Evaluation and modeling of the mechanical properties of graphite nanoplatelets based rubber nanocomposites for pressure sensing applications

Acrylonitrile butadiene rubber (NBR) compounds filled with different concentrations of graphite nanoplatelets were experimentally investigated. The stress–strain curves of the nanocomposites were studied, which suggest good filler–matrix adhesion. The large reinforcement effect of the filler followed the Guth model for non‐spherical particles. The effect of graphite nanoplatelets on the cyclic fatigue and hysteresis was also examined. The loading and unloading stress–strain relationships for any cycle were described by applying Ogden's model for rubber nanocomposites. With this model for incompressible materials, expressions may be developed to predict the stress–strain relationship for any given cycle. The dissipated energy increased with graphite nanoplatelets concentrations and decrease with number of cycles. The rate of damage accumulation becomes marginal after first ten cycles. The rate of damage increases as the amount of graphite nanoplatelets increase into the rubber matrix. Copyright © 2011 John Wiley & Sons, Ltd.     

Direct diazotization of graphite nanoplatelets with melamine and their favorable application in epoxy resins

The ease of undesirable agglomeration and a low efficiency are two problems that restrict the application of graphite nanoplatelets (GNPs) in epoxy resins (EP). Herein, a new strategy with melamine (MEL) as the precursor to functionalize GNPs chemically, which form a bonding layer that is compatible with epoxy matrix, is reported. The MEL fragments with secondary amine groups were grafted uniformly on the GNPs surface by covalent junctions to exploit the diazonium chemistry. This behavior led to a better dispersion and a stronger interaction with the epoxy matrix and resulted in an enhanced glass transition temperature and bending strength, compared with the pure EP. When only 1 wt% functionalized GNPs (f‐GNPs) was used, the Tg of the modified EP raised of about 15°C compared with pure EP, and the bending strength increased by approximately 39%. The dielectric constant of the EP with f‐GNPs was impacted slightly, and the dielectric loss decreased. At 10⁵ Hz, the dielectric loss of the EP with 1 wt% f‐GNPs decreased by approximately 11% compared with pure EP. Therefore, diazotization modification of the GNPs is a useful approach to improve the compatibility in nanoparticle networks.     

Unique rheological behavior of rubber based nanocomposites

Montmorillonite clay (N) based nanocomposites were prepared using three different grades of acrylonitrile butadiene rubber (NBR) (19%, 34%, and 50% acrylonitrile contents), styrene butadiene rubber (SBR), and polybutadiene rubber (BR). Rheological study was carried out on these nanocomposites at three different temperatures (110 °C, 120 °C, and 130 °C) over a range of shear rates for comparison. The results showed that the shear viscosity decreased with increasing shear rate and incorporation of the unmodified (N) and the modified (OC) fillers up to a certain loading, when the results were compared with the gum rubber. This effect became more prominent with increasing polarity of the rubber. The die swell, on the other hand, decreased with loading of N and OC. With increasing filler volume fraction, the die swell further decreased. Decrease of viscosity with concomitant decrease of die swell is unique in such systems. Consecutive runs of the same sample over different shear rates increased the viscosity. The results were explained with the help of X‐Ray Diffraction (XRD) data and Transmission Electron Microscopy (TEM).© 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1854–1864, 2005     

Facile synthesis of mesophase pitch/exfoliated graphite nanoplatelets nanocomposite and its application as anode materials for lithium-ion batteries

Mesophase pitch (MP)/exfoliated graphite nanoplatelets (GNPs) nanocomposite has been prepared by an efficient method with an initiation of graphite intercalation compounds (GIC). X-ray diffraction, optical microscopy, high-resolution transmission electron microscopy and scanning electron microscopy analysis techniques are used to characterize the samples. It is observed that GIC has exfoliated completely into GNPs during the formation of MP/GNPs nanocomposite and the GNPs are distributed uniformly in MP matrix, which represent a conductive path for a movement of electrons throughout the composites. Electrochemical tests demonstrate that the carbonized MP/GNPs nanocomposite displays higher capacity and better cycle performance in comparison with the pure carbonized MP. It is concluded that such a large improvement of electrochemical performance within the nanocomposite may in general be related to the enhanced electronic conductivity, which is achieved by good dispersion of GNPs within MP matrix and formation of a 3D network of GNPs.     

Nonlinear conduction in nylon-6/foliated graphite nanocomposites above the percolation threshold

The nonlinear conduction behavior of composite materials of foliated graphite nanosheets and nylon-6 subjected to a variable direct-current electric field has been studied. Corresponding to the onset of the nonlinearity, there is a crossover current density/electric field (or current–voltage) couple. The current density or current decreases as the foliated graphite concentration decreases. Through discussions of the nonlinearities within the frameworks of the two theoretical models, the nonlinear random resistor network and the dynamic random resistor network, it is shown that neither of these models can explain fully the results obtained for this system. On the basis of the microscopic structures and conduction processes of the nanocomposites, it is found that a combination of the models can generally account for the nonlinear characteristics. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 155–167, 2004     

Polyethylene/graphite nanocomposites obtained by in situ polymerization

The synthesis of polyethylene/graphite nanocomposites by in situ polymerization was achieved using the catalytic system Cp₂ZrCl₂ (bis(cyclopentadienyl)zirconium(IV) dichloride)/methylaluminoxane (MAO). Graphite with nano dimensions, previously treated with MAO, was added into the reactor as filler at percentages of 1, 2, and 5% (w/w). XRD analysis showed that the chemical and thermal treatments employed preserve the structure of the graphite sheets. The formation of graphite nanosheets and nanocomposites was confirmed by TEM and AFM. TEM micrographics showed that the polyethylene grew between the graphene nanosheets, giving intercalated and exfoliated graphite nanocomposites. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 692–698, 2010     

The nanomechanical behavior of a graphite nanoplatelet/polycarbonate nanocomposite

Quasi-static nanoindentation has been used to characterize the mechanical properties of polycarbonate reinforced with graphite nanoplatelets (GNPs). Poor dispersion or low quality interfacial interactions of GNPs in a polymer matrix can significantly decrease the relative improvement in the material's mechanical strength and stiffness. In this study, the surfaces of GNPs were modified to achieve better dispersion and interfacial interaction between fillers and matrix. The GNP/PC nanocomposite has a heterogeneous microstructure, and the original mechanical properties between filler and matrix have large differences. Using a spatially sensitive probe method leads to measured values of modulus and hardness that correlate with the indentation sampled volume. A grid indentation procedure was performed with variable sampling volumes to provide a statistical measurement of modulus and hardness for the nanocomposite materials. The surface treatment leads to a significant increase in both stiffness and hardness for GNP reinforced composites.     

Fabrication of exfoliated graphite nanoplatelets-reinforced aluminum composites and evaluating their mechanical properties and corrosion behavior

Aluminum composites with different amounts of exfoliated graphite nanoplatelets particles were fabricated by powder metallurgy method. The mixture powders were consolidated at 520 MPa for 5 min and followed by pressureless sintering at 600 °C for 6 h. The mechanical properties of composites were evaluated by compression and hardness tests. The corrosion behavior in 3.5% NaCl solution was investigated using potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) measurements. The mechanical testing results showed that the maximum strength and Vickers hardness increase as a function of exfoliated graphite nanoplatelets content. Corrosion data indicated that the presence of exfoliated graphite nanoplatelets and the increase of its concentration raise the corrosion rate and reduce the polarization resistance of Al. SEM/EDX investigations revealed that the presence of exfoliated graphite nanoplatelets activates the corrosion of Al due to the occurrence of galvanic corrosion. SEM/EDX investigations confirmed the electrochemical measurements showing that the increase of exfoliated graphite nanoplatelets content increases the corrosion of Al.     

Thermal conductivity of exfoliated graphite nanocomposites

Since the late 1990’s, research has been reported where intercalated, expanded, and/or exfoliated graphite nanoflakes could also be used as reinforcements in polymer systems. The key point to utilizing graphite as a platelet nanoreinforcement is in the ability to exfoliate graphite using Graphite Intercalated Compounds (GICs). Natural graphite is still abundant and its cost is quite low compared to the other nano–size carbon materials, the cost of producing graphite nanoplatelets is expected to be ~$5/lb. This is significantly less expensive than single wall nanotubes (SWNT) (>$45000/lb) or vapor grown carbon fiber (VGCF) ($40–50/lb), yet the mechanical, electrical, and thermal properties of crystalline graphite flakes are comparable to those of SWNT and VGCF. The use of exfoliated graphite flakes (xGnP) opens up many new applications where electromagnetic shielding, high thermal conductivity, gas barrier resistance or low flammability are required. A special thermal treatment was developed to exfoliate graphite flakes for the production of nylon and high density polypropylene nanocomposites. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to assess the degree of exfoliation of the graphite platelets and the morphology of the nanocomposites. The thermal conductivity of these composites was investigated by three different methods, namely, by DSC, modified hot wire, and halogen flash lamp methods. The addition of small amounts of exfoliated graphite flakes showed a marked improvement in thermal and electrical conductivity of the composites.     

Evaluation of air permeability characteristics on the hybridization of carbon black with graphene nanoplatelets in bromobutyl rubber/epoxidized natural rubber composites for inner‐liner applications

Nanotechnology has been explored recently as a means of enhancing the properties of conventional elastomers for engineering applications. In the current study, the effect of nanofillers on air impermeability properties of Brominated isobutylene‐isoprene rubber (BIIR)/Epoxidized natural rubber (ENR) blend has analyzed for automotive applications. The ENR chosen is ENR 25 and ENR 50 (25 and 50% epoxidation) and prepared the blends in a ratio of 75:25 (BIIR:ENR), and from both blend based composites, a part of carbon black replaced with graphene nanoplatelets (GNP). The physical and thermal properties were compared for both binary blend nanocomposites to study the level of exfoliation and reinforcement behavior of GNP. Morphology studies were employed to reveal the level of interaction between GNP and carbon black in both blends. The influence of epoxidation in the formation of nanostructures in both blends have been evaluated, and the effect of nanostructures on air permeability properties was studied. The air impermeability of BIIR‐ENR 50 nanocomposites were improved with increasing platelet concentration, a 30% improvement in air permeability is obtained for BIIR‐ENR 50 composites over BIIR ‐ENR 25.     

Creep resistance of HDPE/PA66 system: Effect of PA66 phase geometry and graphite nanoplatelets addition

Microfibrillar composites (MFC) with in-situ generated short polymeric fibres feature, unlike composites containing inorganic rigid fibres/particles, lower creep resistance in comparison with analogous blends containing spheres. Further attribute is unprecedented decrease in creep resistance of the blend by graphite nanoplatelets (GNP). Explanation of this behaviour of the HDPE/PA66/GNP system consists in characterization of structure and finite element analysis (FEA) „mapping“ the effect of reinforcement and interface parameters on creep behaviour. Lowering of reinforcement modulus and its viscoelasticity may lead to worse creep resistance of fibrous composites. FEA also indicates marked negative effect of the soft interface, i.e. GNP-reduced crystallinity of HDPE near the interface, on creep resistance of the spheres-reinforced system in contrast to MFC. Structural changes are indicated by polarized light microscopy, SEM and TEM. The results reveal so far unknown complexity of the performance of polymer/polymer composites which may cause unprecedented antagonistic effects.     

Facile synthesis of highly conductive polyaniline/graphite nanocomposites

A facile process for the synthesis of exfoliated graphite and polyaniline/graphite (PANI/graphite) nanocomposite was developed. Graphite nanosheets were prepared via the microwave irradiation and sonication from synthesized expandable graphite. The nanocomposites were fabricated via in situ polymerization of aniline monomer in the presence of graphite nanosheets. The nanoscale dispersion of graphite sheets was evidenced by the SEM and TEM examinations. According to the electrical conductivity test, the conductivity of the final PANI/graphite nanocomposites were dramatically increased compared with pristine PANI. From the thermogravimetric analysis, the introduction of graphite exhibits a beneficial effect on the thermal stability of PANI.     

Reverse atom transfer radical random copolymerization of styrene and methyl methacrylate in the presence of diatomite nanoplatelets

Diatomite nanoplatelets were used for in situ random copolymerization of styrene and methyl methacrylate by reverse atom transfer radical polymerization to synthesize different well‐defined nanocomposites. Inherent features of the pristine diatomite nanoplatelets were evaluated by Fourier transform infrared spectroscopy, nitrogen adsorption/desorption isotherm, scanning electron microscope, and transmission electron microscope. Gas and size exclusion chromatography was also used to determine conversion and molecular weight determinations, respectively. Considerable increment in conversion (from 81% to 97%) was achieved by adding 3 wt% diatomite nanoplatelets in the copolymer matrix. Moreover, molecular weight of random copolymer chains was increased from 12 890 to 13 960 g·mol⁻¹ by addition of 3 wt% diatomite nanoplatelets; however, polydispersity index (PDI) values increases from 1.36 to 1.59. Proton nuclear magnetic resonance spectroscopy was used to evaluate copolymers composition. Thermal gravimetric analysis results indicate that thermal stability of the nanocomposites is improved by adding diatomite nanoplatelets. Differential scanning calorimetry shows an increase in glass transition temperature from 66°C to 71°C by adding 3 wt% of diatomite nanoplatelets.     

Synthesis and characterization of polyaniline/graphite conducting nanocomposites

A new method for the synthesis of exfoliated graphite and polyaniline (PANI)/graphite nanocomposites was developed. Exfoliated graphite nanosheets were prepared through the microwave irradiation and sonication of synthesized expandable graphite. The nanocomposites were fabricated via the in situ polymerization of the monomer at the presence of graphite nanosheets. The as-synthesized graphite nanosheets and PANI/graphite nanocomposite materials were characterized with Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis (TGA). The conductivity of the PANI/graphite nanocomposites was dramatically increased over that of pure PANI. TGA indicated that the incorporation of graphite greatly improved the thermal stability of PANI. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1972–1978, 2004     

Flame retardant effects of organic inorganic hybrid intumescent flame retardant based on expandable graphite in silicone rubber composites

In this work, an organic inorganic hybrid intumescent flame retardant (functionalized expandable graphite, FEG) was synthesized and characterized by Fourier transform infrared spectrometry (FTIR). The flame retardant effects of FEG in silicone rubber (SR) composites were investigated by cone calorimeter test (CCT), and the thermal stability of SR composites was studied using TGA. The CCT results showed that FEG can effectively reduce the flammable properties including peak heat release rate (PHRR), total heat release (THR), smoke production rate (SPR), total smoke release (TSR), and smoke factor (SF). An improvement of thermal stability of SR/FEG was also observed. Compared with EG, FEG can further reduce THR, SPR, and TSR of SR/FEG composites in combustion process. Moreover, there is a more obvious intumescent char layer formed from the sample with FEG than the sample with EG at the same loading in SR composites. Copyright © 2014 John Wiley & Sons, Ltd.     

Formation of nanocomposites of styrene and its copolymers using graphite as the nanomaterial

Graphite‐polymer nanocomposites were prepared by melt blending of various graphites (virgin graphite, expandable graphites, and expanded graphite) with polystyrene and its copolymers (acrylonitrile‐butadiene‐styrene (ABS) and high‐impact polystyrene (HIPS)). Nanocomposites were characterized by X‐ray diffraction, cone calorimetry, thermogravimetric analysis and evaluation of mechanical properties. Nanocomposite formation occurs at higher loadings (3–5%) of expandable graphites but not for virgin or expanded graphite. Copyright © 2005 John Wiley & Sons, Ltd.     

High strain rate behavior of graphene-epoxy nanocomposites

This work consists of the synthesis of high purity graphene nanoflakes (GNF), the manufacturing of GNF-epoxy nanocomposites and the mechanical characterization of the nanocomposite at high and quasi static strain rates, (2750/s - 1.E−5/s). GNF were synthesized by using the electric arc discharge technique. Thermogravimetry/Differential Thermal Analysis (TG/DTA) of synthesized graphene reveals high purity and high crystallinity. Raman spectra and the broad Brunauer-Emmet-Teller (BET) specific surface area indicate that the synthesized graphene has several layers. Following the solution mixing manufacturing process of GNF-epoxy nanocomposites, the influences of strain rate on the mechanical behaviors are investigated under quasi static and dynamic loadings. High strain rate uniaxial compression tests (1270–2750/s) using Split Hopkinson Pressure Bar (SHPB) and quasi static compression tests (1.E−3 and 1.E−5/s) of GNF-epoxy with two graphene contents (0.1 and 0.5 wt %) are performed at room temperature. The maximum elasticity modulus achieved by the GNF-epoxy with 0.5 wt% at the strain rate of 2350/s corresponds to a 68% increase compared to the neat epoxy. The yield strength of the material is doubled under dynamic loading conditions compared to the quasi static loading.     

Investigating the ageing behavior of polysiloxane nanocomposites by degradative thermal analysis

The ageing behavior of novel polysiloxane nanocomposite elastomers is reported. A series of model polysiloxane nanocomposites has been prepared incorporating the montmorillonite nanoclay Cloisite 6A. The nanoclay dispersion has been characterized with X-ray Diffraction (XRD) and Transmission Electron Microscopy (TEM). TGA has been utilized to study the effects of ageing on the non-oxidative stability of the nanocomposite systems. The complex evolution of volatiles that occurs during ageing has been studied using Sub-Ambient Thermal Volatilization Analysis (SATVA). Results indicate that significant chemical changes take place within the nanocomposites upon ageing; acid catalyzed hydrolysis, chain backbiting and recombination reactions are re-structuring the polymer-filler network into a more thermodynamically stable form.     

Improved polyvinylpyrrolidone (PVP)/graphite nanocomposites by solution compounding and spray drying

In order to evaluate the roles of graphite dispersion on the functional properties of the composites, PVP/graphite nanocomposites were prepared by blending the aqueous suspension of expanded graphite sheets and polyvinylpyrrolidone (PVP) aqueous solution by ultrasonic treatment, followed by spray drying and direct drying as a comparison individually. The effects of graphite loading and drying method on the dispersion of graphite and the resultant properties of the composites such as electrical and thermal conductivity, friction, and dynamic mechanical properties were studied. The results from transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X‐ray diffraction showed that the composites prepared by fast spray drying exhibited a higher degree of exfoliation and a better dispersion of graphite sheets in the PVP matrix than the corresponding composites prepared by direct drying, leading to a conclusion that fast spray drying can effectively prevent from re‐stacking of the exfoliated graphite sheets as illustrated. As a result, dynamic mechanical thermal analysis showed significant increases in the storage modulus and glass transition temperature for the composites prepared by spray drying. Besides, the spray drying as well greatly improved the electrical and thermal conductivity of the composites. It was also found that the electrical and thermal conductivity of the composites strongly depended on the graphite dispersion, while the friction coefficient unexpectedly does not. Increasing graphite loading level might enhance the probability of graphite sheets re‐stacking, resulting in poor graphite dispersion. Copyright © 2011 John Wiley & Sons, Ltd.     

Multilayer graphene/chlorine‐isobutene‐isoprene rubber nanocomposites: the effect of dispersion

Multilayer graphene (MLG) is composed of approximately 10 sheets of graphene. It is a promising nanofiller just starting to become commercially available. The dispersion of the nanofiller is essential to exploit the properties of the nanocomposites and is dependent on the preparation method. In this study, direct incorporation of 3 parts per hundred of rubber (phr) MLG into chlorine‐isobutene‐isoprene rubber (CIIR) on a two‐roll mill did not result in substantial enhancement of the material properties. In contrast, by pre‐mixing the MLG (3 phr) with CIIR using an ultrasonically assisted solution mixing procedure followed by two‐roll milling, the properties (rheological, curing, and mechanical) were improved substantially compared with the MLG/CIIR nanocomposites mixed only on the mill. The Young's moduli of the nanocomposites mixed in solution increased by 38%. The CIIR/MLG nanocomposites produced via solution showed superior durability against weathering exposure. Copyright © 2016 John Wiley & Sons, Ltd.