The influence of microstructure on the corrosion behaviour of magnesium alloys has been investigated using advanced microscopy approaches including optical microscopy, SEM, TEM and SKPFM with a focus on the effect of melt-conditioned twin roll casting (MCTRC) and friction stir welding (FSW) on the resultant microstructure of magnesium alloys.The microstructure characterization revealed that intense shearing, generated through the advanced shear technology, resulted in grain refinement and a uniform distribution of the β-phase and reduced micro-porosity in the MCTRC Mg-Al alloys, of which were attributed to the enhanced heterogeneous nucleation, which resulted in a highly refined grain structure. The TRC Mg-Al alloys displayed a coarse grained microstructure, with a random distribution of grain sizes. Deformation features like twinning, localized shear, microporosity and centre-line segregation were some of the commonly observed defects in the TRC alloys. The general microstructure of the AZ series Mg-Al alloys was composed of α-Mg grains, the β-phase, rosette-shaped Al8Mn5 intermetallic particles and β-precipitates.The MCTRC Mg-Al alloys showed improved corrosion resistance owing to the reduced grain size and the β-phase network acting as a corrosion barrier, thereby retarding the corrosion process. The TRC Mg-Al alloys exhibited higher susceptibility to galvanic corrosion due to the coarse and random distribution of grain sizes, and segregation. The corrosion testing results showed different corrosion morphologies, including filiform-like and spherical channel-like along with overall general corrosion. However, galvanic corrosion, initiating at localized sites due to Al8Mn5 intermetallic particles and the Si/Fe impurities accounted for a major deterioration in the performance of the Mg-Al alloys. The polarization curves revealed no evidence of passivation, suggesting that the alloy surface was continuously attacked. SKPFM results indicated that the micro-constituents, namely Al8Mn5 intermetallic particles and the β-phase exhibited higher nobility relative to the α-Mg matrix, suggesting formation of micro-galvanic couples at localized sites leading to the initiation of galvanic corrosion.The AM60 and AZ91 Mg-Al alloys, subjected to FSW, revealed that the traverse speed had a direct influence on the weld zone microstructure, where the size of the friction stir/weld nugget zone decreased with increase in the traverse speed and the increase in the rate of deformation, led to widening of the friction stir zone, below the shoulder. The weld microstructure displayed a prominent friction stir zone, with an ultrafine grain structure of an average grain size ranging from 2-10 μm. The localized increase in temperatures, in the TMAZ, due to the lower tool rotation rates and traverse speeds, which rise above the eutectic melting point (430°C), showed evidence of partial melting followed by re-solidification of the β-phase and evidence of liquation below the shoulder regions in the TMAZ. The morphology of the β-phase clearly revealed solute segregation, inconsistent with the β-phase observed in the parent alloy microstructure.The polarization curves obtained from the weld zones in the FSW AM60 alloy showed an improved corrosion resistance compared with the parent metal zone. SKPFM results revealed that the α-Mg matrix in the friction stir zone showed higher surface potential values compared with the parent alloy microstructure, due to the dissolution of the β-phase, suggesting higher nobility. However, the polarization behaviour of the AZ91 alloys did not show a significant difference in the corrosion resistance in the weld zones due to the higher volume fraction of the β-phase in the AZ91 alloys. The immersion testing results revealed higher susceptibility to corrosion in the transition zone due to the flash formation and the banded microstructure leading to failure of the weld zone.

The local corrosion behavior of duplex stainless steel (DSS)is affected by a wide variety of factors. Localized corrosionof DSS frequently starts at micrometer scale inclusions orprecipitates, which are often segregated in theaustenite-ferrite boundary regions. Moreover, due to thepartitioning of the key alloying elements of ferrite (Cr andMo) and austenite (N and Ni), the local interactions betweenthe phases must also be considered. The aim of this doctoral study was to increase the knowledgeabout the local dissolution behavior of DSS in acidic-chlorideenvironments. The recent developments of new local probingtechniques have opened a new frontier in corrosion science,providing valuable local information not accessible in thepast. The local techniques used include electrochemicalscanning tunneling microscopy (EC-STM), scanning probe forcemicroscopy (SKPFM), magnetic force microscopy (MFM), andscanning Auger electron Spectroscopy (SAES), all withmicrometer or sub-micrometer resolution. With EC-STM, it was possible to monitor local dissolutionprocesses on DSS in situ, and in real time. MFM was capable ofimaging the phase distribution in DSS without the need of thetraditional surface etching, while SKPFM revealed that theVolta potential difference between the two phases wasmeasurable and significant. SAES showed that the compositiongradient at the phase boundaries is narrower than 2µm. Different types of DSSs have been studied, from low-alloyedDSS to superduplex. Higher contents of Cr, Mo and Nstrengthened both phases as well as the phase boundaries,resulting in phases having similar corrosion resistance thatshowed a more uniform dissolution behavior. However, the Voltapotential difference between the phases proved to be of thesame order for all the DSSs studied. Austenite was in generalassociated to regions displaying a more noble Volta potentialthan ferrite, resulting in a higher dissolution rate of theferrite next to the austenite phase. <b>Key words:</b>In situ, local dissolution, electrochemical,STM, SKPFM, MFM, SAES, duplex stainless steel, acidic-chloridesolution.

<p>The local corrosion behavior of duplex stainless steel (DSS)is affected by a wide variety of factors. Localized corrosionof DSS frequently starts at micrometer scale inclusions orprecipitates, which are often segregated in theaustenite-ferrite boundary regions. Moreover, due to thepartitioning of the key alloying elements of ferrite (Cr andMo) and austenite (N and Ni), the local interactions betweenthe phases must also be considered.</p><p>The aim of this doctoral study was to increase the knowledgeabout the local dissolution behavior of DSS in acidic-chlorideenvironments. The recent developments of new local probingtechniques have opened a new frontier in corrosion science,providing valuable local information not accessible in thepast. The local techniques used include electrochemicalscanning tunneling microscopy (EC-STM), scanning probe forcemicroscopy (SKPFM), magnetic force microscopy (MFM), andscanning Auger electron Spectroscopy (SAES), all withmicrometer or sub-micrometer resolution.</p><p>With EC-STM, it was possible to monitor local dissolutionprocesses on DSS in situ, and in real time. MFM was capable ofimaging the phase distribution in DSS without the need of thetraditional surface etching, while SKPFM revealed that theVolta potential difference between the two phases wasmeasurable and significant. SAES showed that the compositiongradient at the phase boundaries is narrower than 2µm.</p><p>Different types of DSSs have been studied, from low-alloyedDSS to superduplex. Higher contents of Cr, Mo and Nstrengthened both phases as well as the phase boundaries,resulting in phases having similar corrosion resistance thatshowed a more uniform dissolution behavior. However, the Voltapotential difference between the phases proved to be of thesame order for all the DSSs studied. Austenite was in generalassociated to regions displaying a more noble Volta potentialthan ferrite, resulting in a higher dissolution rate of theferrite next to the austenite phase.</p><p><b>Key words:</b>In situ, local dissolution, electrochemical,STM, SKPFM, MFM, SAES, duplex stainless steel, acidic-chloridesolution.</p>

The excellent corrosion resistance of stainless steels arises from the presence of a passive film on its surface. Above 10.5wt% Cr a chromium oxide of 1-3 nm is formed on the surface of the metal that in case of damage will reform and hinder further dissolution of the metal. However, the passivity of the stainless steel can be altered by material factors and external factors; such as the composition of the underlying phases, external loads or thermal treatments. In this work the local electrochemical techniques Scanning Vibrating Electrode Technique (SVET) and Scanning Kelvin Probe Force Microscopy (SKPFM) and the local characterization techniques X-ray Photoelectron Spectroscopy (XPS) and Auger Electron Spectroscopy (AES) have been used to investigate corrosion phenomena of stainless alloys based on measurements of corrosion current density, work function, thickness and composition of the oxide. The effect on work function of the thickness of the passive film and composition of the underlying phases was investigated for 301LN austenitic stainless steel (Paper I) and a heat treated superduplex 25Cr7Ni type stainless steel (Paper II). It was shown that the work function can be an indicator of corrosion resistance of the phases in the microstructure, and that the composition of the underlying phases had a greater effect on the work function than the thickness of the passive film. External factors such mechanical deformation (Paper I) and welding (Paper III) altered the passivity of the steel and work function. It was found that plastic deformation decreased irreversibly the work function, whereas elastic deformation did not have any permanent effect. Thermal oxides affected the passivity of stainless steels welded joints and were detrimental for its corrosion resistance. Anodic activity, observed with SVET, and pitting corrosion were detected at the heat tint and attributed to the interaction between the composition and the thickness of the oxide. Brushing combined with pickling was recommended for recovering the passivity of stainless steels. / <p>QC 20160516</p>

Dans un contexte normatif toujours plus sévère concernant les rejets automobiles polluants, la substitution des aciers par des alliages d’aluminium dans les structures des véhicules est en plein essor. Ce projet de thèse, qui s’inscrit dans un programme de développement de la société Constellium, cible plus précisément les alliages d’aluminium de la série 7xxx (Al-Zn-Mg) qui, malgré leurs propriétés mécaniques élevées, peuvent présenter une sensibilité à la corrosion sous contrainte (CSC) liée au phénomène de fragilisation par l’hydrogène (FPH). La compréhension des mécanismes mis en jeu dans ce type d’endommagement constitue donc une première étape vers une optimisation métallurgique en vue d’une industrialisation future de ces alliages dans le secteur automobile. La première partie de ces travaux est consacrée à l’étude de l’influence de l’état métallurgique de l’alliage 7046 sur son comportement en CSC et à l’identification des mécanismes de dégradation. Un lien direct a pu être mis en évidence entre l’abattement des propriétés mécaniques et les modes de rupture actifs et la quantité d’hydrogène dans l’alliage. Les deux modes d’endommagement observés, intergranulaire-fragile et transgranulaire-fragile, ont respectivement été attribués à un enrichissement en hydrogène aux joints de grains et au piégeage de l’hydrogène au niveau des précipités intragranulaires. Les interactions entre l’hydrogène et les précipités fins d’une part et les dislocations d’autre part, identifiés comme deux hétérogénéités microstructurales critiques vis-à-vis de la FPH, ont été étudiées à une échelle plus locale dans la seconde partie du travail de thèse. Les essais ont été réalisés sur des échantillons modèles, chargés en hydrogène en milieu H2SO4 sous polarisation cathodique et la profondeur de pénétration de l’hydrogène a été évaluée par SKPFM (Scanning Kelvin Probe Force Microscopy). L’ensemble des résultats obtenus met en évidence : 1/ un effet « barrière » des précipités fins et des dislocations sur la diffusion de l’hydrogène en relation avec un abattement des propriétés mécaniques moins important, 2/ un transport possible de l’hydrogène par les dislocations et 3/ l’efficacité du SKPFM pour déterminer précisément des coefficients de diffusion apparents de l’hydrogène. Ces résultats ouvrent ainsi de nouvelles pistes vers la compréhension des mécanismes de CSC dans les alliages Al-Zn-Mg. / Automotive industry is increasingly affected by standards requiring a major cut of polluting emissions, leading R&D policies to focus on replacing steel by aluminum alloys. This thesis project, initiated by the manufacturer Constellium, focuses on 7xxx (Al-Zn-Mg) aluminum alloys known to have high mechanical properties but also to be susceptible to stress corrosion cracking (SCC) partly attributed to hydrogen embrittlement (HE). Understanding the mechanisms involved would be a first step towards a metallurgical optimization and a future industrialization of these alloys. The first part focuses on the SCC behavior of the 7046 aluminum alloy, related to its microstructure, and the identification of degradation mechanisms involved. A hydrogen amount – loss of mechanical properties relationship was highlighted. The damage observed was explained by the presence of hydrogen in the grain boundaries and by a trapping effect of the intragranular hardening precipitates, limiting the hydrogen diffusion to the grain boundaries. Interactions between hydrogen and hardening precipitates and dislocations, both identified as critical microstructural heterogeneities for HE, are studied at a local scale in a second part. The hydrogen effect was characterized by penetration depth measurements made by SKPFM (Scanning Kelvin Probe Force Microscopy) on “model” samples cathodically charged in H2SO4. The whole results finally highlight: 1/ a “shielding” effect of fine precipitates and dislocations on hydrogen diffusivity related to a lower susceptibility to HE, 2/ hydrogen transport by dislocations and 3/ the efficiency of SKPFM to precisely measure effective diffusion coefficients of hydrogen. These results lead to new opportunities to understand SCC mechanisms in Al-Zn-Mg alloys.

Dans un contexte normatif toujours plus sévère concernant les rejets automobiles polluants, la substitution des aciers par des alliages d’aluminium dans les structures des véhicules est en plein essor. Ce projet de thèse, qui s’inscrit dans un programme de développement de la société Constellium, cible plus précisément les alliages d’aluminium de la série 7xxx (Al-Zn-Mg) qui, malgré leurs propriétés mécaniques élevées, peuvent présenter une sensibilité à la corrosion sous contrainte (CSC) liée au phénomène de fragilisation par l’hydrogène (FPH). La compréhension des mécanismes mis en jeu dans ce type d’endommagement constitue donc une première étape vers une optimisation métallurgique en vue d’une industrialisation future de ces alliages dans le secteur automobile. La première partie de ces travaux est consacrée à l’étude de l’influence de l’état métallurgique de l’alliage 7046 sur son comportement en CSC et à l’identification des mécanismes de dégradation. Un lien direct a pu être mis en évidence entre l’abattement des propriétés mécaniques et les modes de rupture actifs et la quantité d’hydrogène dans l’alliage. Les deux modes d’endommagement observés, intergranulaire-fragile et transgranulaire-fragile, ont respectivement été attribués à un enrichissement en hydrogène aux joints de grains et au piégeage de l’hydrogène au niveau des précipités intragranulaires. Les interactions entre l’hydrogène et les précipités fins d’une part et les dislocations d’autre part, identifiés comme deux hétérogénéités microstructurales critiques vis-à-vis de la FPH, ont été étudiées à une échelle plus locale dans la seconde partie du travail de thèse. Les essais ont été réalisés sur des échantillons modèles, chargés en hydrogène en milieu H2SO4 sous polarisation cathodique et la profondeur de pénétration de l’hydrogène a été évaluée par SKPFM (Scanning Kelvin Probe Force Microscopy). L’ensemble des résultats obtenus met en évidence : 1/ un effet « barrière » des précipités fins et des dislocations sur la diffusion de l’hydrogène en relation avec un abattement des propriétés mécaniques moins important, 2/ un transport possible de l’hydrogène par les dislocations et 3/ l’efficacité du SKPFM pour déterminer précisément des coefficients de diffusion apparents de l’hydrogène. Ces résultats ouvrent ainsi de nouvelles pistes vers la compréhension des mécanismes de CSC dans les alliages Al-Zn-Mg.

The formation of conversion coatings based on Ce, trivalent Cr and Ti/Zr is triggered by the local pH increase at cathodic IM sites of the aluminium alloy microstructure. The pH gradient is created over the cathodic intermetallic (IM) sites of the microstructure and its intensity is influenced by their activity which depends on their chemical composition, their size, and spatial distribution. Furthermore, the pre-treatment applied also affects the surface reactivity. The role of each of the microstructural features on the increased pH gradient and the subsequent triggering of local conversion coating deposition remains to be understood. To address the knowledge gap, model cast Al-Si-Fe and Al-Si-Cu-Fe alloys have been designed. Cerium based conversion coating treatment with standard parameters is applied to investigate the microstructure’s influence. Furthermore, four different surface pre-treatments’ effect on the topographical and electrochemical properties have been investigated by localized techniques and have been correlated with deposition experiment observations to prove surface reactivity. In this study, it was found that the four surface pre-treatments – polishing, NaOH, NaOH-HNO3, NaOH-H2SO4 activate the surface of alloys containing Fe-rich IM and Cu-rich IM differently. The surface pre-treatment NaOH-HNO3 was found most detrimental to the surface reactivity as the pre-treatment resulted in passivation of the IM and a drastic reduction in its volta potential. The best pre-treatment for the alloy Al-Si-Fe was found to be one with NaOH etching. In the case of Al-Si-Cu-Fe alloy, pre-treatments where a pickling step (with either H2SO4 or HNO3) was applied followed a NaOH etching step, the surface of the IM was activated more than other pre-treatments due to selective Al dealloying and Cu-redeposition. The extent of Cu-redeposition was observed to be the most when surfaces were pickled with HNO3 solution and with the NaOH- HNO3 pre-treatment, fastest deposition kinetics were observed. In the cast Al-Si-Cu-Fe alloy, the localized deposits were preferentially observed to form on only strong cathodic Cu-rich IM. The size (surface area) of the Cu-rich IM correlated linearly with the lateral deposition area as well as z-direction spread. It was found that the pH gradient resulting from the oxygen reduction reaction near an IM is very local and does not affect pH gradients of a neighbouring Cu-rich IM. The size did not have a profound impact on the extent of deposition occurring on a Cu-rich IM, but it was found that big Cu-rich IM activated faster for deposition reaction than small Cu-rich IM. When the progression of deposition on both coarse and fine microstructure cast Al-Si-Cu-Fe was quantitatively monitored at increasing conversion coating times 0.5h, 1h and 2h, it was observed that big Cu-rich IM in the coarse alloy triggered deposition faster than small Cu-rich IM. Deposition mechanism on Fe-rich IM was found to be composition specific. In the cast of big Fe-rich β-Al5FeSi IM, localized deposition initiated at the border on the IM and is explained based on Si content in the composition of the IM, which has very high resistivity. In another Fe-rich IM, although of a much smaller size, which had lower Si content and was richer in Fe, a localized deposition was observed on the entire IM. / Bildning av omvandlingsbeläggningar baserade på Ce, trivalent Cr och Ti/Zr initieras av lokalt förhöjd pH vid katodiska intermetalliska platser I aluminiumlegeringens mikrostruktur. Utbredningen av den starka pH-gradientens uppkomst över katodiska intermetalliska (IM) platser av mikrostrukturen påverkas av dess aktivitet som i sin tur beror på dess kemiska sammansättning, storlek, och rumslig fördelning. Ytans reaktivitet påverkas dessutom av dess förbehandling. Rollen av mikrostrukturens egenskaper på den förhöjda pH-gradienten och efterföljande initiering av lokal omvandlingsbeläggning återstår att förstå. För att komplettera detta kunskapsgap har Al-Si-Fe och Al-Si-Cu-Fe modellgjutlegeringar utformats. Cerium-baserade behandlingar för omvandlingsbeläggning med standardparametrar tillämpas för undersökning av mikrostrukturens påverkan. Effekten av fyra olika ytförbehandlingar på topografiska och elektrokemiska egenskaper har dessutom undersökts med lokaliserade metoder och har korrelerats med observationer vid depositionsexperient för att bevisa ytreaktivitet. I denna studie har det visats att de fyra ytförbehandlingarna – polering, NaOH, NaOH-HNO3, NaOH-H2SO4 – aktiverar ytan hos legeringar innehållande Fe-rika intermetaller och Cu-rika intermetaller på olika vis. Ytförbehandlingen med NaOH-HNO3 visades vara skadligast för ytans reaktivitet eftersom förbehandlingen resulterade i passivering av IM och en drastisk sänkning av dess volta-potential. Den bästa förbehandlingen för Al-Si-Fe-legeringen visades vara med NaOH-etsning. I Al-Si-Cu-Fe-legeringens fall, var förbehandling där ett betningssteg (antingen med H2SO4 eller HNO3) tillämpades följt av etsning med NaOH, aktiverades ytan av IM mer än med andra förbehandlingar på grund av selektiv korrosion av Al och Cu-återdeposition. Utbredningen av Cu-återdeposition observerades vara störst när ytor var betade med HNO3-lösning och depositionens kinetik var som hastigast vid förbehandling med NaOH-HNO3. I den gjutna Al-Si-Cu-Fe-legeringen observerades lokaliserade depositionerna att bildas endast på starkt katodiska Cu-rika IM. Storleken (ytarea) på de Cu-rika IM korrelerade linjärt med den laterala depositionsytan samt med spridning i z-riktning. Det visade sig att pH-gradienten som uppkom via syrereduktionsreaktionen nära IM är väldigt lokal och påverkar ej pH-gradienter vid närliggande Cu-rik IM. Storleken hade ingen anmärkningsvärd verkan på utbredningen av deposition på Cu-rik IM, men stora Cu-rika IM visade sig aktiveras snabbare för depositionsreaktion än små Cu-rika IM. När depositionens framfart över grov och fin mikrostruktur i gjuten Al-Si-Cu-Fe följdes kvantitativt vid ökande omvandlingsbeläggningstid 0,5h; 1h och 2h, så observerades att stora Cu-rika IM i den grova legeringen påbörjade depositionen snabbare än små Cu-rika IM. Depositionsmekanismen på Fe-rika IM visades vara specifik för sammansättning. I gjutgodset med stora Fe-rika β-Al5FeSi IM visades lokaliserad deposition initieras vid gränsen av IM vilket förklaras baserat på Si-halt i IM sammansättning, som har väldigt hög resistivitet. I en annan Fe-rik IM, dock av mycket mindre storlek, som hade lägre Si-halt och rikare med Fe, en lokaliserad deposition var observerad över hela IM.

A multi-analytical approach based on in-situ and ex-situ local probing techniques was employed to investigate localized corrosion mechanisms of some aluminum alloys in chloride containing solutions, focusing on the influence of intermetallic particles (IMPs) in the alloys. In the EN AW-3003 alloy, SEM-EDS analysis revealed constituent and dispersoid IMPs. There are two types of constituent IMPs, with size ranging from 0.5 to several μm, and composition typically Al6(Fe,Mn) or Al12(Mn,Fe)3Si, respectively,having a Mn/Fe ratio of about 1:1. Fine dispersoids of 0.5 μm or less in size normally have the composition Al12Mn3Si1-2. Scanning Kelvin probe force microscopy (SKPFM measurements showed that the constituent IMPs have a higher Volta potential compared to the matrix, and the Volta potential difference increased with particle size, probably related to the composition of the IMPs. The SKPFM results also showed a Volta potential minimum in the boundary region adjacent to some larger IMPs. The open-circuit potential and electrochemical impedance spectroscopy measurements indicated local electrochemical activities occurring on the surface, and active-like dissolution in the acidic solutions, but a passive-like behavior in the near-neutral solutions. Infrared reflection-absorption spectroscopy measurements after exposure and thermodynamic calculations suggested the formation of mixtures of aluminum oxyhydroxide and acetate on the surface in acetic acid solutions. The formation and fraction of dominant species of the corrosion products depend on the pH of the solution, and aluminum chloride compounds may form at very low pH. Moreover, an integrated in-situ atomic force microscopy (AFM) and scanningelectrochemical microscopy (SECM) set-up was used to investigate the localized activities on the surface. With a dual mode probe, acting as both AFM tip and SECM microelectrode, concurrent topography and electrochemical current images were obtained on the same area of the surface. Numerical simulations of the SECM suggested a micrometer lateral resolution under favorable conditions and the ability to resolve μmsized active sites with a separation distance of about 3 μm or larger. The simulations were verified by SECM mapping of the aluminum alloys in the chloride solutions. The AFM/SECM measurements revealed enhanced cathodic activity on some larger IMPs and local anodic dissolution around larger IMPs. In-situ AFM monitoring confirmed preferential dissolution in the boundary region adjacent to some of these IMPs. The results elucidate the micro-galvanic effect and size effect of the IMPs during the initiation of localized corrosion of the Al alloys. Furthermore, differences in corrosion properties between EN AW-3003 and a newly developed Al–Mn–Si–Zr alloy were studied with a similar approach. Compared to EN AW-3003, the new alloy had a smaller number of particles with a large Volta potential difference relative to the matrix. In slightly corrosive solutions extensive localized dissolution and deposition of corrosion products occurred on EN AW-3003, whereas only a small number of corroding sites and “tunnel-like” pits occurred on the Al–Mn–Si–Zr alloy. The lower corrosion activity and the smaller tunnel-like pits resulted in lower material loss of the Al–Mn–Si–Zr alloy, which is beneficial for applications using a thin material. / QC 20100702