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.     

Preparation of functional reduced graphene oxide and its influence on the properties of polyimide composites

Homogeneous dispersion and strong filler–matrix interfacial interactions were vital factors for graphene for enhancing the properties of polymer composites. To improve the dispersion of graphene in the polymer matrix and enhance the interfacial interactions, graphene oxide (GO), as an important precursor of graphene, was functionalized with amine‐terminated poly(ethylene glycol) (PEG–NH₂) to prepare GO–poly(ethylene glycol) (PEG). Then, GO–PEG was further reduced to prepare modified reduced graphene oxide (rGO)–PEG with N₂H₄·H₂O. The success of the modification was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, and Raman spectroscopy. Different loadings of rGO–PEG were introduced into polyimide (PI) to produce composites via in situ polymerization and a thermal reduction process. The modification of PEG–NH₂ on the surface of rGO inhibited its reaggregation and improved the filler–matrix interfacial interactions. The properties of the composites were enhanced by the incorporation of rGO–PEG. With the addition of 1.0 wt % rGO–PEG, the tensile strength of PI increased by 81.5%, and the electrical conductivity increased by eight orders of magnitude. This significant improvement was attributed to the homogeneous dispersion of rGO–PEG and its strong filler–matrix interfacial interactions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45119.     

Improvement of the polarity of polyethylene with oxidized Fischer–Tropsch paraffin wax and its influence on the final mechanical properties

The easy, low‐cost modification of the polarity of low‐density polyethylene (LDPE) and high‐density polyethylene (HDPE) through blending with oxidized Fischer–Tropsch wax was investigated. A 10 wt % concentration of the wax increased the polar component of the total surface free energy 10 times for LDPE and 4.5 times for HDPE. Modified LDPE also had significantly higher adhesion to the polar substrate, which was represented by a crosslinked epoxy‐based resin. This behavior was not observed for HDPE. The conservation of the good mechanical properties of polyethylene was observed. The wax content had only a moderate influence on the mechanical properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1164–1168, 2005     

Thin polymer films based on poly(vinyl alcohol) containing graphene oxide and reduced graphene oxide with functional properties

In this article, the effect of the addition of graphene oxide (GO) and reduced graphene oxide (rGO) on the mechanical properties, thermal stability, and electrical conductivity of polyvinyl alcohol (PVA) has been investigated. Different weight percentages of nanofillers ranging from 0.5 to 5 wt% have been combined with PVA. The ultrasonic technique has been applied to disperse nanofillers in the PVA solution. The nanocomposite films have been prepared via solution casting technique and the dispersion of nanofillers into the PVA has been studied through optical microscopy. The microstructure, crystallization behavior, and interfacial interaction were characterized through X-ray diffraction and Fourier transform infrared spectroscopy. Differential scanning calorimetry (DSC) and thermogravimetric analysis have been applied to study the thermal properties of the prepared nanocomposites. The DSC results revealed that the crystallization temperature and melting temperature were enhanced in the presence of GO nanofiller. Besides, the tensile strength at break was improved along with the addition of GO; however, elongation at break for PVA/GO and PVA/rGO was diminished. Moreover, all specimens showed insulating behavior and the only sample was electrically conducting, which contain a high amount of rGO (5 wt%).     

Layer‐structured poly(vinyl alcohol)/graphene oxide nanocomposites with improved thermal and mechanical properties

Layer‐structured poly(vinyl alcohol)/graphene oxide nanocomposites in the form of films are prepared by simple solution processing. The structure and properties of these nanocomposites are studied using X‐ray diffractions, scanning electron microscopy, Fourier‐transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. The results indicate that graphene oxide is dispersed on a molecular scale and aligned in the poly(vinyl alcohol) matrix, and there exists strong interfacial interactions between both components, which are responsible for the significant improvement in the thermal and mechanical properties of the nanocomposites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal and mechanical properties of linear low‐density polyethylene/low‐density polyethylene/wax ternary blends

The thermal and mechanical properties of uncrosslinked three‐component blends of linear low‐density polyethylene (LLDPE), low‐density polyethylene (LDPE), and a hard, paraffinic Fischer–Tropsch wax were investigated. A decrease in the total crystallinity with an increase in both LDPE and wax contents was observed. It was also observed that experimental enthalpy values of LLDPE in the blends were generally higher than the theoretically expected values, whereas in the case of LDPE the theoretically expected values were higher than the experimental values. In the presence of higher wax content there was a good correlation between experimental and theoretically expected enthalpy values. The DSC results showed changes in peak temperature of melting, as well as peak width, with changing blend composition. Most of these changes are explained in terms of the preferred cocrystallization of wax with LLDPE. Young's modulus, yield stress, and stress at break decreased with increasing LDPE content, whereas elongation at yield increased. This is in line with the decreasing crystallinity and increasing amorphous content expected with increasing LDPE content. Deviations from this behavior for samples containing 10% wax and relatively low LDPE contents are explained in terms of lower tie chain fractions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1748–1755, 2005     

Influence of structure of amines on the properties of amines‐modified reduced graphene oxide/polyimide composites

Graphene oxide (GO), as an important precursor of graphene, was functionalized using alkyl‐amines with different structure and then reduced to prepare reduced amines grafted graphene oxide (RAGOs) by N₂H₄ · H₂O. The successful chemical amidation reaction between amine groups of alkyl‐amines and carboxyl groups of GO was confirmed by Fourier transform infrared (FTIR), X‐ray photoelectron spectroscopy (XPS), and thermal gravimetric analysis (TGA). Then RAGOs/polyimide nanocomposites were prepared via in situ polymerization and thermal curing process with different loadings of RAGOs. The modification of amine chains lead to homogenous dispersion of RAGOs in the composites and it formed strong interfacial adhesion between RAGOs and the polymer matrix. The mechanical and electrical properties of polyimide (PI) were significantly improved by incorporation of a small amount of RAGOs, the influence of structure of amines grafted on RAGOs on the enhancement effects of composites was discussed. The research results indicated that the proper structure of amine could effectively enhance the properties of composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43820.     

Preparation of graphene/poly(vinyl alcohol) nanocomposites with enhanced mechanical properties and water resistance

The control and dispersal of graphene nanosheets in polymer hosts are challenges in the development of high‐performance graphene‐based nanocomposites due to the strong interlayer cohesive energy and surface inertia. Here we report a simple and practical approach to synthesize graphene‐reinforced poly(vinyl alcohol) (PVA) composite films by incorporating graphene oxide and graphene into PVA aqueous solution. The resulting nanocomposites revealed increases of up to 212% in tensile strength and 34% in elongation at break with only 0.5 wt% graphene content. Water absorption measurements showed that the water absorption ratio of the graphene/PVA composites decreased from 105.2 to 48.8%, and the barrier properties were obviously improved. Contact angle measurements showed that the composites were hydrophobic (θ > 90°) in contrast to the highly hydrophilic (θ < 90°) pure PVA. Copyright © 2011 Society of Chemical Industry     

Reinforcement of the mechanical properties in nitrile rubber by adding graphene oxide/silicon dioxide hybrid nanoparticles

Graphene oxide (GO) and silicon dioxide (SiO₂) nanoparticles have been hybridized for improving the mechanical and dynamic mechanical properties of nitrile rubber (NBR). SiO₂ nanoparticles were homogeneously dispersed on the surface and between layers of GO, and the new hybrid nanoparticles formed (GO/SiO₂₎ had better thermal stability than GO. To evaluate the mechanical properties, GO/SiO₂/NBR nanocomposites were prepared by solution blending and mechanical solution methods. It was observed that tensile strength increased in a larger grade in GO/SiO₂/NBR nanocomposites than that in GO/NBR and SiO₂/NBR nanocomposites, while the elongation at break only changes smoothly. Moreover, dynamics measurements also indicated that the elasticity increased after adding GO/SiO₂ hybrid nanoparticles in NBR. From morphology's analysis of GO/SiO₂/NBR and GO/NBR nanocomposites, it is was conclude that the hybridization of the GO/SiO₂ was the determining factor for the reinforcement of the mechanical properties and elasticity of the NBR. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46091.     

High-density polyethylene reinforced by low loadings of electrochemically exfoliated graphene via melt recirculation approach

The purpose of the paper is to demonstrate the effectiveness of high-aspect ratio electrochemically exfoliated graphene (EEG) as a filler in high-density polyethylene (HDPE); we use an industrially viable polymer processing technique (melt blending with melt recirculation) to ensure excellent dispersion and reinforcement at low loadings. The effects of nanofiller loading were evaluated for two different HDPE grades with two different melt flow indices (MFI) based on crystallization, tensile, and rheological properties. The findings indicate improvements in mechanical properties (tensile modulus and tensile strength) for all HDPE/EEG nanocomposite samples; however, the reinforcement was more pronounced at 0.2 wt% loading, indicating a transition from excellent dispersion at lower loadings to aggregated at higher loadings. The low and high MFI HDPE/EEG nanocomposites at 0.2 wt% EEG loading displayed an improvement of 31% and 40% in tensile modulus and 19% and 33% in tensile strength, respectively. The improved mechanical response with higher MFI nanocomposites is likely due to enhanced dispersion associated with the lower melt viscosity. Similarly, the rheological results also showed maximum increase in storage and loss modulus at a loading of 0.2 wt% EEG. In conclusion, EEG can be an effective filler if proper dispersion is achieved, which is challenging at high loadings.     

In situ preparation of reduced graphene oxide reinforced acrylic rubber by self-assembly

Reduced graphene oxide reinforced acrylic rubber (ACM/RGO) was in situ prepared via self-assembly method in the presence of hydrazine hydrate as reducing agent. X-ray diffraction and X-ray photoelectron spectroscopy confirmed the chemical structure of ACM/RGO, and transmission electron microscope and scanning electron microscope demonstrated that RGO was uniformly dispersed in ACM matrix. Due to the barrier role of RGO sheets, the resistances to heat and water of ACM/RGO were obviously improved. Furthermore, the mechanical properties were also largely affected by the incorporation of RGO. With 2 parts per hundred rubber of RGO, the tensile strength and Shore A hardness of ACM/RGO reached 18.8 MPa and 73, and the elongation at break maintained at 236%. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47187.     

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.     

Chitosan–graphene oxide nanocomposites: Effect of graphene oxide nanosheets and glycerol plasticizer on thermal and mechanical properties

In this study, graphite oxide (GO) is synthesized from natural graphite flakes by the modified Hummers method. Characterization by Fourier transform infrared, X‐ray photoelectron, Raman and ultraviolet‐visible spectroscopies, X‐ray diffraction, and thermogravimetric analysis is conducted on GO to confirm the oxidation of graphite. Unplasticized and glycerol plasticized chitosan/graphene oxide (CS/GO) nanosheets nanocomposites with different GO loadings are prepared by solution casting. The combined effect of GO and glycerol on structure, thermal and mechanical properties of nanocomposite films is studied. GO nanosheets are well dispersed throughout the CS matrix due to the hydrogen bonding and electrostatic interactions between CS and GO nanosheets. The incorporation of GO within the CS matrix results in a decrease of the crystallinity, an improvement of thermal stability, and a significant enhancement of the stiffness and tensile strength that is emphasized by the glycerol. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45092.     

Polyaniline nanorod adsorbed on reduced graphene oxide nanosheet for enhanced dielectric,viscoelastic and thermal properties of epoxy nanocomposites

In this work, polyaniline nanorod adsorbed on reduced graphene oxide (P@G) hybrid filler was prepared via in situ polymerization of aniline monomer in the presence of reduced graphene oxide as template. Fourier transform infrared, X-ray diffraction, field emission scanning electron microscopy, and high-resolution transmission electron microscopy images revealed the formation of P@G hybrid. The P@G hybrid was dispersed in dichlorobenzene and then introduced into epoxy resin at different loadings. The epoxy nanocomposites containing 9 wt% P@G hybrids (E/P@G9) exhibited a maximum DC conductivity of 1.34 × 10⁻⁵ S/cm that is eight orders higher compared to pure epoxy. At 10³ Hz, a dielectric constant (ε′) of 163 was attained for E/P@G9, nearly 34 times higher than pure epoxy. A percolation threshold of 4 vol% was observed for ε′. Dynamic mechanical studies showed that significant enhancement in storage modulus values were exhibited for 3 and 5 wt% of hybrids. The glass transition temperature showed a maximum shift of 10°C to higher temperatures at 3 wt% loading of P@G hybrids (E/P@G3). The tensile strength, Young's modulus, and impact strength of the E/P@G3 nanocomposites enhanced by 19.7, 72, and 12%, respectively. The thermal stability of the epoxy nanocomposites also enhanced with the addition of P@G hybrid.     

Effect of oxygen functional groups of reduced graphene oxide on the mechanical and thermal properties of polypropylene nanocomposites

Reduced graphene oxide (rGO) with various surface structures was prepared by reducing graphene oxide (GO) with hydrazine hydrate (N₂H₄), sodium borohydride (NaBH₄) and l ‐ascorbic acid, respectively. The resulting rGO were used to fabricate rGO/polypropylene (PP) nanocomposites by a melt‐blending method. The surface structure of rGO as well as multifunctional properties of rGO/PP nanocomposites were thoroughly investigated. It was shown that rGO with highest C/O ratio could be obtained by reducing GO with N₂H₄. The crystallization behaviors, tensile strength, thermal conductivity and thermal stability of rGO/PP nanocomposites were significantly improved with the increase of C/O ratio of rGO. For example, with only 1 phr (parts per hundred PP) rGO reduced by N₂H₄, the degree of crystallinity, tensile strength, maximum heat decomposition temperature and thermal conductivity of PP nanocomposite were increased by 6.2%, 20.5%, 48.0 °C and 54.5%, respectively, compared with those of pure PP. Moreover, the thermal degradation kinetics indicated that the decomposition activation energy of rGO/PP nanocomposites could be enhanced by adding rGO with higher C/O ratio. © 2018 Society of Chemical Industry     

Rheological behavior and mechanical properties of sawdust/polyethylene composites

We have characterized the melt rheological behavior and the solid tensile properties of sawdust/polyethylene composites prepared in an internal mixer. Various concentrations (from 0 to 60 wt %) and three particle sizes have been tested, in presence of a coupling agent (maleic anhydride grafted polyethylene). In the molten state, for each particle size, a mastercurve of the complex viscosity as function of frequency can be plotted, using a shift factor depending on weight fraction. We show that the shift factors can be described by a Krieger‐Dougherty law, leading to a “universal” viscosity law of the Carreau‐Yasuda type. In the solid state, the presence of sawdust increases Young modulus in uniaxial elongation, mainly for small size particles, but reduces dramatically deformation at break and tensile strength. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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.     

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.     

Interface adjustment between poly(ethylene terephthalate) and graphene oxide in order to enhance mechanical and thermal properties of nanocomposites

There is great interest in the use of graphene and derivatives in the production of polymer nanocomposites as it provides improvements in the properties of the materials to which they are associated. Such improvements depend heavily on filler dispersion and the interaction between the nanomaterials and the matrix. This work aimed to study the compatibility of graphene oxide (GO) with a poly(ethylene terephthalate) matrix. For this, graphite was modified using Hummers method, using reaction times of 3 and 6 h. The obtained GO was functionalized with amine, amide, and magnetite groups (FGO). The effects of the oxidation degree, functionalization and concentration of the nanofillers on the dispersion and consequently on the properties of the polymer nanocomposites were evaluated. The nanocomposites were synthesized by the solid–solid deposition method followed by the melt mixing technique. It was observed that lower concentrations of nanofiller associated with the lower degree of oxidation and functionalization improved the interaction of the nanofillers with the matrix, which resulted in better mechanical properties under tensile stresses for strain at break, maximum stress, Young's modulus and toughness. It was also observed that the glass transition and crystallization of nanocomposites increased due to a nucleating effect of the nanofillers.     

Preparation and mechanical properties of composite of fibrous cellulose and maleated polyethylene

Fibrous cellulose and maleated polyethylene (FC–MPE) composites were prepared under melt mixing by maleation of polyethylene (PE) to obtain maleic anhydride (MA) grafted PE (MPE) and successive compounding of the resultant MPE with fibrous cellulose (FC). When increasing the content of added MA to 2 wt %, the grafting efficiency of MA decreases gradually to 84% and the grafted MA chains become longer. Scanning electron microscopy (SEM) reveals strong adhesion of MPE to FC in the FC–MPE composite, which is probably due to the increased compatibility between MPE and FC, in contrast to no adhesion of unmaleated PE (UPE) to FC in the FC–UPE composite. This difference in interfacial structure between the FC–MPE and FC–UPE composites results in quite different mechanical properties for them. With an increase in the FC content to 60 wt %, the tensile strength of the FC–MPE composite increases significantly and reaches 125% that of pure PE. Furthermore, the larger Young's modulus, larger bending elastic modulus, and smaller elongation of the FC–MPE composite strongly indicate effective transfer of the high tensile strength and elasticity of FC to the MPE matrix through the strong adhesion between FC and MPE. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1971–1980, 2002; DOI 10.1002/app.10428