Monte Carlo simulation studies of the interfaces between polymeric and other solids as models for fiber-matrix interactions in advanced composite materials

As a coarse-grained model for dense amorphous polymer systems interacting with solid walls (i.e., the fiber surface in a composite), the bond fluctuation model of flexible polymer chains confined between two repulsive surfaces is studied by extensive Monte Carlo simulations. Choosing a potential for the length of an effective bond that favors rather long bonds, the full temperature region from ordinary polymer melts down to the glass transition is accessible. It is shown that in the supercooled state near the glass transition an “interphase” forms near the walls, where the structure of the melt is influenced by the surface. This “interphase” already shows up in static properties, but also has an effect on monomer mobilities and the corresponding relaxation behavior of the polymer matrix. The thickness of the interphase is extracted from monomer density oscillations near the walls and is found to be strongly temperature dependent. It is ultimately larger than the gyration radius of the polymer chains. Effects of shear deformation on this model are simulated by choosing asymmetric jump rates near the moving wall (large jump rate in the direction of motion, and a small rate against it). It is studied how this dynamic perturbation propagates into the bulk of the polymer matrix.     

Effect of fiber surface treatments on the essential work of fracture of HDPE-continuous henequen fiber-reinforced composites

Lignocellulosic fibers, such as henequen, sisal, coconut fiber (coir), jute, palm and bamboo, have been used as reinforcement materials for different thermosetting and thermoplastic resins because of their attractive physical and mechanical properties. Unlike the traditional engineering fibers, e.g. glass and carbon fibers, and mineral fillers, these lignocellulosic fibers are able to impart certain benefits such as low density, less machine wear, no health hazards, and a high degree of flexibility to the composite. The last attribute is especially true because these lignocellulosic fibers will bend rather than fracture, like glass fibers do, during processing of the composite. The mechanical properties and fracture behavior of a natural fiber reinforced polymer composite depend, not only on the properties of constituents, but also on the properties of the region surrounding the fiber, known as the interphase, where the stress transfer takes place. Moreover, the tailoring of the interphase by means of surface treatments, and carefully characterizing it, gives a better understanding of the performance of natural-fiber reinforced composites. The fracture toughness resulting from the use of natural fibers as reinforcing materials is quite different between ductile and brittle polymers, as well as between quasi-static and impact loading rates. The aim of this paper is to study the effect of the interphase properties, resulting from well controlled surface treatment of the natural fibers, on the behavior of a ductile polymer matrix composite under quasi-static loading using the essential work of fracture criteria. Specifically, the contribution of each of the different fiber-matrix interfacial adhesion levels towards the dissipation energy were analyzed and discussed. In the case of the plastic work βw_p, there seems to be a synergy between the frictional and chemical interactions observed for both, low and high strain rates. The nonlinear mechanical behavior of the natural fiber under combined tensile-shear loads has also an effect on the fracture behavior of the composite. Additionally, different fiber surface treatments change the microstructural nature of the natural fiber, further affecting its behavior, particularly under high loading rates.     

Solid state NMR of a polymer composite and of a polymer blend

Although nuclear magnetic resonance may not seem the technique of choice to study interfaces between components in a polymer composite or polymer blend because of its inherent low sensitivity, for certain systems solid state NMR techniques can emphasize the signals from these interfaces. In case of a composite material with an inorganic filler (particles, fibers) cross-polarization or dipolar dephasing techniques from protons in the organic matrix or in the interphase to nuclei in the filler can be used to selectively observe the nuclei in the surface of the filler. Any changes at the filler surface caused by the presence of the matrix or coupling agent can then be detected. An example of glass reinforced nylon modelcomposites is discussed. The same techniques can also be used to study interphases in polymer blends when one of the components contains a NMR nucleus that is not present in the other component. As an example the blend poly(vinylidene fluoride)-poly(methyl methacrylate) is studied and it is shown that such techniques can provide very detailed information about the miscibility at a molecular scale.     

The concept of boundary interphase in composite mechanics

Summary The thermomechanical behaviour of a particle composite was evaluated under the assumption that a boundary interphase between the matrix and the filler particles develops, upon the thermomechanical properties of which the overall behaviour of the composite depends. This interphase exists in reality and it contains both areas of adsorption interaction in polymer surface layers onto filler particles as well as areas of mechanical imperfections. Under the assumption that the interphase is homogeneous and isotropic exhibiting perfect adhesion with both main phases a theory was developed providing quantitative means of assessing the adhesion efficiency between the phases and its effect on the thermomechanical behaviour of the composite. Experimental results are in good agreement with theoretical predictions.With 4 figures     

Interfacial properties of glassy polymer melts: A Monte Carlo study

The properties of the interface between a polymer melt and a solid wall are studied over a wide range of temperatures by dynamic Monte Carlo simulations. It is shown that in the supercooled state near the glass transition of the melt an “interphase” forms, the structure of which is influenced by the wall. The thickness of this interphase is determined from the monomer density profile near the surface and is strongly temperature dependent. At low glass-like temperatures it is larger than the bulk radius of gyration of the chains.     

Adhesion efficiency between phases in fibre-reinforced polymers by means of the concept of boundary interphase

Summary The role of the boundary interphase on the adhesion efficiency between fiber and matrix in the case of polymers reinforced with unidirectional fibers was investigated. A theoretical model was introduced considering that the composite material consists of three phases; that is, the fiber, the matrix and the interphase, material which is the part of the polymer matrix lying at the close vicinity of the fiber surface. The interphase material, having different physical properties from those of the bulk matrix, affects the overall behavior of the composite. Moreover, the quality of adhesion between the two main phases depends greatly on the nature of the interphase material. In this study we have considered that the interphase material is inhomogeneous in nature, with properties varying continuously from the fiber surface to the bulk matrix. The theory developed resulted in a criterion of the adhesion quality and in a prediction of the longitudinal modulus of elasticity of the fiber-composite.With 4 figures and 1 table     

Durability and integrity studies of environmentally conditioned interfaces in fibrous polymeric composites: Critical concepts and comments

Fibre reinforced polymer (FRP) composites are the most promising and elegant material of the present century. Their durability and integrity in various service environments can be altered by the response of its constituent i.e. fibre, polymer matrix, and the existing interface/interphase between the fibre and polymer matrix, in that particular environment. The interphase is generally manifested by chemical bonding, molecular segregation and also by van der Waals bonding. The sizing of fibres generally influences the chemistry and character of the interface/interphase and might generate structural gradient in the polymer matrix. Their susceptibilities to degradation are dependent of the nature of environments and each of the constituents' responds differently and uniquely. Amongst the three constituents, the interface/interphase has a very critical role to play on the performance and reliability of FRP composites. The reduced glass transition temperature of the interphase may induce low modulus area, which subsequently affects fracture toughness and local stresses of the composite. These result in high fracture toughness at ambient temperatures, but significantly reduced performance at high temperatures.     

Interfacial design in fiber reinforced polymers

Different interphases have been created with different film formers and coupling agents on glass and carbon single filaments embedded in thermoplastic and thermosetting matrices. Three micromechanical procedures (pull‐out test, fragmentation test and a version of microbond test in which crack propagation was continuously monitored by optical microscopy) were used to measure fiber/matrix interfacial bond strengh. The effect of interphase microstructure, transcrystallinity as well as matrix molecular weight on the measured bond strength, failure mode, and local properties of the interphase was examined. The possibilities of controlling bond strength between fiber surface and polymer matrix are discussed.     

Kinetics of water sorption in flax and PET fibers

Composite materials are usually reinforced by synthetic fibers as carbon, glass etc…. Because of their good mechanical properties and low density, natural fibers are being considered more preferentially as reinforcement. The application of natural fibers as reinforcements in composite materials requires a strong adhesion between the fiber and the matrix. The poor resistance towards water absorption is one of the drawbacks of natural fibers which makes it more important to understand the dynamic properties of penetration of water molecules through these heterogeneous materials. Water vapour sorption kinetics in natural flax fibers have been performed at 25 °C by using an electronic microbalance (IGA, Hiden). By using the Fickian model for a complete cylinder water diffusion coefficients have been determined and calculated at short times (first half-sorption) and long times (second half-sorption) of kinetic curve and for different water activities. The values obtained for D₁ and D₂ are rather similar on the all range of water activity. Generally, water diffusivity increases and then decreases with water activity. The increase of diffusivity at low water activities may be explained on the basis of the dual mode sorption (Langmuir and Henry sorption’s combination) whereas the decrease for the higher activities can be attributed to the immobilization of sorbed water molecules due to the water clustering.     

Visualization of structural rearrangements during annealing of solvent-crazed poly(ethylene terephthalate)

A direct microscopic procedure is used for studying structural rearrangements during the annealing of PET samples after solvent crazing. Even at room temperature, solvent-crazed PET samples experience shrinkage which is provided by processes taking place in crazes. This shrinkage is observed at temperatures up to the glass transition temperature of PET and proceeds via drawing together of crack walls. Once the glass transition temperature is attained during annealing, the spontaneous self-elongation of the polymer sample occurs. The mechanism of this phenomenon is proposed. The low-temperature shrinkage of the polymer sample is related to the entropy contraction of highly dispersed material in crazes that has a lower glass transition temperature than that of the bulk polymer. This shrinkage cannot be complete, owing to crystallization of the oriented polymer in the volume of the crazes. As a result of crystallization, the oriented and crystallized polymer in the crazes coexists with the regions of the unoriented initial PET. As the annealing temperature approaches the glass transition temperature of the bulk PET, its strain-induced crystallization takes place. As a result, the regions of the unoriented polymer between crazes are elongated along the direction of tensile drawing and the sample experiences contraction in the normal direction.     

A Single Glass Fiber with Ultrathin Layer of Carbon Nanotube Networks Beneficial to In-Situ Monitoring of Polymer Properties in Composite Interphases

Electrophoretic deposition (EPD) is used to deposit multiwalled carbon nanotube networks (CNTs) onto electrically insulating glass fiber surfaces. We found that the thin networks on a single glass fiber surface exhibit semiconducting properties. This enables us to realize a single CNT-glass fiber as a probe with novel multifunctional capabilities for in-situ monitoring of various chemical/physical transitions, particularly in the interphase region between polymer and glass fiber. Because of the intimate interaction between CNTs and polymers in the vicinity of a glass fiber, our CNT probe can rapidly sense the local changes of fundamental polymer properties, such as glass transition, reaction activation energy, cross-linking reaction, and crystallization.     

Nucleation and growth of crazes in amorphous polychlorotrifluoroethylene in liquid nitrogen

The density of mature crazes initially increases linearly with stress and then more rapidly at higher stresses. Once the crazes become observable then density was independent of time. The lowest stress at which an appreciable density of crazes was produced corresponds to the proportional limit. The average velocity of mature crazes was constant for a given stress and varied exponentially with the stress. The velocity depended on stress in the same way that the post-yield point stress depended on strain rate, whereas the yield point varied differently being a nonlinear function of the logarithm of the strain rate. The density of crazes was quantitatively related to the concentration of surface defects at which the crazes nucleate. The craze velocity was directly related to the diffusion coefficient of N₂ into the polymer. The analysis indicates that bulk diffusion of the N₂ governs the craze velocity and that plasticization of the tip of the craze is most important for the nucleation and growth of a craze in PCTFE.     

A review on the structure and characterization techniques of silane/matrix interphases

Recent studies regarding the interphase of silane coupling agents and organic polymer matrices are reviewed with emphasis on its structure and property, and characterization techniques for the interphase. Chemical, physical and physicochemical effects on the formation of silane/matrix interphase and resultant properties are discussed. Improvements of the performance of composite materials are also discussed in relation to the interphase structure. Several representative characterization techniques for interphase are also described.     

The effect of moisture absorption on the thermomechanical properties of particulates

Water absorption in particulate composites at ambient temperature influences their thermomechanical properties. Second Fick's law of diffusion was used in this paper to predict the diffusion coefficient of the composite materials tested. In all cases the matrix material was a diglycidyl ether of bisphenol-A polymer cured with 8 phr triethylene tetramine and filled with iron particles with an average diameter 150 μm at five distinct volume fractionsv _f =0, 0.05, 0.10, 0.16 and 0.20. The modification of the modulus of elasticity, ultimate stress, breaking strain and breaking energy due to moisture absorption was examined. Moreover, differential scanning calorimetry was used to study the influence of the time exposure into water and the filler concentration of the particulates on their glass transition temperature. Finally, the void occupancy in the composite was evaluated from free volume considerations.     

Optical properties of polybutadiene in the bulk and near a gold interface

We have investigated thick films from polybutadiene on gold-coated glass using surface plasmon resonance / leaky optical waveguide spectroscopy with the aim of investigating differences in bulk and interphase properties in a single measurement. A broad range of molar masses was studied. Drying under ambient conditions leads to an exponential decay of the film thickness. Subsequent vacuum drying does not result in any further changes in the bulk part of the film but at the polymer-solid interface, indicating the absence of residual solvent. For all molar masses studied, the surface plasmon resonance is observed at angles which are incompatible with the properties of the bulk part of the film. A polymer interphase is thus present next to the gold layer which has a refractive index lower than in the bulk. Using transversal magnetic- and transversal electric polarized light, an optical anisotropy is found in the interphase which is attributed to segment alignment along the interface with gold.     

Functionalized SWNT/polymer nanocomposites for dramatic property improvement

In this paper, we present results for polymer nanocomposites of poly‐ (methyl methacrylate) (PMMA) and amide‐functionalized SWNTs. The results demonstrate that even at very low loadings, 1 wt % (0.5 vol %), the mechanical and electrical properties are significantly improved. The improvement over PMMA properties exceeds the theoretical bounds for composites with the same volume fraction loading of randomly oriented, straight, individually dispersed nanotubes. The modeling and experimental results thus suggest that the nanotube bundles are well dispersed in the polymer matrix, that the functionalization significantly improves interaction with polymer, and that the interphase formed has improved mechanical properties over that of the matrix material. Loss modulus results indicate a significant difference between functionalized and nonfunctionalized tubes in the composite. Functionalized tubes result in a composite in which relaxation mechanisms are shifted by 30 °C from that of the matrix material, indicating extensive interphase regions and absence of PMMA with bulk properties. Unfunctionalized composites demonstrate a broadening of relaxation modes, but still retain the signature of bulk PMMA properties. These data suggest a morphological difference with a discrete interphase layer in unfunctionalized composites and a fully transformed matrix in the case of functionalization. This difference is consistent with electrical and mechanical property data. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2269–2279, 2005     

偶联剂对玻璃纤维/环氧树脂基复合材料介电性能的影响

偶联剂对玻璃纤维／环氧树脂基复合材料介电性能的影响陈平刘胜平张明艳（哈尔滨理工大学电工材料系哈尔滨１５００４０）关键词环氧树脂基复合材料，介电性能，偶联剂，浸润性玻璃纤维／环氧树脂基复合材料（ＧＦＲＰ）具有优异的电气和力学性能．然而孔隙的存在强烈地...     

Effect of filler on kinetic characteristics of glass transition in polymer composite materials

Dynamic mechanical spectroscopy and differential scanning calorimetry were used to study the effect of various fillers (carbon fiber, glass fiber, and aramid fiber) on the kinetic characteristics of glass transition in polymer composite materials based on epoxy resin. It is shown that the composite based on carbon fiber is the most fragile among the materials studied, whereas the polymer composite material based on aramid fiber exhibits the lowest rate of variation of the relaxation time above the glass-transition temperature. A relationship is determined between the heat conductivity and fragility of polymer composite materials. The effect of various fillers on the curing kinetics of the epoxy matrix upon glass transition is prognosticated, with the difference in the degree of curing reaching a value of 4–5%. The strongest filler effect on the curing kinetics is observed in the chemically controlled region, which may be due to the catalytic effect of functional groups on the fiber surface.     

Thermo-mechanical characterisation of in-plane properties for CSM E-glass epoxy polymer composite materials – Part 1: Thermal and chemical strain

The in-plane thermo-mechanical properties and residual stresses of a CSM E-glass/Epoxy material are characterised through the use of DSC and TMA. The measured data is used to generate material models which describe the mechanical behaviour as a function of conversion and temperature. The in-plane thermal expansion coefficient (α) of the composite material decreases above the glass transition temperature (T_g), which is compensated by a higher out of plane deformation above T_g. Comparison of α and chemical shrinkage measurements suggests that chemical bonds between the polymer matrix and the glass fibres are formed prior to shrinkage of the epoxy matrix, i.e., at an early processing stage. This suggests that production of composites with low residual stresses requires focus on reactivity between the matrix and the sizing rather than the matrix cure properties. As a consequence, residual stresses in the composite material are mainly a result of restricted cure shrinkage rather than mismatch between thermal expansion coefficients.     

Effect of the feeding mode of cross-linker and microcapsule on the corrosion resistance and hydrophobicity of composite coatings

The interface combination of anti-corrosive materials and polymer matrix has a significant effect on the overall performance of the composite coating. However, past research has focused on blending anti-corrosive materials to improve the performance of the polymer matrix. Herein, we proposed a layer-by-layer spray-coating process to further enhance the reinforcing effect of anti-corrosive materials on the polymer matrix by changing their feeding modes. In this paper, taking waterborne polyacrylate (WPA) as an example, two kinds of reinforcement materials commonly used to improve the corrosion resistance of polymer matrix were introduced into the coating system and then applied to the tinplate: cross-linker and microcapsule. Firstly, five types of WPA composite coating systems were designed according to the feeding mode of aziridine cross-linker and the position of benzotriazole@zinc oxide microcapsules (BTA@ZnO MCs). Electrochemical impedance spectroscopy (EIS) and electrical equivalent circuits were used to evaluate the corrosion resistance of these composite coating systems and analyze their electrochemical processes. By spraying the mixture of WPA and aziridine crosslinker as the bottom layer and BTA@ZnO MCs as the top layer, the resulting composite coating exhibited higher corrosion resistance and hydrophobic properties. Scanning electron microscope (SEM) and contact angle tests indicated that the feeding mode of aziridine cross-linker and the position of BTA@ZnO MCs played important roles in the compactness and hydrophobicity of the composite coating. Subsequently, the effects of the amount of aziridine cross-linker and BTA@ZnO MCs on the corrosion resistance and physical properties of the composite coating were further analyzed by EIS, water absorption test, contact angle test and atomic force microscopy (AFM). The significant improvement in the corrosion resistance of this composite coating was mainly attributed to the synergistic effect of highly cross-linked network structure and superhydrophobic surface.