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.     

Diazonium functionalization of graphene nanosheets and impact response of aniline modified graphene/bismaleimide nanocomposites

For developing high performance of graphene-based nanocomposites, dispersibility of graphene sheets in matrices and interfacial interaction are challenging due to the strong tendency of agglomeration and surface inertia of graphene. Here we report an efficient way to functionalize graphene nanosheets with aniline groups on their surfaces, to attain the functionalized graphene nanosheets (FGS) by diazonium treatment following reduction of graphene oxide with hydrazine hydrate. Two kinds of nanocomposites based on diallyl bisphenol A modified bismaleimide (BMI-BA) resin which was filled with functionalized graphene and reduced graphene oxide nanosheets were prepared, and the FGS were linked with BMI resin by chemical bonds. The FGS/BMI-BA composite at a loading of 0.3 wt% revealed a 39% increase in impact strength and a slightly improvement in flexural strength, and the resulting composite remains stable at high temperature. This work provides more possibilities for incorporation of graphene into polymer matrices and an efficient method to toughening the BMI resin.     

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.     

High performance polyurethane/functionalized graphene nanocomposites with improved mechanical and thermal properties

This communication reported the substantial improvement in the mechanical and thermal properties of a polyurethane (PU) resulting from the incorporation of well-dispersed graphene oxide (GO). The stress transfer benefited from the covalent interface formed between the PU and GO. The Young’s modulus of the PU was improved by ∼7 times with the incorporation of 4 wt% GO, and the improvement of ∼50% in toughness was achieved at 1 wt% loading of GO without losing elasticity. Significant improvements were also demonstrated in the hardness and scratch resistance measured by nano-indentation. Thermogravimetric analysis revealed that the decomposition temperature was increased by ∼50 °C with the addition of 4 wt% GO.     

Highly conductive graphene oxide/polyaniline hybrid polymer nanocomposites with simultaneously improved mechanical properties

Graphene oxide (GO) was added to a polymer composites system consisting of surfactant-wrapped/doped polyaniline (PANI) and divinylbenzene (DVB). The nanocomposites were fabricated by a simple blending, ultrasonic dispersion and curing process. The new composites show higher conductivity (0.02–9.8 S/cm) than the other reported polymer system filled with PANI (10⁻⁹–10⁻¹ S/cm). With only 0.45 wt% loading of GO, at least 29% enhancement in electric conductivity and 29.8% increase in bending modulus of the composites were gained. Besides, thermal stability of the composites was also improved. UV–Vis spectroscopy, X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM) revealed that addition of GO improves the dispersion of PANI in the polymer composite, which is the key to realize high conductivity.     

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.     

Highly aligned,ultralarge-size reduced graphene oxide/polyurethane nanocomposites: Mechanical properties and moisture permeability

Polyurethane (PU) nanocomposite films containing highly-aligned graphene sheets are produced. Aqueous dispersion of ultralarge-size graphene oxide (GO) is in situ reduced in waterborne polyurethane, resulting in fine dispersion and high degree of orientation of graphene sheets, especially at high graphene contents. The PU/reduced GO nanocomposites present remarkable 21- and 9-fold increases in tensile modulus and strength, respectively, with 3 wt.% graphene content. The agreement between the experiments and theoretical predictions for tensile modulus proves that the graphene sheets are indeed dispersed individually on the molecular scale and oriented in the polymer matrix to form a layered structure. The moisture permeability of the nanocomposites presents a systematic decrease with increasing graphene content, clearly indicating the impermeable graphene sheets acting as moisture barrier. The synergy arising from the very high aspect ratio and horizontal alignment of the graphene sheets is responsible for this finding.     

The synthesis of graphene nanoribbon and its reinforcing effect on poly (vinyl alcohol)

The graphene nanoribbon was prepared from the carbon nanotubes using the chemical approach, and was used for preparing the poly (vinyl alcohol) nanocomposites. It was discovered that the prepared graphene nanoribbon contained a lot of oxygen groups. Due to the presence of these oxygen groups, the nanoribbon could homogeneously disperse in both water and poly (vinly alcohol) matrix. It was also found that there were strong interactions between the graphene nanoribbon and the poly (vinyl alcohol) through hydrogen bonding. The interactions gave rise to the thermal stability of the host polymer. Furthermore, the presence of the nanofiller also resulted in a significant improvement of the mechanical performance of the prepared nanocomposites. The tensile strength and the Young’s modulus of the nanocomposite loaded with 2.0 wt% graphene nanoribbon increased by 85.7% and 65.2% respectively. The overall results indicate that the graphene nanoribbon is suitable for preparing high-performance polymer composites.     

Multi-step microwave reduction of graphite oxide and its use in the formation of electrically conductive graphene/epoxy composites

The multi-step MW reduction technique was developed in this study to obtain reduced graphene oxides; EG, RGO-1, and RGO-2 with MW irradiation time of 1, 2, and 3 min, respectively. Results of TGA, IR, and elemental analysis demonstrated that the degree of reduction of GO increased with increasing the MW irradiation time. Overall, 3 min of MW irradiation of GO in 3 steps was sufficient to obtain highly reduced GO (C/O ratio 10.38 by elemental analysis). The electrical percolation threshold of composites was observed as 1 wt% and 0.3 wt% for RGO-1 and RGO-2, respectively. Even at 0.5 wt% loading of RGO-2 in epoxy, the T_g value of the composite increased by 10 °C, indicating a strong interfacial interaction between graphene and epoxy resin.     

Improving the through-thickness thermal and electrical conductivity of carbon fibre/epoxy laminates by exploiting synergy between graphene and silver nano-inclusions

Fibre-reinforced polymer composites typically feature low functional (e.g., electric and thermal conductivity) and structural (e.g. mechanical strength and fracture toughness) properties in the laminate’s thickness direction. In the event of lightning strikes, overheating, and impact by foreign objects, composite laminates may suffer wide spread structural damage. This research explores the synergistic physical interaction between two-dimensional nanostructured (graphene nano-platelets) and, zero- or one-dimensional conductive fillers (silver nanoparticles or silver nanowires, respectively) when both are dispersed in fibre–polymer laminates. The results reveal a synergistic improvement in the through-thickness thermal conductivity that is more than the additive improvements by each constituent. Specifically, the simultaneous inclusion of graphene nano-platelets and silver nanoparticles/nanowires at a combined loading of 1 vol% resulted in approximately 40% enhancement in the through-thickness thermal conductivity while the inclusion of graphene nano-platelets alone at the same loading resulted only in 9% improvement. Similarly, the through-thickness electrical conductivity of carbon fibre/epoxy laminates incorporating graphene nano-platelets together with silver nanoparticles/nanowires was notably higher (⩾70%) than can be achieved by graphene nano-platelets alone (∼55%). These results demonstrate that the presence of nano-reinforcements exhibiting varied phonon transport and electron transfer pathways, and geometric aspect ratios promote synergistic physical interactions. Small improvements were found in the mechanical properties, including tensile, flexural or compressive properties of the carbon fibre-reinforced laminates, due to the relatively low concentrations of the nano-fillers.     

Study on thermal properties of graphene foam/graphene sheets filled polymer composites

The polymer composites composed of graphene foam (GF), graphene sheets (GSs) and pliable polydimethylsiloxane (PDMS) were fabricated and their thermal properties were investigated. Due to the unique interconnected structure of GF, the thermal conductivity of GF/PDMS composite reaches 0.56 W m⁻¹ K⁻¹, which is about 300% that of pure PDMS, and 20% higher than that of GS/PDMS composite with the same graphene loading of 0.7 wt%. Its coefficient of thermal expansion is (80–137) × 10⁻⁶/K within 25–150 °C, much lower than those of GS/PDMS composite and pure PDMS. In addition, it also shows superior thermal and dimensional stability. All above results demonstrate that the GF/PDMS composite is a good candidate for thermal interface materials, which could be applied in the thermal management of electronic devices, etc.     

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.     

Microstructure changes of polyurethane by inclusion of chemically modified carbon nanotubes at low filler contents

The surface of multi-walled carbon nanotubes (MWCNTs) was modified to introduce acidic groups in either covalent or van der Waals interaction bonding environments to establish cross-linking sites with a host polymer. Nanocomposites based on a polyurethane matrix (PU) containing chemically functionalised multi-walled carbon nanotubes (MWCNTs) have been shown to alter its mechanical performance depending on the nature of the surface functional groups on MWCNTs, which correlates to the type of bonding interaction of the surface group and also the dispersibility of MWCNTs and their influence on the domain structure of polyurethane. The stress at break for nanocomposites containing 0.25 wt% of acid-oxidised MWCNTs (MWCNT-ox), bearing covalently attached carboxylic, lactone and phenolic groups, was twice that of the native PU and Young’s Modulus for the nanocomposites increased by four times. Whereas when hemin, which contains carboxylic functionality, was immobilised to the surface of pure MWCNTs, the improvement in Young’s Modulus was only around twice that of pure PU. Differences in the disaggregation of MWCNTs into PU were observed between the samples as well as variation of the native domain structure of PU. The results also infer that the purification of MWCNTs from acid-oxidative lattice fragments (fulvic acids) is vital prior to conducting surface chemistry and polymerisation in order to ensure maximum mechanical performance enhancement in their reinforcement of the host polymer.     

Preparation,characterization and properties of polycaprolactone diol-functionalized multi-walled carbon nanotube/thermoplastic polyurethane composite

Multi-walled carbon nanotubes (MWCNTs) were chemically functionalized to prepare thermoplastic polyurethane (PU) composites with enhanced properties. In order to achieve a high compatibility of functionalized MWCNTs with the PU matrix, polycaprolactone diol (PCL), as one of PU’s monomers, was selectively grafted on the surface of MWCNTs (MWCNT–PCL), while carboxylic acid groups functionalized MWCNTs (MWCNT–COOH) and raw MWCNTs served as control. Both MWCNT–COOH and MWCNT–PCL improved the dispersion of MWCNTs in the PU matrix and interfacial bonding between them at 1 wt% loading fraction. The MWCNT–PCL/PU composite showed the greatest extent of improvement, where the tensile strength and modulus were 51.2% and 33.5% higher than those of pure PU respectively, without sacrificing the elongation at break. The considerable improvement in both mechanical properties and thermal stability of MWCNT–PCL/PU composite should result from the homogeneous dispersion of MWCNT–PCL in the PU matrix and strong interfacial bonding between them.     

Functional shape memory composite nanofibers with graphene oxide filler

In the present study, we prepared a series of graphene oxide (GO) filled shape memory polyurethane (SMPU) nanofibers and systematically investigated the morphological, thermal and mechanical properties, surface wettability, and the shape memory effect (SME) followed by the proposed programming model. The results show that GO can be well dispersed within the SMPU matrix, and the introduction of GO significantly improves the mechanical strength, surface wettability, and thermal stability of the SMPU. Compared with pristine SMPU nanofibrous mats, the prepared SMPU/GO nanofibrous mats have better SME and lower thermal shrinkage. When the loading amount of GO increased to 4.0 wt%, the thermal shrinkage ratio (R_ts) of composite nanofibrous mats could be as low as 4.7 ± 0.3%, while the average fixation ratio (R_f) and recovery ratio (R_r) could be as high as 92.1% and 96.5%, respectively. The study indicates that GO is a desirable reinforcing filler for preparing shape memory nanofibers with improved properties.     

Effect of ZnO nanoparticles doped graphene on static and dynamic mechanical properties of natural rubber composites

In this work, effect of ZnO nanoparticles doped graphene (Nano-ZnO–GE) on static and dynamic mechanical properties of natural rubber composites were studied. Nano-ZnO–GE was synthesized by sol–gel method and thermal treatment. With the incorporation of nano-ZnO–GE into the matrix, the mechanical properties of NR nanocomposite significantly improved over that of NR composite containing with 5 phr of conventional-ZnO. The results demonstrated that the presence of nano-ZnO on the surface of graphene sheets not only conduces to suppressing aggregation of graphene sheets but also acts as a more efficient cure-activator in vulcanization process, with the formation of excellent crosslinked network at low nano-ZnO–GE content. This work also showed that NR/Nano-ZnO–GE nanocomposites exhibited higher wet grip property and lower rolling resistance compared with NR/Conventional-ZnO composite, which makes nano-ZnO–GE very competitive for the green tire application as a substitute of conventional-ZnO, enlarging versatile practical application to prepare high-performance rubber nanocomposites.     

Structural characterization, thermal and mechanical properties of polyurethane/CoAl layered double hydroxide nanocomposites prepared via in situ polymerization

Dodecyl sulfate (DS), one kind of sulfate anion, was intercalated in the interlayer space between CoAl layered double hydroxide (CoAl-LDH) layers, and then polyurethane (PU) based nanocomposites were prepared by in situ intercalation polymerization with different amounts of the organo-modified CoAl-LDH. An exfoliated dispersion of CoAl-LDH layers in PU matrix was verified by the disappearance of the (0 0 3) reflection of the XRD results when the LDH loading was less than 2.0 wt%. Tensile testing indicated that excellent mechanical properties of PU/LDH nanocomposites were achieved. The weak alkaline catalysis of DS to polyurethane chains, combined with the dehydration and structural degradation of the LDH below 300 °C, accounted for the process of proceeded degradation as shown in TGA results. The real-time FTIR revealed that the as-prepared nanocomposites had a slower thermo-oxidative rate than neat PU from 160 °C to 340 °C, probably due to the barrier effect of LDH layers. These results suggested potential applications of CoAl-LDH as a promising flame retardant in PUs.     

Mechanical properties of graphene films enhanced by homo-telechelic functionalized polymer fillers via π–π stacking interactions

Most researches on graphene/polymer composites are focusing on improving the mechanical and electrical properties of polymers at low graphene content instead of paying attention to constructing graphene’s macroscopic structures. In current study the homo-telechelic functionalized polyethylene glycols (FPEGs) were tailored with π-orbital-rich groups (namely phenyl, pyrene and di-pyrene) via esterification reactions, which enhanced the interaction between polyethylene glycol (PEG) molecules and chemical reduced graphene oxide (RGO) sheets. The π–π stacking interactions between graphene sheets and π-orbital-rich groups endowed the composite films with enhanced tensile strength and tunable electrical conductivity. The formation of graphene network structure mediated by the FPEGs fillers via π–π stacking non-covalent interactions should account for the experimental results. The experimental investigations were also complemented with theoretical calculation using a density functional theory. Atomic force microscope (AFM), scanning electron microscope (SEM), X-ray diffraction (XRD), nuclear magnetic resonance (NMR), thermal gravimetric analysis (TGA), UV–vis and fluorescence spectroscopy were used to monitor the step-wise preparation of graphene composite films.     

Preparation of thermally reduced graphene oxide and the influence of its reduction temperature on the thermal,mechanical, flame retardant performances of PS nanocomposites

In this article, we investigated the influence of thermally reduced graphene oxides (TGOs) at different reduction temperatures on the thermal, mechanical and flame retardant performances of polystyrene (PS). The results indicated that disordered expanded layer structure can be obtained as the reduction temperature increases from 200 to 500 and 800 °C (the resulted composites are named as PS/TGO2, PS/TGO5 and PS/GTO8, respectively), which could lead to better dispersion of TGO sheets in PS matrix. Dynamic mechanical thermal analysis showed that both the storage modulus and T_g of PS/TGO5 and PS/TGO8 nanocomposites are significantly improved compared with that of neat PS. Noticeable improvement in flame retardant performance were achieved with the addition of TGO5 and TGO8, particularly TGO8, due to the removal of the functional oxygen groups from GO and the barrier effect of intumescent and loosely structure of char layers.     

Polydopamine coating layer on graphene for suppressing loss tangent and enhancing dielectric constant of poly(vinylidene fluoride)/graphene composites

Graphene with polydopamine (PDA) coating layer which displays promoted dispersibility in organic solvent was prepared through self-polymerization of dopamine onto graphene oxide (GO) and subsequent chemical reduction. The PDA coated reduced GO (RDGO) is homogeneously incorporated into poly(vinylidene fluoride) (PVDF) matrix, which exhibit a percolation threshold at 0.643 wt%. The dielectric constant of PVDF with 0.70 wt% RDGO increases to 176, about 17 times of neat PVDF. Importantly, the loss tangent is suppressed to 0.337 due to reduction of the concentration and mobility of ionizable carboxylic groups by PDA. The enhancement of dielectric constant probably rises from duplex interfacial polarization induced by graphene–semiconductor interface, and semiconductor–insulator interface. The composites displays advantages in excellent dielectric properties and good flexibility and processability guaranteed by low loading of RDGO, which is suitable for the development of dielectric materials for energy storage.