The addition of functionalized graphene oxide to polyetherimide to improve its thermal conductivity and mechanical properties

The thermal and electrical conductivity and mechanical properties of polyetherimide (PEI) containing either alkyl‐aminated (enGO) or phenyl‐aminated graphene (pnGO) oxides were studied. A solution casting method was used to prepare functionalized graphene oxide/PEI composites with different filler contents. The introduction of functionalized graphene oxide to the PEI matrix improved the thermal conductivity, electrical conductivity, and mechanical properties. The thermal conductivities of the enGO 3 wt%/PEI and pnGO 3 wt%/PEI composites were 0.324 W/mK and 0.329 W/mK, respectively, due to the high thermal conductivity of the graphene‐based materials and the strong interface adhesion due to the filler surface treatment between the fillers and the matrix. The electrical conductivities of the functionalized graphene oxide/PEI composites were larger than that of PEI, but the electrical conductivity values were generally low, which is consistent with the magnitude of the insulator. The strong interfacial adhesion between the fillers and the matrix led to improved mechanical properties. Copyright © 2014 John Wiley & Sons, Ltd.     

Lignosulfonate/silica hybrid nanoparticles as a novel biobased filler in polybenzoxazine matrix

Lignin is an abundant and sustainable resource that exhibits numerous attractive functional properties as a reinforcing agent for benzoxazine-based composites, due to its stiffness, thermal stability, and high carbon content. However, the low quality of lignin particles dispersions associated with the weak particles-matrix interactions reduces the reinforcement capability. In this work, hybrid lignin/silica (NaLS/SiO₂) nanoparticles were obtained from sodium lignosulfonate (NaLS) and tetraethylorthosilicate (TEOS) under basic conditions. The particles were characterized by transmission electron microscopy (TEM) confirming their spherical morphology and narrow nanometric-size distributions. The hybrid particles were incorporated into conventional benzoxazine (BA-a) and a difuran biobased benzoxazine (SA-dfda) to prepare nanocomposites with different mass compositions (3, 5, and 10 wt%). Morphological, mechanical, dynamo-mechanical, and thermal properties of the obtained composites were assessed. All the materials exhibited a homogenous filler dispersion that contributed to improve the reinforcement properties. Hybrid nanoparticles proved to be an interesting alternative as a filler in the benzoxazine matrix to prepare high-performance thermosetting composites.     

The effect of hard and soft segment composition and molecular architecture on the morphology and mechanical properties of polystyrene-polyisobutylene thermoplastic elastomeric block copolymers

This paper reports the effects of hard (polystyrene, PS) and soft (polyisobutylene, PIB) segment composition and the molecular architecture (linear versus star, PS and PIB block length) on the morphology and mechanical properties of polystyrene/polyisobutylene (SIBS) block copolymers synthesized by living carbocationic polymerization. Atomic force microscopy, dynamic mechanical thermal analysis and tensile testing verified the phase-separated nature of the block copolymers, which behaved as thermoplastic elastomers (TPEs). The morphology of these TPEs is similar to polydiene-based TPEs, and is defined by the soft/hard segment composition. Interestingly, topology (linear vs star) did not have a major influence on morphology. Tensile testing showed that for both linear and three-arm star block copolymers, the modulus and tensile strength increased while elongation at break decreased with higher PS content. However, three-arm star block copolymers showed larger moduli than their linear homologues with similar PS content and PIB arm length, indicating the influence of molecular architecture on mechanical properties. These results might serve as a foundation for macromolecular engineering design for optimizing properties.     

Fabrication of thermoplastic polyurethane composites with a high dielectric constant and thermal conductivity using a hybrid filler of CNT@BaTiO3

Thermoplastic polyurethane composites with an excellent dielectric constant and high thermal conductivity were obtained using CNT@BaTiO₃ as a filler through a low-speed melt extrusion method. Before preparing the hybrid filler for the composite, the filler particles were surface modified to ensure that the outer surfaces could facilitate the reaction among particles to form the hybrid and ensure complete dispersion in the thermoplastic polyurethane matrix. After confirming the proper surface treatment of the filler particles using infrared spectroscopy, thermal degradation analysis and field emission scanning electron microscopy, they were used to prepare the composite materials at a processing temperature of 200 °C. The thermal stability, thermomechanical properties, mechanical properties, thermal conductivity, and dielectric properties of the composites were investigated. Compared to the neat thermoplastic polyurethane matrix, the prepared composite exhibited a higher thermal stability, approximately 300% higher storage modulus, higher tensile strength and elongation at break values, approximately three times higher thermal conductivity (improved from 0.19 W/(m.K) to 0.38 W/(m.K), and approximately five times larger dielectric constant at high frequencies (at 1 MHz a dielectric constant of 19.2 was obtained).     

Bentonite Reinforced Tough Composite Hydrogels as Potential Artificial Articular Cartilage

Novel tough composite hydrogels were prepared from inorganic bentonite(IB), polyvinyl alcohol(PVA) and polyethylene glycol(PEG) by means of a freeze-thaw technique, during which IB acted as multifunctional physically crosslinking junction and a filler to bridge the 3D network hydrogel; while the physical adsorption between IB and the polymer chains served as sacrificial bonds and increased the energy dissipation efficiency. The effects of different content of IB(w_IB) on the morphological, thermal, swelling, and mechanical properties of the hydrogels were investigated. It was found that the added IB promoted the material crosslinking and stability, and the mechanical properties of the hydrogels were significantly improved with increasing w_IB. The highest tensile stress of the hydrogel was achieved(1.1 MPa) when w_IBwas 5%. The synthesized hydrogels with high mechanical strength and low friction coefficient are potential candidate materials for artificial cartilage.     

Thermal stability and flame retardancy of LDPE/EVA blends filled with synthetic hydromagnesite/aluminium hydroxide/montmorillonite and magnesium hydroxide/aluminium hydroxide/montmorillonite mixtures

The combination of organophillised montmorillonite (MMT), synthetic hydromagnesite and aluminium hydroxide (ATH) as flame retardant system for polyethylene-based materials was studied and compared with a similar system with magnesium hydroxide, ATH and MMT. The thermal stability and the flame retardant properties were evaluated by thermogravimetric analysis (TGA), differential thermal analysis (DTA), limiting oxygen index (LOI) and cone calorimeter tests. The results indicated that the addition of montmorillonite makes it possible to reduce the total filler content to achieve the flame retardant requirements. The thermal stability of filled LDPE/EVA blends increases to a higher extent for the samples containing MMT. In the cone calorimeter tests we observed a reduction of the peak heat release rate for the sample containing montmorillonite in comparison with a sample with higher filler loading without this nanoclay. An increase of the stability of the char formed could be responsible for this favourable behaviour when montmorillonite is added.In addition, mechanical properties significantly improved for the composites containing montmorillonite both for the filler loading reduction and the reinforcement effect of the nanoclay.     

Effect of walnut shells and silanized walnut shells on the mechanical and thermal properties of rigid polyurethane foams

In the study walnut shells (WS) and silanized walnut shells (S_WS) were used as cellulosic fillers for novel polyurethane (PU) composite foams. The impact of 1, 2 and 5 wt% of WS and S_WS on the foaming parameters, mechanical and thermo-mechanical properties of obtained materials were evaluated. The results have shown that compared to untreated WS filler, the application of S_WS leads to PU foams with more regular structure and improved physico-mechanical behavior of PU materials. For example, compared to controlled WS_0 foam, PU foams enhanced with 1 wt% of the S_WS exhibited better mechanical properties, such as higher compressive strength (~15% of improvement), better impact strength (~6% of improvement), and improved tensile strength (~9% of improvement). The addition of S_WS improved the thermomechanical stability of PU foams. This work provides a better understanding of a relationship between the surface modification of the walnut shell filler and the mechanical, insulating and thermal properties of the PU composites. Due to these positive and beneficial effects, it can be stated that the use of WS and S_WS as natural fillers in PU composite foams can promote a new application path in converting agricultural waste into useful resources for creating a new class of green materials.     

Physical characterization of commercial polyolefinic thermoplastic elastomers

In this work, a systematic study of physical characterization on a series of commercial polyolefinic thermoplastic elastomers (TPEs), is reported. Formulations from different manufacturers, having a wide range of Shore hardness values (from A45 to D51), were examined using simple, inexpensive and standard laboratory methods. From this analysis, the TPE chemical composition and its relationship with hardness and tensile set—the key parameters that define the TPE performance in most of the applications—could be established.

It was found that the strategy followed by the manufacturers to design TPEs is very similar. The EPDMs used for the different formulations look similar in ethylene content and thermal properties. Therefore, the TPE bulk modulus (or hardness) is mainly controlled by the PP content. Nice elastomeric behavior was observed only in grades with a dominant proportion of EPDM, in agreement with the deformation mechanism generally accepted for this type of materials. Grades with higher hardness values—and a dominant proportion of PP—showed a mechanical response corresponding to a toughened thermoplastic, even when these grades are marketed by the producers as “thermoplastic elastomers”. Differently from conventional crosslinked elastomers, where hardness and ability to recover from highly deformed states can be simultaneously controlled by changing the degree of crosslinking, the results of this work indicate that it is very difficult to increase TPE hardness without sacrificing elastomeric properties.     

Ethylene-vinyl acetate (EVA)/polycaprolactone (PCL)–Fe3O4 composites

In this study, we investigate the effect of nano sized Fe₃O₄ nanoparticles on the mechanical and thermal properties of EVA/PCL–Fe₃O₄ composites. Composites were prepared using the melt mixing technique on a Rheomex mixer coupled to a single screw extruder. The fine dispersion of nano-Fe₃O₄ aggregates in the polymer matrices led to a significant improvement in the crystallinity, thermal and mechanical properties of EVA/PCL–Fe₃O₄ nanocomposites compared to that of native polymers due to improved interface bonding between the filler and the polymer matrix. Techniques such as scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and Instron for mechanical properties were used to characterize nanocomposites samples. The results obtained from this investigation demonstrated that composite materials could be promising raw materials in industry.     

Nutmeg filler as a natural compound for the production of polyurethane composite foams with antibacterial and anti-aging properties

Polyurethane (PU) composite foams were successfully reinforced with different concentrations (1 wt%, 2 wt%, 5 wt%) of nutmeg filler. The effect of nutmeg filler concentration on mechanical, thermal, antimicrobial and anti-aging properties of PU composite foams was investigated. PU foams were examined by rheological behavior, processing parameters, cellular structure (Scanning Electron Microscopy analysis), mechanical properties (compression test, impact test, three-point bending test, impact strength), thermal properties (Thermogravimetric Analysis), viscoelastic behavior (Dynamic Mechanical Analysis) as well as selected application properties (thermal conductivity, flammability, apparent density, dimensional stability, surface hydrophobicity, water absorption, color characteristic). In order to Disc Diffusion Method, all PU composites were tested against selected bacteria (Escherichia coli and Staphylococcus aureus). Based on the results, it can be concluded that the addition of 1 wt% of nutmeg filler leads to PU composite foams with improved compression strength (e.g. improvement by ~19%), higher flexural strength (e.g. increase of ~11%), improved impact strength (e.g. increase of ~32%) and comparable thermal conductivity (0.023–0.034 W m⁻¹ K⁻¹). Moreover, the incorporation of nutmeg filler has a positive effect on the fire resistance of PU materials. For example, the results from the cone calorimeter test showed that the incorporation of 5 wt% of nutmeg filler significantly reduced the peak of heat release rate (pHRR) by ca. 60% compared with that of unmodified PU foam. It has been also proved that nutmeg filler may act as a natural anti-aging compound of PU foams. The incorporation of nutmeg filler in each amount successfully improved the stabilization of PU composite foams. Based on the antibacterial results, it has been shown that the addition of nutmeg filler significantly improved the antibacterial properties of PU composite foams against both Gram-positive and Gram-negative bacteria.     

Multigraft copolymer superelastomers: Synthesis morphology, and properties

The synthesis of well-defined multigraft copolymers having a polydiene backbone with polystyrene side chains is briefly reviewed, with particular focus on controlling branch point spacing and branch point functionality. Use of living anionic polymerization and chlorosilane linking chemistry has led to the synthesis of series of materials having regularly spaced trifunctional (comb), tetrafunctional (centipede), and hexafunctional (barbwire) branch points. The morphologies of these materials were characterized by transmission electron microscopy and small-angle X-ray scattering, and it was found that the morphologies were controlled by the local architectural asymmetry associated with each branch point. Mechanical properties studies revealed that such multigraft copolymers represent a new class of thermoplastic elastomers (TPEs) with superior elongation at break and low residual strains as compared to conventional TPEs.     

Mechanical,dynamic mechanical,and thermal analysis of Shorea robusta-dispersed polyester composite

The influence of Shorea robusta natural filler loading (5, 10, 15, 20, and 25 v/v%) on the mechanical, dynamic mechanical, biodegradability, and thermal stability of the polyester composite was analyzed. The composites were fabricated using hand lay-up method. The maximum mechanical properties, storage modulus, and glass transition temperature were observed for the composite with 20 v/v% filler. The peak height of Tanδ was found to be lesser for the same. Thermal analysis results revealed that the thermal stability of composite increased with the incorporation of Shorea robusta as natural filler. Biodegradability testing showed that the addition of filler resulted in weight loss of the composite under soil burial test.     

Enhancement of tensile,electrical and thermal properties of epoxy nanocomposites through chemical hybridization of polypyrrole and graphene oxide

This paper presents the properties of epoxy nanocomposites, prepared using a synthesized hybrid Polypyrrole-Graphene Oxide (PPy-GO) filler, via in-situ chemical polymerization, at various filler loadings (i.e., 0.5–2 w. t %). The microstructures and properties of the PPy-GO hybrids and epoxy nanocomposites were studied via Fourier transform infrared (FTIR), X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), mechanical (Tensile Properties), electrical, Dynamic mechanical thermal analysis (DMTA) and thermogravimetric analyses (TGA). Morphological study demonstrated that varying the nanofiller nature (PPy-GOs, PPy or GO) lead to different states of dispersion. Mechanical, electrical and thermal analysis demonstrated that the hybrid concentration and its architecture (PPy:GO ratio) are interesting factors significantly affected the properties of the epoxy based nanocomposites. On the other hand, the mechanical performance of the cured nanocomposites outperformed the PPy-GO, with enhancements of 78% and 51% of Young's modulus and strength, respectively. Here it has been established that the embedding of PPy-GO hybrids into pristine epoxy endows optimum dispersion of PPy and GO as well as better interfacial adhesion between the fillers and matrix, which results in a significant improvement in load transfer effectiveness. Electrical conductivity measurements showed that conductivity of epoxy filled nanocomposites increased up 10⁻⁴ S/cm for Epoxy/PPy-GO nanocomposites. DMTA test indicated that incorporation of PPy-GO resulted in a significantly increase in Tg of the resultant nanocomposites, which is attributed to the highly exfoliation structure and the stronger interfacial interaction. The PPy-GO particles enhanced electrical, thermal and mechanical properties of nanocomposites, confirming the synergistic effect of PPy-GO as multifunctional filler.     

Dielectric,mechanical and electro-stimulus response properties studies of polyurethane dielectric elastomer modified by carbon nanotube-graphene nanosheet hybrid fillers

The typical nano-carbon materials, 1D fiber-like carbon nanotubes (CNTs) and 2D platelet-like graphene nanosheets (GRNs), that have attracted tremendous attention in the field of polymer nanocomposites due to their unprecedented properties, are used as conducting filler to induce a considerable improvement in the mechanical, thermal and electrical properties of the resulting graphene/polymer nanocomposites at very low loading contents. This study deals with the preparation and electro-stimulus response properties of polyurethane (PU) dielectric elastomer films with such 1D and 2D nanocarbon fillers embedded in the polymer matrix. The various forms of carbon used in composite preparation include CNT, GRN and CNT-GRN hybrid fillers. Results indicate that the dielectric, mechanical and electromechanical properties depend on the carbon filler type and the carbon filler weight fraction. Here, it has been also established that embedding CNT-GRN hybrid fillers into pristine polyurethane endows somewhat better dispersion of CNTs and GRNs as well as better interfacial adhesion between the carbon fillers and matrix, which results in an improvement in electric-induced strain. Therefore, the nanocomposites seem to be very attractive for microelectromechanical systems applications.     

An investigation of the properties of poly(dimethylsiloxane)-bioinspired silica hybrids

Elastomers typically require the incorporation of reinforcing fillers in order to improve their mechanical properties. For commercial silicone systems silica and titania are typically used as fillers. Fumed and precipitated silica are made on an industrial scale for many applications; however, we have shown recently that biological and synthetic macromolecules can generate new silica structures using a bioinspired route. Herein we have incorporated bioinspired silica fillers into poly(dimethylsiloxane) (PDMS) elastomers and investigated their mechanical, morphological and thermal properties as a function of filler loading. The equilibrium stress-strain characteristics of the PDMS-bioinspired silica hybrids were determined as a function of bioinspired filler loading and the Mooney-Rivlin constants (2C₁ and 2C₂) were calculated. The thermal characteristics, in particular glass transition temperatures (T_g) and melting points (T_m), of the PDMS-bioinspired silica hybrids were characterized using differential scanning calorimetry (DSC). The thermal stability of these hybrid materials were investigated using thermogravimetric analysis (TGA). The morphology of the samples was characterized using scanning electron microscopy (SEM), and the filler dispersion was characterized using ultra small angle X-ray scattering (USAXS) and scanning electron microscopy (SEM). Although spherical silica particles were used here, we have demonstrated elsewhere that this bioinspired synthetic route also enables highly asymmetric silica structures to be prepared such as fibres and sheets. This methodology therefore offers the interesting possibility of preparing new hybrid systems where the properties are highly anisotropic.     

Influence of chitosan on the mechanical and biological properties of HDPE for biomedical applications

High density polyethylene (HDPE) is widely used in biomedical field, except when strong cell-material interactions and high mechanical properties are required. To address this pitfall, two kinds of chitosan in different amounts were used as filler in the present research. Composites were prepared by melt extrusion process and their microstructural, thermal and mechanical properties were widely investigated. Also roughness and wettability were studied, as features of paramount importance in dictating cell response.Both types of chitosan endowed HDPE with higher Young modulus and lower elongation at break. Interestingly, fibroblast adhesion and viability were enhanced when a low amount of filler was used. The interaction of HDPE/chitosan composites with biological environment was investigated for the first time in order to assess the feasibility of these composites as materials for biomedical application.     

Epoxy nanocomposites with high thermal conductivity and low loss factor: Realize 3D thermal conductivity network at low content through core-shell structure and micro-nano technology

Dielectric polymers with high thermal conductivity are very promising in the fields of aerospace and electronic device packaging. However, composites with excellent dielectric properties usually have low thermal conductivity. It is usually to fill the polymer with thermal conductivity particles to improve the thermal conductivity, but the high content of filler often reduces the mechanical properties of the polymer. In this paper, the traditional insulating polymer epoxy resin was used as the matrix, by covering the surface of silicon carbide with graphene to form a core-shell structure and co-filled with nano diamonds to achieve the preparation of high-performance epoxy resin at low content. The results showed that at the filling content of 30 wt%, the thermal conductivity of epoxy nanocomposites showed a dramatic thermal conductivity enhancement of 1263%, the energy storage modulus increased by 1.1 GPa, and the dielectric loss remained unchanged at 50 Hz. The advantages of the composite are the structural design and surface modification of the filler, which not only take advantage of its inherent advantages, but also improve the interface area with the epoxy matrix. The composite materials with excellent properties are expected to provide theoretical guidance for the application of high thermal conductivity dielectric materials.     

Thermal Conductance of Graphene-Titanium Interface: A Molecular Simulation

Titanium is a commonly used material in aviation, aerospace, and military applications, due to the outstanding mechanical properties of titanium and its alloys. However, its relatively low thermal conductivity restricts its extended usage. The use of graphene as a filler shows great potential for the enhancement of thermal conductivity in titanium-based metal-matrix composites (MMCs). We used classical molecular dynamics (MD) simulation methods to explore the thermal conductance at the titanium–graphene (Ti/Gr) interface for its thermal boundary conductance, which plays an important role in the thermal properties of Ti-based MMCs. The effects of system size, layer number, temperature, and strain were considered. The results show that the thermal boundary conductance (TBC) decreases with an increasing layer number and reaches a plateau at n = 5. TBC falls under tensile strain and, in turn, it grows with compressive strain. The variation of TBC is explained qualitatively by the interfacial atomic vibration coupling factor. Our findings also provide insights into ways to optimize future thermal management based on Ti-based MMCs materials.     

Effect of carbon black type and concentration on the performance of semiconductive shielding material of high-voltage cable

Semiconductive shielding layer as an important part of high-voltage cable, its performance directly affects the safe operation and the service life of the cable. Carbon black (CB) is the main conductive filler of shielding materials, and its type and concentration directly affect the performance of the shielding layer. In this paper, CB-A with higher structure and CB-B with lower structure were used as conductive fillers and EBA was chosen as the matrix resin to prepare the shielding materials. The CB concentrations of the shielding materials were 35, 45, and 55 phr. The influences of CB type and concentration on the physicochemical, electrical, thermal and mechanical properties of the shielding materials were investigated. The research shows that when the CB types are the same, the higher the concentration of CB, the more intensive the CB network in the shielding material, and the more serious the CB agglomeration phenomenon. With increasing CB concentration, shielding materials show a decreasing trend of volume resistivity, an increasing trend of thermal conductivity, and a decreasing trend of mechanical properties. When the CB concentration is the equal, the CB-A has better dispersion in the matrix resin, CB-A/EBA shielding material has lower volume resistivity and weaker PTC effect, CB-A/EBA shielding material has higher thermal conductivity at low temperature and CB-B/EBA shielding material has higher thermal conductivity at high temperature, CB-A/EBA shielding material has better mechanical properties. A comprehensive comparison shows that CB-A/EBA shielding material with a concentration of 45 phr has excellent overall performance, with volume resistivity of 15.3 and 68 Ω·cm at 25°C and 90°C, respectively. The thermal conductivity is 0.434 W/(m K) at room temperature and 0.536 W/(m K) at 90°C. The stress is 31.08 MPa and the strain is 570.2%. This work has important reference for the selection of conductive fillers and performance improvement of semiconductive shielding materials.     

In situ silica reinforcement of natural rubber by sol–gel process via rubber solution

The in situ silica filling of natural rubber (NR) was carried out via the sol–gel reaction using tetraethoxysilane. The effect of the in situ silica content on the curing, mechanical, dynamic mechanical and thermal properties of the composite vulcanizate materials was investigated in comparison to that with a commercial silica preparation. The Mooney viscosity of the in situ silica filled NR vulcanizates showed a lower value compared with that of the commercial filled ones. The mechanical properties of the in situ silica composite materials, i.e., the moduli and compression set, were improved compared with the commercial silica filler NR vulcanizates. The reinforcement effect of in situ silica did not accord with the Smallwood equation but in contrast was in good agreement with the Guth and Gold equation using a shape factor (f) which itself was in close agreement with estimates derived from independent TEM analysis. The pseudo-network structure of the in situ silica was low, which resulted in a lower storage modulus at 25 °C. By filling NR with in situ silica, the thermal properties of the composite vulcanized material were also improved, and well dispersed in situ silica particles within the NR matrix were also observed.