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.     

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).     

Facile preparation of graphene nanoribbon filled silicone rubber nanocomposite with improved thermal and mechanical properties

In the present study, graphene nanoribbon was prepared through unzipping the multi walled carbon nanotubes, and its reinforcing effect as a filler to the silicone rubber was further investigated. The results showed that carbon nanotubes could be unzipped to graphene nanoribbon using strong oxidants like potassium permanganate and sulfuric acid. The prepared graphene nanoribbon could homogeneously disperse within silicone rubber matrix using a simple solution mixing approach. It was also found from the thermogravimetric analysis curves that the thermal stability of the graphene nanoribbon filled silicone rubber nanocomposites improved compared to the pristine silicone rubber. Besides, with the incorporation of the nanofiller, the mechanical properties of the resulting nanocomposites were significantly enhanced, in which both the tensile stress and Young’s modulus increased by 67% and 93% respectively when the mass content of the graphene nanoribbon was 2.0 wt%. Thus it could be expected that graphene nanoribbon had large potentials to be applied as the reinforcing filler to fabricate polymers with increased the thermal and mechanical properties.     

Effect of graphene oxide on the physical,mechanical and thermo-mechanical properties of neoprene and chlorosulfonated polyethylene vulcanizates

The present research work demonstrated the effect of graphene oxide (GO) on the physical, mechanical, thermo-mechanical etc., properties of neoprene (CR) and chlorosulfonated polyethylene (CSPE) vulcanizates. CR and CSPE based nanocomposites were prepared by both solution intercalation and melt intercalation methods. The changes obtained in the morphology, cure characteristics, mechanical, thermal, thermo-mechanical properties of the rubber nanocomposites have been widely investigated. X-ray diffraction analysis (XRD) and transmission electron microscopic (TEM) analysis of the samples revealed partial exfoliated structure of GO containing rubber composites. Mechanical, thermal, cure and thermo-mechanical properties of the elastomeric nanocomposites were improved compared to the neat rubbers.     

纳米氧化锌负载氧化石墨烯/环氧树脂复合材料性能研究

氧化石墨烯(GO)和纳米氧化锌(ZnO)具有优异的性能,但在环氧树脂中容易出现团聚现象,为解决这一问题,必须对其进行表面改性。以七水合硫酸锌为原料,将ZnO负载到GO表面,通过FT-IR,XRD,SEM,EDS,TG和接触角测试,纳米ZnO均匀分散在GO基体上,并可以在不改变GO片层结构的条件下,改善GO的团聚问题的同时降低GO的亲水性。然后将ZnO负载GO与环氧树脂制备纳米ZnO负载GO/环氧复合材料。结果表明:纳米ZnO负载GO/环氧复合材料力学性能和热稳定性明显提高,当ZnO/GO加入量为0.250%(质量分数)时复合材料综合性能最佳,拉伸强度、拉伸模量、断裂伸长率和冲击强度分别比纯环氧树脂提高了99.87%,12.09%,98.35%和151.48%,吸水率比纯环氧树脂降低了81.48%。     

石墨烯微片/天然橡胶纳米复合材料的研究

目的 研究石墨烯微片的添量对石墨烯微片/天然橡胶纳米复合材料性能的影响,并对机械共混法和胶乳共混法进行比较。方法 探索复合材料的制备工艺,利用扫描电镜(SEM)、透射电镜(TEM)、拉曼光谱(RDS)、万能力学试验机等对石墨烯微片和石墨烯微片/天然橡胶纳米复合材料的形貌、结构以及性能进行分析和研究。结果 测试结果表明,石墨烯微片作为填料添加到复合材料中,使复合材料的性能得到了增强。相比纯橡胶而言,石墨烯微片(10 phr)/天然橡胶复合材料的拉伸强度增加了41.5%,热导率增加了153.3%。结论 石墨烯微片可以大幅度提高复合材料的性能,并且胶乳共混法制备的复合材料的性能要优于机械共混法制备的复合材料的性能。     

Functionalized graphene sheets filled isotactic polypropylene nanocomposites

The graphene oxide sheets (GOs) reacted with 4,4′-diphenylmethane diisocyanate (MDI) and then stearic acid to form the functionalized graphene sheets (FGs), in order to improve their compatibility with isotactic polypropylene (iPP). The iPP incorporated with FGs were adequately mixed in a Haaker mixer and then compression molded to obtain the iPP/FGs nanocomposites. The crystallization, thermal stability and mechanical properties of the nanocomposites together with iPP/graphite sheets (Gs) and iPP/GOs composites were investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and tensile test. The FGs achieved good dispersion with exfoliated and intercalated nanostructure and strong interfacial adhesion with iPP, which made the nanocomposites have a significant enhancement of thermal stability and mechanical properties at low FGs loadings.     

Thermal conductivity and dynamic mechanical analysis of NiZn ferrite nanoparticles filled thermoplastic natural rubber nanocomposite

The effect of NiZn ferrite nanoparticles on the thermal behaviour of thermoplastic natural rubber (TPNR) composite is investigated. Melt blending technique was employed to prepare TPNR matrix, which comprised of natural rubber (NR), liquid natural rubber (LNR) and high-density polyethylene (HDPE) in a ratio of 20:10:70. Dynamic mechanical analysis results show that the thermal stability of the nanocomposites enhanced with increasing filler loading. Moreover, thermal conductivity of the nanocomposites increased with filler content until 8 wt%, which is believed to be the optimum loading that formed the suitable percolated network for phonon conduction facilitation.     

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.     

Crosslinked natural rubber nanocomposites reinforced with cellulose whiskers isolated from bamboo waste: Processing and mechanical/thermal properties

Crosslinked natural rubber (NR) nanocomposites were prepared using cellulose nanowhiskers (CNWs) that were extracted from bamboo pulp residue of newspaper production, as the reinforcing phase. The coagulated NR latex containing bamboo nanowhiskers (master batch) was compounded with solid NR and vulcanizing agents using a two-roll mill and subsequently cured to introduce crosslinks in the NR phase. No evidence of micro-scaled aggregates of cellulose nanowhiskers in NR matrix was observed in Scanning Electron Microscopy (SEM) images. The addition of CNWs had a positive impact on the tensile strength, E-modulus, storage modulus, tan delta peak position and thermal stability of the crosslinked NR. Theoretical modeling of the mechanical properties showed a lower performance than predicated and therefore further process optimization and/or compatibilization are required to reach the maximum potential of these nanocomposites.     

Effect of multi-wall carbon nanotubes on the mechanical properties of natural rubber

Multi-walled carbon nanotubes (MWNTs) were used to prepare natural rubber (NR) nanocomposites. Our first effort to achieve nanostructures in MWNTs/NR nanocomposites were formed by incorporating carbonnanotubes in a polymer solution and subsequently evaporating the solvent. Using this technique, nanotubess can be dispersed homogeneously in the NR matrix in an attempt to increase the mechanical properties of these nanocomposites. The properties of the nanocomposites such as tensile strength, tensile modulus, tear strength, elongation at break and hardness were studied. Mechanical test results show an increase in the initial modulus for up to 12 times in relation to pure NR. In addition to mechanical testing, the dispersion state of the MWNTs into NR was studied by transmission electron microscopy (TEM) in order to understand the morphology of the resulting system. According to the present study, application of the physical and mechanical properties of carbon nanotubes to NR can result in rubber products which have improved mechanical, physical and chemical properties, compared with existing rubber products reinforced with carbon black or silicone.     

Improvement of impact property of natural fiber–polypropylene composite by using natural rubber and EPDM rubber

In this research, vetiver grass was used as a filler in polypropylene (PP) composite. Chemical treatment was done to modify fiber surface. Natural rubber (NR) and Ethylene Propylene Diene Monomer (EPDM) rubber at various contents were used as an impact modifier for the composites. The composites were prepared by using an injection molding. Rheological, morphological and mechanical properties of PP and PP composites with and without NR or EPDM were studied. Adding NR or EPDM to PP composites, a significant increase in the impact strength and elongation at break is observed in the PP composite with rubber content more than 20% by weight. However, the tensile strength and Young’s modulus of the PP composites decrease with increasing rubber contents. Nevertheless, the tensile strength and Young’s modulus of the composites with rubber contents up to 10% are still higher than those of PP. Moreover, comparisons between NR and EPDM rubber on the mechanical properties of the PP composites were elucidated. The PP composites with EPDM rubber show slightly higher tensile strength and impact strength than the PP composites with NR.     

Free-volume correlation with mechanical and dielectric properties of natural rubber/multi walled carbon nanotubes composites

The microstructure, mechanical strength, dielectric properties, Doppler broadening measurements and positron life time studies of the composites containing multi walled carbon nanotubes (MWCNTs) and natural rubber (NR) are investigated. The uniform distribution of MWCNTs in the elastomer medium is studied by Raman spectroscopy and the electron microscopy images show the composite’s internal microstructure. Free volume sizes and interstitial mesopore sizes of the nanocomposites are determined by positron annihilation lifetime spectroscopy (PALS). PALS investigates the influence of the nanotubes in regulating the interphase nanoscale character. Strong interfacial interaction causes an apparent reduction of the free-volume fraction of NR probably by depressing the formation of free-volume holes in the interfacial region. The mechanical percolation and percolation observed from the dielectric measurements are correlated with the life time values. It is established that the sub-nano level free volumes and nano level structure of the composites have significant roles in regulating the mechanical properties.     

Preparation of halloysite nanotubes supported 2-mercaptobenzimidazole and its application in natural rubber

To improve the antioxidative efficiency of 2-mercaptobenzimidazole (MB) and strengthen the interaction between halloysite nanotubes (HNTs) and natural rubber (NR), HNTs supported 2-mercaptobenzimidazole (HNTs-s-MB) was prepared by reacting MB with chlorosilane modified HNTs (m-HNTs). FTIR, XPS and TGA confirmed that MB was chemically bonded onto the surface of HNTs. HNTs-s-MB could be homogeneously dispersed in the NR matrix and there was a strong interfacial interaction between HNTs-s-MB and NR, leading to the better mechanical performances of NR/HNTs-s-MB nanocomposites than those of NR/HNTs nanocomposites. Based on the measurements of the thermo-oxidation activation energy of NR/HNTs-s-MB and NR/m-HNTs/MB nanocomposites containing equivalent antioxidant component, it was found that the antioxidative efficiency of HNTs-s-MB was superior to that of the corresponding low molecular MB owing to the much lower migration and volatility of HNTs-s-MB than those of MB.     

High performance natural rubber/thermally reduced graphite oxide nanocomposites by latex technology

The latex technology is an innovative alternative for the preparation of composites of natural rubber (NR) and thermally reduced graphite oxide (TRGO). To achieve an improvement of material properties is indispensable to prepare stable suspensions of TRGO. In this work the influence of two surfactants, such as sodium dodecyl sulfate (SDS), as ionic, and Pluronic F 127 as non-ionic surfactant, on the dispersion of TRGO in NR latex and the mechanical and physical properties of the composites were studied. The results showed that the SDS surfactant is ideal for preparing latex NR/TRGO nanocomposite. An optimum dispersion of the nanoparticles in the polymer matrix was achieved in the presence of SDS, as reflected in a considerable improvement of the physical and mechanical properties of the material. Thus, the nanocomposites with 3 phr of TRGO exhibited an improvement of nearly 400% in the maximum strength and an electrical percolation threshold with values around 10⁻⁶ S/cm, above the static limit.     

纳米氧化锌对液体硅橡胶导热性能的改进研究

以直接沉淀法合成了纳米氧化锌(ZnO),使用硅烷偶联剂对其进行表面改性,并制备了纳米ZnO与液体硅橡胶的复合材料,对改性前后纳米ZnO的结构进行了表征,并对复合材料的相关性能进行了研究。结果表明:通过接枝反应,硅烷偶联剂可以接枝到纳米ZnO表面,改性前后ZnO的晶型不发生变化;在较低添加量的情况下,纳米ZnO可以在一定程度上提高液体硅橡胶的力学性能,当添加量为2%时,改性前后纳米ZnO制备的液体硅橡胶复合材料的导热系数可以从0.189W/m.K分别提高到0.506W/m.K和0.61W/m.K。     

The mechanics of graphene nanocomposites: A review

The preparation and characterisation of the different forms of graphene are reviewed first of all. The different techniques that have been employed to prepare graphene such as mechanical and solution exfoliation, and chemical vapour deposition are discussed briefly. Methods of production of graphene oxide by the chemical oxidation of graphite are then described. The structure and mechanical properties of both graphene and graphene oxide are reviewed and it is shown that although graphene possesses superior mechanical properties, they both have high levels of stiffness and strength. It is demonstrated how Raman spectroscopy can be used to characterise the different forms of graphene and also follow the deformation of exfoliated graphene, with different numbers of layers, in model composite systems. It is shown that continuum mechanics can be employed to analyse the behaviour of these model composites and used to predict the minimum flake dimensions and optimum number of layers for good reinforcement. The preparation of bulk nanocomposites based upon graphene and graphene oxide is described finally and the properties of these materials reviewed. It is shown that good reinforcement is only found at relatively low levels of graphene loading and that, due to difficulties with obtaining good dispersions, challenges still remain in obtaining good mechanical properties for high volume fractions of reinforcement.     

不同维数填料对橡胶Payne效应的影响

在变外力作用下,填充橡胶的动态模量会随着应变的增加而急剧下降的现象称为Payne效应。研究填充橡胶的Payne效应可以保证橡胶制品在使用过程中的安全性和可靠性,同时获得具有良好力学性能的橡胶制品。文中通过胶乳-双辊连用法制备了炭黑/天然橡胶复合材料(RCB)、碳纳米管/天然橡胶复合材料(RCNT)和石墨烯/天然橡胶复合材料(RGE)。扫描电镜和透射电镜图像显示,该方法可以将填料均匀分散在橡胶基体中。Mooney-Rivlin曲线和动态力学性能测试显示RGE复合材料的Payne效应最强,RCB复合材料的Payne效应最弱。     

Free-standing functional graphene reinforced carbon films with excellent mechanical properties and superhydrophobic characteristic

In this work, we reported a simple method to fabricate novel free-standing stiff carbon-based composite films with excellent mechanical properties and superhydrophobic behaviors. The free-standing stiff carbon composite films based on reduced graphene oxide/glassy carbon (rGO/GC) were prepared by the combination of in-situ polymerization and carbonization process. The obtained composite films exhibited excellent mechanical properties by the addition of rGO nanosheets. It was found that incorporating 0.5 wt.% of rGO sheets in GC precursors resulted in enhancements of 99% in strength (202.6 MPa) and 184% in modulus (33.8 GPa), respectively. More interestingly, carbon nanoarrays were uniformly grown on the surface of composite films by the incorporation of rGO sheets. Superhydrophobic surfaces of carbon films were subsequently formed through functionalizing carbon nanoarrays with Trichloro(1H, 1H, 2H, 2H-perfluorodecyl)silane. Contact angle (CA) analysis suggested that superhydrophobic surfaces with a CA as high as 155° could be formed through optimizing the fabrication process.     

Ultra high molecular weight polyethylene/graphene oxide nanocomposites: Thermal,mechanical and wettability characterisation

Numerous carbon nanostructures have been investigated in the last years due to their excellent mechanical properties. In this work, the effect of the addition of graphene oxide (GO) nanoparticles to UHMWPE and the optimal %wt GO addition were investigated. UHMWPE/GO nanocomposites with different GO wt% contents were prepared and their mechanical, thermal, structural and wettability properties were investigated and compared with virgin UHMWPE. The results showed that the thermal stability, oxidative resistance, mechanical properties and wettability properties of UHMWPE were enhanced due to the addition of GO. UHMWPE/GO materials prepared with up to 0.5 wt% GO exhibited improved characteristics compared to virgin UHMWPE and nanocomposites prepared with higher GO contents.