Ageing effects in the growth of chromate conversion coatings on aluminium

Conversion coatings have been formed in two stages on sputtering-deposited aluminium using a chromate/fluoride bath. The first stage, common to all specimens, was conversion treatment for 1 min to produce a coating of thickness of about 70 nm, with associated thinning of the aluminium substrate. Further treatment was then carried out for 13 min, either immediately or with intervening ageing in humid air, water or laboratory air. Notably, ageing in laboratory air for 1 h was sufficient to prevent significant growth of new coating material upon re-immersion in the coating bath. In contrast, ageing in humid air or water allowed additional thickening of the coating, although with a reduced growth rate. The behaviour appears to be related to loss of free or weakly bound water from the coatings in laboratory air, with the composition and structure of the coating being modified such that transport of reactant and product species of the coating process is impeded.     

Chromate conversion coatings on aluminium: influences of alloying

The growth kinetics of chromate/fluoride conversion coatings are examined for 99.99% aluminium, and Al-2.3at.%Cu, Al-1.9at.%Au and Al-20at.%Au alloys. The thickening of coatings and thinning of substrates, the latter deposited by magnetron sputtering, are determined by transmission electron microscopy. The results reveal consumption of substrates during the coating process, to the maximum immersion time of 24 min. Initial relatively rapid thinning in the period to 6 min is followed by slower, approximately constant thinning at about 9.3, 6.2, 6.0 and 5.4 nm min⁻¹ for the 99.99%Al, Al-2.3at.%Cu, Al-1.9at.%Au and Al-20at.%Au alloys respectively. The ratio of the number of chromium atoms in the conversion coating, determined by Rutherford backscattering spectroscopy, to the number of oxidized substrate atoms is about 3, indicating a low efficiency of coating growth. Alloying decreases the coating thickness, as well as metal consumption. Alloying elements initially enrich beneath the coating, in alloy layers of a few nanometres thickness. Later, copper may be oxidized, and then enter the coating, whereas gold is occluded as nanoparticles. The gold nanoparticles act as markers to indicate formation of coating material at the metal/coating interface. Sudden loss of coating on the alloys, after about 6-9 min, occurs soon after entry of alloying element species into the coating. The loss may be related to the presence of nanoparticles of gold and copper near the alloy/coating interface, the latter possibly forming by reduction of copper species, that disrupt the bonding of the coating either directly though their presence or through their action as local cathodes.     

Corrosion resistance of cerium‐based chemical conversion coatings on AA5083 aluminium alloy

In this paper the effect of several parameters, such as temperature, time of immersion, cerium ions and hydrogen peroxide concentration, pH of the conversion solution, on the composition and morphology of the conversion layer are investigated as well as on its corrosion resistance in chloride environments. The cerium‐based chemical conversion coatings ennobles the corrosion potential and inhibits both the cathodic and anodic reactions rate. Using a cerium (III) chloride solution a not homogeneous coating is obtained and agglomerates with a “dry‐mud” morphology of mixed cerium‐aluminium oxide are deposited above the cathodic intermetallic particles, while using a cerium (III) nitrate solution the coating is more uniform but thinner than that obtained with cerium (III) chloride. Solution temperature below 50°C and time of immersion of 10 minutes produces a coating with better corrosion resistance.     

In-situ study of the formation process of stannate conversion coatings on AZ91D magnesium alloy using electrochemical noise

The formation process of stannate conversion coating (CC) on AZ91D alloy was in-situ investigated by electrochemical noise (EN). The wavelet transform, as well as noise resistance (R_n) and spectral noise resistance (R_sn), had been employed to analyze the EN data. It was revealed that there exist two distinguishing stages of stannate CC formation process on AZ91D alloy, including an incubation stage companying with the nucleation and nuclei dissolution process, a periodical growth stage involving hemispherical particles growth and coating dissolution process. Furthermore, the results demonstrated that EN was a powerful tool to investigate rapid electrochemical process, such as CC formation process.     

Evaluation of anodic coatings on small decorative aluminium parts

A simple and rapid electrochemical method for the checking of the quality of anodic coatings on small decorative parts of aluminium is presented. This so-called ALU-buckle-test was developed and optimized for the quality control of anodized coloured and sealed buckles for watch bracelets. In the test the buckle is made the cathode in an electrochemical cell. The time it takes to reach a defined current density induced by an applied voltage, typically 1.6 V, is taken as the criterion of quality. The influence of different production conditions such as time of anodizing and time of sealing on the testing results has been studied. The results of the electrochemical test were observed to be affected by the quality of sealing, the coating thickness and the presence of flaws. It was found that this test provides an excellent criterion for the coating quality that correlates excellently with the well-known Alcoa test (ISO 3210) and a gravimetric method for the determination of the porosity of porous surface coatings.     

Substitution of hexavalent chromate conversion treatment with a plasma electrolytic oxidation process to improve the corrosion properties of ion vapour deposited AlMg coatings

In this paper plasma electrolytic oxidation (PEO) is examined as a potentially beneficial post-deposition treatment for Al-5 wt.%Mg coatings deposited onto Ti alloy substrates using Ion Vapour Deposition (IVD), with a view to replacing toxic hexavalent chromate conversion treatments and at the same time enhancing the barrier protection properties of such IVD coatings. The aqueous corrosion behaviour of PEO layers formed on IVD coatings was evaluated by means of potentiodynamic polarisation scans, open circuit potential measurements and electrochemical impedance spectroscopy. Normally, IVD aluminium-based coatings require a post-coat shot peening treatment to densify the coating structure; however it was found that PEO layers could be formed successfully on as-deposited IVD coatings deposited onto Ti alloy substrates, providing a cost effective process to improve corrosion behaviour. PEO treatment provides unique improvements in the corrosion resistance of IVD coatings; the PEO layer possesses effective anticorrosion properties in aqueous environments containing Cl⁻ ions. A more positive corrosion potential, lower corrosion current and increased polarisation resistance were recorded for PEO layers, compared to traditional chromate conversion treatments.     

铝型材表面环保型稀土转化膜制备与工艺优化

采用Ce（NO3）3作为稀土转化膜的主要成膜成分以及KMnO4作为成膜氧化剂在6063铝合金型材表面制备了无铬环保型稀土转化膜,利用正交试验法对转化膜处理溶液配方进行了优化,采取点滴试验法对稀土转化膜的耐腐蚀性能进行了比较,并对稀土转化膜的表面形貌进行了研究,分析了处理工艺参数对转化膜厚度、形貌与耐腐蚀性能的影响,优化出较好的非铬铝合金表面转化膜处理工艺。     

Correlation between electrochemical impedance and noise measurements of waterborne coatings

A modified equivalent electric circuit is proposed to establish correspondence between impedance and noise measurements in waterborne coatings in saline media (NaCl). The polarization resistance (R_p) given by the impedance modulus when frequency approaches to zero can not directly be compared with noise measurements since this latter accounts only for the pore resistance of the paint of low barrier protective coatings while R_p parameter represents the sum of all the resistances at the system. The results have shown that the pore resistance data can be attributed to noise resistance when (i) the coating exhibit porosity presenting diffusion mechanism as rate-determining step, and (ii) when the sampling frequency of recorded data gives a Nyquist frequency of 1 Hz.     

The use of macroscopic modelling of intermetallic phases in aluminium alloys in the study of ferricyanide accelerated chromate conversion coatings

Intermetallic (IM) second phases of FeAl₃, Cu₂FeAl₇, and CuAl₂, were coupled to aluminium for the macroscopic study of the deposition of chromate conversion coatings. Characterisation of the coating deposition was done using X-ray photoelectron spectroscopy, Rutherford backscattering spectroscopy, Auger electron spectroscopy, scanning electron microscopy with X-ray analysis, and Fourier transform infrared spectroscopy. The coatings covering the IM phases were only one-tenth the thickness of the matrix, and contained higher levels of F, Al, and O. Cr, O, Fe, and N, indicative of a chromate conversion coating, were detected over the matrix. Over IM phases, decomposition of [Fe(CN)₆]3−/4−, and fluoride ion attack were found to be responsible for reduced rates of deposition.     

Analysis of electrochemical noise obtained from pure aluminium in neutral chloride and alkaline solutions

The present work involves the analysis of electrochemical noise obtained from pure aluminium during breakdown of the oxide film in aqueous neutral chloride solution and hydrogen evolution in alkaline solution. Since the noise data involve information on such stochastic processes as uniform corrosion, breakdown of the oxide film and hydrogen evolution, they were analysed based upon a stochastic theory: the plot of the cumulative probability numerically calculated was first transformed from the domain of the frequency of events to the mean free time domain and then, the Weibull probability plot was constructed by fitting Weibull distribution function to the calculated cumulative probability. Finally, the conditional event generation rate was numerically determined as a function of time. From two linear regions in one Weibull probability plot, it was concluded that breakdown of the oxide film and hydrogen evolution, respectively, were clearly distinguished from uniform corrosion in the Weibull probability plot. In addition, the roles of anion additives in breakdown of the oxide film and hydrogen evolution were also discussed in terms of the distribution of the mean free time and the conditional event generation rate.     

Formation and characterisation of a chromate conversion coating on AA6060 aluminium

AA6060-T6, an AlMg0.5Si0.4 model alloy and α-Al(Fe,Mn)Si phase electrodes have been subjected to chromate treatment in a commercial chromate-fluoride based solution. The coated surfaces were subsequently examined by use of field emission SEM, TEM, AES and electrochemical measurements in 0.1 M NaCl solution in order to study the effect of substrate microstructure on coating formation and properties. Non-uniform growth of the chromate conversion coating (CCC) on AA6060-T6 resulted in a porous morphology, with cracks extending down to the base metal. Poor coverage was particularly observed at the grain boundaries. The thickness of the CCC after completed treatment was about 150-200 nm, while significantly thinner films were formed on the α-Al(Fe,Mn)Si particles. AlMg0.5Si0.4 in the artificially aged (T6) condition exhibited a coating morphology similar to AA6060-T6, while CCC formation on homogenised AlMg0.5Si0.4 was characterised by growth of localised oxide particles and filaments, resulting in poor coverage. These observations indicated that precipitation of Mg₂Si particles due to heat treatment promoted nucleation of the CCC. Chromate treatment caused a significant reduction of cathodic activity on AA6060 during subsequent polarisation in chloride solution. This was attributed to rapid formation of a thin chromium oxide film on the α-Al(Fe,Mn)Si particles during the chromate treatment, resulting in significant cathodic passivation of the phase. Inhibition of the oxygen reduction reaction at cathodic intermetallic particles is suggested as an important factor contributing to the high performance of chromate pre-treatments on aluminium.     

Mg-10Li-1Zn合金锡酸盐转化膜的制备及其耐蚀性能研究

采用含有锡酸钠和磷酸二氢钾两种成分的转化液,在Mg-10Li-1Zn合金表面上得到锡酸盐化学转化膜,研究了该转化膜的微观结构、成膜机制及抗腐蚀性能。结果表明,此膜层均匀、连续,主要由MgSnO3、Mg3（PO4）2和SnO组成。腐蚀试验结果显示,该转化膜改善了基体合金的抗腐蚀能力。     

Growth and corrosion resistance of molybdate modified zinc phosphate conversion coatings on hot-dip galvanized steel

The modified zinc phosphate conversion coatings（ZPC） were formed on hot-dip galvanized（HDG） steel when 1.0 g/L sodium molybdate were added in a traditional zinc phosphate solution. The growth performance and corrosion resistance of the modified ZPC were investigated by SEM, open circuit potential（OCP）, mass gain, potentiodynamic polarization and electrochemical impedance spectroscopy（EIS） measurements and compared with those of the traditional ZPC. The results show that if sodium molybdate is added in a traditional zinc phosphate solution, the nucleation of zinc phosphate crystals is increased obviously; zinc phosphate crystals are changed from bulky acicular to fine flake and a more compact ZPC is obtained. Moreover, the mass gain and coverage of the modified ZPC are also boosted. The corrosion resistance of ZPC is increased with an increase in coverage, and thus the corrosion protection ability of the modified ZPC for HDG steel is more outstanding than that of the traditional ZPC.     

On the determination of electrochemical noise resistance

The effects of sampling duration and sampling frequency on noise resistance were investigated for Type 316 stainless steel in accordance with a standard procedure employed in polarization resistance measurements. Noise resistance was also determined by wavelet transform and compared with that from AC impedance measurements. An optimum sampling duration for noise resistance determination is shown to be 600 s in comparison to the polarization resistance data, and the sampling frequency of 10 Hz is recommended in noise resistance measurements based on the level of instrumental noise and from the comparison with the polarization resistance data. After wavelet transform, the value of noise resistance for smooth coefficients in the lower level of decomposition tends to be independent of the level of decomposition, but the trend is not observed in detail coefficients. Noise resistance is suggested to be determined at a smooth coefficient with the largest level of decomposition in the independent region.     

Investigation of the protective action of chromate coatings on hot-dip galvanized steel: role of wetting agents

Chromating is applied on hot-dip galvanized (HDG) steels in order to improve the protective action of metallic zinc coatings. In this study the influence of chromating on the corrosion resistance of zinc coating is investigated with the scanning Kelvin probe (SKP), XPS and AES surface analysis techniques. The combination of electrochemical local techniques and surface analysis is helpful to corrosion investigation of materials, for instance the paper focuses on the synergetic effect of three different constituents of the chromating product well known for their efficiency: phosphates, chromates and surfactants.For this purpose two types of products have been compared, an industrial formulation (P_Ind) which is currently applied in the industrial lines and a reference product which has been formulated in the laboratory (P_Lab) in order to sort out the effect of each constituent.     

Novel corrosion experiments using the wire beam electrode. (I) Studying electrochemical noise signatures from localised corrosion processes

This series of papers presents four novel experiments that were designed to study localised corrosion phenomena using an electrochemically integrated multi-electrode array namely the wire beam electrode (WBE). This present paper reports a WBE based experimental method that has been employed, for the first time, to study electrochemical noise patterns (called noise signatures) from localised corrosion processes. The objective of this work is to demonstrate the applicability of the WBE for investigating the origin of spontaneous electrode potential/current fluctuations and their effects on electrochemical processes. The key strategy of this work is to apply the WBE in a novel experimental set-up to simultaneously measure electrode potential noise and WBE current distribution maps--an approach that allows the direct comparison and correlation of electrochemical noise and corrosion events. Preliminary experiments have been carried out using a classic pitting corrosion system: stainless steel in a solution containing FeCl₃. A large number of anodic sites were found to exist on WBE surface at the very beginning of its exposure to the corrosion environment. Correlation between characteristic patterns in electrode potential noise and corrosion behaviour has been observed. More specifically, the characteristic sharp peaks in potential noise data (called noise signature I) were found to correlate with the sudden disappearance of single unstable anode in WBE current distribution maps. The characteristic noise pattern of quick potential changes followed by partial or no recovery (called noise signature II) was found to correspond with the massive disappearance of minor anodes in WBE current distribution maps. This result suggests that, in the corrosion system under study, electrode noise activities were associated with the disappearance of minor anodic sites, which lead to the eventual disappearance of most anodic sites. Localised corrosion was the result of the accelerated anodic dissolution of a small number of remaining anodic sites. The characteristics features in electrochemical noise and in WBE maps were reproducible.     

Comparison of susceptibility to pitting corrosion of AA2024-T4, AA7075-T651 and AA7475-T761 aluminium alloys in neutral chloride solutions using electrochemical noise analysis

The susceptibility to pitting corrosion of AA2024-T4, AA7075-T651 and AA7475-T761 aluminium alloys was investigated in aqueous neutral chloride solution for the purpose of comparison using electrochemical noise measurement. The experimentally measured electrochemical noises were analysed based upon the combined stochastic theory and shot-noise theory using the Weibull distribution function. From the occurrence of two linear regions on one Weibull probability plot, it was suggested that there existed two stochastic processes of uniform corrosion and pitting corrosion; pitting corrosion was distinguished from uniform corrosion in terms of the frequency of events in the stochastic analysis. Accordingly, the present analysis method allowed us to investigate pitting corrosion independently. The susceptibility to pitting corrosion was appropriately evaluated by determining pit embryo formation rate in the stochastic analysis. The susceptibility was decreased in the following order: AA2024-T4 (the naturally aged condition), AA7475-T761 (the overaged condition) and AA7075-T651 (the near-peak-aged condition).     

热镀锌层上磷酸锌转化膜的生长与耐蚀性

热镀锌钢板在pH3.0、45℃的磷酸锌溶液中磷化2～600s,用扫描电镜、能谱仪和X射线衍射仪分析磷化膜的组织形貌和成分,并探讨膜层的生长行为。结果表明:磷酸锌晶体在锌晶粒内及晶界处均可成核,开始是以接近平行的片状生长,并逐渐向多方向生长成扇骨状的晶片。随着磷酸锌晶体的成核和生长,磷化膜的覆盖率增加,但晶体之间的孔隙难以完全消除;长大的磷酸锌晶片容易折断脱落,导致磷化后期膜层的质量增量减小;磷化膜主要由Zn3(PO4)2.4H2O组成。热镀锌钢板经磷化处理后,耐蚀性显著提高,磷化膜的耐蚀性随磷化时间和膜层覆盖率的增加而提高。     

Determining the probability of stable pit initiation on aluminium alloys using potentiostatic electrochemical measurements

A method is described that determines the probability of stable corrosion pits being formed on aluminium alloys. The method employs potentiostatic measurements of metastable pit equivalent volumes, in coulombs, at the open circuit potential. The metastable pit volumes are statistically analysed using an extreme value statistics procedure that returns an expected distribution of metastable pit volumes. This enables the probabilities of the occurrence of metastable pits of given volumes with time to be calculated. The size requirement for a metastable pit to transition into a stable pit was then determined using both optical microscopy and electrochemical tests. This size requirement when combined with the metastable pit size distributions was used to determine the probability of the formation of a stable pit. The method is demonstrated for aluminium alloy AA2024-T3 in chloride media with and without chromate additions and validated against optically measured pitting rates.     

Determination of the protective properties of electrodeposited organic epoxy coatings on aluminium and modified aluminium surfaces

The electrochemical and transport properties and thermal stability of epoxy coatings electrodeposited on aluminium and modified aluminium surfaces (anodized, phosphatized and chromatized-phosphatized aluminium) have been investigated during exposure to 3% NaCl solution. From the results obtained from electrochemical impedance spectroscopy (EIS), gravimetric liquid sorption experiment and thermogravimetric analysis (TGA) it can be concluded that electrochemical and transport properties of epoxy coatings on anodized and chromatized-phosphatized aluminium are significantly improved with respect to the same epoxy coatings on aluminium and phosphatized aluminium: higher values of pore resistance and charge-transfer resistance and lower values of coating capacitance and double-layer capacitance, from EIS; smaller values of diffusion coefficient of water through epoxy coating, from sorption measurements and smaller amount of absorbed water inside the coating, from TGA. On the other hand, the somewhat lower thermal stability of these coatings was obtained.