A study of graphene oxide‐reinforced rubber nanocomposite

Graphene oxide‐reinforced acrylonitrile–butadiene rubber nanocomposites were prepared via solution mixing. The morphology of the graphene oxide was studied, and its successful dispersion within the rubber matrix was confirmed by transmission electron microscopy, scanning electron microscopy, and X‐ray diffraction studies. The strong rubber‐to‐filler interaction was confirmed by swelling and mechanical reinforcing behaviors and thermal stability. Dielectric spectroscopy test indicated a marked improvement of about five times in the real part of permittivity. The electrical conductivity level was close to that of nonconductive materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40640.     

Effects of substitution for carbon black with graphene oxide or graphene on the morphology and performance of natural rubber/carbon black composites

In this study, nanosheets including graphene oxide (GO) and reduced graphene oxide (rGO), were incorporated into natural rubber (NR), to study the effects of substituting GO or rGO for carbon black (CB) on the structure and performance of NR/CB composites. The morphological observations revealed the dispersion of CB was improved by partially substituting nanosheets for CB. The improvements in static and dynamic mechanical properties were achieved at small substitution content of GO or rGO nanosheets. With substitution of rGO nanosheets, significant improvement in flex cracking resistance was achieved. NR/CB/rGO (NRG) composites has a much lower heat build‐up value compared with NR/CB/GO (NG) composites at a high load of nanosheets. However, both GO and rGO tended to aggregate at a high concentration, which led to the poor efficiency on enhancing the dynamic properties, or even deteriorate the performance of rubber composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41832.     

Carbon nanotubes/polyaniline nanocomposite coatings: Preparation,rheological behavior,and their application in paper surface treatment

Conventional cellulosic paper, rendered electro‐conductive, may hold considerable promise for diversified applications in such areas as electro‐magnetic interference shielding and energy storage. Here, an electro‐conductive cellulosic paper was prepared by surface application of multi‐walled carbon nanotubes (MWCNTs)/polyaniline (PANI) nanocomposites onto a conventional base paper. MWCNTs/PANI nanocomposites were prepared by in situ polymerization of aniline with different contents of MWCNTs and used as electro‐conductive filler for the fabrication of electro‐conductive surface‐coated paper. The achieved MWCNTs/PANI nanocomposites exhibited a core‐shell structure, as evidenced by TEM. Effects of feeding ratios of MWCNTs on the rheological behavior of nanocomposite coatings, as well as the mechanical properties and electrical conductivity of surface‐coated paper were studied. Results revealed that the rheological behavior of the nanocomposite coatings showed strong dependence on the MWCNTs content. Moreover, both the electro‐conductivity and mechanical properties of surface‐coated paper were improved as a function of surface application of MWCNTs/PANI nanocomposites, particularly, in presence of an optimum content of MWCNTs. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46329.     

Magnetically aligning multilayer graphene to enhance thermal conductivity of silicone rubber composites

The increasing demand for packaging materials calls for new technologies to achieve excellent thermal conductivity of polymer composites with low content of thermal conductive filler. This article prepared a kind of magnetically functionalized multilayer graphene (Fe₃O₄@MG) via electrostatic interactions, which efficiently enhanced the thermal conductivity of silicone rubber (SR) composites by the alignment of Fe₃O₄@MG in an external magnetic field. The morphology and structure of the Fe₃O₄@MG together with the thermal conductivity of corresponding Fe₃O₄@MG/SR composites were systematically investigated by SEM, TEM, XRD, elemental mapping, and thermal conductivity tester. The obtained results showed that Fe₃O₄@MG was induced to form chain-like bundles in silicone rubber matrix under the applied magnetic field, which enhanced the MG–MG interaction, and formed effective thermal pathways in the alignment direction. Furthermore, as coating mass ratio of Fe₃O₄@MG increased, the thermal conductivity of randomly oriented Fe₃O₄@MG/silicone rubber composites (R-Fe₃O₄@MG/SR) decreased gradually, whereas the through-plane thermal conductivity of vertically aligned Fe₃O₄@MG/silicone rubber composites (V-Fe₃O₄@MG/SR) increased even filled with same contents of thermal conductive filler. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47951.     

Synthesis and electrochemical properties of graphene oxide/nanosulfur/polypyrrole ternary nanocomposite hydrogel for supercapacitors

A method for synthesizing Graphene oxide (GO)/nano‐sulfur/polypyrrole (PPy) ternary nanocomposite hydrogel is depicted. The higher surface area of GO, PPy porous structure and their excellent conductivity are utilized, and the GO hydrogel can be made easily. The products are characterized by field‐emission scanning electron microscopy (FESEM), X‐ray diffraction (XRD), Fourier transform infrared (FTIR) spectra, and electrochemical workstation. The results demonstrated that GO/nano‐S/PPy ternary nanocomposite hydrogel is successfully synthesized. The electrochemical properties are investigated by cyclic voltammetry, galvanostatic charge/discharge measurements, and cycling life in a three‐electrode system in 1M Li₂SO₄ electrolyte solution. The GO/nano‐S/PPy ternary nanocomposite hydrogel exhibit a high specific capacitance of 892.5 F g^?1 at scan rates of 5 mV s^?1 and the capacitance retain about 81.2% (594.8 F g^?1) of initial capacitance (732.5 F g^?1) after 500 cycles at a current density of 1 A g^?1. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40814.     

Melt spinning of conductive textile fibers with hybridized graphite nanoplatelets and carbon black filler

In this study, two different carbon fillers: carbon black (CB) and graphite nanoplatelets (GNP) are studied as conductive fillers for the preparation of conductive polypropylene (PP) nanocomposites. In order to obtain a homogenous dispersion of GNP, GNP/PP composites were prepared by two different methods: solid state mixing (SSM) and traditional melt mixing (MM). The result shows that MM is more efficient in the dispersion of GNP particles compared to SSM method. PP nanocomposites containing only one conductive filler and two fillers were prepared at different filler concentrations. Based on the analysis of electrical and rheological properties of the prepared nanocomposites, it shows that a hybridized composite with equal amounts of GNP and CB has favorable processing properties. Conductive fibers with a core/sheath structure were produced on a bicomponent melt spinning line. The core materials of these fibers are the hybridized GNP/CB/PP nanocomposite and the sheath is pure polyamide. It was found that GNPs were separated during melt and cold drawing which results in the decrease of conductivity. However, the conductivity could partly be restored by the heat treatment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2579–2587, 2013     

Synergistic effects of carbon nanotubes and carbon black on the fracture and fatigue resistance of natural rubber composites

The quasi‐static fracture and dynamic fatigue behaviors of natural rubber composites reinforced with hybrid carbon nanotube bundles (CNTBs) and carbon black (CB) at similar hardness values were investigated on the basis of fracture mechanical methods. Mechanical measurement and J‐integral tests were carried out to characterize the quasi‐static fracture resistance. Dynamic fatigue tests were performed under cyclic constant strain conditions with single‐edged notched test pieces. The results indicate that synergistic effects between CNTBs and CB on the mechanical properties, fracture, and fatigue resistance were obtained. The composite reinforced with 3‐phr CNTBs displayed the strongest fatigue resistance. The synergistic mechanisms and dominating factors of quasi‐static and dynamic failure, such as the dispersion state of nanotubes, hybrid filler network structure, strain‐induced crystallization, tearing energy input, and viscoelastic hysteresis loss, were examined. The weakest fatigue resistance of the composite filled with 5‐phr CNTBs was ascribed to its strikingly high hysteresis, which resulted in marked heat generation under dynamic fatigue conditions. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42075.     

The effect of partial replacement of carbon black by carbon nanotubes on the properties of natural rubber/butadiene rubber compound

The basic objective of this study is to investigate the mechanical properties of tyre tread compounds by gradual replacement of carbon black by multiwalled carbon nanotubes (MWCNTs) in a natural rubber–butadiene rubber‐based system. A rapid change in the mechanical properties is noticed even at very low concentrations of nanotubes though the total concentration of the filler is kept constant at 25 phr (parts per hundred rubber). The correlation of the bound rubber content with MWCNT loading directly supports the conclusion that MWCNTs increase the occluded rubber fraction. Transmission electron microscopy reveals a good dispersion of the MWCNT up to a certain concentration. In the presence of MWCNT, a prominent negative shift of the glass transition temperature of the compound is found. Thermal degradation behavior, aging, and swelling experiments were also carried out to understand the resulting effect of the incorporation of MWCNT in the rubber matrix. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3153–3160, 2013     

Electrically conductive polymeric bi‐component fibers containing a high load of low‐structured carbon black

Melt spinning at semi‐industrial conditions of carbon black (CB) containing textiles fibers with enhanced electrical conductivity suitable for heating applications is described. A conductive compound of CB and high density polyethylene (HDPE) was incorporated into the core of bi‐component fibers which had a sheath of polyamide 6 (PA6). The rheological and fiber‐forming properties of a low‐structured and a high‐structured CB/HDPE composite were compared in terms of their conductivity. The low‐structured CB gave the best trade‐off between processability and final conductivity. This was discussed in terms of the strength of the resulting percolated network of carbon particles and its effect on the spin line stability during melt spinning. The conductivity was found to be further enhanced with maintained mechanical properties by an in line thermal annealing of the fibers at temperatures in the vicinity of the melting point of HDPE. By an adequate choice of CB and annealing conditions a conductivity of 1.5 S/cm of the core material was obtained. The usefulness of the fibers for heating applications was demonstrated by means of a woven fabric containing the conductive fibers in the warp direction. By applying a voltage of 48 V the surface temperature of the fabric rose from 20 to 30°C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42255.     

Polyvinyl alcohol/chitosan/carbon nanotubes electroactive shape memory nanocomposite hydrogels

Shape memory nanocomposite hydrogels are intelligent soft materials in which, the nanoparticles can impart desirable mechanical properties to the polymeric matrix. The main challenge is the capability to program from permanent to temporary shapes and vice versa under the direct and indirect thermal stimuli. In this work, carbon nanotubes (CNT) with a high modulus of 1 TPa, was used to mechanically reinforce polyvinyl alcohol (PVA) and polyvinyl alcohol/chitosan (PVA/Cs) hydrogel networks. Adding appropriate amount of conductor component enables the system to be electrically activated, which leads to achieving the original permanent shape without applying mechanical external force. The PVA/Cs/CNT hydrogel containing 0.25 wt% of CNT, showed electrical conductivity greater than 9 mS cm⁻¹. Because of the presence of CNT, the shape memory behavior of PVA and PVA/Cs hydrogels was improved by 170 and 260%, respectively. The electroactive shape memory nanocomposite hydrogels exhibited complete recovery under indirect stimulation by generating Joule heating in the system.     

Preparation and properties of styrene‐butadiene rubber nanocomposites blended with carbon black‐graphene hybrid filler

Graphene has become an attractive reinforcing filler for rubber materials, but its dispersion in rubber is still a big challenge. In this work, a novel carbon black‐reduced graphene (CB‐RG) hybrid filler was fabricated and blended with styrene‐butadiene rubber (SBR) via simple two‐roll mill mixing. The prepared CB‐RG hybrids had a microstructure with small CB agglomerates adsorbed onto graphene surfaces. CB acted as a barrier preventing the RG sheets from restacking even after drying. Homogeneous dispersion of graphene sheets in SBR matrix was observed by the mechanical mixing method based on the application of the CB‐RG hybrid fillers. Dynamic mechanical analysis showed that Tg of the SBR/CB‐RG blend was higher than that of the SBR/CB blend indicating strong interfacial interactions between RG and SBR due to the high surface area of graphene and the π‐π interaction between SBR and graphene. The tensile properties of SBR/CB‐RG composites improved significantly and the volume resistivity decreased compared with the SBR/CB blends. The thermal stability of SBR composites filled with CB and CB‐RG showed slight difference. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41309.     

Preparation and electrochemical properties of polyaniline/reduced graphene oxide composites

Polyaniline (PANI)/reduced graphene oxide (rGO) composites were synthesized by in situ oxidative polymerization of aniline on reduced graphene sheets. Fourier transform infrared spectroscopy, X‐ray diffraction, thermogravimetric analysis, transmission electron microscopy, and scanning electron microscopy were used to characterize the composites. The results indicated PANI/rGO composites were produced and contained covalent bonds between the functional groups of PANI and rGO. A uniform coating of PANI on the rGO sheets had a synergistic effect on the properties of the composites. The electrochemical properties of the PANI/rGO composites produced using different feed ratios of aniline to rGO were studied. The results showed that the composites exhibited a maximum specific capacitance of 797.5 F/g at 0.5 A/g and minimum charge transfer resistance of 0.98 Ω when the feed ratio of aniline to rGO was 2:1. These values were superior to those of pure PANI and rGO. The composites also displayed excellent cycling stability, with specific capacitance retention of 92.43% after 1000 cycles. These stable structural composites show promise for the development of new supercapacitor applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46103.     

Ionic liquids as dispersing agents of graphene nanoplatelets in poly(methyl methacrylate) composites with microwave absorbing properties

Graphene nanoplatelets (GNP) is noncovalently functionalized with imidazolium-, pyridinium-, and vinyl-pyridinium-based ionic liquids containing bromide or bis(trifluoromethyl-sulfonyl)imide (TFSI) as the counteranions, and used to prepare poly (methyl methacrylate) (PMMA) nanocomposites by solution casting approach followed by compression molding technique. The PMMA composites loaded with 1.9 and 1.8 wt% of GNP in PMMA/GNP composite and PMMA/GNP/ionic liquids, respectively, were characterized by melting viscosity, thermogravimetric analysis and AC electrical conductivity (σ_AC). The microwave absorption properties at the X-band (8.2–12.4 GHz) frequency were measured for systems with 1 mm thickness using the metal-backed configuration. PMMA nanocomposites loaded with GNP/N-dodecyl-4-vinyl-pyridinium.TFSI (C₁₂ViPy.TFSI) displayed higher thermal stability and higher σ_AC. This system also presented the best response in terms of microwave absorbing properties, with minimum reflection loss (RL) of around −6 dB at 8.7 GHz. Triple layered composite structures with layers of different conductivities and different stacking orders were also investigated in terms of reflection loss. Broadband absorption with minimum RL ≤ −10 dB (90% of electromagnetic attenuation) in the frequency between 10.2 and 12.4 GHz and better absorbing effectiveness were observed for the PMMA/GNP-PMMA/GNP/C₁₂ViPy.TFSI-PMMA/GNP/C₁₂ViPy.Br triple-layered system with 3 mm thickness.     

Graphene nanoplatelets composite membranes for thermal comfort enhancement in performance textiles

The advent of 2D nanostructured materials as advanced fillers for polymer matrix composites has opened the doors to a plethora of new industrial applications requiring both electric and thermal management. Unique properties, in fact, can arise from accurate selection and processing of 2D fillers and their matrix. Here, we report an innovative family of nanocomposite membranes based on polyurethane (PU) and graphene nanoplatelets (GNPs), designed to improve thermal comfort in functional textiles. GNP particles were thoroughly characterized (through Raman, atomic force microscopy, high-resolution TEM, scanning electron microscope), and showed high crystallinity (I_D/I_G = 0.127), low thickness (D50 < 6–8 layers), and high lateral dimensions (D50 ≈ 3 μm). When GNPs were loaded (up to 10% wt/wt) into the PU matrix, their homogeneous dispersion resulted in an increase of the in-plane thermal conductivity of composite membranes up to 471%. The thermal dissipation of membranes, alone or coupled with cotton fabric, was further evaluated by means of an ad hoc system designed to simulate a human forearm. The results obtained provide a new strategy for the preparation of membranes suitable for technical textiles, with improved thermal comfort.     

Synergistic effects of carbon nanotubes and exfoliated graphite nanoplatelets for electromagnetic interference shielding and soundproofing

Polypropylene/carbon nanotube/exfoliated graphite nanoplatelet (PP/CNT/xGnP) composites have been fabricated to evaluate their electromagnetic interference shielding effectiveness (EMI SE) and soundproofing. An EMI SE of 36.5 dB at 1250 MHz was measured for the 80/10/10 wt % PP/CNT/xGnP composite; its sound transmission loss was more than 5 dB higher than that for pure PP at low frequencies (520–640 Hz). These results indicate simultaneous EMI SE and soundproofing. Transmission electron microscopy was used to study the microstructure and to probe synergetic effects between the CNTs and xGnPs. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3947–3951, 2013     

Probing the reinforcing mechanism of graphene and graphene oxide in natural rubber

Natural rubber (NR) containing graphene (GE) and graphene oxide (GO) were prepared by latex mixing. The in situ chemically reduction process in the latex was used to realize the conversion of GO to GE. A noticeable enhancement in tensile strength was achieved for both GO and GE filled NR systems, but GE has a better reinforcing effect than GO. The strain‐induced crystallization was evaluated by synchrotron wide‐angle X‐ray diffraction. Increased crystallinity and special strain amplification effects were observed with the addition of GE. The incorporation of GE produces a faster strain‐induced crystallization rate and a higher crystallinity compared to GO. The entanglement‐bound tube model was used to characterize the chain network structure of composites. It was found that the contribution of entanglement to the conformational constraint increases and the network molecular parameters changes with the addition of GE and GO, while GE has a more evident effect than GO. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Crack growth behavior of natural rubber influenced by functionalized carbon nanotubes

In this work, the silane coupling agent bis‐(triethoxysilylpropyl) ‐tetrasulfide (TESPT) is used to modify the carbon nanotubes. After modification, carbon nanotubes can be well dispersed in the natural rubber (NR) matrix and form a strong and flexible network. Based on the original real‐time crack tip morphology monitoring, crack propagation and scanning electronic microscopy tests, it is revealed that modified carbon nanotubes filled NR samples (NR/F‐CNTs) have better crack resistance. It is found that modified carbon nanotubes can resist the cavitation process during cyclic loading. Crack tip morphology monitoring tests indicate that the crack tip of NR/F‐CNTs is rougher and the ligaments are thinner and densely distributed. A crack branching phenomenon is also observed. It proves that F‐CNTs increase the energy consumption of NR during cyclic loading. It is concluded that the F‐CNTs used in this work improve the crack resistance of NR in two ways: the one is cavitation resistance and the other is the increase of energy consumption for crack propagation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44527.     

Improving electrical conductivity of poly methyl methacrylate by utilization of carbon nanotube and CO2 laser

In this work, the electrical surface conductivity enhancement of injection‐molded multiwalled carbon nanotube (MWCNT)/poly(methyl methacrylate) (PMMA) nanocomposite by using CO₂ laser processing was studied. Variable input factors are considered as MWCNT concentration (in three levels 0.5, 1, and 1.5 wt %), the laser feed angle with the flow direction (in five levels 0°, 30°, 45°, 75°, and 90°), and the cavity machining method that were produced by electrodischarge machining and computer numerical control milling with finishing process. The studies show that the irradiation of laser and utilization of covering gas could enhance the CNT–CNT contacts and the surface electrical conductivity. The morphology of laser‐irradiated surface by using scanning electron microscope certified that the conductive network generated from CNT–CNT contacts can transfer the electrical current. The findings clearly show that the laser feed angle with the flow direction influenced the electrical conductivity. The maximum conductivity (～ 5.310 × 10^?4 S) was observed at 75°. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42671.     

Simultaneous reduction and surface functionalization of graphene oxide and the application for rubber composites

The simultaneous reduction and functionalization of graphene oxide (GO) was realized through a chemical grafting reaction with a functionalization agent N,N-bis(3-aminopropyl)methylamine (APMEL). The reduced and functionalized reduced GO (rGO-APMEL) sheets can be well dispersed in water without any added surfactant and the formed stable rGO aqueous dispersion can be kept for a long time, which can be used for the preparation of rubber–graphene (GE) composites by latex mixing. The electrostatic interaction between rGO–APMEL (positively charged) and natural rubber latex particles (negatively charged) leads to the formation of NR/rGO–APMEL composites with strong interaction. Compared with blank NR, the tensile strength and modulus for NR/rGO–APMEL increase with the rGO–APMEL loading. Especially, when the filler content is 5 phr, the tensile strength of NR/rGO–APMEL-5 increases by 32.7%, as a control the tensile strength of NR/GO-5 and NR/rGO-5 decrease by 20.1 and 15.6%, respectively. The entanglement-bound rubber tube model was used to analyze the reinforcing effect of GE on NR/rGO–APMEL nanocomposites at a molecular level. This study may provide us a novel approach to prepare well dispersed and exfoliated rGO–polymer nanocomposites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47375.     

Studies of nanocomposites based on carbon nanomaterials and RTV silicone rubber

The mechanical and electrical properties were investigated for nanocomposites based on carbon nanotubes (CNTs) and conductive carbon black (CB). Solution room‐temperature‐vulcanized silicone rubber was used as a matrix. Vulcanizates based on CNTs and CB was prepared by solution mixing. With the addition of 2 phr of CNTs to the rubber matrix, the Young's modulus increased by 272% and reached as high as ～706% at 8 phr, whereas the modulus increased only 125% for CB specimens at 10 phr. Similarly, the electrical properties at 5 phr content of CNT were ～0.7 kΩ against ～0.9 kΩ at 20 phr CB. The Kraus plot from equilibrium swelling tests shows that the high properties for CNT specimens are due to high polymer–filler interfacial interactions, the small particle size that improves the distribution of the filler in a highly exfoliated state, and high electrical connective networks among the filler particles. These improvements can especially influence medical products such as feeding tubes, seals and gaskets, catheters, respiratory masks and artificial muscles. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44407.