Highly filled graphite polybenzoxazine composites for an application as bipolar plates in fuel cells

Highly filled graphite polybenzoxazine composites as bipolar plate material for polymer electrolyte membrane fuel cell (PEMFC) are developed. At the maximum graphite content of 80 wt % (68 vol %), storage modulus was increased from 5.9 GPa of the neat polybenzoxazine matrix to 23 GPa in the composite. Glass transition temperatures (T_g) of the composites were ranging from 176°C to 195°C and the values substantially increased with increasing the graphite contents. Thermal conductivity as high as 10.2 W/mK and electrical conductivity of 245 S cm^?1 were obtained in the graphite filled polybenzoxazine at its maximum graphite loading. The obtained properties of the graphite filled polybenzoxazine composites exhibit most values exceed the United States department of energy requirements for PEMFC applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3909–3918, 2013     

Experimental investigation and numerical simulation of granite powder filled polymer composites for wind turbine blade: A comparative analysis

This paper describes the mechanical, thermo‐mechanical, and thermal behavior of unfilled E‐glass fiber (10–50 wt%) reinforced polymer (GFRP) composites and granite powder filled (8–24 wt%) GFRP composite in different weight percentages, respectively. The void fraction of unfilled glass epoxy composite is decreased from 7.71% to 3.17% with the increase in fiber loading from 10 to 50 wt%. However, void fraction for granite powder filled GFRP composites show reverse in trend. The granite powder addition in glass‐epoxy composites show significant improvement in hardness (37–47 Hv), impact strength (31.56–37.2 kJ/m²), and stress intensity factor (by 14.29% for crack length of 5 mm) of the composites. The thermo‐mechanical analyses also show strong correlation with the mechanical performance of the composites. The minimum difference of 0.17 GPa in storage and flexural moduli are observed for unfilled 20 wt% glass epoxy composite; whereas, maximum difference of 0.71 GPa is recorded for unfilled 50 wt% glass epoxy composite. Moreover, the numerical and experimentally measured thermal conductivity of unfilled and granite powder filled epoxy composites are within the lower and upper bound values. Hence, a successful attempt is presented for mechanical analysis of full scale model by finite element analysis. The results show that finite element analysis predicted reasonably actual stress value and tip deflection of wind turbine blade. POLYM. COMPOS., 38:1335–1352, 2017. © 2015 Society of Plastics Engineers     

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     

High electromagnetic interference shielding effectiveness achieved by multiple internal reflection and absorption in polybenzoxazine/graphene foams

Electromagnetic interference (EMI) is an increasingly severe issue in modern life and high-performance EMI shielding materials are in desperate need. To achieve high EMI shielding effectiveness (EMI SE), a series of polybenzoxazine/graphene composites foams are developed using a simple sol–gel method. When the graphene loading increases from 1 to 20 wt%, the density of the composites foams drops from 0.4143 g/cm³ to 0.1654 g/cm³. Meanwhile, an electrically conductive path is formed at around 7 wt% of graphene. Below the percolation threshold, the dielectric constant increases with graphene content and composite foam with 5 wt% graphene shows dielectric constant of 10.8 (1 MHz). At the highest graphene content of 20 wt%, the electric conductivity reaches 0.02 S/cm, 10 orders of magnitude higher than pure polybenzoxazine foam. Benefiting from the high electrical conductivity and lightweight porous structure, the composite foam PF/20G delivers an EMI SE of 85 dB and a specific SE of 513.9 dB·cm³/g. Importantly, the EMI shielding is dominated by absorption attenuation, with PF/20G shows absorption ratio higher than 98% in the range of 8.4–11.0 GHz, which is believed to be caused by multiple internal reflection and absorption inside the conductive foam.     

Electrical and thermal conductivity and tensile and flexural properties of carbon nanotube/polycarbonate resins

Adding conductive carbon fillers to insulating thermoplastic polymers increases the resulting composite's electrical conductivity. Carbon nanotubes (CNTs) are very effective at increasing composite electrical conductivity at low loading levels without compromising composite tensile and flexural properties. In this study, varying amounts (2–8 wt %) of CNTs were added to polycarbonate (PC) by melt compounding, and the resulting composites were tested for electrical conductivity (1/electrical resistivity), thermal conductivity, and tensile and flexural properties. The percolation threshold was less than 1.4 vol % CNT, likely because of CNTs high aspect ratio (1000). The addition of CNT to PC increased the composite electrical and thermal conductivity and tensile and flexural modulus. The 6 wt % (4.2 vol %) CNT in PC resin had a good combination of properties for electrical conductivity applications. The electrical resistivity and thermal conductivity were 18 Ω‐cm and 0.28 W/m · K, respectively. The tensile modulus, ultimate tensile strength (UTS), and strain at UTS were 2.7 GPa, 56 MPa, and 2.8%, respectively. The flexural modulus, ultimate flexural strength, and strain at ultimate flexural strength were 3.6 GPa, 125 MPa, and 5.5%, respectively. Ductile tensile behavior is noted in pure PC and in samples containing up to 6 wt % CNT. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

High performance wood composites from highly filled polybenzoxazine

Highly filled systems prepared by compression molding of Hevea brasiliensis woodflour filled polybenzoxazine composites with high mechanical properties and reduced water uptake has been developed. The effects of percent filler content and particle size of woodflour on the obtained composite's properties were examined. The low melt viscosity of BA‐a type polybenzoxazine allows substantial amount of woodflour to be easily incorporated into the composites. The results showed that mechanical properties from dynamic mechanical analysis and flexural test at filler content below the optimum filler packing show approximately linear relationship with filler loading. The outstanding compatibility between the woodflour and the polybenzoxazine matrix is evidently seen from the large improvement in the composite's T_g and char yield. Scanning electron micrographs of the composite also reveals substantially strong interface between the woodflour filler and the polybenzoxazine matrix. Water absorption of the composites is greatly reduced with increasing the amount of polybenzoxazine due to the inherent low water absorption of the matrix. The polybenzoxazine is; therefore, a highly attractive candidate as high performance lignocellulosic binder or adhesive and other related applications. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1240–1253, 2006     

Comparative study of aluminum diethylphosphinate and aluminum methylethylphosphinate‐filled epoxy flame‐retardant composites

Epoxy resin (EP) is one of the main polymers in electrical and electronic applications. In this work, flame‐retardant epoxy resin composites based on aluminum diethylphosphinate (Al(DEP)) and aluminum methylethylphosphinate (Al(MEP) were prepared using aromatic amine 4, 4‐diaminodiphenylmethane as curing agent. The flammability, thermal degradation, flexural properties, and morphologies of composites were investigated with respect to the filler loading and filler type. Results showed that both Al(MEP) and Al(DEP) were efficient flame retardants for EP and a low dosage (15 wt%) is enough to achieve the important criterion UL 94 V‐0. Limiting oxygen index (LOI) of composites is increased with filler loading (phosphorus content) and reached of 32.2% for 15 wt% of Al(MEP) and 29.8 for 15 wt% of Al(DEP). The char formation and flexural modulus of composites are also improved by adding the two fillers. However, the flexural strength of all the composites decreased with increasing filler loading. In comparison with Al(DEP)/EP, Al(MEP)/EP provides a higher flammability, better thermal stability and char formation but inferior flexural properties. Scanning electron microscopy revealed that the dispersion of Al(DEP) filler in the EP matrix is more uniform and exhibits better compatibility with EP matrix, which in turn generates better flexural strength and higher modulus when compared with Al(MEP)‐filled EP composites. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Dielectric,electrical, and rheological characterization of graphene‐filled polystyrene nanocomposites

A series of nanographene filled polystyrene (GPS) nanocomposites was prepared by in situ polymerization of styrene in the laboratory. The concentration of graphene was changed in the step of 0.25 wt% and a total of eight composites (including control) were prepared to obtain a threshold concentration of graphene. These composites, prepared by in situ polymerization followed by compression moulding, were characterized for their structural (using XRD), morphological (SEM), thermal (DSC, TGA, DTGA), dielectric behavior (ɛ', ɛ''') and DC conductivity. It was observed that the thermal stability as well as electrical and rheological properties of graphene‐polystyrene nanocomposites significantly improved due to the homogeneous dispersion, intercalation and exfoliation of the graphene layers in the Polystyrene matrix. It was also observed that at room temperature dielectric constant (ε′) decreased with increasing concentration of graphene and reached a minimum at a certain filler concentration of 0.25 wt% (PSG025) when frequency is kept constant. Rheological study showed an improvement in the storage modulus (G′) with incorporation of graphene as nanofiller. Loss modulus (G′) and complex viscosity (η*) also increased with increasing graphene weight percentage. Relaxation time also increased at high graphene loading because of the pseudo‐solid like behavior of polymer melt. POLYM. COMPOS., 34:2082–2093, 2013. © 2013 Society of Plastics Engineers     

The effect of graphene flake size on the properties of graphene-based polymer composite films

In this work, the role of graphene flake size on the properties of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) composites was studied. Graphene flakes were added to PVDF-HFP using a solution mixing and molding process. By increasing graphene particle size and its concentration in the composites, higher electrical conductivity, in-plane thermal conductivity, and elastic modulus were achieved. Maximum tensile strength was obtained for the composites with average graphene flake size of 2, 5, and 7 μm at graphene concentrations of 10 wt%, 5 wt%, and 20 wt%, respectively. Thick flexible composite films (0.2–0.4 mm) with ultra-high in-plane electrical conductivity (~4500 S/m), in-plane thermal conductivity (~26 W/m/K), and tensile strength (~50 MPa) were obtained for the samples containing the graphene flakes with a larger average particle size of 7 μm. To our knowledge, the first two values are larger than any other values reported in the literature for PVDF-based composites.     

Graphene nanoplate and multiwall carbon nanotube–embedded polycarbonate hybrid composites: High electromagnetic interference shielding with low percolation threshold

This study has reported the preparation of polycarbonate (PC)/graphene nanoplate (GNP)/multiwall carbon nanotube (MWCNT) hybrid composite by simple melt mixing method of PC with GNP and MWCNT at 330°C above the processing temperature of the PC (processing temperature is 280°C) followed by compression molding. Through optimizing the ratio of (GNP/MWCNT) in the composites, high electromagnetic interference shielding effectiveness (EMI SE) value (∼21.6 dB) was achieved at low (4 wt%) loading of (GNP/MWCNT) and electrical conductivity of ≈6.84 × 10⁻⁵ S.cm⁻¹ was achieved at 0.3 wt% (GNP/MWCNT) loading with low percolation threshold (≈0.072 wt%). The high temperature melt mixing of PC with nanofillers lowers the melt viscosity of the PC that has helped for better dispersion of the GNPs and MWCNTs in the PC matrix and plays a key factor for achieving high EMI shielding value and high electrical conductivity with low percolation threshold than ever reported in PC/MWCNT or PC/graphene composites. With this method, the formation of continuous conducting interconnected GNP‐CNT‐GNP or CNT‐GNP‐CNT network structure in the matrix polymer and strong π–π interaction between the electron rich phenyl rings and oxygen atom of PC chain, GNP, and MWCNT could be possible throughout the composites. POLYM. COMPOS., 37:2058–2069, 2016. © 2015 Society of Plastics Engineers     

Development of highly conductive graphite-/graphene-filled polybenzoxazine composites for bipolar plates in fuel cells

Superior conductive fillers reinforced polymer composites are ideal alternatives to graphitic and metallic materials in proton exchange membrane fuel cells (PEMFCs) for high thermal and electrical conductive bipolar plates. Polymer composites are known to be adversely influenced from high contact resistance thus to minimize such resistance, highly graphite-/graphene-filled polybenzoxazine (PBA) composites are developed in this work. A very low melt viscosity of benzoxazine resin with graphite loading as high as 83 wt % is used for the samples. With an addition of graphene platelet, thermal and electrical conductivities of the specimens having 75.5 wt % of graphite in a combination of 7.5 wt % of graphene are significantly enhanced to 14.5 W mK⁻¹ and 323 S cm⁻¹, respectively. Properties of highly graphite-/graphene-filled PBA composites exhibit most values exceed those requirements by the U.S. Department of Energy for PEMFCs applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47183.     

Thermal and mechanical properties enhancement obtained in highly filled alumina‐polybenzoxazine composites

Highly filled polymer composites based on bisphenol‐A/aniline based polybenzoxazine (PBA‐a) and alumina particles were investigated. A very low A‐stage viscosity of benzoxazine monomer gives it excellent processability exhibiting maximum alumina content as high as 83% by weight (60% by volume) which is one of the highest maximum packing values with negligible void contents. The storage modulus (E′) at room temperature was increased from 5.93 GPa of the polybenzoxazine to 45.27 GPa of the composites. The significant high microhardness of the composites up to 1124 MPa was obtained and the behavior can be well predicted by the Halpin‐Tsai model. Moreover, the modulus dependence of the composites on the alumina contents is well fitted by Lewis‐Nielsen equation. Glass transition temperatures, degradation temperature, and solid residue of the composites also significantly increased with increasing the alumina contents. Finally, the scanning electron microscope of the composite fracture surface indicated a good distribution of the alumina particles in the PBA‐a matrix. The resulting PBA‐a/alumina composites are a highly attractive for an application that requires high modulus and hardness as well as high thermal stability. POLYM. COMPOS., 35:2269–2279, 2014. © 2014 Society of Plastics Engineers     

Graphene nanosheets‐filled epoxy composites prepared by a fast dispersion method

Graphene nanosheets‐filled epoxy composites (GNS/Epoxy) were prepared at different filler loading levels from 0.25 to 3.00 wt %. A fast dispersion method as short as 5 min is employed to disperse GNS in epoxy matrix, which was enough for the homogeneous dispersion of GNS with the help of high ultrasonic frequency of 100 kHz and power of 200 W and high heat treatment temperature of 70 °C. The maximum electrical conductivity and thermal conductivity of the composites achieved 0.058 S m^?1 and 0.57 W m^?1 K^?1, respectively, with a low electrical percolation threshold of 1.50 wt %. The electrical conductivities were further predicted by percolation theory and found to agree well with the experimental results, which indicated that the graphene nanosheets dispersed very well in the matrix even at very short processing time. The results showed that the microstructures, thermal, electrical, and mechanical properties of epoxy polymer were significantly improved by adding a low amount of graphene nanosheets. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45152.     

Synthesis of highly conductive PPy/graphene nanosheets/NiO composite using ultrasonic technique

Highly conductive polypyrrole/graphene nanosheets/NiO (PPy/GNS/NiO) composites are fabricated via ultrasound technique using p‐toluenesulfonic acid as a dopant and FeCl₃ as an oxidant. The effects of the GNS and NiO loading on the electrical conductivity are investigated. The maximum conductivity of PPy/GNS/NiO composites about 24.39 S/cm found with 3 wt% GNS and 48.7 wt% NiO at room temperature. The results showed that the high‐aspect‐ratio structure of GNS played an important role in forming a conducting network in PPy matrix. The microstructures of PPy/GNS/NiO are evidenced by the scanning electron microscope and transmission electron microscope examinations. The cyclic voltammetry curves can be seen that the PPy/GNS/NiO composites also have good electrochemical performance, and it can be used as a supercapacitor electrode material. POLYM. COMPOS., 34:997–1002, 2013. © 2013 Society of Plastics Engineers     

Preparation and thermal effects of polyarylene ether nitrile aluminium nitride composites

Particulate‐filled polyarylene ether nitrile (PEN) composites were prepared using methyltriethoxy‐silane‐treated aluminium nitride (AlN) as the filler for thermal modification. The effects of AlN fraction, particle size and surface treatment on the thermal performance of PEN were investigated. The thermal conductivities of the composites increased when the AlN filler concentration was increased, as well as with decrement of the filler size. The thermal conductivity value of the composites increased up to 0.779 W m^?1 K^?1 when the AlN weight loading was 60 wt%. The trend of the thermal conductivities of the composites can be more efficiently predicted by theoretical models than empirical models. The composites exhibited stable performances of thermal decomposition and thermal expansion when AlN filler faction in the composites increased. © 2013 Society of Chemical Industry     

Effects of polyol molecular weight on properties of benzoxazine–urethane polymer alloys

Recently, a new thermoset resin namely benzoxazine (BA) resin has been developed. The polymer possesses several outstanding properties, such as, ease of synthesis, low viscosity, near‐zero shrinkage, lack of by‐product upon curing, high thermal stability, and high mechanical property. Moreover, the benzoxazine resins can be alloyed with various types of resins because of the various function groups in their structure. In this work, urethane elastomer (PU) is used to enhance toughness of the polybenzoxazine. The effects of polyol molecular weights on the properties of BA: PU polymer alloys are investigated. The experiment reveals that the similar curing peaks of the matrices at various polyol molecular weights, with the same urethane mass fraction, in the resin mixtures are obtained. The glass transition temperature increases from 160°C of polybenzoxazine to 240–245°C in the 70:30 BA:PU system. In addition, the char yield increases when the higher molecular weight of polyol is added. The flexural modulus of polybenzoxazine decreases from 6.2 GPa to be in the range of 2.2–2.8 GPa when 30 wt% of PU is presented in the alloys. Furthermore, the synergism with ultimate flexural strength is observed in the 90:10 BA:PU alloy for all molecular weights of the polyol used. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Electrical conductivity of epoxy/silicone/carbon black composites: Effect of composite microstructure

The objective of this work is to study the effect of electrical conductivity and physical‐mechanical properties of carbon black (CB) filled polymer composites. This goal is achieved by synthesizing epoxy/silicon phase separated blend structure of composites filled with CB. The percolation threshold of epoxy/silicone/CB composites decreased and the total conductivity increased compared to the pure epoxy/CB composite. A threefold increase was obtained with tensile strength of epoxy/silicone/CB composite with 25 wt% of silicone and 5 wt% of CB in comparison with epoxy/CB systems. This composite has conductivity of about 10⁻⁶ S/cm, which is six orders of magnitude higher than for epoxy/CB composites at the same concentration of CB. POLYM. COMPOS., 35:2234–2240, 2014. © 2014 Society of Plastics Engineers     

Development of Ethylene‐Vinyl Acetate Composites Reinforced with Graphene Platelets

Composites of ethylene‐vinyl acetate (EVA) reinforced with graphene platelets are fabricated. Morphological, thermal, mechanical, electrical properties as well as moisture absorption of the composites are characterized. Transmission electron microscopy shows a good dispersion of graphene platelets in the matrix. The unidirectional orientation of graphene platelets parallel to the surface of the composites is revealed by field emission scanning electron microscopy and is validated using the Halpin–Tsai model. Tensile strength and elongation of the composites are respectively improved by 109 and 83%, after the addition of 3 wt% graphene platelets. The incorporation of 5 wt% graphene platelets enhances the char residue of the composites from 0.544% for pure EVA to 6.63% for the composites. The electrical conductivity of the composite with 3 wt% graphene platelets is two orders of magnitude higher than that of pure EVA with 10⁻¹³ S cm^–1 electrical conductivity.

     

Electromagnetic interference shielding effectiveness of MWCNT filled poly(ether sulfone) and poly(ether imide) nanocomposites

Multiwalled carbon nanotube (MWCNT) filled poly(ether sulfone) (PES) and poly(ether imide) (PEI) composites were prepared with different MWCNT weight fractions (0.5–5wt%) by a solution mixing technique. Their electrical conductivities, electromagnetic interference (EMI), shielding effectiveness (SE), return loss (RL), and absorption loss (AL) were investigated. Morphologies of the fracture surfaces of nanocomposites studied by scanning electron and transmission electron microscopy showed relatively good MWCNT dispersion and distribution. The electrical conductivity of compression molded samples measured at room temperature indicated that the electrical percolation network was achieved already at 0.5% loading. The measurements of shielding effectiveness (SE) carried out in the frequency range of 8 to 12 GHz (X‐band range) showed that SE increases with measurement frequency and with filler loading, whereby no significant differences could be observed between PES and PEI as matrices. The nanocomposites based on both matrices with 5 wt% loading of MWCNT exhibited shielding levels at 8 GHz between 42 and 45 dB in comparison with the pure polymers which showed value in the range of 1 to 2 dB. RL and AL showed significantly lower values for the composites as compared to unfilled polymers, but no systematic trends were observed on frequency. POLYM. ENG. SCI., 54:2560–2570, 2014. © 2013 Society of Plastics Engineers     

Carbon‐Polymer Composite Bipolar Plate for HT‐PEMFC

Graphene reinforced carbon‐polymer composite bipolar plate is developed using resole phenol formaldehyde resin, and conductive reinforcements (natural graphite, carbon black, and carbon fiber) using compression molding technique. Graphene is reinforced into the composite to alter various properties of the composite bipolar plate. The developed composite bipolar plate is characterized and the effect of temperature on mechanical and electrical properties is investigated with an overall aim to achieve benchmark given by US‐DOE and Plug Power Inc. The flexural strength and electrical conductivity of the composites was almost stable with the increase in temperature upto 175 °C. The composite bipolar plate maintained high in‐plane and through‐plane electrical conductivities, which is about 409.23 and 98 S cm^–1, respectively, at 175 °C. The flexural strength and shore hardness of the developed composite was around 56.42 MPa and 60, respectively, at 175 °C, and on further increase in the temperature the mechanical strengths deceases sharply. The electrical and mechanical properties of the composite bipolar plates are within the US‐DoE target. However, the various properties of the composite bipolar plate could not be sustained above 175 °C.