Preparation of transparent nanocomposites from UV‐ and thermo‐curable epoxyacrylate and graphene oxide for the application of corrosion protection coatings

In this study, we report UV‐ and thermo‐curable epoxyacrylate/graphene oxide (EA/GO) nanocomposites that present good transparency, excellent pencil hardness and promising improvement in corrosion protection. A dual‐curable EA oligomer with one terminal epoxide and one double bond at the other end was synthesized by reaction of diglycidyl ether of bisphenol‐A and acrylic acid. After mixing EA and GO with the curing agents and reactive diluent followed by UV cure and thermo‐cure, the resulting EA/GO films on a glass slide with GO loading up to 3 phr exhibited over 86% light transmittance. Furthermore, the pencil hardness was enhanced from 3H for EA to 6H for the EA/GO composite at 2 phr GO loading. The corrosion protection of the EA/GO coatings was evaluated by a potentiodynamic polarization technique and electrochemical impedance spectra. The corrosion potential (E_corr) of the EA/GO‐coated steel increased with increasing GO loading. Meanwhile, Nyquist and Bode plots indicated that the higher the GO content in the EA/GO coating was, the higher was the coating resistance and also the charge transfer resistance after immersion in salt solution. All these results proved that the GO had positive effects on enhancement of the corrosion resistance. The improved corrosion protection by the EA/GO coatings was mainly due to the enhanced hydrophobicity, the deviation of electron transfer and the increased tortuosity of the diffusion path. The improved corrosion protection and hardness together with the useful dual‐curability make the EA/GO nanocomposite a competitive candidate for corrosion protection coatings. © 2019 Society of Chemical Industry     

Incorporation of silica network and modified graphene oxide into epoxy resin for improving thermal and anticorrosion properties

In this study, the silica network and functionalized graphene oxide (GO) were incorporated into the epoxy coating systems, which was aimed to improve the thermal property and corrosion resistance of epoxy coatings. First, tetraethyl orthosilicate (TEOS) oligomers and epoxy hybrid was fabricated through sol–gel method. Then the (3-aminopropyl) triethoxysilane (APTES) modified graphene oxide (FGO) was added into the epoxy hybrid composite to obtain anticorrosion coatings. Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA), Raman spectrum, and X-ray photoelectron spectrum were conducted to evaluate the structural information of GO and APTES modified GO nanosheets. The results indicated that the APTES successfully grafted onto the surface of GO sheets. Besides, TGA curves, electrochemical measurements and salt spray test were also carried out to characterize the thermal performance and corrosion resistance of GO based epoxy coatings. The TGA results revealed that the thermal performance of epoxy coating containing silica network and FGO nanofiller (ES/FGO) was significantly strengthened compared to pure epoxy. The initial degradation temperature of epoxy coating was increased from 300 to 343.7°C after incorporation of silica component and FGO. The EIS measurements demonstrated that the impedance modulus of ES/FGO was significantly higher than neat epoxy, which indicated that the corrosion resistance of epoxy was substantially strengthened after introduction of silica component and FGO. The corrosion rate and inhibition efficiency of epoxy composite coatings were also shifted from 1.237 × 10⁻⁷ mm/year and 76.6% (for neat epoxy) to 1.870 × 10⁻⁹ mm/year and 99.6% (for ES/FGO), respectively. The salt spray test also revealed that the silica and FGO can improve the corrosion resistance of epoxy coating. Additionally, the dispersion of GO sheets was also enhanced after the modification of APTES siloxane.     

Electrodeposition of graphene oxide-hydroxyapatite composite coating on titanium substrate

In this work, graphene oxide (GO)/hydroxyapatite (HA) composite coatings were successfully prepared on titanium substrate by electrophoretic deposition technology. Subsequently, microstructure, phase composition, adhesion strength, hydrophilicity, corrosion resistance, bioactivity, antibacterial activity and biocompatibility of the coating were evaluated. The adhesion strength of coating increased by 76% from 6.46 MPa to 17.81 MPa with 0 wt% GO to 12 wt% GO and the corrosion rate of coating with 8 wt% GO was achieved at the minima of (1.493 × 10^-3mm/a). Biomineralization experiment indicated the excellent bioactivity of GO/HA composite coatings. The water contact angle of the composite coatings increased from 20.6°(0 wt% GO) to 38.1°(12 wt%GO). The antibacterial rates of coating with 5 wt% GO was 96.7%, while declined to 25% after thermal treatment. In-vitro L929 cell culture experiments indicated the composite coatings with 5 wt% GO exhibited good biocompatibility.     

Latex co‐coagulation approach to fabrication of polyurethane/graphene nanocomposites with improved electrical conductivity,thermal conductivity,and barrier property

This study describes a simple and effective method of synthesis of a polyurethane/graphene nanocomposite. Cationic waterborne polyurethane (CWPU) was used as the polymer matrix, and graphene oxide (GO) as a starting nanofiller. The CWPU/GO nanocomposite was prepared by first mixing a CWPU emulsion with a GO colloidal dispersion. The positively charged CWPU latex particles were assembled on the surfaces of the negatively charged GO nanoplatelets through electrostatic interactions. Then, the CWPU/chemically reduced GO (RGO) was obtained by treating the CWPU/GO with hydrazine hydrate in DMF. The results of X‐ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and Raman analysis showed that the RGO nanoplatelets were well dispersed and exfoliated in the CWPU matrix. The electrical conductivity of the CWPU/RGO nanocomposite could reach 0.28 S m^?1, and the thermal conductivity was as high as 1.71 W m^?1 K^?1. The oxygen transmission rate (OTR) of the CWPU/RGO‐coated PET film was significantly decreased to 0.6 cm³ m^?2 day^?1, indicating a high oxygen barrier property. This remarkable improvement in the electrical and thermal conductivity and barrier property of the CWPU/RGO nanocomposite is attributed to the electrostatic interactions and the molecular‐level dispersion of RGO nanoplatelets in the CWPU matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43117.     

ZrO2 functionalized graphene Oxide/SEBS‐Based nanocomposites for efficient electromagnetic interference shielding applications

ZrO₂‐coated graphene oxide (GO)/SEBS(styrene‐ethylene‐butylene‐styrene)‐based nanocomposites were prepared for use as an electromagnetic interference (EMI) shielding material. Transmission electron microscopy (TEM) reveals almost every individual GO is fully and homogeneously covered with uniform ZrO₂. X‐ray diffraction (XRD) patterns and Differential scanning calorimetry (DSC) revealed increased ordering of ‐(CH₂‐CH₂)n segments in the poly(ethylene‐co‐1‐butene) block of the SEBS matrix in the case of SEBS/ZrO₂‐coated graphene oxide composites than in the SEBS/pristine graphene oxide nanocomposite. Thermogravimetric analysis (TGA) proved better oxidation resistance of SEBS/ZrO₂‐coated GO nanocomposite compared to that of SEBS/pristine GO nanocomposite. The present nanocomposites exhibited excellent EMI shielding effectiveness (SE) over X‐band (8.2 GHz–12.4 GHz) with EMI SE of 37.9 dB. J. VINYL ADDIT. TECHNOL., 25:E130–E136, 2019. © 2018 Society of Plastics Engineers     

Polydopamine functional reduced graphene oxide for enhanced mechanical and electrical properties of waterborne polyurethane nanocomposites

Waterborne polyurethane/polydopamine (PDA) functional reduced graphene oxide (WPU/PDRGO) nanocomposites were prepared by in situ emulsification method. The presence of a PDA layer and the partial reduction of GO by PDA were confirmed by FTIR, XRD, Raman spectra, and TGA. It was found that the interfacial PDA layers facilitated the dispersion of the PDRGO sheets in the WPU matrix and enhanced mechanical properties of the WPU matrix. The resulting WPU/PDRGO nanocomposite coatings show excellent electrical conductivity (9.9?×?10^?6–1.1?×?10^?4 S cm^?1) corresponding to a PDRGO content of 1–16 wt%. The obtained waterborne polyurethane/graphene nanocomposite dispersions are promising for anticorrosion, antistatic, conductive, and electromagnetic interference shielding coatings.     

Evaluation of the protective nature of GO–BCP nanocomposite coatings on 316L SS in artificial body fluid

This work reports on a novel approach to deposit composite coatings based on biphasic calcium phosphate (BCP) incorporating graphene oxide (GO) on 316L stainless steel (316L SS) and on its protective nature against corrosion in the simulated body fluid (SBF). For this purpose, 2-dimensional GO was successfully incorporated in 1% and 3% weight ratios as mechanical strength enhancer and pore size reducer for the prepared coatings. It was observed that upon increasing the GO content, the corrosion rate was drastically decreased when compared to pristine BCP coating. The corrosion resistance polarization results are in good agreement with the test results obtained for SBF immersion study. The size of the particles has significantly decreased, as shown by transmission electron microscopy (from 190 to 27 nm). The experimental results indicate that the composite hydroxyapatite–β-tricalcium phosphate–GO (HAp–β-TCP–GO) coatings enhanced the corrosion resistance of the surgical grade 316L SS, turning it a better implanting option for orthopedic applications.     

Tribological and corrosion performance of epoxy resin composite coatings reinforced with graphene oxide and fly ash cenospheres

In this work, a novel graphene oxide (GO)-fly ash cenospheres (FACs) hybrid fillers was introduced to improve the wear and corrosive resistance of epoxy resin (ER) composite coatings. The tribological behavior and the corrosion performance of three kinds of coatings (pure ER, GO/ER and GO-FACs/ER coatings) were studied and the reinforced mechanisms of coatings filled by different fillers were analyzed. The friction coefficient and wear rate of the ER coatings were decreased with the addition of GO-FACs hybrids. The scanning electron microscope images showed that the dispersibility and compatibility of GO-FACs hybrids were effectively improved compared with that of GO sheet. The water contact angle examination indicated that the hydrophobicity of the GO-FACs/ER coatings increased. The electrochemical impedance spectroscopy (EIS) results demonstrated that the GO-FACs/ER coatings have better anticorrosion performance compared with the pure ER coatings and the GO/ER coatings. The hydrophobic surface and the well dispersed fillers constitute the dual barrier to resist the corrosion medium.     

Development of poly(vinylcarbazole)/alumina nanocomposite coatings for corrosion protection of 316L stainless steel in 3.5% NaCl medium

Poly(vinylcarbazole) (PVK) and PVK‐alumina (Al₂O₃) nanocomposite coatings were electrochemically coated on 316 L stainless steel (SS) substrates for corrosion protection of 316 L SS in 3.5 weight (wt) % NaCl medium. The formation of PVK and incorporation of nanoalumina particles in PVK‐Al₂O₃ nanocomposite coatings were confirmed from attenuated total reflectance‐infrared spectroscopy (ATR‐IR). Thermal analysis (TG) results showed enhanced thermal stability for the composites relative to PVK. Incorporation of Al₂O₃ nanoparticles enhanced the micro hardness of PVK coated 316 L SS. The dispersion of alumina nanoparticles was examined via scanning electron microscope (SEM) and tunneling electron microscopy (TEM) and revealed distinct features. The influence of nanoparticles on the barrier properties of PVK and PVK‐Al₂O₃ nanocomposites was evaluated in aqueous 3.5 wt % NaCl by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) studies. The results proved that PVK nanocomposite coatings provided better protection for 316 L SS than PVK coatings. The drastic increase in impedance values is due to the high corrosion resistance offered by the PVK nanocomposite coatings that arises due to the interaction between Al₂O₃ nanoparticles and PVK. The highest corrosion protection shown by the 2 wt % nano Al₂O₃ incorporated PVK composite coatings proved enhanced corrosion resistance compared to PVK. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44937.     

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

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

Preparation of polyvinylpyrrolidone/graphene oxide/epoxy resin composite coatings and the study on their anticorrosion performance

Waterborne epoxy resin (EP) is often used as anticorrosive coating in the industrial field. However, small holes and gaps can be formed during the curing process. The corrosive medium easily penetrates the anticorrosive coating and corrodes the metal matrix. Herein, polyvinylpyrrolidone (PVP) and graphene oxide (GO) were doped into EP to improve the shielding and resistance to corrosive media. The composite coatings were prepared successfully by solution blending method. In the PVP/GO composite materials, original spatial structure of GO was changed and the composite was mainly combined by covalent bonding. The surface morphology of hybrid filler was flat and uniform, and the structural defects of GO was reduced. Compared with single-layer anticorrosive coating, the corrosion potential of PVP/GO/EP coating moved forward and the corrosion current density decreased. The ideal corrosion resistance of PVP/GO/EP composite coatings was mainly because agglomeration of GO sheet was obviously avoided after it was modified by PVP. Furthermore, the hybrid filler can be uniformly dispersed in the aqueous EP. It blocked the gaps and holes inside the coatings, which could contribute to form anticorrosive coatings.     

Enhanced thermal conductivity and dimensional stability of flexible polyimide nanocomposite film by addition of functionalized graphene oxide

Polyimide (PI) nanocomposites with both enhanced thermal conductivity and dimensional stability were achieved by incorporating glycidyl methacrylate‐grafted graphene oxide (g‐GO) in the PI matrix. The PI/g‐GO nanocomposites exhibited linear enhancement in thermal conductivity when the amount of incorporated g‐GO was less than 10 wt%. With the addition of 10 wt% of g‐GO to PI (PI/g‐GO‐10), the thermal conductivity increased to 0.81 W m^?1 K^?1 compared to 0.13 W m^?1 K^?1 for pure PI. Moreover, the PI/g‐GO‐10 composite exhibited a low coefficient of thermal expansion (CTE) of 29 ppm °C^?1. The values of CTE and thermal conductivity continuously decreased and increased, respectively, as the g‐GO content increased to 20 wt%. Combined with excellent thermal stability and high mechanical strength, the highly thermally conducting PI/g‐GO‐10 nanocomposite is a potential substrate material for modern flexible printed circuits requiring efficient heat transfer capability.     

Novel surfactant-free waterborne acrylic-silicone modified alkyd hybrid resin coatings containing nano-silica for the corrosion protection of carbon steel

We report a novel waterborne acrylic-silicone modified alkyd nanocomposite latex containing nano-silica prepared by the surfactant-free miniemulsion polymerization. The influences of γ-methacryloxy-propyltrimethoxysilane- (MPS-) modified nano-silica particle contents to the thermal, mechanical and anti-corrosion performance of hybrid latex coatings were studied. The results revealed that the incorporation of nano-silica particles into latex films could directly increase the thermal stability and mechanical properties. Electrochemical corrosion studies revealed that these nanocomposite coatings exhibited superior corrosion resistance performance (inhibition efficiency 99.36% and corrosion rate 1.09 × 10 ^?3 mm per year) than that of the control system (without SiO₂ NPs).     

Synergic enhancement of the anticorrosion properties of an epoxy coating by compositing with both graphene and halloysite nanotubes

The aim of this research was to improve the corrosion resistance of metal surfaces with polymer coatings. Both graphene and halloysite nanotubes (HNTs) were introduced together into the epoxy resin coating for the enhanced barrier protection of the metallic surface. The anticorrosion behaviors of different coatings were comparatively evaluated by the potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), and neutral salt spray (NSS) tests. The potentiodynamic polarization curves showed that the coating containing 0.5 wt % HNTs and 0.8 wt % graphene (H05G08EP) together had the most positive corrosion potential and the minimum corrosion current density. The EIS results revealed that graphene endowed the composite coatings with excellent electrochemical performance for anticorrosive purposes. The NSS tests indicated that H05G08EP endured the longest NSS time. These results suggest that H05G08EP had the best corrosion resistance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47562.     

Ternary hydroxyapatite/chitosan/graphene oxide composite coating on AZ91D magnesium alloy by electrophoretic deposition

In this work, ternary HA/chitosan/graphene oxide (GO) coating was applied via electrophoretic deposition on AZ91D magnesium alloy as bone implants, successfully. Subsequently, phase composition, surface morphology, hardness, corrosion behavior, bioactivity and antibacterial of the composite coatings were studied. Hardness and Young's modulus of the composite coatings increased from 40 ± 1.5 MPa and 3.1 ± 0.42 GPa to 60 ± 3.12 MPa and 8 ± 0.53 GPa for composite coatings with 0 and 2 wt% GO, respectively. The results of the SBF solution soaking of the composites after 24 days, indicated the improvement of HA growth due to the increasing of the GO addition in composite coating. New HA grains with leaf-like morphology grew uniformly at higher amounts of GO (1 and 2 %wt) in a perfectly balanced composition. Rate of the substrate corrosion significantly decreased from 4.3 to 0.2 (mpy), when the amount of GO increased from 0 to 2 wt% due to reduction of the surface cracks at the presence of the GO reinforcement. Also, there was no Escherichia coli and Staphylococcus aureus bacteria growth in broth medium after 24 h and OD₆₀₀ results at 24 h post inoculation for the 2%wt GO addition in coating.     

Physicochemical and antibacterial properties of chitosan‐polyvinylpyrrolidone films containing self‐organized graphene oxide nanolayers

Chitosan films have a great potential to be used for wound dressing and food‐packaging applications if their physicochemical properties including water vapor permeability, optical transparency, and hydrophilicity are tailored to practical demands. To address these points, in this study, chitosan (CS) was combined with polyvinylpyrrolidone (PVP) and graphene oxide (GO) nanosheets (with a thickness of ～1 nm and lateral dimensions of few micrometers). Flexible and transparent films with a high antibacterial capacity were prepared by solvent casting methods. By controlling the evaporation rate of the utilized solvent (1 vol % acidic acid in deionized water), self‐organization of GO in the polymer matrix was observed. The addition of PVP to the CS/GO films significantly increased their water vapor permeability and optical transmittance. A blue shift in the optical absorption edge was also noticed. Thermal analysis coupled with Fourier transform infrared spectroscopy suggested that the superior thermal stability of the nanocomposite films was due to the formation of hydrogen bonds between the functional groups of chitosan with those of the graphene oxide. An improved bactericidal capacity of the nanocomposite films against gram‐positive Staphylococcus aureus and gram‐negative Escherichia coli bacteria was also observed. Highly flexible, transparent (opacity of 6.95), and antimicrobial CS/25 vol % PVP/1 wt % GO films were prepared. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43194.     

几种新型富锌涂料的研究进展

介绍了氧化石墨烯改性水性环氧富锌涂料、石墨烯纳米片/环氧富锌(Gnps/ZRE)复合涂料、高柔韧性、高附着力水性无机富锌涂料、石墨烯硅酸盐富锌防腐蚀涂料、水性聚苯胺/氧化石墨烯改性低锌粉含量防腐涂料、还原-氧化石墨烯(r-GO)改性环氧富锌涂料、耐盐雾双组分水性环氧富锌涂料、石墨烯浆料改性水性环氧富锌涂料、双电层水性无机富锌涂料、SnCl2/EtOH溶液法还原氧化石墨烯环氧富锌涂料、有机-无机杂化水性富锌涂料、水性富锌铝涂料、低锌含量石墨烯长效防腐涂料、自固化醇溶性无机富锌底漆和冷镀锌喷漆等几种新型富锌涂料的研究进展。     

Thermomechanical and corrosion inhibition properties of graphene/epoxy ester–siloxane–urea hybrid polymer nanocomposites

The effect of graphene on the corrosion inhibition properties of a hybrid epoxy–ester–siloxane–urea polymer was investigated. The weight fraction of graphene was varied from 1 to 2 wt%. Direct current polarization (DCP) and electrochemical impedance spectroscopic (EIS) techniques were used to measure the polarization and coating resistance of the coated aluminum alloy substrate. The grapheme/hybrid polymer composite coatings showed much higher corrosion inhibition property when compared to the neat hybrid polymer coating. An increase in glass transition temperature and rubbery region modulus was also observed for composites containing 1–2 wt.% of graphene. A direct correlation between the rubbery plateau modulus of free standing composite thin films and corrosion resistance of the composite coatings was made, indicating that the corrosion protection mechanism is due to restriction of the polymer chain motion by graphene which causes a decrease in coating permeability.     

Study on electrochemical behavior of Nano‐ZnO modified alkyd‐based waterborne coatings

A nano‐composite coating was formed using nano‐ZnO as pigment in different concentrations, to a specially developed alkyd‐based waterborne coating. The nano‐ZnO modified composite coatings were applied on mild steel substrate by dipping. The dispersion of nano‐ZnO particles in coating system was investigated by scanning electron microscopic and atomic force microscopic techniques. The effect of the addition of these nano‐pigments on the electrochemical behavior of the coating was investigated in 3.5% NaCl solution, using electrochemical impedance spectroscopy. Coating modified with higher concentration of nano‐ZnO particles showed comparatively better performance as was evident from the pore resistance (R_po) and coating capacitance (C_c) values after 30 days of exposure. In general, the study showed an improvement in the corrosion resistance of the nano‐particle modified coatings as compared with the neat coating, confirming the positive effect of nano‐particle addition in coatings. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

石墨烯对水性环氧富锌涂料中锌粉的取代能力研究

针对水性重防腐涂层体系中水性环氧富锌底漆高锌粉含量所带来的生产成本高、不易贮存、环境污染大等问题,采用在涂料中添加少量石墨烯以取代部分锌粉的改进方法。通过动电位极化曲线、电化学阻抗谱等方法研究了锌粉含量以及石墨烯添加量对环氧富锌涂料性能的影响,结果表明：涂层的耐腐蚀性随着锌粉含量增加而提高,锌粉占锌粉与硫酸钡总质量的 80%时,腐蚀速率为 0. 002 03毫米 /年（ mm/y）,当涂层中锌粉占锌粉与硫酸钡的总质量的 20%时,随着石墨烯添加量从占锌粉、硫酸钡与石墨烯总质量的 0增加至 0. 8%,腐蚀速率先上升后下降,当石墨烯含量达到 0. 6%时,腐蚀速率为 0. 0 038 mm/y,涂层的耐腐蚀性达到最大值。