Studying the effects of micro and nano sized ZnO particles on the corrosion resistance and deterioration behavior of an epoxy-polyamide coating on hot-dip galvanized steel

The effects of micro and nano sized ZnO particles on the corrosion resistance and hydrolytic degradation of an epoxy coating were studied. Different analytical techniques including scanning electron microscope (SEM), electrochemical impedance spectroscopy (EIS), dynamic thermal mechanical analysis (DMTA) and nano-indentation were utilized to evaluate the hydrolytic degradation as well as the corrosion resistance of the coatings in exposure to 3.5 wt% NaCl solution. It was found that the epoxy coating resistance against corrosive electrolyte was significantly improved using nano and micro sized ZnO particles. The corrosion resistance of the nanocomposite was considerably greater than the one reinforced with the micro-ZnO particles. Moreover, the resistance of the coating reinforced with the nano sized particles against hydrolytic degradation in exposure to the corrosive electrolyte was considerably greater than the one reinforced with the micro sized particles. Decrease in both nano hardness and cross-linking density of the epoxy coating reinforced with nanoparticles after exposure to the corrosive electrolyte were considerably lower than the blank sample and the sample reinforced with the micro sized ZnO particles. Using nano sized particles the coating adhesion loss decreased.     

十八胺改性纳米SiO2制备及在水性环氧防腐涂料中的应用

摘要：以正硅酸四乙酯（TEOS）、十六烷基三甲基溴化铵（CTAB）、γ-(2，3-环氧丙氧基)丙基三甲氧基硅烷（KH560）为原料，采用溶胶-凝胶法制备表面环氧基化的纳米SiO2，通过十八胺（ODA）的伯胺端基与纳米SiO2表面的环氧基进行反应得到ODA-SiO2，用于制备水性环氧防腐涂料。通过傅里叶变换红外光谱（FTIR）、热重测试（TG）、X射线光电子能谱仪（XPS）、扫描电镜（SEM）表征ODA成功接枝到SiO2表面；通过电化学测试、耐盐雾性能测试对水性环氧涂层的防腐性能进行了分析。结果表明，含0.3wt%ODA-SiO2的水性环氧涂层具有较好的防腐蚀性能，耐盐雾时间500h。     

Stearic acid grafted chitosan/epoxy blend surface coating for prolonged protection of mild steel in saline environment

Chitosan (CS) is a promising candidate for green anticorrosive coating owing to its film forming nature, complexation with metals, biocompatibility, and varied surface functionalization. This paper illustrates the surface properties of chitosan film which is modified by grafting with stearic acid via a water-soluble coupling agent, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC). The interaction between chitosan and stearic acid were investigated theoretically by Gaussian 09 package. The purified co polymeric films so formed were characterized by FTIR-ATR, NMR, XRD, TGA, CHNSO, SEM, AFM and EDX techniques. Stearic acid grafted CS film was developed on mild steel surface via dip coating technique and investigated for its corrosion resistance in 3.5% NaCl via electrochemical techniques. EIS measurements and potentiodynamic polarization studies have proven that the grafted CS when blended with epoxy resin offers better corrosion protection to mild steel in saline environment. The coating offers prolonged protection for the metal surface with enhanced barrier properties and hydrophobic nature.     

Anti-corrosive properties of waterborne polyurethane/poly(o-toluidine)-ZnO coatings in NaCl solution

The aim of this research was to prepare waterborne polyurethane (WPU) coating blended with a series of poly(o-toluidine)-nano ZnO composites and study its anti-corrosion performance after its application over carbon steel. The synthesized composites were characterized by X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The corrosion resistance of coatings with and without nano ZnO were studied in 3.5% NaCl solution at a temperature of 25?°C, by electro-chemical techniques such as potentiodynamic polarization measurements and electrochemical impedance spectroscopy (EIS). It was observed that the composite coating containing 7% poly(o-toluidine)-nano ZnO composite had higher corrosion resistance than poly(o-toluidine) and 14% poly(o-toluidine)-nano ZnO composite. The presence of appropriate amount of ZnO significantly improved the corrosion resistance, due to the formation of passive layer on steel surface and the synergistic effects of poly(o-toluidine) along with a suitable amount of nano-ZnO reduced the porosity of the coating surface.     

纳米SiO2改性阴极电泳漆的制备及耐蚀性研究

以获得纳米二氧化硅改性阴极电泳漆为目的,用硅烷偶联剂在水介质中分散纳米SiO2粉体,通过分散液的吸光度来评价分散效果.然后将分散后的纳米粉体添加到阴极电泳漆中得到纳米改性电泳漆.试片经磷化-电泳涂装后得到复合涂层,并对复合涂层的耐蚀性能进行评价.金相显微观测表明,纳米改性电泳漆膜表面有较均匀的小突起,而未改性复合膜层表面比较光滑.吸水性测试表明,与未改性复合漆膜相比,改性后的复合涂层漆膜疏水性能有一定提高.耐酸、碱性试验表明,改性复合膜层的耐酸性明显优于未改性复合膜层,两种复合膜层的耐碱性都较好.     

Preparation of Poly(<Emphasis Type="Italic">o</Emphasis>-toluidine)/Nano Zirconium Dioxide (ZrO<Subscript>2</Subscript>)/Epoxy Composite Coating and Its Corrosion Resistance

Conducting polymers represent a promising application prospect in the field of metal corrosion control. In this investigation, poly(o-toluidine) (POT)/nano zirconium dioxide (ZrO₂) composite were prepared by in situ polymerization of o-toluidine monomer in the presence of nano ZrO₂ particles. Fourier transformation infrared spectroscopy, UV–visible spectroscopy, X-ray diffraction and Scanning electron microscopy were used to characterize the composition and the structure of the composite. POT/nano ZrO₂ composite was mixed with epoxy resin (EP) through a solution blending method and the three components POT/nano ZrO₂/epoxy composite coating was coated onto the surface of steel coupon, and its corrosion protective efficiency was studied by electrochemical measurements and immersion test in 3.5 % NaCl solution as corrosion environment and also compared with that of POT/epoxy composite coated steel, polyaniline (PANI)/epoxy composite coated steel and pure epoxy coated steel. According to the results, POT/nano ZrO₂/epoxy composite coated steel has got higher corrosion resistance than that of POT/epoxy composite coated steel and PANI/epoxy composite coated steel. It was found that POT powders dispersed in the epoxy and polyamide system improved the barrier and electrochemical protection properties of epoxy coating and the addition of nano ZrO₂ particles increased the tortuosity of the diffusion pathway of corrosion substances.     

A study on the anticorrosion performance of the epoxy-polyamide nanocomposites containing ZnO nanoparticles

Epoxy nanocomposites were prepared using different loadings (2, 3.5, 5 and 6.5 wt%) of ZnO nanoparticles. Nanocomposites were applied on steel substrates. Samples were immersed in 3.5 wt% NaCl solution for 1344 h. Corrosion resistance of the coatings was studied by an electrochemical impedance spectroscopy (EIS). The effects of addition of nanoparticles on the mechanical properties of the epoxy coating were studied by a dynamic mechanical thermal analysis (DMTA). Curing behavior of the coatings containing nanoparticles was studied by a differential scanning calorimeter (DSC). Atomic force microscope (AFM) was utilized to investigate the surface topography and surface morphology of the coatings. Coating resistance against hydrolytic degradation was studied by FTIR (Fourier Transform Infrared).Results showed that addition of low loadings of nanoparticles can increase T_g of the composite. Decrease in T_g and cross-linking density of the coating were observed at high loadings of nanoparticles. It was found that nanoparticles can influence the curing behavior of the epoxy coating. Nanoparticles improved the corrosion resistance of the epoxy coating. Increase in coating resistance against hydrolytic degradation was obtained using nanoparticles.     

Highly transparent and organosoluble polyimides derived from 2,2′‐disubstituted‐4,4′‐oxydianilines

Polypyrrole (PPy) and Polypyrrole‐ZnO (PPy‐ZnO) nanocomposites were electrodeposited on mild steel and its corrosion protection ability was studied by Tafel and Impedance techniques in 3.5% NaCl solution. Pure Polypyrrole film was not found to protect the mild steel perfectly but the coating with nano‐sized ZnO (PPy‐ZnO) has dramatically increased the corrosion resistance of mild steel. Electrochemical Impedance Spectroscopy (EIS) measurements indicated that the coating resistance (R_coat) and corrosion resistance (R_corr) values for the PPy‐ZnO nanocomposite coating was much higher than that of pure PPy coated electrode. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Characterization of the fracture behavior and viscoelastic properties of epoxy-polyamide coating reinforced with nanometer and micrometer sized ZnO particles

The mechanical and viscoelastic properties of an epoxy-polyamide coating containing nano and micro sized ZnO particles were studied. The nanocomposites were prepared at different loadings of the nano sized ZnO particles. The composites were also prepared using micro sized ZnO particles at different lambdas (lambda (λ) = PVC/CPVC). The optical properties of each nanocomposite were studied by UV–vis technique. Dynamic mechanical thermal analysis (DMTA) and micro-Vickers were used to investigate the mechanical properties of the composites. The viscoelastic properties of the composites were studied by a tensile test. The fracture morphologies of the composites were studied by a scanning electron microscope (SEM). An increase in Tg together with a decrease in cross-linking density of the composites was obtained when the coating was reinforced with the micro sized ZnO particles. On the other hand, the Tg and cross-linking density of the composites were decreased using nano sized ZnO particles. It was also found that, the Young's modulus and the fracture energy of the coating were decreased using micro and nano sized ZnO particles. The greater toughness as well as fracture energy of the composite was obtained when it was reinforced with the nano sized ZnO particles. The curing behavior of the epoxy coating was affected in the presence of the micro and nano sized ZnO particles.     

Effect of silane modified nano ZnO on UV degradation of polyurethane coatings

Nanosized ZnO modified by 2-aminoethyl-3-aminopropyltrimethoxysilane (APS) was prepared using the precipitation method. Modified nano ZnO by silane (ZnO-APS) was characterized by XRD, SEM, TEM and UV–vis measurements. The degradation of the polyurethane coating, the polyurethane coatings containing 0.1 wt% nano ZnO and the polyurethane coatings containing nano ZnO-APS at two concentrations (0.1 and 0.5 wt%) during QUV test was evaluated by gloss measurement and electrochemical impedance spectroscopy. The coating surface after QUV test was observed with SEM. The results show that nano ZnO-APS has spherical structure with particle size around 10–15 nm. Nano ZnO improved the UV resistance of the PU coating and surface treatment by APS enhanced the effect of nano ZnO. The presence of nano ZnO-APS at 0.1 wt% concentration significantly improved the UV resistance of polyurethane coating.     

Epoxy/polyaniline–ZnO nanorods hybrid nanocomposite coatings: Synthesis,characterization and corrosion protection performance of conducting paints

The objective of this research is the production of an epoxy coating blended with organic–inorganic hybrid nanocomposite as a corrosion inhibiting pigment applied over carbon steel grade ST37. A series of conducting polyaniline (PANI)–ZnO nanocomposites materials has been successfully prepared by an in situ chemical oxidative method of aniline monomers in the presence of ZnO nanorods with camphorsulfonic acid (CSA) and ammonium peroxydisulfate (APS) as surfactant and initiator, respectively. The synthesized polymers were characterized by X-ray diffraction pattern (XRD), Fourier transform infrared (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA) and electrical conductivity techniques. Synthesized nanocomposites were solved in tetraethylenpentamine (TEPA), and then prepared solution was mixed with epoxy and then was applied as a protective coating on carbon steel plates. The anti-corrosion behavior of the epoxy binder blended with PANI–ZnO nanocomposites were studied in 3.5% NaCl solution at a temperature of 25 °C by electrochemical techniques including electrochemical impedance spectroscopy (EIS) and chronopotentiometry at open circuit potential (OCP). It was observed that the epoxy coating containing conducting PANI–ZnO nanocomposites exhibited higher corrosion resistance and provided better barrier properties in the paint film in comparison with pure epoxy and epoxy/PANI coatings. In the case of conducting coatings, the OCP was shifted to the noble region due to presence of PANI pigments. Additionally, the possibility of formation of a passive film in the presence of PANI was reinforced at the substrate–coating interface. SEM studies taken from surface of the coatings showed that epoxy/PANI–ZnO hybrid nanocomposite coating systems (EPZ) are crack free, uniform and compact. Furthermore, it was found that the presence of ZnO nanorods beside PANI can significantly improve the barrier and corrosion protection performance of the epoxy coating due to the flaky shaped structure of the PANI–ZnO nanocomposites.     

环氧／纳米ZnO复合涂层对镁锂合金耐腐蚀性的影响

以聚丙烯酰胺凝胶法制备了纳米ZnO,并对其进行改性,得到了环氧/纳米ZnO复合涂层.采用XRD和SEM对环氧/纳米ZnO复合涂层进行了表征.通过极化曲线和交流阻抗研究了裸基、复合涂层以及经锡酸盐转化处理后涂覆环氧/纳米ZnO的复合涂层的耐蚀性能.结果表明:复合涂层呈明显的两相结构,纳米ZnO分布均匀;复合涂层和锡酸盐转化协同,提高了镁锂合金的耐腐蚀性能.涂层中纳米ZnO质量分数不同,对镁锂合金耐蚀性能有不同的影响,纳米ZnO质量分数为2%时,复合涂层对镁锂合金的保护作用最强.     

Effect of nano-sized mesoporous silica MCM-41 and MMT on corrosion properties of epoxy coating

This study investigated the effect of co-incorporation of two different kinds of nano materials with different forms, layers (Na-MMT) and mesoporous silica particles (MCM-41), into the polymer matrix on the corrosion performance of epoxy resin. Correspondingly corrosion performance of the coatings was studied by electrochemical impedance spectroscopy (EIS) in 3.5% NaCl aqueous solution and salt spray test. The X-ray diffraction (XRD) measurement showed that the Na-MMT layers were exfoliated and the hexagonal framework structure of MCM-41 was retained during and after the composite preparation. The co-incorporation of Na-montmorillonite (Na-MMT) and MCM-41 into the epoxy coating possessed the best corrosion resistance than incorporating either Na-MMT or MCM-41 particles separately due to different interfacial structures between the fillers and the matrix.     

An investigation of the effects of polymer binder compositional variables on the corrosion control of aluminum alloys using magnesium-rich primers

It has recently been shown that magnesium (Mg) particles possessing a thin oxide surface layer can be used to produce primers that provide corrosion protection to aluminum (Al) alloys through a galvanic coupling mechanism. In addition to the Mg particles, polymer binder properties also affect corrosion protection. As a result, the effects of compositional variables associated with a two-component epoxy binder system on the ability of Mg-rich primers to protect an aerospace Al alloy were determined. The variables investigated were epoxy resin molecular mass, curing agent functionality, epoxy/NH ratio, and Mg content. All of the variables investigated had a significant effect on coating system performance and an optimized coating composition was identified that showed very good corrosion protection for at least 3,000 h of ASTM B117 salt spray exposure.     

纳米改性工业防腐蚀涂料的研制与应用

介绍了纳米改性工业防腐蚀涂料的制备工艺,包括纳米浓缩浆、纳米改性环氧封闭漆、纳米改性环氧云铁中间漆以及纳米改性含氟聚氨酯面漆等系列产品的制备与表征。测试结果表明,纳米材料在纳米浆及涂料中获得了良好分散,纳米改性复合涂层(即喷铝涂层+纳米改性环氧封闭漆+纳米改性云铁中间漆+纳米改性含氟聚氨酯面漆)的物理机械性能以及耐久性均得到显著提高,产品在实际工程应用中也取得了可喜成果。该纳米改性工业防腐蚀涂料具有良好的应用前景。     

Fabrication and properties of nano‐ZnO/glass‐fiber‐reinforced polypropylene composites

Polypropylene (PP) is widely used in many fields, such as automobiles, medical devices, office equipment, pipe, and architecture. However, its high brittle transformation temperature, low mechanical strength, dyeing properties, antistatic properties, and poor impact resistance, considerably limit its further applications. Nano‐ZnO treated by KH550 coupling agent and glass fibers (GFs) were introduced in order to improve the mechanical performance and flowability of PP in this research. The crystallization behavior and microstructure of nano‐ZnO/GFs/PP hybrid composites were analyzed by differential scanning calorimetry, transmission electron microscopy, and scanning electron microscopy. The effect of crystallization behavior on the mechanical properties of the nanocomposites was investigated and analyzed. The results indicated that nano‐ZnO surface‐coupled by KH550 could be uniformly dispersed in the PP matrix. The incorporation of nano‐ZnO and GFs resulted in increases of the crystallization temperature and crystallization rate of PP and a decrease of the crystallization degree. The introduction of nano‐ZnO and GFs also enhanced the tensile strength and impact toughness of the hybrid composites and improved their fluidity. Composites containing 2% of nano‐ZnO and 40% of GFs possessed the optimum mechanical properties. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

环氧涂膜交联密度与耐蚀性

环氧涂膜的交联密度表征涂膜网络结构的致密程度。着重叙述环氧涂膜交联密度与防水蒸汽透过量的关系;高固体分环氧铁红涂料和环氧铁红粉末涂料形成涂膜的交联密度与涂膜耐蚀性的关系。TY650聚酰胺与胺加成物制备复配型固化剂明显提升环氧涂膜的耐蚀性;新开发的快干型固化剂可使环氧粉末涂料在175％／3min实现固化,为节能型环氧粉末涂料品种增添了新成员。     

Investigation of corrosion protection properties of an epoxy nanocomposite loaded with polysiloxane surface modified nanosilica particles on the steel substrate

In this study, it has been aimed to investigate the corrosion protection properties of an epoxy/polyamide coating loaded with different concentrations (ranged from 3 to 6% (w/w)) of the polysiloxane surface modified silica nanoparticles (nano-SiO₂). The nanocomposites were applied on the steel substrates. Field emission scanning electron microscope (FE-SEM) and UV–vis techniques were utilized in order to investigate the nanoparticles dispersion in the coating matrix. The effects of addition of nanoparticles on the corrosion resistance of the coating were studied by an electrochemical impedance spectroscopy (EIS) and salt spray test. The coating surface degradation was studied by optical microscope and Fourier transform infrared radiation (FT-IR) spectroscopy. Results obtained from UV–vis and FE-SEM analyses revealed proper and uniform distribution of surface modified nanoparticles in the epoxy coating matrix. It was shown that the coating corrosion protection properties were significantly enhanced in the presence of 5 wt% silica nanoparticles. Less degradation occurred on the surface of the coatings loaded with 5 wt% nanoparticles.     

Preparation and characterization of a novel conducting nanocomposite blended with epoxy coating for antifouling and antibacterial applications

In this study, novel epoxy-based paint was synthesized to be applied on carbon steel. The composition of the paint mainly contains epoxy mixed with an electronically conductive polymer, polyaniline (PANI), alone and combined with its nanocomposite derivation containing ZnO nanorods as an additive. The antifouling properties of the paint applied on carbon steel were investigated. The conductive nanocomposite was synthesized by an in situ chemical oxidative method of aniline in the presence of ZnO nanorods and then well characterized. The antifouling behavior was evaluated for 9 months in the Caspian Sea and Persian Gulf. Results revealed that epoxy/PANI–ZnO nanocomposite coating can prevent accumulation of marine macroorganisms on the coated panel. In addition, the epoxy coating comprising PANI–ZnO nanocomposite as well as the epoxy/ZnO coating exhibit significant antibacterial characteristics against (E. coli and S. epi). We interpret the antifouling and antibacterial behavior of the paint with (i) the presence of emeraldine salt structure in PANI which develops a surface pH in a range of 4–5 preventing the adhesion of microorganisms on the surface and (ii) the antibacterial and antifouling properties of zinc oxide nanorods that occurred by the production of hydrogen peroxide on the surface of the coating.