The Role of Interfacial Interactions in the Toughening of Precipitated Calcium Carbonate–Polypropylene Nanocomposites

This paper investigates the effect of the interphase properties and the interfacial interactions between matrix and filler on mechanical properties of precipitated calcium carbonate (PCC)–polypropylene nanocomposites. PCC particles were coated with stearic acid (SA). The weight ratio of SA on the particles (w _SA) ranged from 0 to 0.135 g SA/g PCC. The introduction of PCC particles resulted in an increase in stiffness and yield stress compared with the pristine polymeric matrix and, at the same time, it increased the impact resistance. The maximum improvement in the impact behaviour was achieved for the composites with w _SA =0.045 corresponding to the theoretical monolayer ratio. A decrease in interfacial interactions between monolayer coated PCCs and the matrix with respect to the uncoated particles was observed by using a semi-empirical equation developed by Pukànszky. The low degree of interfacial interactions between particulate filler and matrix allows a matrix–particle debonding phenomenon, as shown by scanning electron microscopy analysis. Extensive plastic deformations were evident as well, promoting an improvement in toughness. The thickness of the interphase between particles and matrix was evaluated by using the Shen–Li model which is based on the hypothesis of a non-homogeneous interphase. It results that the thickness increased in the order uncoated < monolayer coated < 3% SA coated ? 13.5% SA coated particles. The thinner and stronger interphase found for the composite with uncoated particles can be explained with the high interaction between matrix and filler and the consequent low mobility of the polymeric chains.     

Dynamic mechanical analysis of the interphase in bacterial polyester/cellulose whiskers natural composites

Nanocomposite materials were prepared from an elastomeric poly(hydroxyoctanoate) (PHO) latex as a fully amorphous or semi-crystalline matrix using a colloidal suspension of hydrolyzed cellulose whiskers as natural and biodegradable filler. After stirring, the preparations were cast and evaporated. High performance materials were obtained from these systems, preserving the natural character of PHO. Interfacial phenomena were assumed to be noticeable owing to the high specific area of this filler. Dynamic mechanical analysis was performed on these systems to test the influence of the interphase on the molecular mobility of the amorphous phase. To quantify the distance away from the surface at which the molecular mobility is restricted, a physical model was used to predict the mechanical loss angle. This allows removal of the filler reinforcement effect keeping only the interfacial effect. It was shown that the local motion at the filler-matrix interface of amorphous PHO chains is strongly affected when an amorphous PHO was used as the matrix. No significant change was observed when a semi-crystalline PHO was used as the matrix. This result was ascribed to a possible trancrystallization phenomenon of semi-crystalline PHO in contact with cellulose whisker surface, which prevents any contact between amorphous PHO chains and filler surface.     

Mechanical properties of flat braided composite with flexible interphase

Textile composites have been used extensively as industrial materials because of the excellent mechanical properties resulting from the continuously oriented fiber bundle. In a study of the mechanical properties, it is important to consider the fiber/matrix interface property as for other composite materials. In a recent study, the fiber/matrix interface is regarded as an interphase that has its own material constants and thickness; consequently, the mechanical properties of a composite can be controlled by specifically designing the interphase. In this study, we applied this concept to braided composites with flexible resin as interphase for the purpose of designing the interphase. In a static tensile test, though there were no improvements in Noncut specimens (normal braided composites), but a Cut specimen (each side of the Noncut specimen was cut) with flexible interphase was improved in fracture load and displacement. The observation of the specimen edge was carried out and it was confirmed that the progress of debonding at the fiber bundle intersection was interrupted by a flexible interphase, and a matrix crack did not occur in the Cut specimen with flexible interphase. In a fiber bundle pull-out test, it was confirmed that debonding progressed not into the fiber/resin interface but into the flexible interphase in the specimen with flexible interphase, and the interfacial property at the fiber bundle intersection was improved.     

A study of damping in fiber-reinforced composites

Damping contributions from the viscoelastic matrix, interphase and the dissipation resulting from damage sites are considered to evaluate composite material damping coefficients in various loading modes. The paper presents the results of the FEM/Strain energy investigations carried out to predict anisotropic-damping matrix comprising of loss factors η₁₁, η₂₂, η₁₂ and η₂₃ considering the dissipation of energy due to fiber and matrix (two phase) and correlate the same with various micromechanical theories. Damping in three phase (i.e., fiber-interphase-matrix) composite is also calculated as an attempt to understand the effect of interphase. The contribution of energy dissipation due to sliding at the fiber-matrix interface is incorporated to evaluate its effect on η₁₁, η₂₂, η₁₂ and η₂₃ in fiber-reinforced composite having damage in the form of hairline debonding. Comparative studies of the various micromechanical theories/models with FEM/Strain energy method for the prediction of damping coefficients have shown consistency when both the effect of variable nature of stress and the fiber interaction is considered. Parametric damping studies for three phase composite have shown that the change in properties of fiber, matrix and interphase leads to a change in the magnitude of effectiveness of interphase, but the manner in which the interphase would affect the various loss factors depends predominately upon whether the hard or soft interphase is chosen. Analysis of the effect of damage on composite damping indicates that it is sensitive to its orientation and type of loading.     

Filler surfaces and composite properties

The formation of stearate on precipitated calcium carbonate (PCC) has been examined. The object of coating the filler surface is to achieve improved mechanical properties in the resulting composite material. The coating of a filler with stearate allows the modification of the energies of interaction, so as to improve dispersion and alter the mechanical properties of the interphase region. In this work, Fourier transform infra-red spectroscopy (FTIR) has been used to characterise the efficiency of stearate formation. X-ray photoelectron spectroscopy (XPS) has been used to estimate the thickness of the stearate coating on the surface of the filler. By using dynamic mechanical analysis (DMTA), a variation in mechanical properties has been demonstrated.     

Physico-chemical characterization of the fibre/matrix interaction in polyethylene fibre/epoxy matrix composites

The interphase in polyethylene fibre/epoxy matrix composites is studied with FT-IR microspectroscopy using a set-up to investigate the matrix as close to the fibre as a few μm or less. It is shown that moisture present on the fibre surface is able to influence the polymerization reaction of the epoxy/anhydride matrix in an irreversible manner. This effect is enhanced for composites from the more hydrophilic polyvinylalcohol fibre. The fibre/matrix interaction in these thermoplastic fibre composites is also studied with DSC through the characterization of the fibre melting. A decreased 'DSC interaction parameter' is found if the composition of the interphase is changed by moisture. For a composite with an epoxy/amine matrix, on the other hand, the DSC interaction parameter is unaffected by moisture from the fibre surface.     

Influence of Ethylene-Butyl Acrylate-Glycidyl Methacrylate Terpolymer on Compatibility of Ethylene Vinyl Acetate Copolymer/Olive Husk Flour Composites

The paper reports some results of an experimental study on ethylene vinyl acetate (EVA) copolymer/olive husk flour (OHF) composites incorporated at various filler ratios (15, 30 and 45 wt%) in the absence and the presence of ethylene-butyl acrylate-glycidyl methacrylate (EBAGMA) terpolymer used as a compatibilizer. The composite samples have been prepared by melt blending and their chemical structure, as well as morphological, mechanical and water absorption properties investigated. It is shown that the compatibility of EVA/OHF composites is improved by the addition of EBAGMA terpolymer. Indeed, FT-IR analysis shows that chemical interactions have occurred between the compatibilizer and the base blend components. Morphological results from SEM shows better dispersion of the wood particles in the EVA matrix and the resulting composite samples exhibit better tensile properties at break and lower water absorption than the uncompatibilized ones. Moreover, the results indicate that the loading concentrations of both OHF and EBAGMA have an effect on the composite properties.     

The effect of accelerator contents on the vulcanizate structures of SSBR/silica vulcanizates

Physical properties of rubber compounds are affected by the filler–rubber interaction, filler dispersion in the rubber matrix, and cross-link structure formed during vulcanization. In particular, the cross-link structure is closely related to the physical properties of vulcanizates and has been analyzed using the swelling test and Flory-Rehner equation. However, the relationship between the structure and physical properties of vulcanizates cannot be explained by the cross-link density obtained using these methods. The cross-link density obtained from the swelling test is a complex result of the filler–rubber interaction occurring during the compounding as well as the chemical cross-link structure formed by sulfur during the vulcanization. Moreover, the rubber vulcanizates that use silica need to be separately analyzed for each factor as its physical properties are affected more by the filler–rubber interaction than by carbon black. Therefore, this study determines the factors that contribute to the total cross-link density of vulcanizates into chemical cross-link density and filler–rubber interaction via quantitative analysis using the swelling test results and Flory-Rehner and Kraus equations. The vulcanizates used for the analysis were carbon black-filled and silica-filled non-functionalized SSBR compounds with varying cure accelerator for each filler loading. Their chemical cross-link density was measured and the effect of the filler–rubber interactions on their mechanical and dynamic viscoelastic properties was investigated. Furthermore, the relationship between the structure and physical properties of rubber vulcanizates was elucidated.     

Multi-scale bending,buckling and vibration analyses of carbon fiber/carbon nanotube-reinforced polymer nanocomposite plates with various shapes

Using a finite element-based multi-scale modeling approach, the bending, buckling and free vibration of hybrid polymer matrix composites reinforced by carbon fibers and carbon nanotubes (CF/CNT-RP) are analyzed herein. Thick composite plates with rectangular, circular, annular and elliptical shapes are considered. First, the equivalent material properties of CF/CNT-RP are calculated for different volume fractions of CF and CNT. To accomplish this aim, a two-step procedure is presented through which the coupled effects of nano- and micro-scale are taken into account. In the first step, modeling of dispersion of CNTs into the polymer matrix is done with considering interphase formed by their chemical interaction with the matrix, and the equivalent properties of resulting composite material are determined accordingly. CFs are then dispersed into CNT-RP which is considered a homogenous material in this step. Both distributions of CNTs and CFs are assumed to be random. After computing the equivalent properties of CF/CNT-RP for different volume fractions of its constituents, the bending, buckling and free vibration analyses of plates with different shapes are performed. It is shown that the reinforcement of the polymer matrix with both CF and CNT significantly affects the bending, buckling and free vibration characteristics of plates.     

有机蒙脱土改性脲醛树脂的结构与纳米力学研究

蒙脱土(MMT)作为一种天然矿物质,在树脂胶粘剂的增强改性方面应用前景广阔。为了探明蒙脱土增强作用机理,本文采用有机蒙脱土改性脲醛树脂,利用傅里叶红外光谱仪(FTIR)和X射线衍射仪(XRD)分析蒙脱土和改性树脂的化学和晶体结构;并制造木质复合材料,采用纳米压痕技术(NI)比较研究复合材料界面区域树脂的纳米力学性能,测定复合材料的宏观胶合强度。FTIR和XRD分析表明,经十六烷基三甲基溴化铵分析纯(CTAB)改性后的蒙脱土在2 929和2 855 cm-1附近出现新的吸收峰,蒙脱土原土中的金属阳离子和有机阳离子实现有效交换,其(001)面强衍射峰向小角度移动,蒙脱土原土纳米片层的间距从1.51 nm增加至2.71 nm,有助于蒙脱土均匀分散于树脂体系中,并与体系中聚合物分子基团发生化学反应。蒙脱土片层的物理填充、化学反应形成的弹性体结构使得胶粘剂在加载过程中可以有效地分散应力,从而有利于提高脲醛树脂的力学性能,有机蒙脱土改性脲醛树脂的微观弹性模量和硬度分别增加了66.9%和24.2%。改性后树脂的耐水性能得到明显改善,木质复合材料的湿胶合强度增加了约97%。     

Adjustment of the burning rate of a composite propellant with regard to its temperature sensitivity

Systematic multifactor experiments aimed at studying the regularities of the adjustment of the burning rate of composite propellants, especially its temperature sensitivity, were performed. It was established that, in contrast to the pressure dependence of the burning rate, which is largely determined by the properties of the base subsystem of components, its temperature sensitivity is influenced by the flame characteristics as well, more specifically, by the properties of the filler particles dispersed into the gas phase, a slowly burning component.     

Use of flow microcalorimetry and dynamic mechanical thermal analysis for probing interphase structure in poly(styrene-b-butadiene-b-styrene)/magnesium hydroxide composites

Interactions between magnesium hydroxide (Mg(OH)₂ particles (both untreated and treated with 16-methyl heptadecanoic acid (isostearic acid)) and low molar mass poly(styrene) (PS) and poly(butadiene) (PB) have been studied by flow microcalorimetry (FMC) and have been related to the interphase structure in poly(styrene-b-butadiene-b-styrene) (SBS)/Mg(OH)₂ composites using dynamic mechanical thermal analysis (DMTA). The FMC studies revealed that both polymers adsorbed strongly onto an untreated magnesium hydroxide surface though the PB showed greater irreversible adsorption from the heptane carrier fluid. Diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) studies on filler samples removed from the FMC cell after the adsorption-desorption cycle confirmed strong polymer filler interaction. Adsorption of the low molar mass samples of PS and PB onto a pre-adsorbed monolayer of isostearic acid on Mg(OH)₂ resulted in a very significant reduction in polymer adsorption activity due to blockage of adsorption sites. DMTA studies revealed that strong adsorption of PS and PB blocks of SBS onto untreated filler in composites containing 60% w/w Mg(OH)₂ gave rise to phase mixing that led to an 18 °C reduction in the T _g of the PS phase relative to that in the unfilled matrix. However, in equivalent composites based on isostearic acid treated filler a smaller reduction (10 °C) was observed, therefore reflecting reduced filler-matrix interaction and reduced phase mixing.     

Interfacial interaction in carbon fiber/thermoplastic composites

This work was undertaken in order to increase the understanding of the mechanism responsible for fiber/matrix interaction in carbon fiber/thermoplastic composite. From results of previous study on carbon fiber/PEEK composite, which suggested that the formation of the fiber/ matrix interaction was primarily related to a chemisorption mechanism, a study was done of the conditions required to obtain efficient fiber/matrix interaction in PA-12 and PP/carbon fiber composites. The interest in studying carbon fiber composite based on PP and PA-12 was that these two matrices are very different in terms of reactivity, polyamide having many more reactive groups than polypropylene. As expected, due to the non-reactive chemical structure of the polypropylene, fiber/matrix interaction in carbon fiber/PP composite occurred only when the matrix was thermally degraded, i.e. when the composite was molded at high temperature or under long residence time at the melt temperature. For the carbon fiber/PA-12 composite, strong fiber/matrix interaction occurred readily at relatively low molding temperature, i.e. well before thermal degradation of the matrix. It was also found that the short beam shear strength in these composites seems to evolve with molding temperature, and a maximum interfacial strength was observed at a molding temperature corresponding to the thermal degradation of the matrix. This indicates that although matrix degradation often results in strong reduction in the composite performance, some matrix degradation can be beneficial in terms of interfacial mechanical properties. Finally, this work demonstrated that while the formation of fiber/matrix interaction seems to be primarily related to a chemisorption mechanism, the contribution of interphase crystallinity to the interfacial strength is not negligible. In fact, interfacial crystallinity was found to be essential to ensure optimum interfacial strength.     

Application of nano-indentation, nano-scratch and single fibre tests in investigation of interphases in composite materials

Three novel experimental techniques were employed in this work in order to investigate the influence of the interphase region in polymer–glass composites on the bulk material properties: (i) the microdroplet test is a single fibre test designed to characterize the fibre–matrix bond (interface region) and to determine the interfacial shear stress in composite material; (ii) the nano-indentation test, a novel nano-hardness technique with ability to produce an indent as low as a few nanometres was employed in order to measure nano-hardness of the fibre–matrix interphase region; and (iii) the nano-scratch test, used in conjunction with the nano-indentation test for measurement of the interphase region width. The microdroplet test (MDT) has been used to characterize the interfacial bond in fibrous composite materials. The specimen consists of a fibre with a drop of cured resin pulled while the drop is being supported by a platinum disc with a hole. A properly tested specimen fails at the droplet’s tip–fibre interface, revealing the ultimate interfacial shear strength. In this study, finite element analysis (FEA) of the MDT has been focused toward simulation of the fibre–matrix interphase region. The influence of several functional variations of the material properties across the interphase layer on the stress distribution at the droplet’s tip was analysed. The results showed that the variation of the interphase properties significantly affects the stress distribution at the fibre–droplet interface, and, therefore, the stress redistribution to composite material. These results led to further experimental investigation of the interphase region, in order to obtain the material properties essential for the interfacial stress analysis. The interphase region in dry and water aged polymer–glass composite materials was investigated by means of the nano-indentation and the nano-scratch techniques. The nano-indentation test involved indentation as small as 30 nm in depth, produced along a 14 μm path between the fibre and the matrix. The distinct properties of the interphase region were revealed by 2–3 indents in dry materials and up to 15 indents in water aged, degraded materials. These results indicated interdiffusion in water aged interphase regions. The nano-scratch test involves moving a sample while being in contact with a diamond tip. The nano-scratch test, used in conjunction with the nano-indentation test, accurately measured the width of the interphase region. The results showed that the harder interphase region dissolved into the softer interphase region (both regions being harder/stronger than the matrix) expanding its width after aging in water.     

Interfacial adhesion of lignocellulosic materials in polymer composites: an overview

Cellulosic materials have long been used as cost-cutting fillers in the plastic industry. Among the various factors which determine the final performance of the composite materials depend, to a large extent, on the adhesion between the polymer matrix and the reinforcements, and, therefore, on the quality of the interface. In fact, the majority of cellulosic raw materials are lignocellulosics of different polarity to plastics, and due to this divergent behavior, the adhesion between cellulosic materials and polymer matrices is very poor. However, a sufficient degree of interaction or adhesion between the surface of the cellulosic materials and matrix resin is usually desired to achieve an optimum performance of the end-product. In many cases surface modification of the cellulosics or the matrix resins, using various additives, vinyl monomers, or coupling agents, are considered to be essential to achieve this goal. The present paper surveys research work published in this field with special emphasis on the cellulosic materials' surface chemistry, morphology, as well as interfacial properties of the composites in order to elucidate the role of surface treatments. In order to elucidate the mechanism of interaction on molecular level, it is necessary to employ various techniques, such as spectroscopy that can measure surface events. In fact, the complexity of the interphase region requires a variety of characterization methods for the thorough understanding of the physical and chemical nature of this region. Moreover, a proper combination of different techniques is necessary to provide a true picture of the interphase.     

Carboxylated acrylo nitrile butadiene rubber latex/kaolin nanocomposites: preparation and properties

Carboxylated nitrile butadiene rubber (XNBR)–based nanocomposites with varying amounts of nanokaolin were produced by latex stage mixing. Sonication of the unmodified kaolin and the technique adopted for the preparation of the composite have helped to get a uniform dispersion of clay in XNBR matrix. Nanokaolin caused enhancement in the mechanical properties of the composites. Proper dispersion of the clay particles, partial exfoliation/intercalation of clay, and interaction of clay with the polar rubber latex made nanokaolin good reinforcing filler in XNBR latex. Swelling studies conducted in methyl ethyl ketone showed a decrease in the swelling index and solvent uptake confirming the hindrance exerted by clay and the possible clay–rubber interaction. Increase in complex modulus obtained from the strain sweep analysis is a further evidence for better rubber filler interaction. The composites were characterized by the scanning electron microscopy, X-ray diffraction analysis, and atomic force microscopy.     

Effect of irradiation on interfacial interaction and structure formation in filled PTFE composites

The supramolecular structure and tribological properties of filled polytetrafluoroethylene composites irradiated above the melting point of the crystalline phase of the polymer component and the phase transitions in them are investigated. In unirradiated composites, phase separation is observed, that is, the separation of the filler from the polymer matrix. The supramolecular structure of the polymer component does not depend on the nature and concentration of the filler, and it is characterized by the formation of lamellae during sintering and subsequent crystallization. Radiation exposure leads to the disappearance of the phase separation and the formation of axiolites with the radial orientation of fibrils, in the center of which the filler particles are located. Changes in the structure are explained by an increase in interfacial interactions through the radiation grafting of macromolecules (and low-molecular-weight products) to the surface of the filler particles. The linear wear rate of irradiated composites is 50 times lower relative to the unirradiated samples because of the transition from the delamination to abrasive wear mechanism.     

Simulation of polyurethane/activated carbon surface interactions

The influence of interfacial structure on interfacial properties between activated carbon filler and surrounding organic matrix of composites has been studied by infrared and NMR spectroscopy. Urea, semicarbazide and ethylurethane, component parts of polyurethane, have been used as organic model compounds in order to predict the interactions between the activated carbon surface and polar groups of real polyurethane molecule. It was shown that organic matrix/activated carbon interphase presented a region where the filler and matrix phases were chemically and/or physically combined. The spectra of the organic matrix undergo significant changes with increase of carbon content. Due to the surface reactive functionalities the activated carbon is considered not only as filler, influenced on the sorption properties of the composition, but also as a physicochemical modifier of the polyurethane matrix.     

Magnetic properties of ferrocholesterics with soft particle anchoring

The influence of the external magnetic field on the orientational structure and magnetic properties of the ferrocholesteric is analyzed. A soft homeotropic coupling between the magnetic particles and the cholesteric molecules is assumed. The diamagnetic anisotropy of the matrix is chosen to be positive. In this case, the dipolar and quadrupolar mechanisms of orientational interaction with the external field compete with each other. The field being applied normal to the helix. Using the continuum theory, the occurrence of magnetic-field-induced ferrocholesteric–ferronematic transition is studied. The transition field as a function of the material parameters of a ferrocholesteric is found. It is shown that rising the field strength in the ferronematic phase leads to a change in the coupling between the particles and the director from homeotropic to planar one. A study on the structure of the domain walls in ferronematic phase is undertaken.