The mode of action of chromate inhibitor in epoxy primer on galvanized steel

Investigations of the mechanism of the protective action of strontium chromate pigment in an epoxy primer were carried out with electrochemical impedance spectroscopy (EIS), atomic absorption spectroscopy (AAS), scanning reference electrode techniques (SRET) and water uptake measurements. Epoxy primers applied to galvanized steel were studied in a corrosion environment which models the atmospheric precipitation of European countries. Corrosion and electrochemical properties of samples of bare galvanized steel and coated galvanized steel were investigated. It was established that the protective function of the chromate in the primer is primarily due to a cathodic/mixed inhibition of the surface of galvanized steel in defect areas of the polymer coating. It is suggested that the process of leaching of chromate ions from epoxy primer into the environment takes place because the decrease in pH at anodic defect sites causes the destruction of the primer film and accelerates the dissolution of the chromate pigment.     

The role of hexafluorozirconate in the formation of chromate conversion coatings on aluminum alloys

Aluminum based surfaces are routinely coated with a chromate based layer that provides unparalleled corrosion protection. Widely used conversion coating treatment formulations contain hexafluorozirconate as a major constituent besides chromate, ferricyanide, fluoride, and fluoborate. The function of hexafluorozirconate is the subject of this study as its function is still largely unknown. Hydrophobicity, surface morphology, and the chemistry of the surface, resulting from treatment with hexafluorozirconate, were studied using contact angle measurements, scanning electron microscopy, and energy dispersive spectroscopy, respectively. X-ray photoelectron spectroscopy was extensively utilized to determine the chemistry of the surface resulting from the hexafluorozirconate pretreatment. Our results indicate that fluoride ion containing hexafluorozirconate complex does not attack the oxide film in a manner that uncomplexed simple fluoride ion does. Hexafluorozirconate is involved in the formation of an Al-Zr-O-F based hydrated layer that increases the hydrophilicity of the surface, activates the surface, and lowers the corrosion resistance. These factors enhance the interaction of chromate with the alloy surface to result in the formation of a uniform conversion coating. Based on these results, a new model has been proposed for the formation of chromate conversion coatings.     

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.     

Microstructure and electrochemical characterization of trivalent chromium based conversion coating on zinc

A trivalent chromium based conversion coating (CCC), based on chromium nitrate solution with Co(II) ions, was developed on Zn substrate. The corrosion resistance of the trivalent CCC, measured in deaerated pH 8.0 borate buffer + 0.01 M NaCl solution using anodic polarization and electrochemical impedance spectroscopy (EIS), was very sensitive to both immersion time and bath pH. Micro-cracks were found on the surface of the CCC. Besides, the density of micro-crack and the coating thickness also depended on immersion time and bath pH. With increasing the coating thickness its pitting potential increased and passive current density decreased. The trivalent CCC formed on Zn for 40 s in pH 1.7 bath showed the best corrosion resistance, and the pitting potential increased significantly from −355 mV_SCE for Zn to 975 mV_SCE for the trivalent CCC on Zn. To explain the corrosion behavior of the trivalent CCC using EIS analysis, a modified equivalent circuit, which considered the micro-cracks in the coating and chromium corrosion product (CCP) deposited in the micro-cracks, was designed and the variation of each electrical parameter was examined. Especially, its corrosion behavior was well described by the variation of the resistance of CCP (R_ccp).     

热浸镀锌层表面偏钒酸盐转化膜

在热浸镀锌试样表面获得了一层均匀、完整的偏钒酸盐转化膜.成膜溶液成分及工艺条件为:NaVO3 5 g/L,pH 1.3,温度30 ℃,时间30 min.对比研究了偏钒酸盐转化膜和铬酸盐转化膜的耐蚀性能.结果表明,偏钒酸盐转化膜由Zn、O、V等元素组成,热浸镀锌层经偏钒酸盐转化处理后电化学阻抗和极化电阻增大,腐蚀电流密度...     

Effect of bath concentration and curing time on the structure of non-functional thin organosilane layers on aluminium

The corrosion resistance of aluminium alloys can be improved by different surface treatments such as painting. A pre-treatment based on chromate is the current method used to increase the corrosion resistance and the adhesion of the organic layer. Silane films seem to be an interesting alternative system to replace the toxic chromates. In this paper, the characterisation of bis-1,2-(triethoxysilyl)ethane (BTSE) thin layers has been evaluated by coupling optical techniques like spectroscopic ellipsometry (SE) and infra-red spectroscopic ellipsometry (IRSE) along with electrochemical methods (electrochemical impedance spectroscopy (EIS)). This approach has been chosen to have a better understanding of the protection provided by these organosilane thin films. It will be demonstrated that the BTSE bath concentration modifies the thickness of the layers and that the curing of this thin film can also improve the barrier properties by forming a denser layer.     

Hybrid nanocomposite coating by sol–gel method: a review

The development of environmentally friendly process for pretreatments of metallic substrates is a field of growing research due to the ban against chromates used as protective pretreatments. Among the possible candidates for environmentally friendly pretreatments of aluminum alloys are the silica-based sol–gel coatings. Such coatings are able to form an Si–O–Al conversion layer providing a stable alumina/sol–gel film interface, which inhibits the onset of corrosion. Sol–gel technology offers a wide range of chemical mechanisms and exhibits high potential substitutes for the environmentally unfriendly chromate metal-surface pretreatment. Sol–gel derived organo-silicate hybrid coatings, preloaded with organic corrosion inhibitors, have been developed to provide active corrosion protection when integrity of the coating is compromised. The incorporation of organic corrosion inhibitors into hybrid coatings has been achieved as a result of physical entrapment of the inhibitor within the coating material at the stage of film formation and cross-linking. Sol–gel derived coatings, especially the hybrid films, provide a dense barrier against electrolyte uptake, and offer a wide range of applications as corrosion protective, hydrophilic coatings, hydrophobic anti-reflective coatings, migration barriers against liquid and volatile compounds, antibacterial modification of textiles and water-repellent antistatic textiles. In this paper, the novel applications of the sol–gel derived coatings are presented and discussed.     

改性低铬钝化膜耐蚀性的研究

由于常规低铬钝化膜的耐蚀性不能达到中性盐雾试验的标准。采用在低铬钝化液中添加钛（ＩＶ）对低铬纯化膜进行改性。利用ＳＥＭ、ＸＰＳ等方法研究了所得钝化膜的形工通过极化电阻的测量和中性盐雾试验研究了钝化膜的耐蚀性。结果发现，钛（ＩＶ）的加入能明显提高钝化膜的耐蚀性，这是由于钝化膜中形成和硫酸氧钛，它们掺杂在钝化膜及其腐蚀产物中，有效抑制了锌镀层的腐蚀。     

Protective properties of cataphoretic epoxy coating on aluminium alloy AA6060 modified with electrodeposited Ce-based coatings: Effect of post-treatment

Ce-based conversion coatings (CeCCs) are a promising alternative to toxic chromate coatings on the metal substrates. In this work the CeCCs were electrodeposited on aluminium alloy AA6060 from aqueous solution of Ce(NO₃)₃ at different potentials (−0.95 V, −1.2 V and −1.4 V). Effect of deposition potential and post-treatment in the phosphate solution on morphology and protective properties of CeCCs with top cataphoretic epoxy coating was studied. To assess the differences between the protective systems, originating from the different CeCCs pre-treatments, electrochemical impedance spectroscopy (EIS), polarization measurements, AFM and SEM/EDS analysis were used. The EIS study was undertaken to follow the evolution of corrosion behaviour of epoxy coating/CeCCs protective systems over prolonged time of exposure to the chloride environment (3 wt.% NaCl). Results suggest significantly improved corrosion stability of epoxy coating on AA6060 with as-deposited CeCCs sub-layers with respect to the same epoxy coatings with phosphate post-treated CeCCs. The far best protective properties, i.e., the greatest value of pore resistance and the lowest value of corrosion current density were provided by the epoxy coating/CeCC protective system with CeCC deposited at −1.2 V and without post-treatment.     

Electrochemical studies of the inhibition of the cathodic delamination of organically coated galvanised steel by thin conversion films

Scanning Kelvin Probe (SKP) measurements of thin amorphous conversion film coated galvanised steel in combination with current density-potential curves and electrochemical impedance spectroscopy (EIS) were performed with the aim to improve the understanding of electrode potentials at the coating/metal interface and their influence on corrosive de-adhesion. The thin hybrid conversion films contained Zn-phosphates, titanates and also complexing organic compounds and led to an inhibition of the cathodic oxygen reduction and anodic zinc dissolution. In the polymer coated area the conversion film leads to a cathodic shift of the potential as measured by means of the SKP. This cathodic potential shift is explained by the substitution of the n-semiconducting Zn-oxide with an insulating inorganic layer. When the SKP detects the potential of freely corroding iron at a defect, where no protective coating layer is, the interfacial potential for the conversion film coated zinc layer is more negative than the defect potential. This leads to a diminished driving force for an oxygen reduction induced delamination process which is of relevance for the understanding of cut-edge corrosion.     

Feasibility study to probe the growth of chromate based conversion on Al by means of rotating ring disc electrode (RRDE) measurements

The use of a rotating ring disc electrode (RRDE) is introduced in this paper to study the formation of chromate-phosphate layers on rolled aluminium surfaces. A RRDE was developed containing an Al disc, which was converted with a chromate phosphate film, and a carbon ring, where the Cr⁶⁺ reduction rate was measured in situ. The principle of the method is that Cr⁶⁺ is transported from the bulk of the solution towards the disc and the ring electrode. At the disc electrode, a fraction of Cr⁶⁺ is consumed during the conversion of the Al disc electrode. This leads to a decrease in ring current, which is directly related to the amount of Cr⁶⁺ being reduced at the disc electrode. For proper operation of the RDDE system, an electrode with optimised geometrical characteristics is used. In order to be sure that the measured current on the ring is in relation with the Cr⁶⁺ reduction rate occurring at the aluminium disc, a number of requirements need to be fulfilled. After showing that the RDDE system is indeed able to monitor in situ the Cr⁶⁺ content during conversion, the amount of Cr⁶⁺ reduced at the disc electrode is calculated from the recorded ring current time curves. The method allows (i) to follow the growth of a conversion layer quantitatively in situ and (ii) to study the influence of important process parameters such as fluoride content, chromate content of the conversion bath and influence of mass transport.     

Investigation of zinc chromatation. I. Application of QCM-ICP coupling

Chromate conversion layers are widely used in various industrial process in order to create performant protective layers. In order to improve the quality of these layers, various analytical techniques were used to understand the deposition mechanism of these films. Unfortunately, it is rather difficult to understand all the subleties and for that reason we propose to couple EQCM measurements with inductively coupled plasma (ICP) analysis. The same zinc sample dipped in a classical chromate conversion bath was examined. Various parameters were obtained by this way such as the corrosion rate of zinc or the film formation rate. An identification of the film was also obtained by estimating the molar mass of the elements.     

铝材磷酸-铬酸盐转化膜与聚偏二氟乙烯涂料的研究

研究了铝合金装饰板和铝型材表面喷涂聚偏二氟乙烯涂料的工艺流程,探讨了铝合金的前处理、磷酸-铬酸盐转化膜和聚偏二氟乙烯底漆与面漆之间的配套性,通过在磷酸-铬酸溶液中添加硝酸镍来改善转化膜性能.对铝合金的磷酸-铬酸盐转化膜配方及工艺进行了筛选,得出了加硝酸镍的铝合金磷酸-铬酸盐转化膜的最佳工艺配方.转化膜的抗蚀性是未加硝酸镍的2倍.还研究了铝合金表面喷涂聚偏二氟乙烯涂料的涂装配套性,得到了在铝合金表面喷涂氟碳涂料的最佳配套体系.     

Corrosion behaviors of Zn/Al-Mn alloy composite coatings deposited on magnesium alloy AZ31B (Mg-Al-Zn)

After being pre-plated a zinc layer, an amorphous Al-Mn alloy coating was applied onto the surface of AZ31B magnesium alloy with a bath of molten salts. Then the corrosion performance of the coated magnesium alloy was examined in 3.5% NaCl solution by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results showed that the single Zn layer was active in the test solution with a high corrosion rate while the Al-Mn alloy coating could effectively protect AZ31B magnesium alloy from corrosion in the solution. The high corrosion resistance of Al-Mn alloy coating was ascribed to an intact and stable passive film formed on the coating. The performances of the passive film on Al-Mn alloy were further investigated by Mott-Schottky curve and X-ray photoelectron spectroscopy (XPS) analysis. It was confirmed that the passive film exhibited n-type semiconducting behavior in 3.5% NaCl solution with a carrier density two orders of magnitude less than that formed on pure aluminum electrode. The XPS analysis indicated that the passive film was mainly composed of AlO(OH) after immersion for long time and the content of Mn was negligible in the outer part of the passive film. Based on the EIS measurement, electronic structure and composition analysis of the passive film, a double-layer structure, with a compact inner oxide and a porous outer layer, of the film was proposed for understanding the corrosion process of passive film, with which the experimental observations might be satisfactorily interpreted.     

Investigation of a transparent chromate (III) passive film on electroless Ni–P coating by XPS and electrochemical methods

A transparent passive film on electroless nickel phosphorus coating (ENPC) was obtained in a chromate (Cr³⁺) bath. An ENPC sample passivated in a Cr⁶⁺-containing bath was used for comparison. The corrosion properties were tested by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). SEM, XPS, and EDX were employed to analyze the chemical composition and surface morphology of the films. SEM results indicate that the passive film is too thin to be observed by SEM. The potentiodynamic polarization tests show that the corrosion currents of the two passivated samples are only about 1/25 of the un-passivated coating. The XPS analysis illustrate that the Cr⁶⁺-treated film comprises Cr, Ni and O, while the Cr³⁺-treated film is made up of Cr, C, O, Ni, P and N. High-resolution XPS analysis show that, both in Cr⁶⁺-treated and Cr³⁺-treated films, element Cr is only in the form of trivalent compounds, no hexavalent chromium existing. By XPSpeak analyzing, trivalent chromium compounds on the two treated surfaces were fitted as Cr(OH)₃ and Cr₂O₃. However, for the Cr³⁺ and Cr⁶⁺ passivation routes, the Cr(OH)₃ and Cr₂O₃ contents in passive films are widely divergent.     

Lithium salts as leachable corrosion inhibitors and potential replacement for hexavalent chromium in organic coatings for the protection of aluminum alloys

Lithium salts are being investigated as leachable corrosion inhibitor and potential replacement for hexavalent chromium in organic coatings. Model coatings loaded with lithium carbonate or lithium oxalate demonstrated active corrosion inhibition and the formation of a protective layer in a damaged area during neutral salt spray exposure. The present paper provides an abridged overview of the initial studies into this novel inhibitor technology for the active corrosion protection of aluminum alloys. Coating defects were investigated by microscopic techniques before and after exposure to corrosive conditions. Scanning electron microscopy analysis of cross-sections of the coating defect area demonstrated that the protective layer comprises a typical three-layered structure, which included a dense layer near the alloy surface, a porous middle layer, and a flake-shaped out layer. Potentiodynamic polarization measurements obtained with a microcapillary cell positioned in the coating defect area and electrochemical impedance spectroscopy confirmed the corrosion protective properties of these protective layers. The long-term corrosion inhibition of the lithium-based coating technology was tested in industrial coating systems.     

Corrosion behaviour of electrogalvanized steel in sodium chloride and ammonium sulphate solutions; a study by E.I.S.

Zinc and zinc-nickel (13% Ni) electrodeposits were passivated by dipping in chromate baths and characterized by scanning electron microscopy. The corrosion behaviour was studied using a.c. electrochemical techniques; electrochemical impedance spectroscopy (EIS) measurements were performed at open circuit and under galvanostatic control during the 24 h immersion time. In sodium chloride solution the zinc-nickel electrodeposits show a better corrosion resistance compared to the pure zinc coatings. During the immersion time, a surface nickel enrichment was observed which, together with the zinc corrosion products, acts as a barrier layer reducing the total corrosion rate. In the same solution the passivation treatment improves the corrosion resistance of the electrodeposits; nevertheless, on zinc substrates, the protection exerted by the chromate film is not, always effective during the immersion time. On the contrary the chromate coating on zinc-nickel substrates induces a remarkable and durable improvement of the corrosion resistance reducing the zinc dissolution almost completely. In the ammonium sulphate solution, the corrosion mechanism is significantly influenced by hydrogen reduction on the zinc-nickel surfaces, and by the production of a local surface acidity which is aggressive for the chromate coatings.     

The role of chromate in filiform corrosion inhibition

This paper is part of a study on filiform corrosion (FFC) on aluminum alloy 2024-T3 and focuses on the surface characterization of corroded samples. Untreated samples were used as well as samples which had undergone pretreatments including polishing, surface etching and chromated conversion coatings (CCC). These samples were coated with both pigmented and non-pigmented epoxy-based coatings. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectroscopy (TOF-SIMS) analysis was used to investigate the nature of the surface as well as optical images to gauge the rate of FFC advancement. FFC corrosion rates decreased on samples which had received a surface etching pretreatment and a chromate conversion coating. Pigmented coatings reduced the rate of FFC further and led to two different types of corrosion surface morphology. On pretreated samples, the corrosion appeared deeper and pit-like, possibly due to an enhanced polymer-substrate bond. On untreated samples, widespread FFC developed. SEM and EDX analysis of various intermetallic particles (IMPs) on all samples, inside and outside of corroded regions, revealed that Cr from pigments was found deposited on Cu-containing intermetallics in corroded areas while Fe/Mn-containing particles were free from all pigment traces. These results suggest that the Cr deposition on Cu particles hinders the cathodic reduction of oxygen necessary for FFC advancement. For this reason, the coating pigments proved, under FFC conditions, to be a more effective inhibitor than the Cr originating from a chromate conversion coating.     

Preparation and characterization of a double-layer coating on magnesium alloy AZ91D

A double-layer coating was prepared on AZ91D alloy by plasma electrolytic oxidation (PEO) plus electroless plating (EP). The plasma eletrolytic oxidation film was prepared in a silicate bath as an inner layer of the coating. Electroless plated Ni-P layer grew from the pores of the PEO film in a nickelous acetate bath and formed as the outer layer of the coating. The microstructure and crystallographic structure was observed with FESEM and XRD. The corrosion resistance of the double-layer coating was evaluated by means of chronopotentiometric (E-t), potentiodynamic polarization (E-i), neutral salt spray test and electrochemical impedance spectroscopy (EIS) test. Compared with the data of as-cast AZ91D magnesium, the open circuit potential of the double-layer coated AZ91D alloy increased by 1.1815 V, while the self-corrosion current density decreased by two orders of magnitude. E-i, EIS result showed that the corrosion resistance of magnesium alloy AZ91D was improved by the double-layer coating. The salt spray test and polarization test results show that the pitting corrosion resistance of AZ91D alloy was improved greatly. An equivalent circuit was proposed to fit the impedance diagrams of AZ91D alloy with the coating.     

铝合金锰(Ⅶ)-钛(Ⅳ)系无铬化学转化成膜工艺

以KMnO4和TiOSO4为钝化剂主要成分,研究6063铝合金锰(VII)-钛(IV)系钝化成膜新工艺,考察钝化液成分、温度、pH值、反应时间对成膜过程及膜耐腐蚀性能的影响,并通过正交实验优化工艺方案,分析转化膜的形貌和化学组成,采用化学方法考察化学转化膜的耐蚀性能. 结果表明,最佳钝化液配方为：KMnO4 5 g/L, TiOSO4 2 g/L, NaF 0.05 g/L, ZnSO4 0.3 g/L. 在钝化温度50℃、钝化时间15 min及pH值2.7的最佳工艺条件下,锰(VII)-钛(IV)系钝化工艺制备的化学转化膜为金黄色,膜质量为589 mg/m2,膜主要由O, Mn, Al, Zn, Ti组成. 锰(VII)-钛(IV)系钝化新工艺环境友好,所制化学转化膜耐CuSO4点滴腐蚀性能优于Cr(VI)转化膜,耐人造海水腐蚀能力与Cr(VI)转化膜相近.