Aluminium alloys are frequently pre-treated by a conversion coating before application of an organic coating in order to improve the corrosion resistance and adhesive properties of the surface and the corrosion resistance provided by the system. Chromate-containing conversion coatings are commonly used for this purpose. However, legislation limits future use of hexavalent chromium compounds due to their toxic and carcinogenic nature. Therefore, alternative, so-called chromium-free conversion coatings are being developed that are more environmentally-compliant.The purpose of the present work has therefore been to contribute to a better understanding of how the aluminium substrate affects the formation and properties of conversion coatings for adhesive bonding. In particular, a chrome-free zirconium-based conversion treatment process has been investigated as a possible replacement for conventional chromate conversion treatment. The influence of the conversion time on the thickness of the formed layer on pure aluminium was investigated using complementary surface analytical techniques. The conversion time was varied between 30 and 600 seconds.In this study, the structure and composition of zirconium-based chromium-free conversion coatings on magnetron sputtered superpure aluminium and a range of aluminium-copper alloys were characterised as a function of immersion time in the aqueous conversion bath to understand the mechanism of coating formation and protection. However, the presence of copper significantly influences the coating development and ultimately the performance of the conversion coatings formed on binary copper-containing aluminium alloys.The morphology and composition of the coatings have been probed using transmission electron microscopy, Rutherford backscattering spectroscopy and glow discharge optical emission spectroscopy, with loss of substrate through growth of the conversion coating also quantified. A comparison of the RBS spectra obtained for the superpure aluminium specimens after different immersion times revealed that zirconium (Zr) and oxygen (O) peaks were wider for longer immersion times, indicating thickening of the coating with increased immersion times. Thus, increasing the immersion time resulted in an increase in coating thickness but little change in coating composition occurred as determined by the RBS RUMP simulations. Alloying decreases the coating thickness, as well as metal consumption. Here, aspects of the corrosion behaviour of superpure aluminium and aluminium-copper alloys were also considered using electronoptical, electrochemical and surface analytical probing. The influence that short and prolonged treatment times exert on the performances of such conversion coating is discussed. The conversion coating formed after 60 s and 180 s of immersion in the zirconium-based conversion coating bath provide good corrosion resistance which can be attributed to the high stability of the compounds that constitute the surface oxide layer, and good adhesion properties.

The replacement of chromate conversion coatings for zinc coated components has been necessitated by the materials finishing industries due to the inherent toxicity issues with Cr(VI) and the legislative enforcement of WEEE and ELV Directives by the European Union. Current replacements are based on non-chromate , Cr(III) systems, these may be perceived by some to be problematic as they still contain chromium . Molybdate based conversion coatings have long been viewed by many researchers to be a viable non-chromium alternative due to their low toxicity. An extensive literature review of the research carried out in the last 20 years was carried out, highlighting areas of interest for improving the corrosion resistance of the coatings studied. These were, primarily, the synergesis that exists with molybdate and phosphate compounds for corrosion resistance and the incorporation of nanoparticle silica into treatment solution. Also discovered was the importance of the acid used to adjust treatment solution pH, immersion time, oxidising agent additions and the incorporation of rare earth metal species. Silicate sealant layers were also highlighted as a post treatment. Molybdate-based coatings were formed on commercial electrodeposited acid zinc surfaces. Many treatment conditions were investigated, and initially performance analysed using DC Linear Polarisation Resistance (LPR) trials. Subsequently, the highest performing coatings were subjected to the more aggressive, industry standard, ASTM B 117 Neutral Salt Spray (NSS) corrosion test. The highest performing molybdate coatings were found to have an average LPR of ~ 9 000 Ω. cm2, in contrast to ~ 12 000 Ω. cm2 for the Cr(VI) based reference. NSS results were amongst the highest performing for molybdate based coatings documented, at 24 h until 5% white rust, however remained inferior to Cr(VI) coatings, which lasted 120 h. The highest performing coatings were characterised using FEG-SEM, Cryofracture EDXA and site specific AES. These techniques revealed that the enhanced molybdate coatings had a columnar structure that was around 300 nm thick, with pores that appeared to expose the substrate. AES showed this type of coating to have a mixed Mo, P and Zn oxide surface. Corrosion initiation was also studied; this can be thought of as an investigation to determine the point(s) of weakness or the mechanism that causes coating failure. Coatings were immersed in 5 % wt/ vol NaCl(aq) until they showed any surface change. Initial signs of corrosion were deemed to be any appearance of pitting or discolouration of the film, not a voluminous corrosion product. Untreated Zn, Cr(VI) and simple molybdate coatings were studied as well as enhanced molybdate coatings. There were clear differences in the way the coatings behaved at the onset of corrosion. Cr(VI) coatings delaminated, leaving an area of decreased Cr concentration. The enhanced molybdate coatings failed by the appearance of localised pores of ~ 70 µm in diameter. Substrate exposure was indisputably the reason for coating failure in chloride environments. In light of the work carried out in the present thesis the outlook for the use of molybdate as a potential replacement for chromate for the conversion coating of electrodeposited zinc surfaces is a positive one.

Physical, chemical and corrosion properties of a hexavalent chromium conversion coating (CCC) and that of a commercial third generation trivalent chromium system; Tripass LT1500, on zinc electrodeposited steel has been studied. Moreover, the role of additives has been studied to elucidate film formation and corrosion resistance mechanisms. Micro-cracking and self-repair corrosion protection behaviour commonly associated with hexavalent CCCs has also been investigated. Scanning Electron Microscopy (SEM) studies showed that for both hexavalent and trivalent CCCs were in general, flat with a spherical-like structure and in the case of the former microcracked beyond 122 nm conversion coating thickness. In general, the micro-crack pattern observed e.g. a dense crack network, depended upon the underlying zinc substrate morphology. The study has also demonstrated the effect of SEM imaging and prior specimen preparation conditions on hexavalent CCC micro-cracking and blistering. X-ray Photoelectron Spectroscopy (XPS), Auger Electron Spectroscopy (AES) and Infrared (IR) data has indicated that the hexavalent CCC film formation appears to be a electrochemical/sol-gel mechanism given the lack of zinc content at surface and subsurface regions within the conversion coating, presence of H2O and in particular the contribution of Cr(OH)3 as opposed to Cr2O3. An alternative film formation mechanism may exist for trivalent CCC given a higher proportion of zinc at surface and sub-surface regions, IR data analysis indicating that chromium is possibly deposited from a chromium (III) complex ion such as [CrC2O4(H2O)4] + , moreover as Cr(OH)3 and Cr2O3 compounds as indicated by XPS data analysis. The role of cobalt nitrate during film formation is unclear given that cobalt was not detected within the trivalent CCC from XPS and AES data. Electrochemical LPR measurements, polarisation curves and XPS data has shown in general, self-repair corrosion protection properties for hexavalent CCC to be lacking. Instead, it is proposed that the corrosion protection behaviour for hexavalent and trivalent CCC to be barrier. Polarisation curves and LPR data showed that the corrosion resistance performance for trivalent CCC was higher than hexavalent CCC, in general. LPR data showed that the omission of cobalt nitrate and increased addition of sodium molybdate content within the Tripass LT1500 treatment solution formulation was found to overall decrease corrosion resistance within the trivalent CCC. In addition, silica based topcoat and black trivalent CCCs was also investigated and characterised using AES, SEM and LPR. Zinc whiskers was also observed from zinc electrodeposits following exposure to thermal treatment (150°C for 1 h). Elemental analysis and grain pattern investigations failed to help determine the cause of zinc whisker initiation. Zinc whiskers was seen to protrude out of hexavalent and trivalent CCCs, with the latter requiring a longer thermal exposure time.

This diploma thesis deals with cerium-based conversion coatings for aluminium alloys. At first the mechanism of protection of metals by inhibitory substances is described in the theoretical section. The next chapter is devoted to application of lanthanide salts as cathodic corrosion inhibitors. Then the characterization of alloy AA 2024 follows. The main part is dedicated to the growth mechanism of the cerium-based mixed conversion coating on the alloy AA 2024. Finally, the factors affecting the character and the quality of obtained coatings are commented. In the experimental part an influence of the thermal activation together with the activation by a hydrogen peroxide was observed. The created film was characterized using SEM and EDS. The level of corrosion protection was evaluated by the polarization resistance measurement. erized using SEM and EDS. The level of corrosion protection was evaluated by the polarization resistance measurement.

Aim of this study is to improve corrosion resistance of magnesium alloy AZ91 by conversion coatings. Influence of alloy microstructure on conversion coating growth and corrosion resistance was evaluated. Properties of pure magnesium and magnesium alloy AZ91 as well as the influence of alloying elements on properties of this alloy are described in theoretical part. Recent results of corrosion protection by conversion coatings on AZ type magnesium alloys are summarised in recherché part. Practical part focuses on preparation of hexavalent chromium based conversion coating and phosphate-permanganate based conversion coating on as cast AZ91 magnesium alloy, these coatings were subsequently applied on annealed AZ91 magnesium alloy. Corrosion protection of the coatings prepared on as cast and annealed alloy was evaluated by potentiodynamic measurements and testing in neutral salt spray. Furthermore the influence of plasma activation on phosphate-permanganate coating surface was studied.

No description available.

No description available.

Les alliages légers d'aluminium de la série 2000 sont utilisés dans l'industrie aéronautique en raison de leurs excellentes propriétés mécaniques. Ils sont néanmoins sensibles à la corrosion localisée, et nécessitent d'être protégés. Les couches de conversion permettent une protection efficace. La conversion utilisée aujourd'hui est à base de chrome hexavalent (CrVI), composé cancérogène, devant être remplacé. L'étude de nouveaux procédés est nécessaire, et ce travail a porté sur l'utilisation de couches de conversion au chrome trivalent (CrIII, procédé TCP), en combinant des méthodes d'analyse des surfaces (XPS, ToF-SIMS, AFM), des essais de corrosion et des mesures électrochimiques. L'influence des prétraitements sur le dépôt de la couche TCP a été étudiée. Lors du décapage sulfo-ferro-nitrique, un enrichissement en cuivre métallique, la dissolution des particules riches en cuivre et le retrait de l'oxyde d'aluminium natif sont observés. La couche de conversion déposée après ce décapage est moins couvrante que sur une surface qui a été nettoyée mais non décapée par cette méthode. Les résultats de tenue en corrosion confirment l'influence néfaste du décapage sur la protection apportée par les couches TCP. Une étude du dépôt de la couche TCP sur un substrat d'aluminium préalablement recouvert par ALD d'une couche fine et homogène d'alumine a été réalisée. Une épaisseur critique d'oxyde d'aluminium a pu être déterminée au-delà de laquelle le dépôt d'une couche TCP est bloqué. Un modèle a été proposé pour expliquer le mécanisme de dépôt de la couche de conversion sur une surface recouverte d'une couche mince d'oxyde d'aluminium. / Light 2xxx aluminium alloys are widely used in the aircraft industry because of their good mechanical properties. However, they are prone to localized corrosion and must be protected. Conversion coatings allow such protection. Nowadays, chromate conversion coatings (CrVI) are still used but they must be replaced. New systems are tested, and in this work we investigated the Trivalent Chromium Process (TCP, CrIII based), by combining surface analysis techniques (XPS, ToF-SIMS, AFM), corrosion tests and electrochemical measurements.The influence of surface pretreatments on the TCP coating deposition has been studied. During the etching step, a metallic copper enrichment, the dissolution of Cu-rich intermetallic particles and the removal of the native aluminium oxide are observed. The subsequent TCP deposited layer is less continuous on such pretreated alloy surfaces than on non-etched, only cleaned alloy surfaces. These results show the importance of the presence of the native oxide layer on the alloy surface. A study of the TCP coating deposition on a pure aluminium pre-coated with a thin homogeneous alumina layer (deposited by Atomic Layer Deposition) shows a critical thickness of the alumina, beyond which, the TCP deposition is blocked. A deposition mechanism of the TCP layer on a thin aluminium oxide is presented.

This thesis describes magnesium alloys, their properties and methods of their production. However, experimental part is focused on AZ91 magnesium alloy. Conversion coatings were prepared on the AZ91 surface – chromate coating, phosphate permanganate coating and fluoride coating. Corrosion resistance of the prepared coatings were compared by immersion tests and by potentiodynamic methods. Evaluation of corrosion resistance by immersion tests was successful only for phosphate permanganate coating. Only this coating was removed during cleaning of the samples. For comparison of corrosion resistance was important to find the correct procedures and optimize the measurements methods. For these purposes have been chosen galvanic zinc coating on steel sheets. Thickness of the zinc coating were 8 and 30 microns. This coatings provide uniform zinc surface without heterogenities which was important for the potentiodynamic measurements. After optimization methods for potentiodynamic measurements by galvanic zinc coatings have been measured magnesium alloy AZ91 uncoated and coated by conversion coatings. For uncoated AZ91 magnesium alloy was determined suitable method so called virgin cathodic curve. On the other hand, for the coated AZ91 magnesium alloys was determined suitable method so called combined curve, within which we measured cyclic voltammetry curve (± 5 mV) and then virgin anodic curve.

In the presented dissertation thesis, I closely focused on corrosion resistance of non-ferrous metals. For full understanding of the possibilities for increasing corrosion resistance, it was vital to initially recognize the influences to the corrosion system of the samples and their surrounding environment. For this purpose, I focused on heat treatment, corrosion, and protective coatings, in the theoretical part of the thesis. For the subsequent research, it was necessary to define several constant variables, first. For this purpose, I have chosen a group of magnesium alloys, namely AZ91 Alloy and 3.5 % NaCl Electrolyte. AZ91 Alloy is of heterogenous structure formed by a solid solution of aluminum in magnesium, intermetallic phase in Mg17Al12, and their eutectic. Local microcells tend to occur in these heterogenities, which leads to faster corrosion. In order to increase corrosion resistance of the alloy, I used a combination of heat treatment and protective phosphate coating. For creating of the desired structure, which further affects compact coating formation, I selected a process involving solution heating with precipitation hardening T6. Secondary goals of the thesis involved optimization of standard technical procedures for the sake of increasing efficiency. With regard to this goal, I introduced optimized heat treatment T6 using accelerated cooling of a sample in water and liquid nitrogen. A modification besides the standard phosphating procedure was carried out with no activation step. For evaluation of corrosion resistance of the samples, I conducted water immersion tests using electrochemical methods; such as potenciodynamic curves combined with electrochemical impedance spectroscopy. In order to streamline the evaluation of the corrosion surface in technical practice, I used automatic detection. Substantial improvement of corrosion resistance of the above mentioned system, compared to heat-untreated samples, was proven through electrochemical methods. Due to accelerated cooling, a more homogeneous structure was achieved, which could be further utilized to create more uniform protective coating. For some phosphate coating, specifically manganese phosphate coating, I identified certain modifications that were in line with the set goals; i.e. skipping the activation phase, and using automatic detection for evaluation of uniform corrosion on the samples.