Anodic films have been produced on zirconium and zirconium alloys potentiostatically (at either 20 or 40 V) in 0.35 M ammonium fluoride in glycerol, with interest in the addition of small amounts of water (up to 5 vol.%) to the electrolyte on their growth, morphologies and compositions. Scanning and transmission electron microscopies have been employed to analyse morphologies of the films, which appeared to be porous under all the investigated conditions.Rutherford backscattering spectroscopy and nuclear reaction analysis, used as techniques to investigate film compositions, disclosed the presence of zirconium, oxygen, fluorine, carbon and nitrogen in the films. The contents of fluorine and oxygen in the films were found to increase and decrease respectively by decreasing the amount of water added to the electrolyte from 5 to 0 vol.%. Moreover, the content of fluorine increased by decreasing the applied formation voltage, from 40 to 20 V, for films formed in electrolytes containing similar amounts of added water.In order to get information on the distribution of the species in the films, cross-sections of selected specimens were produced by focused ion beam and analysed by analytical transmission electron microscopy. Oxide-rich nanotubes were revealed embedded in a fluoride-rich matrix, suggesting that the mechanism of growth of the anodic films is governed by different migration rates of the anionic species in the film base, with F- ions, being the fastest anions. The relative amounts of the oxide-rich and fluoride-rich materials were related to the composition of the electrolyte, with the fluoride regions being less extensive and the oxide-rich nanotubes being thicker-walled by adding small amounts of water. Moreover, nanotubes are constituted of two shells (an outer one surrounding the pores and an inner one located between the outer shell and the matrix), suggesting differences in the composition in these two regions, presumed to be due to the incorporation of carbon species, being the slowest migrating species, in the outer shell. The fluoride-rich matrix chemically dissolved following 1 h immersion of the specimens in the formation electrolytes, promoting the transition from porous to nanotubular morphologies. Ageing of the specimens in deionized water for similar times did not significantly influence the morphologies and compositions of the anodic films.

La problématique de l’élimination de l’excès d’ions fluorure présents dans les eaux de forage destinées à la consommation humaine peut être résolue en utilisant plusieurs méthodes. Dans cette thèse, les procédés testés sont : l’adsorption sur des particules d’os de seiche, l’adsorption sur des particules de calcite en présence d’acide acétique, la nanofiltration et l’échange d’ions. L’objectif est d’optimiser les différents procédés pour des solutions modèles en ions fluorure, puis de réaliser pour ces conditions optimales le traitement d’une eau de forage tunisienne. La concentration limite en ions fluorure imposée par la WHO est de 1.5 mg.L-1. Les essais d’adsorption en utilisant l’os de seiche, disponible en Tunisie, sont simples à mettre en œuvre et permettent des traitements à petite échelle avec des coûts très compétitifs en utilisant un matériau non toxique. La défluoration de l'eau souterraine avec l’os de seiche présente une concentration résiduaire en fluorure de 1,3 mg.L-1 (TR = 61,5%). Dans le cas de la précipitation des ions fluorures sous forme de fluorite suivi de microfiltration, l’addition d’acide acétique aux particules de calcite (CaCO3) favorise l’élimination des ions fluorure. La défluoration de l'eau souterraine montre que l’eau traitée présente une concentration résiduaire en fluorure de 1,24 mg.L-1 (TR = 53,7%). En utilisant une résine échangeuse d’ions Purolite A520E, la défluoration de l'eau souterraine montre que l’eau traitée présente une concentration résiduaire en fluorure de 1,2 mg.L-1 (TR = 54%). La nanofiltration permet de traiter des volumes importants d’eau et les taux de rétention des ions fluorure sont satisfaisants (88% et 57%) / The issue of the removal of excess fluoride ions present in well water for human consumption can be solved using several methods. In this PhD thesis, four processes have been tested: adsorption using cuttlefish bone particles, adsorption on calcite particles with acid acetic addition, nanofiltration and ion exchange. The aim is to optimize the different processes by using model solutions of fluoride ions, and to treat a Tunisian groundwater at these optimal conditions. The limiting concentration given by the WHO is 1,5 mg.L-1. The adsorption using cuttlefish bone, available in Tunisia, is simple to implement and provides treatment at small scale with very competitive costs by using a non-toxic material. Defluorination of groundwater shows that the water treated with cuttlefish bones has a residual fluoride concentration of 1.3 mg L-1 (TR = 61.5%). In the case of precipitation of fluoride ions in the form of fluorite followed by microfiltration, the addition of acetic acid to the particles of calcite (CaCO3) promotes the removal of fluoride. Defluorination groundwater shows that the treated water has a residual fluoride concentration of 1.24 mg L-1 (TR = 53.7 %). Using a ion exchange resin Purolite A520E, defluorination groundwater shows that water treated has a residual fluoride concentration of 1.2 mg L-1 (TR = 54%). Nanofiltration is particularly interesting as it allows the treatment of large volumes. The retention of fluoride ions are again satisfactory (88% and 57%)

This doctoral thesis deals with the determination of the influence of plasma electrolytic oxidation (PEO) on fatigue behaviour of extruded AZ61 magnesium alloy in air and in the 3.5% NaCl solution. The coatings were formed in the silicate-phosphate electrolyte under pulsed current conditions at a frequency of 50 Hz. The influence of current density on coating formation was examined under current densities of 70, 130 and 200 mA cm-2 for different durations up to a maximum of 1800 s. 8 g dm-3 of KF were added to the electrolyte to study the influence of fluoride ions in plasma electrolytic oxidation. It is shown that fluoride ions inhibit localised oxidation in the initial stage of the process, associated with the secondary particles based on Al–Mn. The presence of fluoride also modified the sparking characteristics, decreased the rate of coating growth and changed the morphologies of the coatings. The influence of fluoride on the coating hardness, and the corrosion resistance of the alloy during exposure to salt spray, was negligible. Based on previous optimised PEO conditions, coatings formed under a current density of 130 mA cm-2 for 300 s in the electrolyte containing KF were chosen for fatigue testing. The high-cycle fatigue tests were carried out on cylindrical samples under a force controlled sinusoidal tension-tension cycle with asymmetry parameter R=0. The experimental data were fitted with Kohout & Věchet function. The fatigue limit of uncoated alloy in air for 107 cycles was determined at 145.4 MPa and the combination of PEO coating with chloride ions caused a reduction of ~55 %. Attention was paid to the fatigue crack initiation in different conditions of cyclic loading. The fracture surfaces underwent detailed fractography analysis including secondary crack observation on the gauge length. The contribution of Al–Mn particles were confirmed on the uncoated alloy in air and the presence of chloride ions were observed as another influential contributor to local corrosion attack. The cyclic loading caused spalling of the outer layer, and the multiple initiation was observed on PEO coated alloy, caused by cracks in the coating and stress transferring to the alloy.

Объектом исследования является фторидная коррозия алюминиевых матриц, вызывающая повышенную адгезию цинкового осадка к алюминиевому катоду. Цель работы – исследовать поведение ионов фтора при разрушении оксидной пленки алюминиевых матриц. В работе проводились термодинамическое моделирование фторсодержащих водных систем. Проведены эксперименты по изучению влияния ионов фтора на цементацию меди и цинка на алюминии. Проведены потенциометрические и гальванометрические исследования, протекающие на границе алюминий – электролит. Изучено влияние фторид-ионов на кинетику процесса разрушения оксидной пленки алюминия. Экспериментально определено влияние предварительной обработки катодов на скорость фторидной коррозии. / The object of the research is the fluoride corrosion of aluminum matrices, which causes an increased adhesion of the zinc precipitate to the aluminum cathode. The aim of this work is to investigate the behavior of fluoride ions during the destruction of an oxide film of aluminum matrices. Thermodynamic modeling of fluorine-containing water systems was carried out in the work. Studies of effect of fluoride ions on the carburization of copper and zinc on aluminum have been carried out. Potentiometric and galvanometric studies are carried out at the aluminum-electrolyte interface. The effect of fluoride ions on the kinetics of the process of destruction of an aluminum oxide film has been studied. The effect of pretreatment of cathodes on the rate of fluoride corrosion is studied experimentally.