A molecular dynamics study of the mechanical properties of hydrogen functionalized graphene

Molecular dynamics simulations have been performed to investigate the mechanical properties of hydrogen functionalized graphene for H-coverages spanning the entire range from graphene (H-0%) to graphane (H-100%). We find that the Young’s modulus, tensile strength, and fracture strain of the functionalized graphene deteriorate drastically with increasing H-coverage up to about 30%. Beyond this limit the mechanical properties remain insensitive to H-coverage. While the Young’s modulus of graphane is smaller than that of graphene by 30%, the tensile strength and fracture strain show a much larger drop of about 65%. We show that this drastic deterioration in mechanical strength arises both from the conversion of sp² to sp³ bonding and due to easy-rotation of unsupported sp³ bonds. Our results suggest that the coverage-dependent deterioration of the mechanical properties must be taken into account when analyzing the performance characteristics of nanodevices fabricated from functionalized graphene sheets.     

Thermal treatment of fluorinated graphene: An in situ Raman spectroscopy study

Fluorinated graphene is a promising material for electronic applications, and its thermal properties are of high importance. Here, the resilience of fluorinated graphene to a range of temperatures is presented. The heating/cooling cycles were carried out on fluorinated monolayer, fluorinated bilayer graphene and non-fluorinated graphene as well, for comparison. In order to follow the changes of the properties of the material, in situ Raman spectra were acquired at different temperature steps. The results show that most of fluorine bonded to graphene can be removed at unusually mild temperatures, but not completely, as some fluorine can still be traced even upon heating at 800 K. Additionally, despite monolayer graphene has a higher level of fluorination than bilayer graphene, after the first heating/cooling cycle a similar amount of fluorine is found on both fluorinated graphene samples.     

Effect of hydrogenation on graphene thermal transport

We studied thermal conductivity of the three most stable hydrogenated graphene (graphane) conformers by means of non-equilibrium molecular dynamics. We estimated thermal conductivity for pristine graphene with sample length 2.1 (2.4) μm as large as κ = 745.4 ± 0.3 and 819.1 ± 0.3 W m⁻¹ K⁻¹ in the armchair and zigzag directions, respectively, in very good agreement with previous theoretical results based on the Boltzmann transport equation. In the case of the three graphane isomers we observed a dramatic κ reduction by at least one order of magnitude with respect to pristine graphene. We elucidated this reduction in terms of different phonon density of states and mean-free path distribution between graphene and graphane. The deterioration of thermal transport upon hydrogenation in graphene, could be proposed as a way to tune thermal transport in graphene for phononic applications such as thermal diodes.     

Patterning of graphene

Two-dimensional atomic sheets of carbon (graphene, graphane, etc.) are amenable to unique patterning schemes such as cutting, bending, folding and fusion that are predicted to lead to interesting properties. In this review, we present theoretical understanding and processing routes for patterning graphene and highlight potential applications. With more precise and scalable patterning, the prospects of integrating flat carbon (graphene) with curved carbon (nanotubes and half nanotubes) and programmable graphene folding are envisioned.     

Synthesis and characterization of fluorinated polyacrylate–cellulose acetate butyrate interpenetrating polymer networks

Fluorinated polyacrylates are highly hydrophobic and oleophobic. However, their poor mechanical properties prevent their development in many applications. Combination of a fluorinated polyacrylate network with a rigid cellulose acetate butyrate (CAB) network in an interpenetrating polymer network (IPN) architecture is an effective method for improving the mechanical properties of fluorinated polyacrylates. IPNs combining poly(3,3,4,4,5,5,6,6,7,7,8,8,8‐tridecafluorooctyl acrylate) (polyAcRf6) with CAB were prepared according to an in situ polymerization/crosslinking synthesis. CAB was crosslinked by addition between unmodified hydroxyl groups and the isocyanate of a pluri‐isocyanate crosslinker. The fluorinated network was obtained through free‐radical copolymerization of 3,3,4,4,5,5,6,6,7,7,8,8,8‐tridecafluorooctyl acrylate with poly(ethylene glycol dimethacrylate). The rates of formation of both networks were followed using Fourier transform infrared spectroscopy. Differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) of IPNs show a single glass transition temperature and a single mechanical relaxation temperature, which are characteristic of a high degree of interpenetration between the partner networks. The mechanical properties of IPNs are greatly improved compared with those of the single fluorinated network. CAB/polyAcRf6 IPNs were prepared, and characterized using DSC and DMTA as well as contact angle measurements for their surface properties. As hoped, the mechanical properties of such materials are much improved compared with those of the fluorinated partner alone. Copyright © 2010 Society of Chemical Industry     

Preparation and properties of fluorinated oligomer with tertiary amine structure in the UV curable coatings

A novel fluorinated oligomer with tertiary amine structure was synthesized by isophorone diisocyanate, 2‐hydroxyethyl acrylate, and fluorinated diol, which was prepared via Michael addition reaction between diethanolamine and dodecafluoroheptyl acrylate. The structure of fluorinated oligomer was confirmed by FTIR. The prepared fluorinated oligomer was added into the UV curable coatings, the influences of fluorinated oligomer on the cured degree and double bond conversion was analyzed by FTIR and gel content. The conversion ratio is increased when the fluorinated oligomer increased, which is due to the tertiary amine structure in the prepared product. The characteristics of UV cured films such as thermal properties, hydrophobicity, chemical resistance, mechanical properties, and hardness were characterized with the TGA, contact angle, and DMA. Results show that thermal stability, hydrophobicity, and chemical resistance are improved when fluorinated oligomer is introduced into the UV curable coatings. The DMA and hardness results indicated that the mechanical properties of UV cured films were improved and the flexibility decreased. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44387.     

Functionalized graphene‐reinforced rubber composite: Mechanical and tribological behavior study

A functionalized graphene, fluorinated graphene nanosheets (FGS), and SiO₂ nanoparticles as reinforcing fillers were employed to improve the mechanical properties of the solution styrene butadiene and butadiene rubber composites (SSBR‐BR). The results showed that the mechanical properties of SSBR‐BR composite filled with FGS were substantially improved than those of the unfilled and equivalent filler loaded graphene oxide (GO) and reduced graphene oxide (rGO) filled SSBR‐BR composites. It can be ascribed to the fact that the hydrophobic surface of FGS can be endowed the good dispersion in rubber matrix and stronger interfacial interaction between rubber and fillers. The tribological properties of these composites are also investigated. The results reveal that incorporation of GO, rGO, and FGS in SSBR‐BR composites can decrease antiwear properties because the existence of layered graphene promotes to tear and peel off. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44970.     

Thermal conductivity and tensile response of defective graphene: A molecular dynamics study

In this study, effects of point vacancy, Stone–Wales and bivacancy defects on thermal conductivity and tensile response of single-layer graphene sheets are studied using classical molecular dynamics (MD) simulations. Using non-equilibrium molecular dynamics (NEMD) method, we found that thermal conductivity of graphene is considerably sensitive to existence of defects. It was observed that only 0.25% concentration of defects in graphene lead to significant reduction of graphene thermal conductivity by around 50%. By applying uniaxial tensile loading, we studied the deformation process of graphene. We found that elastic modulus, tensile strength and strain at failure of graphene decrease by increase of defects concentrations. Obtained results suggest that thermal conduction in graphene is much more vulnerable to defects in comparison with mechanical properties. Reported results by this work provide an overall viewpoint concerning the intensity of defects’ effects on the graphene thermal and mechanical response.     

Tuning the electronic transport properties of grapheme through functionalisation with fluorine

We demonstrate the possibility to tune the electronic transport properties of graphene mono-layers and multi-layers by functionalisation with fluorine. For mono-layer samples, with increasing the fluorine content, we observe a transition from electronic transport through Mott variable range hopping (VRH) in two dimensions to Efros-Shklovskii VRH. Multi-layer fluorinated graphene with high concentration of fluorine show two-dimensional Mott VRH transport, whereas CF_0.28 multi-layer flakes exhibit thermally activated transport through near neighbour hopping. Our experimental findings demonstrate that the ability to control the degree of functionalisation of graphene is instrumental to engineer different electronic properties in graphene materials.     

Investigation of mechanical and thermal properties of nanostructure-doped bulk nanocomposite adhesives

ABSTRACT

In recent years, findings in nanoscience and nanotechnology have deeply influenced many disciplines including the material and mechanical sciences. Polymers including nanostructures have attracted attention as their adoptions in general engineering composites have yielded efficient results. In this study, three different two-component (epoxy-hardener) adhesives were doped with graphene nanoplatelets, graphene oxide nanoplatelets, carbon nanotube, and fullerene C60 at three different rates (0.5%, 1%, and 2% by weight) and the mechanical and thermal properties of the nanocomposite adhesives were examined. The nanocomposite adhesives’ mechanical properties were analyzed via tensile tests and thermal properties were analyzed via Differential Scanning Calorimeter (DSC) thermograms and Fourier Transform Infrared Spectroscopy (FT-IR) spectra. Results showed that doping nanostructures improve the stress-strain capacity of the adhesives. Both mechanical and thermal properties of the nanocomposite adhesives seem to change depending on the amount of nanostructure. Additionally, DSC and FT-IR curves showed an agreement with these improvements in the adhesives’ mechanical properties.     

Direct fluorination of Twaron fiber and investigation of mechanical thermal and morphological properties of high density polyethylene and Twaron fiber composites

Composites consisting of high density polyethylene (HDPE) reinforced with randomly oriented chopped Twaron fibers (both fluorinated and nonfluorinated) show a significant increase in mechanical and thermal properties. To increase the better fiber matrix adhesion, the Twaron fiber is surface fluorinated using elemental fluorine. The surface of the Twaron fiber becomes very rough and the diameter of Twaron fiber increases from ～ 12 to 14 μm after fluorination. The composites were prepared using solution method to overcome the damage of the fiber. The tensile strength and the Young's modulus increases with increasing fiber content. The tensile strength and modulus of modified fiber (fluorinated Twaron fiber) composites is much higher than nonmodified fiber composites indicating that there is better mechanical interlocking between the modified fiber and the matrix. Thermal properties obtained from DSC and DTA‐TG analysis of the fluorinated fiber composites are also improved. Contact angle measurements, as well as the surface energy measurements, indicate that the composites are more wettable and is maximum for fluorinated fiber composites i.e., surface energy for fluorinated fiber composites is highest. Crystallinity is also higher for fluorinated fiber composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Recent Progress of Graphene‐Containing Polymer Hydrogels: Preparations,Properties, and Applications

Polymer hydrogels have attracted much attention due to their mechanical, biological, and physicochemical properties. Incorporation of functional material enlarges their applications. Graphene, as a promising additive, has received great attention due to its large specific surface area, ultrahigh conductivity, strong antioxidant, thermal stability, high thermal conductivity, and good mechanical properties. In this brief review, graphene‐containing polymer hydrogels with special properties are summarized including their preparations, properties, and applications. In addition, future perspectives of polymer hydrogels containing graphene are briefly discussed.     

氟化石墨烯/水滑石改性环氧树脂胶黏剂的性能研究

采用尿素法制备CO3^2-型锌铝水滑石(ZnAlCO3-LDH),并将其与氟化石墨烯(FG)复合,制备不同质量比的FG-ZnAl-LDH,然后将其作为填料对环氧胶黏剂进行改性。通过红外光谱、X射线衍射和扫描电镜对填料进行表征,同时,研究填料添加量及质量比(FG∶LDH)对环氧树脂胶黏剂黏接性能、疏水性能和热稳定性能的影响规律。结果表明,采用尿素法制备的LDH及FG-ZnAl-LDH为二维片层结构,LDH特征峰强度随FG比例增加而逐渐降低。填料添加量为2%,FG∶LDH=1∶1时,FG-ZnAl-LDH改性环氧树脂胶黏剂的性能最佳,其剪切强度较改性前提高26.32%,水接触角提高32.9%,热分解温度提高约5℃。研究表明氟化石墨烯/水滑石的添加,可在环氧树脂胶黏剂中起到增强效果,其不仅可以提高胶黏剂的黏接强度,而且对胶黏剂的疏水性和热稳定性也具有显著的提升作用。     

Perfluoropolyether polymers by UV curing: design,synthesis and characterization

Perfluoropolyether (PFPE) structures can be functionalized with acrylic groups using appropriate hydrogenated acrylic monomers: the macromers obtained are highly reactive under UV irradiation, and fluorinated polymers can be obtained. In the first part of this work is described the synthesis of new PFPE (meth)acrylic oligomers by extending OH‐terminated fluorinated chains with urethane groups and reactive acrylic functions. The photopolymerization reaction of each product is then reported followed by the characterisation of the main thermal, mechanical and surface properties of UV‐cured coatings. The polymers have good thermal resistance and fair mechanical and chemical resistance. More interestingly they show very low refractive index and low surface tension. For these latter properties the products can be advantageously used in highly demanding applications such as photonic devices and nano‐patterning. Copyright © 2011 Society of Chemical Industry     

PE-LD/硅烷偶联剂改性石墨烯复合薄膜的制备及性能表征

将硅烷偶联剂KH-560接枝到氧化石墨烯上制得KH-560改性氧化石墨烯（KGO）,通过水合肼还原得到KH 560改性石墨烯（KG）,最后将KG和石墨烯（G）分别与低密度聚乙烯（PE-LD）熔融共混、中空吹塑成PE LD/KG复合薄膜和PE-LD/G复合薄膜。对样品的结构、形貌、光学性能、阻透性能、热性能和力学性能等进行表征。结果表明,KH-560成功接枝到KG上;KG无序度增加,KG的层间距比G增加约80 %;KG在PE-LD中分散均匀,团聚较少;G对复合薄膜的光学性能和阻透性能的增强效果优于KG;而KG对复合薄膜的热性能和力学性能的改善明显优于G;当KG的含量为0.5 %（质量分数,下同）时,PE-LD/KG复合薄膜的结晶度和弹性模量分别比纯PE-LD薄膜提高了8.4 %和63.9 %。     

Novel, water-based fluorinated polymers with excellent antigraffiti properties

In this article we describe novel, water-based, crosslinkable fluorinated polymers that form coatings with excellent antigraffiti properties. The synthesis of the binders and the surface and bulk properties of their coatings are discussed. The surface properties of these coatings are characterized in terms of their surface-free energy, as calculated from static contact angle measurements. The distribution of the fluorine atoms throughout the coating is measured by X-ray photoelectron spectroscopy (XPS). The bulk properties are studied by determining the crosslink density through dynamic mechanical thermal analysis (DMTA), and the effect of the crosslinking conditions on the crosslink density and the antigraffiti properties is discussed. The results indicate that a combined action of surface and bulk properties gives these coatings their excellent antigraffiti properties. The applicability of these polymers as protective coatings for metal and concrete surfaces are demonstrated. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL     

Progression from Graphene and Graphene Oxide to High Performance Polymer-Based Nanocomposite: A Review

In this article, various types of carbon nanofiller and modification of graphene oxide and graphene for the preparation of polymer-based nanocomposites are reviewed. Recently, polymer/graphene and graphene oxide-based materials have attracted tremendous interest due to high performance even at low filler content. The property enhancement is due to the high aspect ratio, high surface area and excellent electrical, thermal and mechanical properties of nanofiller. Different techniques have been employed to fabricate polymer/graphene and graphene oxide nanocomposite with uniform dispersion due to fine matrix/nanofiller interaction. Here we discuss the structure, properties and preparation of these nanocomposites.     

Highly filled multilayer thermoplastic/graphene conducting composite structures with high strength and thermal stability for electromagnetic interference shielding applications

Polyvinyl chloride (PVC)/graphene and poly(methyl methacrylate) (PMMA)/graphene nanocomposites were made by solution casting technique with graphene weight fractions of 1, 5, 10, 15, and 20%. Multilayer structures of the composites were made by hot compression technique to study their electromagnetic interference shielding effectiveness (EMI SE). Tensile strength, hardness, and storage modulus of the nanocomposites were studied in relation with graphene weight fraction. There has been a substantial increase in the electrical conductivity and EMI SE of the composites with 15–20% filler loading. Differential thermal analysis of the composites shows improved thermal stability with an increase in graphene loading. PMMA/graphene composites have better thermal stability, whereas PVC/graphene composites have superior mechanical properties. About 2 mm thick multilayer structures of PMMA/graphene and PVC/graphene composites show a maximum EMI SE of 21 dB and 31 dB, respectively, in the X band at 20 wt % graphene loading. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47792.     

Recent Developments in Epoxy/Graphite,Epoxy/Graphene,and Epoxy/Graphene Nanoplatelet Composites: A Comparative Review

Development in graphite, graphene, and graphene nanoplatelet composites with epoxy matrix is presented here. Graphite and its modified forms propose exclusive properties to composites. Graphene has developed as subject of huge scientific attention due to excellent electron transport, mechanical properties, and high surface area. When combined appropriately with epoxy, these atomically thin carbon sheets can expressively progress physical properties even at very small loading. Epoxy/graphene nanoplatelet nanocomposite with enhanced properties was also reported. We summarized and compared electrical, thermal, and mechanical properties of epoxy composites derived from these three nanofillers. Potential of carbon fillers with epoxy matrix is also discussed.