Computer simulation of the damage evolution of fiber-reinforced polypropylene-matrix composites with matrix defects

The damage evolution of fiber-reinforced polypropylene-matrix composites with matrix defects was studied via a Monte Carlo technique combined with a finite element method. A finite element model was constructed to predict the effects of various matrix defect shapes on the stress distributions. The results indicated that a small matrix defect had almost no effect on fiber stress distributions other than interfacial shear stress distributions. Then, a finite element model with a statistical distribution of the fiber strength was constructed to investigate the influences of the spatial distribution and the volume fraction of matrix defects on composite failure. The results showed that it was accurate to use the shear-lag models and Green's function methods to predict the tensile strength of composites even though the axial stresses in the matrix were neglected.

Surface morphology evolution of poly (styrene-block-4-vinylpyridine) (PS-b-P4VP)(H+) and poly(methyl methacrylate)-dibenzo-18-crown-6-poly(methyl methacrylate) (PMCMA) supramolecular film

Well-ordered nanostructured polymeric supramolecular thin films were fabricated from the supramolecular assembly of poly(styrene-block-4-vinylpyridine) (PS-b-P4VP)(H+) and poly(methyl methacrylate)-dibenzo-18-crown-6-poly(methyl methacrylate) (PMCMA). A depression Of cylindrical nanodomains was formed by the block of P4VP(H+) and PMCMA associates surrounded by PS. The repulsive force aroused from the incompatibility between the block of P4VP(H+) and PMCMA was varied through changing the molecule weight (M-w) of PMCMA, the volume fraction of the block of P4VP(H+), and annealing the film at high temperature. Increasing the repulsive force led to a change of overall morphology from ordered nanoporous to featureless structures. The effects of solvent nature and evaporation rate on the film morphology were also investigated. Further evolution of surface morphologies from nanoporous to featureless to nanoporous structures was observed upon exposure to carbon bisulfide vapors for different treatment periods. The wettability of the film surface was changed from hydrophilicity to hydrophobicity due to the changes of the film surface microscopic composition.

Control of self-organized low-dimensional morphology in Poly(styrene-b-4vinylpyridine)/polystyrene blend thin films

The surface morphologies of poly(styrene-b-4vinylpyridine) (PS-b-P4VP) diblock copolymer and homopolystyrene (hPS) binary blend thin films were investigated by atomic force microscopy as a function of total volume fraction of PS (phi(PS)) in the mixture. It was found that when hPS was added into symmetric PS-b-P4VP diblock copolymers, the surface morphology of this diblock copolymer was changed to a certain degree. With phi(PS) increasing at first, hPS was solubilized into the corresponding domains of block copolymer and formed cylinders. Moreover, the more solubilized the hPS, the more cylinders exist. However, when the limit was reached, excessive hPS tended to separate from the domains independently instead of solubilizing into the corresponding domains any longer, that is, a macrophase separation occurred. A model describing transitions of these morphologies with an increase in phi(PS) is proposed. The effect of composition on the phase morphology of blend films when graphite is used as a substrate is also investigated.

Temperature and pressure dependence of phase separation of trans-decahydronaphthalene/polystyrene solution

The cloud-point temperatures (T-c1's) of ti-ans-decahydronaphthalene (TD)/polystyrene (PS, M-w = 270 kg/mol) solutions were determined by fight scattering measurements over a range of temperatures (1-16 degreesC), pressures (100-900 bar), and compositions (4.2-21.6 vol% polymer). The system phase separates upon cooling and the T-c1 was found to increase with the rising pressure for the constant composition. In the absence of special effects this finding indicates positive excess volumes. The special attention was paid to the demixing temperatures as a function of the pressure for the different polymer solutions and the plots in the T-volume fraction plane and P-volume fraction plane. The cloud-point curves of polymer solutions under changing pressures were observed for different compositions, demonstrates that the TD/PS system exhibits UCST (phase separation upon cooling) behavior. With this data the phase diagrams under pressure were calculated applying the Sanchez-Lacombe (SL) lattice fluid theory. Furthermore, the cause of phase separation, i.e., the influence of Flory-Huggins (FH) interaction parameter under pressure was investigated.

Tunable photonic crystals by mixed liquids

Tunable photonic crystals were prepared by infiltrating mixed liquids into the voids of silica opals. The stop bands of the tunable photonic crystals were continuously tuned by changing the relative refraction index contrast n(mix)/ns(pheres) of the spheres and the mixed liquids by varying the volume fraction of the component of the mixed liquids. The peak wavelengths of the stop band have a red shift as the refractive index of the mixed liquids increases. The transmittance at the stop band decreases with the increase of the refractive index contrast n(mix)/n(spheres). The larger the diameter of silica opals is, the wider the tunable range of the stop band is. The position and transmittance of the peak wavelength obtained by the photonic band calculations agreed very well with the experimental data.

Stress transfer and damage evolution simulations of fiber-reinforced polymer-matrix composites

The stress transfer from broken fibers to unbroken fibers in fiber-reinforced thermosetting polymer-matrix composites and thermoplastic polymer-matrix composites was studied using a detailed finite element model. In order to check the validity of this approach, an epoxy-matrix monolayer composite was used as thermosetting polymer-matrix composite and a polypropylene (PP)-matrix monolayer composite was used as thermoplastic polymer-matrix composite, respectively. It is found that the stress concentrations near the broken fiber element cause damage to the neighboring epoxy matrix prior to the breakage of other fibers, whereas in the case of PP-matrix composites the fibers nearest to the broken fiber break prior to the PP matrix damage, because the PP matrix around the broken fiber element yields. In order to simulate composite damage evolution, a Monte Carlo technique based on a finite element method has been developed in the paper. The finite element code coupled with statistical model of fiber strength specifically written for this problem was used to determine the stress redistribution. Five hundred samples of numerical simulation were carried out to obtain statistical deformation and failure process of composites with fixed fiber volume fraction.

Conductive hybrids from water-borne conductive polyaniline and (3-glycidoxypropyl)trimethoxysilane

Free-standing conductive films of organic-inorganic hybrids were prepared employing the sol-gel process of (3-glycidoxypropyl)trimethoxysilane (GPTMS) and water-borne conductive polyaniline (cPANI) in water/ethanol solution. The hybrids displayed a percolation threshold for electrical conductivity at a volume fraction of 2.1% polyaniline (PANI); the maximum conductivity of the hybrids reached 0.6 S/cm. GPTMS showed good compatibility with water-borne cPANI during the sol-gel process, and freestanding conductive films were obtained at room temperature. Transmission electron microscopy images of the hybrids indicated that the cPANI was dispersed in the inorganic phase in nanoscale. Because of good confinement of cPANI chains in the inorganic network, water resistance of the hybrid films was significantly improved compared with that of pure cPANI; the electrical conductivity of the films kept stable for 6-7 days soaking in water, whereas it decreased sharply for 1 day soaking for the pure cPANI.

Rheology and morphology of reactively compatibilized PP/PA6 blends

This work aims to use the Palierne emulsion type model to describe the relationship between the rheological response to small amplitude oscillatory deformation and morphology of polypropylene/polyamide 6 (PP/PA6) blends compatibilized with maleic anhydride grafted polypropylene (PP-g-MAH). It was found that the Palierne emulsion type model could describe very well the linear viscoelastic responses of binary uncompatibilized PP/PA6 blends and failed to describe the ternary compatibilized PP/PP-g-MAH/PA6 blends. These features could be attributed to the fact that the morphology of the ternary blends was not of the emulsion type with the PA6 particles dispersed in the PP matrix but of an emulsion-in-emulsion type, i.e., PA6 particles dispersed in the PP matrix themselves contained PP or PP-g-MAH inclusions. By consideration of PP-in-PA6 particles as pure PA6 particles, where the volume fraction of the PA6 phase was increased accordingly, the Palierne emulsion type model could work very well for a ternary blending system. Preshear at low frequencies modified the morphology of both binary and ternary blends. The particles of the dispersed phase (PA6) became more uniform. These results suggested that the Palierne emulsion type model could be used to extract information on rheological properties and interfacial tension of polymer blends from known morphology and vice versa.

Tensile modulus of polymer nanocomposites

Based on Takayanagi's two-phase model, a three-phase model including the matrix, interfacial region, and fillers is proposed to calculate the tensile modulus of polymer nanocomposites (E-c). In this model, fillers (sphere-, cylinder- or plate-shape) are randomly distributed in a matrix. If the particulate size is in the range of nanometers, the interfacial region will play an important role in the modulus of the composites. Important system parameters include the dispersed particle size (t), shape, thickness of the interfacial region (tau), particulate-to-matrix modulus ratio (E-d/E-m), and a parameter (k) describing a linear gradient change in modulus between the matrix and the surface of particle on the modulus of nanocomposites (E-c). The effects of these parameters are discussed using theoretical calculation and nylon 6/montmorillonite nanocomposite experiments. The former three factors exhibit dominant influence on E-c At a fixed volume fraction of the dispersed phase, smaller particles provide an increasing modulus for the resulting composite, as compared to the larger one because the interfacial region greatly affects E-c. Moreover, since the size of fillers is in the scale of micrometers, the influence of interfacial region is neglected and the deduced equation is reduced to Takayanagi's model. The curves predicted by the three-phase model are in good agreement with experimental results. The percolation concept and theory are also applied to analyze and interpret the experimental results.

Preparation and gas sensitivity of octa-n-butoxy-2,3-naphthalocyanine copper(II) Langmuir-Blodgett film

The formation process of monolayer of octa-n-butoxy-2,3-naphthalocyanine copper ( I), [CuNc(OBu)(8)], on water subphase was studied. Its multilayers were successifully deposited on the hydrophilic substrates by Z-type deposition mode using LB technique. Stable solid film with a limiting molecular area of 0.74 nm(2) and a collapse pressure of 55 mN/m were formed. The LB film structure was characterized by IR and electronic absorption spectra. Macrocycle of CuNc (OBu)(8) molecules have a face-to-face arrangement in the multilayers. These films have good sensitivities to vapor of alcohols, with the following sequence of sensitivities: i-PrOH>EtOH>MeOH. The response time and recovery time of the LB films to vapor of MeOH, EtOH and i-PrOH[volume fraction (1-5) X 10(-5)] were within 2 and 5 seconds respectively, while those of the LB films to ammonia(1 X 10(-4)) were 30-60 seconds and 4-5 minutes respectively.

Initiation and termination of crazes in high impact polystyrene

Initiation and termination of crazes in high impact polystyrene (HIPS) were studied by transmission electron microscope. Instead of the first initiation of crazes in the vicinity of the equator or rubber particles, ribbon-shaped crazes beyond the region were observed on the TEM photos. The starting point and the end point of each ribbon were noticed not to be randomly located on the surface of the cellar particles in HIPS. The spots connecting to the ligaments between the PS rigid inclusions in the cellar particle are found to be the locations where crazes were initiated and terminated preferentially. In addition, the crazes generated at those spots were much thicker and longer. The thoughness of high impact polystyrene was enhanced by the multiple crazes formed in the matrices, through the reduction of the craze stress at room temperature with increasing the volume fraction of polybutadiene at these spots in the dispersed phase. These results conducted that not only the cell structure of the domains in HIPS was not homogeneous but also the polybutadiene ligaments between PS rigid inclusions in the domains were inhomogeneous. Therefore, the responsibility of those polybutadiene ligaments with different thickness to the stresses was different and it forced the crazing initiation and growing preferentially. The crazes were created in some regions in the matrices; On the contrary, rare crazes were formed in the other regions in spite of these regions surrounded around the same dispersed particles. The relation between the spots on the surface and the inner structure of the cellar particle was discussed in this paper.

Gas permeability and permselectivity of photochemically crosslinked copolyimides

A series of copolyimides were prepared from 2,4,6-trimethyl-1,3-phenylenediamines (3MPDA), 3,3',4,4'-benzophenone tetracarboxyl dianhydride (BTDA), and pyromellitic dianhydride (PMDA). Modification of the copolyimides by ultraviolet irradiation were carried out. Gas permeabilities of H-2, O-2, and N-2 through the copolyimides and photochemically crosslinked copolyimides were measured at temperatures from 30 to 90 degrees C. The relationships between gas permeabilities and temperature are in agreement with the Arrhenius equation. The structure of photochemically crosslinked copolyimides were characterized by Fourier transform infrared and gel measurement methods. Linear relationships between both log P and E-p and the volume fraction of PMDA-3MPDA exist. Photochemically crosslinking modification result in a decrease in gas permeability and an increase in E-p and alpha(H-2/N-2) for all the copolyimides. For H-2/N-2 separation, photochemically crosslinked copolyimides are of higher gas permeabilities and permselectivities simultaneously than normal polyimides. (C) 1999 John Wiley & Sons, Inc.

Monte Carlo simulation of phase separation of A/B/A-B ternary mixtures

Monte Carlo simulations were used to model A/B/A-B ternary mixtures with different AB diblock copolymer volume fractions for which both the dispersed and continuous phase volume fractions were kept constant. For concentrations of the diblock copolymer below a critical value, the domain size increment of the dispersed phase decreases linearly with the copolymer concentration. This is in agreement with the predictions of Noolandi and Hong. The dependence of the domain size as a function of the copolymer volume fraction can also be fitted by the equation of Tang and Huang. Our simulations indicate, for the first time, that the micelles form before saturation of the interface occurs. This means that the formation of the micelles is not a result of the saturation of the interface.

Phase-separation behavior of the system PES/phenoxy: An application of the Sanchez-Lacombe lattice fluid theory

Cloud-point curves reported for the system polyethersulfone (PES)/phenoxy were calculated by means of the Sanchez-Lacombe (SL) lattice fluid theory. The one adjustable parameter epsilon(12)*/k (quantifying the interaction energy between mers of the different components) can be evaluated by comparison of the theoretical and experimental phase diagrams. The Flory-Huggins (FH) interaction parameters are computed based on the evaluated epsilon(12)*/k and are approximately a linear function of volume fraction and of inverse temperature. The calculated enthalpies of mixing of PES/phenoxy blends for different compositions are consistent with the experimental values obtained previously by Singh and Walsh [1].

Cure processing modeling and cure cycle simulation of epoxy-terminated poly(phenylene ether ketone) .3. Determination of the time of pressure application

The curing temperature, pressure, and curing time have significant influence on finished thermosetting composite products. The time of pressure application is one of the most important processing parameters in the manufacture of a thermosetting composite. The determination of the time of pressure application relies on analysis of the viscosity variation of the polymer, associated with curing temperature and curing time. To determine it, the influence of the time of pressure application on the physical properties of epoxy-terminated poly(phenylene ether ketone) (E-PEK)-based continuous carbon fiber composite was studied. It was found that a stepwise temperature cure cycle is more suitable for manufacture of this composite. There are two viscosity valleys, in the case of the E-PEK system, associated with temperature during a stepwise cure cycle. The analysis on the effects of reinforcement fraction and defect content on the composite sheet quality indicates that the width-adjustable second viscosity valley provides a suitable pressing window. The viscosity, ranging from 400 to 1200 Pa . s at the second viscosity valley, is the optimal viscosity range for applying pressure to ensure appropriate resin flow during curing process, which enables one to get a finished composite with optimal fiber volume fraction and low void content. (C) 1997 John Wiley & Sons, Inc.