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).

La corrosion dans le béton précontraint est considérée parmi les pathologies les plus dangereuses dans le secteur du génie civil. En effet ce phénomène se caractérise par la gravité de ses conséquences économiques et sécuritaires. L’objectif de ce travail consiste à évaluer l’efficacité d’un inhibiteur à base de phosphates Na3PO4.12H2O contre la corrosion des aciers de précontrainte. L’étude a été d’abord menée en milieu synthétique simulant le béton chloruré sur des armatures tendues à 80% Rm, puis d’une part sur des éprouvettes en mortier précontraint conçues à l’échelle laboratoire, et d’autre part en utilisant la technique de cellule de diffusion pour tester l’efficacité de l’inhibiteur à long terme. Les résultats issus de l’étude réalisée dans le milieu simulant ont révélé que la présence des phosphates entraine l’augmentation du seuil critique d’amorçage de corrosion localisée R=[Cl-]/[OH-] jusqu’à la valeur de 5 au lieu de 0,4. Ceci semble être dû à deux actions inhibitrices des phosphates à savoir : la stabilisation de la couche protectrice à base d’oxyde de fer et la formation de composés phosphatés très peu solubles qui bloquent les sites anodiques actifs, augmentant ainsi la résistance de l’acier à la corrosion localisée. L’emploi de Na3PO4.12H2O en tant qu’adjuvant diminue légèrement la résistance à la compression du mortier. Cependant les composés phosphatés provenant de la réaction de l’inhibiteur avec les hydrates de ciment colmatent les pores du mortier et freinent la diffusion des chlorures. Ceci améliore le comportement à la corrosion des armatures enrobées de mortier précontraint. Enfin, lorsque le triphosphate de sodium est utilisé comme inhibiteur migrateur ou comme moyen de prétraitement des armatures, la technique de la cellule de diffusion a montré son efficacité à long terme, grâce à l’augmentation de la période précédant l’amorçage d’une corrosion localisée, où l’armature est en état passif. / Corrosion in prestressed concrete is considered among the most dangerous pathologies in the civil engineering sector. Indeed, this phenomenon is characterized by the seriousness of its economic and security consequences. The objective of this work is to evaluate the efficiency of a phosphate based inhibitor Na3PO4.12H2O against the corrosion of prestressing steels. The study was first conducted on wires tensioned at 80% Rm and immersed in simulating concrete pore solution. Then it concerned, on one hand, prestressed mortar specimens designed on a laboratory scale and, on the other hand, the long term efficiency of the inhibitor using diffusion cell technique. The results obtained from the study carried out in the concrete simulating medium revealed that the presence of the phosphates causes the increase in the critical threshold of localized corrosion initiation R = [Cl -] / [OH-] up to the value of 5 instead of 0.4. This seems to be due to two phosphate inhibiting actions, namely: the stabilization of the iron oxide protective layer and the formation of very insoluble phosphate compounds which block the active anodic sites, increasing prestressing steel resistance to localized corrosion. The use of Na3PO4.12H2O as an additive slightly reduces the compressive strength of the mortar. However, phosphate compounds resulting from the reaction of the inhibitor with the cement hydrates clog the pores of the mortar and slow down the diffusion of the chlorides. This improves the corrosion behavior of prestressed mortar reinforcement. Finally, when sodium triphosphate is used as a migratory inhibitor or as a means of steel reinforcement pretreatment, the diffusion cell technique has shown its long-term efficiency, thanks to the increase of the period preceding the initiation of a localized corrosion, where the reinforcement is in a passive state.

Metal dusting is a kind of catastrophic corrosion phenomenon that can be observed in several of petrochemical processes. It occurs on iron-, nickel- and cobalt-base metals in carbonaceous atmospheres at high temperature when gaseous carbon activity is higher than one. The process is particularly rapid for ferritic alloys The aim of this project was to compare the dusting kinetics of pure iron and a 2.25Cr-1Mo alloy steel under CO-H2-H2O atmosphere at 650??C. Polished (3??m) samples of iron and the steel were exposed to flowing CO-H2-H2O gas atmospheres at 650??C, when the gases were supersaturated with respect to graphite. The partial pressure of CO was varied between 0.25 and 0.9 atm, and the carbon activity was varied from 2.35 to 16, in order to obtain a series of experimental conditions. In most experiments, pO2 was less than 7.37E-24 atm, and no iron oxide could form. However, Cr2O3 would always have been stable. When exposed to these gases, both iron and steel developed a surface scale of Fe3C which was buried beneath a deposit of carbon, containing iron-rich nanoparticles (the dust). Examination by Scanning Electron Microscopy allowed the observation of fine and coarse carbon nanotubes, and also spiral filaments. However, the morphology of the graphitic carbon was not sensitive to pCO and aC. Moreover, the carbon deposit was gas permeable, allowing continuing gas access to the underlying metal. At a fixed=4.5, the carburizing rate clearly increased with CO content from 0.25 to 0.68 atm. However, increasing the CO content to higher value led to decreased rates, indicating that carburizing rate reaches a maximum value at pCO=0.68 atm. When pCO was fixed at 0.25 atm and 0.68 atm, and carbon activity was varied. The induction period was extended by the formation of protective oxide layers at low values of carbon activity (aC= 2.35 and 2.55) where pO2 exceed the iron oxide formation value. For other reaction conditions, the carbon uptake rate for iron and steel did not increase with aC. The present work showed that the carbon deposition rates were not proportional to pCO or pCOpH2. Instead, the rate was affected by the partial pressure of all three reaction gases, and the carbon uptake rate for both materials could be expressed at r=k1pCOpH2+k2pCO2+k3pH22 and the rate constant k3 has a negative value, corresponding to coke gasification. From XRD analyses, it was found that cementite was the only iron-containing phase in the dusting product. The cementite particles acted as catalysts for carbon deposition from the gas. The same deposition process at the surface of the cementite layer led to its disintegration, thereby producing the particles. This disintegration process was faster on the steel than on pure iron. Consequently, the rates of both metal wastage and coke accumulation were faster for the steel. It is concluded that chromium and molybdenum do not stabilize the carbide but accelerate its disintegration process. It is suggested that Cr2O3 fine particles in the cementite layers provide more nucleation sites in the cementite layer on steel, explaining its more rapid dusting kinetics. However, appropriate methods of proving this assumption, such as TEM and FIB, are required.

The corrosion protection of aluminium alloys is of high importance, particularly in the aerospace industry. The most widely used technologies utilise Chromium(VI) compounds for conversion coatings and primer additives in paint systems to provide corrosion protection to these alloys. These compounds are highly toxic, carcinogenic and detrimental to the environment, therefore the identification of alternative systems that are safe and environmentally benign, that meet or exceed the current levels of corrosion protection is vital. This research program examines the corrosion inhibition effectiveness of selected rare earth diphenyl phosphates (RE(dpp)3). These compounds incorporate known inhibitor species, namely rare earth metals, organics and phosphates into a single complex, with the aim of achieving synergistic inhibition in corrosive environments. A screening study utilising immersion and weight loss experiments identified Cerium diphenyl phosphate (Ce(dpp)3) and Mischmetal diphenyl phosphate (Mm(dpp)3) as the most effective inhibitors of corrosion for AA2024-T3. The inhibiting efficiency, mechanism of inhibition and surface interaction of these complexes on aluminium alloy AA2024-T3 was characterised using a range of electrochemical and surface techniques. A similar study was carried out using AA7075-T6 to assess the adaptability of the RE(dpp)3 compounds to protect different alloy compositions. The complexes were effective in significantly reducing the corrosion rate of the alloys, with both the cathodic and anodic corrosion processes being suppressed. This mixed inhibition was not attained with the constituent rare earth and diphenyl phosphate ions individually, indicating the need for the complex to remain intact in solution to achieve the high level of corrosion protection observed. The initiation and propagation of surface pits was effectively suppressed by the RE(dpp)3 complexes. The combination of electrochemical and surface characterisation techniques has for the first time allowed insights into the mechanism of action of these compounds on aluminium alloys, and indicated deposition was initiated at electrochemically active intermetallic particles. The mixed rare earth phases present in Mm(dpp)3 produced a synergistic effect, providing a greater degree of corrosion protection compared with Ce(dpp)3, particularly on AA2024-T3. In the final phase of this research project the RE(dpp)3 inhibitor compounds were incorporated into an epoxy coating system, and demonstrated that the initiation of filiform corrosion on AA2024-T3 could be reduced by up to a factor of 3 by their addition. The growth rate of filaments was also impeded.

Thesis (Ph. D.)--University of Rhode Island, 2006. / Typescript. Includes bibliographical references (leaves 126-134).

In view of the excellent mechanical, chemical and opticalproperties, AlON (Aluminum oxynitride) as well as MgAlON(Magnesium Aluminum oxynitride) have drawn the attention ofmaterials scientists in past decades. In this thesis,thermodynamic properties, synthesis and corrosion resistance tooxygen and slag of AlON and MgAlON ceramics have beeninvestigated. Gibbs energy of AlON and MgAlON with different compositionsand temperatures were estimatedby using thermodynamicquasi-parabola rule. Phase stability diagrams of Al-O-N andMg-Al-O-N systems at different conditions have been calculated.On the basis of thermodynamic analysis, AlON and MgAlONceramics were synthesized by hot-press sintering andcharacterized by XRD, TEM and HREM analyses. An X-raydiffraction standard file of MgAlON is suggested and sent toJCPDS. The density of AlON synthesized was 3.63g/cm3, about 97.8% of its theoretical density. Thedensity of MgAlON is 3.55 g/cm3. Fracture toughness of AlON and MgAlON is 3.96 and4.06 MPa.m1/2. Three-point bending strength of AlON and MgAlONare 248 and 268 MPa, respectively, at room temperature andkeeps very high until 1723K. However the strength drops 189 and202 MPa for AlON and MgAlON, respectively, at 1723K. Thefracture section of AlON and MgAlON were examined and found tobe a mixed fracture of intercrystalline and cleavage fracturefor AlON and a mixed intercrystalline and transcrystallinefracture for MgAlON. Oxidation experiments of AlON and MgAlON and a comparison ofthe oxidation behavior of AlON, MgAlON, O'SiAlON-ZrO2and NB-ZCM have been carried out. Undernon-isothermal oxidation conditions, oxidation of AlON exhibitstwo steps with a "S"-shaped curve due to the phasetransformation of oxidation product. As temperature increases,the oxidation product, γ -Al2O3formed at lower temperatures will transform intoα-Al2O3. Due to the differences in the molar volumesbetween α-Al2O3and γ -Al2O3, cracks are likely to be formed in the productlayer promoting further oxidation. MgAlON, O'SiAlON-ZrO2and NB-ZCM show only one step with paraboliccurves. Isothermal oxidation experiments of AlON, MgAlON,O'SiAlON-ZrO2and NB-ZCM have been carried out in thetemperature range of 1373-1773K. At lower temperatures, MgAlONshows the best resistance to oxidation. But at highertemperatures, such as 1773K, AlON shows the best resistance tooxidation. O'SiAlON-ZrO2shows very good oxidation resistance in the lowtemperature range up to 1673K. But, as the temperature goes upabove 1673K, there is liquid phase produced during theoxidation process. Gas bubbles are also formed in the productlayer causing the flaking-off of some parts of the productlayer. Therefore its oxidation rate increases greatly astemperature rises to 1673K. In the case of BN-ZCM ceramics, dueto the evaporation of B2O3, the oxidation resistance seems to be poorest. Thechemical reaction activation energies for the initial stage ofoxidation of AlON, MgAlON, O'SiAlON-ZrO2and BN-ZCM are 218, 330, 260 and 254 kJ/molerespectively. And the activation energies at the laterdiffusion controlling stages are 227, 573, 367 and 289 kJ/molefor AlON, MgAlON, O'SiAlON-ZrO2and BN-ZCM respectively. The roughness of the oxidation sample surfaces has beenmeasured by Atomic Force Microscope. As the temperatureincreases, the degrees of roughness of AlON and MgAlON surfacesincrease slightly due to the growth of crystal grain. Theroughness degree of BN-ZCM increases greatly because of theevaporation of B2O3. However the roughness of O'SiAlON-ZrO2decreases as the temperature increases from 1473Kto 1673K. The main reason is that the liquid phase (glass)produced during the oxidation process at high temperatures suchas 1673K and 1773K. The roughness degree of MgAlON, AlON,O'SiAlON-ZrO2and BN-ZCM are 234, 174, 75 and 63 nm respectivelyat 1473K, and 297, 284, 52 and 406 nm respectively at1673K. Experiments of corrosion of AlON by CaO-MgO-"FeO"-Al2O3-SiO2slags were conducted in the temperature range of1693-1753K under static conditions as well as under forcedconvection. XRD, SEM-EDS and TEM analyses on the corrodedsamples were carried out. The results showed that the diffusion was therate-controlling step in the initial stage of the corrosion.Thereafter, the slag formation (the product layer dissolvinginto the liquid slag) became more and more important. Thisaspect was further confirmed by fractal dimension analysis ofthe interface. The overall activation energy for the corrosionprocess with slag No.1 was evaluated to be 1002 kJ. Adding"FeO" to the slag greatly enhanced the corrosion rate probablydue to the reaction of the sample with "FeO". <b>Key words:</b>AlON, MgAlON, Thermodynamics, Synthesis,Oxidation, Slag corrosion

In recent years, the demand for alternatives to fossil fuels has risen dramatically, and ethanol fuel has become an important liquid fuel alternative globally. The most efficient mode of transportation of petroleum-based fuel is via pipelines, and due to the 300% increase in ethanol use in the U.S. in the past decade, a similar method of conveyance must be adopted for ethanol. Low-carbon, low-alloy pipeline steels like X52, X60, and X65 comprise the existing fuel transmission pipeline infrastructure. However, similar carbon steels, used in the ethanol processing and production industry, were found to exhibit stress corrosion cracking (SCC) in ethanol service. Prior work has shown that contaminants absorbed by the ethanol during distillation, processing or transport could be the possible determinants of SCC susceptibility; 200 proof ethanol alone was shown not to cause SCC in laboratory studies. To ensure the safety and integrity of the pipeline system, it was necessary to perform a mechanistic study of SCC of pipeline steel in fuel grade ethanol (FGE). The objective of this work was to determine the environmental factors relating to SCC of X65 steel in fuel grade ethanol (FGE) environments. To accomplish this, a systematic study was done to test effects of FGE feedstock and common contaminants and constituents such as water, chloride, dissolved oxygen, and organic acids on SCC behavior of an X65 pipeline steel. Slow strain rate tests (SSRT) were employed to evaluate and compare specific constituents' effects on crack density, morphology, and severity of SCC of X65 in FGE. SCC did not occur in commercial FGE environments, regardless of the ethanol feedstock. In both FGE and simulated fuel grade ethanol (SFGE), SCC of carbon steel was found to occur at low water contents (below 5 vol%) when chloride was present above a specific threshold quantity. Cl- threshold for SCC varied from 10ppm in FGE to approximately 1 ppm in SFGE. SCC of carbon steel was inhibited when oxygen was removed from solution via N2 purge or pHe was increased by addition of NaOH. During SSRT, in-situ¬ electrochemical measurements showed a significant role of film rupture in the SCC mechanism. Analysis of repassivation kinetics in mechanical scratch tests revealed a large initial anodic dissolution current spike in SCC-causing environments, followed by repassivation indicated by current transient decay. In the deaerated environments, repassivation did not occur, while in alkaline SFGE repassivation was significantly more rapid than in SCC-inducing SFGE. Composition and morphology of the passive film on X65 during static exposure tests was studied using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Results showed stability of an air-formed native oxide under static immersion in neutral (pHe = 5.4) SFGE, and dissolution of the film when pHe was decreased to 4.3. XPS spectra indicated changes in film composition at high pHe (near 13) and in environments lacking sufficient water. In light of all results, a film-rupture anodic-dissolution mechanism is proposed in which local plastic strains facilitates local breakdown of the air-formed oxide film, causing iron to dissolve anodically. During crack propagation anodic dissolution occurs at the crack tip while crack walls repassivate preserving crack geometry and local stress concentration at the tip. It is also proposed that SCC can be mitigated by use of alkaline inhibitors that speed repassivation and promotes formation of a more protective Fe(OH)3 film.

No description available.

Metals in industrial settings such as power plants are often subjected to high temperature and pressure aqueous environments, where failure to control corrosion compromises worker and environment safety. For instance, zircaloy (1.2-1.7 wt.% Sn) fuel rods are exposed to aqueous 250-310 oC coolant in CANDU reactors. The Pourbaix (EH-pH) diagram is a plot of electrochemical potential versus pH, which shows the domains of various metal species and by inference, corrosion susceptibility. Elevated temperature data for tin +II and tin +IV species were obtained using solid-aqueous phase equilibria with the respective oxides, in a batch vessel with in-situ pH measurement. Solubilities, determined via spectroscopic techniques, were used to calculate equilibrium constants and the Gibbs energies of Sn complexes for E-pH diagram construction. The SnOH3+ and Sn(OH) species were incorporated, for the first time, into the 298.15 K and 358.15 K diagrams, with novel G ͦ values determined at 358.15 K. / UOIT

Crevice corrosion is a form of galvanic corrosion that occurs when a metal is exposed to different environments. This occurs when the oxygen within the crevice gets depleted, thus acting as the anodic site for metal dissolution reaction. The anodic site thus encourages the migration of Cl- ions into the crevice leading to the development of an aggressive local solution. The acidic conditions present in the crevice reaches a critical crevice solution composition and results in the loss of stability of the passive film which further leads to a rapid breakdown of these films on the metal thus indicating the onset of active corrosion.<p> In this research, it is hypothesized that the onset of crevice corrosion can be detected by measuring the galvanic coupling current between electrodes in a crevice and an external metal surface composed of the same material as the electrodes. To prove this hypothesis an engineered crevice was designed to measure IR controlled crevice currents along the crevice length of AISI 304 stainless steel immersed in a 0.5 M solution and a 1 M NaCl solution. Varying crevice openings were used to determine the effect of crevice gap (G) on the initiation of crevice corrosion and the position of the accelerated attack within the crevice.<p> Multiplexed corrosion potential measurement and galvanic corrosion measurement techniques were used to measure the change in the open circuit potential (OCP) and the galvanic current for the four channels along the crevice length of the galvanic couple. The results obtained from the MGC test for the 100 µm crevice width immersed in 0.5 M NaCl solution showed good results with high anodic current at approximately 1 cm from the crevice mouth. This finding was in close agreement with the peak pH value observed at the position closest to the crevice mouth in the work of Alavi and Cottis (1987) and the model prediction of Kennell et al. 2009. However, for test samples with crevice width ≥ 200 µm, there was no initiation of crevice corrosion and the results obtained were discarded. The Linear polarization resistance scan and Potentiodynamic polarization scan carried out along the crevice to measure the polarization resistance, Rp , and to obtain the region of passivity along an AISI 304 SS crevice did not yield good results. Low corrosion rate in the range of 0.06 mm/yr was calculated for the AISI 304 stainless steel crevice.