Chemically Functionalized Graphene Nanosheets and Their Influence on Thermal Stability,Mechanical, Morphological,and Electrical Properties of Poly(methyl methacrylate)/Poly(ethylene Oxide) Blend

Poly(methyl methacrylate)/poly(ethylene oxide) (90/10) blend containing various contents of functionalized graphene was prepared through solution technique and characterized to investigate the effects of functionalized graphene content on mechanical, thermal, and electrical properties of the nanocomposites. Infrared results revealed the interaction between matrix and functionalized graphene. Electron microscopy images of the nanocomposites exhibited a good dispersion of functionalized graphene nanosheets in the blend. The incorporation of functionalized graphene significantly increased the thermal stability and mechanical properties of poly(methyl methacrylate)/poly(ethylene oxide) blend. At electrical percolation threshold achieved at functionalized graphene loading of 4.27?wt%, the conductivity of the nanocomposites was increased by more than eight orders of magnitude.     

Performance enhancement of polylactide by nanoblending with POSS and graphene oxide

We report the effect of filler modification on the properties of polylactide (PLA)‐based nanocomposites, where graphene oxide (GO) nanosheets and polyhedral oligomeric silsesquioxane (POSS) nanocages are employed as nanofillers. The organically treated nanofillers are termed as GO‐functionalized and POSS‐functionalized. The synthesis of the nanocomposites was carried out via in situ ring‐opening polymerization of lactic acid (LA). The following four naocomposite systems were prepared, characterized, and compared to achieve a better understanding of structure‐property relationship (1) PLA/GO‐functionalized, (2) PLA/POSS‐functionalized, (3) PLA/physical mixture of GO‐functionalized and POSS‐functionalized, and (4) PLA/GO‐graft‐POSS (with eight hydroxyl groups). As revealed by the thermal and mechanical (nanoindendation) characterization, that the nanocomposites having a combination of GO and POSS as nanofiller, either as physical mixture of GO‐functionalized and POSS‐functionalized or as GO‐graft‐POSS, is far more superior as compared with the nanocomposites having individually dispersed nanofillers in the PLA matrix. Observed enhancement is attributing to the synergistic effect of the nanofillers as well as better dispersion of the modified‐fillers in the matrix. POLYM. COMPOS., 35:118–126, 2014. © 2013 Society of Plastics Engineers     

Preparation of polyimide/siloxane‐functionalized graphene oxide composite films with high mechanical properties and thermal stability via in situ polymerization

An effective approach to prepare polyimide/siloxane‐functionalized graphene oxide composite films is reported. The siloxane‐functionalized graphene oxide was obtained by treating graphene oxide (GO) with 1,3‐bis(3‐aminopropyl)‐1,1,3,3‐tetra‐methyldisiloxane (DSX) to obtain DSX‐GO nanosheets, which provided a starting platform for in situ fabrication of the composites by grafting polyimide (PI) chains at the reactive sites of functional DSX‐GO nanosheets. DSX‐GO bonded with the PI matrix through amide linkage to form PI‐DSX‐GO films, in which DSX‐GO exhibited excellent dispersibility and compatibility. It is demonstrated that the obvious reinforcing effect of GO to PI in mechanical properties and thermal stability for PI‐DSX‐GO is obtained. The tensile strength of a composite film containing 1.0 wt% DSX‐GO was 2.8 times greater than that of neat PI films, and Young's modulus was 6.3 times than that of neat PI films. Furthermore, the decomposition temperature of the composite for 5% weight loss was approximately 30 °C higher than that of neat PI films. © 2015 Society of Chemical Industry     

In situ Synthesis and mechanical,thermal properties of polyimide nanocomposite film by addition of functionalized graphene oxide

Polyimide (PI) and chemical modified graphene oxide nanocomposite films are prepared by in situ polymerization from solutions of pyromellitic dianhydride and 4,4′‐oxydianiline with various amount (0.5–2 wt%) of 3‐aminopropyltriethoxysilane (APTS) functionalized graphene oxide (GO) sheets in dimethylacetamide. The APTS functionalized GO (GO‐APTS) is a versatile platform for polymer grafting, improving excellent dispersion of GO in the PI matrix, and forming strong interaction with the PI matrix. The GO‐APTS/PI nanocomposites exhibited improvement in mechanical and thermal properties by addition of a small amount of GO‐APTS. With the addition of a small amount of GO‐APTS (1.5 wt%) to PI matrix, mechanical properties with the tensile strength and Young's modulus improved by 45% and 15%, respectively. The thermal analysis showed that the thermal stability of PI was slightly enhanced by the incorporation of GO‐APTS (1.5 wt%). This approach provides a strategy for developing high performance functionalized GO‐polymer composite materials. POLYM. COMPOS., 37:907–914, 2016. © 2014 Society of Plastics Engineers     

The preparation and properties of polystyrene/functionalized graphene nanocomposite foams using supercritical carbon dioxide

In this work, polystyrene (PS)/functionalized graphene nanocomposite foams were prepared using supercritical carbon dioxide. Thermally reduced graphene oxide (TRG) and graphene oxide (GO) were incorporated into the PS. Subsequently, the nanocomposites were foamed with supercritical CO₂. The morphology and properties of the nanocomposites and the nucleation efficiency of functionalized graphene in foaming PS are discussed. Compared with GO, TRG exhibited a higher nucleation efficiency and more effective cell expansion inhibition thanks to its larger surface area and better exfoliated structure. It is suggested that the factors that have a significant influence on the nucleation efficiency of TRG and GO originate from the differences in surface properties and chemical structure. Furthermore, PS/TRG nanocomposites and their nanocomposite foams also possess good electrical properties which enable them to be used as lightweight functional materials.© 2012 Society of Chemical Industry     

In situ development of bio‐based polyurethane‐blend‐epoxy hybrid materials and their nanocomposites with modified graphene oxide via non‐isocyanate route

We developed a series of sunflower oil‐based non‐isocyanate polyurethane (NIPU)‐blend‐epoxy hybrid materials (HNIPUs) and their nanocomposites with amine‐functionalized graphene oxide (AF‐GO). Firstly, carbonated sunflower oil (CSFO) containing five‐membered cyclocarbonate groups was synthesized by the reaction of epoxidized sunflower oil with carbon dioxide (CO₂) at a pressure of 50 bar and temperature of 110 °C. Then, a series of HNIPUs were synthesized using a mixture of CSFO and a commercially available epoxy resin in various amounts (10, 20 and 30 wt% with respect to CSFO) using isophorone diamine as the curing agent. The HNIPU with 30 wt% epoxy showed the best mechanical properties. Finally, nanocomposites of 30 wt% HNIPU‐based composition were prepared with various amounts of AF‐GO (0.3, 0.6 and 1.0 wt%) and were characterized using Fourier transform infrared and ¹H NMR spectroscopies, X‐ray diffraction and scanning electron microscopy. These results emphasize the potentiality of this environmentally friendly approach for preparing renewable HNIPU and nanocomposite materials of high performances. © 2018 Society of Chemical Industry     

Graphene oxide-anchored reactive sulfonated copolymer via simple one pot condensation polymerization: proton-conducting solid electrolytes

A rapid and efficient post-polymerization functionalization of poly(urea-co-urethane) (PUU) onto the graphene oxide (GO) nanosheets has been developed to produce super-acidic polymer/GO hybrid nanosheets. Thus, the surface of GO nanosheets were functionalized with 3-(triethoxysilyl)propyl isocyanate (TESPIC) from hydroxyl groups to yield isocyanate functionalized graphene oxide nanosheets. Then, sulfonated polymer/GO hybrid nanosheets were prepared by condensation polymerization of isocyanate-terminated pre-polyurea onto isocyanate functionalized graphene oxide nanosheets through the formation of carbamate bonds. FTIR and TGA results indicated that TESPIC modifier agent and poly(urea-co-urethane) were successfully grafted onto the GO nanosheets. The grafting efficiency of poly(urea-co-urethane) polymer onto the GO nanosheets was estimated from TGA thermograms to be 205.9%. Also, sulfonated polymer/GO hybrid nanosheets showed a proton conductivity as high as 3.7 mS cm^?1. Modification and morphology of GO nanosheets before and after modification processes were studied by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD).     

Characterization and performance of dodecyl amine functionalized graphene oxide and dodecyl amine functionalized graphene/high‐density polyethylene nanocomposites: A comparative study

Dodecyl amine (DA) functionalized graphene oxide(DA‐GO) and dodecyl amine functionalized reduced graphene oxide (DA‐RGO) were produced by using amidation reaction and chemical reduction, then two kinds of well dispersed DA‐GO/high‐density polyethylene (HDPE) and DA‐RGO/HDPE nanocomposites were prepared by solution mixing method and hot‐pressing process. Thermogravimetric, X‐ray photoelectron spectroscopy, Fourier transforms infrared spectroscopy, X‐ray diffractions, and Raman spectroscopy analyses showed that DA was successfully grafted onto the graphene oxide surface by uncleophilic substitution and the amidation reaction, which increased the intragallery spacing of graphite oxide, resulting in the uniform dispersion of DA‐GO and DA‐RGO in the nonpolar xylene solvent. Morphological analysis of nanocomposites showed that both DA‐GO and DA‐RGO were homogeneously dispersed in HDPE matrix and formed strong interfacial interaction. Although the crystallinity, dynamic mechanical, gas barrier, and thermal stability properties of HDPE were significantly improved by addition of small amount of DA‐GO or DA‐RGO, the performance comparison of DA‐GO/HDPE and DA‐RGO/HDPE nanocomposites indicated that the reduction of DA‐GO was not necessary because the interfacial adhesion and aspect ratio of graphene sheets had hardly changed after reduction, which resulting in almost the same properties between DA‐GO/HDPE and DA‐RGO/HDPE nanocomposites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39803.     

Enhancement in Performance of Sulfonated PES Cation-Exchange Membrane by Introducing Pristine and Sulfonated Graphene Oxide Nanosheets Synthesized through Hummers and Staudenmaier Methods

Sulfonated polyether sulfone-based cation-exchange membranes are prepared by incorporating different amounts of graphene oxide and sulfonated graphene oxide nanosheets. The graphene oxide nanosheets are synthesized according to Staudenmaier and Hummer methods and functionalized using 3-mercaptopropyl trimethoxysilane. Transport properties of nanocomposite membranes including ion-exchange capacity, transport number, and conductivity as well as their thermal stabilities are enhanced by incorporating sulfonated graphene oxide rather than graphene oxide. Also, the enhancement is more significant for the nanocomposites having functionalized graphene oxide synthesized by Staudenmaier method than those by Hummers method due to higher density of active sites in the Staudenmier graphene oxides for functionalization.     

Synergetic association of grafted PLA and functionalized graphene on the properties of the designed nanocomposites

The synergetic association of poly(lactic acid) grafted with maleic anhydride (MA-g-PLA) containing 0.44 wt% of maleic anhydride and epoxy-functionalized graphene (GFe) on the properties of the designed nanocomposites was studied. Rheological, mechanical and barrier properties of PLA nanocomposites were studied using different content of epoxy-functionalized graphene and MA-g-PLA compatibilizer. The PLA/MA-g-PLA/GFe nanocomposites prepared by melt blending, containing 5 wt% of MA-g-PLA, yield a maximum in storage modulus G′ and a rheological plateau at low frequencies, with a content of epoxy-functionalized graphene comprised between 4 and 7 wt%. This phenomenon was ascribed to a pseudo-solid behavior resulting from the high degree of epoxy-functionalized graphene exfoliation due to strong interfacial interactions with PLA and epoxy-functionalized graphene. The better mechanical and barrier performances were obtained with PLA/GFe containing 10 wt% of epoxy-functionalized graphene and 5 wt% of MA-g-PLA compatibilizer. The variation of the percentage of compatibilizer showed that 5 wt% of maleated PLA was sufficient to improve the thermal, rheological, mechanical and barrier properties of the PLA nanocomposite containing 7 wt% of epoxy-functionalized graphene.     

Preparation and characterization of amidated graphene oxide and its effect on the performance of poly(lactic acid)

An improved Hummers method was used to prepare graphene oxide (GO). Then, the orthogonal experiment design methods were used to select the optimum conditions of the preparation for amidated graphene oxide (AGO) via amidation. The optimum scheme was followed by: reaction temperature 70 °C, reaction time 5 h and GO: benzohydrazide of 1:3 (g:g). The structure of AGO was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy, X-ray diffraction, and transmission electron microscope (TEM) techniques, which demonstrated that the amidation of GO was successful. Furthermore, poly(lactic acid) (PLA)/AGO nanocomposites were prepared by melt blending to improve the comprehensive performance of PLA. Mechanical properties, thermal stabilities, crystallization properties, and rheological behavior of PLA/AGO nanocomposites were investigated, which showed that the addition of 0.3 wt % of AGO increased the tensile strength, elongation-at-break, and impact strength of PLA/AGO nanocomposites by 7.68, 47.32 and 41.27%, respectively, compared with neat PLA. Scanning electron microscopy analysis showed ductile fracture of the PLA/AGO nanocomposites. TEM analysis showed that nano-AGO single layers were evenly dispersed in the PLA matrix, confirming the formation of an exfoliated nanocomposite structure. Differential scanning calorimetry demonstrated that AGO eliminated the cold crystallization of PLA matrix and improved the crystallinity of PLA by 34.1%. In all, this study provided an effective and feasible method for improving the comprehensive performance of PLA.     

Relevance of graphene oxide as nanofiller for geometrical variation in unidirectional carbon fiber/epoxy composite

Curved geometry in unidirectional CFRP (UD-CFRP) demands ideal shape optimization to attain superior performance while maintaining the desired high strength to weight ratio. Herein, the effect of graphene oxide (GO) as the potential filler to improve the mechanical and thermal properties of flat and curved specimens of UD-CFRP was investigated. The GO was synthesized using Hummer's method and introduced in the epoxy resin by wet transfer technique. Three-point and four-point bending analysis of UD-CFRP showed maximum flexural strength and modulus at 0.3 wt% GO addition in UD-CFRP. The improved interfacial adhesion of 0.3 wt% GO incorporated UD-CFRP was realized by calculating storage modulus, reinforcement efficiency factor (r), C-factor, adhesion factor, cross-linking density, and glass transition temperature (T_g) from dynamic mechanical analyzer. Fracture analysis by scanning electron microscope showed the superior interlocking in carbon fiber, and epoxy polymer at 0.3 wt% GO addition.     

Graphene and graphene oxide and their uses in barrier polymers

Currently, there is great interest in graphene‐based devices and applications because graphene has unique electronic and material properties, which can lead to enhanced material performance. Graphene may be used in a wide variety of potential applications from next‐generation transistors to lightweight and high‐strength polymeric composite materials. Graphene, which has atomic thickness and two‐dimensional sizes in the tens of micrometer range or larger, has also been considered a promising nanomaterial in gas‐ or liquid‐barrier applications because perfect graphene sheets do not allow diffusion of small gases or liquids through its plane. Recent molecular simulations and experiments have demonstrated that graphene and its derivatives can be used for barrier applications. In general, graphene and its derivatives can be applied via two major routes for barrier polymer applications. One is the transfer or coating of few‐layered, ultrathin graphene and its derivatives, such as graphene oxide (GO) and reduced graphene oxide (rGO), on polymeric substrates. The other is the incorporation of fully exfoliated GO or rGO nanosheets into the polymeric matrix. In this article, we review the state‐of‐the‐art research on the use of graphene, GO, and rGO for barrier applications, including few‐layered graphene or its derivatives in coated polymeric films and polymer nanocomposites consisting of chemically exfoliated GO and rGO nanosheets, and their gas‐barrier properties. As compared to other nanomaterials being used for barrier applications, the advantages and current limitations are discussed to highlight challenging issues for future research and the potential applications of graphene/polymer, GO/polymer, and rGO/polymer composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39628.     

Effect of incorporation of graphene oxide and graphene nanoplatelets on mechanical and gas permeability properties of poly(lactic acid) films

Nanocomposite thin films of poly(lactic acid) (PLA) were produced incorporating small amounts (0.2 to 1 wt%) of graphene oxide (GO) and graphene nanoplatelets (GNP). The films were prepared by solvent‐casting. Mechanical properties were evaluated for plasticized (by residual solvent) and unplasticized films. Plasticized nanocomposite films presented yield strength and Young's modulus about 100% higher than those of pristine PLA. For unplasticized films improvements in tensile strength and Young's modulus were about 15 and 85%, respectively. For both film types, a maximum in mechanical performance was identified for about 0.4 wt% loadings of the two filler materials tested. Permeabilities towards oxygen and nitrogen decreased, respectively, three‐ and fourfold in films loaded with both GO or GNP. The glass transition temperature showed maximum increases, in relation to unloaded PLA films, of 5 °C for 0.4 wt% GO and 7 °C for 0.4 wt% GNP, coinciding with the observed maxima in mechanical properties. Copyright © 2012 Society of Chemical Industry     

GO表面原位生长CNTs改善聚丙烯导热复合材料分散与界面形态

二维结构氧化石墨烯(GO)纳米片在高分子导热复合材料领域有良好应用前景,但常受限于片层间相互作用过大导致的局部团聚,不利于力学性能和导热性能的提高。借助GO纳米片表面和边缘提供的大量活性位点以吸附铁基催化剂,进而通过微波辅助合成方法在GO表面原位生长碳纳米管(CNTs)的策略,在数分钟内合成具有三维多层次结构的纳米杂化体(GO-CNT)。通过常规熔融共混方法,可获得GO-CNT在聚丙烯(PP)基体中良好剥离与均匀分散形态,明显不同于GO/PP复合体系中严重的局部团聚现象。均匀分散的GO-CNT对PP复合材料的力学性能和导热性能提升效果显著：在3%(质量分数)含量下,复合材料的屈服强度和热导率分别达到了38.0 MPa和0.76 W/(m·K),较纯PP增幅分别为20%和230%,明显优于传统GO改性复合材料。本研究为解决纳米片状填料在导热复合材料中的应用瓶颈提供了可行的结构设计策略和复合材料制备方法。     

Functionalized Graphene Oxide Based on Hydrogen‐Bonding Interaction in Water: Preparation and Flame‐Retardation on Epoxy Resin

A novel functionalized graphene oxide (f‐GO) decorated with phosphorus/nitrogen (P/N)‐containing molecules is fabricated using a facile water‐based procedure. The chemical structure and micro‐morphology are well characterized by a combination of experimental and theoretical methods. Reactive force field‐based molecular dynamics simulations reveal at the atomic level that the GO sheets are successfully functionalized with P‐N flame‐retardant molecules by means of hydrogen bonds. Subsequently, f‐GO with extremely low loading is introduced into epoxy resin (EP) for reducing its flammability. Thermogravimetric analysis suggests that f‐GO significantly reduces the maximum mass loss rate of EP and enhances the char‐yield during heating. Combined with the results of a microscale combustion calorimeter and limiting oxygen index, EP/f‐GO2 shows better flame retardancy than the other nanocomposites. Furthermore, the presence of 2 wt% f‐GO substantially reduces the fire hazard of EP, resulting in 29.3% decline in the peak heat release rate, as well as 73% and 65% reduction in total smoke production and rate of smoke release, respectively, according to cone calorimetric tests. Based on the analyses of the char layers, f‐GO is determined to promote the formation of a more protective phosphorus‐containing char barrier for EP during combustion, indicating an effective condensed phase flame‐retardant mechanism.     

The role of functional groups on graphene oxide in epoxy nanocomposites

The role of functional groups on the surface of graphene oxide (GO) upon its ability to reinforce an epoxy resin has been investigated. It is known that a base-washing process removes oxidative debris from as-prepared GO and reduces the number of functional groups in the material. Both as-prepared (aGO) and base-washed graphene oxide (bwGO) fillers were incorporated into an epoxy resin matrix and the mechanical properties of the different nanocomposites were investigated. The best levels of reinforcement were found with the addition of low loadings of aGO while the bwGO gave inferior levels of reinforcement at the same loading level. Raman spectroscopy was used to both assess the dispersion of the fillers and efficiency of stress transfer to the GO in the nanocomposites during deformation. It was found that for a given filler loading the aGO materials had the most uniform dispersion of filler and the largest Raman band shifts per unit strain, indicating the importance of the presence of functional groups in both dispersing the GO and giving good interfacial stress transfer in the nanocomposites.     

Polyimide/Graphene Nanocomposites with Improved Gas Barrier and Thermal Properties due to a “Dual‐Plane” Structure Effect

Graphene nanosheets are prepared by solution‐phase exfoliation of graphite and successfully incorporated with polyimide to obtain polyimide/graphene (DABPI/G) nanocomposites via in situ polymerization. Compared with those of pure DABPI, the DABPI/G nanocomposites exhibit better barrier and thermal properties. The oxygen and water vapor transmission rates of the DABPI/G (0.5 wt%) nanocomposite are 0.69 cm³ m^?2 d^?1 and 0.44 g m^?2 d^?1, respectively, which are 92 and 85% lower than those of pure DABPI. Meanwhile, the DABPI/G (0.5 wt%) nanocomposite exhibits excellent thermal stability with a T_d5% of 578 °C and a coefficient of thermal expansion of ?0.19 ppm K^?1. The excellent barrier and thermal properties of DABPI/G nanocomposites are mainly attributed to the fine dispersion and orientation of the graphene nanosheets, increased crystallinity, and low free volume of the DABPI matrix. These are the result of the “dual‐plane” structure effect, which is the synergistic orientation effect between the rigid planar molecular chains of DABPI and the nanosheets of graphene.     

In-situ polymerization and characteristic properties of the waterborne poly(siloxanes-urethane)s nanocomposites containing graphene

In this study, graphene oxide (GO) was chemically reduced into reduced GO (RGO) by using hydrazine and a series of waterborne RGO/poly(siloxane-urethane) (SWPU) nanocomposites with various amounts of RGO were synthesized through in-situ polymerization. Siloxane units were incorporated into the nanocomposites to cause the cross-linking reaction in polyurethane (PU) units. Changes in the structure of the nanocomposites were examined through X-ray diffractometry (XRD). The results revealed two broad peaks at 2θ?=?10° and 20°, indicating the existence of short-range ordering in the hard domains. The relative intensities of the two XRD peaks varied with the RGO content orderly. Additionally, thermogravimetric analysis, dynamic mechanical analysis, tensile testing, hardness measurement, and thermal conductivity analysis were conducted to investigate the thermal and mechanical properties of the nanocomposites. The results suggest that the thermal decomposition temperature (Td), dynamic glass transition temperature (Tgd), tensile strength, and Young’s modulus were at their optimal levels with 0.3 wt% of RGO, and an RGO amount greater than 0.3 wt% weakened the thermal and mechanical properties of the nanocomposites. The surface morphology of the nanocomposites was determined using a scanning electron microscope, atomic-force microscope and contact angle meter. The results suggest that surface roughness and contact angle increased considerably with RGO content. In addition, the electrical and thermal conductivities of the nanocomposites increased with increasing RGO content.     

纳米纤维素的表面修饰及对聚乳酸膜的力学性能和阻隔性能的影响

本实验通过化学水解法从农林废弃物油茶果壳中提取出油茶果壳纳米纤维素（cellulose nanocrystals, CNC）,经丁酸酐表面修饰获得丁酸酯化纳米纤维素（butyrated cellulose nanocrystals, BCNC）后,通过溶液浇铸法制备得到了BCNC/聚乳酸（PLA）复合材料,研究了CNC改性后的形貌及性能变化,以及BCNC对PLA力学性能、阻隔性能及透光率的影响。研究结果表明,经改性后,纳米纤维素的团聚现象得到改善并能稳定的分散在非极性有机溶剂中。在PLA复合材料中,BCNC对PLA有增强增韧的效果,添加5 wt%的BCNC时,PLA膜的拉伸强度提升了30.1%。添加5 wt%的BCNC,PLA复合膜的水蒸气透过率和氧气透过率分别下降了60.0%和35.0%,且仍具有较高的透光率。由于BCNC在基体中有更好的分散性和界面结合,对提升PLA力学性能和阻隔性能的效果均优于CNC。