Facile preparation of graphene nanoribbon filled silicone rubber nanocomposite with improved thermal and mechanical properties

In the present study, graphene nanoribbon was prepared through unzipping the multi walled carbon nanotubes, and its reinforcing effect as a filler to the silicone rubber was further investigated. The results showed that carbon nanotubes could be unzipped to graphene nanoribbon using strong oxidants like potassium permanganate and sulfuric acid. The prepared graphene nanoribbon could homogeneously disperse within silicone rubber matrix using a simple solution mixing approach. It was also found from the thermogravimetric analysis curves that the thermal stability of the graphene nanoribbon filled silicone rubber nanocomposites improved compared to the pristine silicone rubber. Besides, with the incorporation of the nanofiller, the mechanical properties of the resulting nanocomposites were significantly enhanced, in which both the tensile stress and Young’s modulus increased by 67% and 93% respectively when the mass content of the graphene nanoribbon was 2.0 wt%. Thus it could be expected that graphene nanoribbon had large potentials to be applied as the reinforcing filler to fabricate polymers with increased the thermal and mechanical properties.     

High thermal conductivity of flexible polymer composites due to synergistic effect of multilayer graphene flakes and graphene foam

Research on flexible thermal interface materials (TIMs) has shown that the interconnected network of graphene foam (GF) offers effective paths of heat transportation. In this work, a variant amount of multilayer graphene flakes (MGFs) was added into 0.2 vol% GF/polydimethylsiloxane (PDMS) composite. A remarkable synergistic effect between MGF and GF in improving thermal conductivity of polymer composites is achieved. With 2.7 vol% MGFs, the thermal conductivity of MGF/GF/PDMS composite reaches 1.08 W m⁻¹ K⁻¹, which is 80%, 184% and 440% higher than that of 2.7 vol% MGF/PDMS, GF/PDMS composites and pure PDMS, respectively. The MGF/GF/PDMS composite also shows superior thermal stability. The addition of MGFs and GF decreases slightly the elongation at break, but observably increases the Young’s modulus and tensile strength of composites compared with pure PDMS. The good performance of MGF/GF/PDMS composite makes it a good TIM for possible application in thermal management of electronics.     

The effect of interfacial state on the thermal conductivity of functionalized Al2O3 filled glass fibers reinforced polymer composites

Rapidly increasing packaging density of electronic devices puts forward higher requirements for thermal conductivity of glass fibers reinforced polymer (GFRP) composites, which are commonly used as substrates in printed circuit board. Interface between fillers and polymer matrix has long been playing an important role in affecting thermal conductivity. In this paper, the effect of interfacial state on the thermal conductivity of functionalized Al₂O₃ filled GFRP composites was evaluated. The results indicated that amino groups-Al₂O₃ was demonstrated to be effective filler to fabricate thermally conductive GFPR composite (1.07 W/m K), compared with epoxy group and graphene oxide functionalized Al₂O₃. It was determined that the strong adhesion at the interface and homogeneous dispersion of filler particles were the key factors. Moreover, the effect of interfacial state on dielectric and thermomechanical properties of GFRP composites was also discussed. This research provides an efficient way to develop high-performance GFRP composites with high thermal conductivity for integrated circuit packaging applications.     

Growing polystyrene chains from the surface of graphene layers via RAFT polymerization and the influence on their thermal properties

The polystyrene (PS) macromolecular chains were grafted on the surface of graphene layers by reversible addition-fragmentation chain transfer (RAFT) polymerization. In this procedure, a RAFT agent, 4-Cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid, was used to functionalize the thermal reduced graphene oxide (TRGO) to obtain the precursor (TRGO-RAFT). It can be calculated that the grafting density of PS/graphene (PRG) composites was about 0.18 chains per 100 carbons. Successful in-plain attachment of RAFT agent to TRGO and PS chain to TRGO-RAFT was shown an influence on the thermal property of the PRG composites. The thermal conductivity (λ) improved from 0.150 W m⁻¹ K⁻¹ of neat PS to 0.250 W m⁻¹ K⁻¹ of PRG composites with 10 wt% graphene sheets loading. The thermal property of PRG composites increased due to the homogeneous dispersion and ordered arrangement of graphene sheets in PS matrix and the formation of PRG composites.     

Combination effect of carbon nanotubes with graphene on intumescent flame-retardant polypropylene nanocomposites

A novel polypropylene (PP) nanocomposite was fabricated by the incorporation of intumescent flame retardant (IFR), carbon nanotubes (CNTs) and graphene into the PP matrix. Results from TEM indicate that IFR, CNTs and exfoliated graphene nanosheets are dispersed finely in the PP matrix, which is supported by the XRD analysis results. Thermogravimetric (TGA) results show that the addition of IFR, CNTs and graphene improved the thermal stability and the char yields of PP. The PP/IFR/CNTs/RGO nanocomposites, filled with 18 wt% IFR, 1 wt% CNTs and 1 wt% graphene, achieve the limiting oxygen index value of 31.4% and UL-94 V0 grade. Cone calorimeter data reveal that combustion behavior, heat release rate peak (PHRR) and average specific extinction area (ASEA) of PP decrease substantially when combination effects of IFR, CNTs and graphene intervene. For the PP/IFR/CNTs/RGO nanocomposites, the PHRR exhibits an 83% reduction and the time of ignition is delayed 40 s compared with neat PP.     

Enhanced thermal resistance of phenolic resin composites at low loading of graphene oxide

By incorporating graphene oxide (GO) into phenolic resin (PR), GO/PR composites were prepared, and the effects of the content and reduction degree of GO on thermal resistance of GO/PR composites were studied. The peak degradation temperature of the PR was increased by about 14 °C with GO which was heat treated. The char yield of GO/PR composite at a GO weight fraction of 0.5% was about 11% greater than that of PR. The interactions such as covalent bonds and π–π stacking between GO and PR were regarded as the main reason for the enhancement. Located at the GO–PR interface, GO effectively anchored and structured PR molecular near the surfaces of GO sheets, and thus facilitated the formation of char. The superiority of GO/PR composites over PR in terms of thermal properties enhancement should also be related to the promoting graphitization by the addition of GO.     

Effects of chitosan as biopolymer coupling agent on the thermal and rheological properties of polyvinyl chloride/wood flour composites

Chitosan (CS) was opted as a novel biopolymer coupling agent for wood flour polyvinyl chloride composites (WF/PVC) to improve interfacial adhesion. This study mainly aimed at investigating the effects after adding CS of different addition amounts and particle sizes on the thermal and rheological properties of WF/PVC composites by the analyses of vicat softening temperature test (VST), differential scanning calorimetry (DSC), thermogravimetry (TGA) and torque rheometry. The results indicated that an optimum addition amount (30 phr) with the particle size (180–220 mesh) could elevate heat resistance capacity, glass transition temperature of composites as well as thermal stability at the early stage of degradation more effectively. In the aspect of rheological characteristics, longer fusion time, lower fusion torque and higher fusion temperature were showed as the CS addition amount increased and the particle size declined. In order to obtain sufficient compaction and ensure proper blending to compounds during extrusion, the higher pressure needed to be supplied when the addition amount of CS exceeded 20 phr.     

Synergistic effect of boron nitride flakes and tetrapod-shaped ZnO whiskers on the thermal conductivity of electrically insulating phenol formaldehyde composites

Tetrapod-shaped zinc oxide (T-ZnO) whiskers and boron nitride (BN) flakes were employed to improve the thermal conductivity of phenolic formaldehyde resin (PF). A striking synergistic effect on thermal conductivity of PF was achieved. The in-plane thermal conductivity of the PF composite is as high as 1.96 W m⁻¹ K⁻¹ with 30 wt.% BN and 30 wt.% T-ZnO, which is 6.8 times higher than that of neat PF, while its electrical insulation is maintained. With 30 wt.% BN and 30 wt.% T-ZnO, the flexural strength of the composite is 312.9% higher than that of neat PF, and 56.2% higher that of the PF composite with 60 wt.% BN. The elongation at break is also improved by 51.8% in comparison with that of the composite with 60 wt.% BN. Such a synergistic effect results from the bridging of T-ZnO whiskers between BN flakes facilitating the formation of effective thermal conductance network within PF matrix.     

The synthesis of graphene nanoribbon and its reinforcing effect on poly (vinyl alcohol)

The graphene nanoribbon was prepared from the carbon nanotubes using the chemical approach, and was used for preparing the poly (vinyl alcohol) nanocomposites. It was discovered that the prepared graphene nanoribbon contained a lot of oxygen groups. Due to the presence of these oxygen groups, the nanoribbon could homogeneously disperse in both water and poly (vinly alcohol) matrix. It was also found that there were strong interactions between the graphene nanoribbon and the poly (vinyl alcohol) through hydrogen bonding. The interactions gave rise to the thermal stability of the host polymer. Furthermore, the presence of the nanofiller also resulted in a significant improvement of the mechanical performance of the prepared nanocomposites. The tensile strength and the Young’s modulus of the nanocomposite loaded with 2.0 wt% graphene nanoribbon increased by 85.7% and 65.2% respectively. The overall results indicate that the graphene nanoribbon is suitable for preparing high-performance polymer composites.     

Engineering the coefficient of thermal expansion and thermal conductivity of polymers filled with high aspect ratio silica nanofibers

The thermomechanical properties of epoxy filled with two different types of silica nanofillers: spherical nanoparticles and nanofibers were investigated as a function of silica nanofiller aspect ratio and concentration. Results indicated that at room temperature and at 8.74% silica nanofiber concentration (by volume) the thermal conductivity of epoxy increased twofold and coefficient of thermal expansion (CET) decreased by ∼40%. Silica nanofiber filled epoxy showed 1.4 times greater CET and 1.5 times greater thermal conductivity compared to spherical nanoparticle filled epoxy. The significant changes observed in thermomechanical properties of silica nanofiber filled epoxy were attributed to its high aspect ratio by constraining the polymer matrix as well as reducing the phonon scattering due to the formation of a continuous fiber network within the matrix. In addition to being electrically insulating, the improved properties of silica nanofiber filled epoxy make it an extremely attractive material as underfill and encapsulant in advanced electronic packaging industry.     

Effect of silica coating thickness on the thermal conductivity of polyurethane/SiO2 coated multiwalled carbon nanotube composites

Silica coated multiwalled carbon nanotubes (SiO₂@MWCNTs) with different coating thicknesses of ∼4 nm, 30–50 nm, and 70–90 nm were synthesized by a sol–gel method and compounded with polyurethane (PU). The effects of SiO₂@MWCNTs on the electrical properties and thermal conductivity of the resulting PU/SiO₂@MWCNT composites were investigated. The SiO₂ coating maintained the high electrical resistivity of pure PU. Meanwhile, incorporating 0.5, 0.75 and 1.0 wt% SiO₂@MWCNT (70–90 nm) into PU, produced thermal conductivity values of 0.287, 0.289 and 0.310 W/mK, respectively, representing increases of 62.1%, 63.3% and 75.1%. The thermal conductivity of PU/SiO₂@MWCNT composites was also increased by increasing the thickness of the SiO₂ coating.     

Enhanced stress transfer and thermal properties of polyimide composites with covalent functionalized reduced graphene oxide

This work prepares (3-aminopropyl) trimethoxysilane (APTMS)-functionalized reduced graphene oxide (APTMS-rGO)/polyimide (PI) composite (APTMS-rGO/PI) through in-situ polymerization. NH₂-functionalized rGO coupled by APTMS demonstrates the good reinforced efficiency in mechanical and thermal properties, which is ascribed to the covalent-functionalized PI matrix by APTMS-rGO sheets. The uniform dispersion of APTMS-rGO increases the glass transition temperature (Tg) and the thermal decomposition temperature (Td), exhibiting 21.7 °C and 44 °C improvements, respectively. The tensile strength of the composites with 0.3 wt% APTMS-rGO is 31% higher than that of neat PI, and Young’s modulus is 35% higher than that of neat PI. Raman spectroscopy show the obvious G band shift, and also clearly demonstrates the enhanced interfacial interaction between rGO nanofillers and PI matrix. The high mechanical property of the APTMS-rGO/PI composites is attributed to the covalent functionalized GO by NH₂ groups and its good dispersion in comparison with GO.     

Effect of fiber loading on the properties of treated cellulose fiber-reinforced phenolic composites

The effect of fiber loading on the properties of treated cellulose fiber-reinforced phenolic composites was evaluated. Alkali treatment of the fibers and reaction with organosilanes as coupling agents were applied to improve fiber–matrix adhesion. Fiber loadings of 1, 3, 5, and 7 wt% were incorporated to the phenolic matrix and tensile, flexural, morphological and thermal properties of the resulting composites were studied. In general, mechanical properties of the composites showed a maximum at 3% of fiber loading and a uniform distribution of the fibers in such composites was observed. Silane treatment of the fibers provided derived composites with the best thermal and mechanical properties. Meanwhile, NaOH treatment improved thermal and flexural properties, but reduced tensile properties of the materials. Therefore, the phenolic composite containing 3% of silane treated cellulose fiber was selected as the material with optimal properties.     

Evaluation of thermal,mechanical, and electrical properties of PVDF/GNP binary and PVDF/PMMA/GNP ternary nanocomposites

Graphene nanoplatelet (GNP) was incorporated into poly(vinylidene fluoride) (PVDF) and PVDF/poly(methyl methacrylate) (PMMA) blend to achieve binary and ternary nanocomposites. GNP was more randomly dispersed in binary composites compared with ternary composites. GNP exhibited higher nucleation efficiency for PVDF crystallization in ternary composites than in binary composites. GNP addition induced PVDF crystals with higher stability; however, PMMA imparted opposite effect. The binary composite exhibited lower thermal expansion value than PVDF; the value further declined (up to 28.5% drop) in the ternary composites. The storage modulus of binary and ternary composites increased to 23.1% and 53.9% (at 25 °C), respectively, compared with PVDF. Electrical percolation threshold between 1 phr and 2 phr GNP loading was identified for the two composite systems; the ternary composites exhibited lower electrical resistivity at identical GNP loadings. Rheological data confirmed that the formation of GNP (pseudo)network structure was assisted in the ternary system.     

Influence of glass microspheres on selected properties of polylactide composites

Comparison of some changes occurring in polylactide (PLA) due to its modification by glass filler being in the form of microspheres (GM) was the objective of the present study. Mechanical and thermal properties, density, mass flow rate, and were determined. In addition, there were examined surface free energy and changes in the surface geometrical structure of sample fractures. It was found that PLA as modified with GM exhibited the enhanced longitudinal modulus of elasticity, flexural modulus, and mass flow rate. The impact strength and flexural strength did not change. The tensile strength and tensile strain at break decreased. The used glass filler did not affect essentially the thermal properties of PLA. The prepared composites exhibited uniform distribution of the dispersed phase in the polymer matrix and adequate adhesion at the interface between the two components. Substantial changes in the properties of the surface layer were observed, mainly in surface free energy.     

Click coupled stitched graphene sheets and their polymer nanocomposites with enhanced photothermal and mechanical properties

The chemically stitched graphene oxide (GO) sheets were obtained using a click chemistry reaction between azide-functionalized GO and alkyne-functionalized GO. The click coupled GO (GO-click-GO) sheets showed the largely increased electrical conductivity and near infrared laser-induced photothermal properties compared to the GO sheets, which result from formation of triazole ring as a bridging linker between the GO sheets. The polyurethane (PU) nanocomposites incorporating the GO-click-GO sheets exhibited enhanced mechanical properties of breaking stress and modulus than the GO/PU nanocomposites. The modulus of GO-click-GO/PU nanocomposites was higher than that of the GO/PU nanocomposites at the same filler loading of 0.1 and 0.5 wt%. The GO-click-GO/PU nanocomposites also showed a significantly improved photothermal properties compared to the GO/PU nanocomposites at the same filler loading. The click coupled stitched GO sheets in this study can be used as the superior reinforcing fillers for mechanically and photothermally high performance polymer nanocomposites.     

Investigation of thermal conductivity and dielectric properties of LDPE-matrix composites filled with hybrid filler of hollow glass microspheres and nitride particles

The hybrid filler of hollow glass microspheres (HGM) and nitride particles was filled into low-density polyethylene (LDPE) matrix via powder mixing and then hot pressing technology to obtain the composites with higher thermal conductivity as well as lower dielectric constant (D_k) and loss (D_f). The effects of surface modification of nitride particles and HGMs as well as volume ratio between them on the thermal conductivity and dielectric properties at 1 MHz of the composites were first investigated. The results indicate that the surface modification of the filler has a beneficial effect on thermal conductivity and dielectric properties of the composites due to the good interfacial adhesion between the filler and matrix. An optimal volume ratio of nitride particles to HGMs of 1:1 is determined on the basis of overall performance of the composites. The thermal conductivity as well as dielectric properties at 1 MHz and microwave frequency of the composites made from surface-modified fillers with the optimal nitride to HGM volume ratio were investigated as a function of the total volume fraction of hybrid filler. It is found that the thermal conductivity increases with filler volume fraction, and it is mainly related to the type of nitride particle other than HGM. The D_k values at 1 MHz and microwave frequency show an increasing trend with filler volume fraction and depend largely on the types of both nitride particles and HGMs. The D_f values at 1 MHz or quality factor (Q × f) at microwave frequency show an increasing or decreasing trend with filler volume fraction and also depend on the types of both nitride particle and HGM. Finally, optimal type of HGM and nitride particles as well as corresponding thermal conductivity and dielectric properties is obtained. SEM observations show that the hybrid filler particles are agglomerated around the LDPE matrix particles, and within the agglomerates the smaller-sized nitride particles in the hybrid filler can easily form thermally conductive networks to make the composites with high thermal conductivity. At the same time, the increase of the value D_k of the composites is restricted due to the presence of HGMs.     

Effect of diisocyanates as compatibilizer on the properties of ramie/poly(lactic acid) (PLA) composites

Ramie/PLA composites with the diisocyanates as compatibilizer were fabricated by extrusion and injection molding. The influence of different diisocyanates and various diisocyanate content on the mechanical properties and thermal properties of the composites was investigated. The presence of the diisocyanates in the composites lead to the improvements in mechanical properties and thermal properties of the composites. The morphologies of fracture surface using scanning electron microscopy (SEM) provided evidence of improved interfacial adhesion between ramie and PLA from the addition of the diisocyanates. The composites containing isophorone diisocyanate (IPDI) showed the best mechanical properties. The comparison of various IPDI content showed that the composites with 1.5% IPDI could get the optimum mechanical properties, and the excess diisocyanate content resulted in the decrease in the mechanical properties of the composites. However, IPDI content had almost no effect on the crystallization and melting behavior of the ramie/PLA composites.     

Study on short ramie fiber/poly(lactic acid) composites compatibilized by maleic anhydride

Short ramie fiber reinforced poly(lactic acid) (PLA) composites without and with maleic anhydride (MA) were developed. The influence of PLA-g-MA as a compatibilizer on the properties of the composites was studied. The tensile, flexural and impact strength of the composites have improvements with the addition of PLA-g-MA. The morphology of fracture surface evaluated by SEM indicates that the composites with the addition of PLA-g-MA can get better adhesion between the fiber and the matrix. And the Vicat softening temperature and the degradation temperature of the composites are increased with the addition of PLA-g-MA. However, PLA-g-MA leads the glass transition temperature (T_g) decrease according to the DSC results.     

The effect of graphene presence in flame retarded epoxy resin matrix on the mechanical and flammability properties of glass fiber-reinforced composites

The effect of adding graphene in epoxy containing either an additive (MP) or reactive-type (DOPO) flame retardant on the thermal, mechanical and flammability properties of glass fiber-reinforced epoxy composites was investigated using thermal analysis; flexural, impact, tensile tests; cone calorimetry and UL-94 techniques. The addition of MP or DOPO to epoxy had a thermal destabilization effect below 400 °C, but led to higher char yield at higher temperatures. The inclusion of 10 wt% flame retardants slightly decreased the mechanical behavior, which was attributed to the poor interfacial interactions in case of MP or the decreased cross-linking density in case of DOPO flame retarded resin. The additional graphene presence increased flexural and impact properties, but slightly decreased tensile performance. Adding graphene further decreased the PHRR, THR and burning rate due to its good barrier effect. The improved fire retardancy was mainly attributed to the reduced release of the combustible gas products.