Statistical Study of the Corrosion Behavior of Al2CuMg Intermetallics in AA2024-T351 by SKPFM

A statistical study combining atomic force microscopy, scanning Kelvin probe force microscopy (SKPFM), and energy-dispersive spectroscopy was carried out on more than 300 Al2CuMg intermetallic particles of AA2024 alloy to determine their corrosion behavior in chloride-containing solutions. The combination of these three techniques allowed the correlation of the dissolution depth of the S-phase particles to their SKPFM potential and their chemical composition. This study also revealed that SKPFM measurements must be carried out with many precautions, but it is a powerful tool for the study of localized corrosion

Combination of AFM, SKPFM, and SIMS to Study the Corrosion Behavior of S-phase particles in AA2024-T351

The dissolution mechanism of S-phase particles in 2024-T351 aluminum alloy at open-circuit potential in chloride-containing sulfate solutions was investigated using atomic force microscopy (AFM), scanning Kelvin probe force microscopy (SKPFM), and secondary ion mass spectroscopy (SIMS). The combination of the three techniques allowed the correlation between SKPFM measurements and the corrosion behavior of AA2024 to be confirmed, leading to a better understanding of the electrochemical behavior of S-phase particles. A three-step mechanism for the dissolution and accompanying processes occurring near S particles was proposed: (i) preferential aluminum and magnesium dissolution, (ii) galvanic coupling between the copper-enriched particles and the surrounding matrix, leading to an increased passivity of the matrix around the particles, and (iii) copper deposition around the corroded particles

Localized approach to galvanic coupling in an aluminum–magnesium system

The corrosion behavior of a pure aluminum/pure magnesium couple in a weakly conductive sodium sulfate solution was investigated. Potential and current distributions on the surface of the model couple at the beginning of immersion were obtained by solving the Laplace equation using a finite element method algorithm. Magnesium acted as the anode of the system while oxygen and water were reduced on aluminum. Calculations predicted a large current peak at the Al/Mg interface related to a local increase in both Mg dissolution and oxygen and water reduction on aluminum, leading to a local pH increase. Optical and scanning electron microscope observations confirmed the strong dissolution of magnesium concomitantly with depassivation of aluminum at the Al/Mg interface. Local electrochemical impedance spectroscopy showed the detrimental effects of the galvanic coupling both on aluminum and magnesium

Simulating the galvanic coupling between S-Al2CuMg phase particles and the matrix of 2024 aerospace aluminium alloy

Study of the corrosion behaviour of a magnetron sputtered Al–Cu/Al–Cu–Mg model alloy couple in sulphate solutions has been undertaken to gain insight into the galvanic coupling between the matrix and SAl2CuMg particles in the 2024 aluminium alloy (AA2024). Polarisation curves and local electrochemical impedance spectroscopy measurements (LEIS) were performed on the individual alloys and on the model alloy couple. SEM enabled correlation of electrochemical phenomena to the observed damage. The corrosion behaviour of the sputtered alloys was shown to be representative of the AA2024, with the Al–Cu–Mg alloy part undergoing localised corrosion and the Al–Cu alloy part remaining passive

Combined Kelvin probe force microscopy and secondary ion mass spectrometry for hydrogen detection in corroded 2024 aluminium alloy

The capability of Kelvin probe force microscopy (KFM) to detect and locate hydrogen in corroded 2024 aluminium alloy was demonstrated. Hydrogen was introduced inside the 2024 alloy following a cyclic corrosion test consisting of cycles of immersion in 1 M NaCl solution followed by exposure to air at -20 °C. The combination of scanning electron microscopy, secondary ion mass spectrometry and KFM demonstrated that the grain and subgrain boundaries were preferential pathways for the short-circuit diffusion of hydrogen but also acted as a source of hydrogen diffusion in the lattice over distances of up to ten microns with non-negligible desorption when exposed to air at room temperature for 24 h

Investigation of Kelvin probe force microscopy efficiency for the detection of hydrogen ingress by cathodic charging in an aluminium alloy

Detecting and locating absorbed hydrogen in aluminium alloys is necessary for evaluating the contribution of hydrogen embrittlement to the degradation of the mechanical properties for corroded or cathodically hydrogen-charged samples. The capability of Kelvin probe force microscopy (KFM) to overcome this issue was demonstrated. Aluminium alloy samples were hydrogenated by cathodic polarisation in molten salts (KHSO4/NaHSO4.H2O). The presence of absorbed hydrogen was revealed; the affected zone depth was measured by secondary ion mass spectroscopy (SIMS) analyses and KFM measurements

Mécanismes de corrosion localisée de l'alliage d'aluminium 2024. Apport de la microscopie à force atomique (AFM) couplée au mode Kelvin (KFM) et des alliages modèles

L'alliage 2024 (Al-Cu-Mg) est, dans le contexte de l'allègement de structure, encore largement utilisé par l'industrie aéronautique. Sa microstructure le rend sensible à la corrosion localisée (corrosion par piqûres, corrosion feuilletante et intergranulaire). Parmi les paramètres microstructuraux, les particules intermétalliques, et notamment les particules de phase S-Al2CuMg, sont dans de nombreux cas un facteur d'endommagement. Ce travail de thèse est donc centré sur leur réactivité ainsi que sur l'apport de techniques locales à cette étude. Dans ce travail, une étude multianalytique a été réalisée. La microscopie à force atomique (AFM pour Atomic Force Microscopy) couplée au mode Kelvin (KFM pour Kelvin Force Microscopy) permettent l'acquisition de la topographie et du potentiel de surface d'un échantillon à l'échelle nanométrique. Le couplage de ces techniques à des analyses chimiques d'extrême surface par SIMS (Secondary Ions Mass Spectroscopy) ainsi que le suivi de la composition des particules lors de leur dissolution (MEB-EDS) ont démontré que l'association AFM-KFM permet le suivi de l'ensemble des phénomènes de dissolution de particules intermétalliques riches en cuivre avec une résolution spatiale de l'ordre de la centaine de nanomètres. En parallèle à ces travaux, l'étude d'alliages et de systèmes modèles par des techniques électrochimiques stationnaires et transitoires telles que la Spectroscopie d'Impédance Electrochimique Locale (SIEL) a été réalisée. Ce travail a permis de montrer la représentativité de ces systèmes pour étudier les phénomènes de microcouplage galvanique entre particules intermétalliques et matrice de l'alliage commercial 2024. La réactivité du couple aluminium/magnésium a été simulée numériquement par la méthode des éléments finis. Les distributions de courant et de potentiel calculées ont été validées par des observations en microscopie optique et électronique. ABSTRACT : 2024 aluminium alloy is often used in aerospace applications in the structure lightening context. Its microstructure makes it very susceptible to localized corrosion (pitting corrosion, exfoliation corrosion and intergranular corrosion). Among the microstructural parameters, intermetallic particles and mainly S-phase (Al2CuMg) particles are an important damaging factor. This work is focused on their reactivity. The local technique contribution was demonstrated. In this work a multianalytical study was developed. Kelvin Force Microscopy (KFM, the Kelvin mode of AFM) allows topographical and surface potential maps of the same zone of the sample surface with submicrometric resolution to be obtained. Coupling of this technique with extreme surface chemical analyses (SIMS) and chemical composition of the particle during dissolution (MEB-EDS) allowed interesting results to be obtained. The possibility of KFM to follow dissolution phenomena of copper rich intermetalics was demonstrated. Model systems and alloys were studied by means of stationary and transient electrochemical techniques as Local Electrochemical Impedance Spectroscopy (LEIS). These model systems were shown to be representative of the galvanic coupling between intermetallics and the matrix of 2024 commercial alloy. Aluminium and magnesium model couple reactivity was simulated by finite element method (FEM) calculations. The current and potential distribution calculated was corroborated by optical and electronic microscope observation

Condition monitoring and prediction of solution quality during a copper electroplating process

This paper presents a method for the monitoring and prediction of the electrolyte quality during the process of copper electroplating. This is important in industry, as any deviation in the solution quality leads to a deterioration of the quality of the processed products. The aim of the study is to identify some physical parameters that are representative of the quality variation during the deposition process. These parameters are then tracked online to continuously assess the solution quality and predict its remaining useful life. To do this, the process behavior is first characterized to derive a nominal model and to identify the physical parameters that can be used to describe the aging variation in the electrolyte quality. The aging model is then explored to assess the current level of the solution quality and to predict its remaining useful life. The proposed method is verified using real data acquired from a specifically designed test bench. The obtained results reveal the efficiency of the method

Effect of the over-ageing treatment on the mechanical properties of AA2024 aluminum alloy.

The evolution of the hardness of the over-ageing AA2024 alloy scale was followed by measurements of Vickers hardness. The nanoindentation is adapted to the determination of elastoplastic properties (hardness and Young’s modulus) of the matrix and also of coarse intermetallic precipitates. Influence of the artificial over-ageing time to hardness and to mechanical properties as the local scale was investigated

Mechanical and barrier properties of MOCVD processed alumina coatings on Ti6Al4V titanium alloy

This study focuses on the implementation of different aluminum oxide coatings processed by metal-organic chemical vapor deposition from aluminum tri-isopropoxide on commercial Ti6Al4V titanium alloy to improve its high temperature corrosion resistance. Films grown at 350 °C and at 480 °C are amorphous and correspond to formulas AlOOH, and Al2O3, respectively. Those deposited at 700 °C are composed of γ-Al2O3 nanocrystals dispersed in a matrix of amorphous alumina. Their mechanical properties and adhesion to the substrates were investigated by indentation, scratch and micro tensile tests. Hardness and rigidity of the films increase with increasing deposition temperature. The hardness of the coatings prepared at 350 °C and 480 °C is 5.8 ± 0.7 GPa and 10.8 ± 0.8 GPa respectively. Their Young's modulus is 92 ± 8 GPa (350 °C) and 155 ± 6 GPa (480 °C). Scratch tests cause adhesive failures of the films grown at 350 °C and 480 °C whereas cohesive failure is observed for the nanocrystalline one, grown at 700 °C. Micro tensile tests show a more progressive cracking of the latter films than on the amorphous ones. The films allow maintaining good mechanical properties after corrosion with NaCl deposit during 100 h at 450 °C. After corrosion test only the film deposited at 700 °C yields an elongation at break comparable to that of the as processed samples without corrosion. The as established processing–structure–properties relation paves the way to engineer MOCVD aluminum oxide complex coatings which meet the specifications of the high temperature corrosion protection of titanium alloys with regard to the targeted applications