En réponse aux exigences de la réglementation REACH qui prévoit que les substances à base de chrome hexavalent devront être soumises à autorisation dès 2017, les industriels du secteur aéronautique mènent depuis plusieurs années des activités de recherche et développement de nouveaux procédés de traitement de surface moins néfastes pour l’environnement et la santé. Le travail prévu dans le programme de recherche NEPAL (NouvellEs Protections des ALuminiums) s’inscrit dans cette dynamique. Les traitements mettant en oeuvre des composés à base de Cr(VI) sont destinés à disparaître dans un proche avenir ; ainsi de nouvelles formulations ont été développées parmi lesquelles des procédés de conversion à base de chrome trivalent. Le projet de thèse vise à renforcer la robustesse de ces procédés en apportant des éléments de compréhension pour ce qui concerne la tenue à la corrosion des alliages d’aluminium revêtus de couches de conversion au chrome trivalent en relation avec leur état microstructural. Les travaux de thèse ont été développés sur une nuance d’alliage d’aluminium 2024, parmi celles les plus utilisées dans le secteur aéronautique. Plusieurs microstructures ont été considérées dans le but de modifier la distribution en éléments d’alliages majoritaires, le cuivre et le magnésium. La caractérisation fine de la microstructure et l’évaluation de la réactivité des échantillons dans les différents bains de traitement de conversion ont permis de mettre en évidence l’influence de la répartition du cuivre dans l’alliage, élément néfaste pour la croissance des couches de conversion lorsqu’il se trouve sous forme de précipités fins. Finalement, l’étude de deux tôles d’alliage d’aluminium d’épaisseurs différentes met en évidence l’influence de nouveaux paramètres microstructuraux tels que les joints de grains ou la précipitation grossière. Ce travail a été réalisé dans le cadre du projet FUI NEPAL. Le CIRIMAT a été financièrement soutenu par le Ministère de l’Économie et de l’Industrie français (BPI-France), la Région Occitanie Pyrénées-Méditerranée et l’Union Européenne (FEDER/ERDF). / In reply to REACH regulation, which stipulates that hexavalent chromium substance shall besubject to authorization in 2017, manufacturers of aeronautic industries have performed, forseveral years, research and development of new surface treatments less harmful for theenvironment and health. The work planned in NEPAL (NEw Protections for ALminium) researchprogram is part of this large program. The chromate-containing treatments, using Cr(VI)compounds, will disappear in the near future; new formulations have been developed includingtrivalent chromium conversion processes. The thesis project aims to reinforce robustness of theseprocesses by providing data useful for understanding the corrosion resistance of aluminium alloyscoated with trivalent chromium coatings, in relation to their microstructural state. The thesis workwas developed on a 2024 aluminium alloy, among those most used in the aeronautics sector.Several microstructures were considered in order to modify the distribution of major alloyselements, copper and magnesium. The fine characterization of the microstructure and theevaluation of the reactivity of the samples in the different conversion treatment baths highlight theinfluence of the copper distribution in the alloy, this alloying element being detrimental to thegrowth of the conversion coating when it is in the form of fine precipitates. Finally, the study of twosheets of aluminium alloy with different thicknesses reveals the influence of new microstructuralparameters such as grain boundaries or coarse precipitation. This work was performed in theframework of the NEPAL FUI project. CIRIMAT was financially supported by the French Ministry ofEconomy and industry (BPI-France), the Région Occitanie Pyrénées-Méditerranée and theEuropean Union (FEDER/ERDF).

Abstract not available

The research presented here is a study to determine the effect of shear reinforcement corrosion on the shear capacity in conventionally reinforced concrete (CRC) bridge elements. A total of 14 CRC beams were tested using three stirrup spacings (8, 10, and 12-inch). Six of the beams included the influence of a 4-inch thick deck, and both positive and negative moment regions were considered. The CRC beams were subjected to an accelerated corrosion process to produce the damage states. Inspection techniques were used to visually correlate corrosion damage with actual structural performance. Severe corrosion damage was shown to have significant effect on the shear performance of the CRC beams. Findings indicate that current inspection ratings for corrosion damage may not adequately identify the extent of structural deterioration. / Graduation date: 2003

The corrosion of current collector materials in MoltenCarbonate Fuel Cells (MCFC) is investigated. The essential aimsof this investigation were to study the corrosion behaviour ofdifferent materials, in varying cathode and anode MCFCenvironments, and to study the contact corrosion resistancesbetween the MCFC current collector and electrodes. For thesepurposes, pure iron, iron-chromium binary alloys and severalcommercial steels were investigated in molten carbonate meltswithin the pot-cell laboratory set-up. In addition, the contactcorrosion resistances, between an AISI 310 current collectorand two cathodes (NiO and LiCoO2), were studied in a laboratory fuel cell.Post-tests were done to study the corrosion products formed atthe surfaces. In cathode environments, corrosion potential increased overtime as a protective corrosion layer slowly formed. Eventually,the potential reached a stable value close to the cathodeoperating potential. The main cathode reaction, as corrosionpotential increased, changed from water reduction to oxygenreduction. Corrosion rate under the operating cathode conditiondepended on the chromium content; the higher the concentrationof chromium, the lower the corrosion rate. The corrosion ratesof ferritic steels, with high chromium content, and AISI 310were higher at the so-called outlet operating condition incomparison to the standard and so-called inlet conditions. Thecorrosion rate was higher at the beginning of the exposure,which resulted in a relatively fast corrosion layer growth thatslowed as the protective layer was formed. It was shown thatthe corrosion layers, formed on iron-chromium alloys, AISI 310and ferritic high chromium-containing steels, consisted of twolayers. The outer layer was porous and iron rich, while theinner layer was quite compact and rich in chromium and/oraluminiumTherefore, the corrosion behaviour was dependent onthe corrosion layer structure at the metal surface. In anode environments, the beneficial behaviour of aluminiumin ferritic alloys, with high aluminium contents, was due tothe formation of aluminium oxide and/or lithium aluminium oxideat the surface. The corrosion rates at the standard and outletconditions were of the same order of magnitude, while thecorrosion rates at the inlet conditions were considerablyhigher. The lower temperatures and higher carbon dioxideconcentrations in the inlet conditions appeared to result in asurface layer deficient in aluminium. A modified theoreticalmodel was developed to evaluate the corrosion current densitiesfrom experimental polarisation curves or linear polarisationresistance measurements in anode environments. The fittingswere found to be very good. An experimental method was developed forin-situmeasurements of the contributions to the totalohmic losses at the cathode in a laboratory scale MCFC. Thecontact resistance between the cathode and current collectorcontributed quite a large value to the total cathodepolarization. The corrosion layer, formed between the LiCoO2cathode and AISI 310 current collector, wasiron-rich and more porous, and contained a small amount ofcobalt. This was deemed to consist of a two-phase oxide, whichresulted in a lower conductivity. The corrosion layer, formedbetween the NiO cathode and AISI 310 current collector, wasrich in nickel. The corrosion layers on the AISI 310, incontact with the cathode, had a different composition comparedto samples immersed in carbonate melts. <b>Key words</b>: molten carbonate fuel cell (MCFC), corrosion,current collector, contact corrosion resistance.

Efficient exploitation and conservation of the oceans poses great technological challenges for scientists and engineers who must develop materials, structures and equipment for use in harsh environment of the oceans. For the applications of materials in marine environment, knowledge of the corrosion properties is essential for selection purposes. Presently, effort is being devoted to exploit deep-sea mineral resources. Deterioration of materials in the deep sea is due to the cumulative effect hydrostatic pressure, temperature, pH, dissolved oxygen, salinity and sea current. For the first time, in-situ corrosion measurements on the effect of deep sea environment on some metallic and composite materials were carried out at depths of 500,1200,3500, and 5100 m for 168,174 and 174 days of exposure in the Indian Ocean. Corrosion rate was obtained from weight loss measurements (mm/year) and surface morphology of as-exposed and cleaned specimens of the above materials was studied under scanning electron microscope and ED AX. Galvanic coupling of steel with zinc, magnesium and aluminium were also studied.. Tensile on metal and alloys and tensile, compressive, flexure and ILSS tests on carbon fibre reinforced composite specimen were performed on exposed specimens. XRD studies were conducted on the corrosion product of materials. In order to correlate the performance of materials in deep-sea environment, seawater current and temperature data were also collected at same period Results reveal that the corrosion behaviour of steels is controlled by dissolved oxygen prevailing and corrosion rate corresponds to dissolved oxygen available at these depth levels. This is due to the fact that oxygen acts as a cathodic deploarizer during corrosion reaction of steels in seawater. Corrosion rate of aluminium increases as the depth increases. This is due to the effect of hydrostatic pressure, which reduces the ionic radii of chlorine ions and facilitates easy penetration of these ions into surface layer. Titanium, titanium alloy (Ti-6A1-4V) and stainless steels did not show any deterioration at all depths studied. Morphology of as exposed and corroded coupons reveal different features. EDS analyses on exposed specimens are analyzed in light of seawater parameters. Carbon fibre reinforced composite did not show any change in properties like tensile, compression flexural and ILSS compared to control (unexposed) specimens. The deposition of calcium carbonate on galvanically coupled mild steel with zinc, aluminium and magnesium corresponds to availability of calcium in the deep ocean. EDS analyses on exposed coupons did not reveal calcium element below the calcium carbonate compensation depth (CCD) at 3800 m in Indian Ocean. Potentiodynamic polarization studies on some metals and alloys indicate that the behaviour of materials in deep-sea environment is a cumulative effect of all oceanographic parameters. Tensile test results on stainless steels SS-304 & SS-316L), titanium and titanium alloy (exposed) specimens did not show any significant change in their tensile properties and is again attributed to the passive film formed on its surface and nearly zero corrosion rate observed. Microbiological investigations on the exposed materials indicate that except carbon fibre reinforced composite all other metals and alloys harboured bacterial colonies. Results have been used to recommend structural materials suitable for the deep-sea applications.

<p>The corrosion of current collector materials in MoltenCarbonate Fuel Cells (MCFC) is investigated. The essential aimsof this investigation were to study the corrosion behaviour ofdifferent materials, in varying cathode and anode MCFCenvironments, and to study the contact corrosion resistancesbetween the MCFC current collector and electrodes. For thesepurposes, pure iron, iron-chromium binary alloys and severalcommercial steels were investigated in molten carbonate meltswithin the pot-cell laboratory set-up. In addition, the contactcorrosion resistances, between an AISI 310 current collectorand two cathodes (NiO and LiCoO₂), were studied in a laboratory fuel cell.Post-tests were done to study the corrosion products formed atthe surfaces.</p><p>In cathode environments, corrosion potential increased overtime as a protective corrosion layer slowly formed. Eventually,the potential reached a stable value close to the cathodeoperating potential. The main cathode reaction, as corrosionpotential increased, changed from water reduction to oxygenreduction. Corrosion rate under the operating cathode conditiondepended on the chromium content; the higher the concentrationof chromium, the lower the corrosion rate. The corrosion ratesof ferritic steels, with high chromium content, and AISI 310were higher at the so-called outlet operating condition incomparison to the standard and so-called inlet conditions. Thecorrosion rate was higher at the beginning of the exposure,which resulted in a relatively fast corrosion layer growth thatslowed as the protective layer was formed. It was shown thatthe corrosion layers, formed on iron-chromium alloys, AISI 310and ferritic high chromium-containing steels, consisted of twolayers. The outer layer was porous and iron rich, while theinner layer was quite compact and rich in chromium and/oraluminiumTherefore, the corrosion behaviour was dependent onthe corrosion layer structure at the metal surface.</p><p>In anode environments, the beneficial behaviour of aluminiumin ferritic alloys, with high aluminium contents, was due tothe formation of aluminium oxide and/or lithium aluminium oxideat the surface. The corrosion rates at the standard and outletconditions were of the same order of magnitude, while thecorrosion rates at the inlet conditions were considerablyhigher. The lower temperatures and higher carbon dioxideconcentrations in the inlet conditions appeared to result in asurface layer deficient in aluminium. A modified theoreticalmodel was developed to evaluate the corrosion current densitiesfrom experimental polarisation curves or linear polarisationresistance measurements in anode environments. The fittingswere found to be very good.</p><p>An experimental method was developed for<i>in-situ</i>measurements of the contributions to the totalohmic losses at the cathode in a laboratory scale MCFC. Thecontact resistance between the cathode and current collectorcontributed quite a large value to the total cathodepolarization. The corrosion layer, formed between the LiCoO₂cathode and AISI 310 current collector, wasiron-rich and more porous, and contained a small amount ofcobalt. This was deemed to consist of a two-phase oxide, whichresulted in a lower conductivity. The corrosion layer, formedbetween the NiO cathode and AISI 310 current collector, wasrich in nickel. The corrosion layers on the AISI 310, incontact with the cathode, had a different composition comparedto samples immersed in carbonate melts.</p><p><b>Key words</b>: molten carbonate fuel cell (MCFC), corrosion,current collector, contact corrosion resistance.</p>

Reproduction de : Habilitation à diriger des recherches : Sciences naturelles. Biologie : Lille 1 : 2005. / Synthèse des travaux. N° d'ordre (Lille 1) : 388. Curriculum vitae. Titre provenant de la page de titre du document numérisé. Bibliogr. p. 80-86. Liste des publications et communications.

Al-Zn-Mg-Cu (7xxx series) aluminium alloys are widely used for aircraft structures. It is difficult to obtain a combination of optimal strength and stress corrosion cracking (SCC) resistance for these alloys. It appears that SCC resistance of these alloys is related to grain boundary precipitate morphology. One technique to control the grain boundary precipitate morphology is to introduce a controlled cooling procedure referred to as High Temperature Pre-precipitation (HTPP) treatment following the solution heat treatment. There is need for a detailed study of the effect of HTPP on the properties of commercial Al-Zn-Mg-Cu alloys using different intermediate temperatures. In this thesis research, the results of ten HTPP processes applied to 7075 and 7050 commercial 7xxx series alloys are presented in terms of hardness, electrical conductivity, corrosion resistance, TEM analysis of grain boundary precipitate morphology and EDS analysis of solute concentration profile at the grain boundary. Results indicate that subsequent to HTPP processing, the 7050 alloy can be precipitation aged to a higher hardness compared to 7075; this result is associated with the modification of 7050 alloy by zirconium versus chromium in 7075 alloy. HTPP heat treatment achieves better SCC resistance compared to standard T6 temper. However, it does not appear that HTPP can achieve a combination of hardness, electrical conductivity and corrosion resistance superior to standard T6 and T7X tempers. / October 2014

published_or_final_version / Mechanical Engineering / Master / Master of Philosophy

The objective of this study was to evaluate galvanic corrosion potential under various pH conditions, buffering capacities, and corrosion inhibitors including zinc orthophosphate (ZOP) and orthophosphate (OP). Bench-scale dump-and-fill experiments evaluated metals release from a lead and copper couple under stagnant conditions. Key findings from this study were that increasing DIC from 3 to 7 or 17 mg CaCO3/L significantly reduced lead release with or without corrosion inhibitor; however, the lowest lead concentrations were observed in water conditions with corrosion inhibitor addition. However, addition of 20 mg PO4/L as OP exacerbated lead release in some cases; though dissolved lead release was always below 28 µg/L, particulate lead was as much as 4 times greater compared to no corrosion inhibitor. Overall, this study demonstrated the potential of high dose ZOP and OP for lead corrosion control in drinking water, however, overdosing OP can lead to exacerbated particulate concentrations.