Spectroscopic and corrosion resistance characterization of GLYMO–TEOS Ormosil coatings for aluminum alloy corrosion inhibition

Corrosion resistance properties of spray- and dip-coated 3-glycidoxypropyltrimethoxysilane (GLYMO)–tetraethoxysilane (TEOS) Ormosil films have been investigated using salt spray analysis. ¹H–¹³C and ¹H–²⁹Si CP/MAS NMR analyses indicate that organic content and hydrolysis water ratio affect the Ormosil structure, and in turn, the corrosion resistance properties of the Ormosil film. For spray-coated samples, films derived from the 11 mol% GLYMO Ormosil prepared using hydrolysis water content (W=2 and 4) provided good corrosion protection, as this combination of organic content, water ratio, and deposition method produced films of the appropriate thickness, hydrophobicity, and density for good corrosion protection. Films prepared from high organic contents (25 and 67 mol% GLYMO) and low hydrolysis water content values (W=1 and 2) exhibited the best corrosion resistance for films prepared by dip coating. Presumably, these films comprise a dense network structure with organic groups dispersed throughout the film, providing a hydrophobic barrier coating capable of repelling water and corrosion initiators.     

Application of laser ablation technique for removal of chemically inert organically modified silicate coatings

Removal of organically modified silicate (Ormosil) coatings from 2024-T3 aluminum alloy substrates has been investigated using a laser ablation technique utilizing a 308 nm excimer laser. Incorporation of UV-absorbing dye molecules containing λ_max in the vicinity of the laser wavelength (butyl-PBD, Furan 2, Morin, HQSA) into the Ormosil thin film was found to facilitate coating removal. Ormosil thin films containing 0.1–0.5 mol% UV-absorbing dye molecules were subjected to laser treatment at various fluences ranging from 0.2 to 0.6 J/cm². The presence of the UV-absorbing dye molecules in the Ormosil thin film was found to facilitate coating removal at a lower fluence as compared to dye-free coatings as determined by scanning electron microscopy. The effectiveness of coating removal was found to depend on several parameters including laser fluence, number of pulses per spot, and dye concentration.     

Evaluation of the corrosion resistance of phosphate coatings obtained by anodic electrochemical treatment

The corrosion resistance of phosphate coating obtained by anodic electrochemical treatment at 4–6 mA/cm² is addressed in this paper. The corrosion performance of these coatings is also compared with the coatings obtained by chemical treatment. The regenerated phosphoric acid under the influence of anodic current causes a large variation in morphological features of the coatings. Immersion and salt spray tests indicate the ability of these coatings to act as a barrier film on mild steel. Polarization and electrochemical impedance spectroscopic (EIS) studies indicate that the corrosion resistance of phosphate coatings obtained by anodic treatment decreases with increase in current density employed for deposition. In spite of their higher coating weight, the corrosion resistance of phosphate coatings obtained by anodic treatment is inferior to those obtained by chemical treatment. The porosity or discontinuities created due to the dissolution of the coating under the influence of anodic current are considered responsible for the inferior corrosion resistance of these coatings. The study concludes that anodic treatment has only a limited scope for preparing phosphate coatings with improved corrosion resistance.     

Corrosion protection of Mg alloys by cathodic electrodeposition coating pretreated with silane

The corrosion resistance characteristics of three coatings on magnesium alloy AZ31—conventional paint with phosphate film, cathodic electrodeposition coating (E-coating), and E-coating pretreated with silane (Mg/silane/E-coating)—have been studied by means of electrochemical impedance spectroscopy (EIS) in a 3.5 wt% NaCl neutral aqueous solution and salt spray test using ASTM B117. Silane film was obtained by dipping AZ31 specimens in diluted hydroalcoholic silanic solutions and successively curing. It was found that the corrosion resistance of the Mg alloy with E-coating was superior to conventional paint and could be further enhanced with silane pretreatment as an interfacial film. The results of water volume fraction (Φ_saturation) and diffusion coefficient (D) also indicated that the Mg/silane/E-coating possessed excellent compactness and corrosion resistance. A model of the corrosion mechanism for Mg/silane/E-coating has been presented through EIS analysis.     

Application of EIS and salt spray tests for investigation of the anticorrosion properties of polyurethane-based nanocomposites containing Cr2O3 nanoparticles modified with 3-amino propyl trimethoxy silane

The Cr₂O₃ nanoparticles were modified with 3-amino propyl trimethoxy silane in order to obtain proper dispersion and increment compatibility with the polyurethane coating matrix. The nanocomposites prepared were applied on the St-37 steel substrates. The existence of 3-amino propyl trimethoxy silane on the surface of the nanoparticles was investigated by Fourier transform infrared (FTIR) spectroscopy and thermal gravimetric analysis (TGA). Dispersion of the surface modified particles in the polyurethane coating matrix was studied by a field emission-scanning electron microscope (FE-SEM). The electrochemical impedance spectroscopy (EIS) and salt spray tests were employed in order to evaluate the corrosion resistance of the polyurethane coatings. Polarization test was done in order to investigate the corrosion inhibition properties of the Cr₂O₃ nanoparticle on the steel surface in 3.5 wt.% NaCl solution. The adhesion strengths of the coatings were evaluated by pull-off adhesion tester before and after 120 days immersion in 3.5 wt.% NaCl solution. FT-IR and TGA analyses revealed that surface modification of the nanoparticles with 0.43 silane/5 g pigment resulted in the greatest amount of silane grafting on the surface of particles. Results obtained from FE-SEM analysis showed that the surface modified nanoparticles dispersed in the coating matrix properly. Results obtained from EIS and salt spray analyses revealed that the surface modified particles enhanced the corrosion protection performance of the polyurethane coating considerably. The improvement was more pronounced for the coating reinforced with 0.43 g silane/5 g pigment. Moreover, the adhesion loss decreased in the presence of surface modified nanoparticles with 0.43 silane/5 g pigment.     

不同镀锌工艺三价铬钝化耐腐蚀性研究

采用中性盐雾试验和电化学阻抗谱,研究了酸性氯化钾镀锌、碱性无氰镀锌和碱性氰化物镀锌3种工艺所得镀锌层经三价铬彩色钝化后钝化膜的耐蚀性.结果表明:钝化后,酸性氯化钾镀锌层的耐蚀性最好,碱性无氰镀锌层次之,碱性氰化物镀锌层最差.在质量分数为1%的氯化钠溶液中,镀锌层钝化膜电阻的大小顺序为:酸性氯化钾镀锌>碱性无氰镀锌>碱性氰化物镀锌.酸性氯化钾镀锌钝化膜的耐蚀性较好可以与所得镀层中有机杂质夹杂较少有关.     

Corrosion behavior of nanohybrid titania–silica composite coating on phosphated steel sheet

Corrosion resistance behavior of sol–gel-derived organic–inorganic nanotitania–silica composite coatings was studied. Hybrid sol was prepared from Ti-isopropoxide and N-phenyl-3-aminopropyl triethoxy silane. The structure, morphology, and properties of the coating were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and thermo gravimetric analysis. The corrosion performances of the sol–gel-coated samples were investigated by electrochemical impedance spectroscopy (EIS) and standard salt spray tests. The hybrid coatings were found to be dense, more uniform, and defect free. In addition, the coatings also proved its excellent corrosion protection on phosphated steel sheet.     

铝合金表面电解沉积稀土转化膜工艺研究

研究了一种通过电解沉积方法在防锈铝LF21表面上生成铈盐转化膜的工艺,应用正交实验研究了有关因素对成膜过程的影响并获得了最佳的技术参数用极化曲线、交流阻抗和中性盐雾试验等方法测试了该工艺形成膜层的耐蚀性能及其组成一结果表明：经过电解沉积稀土转化膜处理后,防锈铝的阳极腐蚀过程受到了阻滞,自然腐蚀电位负移;与经过化学转化膜处理后相比,其耐蚀性能有显著提高,可通过400h的中性盐雾实验,亲水性能亦有明显提高。     

片状玻璃对水性复合锌铝合金涂层耐蚀性的影响

为了改善水性锌铝合金涂层的耐蚀性能,在硅烷钝化液中加入玻璃粉制备了玻璃/水性锌铝涂层,采用中性盐雾试验、电化学阻抗谱、极化曲线等方法研究了玻璃粉用量对 Q235 钢表面该涂层耐蚀性能的影响,利用扫描电镜、能谱、X 射线衍射等技术分析了涂层的形貌、组成以及元素分布状况。结果表明,添加片状玻璃粉可以提高涂层的耐蚀性能。玻璃粉与金属粉以平行叠加的方式排列在锌铝合金涂层中,部分玻璃粉包覆在涂层的外围形成致密的网状结构。当玻璃粉的添加量为 20 g/L时,涂层的耐蚀性能最好,耐中性盐雾试验时间为 3 100 h,是不添加玻璃粉涂层的 5 倍。     

Corrosion resistance of phosphate coatings obtained by cathodic electrochemical treatment: Role of anode–graphite versus steel

The formation of phosphate coatings by cathodic electrochemical treatment using graphite and steel anodes and evaluation of their corrosion resistance is addressed in this paper. The type of anode used, graphite/steel, has an obvious influence on the composition of the coating, resulting in zinc–zinc phosphate composite coating with graphite anode and zinc–iron alloy–zinc phosphate–zinc–iron phosphate composite coating with steel anode. The corrosion resistance of the coating is found to be a function of the composition of the coating. The deposition of zinc/zinc–iron alloy along with the zinc phosphate/zinc and zinc–iron phosphate using graphite/steel anodes has caused a cathodic shift in the E_corr compared to uncoated mild steel substrates. The i_corr values of these coatings is very high. EIS studies reveal that zinc/zinc–iron alloy dissolution is the predominant reaction during the initial stages of immersion. Subsequently, the formation of zinc and iron corrosion products imparts resistance to the charge transfer process and increases the corrosion resistance with increase in immersion time. The corrosion products formed might consist of oxides and hydroxychlorides of zinc and iron. The study suggests that cathodic electrochemical treatment could be effectively utilized to impart the desirable characteristics of the coating by choosing appropriate anode materials, bath composition and operating conditions.     

Electrochemical impedance studies of corrosion protected surfaces covered by epoxy polyamide coating systems

Electrochemical impedance spectroscopy (EIS) was used to study the corrosion behavior of different types of commercial quality epoxy polyamide dry coatings on mild steel, with thickness between 150 and 250 μm, which were previously weather accelerated in a wet chamber. The following data were established on the basis of impedance curves and corresponding equivalent circuits: the coating capacity that relates to the coating dimension, the pore resistance that represents conductive paths through the pores, and Warburg coefficients, which are the measure of ion diffusion through the coating. EIS data were compared with a criterion in the European standard, and samples were classified on the basis of their quality, also receiving a final ranking by summing-up all the individual rankings. Suggestions have been made, namely that the use of anticorrosive active pigments is obsolete, when the thickness of the coatings exceeds 200 μm.     

Real time mapping of corrosion activity under coatings

Current accelerated testing of aircraft coating systems for corrosion protection relies heavily on salt spray methods. Electrochemical techniques such as electrochemical impedance spectroscopy (EIS) and electrochemical noise methods (ENM) provide insight into the global properties of a coating system, and both techniques are being used on a limited basis. However, there is a need to investigate corrosion events with greater spatial resolution under coatings at the metal/coating interface. Such corrosion activity may be related to coating defects and variations in the surface chemistry of the underlying metal.

The scanning vibrating electrode technique (SVET) has been developed to allow high spatial resolution investigation of localized corrosion activity that may be associated with coating defects or galvanic coupled regions of the metal surface. The SVET offers high resolution in current measurements of the order of 0.5 μA/cm² and is able to detect in-situ initiation and progress of corrosion activity under a protective coating. Using the SVET, minute variations in d.c. current associated with localized corrosion activity are detected and used to map both anodic and cathodic corrosion activities in a localized area. The difference in initial corrosion activity under various coatings can be correlated to the performance life of the coatings. The application of SVET to aircraft coatings and corrosion is reported to demonstrate the utility of this important new electrochemical tool.

In the current study, the SVET was used to discriminate the corrosion protection performance of selected sol–gel based coating systems. Sol–gel based surface treatments are being developed as part of an environmentally compliant coating system alternative to the currently used chromate-based systems. The SVET results are compared with data obtained from chromium inhibition coating systems. The SVET analyses are compared with electrochemical impedance measurements. The comparison of such data will provide the basis to adopt SVET measurements as an early performance discriminator for newly developed coating systems.     

Corrosion resistance performance of cerium doped silica sol–gel coatings on 304L stainless steel

The aim of this work is the synthesis and investigation of silane based organic–inorganic hybrid coatings, which can be used to improve the corrosion performance of steel structures subjected to a marine environment. The silane based sol–gel coatings were prepared by dip coating 304L stainless steel in a solution of organically modified silica sol made through hydrolysis and condensation of 3-glycidoxypropyl-trimethoxysilane (GPTMS) as precursor and bisphenol A (BPA) as a cross-linking agent in an acid catalyzed condition. The influence of the addition of cerium and the use of bisphenol A as a cross-linking agent on the microscopic features and morphology as well as on the corrosion resistance of the coatings were examined using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), neutral salt spray tests, potentiodynamic polarization and electrochemical impedance techniques. Results show that cerium modified nano-hybrid coatings exhibit a superior corrosion inhibition performance to that displayed by silica hybrid coatings. Additionally, data showed that the bisphenol A as a cross-linking agent has a significant effect on the morphology and corrosion resistance of the cerium doped silica coating. Omitting the use of bisphenol A causes the creation of defects/cracks in the coating, thereby promoting diffusion of the aggressive electrolyte toward the substrate and decreasing the corrosion resistance of the coating.     

Mica/polypyrrole (doped) composite containing coatings for the corrosion protection of cold rolled steel

Micas/polypyrroles (PPys) doped with molybdate, p-toluene sulfonate, dodecyl benzene sulfonate, and 2-naphthalene sulfonate composite pigments were synthesized by chemical oxidative polymerization and characterized in coatings for corrosion protection on cold rolled steel substrate by various electrochemical techniques. Synthesized composite pigments were characterized for morphology by scanning electron microscopy, which indicated physical formation of PPy on the surface of mica. Chemical composition of the composite pigments was analyzed by X-ray photoelectron spectroscopy which chemically confirmed doped PPy formation on the mica surface. Coatings were formulated at 20% pigment volume concentration (composite pigments or as-received mica pigment) and were applied on cold rolled steel substrate. Coatings were exposed to salt spray test conditions (ASTM B117) for 30 days and were periodically assessed for corrosion with electrochemical impedance spectroscopy (EIS), open circuit potential (OCP), and potentiodynamic polarization. EIS and circuit modeling results demonstrated higher coating resistance (R _c) for mica/PPy (doped) composite coatings as compared to as-received mica pigment containing coating after 30 days of salt spray exposure. Lower current density and more positive corrosion potential values were observed for mica/PPy (doped) composite coatings as compared to mica pigment-based coating in potentiodynamic polarization measurements, indicating improved corrosion protection for cold rolled steel substrate. OCP measurements revealed more positive values for mica/PPy (doped) composite coatings as compared to mica pigment-based coating suggesting superior corrosion protection for mica/PPy (doped) composites.     

富锌涂层在模拟海水中的失效机制

在筛选试验涂层体系基础上,通过浸泡、盐雾、阴极剥离、腐蚀电位监测和微观形貌分析,对12种舰船常用的无机富锌和有机富锌配套体系的腐蚀失效行为和机理进行研究。结果表明:在NaCl模拟海水条件下,无机富锌耐阴极剥离性能差;基于无机富锌涂层与有机富锌涂层配套体系的阻抗谱,环氧富锌涂层将比无机富锌具有明显的防护效果。     

Water uptake of epoxy coatings modified with γ-APS silane monomer

Epoxy resin was modified by a silane monomer, γ-aminopropyltrimethoxy silane (γ-APS), and was used as the protective coatings for LY12 aluminum alloys. The aim of the modification is to reduce the water uptake of polymeric coatings. The water absorption of coatings was measured by coating capacitance method in 3.5 wt.% NaCl aqueous solution. The result indicates that water uptake of epoxy coatings modified with 1.0 wt.% γ-APS decreases compared with pure epoxy coatings, whereas larger amounts of sliane result in the deterioration in performance against water permeation, due to the excessive consumption of epoxide group in epoxy resin by amino-group in silane agent, thus reduce the cross-linking of epxoy coating as a result of presence of excessive curing agent (polyamide). T_g of silane-modified coatings increases slightly after immersion, extremely contrasting with that of pure epoxy coating, which was observed to decrease significantly after water permeation. The formation of Si–O–Si structure resulting from the hydrolysis and condensation of silane components during the immersion in aqueous media may be a reasonable explanation for the abnormal change in T_g of silane-modified coatings. In addition, all silane-modified coatings display better protection performance, which is characterized by higher charge transfer resistances (R_ct) and lower double layer capacitance (C_dl) at substrate/electrolyte interface.     

Development of a new experimental method to determine critical pigment–volume–concentrations using impedance spectroscopy

The critical pigment–volume–concentration (CPVC) of a solvent-based epoxy coating with various pigment–volume–concentrations (PVC) was analyzed. It was shown that electrochemical impedance spectroscopy (EIS) is a suitable method to detect the CPVC of coatings. The CPVC can be derived from EIS Bode plots or by fitting the EIS-curves using simple equivalent circuit diagrams. The parameters pore resistance R_P, capacitance C of the constant phase element (CPE), the relative dielectric constant _R derived from C, and the exponent n of the CPE allow the determination of the CPVC.     

The corrosion resistance of 316L stainless steel coated with a silane hybrid nanocomposite coating

The present work aims at evaluating the corrosion resistance of 316L stainless steel pre-treated with an organic–inorganic silane hybrid coating. The latter was prepared via a sol–gel process using 3-glycidoxypropyl-trimethoxysilane as a precursor and bisphenol A as a cross-linking agent. The corrosion resistance of the pre-treated substrates was evaluated by neutral salt spray tests, linear sweep voltammetry and electrochemical impedance spectroscopy techniques during immersion in a 3.5% NaCl solution. In addition, the effect of the drying method as an effective parameter on the microscopic features of the hybrid coatings was studied using Fourier transform infrared spectroscopy and scanning electron microscopy. Results show that the silane hybrid coatings provide a good coverage and an additional corrosion protection of the 316L substrate.     

Mercapto functional azole compounds as organic corrosion inhibitors in a polyester-melamine coating

The corrosion inhibition of two mercapto functional azole compounds including 2-mercaptobenzimidazole (MBI) and 2-mercaptobenzoxazole (MBO) for mild steel in 1 M NaCl solution was studied by electrochemical impedance spectroscopy (EIS), then their impact on the protective performance of a polyester-melamine coating was evaluated using salt spray. EIS results revealed a higher corrosion inhibitive activity of MBI compared to that of MBO. Corrosion products were examined by SEM-EDX and FTIR. The results showed modification of the corrosion products in the presence of MBI and MBO. The salt spray results revealed an improved corrosion protection of the coatings formulated with MBI and MBO. There was almost no impact of MBI and MBO on adhesion strength and glass transition temperature of the coatings, meaning that their impact on the corrosion protection performance of the formulated coating could only be attributed to their effect on the corrosion products.     

咪唑啉季铵盐缓蚀剂改性蒙脱土/水性环氧纳米复合涂料

以油酸、二乙烯三胺和氯化苄为原料,合成了油酸基咪唑啉季铵盐缓蚀剂。通过FTIR、¹HNMR对其结构进行了表征,并离子交换至钠基蒙脱土(DK0)层间,制备了缓蚀剂改性蒙脱土(QACDK0)。通过XRD、TGA和UV-Vis对其结构、组成及层间缓蚀剂释放性能进行了表征。结果表明,咪唑啉季铵盐缓蚀剂约占QACDK0质量的38.96%,并将蒙脱土层间距由1.28 nm(DK0)扩大至3.98 nm(QACDK0)。利用DLS及Zeta电位对添加有QACDK0的水性环氧树脂进行了稳定性测试,其Zeta电位为–27.8 m V,具有较高的稳定性。电化学阻抗谱(EIS)测试表明,在腐蚀介质中浸泡30 d后,基于QACDK0制备的清漆漆膜仍具有2.29×10⁸?·cm²的高阻抗,表明涂层具有较好的耐腐蚀性。并且在耐中性盐雾测试中,QACDK0对应的防腐色漆耐盐雾时间最长,验证了该涂层具有良好的耐盐雾性能。