HMMM cured corrosion resistance waterborne ormosil coating for aluminum alloy

Due to the exceptional advantages of sol–gel process, organically modified silane (ormosil) coating has been applied to study the corrosion protection of aluminum alloy. In the present work, GPTMS/MTMS sol–gel solution was prepared by hydrolysis and condensation of 3-glycidoxypropyltrimetoxysilane (GPTMS) and methyltrimethoxysilane (MTMS) in aqueous solution of 0.05 M acetic acid in molar ratios 3:1. To prepare the ormosil coating solutions, a crosslinking agent hexamethoxymethylmelamine (HMMM) and a blocked acid catalyst p-toluenesulphonic (p-TSA) were combined with the sol–gel solution. Aluminum substrates were dip coated and cured at 130 °C for 45 min. Effectiveness of HMMM as a crosslinking agent was analyzed by evaluating corrosion resistance, chemical resistance and hydrophobicity of coating using potentiodynamic polarization method, immersion test and water contact angle, respectively. UV stability of sol–gel solution, ormosil coating formulation and coated substrate was also studied using UV–vis spectroscopy and UV-weatherometer to see performance of coating in outdoor application. Thermal behavior of ormosil was characterized using TGA and DSC. Surface morphology and structural characteristics were also characterized using SEM, AFM and FT-IR-RAS (reflection absorption spectroscopy). Pencil hardness, impact test and bend test were carried out to determine the adhesion, hardness and flexibility of coating.     

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.     

Electrochemical and salt spray analysis of multilayer ormosil/conversion coating systems for the corrosion resistance of 2024-T3 aluminum alloys

The corrosion resistance characteristics of multilayer coating systems comprised of a conversion coating base layer and an organically modified silicate (ormosil) topcoat have been analyzed using salt spray and potentiodynamic polarization curve analyses. The effectiveness of the multilayer coating systems was found to depend on the presence of an electrochemically active species in the conversion coating and on the presence of a curing agent in the ormosil system. Multilayer coatings systems comprised of conversion coatings that contain active corrosion inhibitors were found to provide high degrees of corrosion protection. In all cases, the presence of the ormosil was found to enhance the corrosion resistance of the underlying conversion coating. The use of multilayer ormosil/conversion coating systems enhances the corrosion protection of 2024-T3 aluminum alloy by combining previously developed corrosion protection methods with emerging sol-gel technology. Environmental Institute, Stillwater, OK 74078.     

铝合金铈盐转化膜的研究

提出了一种铝合金铈盐化学转化成膜工艺,利用电化学方法研究了铝合金铈盐化学转化膜的成膜过程及耐蚀性能,结果表明,成膜促进剂的加入能有效提高铈盐转化膜的成膜速度,所得转化膜对铝合金的点蚀有较好的抑制作用。     

Comparison of corrosion performance of various conversion coatings on magnesium alloy using electrochemical techniques

Comparative studies on some of the important chemical conversion coatings, namely, phosphate–permanganate, galvanic black anodizing, dichromate treatment, and micro arc oxidized and modified acid fluoride anodizing on magnesium alloy AZ31B have been conducted. The surface morphology and composition of the coatings were examined through SEM and EDX techniques. Corrosion resistances of these coatings were compared using electrochemical impedance spectroscopy (EIS) and linear polarization studies. The corrosion resistances of the coatings investigated were found to be according to the order as follows: modified acid fluoride > micro arc oxidized phosphate > micro arc oxidized silicate > dichromate > galvanic black anodizing > phosphate-permanganate > bare magnesium.     

铝合金表面的缓蚀作用研究

首先借助扫描电镜观察了铝合金表面经不同pH水溶液腐蚀后的微观变化。SEM结果表明,在酸、碱条件下因腐蚀机理的不同,铝合金表面的微观变化也有明显差异。同时研究了常用的5种表面活性剂和2种工业缓蚀剂的缓蚀作用。实验结果表明,在pH=2的酸性条件下,表面活性剂中C12～14烷基糖苷(APG)、椰油脂肪酸二乙醇酰胺(6501)和烷基苯磺酸钠(LAS)的缓蚀效果较好;pH=9的碱性条件下,APG和6501的缓蚀效果较好;综合分析APG的缓蚀作用最佳;而对于2种工业缓蚀剂,在酸、碱条件下均有一个最佳缓蚀浓度。     

Investigation of fluoacid based conversion coatings on aluminum

Conversion coatings on metals enhance paint or lacquer adhesion and promote corrosion resistance. Traditionally, these conversion coatings were based on chromium chemistry. In recent years, formulations based on fluotitanic or fluozirconic acid and polymer have demonstrated performance on a par with chromium-based treatments. The choice of fluoacid and polymer in the treatment has a strong impact on coating performance. The impact of pretreatment composition was demonstrated for aluminum extrusion processes. Electrochemical investigation, including linear polarization and electrochemical impedance spectroscopy, was used to differentiate corrosion resistance among the various treatments. Scanning electron microscopy, grazing angle infrared spectroscopy, and X-ray photoelectron spectroscopy were used to elucidate chemical composition of the treated aluminum surfaces.     

Electropolymerized polyaniline coatings on aluminum alloy 3004 and their corrosion protection performance

Homogeneous and adherent polyaniline coatings were electrosynthesized on aluminum (Al) alloy 3004 (AA 3004) from an aqueous solution containing aniline and oxalic acid by using the galvanostatic polarization method. A higher applied current density in the polymerization stage proved to be the best condition to adopt for the synthesis of more compact and strongly adherent polyaniline coatings on Al. The corrosion performances of polyaniline coatings were investigated in 3.5% NaCl solution by the potentiodynamic polarization technique and electrochemical impedance spectroscopy (EIS).Potentiodynamic polarization and electrochemical impedance spectroscopy studies reveal that the polyaniline acts as a protective layer on Al against corrosion in 3.5% NaCl solution. The current corrosion decreases significantly from 6.55 μA cm⁻² for uncoated Al to 0.158 μA cm⁻² for polyaniline-coated Al. The corrosion rate of the polyaniline-coated Al is found to be 5.17 × 10⁻⁴ mm year⁻¹, which is ∼40 times lower than that observed for bare Al. The potential corrosion increases from −1.015 V versus SCE for uncoated Al to ∼−0.9 V versus SCE for polyaniline-coated Al electrodes. The positive shift of ∼0.11 V in potential corrosion indicates the protection of the Al surface by the polyaniline coatings.The synthesized coatings were characterized by UV-visible absorption spectrometry, Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). Optical absorption spectroscopy reveals the formation of the emeraldine form of polyaniline. The results of this study clearly ascertain that the polyaniline has outstanding potential to protect the AA 3004 alloy against corrosion in a chloride environment.     

Electrospun polymeric coatings on aluminum alloy as a straightforward approach for corrosion protection

Several metals and alloys are susceptible to corrosion attack and this usually implies the accurate selection of a specific material depending on the working conditions and the characteristics of the environment to which it will be exposed to. However, it could represent a restriction at the same time because a limited range of materials can be practically considered. In addition, they could be also characterized by unsuitable properties for the intended application and high costs. To address this issue, polymeric coatings exhibit high potentiality to be a valid alternative to toxic chromates, allowing to deal with the most appropriate metallic materials and affordable deposition procedures. In this work, polyvinyl alcohol (PVA) fibrous coating was successfully collected onto aluminum alloy‐6082 by means of electrospinning technique. The anticorrosion performance of the final system has been evaluated in 3 wt % NaCl solution by means of electrochemical impedance spectroscopy (EIS). To avoid PVA disintegration in aqueous environment, several crosslinking procedures were assessed using glyoxal. The two most promising ones (120°C for 60 min and 150°C for 15 min) were then considered for a further investigation. Crosslinked PVA mats showed improved properties as compared to the as‐spun case, as demonstrated by mechanical and thermal analyses. Electrochemical tests revealed that crosslinked coatings can protect aluminum substrates against corrosion, especially for the electrospun PVA coating treated at 120°C. In this case, after 270 h, a significant corrosion resistance of about 26 kΩ was recorded with respect to the blank alloy (about 3.8 kΩ). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41250.     

Effective corrosion protection of 8090 alloy by cerium conversion coatings

Conversion treatments based on immersion in Cr(VI) aqueous solutions are key technologies that combine low cost, easy application and high performance. However, they are environmentally problematic due to their carcinogenity and genotoxicity. Among the potential alternatives, treatments based on rare-earth compounds have drawn attention due to the stability of their oxides and their environmental acceptability. Despite the amount of work published, there is not yet an industrially suitable alternative treatment for aircraft aluminium alloys that is able to provide the required corrosion protection. A common feature of these alloys is the high level of copper in their chemical composition. Although the presence of copper in an alloy may enhance cerium deposition, high copper content alloys (AA2024, AA7075) have proven the most difficult to protect with Ce conversion coatings.In the present work, a commercial 8090-T8 aluminium alloy containing 1.15 weight percent (wt.%) Cu was coated with a Ce conversion coating at room temperature from a Ce bath without prior pretreatment of the specimens. Polarisation curves revealed that the presence of a cerium conversion coating (CeCC) reduces by two orders of magnitude the corrosion rate of the AA8090 alloy in a sodium chloride solution. Impedance measurements exhibited capacitive behaviour for the CeCC up to 216 h, showing that the cerium layer protects the bare alloy in the aggressive solution.Electrochemical tests have therefore revealed that these conversion layers afford long-lasting protection; withstanding up to 168 h in Salt Spray test.     

Influence of buffering on the spontaneous deposition of cerium conversion coatings for corrosion protection of AA2024-T3 aluminum alloy

Cerium-based conversion coatings were spontaneously deposited on AA2024-T3 alloy at 60 °C using buffered and non-buffered CeCl₃ solutions in the presence of H₂O₂. Malonic acid or amino-acetic acid (glycine) was used as buffering additives. The deposition process and the properties of the coatings obtained were followed by linear voltammetry and electrochemical impedance spectroscopy. The surface morphology was studied by scanning electron microscopy. It was found that buffering complicates the conversion process and hampers the deposition rate. The coatings deposited using buffered baths had lower barrier ability and corrosion durability in 3.5 % NaCl corrosive medium compared to those deposited in the absence of buffers.     

LY12铝合金表面钒–钛复合转化膜的制备与耐蚀性研究

为解决单一钒酸盐转化膜表面因存在裂纹而耐蚀性不佳的问题,采用由硫酸氧钛(Ti OSO4)、偏钒酸钠(Na VO3)组成的转化液,在LY12铝合金表面制备出钒–钛复合转化膜。通过中性盐雾(NSS)测试讨论了Ti OSO4和Na VO3质量浓度、时间、温度、p H等工艺条件对转化膜耐蚀性的影响,并通过单因素试验得到了最佳转化条件:Ti OSO4 0.5 g/L,Na VO3 0.4 g/L,p H 4.0,温度25°C,转化时间10 min。用扫描电镜和能谱分析了转化膜的表面形貌及元素组成。结果表明,由O、Ti、V、Al、Mg等元素组成的钒–钛复合转化膜无裂纹。LY12铝合金经转化处理后,在3.5%Na Cl溶液中的腐蚀电位较转化前正移56 m V,腐蚀电流密度减小约1/5,耐盐雾时间达到91 h,耐蚀性得到显著提高。     

铝合金表面钛酸盐化学转化膜研究

基于含铬处理对环境影响的考虑,世界范围内都在积极开发有效的替代技术,用于铝合金腐蚀保护从而代替铬酸盐转化处理。研究了铝合金钛酸盐处理技术。通过循环极化曲线和盐雾试验测定,钛酸盐和铬酸盐化学转化膜都有非常宽的钝化区,在NaC l(c=0.5 mol/L)溶液中2种氧化转化膜均没有击穿电位;钛酸盐转化处理的样品经336 h盐雾试验表面无点腐蚀发生。钛酸盐转化膜可以为铝合金提供良好的腐蚀保护作用。     

Study on the effect of vanillin on the corrosion inhibition of aluminum alloy

The effect of vanillin on the corrosion inhibition of aluminum (Al) alloy in seawater was studied by potentiodynamic polarization (PP), linear polarization resistance (LPR), and electrochemical impedance spectroscopy (EIS) techniques. The surface morphology after its exposure to seawater with and without vanillin was examined by scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS). All the studied parameters showed good inhibitive characteristics against the corrosion of Al alloy in the tested solution, and their performance was observed to increase with the inhibitor concentration. Polarization data indicated that the studied inhibitor is a mixed-type inhibitor. Linear polarization and EIS studies showed that there were significant increases in the overall resistance after the addition of vanillin. The adsorption of inhibitor on Al alloy was found to obey the Langmuir adsorption isotherm. The analysis of SEM and EDS confirmed the formation of precipitates of vanillin on the metal surface, which reduced the overall corrosion reaction.     

Effective corrosion protection of AA6061 aluminum alloy by sputtered Al-Ce coatings

Al-Ce coatings were deposited on silicon and AA6061 aluminum alloy substrates by DC magnetron sputtering using aluminum in combination with pure cerium targets. The materials were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and electrochemical impedance spectroscopy (EIS) in order to consider their application as high corrosion resistance coatings. The corrosion behavior of the films was studied using a NaCl aqueous solution (3.5 wt%). As for the characterization results, an apparent amorphous phase of aluminum oxide with small cerium compounds embedded in the matrix was detected by the X-ray diffraction patterns and HRTEM on the deposited films at 200 W and 4 Pa. At these conditions, AFM and SEM images evidenced crack-free coatings with low-roughness nanometric structures and columnar growth. EIS and Tafel results converged to indicate an inhibition of the corrosion reactions. The film displayed good stability in the aggressive medium and after 1 day of exposure underwent very little degradation. The variations in the impedance and Tafel characteristics were found to occur as a function of cerium content, which provokes important changes in the film protective properties.     

铝及铝合金无铬氟锆酸盐化学转化膜

研究了一种适用于铝及铝合金的无铬化学转化工艺,探讨了转化液的主要成分和工艺条件对转化膜质量的影响,得到了较好的工艺条件:氟锆酸钾1.0～2.0 g/L,氢氟酸0.5 ～ 1.5 mL/L,促进剂4～6g/L,氧化剂(硝酸镁)8～12g/L,pH 3.5～4.0,温度40～60℃,氧化时间4～6min.按此工艺制备的转化...     

氯离子对6063铝合金铈-锰转化膜耐蚀性的影响

在Ce-Mn稀土钝化液中添加Cl-作为促进剂,以6063铝合金为基体制备了Ce-Mn转化膜。分别采用扫描电镜(SEM)和能谱仪(EDS)研究了转化膜的表面形貌及元素组成,并采用硫酸铜点滴腐蚀实验、动电位极化曲线以及电化学阻抗谱(EIS)研究了Ce-Mn转化膜的耐蚀性。结果表明,Ce-Mn转化膜主要由Ce、Mn、O等元素组成,往稀土钝化液中添加Cl-可使膜层更平整、致密,转化膜的平均耐点滴时间从50s提高至100s,在NaCl质量分数为3.5%的腐蚀介质中的腐蚀电流密度明显降低,转化膜极化电阻增大,铝合金的耐蚀性显著提高。     

Mechanism of corrosion protection of aluminum alloy substrate by hybrid polymer nanocomposite coatings

The corrosion protection of polymer clay nanocomposite, PCN coatings consisting of polyurea, siloxanes, epoxy ester and montmorillonite clay was determined. Corrosion resistance of the coating, was assessed by monitoring the polarization resistance and impedance of coated aluminum alloy, Al 2024-T3, coupons immersed in 3.5 wt.% of sodium chloride, NaCl, solution. Direct current polarization and electrochemical impedance spectroscopic techniques were used to measure polarization resistance and impedance of the samples, respectively. Diffusion of saturated salt solution into free-standing PCN films was measured gravimetrically and diffusivity of the nanocomposites was determined. The presence of clay decreases diffusivity and increases corrosion resistance of the non-scribed coatings containing up to 10 wt.% of clay. A correlation between polarization resistance and diffusivity was made. It was shown that for non-scribed coatings, polarization resistance increases with decreasing diffusivity. A relationship between coating's diffusivity and weight fraction of clay was established. Increasing clay concentration also resulted in decreasing diffusivity. The scribed nanocomposite coatings show slightly decreasing polarization resistance with increasing weight fraction, however, the polarization resistance of scribed coatings containing low clay weight fraction in the range between 0.5 and 2.0 wt.% was higher than that for the matrix. A barrier mechanism of corrosion prevention of the coated substrate is proposed for non-scribed coatings. The viscoelastic property of the nanocomposites was determined by using dynamic mechanical spectrometer. A correlation between polarization resistance of the coatings and the rubbery plateau modulus on the one hand and polarization resistance and tan δ peak area for α-transition of the nanocomposites is made. Decreasing tan δ peak area for α-transition and increasing rubbery plateau modulus resulted in increasing coatings polarization resistance.     

The formation and corrosion behavior of a zirconium-based conversion coating on the aluminum alloy AA6061

To understand the mechanism of the coating formation, the formation process of a zirconium-based conversion coating on aluminum alloy 6061 has been studied by means of AFM in PeakForce Kelvin Probe Force Microscope (PF-KPFM) mode which could provide direct evidence for the existence of driving force for the film formation. In addition, various techniques including SEM, XPS, EIS, salt spray test, and scanning electrochemical microscope were used to investigate the surface state and corrosion behavior of the conversion film. The direct driving force for the coating formation is the Volta potential difference between the intermetallic particles and matrix. That difference produces an ocean of micro electrochemical cells in which the intermetallic particles act as cathodic sites for the film deposition. However, the precipitation of the layer is a self-limited process in which the driving force gradually decreases as the conversion layer covers the surface of the aluminum alloys. The anti-corrosion performance of the film is unfavorable compared to the conventional chromate conversion coatings due to the pitting corrosion that occurs when exposed to harsh environment containing chloride. Furthermore, the zirconium-based conversion coating possesses no self-healing ability leading to the continuous degradation of the film until it completely lose efficacy.     

Application and evaluation of environmentally compliant spray-coated ormosil films as corrosion resistant treatments for aluminum 2024-T3

An epoxide modified silicate sol–gel film spray coated on an aluminum alloy 2024-T3 coupon was demonstrated to provide exceptional barrier and corrosion protection when compared to chromate-based surface treatments. Surface characterization indicated that the applied film was 2.2 μm thick and crack free. Potentiodynamic evaluation revealed that the film provided a continuous barrier of protection over a broad potential range. Comparison with standard Alodine-1200 type surface treatment indicated several orders of magnitude improvement in barrier protection and enhanced protection under accelerated corrosion test.