Selective localization of reduced graphene oxides at the interface of PLA/EVA blend and its resultant electrical resistivity

Cocontinuous PLA/EVA (60/40 wt%) blends were filled with reduced graphene oxides (0.1–3 wt%) through the master batches of PLA/rGOs and EVA/rGOs, respectively. The results show that rGOs are located at the interface when the blend nanocomposites were prepared from PLA masterbatch. On the other hand, rGOs are located in EVA component when the blend nanocomposites were prepared from EVA/rGOs materbatch. The underlying mechanism for selective localization of rGOs in PLA/EVA was systematically investigated. First, theoretical prediction indicates the interface energies between two polymer components and rGOs are similar and rGOs prefer to locate at the interface of blend. Therefore, kinetic effects, including interfacial stability of rGOs and viscoelastic properties of polymer, play an important role on the selective localization of rGOs migration. Finally, The electrical resistivity measurements show that nanocomposites with rGOs locating at the interface is endowed much lower resistivity and percolation threshold compared to the blend nanocomposites with rGOs locating at EVA component. POLYM. COMPOS., 38:1982–1991, 2017. © 2015 Society of Plastics Engineers     

Influence of hydrogen functionalization on the fracture strength of graphene and the interfacial properties of graphene–polymer nanocomposite

Using molecular dynamics and classical continuum concepts, we investigated the effects of hydrogen functionalization on the fracture strength of graphene and also on the interfacial properties of graphene–polymer nanocomposite. Moreover, we developed an atomistic model to assess the temperature and strain rate dependent fracture strength of functionalized graphene along various chiral directions. Results indicate that hydrogen functionalization at elevated temperatures highly degrade the fracture strength of graphene. The functionalization also deteriorates the interfacial strength of graphene–polymer nanocomposite. Near-crack-tip stress distribution depicted by continuum mechanics can be successfully used to investigate the impact of hydrogen passivation of dangling carbon bonds on the strength of graphene. We further derived a continuum-based model to characterize the non-bonded interaction of graphene–polymer nanocomposite. These results indicate that classical continuum concepts are accurate even at a scale of several nanometers. Our work provides a remarkable insight into the fracture strength of graphene and graphene–polymer nanocomposites, which are critical in designing experimental and instrumental applications.     

Allyl-Functionalization enhanced thermally stable graphene/fluoroelastomer nanocomposites

Development of new elastomers with novel functionality has continued since their discovery in order to meet industrial and defense needs in harsh environments. The recent advance of carbon nanomaterials inspired innovative material design strategies and enable more effective production of high-performance elastomers. In this paper, the free radical initiated crosslinking reaction in graphene/fluoroelastomer nanocomposites was studied and the effects of chemical functionalization of graphene nanosheets were analyzed. It indicated that graphene oxide (GO) enhanced fluoroelastomer nanocomposites demonstrated poor high-temperature stability due to the pyrolysis at around 200 °C. In contrast, reduced graphene oxide (RGO) enhanced fluoroelastomer exhibited good thermal stability, but RGO didn't participate in the crosslinking, resulting in very limited improvement in mechanical properties. In this paper, reduced allyl functionalized graphene was studied for the first time to enhance free radical initiated elastomers. The reduced allyl functionalization of graphene was demonstrated to impart superior thermal stability and enhanced mechanical properties to the elastomer matrices. The study of vulcanization kinetics provided insights that the allyl functional groups participated in and accelerated the crosslinking. These results indicated a scalable method to incorporate the advantages of graphene into polymer matrices through free radical reaction. The discovery is very promising to be used in the industry to fabricate gaskets, o-rings, and membranes for high temperature applications.     

Morphology,thermal, mechanical,and barrier properties of graphene oxide/poly(lactic acid) nanocomposite films

To improve the physical and gas barrier properties of biodegradable poly(lactic acid) (PLA) film, two graphene nanosheets of highly functionalized graphene oxide (0.3 wt% to 0.7 wt%) and low-functionalized graphene oxide (0.5 wt%) were incorporated into PLA resin via solution blending method. Subsequently, we investigated the effects of material parameters such as loading level and degree of functionalization for the graphene nanosheets on the morphology and properties of the resultant nanocomposites. The highly functionalized graphene oxide (GO) caused more exfoliation and homogeneous dispersion in PLA matrix as well as more sustainable suspensions in THF, compared to low-functionalized graphene oxide (LFGO). When loaded with GO from 0.3 wt% to 0.7 wt%, the glass transition temperature, degree of crystallinity, tensile strength and modulus increased steadily. The GO gave rise to more pronounced effect in the thermal and mechanical reinforcement, relative to LFGO. In addition, the preparation of fairly transparent PLA-based nanocomposite film with noticeably improved barrier performance achieved only when incorporated with GO up to 0.7wt%. As a result, GO may be more compatible with hydrophilic PLA resin, compared to LFGO, resulting in more prominent enhancement of nanocomposites properties.     

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.     

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 physical properties of an epoxy nanocomposite with amine‐functionalized graphenes

Graphene, consisted of a single layer of carbon atom in a two‐dimensional lattice, has superior electrical and physical properties that promise many exciting applications. In this study, graphenes were prepared from graphite powder by chemical method and their images were investigated by TEM and SEM. To develop high performance epoxy nanocomposites with good dispersion of graphenes and strong epoxy‐graphene interfacial bonding, graphenes were amine‐functionalized and the effects of the amine‐functionalization on the curing behavior and physical properties of epoxy/graphene nanocomposites were studied. FTIR spectra confirmed the amine‐functionalization. The physical properties of the nanocomposites were investigated by DSC, DMA, TMA, and impact tester. Fracture surfaces were investigated by SEM. The physical properties of the nanocomposites could be improved considerably by the amine‐functionalization of graphenes. POLYM. ENG. SCI., 54:985–991, 2014. © 2012 Society of Plastics Engineers     

Synergetic association of grafted PLA and functionalized graphene on the properties of the designed nanocomposites

The synergetic association of poly(lactic acid) grafted with maleic anhydride (MA-g-PLA) containing 0.44 wt% of maleic anhydride and epoxy-functionalized graphene (GFe) on the properties of the designed nanocomposites was studied. Rheological, mechanical and barrier properties of PLA nanocomposites were studied using different content of epoxy-functionalized graphene and MA-g-PLA compatibilizer. The PLA/MA-g-PLA/GFe nanocomposites prepared by melt blending, containing 5 wt% of MA-g-PLA, yield a maximum in storage modulus G′ and a rheological plateau at low frequencies, with a content of epoxy-functionalized graphene comprised between 4 and 7 wt%. This phenomenon was ascribed to a pseudo-solid behavior resulting from the high degree of epoxy-functionalized graphene exfoliation due to strong interfacial interactions with PLA and epoxy-functionalized graphene. The better mechanical and barrier performances were obtained with PLA/GFe containing 10 wt% of epoxy-functionalized graphene and 5 wt% of MA-g-PLA compatibilizer. The variation of the percentage of compatibilizer showed that 5 wt% of maleated PLA was sufficient to improve the thermal, rheological, mechanical and barrier properties of the PLA nanocomposite containing 7 wt% of epoxy-functionalized graphene.     

Preparation and properties of polylactide–silica nanocomposites

Poly(lactic acid) (PLA)/SiO₂ nanocomposites were prepared via melt mixing with a Haake mixing method. To improve the dispersion of nanoparticles and endow compatibility between the polymer matrix and nanosilica, SiO₂ was surface‐modified with oleic acid (OA). The interfacial adhesion of the PLA nanocomposites was characterized by field‐emission scanning electron microscopy. The storage modulus and glass‐transition temperature values of the prepared nanocomposites were measured by dynamic mechanical thermal analysis. The linear and nonlinear dynamic rheological properties of the PLA nanocomposites were measured with a parallel‐plate rheometer. The effects of the filling content on the dispersability of the OA–SiO₂ nanoparticles in the PLA matrix, the interface adhesion, the thermomechanical properties, the rheological properties, and the mechanical properties were investigated. Moreover, the proper representation of the oscillatory viscometry results provided an alternative sensitive method to detect whether aggregation formed in the polymeric nanocomposites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Strategies for interfacial localization of graphene/polyethylene-based cocontinuous blends for electrical percolation

We have investigated melt blending approaches to interfacial localization of few-layer graphene in cocontinuous polymer blends with polyethylene as one of the components. When linear low-density polyethylene (LLDPE)/polypropylene (PP) or high-density polyethylene (HDPE)/polylactic acid (PLA) and graphene were mixed all together, graphene preferred polyethylene over PP or PLA. When PP and graphene were premixed and blended with polyethylene, some graphene was trapped at the blend interface but not enough to cover the large interfacial area. In contrast, an ultralow electrical percolation was achieved (< 0.1 vol%) in HDPE/PLA blend due to smaller interfacial area. In another approach, polystyrene was added as a tertiary minor component to HDPE/PLA blends. This continuous interfacial layer containing graphene led to a low electrical percolation threshold (< 0.2 vol%). From these investigations, we suggest general ways to reduce a percolation threshold by kinetic control of the morphology of cocontinuous polymer blends.     

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.     

Highly toughened poly(lactic acid) blends prepared by reactive blending with a renewable poly(ether-block-amide) elastomer

Renewable poly(ether-block-amide) (PEBA) elastomer was grafted with glycidyl methacrylate (GMA) to prepare PEBA-GMA, then it was melting blended with poly (lactic acid) (PLA) in an effort to achieve fully bio-based super-toughened PLA materials. The notched Izod impact strength of PLA/PEBA-GMA blend was significantly enhanced when the content of PEBA-GMA was higher than 20 wt%, and the tensile toughness was also improved. It was found a new copolymer was formed at the interface due to the reaction of the end groups ( OH,  COOH) of PLA with the epoxide group of PEBA-GMA. This greatly improves the interfacial adhesion between PLA and PEBA-GMA component, leading to finer dispersed particles of PEBA-GMA which were better wetted by the PLA matrix. Therefore, the highly enhanced notched impact strength was ascribed to the effective reactive compatibilization promoted by the interfacial reaction. This provides a new idea for preparing super tough PLA materials with bio-based elastomer, which will widely extend the application of PLA.     

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     

Fabrication of microcellular polymer/graphene nanocomposite foams

Graphene has recently gained revolutionary aspirations because of its remarkable electronic, thermal and mechanical properties. These unique properties make it promising for preparing multifunctional nanocomposites. In recent years, polymer foams based on graphene have also received increasing attention in both the scientific and industrial communities. This review presents an overview of polymer/graphene nanocomposite foams discussing the production of graphene, the polymer functionalization of graphene and different polymer/graphene foams with different properties. One of the most promising avenues is to fabricate tough and lightweight materials with superior electrical and electromagnetic interference shielding properties. Copyright © 2012 Society of Chemical Industry     

Effect of polyphosphazene elastomer on the compatibility and properties of PES/TLCP composites

In this article, the chemistry of interfacial adhesion between different additive systems has been dealt with to develop a high performance nanocomposite and in the process, a comprehensive study on the reinforcing effect of nanosilica has been carried out. The base polymer was considered as the blends of Poly ethersulfone (PES) and thermotropic liquid crystalline polymer (TLCP). A novel polymeric compatibilizer, polyphosphazene elastomer, has been utilized and the interchain crosslinking has been explained. Results of experimental investigations demonstrate that the nanofillers play an important role in reducing the interfacial tension. However, the presence of Polyphosphazene elastomer, acted as compatibilizer further reducing the interfacial tension through the inter‐molecular interaction. The nanocomposites, thus developed, have better thermal stability and improved rheological properties. In addition, it has also been observed that Polyphosphazene elastomer impart flexibility in the composite. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Effects of facile amine‐functionalization on the physical properties of epoxy/graphene nanoplatelets nanocomposites

Graphene nanoplatelets (GNPs) have excellent thermal, electrical, and mechanical properties. The incorporation of GNPs into a polymer can remarkably enhance the thermal and mechanical properties of the polymer especially when GNPs are well dispersed in the polymer matrix with strong interfacial bonding. Therefore, in this study, GNPs were amine‐functionalized by covalently bonding 4,4′‐methylene dianiline onto their surfaces via a facile synthetic route. The amine‐functionalization was confirmed by FTIR spectroscopy and TGA. Epoxy/GNPs nanocomposites were prepared and their curing behavior, thermomechanical properties and impact strength were investigated. The amine‐functionalization increased curing rate, storage modulus, thermal dimensional stability, and impact strength of the nanocomposites. The SEM images for the fracture surface of the nanocomposite with amine‐functionalized GNPs showed a smooth and ductile failure‐like surface, resulted from the improved interfacial bonding between GNPs and the epoxy matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42269.     

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.     

Graphene Nanoplatelets as Novel Reinforcement Filler in Poly(lactic acid)/Epoxidized Palm Oil Green Nanocomposites: Mechanical Properties

Graphene nanoplatelet (xGnP) was investigated as a novel reinforcement filler in mechanical properties for poly(lactic acid) (PLA)/epoxidized palm oil (EPO) blend. PLA/EPO/xGnP green nanocomposites were successfully prepared by melt blending method. PLA/EPO reinforced with xGnP resulted in an increase of up to 26.5% and 60.6% in the tensile strength and elongation at break of the nanocomposites respectively, compared to PLA/EPO blend. XRD pattern showed the presence of peak around 26.5° in PLA/EPO nanocomposites which corresponds to characteristic peak of graphene nanoplatelets. However, incorporation of xGnP has no effect on the flexural strength and modulus. Impact strength of PLA/5 wt% EPO improved by 73.6% with the presence of 0.5 wt% xGnP loading. Mechanical properties of PLA were greatly improved by the addition of a small amount of graphene nanoplatelets (<1 wt%).     

Single and hybrid organoclay-filled PLA nanocomposites: Mechanical properties,viscoelastic behavior and fracture toughening mechanism

Poly (lactic acid) (PLA) nanocomposites based on single and hybrid organic-modified montmorillonites were previously studied in terms of their morphological, thermal and fire performance. As surfactants of the organoclays influenced the compatibility between the nanofillers and PLA with different degrees of clay platelets dispersion, the present work investigated the effect of these features in the mechanical properties of PLA nanocomposites. PLA nanocomposites specimens were analyzed by dynamic-mechanical-thermal analysis, which pointed out changes in the viscoelastic behavior of the materials by the incorporation of the organoclays, namely the increase of the storage modulus due to polymer chains movements restriction and reinforcement effects associated with the dispersion of the nanofillers. Flexural and impact testing showed that hybrid organomontmorillonites containing ester ammonium and ethoxylated amine improved PLA's ductility, toughness and impact resistance. This behavior was explained by the high level of compatibility and interaction between the surfactants and PLA chains due to the polar groups in their structures. These organoclays caused a transition on PLA's fracture from brittle to ductile in a way that the toughening mechanism was explained by crazing and multi-shear banding induced by the plasticized interfacial region around these organoclays.     

共混顺序对石墨烯微片在PP/PA6/SEBS共混物中的选择性分布和迁移的影响

研究了聚丙烯(PP)/聚酰胺6(PA6)/氢化苯乙烯-丁二烯嵌段共聚物(SEBS)/石墨烯微片(GNPs)纳米复合材料在不同共混顺序下的微观形貌、导电及导热性能,分析了GNPs在复合体系中的选择性分布和迁移及其对复合材料性能的影响.结果表明,在PP/PA6/SEBS/GNPs共混体系中,GNPs在界面张力的作用下趋向于...