Electrical properties of carbon black‐filled polymer composites

This work deals with the dielectric properties of conductive composite materials, which consist of thermoplastic polypropylene (PP) matrix filled with carbon black (CB). The CB concentration was systematically varied in a wide range. Our main interest is focused on the investigation of electrical conductivity mechanism and related percolation phenomena in these materials. To study the electrical and dielectric properties of composites we used broadband ac dielectric relaxation spectroscopy (DRS) techniques in a wide temperature range. By measurements of complex dielectric permittivity, ϵ*, the dependence of ac conductivity, σ_ac, and dc conductivity, σ_dc, on the frequency, the temperature and the concentration of the conductive filler was investigated. The behavior of this system is described by means of percolation theory. The percolation threshold, P_C, value was calculated to be 6.2 wt.% CB. Both, dielectric constant and dc conductivity follow power‐law behavior, yielding values for the critical exponents, which are in good agreement with the theoretical ones. Indications for tunneling effect in the charge carriers transport through the composites are presented. The temperature dependence of dc conductivity gives evidence for the presence of positive temperature coefficient (PTC) effect.     

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。     

Photo-optical properties of polymer composites based on stretched porous polyethylene filled with photoactive cholesteric liquid crystal

A new type of polymer-liquid crystal composite with photovariable dichroism and birefringence is described. Porous stretched polyethylene films were used as polymer matrices. To induce a cholesteric phase in a commercial nematic host, a chiral photochromic dopant based on sorbide and cinnamic acid capable of E-Z isomerization under UV irradiation was used. A merocianine-type substance was selected as a dichroic dye. Introduction of a dye-doped cholesteric mixture with a helical pitch higher than ∼300 nm to polymer film led to an almost complete transition from a cholesteric to an oriented nematic phase, as well as to an increase in birefringence and the appearance of dichroism. Decrease of the helical pitch by increasing in the chiral dopant concentration in the liquid crystal-polymer composite results in a reduction of the dichroism values. UV irradiation of polymer composite leading to an isomerization of the chiral dopant and helix untwisting induces a noticeable gradual growth of dichroism and birefringence. These new composites can be considered as promising materials for optical applications.     

Mechanical properties of oriented polyvinylchloride composites filled with ultrafine particles

The tensile stress-strain behaviour of undrawn and drawn polyvinylchloride (PVC) composites filled with ultrafine SiO₂ and micron sized glass particles were discussed as functions of filler content and size. For the undrawn PVC composites filled with ultrafine SiO₂ particles, Young's moduli, yield and breaking stresses increased with filler content and decreasing filler size. Whereas for the composites filled with micron sized glass particles, their Young's moduli slightly increased with filler content but both the yield and breaking stresses decreased. Oriented PVC composites were made by uniaxially drawing to × 2.5 at 100 °C. Anisotropic mechanical properties of oriented specimens were discussed in terms of compliance tensor and yield stress measured in the direction of 0°, 45° and 90° to the original stretching direction at room temperature. In the case of 70A SiO₂, all the compliance decreased with filler content, whereas those of 65μ glass, this relation was reversed. The yield stress of the oriented PVC composites showed filler size dependence similar to Young's moduli. The anisotropic yield stress of oriented PVC composites were reasonably analysed by Hill's yield criterion.     

膨胀蛭石填充聚甲醛复合材料的制备与性能

采用经硅烷偶联剂和十六烷基三甲基溴化铵有机插层处理的膨胀蛭石微粉(EV)填充改性聚甲醛(POM),通过熔融共混制备POM/EV复合材料,并讨论了EV含量对复合材料的力学性能及热稳定性的影响.研究结果表明:当EV添加量为2%(w)时,复合材料的断裂伸长率为66.2%,较纯POM提高44.5%;弯曲强度和缺口冲击强度分别为77.7 MPa和6.15 kJ/m~2,分别较纯POM降低了7.9%和2.4%.此外,当EV的添加量为5%(w)时,复合材料的结晶点较纯POM提高了1.4℃;且随着EV添加量的增加,复合材料的热稳定性越好.     

Controlling the properties of epoxy composites filled with brick dust

Treatment of the filler surface with a silane dressing agent, ensuring the chemical interaction on the filler–binder interface, and ultrasonic treatment of the compound enhance the physicomechanical properties of the epoxy composite: The failure stress and bending elastic modulus increase by a factor of 2–3. Considerable (2.5- fold) increase in the impact resilience even at 50% filling should be particularly noted. Introduction of modified brick dust enhances the heat resistance and thermal conductivity of the epoxy composite.     

Thermogravimetric analysis of rice husk flour filled thermoplastic polymer composites

The thermal degradation and thermal stability of rice husk flour (RHF) filled polypropylene (PP) and high-density polyethylene (HDPE) composites in a nitrogen atmosphere were studied using thermogravimetric analysis. The thermal stability of pure PP and HDPE was found to be higher than that of wood flour (WF) and RHF. As the content of RHF increased, the thermal stability of the composites decreased and the ash content increased. The activation energy of the RHF filled PP composites increased slowly in the initial stage until α=0.3 (30% of thermal degradation region) and thereafter remained almost constant, whereas that of the RHF filled HDPE composites decreased at between 30 and 40 mass% of RHF content. The activation energy of the composites was found to depend on the dispersion and interfacial adhesion of RHF in the PP and HDPE matrix polymers. This revised version was published online in July 2006 with corrections to the Cover Date.     

Crystallization properties and thermal stability of polypropylene composites filled with wollastonite

The influence of wollastonite (CaSiO₃) content on the crystallization properties and thermal stability of polypropylene (PP) composites was investigated. The results showed that the crystallization temperature, crystallization end temperature and crystallization temperature interval, as well as the degree of crystallinity of the composites, were higher than those of the unfilled PP resin, while the crystallization onset temperature was little changed from that of the unfilled PP resin. The increase of degree of crystallinity for the composites could be attributed to the heterogeneous nucleation of the CaSiO₃ in the PP matrix. The thermal stability increased with increasing filler weight fraction (ϕ_f); the thermal decomposition rate decreased nonlinearly with increasingϕ_f. Finally, the dispersion of the filler particles in the matrix was observed, and the mechanisms of thermal stability and crystallizing behavior were discussed.     

The production and properties of polylactide composites filled with expanded graphite

Composites have been produced by melt-blending biodegradable polylactide (PLA) with commercially available expanded graphite (EG). Using different techniques of addition, the manifold effects of EG on PLA molecular, thermo-mechanical and fire-retardant properties were evaluated. The EG nanofiller provides PLA composites with competitive functional properties. They have a high rigidity, with Young's modulus and storage modulus increasing with EG content. They also have excellent thermal stability while preserving the glass transition and melting temperature of the original PLA matrix. Purification and pre-dispersion of EG nanofiller proved beneficial for preserving PLA molecular weights and led to improved mechanical performance. The presence of dispersed graphene nanolayers in PLA significantly accelerated the polyester crystallization process. The flame retardant properties also displayed improvements with a large decrease in the maximum rate of heat release as recorded by cone calorimetry, whereas the horizontal burning test (UL94 HB) was successfully passed revealing non-dripping and char formation.     

Date palm fibre filled recycled ternary polymer blend composites with enhanced flame retardancy

Flammability of recycled polypropylene (PP)/low density polyethylene (LDPE)/high density polyethylene (HDPE) ternary blends containing date palm fibres is investigated in this study. Melt blending is used for the composite preparation and the palm fibres induce good mechanical strength to the blend composites. The effect of flame retardant magnesium hydroxide, is studied through the limiting oxygen index analysis and cone calorimeter studies. Morphology of the palm fibres in presence of fire retardant reveals interesting facts of base hydrolysis. Since the polymers used are recycled ones and the fibres are obtained from the date palm leaves, the whole composite manufactured stands as low cost, less energy consuming and environmental friendly. Though the flame retardant reduced the mechanical properties, the palm fibres strengthened the whole composite thus helping to achieve the flame retardancy and mechanical properties simultaneously. Flame retardancy is correlated with the thermal degradation and thermal conductivity of the blend fibre composites as well.     

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.     

Dielectric properties of moist CaCO3 filled polyethylene composites

The capacitance and the dielectric loss tangents of CaCO₃ filled polyethylene composites were studied. Composite samples, prepared by polymerizing ethylene on the surfaces of fillers, pre-treated by polymerization catalysts, were compared to normal mechanical mixtures. Dielectric dispersion,, and loss, , proved to be sensitive to heating or vacuum treatment. Investigation of samples under conditions of different relative humidities showed that the dielectric dispersion is due to adsorbed water. Both and increased with decreasing frequency and the ratio of loss and dispersion was nearly constant. Dielectric data measured at different relative humidities could be represented by a single Cole-Cole plot. Samples soaked in water for different periods yielded qualitatively similar but quantitatively different Cole-Cole plots. Composite samples showed higher losses at similar humidities.Possible interpretations in terms of a molecular relaxation model, an interfacial relaxation model, including a charged double layer mechanism, percolation theory and the universal response theory were examined, but none was able to fully explain the observed phenomena.     

Control of microstructure and properties of filled polymer compositions

The problem of controlling the structure and properties of filled polymer compositions based on epoxy materials and various fibrous and disperse fillers is investigated. Four scale levels of the filled polymer materials are considered, and examples of their structure at different stages of the fracture process are given.     

Time dependence of piezoresistance for the conductor‐filled polymer composites

The piezoresistance and its time dependence of conductor‐filled polymer composites have been investigated. To reveal the origin of the time dependence of piezoresistance, the creep of the polymer matrix is also studied. Based on the interparticle separation change under the applied stress, a model has been developed to predict the piezoresistance and its time dependence. By analyzing this model, the influences of applied stress, filler particle diameter, filler volume fraction, matrix compressive modulus, potential barrier height, and the matrix creep behavior on the piezoresistance and its time dependence are interpreted quantitatively. These predicted results are compared with the experimental data obtained on the polymer composites filled with conductor fillers, and good agreements were obtained. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2739–2749, 2000     

Structure and properties of nickel-organosilicon polymer composites

Preparation of an electrically conducting heat-resistant composite from nickel powder (conducting component) and plasticized or unplasticized polymethylphenylsiloxane (binding matrix) was studied. The optimal preparation conditions and component ratio were determined. The phase composition, thermal resistance, and electrical conductivity of a coating based on this composite were studied in relation to the preparation temperature.     

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     

Mechanical properties and morphology for polypropylene composites filled with microencapsulated red phosphorus

The effects of the microencapsulated red phosphorus (MRP) content and specimen thickness on the mechanical properties of the filled polypropylene (PP) composites were studied at room temperature. The results showed that the influence of the MRP on the tensile and impact properties of the composites was significant, and the Young's modulus and impact strength of the composites increased nonlinearly while the tensile strength decreased slightly with increasing the MRP weight fraction; the tensile elongation at break increased outstandingly when the MRP weight fraction was less than 2% and then decreased with increasing the MRP weight fraction. Furthermore, the impact fracture surface was examined by scanning electronic microscope. The results suggested that the toughening effect was attributed to the absorption of impact fracture energy by the microencapsulated layer. Copyright © 2014 John Wiley & Sons, Ltd.     

Stability of electrical properties of conducting polymer composites

The effect of slow cycle heating and cooling on the stability of electrical properties of two polymer composites‐ polypropylene/polypyrrole (PP/PPy) and polypropylene/carbon black (PP/CB) ‐ was investigated. Conductivity in composites was measured in heating/cooling cycles in the temperature range from 16°C to 105°C in PP/PPy and to 125°C in PP/CB, respectively. It was found that the thermal treatment caused the decrease of PP/PPy conductivity while in case of PP/CB the treatment increased the electrical conductivity. The positive effect was explained by increased crystallinity in the thermally treated composite.     

Surface functionalized boehmite sheets filled epoxy composites with enhanced mechanical and thermal properties

Boehmite (AlOOH) sheets were synthesized via a hydrothermal method and then successfully functionalized with a bi‐functional coupling agent, γ‐aminopropyl‐ triethoxysilane (APTES), through a facile neutral solvent method. Scanning electron microscope and transmission electron microscopy images showed a uniform morphology of AlOOH sheets. APTES was found to be covalently bound with AlOOH sheets. The linked APTES can be combined with an epoxy oligomer through a ring opening addition reaction. The modified AlOOH was used as reinforcing agent to reinforce the epoxy resin cured by 4,4‐diaminodiphenylsulfone. The results of tensile and differential scanning calorimetric test revealed the tensile strength and glass transition temperature (Tg) firstly increase and then decrease with the increase of functionalized AlOOH sheets loading. When the loading of functionalized AlOOH sheets increased to 5 parts per hundred resin, the highest tensile strength and Tg were obtained. They are 100.8 MPa and 174.5 °C. Microscopic examinations revealed the presence of large plastic deformations at the micronscale in the formed composites in agreement with the observed strengthening effect of functionalized AlOOH sheets. Copyright © 2014 John Wiley & Sons, Ltd.     

Liquid-crystalline polymer composites with CdS nanorods: structure and optical properties

We report on the structure, uniaxial orientation, and photoluminescent properties of CdS nanorods that form stable nanocomposites with smectic C hydrogen-bonded polymers from the family of poly(4-(n-acryloyloxyalkoxy)benzoic acids. TEM analysis of microtomed films of nanocomposites reveals that CdS nanorods form small domains that are homogeneously distributed in the LC polymer matrix. They undergo long-range orientation with the formation of one-dimensional aggregates of rods when the composite films are uniaxially deformed. The Stokes photoluminescence was observed from CdS NRs/LC polymer composites with emission peak located almost at the same wavelength as that of NRs solution in heptane. An anti-Stokes photoluminescence (ASPL) in polymer nanocomposites was found under the excitation below the nanoparticles ground state. The mechanism of ASPL was interpreted in terms of thermally populated states that are involved in the excitation process. These nanocomposites represent an unusual material in which the optical properties of anisotropic semiconductor nanostructures can be controlled by mechanical deformation of liquid-crystalline matrix.