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.     

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     

One‐step synthesis of highly conductive PPy/graphite nanosheets/Gd3+ composites

Highly conductive polypyrrole/graphite nanosheets/Gd³⁺ (PPy/nanoG/Gd³⁺) composites are fabricated via in situ polymerization using p‐toluenesulfonic acid as a dopant and FeCl₃ as an oxidant. The effects of the graphite nanosheets and Gd³⁺ loading on the electrical conductivity are investigated. The maximum conductivity of PPy/nanoG/Gd³⁺ composites about 17.86 S/cm found with 3 wt% graphite nanosheets and 6 wt% Gd³⁺ at room temperature. The results showed that the high‐aspect‐ratio structure of graphite nanosheets played an important role in forming a conducting network in PPy matrix. Thermal gravimetric analysis demonstrates an improved thermal stability of PPy in the PPy/nanoG/Gd³⁺ composites. The microstructures of PPy/nanoG/Gd³⁺ are evidenced by the SEM and TEM examinations. POLYM. COMPOS., © 2011 Society of Plastics Engineers.     

A study on electrical and thermal conductivities of ethylene–octene copolymer/expandable graphite composites

A series of ethylene–octene copolymer (EOC) composites have been prepared by melt‐mixing with different weight ratios of expandable graphite filler (0–50% by weight). Electrical conductivity [both alternating current (AC) and direct current (DC)] and thermal conductivity studies were carried out. Effect of filler loading and frequency on electrical conductivity was studied. DC conductivity has increased from 1.51 × 10^?13 S cm^?1 to 1.17 × 10^?1 S cm^?1. Percolation threshold by DC and also AC methods was observed at about 16 vol% of the filler. Real part of permittivity was found to be decreasing with increase in frequency while conductivity was increasing. Thermal conductivity was also found to be increasing gradually from 0.196 to 0.676 Wm^?1 K^?1 which is about 245% increase. Graphite not only increases the electrical and thermal conductivities but at and above 40 wt%, also acts as a halogen‐free, environmental friendly flame retardant. Shore‐A hardness of EOC/graphite composites shows that even with high graphite loading, the hardness is increased from about 50–68 only so that the rubbery nature of the composite is not affected very much. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Preparation of polystyrene/graphite nanosheet composite

A new process for the dispersion of graphite in the form of nanosheets in a polymer matrix was developed via in situ polymerization of monomer at the presence of sonicated expanded graphite during sonication. Graphite nanosheets prepared via powdering the expanded graphite had a thickness ranging 30-80 nm and a diameter ranging 0.5-20 μm and was an excellent nanofiller for the fabrication of polymer/graphite conducting nanocomposite. The process fabricated electrically conducting polystyrene/graphite nanosheet nanocomposite films with much lower percolation threshold and much higher conductivities than those of composites made by conventional methods.     

Material characterization of graphite nanosheet composites

Three sets of expanded graphite‐filled polymers, having three different particle sizes, were reinforced with 1–5% by weight. The structural, mechanical, electrical, and thermal properties of these composites were studied and compared. After dispersion, the particles were reduced to nanometer size through exfoliation, sonication, and high‐shear strain rate mixing, which further breaks and delaminates them. In addition, scanning electron microscope characterizations were performed. The expanded graphite‐filled polymer material could be tailored to be high conducting. Compared with the pure polymer, the polymers filled with 5 wt% expanded graphite have seen a significant reduction in electrical resistivity by orders. The thermal expansion coefficient and water absorption for the weight containing 5 wt% expanded graphite has also been drastically improved, decreasing with the weight percentage of graphite content. Compression and impact tests were conducted. The influence of dispersion on the material behavior was studied. Some fracture modes associated with the layered microstructures of the graphite nanosheets were observed. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Structure and electrical properties of grafted polypropylene/graphite nanocomposites prepared by solution intercalation

A novel process was developed to prepare electrically conducting maleic anhydride grafted polypropylene (gPP)/expanded graphite (EG) nanocomposites by solution intercalation. The conducting percolation threshold at room temperature (Φ_c) of the nanocomposites was 0.67 vol %, much lower than that of the conventional conducting composites prepared by melt mixing (Φ_c = 2.96 vol %). When the EG content was 3.90 vol %, the electrical conductivity (σ) of the former reached 2.49 × 10^?3 S/cm, whereas the σ of the latter was only 6.85 × 10^?9 S/cm. The TEM, SEM, and optical microscopy observations confirmed that the significant decrease of Φ_c and the striking increase of σ might be attributable to the formation of an EG/gPP conducting multiple network in the nanocomposites, involving the network composed of particles with a large surface‐to‐volume ratio and several hundred micrometers in size, and the networks composed of the boards or sheets of graphite with high width‐to‐thickness ratio and particles of fine microscale or nanoscale sizes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1864–1869, 2003     

Synthesis and properties of poly(4,4′-oxybis(benzene)disulfide)/graphite nanocomposites via in situ ring-opening polymerization of macrocyclic oligomers

An effective method for the preparation of poly(4,4′-oxybis(benzene)disulfide)/graphite nanosheet composites via in situ ring-opening polymerization of macrocyclic oligomers were reported. Completely exfoliated graphite nanosheets were prepared under the microwave irradiation followed by sonication in solution. The nanocomposites were fabricated via in situ melt ring-opening polymerization of macrocyclic oligomers in the presence of graphite nanosheets. The graphite nanosheets and resulted poly(arylene disulfide)/graphite nanocomposites were characterized with field emission scanning electron microscope (FE-SEM), transmission electron microscope (TEM), tensile tester and electrical conductivity measurements. Compared with pure polymer, the electrical conductivity of the poly(arylene disulfide)/graphite nanocomposites were dramatically increased and had a value of about 10⁻³ S/cm for the nanocomposite containing 5 wt% graphite. The nanocomposites exhibit as both high performance polymeric material and electrically conductive material. Therefore, they show potential applications as high temperature conducting materials.     

Fabrication of polyethylene/graphite nanocomposite from modified expanded graphite

A novel process was employed to fabricate a polymer/expanded graphite nanocomposite by modifying the conducting filler expanded graphite (EG) with unsaturated polyester resin (UPR). The modified expanded graphite (MEG) was prepared from EG in which the graphite nanosheets, already present in EG, were wrapped and isolated by the UPR during processing. The as‐prepared MEG was reduced to powder form to improve its dispersion in the matrix. MEG powders were embedded into a high‐density polyethylene (HDPE) matrix via melt‐extrusion in a single‐screw extruder to prepare the conducting composite. The as‐prepared HDPE/EG conducting composite exhibited a low percolation threshold of ～5.7 wt% due to the high aspect ratio of graphite nanosheets. Mechanical properties such as the tensile and impact strength were also studied. Scanning electron microscopy was used to characterize the microstructure of EG, MEG powder and the resulting nanocomposites. Copyright © 2006 Society of Chemical Industry     

Expanded Graphite–Epoxy–Flexible Silica Composite Bipolar Plates for PEM Fuel Cells

Silica impregnated expanded graphite–epoxy composites are developed as bipolar plates for proton exchange membrane (PEM) fuel cells. These composite plates were prepared by solution impregnation, followed by compression molding and curing. Mechanical properties, electrical conductivities, corrosion resistance, and contact angles were determined as a function of impregnated content. The plates show high flexural strength with 5% methyltrimethoxysilane (MTMS) addition (20 MPa) and in‐plane conductivity of 131 S cm⁻¹ that meet the DOE target (>100 S cm⁻¹). Corrosion current values as low as 1.09 μA cm⁻² were obtained. The contact angle was found to be 80°. Power density of 1 W cm⁻² was achieved with custom made expanded graphite–polymer composite plates. High efficiency values were obtained at low current regions.     

Graphite-Filled Polyethylene/Epoxy Blend for High-Conductivity Applications: The Immiscibility Edge

ABSTRACT

Polyethylene (PE)/epoxy blends filled with graphite were prepared and studied in this work. The in-plane and through-plane conductivities of the composites increased from 11.68 Scm^?1 to 73.11 Scm^?1 and 0.20 Scm^?1 to 4.12 Scm^?1, respectively, as graphite content increased from 30 to 80 wt%. Phase bonding effect of the compatibilizer and reinforcing effect of the filler enhanced the flexural modulus and strength of the composites up to 70 wt% filler content. The electrical conductivities attained by these composites being significantly higher than comparable composite formulations in literature show the edge of immiscible PE/epoxy blend for achieving high-conductivity polymer composites.     

Preparation of conducting composites of polypyrrole using supercritical carbon dioxide

Supercritical carbon dioxide, saturated with pyrrole, was brought into contact with oxidant‐impregnated films of poly(chlorotrifluoroethylene) (PCTFE), crosslinked poly(dimethylsiloxane) (PDMS), poly(methyl methacrylate) (PMMA), and porous crosslinked polystyrene (PS) in order to form conducting composites via the in situ polymerization of pyrrole. The two nonporous hosts—PCTFE and crosslinked PDMS—did not form conducting composites with polypyrrole (PPy). On the other hand, the electrical conductivity of the PPy composites with carbon dioxide‐swollen PMMA and porous PS ranged from 1.0 × 10^?4 S/cm to 3.0 × 10^?5 S/cm. In these two cases, the level of pyrrole polymerized on the surface or in the pores of the host polymer was sufficient to attain the interconnected conducting polymer networks necessary for electrical conductivity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1113–1116, 2003     

High Thermal Conductivity Nanocomposites Based on Conductive Polyaniline Nanowire Arrays on Boron Nitride

With the development of soft electronics, conductive composites are garnering an increasing amount of attention. The electrical conductivity, thermal conductivity, and electrical stability of conductive composites are all very important. In particular, the thermal conductivity of conductive composites is critical to the stability of their conductive properties. However, little is reported on thermal management in conductive systems. Herein, sufficiently hydroxylated boron nitride nanosheets (BN‐OH)@polyaniline (PANI) composite nanosheets with a high thermal conductivity and outstanding conductance stability are reported. PANI nanowire arrays are aligned vertically on BN‐OH. This well‐ordered nanostructure provides the means to form a good conductive and thermally conductive path. Notably, the composite through‐plane thermal conductivity is 2.1 W m^?1 K^?1(≈1000% that of pure PANI) and that the resistivity of the composite is 1.38 Ω cm. Importantly, the resistivity of the composite remains unchanged after 1 h of work. The results show that this composite has prospective applications for use in soft electronics.     

Preparation of polyaniline/vermiculite clay nanocomposites by in situ chemical oxidative grafting polymerization

BACKGROUND: Recently, conducting polymers have attracted much attention, since they have interesting physical properties and many potential applications, such as in conductive coating charge storage. Hence the synthesis of conducting polymer nanocomposites is also an area of increasing research activity. RESULTS: Vermiculites (VMTs) were successfully delaminated using an acid treatment. Polyaniline (PANI)/VMT nanocomposites were prepared by in situ chemical oxidative grafting polymerization. CONCLUSION: The chemical grafting of PANI/VMTs was confirmed by Fourier transform infrared and UV‐visible spectroscopy. The percentage of grafted PANI was 142.7 wt% as a mass ratio of the grafting PANI and charged nano‐VMTs, investigated using thermogravimetric analysis. In addition, characteristic agglomerate morphology of PANI was observed in the composites using scanning electron microscopy. Thermal analyses indicated that the introduction of VMT nanosheets had a beneficial effect on the thermal stability of PANI. The electrical conductivity of the nanocomposites was 3.9 × 10^?3 S cm^?1, a value typical for semiconductors. Copyright © 2009 Society of Chemical Industry     

Single‐walled carbon nanotube/poly(methyl methacrylate) composites for electromagnetic interference shielding

Single‐walled carbon nanotube (SWNT)/poly(methyl methacrylate) (PMMA) composites were prepared using coagulation method. The electrical conductivity and the electromagnetic interference (EMI) shielding of SWNT/PMMA composites over the X‐band (8–12 GHz) and the microwave (200–2000 MHz) frequency range have been investigated. The electrical conductivity of composites increases with SWNT loading by 13 orders of magnitude, from 10^?15 to 10^?2 Ω^?1 cm^?1 with a percolation threshold of about 3 wt% SWNTs. The effect of the sample thickness on the shielding effectiveness has been studied, and correlated to the electrical conductivity of composites. The data suggest that SWNT/PMMA composites containing higher SWNT loading (above 10 wt%) be useful for EMI shielding and those with lower SWNT loading be useful for electrostatic charge dissipation. The dominant shielding mechanism of SWNT/PMMA composites was also discussed. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

High-yield water-phase exfoliated few-defect graphene for high performance polymer nanocomposites

Application of graphene requires a high-yield, low-cost, scalable production method, but it remains highly challenging. We here report a water-phase technique to produce few-defect graphene nanosheets (FGS) with a high exfoliation yield (92%), based on the chemically expanded graphite with ultrahigh specific surface areas, and demonstrate the application in graphene-polymer nanocomposites. The exfoliated FGS has low degree of oxidation and preserves good mechanical and electrical properties, revealing promising potential for improving comprehensive properties of polymer composites. When 0.5 wt% FGS was incorporated to poly(methyl methacrylate) (PMMA), the 5% weight loss temperature and storage modulus increase by 87°C and 21%, respectively, relative to the neat polymer. With increasing the content of FGS to 4.6 wt%, the glass transition temperature of the composite increases by 25°C. In addition, the composites show a percolation threshold as low as 0.25 vol% and excellent electrical conductivity (50 S/m for 2.7 vol% FGS-PMMA composite).     

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     

Effects of filler geometry on internal structure and physical properties of polycarbonate composites prepared with various carbon fillers

BACKGROUND: The effects of filler geometry are important for understanding the internal structure and physical properties of polymer composites. To investigate the effects of filler geometry on electrical conductivity as well as morphological and rheological properties, three types of polycarbonate (PC) composites were prepared by melt compounding with a twin‐screw extruder. RESULTS: The electrical conductivity of PC/carbon black (CB) and PC/graphite (carbon) nanofibre (CNF) composites did not show a percolation threshold through the entire filler loading ranges. However, PC‐blend‐carbon nanotube (CNT) composites showed a percolation electrical threshold for a filler loading of 1.0 to 3.0 wt% and their maximum electrical conductivity approached 10^?3 S m^?1. PC‐blend‐CB and PC‐blend‐CNF composites showed Newtonian behaviour like pure PC matrix, but PC‐blend‐CNT composites showed yield stress as well as increased storage modulus and strong shear thinning behaviour at low angular frequency and shear rate due to strong interactions generated between CNT–CNT particles as well as PC molecules and CNT particles on the nanometre scale. CONCLUSIONS: The electrical conductivity of the PC composites with different carbon constituents was well explained by the continuous network structure formed between filler particles. The network structure was confirmed by the good dispersion of fillers as well as by the yield stress and solid‐like behaviour observed in steady and dynamic shear flows. Copyright © 2009 Society of Chemical Industry     

Preparation of highly conductive reduced graphite oxide/poly(styrene-co-butyl acrylate) composites via miniemulsion polymerization

Polymer/reduced graphite oxide (rGO) composite nanoparticles with a high electrical conductivity were synthesized using the miniemulsion polymerization technique. The rGO was modified with a reactive surfactant, 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), to facilitate monomer intercalation into the rGO nanogalleries. The AMPS-modified rGO was emulsified in the presence of styrene (St) and butyl acrylate (BA) monomers, and the stable miniemulsion was polymerized to form poly(St-co-BA)/rGO composite latex nanoparticles. The transition in the composite nanoparticles from an electrical insulator to an electrical conductor occurred at an rGO content of 10 wt% (relative to the monolayer content), yielding an electrical conductivity of 0.49 S/cm. The electrical conductivity of the composite nanoparticles reached 2.22 S/cm at 20 wt% rGO, yielding a much better conductivity than other polymer composites prepared using a GO filler. Importantly, the miniemulsion polymerization method for fabricating poly(St-co-BA)/rGO composite nanoparticles is easy, green, low-cost, and scalable, providing a universal route to the rational design and engineering of highly conductive polymer composites.     

新型导电填料——纳米石墨微片

经过超声波粉碎,可将膨胀石墨制备成一种新型导电填料——纳米石墨微片。它的厚度为纳米,直径在微米范围,具有很大的形状比。将纳米石墨微片分散于聚乙烯、聚苯乙烯、聚甲基丙烯酸甲酯、尼龙等聚合物基体中制备导电复合材料,其渗滤阀值远低于一般的导电填料复合体系。纳米石墨微片有望在导电材料、电磁屏蔽材料、电加热材料等领域得到应用。