Effects of functional groups on the graphene sheet for improving the thermomechanical properties of polyurethane nanocomposites

Dispersibility of graphene sheets in polymer matrices and interfacial interaction are challenging for producing graphene-based high performance polymer nanocomposites. In this study, three kinds nanofillers; pristine graphene nanoplatelets (GNPs), graphene oxide (GO), and functionalized graphene sheet (FGS) were used to prepare polyurethane (PU) composite by in-situ polymerization. To evaluate the efficacy of functional groups on the graphene sheets, PU reinforced with GNPs, GO, and FGS were compared through tensile testing and dynamic mechanical thermal analysis. The Young's moduli of 2 wt% GO and FGS based PU nanocomposites were found significantly higher than that of same amount of GNPs loading as an evidence of the effect of functional groups on graphene sheets for the mechanical reinforcement. The strong interaction of FGS with PU was responsible to exhibit notably high modulus (25.8 MPa) of 2 wt% FGS/PU composite than the same amount of GNPs and GO loading even at elevated temperature (100 °C).     

Click coupled stitched graphene sheets and their polymer nanocomposites with enhanced photothermal and mechanical properties

The chemically stitched graphene oxide (GO) sheets were obtained using a click chemistry reaction between azide-functionalized GO and alkyne-functionalized GO. The click coupled GO (GO-click-GO) sheets showed the largely increased electrical conductivity and near infrared laser-induced photothermal properties compared to the GO sheets, which result from formation of triazole ring as a bridging linker between the GO sheets. The polyurethane (PU) nanocomposites incorporating the GO-click-GO sheets exhibited enhanced mechanical properties of breaking stress and modulus than the GO/PU nanocomposites. The modulus of GO-click-GO/PU nanocomposites was higher than that of the GO/PU nanocomposites at the same filler loading of 0.1 and 0.5 wt%. The GO-click-GO/PU nanocomposites also showed a significantly improved photothermal properties compared to the GO/PU nanocomposites at the same filler loading. The click coupled stitched GO sheets in this study can be used as the superior reinforcing fillers for mechanically and photothermally high performance polymer nanocomposites.     

Morphology, mechanical and thermal properties of graphene-reinforced poly(butylene succinate) nanocomposites

Graphene nanosheets (GNSs) reinforced poly(butylene succinate) (PBS) nanocomposites are facilely obtained by a solution-based processing method. Graphene nanosheets, which are derived from chemically reduced graphite oxide (GO), are characterized by AFM, TEM, XRD and Raman spectra. The state of dispersion of the GNSs in the PBS matrix is examined by SEM observations that reveals homogeneous distribution of GNSs in PBS matrix. A 21% increase in tensile strength and a 24% improvement of storage modulus are achieved by addition of 2.0 wt% of GNS. The electrical conductivity and thermal stability of the graphene-based nanocomposite are also improved. DSC measurement indicates that the presence of graphene sheets does not have a remarkable impact on the crystallinity of the nanocomposites. Therefore, the high performances of the nanocomposites are mainly attributed to the uniform dispersion of GNSs in the polymer matrix and strong interfacial interactions between both components.     

Crystallization,mechanical performance and hydrolytic degradation of poly(butylene succinate)/graphene oxide nanocomposites obtained via in situ polymerization

Poly(butylene succinate) (PBS)/graphene oxide (GO) nanocomposites were fabricated via in situ polymerization with very low GO content (from 0.03 to 0.5 wt%). The microstructures of the nanocomposites were characterized with Raman spectroscopy, fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), sedimentation experiments and atomic force microscopy (AFM). The results showed that PBS chains have been successfully grafted onto GO sheets during in-situ polymerization, accompanied by the thermo-reduction from GO to graphene. The grafted GO displayed a great nucleating effect on PBS crystallization, resulting in largely improved crystallization temperature and decreased spherules size. A simultaneous enhancement in tensile strength and elongation was achieved for PBS/GO nanocomposites fiber. Meanwhile, increase in hydrolytic degradation rate was also observed for these nanohybrids. Our result indicates that using very low content GO is a simple way to achieve good dispersion yet with remarkable property enhancement for polymer/GO nanocomposites.     

Noncovalently functionalized multiwalled carbon nanotubes by chitosan-grafted reduced graphene oxide and their synergistic reinforcing effects in chitosan films

Water-soluble chitosan-grafted reduced graphene oxide (CS-rGO) sheets are successfully synthesized via amidation reaction and chemical reduction. CS-rGO possesses not only remarkable graphitic property but also favorable water solubility, which is found to be able to effectively disperse multiwalled carbon nanotubes (MWCNTs) in acidic solutions via noncovalent interaction. The efficiency of CS-rGO in dispersing MWCNTs is tested to be higher than that of plain graphene oxide (GO) and a commercial surfactant, sodium dodecyl sulfate (SDS). With incorporation of 1 wt % CS-rGO dispersed MWCNTs (CS-rGO-MWCNTs), the tensile modulus, strength and toughness of the chitosan (CS) nanocomposites can be increased by 49, 114, and 193%, respectively. The reinforcing and toughening effects of CS-rGO-MWCNTs are much more prominent than those of single-component fillers, such as MWCNTs, GO, and CS-rGO. Noncovalent π-π interactions between graphene sheets and nanotubes and hydrogen bonds between grafted CS and the CS matrix are responsible for generating effective load transfer between CS-rGO-MWCNTs and the CS matrix, causing the simultaneously increased strength and toughness of the nanocomposites.     

聚氯乙烯/氧化石墨烯薄膜的力学性能和热稳定性能

通过溶液共混法制备了氧化石墨烯(GO)分散均匀的聚氯乙烯(PVC)/GO纳米复合薄膜,研究了薄膜的力学性能和热稳定性能。结果表明,微量GO能大幅度提高PVC的模量和拉伸强度,且保持较高的断裂伸长率。在PVC中添加质量分数为0.12%的GO,PVC的拉伸强度提高63%,杨氏模量提高20%;添加量为0.60%时,PVC的拉伸强度提高125%,杨氏模量提高126%.添加GO还能提高PVC的起始分解温度、最大分解温度以及PVC的成碳量。GO片层具有较高的强度和模量、GO在高分子基体内的均匀分散、GO和PVC之间较强的相互作用、GO与PVC的层状结构,是其力学性能提高的主要原因.     

Preparation and properties of reduced graphene oxide/polyacrylonitrile nanocomposites using polyvinyl phenol

Nanocomposites of polyacrylonitrile (PAN) with reduced graphene oxide (rGO) were prepared using a solution mixing technique employing polyvinyl phenol (PVP) as a compatibilizer. The PVP can facilitate composite formation by interacting with both rGO and PAN via π-π and H-bonding respectively. Various amounts of rGO were used to prepare PAN nanocomposites. The cross-sectional morphology of the composite films shows a uniform dispersion of rGO sheets in the PAN matrix. The Fourier transform infrared (FT-IR) studies revealed that good interaction of the rGO/PVP hybrid with PAN. The wide angle x-ray diffraction (WAXS) study confirms that the rGO sheets were uniformely dispersed as individual sheets in the PAN matrix. Thermogravimetric analysis shows enhanced thermal stability of the composite compared to pure PAN. The tensile strength and elastic modulus of the nanocomposites increased with increasing rGO content. A 102% enhancement in tensile strength and a 62.9% enhancement in elastic modulus were observed in the nanocomposite with 5% rGO.     

Graphene oxide reinforced polyimide nanocomposites via in situ polymerization

Graphene oxide (GO) reinforced polyimide nanocomposites were synthesized by in situ polymerization of monomers in the presence of GO sheets dispersed in N,N-Dimethylacetamide (DMAc). The functional groups (e.g., hydroxyl, epoxide, and carboxyl groups) associated with the GO make GO excellent dispersion in the organic solvent, which benefits the subsequent in situ polymerization. This process enabled uniform dispersion of GO sheets in the polymer matrix. The resultant GO-polyimide nanocomposite films were studied by tensile test, TGA and SEM. The results showed that the GO sheets incorporated in the polymer matrix exhibited a layer-aligned structure without destruction of the thermal stability of the polymer matrix, and a loading of GO (10 wt%) resulted in a significant enhancement in elastic modulus (86.4%).     

Excellent photocatalytic performance under visible-light irradiation of ZnS/rGO nanocomposites synthesized by a green method

ZnS/graphene nanocomposites with different graphene concentrations (5, 10 and 15 wt.%) were synthesized using L-cysteine as surfactant and graphene oxide (GO) powders as graphene source. Excellent performance for nanocomposites to remove methylene blue (MB) dye and hexavalent chromium (Cr(VI)) under visible-light illumination was revealed. TEM images showed that ZnS NPs were decorated on GO sheets and the GO caused a significant decrease in the ZnS diameter size. XRD patterns, XPS and FTIR spectroscopy results indicated that GO sheets changed into reduced graphene oxide (rGO) during the synthesis process. Photocurrent measurements under a visiblelight source indicated a good chemical reaction between ZnS NPs and rGO sheets.     

Graphene oxide and hydroxyapatite as fillers of polylactic acid nanocomposites: preparation and characterization

Graphene and its derivatives have attracted great research interest for their potential applications in electronics, energy, materials and biomedical areas. When incorporated appropriately, these atomically thin carbon sheets are expected to improve physical properties of host polymers at extremely small loading. Herein, we report a novel two-step method for the preparation of PLLA/Hap/graphene oxide nanocomposites with augmented mechanical properties when compared to PLLA/Hap and neat PLLA. The presence of graphene oxide (GO) had a positive effect on the dispersion of hydroxyapatite particles on the polymeric matrix contributing for a good homogeneity of the final nanocomposite. PLLA nanocomposites prepared with 30% (w/w) of Hap and 1% (w/w) of GO showed the highest hardness and storage modulus values indicating an efficient load transfer between the fillers and the PLLA matrix. These materials may find interesting biomedical applications as for example bone screws. The following step on the study of these materials will be in vitro tests to access the biocompatibility of these new nanocomposites.     

Graphene/thermoplastic polyurethane nanocomposites: Surface modification of graphene through oxidation,polyvinyl pyrrolidone coating and reduction

Herein, oxidation, polyvinyl pyrrolidone (PVP) coating and reduction are used to modify the surface of graphene in thermoplastic polyurethane (TPU)/graphene nanocomposites. It is demonstrated that graphene could be easily dispersed in TPU with PVP absorbed on reduced graphene oxide (RGO) as stabilizer during reduction. In the stress–strain curves for these composites containing GO, PVP coated GO (GO/PVP) and reduced GO/PVP (RGO/PVP) as filler, PVP coating and reduction can largely enhance the stress in low modulus region. It is thought to largely related with enhanced interfacial interaction between filler and matrix and healing of graphene structure during reduction. Consequently, the modulus of TPU/GO/PVP and TPU/RGO/PVP is significantly increased. Meanwhile, an electrical percolation threshold of 0.35 wt.% is obtained for TPU/RGO/PVP. Comparing with the results in literature, the filler surface modification used in this study has created nanocomposites with a good balance between electrical conductivity and mechanical properties.     

Graphene oxides nanosheets mediation of poly(vinyl alcohol) films in tuning their structural and opto-mechanical attributes

Herein, we report successful incorporation of graphene oxide (GO) nanosheets into poly(vinyl alcohol) (PVA) matrix by employing solution casting method. The effect of GO loadings on structural, optical and mechanical properties of PVA films was investigated. Most of the optical properties of such films are reported for the first time in the present study. On incorporating GO nanosheets into PVA matrix, the properties of nanocomposites were changed entirely. The tensile strength and Young’s modulus of nanocomposites were enhanced. Alongside, a variation in absorption edge, direct/indirect band gap, Urbach energy, refractive index, optical dielectric constant, optical conductivity and dispersion parameters were noticed. The band gap and dispersion parameters were calculated using Tauc’s and Wemple–DiDomenico models, respectively. Helpin–Tsai and mixture rule models were employed to calculate Young’s modulus. The applied models reinforced the experimental results in the present study. Advanced analytical techniques were employed to characterize the nanocomposites films. The prepared nanocomposites might be used in designing the opto-electronic devices.     

Non-covalently modified reduced graphene oxide/polyurethane nanocomposites with good mechanical and thermal properties

Non-covalently modified graphene nanosheets were prepared by reduction graphene oxide with hydrazine hydrate and simultaneous non-covalent functionalization via 1-allyl-methylimidazolium chloride (AmimCl) ionic liquid. Atomic force microscopy revealed that AmimCl ionic liquid modified graphene (IL-G) was well-dispersed in a single exfoliation with a thickness of around 0.96 nm in DMF. Subsequently, the prepared IL-G nanosheets were incorporated into polyurethane (PU) to fabricate IL-G/PU nanocomposites by solution blending. X-ray diffraction disclosed an exfoliated morphology of IL-G nanosheets dispersed in the PU matrix, while the fractured morphology of the IL-G/PU nanocomposites showed that IL-G nanosheets presented a wrinkled morphology when dispersed in the matrix. Both techniques revealed homogeneous dispersion and good compatibility of IL-G nanosheets with PU matrix, indicating the existence of interfacial interactions. At 0.608 wt% loadings of IL-G nanosheets, the tensile strength and storage modulus of the composites were increased by 68.5 and 81.1 %, respectively. High thermal properties were also achieved at a low loading of IL-G nanosheets. An approximately 40 °C improvement in temperature of 5 % weight loss and 34 % increase in thermal conductivity were obtained at just 0.608 wt% loading of IL-G nanosheets.     

Improved dispersion of attapulgite nanorods in polymer with graphene oxide nanosheets

To improve the dispersion stability of rod-like attapulgite (ATT) in polymers, a small amount of graphene oxide (GO) nanosheets were employed as a supporter to fix ATT before introducing into polymer. The ATT nanorods were found attached tightly and dispersed uniformly on the GO nanosheets from TEM images of GO-ATT hybrids. The dispersion stability of ATT in water was also improved after being attached on GO nanosheets due to the abundant hydrophilic groups of GO, which was paramount for introducing them into polymers through water blending method. Poly(vinyl alcohol) (PVA) was then chosen to be reinforced by these GO-supported ATT via water blending method. Compared to the heavy aggregation of neat ATT in PVA, a homogeneous distribution of ATT nanorods in the matrix was achieved by introducing them in the form of GO-ATT, indicating a favorable assisted dispersion effect of GO nanosheets for ATT. Furthermore, PVA/GO-ATT nanocomposites containing only 2 wt% GO-ATT exhibited a significantly increase of 41.4 and 83.6 % in tensile strength and storage modulus, respectively.     

Eco-friendly nanocomposites between carboxylated acrylonitrile–butadiene rubber (XNBR) and graphene oxide or graphene at low content with enhanced mechanical properties

A crucial step in rubber nanocomposites is the homogenous dispersion of the nanofillers within the elastomer matrix. Herein, a green and modified latex co-coagulation strategy was conducted to develop high-performance nanocomposite materials based on carboxylated acrylonitrile-butadiene rubber (XNBR) latex with graphene oxide (GO) or reduced graphene oxide (RGO). Aqueous solutions with different concentrations of GO or RGO were mixed with XNBR rubber latex under vigorous magnetic stirring. The incorporation of graphene-derivative fillers in the XNBR matrix provided significant improvements in the rheological and mechanical properties compared to the unfilled rubber. Indeed, with increasing fillers loading, the maximum torque, tensile strength and crosslink density of obtained nanocomposites were found to increase. These results were correlated to the better dispersion of fillers through the matrix and, thus, to stronger interactions between the oxygen-containing functional groups of fillers and the carboxyl ones in XNBR matrix.     

Enhanced stress transfer and thermal properties of polyimide composites with covalent functionalized reduced graphene oxide

This work prepares (3-aminopropyl) trimethoxysilane (APTMS)-functionalized reduced graphene oxide (APTMS-rGO)/polyimide (PI) composite (APTMS-rGO/PI) through in-situ polymerization. NH₂-functionalized rGO coupled by APTMS demonstrates the good reinforced efficiency in mechanical and thermal properties, which is ascribed to the covalent-functionalized PI matrix by APTMS-rGO sheets. The uniform dispersion of APTMS-rGO increases the glass transition temperature (Tg) and the thermal decomposition temperature (Td), exhibiting 21.7 °C and 44 °C improvements, respectively. The tensile strength of the composites with 0.3 wt% APTMS-rGO is 31% higher than that of neat PI, and Young’s modulus is 35% higher than that of neat PI. Raman spectroscopy show the obvious G band shift, and also clearly demonstrates the enhanced interfacial interaction between rGO nanofillers and PI matrix. The high mechanical property of the APTMS-rGO/PI composites is attributed to the covalent functionalized GO by NH₂ groups and its good dispersion in comparison with GO.     

P25/graphene nanocomposites as a high-performance anode material for lithium ion batteries

P25/graphene nanocomposites were successful synthesized in a water-ethanol solvent under hydrothermal conditions. During the process of the reduction of GO into graphene (GR), the P25 nanoparticles were decorated on graphene sheets simultaneously. Moreover, the GR content in the as-synthesized nanocomposites can be easily adjusted by changing the dosage of P25. The interesting P25/GR nanocomposites were found to be a promising anode material for lithium-ion batteries and showed significantly enhanced Li-ion insertion/extraction performance. The optimal weight percentage of GR was found to be 29.9%, which resulted in a high capacity of 282.8 mAh g⁻¹ after 50 cycles at a current rate of 0.5 C. The improved capacity may be attributed to the synergetic effect between graphene sheets and P25 nanoparticles.     

Preparation and properties of polystyrene nanocomposites with graphite oxide and graphene as flame retardants

In this study, graphite oxides (GOs) with different oxidation degrees and graphene nanosheets were prepared by a modified Hummers method and thermal exfoliation of the prepared GO, respectively. Polystyrene (PS)/GO and PS/graphene nanocomposites were prepared via melt blending. X-ray diffraction results showed that GOs and graphene were exfoliated in the PS composites. It could be observed from the scanning electron microscope images that GOs and graphene were well dispersed throughout the matrix without obvious aggregates. Dynamic mechanical thermal analysis suggested that the storage modulus for the PS/GO1 and PS/graphene nanocomposites was efficiently improved due to the low oxygen content of GO1 and the elimination of the oxygen groups from GO. The flammability of nanocomposites was evaluated by thermal gravimetric analysis and cone calorimetry. The results suggested that both the thermal stability and the reduction in peak heat release rate (PHRR) decreased with the increasing of the oxygen groups in GOs or graphene. The optimal flammability was obtained with the graphene (5 wt%), in which case the reduction in the PHRR is almost 50 % as compared to PS.     

In situ thermal reduction of graphene oxide for high electrical conductivity and low percolation threshold in polyamide 6 nanocomposites

Electrically conductive and thermally stable polyamide 6 (PA 6) nanocomposites were prepared through one-step in situ polymerization of ε-caprolactam monomer in the presence of electrically insulating and thermally unstable graphene oxide (GO) nanosheets. These nanocomposites show a low percolation threshold of ∼0.41 vol.% and high electrical conductivity of ∼0.028 S/m with only ∼1.64 vol.% of GO. Thermogravimetric analysis and X-ray photoelectron spectroscopy results of GO before and after thermal treatment at the polymerization temperature indicate that GO was reduced in situ during the polymerization process. X-ray diffraction patterns and scanning electron microscopy observation confirm the exfoliation of the reduced graphene oxide (RGO) in the PA 6 matrix. The low percolation threshold and high electrical conductivity are attributed to the large aspect ratio, high specific surface area and uniform dispersion of the RGO nanosheets in the matrix. In addition, although GO has a poor thermal stability, its PA 6 nanocomposite is thermally stable with a satisfactory thermal stability similar to those of neat PA 6 and PA 6/graphene nanocomposite. Such a one-step in situ polymerization and thermal reduction method shows significant potential for the mass production of electrically conductive polymer/RGO nanocomposites.     

低温剥离法制备高性能石墨烯/ZnO复合材料

采用氧化石墨和七水合硫酸锌作为初始反应物, 在低温下(80℃)合成了氧化石墨/ZnO, 然后通过低温剥离法制备了高质量石墨烯/ZnO (GNS/ZnO)复合材料. 采用X射线衍射(XRD)、傅里叶变换红外(FTIR)光谱、热重分析仪(TG)、X射线光电子能谱(XPS)、拉曼光谱(RS)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等分析手段对石墨烯/ZnO样品进行了表征. 结果表明: 氧化石墨还原彻底, 纳米ZnO成功地负载到了石墨烯上, 有效地减少了石墨烯片层间的团聚现象. 通过对ZnO和石墨烯/ZnO荧光性能测试, 结果表明: 石墨烯/ZnO发生了荧光淬灭现象, 在光电子领域拥有广阔的应用前景.