Fibrillar polymer–polymer composites: morphology, properties and applications

Micro- or nano-fibrillar composites (MFCs or NFCs) are created by blending two homopolymers (virgin or recycled) with different melting temperatures such as polyethylene (PE) and poly(ethylene terephthalate) (PET), and processing the blend under certain thermo-mechanical conditions to create in situ fibrils of the polymer that has the higher-melting temperature. These resulting fibrillar composites have been reported to possess excellent mechanical properties and can have wide ranging applications with suitable processing under controlled conditions. However, the properties and applications very much depend on the morphology of created polymer fibrils and their thermal stability. The present paper develops an understanding of the mechanism of micro-/nano-fibril formation in PE/PET and polypropylene (PP)/PET blends by studying their morphology at various stages of extrusion and drawing. It is revealed that this subsequent mechanical processing stretches the polymer chains and creates fibrils of very high aspect ratios, thus resulting in superior mechanical performance of the composites compared to the raw blends. The study also identifies the primary mechanical properties of the main types of MFCs, as well as quantifying their enhanced resistance to oxygen permeability. Furthermore, the failure phenomena of these composites are studied via application of the modified Tsai–Hill criterion. In addition to their usage as input materials in different manufacturing processes, possible applications of these fibrillar composites in two different areas are also discussed, namely food packaging with controlled oxygen barrier properties and biomedical tissue scaffolding. Results indicate a significant scope for using these materials in both areas.     

Solution-processed Ni–CNTs filled ferroelectric P(VDF–TrFE) composites with improved dielectric properties and thermal conductivity

Dielectric composites made using two kinds of poly(vinylidene fluoride–trifluoroethylene) [P(VDF–TrFE)] (70/30 and 80/20 mol%) as polymer matrices and nickel particles coated carbon nanotubes (Ni–CNTs) as filler were developed via solution-processed method. The scanning electron microscopy (SEM) indicated good compatibility and dispersion of Ni–CNTs in the P(VDF–TrFE) matrix. Ni–CNTs/P(VDF–TrFE) composites exhibited high dielectric constants with low dielectric losses. The maximum dielectric constants of Ni–CNTs/P(VDF–TrFE) composites of 198 and 185 at 100 Hz were obtained at 18.0 wt% Ni–CNTs loading, respectively. The incorporation of Ni–CNTs in the P(VDF–TrFE) matrix resulted in enhanced thermal conductivity. The highest values, obtained at 18.0 wt% Ni–CNTs loading, were 1.05 and 1.03 W/m K, respectively. Although there were no very obvious difference, the dielectric properties and thermal conductivity of Ni–CNTs/P(VDF–TrFE) 70/30 mol% composites were slightly better to those of Ni–CNTs/P(VDF–TrFE) 80/20 mol% composites in many cases. The aforementioned results suggest that these high-performance composites hold great promise for application in electrical and electronic field.     

Ceramic–metal and ceramic–polymer composites prepared by a biomimetic process

A biomimetic process was developed to prepare apatite–metal and apatite–polymer composites. A variety of metals and organic polymers incorporated surface functional groups such as Si–OH, Ti–OH or Ta–OH to induce formation of a biologically active bonelike apatite by chemical treatment or physical adsorption. Subsequent immersion in a simulated body fluid (SBF) with ion concentrations nearly equal to those of human blood plasma or 1.5 SBF led to the formation of a dense and uniform bonelike apatite layer on the surface. Apatite–metal and apatite–polymer composites prepared in this way are believed to be very useful as artificial bone substitutes.     

Effects of coupling agent on the preparation and dielectric properties of novel polymer–ceramic composites for embedded passive applications

The study was carried out to investigate the effects of silane coupling agent, γ-aminopropyl triethoxy silane (KH-550), on the preparation and dielectric properties of Barium titanate (BaTiO₃)/Bisphenol-A dicyanate (2,2′-bis (4-cyanatophenyl) isopropylidene)(BADCy) composites for embedded passive implications. It was found that KH-550 accelerated the polymerization of BADCy and was beneficial to improve the compatibility between BaTiO₃ particles and BADCy matrix. The dielectric constant (ε) and dielectric loss (tanδ) both increased at first and then decreased with the increase of the KH-550 content. With the increase of the frequency, the variation ranges of the dielectric constant and dielectric loss of these composites were not obvious since the dielectric properties of cyanate ester were stable at various frequencies.     

All-organic PANI–DBSA/PVDF dielectric composites with unique electrical properties

Novel all-organic polymer high-dielectric permittivity composites of polyaniline (PANI)/poly (vinylidene fluoride) (PVDF) were prepared by solution method and their dielectric and electric properties were studied over the wide ranges of temperatures and frequencies. To improve the interface bonding between two polymers, dodecylbenzenesulfonic acid (DBSA), a bulky molecule containing a polar head and a long non-polar chain was used both as a surfactant and as dopant in polyaniline (PANI) synthesis. Synthesized conducting PANI–DBSA particles were dispersed in poly(vinylidene fluoride) (PVDF) matrix to form an all-organic composite with different PANI–DBSA concentrations. Near the percolation threshold, the dielectric permittivity of the composites at 100 Hz frequency and room temperature was as high as 170, while the dielectric loss tangent value was as low as 0.9. Like typical percolation system, composites experienced high dielectric permittivity at low filler concentrations. However, their dielectric loss tangent was low enough to match with non-percolative ceramic filler-based polymer composites. Maximum electrical conductivity at 24 wt% of PANI–DBSA was mere 10^?6 S/cm, a remarkably low value for percolative-type composites. Increase in the dielectric permittivity of the composites with increase in temperature from 25 to 115 °C for different PANI–DBSA concentrations was always in the same range of 50–60 %. However, the degree of increase in the electrical conductivity with the temperature was more prominent at low filler concentrations compared with high filler concentrations. Distinct electrical and their unique thermal dependence were attributed to an improved interface between the filler and the polymer matrix.     

Hybrid carbon nanotube–carbon fiber composites with improved in-plane mechanical properties

In this study carbon nanotubes (CNTs) were grown on carbon fibers to enhance the in-plane and out-of-plane properties of fiber reinforced polymer composites (FRPs). A relatively low temperature synthesis technique was utilized to directly grow CNTs over the carbon fibers. Several composites based on carbon fibers with different surface treatments (e.g. growing CNTs with different lengths and distribution patterns and coating the fibers with a thermal barrier coating (TBC) layer) were fabricated and characterized via on- and off-axis tensile tests. The on-axis tensile strength and ductility of the hybrid FRPs were improved by 11% and 35%, respectively, due to the presence of the TBC and the surface grown CNTs. This configuration also exhibited 16% improvement on the off-axis stiffness. Results suggest that certain CNT growth patterns and lengths are more pertinent than the other surface treatments to achieve superior mechanical properties.     

Structural,physical and damping properties of melt-spun Ni–Mn–Ga wire-epoxy composites

Ni–Mn–Ga is a ferromagnetic shape memory alloy that exhibits large, magnetic-field- and stress-induced strains via energy dissipating twinning when processed into single crystals. Grain boundaries suppress twinning and render polycrystalline Ni–Mn–Ga brittle. Ni–Mn–Ga/polymer composites overcome the drawbacks of polycrystals and could thus provide a less expensive and easier to handle alternative to Ni–Mn–Ga single crystals for damping applications. Ni–Mn–Ga wires were produced by melt-spinning and were polycrystalline in the as-spun state. Annealed wires were ferromagnetic at room temperature with non-modulated martensite and a bamboo microstructure. The annealed wires displayed a hysteretic stress–strain behavior typical for twinning. Ni–Mn–Ga wire-epoxy matrix composites were fabricated with as-spun and annealed wires. The damping behavior of annealed Ni–Mn–Ga wire-epoxy matrix composites was higher than that of as-spun Ni–Mn–Ga wire-epoxy matrix composites and of pure epoxy.     

Microstructure and dielectric properties of BF–PFN ceramics with negative dielectric loss

Multiferroics with negative value of dielectric constant are very promising materials because of their modern applicability. These materials can be used as materials for the construction of electromagnetic radiation shields. The subject of the research is multiferroic BiFeO₃–PbFe_1/2Nb_1/2O₃ (BF–PFN) ceramics. For all multiferroic materials the following studies are conducted: SEM, EDS and the temperature dependence of dielectric constant ε′(T). Above a certain temperature (different for different chemical compositions) the value of dielectric constant reaches negative values. Such the behavior of the dielectric constant may indicate that the polarization inside the material has a reverse direction to the external electric field. That is, the electric field inside the material counteracts the applied external electric field. The obtaining materials also show negative dielectric losses. The Axelrod model is used to explain the mechanism that causes negative dielectric loss.     

Polypropylene–microcrystalline cellulose composites with enhanced compatibility and properties

Polypropylene (PP)–microcrystalline cellulose (MCC) composites were prepared containing Poly(propylene-graft-maleic anhydride) (PP-g-MA) and MCC treated with silicone oil, stearic acid or alkyltitanate coupling agent to promote matrix–filler dispersion and compatability. Infrared spectroscopy confirmed surface treatment. MCC content and PP-g-MA increased PP thermal stability and crystallisation temperature (T_c), though reduced crystallinity due to cellulose II crystals. Tensile stress–strain analysis revealed increased modulus with MCC content, PP-g-MA, alkyltitanate and stearic acid. MCC and PP-g-MA reduced creep deformation and increased permanent strain. Storage modulus, loss modulus and glass transition temperature increased with MCC concentration due to effective interaction between PP and MCC.     

A tribological and biomimetic study of PI–CNT composites for cartilage replacement

This article presents an investigation into the possible matching of mechanical properties of a polyimide (PI)–carbon nanotube (CNT) composite system to natural cartilage tissue. Currently used ultrahigh molecular weight polyethylene (UHMWPE) used in total joint replacements presents certain drawbacks due to a mismatch in mechanical and tribological properties with those of a natural bone joint. Natural cartilage tissue is a composite material itself, being composed of collagen fibers, hydrophilic proteoglycan molecules, cells and other constituents. The current investigation attempts to mimic the mechanical and tribological properties of natural cartilage tissue by varying the CNT concentration in a PI matrix. Nanoindentation and pin-on-flat tribological tests were conducted for this purpose. It was found that the coefficient of friction (COF) reached a minimum at a concentration of 0.5% CNT (by volume) when articulated against Ti6Al4V alloy. When articulated against Ti6Al4V alloy in the presence of a lubricant, the minimum COF was obtained at a concentration of 0.2% CNT. The maximum penetration depth under nanoindentation varied with CNT concentration and indicated that the mechanical properties could be tailored to match that of cartilage tissue. A closer investigation into this behavior was carried out using scanning electron, transmission electron, and atomic force microscopy. It was noticed that there is good bonding between the CNTs and polyimide matrix. There was a ductile to brittle transition as the concentration of CNT was increased. Competing interactions between nanotube–matrix and nanotube–nanotube are possible reasons for the deformation and friction behavior identified.     

Tensile properties of carbon fibres and carbon fibre–polymer composites in fire

The effect of fire on the tensile properties of carbon fibres is experimentally determined to provide new insights into the tensile performance of carbon fibre–polymer composite materials during fire. Structural tests on carbon–epoxy laminate reveal that thermally-activated weakening of the fibre reinforcement is the dominant softening process which leads to failure in the event of a fire. This process is experimentally investigated by determining the reduction to the tensile properties and identifying the softening mechanism of T700 carbon fibre following exposure to simulated fires of different temperatures (up to 700 °C) and atmospheres (air and inert). The fibre modulus decreases with increasing temperature (above ～500 °C) in air, which is attributed to oxidation of the higher stiffness layer in the near-surface fibre region. The fibre modulus is not affected when heated in an inert (nitrogen) atmosphere due to the absence of surface oxidation, revealing that the stiffness loss of carbon fibre composites in fire is sensitive to the oxygen content. The tensile strength of carbon fibre is reduced by nearly 50% following exposure to temperatures over the range 400–700 °C in an air or inert atmosphere. Unlike the fibre modulus, the reduction in fibre strength is insensitive to the oxygen content of the atmosphere during fire. The reduction in strength is possibly attributable to very small (under ～100 nm) flaws and removal of the sizing caused by high temperature exposure.     

Compressive mechanical properties of closed-cell aluminum foam–polymer composites

The compressive mechanical properties of two kinds of closed-cell aluminum foam–polymer composites (aluminum–epoxy, aluminum–polyurethane) were studied. The nonhomogeneous deformation features of the composites are presented based on the deformation distributions measured by the digital image correlation (DIC) method. The strain fluctuations rapidly grow with an increase in the compressive load. The uneven level of the deformation for the aluminum–polyurethane composite is lower than that for the aluminum–epoxy composite. The region of the preferentially fractured aluminum cell wall can be predicted by the strain distributions in two directions. The mechanical properties of the composites are investigated and compared to those of the aluminum foams. The enhancement effect of the epoxy resin on the Young’s modulus, the Poisson’s ratio and the compressive strength of the aluminum foams is greater than that of the polyurethane resin.     

Bioactivity of ceramic–polymer composites with varied composition and surface topography

HAPEX trade mark (40 vol % hydroxyapatite in a high-density polyethylene matrix) and AWPEX (40 vol % glass-ceramic apatite-wollastonite in a high-density polyethylene matrix) are composites designed to provide bioactivity and to match the mechanical properties of human cortical bone. HAPEX trade mark has had clinical success in middle ear and orbital implants, and there is great potential for further orthopaedic applications of these materials. However, more detailed in vitro investigations must be performed to better understand the biological interactions of the composites. In this study, the bioactivity of each material was assessed. Specifically, the effects of controlled surface topography and ceramic filler composition on apatite layer formation in acellular simulated body fluid (SBF) with ion concentration similar to those of human blood plasma were examined. Samples were prepared as 1 x 10 x 10 mm(3) tiles with polished, roughened or parallel-grooved surface finishes, and were incubated in 20 ml of SBF at 36.5 degrees C for one, three, seven or 14 days. The formation of an apatite layer on the composite surface after immersion was demonstrated by thin-film X-ray diffraction, environmental scanning electron microscopy and energy dispersive X-ray analysis. Variations in sample weight and solution pH over the period of incubation were also recorded. Significant differences were found between the two materials tested, with greater bioactivity in AWPEX than HAPEX trade mark. Results also showed surface topography to be important, with rougher samples correlated to earlier apatite formation. Osteoblast-like cells proliferated favourably on both composite materials, with many filopodia connections, preferential attachment to ceramic particles and contact guidance effects evident.     

γ-Aminopropyl triethoxysilane functionalized graphene oxide for composites with high dielectric constant and low dielectric loss

A facile and efficient approach was developed to simultaneously functionalize and tune the reduction state of graphene oxide (GO) with γ-aminopropyl triethoxysilane (APTES) aided by NH₃ solution. X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy indicated that many surface groups of GO sheets were removed, and APTES were successfully functionalized onto GO sheets. The APTES-functionalized GO sheets (GO-APTES) were dispersed in water and further incorporated into nitrile butadiene rubber (NBR) by latex co-coagulation to form GO-APTES/NBR composites. These composites featured high degrees of exfoliation and intercalation of GO-APTES sheets throughout the NBR matrix. More significantly, the GO-APTES/NBR composites exhibited a relatively high dielectric constant (∼30.8) and a small loss factor (<0.04) at 1.0 kHz, combining with a good insulating property. The unique dielectric responses of GO-APTES/NBR composites open up the potential applications of these materials in resistive and capacitive field grading materials.     

Polymer composites filled with core–shell structured nanofillers: effects of shell thickness on dielectric and thermal properties of composites

Journal of Materials Science: Materials in Electronics - In this study, we explore poly(vinylidene fluoride) (PVDF) filled with the core–shell nanofillers of silicon dioxide-coated...     

High strain recovery with improved mechanical properties of gelatin–silica aerogel composites post-binding treatment

Silica aerogels are very light and highly porous materials that are intriguingly and complexly networked with large internal surface area, high hydrophobicity with extremely low density and thermal conductivity. These features make them ideal choice for applications as thermal and acoustics insulators or as optical, electrical, and energy storing devices. However, their exploitation for structural applications is primarily inhibited by their brittleness. The brittleness of the silica aerogels makes their processing and handling difficult. Volumetric shrinkage occurs, which becomes more apparent at elevated temperatures. While there are hybrid silica aerogels doped with materials such as polymer, ceramics, metals in the market, the improvements in the mechanical properties are compromised with tremendous increase in density and reduction in the insulation performance. Post-synthesis binding treatment of silica aerogels composites are not extensively explored due to the chemically inert trimethylsilyl (TMS) terminal groups on the surface of the hydrophobic silica aerogels. This paper discusses a unique fabrication method of developing a ductile silica aerogel composite solid via post-synthesis binding treatment. Gelatin–silica aerogel (GSA) and GSA–sodium dodecyl sulfate (SDS) composite blocks were produced by mixing hydrophobic aerogel granulates in a gelatin–SDS foamed solution by frothing method. The entire fabrication process and grounds for using a controlled % of gelatin as the main binder and SDS as an additive are explained. The compression testing of the blocks is presented. The associated strain recovery—an unusual phenomenon with brittle silica aerogels, observed upon unloading is highlighted and studied. The microstructure and surface characterization of these composites was examined via FESEM/EDX and XPS/ESCA, respectively. The dependency of process variables involved were analyzed through analysis of variance (ANOVA) model. Empirical models that relate the composition of gelatin, aerogel, and SDS to achieve the optimal strain recovery with the associated compressive modulus and strength and density are established. The transition from brittleness to ductility is measured in terms of compressive stress versus strain behavior for various mass fractions of gelatin and SDS. The test data presented indicate analogous behavior of these to creep-like behavior of a material typically identified as the primary, secondary, and tertiary stages. The rationale and mechanisms behind such creep-like three stages are explained using schematic diagrams.     

Processing and properties of 15–70 MHz 1–3 PZT fiber/polymer composites

This paper reports on the fabrication and characterization of fine scale piezoelectric composites with 1–3 connectivity using fibers derived from a metal alkoxide sol-gel process. Using this technique, pure thickness mode resonance for this type of composite has been increased from 15 MHz up to 70 MHz by maintaining pillar aspect ratio requirements. Piezoceramic fibers of Nb or La modified lead zirconate titanate (PZT) were produced with final diameters ranging from 15 to 50 μm. Composites having 1–3 connectivity were produced using the fibers as pillars. Composites could be fabricated with volume fractions from 10 to 45% allowing tailoring of both the dielectric constant and acoustic impedance without degrading coupling. Dielectric constant, polarization and coercive field values varied slightly from bulk values due to clamping by the polymer matrix, increasing as the fiber diameter decreased. Composites with resonance frequencies ranging from 15 to 70 MHz were studied. The thickness dependence of the properties gave indications to radial mode/thickness mode interactions at pillar aspect ratios near 1.7 to 1 thickness to diameter. Coupling coefficients (k_t) from 58% to 73% with mechanical quality factors <15 were detected. Received: 4 April 2000 / Reviewed and accepted: 8 June 2000     

Mechanical and tribological properties of acrylonitrile–butadiene rubber filled with graphite and carbon black

In this work, acrylonitrile–butadiene rubber (NBR)/expanded graphite (EG)/carbon black (CB) micro- and nanocomposites were prepared by two different methods, and the resulting mechanical and tribological properties were compared with those of NBR/CB composites. Meanwhile, the effects of graphite dispersion and loading content, as well as the applied load and sliding velocity on the tribological behavior of the above composites under dry friction condition were also evaluated. The worn surfaces were analyzed by scanning electron microscopy (SEM) to disclose wear mechanism. As expected, the better the dispersion of graphite, the more remarkable enhancement on tensile and dynamic mechanical properties, and the greater reduction in the coefficient of friction (COF) and specific wear rate (W_s). It was found that a small amount of EG could effectively decrease COF and W_s of NBR/CB composites because of the formation of graphite lubricant films. The COF and W_s of NBR/CB/EG composites show a decreasing trend with a rise in applied load and sliding velocity. NBR/CB/EG nanocomposite always shows a stable wearing process with relatively low COF and W_s. It is thought that well-dispersed graphite nano-sheets were beneficial to the formation of a fine and durable lubricant film.     

Production and properties of steel–TiC composites for Wear applications

Abstract

Fe–(WTi)C composite granules containing up to 80 wt-% carbide have been produced by a selfpropagating high temperature synthesis reaction. These can be readily distributed in conventional steel melts. Additions up to 17 wt-% carbide have been made to a 0·4 wt-%C steel which was subsequently cast and hot rolled to plate. The microstructures of cast, rolled, and heat treated. samples display a homogeneous distribution of carbides which do not significantly affect the rolling performance of the steels. The carbides and grain refinement in heat treated samples result in a marked improvement in mechanical properties. The most significant improvement as a fraction of carbide additions is seen in abrasive wear performance.

MST/3196