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.     

Morphology and electrical conductivity of polyethylene/polypropylene blend filled with thermally reduced graphene oxide and surfactant exfoliated graphene

High‐density polyethylene (HDPE)/polypropylene (PP) composites with graphenes were prepared by melt‐compounding method. Graphene sheets were prepared through thermally reduced graphene oxide (TRG) and surfactant exfoliated graphene (SEG), respectively. Structural characterization showed that the TRG sheets exhibited a few‐layers composition with more defects compared to the SEG sheets. Morphological observations of the composites demonstrated that the graphene was preferentially dispersed in the HDPE phase and the addition of graphene (TRG and SEG) influenced the phase structure of the HDPE/PP composites. The distribution of the TRG sheets in the HDPE phase was better than the SEG sheets, and the obtained HDPE/PP composites exhibited a low electrical percolation threshold with the highly dispersed graphene. The TRG/HDPE/PP composite showed a low electrical percolation threshold of 3 wt% (1.25 vol%). For the SEG/HDPE/PP system, the percolation threshold was 7 wt% (2.98 vol%). Differences in the behavior of the two graphene components (TRG and SEG) in the HDPE/PP composites influenced the formation of percolation networks and electrical properties. POLYM. COMPOS., 38:2098–2105, 2017. © 2015 Society of Plastics Engineers     

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.     

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.     

Effect of the molecular chains grafted on graphene nanosheets on the properties of poly(l‐lactic acid) nanocomposites

We prepared thermally reduced graphene oxide (TRG) grafted with polymethyl methacrylate (PMMA) and polyvinyl acetate (PVAc) (TRG‐g‐PMMA and TRG‐g‐PVAc) by γ‐ray irradiation‐induced graft polymerization and studied their effects on poly(l ‐lactic acid) (PLLA) nanocomposites. PMMA and PVAc chains were proved to be grafted on the TRG surface successfully. TRG‐g‐PMMA and TRG‐g‐PVAc was found to restrict the crystallization behavior of PLLA compared with TRG. Moreover, tensile‐test results showed that TRG‐g‐PMMA and TRG‐g‐PVAc could enhance the elongation at break of PLLA nanocomposites without reducing the tensile strength and modulus compared with TRG, which indicated that the grafting of PMMA and PVAc chains on TRG could improve the toughness of PLLA nanocomposites. POLYM. COMPOS., 38:5–12, 2017. © 2015 Society of Plastics Engineers     

Electrical behavior and positive temperature coefficient effect of graphene/polyvinylidene fluoride composites containing silver nanowires

Polyvinylidene fluoride (PVDF) composites filled with in situ thermally reduced graphene oxide (TRG) and silver nanowire (AgNW) were prepared using solution mixing followed by coagulation and thermal hot pressing. Binary TRG/PVDF nanocomposites exhibited small percolation threshold of 0.12 vol % and low electrical conductivity of approximately 10^-7 S/cm. Hybridization of TRGs with AgNWs led to a significant improvement in electrical conductivity due to their synergistic effect in conductivity. The bulk conductivity of hybrids was higher than a combined total conductivity of TRG/PVDF and AgNW/PVDF composites at the same filler loading. Furthermore, the resistivity of hybrid composites increased with increasing temperature, giving rise to a positive temperature coefficient (PTC) effect at the melting temperature of PVDF. The 0.04 vol % TRG/1 vol % AgNW/PVDF hybrid exhibited pronounced PTC behavior, rendering this composite an attractive material for making current limiting devices and temperature sensors.     

Enhanced interfacial interaction for effective reinforcement of poly(vinyl alcohol) nanocomposites at low loading of graphene

The graphene/poly(vinyl alcohol) (PVA) nancomposites with homogeneous dispersion of the nanosheet and enhanced nanofiller–matrix interfacial interaction were fabricated via water blending partially reduced graphene oxide and PVA. The nanocomposites were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and thermogravimetry. The graphene nanosheets were fully exfoliated in the PVA matrix and a new covalent linkage was formed between graphene and PVA matrix. Uncommon to conventional method, the enhanced interfacial adhesion resulted from covalent interaction and hydrogen bondings between graphene and PVA backbone. The mechanical and thermal properties of the nanocomposites were significantly improved at low graphene loadings. An 116% increase in tensile strength and a 19 °C improvement of onset thermal degradation temperature were achieved by the addition of only 0.8 wt% graphene.     

The preparation and properties of polystyrene/functionalized graphene nanocomposite foams using supercritical carbon dioxide

In this work, polystyrene (PS)/functionalized graphene nanocomposite foams were prepared using supercritical carbon dioxide. Thermally reduced graphene oxide (TRG) and graphene oxide (GO) were incorporated into the PS. Subsequently, the nanocomposites were foamed with supercritical CO₂. The morphology and properties of the nanocomposites and the nucleation efficiency of functionalized graphene in foaming PS are discussed. Compared with GO, TRG exhibited a higher nucleation efficiency and more effective cell expansion inhibition thanks to its larger surface area and better exfoliated structure. It is suggested that the factors that have a significant influence on the nucleation efficiency of TRG and GO originate from the differences in surface properties and chemical structure. Furthermore, PS/TRG nanocomposites and their nanocomposite foams also possess good electrical properties which enable them to be used as lightweight functional materials.© 2012 Society of Chemical Industry     

Templated growth of polyaniline on exfoliated graphene nanoplatelets (GNP) and its thermoelectric properties

Polyaniline (PANi)/exfoliated graphene nanoplatelets (GNP) nanocomposites were prepared by in situ polymerization of aniline monomer in the presence of GNP for thermoelectric applications. PANi has a strong affinity for GNP due to π electron interactions, forming a uniform nanofibril coating. A paper-like nanocomposite was prepared by controlled vacuum filtration of an aqueous dispersion of PANi decorated GNP. The Seebeck coefficient of the resulting nanocomposite changes with initial concentration of aniline in the solution as well as the protonation of PANi, reaching as high as 33 μV/K for nanocomposites containing approximately 40 wt% of PANi and with a protonation ratio of 0.2. The presence of GNP improved the electrical conductivity of the nanocomposites to 59 S/cm. As a result, thermoelectric figure of merit ZT of the nanocomposites is 2 orders of magnitude higher than either of the constituents, exhibiting a significant synergistic effect.     

Reinforcement in melt-processed polymer–graphene composites at extremely low graphene loading level

We have prepared polymer nanocomposites reinforced with exfoliated graphene layers solely via melt blending. For this study polyethylene terephthalate (PET) was chosen as the polymer matrix due to its myriad of current and potential applications. PET and PET/graphene nanocomposites were melt compounded on an internal mixer and the resulting materials were compression molded into films. Transmission electron microscopy and scanning electron microscopy revealed that the graphene flakes were randomly orientated and well dispersed inside the polymer matrix. The PET/graphene nanocomposites were found to be characterized by superior mechanical properties as opposed to the neat PET. Thus, at a nanofiller load as low as 0.07 wt%, the novel materials presented an increase in the elastic modulus higher than 10% and an enhancement in the tensile strength of more than 40% compared to pristine PET. The improvements in the tensile strength were directly correlated to changes in elongation at break and indirectly correlated to the fracture initiation area. The enhancements observed in the mechanical properties of polymer/graphene nanocomposites achieved at low exfoliated graphene loadings and manufactured exclusively via melt mixing may open the door to industrial manufacturing of economical novel materials with superior stiffness, strength and ductility.     

High-yield water-phase exfoliated few-defect graphene for high performance polymer nanocomposites

Application of graphene requires a high-yield, low-cost, scalable production method, but it remains highly challenging. We here report a water-phase technique to produce few-defect graphene nanosheets (FGS) with a high exfoliation yield (92%), based on the chemically expanded graphite with ultrahigh specific surface areas, and demonstrate the application in graphene-polymer nanocomposites. The exfoliated FGS has low degree of oxidation and preserves good mechanical and electrical properties, revealing promising potential for improving comprehensive properties of polymer composites. When 0.5 wt% FGS was incorporated to poly(methyl methacrylate) (PMMA), the 5% weight loss temperature and storage modulus increase by 87°C and 21%, respectively, relative to the neat polymer. With increasing the content of FGS to 4.6 wt%, the glass transition temperature of the composite increases by 25°C. In addition, the composites show a percolation threshold as low as 0.25 vol% and excellent electrical conductivity (50 S/m for 2.7 vol% FGS-PMMA composite).     

Effects of Epoxy Resin on Gelcasting Process and Mechanical Properties of Alumina Ceramics

A gelling system based on the polymerization of epoxy resin ethylene glycol diglycidyl ether (EGDGE) and 3,3′‐Diaminodipropylamine (DPTA) was developed for gelcasting alumina ceramics. The gelation process of 50 vol% alumina‐epoxy resin suspensions were investigated in accordance with the change in temperature and epoxy resin concentration. The activation energy E_a of polymerization reaction was 63.76 kJ/mol and no significant gelation was observed at 25°C during the test for 50 vol% Al₂O₃ suspensions with 10 wt% EGDGE. With the increase in EGDGE concentration, Al₂O₃ green bodies exhibited higher relative density, flexural strength, and Weibull modulus, reaching 64.4%, 41.03 MPa, and 12.51, respectively, when EGDGE concentration was 20 wt%. However, for sintered Al₂O₃ bodies, the highest characteristic strength and Weibull modulus were obtained for 15 wt% EGDGE concentration, reaching 367.57 MPa and 14.52, respectively.     

Carbon nanohorn and graphene nanoplate based polystyrene nanocomposites for superior electromagnetic interference shielding applications

In this article is reported the preparation of carbon nanohorn (CNH)/graphene nanoplates (GNP)/polystyrene (PS) nanocomposites through in‐situ bulk polymerization of styrene monomer in the presence of CNH, followed by the addition of suspension polymerized GNP/PS bead during polymerization of styrene, as next‐generation multifunctional material for high electrical conductivity and electromagnetic interference shielding effectiveness (EMI SE) applications. Morphological analysis revealed selective dispersion of CNH in bulk polymerized PS matrix, where GNP/PS beads were randomly distributed. The formation of continuous CNH–CNH conductive path and GNP–CNH–GNP or CNH–GNP–CNH conductive network throughout the PS matrix at exceptionally low loading of CNH (1.0 wt %) and GNP (0.15 wt %) leads to high electrical conductivity (6.24 × 10^?2 S cm^?1) and EMI SE ～(?24.83 dB) when the nanocomposites was prepared in the presence of 75 wt % GNP/PS bead. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42803.     

多巯基树脂固化聚氨酯丙烯酸树脂的研究

采用凝胶时间测试和实时红外光谱(RT-IR)研究了不同固化剂、稀释剂及促进剂用量对聚氨酯丙烯酸树脂(PUA)/稀释剂二缩三丙二醇二丙烯酸酯(TPGDA)/自制多巯基树脂固化剂(T-41)/促进剂1,8-二氮杂环[5,4,0]-十一烯(DBU)体系固化速度的影响及固化过程中转化率与反应时间的对应关系。结果表明,该体系中,TPG-DA用量存在一最佳值,使体系凝胶时间最短。凝胶时间随烯烃双键/巯基比例的增加而缩短,随促进剂用量的增加而缩短。通过改变各组分配比,体系的固化时间可控制在数分钟到数十分钟之间,实现PUA的快速固化。     

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%).     

Electrically and thermally conductive elastomer/graphene nanocomposites by solution mixing

The greatest challenge in developing polymer/graphene nanocomposites is to prevent graphene layers stacking; in this respect, we found effective solution-mixing polymers with cost-effective graphene of hydrophobic surface. Since graphene oxide is hydrophilic and in need of reduction, highly conducing graphene platelets (GnPs) of ∼3 nm in thickness were selected to solution-mix with a commonly used elastomer – styrene–butadiene rubber (SBR). A percolation threshold of electrical conductivity was observed at 5.3 vol% of GnPs, and the SBR thermal conductivity enhanced three times at 24 vol%. Tensile strength, Young's modulus and tear strength were improved by 413%, 782% and 709%, respectively, at 16.7 vol%. Payne effect, an important design criteria for elastomers used in dynamic loading environment, was also investigated. The comparison of solution mixing with melt compounding, where the same starting materials were used, demonstrated that solution mixing is more effective in promoting the reinforcing effect of GnPs, since it provides more interlayer spacing for elastomer molecules intercalating and retains the high aspect ratio of GnPs leading to filler–filler network at a low volume fraction. We also compared the reinforcing effect of GnPs with those of carbon black and carbon nanotubes.     

Melt crystallization of poly(ethylene terephthalate): Comparing addition of graphene vs. carbon nanotubes

Poly(ethylene terephthalate) (PET)-based nanocomposites with graphene or multi-wall carbon nanotubes (MWCNT) were prepared by melt mixing. Aspect ratio, A_f, and interparticle distance, λ, of graphene in the nanocomposites were obtained from melt rheology and transmission electron microscopy respectively. λ of PET/graphene nanocomposites was much smaller than λ in PET/MWCNT. For PET/graphene with highest A_f, λ became <1 μm at more than 0.5 wt% graphene. Non-isothermal crystallization behavior from the melt was investigated by differential scanning calorimetry. The crystallization temperatures suggest that the nucleation effect of graphene was stronger than that of MWCNT. The half crystallization time of PET/graphene became longer than PET/MWCNT with increasing graphene loading, suggesting that confinement by graphene suppressed the crystal growth rate. XRD analysis indicated that smaller crystals formed in PET/graphene than in PET/MWCNT. From Raman spectroscopy, the π–π interaction between PET and graphene was stronger than that between PET and MWCNT. This stronger interaction in PET/graphene appears to result in formation of crystals with higher perfection.     

Electromagnetic interference shielding behavior of chemically and thermally reduced graphene based multifunctional polyurethane nanocomposites: A comparative study

This article presents the effect of exfoliation, dispersion, and electrical conductivity of graphene sheets onto the electrical, electromagnetic interference (EMI) shielding, and gas barrier properties of thermoplastic polyurethane (TPU) based nanocomposite films. The chemically reduced graphene (CRG) and thermally reduced/annealed graphene (TRG) having Brunauer–Emmett–Teller surface areas of 18.2 and 159.6 m²/g, respectively, when solution blended with TPU matrix using N,N-dimethylformamide as a solvent. Graphene sheets based TPU nanocomposites have been evaluated and compared for EMI shielding in Ku band, electrical conductivity, and gas barrier property. TRG/TPU nanocomposite films showed excellent gas barrier against N₂ gas as compared to CRG/TPU. The EMI shielding effectiveness for neat CRG and TRG graphene sheets is found to be −80, −45 dB, respectively, at 2 mm thickness. The EMI shielding data revealed that TRG/TPU nanocomposites showed better shielding at lower concentration (10 wt %), while CRG displayed better attenuation at higher concentrations. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47666.     

Thermo-physical and impact properties of epoxy nanocomposites reinforced by single-wall carbon nanotubes

The thermo-physical properties and the impact strength of diglycidyl ether of bisphenol F (DGEBF) epoxy nanocomposites reinforced with fluorinated single-wall carbon nanotubes (FSWCNT) are reported. A sonication technique was used to disperse FSWCNT in the glassy epoxy network resulting in nanocomposites having large improvement in modulus with extremely small amount of FSWCNT. The glass transition temperature decreased approximately 30 °C with an addition of 0.2 wt% (0.14 vol%) FSWCNT, without adjusting the amount of the anhydride curing agent. This was because of non-stoichiometry of the epoxy matrix that was caused by the fluorine on the single-wall carbon nanotubes. The correct amount of the anhydride curing agent needed to achieve stoichiometry was experimentally examined by dynamic mechanical analysis (DMA). The storage modulus of the epoxy at room temperature (which is below the glass transition temperature of the nanocomposites) increased up to 0.63 GPa with the addition of only 0.30 wt% (0.21 vol%) of FSWCNT, representing an up to 20% improvement compared with the neat epoxy. The Izod impact strength slightly decreased when the amount of FSWCNT was increased to 0.3 wt%. The excellent improvement in the storage modulus was achieved without sacrificing impact strength.     

Bottom-up synthesis of PS-CNF nanocomposites

Polystyrene-carbon nanofiber (CNF) nanocomposites have been synthesized by a ‘bottom-up’ method through electrostatic assembly. First, a cationic polystyrene (PS) latex was synthesized by conventional emulsion polymerization. The latex was mixed with an aqueous suspension of oxidized CNF. PS-CNF nanocomposites were obtained by heterocoagulation due to the electrostatic interaction between cationic PS latex and anionic CNF. Thermal properties were characterized by DSC and TGA, while morphologies of the nanocomposites were studied by SEM. Electrical resistivity results showed that the percolation threshold in our PS-CNF nanocomposites was below 2 wt% (1 vol%). This low percolation threshold is related to the dispersion, and thus a superior network formation of CNF in PS matrix.