The present study investigates the effect of fluorine species during anodizing of aluminium and AA2024-T3 alloy in sulphuric acid and tartaric-sulphuric acid (TSA) electrolytes. The investigation comprises four main parts; (i) Effects of fluoride on barrier film formation on aluminium. (ii) Effects of fluoride and fluorozirconic acid (FZ) on porous film growth on aluminium in sulphuric acid. (iii) Effects of FZ on porous film growth on aluminium and AA 2024-T3 alloy in sulphuric acid and TSA. (iv) Effects on anodizing of other fluoroacids (fluoroboric (FB), fluorosilicic (FS) and fluorotitanic acid (FT)). The anodic films were examined by analytical scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, Rutherford backscattering spectroscopy, nuclear reaction analysis and glow discharge optical emission spectroscopy. The behaviour of fluoride ions during the growth of barrier-type films on aluminium was investigated in ammonium pentaborate solution with added sodium fluoride. Additions of up to 3.5 x 10-3 M sodium fluoride had a negligible influence on the film growth. In contrast, 3.5 x 10-2 M sodium fluoride reduced the efficiency to 60% as fluoride ions promoted field-assisted ejection of Al3+ ions from the film. Incorporated fluoride ions migrated inwards at a rate about twice that of O2- ions, forming a fluoride-rich layer at the film base. The study of the influence of FZ on formation of porous anodic films in sulphuric acid and TSA employed a range of anodizing voltages, electrolyte temperatures and anodizing times. Fluoroacid increased the growth rate, with a reducing influence as the temperature increased. The films contained fluoride and sulphate ions, zirconium was not detected. The fluoride concentration decreased with increasing temperature, whereas the sulphate concentration was unaffected. Anodizing aluminium and AA 2024-T3 alloy in other fluoroacids resulted in similar influences on the anodizing behaviour as FZ. The differences in growth rate, film composition and film morphology were comparatively small and did not show a systematic dependence on the type of fluoroacid employed. Boron, silicon and titanium were not detected in the films.

In this work, the nucleation and growth of pores in anodic films formed on aluminium in chromic acid and the effect of low levels of sulphate impurity in the anodizing bath on the formation of the films on aluminium and AA 2024 alloy are investigated. The sulphate concentrations considered include levels within specified limits for industrial processing. The anodizing is carried out either potentiostatically or by stepping the voltage. The films are examined by scanning electron microscopy, transmission electron microscopy and atomic force microscopy to determine the pore spacing, pore population densities, pore diameters and film thicknesses. Film compositions were determined using energy-dispersive X-ray spectroscopy, Rutherford backscattered microscopy and nuclear reaction analysis. In order to investigate the mechanism of pore formation, two tracer methods are employed. In one method, anodic films are formed first in an arsenate electrolyte in the second method, a tungsten tracer band deposited by magnetron sputtering. The behaviours of arsenic and the tungsten are investigated during the subsequent anodizing in chromic acid. The results suggest that the initiation and growth of pores in occurred as a result of electric field assisted chemical dissolution. The effect of sulphate impurity in the chromic acid is investigated using electrolytes with different sulphate content. In the initial stages of anodizing aluminium at 100 V, sulphate impurity at a level of 38 ppm in the chromic acid is shown to lead to significant incorporation of sulphate ions into the anodic film, a lower current density, a smaller cell size and less feathering of the pore walls. In addition, the efficiency of film formation is increased. In later stages of anodizing, the growth of larger pores and cells, leads to a duplex film morphology, with finer pores in the outer region. The change in pore size correlates with a reduction in the incorporation of sulphate into the film. From the results of sequential anodizing experiments, it is suggested that incorporated sulphate ions generate a space charge layer, which has an important role in determining the current density. The effects of higher sulphate concentrations up to 3000 ppm are investigated, which are shown to significantly affect the current density and the pore diameter. Anodizing of aluminium and AA 2024 alloy was also carried out according to industrial practice. The results show that there is significant effect of sulphur impurity on the film thickness. Corrosion tests in 3.5 % NaCl solution for the alloy after anodizing in low (smaller or equal to 1.5 ppm) and high (~38 ppm) sulphate-containing chromic acid electrolytes demonstrate a better corrosion resistance with films formed in the latter electrolyte.

Le coût de la maintenance aéronautique pourrait être réduit en proposant des stratégies d’inspection « intelligentes » intégrant des outils prédictifs de l’évolution des défauts, comme la vitesse de propagation de la corrosion intergranulaire.Dans cette thèse, nous avons cherché à quantifier les deux modes d’endommagement associés à la corrosion intergranulaire sur un alliage 2024 : la composante « perforante » (dissolution des pointes de joint de grain) et la composante « émoussante » (dissolution des parois des grains dans les cavités intergranulaires). Pour évaluer la composante « perforante », nous proposons une nouvelle variante de la méthode TFP (méthode OTFP) plus complète car elle ne se limite pas à caractériser le défaut le plus rapide mais permet de suivre l’ensemble des défauts perforants grâce à la nature optique de la détection. Dans cette méthode, le dispositif expérimental laisse libre la face de détection, ce qui permet de prélever l’électrolyte issu des cavités intergranulaires et de procéder à son analyse chimique. Cette donnée, peu connue à ce jour, a été utilisée pour valider des modèles de « transport réactif » qui pourront servir de base à des simulations prédictives intégrant l’effet de la nature de l’environnement. La porosité au sein du matériau induite par la corrosion intergranulaire et amplifiée par la dissolution « émoussante » a été suivie en temps réel par mesure de la conductivité électrique avec une sonde à courants de Foucault. D’abord calibrées en régime potentiostatique, ces méthodes se sont par la suite révélées efficaces pour évaluer l’endommagement associé à la corrosion intergranulaire lors d’une corrosion de type atmosphérique. / Costs of aeronautical maintenance can be reduced by implementation of “smart” inspection strategies integrating predictive data on the evolution of defects such as the propagation rate of intergranular corrosion.In this work, intergranular corrosion damage on 2024 aluminium alloy was characterized by two modes : the “perforating” damage (dissolution of the grain boundary tips) and the “blunting” damage (dissolution of the grain walls in the intergranular cavities). To evaluate the “perforating” damage, a new version of the TFP method (OTFP method) which is more complete, was designed. The OTFP method allows to detect all the intergranular corrosion defects and not only the fastest full penetrating grain boundary thanks to the optical nature of the detection. In this method the detection backside of the thin foil is free, which makes possible the collection of the trapped electrolyte in the intergranular cavities to carry out its chemical analysis. This not well-known data, was used to validate “mass-transport” models which could be implemented in predictive simulations considering the effect of the environmental conditions. The porosity inside the foil induced by the intergranular corrosion and enhanced by the “blunting” dissolution was followed in real-time by measuring the electrical conductivity using an eddy current probe.These methods were first calibrated in potentiostatic tests and then successfully applied to evaluate the intergranular corrosion damage in atmospheric corrosion conditions.

Aluminum alloys have been used for decades in aircraft as they offer a wide range of properties explicitly developed to provide a set of characteristics adapted to structural and non-structural components. However, aircraft components inevitably undergo degradation during service due to their extensive use and exposure to harsh environments. Typical repair methods are either not efficient for large scale repairs due to their low material growth rate, not suitable for field repair or involve the use of high process temperatures. The present research aims at evaluating the cold gas dynamic spray (CGDS) as a potential repair technology to restore Al7075-T6 nose landing gear steering actuator threads found on the Boeing 757 aircraft. Moreover, it studies the suitability of using cold spray to deposit Al2024 material. The influence of process parameters and substrate surface preparation on the material deposition efficiency and resulting microstructural and mechanical repair properties is also evaluated.