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.     

Effect of octa(aminopropyl) polyhedral oligomeric silsesquioxane (OapPOSS) functionalized graphene oxide on the mechanical,thermal, and hydrophobic properties of waterborne polyurethane composites

A novel graphene nanomaterial functionalized by octa(aminopropyl) polyhedral oligomeric silsesquioxane (OapPOSS) was synthesized and then confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA), Raman spectroscopy, X‐ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscopy with energy‐dispersive X‐ray spectroscopy (SEM EDX), atomic force microscopy, and X‐ray diffraction. The obtained functionalized graphene (OapPOSS‐GO) was used to reinforce waterborne polyurethane (WPU) to obtain OapPOSS‐GO/WPU nanocomposites by in situ polymerization. The thermal, mechanical, and hydrophobic properties of nanocomposites as well as the dispersion behavior of OapPOSS‐GO in the polymer were investigated by TGA, a tensile testing machine, water contact angle tests, and field emission SEM, respectively. Compared with GO/WPU and OapPOSS/WPU composites, the strong interfacial interaction between OapPOSS‐GO and the WPU matrix facilitates a much better dispersion and load transfer from the WPU matrix to the OapPOSS‐GO. It was found that the tensile strength of the OapPOSS‐GO/WPU composite film with 0.20 wt % OapPOSS‐GO exhibited a 2.5‐fold increase in tensile strength, compared with neat WPU. Better thermal stability and hydrophobicity of nanocomposites were also achieved by the addition of OapPOSS‐GO. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44440.     

Mechanical and thermal properties of hierarchical composites enhanced by pristine graphene and graphene oxide nanoinclusions

Epoxy resin nanocomposites incorporated with 0.5, 1, 2, and 4 wt % pristine graphene and modified graphene oxide (GO) nanoflakes were produced and used to fabricate carbon fiber‐reinforced and glass fiber‐reinforced composite panels via vacuum‐assisted resin transfer molding process. Mechanical and thermal properties of the composite panels—called hierarchical graphene composites—were determined according to ASTM standards. It was observed that the studied properties were improved consistently by increasing the amount of nanoinclusions. Particularly, in the presence of 4 wt % GO in the resin, tensile modulus, compressive strength, and flexural modulus of carbon fiber (glass fiber) composites were improved 15% (21%), 34% (84%), and 40% (68%), respectively. Likewise, with inclusion of 4 wt % pristine graphene in the resin, tensile modulus, compressive strength, and flexural modulus of carbon fiber (glass fiber) composites were improved 11% (7%), 30% (77%), and 34% (58%), respectively. Also, thermal conductivity of the carbon fiber (glass fiber) composites with 4% GO inclusion was improved 52% (89%). Similarly, thermal conductivity of the carbon fiber (glass fiber) composites with 4% pristine graphene inclusion was improved 45% (80%). The reported results indicate that both pristine graphene and modified GO nanoflakes are excellent options to enhance the mechanical and thermal properties of fiber‐reinforced polymeric composites and to make them viable replacement materials for metallic parts in different industries, such as wind energy, aerospace, marine, and automotive. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40826.     

Enhanced mechanical and thermal properties of biodegradable poly(butylene succinate‐co‐adipate)/graphene oxide nanocomposites via in situ polymerization

Poly(butylene succinate‐co‐butylene adipate) (PBSA)/graphene oxide (GO) nanocomposites were synthesized via in situ polymerization for the first time. Atomic force microscopy demonstrated the achievement of a single layer of GO, and transmission electron microscopy proved the homogeneous distribution of GO in the PBSA matrix. Fourier transform infrared spectroscopy results showed the successful grafting of PBSA chains onto GO. With the incorporation of 1 wt % GO, the tensile strength and flexural modulus of the PBSA were enhanced by 50 and 27%, respectively. The thermal properties characterized by differential scanning calorimetry and thermogravimetric analysis showed increases in the melting temperatures, crystallization temperatures, and thermal stability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4075–4080, 2013     

In situ polymerization of polyimide‐based nanocomposites via covalent incorporation of functionalized graphene nanosheets for enhancing mechanical,thermal, and electrical properties

In this study, we report an effective method to fabricate high‐performance polyimide (PI)‐based nanocomposites using 3‐aminopropyltriethoxysilane functionalized graphene oxide (APTSi‐GO) as the reinforcing filler. APTSi‐GO nanosheets exhibit good dispersibility and compatibility with the polymer matrix because of the strong interfacial covalent interactions. PI‐based nanocomposites with different loadings of functionalized graphene nanosheets (FGNS) were prepared by in situ polymerization and thermal imidization. The mechanical performance, thermal stability, and electrical conductivity of the FGNS/PI nanocomposites are significantly improved compared with those of pure PI by adding only a small amount of FGNS. For example, a 79% improvement in the tensile strength and a 132% increase in the tensile modulus are achieved by adding 1.5 wt % FGNS. The electrical and thermal conductivities of 1.5 wt % FGNS/PI are 2.6 × 10^?3 S/m and 0.321 W/m·K, respectively, which are ～10¹⁰ and two times higher than those of pure PI. Furthermore, the incorporation of graphene significantly improves the glass‐transition temperature and thermal stability. The success of this approach provides a good rationale for developing multifunctional and high‐performance PI‐based composite materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42724.     

Additive Manufacturing of Graphene–Hydroxyapatite Nanocomposite Structures

In this article, a powder‐bed class of additive manufacturing (AM) is incorporated into the manufacturing of graphene nanocomposite 3D structures. For AM of graphene‐based 3D structures, graphene oxide (GO)/hydroxyapatite (Hap) nanocomposite (GHN) was synthesized at different GO to Hap percentage (wt.%), including 0.2% and 0.4% to develop a printable powder. The synthesized powder was utilized in a powder‐bed AM system to fabricate 3D porous structures of GHN powder. It was shown that at layer thickness of 125 μm and core binder saturation level of 400%, the compressive mechanical strength of the samples with higher content of graphene was improved significantly.     

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.     

Effect of flake size on thermal properties of graphene oxide/poly(methyl methacrylate) composites prepared via in situ polymerization

The effect of graphene oxide (GO) flake size on thermal properties of GO/poly(methyl methacrylate) (GO/PMMA) composites prepared via in situ polymerization was investigated. Two styles of GO sheets were synthesized from different sizes of graphite powders by modified Hummers' method and GO/PMMA composites with GO of different sizes were prepared via in situ polymerization. Transmission electron microscopy verified that GO sheets produced from large graphite powders was obviously larger than that from small graphite powders. The similar number of layers and disorder degree of two types of GO sheets were proved by X‐ray diffraction and Raman, respectively. X‐ray diffraction and scanning electron microscopy results of GO/composites proved the homogenous dispersion of both two types of GO sheets in polymer matrix. Dynamic mechanical analysis and thermogravimetric analysis results showed that large GO sheets exhibit better improvement than small GO sheets in thermal properties of the composites. Compared with neat PMMA, the glass transition temperature and decomposition temperature of the composites with large GO sheets (0.20 wt %) were increased by 15.9 and 25.9 °C, respectively. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46290.     

Morphology and properties of shape memory thermoplastic polyurethane composites incorporating graphene‐montmorillonite hybrids

A novel hybrid containing graphene oxide (GO) and montmorillonite (MMT) was first synthesized by solution reaction. Then shape memory thermoplastic polyurethane (TPU) composites incorporating MMT–GO hybrid was fabricated via melt blending. Infrared spectra indicated that GO and MMT have been combined together through chemical hydrogen bonding. Tensile tests showed that MMT‐GO hybrids provided substantially greater mechanical property enhancement than using MMT or GO as filler alone. With only 0.25 wt % loading of MMT–GO hybrid (the mass ratio of MMT:GO is 1:1), there was a relatively high improvement in tensile properties of TPU composites, compared with those of TPU/GO and TPU/MMT composites at the same filler content. Thermal analysis indicated that MMT‐GO hybrids enhanced the thermal decomposition temperatures of TPU composites. Shape memory property tests showed that the shape fixing rate of TPU composites was effectively enhanced by incorporating MMT–GO hybrid. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46149.     

Preparation of polyester resin/graphene oxide nanocomposite with improved mechanical strength

Graphene oxide (GO) has attracted huge scientific interest due to its unique physical and chemical properties as well as its wide‐scale applicability including facile synthesis and high yield. Here, we report preparation of nanocomposites based on GO and unsaturated polyester resin (PE). The synthesized samples were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, thermogravimetric analysis, and tensile strength measurements. A good dispersion of the GO sheets within the resin matrix was observed from the morphological analysis. A significant enhancement in mechanical properties of the PE/GO composites is obtained at low graphene loading. Around 76% improvement of tensile strength and 41% increase of Young's modulus of the composites are achieved at 3 wt % loading of GO. Thermal analysis of the composite showed a noticeable improvement in thermal stability in comparison to neat PE. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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.     

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.     

Comparison of graphene oxide and graphitic carbon nitride filled carbon–phenolic composites: Thermomechanical properties and role of the strong electronegativity of nanofillers

Carbon–phenolic (CF–PR) composites with 0.1 wt % graphene oxide (GO) and acidified graphitic carbon nitride (ag‐C₃N₄) were synthesized and characterized to understand their thermal properties. The thermal conductivity, coefficient thermal expansion, dynamic mechanical analysis, and scanning electron microscopy were used in our experimental efforts. The results demonstrate that the ag‐C₃N₄‐filled composite had 17.17% and 54% reductions in the thermal conductivity and coefficient thermal expansion, respectively, when compared with the neat composite, although the GO‐filled showed a 8.54% decrease and a 30% increase, respectively. Furthermore, reactive molecular dynamics simulation was used to investigate the mechanisms at the atomistic level when the composites are subjected to thermal behavior. The simulated results show that the influence of GO and ag‐C₃N₄ on the thermal conductivities of the composites was different. Lowly loaded GO favored the more interfacial thermal resistance. However, the stronger electronegativity in ag‐C₃N₄ favored the formation of a vacuum zone in the matrix; this contributed to increasing the interfacial boundaries and defect scattering. The simulation results are expected to be of great help to serve as a guide for further experiments concerning the thermal properties. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46242.     

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.     

Highly flame‐retardant polyurethane foam based on reactive phosphorus polyol and limonene‐based polyol

Polyurethane foams are in general flammable and their flammability can be controlled by adding flame‐retardant (FR) materials. Reactive FR have the advantage of making strong bond within the polyurethane chains to provide excellent FR over time without compromising physico‐mechanical properties. Here, phenyl phosphonic acid and propylene oxide‐based reactive FR polyol was synthesized and used along with limonene based polyol for preparation of FR polyurethanes. All the obtained foams showed higher closed cell content (above 96%). By the addition of FR–polyol, the compressive strength of the foams showed 160% increment which could be due to reactive nature of FR–polyol. Moreover, 1.5 wt % of phosphorus (P) content reduced the self‐extinguishing time of the foam from 81 (28% weight loss) to 11.2 s (weight loss of 9.8%). Cone test showed 68.6% reduction in peak heat release rate along with 23.4% reduction in thermal heat release. The change in char structure of carbon after burning was analyzed using Raman spectra which, suggests increment in the graphitic phase of the carbon over increased concentration of phosphorus. It can be concluded from this study that phosphorous based polyol could be blended with bio‐based polyols to prepare highly FR and superior physico‐mechanical rigid polyurethane foams. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46224.     

Coupling hybrid of graphene oxide and layered zirconium phosphonate to enhance phenolic resin–based friction materials

A two‐dimensional (2D) heterogeneous coupling nanoparticle composed of graphene oxide and zirconium phosphonate (GO‐ZrP) was synthesized layer by layer in a self‐assembly manner. A rigid layer of zirconium phosphonate can inhibit the curling of graphene oxide and then improve its dispersion. The GO‐ZrP was then applied to phenolic resin–based friction materials by blending and hot pressing to improve their friction properties. The results show that the phenolic resin–based friction materials modified by GO‐ZrP possess excellent tribological, mechanical, and thermal properties. Also, the specific wear rate of the material decreased nearly fivefold with the optimal loading, while the friction coefficient was basically stable. Synergistic effects between GO and ZrP nanosheets provide good prospects for the application of 2D nanofillers in friction materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46543.     

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     

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.     

Synergistic effect of graphene oxide‐silver nanofillers on engineering performances of polyelectrolyte complex nanofiber membranes

The poor mechanical and antibacterial performance has become a big hurdle for extending the application of polyelectrolyte complex (PEC) nanofibers in various fields. In this study, chitosan/gelatin (CG) composite nanofiber system was used for portraying the synergistic enhancement of mechanical and antibacterial properties of PEC nanofiber membranes by inclusion of graphene oxide‐silver (GO‐Ag) nanofillers. In particular, the introduction of 1.5 wt % GO‐Ag has raised the elastic modulus and tensile strength of CG nanofiber membrane by 105% and 488%, respectively, which are partially attributed to the alleviated restacking of graphene sheets by the anchored AgNPs. Meanwhile, the diameters of inhibition zone against Escherichia coli and Staphylococcus aureus on LB‐agar plates induced by GO‐Ag/CG nanofiber membranes are increased by 80.5% and 50.1%, respectively, compared to that by CG membrane. The synergistic improvement of antimicrobial performance of GO‐Ag/CG may be related to the accumulation of microorganisms induced by GO. In summary, the incorporation of GO‐Ag composite nanofillers has emerged as an effective strategy for engineering PEC nanofiber membranes for potential applications in nanomedicine and tissue engineering. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46238.     

Preparation and characterization of graphene oxide reinforced PVA film with boric acid as crosslinker

PVA films were prepared through aqueous solution method, and boric acid (BA) as well as graphene oxide (GO) was added to improve the mechanical and thermal properties. It was found that 5 wt % BA could increase the tensile strength threefold (from 23.3 to 67.7 MPa), and the incorporation of 0.2 wt % GO would provide additional percentage growth of 30% (from 67.7 to 88.5 MPa). Moreover, an enhancement of thermal stability of PVA film was found when BA or GO filler was added. The reinforcement mechanisms of both BA and GO were investigated, and a competitive phenomenon that the addition of BA would influence the reinforcement effect of GO sheets was found. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42000.