Preparation of UV-curable functionalized graphene/polyurethane acrylate nanocomposite with enhanced thermal and mechanical behaviors

Functionalized graphene nanosheets (f-GNSs) were synthesized by a simple covalent functionalization of graphene with 3-methacryloxypropyl trimethoxysilane (MPTES). The results from FTIR, XPS and XRD showed that MPTES was successfully attached onto the surface of graphene. Functionalized graphene/polyurethane acrylate (f-GNS/PUA) nanocomposites were prepared by UV radiation of PUA with f-GNS. The onset thermal degradation temperature of f-GNS/PUA nanocomposite was increased by 16 °C, at an f-GNS content of 1 wt%. Meanwhile, the storage modulus and glass transition temperature of the nanocomposites were enhanced by incorporating f-GNS into the PUA. This is believed to be attributed to that the covalent functionalization of graphene can improve both the dispersion of f-GNSs in the polymer matrix and the interfacial interactions between f-GNSs and PUA.     

Improving interfacial interaction of l‐phenylalanine‐functionalized graphene nanofiller and poly(vinyl alcohol) nanocomposites for obtaining significant membrane properties: Morphology,thermal, and mechanical studies

In polymer nanocomposite synthesis, the challenges are achieving well dispersion of nanofiller and its maximum interfacial interaction with polymer matrix at low loading percent. In this study, the preparation of poly (vinyl alcohol) (PVA) nanocomposites with l ‐phenylalanine‐functionalized graphene (f‐graphene) using a simple water solution processing method is reported. Graphene layers were functionalized with l ‐phenylalanine amino acid as a biocompatible and environmentally friendly modifier. The obtained PVA/f‐graphene nanocomposite membranes were smooth, uniform, and flexible. Efficient interaction was found between f‐graphene and PVA matrix, which caused significant improvement in mechanical and thermal properties of the graphene‐based nanocomposite with homogeneous dispersion. POLYM. COMPOS., 37:1924–1935, 2016. © 2015 Society of Plastics Engineers     

Preparation and characterization of graphene/poly(vinyl alcohol) nanocomposites

Graphene (GE)‐based nanocomposites are emerging as a new class of materials that hold promise for many applications. In this article, we present a general approach for the preparation of GE/poly(vinyl alcohol) (PVA) nanocomposites. The basic strategy involved the preparation of graphite oxide from graphite, complete exfoliation of graphite oxide into graphene oxide sheets, followed by reduction to GE nanosheets, and finally, the preparation of the GE/PVA nanocomposites by a simple solution‐mixing method. The synthesized products were characterized by X‐ray diffraction, field emission scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetry, and differential scanning calorimetry analysis. The GE nanosheets were well dispersed in the PVA matrix, and the restacking of the GE sheets was effectively prevented. Because of the strong interfacial interaction between PVA and GE, which mainly resulted from the hydrogen‐bond interaction, together with the improvement in the PVA crystallinity, the mechanical properties and thermal stability of the nanocomposites were obviously improved. The tensile strength was increased from 23 MPa for PVA to 49.5 MPa for the nanocomposite with a 3.25 wt % GE loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of graphene functionalized with zinc dimethacrylate on the mechanical and thermal properties of natural rubber nanocomposites

An effective approach is developed to synthesize zinc dimethacrylate functionalized graphene (ZDMA‐GE) as reinforcing nanofiller for natural rubber (NR). The morphology and structure of ZDMA‐GE were characterized to confirm the exfoliation and functionalization of GE. The as‐prepared nanocomposites were investigated by transmission electron microscopy, mechanical analysis, crosslinked network analysis, and the analysis of thermal conductivity. The results demonstrated that there is strong interfacial interaction between GE and rubber matrix due to good dispersion and special two‐dimensional structure of GE. The crosslink density of the nanocomposites is greatly improved with the introduction of ZDMA‐GE because of the homopolymerization and graft polymerization of ZDMA. It is also noticed that the tensile strength, tear strength, and modulus at 300% elongation of NR nanocomposites with 15 phr ZDMA‐GE have been improved by 133, 42, and 174%, respectively. The thermal conductivity of nanocomposites with 40 phr ZDMA‐GE is enhanced 1.3 times as that of the pure NR. This remarkable improvement is attributed to the formation of covalent crosslinked network and ionic crosslinked network, good dispersion of GE, and efficient interfacial interaction between GE and NR matrix. This method provides the potential applications of functionalized GE in the polymer composites. POLYM. COMPOS., 36:1775–1785, 2015. © 2014 Society of Plastics Engineers     

Citric acid crosslinking of poly(vinyl alcohol)/starch/graphene nanocomposites for superior properties

Polyvinyl(alcohol)/starch/graphene nanocomposites with enhanced properties were prepared by solution mixing and casting process with the aid of glycerol as plasticizer and citric acid (CA) as crosslinker. The dispersion of graphene in water was made by sonication prior to mixing it with PVA/starch solution. The effect of varying the concentration of CA crosslinker in PVA/starch nanocomposite with 0.5 wt% of graphene was studied in detail. The structural changes, properties and morphologies were characterized by different techniques. The FTIR results revealed that the crosslinking reaction enhanced the interaction between the hydroxyl groups in PVA and/or starch and the oxygen-containing groups present on the graphene sheets. The mechanical properties were also improved by the crosslinking reaction and reinforcing with graphene. The formation of PVA crystal from solution was interrupted to a large extent by the interface at the amorphous zone of polymers and also the crosslinks between the PVA and starch polymer chains. The total crystallinity of the system was found to decrease with increase in degree of crosslinking. There was a marked increase in the thermal stability as the blend system was crosslinked with CA. CA crosslinking produced compact bulk morphology and improved the homogeneity between PVA and starch. The results of this study illustrate that citric acid can be an effective crosslinker and/or compatibilizer in PVA/starch/graphene nanocomposites for improving properties, and for this reason it is a candidate to replace non-biodegradable plastic films in food packaging sector.     

Effect of graphene loading on thermomechanical properties of poly(vinyl alcohol)/starch blend

Polymer nanocomposites based on poly(vinyl alcohol) (PVA)/starch blend and graphene were prepared by solution mixing and casting. Glycerol was used as a plasticizer and added in the starch dispersion. The uniform dispersion of graphene in water was achieved by using an Ultrasonicator Probe. The composites were characterized by FTIR, tensile properties, X‐ray diffraction (XRD), thermal analysis, and FE‐SEM studies. FTIR studies indicated probable hydrogen bonding interaction between the oxygen containing groups on graphene surface and the –OH groups in PVA and starch. Mechanical properties results showed that the optimum loading of graphene was 0.5 wt % in the blend. XRD studies indicated uniform dispersion of graphene in PVA/starch matrix upto 0.5 wt % loadings and further increase caused agglomeration. Thermal studies showed that the thermal stability of PVA increased and the crystallinity decreased in the presence of starch and graphene. FE‐SEM studies showed that incorporation of graphene increased the ductility of the composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41827.     

Eco-friendly poly(vinyl alcohol)/delaminated V2C MXene high-k nanocomposites with low dielectric loss enabled by moderate polarization and charge density at the interface

High-dielectric-constant (high-k) polymer/conductor composites with low dielectric loss are desirable for energy storage. However, high leakage currents from interfacial regions with high charge density are difficult to handle. In this work, high permittivity and low dielectric loss were achieved in poly(vinyl alcohol) (PVA)/V₂C MXene nanocomposite films fabricated by solution casting by taking advantage of the interfacial compatibility and moderate interfacial charge density of the nanocomposites. Water-soluble PVA was utilized as the polymer matrix. Delaminated V₂C MXene nanosheets with appropriate conductivity were prepared and used as the filler. The mild interface polarization of the nanocomposites was responsible for achieving favourable permittivity values. The small gap between the work functions of PVA and V₂C contributed to moderate interfacial charge density values and thus low dielectric loss values. A proportional correlation between the interfacial charge density and the conductivity of composites was also verified. The depth of charge injection from the MXene to PVA was found to be half of the interlamellar spacing of the delaminated MXene. The dependence of the electrical properties of the nanocomposites on the frequency and MXene content was also studied. The composite with 4 wt% MXene exhibited a permittivity of ~24 (16 times that of PVA) and a dielectric loss of ~0.14 (1.5 times that of PVA) at 1 kHz, as well as breakdown strength of ~31 MV m⁻¹ (63% of PVA). This work might enable environmentally friendly fabrication of promising composite dielectrics.     

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%).     

Synthesis and characterization of layer-aligned poly(vinyl alcohol)/graphene nanocomposites

Layer-aligned poly(vinyl alcohol)/graphene nanocomposites in the form of films are prepared by reducing graphite oxide in the polymer matrix in a simple solution processing. X-ray diffractions, scanning electron microscopy, Fourier-transform infrared spectroscopy, differential scanning calorimetry and thermogravimetric analysis are used to study the structure and properties of these nanocomposites. The results indicate that graphene is dispersed on a molecular scale and aligned in the poly(vinyl alcohol) (PVA) matrix and there exists strong interfacial interactions between both components mainly by hydrogen bonding, which are responsible for the change of the structures and properties of the PVA/graphene nanocomposites such as the increase in T_g and the decrease in the level of crystallization.     

Preparation and crystallization behavior of multiwalled carbon nanotubes/poly(vinyl alcohol) nanocomposites

The poly(vinyl alcohol) (PVA)‐based nanocomposites embedded with modified multiwalled carbon nanotubes (MWCNTs) were prepared. To enhance the interfacial interaction between MWCNTs and PVA, acid‐treated MWCNTs were grafted with PVA chains, compatibilizing MWCNTs and the matrix. The better dispersion of MWCNTs in PVA matrix was obtained by the introduction of MDI reaction bridges and then PVA molecules onto the surface of MWCNTs. Moreover, strong interaction between MWCNTs and PVA matrix was evidenced through the measurement results of the melting behavior, polarized Raman measurement, and nonisothermal crystallization behavior of the nanocomposites. Owing to the reinforcement of MWCNTs, the tensile strength and modulus of PVA nanocomposite containing 0.9 wt% MWCNTs were increased by 160.7 and 109.2%, respectively, compared to neat PVA. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Construction of electrostatic and π–π interaction to enhance interfacial adhesion between carbon nanoparticles and polymer matrix

In this study, an efficient method by constructing electrostatic and π–π interaction to enhance interfacial adhesion of nanocomposites was contrived. As commercial products and commonly used reinforcements, carbon nanotubes (CNTs) and graphene oxide (GO) were selected as fillers. Two kinds of interactions between carbon nanoparticles and polymer matrix were constructed by adding auxiliary comonomers (ACMs) into nanocomposites, in which one was the electrostatic interaction between quaternary ammonium cationic groups on ACMs as well as oxygen-containing groups of carbon nanoparticles, while the other was the π–π interaction between benzene rings on ACMs and conjugated structure on nanoparticles. Poly(methyl methacrylate) (PMMA) was chosen as a polymer matrix. It was found that carbon nanoparticles dramatically improved properties of nanocomposites, including thermal and mechanical performances due to the construction of electrostatic and π–π interaction on the interface. Compared with PMMA, the tensile strength of CNTs and GO reinforced nanocomposites was improved by 43.1 and 57.5%, respectively. The thermal decomposition temperature of CNTs and GO reinforced nanocomposites was improved by 21 and 23°C, respectively. Interesting and convincing results proved that the construction of multiple interactions can provide a promising method to effectively enhance interfacial adhesion of nanocomposites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48633.     

The effect of graphene nanofiller on the crystallization behavior and mechanical properties of poly(vinyl alcohol)

The effect of graphene on the crystallization behavior of graphene/poly(vinyl alcohol) (PVA) nanocomposites is investigated in terms of the heterogeneous nucleation effect using Fourier transform infrared spectroscopy and differential scanning calorimetry. Nanometer‐sized graphenes with disc‐type shape are successfully fabricated by transversal cutting of platelet carbon nanofibers, and the graphene/PVA nanocomposites are prepared by varying the concentration of graphene using a solution‐casting method. The graphene/PVA nanocomposites exhibit an enhanced degree of crystallization, increasing to 18.8% at a graphene concentration of 0.5 wt%. The graphene acts as an effective nucleating agent during the crystallization process, enhancing the degree and rate of crystallization. In addition, the graphene/PVA nanocomposites with a high graphene content have markedly improved mechanical properties. Mechanical properties, including hardness and elastic modulus, of the prepared graphene/PVA nanocomposites are analyzed using an atomic force microscopy nanoindentation method. The graphene plays a key role in increasing the crystallinity by acting as an effective nucleating agent at low concentrations (<1.0 wt%) and in enhancing the mechanical properties by acting as a nanofiller at high concentrations (>1.0 wt%).     

Duality of the interfacial thermal conductance in graphene-based nanocomposites

The thermal conductance of graphene–matrix interfaces plays a key role in controlling the thermal properties of graphene-based nanocomposites. Using atomistic simulations, we found that the interfacial thermal conductance depends strongly on the mode of heat transfer at graphene–matrix interfaces: if heat enters graphene from one side of its basal plane and immediately leaves it through the other side, the corresponding interfacial thermal conductance, G_across, is large; if heat enters graphene from both sides of its basal plane and leaves it at a position far away on its basal plane, the corresponding interfacial thermal conductance, G_non-across, is small. For a single-layer graphene immersed in liquid octane, G_across is ∼150 MW/m²K while G_non-across is ∼5 MW/m²K. G_across decreases with increasing multi-layer graphene thickness (i.e., number of layers in graphene) and approaches an asymptotic value of 100 MW/m²K for 7-layer graphenes. G_non-across increases only marginally as the graphene sheet thickness increases. Such a duality of the interface thermal conductance for different probing methods and its dependence on graphene sheet thickness can be traced ultimately to the unique physical and chemical structure of graphene materials. The ramifications of these results in areas such as the optimal design of graphene-based thermal nanocomposites are discussed.     

Synthesis and characterization of bionanocomposites of poly(lactic acid) and TiO2 nanowires by in situ polymerization

Bionanocomposites from biopolymers and inorganic nanoparticles are of great interest for packaging materials due to their enhanced physical, thermal, mechanical, and processing characteristics. In this study, poly(lactic acid) (PLA) nanocomposites with covalent bonding between TiO₂ nanowire surface and PLA chains were synthesized through in situ melt polycondensation. Molecular weight, structure, morphology, and thermal properties were characterized. Fourier transform infrared spectroscopy confirmed that PLA chains were covalently grafted onto TiO₂ nanowire surface. Transmission electron microscopy images also revealed clearly a third phase presence on the nanowires after the grafting process. Those grafted PLA chains exhibited significantly increased glass transition temperature and thermal stability, compared with pure PLA. The weight-average molecular weight of PLA/2% TiO₂ nanowire bulk nanocomposites increased by 66% compared with that of pure PLA. The electron microscopy results showed that strong interfacial interaction and homogeneous distribution were achieved between inorganic nanowires and organic PLA matrix in the bulk nanocomposites. The PLA matrix in bulk nanocomposites exhibited elevated glass transition temperature and decreased crystallization ability as the TiO₂ nanowire concentrations were increased from 0 to 2%.     

Synergistic strengthening of composite films by crosslinking graphene oxide reinforcement and poly(vinyl alcohol) with dicarboxylic acids

High‐strength plastic materials with excellent biodegradability, non‐toxicity and economically wide availability are in high demand. Herein, we demonstrate graphene oxide (GO) composite of poly(vinyl alcohol) (PVA) as a potential bioplastic material by chemical crosslinking. For a potential bioplastic material, PVA has to be addressed for its high water absorbing capacity along with improvement in tensile strength and thermal stability. These issues were addressed by enhancing the interfacial binding between PVA and GO, covalent bonds between the two being introduced by crosslinking with dicarboxylic acids, namely succinic acid (SuA) and adipic acid (AdA). Crosslinking of neat PVA with dicarboxylic acids also resulted in enhanced swelling resistance and thermal stability. The greatest improvement in tensile strength and swelling resistance was observed for a GO crosslinked with diacids due to the synergistic effect of reinforcement and crosslinking. Improvements of 225 and 234% in the tensile strength of PVA (31.19 MPa) were observed for 5% GO–PVA samples crosslinked with 6.25 mmol AdA and 7.5 mmol SuA, respectively. For the same samples, water uptake was 44 and 29%, respectively, compared to the non‐crosslinked PVA (359%). © 2017 Society of Chemical Industry     

Functionalized graphenes with polymer toughener as novel interface modifier for property-tailored polylactic acid/graphene nanocomposites

In this work, an effective strategy for engineering the interfacial compatibility between graphene and polylactic acid (PLA) was developed by manipulating the functionalization of graphene and introducing an epoxy-containing elastomer modifier. Curing between the functional groups of the modified graphene and the epoxy groups of the elastomer modifier resulted in controlled dispersion and distribution of graphene in the composite system and hence improved the interfacial adhesion between PLA and graphene. Effects of different graphene functionalization with polymer toughener on morphology, viscoelasticity, and thermal properties of the resulting PLA nanocomposites were thoroughly examined. The resulting percolated structures were the origin of the improved properties of PLA/graphene nanocomposites. The mechanism on property tailoring from interface engineering through dual modifiers are also proposed. Overall, the insight into the interface engineering between the functionalized graphene and the matrix through an elastomer modifier offers a novel way for the future design of graphene polymer nanocomposites.     

Hybrid polyvinyl alcohol/polyvinyl chloride nanocomposites reinforced with graphene-carbon nanotube for acid red environmental treatments

ABSTRACT

Hybrid polyvinyl alcohol and polyvinyl chloride/graphene and carbon nanotube nanocomposites PVA–PVC/Gr–CNTs_a-e were successfully synthesized by a solution-casting method. Mixed Gr–CNTs ratio (50%:50%) was prepared in 2, 5, 10, 15, and 20 wt% and added to the host polymers (PVA/PVC). The characterization tools for the fabricated nanocomposites show homogenous interaction between the fillers and PVA/PVC polymer matrix. A significant improvement in the thermal properties of the (PVA/PVC) matrix was observed by adding mixed fillers, even at low loadings of mixed Gr–CNTs on to the matrix. Scanning electron microscopy and transmission electron microscopy images of the prepared composites show a good dispersion of PVA–PVC and mixed Gr–CNTs and present core-shell morphology. Impressive improvement in the percentage of acid red removal using PVA–PVC/Gr–CNTs_a–e was achieved and improved with time, solution temperature, and composites mass. The process of removing acid red was described kinetically and thermodynamically. The pseudo-second-order kinetic model is the most appropriate kinetic model to describe the adsorption of acid red by PVA–PVC and PVA–PVC/Gr–CNTs_d nanocomposites from an aqueous solution. Our results offer a facile method for the removal of acid red from three types of water: red sea, tap water, and distilled water.     

The influence of dehydration on the interfacial bonding,microstructure and mechanical properties of poly(vinyl alcohol)/graphene oxide nanocomposites

The relationship between the interfacial bonding, microstructure and mechanical properties of the poly(vinyl alcohol)/graphene oxide nanocomposites (PVA/GO) has been investigated by controlling the water content through a dehydration process. The interfacial bonding in PVA/GO was predominantly by hydrogen bonds which were strongly affected by the dehydration process. Micro-voids in the microstructure formed after dehydration due to the shrinkage of the fibrils. A variety of hydrogen bonds including water–water, water–GO and water–PVA can be replaced with the strong PVA–GO interfacial bond resulting in a transition from ductile to brittle fracture. The tensile modulus and strength properties of the PVA and PVA/GO increased as the amount of residual water reduced, while the fracture strain was decreased. The surface mechanical properties of PVA/GO measured by nanoindentation showed broadly similar trends with water content as the bulk mechanical properties. However, there was a threshold value of approximately 3 wt.% water below which the surface mechanical properties decrease slightly. The indentation modulus was higher than the tensile modulus by a factor of at least three. The combined influence of the microstructure and the distribution of water in the nanocomposite is considered to be responsible for this.     

Preparation and characterization of covalently functionalized graphene using vinyl‐terminated benzoxazine monomer and associated nanocomposites with low coefficient of thermal expansion

We describe the preparation of vinyl‐terminated benzoxazine‐functionalized graphene using free radical grafting. The resulting functionalized graphene (f‐graphene) was incorporated into bis(3‐allyl‐3,4‐dihydro‐2H‐1,3‐benzoxazinyl)methane (V‐BF‐a) monomer in order that nanocomposites could be prepared. Results of scanning electron microscopy and transmission electron microscopy revealed that the sheets of f‐graphene were well dispersed throughout the matrix, and there was a strong interfacial interaction between the f‐graphene and polyV‐BF‐a. The inclusion of f‐graphene into the nanocomposites resulted in a material with a high thermal stability and a low coefficient of thermal expansion (CTE); increasing the content of f‐graphene reduced the CTE significantly more. A reduction in the CTE of up to 48% was produced by adding just 1 wt% of f‐graphene; this corresponded to an increase of 12 °C in the glass transition temperature. These results suggest that f‐graphene nanocomposites can be ‘tuned’ to give materials with both a low CTE and a high thermal stability, and that graphene composites of this type can thus be manufactured to withstand a wider range of temperatures.     

Fabrication of exfoliated graphene-based polypropylene nanocomposites with enhanced mechanical and thermal properties

Despite the great potential of graphene as the nanofiller, to achieve homogeneous dispersion remains the key challenge for effectively reinforcing the polymer. Here, we report an eco-friendly strategy for fabricating the polymer nanocomposites with well-dispersed graphene sheets in the polymer matrix via first coating graphene using polypropylene (PP) latex and then melt-blending the coated graphene with PP matrix. A ～75% increase in yield strength and a ～74% increase in the Young’s modulus of PP are achieved by addition of only 0.42 vol% of graphene due to the effective external load transfer. The glass transition temperature of PP is enhanced by ～2.5 °C by incorporating only 0.041 vol% graphene. The thermal oxidative stability of PP is also remarkably improved with the addition of graphene, for example, compared with neat PP, the initial degradation temperature is enhanced by 26 °C at only 0.42 vol% of graphene loading.