Influence of interfacial adhesion and the nonequilibrium glassy structure of a polymer on the enthalpy of mixing of polystyrene-based filled composites

For composites based on polystyrene, the styrene-butadiene copolymer, and polybutadiene filled with various kinds of zinc oxide powder, the enthalpy of mixing is calculated in the entire range of filler contents on the basis of calorimetric measurements with the use of the thermochemical cycle. It is shown that, when the polymer is in excess in the composites based on polystyrene and its copolymer, the enthalpy of mixing is negative, whereas at a high content of the filler, this value is positive. The alternating-sign pattern of the concentration dependence of the enthalpy of mixing is interpreted in terms of the superposition of the negative contribution of the enthalpy of the interfacial-adhesion interaction of a polymer matrix with the filler and the positive contribution due to a gain in the level of nonequilibrium of the glassy matrix near the surface. A thermodynamic model that makes it possible to separate these contributions and to describe the experimental curves of the enthalpy of mixing for the composites is advanced.     

Effect of the chemical nature of metal oxide on adhesion to the polyacrylate matrix in filled nanocomposites

The morphology, particle size, and thermochemical properties of the surface of oxides Al₂O₃, NiO, TiO₂, ZnO, and ZrO₂ obtained by the wire electroexplosion method were studied. The nanoparticles are spherical, with a mean diameter of 54–86 nm depending on the nature of the oxide. The hydrophilicity of the surface of metal oxide nanopowders was found to change in the series NiO-ZrO₂-TiO₂-ZnO-Al₂O₃. Nanocomposites with widely varied compositions were obtained from butyl methacrylate copolymer with 5 wt % methacrylic acid and the oxides under study. The enthalpies of dissolution of the composites in chloroform were determined by Calvet calorimetry. The enthalpies of copolymer mixing with oxides were calculated using the thermochemical cycle. The limiting enthalpies of copolymer adhesion to the oxide surface were calculated from the thermochemical data. The limiting adhesion enthalpy was shown to be negative for all oxides under study; these values decreased in magnitude as the surface hydrophilicity increased. The results were analyzed from the viewpoint of balance between the specific and dispersion interactions at the interface.     

Effect of the polymer matrix on the properties of advanced composites

The relationships discussed here clearly show that for the development of composite materials a multidisciplinary approach encompassing polymer chemistry, physics, engineering and material science is necessary. The complex composition of fiber reinforced polymeric composite materials, involving the synergistic interplay of individual components, requires new methods for the development of materials, which are not solely based on the formulation chemistry of the components. In the future, resistance against the application of advanced composites must be reduced, by gaining more confidence in the performance of this new class of materials with a fundamental understanding of their properties and potential. It will thus be possible to abolish unreasonable test methods and to use design characteristics which take maximum advantage of this material class.     

Structure-electrical properties relationships of polymer composites filled with Fe-powder

Structure-properties relationships of composite materials, consisting of a polymer matrix and metal inclusions, is very important for designing new materials with desirable properties. In the present work the electrical and dielectric properties of several composites, consisting of a polymer matrix and iron (Fe) particles as filler, were investigated. Broadband dielectric relaxation spectroscopy measurements were carried out. The electrical behaviour of the composites is described in terms of the percolation theory. Percolation threshold values were calculated and the values of the dielectric permittivity critical exponent were found in good agreement with the theoretical ones. The influence of using different polymer matrices on the physical properties of the composites was also of particular interest. The results were related to the microstructure of the composites and a schematic model was proposed.     

碲化镉纳米晶与聚合物复合研究进展

综述了近年来半导体纳米晶CdTe/聚合物复合材料在电致发光器件和复合发光材料方面的研究和应用进展情况,详细介绍了CdTe与水溶性高分子,非水溶性高分子以及生物大分子的复合情况,并展望了其发展前景。     

Electric conductivity of polymer films filled with magnetic nanoparticles

The conductivity of polymer composites with magnetic nanoparticles (MNP) containing magnetite and other MNP (Ni, Cu–Ni) in the layers and planar cells with Al electrodes is studied. For soluble polymers (polyvinylpyrrolidone and polyvinyl alcohol) containing 1–10 wt % of magnetite MNP, a substantial effect of MNP on surface conductivity is detected over a wide range (from 10^–10 to 10^–3 Ω^–1). It is shown that the addition of magnetite MNP not only results in a considerable change in cell conductivity, but also leads to its partially irreversible variation (by an order of magnitude or more) via minor modifications of the experimental conditions (temperature, electric field). For high-resistance samples with low probabilities of conducting chain formation, temperature current peaks are observed upon moderate heating (up to 350 K). These peaks are similar to the maxima observed upon polymer electret thermodischarges when the charges are captured by the deep centers associated with separate MNP or MNP aggregates. The type and position of the maxima are determined by the characteristics of the polymer matrix. For polyvinylpyrrolidone composites, the maxima are observed some time after heating (the echo effect). With composites based on solventborne polymers (polyalkanesterimides, soluble polyimide) and Ni, Cu–Ni MNP, no change in film conductivity measured electrophotographically is observed, due to the formation of a dielectric coating formed by polymer macromolecules adsorbed on the MNP surface. An explanation based on the possible formation of magnetic aggregates of magnetite MNP and conducting chains is proposed. Magnetic aggregation IPM is proposed as one way of controlling cell conductivity.     

Properties of wood-polymer composites with a polymer matrix containing sevilens

The effect of vinylacetate unit content in sevilen used as a polymer matrix or polyethylene compatibilizer on the properties of wood-polymer composites with a thermoplastic binders and filler of plant origin is studied. It is shown that the introduction of vinylacetate units decreases the tensile strength, contact elastic modulus, Brinell hardness, and water absorption of the composites, but increases the relative tensile elongation and impact viscosity without notch.     

Effect of polymer nature on the structure and properties of gel composites with incorporated bentonite particles

Composite gels based on polyacrylamide and poly(N-isopropyl acrylamide) with incorporated sodium bentonite particles are synthesized. It is shown that the presence of hydrophobic isopropyl groups in a polymer molecule promotes the subsequent formation of highly ordered aggregates of clay and cetylpyridinium chloride in a gel composite. An increase in temperature results in the collapse of composite gels based on poly(N-isopropyl acrylamide); however, no marked changes in the structure of lamellar aggregates of clay and surfactant are observed. It is revealed that the gel can stabilize lamellar structures formed in organoclay suspension prior to the incorporation into swollen polymer network.     

Carboxymethyl chitin as a matrix for composites with iron nanoparticles

The stabilizing effect of a biodegradable polymer in a macromolecular system based on 6-O-carboxymethyl chitin polyelectrolyte and iron nanoparticles is studied. Stabilization is associated with hydrogen bonding between the functional groups of the polymer and a surfactant forming the shell of a metal nanoparticle micelle. Composite film materials containing iron nanoparticles 2–4 nm in size are obtained.     

Molecular modeling of matrix chain deformation in nanofiber filled composites

The effects of the oriented fiber filler particles on the microscopic properties of the matrix network chains were investigated by using nanofiber filler particles as reinforcing material. Monte Carlo Rotational Isomeric State simulations were carried out for filled poly(ethylene) (PE) networks to study the dependence of the conformational distribution functions of polymer chains and their elastomeric properties on filler loadings. We were especially interested how the excluded volume effect of the nanofiber particles and their orientation (specifically orientational anisotropy) in the matrix influence elastomeric properties of the network. Distribution functions of the end-to-end distances of polymer chains for both unfilled and filled networks were calculated. Effects of nanofiber reinforcements with varying fiber radii and fiber volume fractions were investigated. We have found that the presence of nanofibers significantly increase the non-Gaussian behavior of polymer chains in the composite. The anisotropic effects of the nanofibers on mechanical properties of polymeric composites were studied as a function of their relative orientation to the direction of deformation. The modulus (reduced nominal stress per unit strain) was calculated from the distribution of end-to-end distances of polymer chains using the Mark–Curro method. Relatively small amount of nanofibers was found to increase the normalized moduli of the composite. Our results are quite in satisfactory qualitative agreement with experimental data reported in the literature. This shows that computer simulations provide a powerful tool in predicting physical properties of composite materials.     

Crystallisation of polypropylene matrix in composites filled with wooden parts of rapeseed straw

Nucleation ability of native and modified rapeseed straw during the polypropylene crystallization from the melt was investigated by the DSC method. Composites were made from isotactic polypropylene and lignocellulosic material using extrusion and injection moulding techniques. They were obtained using polypropylenes differing with respect to melt flow rates and different varieties of rapeseed straw. Chemical modification was carried out in two stages: through mercerisation and treatment with acetic acid anhydride. In the course of investigations, it was found that both native and modified rapeseed straw acted as an active nucleant of polypropylene crystallisation characterised by low values of MFR indices. It was found that for polypropylenes with high MFR values, the values of crystallization temperatures and crystallization half-time in composites were identical when compared with non-filled polymers. The investigations demonstrated that there were insignificant differences among composites containing straw from different varieties of rapeseed. The analysis of crystallization temperatures confirmed that rapeseed straw modification failed to change this parameter of the crystallization process. A similar tendency was observed in the case of changes of the half-time crystallization process. Moreover, the analysis of the crystallization temperature and crystallization half-time showed that the presence in composites of lignified rapeseed straw particles played an important role in the crystallization conditions.     

Effect of GMA polymer compatibilizers on highly filled composites of low density polyethylene/magnesium hydroxide

Functional polymers such as polyethylene grafted glycidyl methacrylate （PE-g-GMA） and ethylene-methyl acrylate-glycidyl methacrylate terpolymer （E/MA/GMA） were used as compatibilizers in the preparation of highly filled composites of polyethylene/magnesium hydroxide（PE/MH）. Comparative studies were performed on the effect of magnesium hydroxide and stearic acid on the interface within polymer and magnesium hydroxide composites. The effect of polymeric compatibilizers on the properties of the composites was studied using tensile and impact tests, torque rheological analysis, differential scanning calorimetry and environmental scanning electron microscopy （ESEM）. The microstructure of highly filled PE/MH composites changed after the addition of functional polymers. The mechanical properties of the composite material increased after compatibilization. The compatibilization processes of PE-g-GMA and E/MA/GMA were different. The grafted polymer was more compatible with polyethylene, which led to a polar polymer phase. In contrast, the tercopolymer tended to adhere to the surface of MH particles.     

Heat effect during the low-temperature oxidation of nickel nanoparticles in a porous matrix

A model of the heat-generating reaction of the low-temperature oxidation of nickel nanoparticles in nickel-supported catalysts is discussed. We use the continuous measurement of magnetization to estimate the heat effect of the reaction, allowing us to measure the heating of nickel nanoparticles in the support matrix, due to the temperature dependence of magnetization.     

Two- and three-body interactions among nanoparticles in a polymer melt

We perform direct three-dimensional density functional theory (DFT) calculations of two- and three-body interactions in polymer nanocomposites. The nanoparticles are modeled as hard spheres, immersed in a hard-sphere homopolymer melt of freely jointed chains. The two-particle potential of mean force obtained from the DFT is in near quantitative agreement with the potential of mean force obtained from self-consistent polymer reference interaction site model theory. Three-body interactions among three nanoparticles are found to be significant, such that it is not possible to describe these systems with a polymer-mediated two-body interaction calculated from the potential of mean force.     

Effect of thermal cycling and open-hole size on mechanical properties of polymer matrix composites

This paper investigates the effects of thermal cycling on mechanical degradation of polymer matrix composites (PMCs). Un-notched and open-hole specimens are tested using developed thermal cycling apparatus and tensile test machine. In addition, the hole-size effect of open-hole tension glass/epoxy composite laminates is investigated. The tensile strength, mass loss and surface degradation of the specimens were obtained during 250 cycles. Experimental results showed that the holes diameter is the main parameter to control the thermal cycling effects on open hole structure. Also, it is found that laminates with smaller holes have higher tensile strength variation than those with larger holes. The results showed that increment of the hole diameter and number of cycles decreases the tensile strength.     

Controlled nucleation and growth of CdS nanoparticles in a polymer matrix

In-situ synchrotron X-ray diffraction (XRD) was used to monitor the thermal decomposition (thermolysis) of Cd thiolates precursors embedded in a polymer matrix and the nucleation of CdS nanoparticles. A thiolate precursor/polymer solid foil was heated to 300 degrees C in the X-ray diffraction setup of beamline W1.1 at Hasylab, and the diffraction curves were each recorded at 10 degrees C. At temperatures above 240 degrees C, the precursor decomposition is complete and CdS nanoparticles grow within the polymer matrix forming a nanocomposite with interesting optical properties. The nanoparticle structural properties (size and crystal structure) depend on the annealing temperature. Transmission electron microscopy (TEM) and photoluminescence (PL) analyses were used to characterize the nanoparticles. A possible mechanism driving the structural transformation of the precursor is inferred from the diffraction features arising at the different temperatures.     

Electrical conduction in composites of a TCNQ anion-radical salt in a polymer matrix

The conduction behavior of composites of the anion-radical salt NaTCNQ (sodium 7,7,8,8-tetracyanoquinodimethanide) in poly(vinyl chloride) plasticized by polyurethane has been studied. TCNQ salt-polymer composites that have good moldability and flexibility are characterized by molecular or granular dispersion of the TCNQ salt in a polar polymer matrix. The conduction mode changes from one due to molecularly dispersed sites (CMDS) to one due to granularly dispersed sites (CGDS) with increasing NaTCNQ content. In the CMDS region, the predominant conduction is ionic; TCNQ anion-radicals migrate toward the anode under a dc biasing voltage and a high-resistivity layer is formed near the cathode. The fixation of TCNQ salt at sites in the polymer matrix is believed to be important for the stabilization of electronic conduction under a dc electric field. In the CGDS region, the conduction is electronic and the current-voltage characteristics of the composite are nonohmic, which indicates that carrier generation depends on the Poole-Frenkel effect.     

Effect of the nature of polymer matrix on the process of cholesterol photooxidation in the presence of immobilized tetraphenylporphyrins

It was shown that carrying out the reaction of cholesterol photosensitized oxidation in the presence of porphyrins immobilized on the hydrolyzed copolymer of tetrafluorethylene and H⁺ form of perfluoro-3,6-dioxo-5-methyl-6-sulfonylfluorideoctene-1 leads to the formation of not previously described new products: 6β-phormyl-B-norcholestan-3β,5β-diol, 6β-chlorocholestan-3β,5α-diol, cholestan-3β,5α,6β-triol, and 5α-chlorocholestan-3β,6β-diol.     

Heat transfer in polymer composites filled with inorganic hollow micro-spheres: A theoretical model

The heat transfer mechanisms in inorganic hollow micro-spheres filled polymer composites are analyzed in the present paper. This heat transfer includes mainly three mechanisms: (1) thermal conduction between solid and gas; (2) thermal radiation between the hollow micro-sphere surfaces; and (3) natural thermal convection of the gas in the micro-hollow spheres. A theoretical model of heat transfer in polymer/inorganic hollow micro-sphere composites is established based on the law of minimal thermal resistance and the equal law of the specific equivalent thermal conductivity, and a corresponding equation of effective thermal conductivity is derived. The effective thermal conductivity (k_eff) of hollow glass bead-filled polypropylene composites is estimated by using this equation, and is compared with the numerical simulations by means of a finite element method. The results show that the variation of the theoretical estimations of k_eff are similar to the numerical simulations at lower filler volume fraction (φ_f20%). Moreover, k_eff decreases linearly with increasing φ_f, and reduces somewhat with increase of filler size.     

Estimation of flocculation structure in filled polymer composites by dynamic rheological measurements

 The frequency and concentration dependences of the storage modulus (G ^′) for carbon black and short-carbon-fiber-filled polymer composites were investigated by means of dynamic rheological measurements. It was found that G ^′ at low frequencies and amplitudes could be used as a sensitive experimental parameter for detecting the flocculation structure of the ultra-fine-particle-filled polymer composites. Correlation of electrical resistivity of the composites to the relative storage modulus, G ^′ _r(=G ^′ _c/ G ^′ _p), revealed that the three-dimensional interparticle networks start to construct through the matrix when G ^′ _r increases to 7 regardless of the composite systems. Quantitative calculations in order to determine the flocculation structure were carried out by means of the modified Kerner equation. A plot of the calculated value, defined as the floc index A, dependence of electrical resistivity for various systems was found to be a universal curve. Accordingly, we suggest that A might universally correspond to the flocculation structure of the filler, which is independent of the nature of the filler, the molecular weight, the chemical composition of the polymer and the temperature at which the measurement is made. This method is particularly effective for estimating the flocculation structure of ultra-fine-particle-filled polymer composites no matter whether the filler is conductive or not. Received: 26 May 1999/Accepted in revised form: 28 September 1999