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.     

Interface engineering for the improvement of mechanical and thermal properties of covalent functionalized graphene/epoxy composites

Functionalized reduced graphene oxide (GO)/epoxy composites are fabricated through solution mixing. GO is functionalized using 3‐amino‐1,2,4‐triazole (TZ) in presence of potassium hydroxide (KOH). KOH is expected to serve dual role as catalyst for nucleophilic addition reaction between GO and TZ, and also as reducing agent. The grafting of TZ moiety on GO is confirmed by Fourier transform infrared spectroscopy, X‐ray diffraction, and thermogravimetric analysis. The prepared composites show remarkable improvement in mechanical and thermal stability. The fracture toughness of the composites (critical stress intensity factor, K_IC) achieved from single edge notched bending testing is improved by ～111% against pure epoxy at 0.1 wt % loading of TZ functionalized GO. Further, the tensile strength and Young's modulus are improved by ～30.5% and 35%, respectively. Thermal stability of the composites as investigated by thermogravimetric analysis showed 29 °C rise in onset degradation temperature for 0.1 wt % TZ functionalized GO incorporated composite. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46124.     

Preparation and properties of dopamine reduced graphene oxide and its composites of epoxy

To improve the thermal and mechanical properties and further to expand its applications of epoxy in electronic packaging, reduced graphene oxide/epoxy composites have been successfully prepared, in which dopamine (DA) was used as reducing agent and modifier for graphene oxide (GO) to avoid the environmentally harmful reducing agents and address the problem of aggregation of graphene in composites. Further studies revealed that DA could effectively eliminate the labile oxygen functionality of GO and generate polydopamine functionalized graphene oxide (PDA‐GO) because DA would be oxidated and undergo the rearrangement and intermolecular cross‐linking reaction to produce polydopamine (PDA), which would improve the interfacial adhesion between GO and epoxy, and further be beneficial for the homogenous dispersion of GO in epoxy matrix. The effect of PDA‐GO on the thermal and mechanical properties of PDA‐GO/epoxy composites was also investigated, and the incorporation of PDA‐GO could increase the thermal conductivity, storage modulus, glass transition (T_g), and dielectric constant of epoxy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39754.     

In situ preparation of transparent polyimide nanocomposite with a small load of graphene oxide

Polyimide (PI) nanocomposites with 4,4′‐bisphenol A dianhydride, 4,4′‐oxydiphthalic anhydride, and diaminodiphenyl methane (MDA) as comonomers and functionalized with graphene oxide (GO), were prepared by in situ polymerization. Only a small amount of GO (0.03–0.12 wt %) is added to improve the mechanical properties of PI and to avoid a substantial decrease of PI transparence. The nanocomposites are characterized by FTIR, X‐ray diffraction, thermogravimetric analysis, transmission electron microscope, tensile test, and UV‐vis spectroscopy. It is demonstrated that the PI/GO composite films possess transmittance of above 80% at wavelengths of 500–800 nm when the GO content is under 0.12 wt %, while the stress intensity and Young's modulus are improved by 29 and 25%, respectively. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A novel polybenzimidazole composite modified by sulfonated graphene oxide for high temperature proton exchange membrane fuel cells in anhydrous atmosphere

A novel functional graphene with high ion exchange capacity (IEC) was prepared by grafting reaction induced by ⁶⁰Co γ‐ray irradiation using graphene oxide. Then, polybenzimidazole/radiation grafting graphene oxide (PBI/RGO) composite membranes were prepared by the solution‐casting method and doped with phosphoric acid (PA) to improve their proton conductivity. The properties of PBI/GO/PA and PBI/RGO/PA membranes including the PA doping level, chemical stability, proton conductivity and mechanical properties were evaluated and compared. The tensile strength of PBI/RGO/PA membranes (ranging from 27.3 to 38.5 MPa) increases at first and then decreases with the increase of the RGO content, and is significantly higher than that of other PA doped PBI‐based membranes. The proton conductivity of PBI/RGO‐3/PA membrane is 28.0 mS cm^?1 at 170 °C without humidity, with an increase of 72.0% compared with that of PBI/PA membrane. These results suggest that PBI/RGO/PA membranes have the potential to be used as high‐temperature proton exchange membranes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44986.     

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     

Epoxy/p‐phenylenediamine functionalized graphene oxide composites and evaluation of their fracture toughness and tensile properties

In an attempt to enhance the mechanical properties of epoxy/graphene‐based composites, the interface was engineered through the functionalization of graphene oxide (GO) sheets with p‐phenylenediamine; this resulted in p‐phenylenediamine functionalized graphene oxide (GO–pPDA). The morphology and chemical structure of the GO–pPDA sheets were studied by spectroscopic methods, thermal analysis, X‐ray diffraction, and transmission electron microscopy. The characterization results show the successful covalent functionalization of GO sheets through the formation of amide bonds. In addition, p‐phenylenediamine were polymerized on graphene sheets to form crystalline nanospheres; this resulted in a GO/poly(p‐phenylenediamine) hybrid. The mechanical properties of the epoxy/GO–pPDA composite were assessed. Although the Young's modulus showed improvement, more significant improvements were observed in the strength, fracture strain, and plane‐strain fracture toughness. These improvements were attributed to the unique microstructure and strong interface between GO–pPDA and the epoxy matrix. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43821.     

The effect of graphene dispersion on the mechanical properties of graphene/epoxy composites

The effect of dispersion state of graphene on mechanical properties of graphene/epoxy composites was investigated. The graphene sheets were exfoliated from graphite oxide (GO) via thermal reduction (thermally reduced GO, RGO). Different dispersions of RGO sheets were prepared with and without ball mill mixing. It was found that the composites with highly dispersed RGO showed higher glass transition temperature (T_g) and strength than those with poorly dispersed RGO, although no significant differences in both the tensile and flexural moduli are caused by the different dispersion levels. In particular, the T_g was increased by nearly 11 °C with the addition of 0.2 wt.% well dispersed RGO to epoxy. As expected, the highly dispersed RGO also produced one or two orders of magnitude higher electrical conductivity than the corresponding poorly dispersed RGO. Furthermore, an improved quasi-static fracture toughness (K_IC) was measured in the case of good dispersion. The poorly and highly dispersed RGO at 0.2 wt.% loading resulted in about 24% and 52% improvement in K_IC of cured epoxy thermosets, respectively. RGO sheets were observed to bridge the micro-crack and debond/delaminate during fracture process due to the poor filler/matrix and filler/filler interface, which should be the key elements of the toughening effect.     

Improved mechanical and barrier properties of starch film with reduced graphene oxide modified by SDBS

Starch is regarded as one of the most promising biopolymers to replace the fossil resources. However, due to the poor mechanical properties, high sensitivity to humidity, and low barrier property, the development of starch‐based materials has been limited. In this study, they improved the mechanical and barrier properties of starch film with reduced graphene oxide (RGO) modified by sodium dodecyl benzene sulfonate (SDBS). The hydrophilia of modified RGO (r‐RGO) was improved and result in a good dispersion in oxidized starch (OS) matrix. The tensile strength of the r‐RGO‐4/OS film increased to 58.5 MPa which was more than three times of the OS film (17.2 MPa). Besides, both the water vapor and oxygen barrier properties of r‐RGO/OS film were improved greatly compared with OS and GO/OS films. Moreover, the r‐RGO/OS film could protect against UV light effectively due to its lightproof performance. In conclusion, the r‐RGO/OS composite film has great potential applications in packaging industry. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44910.     

Mechanical and thermal properties of biphenyldiol formaldehyde resin/gallic acid epoxy composites enhanced by graphene oxide

In this study, the gallic acid‐based epoxy resin (GA‐ER) and alkali‐catalysed biphenyl‐4,4′‐diol formaldehyde resin (BPFR) are synthesized. Glass fibre‐reinforced GA‐ER/BPFR composites are prepared. Graphene oxide (GO) is used to improve the mechanical and thermal properties of GA‐ER/BPFR composites. Dynamic mechanical properties and thermal, mechanical, and electrical properties of the composites with different GO content are characterized. The results demonstrate that GO can enhance the mechanical and thermal properties of the composites. The glass transition temperature, T_g, of the BPFR/GA‐ER/GO composites is 20.7°C higher than the pure resin system, and the 5% weight loss temperature, T_d5, is enhanced approximately 56.6°C. When the BPFR: GA‐ER mass ratio is at 4 : 6 and GO content is 1.0–1.2 wt %, the tensile and impact strengths of composites are 60.97 MPa and 32.08 kJ/m² higher than the pure resin composites, respectively. BPFR/GA‐ER composites have better mechanical properties, and can replace common BPA epoxy resins in the fabrication of composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42637.     

Thermal,electrical, and dielectric properties of reduced graphene oxide–polyaniline nanotubes hybrid nanocomposites synthesized by in situ reduction and varying graphene oxide concentration

In this study, reduced graphene oxide (RGO) has been introduced as conductive filler within polyaniline (PAni) nanotubes (PAniNTs) by in situ chemical reduction method to enhance the properties of PAniNTs. The effect of varied concentration of in situ reduced GO on the structural, thermal, electrical, and dielectric properties of RGO–PAniNTs nanocomposites have been investigated by high resolution transmission electron microscope, X‐ray diffraction, Fourier transform infrared, thermogravimetric analysis, I–V characteristics, and impedance analyzer. The enhanced thermal stability of the nanocomposites has been analyzed from the derivative thermogravimetric curves in terms of onset and rapid decomposition temperature. The transport mechanisms have been studied by fitting the nonlinear I–V characteristics to the Kaiser model. The dielectric relaxation phenomena have been investigated by permittivity and modulus formalisms. Characteristic relaxation frequency of RGO–PAniNTs nanocomposites shifts toward higher frequency with increasing RGO concentration indicating a distribution in conductivity relaxation. The distribution of relaxation time has been studied by fitting the imaginary modulus spectra of the nanocomposites to Bergman modified KWW function. The ac conductivity spectra are fitted to the Jonscher's power law equation and enhanced conductivity value of 1.26 × 10⁻³ S cm⁻¹ is obtained for 40 wt % of RGO compared to 1.22 × 10⁻⁴ S cm⁻¹ for PAniNTs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45883.     

Mechanical and piezo‐resistive properties of styrene–butadiene–styrene copolymer covalently modified with graphene/styrene–butadiene–styrene composites

As novel piezoelectric materials, carbon‐reinforced polymer composites exhibit excellent piezoelectric properties and flexibility. In this study, we used a styrene–butadiene–styrene triblock copolymer covalently grafted with graphene (SBS‐g‐RGO) to prepare SBS‐g‐RGO/styrene–butadiene–styrene (SBS) composites to enhance the organic solubility of graphene sheets and its dispersion in composites. Once exfoliated from natural graphite, graphene oxide was chemically modified with 1,6‐hexanediamine to functionalize with amino groups (GO–NH₂), and this was followed by reduction with hydrazine [amine‐functionalized graphene oxide (RGO–NH₂)]. SBS‐g‐RGO was finally obtained by the reaction of RGO–NH₂ and maleic anhydride grafted SBS. After that, X‐ray diffraction, X‐ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, and other methods were applied to characterize SBS‐g‐RGO. The results indicate that the SBS molecules were grafted onto the graphene sheets by covalent bonds, and SBS‐g‐RGO was dispersed well. In addition, the mechanical and electrical conductivity properties of the SBS‐g‐RGO/SBS composites showed significant improvements because of the excellent interfacial interactions and homogeneous dispersion of SBS‐g‐RGO in SBS. Moreover, the composites exhibited remarkable piezo resistivity under vertical compression and great repeatability after 10 compression cycles; thus, the composites have the potential to be applied in sensor production. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46568.     

Preparation and characterization of graphene‐agar and graphene oxide‐agar composites

Biodegradable counterparts of petro plastics for packaging applications are highly desired due to environmental considerations. Agar can be a potential material due to its availability and biodegradability. However, moderate mechanical strength and thermal stability, in addition to poor resistance against water, needs to be addressed before agar can be commercially implemented as packaging material. As a step toward this objective, graphene oxide (GO) and reduced GO (RGO) were incorporated in agar and were solution casted in the form of films. The tensile strength was increased by 118.4% and 69.4% at 2% GO and 2% RGO loading, respectively. Higher interfacial bonding between GO and agar compared to that of RGO and agar was attributed for the observed mechanical properties. Resistance to swelling and hydrophobicity (contact angle) of the composite were improved as well when compared to pure agar. The tensile strength and the contact angle values were however, decreased after the addition of 2% GO and 2% RGO. The morphological investigation showed that the formation of pores at higher concentration of reinforcement was the contributing factor for the decrease in tensile strength. No significant change in thermal properties was observed. The transmittance value was reduced to 0% after the incorporation of GO and RGO. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45085.     

Incorporation of hyperbranched polyamide‐functionalized graphene oxide into epoxy for improving interfacial and mechanical properties

The incorporation of hyperbranched polyamide‐functionalized graphene oxide (HPA‐GO) into epoxy was proposed to improve the interfacial and mechanical properties. Benefiting from improved dispersion and strengthened interfacial interaction, epoxy composites with HPA‐GO showed significant improvements in mechanical and thermomechanical properties at low GO loading. The interaction at the HPA‐GO/epoxy interface was investigated to confirm the occurrence of chemical bonding. Strong interfacial bonding improved the stress transfer and distribution of HPA‐GO/epoxy interface. Accordingly, the overall strength of epoxy composites was effectively improved on account of the uniform dispersion of HPA‐GO and interfacial chemical interaction between HPA‐GO and epoxy. Compared with neat epoxy resin, the inclusion of 0.10 wt% HPA‐GO led to 310.5 and 37.2% increase in impact strength and tensile strength, respectively. © 2019 Society of Chemical Industry     

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     

Effects of crosslinking agents on the physical properties of polyimide/amino‐functionalized graphene oxide hybrid films

The effects of crosslinking agents (crosslinkers) on polyimide (PI)/graphene oxide (GO) hybrid films were extensively investigated. The surface of GO was modified with amino groups using 4‐aminobenzylamine to improve compatibility with pyromellitic dianhydride/4,4′‐oxydianiline PI, and two kinds of crosslinkers were used: tris(4‐aminophenyl)amine and 1,3,5‐triazine‐2,4,6‐triamine (melamine). The mechanical, thermal and optical properties of the PI hybrid films were investigated. In particular, the transparency and physical properties of the PI hybrid films containing amino‐functionalized GO with homogeneous dispersion were improved. As the content of the crosslinker increased, a crosslinking network was formed between the PI chains, and the stiffness of the hybrid films was increased. The glass transition temperature, heat resistance and mechanical properties were also enhanced. The PI hybrids prepared with a rigid crosslinker exhibited higher optical transparency due to the reduction of the intermolecular charge transfer interactions with increasing interchain spacing between the PI chains. © 2018 Society of Chemical Industry     

Thermal and mechanical properties of liquid silicone rubber composites filled with functionalized graphene oxide

To improve the thermal and mechanical properties of liquid silicone rubber (LSR) for application, the graphene oxide (GO) was proposed to reinforce the LSR. The GO was functionalized with triethoxyvinylsilane (TEVS) by dehydration reaction to improve the dispersion and compatibility in the matrix. The structure of the functionalized graphene oxide (TEVS‐GO) was evaluated by Thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectra, X‐ray diffraction (XRD), and energy dispersive X‐ray spectroscopy (EDX). It was found that the TEVS was successfully grafted on the surface of GO. The TEVS‐GO/LSR composites were prepared via in situ polymerization. The structure of the composites was verified by FTIR, XRD, and scanning electron microscopy (SEM). The thermal properties of the composites were characterized by TGA and thermal conductivity. The results showed that the 10% weight loss temperature (T₁₀) increased 16.0°C with only 0.3 wt % addition of TEVS‐GO and the thermal conductivity possessed a two‐fold increase, compared to the pure LSR. Furthermore, the mechanical properties were studied and results revealed that the TEVS‐GO/LSR composites with 0.3 wt % TEVS‐GO displayed a 2.3‐fold increase in tensile strength, a 2.79‐fold enhancement in tear strength, and a 1.97‐fold reinforcement in shear strength compared with the neat LSR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42582.     

Synthesis and properties of click coupled graphene oxide sheets with three‐dimensional macromolecules

A facile click chemistry approach to the functionalization of three‐dimensional hyperbranched polyurethane (HPU) to graphene oxide (GO) nanosheets is presented. HPU‐functionalized GO samples of various compositions were synthesized by reacting alkyne‐functionalized HPU with azide‐functionalized GO sheets. The morphological characterization of the HPU‐functionalized GO was performed using transmission electron microscopy and its chemical characterization was carried out using Fourier transform‐infrared spectroscopy, nuclear magnetic resonance spectroscopy, and X‐ray photoelectron spectroscopy. The graphene sheet surfaces were highly functionalized, leading to improved solubility in organic solvents, and consequently, enhanced mechanical, thermal, and thermoresponsive and photothermal shape memory properties. The strategy reported herein provides a very efficient method for regulating composite properties and producing high performance materials. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43358.     

Effects of graphene oxide and chemically reduced graphene oxide on the curing kinetics of epoxy amine composites

The curing kinetics of epoxy nanocomposites prepared by incorporating graphene oxide (GO) and chemically reduced graphene oxide (rGO) have been studied using isothermal and nonisothermal differential scanning calorimetry. The kinetic parameters of the curing processes in these systems have been determined by a Kamal and Sourour phenomenological model expanded by a diffusion factor. The predicted curves determined using the kinetic parameters fit well with the isothermal DSC thermograms revealing the proposed kinetic equation clearly explains the curing kinetics of the prepared epoxy amine nanocomposites. Experimental and modeling results demonstrate the presence of an accelerating effect of the GO on the cure of the resin matrix. The use of rGO instead of GO resulted in a slight acceleration reaction rate due to the reduced presence of oxidation groups in rGO. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44803.     

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