Radiation cured epoxy acrylate composites based on graphene, graphite oxide and functionalized graphite oxide with enhanced properties

Epoxy acrylate (EA) composites containing graphite oxide (GO), graphene and nitrogen-double bond functionalized graphite oxide (FGO) were fabricated using UV-radiation and electron beam radiation via in-situ polymerization. Graphene and FGO were homogenously dispersed in EA matrix and enhanced properties, including thermal stability, flame retardancy, electrical conductivity and reduced deleterious gas releasing in thermo decomposition were obtained. Microscale combustion colorimeter results illustrated improved flame retardancy; EA/FGO composites achieved a 29.7% reduction in total heat release (THR) when containing only 0.1% FGO and a 38.6% reduction in peak-heat release rate (PHRR) when containing 3% FGO. The onset decomposition temperatures were delayed and the maximum decomposition values were reduced, according to thermogravimetric analysis which indicated enhanced thermal stabilities. The electrical conductivity was increased by 6 orders of magnitude (3% graphene) and the deleterious gas released during the thermo decomposition was reduced with the addition of all the graphite samples. This study represented a new approach to functionalize GO with flame retardant elements and active curable double bond to achieve better dispersion of GO into polymer matrix to obtain nanocomposites and paved a way for achieving graphene-based materials with high-performance of graphene in enhancement of flame retardancy of polymers for practical applications.     

Sandwiched epoxy–alumina composites with synergistically enhanced thermal conductivity and breakdown strength

Development of polymer-based composites with simultaneously high thermal conductivity and breakdown strength has attracted considerable attentions owing to their important applications in both electronic and electric industries. In this study, we successfully design novel epoxy-based composites with nano-Al₂O₃/epoxy composite layer sandwiched between micro-Al₂O₃/epoxy composite layers, which show synergistically and significantly enhanced thermal conductivity and breakdown strength. Compared with the traditional composites, the bottleneck that both thermal conductivity and breakdown strength cannot be simultaneously enhanced can be overcome successfully. An optimized sandwiched alumina–epoxy composite with 70 wt% micro-Al₂O₃ fillers in the outer layers and 3 wt% nano-Al₂O₃ in the middle layer simultaneously displays a high thermal conductivity of 0.447 W m^?1 K^?1 (2.4 times of that of epoxy) and a high breakdown strength of 68.50 kV mm^?1, which is 6.3 % higher than that of neat epoxy (64.45 kV mm^?1). The experimental results on the thermal conductivity of multi-layered alumina–epoxy composites were in well accordance with the theoretical values predicted from the series conduction model. This novel technique simultaneously improves thermal conductivity and breakdown strength, which is of critical importance for design of perspective composites for electronic and electric equipments.     

Intumescent flame retardant polyurethane/reduced graphene oxide composites with improved mechanical, thermal, and barrier properties

Intumescent flame retardant polyurethane (IFRPU) composites were prepared in the presence of reduced graphene oxide (rGO) as synergism, melamine, and microencapsulated ammonium polyphosphate. The composites were examined in terms of thermal stability (both under nitrogen and air), electrical conductivity, gas barrier, flammability, mechanical, and rheological properties. Wide-angle X-ray scattering and scanning electron microscopy indicated that rGO are well-dispersed and exfoliated in the IFRPU composites. The limiting oxygen index values increased from 22.0 to 34.0 with the addition of 18 wt% IFR along with 2 wt% rGO. Moreover, the incorporation of rGO into IFRPU composites exhibited excellent antidripping properties as well as UL-94 V0 rating. The thermal stability of the composites enhanced. This was attributed to high surface area and good dispersion of rGO sheets induced by strong interactions between PU and rGO. The oxygen permeability, electrical, and viscoelasticity measurements, respectively, demonstrated that rGO lead to much more reduction in the gas permeability (by ~90 %), high electrical conductivity, and higher storage modulus of IFRPU composites. The tensile strength, modulus, and shore A remarkably improved by the incorporation of 2.0 wt% of rGO as well.     

Graphene oxide-filled conducting polyaniline composites as methanol-sensing materials

Polyaniline/graphene oxide (PANI/GO) composites were prepared by polymerization of aniline monomer in the presence of GO under acidic conditions. The synthesized samples were characterized by Fourier transform infra red spectroscopy, ultraviolet–visible absorption, Raman spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and thermogravimetric analysis. The direct current electrical conductivity of the composite was calculated by a four-probe technique. It is found that the conductivity dramatically increased to 241 S m^?1 for PANI/GO (5 wt%) composite at 110 °C compared to pure PANI (7.5 S m^?1). The composite material was investigated as a methanol vapour sensor and compared with pure PANI. The methanol-sensing characteristics of the prepared composite was monitored by measuring the change in electrical resistivity on exposure to methanol vapour at different concentrations. The resistivity of PANI increases on exposure to methanol vapour because of strong hydrogen bonding between methanol with the polymer chain. A density functional theory study was carried out to verify the proposed concept of hydrogen bonding between the polymer chains and methanol. The presence of GO in PANI/GO composite increases the sensitivity towards methanol as compared with the pure PANI.     

Decoration of reduced graphene oxide with dandelion-like TiO2 and their dielectric properties in poly(arylene ether nitriles) composites

Novel dandelion-like titanium oxide (TiO₂) decorated reduced graphene oxide (rGO@TiO₂) hybrids were obtained by a one-step solvent-thermal reduction of GO and tetrabutyl titanate simultaneously. The hybrids were used as a novel filler for high performance poly(arylene ether nitriles) (PEN) composites. The thermal stability and morphological properties of the PEN composites were, respectively, investigated by the thermo gravimetric analysis and scanning electron microscope, aiming at examining the effect of surface decoration on the dispersion of rGO@TiO₂ in PEN matrix. The results indicated that the rGO@TiO₂ present better dispersion in the PEN matrix. Meanwhile, the derived composite films exhibited high thermal stability with initial decomposition temperatures (T _id ) in the range of 477–487 °C. DSC curves showed that the glass transition temperatures were in the range of 219–227 °C. Moreover, all of the composite films also showed excellent flexibility and mechanical properties. The tensile modulus and strength were increased about 4 and 6 % with 5 wt% rGO@TiO₂ loading, respectively. More importantly, for 30 wt% rGO@TiO₂ reinforced PEN composite film, the dielectric permittivity dramatically increased from 3.8 to 81 at 1 kHz.     

Non-covalently modified reduced graphene oxide/polyurethane nanocomposites with good mechanical and thermal properties

Non-covalently modified graphene nanosheets were prepared by reduction graphene oxide with hydrazine hydrate and simultaneous non-covalent functionalization via 1-allyl-methylimidazolium chloride (AmimCl) ionic liquid. Atomic force microscopy revealed that AmimCl ionic liquid modified graphene (IL-G) was well-dispersed in a single exfoliation with a thickness of around 0.96 nm in DMF. Subsequently, the prepared IL-G nanosheets were incorporated into polyurethane (PU) to fabricate IL-G/PU nanocomposites by solution blending. X-ray diffraction disclosed an exfoliated morphology of IL-G nanosheets dispersed in the PU matrix, while the fractured morphology of the IL-G/PU nanocomposites showed that IL-G nanosheets presented a wrinkled morphology when dispersed in the matrix. Both techniques revealed homogeneous dispersion and good compatibility of IL-G nanosheets with PU matrix, indicating the existence of interfacial interactions. At 0.608 wt% loadings of IL-G nanosheets, the tensile strength and storage modulus of the composites were increased by 68.5 and 81.1 %, respectively. High thermal properties were also achieved at a low loading of IL-G nanosheets. An approximately 40 °C improvement in temperature of 5 % weight loss and 34 % increase in thermal conductivity were obtained at just 0.608 wt% loading of IL-G nanosheets.     

Titania-reduced graphene oxide nanocomposite as a promising visible light-active photocatalyst for continuous degradation of VVOC in air purification process

Titania-reduced graphene oxide nanocomposites have been prepared through facile hydrothermal method by a reaction between P25 as TiO₂ source and graphene oxide. Reduction of graphene oxide and its reaction with P25 nanoparticles were achieved simultaneously at high temperature and pressure during the hydrothermal process with the minimum organic solvents. Chemical bonds, crystalline structure, morphology, porosity and light absorption of composites along with their photocatalytic activity under UV and visible light irradiation were investigated. Transmission electron microscopy images showed that P25 nanoparticles, with diameters about 25 nm, were dispersed on the sheets of reduced graphene oxide (RGO) homogeneously. A stronger interaction between P25 and RGO provided a red shift about 20 nm in the absorption edge of the composites. To set up a continuous tubular reactor made from thin layer of the prepared material, composite films were coated on the external surface of a steel tube to make an annular reactor. The reactor was equipped with UV or visible light sources to investigate the photocatalytic activity of the prepared composites in a continuous air flow contaminated with specified amount of acetaldehyde as a VVOC (very volatile organic compound) model molecule. Degradation efficiency of P25–RGO with 0.5 wt% RGO was significantly high under visible light irradiation, and about 70% conversion was observed using an air flow at normal conditions with specific flow rate of 17 ml min^?1 and 500 ppm acetaldehyde, by 30 mg of the coated composite in the reactor. Composites with low amount of RGO would be an appropriate photosensitizer and electron acceptor to suppress the recombination of photogenerated electron–hole pairs to enhance the photocatalytic performance.     

Mechanical properties of graphene films enhanced by homo-telechelic functionalized polymer fillers via π–π stacking interactions

Most researches on graphene/polymer composites are focusing on improving the mechanical and electrical properties of polymers at low graphene content instead of paying attention to constructing graphene’s macroscopic structures. In current study the homo-telechelic functionalized polyethylene glycols (FPEGs) were tailored with π-orbital-rich groups (namely phenyl, pyrene and di-pyrene) via esterification reactions, which enhanced the interaction between polyethylene glycol (PEG) molecules and chemical reduced graphene oxide (RGO) sheets. The π–π stacking interactions between graphene sheets and π-orbital-rich groups endowed the composite films with enhanced tensile strength and tunable electrical conductivity. The formation of graphene network structure mediated by the FPEGs fillers via π–π stacking non-covalent interactions should account for the experimental results. The experimental investigations were also complemented with theoretical calculation using a density functional theory. Atomic force microscope (AFM), scanning electron microscope (SEM), X-ray diffraction (XRD), nuclear magnetic resonance (NMR), thermal gravimetric analysis (TGA), UV–vis and fluorescence spectroscopy were used to monitor the step-wise preparation of graphene composite films.     

Conducting polymer and reduced graphene oxide Langmuir–Blodgett films: a hybrid nanostructure for high performance electrode applications

In this work, we prepared a reduced graphene oxide (RGO)/poly(3,4-ethylenedioxythiophene) (PEDOT) hybrid composite with well defined nanostructure. The graphene oxide (GO) was first deposited on substrate through the Langmuir–Blodgett (LB) deposition, which provided a tunable and ordered GO arrangement on substrate. Then the GO LB films were reduced to RGO by following thermal treatment, and a ultrathin conducting polymer (CP) PEDOT was directly coated on RGO through a vapor phase polymerization process. The RGO/PEDOT nanocomposite exhibits excellent electrical conductivity about 377.2 S/cm. Electrochemical activity investigation revealed that this nanocomposite exhibits 213 F/g high specific capacitance at a 0.5 A/g current density and shows better capacitance retention rate than pure PEDOT. The detailed study also confirmed that the arrangement of RGO shows distinct influence on the electrical and electrochemical properties of obtained nanocomposite. Large area RGO/PEDOT nanocomposite with high conductivity and electrochemical activity can be deposited on different substrates. Such high conductivity and electrochemical activity RGO/CP nanocomposite shows promising application future in organic and flexible electrode materials for sustainable energy storage.     

Physico-chemical properties of Bismuth nitrate filled PVA–LiClO<Subscript>4</Subscript> polymer composites for energy storage applications

A series of polymer composites were prepared by the addition of Bismuth nitrate (Bi(NO₃)₃) and Lithium perchlorate (LiClO₄) to poly(vinyl alcohol) (PVA) polymer matrix by solvent casting method. The microstructures and surface morphology were systematically characterized by FTIR spectroscopy, X-ray diffraction, AFM and SEM analysis. The DSC thermal studies exhibit the transformations in the composites due to the effect of Bi(NO₃)₃. The mechanical strength, ac and dc conducting properties were studied. The variation of ac conductivity of the composites with frequency follows Jonscher’s universal power law and found to be increased with increasing temperature. The sample containing 10 wt% Bi(NO₃)₃ exhibits good mechanical strength, high conductivity and dielectric constant at room temperature. The variation of conducting properties of 10 wt% Bi(NO₃)₃ filled composite with temperature has been explained based on hopping mechanism. The frequency exponent (s) have been well fitted with the proposed correlation equation of the barrier hopping model. The transport parameters are estimated using Rice and Roth model. The activation energy is calculated for the sample PVA–LiClO₄ matrix filled with 10 wt% Bi(NO₃)₃ using Arrhenius equation.     

Glass transition improvement in epoxy/graphene composites

Graphene oxide nanoplatelets (GO) were prepared from expanded graphite (EG) and functionalized with triethylenetetramine (GO-TETA). The GO-TETA consisted of a few layers of graphene (~4–6 layers), as determined by atomic force microscopy and Raman spectroscopy. X-ray photoelectron spectroscopy showed that the TETA was covalently linked to the GO in the GO-TETA sample. Epoxy composites based on the diglycidyl ether of bisphenol A with TETA as a hardener and with 0.5–3.0 wt% additions of EG and GO-TETA were investigated. The results showed that the addition of the nanofillers led to an increase of ~20 °C in the glass transition temperature. A slight increase in the ratio of the elastic modulus/hardness of the nanocomposites was observed by nanoindentation tests carried out at a depth range of 300 nm–1.3 μm; these tests indicated a tendency of increased fracture toughness. Microindentation had an enhancement of 40 % in hardness for the 1 wt% composite with GO-TETA relative to the corresponding value for the neat epoxy.     

Al2Mo3O12/polyethylene composites with reduced coefficient of thermal expansion

Recently, polymer composites reinforced with low fractions of thermomiotic nanoceramics have triggered a lot of research. The efforts have been focused on achieving considerable reduction of the coefficient of thermal expansion (CTE) of polymeric materials without deterioration of other physical properties. In this context, polyethylene (PE) composites reinforced with different loads of Al₂Mo₃O₁₂ nanofillers (0.5–4 mass %) were fabricated by micro-compounding. To enhance the interfacial interaction between the two components, chemical functionalization of Al₂Mo₃O₁₂ was performed with vinyltrimethoxysilane (VTMS) prior to micro-compounding. Infrared spectroscopy and thermogravimetry demonstrated the successful grafting of VTMS on the Al₂Mo₃O₁₂ surface. The composites showed strongly decreased CTEs, up to 46 % reduction for loadings of 4 mass % compared with neat PE, suggesting intimate filler–matrix interactions. The variation of CTEs of the composites in terms of the filler fraction was successfully described by Turner’s model allowing calculation of the bulk modulus of monoclinic Al₂Mo₃O₁₂ (13.6 ± 2.6 GPa), in agreement with the value obtained by an ultrasonic method. The thermal stability of the composites was improved, although the addition of functionalized fillers decreased the degree of crystallinity of the PE to a small extent. The Young’s modulus and yield strength of the composites increased from 6.6 to 19.1 % and 4.0–6.0 %, respectively, supporting the existence of strong filler–matrix interactions, contributing to an efficient load transfer. Finite element analysis of thermal stresses indicated absence of plastic deformation of the matrix or fracture of the nanofillers, for a 100 K temperature drop.     

KH560功能化氧化石墨烯/光敏性不饱和聚酯树脂复合材料的制备与性能

合成了γ-缩水甘油醚氧丙基三甲氧基硅烷（KH560）功能化氧化石墨烯（FGO）,通过红外光谱和热重进行了表征分析。通过加入FGO对混杂型（自由基-阳离子混杂机制）光敏树脂（CRCPR）进行改性,探讨了FGO的加入对CRCPR的黏度、凝胶率和体积收缩率的影响,并测试了固化FGO/CRCPR复合材料的力学性能。结果表明：与氧化石墨烯（GO）相比,由于功能团的引入,FGO在树脂中呈现良好的分散性,少量FGO的引入既未明显改变树脂的黏度,也未降低树脂的凝胶率;同时,极少量FGO的加入即可大幅提高固化FGO/CRCPR复合材料的力学性能,当FGO的质量分数为0.06%时,体积收缩率降低了37%,拉伸强度和弯曲强度分别提高了71.8%和26.9%,冲击强度也提高了49.7%。良好的力学性能与FGO良好分散性及FGO与CRCPR基体良好的界面性能有关。     

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.     

Electrical and mechanical properties of PMMA/reduced graphene oxide nanocomposites prepared via in situ polymerization

We report the effect of filler incorporation techniques on the electrical and mechanical properties of reduced graphene oxide (RGO)-filled poly(methyl methacrylate) (PMMA) nanocomposites. Composites were prepared by three different techniques, viz. in situ polymerisation of MMA monomer in presence of RGO, bulk polymerization of MMA in presence of PMMA beads/RGO and by in situ polymerization of MMA in presence of RGO followed by sheet casting. In particular, the effect of incorporation of varying amounts (i.e. ranging from 0.1 to 2 % w/w) of RGO on the electrical, thermal, morphological and mechanical properties of PMMA was investigated. The electrical conductivity was found to be critically dependent on the amount of RGO as well as on the method of its incorporation. The electrical conductivity of 2 wt% RGO-loaded PMMA composite was increased by factor of 10⁷, when composites were prepared by in situ polymerization of MMA in the presence of RGO and PMMA beads, whereas, 10⁸ times increase in conductivity was observed at the same RGO content when composites were prepared by casting method. FTIR and Raman spectra suggested the presence of chemical interactions between RGO and PMMA matrix, whereas XRD patterns, SEM and HRTEM studies show that among three methods, the sheet-casting method gives better exfoliation and dispersion of RGO sheets within PMMA matrix. The superior thermal, mechanical and electrical properties of composites prepared by sheet-casting method provided a facile and logical route towards ultimate target of utilizing maximum fraction of intrinsic properties of graphene sheets.     

Performance of graphite nanoplatelet/silicone composites as thermal interface adhesives

Graphite nanoplatelets (GNP)/silicone composites are potential thermal interface materials due to their high thermal conductivity and compliance. In this study, performance as thermal interface materials is studied by measuring thermal contact resistance. The effect of surface roughness, particle size of GNPs, wt% GNPs, temperature and applied pressure on the thermal contact resistance of the composite coatings was determined. The GNP/silicone coating performed much better on rough surfaces than on smooth surfaces. The composite coating consisting of large GNPs is more effective than small GNPs probably due to the two times higher thermal conductivity of the former. The thermal contact resistance of the GNP/silicone composite increased by ~3–10% with an increase of temperature but remained unaffected by an increase of pressure. The comparison of GNP/silicone composite coatings with GNP-based thermal pastes showed that the former perform much better in thick bond lines.     

Effect of processing routes on mechanical and thermal properties of copper–graphene composites

In this paper, copper–graphene composites were fabricated by using two different processing routes (ball milling (BM) and ultrasonication) followed by spark plasma sintering. Vickers hardness and anisotropic thermal conductivity of the composites were measured and observed that ultrasonicated fabricated composites gave better result compared with BM composite and even from pure copper. The hardness values obtained for ultrasonicated copper–graphene composite were 69?HV (57% higher) and thermal conductivity 387?W/m?K (13% higher) by using only 0.5?wt-% of graphene, while for pure copper the values were 44?HV and 341?W/m?K. The value of anisotropic thermal conductivity ultrasonicated composites was also 1.97 which is much higher than pure copper 0.94.     

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.     

Highly conductive graphene oxide/polyaniline hybrid polymer nanocomposites with simultaneously improved mechanical properties

Graphene oxide (GO) was added to a polymer composites system consisting of surfactant-wrapped/doped polyaniline (PANI) and divinylbenzene (DVB). The nanocomposites were fabricated by a simple blending, ultrasonic dispersion and curing process. The new composites show higher conductivity (0.02–9.8 S/cm) than the other reported polymer system filled with PANI (10⁻⁹–10⁻¹ S/cm). With only 0.45 wt% loading of GO, at least 29% enhancement in electric conductivity and 29.8% increase in bending modulus of the composites were gained. Besides, thermal stability of the composites was also improved. UV–Vis spectroscopy, X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM) revealed that addition of GO improves the dispersion of PANI in the polymer composite, which is the key to realize high conductivity.     

Electrohydrodynamic atomization approach to graphene/zinc oxide film fabrication for application in electronic devices

Graphene-based composites represent a new class of materials with potential for many applications. Metal, semiconductor, or any polymer properties can be tuned by attaching it to graphene. Here, a new route for fabrication of graphene based composites thin films has been explored. Graphene flakes (<4 layers) and a well-known semiconductor zinc oxide (ZnO) (<50 nm particle size) have been dispersed in N-methylpyrrolidone and ethanol, respectively. Thin film of graphene flakes is deposited and decorated with ZnO nanoparticles to fabricate graphene/ZnO composite thin film on silicon substrate by electro hydrodynamic atomization technique. Graphene/ZnO composite thin film has been characterized morphologically, structurally and chemically. To investigate electronic behavior of the composite thin film, it is deployed as cathode in a diode device i.e. indium tin oxide/poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate)/polydioctylfluorene-benzothiadiazole/(graphene/ZnO). The J–V analysis of diode device has shown that at voltage of 1 V, the current density in organic structure is at low value of 4.69 × 10^?3 A/cm² and when voltage applied voltage is further increased; the device current density has increased by the order of 200 that is 1.034 A/cm² at voltage of 12 V.