In situ preparation of graphene‐ZnO composites for enhanced graphite exfoliation and graphene‐nylon‐6 composite films

An effective method for the fabrication of graphene‐ZnO nanoparticle (GZN) composites has been developed. GZN composites with high electrical conductivity (18,607 S/m) are prepared in situ from graphite‐ZnO composites. The GZN composites also exhibit visible‐light absorption and enable the effective exfoliation of graphite. The presence of the ZnO nanoparticles assists the exfoliation of graphite and enables the preparation of solutions of highly dispersed and concentrated graphene sheets (2.7 mg/mL) that exhibit high electrical conductivity without reduction (40,404 S/m). A solution of graphene sheets was used to produce a graphene‐nylon‐6 film with an excellent Young's modulus (3 GPa) and a high tensile strength (109 MPa). An exclusive mechanism was proposed for the improvement of mechanical properties of the nylon‐6 composite film. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45034.     

Preparation of graphite composite bipolar plate for PEMFC

This research studied the preparation of graphite composite using liquid thermosetting plastic such as polyester resin (POE), phenolic modified alkyd resin (PhA) and mixed resin (POE with 10% PhA) as a binder. The morphology, physical, electrical and mechanical properties of the graphite composites were analyzed. The results showed that POE could combine with graphite powder (the 66% wt. saturated of graphite powder) better than PhA and mixed resin and gave higher electrical conductivity (4.52 S/cm). It was also found that epoxy resin could improve the mechanical property of composite plate. The addition of TiO₂ and ZnSt slightly decreased the electrical conductivity and the water absorption. Moreover, it was proposed that TiO₂ could improve the mechanical property. Carbon fiber can increase electrical and mechanical properties and water absorption of the composite with POE as a binder. The mixing of wet-lay mixture with graphite, carbon fiber and POE composite improved the mechanical property and decreased the water absorption.     

Electrical conductivity of graphite/polystyrene composites made from potassium intercalated graphite

Composites between graphite and polystyrene have been synthesized starting from potassium intercalated graphite and styrene vapor. This in situ polymerization process can be used to make electrically conductive composites containing well-dispersed thin graphite sheets. The conductivities of the composites increase as the number of ordered carbon layers increases. With only 10% graphite in a polystyrene matrix, an electrical conductivity up to 1.3 × 10⁻¹ S/cm can be obtained. The key is synthesizing a material with at least four ordered graphite layers (a stage IV complex) separated by polystyrene. This composite shows an improvement in conductivity over a control composite made by radical polymerization of styrene containing the same amount of dispersed graphite which had a conductivity of 5.0 × 10⁻³ S/cm. Characterization of the complexes by powder X-ray diffraction, scanning electron microscopy and electrical conductivity is presented.     

Preparation of polystyrene–graphite conducting nanocomposites via intercalation polymerization

In situ polymerization of styrene was conducted in the presence of expanded graphite obtained by rapid heating of a graphite intercalation compound (GIC), to form a polystyrene–expanded graphite conducting composite. The composite showed excellent electrically conducting properties even though the graphite content was much lower than in normal composites. The transition of the composite from an electrical insulator to an electrical semiconductor occurred when the graphite content was 1.8 wt%, which is much lower than that of conventional conducting polymer composites. TEM, SEM and other studies suggest that the graphite was dispersed in the form of nanosheets in a polymer matrix with a thickness of 10–30 nm, without modification of the space between carbon layers and the structure of the graphite crystallites. The composite exhibited high electrical conductivity of 10^?2 S cm^?1 when the graphite content was 2.8–3.0 wt%. This great improvement of conductivity could be attributed to the high aspect ratio (width‐to‐thickness) of the graphite nanosheets. The rolling process strongly affected the conductivity and the mechanical properties of the composite. © 2001 Society of Chemical Industry     

Preparation of polymer/graphite conducting nanocomposite by intercalation polymerization

An in situ polymerization was conducted in the presence of expanded graphite obtained by rapid heating of the graphite intercalation compound (GIC) to form a polymer/expanded graphite conducting composite. Study showed that the graphite was dispersed in the form of nanosheets in the polymer matrix. The transition from an electrical insulator to an electrical semiconductor for the composite occurred when the expanded graphite content was 1.8 wt %, which was much lower than that of conventional conducting polymer composite. The composite exhibited high electrical conductivity of 10⁻² S/cm when the graphite content was 3.0 wt %. This great improvement of conductivity could be attributed to the high aspect ratio (width-to-thickness) of the graphite nanosheets. Study suggested that extensive rolling of the blend greatly affected the conductivity of the composite. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2506–2513, 2001     

Improved thermal conductivity for chemically functionalized exfoliated graphite/epoxy composites

Chemically functionalized exfoliated graphite-filled epoxy composites were prepared with load levels from 2% to 20% by weight. The viscosities of the composites having load levels >4% by weight were over the processing window for the vacuum-assisted resin transfer molding process. Wide-angle X-ray diffraction revealed a rhombohedral carbon structure in the filler. Enhanced interaction between the epoxy and the graphite filler was evidenced by an improvement in the rubber modulus for the chemically functionalized graphite/epoxy composites. The thermal and electrical properties of the nanoparticle-filled epoxy composites were measured. The electrical property of the chemically functionalized graphite/epoxy composite deteriorated. Thermal conductivity of the chemically functionalized graphite/epoxy composite, however, increased by 28-fold over the pure epoxy resin at the 20% by-weight load level, increasing from 0.2 to 5.8 W/m K.     

Electrical,mechanical, and thermal properties of exfoliated graphite/phenolic resin composite bipolar plate for polymer electrolyte membrane fuel cell

Exfoliated graphite (EG) was synthesized from natural flake graphite by acid treatment followed by microwave irradiation. A maximum expanded volume of 560 mL/g was achieved for this exfoliation of graphite. EG/phenolic resin composite bipolar plates for polymer electrolyte membrane fuel cell were fabricated with a high loading of EG by compression molding. The composites possess low density, high electrical conductivity, high thermal stability, and high compressive strength. The composite bipolar plates were also characterized by X‐ray diffraction, scanning electron microscopy, thermogravimetric analysis, and so on. The composite prepared with 50 wt% of EG has shown the desired properties for bipolar plate as per the US Department of Energy (DOE‐2015) targets. As a result, the EG–resin composites can be used as bipolar plates for polymer electrolyte membrane fuel cell applications. POLYM. ENG. SCI., 55:917–923, 2015. © 2014 Society of Plastics Engineers     

Modeling the in-plane thermal conductivity of a graphite/polymer composite sheet with a very high content of natural flake graphite

Natural flake graphite/polymer composite sheets were prepared using tape casting method. The in-plane thermal conductivities, i.e. the thermal conductivities along the tape casting plane, of the composites were measured and the results compared to the predictions by the Maxwell and Agari models. The comparison indicated that both models cannot predict the thermal conductivity of the natural flake graphite/polymer composite at a very high graphite concentration where the flakes were shown from scanning electron microscopy (SEM) images to have a good orientation parallel to the tape casting direction. The SEM images also illustrated that the well oriented flakes formed a continuous graphite–graphite network. Based on the observed structure, a new thermal conductivity model was constructed. The new model applies well to the composites at a large content of highly oriented graphite flakes. The model was also validated by the experimental results from samples with the same graphite content but with different degrees of graphite flake orientation.     

Performance of graphite filled composite based on benzoxazine resin

In this study, we aimed to prepare and characterize graphite filled composites based on benzoxazine resin for the bipolar plate in fuel cell. Three kinds of graphite (synthetic graphite, natural graphite, and expanded graphite) were used for the preparation of the graphite filled composites. The composites were prepared by means of the compression molding of mixtures of graphite and benzoxazine resin. The properties of the graphite filled composites based on benzoxazine resin were estimated by mechanical property, gas permeability, and electrical conductivity. As a result, it was found that graphite filled composites based on benzoxazine resin showed good gas impermeability, electrical conductivity and mechanical property compared with those of the graphite filled composites based on the conventional phenolic resin. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Characterizations of expanded graphite/polymer composites prepared by in situ polymerization

Poly(styrene-co-acrylonitrile)/expanded graphite composite sheets with very low in-plane (8.5 × 10⁻³ Ω cm) and through-thickness (1.2 × 10⁻² Ω cm) electrical resistivities have been prepared. The expanded graphite was made by oxidation of natural graphite flakes, followed by thermal expansion at 600 °C. Microscopic results disclosed that the expanded graphite has a legume-like structure, and each “legume” has a honeycomb sub-structure with many diamond-shaped pores. After soaking the expanded graphite with styrene and acrylonitrile monomers, the polymer/expanded graphite composite granules were obtained by in situ polymerization of the monomers inside the pores at 80 °C. The functional groups and microstructures of the oxidized graphite, expanded graphite and composites in the forms of particles or sheets were carefully characterized using various techniques, including X-ray powder diffraction, thermogravimetry, optical and electron microscopy. It was found that the honeycomb sub-structure survived after hot-pressing, resulting in a graphite network penetrating through the entire composite body, which produces a composite with excellent electrical conductivity.     

Effect of shear on the electrical conductivity of suspensions of graphite in an unsaturated polyester resin

The effect of shear on the electrical conductivity of suspensions of conductive graphite particles in a nonconductive unsaturated polyester resin was investigated. At graphite loadings near 30 wt% the electrical conductivity was higher when the suspension was undergoing shear than when shearing stopped. Moreover, shearing caused a large permanent increase in the electrical conductivity of the suspension. When shear was restarted after a period of rest the transient response of the electrical conductivity depended on the direction of previous shear, indicating that the suspension acquires an anisotropic structure under shear. The transition upon shear reversal was strain‐dependent. Surprisingly, at graphite loadings near 50 wt% the effect of shear on the electrical conductivity was the opposite of that at loadings near 30 wt%. At intermediate loadings the effect of shear on the electrical conductivity was less clear. The results may have applications in the manufacture of composite bipolar plates for fuel cells and of various other parts made from conductive polymers. POLYM. ENG. SCI., 45:1540–1545, 2005. © 2005 Society of Plastics Engineers     

Dispersion of graphite nanosheets in a polymer matrix and the conducting property of the nanocomposites

Poly(methyl methacrylate)(PMMA)/expanded graphite composite has been made via an in situ polymerization of methyl methacrylate(MMA) in the presence of expanded graphite obtained by rapid heating of the graphite intercalation compound (GIC). The composite was then blended with poly(vinyl chloride) (PVC) to form an electrically conducting composite. SEM, TEM and XRD showed that the graphite had been dispersed throughout the polymer matrix in the form of nanosheets with thicknesses of about 20 nm. The resulting composite showed excellent electrical conductivity despite a low concentration of graphite. The transition from an electrical insulator to an electrical semiconductor for the composite occurred when the graphite content was 3.5 wt%, much lower than that of conventional conducting polymer composites. Conductivity reached a maximum of 10^?4 s/cm at a graphite concentration of 5.0 wt%. This improvement of conductivity could be attributed to the high aspect ration (width‐to‐thickness) of the graphite nanosheets dispersed in the polymer matrix.     

Dielectric properties of epoxy/graphite flakes composites: Influence of loading and surface treatment

Epoxy-rich carbon-based composites are well recognized materials in industries owing to their good mechanical properties and thermal stability. Here, dielectric properties of composites based on bisphenol-A-epoxy resin loaded with 5, 6, 10, and 15 wt% of graphite flakes (GF) have been studied. The frequency and temperature dependence of the dielectric permittivity, dielectric loss, and ac conductivity have been examined in temperature (−103 to 97°C) and frequency (20 Hz–200 kHz) range. Influence of the filler surface chemistry have been studied for composites loaded with 5 wt% GF obtained: (i) under wet milling, without or with adding Triton-100x as a surfactant, or (ii) under dry milling in the presence of KOH. The composite made of epoxy loaded with 5 wt% exfoliated expanded graphite flakes (EEG), was also prepared. The surface treatment with KOH notably increased dielectric constant of the composite, keeping low dielectric loss, while treatment with Triton-100x significantly increased tanδ. The composite loaded with exfoliated expanded graphite shows higher ac conductivity than those obtained with flaky graphite, GF. Possibility to change dielectric properties of the composites without changing the loading content can be used as an approach in tailoring one with desired dielectric properties.     

The effect of methyl-tri-n-butylammonium methylsulfate and graphite nanoplates on production of antistatic acrylic polymer

Methyl-tri-n-butylammonium methylsulfate (BIL) was incorporated into acrylic resin to improve antistatic property of acrylic polymer (AP). In order to avoid reduction in the mechanical properties of acrylic film and to reach higher electrical conductivity values, the combination of graphite nanoplates (Gr) and BIL was used. The effects of incorporation of BIL and Gr into AP on UV-blocking properties and UV transmittance data of acrylic films were measured. After 120 days, AP containing 5 wt% BIL and 0.01 wt% Gr, and AP+15 wt% BIL exhibited antistatic property. While BIL incorporation into acrylic resin deteriorated the mechanical properties, 0.01 wt% Gr incorporation increased the tensile strength by 83%.     

Free-standing diamond films deposited by DC arc plasma jet on graphite substrates with a destroyable Ti interlayer

A destroyable Ti interlayer on graphite substrate was used for fabrication of crack-free free-standing diamond films by high-power DC Arc Plasma Jet. Ti interlayer was arc ion plated on the polycrystalline graphite substrate. The thickness, morphology and composite phase of the Ti interlayer were examined by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Titanium carbide (TiC) was detected in both sides of the interlayer, which played an important role with respect to reasonable adhesion and diamond nucleation. Semi-translucent and crack-free diamond films were obtained and characterized by SEM and Raman spectroscopy. It is shown that the diamond films so obtained have excellent Raman signature. The overall results suggest that plating Ti interlayer on graphite substrate is an effective way to obtain potentially crack-free free-standing diamond films.     

Amorphous silica-coated graphite particles for thermally conductive and electrically insulating resins

A thermally conductive and electrically insulating composite filler was produced by surfactant assisted sol–gel coating of amorphous silica on flake graphite. Amorphous silica-coated graphite (a-Si coated grp) obtained using a cationic surfactant showed the best enhancement of the insulating coating. The resulting a-Si coated grp/boehmite/polybutylene terephthalate polyester resin composite exhibited a high volume resistivity, exceeding 1.0 × 10¹⁴ Ω cm at an applied voltage of 500 V, and a thermal conductivity of 3.3 W/m K at 22.9 vol.% a-Si coated grp loading. The heat releasing performance of the developed resin composite in actual light-emitting diodes bulb housings was compared with conventionally used thermally and electrically conductive resin. This comparison revealed that the new composite released heat more effectively. This innovative technology, which may solve the trade-off between material properties and cost, will be available for a broad range of thermally conductive resin applications that simultaneously require thermal conduction and electrical insulation.     

Synergistic Effects of Carbon Fillers of Phenolic Resin Based Composite Bipolar Plates on the Performance of PEM Fuel Cell

The most essential and costly component of polymer electrolyte membrane fuel cells is the bipolar plate. The production of suitable composite bipolar plates for polymer electrolyte membrane fuel cell with good mechanical properties and high electrical conductivity is scientifically and technically very challenging. This paper reports the development of composite bipolar plates using exfoliated graphite, carbon black, and graphite powder in resole‐typed phenol formaldehyde. The exfoliated graphite with maximum exfoliated volume of 570 ± 10 mL g⁻¹ used in this study was prepared by microwave irradiation of chemically intercalated natural flake graphite in a few minutes. The composite plates were prepared by varying exfoliated graphite content from 10 to 35 wt.% in phenolic resin along with fixed weight percentage of carbon black (5 wt.%) and graphite powder (3 wt.%) by compression molding. The composite plates with filler weight percentage of 35/5/3/exfoliated graphite/carbon black/graphite powder offer in‐plane and trough‐plane electrical conductivities of 374.42 and 97.32 S cm⁻¹, bulk density 1.58 g cm⁻³, compressive strength 70.43 MPa, flexural strength 61.82 MPa, storage modulus 10.25 GPa, microhardness 73.23 HV and water absorption 0.22%. Further, I–V characteristics notify that exfoliated graphite/carbon black/graphite powder/resin composite bipolar plates in unit fuel cell shows better cell performance compared exfoliated graphite/resin composite bipolar plates. The composite plates own desired mechanical properties with low bulk density, high electrical conductivity, and good thermal stability as per the U.S. department of energy targets at low filler concentration and can be used as bipolar plates for proton exchange membrane fuel cells.     

天然鳞片石墨/环氧树脂复合材料的制备及导热性能研究

以天然鳞片石墨为导热填料,E44型环氧树脂为基体,采用超声分散法制备天然鳞片石墨/环氧树脂复合导热材料.系统考察了天然鳞片石墨用量、石墨粒度和炭黑添加量等因素对复合材料导热性能的影响.结果表明:随着天然鳞片石墨用量增加,复合材料的导热系数增大,抗压强度先增加后减小;复合材料的导热系数随天然石墨粒径的增大而增大,抗压强度先减小后增加;在石墨/环氧树脂复合导热材料中添加不同用量的炭黑时,随着炭黑添加量的增加,复合材料的抗压强度增大,导热系数先增大后减小.制备天然鳞片石墨/环氧树脂复合导热材料的最佳配方为天然鳞片石墨用量45％,粒径≤270 μm,炭黑用量2％.     

Monolayer graphene from graphite oxide

Graphene, a new carbon material, is attracting presently an increasing research interest. It stems from the unique electrical and mechanical properties of graphene predicted by theory. Experimental studies of graphene are, however, severely curtailed by a lack of an appropriate technique for its preparation. Mechanical cleavage of graphite proved to be ineffective, since it yields only very small (a few microns in size) particles of monolayer graphene. The rapidly developing approach based on chemical exfoliation of graphite produces large-area coatings composed primarily of arbitrarily oriented multilayer graphene particles. We have developed a technique for preparation of monolayer graphene sheets involving liquid exfoliation of crystalline graphite, which includes synthesis of graphite oxide by deep oxidation as an intermediate stage. Electron diffraction traces, as well as the variation of diffracted intensities with local orientation of graphene sheets, AFM, and HRTEM images testify to a remarkably good monolayer structure of the graphite oxide particles obtained by our technique. These results open a way to setting up high-efficiency production of monolayer graphene sheets appropriate for electrical and optical measurements and fabrication of structures for use in the field of applications.     

Electronic transport in composites of graphite oxide with carbon nanotubes

We show that the presence of electrically insulating graphite oxide (GO) within a single wall carbon nanotube (SWCNT) network strongly enhances electrical conductivity, whereas reduced graphite oxide, even though electrically conductive, suppresses electrical conductivity within a composite network with SWCNTs. Measurements of Young’s modulus and of Raman spectra strongly support our interpretation of the “indirect” role of the oxide groups, present in GO within the SWCNT-GO composite, through electronic doping of metallic SWCNTs.