an electric tree, resulting in a more premature breakdown than expected. Therefore, realizing a well-aligned 2D nanosheet layer with a small amount is a key challenge; it can inhibit the growth of conduction paths without degrading the performance of the material. Here, an ultrathin Sr_1.8Bi_0.2Nb₃O₁₀ (SBNO) nanosheet filler is added as a layer into poly(vinylidene fluoride) (PVDF) films via the Langmuir–Blodgett method. The structural properties, breakdown strength, and energy storage capacity of a PVDF and multilayer PVDF/SBNO/PVDF composites as a function of the thickness-controlled SBNO layer are examined. The seven-layered (only 14 nm) SBNO nanosheets thin film can sufficiently prevent the electrical path in the PVDF/SBNO/PVDF composite and shows a high energy density of 12.8 J cm⁻³ at 508 MV m⁻¹, which is significantly higher than that of the bare PVDF film (9.2 J cm⁻³ at 439 MV m⁻¹). At present, this composite has the highest energy density among the polymer-based nanocomposites under the filler of thin thickness.     

Effect of filler geometry on interfacial friction damping in polymer nanocomposites

Single-walled carbon nanotube polycarbonate and C60 polycarbonate nanocomposites were fabricated using a solution mixing method. The composite loss modulus was characterized by application of dynamic (sinusoidal) load to the nanocomposite and the pure polymer samples. For a loading of 1 weight %, the single-walled nanotube fillers generated more than a 250% increase in loss modulus compared to the baseline (pure) polycarbonate. Even though the surface area to volume ratio and surface chemistry of C60 is similar to that for nanotubes, we report no significant increase in the energy dissipation for the 1% weight C60 nanoparticle composite compared to the pure polymer. We explain these observations by comparing qualitatively, the active sliding area (considering both normal and shear stresses) for a representative volume element of the nanotube and the nanoparticle composites. These results highlight the important role played by the filler geometry in controlling energy dissipation in nanocomposite materials.     

Influence of Surface-functionalized Graphene Oxide on the Cell Morphology of Poly(methyl methacrylate) Composite

The surface chemistry of filler is closely related to the structure and morphology of nanocomposite foams.Changing the property of filler is widely used to control the cell structures and functionalize the composite foams.Surface-functionalized graphene oxide(GO-ODA) was prepared by grafting octadecylamine(ODA) on the surface of graphene oxide(GO) to make the filler disperse better in the nanocomposites and have a strong interfacial interaction with polymer matrix.Poly(methyl methacrylate)(PMMA)/GO-ODA nanocomposite foams were obtained by solution blending and foamed using supercritical carbon dioxide(scCO_2).Compared to neat PMMA and PMMA/GO samples,the PMMA/GO-ODA nanocomposite foams showed improved cell structures with smaller size,higher cell density and more homogeneous distribution,which should be attributed to the heterogeneous nucleation caused by well-dispersed GO-ODA nanosheets.This work not only improved the compatibility and interfacial interaction of GO with polymer matrix but also indicated that the modified GO sheets can act as ideal filler to control the cell density,size and size distribution efficiently.     

氧化锌晶须/环氧树脂导热绝缘复合材料的制备与性能

以环氧树脂(E-44)为聚合物基体,四针状氧化锌晶须(ZnOw)为填充材料,制备了氧化锌晶须/环氧树脂导热绝缘复合材料,研究了ZnOw含量对复合材料的导热性能、电性能的影响,并用扫描电子显微镜对断口形貌进行了观察。结果表明,较少量ZnOw的加入(体积分数<10%),复合材料的导热性能得到有效改善,但仍维持了聚合物材料所具有的电绝缘和低介电常数、低介电损耗的特点。其中当ZnOw体积分数为10%时,ZnOw/EP复合材料的热导率达到0.68W/(m·K),相比纯环氧树脂提高了3倍。     

Thermal conductivity of ceramic particle filled polymer composites and theoretical predictions

Models and theories for predicting the thermal conductivity of polymer composites were discussed. Effective Medium Theory (EMT), Agari model and Nielsen model respectively are introduced and are applied as predictions for the thermal conductivity of ceramic particle filled polymer composites. Thermal conductivity of experimentally prepared Si₃N₄/epoxy composite and some data cited from the literature are discussed using the above theories. Feasibility of the three methods as a prediction in the whole volume fraction region of the filler from 0 to 1 was evaluated for a comparison. As a conclusion: both EMT and Nielsen model can give a well prediction for the thermal conductivity at a low volume fraction of the filler; Agari model give a better prediction in the whole range, but with larger error percentage.     

The effect of partially stabilized zirconia on the mechanical properties of the hydroxyapatite–polyethylene composites

The effect of partially stabilized zirconia (PSZ) on the mechanical properties of the hydroxyapatite-high density polyethylene composites was studied by investigating the effect of hydroxyapatite and the simultaneous effect of hydroxyapatite and PSZ volume fractions on fracture strength, modulus of elasticity, and absorbed energy in the composite samples. The results showed a decrease in fracture strength, and absorbed energy with an increase in the volume fraction of hydroxyapatite content in the hydroxyapatite-polyethylene samples. Partial replacement of hydroxyapatite with PSZ particles was beneficial in the improvement of both the fracture strength and failure energy values in the composite samples. A transition from ductile to brittle behavior was observed as the volume fraction of ceramic filler particles increased in the samples.     

Composites of Poly(Acrylate) Copolymer filled with diatomaceous earth: morphology and mechanical behaviour

Failure mechanisms of poly(acrylate) (PA) copolymer system filled with a diatom filler have been studied. The natural diatom filler is characterised by the original skeletal structure which allows high "inner" porosity and thus matrix penetration inside the filler particles and agglomerates of various shapes in PA composite. High diatom filler crystallinity influences the matrix re-structurization by changing the intensity ratio of matrix amorphous halos indicating the increased composite film inhomogeneity. Interactions at the interface between diatom filler and PA copolymer matrix, specially for coarse cylindrical-shaped particles are low, showing low adhesion in the composite. We see composite weakening with the increased filler volume fraction, i.e. lowering the composite strength at break as a consequence of lower degree of interactions. On the other hand, the composite modulus and the yield strength increased as a result of matrix hardening due to the pronounced matrix penetration inside the porous diatom filler. The mechanisms of failure depend on the location with the lowest product of composite module and break energy. Because dewetting occurred, it is the product EG in the interfacial region between PA matrix and diatom filler particles that was relevant. The effects of filler characteristics, may be followed through an interaction coefficients calculated from a model equations. The numerical values of coefficients in the model are only comparative, but the relative values can be connected with changes at the interface. Electronic Publication     

The effect of low energy impact on the tensile strength of coated and uncoated glass particulate composites

The residual tensile strength of glass filled particulate composites has been determined after low energy impact for various energy values. The material systems constructed for the needs of this research consisted of epoxy resin filled with glass beads. The glass beads were either uncoated or alternatively coated with a reactive silane based bonding agent. Specimens with various filler volume fractions were available. The effect of silane coating as well as the filler volume fraction was analytically discussed. Finally, a model developed in previous work for continuous fibre reinforced composite laminates was adopted to describe the residual tensile strength after impact. In most of the cases the predicted curves fit the experimental results very well.