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Segregated Network Polymer Composites with High Electrical Conductivity and Well Mechanical Properties based on PVC, P(VDFTFE), UHMWPE, and rGO
The formation of a segregated network structure (wittingly uneven distribution of a filler) is one of the most promising strategies for the fabrication of electrically conductive polymer composites at present. However, the simultaneous achievement of high values of electrical conductivity with the retention of well mechanical properties within this approach remains a great challenge. Here, by means of X-ray photoelectron spectra (XPS), near-edge X-ray absorption fine structure (NEXAFS) spectra, scanning electron microscopy (SEM), dielectric spectroscopy, and compression engineering stress-strain curve analysis, we have studied the effect of a segregated network structure on the electrical conductivity and mechanical properties of a set of polymer composites. The composites were prepared by applying graphene oxide (GO) with ultralarge basal plane size (up to 150 μm) onto the surface of polymer powder particles, namely, poly(vinyl chloride) (PVC), poly(vinylidene fluoride-co-tetrafluoroethylene) (P(VDF-TFE)), and ultrahigh-molecular-weight poly(ethylene) (UHMWPE) with the subsequent GO reduction and composite hot pressing. A strong dependence of the segregated network polymer composites' physical properties on the polymer matrix was demonstrated. Particularly, 12 orders of magnitude rise of the polymers' electrical conductivity up to 0.7 S/m was found upon the incorporation of the reduced GO (rGO). A 17% increase in the P(VDF-TFE) elastic modulus filled by 1 wt % of rGO was observed. Fracture strength of PVC/rGO at 0.5 wt % content of the filler was demonstrated to decrease by fourfold. At the same time, the change in strength was not significant for P(VDF-TFE) and UHMWPE composites in comparison with pure polymers. Our results show a promise to accelerate the development of new composites for energy applications, such as metal-free supercapacitor plates and current collectors of lithium-ion batteries, bipolar plates of proton-exchange membrane fuel cells, antistatic elements of various electronic devices, etc. © 2020 American Chemical Society.
Temperature-Dependent Reinforcement of Hydrophilic Rubber Using Ice Crystals
This is the first study on the impact of ice crystals on glass transition and mechanical behavior of soft cross-linked elastomers. A hydrophilic elastomer such as epichlorohydrin-ethylene oxide-allyl glycidyl ether can absorb about ∼40 wt % of water. The water-swollen cross-linked network exhibits elastic properties with more than 1500% stretchability at room temperature. Coincidently, the phase transition of water into solid ice crystals inside of the composites allows the reinforcement of the soft elastomer mechanically at lower temperatures. Young's modulus of the composites measured at -20 °C remarkably increased from 1.45 to 3.14 MPa, whereas at +20 °C, the effect was opposite and the Young's modulus decreased from 0.6 to 0.03 MPa after 20 days of water treatment. It was found that a part of the absorbed water, ∼74% of the total absorbed water, is freezable and occupies nearly 26 vol % of the composites. Simultaneously, these solid ice crystals are found to be acting as a reinforcing filler at lower temperatures. The size of these ice crystals is distributed in a relatively narrow range of 400-600 nm. The storage modulus (E′) of the ice crystal-filled composites increased from 3 to 13 MPa at -20 °C. The glass transition temperature (-37 °C) of the soft cross-linked elastomer was not altered by the absorption of water. However, a special transition (melting of ice) occurred at temperatures close to 0 °C as observed in the dynamic mechanical analysis of the water-swollen elastomers. The direct polymer/filler (ice crystals) interaction was demonstrated by strain sweep experiments and investigated using Fourier transform infrared spectroscopy. This type of cross-linked rubber could be integrated into a smart rubber application such as in adaptable mechanics, where the stiffness of the rubber can be altered as a function of temperature without affecting the mechanical stretchability either below or above 0 °C (above the glass temperature region) of the rubber.
Production and characterization of brass-matrix composites reinforced with Ni59Zr20Ti16Si2Sn3 glassy particles
Brass-matrix composites reinforced with 40 and 60 vol.% of Ni59Zr20Ti16Si2Sn3 glassy particles were produced by powder metallurgy. The crystallization behavior and the temperature dependence of the viscosity of the glass reinforcement were studied in detail to select the proper sintering parameters in order to avoid crystallization of the glassy phase during consolidation. The brass-glass powder mixtures were prepared through manual blending as well as by ball milling to analyze the effect of the matrix ligament size on the mechanical properties of the composites. The powder mixtures were then consolidated into highly-dense bulk specimens at temperatures within the supercooled liquid region by hot pressing followed by hot extrusion. The preparation of the powder mixtures has a strong influence on the mechanical behavior of the composites. The strength increases from 500 MPa for pure brass to 740 and 925 MPa for the blended composites with 40 and 60vol.% of glass reinforcement, while the strength increases to 1,240 and 1,640 MPa for the corresponding composites produced by ball milling. Modeling of the mechanical properties indicates that this behavior is related to the reduced matrix ligament size characterizing the milled composites.
Glass-forming ability, phase formation and mechanical properties of glass-forming Cu-Hf-Zr alloys
The influence of Hf additions on the glass-forming ability (GFA), phase formation and mechanical properties of Cu50HfxZr50-x (x = 2,5,10,20 at.%) alloys has been systematically investigated. We report on a distinct correlation between phase formation and GFA of Cu50Zr50-based alloys. Increasing additions of Hf reduce the thermal stability of the high-temperature B2 Cu(Hf,Zr) phase, while the thermal stability of the corresponding undercooled melt is enhanced. The GFA of these alloy series gradually raises up to 10 at.% Hf, whereas at 20 at.%Hf, the GFA is drastically lowered, since the B2 Cu(Hf,Zr) phase becomes unstable and the precipitation of the low-temperature equilibrium phases is favoured. This interrelation determines the microstructure and results in the formation of Cu-Hf-Zr-based bulk metallic glass composites. These composites not only show appreciable macroscopic plastic strain, but also high yield strength.
Fe3O4 Nanoparticles Grown on Cellulose/GO Hydrogels as Advanced Catalytic Materials for the Heterogeneous Fenton-like Reaction
Cellulose/graphene oxide (GO)/iron oxide (Fe3O4) composites were prepared by coprecipitating iron salts onto cellulose/GO hydrogels in a basic solution. X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared, and X-ray diffraction characterization showed that Fe3O4 was successfully coated on GO sheets and cellulose. Cellulose/GO/Fe3O4 composites showed excellent catalytic activity by maintaining almost 98% of the removal of acid orange 7 (AO7) and showed stability over 20 consecutive cycles. This performance is attributable to the synergistic effect of Fe3O4 and GO during the heterogeneous Fenton-like reaction. Especially, the cellulose/GO/Fe3O4 composites preserve their activity by keeping the ratio of Fe3+/Fe2+ at 2 even after 20 catalysis cycles, which is supported by XPS analysis.
Electrolytic Surface Treatment for Improved Adhesion between Carbon Fibre and Polycarbonate
To achieve good mechanical properties of carbon fibre-reinforced polycarbonate composites, the fibre-matrix adhesion must be dialled to an optimum level. The electrolytic surface treatment of carbon fibres during their production is one of the possible means of adapting the surface characteristics of the fibres. The production of a range of tailored fibres with varying surface treatments (adjusting the current, potential, and conductivity) was followed by contact angle, inverse gas chromatography and X-ray photoelectron spectroscopy measurements, which revealed a significant increase in polarity and hydroxyl, carboxyl, and nitrile groups on the fibre surface. Accordingly, an increase in the fibre-matrix interaction indicated by a higher interfacial shear strength was observed with the single fibre pull-out force-displacement curves. The statistical analysis identified the correlation between the process settings, fibre surface characteristics, and the performance of the fibres during single fibre pull-out testing.
Prediction of Short Fiber Composite Properties by an Artificial Neural Network Trained on an RVE Database
In this study, an artificial neural network is designed and trained to predict the elastic properties of short fiber reinforced plastics. The results of finite element simulations of three-dimensional representative volume elements are used as a data basis for the neural network. The fiber volume fraction, fiber length, matrix-phase properties, and fiber orientation are varied so that the neural network can be used within a very wide range of parameters. A comparison of the predictions of the neural network with additional finite element simulations shows that the stiffnesses of short fiber reinforced plastics can be predicted very well by the neural network. The average prediction accuracy is equal or better than by a two-step homogenization using the classical method of Mori and Tanaka. Moreover, it is shown that the training of the neural network on an extended data set works well and that particularly calculation-intensive data points can be avoided without loss of prediction quality.
Devulcanization of Waste Rubber and Generation of Active Sites for Silica Reinforcement
Each year, hundreds of millions of tires are produced and ultimately disposed into nature. To address this serious environmental issue, devulcanization could be one of the sustainable solutions that still remains as one of the biggest challenges across the globe. In this work, sulfur-vulcanized natural rubber (NR) is mechanochemically devulcanized utilizing a silane-based tetrasulfide as a devulcanizing agent, and subsequently, silica (SiO2)-based rubber composites are prepared. This method not only breaks the sulfur–sulfur cross-links but also produces reactive poly(isoprene) chains to interact with silica. The silica natural rubber composites are prepared by replacing 30% fresh NR by devulcanized NR with varying contents of silica. The composites exhibit excellent mechanical properties, tear strength, abrasion resistance, and dynamic mechanical properties as compared with the fresh natural rubber silica composites. The tensile strength of devulcanized rubber-based silica composites is ∼20 MPa, and the maximum elongation strain is ∼921%. The devulcanized composites are studied in detail by chemical, mechanical, and morphological analyses. Thus, the value added by the devulcanized rubber could attract the attention of recycling community for its sustainable applications.
Morphology and crystallization of polypropylene/microfibrillated cellulose composites
Microfibrillated cellulose (MFC) was prepared by controlling the re-precipitation of cellulose prepared in the mixture form of NaOH/Urea solubilized microcrystalline cellulose (MCC) and starch. The cellulose re-precipitation was carried-out in an HCl bath, resulting in a MFC form having relatively lower crystallinity than MCC. The XRD pattern of MFC indicated the partially crystalline structure arising from the imperfect orientation of a cellulose chain obstructed by a starch molecule in the precipitation step. Interestingly, the MFC morphology exhibited a web-like structure with a diameter in the range of 10-20 nm. The water retention value of MFC was extraordinarily high due to its extremely small diameter having high surface area. Further, surface silanization of MFC with organosilane was carried out. Then, the modified MFC was melt-mixed with polypropylene (PP) matrix via a simple melt mixing technique. The morphology and crystallization of the PP/MFC composites were measured. The morphology of organosilane treated MFC exhibited agglomeration of 10 microns in diameter with layered structures arising from the packing of microfibrils. The FTIR spectra showed hydrophobic characteristics of treated MFC observed by the disappearance of original cellulose hydroxyl group and bound water. The crystallinity of treated MFC increased when compared to the untreated MFC, indicating that cellulose chains of unmodified MFC underwent re-orientation occurring in the modification step due to its high crystallinity characteristic. For the PP/MFC-composite containing MFC loading, faster crystallization and higher spherulite growth rate, in case of higher MFC loading, were observed. In addition, the spherulite size decreased with an increase in the crystallization temperature. However, the degree of crystallinity was fairly independent on the MFC-loading. Therefore it can be concluded that the addition of MFC might enable shorter cycle times, resulting in cheaper processing cost in a view point of polymer processing.
Strengthening of Al-Fe3Al composites by the generation of harmonic structures
Strengthening of alloys can be efficiently attained by the creation of harmonic structures: bimodal microstructures generated by controlled milling of the particulate precursors, which consist of coarse-grained cores embedded in a continuous fine-grained matrix. Here, we extend the concept of harmonic structures to metal matrix composites and analyze the effectiveness of such bimodal microstructures for strengthening composites consisting of a pure Al matrix reinforced with Fe3Al particles. Preferential microstructural refinement limited to the surface of the particles, where the Fe3Al phase is progressively fragmented, occurs during ball milling of the Al-Fe3Al composite powder mixtures. The refined surface becomes the continuous fine-grained matrix that encloses macro-regions with coarser reinforcing particles in the harmonic composites synthesized during subsequent powder consolidation. The generation of the bimodal microstructure has a significant influence on the strength of the harmonic composites, which exceeds that of the conventional material by a factor of 2 while retaining considerable plastic deformation. Finally, modeling of the mechanical properties indicates that the strength of the harmonic composites can be accurately described by taking into account both the volume fraction of reinforcement and the characteristic microstructural features describing the harmonic structure.