L’oxydation par plasma électrolytique (ou oxydation micro-arc) est un procédé de traitement des alliages légers (Al, Mg, V, Ti, etc.) apte à pallier les limites de l’anodisation, en particulier au regard des contraintes environnementales. Bien que connu depuis de nombreuses années, les mécanismes sous-jacents à ce procédé assisté par des micro-décharges restent peu ou mal compris. L’objectif de ce travail est de cerner les mécanismes de formation et de développement des micro-décharges et d’associer leurs caractéristiques aux propriétés des couches d’oxyde élaborées sur l’alliage d’aluminium Al2214.La démarche adoptée consiste à associer étroitement l'étude des micro-décharges, la caractérisation des couches élaborées, et les mécanismes de claquage de la couche d'oxyde en cours de croissance. A l’aide de moyens originaux de vidéo rapide (> 125 000 images/s) et d'ombroscopie, la dépendance de l’évolution des micro-décharges aux paramètres macroscopiques du procédé a clairement été établie. L’importance de la présence et de la position de contre-électrodes a été mise en évidence et étudiée. Il est également montré que le choix judicieux de la fréquence et de la densité de courant anodique améliore la qualité des couches obtenues. Une fréquence de l’ordre du kHz semble la mieux appropriée.Enfin, à partir de mesures synchrones, un retard à l’apparition des micro-décharges par rapport au front montant des impulsions de courant a été mis en exergue. Très sensible aux paramètres du procédé, ce retard est probablement lié aux mécanismes de claquage de la couche d'oxyde isolante. Des scénarios concernant ces mécanismes ont ainsi été proposés. / Plasma electrolytic oxidation is a surface treatment process applied to light weight alloys (Al, Mg, V, Ti, etc.) which may advantageously replace conventional anodizing, especially regarding environmental issues. Though this process has been known for many years, the underlying mechanisms that govern this micro-discharge assisted process remain poorly understood. This work aims at better identifying the breakdown and development mechanisms of the micro-discharges and at correlating the micro-discharge characteristics to the properties of the layers grown onto Al2214 aluminium alloy samples. The approach consists in coupling the study of the micro-discharges, the characterization of the grown layers and the breakdown mechanisms. By means of high rate video recording (> 125 000 frames/s) and shadowgraph techniques, the dependence of the evolution of the micro-discharges with the macroscopic process parameters has been clearly established. The important role of counter-electrodes and their respective position with respect to the sample have been identified and studied. It is also shown that the suitable choice of current frequency and anodic current density may greatly improve the quality of the resulting oxide layers. Current frequency in the kHz range seems most appropriate to grow thick and defect-free homogeneous layers.Finally, from synchronous measurements, it has been pointed out a delay in the onset of micro-discharges with respect to the rising edge of the current pulses. Besides this delay is strongly sensitive to the process parameters, it is probably related to the breakdown mechanisms of the insulating layer. Scenarios for these mechanisms have been proposed.

L’objectif de cette thèse consiste en une étude fondamentale de différentes approches pour la modification de surfaces d’alliages d’aluminium. Elle s’inscrit dans le cadre du projet FLYCOAT, subventionné par la région Wallonne. Ce dernier avait pour objectif le développement d’alternatives au couplage classique d’un procédé d’anodisation utilisant des bains de Cr (VI) aux résines époxy pour la protection des alliages d’aluminium contre la corrosion. Dans un premier temps, la synthèse par plasma atmosphérique dans un réacteur de type décharge à barrière diélectrique (DBD) de films riches en groupements carboxyliques à partir de 8 précurseurs organiques est étudiée. Une attention particulière est portée à la compréhension fondamentale des mécanismes de polymérisation de ces précurseurs. L’influence significative de minimes variations de la structure chimique du précurseur est étudiée. Concrètement, nous démontrons l’impact de la présence et de la position de doubles liaisons ou encore le ratio C/O dans le monomère injecté sur le mécanisme de synthèse des couches déposées. Pour ce faire, une méthodologie combinant des analyses de la phase plasma et des films déposés est proposée. Les propriétés électriques de la DBD d’argon sont évaluées par oscilloscope avant et durant l’injection des différents précurseurs. La quantité d’énergie transférée de la décharge vers le précurseur est évaluée par spectroscopie d’émission optique et corrélée à sa structure. Une fragmentation réduite est mise en évidence par spectrométrie de masse pour les monomères contenant une double liaison. Ces analyses de la phase plasma sont alors corrélées avec les propriétés physiques et chimiques des films synthétisés. Les compositions chimiques de surface et de la matrice des couches minces sont étudiées par spectroscopie à photoélectrons X (XPS) et infrarouge. Le rôle essentiel de la présence et de la position de la double liaison dans la molécule injectée est démontré. Les vitesses de dépôt et la rugosité des films déposés par plasma atmosphérique avec l’injection des 8 précurseurs sont évaluées par profilométrie à stylet. Dans la seconde partie, le couplage de deux méthodes de plasma atmosphérique est proposé pour la synthèse de couches d’alumine aux propriétés adaptables. Le premier traitement consiste en un nombre varié de passages d’une torche plasma opérant dans un régime d’arc. L’effet du nombre de passages sur les propriétés physiques et chimiques du substrat est étudié par XPS, angle de contact, microscopie électronique à balayage et mesures de diffraction à rayons X. Une corrélation est suggérée entre le nombre de passages de la torche et les propriétés électrochimiques du substrat. L’influence de ce premier traitement sur les propriétés de la couche d’oxyde d’aluminium synthétisée par oxydation par plasma électrolytique est mise en évidence. Dans un troisième temps, le plasma pouvant être considéré comme un réservoir d’énergie, une étude de faisabilité est réalisée afin d’évaluer sa potentielle utilisation pour la réticulation d’une résine de type benzoxazine. L’efficacité du traitement par DBD atmosphérique d’argon ou hélium est comparée et discutée. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

In the present investigation, surface coatings employing laser surface alloying (LSA) and plasma electrolytic oxidation (PEO) processes have been prepared on Mg alloys. The coatings have been investigated for corrosion and wear behaviour. Two important Mg alloys based on Mg–Al system were selected namely, MRI 230D and AM50 as substrates. LSA coatings have been prepared employing Al and Al2O3 as precursors using different laser scan speeds. PEO coatings were prepared in standard silicate and phosphate based electrolytes employing unipolar, pulsed DC. Hybrid coatings using a combination of the two processes were also produced and investigated for corrosion and wear behaviour. Hybrid coatings of LSA followed by PEO (LSA+PEO) were investigated for effectiveness of sealing the cracks in the LSA coatings by subsequent PEO process and consequent improvement in the corrosion resistance. Hybrid coatings of PEO followed by LSA (PEO+LSA) were prepared with an objective of sealing the pores in the PEO coating LSA treatment. In an attempt to produce more compact PEO coatings, electrolyte containing montmorillonite clay additives was employed for the PEO process of AM50 Mg alloy. The coatings were produced employing different current densities and the effect of current density on the microstructure and corrosion behaviour of coating was investigated. Electrochemical corrosion tests of uncoated and coated alloys were carried out in 3.5 wt.% (0.6M)NaCl, neutral pH, solution with an exposed area of 0.5 cm2 for a time duration of 18.5 h. For the PEO coatings with clay additives, corrosion tests were conducted additionally in 0.5 wt.% (0.08 M) NaCl, neutral pH, solution for a time duration of 226.1 h. Wear behaviour of LSA coatings was analyzed by employing a pin on disc tribo–tester conforming to ASTM G–99 standard at ambient conditions with ground EN32 steel disc of hardness Rc 58 as the counterface. Tests were conducted under dry sliding conditions for a sliding distance of 1.0 km at a sliding velocity of 0.837 m/s employing normal loads of 10, 20, 30 and 40 N. Friction and wear behavior of PEO and PEO+LSA coatings were analyzed at ambient conditions by employing a ball−on−flat linearly oscillating tribometer conforming to ASTM G–133 standard. AISI 52100 steel ball of diameter 6 mm was employed as the friction partner. Wear tests were conducted under dry sliding conditions for a total sliding distance of 100 m at normal loads of 2 N and 5 N with oscillating amplitude of 10 mm and mean sliding speed of 5 mm/s. LSA coatings could not improve the corrosion resistance of MRI 230D Mg alloy. This was attributed to the presence of cracks in the LSA coating, which resulted in the accelerated galvanic corrosion of the substrate. LSA coatings improved the wear resistance at all loads. The improved wear resistance was attributed to β (Mg17Al12) phase and Al2O3 particles in the coating which increased the hardness of the LSA layer. No trend in corrosion and wear resistance with laser scan speed was observed for LSA coatings. PEO coatings improved the corrosion resistance of the MRI 230D Mg alloy significantly. The improved corrosion resistance was attributed to the enhanced barrier protection provided by dense barrier layer formed at the substrate/coating interface and to the insoluble phase constituents in the coatings. PEO coating was effective in improving the wear resistance at low loads/contact pressures. At higher loads, the coating underwent micro–fracture as a result of the porosity in the coatings. Hybrid coatings of LSA followed by PEO (LSA+PEO) in silicate based electrolyte improved the corrosion resistance of LSA coatings. However, the corrosion resistance was not improved to the extent of PEO coatings on as–cast alloy as a result of cracks in the primary coatings, which were not fully sealed by the plasma conversion products. No trend in corrosion resistance with laser scan speed was observed for LSA+PEOcoatings. In hybrid coatings of PEO followed by LSA (PEO+LSA), primary PEO coating was completely melted and mixed with applied precursor to form a single composite LSA layer. The corrosion resistance of the hybrid coatings was observed to be lower than that of the as–cast alloy. The presence of solidification cracks reduced the barrier properties and resulted in the accelerated galvanic corrosion of the substrate similar to LSA coatings. Hybrid (PEO+LSA) coatings exhibited improved wear resistance as compared to as–cast alloy at lower loads as a result of increase in the hardness due to β (Mg17Al12) phase and oxide/ceramic particles in the hybrid layer. At higher loads, hybrid coatings exhibited higher wear rate as compared to as–cast alloy and PEO coatings. This was attributed to three–body abrasive wear as a result of dislodged hard oxide/ceramic particles in the wear tracks. No trend in corrosion and wear resistance with laser scan speed was observed for PEO+LSA coatings. PEO coatings on AM50 Mg alloy by employing clay additives in the electrolyte resulted in the reactive uptake of clay particles producing a predominantly amorphous coating at low current density. Clay additives were effective in improving the compactness of the coating at lower current density. At higher current densities, the porosity of the coatings increased. The clay particles got re–constituted producing increasing amount of crystalline phases with increase in current density. Long term impedance measurements showed that clay addition as well as increased current density employed for the PEO process was not effective in improving the corrosion resistance of the coatings. At low current density, even though the coating with clay additives was more compact, it was deficient in MgO and consisted predominantly of an amorphous phase, which underwent fast dissolution in electrolyte thereby resulting in an early loss of barrier properties. At higher current densities, even though the coatings consisted of increased amount of MgO and crystalline phases, which resist dissolution in the electrolyte, the increased porosity and defective barrier layer resulted in easy permeation of the electrolyte into the substrate/coating interface, which resulted in much earlier loss of barrier properties and inferior corrosion resistance.

Das Ziel dieser Dissertation besteht darin, einen Beitrag zur technologischen, ökonomischen und ökologischen Weiterentwicklung der anodischen Verfahren zur Oberflächenkeramisierung von Aluminium zu leisten. Die Arbeit ist in zwei thematische Schwerpunkte untergliedert. Im ersten Teil wird für die Hartanodisation eine hinsichtlich eines geringeren Energieeinsatzes optimierte Elektrolytzusammensetzung identifiziert und mit einem optimierten galvanostatischen Pulsmuster simultan appliziert. Im Ergebnis kann die Gesamtleistungsaufnahme um ca. 6 % reduziert werden, ohne die mechanischen Eigenschaften der Oxidschichten zu mindern. Im zweiten Schwerpunkt werden das Lichtbogen- und das Flammspritzen mit der plasmaelektrolytischen anodischen Oxidation kombiniert, um verschleißbeständige Aluminiumoxidschichten auf Stahl-, Titan- und Magnesiumsubstraten zu applizieren. Neben einer umfangreichen Mikrostrukturanalyse (REM, EDX, XRD, EBSD) werden die mechanischen Eigenschaften der Schichten untersucht und mit atmosphärisch plasmagespritzten Al2O3-Schichten verglichen. Insbesondere Oxidschichten auf lichtbogengespritztem AlCu4Mg1 zeigen dabei eine hohe Härte sowie eine sehr gute Verschleißbeständigkeit. / The aim of the present work is to contribute to the technological, economic and ecological improvement of the anodic processes for the surface ceramization of aluminum. The work is subdivided into two thematic priorities. In the first part, for the hard anodizing process an optimized electrolyte composition for a lower energy input is identified and applied simultaneously with an optimized galvanostatic pulse regime. As a result, the total power consumption can be reduced by approximately 6% without reducing the mechanical properties of the oxide coatings. In the second focus, arc and flame spraying are combined with plasma electrolytic anodic oxidation to apply wear resistant aluminum oxide coatings on steel, titanium and magnesium substrates. In addition to a comprehensive microstructural analysis (SEM, EDX, XRD, EBSD), the mechanical properties of the layers are investigated and compared with atmospheric plasma sprayed Al2O3 coatings. In particular, oxide layers formed on arc sprayed AlCu4Mg1 coatings show a high hardness as well as very good wear resistance.

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.

Additive manufacturing of Nitinol is a promising field, as it can circumvent the challenges associated with its conventional production processes and unlock unique advantages. However, the accompanying surface features such as powder adhesions, spatters, ballings, or oxide discolorations are undesirable in engineering applications and therefore must be removed. Plasma electrolytic polishing (PeP) might prove to be a suitable finishing process for this purpose, but the effects of post-processing on the mechanical and functional material properties of additively manufactured Nitinol are still largely unresearched. This study seeks to address this issue. The changes on and in the part caused by PeP with processing times between 2 and 20 min are investigated using Nitinol compression springs manufactured by Laser Beam Melting. As a benchmark for the scanning electron microscope images, the differential scanning calorimetry (DSC) measurements, and the mechanical load test cycles, conventionally fabricated Nitinol springs of identical geometry with a medical grade polished surface are used. After 5 min of PeP, a glossy surface free of powder adhesion is achieved, which is increasingly levelled by further polishing. The shape memory properties of the material are retained without a shift in the transformation temperatures being detectable. The decreasing spring rate is primarily attributable to a reduction in the effective wire diameter. Consequently, PeP has proven to be an applicable and effective post-processing method for additively manufactured Nitinol.

In many cases, the functional performance of additively manufactured components can only be ensured by finishing the functional surfaces. Various methods are available for this purpose. This paper presents a procedure for selecting suitable processes for finishing laser beam melting additive–manufactured parts which is ultimately based on technological knowledge. It was experimentally proven that the use of several consecutive finishing processes is beneficial to achieve better surface quality. One finishing process chain was particularly effective (namely particle blasting/vibratory grinding/plasma electrolytic polishing) and the technological limits of this method were investigated in this study. The optimal parameters for this process combination ensured a surface roughness Sa < 1 µm.

Das Ziel dieser Dissertation besteht darin, einen Beitrag zur technologischen, ökonomischen und ökologischen Weiterentwicklung der anodischen Verfahren zur Oberflächenkeramisierung von Aluminium zu leisten. Die Arbeit ist in zwei thematische Schwerpunkte untergliedert. Im ersten Teil wird für die Hartanodisation eine hinsichtlich eines geringeren Energieeinsatzes optimierte Elektrolytzusammensetzung identifiziert und mit einem optimierten galvanostatischen Pulsmuster simultan appliziert. Im Ergebnis kann die Gesamtleistungsaufnahme um ca. 6 % reduziert werden, ohne die mechanischen Eigenschaften der Oxidschichten zu mindern. Im zweiten Schwerpunkt werden das Lichtbogen- und das Flammspritzen mit der plasmaelektrolytischen anodischen Oxidation kombiniert, um verschleißbeständige Aluminiumoxidschichten auf Stahl-, Titan- und Magnesiumsubstraten zu applizieren. Neben einer umfangreichen Mikrostrukturanalyse (REM, EDX, XRD, EBSD) werden die mechanischen Eigenschaften der Schichten untersucht und mit atmosphärisch plasmagespritzten Al2O3-Schichten verglichen. Insbesondere Oxidschichten auf lichtbogengespritztem AlCu4Mg1 zeigen dabei eine hohe Härte sowie eine sehr gute Verschleißbeständigkeit. / The aim of the present work is to contribute to the technological, economic and ecological improvement of the anodic processes for the surface ceramization of aluminum. The work is subdivided into two thematic priorities. In the first part, for the hard anodizing process an optimized electrolyte composition for a lower energy input is identified and applied simultaneously with an optimized galvanostatic pulse regime. As a result, the total power consumption can be reduced by approximately 6% without reducing the mechanical properties of the oxide coatings. In the second focus, arc and flame spraying are combined with plasma electrolytic anodic oxidation to apply wear resistant aluminum oxide coatings on steel, titanium and magnesium substrates. In addition to a comprehensive microstructural analysis (SEM, EDX, XRD, EBSD), the mechanical properties of the layers are investigated and compared with atmospheric plasma sprayed Al2O3 coatings. In particular, oxide layers formed on arc sprayed AlCu4Mg1 coatings show a high hardness as well as very good wear resistance.

A novel, environmentally friendly, fast, and flexible polishing process for Nitinol parts is presented in this study. Nitinol samples with both superelastic and shape memory properties at room temperature were investigated. The chemical contamination and surface roughness of superelastic Nitinol plates were examined before and after plasma electrolytic polishing. The shift in phase transformation temperature and tensile strength before and after the polishing process were analysed using Nitinol wire with shape memory properties. The obtained experimental results were compared to the data obtained on reference samples examined in the as-received condition. It was found that plasma electrolytic polishing, when the right process parameters are applied, is capable of delivering Nitinol parts with extremely high surface quality. Moreover, it was experimentally proven that plasma electrolytic polishing does not have a negative impact on functionality or mechanical properties of polished parts.