Dissertationen zum Thema „Chromium Oxidation“
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1
Gould, Peter John. „The high temperature oxidation of chromium and chromium implanted with cerium“. Thesis, Imperial College London, 1991. http://hdl.handle.net/10044/1/46790.
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Villalobos, Aragon Alejandro. „Using chromium stable isotopes to monitor chromium reactive transport oxidation experiments and field studies /“. To access this resource online via ProQuest Dissertations and Theses @ UTEP, 2009. http://0-proquest.umi.com.lib.utep.edu/login?COPT=REJTPTU0YmImSU5UPTAmVkVSPTI=&clientId=2515.
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Sole, Kathryn Clare. „The kinetics and mechanism of the oxidation of chromium (III) chloride“. Thesis, Rhodes University, 1989. http://hdl.handle.net/10962/d1004921.
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The kinetic behaviour of anhydrous CrCl₃ in gaseous oxidising atmospheres has been examined in the temperature range 350 to 630°C in order to identify optimum reaction conditions and to establish the mechanism by which the reaction is controlled. The reaction under consideration is CrCl₃ (s) + ¾ O₂ (g) → ½ Cr₂O₃ (s) + ³/₂ Cl₂ (g). The main experimental techniques used were isothermal and programmed-temperature thermogravimetry, supplemented by scanning electron-microscopy, surface-area determinations and porosity measurements. The effects of sample pelletisation, gas flowrate, temperature, oxygen partial pressure, pellet porosity and the addition of other oxide species on the rate and extent of reaction have been studied. The reaction is shown to occur in a single step, starting at -350°C under non-isothermal conditions, and exhibiting a deceleratory rate over most of the reaction. Isothermal thermogravimetric curves were fitted to a number of kinetic rate expressions, and a series of statistical analyses used to identify the rate equation which best describes the experimental data. Supporting evidence was provided by scanning electron-microscopic examination of partially-reacted samples. It is concluded that the reaction is under chemical control, and that reaction occurs by means of a linearly-advancing reactant-product interface. The reaction kinetics can be described by a contracting-geometry rate expression.KMBT_363
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Susanto, Benny Laurensius Materials Science & Engineering Faculty of Science UNSW. „Kinetics of carbide dissolution in chromium + molybdenum steels during oxidation“. Awarded by:University of New South Wales. Materials Science and Engineering, 2004. http://handle.unsw.edu.au/1959.4/19385.
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Iron-based alloys containing 15% chromium, 2-3% molybdenum and 0.02-1.7% carbon, consisting of M23C6 and M6C carbides in an austenitic matrix were oxidised at 8500C to study their oxidation resistance and a precipitate-free zone formation. Alloy design was carried out using a thermodynamic software Thermo-Calc. Carbides in these alloys were expected to dissolve during oxidation, releasing chromium required for the protective oxide formation. Decarburisation of the matrix was expected to trigger the carbide dissolution, and form a precipitate-free zone. Transformation of the austenitic into ferritic matrix in the precipitate-free zone was expected be essential for providing a fast chromium supply to the oxide/alloy interface. Upon exposure to pure oxygen, most of the alloys oxidised non-protectively due to the fast oxidation attack and low chromium content in the matrix, while carbide dissolution was too slow. The alloys were then pre-oxidised in H2+10%H2O to grow a purely chromia scale. In this low oxygen partial pressure environment, carbides in the alloy's sub-surface dissolved and formed a ferritic precipitate-free zone. The precipitate dissolution model developed by previous investigators was then tested and proven to be valid in this iron-based alloy system. The endurance of the pre-formed chromia scale with its underlying precipitate-free zone was then tested in pure oxygen environment. All of the alloys that had successfully developed a ferritic precipitate-free zone in the pre-oxidation stage, survived the subsequent oxidation in pure oxygen up until 3 weeks observation. Although x-ray diffraction found some minor iron oxides, the oxide consisted of mainly Cr2O3. Since iron activity had increased and iron oxides had become stable after the pure oxygen gas was introduced, the growth of the precipitate-free zone had to compete with the rate at which it was consumed by oxidation. It was concluded that the transformation from austenite to ferrite at the subsurface region of the alloy could be achieved provided that the volume fraction of the carbides did not exceed 0.2. Evidence indicated that the chromia scale grew by chromium provided by the dissolving carbides. Pre-oxidation led to a promising use of the alloys at atmospheric oxygen pressure.
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JACOB, YVAN PIERRE. „A pre-normative research on the isothermal and cyclic oxidation high temperature oxidation behaviour of chromium“. Clermont-Ferrand 2, 2001. http://www.theses.fr/2001CLF22279.
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De nombreux parametres experimentaux intervenant lors de l'oxydation du chrome a haute temperature ont ete etudies afin de comprendre leurs effets sur la croissance et l'integrite de la couche de chromine qui se forme lors de cette oxydation. Hormis les techniques classiques utilisees pour l'etude de l'oxydation a haute temperature, nous nous sommes servis de la methode d'activation nucleaires des couches minces (tla) permettant de quantifier les pertes eventuelles d'oxyde par ecaillage lors d'oxydations isothermes ou cycliques. Le but de ce travail, par l'etude systematique de differents parametres, est de servir de reference et de permettre une comparaison et une traduction correcte des resultats provenant de differentes etudes. Nous avons montre que l'oxydation isotherme du chrome suit un regime parabolique avec une fracturation periodique de la chromine due a une nitruration du metal (diffusion d'azote dans le metal). En cyclage, a 1000\c, nous avons detecte un decollement de l'oxyde principalement dans les angles des echantillons. Nous avons egalement mis en evidence le role benefique du si et negatif du c (present sous forme d'impuretes) sur l'oxydation. En atmosphere humide, l'oxygene de la vapeur d'eau participe a la formation de la chromine. Enfin, nous avons observe que la diffusion aux joints de grains de l'oxyde augmente en presence d'azote et/ou de vapeur d'eau. Plus la frequence de cyclage est faible et plus nous avons un ecaillage important de l'oxyde du a une accumulation des contraintes de croissance. Les echantillons de petites dimensions montrent des decollements proportionnellement plus important lors d'oxydations cycliques a 1000\c. Nous avons egalement montre que la preparation de la surface n'a pas d'effet sur le mecanisme et la vitesse d'oxydation. Enfin l'yttrium implante a un effet benefique uniquement a 800 et 900\c en limitant la prise de masse, la diffusion d'azote et la fracturation de la couche.
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Van, der Merwe Werner. „Ozone treatment of chromium waste materials / Werner van der Merwe“. Thesis, North-West University, 2011. http://hdl.handle.net/10394/9392.
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Ozonation, or advanced oxidation processes (utilising ozone decomposition products as oxidants) are widely used in industrial waste water and drinking water treatment plants. In these applications the use of ozone is based on ozone and its decomposition by-products being strong oxidants. A case study revealed that several waterworks in South Africa successfully utilise ozone as a pre-oxidant for the treatment of raw waters.
South Africa holds more than three quarters of the world’s viable chromium ore (chromite) reserves. Subsequently the Cr-related industry-within is considerable in size and a major producer of large volumes of waste materials. Chromium also occurs commonly in other industrial waste materials (e.g. fly ash and clinkers originating from coal combustion) and is a natural occurring element in natural sediments, since chromium is the 21st most abundant element in the earth’s crust with an average concentration of approximately 100 ppm. Considering the abundance of natural and anthropogenic Cr-containing materials in South Africa the possibility exists that some of these materials might be suspended in raw water entering water treatment facilities.
In this dissertation, the possible oxidation of non-Cr(VI) Cr-containing materials suspended in water during ozonation, is presented within the context of water treatment applications (Chapter 4). The results indicate that in situ formation of hazardous Cr(VI) is possible during aqueous ozonation. pH had a significant influence, since the decomposition products of aqueous O3, i.e. hydroxyl radicals that form at higher pH levels, were found to be predominantly responsible for Cr(VI) formation. Increased ozonation contact time, water temperature and solid loading also resulted in elevated Cr(VI) concentrations being formed. Occasionally these values exceeded the drinking water standard 50 ppb Cr(VI). The results therefore indicate the importance of removing suspended particulates from water prior to ozonation. Additionally, pH-control could be used to mitigate the possible formation of Cr(VI) during ozonation.
In Chapter 5, exploratory work is presented on the possibility of utilising Cr(VI) formation via ozonation as a means of recovering chromium from Cr-containing waste materials. Such a study is of particular interest within the local context, considering the large volumes of waste produced by the Cr-related industry in South Africa. This exploratory work is based on the fact that unlike Cr(0) and Cr(III), most Cr(VI) compounds are relatively soluble in water. Cr(VI) is a carcinogen if inhaled, however the probability of negative health effects are substantially reduced if it occurs in solution. Thus a hydrometallurgical route of recovering Cr-units via Cr(VI) generation represents the safest route with regard to Cr(VI) exposure. Such a hydrometallurgical route could also addresses the limitations of the physical separation methods currently applied, which fails to recover fine Cr-containing solids. The degree of Cr2O3-liberation achieved in this exploratory work was relatively low. However, the Cr2O3-liberation achieved for the ferrochromium slag (15%) indicated some promise, considering the limitations of this exploratory work. Several steps can be considered in future studies, which would in all likelihood improve the Cr2O3-liberation further.Thesis (MSc (Chemistry))--North-West University, Potchefstroom Campus, 2012
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Rogers, Nathan D. „Chromium Oxidation by Disinfectants and Oxidants Used in Drinking Water Treatment“. DigitalCommons@USU, 2016. https://digitalcommons.usu.edu/etd/5028.
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The USEPA Maximum Contaminant Level (MCL) for Total Chromium in drinking water is 100 μg/L. Total chromium includes both trivalent chromium (Cr(III), a trace nutrient) and hexavalent chromium (Cr(VI), a probable human carcinogen). The State of California set a Cr(VI)-specific MCL of 10 μg/L in 2014, and USEPA is considering a new federal MCL for Cr(VI). This would have a significant impact on drinking water systems across the US, with estimated annual cost of compliance between $0.6 to 5.1 billion per year.
While Cr(VI) is the species of concern for health effects, water utilities must also consider Cr(III) since it can be oxidized to Cr(VI) by various chemicals. This oxidation has been documented for commonly used disinfectants. However, past studies were conducted with higher levels of chromium (e.g., 20 to 500 μg/L) and it is unknown if the reactions proceed at the same rate and extent at the lower concentrations relevant to most water treatment plants (< 10 μg/L).
This project, funded by the Water Research Foundation, systematically evaluated the extent of oxidation of Cr(III) by drinking water oxidants under conditions relevant to drinking water utilities. Five oxidants (chlorine, monochloramine, chlorine dioxide, potassium permanganate, and ozone) were tested. Two doses were used for each chemical with their respective reaction times reflecting the typical application of the chemical in treatment. Three different water qualities were evaluated, each at pH 5.5, 7, and 9, and at two different temperatures (5 and 16 °C).
Chlorine consistently oxidized an average of 80% of the available Cr(III), with the majority of the oxidation happening within the first 7 hours. Monochloramine did not significantly oxidize Cr(III) at any of the conditions tested. Chlorine dioxide was an effective oxidant at pH 7, with complete oxidation occurring in 6 hours, but was less effective at pH 5.5 and 9. Potassium permanganate achieved complete oxidation in 4 hours at each pH, with pH 7 experiencing the fastest oxidation. Ozone oxidized all available Cr(III) within minutes at all pH values. Quantifying the Cr(III) oxidation as a result of using these oxidants provides understanding of potential Cr(VI) addition into drinking water.
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Wang, Haijuan. „Investigations on the Oxidation of Iron-chromium and Iron-vanadium Molten Alloys“. Doctoral thesis, KTH, Materialens processvetenskap, 2010. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-12955.
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With the progress of high alloy steelmaking processes, it is essential to minimize the loss of valuable metals, like chromium and vanadium during the decarburization process, from both economic as well as environmental view points. One unique technique to realize this aim, used in the present work, is the decarburization of high alloy steel grades using oxygen with CO2 in order to reduce the partial pressure of oxygen. In the present work, the investigation on the oxidation of iron-chromium and iron-vanadium molten alloys under CO2-O2 mixtures was carried out and presented in this dissertation. For oxidation study on Fe-Cr molten alloy with CO2-O2 mixtures, on the basis of thermodynamic analysis, energy balance calculation and modeling results, experimental validation in laboratory was carried out, and later on, the oxidation kinetics of Fe-Cr and Fe-Cr-C melts under controlled partial pressure of oxygen was investigated. Thermodynamics calculation and energy balance estimation demonstrated that, it is possible to use CO2 or CO2-O2 mixtures as decarburizers during EAF process and high initial carbon contents in the steel can be adopted at the beginning in order to reduce the cost. A generic model has been developed to describe the overall process kinetics prevailing in metallurgical reactors containing liquid metal and gas bubbles. This model is general and can be extended further to consider any gas liquid reactions in any chemical engineering reactor, and especially the metallurgical ones, like AOD. In the present dissertation, the model is applied in predicting the evolution of Cr and C contents in a Fe-C-Cr melt during injection of different O2-CO2 mixtures. The related simulation results illustrated that CO2 is efficient in Cr retention. In order to verify the modeling results, 1kg induction furnace experiments were carried out in the present laboratory. The results indicated that the predictions of the model are in good agreement with the experimental results. Meanwhile, the experimental results indicated that the Cr-losses can be significantly lowered by replacing the oxygen with CO2 in the injected gas, specifically for Fe-Cr-C melts with carbon levels higher than about 0.8 mass%. Subsequently, the oxidation kinetics of Fe-Cr and Fe-Cr-C melts was investigated under different CO2-O2 mixtures. It is indicated that, the oxidation rate is controlled by the chemical reaction at the initial stage and the reaction rate can be expressed as at the Cr range of 11-21 mass% in the Fe-Cr melt. For oxidation study on Fe-V liquid alloy, the investigation of the oxidation kinetics was carried out under CO2-O2 mixtures, which is followed by the study on thermodynamic properties of vanadium containing slags. During oxidation of Fe-V melt, in the case of alloys with vanadium contents exceeding 10 mass%, there exists an incubation period before the chemical reactions prevail the process. In addition, the ‘incubation time’ increased with the increase of temperature and the vanadium content, whereas it decreased with the increase of oxygen partial pressure in the oxidant gas. High-temperature mass spectrometric method was used to determine the activity of the vanadium oxide in CaO-MgO-Al2O3-SiO2-V2O3 slags, whereas, the oxidation states of vanadium in the CaO-MgO-Al2O3-SiO2-VOxslag system was studied by XANES method. The results indicated that, higher basicities stabilize higher vanadium oxidation state, whereas, higher temperature stabilizes lower vanadium oxidation state. The present work, which was carried out within the ECO-STEELMAKING project funded by MISTRA via Jernkontoret is expected to lead to implementation of some modifications in high alloy steel production based on fundamental concepts towards more environment-friendly steel processing.QC20100628
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Soleimani-Dorcheh, Ali [Verfasser]. „Oxidation-Nitridation of Chromium at High Temperatures and its Mitigation by Alloying / Ali Soleimani-Dorcheh“. Aachen : Shaker, 2017. http://d-nb.info/1138178543/34.
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Zimmermann, Janina [Verfasser]. „Atomistic modeling of the oxidation of titanium nitride and cobalt-chromium alloy surfaces / Janina Zimmermann“. Aachen : Shaker, 2010. http://d-nb.info/1122546599/34.
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李偉安 und Wai-on Lee. „Oxidation chemistry and electrochemistry of ruthenium and chromium complexes of macrocyclic tertiary amines and aromatic diimines“. Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1989. http://hub.hku.hk/bib/B31231846.
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Lee, Wai-on. „Oxidation chemistry and electrochemistry of ruthenium and chromium complexes of macrocyclic tertiary amines and aromatic diimines /“. [Hong Kong : University of Hong Kong], 1989. http://sunzi.lib.hku.hk/hkuto/record.jsp?B12505286.
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Ventura, Julieta Angelica. „High temperature oxidation behavior of Nb-20Mo-15Si-5B-20Cr alloy“. To access this resource online via ProQuest Dissertations and Theses @ UTEP, 2009. http://0-proquest.umi.com.lib.utep.edu/login?COPT=REJTPTU0YmImSU5UPTAmVkVSPTI=&clientId=2515.
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Hamdani, Fethi. „Improvement of the corrosion and oxidation resistance of Ni-based alloys by optimizing the chromium content“. Thesis, Lyon, INSA, 2015. http://www.theses.fr/2015ISAL0012/document.
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Cette étude fondamentale est dédiée à la compréhension de l’influence de la composition chimique, notamment la teneur en chrome, des alliages base de nickel sur leur mécanismes de corrosion et d’oxydation. La corrosion sous contrainte intergranular (CSCIG) est un mode de dégradation qui affecte de nombreux alliages au sein des réacteurs à eau pressurisé. En particulier, les alliages base nickel tubes des générateur de vapeur (GV). La sensibilité à la CSC est désormais dépend de la teneur en chrome, ce qui a conduit au remplacement de l’alliage 600 (Ni-16Cr-9Fe) par l’alliage 690 (Ni-30Cr-9Fe). Cependant le bon comportement de l’alliage 690 en termes de résistance à la corrosion restes mal défini. L’objective de cette thèse est double : i) déterminer l’effet de la teneur en chrome, ii) contribuer à la compréhension de l’effet de fer étant un élément d’addition sur la résistance à la corrosion et l’oxydation généralisée des alliages base nickel en milieu primaire assimilé et en vapeur surchauffée à 700°C. Par ailleurs, des analyses électrochimiques pertinentes dans la température ambiante ont été mené afin d’établir une corrélation entre les propriétés physiques de film passive susceptible de protéger le matériau et de la teneur en chrome. Des alliages modèles binaires Ni-Cr, à teneur de chrome varie entre 14 et 30 % en poids, des alliages ternaires Ni-Cr-8Fe et l’alliage 600 ont été étudies. L’aspect expérimental de cette étude repose sur des techniques conventionnelles: SEM, STEM, EDX, Potentiodynamique, EIS, Chronoamperometrie, Mott-Schottky. La cinétique d’oxydation en vapeur surchauffée a été déterminée en mesurant l’apport de masse. L’impact de l’état de surface sur le processus de la corrosion et l’oxydation a été mis en évidence. Les polissages miroir et électrochimique ont été réalisés afin de découpler l’effet de l’écrouissage développé en subsurface, induit par la préparation de surface, et la composition chimique de l’alliage. La teneur en chrome limite à partir de laquelle l’alliage a un comportement satisfaisant en corrosion a été déterminé à 20% dans le milieu primaire. Cependant les analyses électrochimiques ont décelé l’existence d’une teneur en chrome optimal à 26%. La cinétique d’oxydation des alliages modèles ainsi que la morphologie des oxydes formés sur ces matériaux dans le milieu vapeur surchauffée ont indiqué l’existence d’une teneur en chrome optimal à 24%. Une dégradation des propriétés des films d’oxydes a été observée en augmentant la teneur en chrome au-dessus de l’optimum. En résumé, ce travail se préoccupe de l’optimisation de la teneur en chrome, méthode plus adéquate, pour l’amélioration de la résistance à la corrosion et l’oxydation des alliages base nickelThis fundamental study is focused on the understanding of the influence of the chemical composition of Ni-based alloys on their corrosion and oxidation mechanisms. This work is not dedicated for a particular application. It is well known for instance that Ni-based alloys are susceptible to intergranular stress corrosion cracking (IGSCC) in primary water. Thus, Alloy600 (Ni-16Cr-9Fe), used in steam generator (SG) tubing, was replaced by higher chromium content material Alloy690 (Ni-30Cr-9Fe). This later shows a better resistance to IGSCC which may be linked to the growth of more protective oxide layer as chromium content is increased to 30 wt.%. The main goal of this study is to investigate: i) the influence of chromium content, ii) impact of iron addition on the corrosion and oxidation resistance of Ni-based alloys in primary water and superheated steam at 700°C. Furthermore, analytical approach in acidic solution is conducted at room temperature. This allowed to establish a relationship between alloying elements and physical properties of the oxide layers. For this purpose, Ni-xCr (14 ≤ x≤ 30 wt.%), Ni-xCr-8Fe (x=14,22 and 30 wt.%) model alloys and industrial material Alloy600 have been studied. To characterize the oxide scales, conventional technics were used: SEM, STEM, EDX, Potentiodynamic, EIS, Chronoamperometry, Mott-Schottky. Furthermore, steam oxidation kinetics was evaluated by means of weight gain measurements. To uncouple the effect of surface cold-work and the chemical composition of the base metal, mirror and electro polishing were carried out. In primary water, critical chromium content (20 wt.%), which corresponds to the minimum amount of chromium required to the transition from non-protective to protective and compact Cr-oxide layer, is determined. However, the analytical approach, using electrochemical technics, at room temperature elucidated the existence of optimum chromium content (26 wt.%) in terms of corrosion resistance. In superheat steam, oxidation kinetics and oxide scale characteristics showed the existence of optimum chromium content (24 wt.%) in terms of oxidation resistance. The corrosion and oxidation resistance is degraded as chromium content was increased more than optimal amount. Iron addition (8 wt.%) had a detrimental effect on the protectivess of the resulting oxide scales. Finally, this study showed that optimizing of chromium content is more appropriate method for enhancing corrosion and oxidation resistance, that increasing chromium content to high level is not necessary beneficial to those parameters. This work provides a useful knowledge to design new alternative materials. For this purpose, more investigations should be conducted to test other parameters such as: weldability, fabricability, thermal conductivity,etc
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Marin, Cordoba Roberto. „Chromium Carcinogenesis: Characterization of DNA damaging Intermediates by EPR 31P NMR, HPLC, ESI-MS and Magnetic Susceptibility“. Ohio University / OhioLINK, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1261417590.
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Portillo, Benedict I. „High temperature oxidation behavior of the Nb-W-Cr system and response of boron additions“. To access this resource online via ProQuest Dissertations and Theses @ UTEP, 2008. http://0-proquest.umi.com.lib.utep.edu/login?COPT=REJTPTU0YmImSU5UPTAmVkVSPTI=&clientId=2515.
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Pillay, Kriveshini. „A kinetic and mechanistic study on the oxidation of chromium oxide in pure chemicals and in ferrometallurgical slags“. Master's thesis, University of Cape Town, 2001. http://hdl.handle.net/11427/5415.
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Bibliography: leaves 103-108.Chromium can exist in a number of oxidation states but the environmentally stable forms are trivalent (Cr(III)) and hexavalent (Cr(VI)) chromium. These two forms are noted for their different degrees of toxicity and mobility. Hexavalent chromium is more toxic and mobile and has been responsible for a number of illnesses in humans (Sheehan et. al., 1991). Elemental chromium and its compounds have a variety of uses in the industrial sector. The ferrometallurgical industry in particular makes use of chromium since this element imparts properties such as hardness and strenght to stainless steel. However, this industry also produces slags that contain residual amounts of chromium oxide (Cr[2]O[3]) along with other constituents such as calcium oxide (CaO). Thermodynamic data from the literature, has shown that Cr[2]O[3] can undergo oxidation at ambient temperature when in contact with CaO and atmospheric oxygen (Kilau and Shah, 1984; Hattori et al., 1978). Furthermore, the oxidation of Cr[2]O[3] in the presence of Ca(OH)[2] has also been observed at ambient temperature (Petersen, 1998).
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Acerson, Mark Jeffrey. „Synthesis of 4'-Ester Resveratrol Analogues, Chromium Trioxide Oxidation of Terpenes, and Synthesis of Mimics of (-)-Englerin A“. BYU ScholarsArchive, 2014. https://scholarsarchive.byu.edu/etd/5458.
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4’ -ester analogues of resveratrol were synthesized using reaction conditions developed to produce mono-ester products in the presence of two other unprotected phenols. Basic conditions were employed to deprotonate the most acidic 4’ phenol followed by addition of anhydrides or acid chlorides to give the ester product. The reaction favored 4’-ester formation in polar aprotic solvents with DMSO being the optimal solvent. (—)-Englerin A is a guaiane-type sesquiterpene containing two ester side chains. Mimics of (—)-englerin A were proposed that retained the ester side chains while replacing the non-polar core with less complicated structures. These proposed mimic cores would maintain the three-dimensional positioning of the esters which are responsible for the anti-cancer activity of (—)-englerin A. Three mimics were synthesized using the bicyclic terpenes borneol and fenchol. Installation of the second ester on the terpene core was accomplished throught the development and optimization of a unique methylene oxidation using chromium trioxide in glacial acetic acid. These mimics were screened against two kidney cancer cell lines. The compounds were shown to have IC50 (inhibitory concentration for 50 % of cells) values above 30 µM.
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Högström, Jonas. „Corrosion and Surface Studies of Stainless Steel and Chromium Carbide Thin-Films“. Doctoral thesis, Uppsala universitet, Institutionen för kemi - Ångström, 2013. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-208410.
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Although the passive films that form on stainless steels have been extensively studied, the concentration depth profiles are not fully understood. Their thinness makes passive films hard to study, but angle-resolved X-ray photoelectron spectroscopy (ARXPS) is a non-destructive technique that can be used to obtain depth information. An iterative approach to deconvolute ARXPS measurements into depth profiles is discussed, and the chemistry of passive films on a molybdenum-containing 316L stainless steel is investigated. Bipolar electrochemistry, in which the sample is placed along an electric field created by two driving electrodes in an electrolyte, is investigated as a screening tool. It is shown that the method is useful to create corrosion gradients on 304 stainless steel, both under pitting and non-pitting conditions. Chromium carbide thin films were deposited by magnetron sputtering with a variety of deposition parameters on stainless steel, and subsequently analyzed. It is shown that these films present a promising material system for protective coatings to improve the corrosion resistance of stainless steels while also maintaining other useful properties, such as low interfacial contact resistance. Particular attention is given to the electrochemical evaluation of the films, whose high carbon concentrations necessitates different interpretations of the electrochemical results compared to for stainless steels.
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Paulo, Glauco Dias. „Estudo da influência do teor de cromo na microestrutura, dureza e oxidação de um ferro fundido branco multicomponente (FFBM)“. Universidade de São Paulo, 2016. http://www.teses.usp.br/teses/disponiveis/97/97134/tde-06022017-104006/.
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Foi estudado o efeito da variação do teor de cromo, em 3%, 6% e 9% em massa, na microestrutura, dureza e oxidação de um ferro fundido branco multicomponente. O Thermo-Calc versão 5 foi a ferramenta utilizada para cálculos termodinâmicos que resultaram na previsão das fases formadas para cada liga. Experimentalmente, foram realizados os seguintes estudos: i) caracterização microestrutural das ligas fundidas com os diferentes teores de cromo na condição bruta de fundição; ii) ensaio de dureza na matriz duplamente revenida em cinco diferentes temperaturas entre 400 °C e 600 °C; e iii) ensaio de termogravimetria em atmosfera controlada de 71,2 % N2 + 17,8 % O2 + 11% H2O, com temperatura constante em 650 °C e por um tempo de 240 minutos. O resultado da caracterização microestrutural permitiu identificar que, com o aumento do teor de cromo, houve aumento da fração volumétrica de carbonetos eutéticos e redução do espaçamento dendrítico secundário. Com as medidas de dureza da matriz após tratamento térmico verificou-se que, independentemente do teor de cromo, o pico de máxima dureza ocorre na temperatura de duplo revenimento de 550°C e, nessa temperatura, a amostra com 9% de cromo exibiu o maior valor de dureza. O ganho de massa das amostras submetidas ao ensaio de termogravimetria foi inversamente proporcional ao aumento de teor de cromo e todas as ligas apresentaram cinética de oxidação parabólica. A caracterização da seção transversal das amostras oxidadas, realizada por meio de um FIB, permitiu identificar, na amostra com 9% de cromo, uma nano camada de óxido de cromo, estrutura decisiva para a menor taxa de oxidação. Os resultados desse estudo permitem concluir que a variação do teor de cromo afeta de maneira significativa a resistência à oxidação, a dureza da matriz e a fração volumétrica de carbonetos eutéticos.The effect of chromium variation, 3%, 6% and 9% Cr in mass in the microstructure, hardness and oxidation of a Multicomponent White Cast Iron was studied. The Thermo-Calc software version 5 was the tool used for thermodynamic calculations to predict the phases formed for each alloy. Experimentally, the following studies were carried out: i) microstructure characterization of the as cast alloys with the different chromium contents, ii) hardness test in the double tempered matrix at five different temperature between 400°C and 600° and iii) themogravimetric test with steam atmosphere composed of 71,2 % N2 + 17,8 % O2 + 11% H2O at constant temperature of 650° for 240 minutes. The result of the microstructure characterization allowed to observe that with increasing chromium content, there was an increase in the volume fraction of eutectic carbides and a reduction of the secondary dendritic spacing. Independently of the chromium content, a maximum hardness was observed always for double tempered at 550°C and the alloy with 9% of chromium exhibited the highest hardness average value. The final weight gain was inversely proportional to the increase in chromium content and all alloys showed parabolic oxidation kinetics. The alloy with 9% Cr showed the lowest final mass gain and the surface characterization of the sample after oxidation was carried out and the cross section of the sample was performed by FIB and was observed the formation of a nano-oxide layer on the alloy surface with 9% Cr. The results of this study leads to the conclusion that the chromium content variation significantly affects the oxidation resistance, the final hardness of the matrix and the volume fraction of eutectic carbides.
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Weaver, Robert M. „Comparison of the Reactivity of Various Mn-Oxides With CrIIIaq: Microscopic and Spectroscopic Observations of Dissolution, Cr-sorption and Cr and Mn Redox Interactions“. Diss., Virginia Tech, 2001. http://hdl.handle.net/10919/29365.
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The interaction between CrIIIaq and seven different Mn-oxides (6 monomineralic, 1 synthetic) have been observed in pH ~4.4 HNO3 and pH ~4.4 ~10-4M CrIIIaq solutions. For each mineral-solution interaction, the aqueous chemical concentrations (e.g. [Mn]aq, [Cr]aq, [CrVIaq]) were measured with time. Reacted samples were examined by XPS to determine if, and to what extent, the surface chemical states of Cr, Mn and O had changed. Microscopic observations of the reacted surfaces were obtained using AFM and high-resolution, low-voltage FESEM. The solubility of the Mn-oxides in the acidic, non-Cr bearing solutions varied inversely with the average Mn valence, but did not show systematic behavior with respect to the mineral structure type (e.g. tunnel, layer, framework). This trend was interpreted as resulting from the relative ability of an adsorbed proton to polarize surface Mn-O bonds, with the polarizability being in the order Mn2+-O > Mn3+-O > Mn4+-O. For samples reacted with CrIIIaq, the rate and extent of reductive dissolution was always greater than for acidic dissolution during the initial time period. The measured ratios of the [Mn]aq : [CrVI]aq were approximately in agreement with the values expected from the proposed stoichiometric reactions. Cr-uptake was observed to occur in undersaturated solutions as a result of adsorption, absorption and surface catalyzed precipitation. The chromium as detected by XPS was predominately CrIII, however pyrolusite contained both CrIII and CrVI. Previous studies have implicated a chromium surface precipitate to be responsible for the cessation of the CrIIIaq oxidation reaction. Our surface sensitive FESEM and AFM observations tend to suggest that Cr-uptake is by isolated site binding, very small (<30 nm) surface clusters or monolayer scale films. Cr-uptake was followed by slow Cr-release on several of the solids (particularly the layered solids) after a substantial portion of the total aqueous Cr had been converted to CrVIaq.
The oxidizing ability of the different Mn-oxides for CrIIIaq is evaluated with regards to the energy level of the redox couple (i.e. the redox potential) as compared with the Fermi energy level of the Mn-oxide. Although these energies were calculated rather than directly measured, the results indicate that electrons originating from adsorbed CrIII ions may be transferred into the conduction band or more likely, into available surface states. The presence of an initial limited quantity of electron accepting surface states likely explains the observation of a rapid initial CrIII-oxidation followed by much slower oxidation. The Mn-oxides that exhibited the greatest and longest lasting CrIII-oxidizing power were the Mn-oxides containing Mn3+, and in particular those containing Mn3+ and Mn2+. It is believed that the combined presence of a reducible Mn ion (e.g. Mn3+) and a highly soluble Mn2+ ion facilitates a sustained CrIII-oxidation reaction because fresh surface is exposed during the reaction.Ph. D.
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O'Neal, Stephen Vernon. „A kinetic study of the chromium (VI) - arsenic (III) reaction in pyridine-pyridinium buffer solutions containing oxalate“. Thesis, Virginia Polytechnic Institute and State University, 1985. http://hdl.handle.net/10919/104524.
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Kamaludeen, Sara Parwin Banu. „Biotic-abiotic transformations of chromium in long-term tannery waste contaminated soils : implications to remediation“. Title page, table of contents and abstract only, 2002. http://web4.library.adelaide.edu.au/theses/09PH/09phk15.pdf.
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Bibliography: leaves 166-180. Determines the effect of chromium on the soil microbial community and its activity, the biotic-abiotic mechanisms involved in chromium oxidation, and phytostabilization of chromium using plants and organic amendment in tannery-waste contaminated soil.
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Soleimani-Dorcheh, Ali Verfasser], Michael [Akademischer Betreuer] Schütze und Wolfgang [Akademischer Betreuer] [Bleck. „Oxidation-nitridation of chromium at high temperatures and its mitigation by alloying / Ali Soleimani-Dorcheh ; Michael Schütze, Wolfgang Bleck“. Aachen : Universitätsbibliothek der RWTH Aachen, 2017. http://d-nb.info/1156923468/34.
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Soleimani-Dorcheh, Ali [Verfasser], Michael Akademischer Betreuer] Schütze und Wolfgang [Akademischer Betreuer] [Bleck. „Oxidation-nitridation of chromium at high temperatures and its mitigation by alloying / Ali Soleimani-Dorcheh ; Michael Schütze, Wolfgang Bleck“. Aachen : Universitätsbibliothek der RWTH Aachen, 2017. http://d-nb.info/1156923468/34.
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Jiang, Wenjun. „The Investigation of Photocatalysts and Iron Based Materials in the Oxidation and the Adsorption of Toxic Organic and Chromium Materials“. FIU Digital Commons, 2013. http://digitalcommons.fiu.edu/etd/1023.
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The presences of heavy metals, organic contaminants and natural toxins in natural water bodies pose a serious threat to the environment and the health of living organisms. Therefore, there is a critical need to identify sustainable and environmentally friendly water treatment processes. In this dissertation, I focus on the fundamental studies of advanced oxidation processes and magnetic nano-materials as promising new technologies for water treatments.
Advanced oxidation processes employ reactive oxygen species (ROS) which can lead to the mineralization of a number of pollutants and toxins. The rates of formation, steady-state concentrations, and kinetic parameters of hydroxyl radical and singlet oxygen produced by various TiO2 photocatalysts under UV or visible irradiations were measured using selective chemical probes. Hydroxyl radical is the dominant ROS, and its generation is dependent on experimental conditions. The optimal condition for generation of hydroxyl radical by of TiO2 coated glass microspheres is studied by response surface methodology, and the optimal conditions are applied for the degradation of dimethyl phthalate. Singlet oxygen (1O2) also plays an important role for advanced processes, so the degradation of microcystin-LR by rose bengal, an 1O2 sensitizer was studied. The measured bimolecular reaction rate constant between MC-LR and 1O2 is ~ 106 M-1 s-1 based on competition kinetics with furfuryl alcohol.
The typical adsorbent needs separation after the treatment, while magnetic iron oxides can be easily removed by a magnetic field. Maghemite and humic acid coated magnetite (HA-Fe3O4) were synthesized, characterized and applied for chromium(VI) removal. The adsorption of chromium(VI) by maghemite and HA-Fe3O4 follow a pseudo-second-order kinetic process. The adsorption of chromium(VI) by maghemite is accurately modeled using adsorption isotherms, and solution pH and presence of humic acid influence adsorption. Humic acid coated magnetite can adsorb and reduce chromium(VI) to non-toxic chromium (III), and the reaction is not highly dependent on solution pH. The functional groups associated with humic acid act as ligands lead to the Cr(III) complex via a coupled reduction-complexation mechanism. Extended X-ray absorption fine structure spectroscopy demonstrates the Cr(III) in the Cr-loaded HA-Fe3O4 materials has six neighboring oxygen atoms in an octahedral geometry with average bond lengths of 1.98 Å.
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Brose, Dominic A. „Oxidation-reduction transformations of chromium in aerobic soils and the role of electron-shuttling quinones in chemical and microbiological pathways“. College Park, Md.: University of Maryland, 2008. http://hdl.handle.net/1903/8316.
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Thesis (M.S.) -- University of Maryland, College Park, 2008.Thesis research directed by: Dept. of Natural Resource Sciences and Landscape Architecture. Title from t.p. of PDF. Includes bibliographical references. Published by UMI Dissertation Services, Ann Arbor, Mich. Also available in paper.
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Bishop, Michael Edward. „Fe(III) reduction in Hanford sediments and its application to chromium immobilization“. Miami University / OhioLINK, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=miami1438442637.
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Marin, Córdoba Roberto. „Chromium carcinogenesis characterization of DNA damaging intermediates by EPR ³¹P NMR, HPLC, ESI-MS and magnetic susceptibility /“. Ohio : Ohio University, 2010. http://www.ohiolink.edu/etd/view.cgi?ohiou1261417590.
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Lindsay, John Christopher. „Stress corrosion cracking and internal oxidation of alloy 600 in high temperature hydrogenated steam and water“. Thesis, University of Manchester, 2015. https://www.research.manchester.ac.uk/portal/en/theses/stress-corrosion-cracking-and-internal-oxidation-of-alloy-600-in-high-temperature-hydrogenated-steam-and-water(1d6b037c-baf1-4397-a6c9-43835e7bb39a).html.
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In this study, the possibility of using low pressure hydrogenated steam to simulate primary water reactor conditions is examined. The oxides formed on Alloy 600 (WF675) between 350 Celsius and 500 Celsius in low pressure hydrogenated steam (with a ratio of oxygen at the Ni/NiO to oxygen in the system of 20) have been characterised using analytical electron microscopy (AEM) and compared to oxide that formed in a high pressure water in a autoclave at 350 Celsius with 30 cc/kg of hydrogen. Preferential oxidation of grain boundaries and bulk internal oxidation were observed on samples prepared by oxide polishing suspension (OPS). Conversely, samples mechanically ground to 600 grit produced a continuous, protective oxide film which suppressed the preferential and internal oxidation. The surface preparation changed the form of the oxides in both steam and autoclave tests. The preferential oxidation rate has been determined to be K_{oxide} = Aexp{-Q/RT}with A = 2.27×10^(−3) m^(2)s^(−1) and Q = 221 kJ.mol^(−1) (activation energy) for WF675 and A = 5.04 × 10^(−7) m^(2)s^(−1) and Q = 171 kJ.mol^(−1) for 15% cold worked WF675. These values are consistent with the activation energy of primary water stress corrosion cracking (PWSCC) initiation. Bulk oxygen diffusivities were calculated from the internal oxidation after 500 h exposures. At 500 Celsius the oxygen diffusivity was determined to be 1.79×10^(−20) m^(2)s^(−1) for WF675 and 1.21×10^(−20) m^(2)s^(−1) for 15% cold worked WF675, the oxygen diffusivity at 400 Celsius in 15% cold worked WF675 was calculated to be 1.49×10^(−22) m^(2)s^(−1).The Cr-depletion associated with preferential oxidation has been assessed by AEM. The Cr-depletion was asymmetric and it could not be accounted for by local variations in the diffusion rate. Chemically induced grain boundary migration is suggested as a possible explanation. Constant load SCC tests conducted in hydrogenated steam at 400 Celsius have shown a similar trend to the classical dependency of PWSCC as a function of potential. The SCC samples were also prepared with two surface finishes, OPS and 600 grit. In all SCC tests, significantly more cracking was observed on the OPS surface and all failures initiated from this surface.
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PILLIS, MARINA F. „Estudo do comportamento de sulfetacao de ligas Fe20Cr“. reponame:Repositório Institucional do IPEN, 2001. http://repositorio.ipen.br:8080/xmlui/handle/123456789/10925.
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Made available in DSpace on 2014-10-09T12:45:38Z (GMT). No. of bitstreams: 0Made available in DSpace on 2014-10-09T14:07:05Z (GMT). No. of bitstreams: 1 07307.pdf: 7122491 bytes, checksum: c6f55b3c5e36e13004a54501231c20a4 (MD5)
Tese (Doutoramento)
IPEN/T
Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP
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Nicolas, André. „Etude de l'Evolution Physico-Chimique du Substrat lors de l'Oxydation à Haute Température des Alliages Modèle Ni-Cr à Faible Teneur en Chrome et de l'Alliage Modèle Ni-16Cr-9Fe“. Phd thesis, Ecole Nationale Supérieure des Mines de Saint-Etienne, 2012. http://tel.archives-ouvertes.fr/tel-00848591.
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Le travail réalisé au cours de cette thèse concerne l'analyse des conséquences de l'oxydation à 950°C des alliages base Ni sur la composition de l'alliage à proximité de l'interface alliage/oxyde. Deux catégories d'alliages ont été analysées : alliages à faible teneur en chrome conduisant à l'oxydation interne et l'alliage chromino-formeur Ni-16Cr-9Fe.Une description complète des mécanismes de l'oxydation interne du chrome est obtenue à partir du développement du modèle analytique de Wagner d'oxydation interne et du développement du modèle numérique de Feulvarch. Ces modèles décrivent l'évolution de l'oxydation interne jusqu'à la transition oxydation interne / oxydation externe à 11 %poids de chrome environ.L'analyse par la spectroscopie d'électrons Auger de l'alliage modèle Ni-16Cr-9Fe à 950°C oxydé pendant 10 heures a permis d'explorer la zone à proximité immédiate de l'interface alliage/oxyde et de déterminer la concentration en chrome à l'interface à 0,5%poids (i.e. dans 20 premiers nanomètres), ce qui est en accord avec le modèle analytique de Wagner d'oxydation en couche compacte. La description des profils de déchromisation et des profils de cavités pour plusieurs temps d'exposition allant de 100h à 5000h a permis de mettre en évidence une corrélation forte entre ces deux phénomènes (même constante parabolique). Pour ces durées d'oxydation les profils de déchromisation présentent un point d'inflexion ce qui se traduit par l'augmentation de la teneur en chrome à l'interface. Les résultats sont interprétés dans le cadre d'un nouveau modèle analytique avec l'hypothèse d'injection des lacunes produites par l'effet Kirkendall au point d'inflexion.
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Evin, Harold. „Low Cr alloys with an improved high temperature corrosion resistance“. Thesis, Dijon, 2010. http://www.theses.fr/2010DIJOS082/document.
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Les aciers ferritiques à faible teneur en chrome tel que le T/P91 sont largement utilisés dans les centrales de productions d’électricité pour leurs bonnes propriétés mécaniques et leur faible coefficient d’expansion thermique. Cependant, la demande croissante en énergie alliée à la nécessité de réduire les émissions de gaz à effet de serre, conduisent à envisager l’augmentation des conditions d’utilisation (température et pression) de ces matériaux. Des études ont montré qu’en modifiant la température de fonctionnement et la pression de vapeur d’eau de 538°C/18.5 MPa à 650°C/30 MPa, le rendement des centrales thermiques progressait d’environ 8%. Se pose alors la question de la tenue à la corrosion à haute température des aciers à 9% de chrome. Au cours de ces travaux, le comportement d’un acier ferritique/ martensitique à 9% de chrome a été étudié à 650°C sous air sec et sous vapeur d’eau de matière isotherme et en conditions de cyclage thermique. La prise de masse des échantillons renseigne sur la cinétique de la réaction d’oxydation et l’adhérence des couches d’oxydes formées. Les produits de corrosion ont été caractérisés par plusieurs techniques d’analyses dans l’optique de clairement identifiés les oxydes en présences et leurs mécanismes de formation. Des oxydes mixtes de fer et de chrome (Cr,Fe)2O3 sont dans un premier temps formés et assurent s’avèrent être temporairement protecteur. Pour des longs temps d’oxydation ou des températures supérieures à 650°C, la magnétite Fe3O4 et l’hématite Fe2O3 sont les principaux oxydes formés, montrant ainsi l’inadéquation des nuances à faible teneur en chrome pour une utilisation dans des conditions aussi drastiques. Dans l’optique d’augmenter la résistance à la corrosion à haute température de cet alliage, diverses solutions ont été envisagées tel que l’aluminisation par cémentation en caisse, les revêtements d’oxydes de terre rare par MOCVD, ou encore l’ajout d’éléments d’addition. Ces solutions ont été également testées à 650°C sous air sec et sous vapeur d’eauThe improvement of high temperature oxidation resistance of low chromium content steels, such as T/P91, is of great interest in regards with their application in thermal power generating plants. Indeed, they possess good creep properties, and low thermal expansion coefficient. Important needs in energy together with environmental issues place power generation plants under constraints which lead to develop high efficiency systems. A usual way to increase the efficiency consists in increasing temperature and pressure parameters of the power generating plant. Studies has shown that the total efficiency of a plant increases by nearly 8 % when changing the steam parameters from 538°C/18.5 MPa to 650°C/30 MPa. Then, the problem of corrosion resistance of 9% chromium steel in those conditions is asked. In this work, the behavior of a ferritic / martensitic 9% chromium steel has been studied at 650°C in dry air and in water vapor containing environment in both isothermal and thermal cyclic conditions. The weight gain of samples provides information on the kinetics of the oxidation reaction and the adhesion of formed oxide scale. Corrosion products were characterized by several analytical techniques in order to identify oxides with accuracy and to understand their formation mechanisms. Mixed iron and chromium oxides (Cr, Fe) 2O3 are initially formed and provide temporary protection to the substrate. For long time exposure or temperatures above 650°C, magnetite, Fe3O4 and hematite Fe2O3 are the main oxides formed, highlighting the fact that low chromium steel are inappropriate for applications in such drastic conditions. In order to increase the high temperature corrosion resistance of this alloy, various solutions have been proposed as aluminizing by pack cementation, reactive element oxides coatings of by MOCVD, or addition of alloying elements in the steel composition. These solutions were then tested at 650 ° C in dry air and in water vapor environments
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Alves, Lucas Campaner. „Caracterização do cromo presente no lodo de galvanoplastia: avaliação técnica e econômica de processos de remoção“. Universidade de São Paulo, 2016. http://www.teses.usp.br/teses/disponiveis/85/85134/tde-29032016-084227/.
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O lodo gerado em processos de galvanoplastia é classificado pela ABNT NBR 10.004/04 como perigoso (classe I). Na literatura encontram-se poucos estudos referentes à recuperação do cromo presente no lodo gerado em sistemas de tratamento de efluentes de indústrias de galvanoplastia. Neste sentido, o presente estudo avaliou a remoção do cromo presente no lodo de galvanoplastia por meio de dois processos, visando avaliar à eficiência técnica e a viabilidade econômica de ambos. O Processo 1 consistiu na remoção do cálcio utilizando o ácido cítrico, seguida de lixiviação ácida. Na etapa de oxidação, variou-se a temperatura em 40ºC, 60ºC e 80ºC e no tempo de 30, 60 e 90 minutos, tendo em vista que a eficiência do processo de oxidação depende da temperatura e tempo. Nesta etapa do processo as concentrações de peroxido de hidrogênio (H2O2) utilizadas foram de 1,50, 3,00 e 4,50 mol.L-1. O Processo 2 realizou a oxidação do cromo sem efetuar as etapas de extração do cálcio e a lixiviação ácida. A oxidação do cromo ocorreu pelo mesmo método apresentado no Processo 1. A caracterização elementar da amostra determinou que o principal elemento constituinte do lodo é o cálcio (20,05% em massa), e que dentre os metais pesados destacam-se o cromo e o níquel (6,52% e 4,33% em massa, respectivamente). A maior eficiência de remoção do cálcio foi obtida na razão mássica de 8,00 (ácido cítrico/hidróxido de cálcio), com 51,76% em massa, seguida pela razão mássica de 5,50 com 36,75% em massa e 2,50 com 24,83% em massa. O melhor resultado de oxidação do cromo no Processo 1 foi obtido com tempo de 30 minutos, temperatura de 60ºC e concentração de peroxido de hidrogênio de 3,00 mol.L-1, com eficiência de 41,09% em massa. No Processo 2, obteve-se a remoção de 37,96% em massa de cromo a temperatura de 80ºC, por uma hora e 3,00 mol.L-1 de peróxido de hidrogênio. Avaliando os custos para remoção do cromo dos dois processos, determinou-se que o Processo 1 foi mais oneroso que o 2, porém ambos não apresentaram viabilidade econômica para aplicação em escala industrial. Nos dois processos efetuou-se a oxidação do cromo presente no lodo de galvanoplastia, permitindo a sua remoção parcial neste resíduo. Com isso obtiveram-se ganhos ambientais, pela diminuição deste elemento no resíduo de galvanoplastia, que na maioria das vezes é disposto em aterros classe I, gerando um passivo ambiental.The sludge generated in electroplating processes is classified by NBR 10.004/04 as a hazardous material (class I). In the literature, few studies report the recovery of chromium present in the electroplating sludge generated in the industries. In this sense, the present study conducted the removal of chromium in the electroplating sludge through two different processes, aiming to evaluate their efficiency and economic viability. The first process removed calcium through the use of citric acid being performed by varying the ratio of citric acid/calcium hydroxide (2.5, 5.5 and 8.0). Then, were performed the leaching of the samples. According to the literature, the efficiency of the oxidation process varies depending on the reaction temperature, time and concentration of hydrogen peroxide. For this reason, samples were heated to a temperature ranging from 40°C, 60°C and 80°C. Also, were conducted variations in the concentrations of hydrogen peroxide (1.5, 3.0 and 4.5 mol.L-1) and reaction time (30, 60 and 90 minutes). The second Process consisted in the chrome recovery by using the galvanic sludge without removal of the calcium and acid leaching. The chrome oxidation occurred by the same method shown in Process 1. Elemental characterization of the samples determined that the primary sludge constituent was calcium (20.05% by weight), and in terms of heavy metals, the chromium and the nickel (6.52% and 4.33% by mass, respectively). Most of calcium removal efficiency was obtained at a rate of 8 with 51.76% by mass, then the ratio of 5.50 to 36.75% by mass and 2.50 to 24.83% by mass. The best oxidation result of chromium in Process 1 was obtained using a time of 30 minutes, 60°C and hydrogen peroxide concentration of 3 mol.l-1, with 41.09 wt% efficiency. In Process 2 was obtained the removal of 37.96% by mass of chromium temperature of 80°C, for one hour and 3,00 mol.l-1 of hydrogen peroxide. Evaluating the costs for chrome removal of the two processes was determined that the Process 1 was more costly than 2, but both showed no economic feasibility for implementation on an industrial scale. However, in both cases occurred the oxidation of chromium present in the electroplating sludge, allowing its removal from the residue. Thus, environmental gains have been achieved by the reduction of this element in electroplating waste, which mostly is intended for landfill class I, generating an environmental liability.
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Schmucker, Éric. „Compréhension et modélisation des mécanismes de corrosion des alliages chromino-formeurs dans les verres nucléaires“. Thesis, Université de Lorraine, 2016. http://www.theses.fr/2016LORR0166/document.
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La gestion des déchets radioactifs se fait par confinement des déchets radioactifs dans une matrice vitreuse. Il est réalisé par fusion inductive à 1150°C dans des pots constitués de superalliages riches en chrome. Ces pots sont soumis à une corrosion par le verre entrainant à terme leur remplacement. La protection contre la corrosion par le verre est assurée par l’établissement d’une couche d’oxyde protectrice Cr2O3 à la surface de l’alliage. Un alliage binaire chromino-formeur (Ni-30Cr) a été choisi comme alliage d’étude. Trois compositions de verre sodo- et borosilicatées sont choisies dans le but de discerner l’influence de la basicité et de la viscosité des verres sur les cinétiques de corrosion. La décorrélation des phénomènes de formation et de dissolution a permis la modélisation des cinétiques de croissance globale de la couche d’oxyde en milieu liquide silicaté. Dans ce cadre, la cinétique de formation de l’oxyde en milieu verre est assimilée à la cinétique d’oxydation de l’alliage Ni-30Cr en milieu gazeux sous des pressions partielles d’oxygène représentatives du pouvoir oxydant d’un verre. Les études des cinétiques d’oxydation ont montré que la cinétique d’oxydation de l’alliage Ni-30Cr est indépendante de la pression d’oxygène entre 10-13 et 10-3 atm O2 à 1150°C. Les travaux réalisés ont montré que la cinétique de dissolution de la couche d’oxyde Cr2O3 est limitée par la diffusion du CrIII dans le verre. Cette cinétique de dissolution a été ainsi évaluée à partir de la limite de solubilité et du coefficient de diffusion du CrIII dans les verres. Enfin, la cinétique de la croissance expérimentale de la couche d’oxyde Cr2O3 dans le verre a été modélisée avec succès pour chacun des verres, à partir de (i) la limite de solubilité du CrIII, (ii) son coefficient de diffusion et (iii) la cinétique d’oxydation de l’alliage. Le modèle établi permet également de quantifier l’influence de ces différents paramètres sur la cinétique de croissance de l’oxyde protecteurNuclear wastes management consists in the confinement of the radioactive wastes in a glass matrix. This is made by inductive melting in a hot crucible at an operating temperature around 1150°C. These crucibles are constituted of nickel based superalloys with high chromium content. They are submitted to a harsh corrosion by the molten glass, eventually leading to their replacement. The protection of the crucible against corrosion is best provided by the establishment of a protective chromium oxide layer at the surface of the alloy. A binary chromia-forming alloy (Ni-30Cr) is studied in this work. Three different binary and ternary glass compositions are chosen in order to understand the influence of the glass basicity and glass viscosity on the corrosion kinetics. Besides, the decorrelation of the formation and dissolution kinetics of the oxide layer allows the modelling of the overall oxide growth in the molten glass. For that purpose, the oxide formation kinetics in molten glass media is assimilated to the oxidation kinetics of the alloy in gaseous media with oxygen partial pressure that are representative of the redox properties of the glasses. Studies of the oxidation kinetics and of the diffusion mechanisms have shown that the oxidation kinetics is independent on the oxygen pressure in the range of 10-13 up to 10-3 atm O2 at 1150°C. The present work has shown that the dissolution kinetics of the oxide layer is governed by the diffusion of CrIII in the glass melt. This dissolution kinetics has been evaluated from the diffusion coefficient and the solubility limit of CrIII in the glass. Finally, the overall growth kinetics of the Cr2O3 layer in the glass has been successfully modelled for each glass, thanks to the knowledge of (i) the solubility limit of CrIII, (ii) its diffusion coefficient in the glasses and (iii) the oxidation kinetics of the alloy. The presented model also allows quantifying the influence of each of these parameters on the protective oxide layer growth kinetics
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Harry, I. D. „Modification and characterisation of carbon fibre ion exchange media“. Thesis, Loughborough University, 2008. https://dspace.lboro.ac.uk/2134/14123.
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This thesis examines the use of electrochemically treated viscose rayon based activated carbon cloth (ACC) for the removal of metal ions from aqueous effluent streams. Two types of treatment were performed: (i) electrochemical oxidation and (ii) electrochemical reduction to enhance cation and anion sorption capacities of the ACC, respectively. Electrochemical oxidation resulted in a loss of 61% BET surface area due to blockage of pores through formation of carboxylic acidic groups but its cation exchange capacity and oxygen content increased by 365% and 121%, respectively. The optimum constant current at which a combination of applied current and oxidation time at any extent of oxidation to produce ACC of maximum cation exchange capacity was found to be 1.1 A, with voltage of 4.2 V and current density of 0.8 mA/m2. Batch sorption experiments showed that the maximum copper and lead sorption capacities for electrochemically oxidised ACC increased 17 and 4 times, respectively, for noncompetitive sorption and 8.8 and 8.6 times, respectively for competitive sorption. Therefore, electrochemically oxidised ACC is an effective adsorbent for treating aqueous solution contaminated with copper/lead in both single component and multi-component systems. Industrial wastewaters are multicomponent systems, therefore, electrochemical oxidation of ACC is an efficient way of enhancing lead and copper ions sorptive capacity for industrial wastewater treatment. Electrochemical reduction resulted in a loss of 28% BET surface area due to formation of ether groups but its anion exchange capacity increased by 292%. The optimum constant current at which a combination of applied current and reduction time at any extent of reduction to produce ACC of maximum anion exchange capacity was found to be 5.5 A, with voltage of 9.8 V and current density of 6.4 mA/m2. Batch sorption experiments showed that the maximum chromium(VI) sorption capacity for electrochemically reduced ACC increased 2.12 times, with highest maximum chromium(VI) sorption capacity of 3.8 mmol/g at solution pH 4. Most industrial wastewaters contaminated with chromium(VI) are highly acidic, therefore, electrochemical reduction of ACC is an efficient way of enhancing chromium(VI) sorptive capacity for industrial wastewater treatment.
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Sakout, Mohammed. „Contribution de la spectrométrie X à l'étude des degrés d'oxydation du vanadium et du chrome dans les oxydes mixtes de structure spinelle“. Rouen, 1989. http://www.theses.fr/1989ROUES002.
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Les déplacements chimiques expérimentaux observés à partir des spectres des oxydes simples et d'oxydes de Cr ou de V de structure spinelle à degré d'oxydation connu permettent d'établir une relation entre la valeur de ce déplacement chimique et le degré d'oxydation. Applications: 1) mise en évidence d'une très faible teneur en V (ii) dans les composés du système Fe(1+x)O(4) 2) dosage semiquantitatif du Cr (vi) dans les catalyseurs "chromite de cuivre"
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Varela, Júnior Jaldyr de Jesus Gomes. „DESEMPENHO DE ELETRODOS Pt/C, Pt3Cr/C E PtCr/C PARA APLICAÇÕES EM CÁTODOS DE CÉLULAS A COMBUSTÍVEL DE METANOL DIRETO“. Universidade Federal do Maranhão, 2006. http://tedebc.ufma.br:8080/jspui/handle/tede/928.
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Previous issue date: 2006-07-14This work presents oxygem reduction reaction (ORR) studies on platinum (Pt/C) and platinum-chromium alloys containing 50% (PtCr/C) or 70% in chromium (Pt3Cr) dispersed on high surface area, in acid aqueous solutions with and without metanol, with cyclic voltammetry, chronoamperometry and rotating disk electrode techniques. Electrochemical measurements have been also performed in a direct methanol unit fuel cell. The electrocatalysts were characterized by energy dispersive X-ray (EDX) and X-ray diffraction (XRD) analyses. The ORR studies in absence of methanol in solution showed that chromium adittion does not change the reaction mechanism observed on the Pt/C and the electrocatalytic activity increases in the order PtCr/C < Pt/C < Pt3Cr/C. Such increase was attributed to a favourable interatomic distance for O2 dissociative adsorption. The alloys showed higher tolerance to methanol presence in solution than Pt, mainly the PtCr electrode due to smaller amount of active sites to methanol adsorption with respect to Pt. In solutions containing low concentration of methanol, the ORR mechanism was not affected by methanol presence. The polarization curves recorded with the unit cell showed that na increase in temperature results in an increase in the electrocatalitic activity of the anode, as well as na increase in methanol diffusion through the Nafion® membrane with consequent cathode depolarization. Furthermore, the system containing Pt3Cr/C as cathodic electrode material presented the best electrochemical performance, with power densities of ~ 55 mW cm-2, in contrast to ~ 40 mW cm-2 for the unit cell with Pt/C cathode and ~ 20 mW cm-2 with PtCr/C.
This work presents oxygem reduction reaction (ORR) studies on platinum (Pt/C) and platinum-chromium alloys containing 50% (PtCr/C) or 70% in chromium (Pt3Cr) dispersed on high surface area, in acid aqueous solutions with and without metanol, with cyclic voltammetry, chronoamperometry and rotating disk electrode techniques. Electrochemical measurements have been also performed in a direct methanol unit fuel cell. The electrocatalysts were characterized by energy dispersive X-ray (EDX) and X-ray diffraction (XRD) analyses. The ORR studies in absence of methanol in solution showed that chromium adittion does not change the reaction mechanism observed on the Pt/C and the electrocatalytic activity increases in the order PtCr/C < Pt/C < Pt3Cr/C. Such increase was attributed to a favourable interatomic distance for O2 dissociative adsorption. The alloys showed higher tolerance to methanol presence in solution than Pt, mainly the PtCr electrode due to smaller amount of active sites to methanol adsorption with respect to Pt. In solutions containing low concentration of methanol, the ORR mechanism was not affected by methanol presence. The polarization curves recorded with the unit cell showed that na increase in temperature results in an increase in the electrocatalitic activity of the anode, as well as na increase in methanol diffusion through the Nafion® membrane with consequent cathode depolarization. Furthermore, the system containing Pt3Cr/C as cathodic electrode material presented the best electrochemical performance, with power densities of ~ 55 mW cm-2, in contrast to ~ 40 mW cm-2 for the unit cell with Pt/C cathode and ~ 20 mW cm-2 with PtCr/C.
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Michau, Alexandre. „Dépôts chimiques en phase vapeur de revêtements à base de chrome sur surfaces complexes pour environnements extrêmes : expérimental et simulation“. Thesis, Toulouse, INPT, 2016. http://www.theses.fr/2016INPT0088/document.
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La protection des gaines de combustible de réacteur nucléaire contre l’oxydation à haute température en conditions accidentelles est essentielle pour garantir leur intégrité, c’est-à-dire celle de la première barrière de confinement. Celle-ci peut s’effectuer par le dépôt d’un revêtement sur leur paroi interne et ce sont les procédés CVD qui sont les plus à même de le faire. Il s’agit plus précisément du procédé DLI-MOCVD qui a été utilisé ici pour déposer des revêtements à base de chrome (chrome métallique Cr(S) cristallisé) et de carbures de chrome (carbures de chrome CrxCy amorphes non recyclés, recyclés et CrxSizCy dopés au Si), réputés pour leur bonne résistance à l’oxydation. Afin d’améliorer la qualité des revêtements, le procédé de dépôt a été optimisé à l’aide de simulations numériques. Après une réflexion sur le mécanisme chimique, un modèle cinétique réactionnel du dépôt d’un revêtement CrxCy amorphe a pu être ajusté et validé. Il a aussi été montré que la solution utilisée de précurseur organométallique bis(arène)chrome et de solvant toluène pouvait être directement recyclée, augmentant ainsi le potentiel d’industrialisation du procédé. Les propriétés physico-chimiques et structurales des revêtements déposés avec ce procédé ont été caractérisées. Une étude des propriétés mécaniques de ces revêtements a par ailleurs été entreprise. Il en ressort que, comparés à des revêtements apparentés déposés par d’autres procédés, ceux déposés par DLIMOCVD possèdent notamment une dureté élevée (jusqu’à une trentaine de GPa), des contraintes résiduelles en compression, une bonne adhérence avec leur substrat et enfin une résistance à l’usure abrasive différente suivant la température. L’évaluation de leur résistance à l’oxydation à 1200 °C a révélé les excellentes performances des revêtements en carbures de chrome amorphes, qui permettent de retarder l’oxydation catastrophique de plus de deux heures pour une épaisseur de 10 µm. Tous les autres revêtements augmentent la tenue en température des substrats en zircaloy mais ne retardent pas autant l’oxydation catastrophiqueNuclear fuel cladding tubes resistance against high temperature oxidation during accident conditions is crucial because it means protecting the first containment barrier. This can be done by coating the inner wall of the cladding tube with CVD processes, which are most likely to do so. More specifically, we used DLI-MOCVD to grow chromium based (Cr(S), metallic crystalline chromium) and chromium carbides based (amorphous chromium carbides CrxCy, recycled CrxCy, silicon doped CrxSizCy) coatings, known for their good oxidation resistance. The coating process was optimized using numerical modelling to improve coatings performance. A reaction kinetics model of the deposition process of amorphous CrxCy coatings was adjusted and validated after the identification of the chemical mechanism. It was also shown that the liquid solution containing organometallic precursor (bis(arene)chromium) and solvent (toluene) could be directly recycled, thereby increasing the industrialization potential of such process. Physical, chemical and structural properties of coatings deposited with this process were characterized. A study of the coatings mechanical properties has also been undertaken. It shows that compared to related coatings grown with other processes, those deposited by DLI-MOCVD exhibit a particularly high hardness (up to 30 GPa), compressive residual stresses, good adhesion with the substrate and finally a different abrasive wear resistance depending on the temperature. The assessment of their oxidation resistance at 1200 °C revealed excellent performances of amorphous chromium carbides coatings, which can delay catastrophic oxidation up to two hours with only a 10 µm thickness. All the other coatings only increase the thermal resistance of zircaloy substrates
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FERNANDES, STELA M. de C. „Influencia de terras-raras sobre a oxidacao de ligas formadoras de cromia“. reponame:Repositório Institucional do IPEN, 1999. http://repositorio.ipen.br:8080/xmlui/handle/123456789/10780.
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Tese (Doutoramento)
IPEN/T
Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP
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Wongpromrat, Wichitra. „Étude de la sublimation du chrome lors de l’oxydation haute température de l’alliage AISI 441 et recherche de solutions de protection“. Thesis, Université Grenoble Alpes (ComUE), 2015. http://www.theses.fr/2015GREAI070/document.
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Les aciers inoxydables ferritiques sont actuellement les meilleurs candidats pour répondre au cahier des charges des matériaux destinés aux interconnexions de piles à combustibles à oxyde solide (SOFC acronyme anglo-saxon pour Solid Oxide Fuel Cell). Cependant, du coté du compartiment cathodique de ces piles, le phénomène de sublimation du chrome à haute température conduit à des dégradations importantes, réduisant ainsi la durée de vie en service des SOFC. Les objectifs de ce travail de thèse sont (i) d'étudier le phénomène de sublimation du chrome sur l'acier inoxydable ferritique AISI 441 et (ii) de rechercher le ou les moyen(s) d'atténuer cette même sublimation. Sur le deuxième point, des méthodes de protection ont été mises en œuvre, en particulier avec le dépôt de films minces de spinelle Mn-Co obtenues via un procédé de galvanoplastie ou bien encore en procédant à des pré-oxydations des alliages dans des atmosphères contrôlées de type argon impur ou mélanges gazeux équimolaires CO / CO2 (250 ° C et 850 ° C, pour une durée totale de 3 h).Concernant l'étude de la sublimation du chrome, des essais d'oxydation simulant les conditions de service ont été conduites dans des mélanges gazeux : 5% de O2 dans H2O à 800 °C pendant 96 h. A vitesse de gaz oxydants faible, de 1 à 3 cm / s, la sublimation du chrome est limitée par un phénomène de diffusion dans la phase gazeuse de l'espèce volatile oxo-hydroxyde de chrome. A vitesse plus élevée, de 3 à 10 cm / s, la sublimation du chrome semble limitée par un phénomène interfacial. La vitesse de sublimation apparait indépendante de la rugosité de surface des échantillons, elle même variant selon la préparation des échantillons. Du point de vue de la caractérisation morphologique des couches d'oxydation thermiques obtenues, sur les surfaces de plus forte rugosité (surface industrielle), nous avons noté le développement de nodules riches en titane et en niobium avec une partie externe et une autre interne. Dans le substrat, des phases de lave de type Fe2Nb ont été observées le long des joints de grain métalliques.Dans une deuxième partie, la sublimation du chrome a été étudiée sur échantillons revêtus ou pré-oxydés. Les films minces de spinelle Mn-Co ne conduisent pas à l'abaissement de la vitesse de sublimation du chrome et sont donc pas protecteurs. L'adhérence de ces revêtements est de mauvaise qualité. Les couches présentent de nombreuses fissures. La pré-oxydation conduit quant à elle à une réduction considérable (jusqu'à un facteur 10) de la vitesse de sublimation du chrome (sauf dans le cas de la pré-oxydation dans l'argon à 850 °C). La formation d'un film riche en fer obtenu à basse température (250 °C) peut expliquer cette réduction par l'établissement d'une barrière de diffusion. Cette même réduction est cependant surprenante sur les films riches en chrome obtenus par pré-oxydation à 850 °C dans CO / CO2. Nous proposons dans ce travail une interprétation originale basée sur les différences de nature semi-conductrice des films de chromine formées à haute pression d'oxygène (proche de l'atmosphère) et identifiés comme étant de type p par rapport à ceux obtenus à basse pression (dans CO/CO2) qui sont connu pour être de type n. Après l'oxydation à haute température de 96 heures, tous les échantillons préalablement pré-oxydés ont été observés comme étant composés d'oxyde de chrome et d'un spinelle Mn-Cr.Au terme de ce travail de thèse, il peut être conclu que la pré-oxydation de l'alliage 441 à basse température (250 °C) dans l'argon ou le mélange CO/CO2 ou encore à plus haute température (850 °C) dans le mélange CO/CO2 sont des traitements qui conduisent à l'abaissement de la vitesse de sublimation du chrome et par voie de conséquence à l'amélioration de la tenue de cet alliage en condition d'oxydation dans le compartiment cathodique des SOFCFerritic stainless steels are the most attractive materials that are able to fulfil SOFC(Solid Oxide Fuel Cell) interconnect properties. However, in cathodic SOFC condition, Crvolatilisation from ferritic steels leads to degradations of interconnect and cathode materialsand shorter service lifetime of SOFC. The objectives of this work are (i) to study Crvolatilisation from AISI 441 ferritic stainless steel and (ii) to find the way out to suppress Crvolatilisation. The Cr volatilisation protective methods used in this work were coating withMn-Co spinel by an electroplating method and preoxidation in the condition of Ar or CO/CO2at either 250°C or 850°C, for 3 h. Cr volatilisation experiments were performed in 5%H2O inO2 at 800°C for 96 h. According to the results, it can be concluded that the preoxidation ofthe AISI 441 in Ar or CO/CO2 at low temperature (250°C) or in the CO/CO2 at a highertemperature (850°C) are treatments that lead to lowering the sublimation rate of the Cr andimprovement in the oxidation resistance of this alloy in the cathodic compartment of theSOFC
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Othman, Norinsan Kamil Materials Science & Engineering Faculty of Science UNSW. „Steam effects on cyclic oxidation of chromia forming alloys“. Awarded by:University of New South Wales. Materials Science & Engineering, 2009. http://handle.unsw.edu.au/1959.4/44528.
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High temperature oxidation of Fe-Cr alloys with Cr levels of 9-30 wt% has been investigated by using isothermal and cyclic experiments at 600, 700 and 950??C. The mixed gases Ar-20%02, Ar-20%02H20, Ar-5%02-20%H20, Ar-10%H2-5%H20 and Ar-10% H2-20%H20 at total pressure of I atm were used. The effect of lanthanum alloying on Fe-Cr alloy oxidation was also studied. In general, increasing alloy chromium levels reduced the oxidation rate. In isothermal oxidation at 700??C, a protective chromia layer was formed in dry oxygen for Fe9Cr. Alloys with Cr???17% formed protective chromia layers in all gas mixtures. In thermal cyclic oxidation, at high Po2, the 9%Cr alloy exhibited breakaway oxidation at an early stage of the reaction at all reaction temperatures. However, for Cr???17%, no breakaway oxidation occurred, and the weight gains were very low at temperatures of 950 and 700?? C. At 600??C, breakaway oxidation was observed on all Fe-Cr alloys in Ar-20%02 and Ar-20%02-5%H20 gases due to scale spallation and the low alloy Cr diffusivity which slows the chromia scale re-healing. Introducing water vapour lo Ar-02 and Ar-H2 accelerated the oxidation of alloys containing ???17% Cr. However, this accelerating effect was not evident for Fe25Cr alloy at 700 and 950??C. At low Po2, breakaway oxidation of alloys with Cr???17% occurred, very early in Ar-10%H2-20%H20 and after 300 cycles in Ar-IO%H2-5%H20. The addition of lanthanum to Fe9Cr and Fe 17Cr led to increased oxidation rates due to enhanced inward oxygen transport, leading to faster scaling, and rapid consumption of chromium at the alloy surface in high H20containing gases in Ar-5%02 and Ar-10%H2 at 700??C. However, the presence of lanthanum in Fe25Cr-0.09La retarded the growth of both Fe-rich oxide and chromia, which in turn decreased the oxidation rate.
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Bataillou, Léa. „Modélisation de l'oxydation à haute température des alliages Ni-Cr“. Thesis, Toulouse, INPT, 2019. http://www.theses.fr/2019INPT0104/document.
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Il est important pour l’industrie nucléaire de mener des études amont pour mieux appréhender les phénomènes en lien avec la corrosion des alliages chromino-formeurs. Cette étude a pour objectif de mieux comprendre les paramètres influant sur les mécanismes et la cinétique de croissance des couches de chromine formées par oxydation à haute température. Ce travail s’articule en deux parties complémentaires : une partie de modélisation qui est focalisée sur les aspects cinétiques, et une partie expérimentale axée sur la compréhension des mécanismes de croissance de la chromine. La partie modélisation a pour objectif de prendre en compte l’effet des courts-circuits de diffusion dans la description des cinétiques de croissance de la chromine. Le but est d’évaluer quantitativement comment une diffusion mixte par le volume et les joints de grains peut influencer la cinétique de croissance d’une couche d’oxyde dont la microstructure évolue avec le temps. Ce travail a été réalisé à l’aide de modèles analytiques et grâce à de nouveaux développements d’un modèle numérique existant (EKINOX). Plusieurs lois de croissance de grains ont été étudiées (croissance parabolique, croissance cubique et prise en compte de l’existence d’un gradient de taille de grains dans la couche d’oxyde). Une étude paramétrique a été réalisée pour étudier l’influence de la vitesse de croissance des grains sur la cinétique de croissance de la couche de chromine. Ces simulations ont permis d’évaluer la déviation de lacinétique d’oxydation par rapport à la loi parabolique simple suivant la vitesse de croissance des grains d’oxyde, choisie comme donnée d’entrée du modèle. Ces calculs permettent également d’évaluer les ordres de grandeurs de la durée du régime transitoire durant lequel l’évolution de la taille de grains de l’oxyde influence la cinétique d’oxydation de façon significative. Les cinétiques d’oxydation calculées pour les différents cas étudiés ont été extrapolées à l’aide des méthodes classiquement utilisées dans le domaine de l’oxydation à haute température : la méthode « log-log» et la méthode dite du « kp local ». La comparaison des extrapolations et des solutions exactes permet de proposer des « bonnes pratiques » à adopter pour interpréter les cinétiques d’oxydation expérimentales. Dans la partie expérimentale de ce travail, des essais d’oxydation d’un alliage modèle Ni-30Cr à 700°C sous atmosphère d’argon technique (10-5 atm de O2) ont été réalisés en thermobalance pour des durées allant de 30 minutes à 50 heures. La couche de chromine formée à l’issue de ces essais a été finement caractérisée afin de déterminer le mécanisme d’oxydation ainsi que l’étape cinétiquement limitante. Dans les conditions de l’étude, la couche d’oxyde formée a été identifiée comme étant de la chromine de structure corindon dont les grains adoptent une orientation préférentielle de croissance <0001>. La cinétique d’oxydation suit une loi parabolique au terme d’un régime transitoire de 3 h environ. La valeur de la constante cinétique parabolique kp a été évaluée pendant le régime stationnaire et est égale à 10-15 cm2 s-1. Des expériences d’oxydation séquencée et de marqueurs ont également été réalisées. Elles ont permis de mettre en évidence une croissance anionique de la couche de chromine. La croissance de l’oxyde apparait, selon les essais de marquage isotopique dans 18O2, contrôlée par la diffusion de l’oxygène par les joints de grains et le volume de l’oxyde. Les analyses complémentaires des couches d’oxyde, par photoélectrochimie, suggèrent que le défaut majoritaire permettant cette diffusion est la lacune d’oxygène. Enfin, la morphologie de la couche d’oxyde indique une croissance plus rapide de la couche au niveau des joints de grains de métalThis thesis aims to better understand the kinetics and mechanisms of growth of chromia scales. This work is articulated in two complementary parts, on the one hand a modeling part which studies the kinetic aspects, and on the other hand an experimental part centered on the characterization of chromia growth understanding of the mechanisms. The purpose of the modeling part is to take into account the effect of diffusion short circuits in chromia the growth kinetics. The aim is to understand how a dual diffusion by both volume and grain boundaries can impact oxidation kinetics. This approach helps to define "good practices" for experimental oxidation kinetics interpretation. This modeling work was done using analytical models EKINOX numerical model. Several grain growth laws have been studied (parabolic growth, cubic growth, and grain size gradient). In addition, a parametric study was carried out to study the influence of grain growth rate on the growth kinetics of chromia. Calculations of oxidation kinetics for the various cases treated made it possible to conclude that the taking into account diffusion short circuits and their proportion evolution in time generates a deviation of the oxidation kinetics from a simple parabolic law. The rate of oxidation kinetics calculated varies with the growth rate of the oxide grains chosen as input data of the modelling. When kinetics are treated using a kinetic law involving a growth rate that changes over time, it is possible to determine the time range for which the evolution of oxide grain size significantly influences the oxidation kinetics. The oxidation kinetics modeled for the different cases were extrapolated using the methods conventionally used in high temperature oxidation, the log-log method and the local kp method. To extrapolate experimental kinetics, it is recommended to use the local kp method beforehand in order to know if the steady state has been reached. For the second experimental part, oxidation tests of the model alloy Ni-30Cr at 700°C in technical argon atmosphere were carried out. The chromia layer formed at the end of these tests was finely characterized in order to determine the oxidation mechanism as well as the kinetically limiting step. Under the conditions of the study, the nature of the oxide layer was identified as chromia. The oxidation kinetics follows a parabolic law after a transient stage that lasts about 3 hours. The stationary kp value has been determined. The mechanism of chromia growth has been identified as the diffusion of oxygen by the grain boundaries and the volume of the oxide. The morphology of the oxide layer indicates a faster oxidation over the grain boundaries of the metal. Finally, the chromine grains adopt a preferential orientation in the <0001> direction of the corundum structure. Chromium depletion profiles have been determined in the metal substrate and indicate a more pronounced chromium depletion at the grain boundaries of the metal. The type of semiconduction was determined in chromine and reveals an n-type semiconduction for an oxidation time of 7 h and an n-type and insulating semiconduction for an oxidation time of 50 h
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Conrath, Élodie. „Élaboration et caractérisation de superalliages base chrome pour utilisation lors du fibrage centrifuge du verre à très haute température“. Thesis, Université de Lorraine, 2016. http://www.theses.fr/2016LORR0018.
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Le procédé industriel TEL permet de fabriquer de la laine de verre en fibrant du verre en fusion. La pièce principale de ce procédé est « l’assiette de fibrage », qui est soumise à de nombreuses contraintes en service (oxydation, corrosion, érosion et fluage). Elle est actuellement élaborée par fonderie et réalisée en superalliage base nickel ou base cobalt. Fibrer de nouveaux types de verre impliquant des températures de travail plus élevées nécessite un nouveau type de superalliage. Le chrome est un candidat idéal pour être l’élément principal d’une assiette de par sa haute température de fusion et de par la résistance qu’il apporte aux superalliages usuels contre l’oxydation et la corrosion grâce à la formation d'une couche de chromine continue à la surface des alliages. Durant ces travaux de doctorat, une centaine d'alliages base chrome de compositions différentes ont été réalisés par fonderie. La découpe de tels alliages a montré un fort manque de ductilité à température ambiante. Des tests de dureté à température ambiante, d'oxydation et de fluage à haute température ont été menés. Une caractérisation métallographique complète a été réalisée sur ces alliages (DRX, MEB, microsonde de Castaing) à l'état brut de coulée, après recuit isotherme et après oxydation isotherme. L’étude approfondie d’alliages simples a permis de découvrir des compositions permettant de régler le problème de fragilité. Les alliages ont ensuite été complexifiés avec l'ajout d'autres éléments, permettant alors de corriger certains problèmes inhérents à des alliages à base de chromeThe TEL process is used to produce glass wool at very high temperature. The main piece of this process is the “spinner”, which is exposed, in service, to numerous operating constraints (oxidation, corrosion, erosion and creep). This spinner is currently made of cobalt- or nickel-based superalloys and is fabricated by casting. To fiberize new glasses or to increase the current maximal fiberizing temperature, a new type of superalloy is required. Chromium is an ideal candidate to be the principal element of a new superalloy because of its very high melting point and its ability to develop a chromia protective scale against oxidation and corrosion at high temperature, reason for which it is usually added to many classical superalloys. During this Ph.D work, the synthesis and the study of more than a hundred of chromium-based alloys with different chemical compositions was done by casting. These alloys are brittle at room temperature during their cutting. Laboratory tests of hardness at room temperature, oxidation and 3 points flexural creep at high temperature were performed. Metallographic characterisations were carried out (XRD, SEM, EPMA) on all alloys in their as-cast state, after isothermal annealing or isothermal oxidation. The detailed study of simple alloys permitted to discover some compositions removing the brittleness problem of these alloys. Then, the enrichment of the composition of the alloys by addition of new elements, allowed to correct some inherent problems of chromium-based alloys
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Woodbridge, Nesta. „Mechanistic studies relevant to chromate toxicity“. Thesis, Imperial College London, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.267077.
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Pansani, Mariele Castilho. „Efeito da suplementação de cromo na resistência insulínica, na dislipidemia, na inflamação e no estresse oxidativo de pessoas HIV-positivo com lipodistrofia“. Universidade de São Paulo, 2017. http://www.teses.usp.br/teses/disponiveis/17/17138/tde-24042018-174804/.
Annotation:
Introdução: Os antirretrovirais (ARV) levam ao desenvolvimento de alterações metabólica, composta por dislipidemias, intolerância à glicose, resistência insulínica, hipertensão e lipodistrofia, associadas ao aumento do risco de doenças cardiovasculares. O cromo é um mineral essencial envolvido no metabolismo dos carboidratos e lipídeos. Ele está relacionado com a melhora da sensibilidade insulínica, das anormalidades metabólicas e da composição corporal. Objetivo: Avaliar o efeito da suplementação com cromo em pessoas HIV-positivo com lipodistrofia em TARV em marcadores do metabolismo da glicose, do metabolismo dos lipídeos, de inflamação e de estresse oxidativo. Materiais e Métodos: Neste estudo de intervenção, duplo-cego, placebo foi avaliado 41 voluntários HIV-positivo com lipodistrofia em TARV. Os voluntários foram randomizados em 2 grupos, 19 no grupo placebo e 22 no grupo cromo. O grupo cromo recebeu 200µg/dia de cromo (Cr3+) quelato 10% por 3 meses. Antes e após intervenção, todos os voluntários foram submetidos às avaliações clínica, nutricional e bioquímica. As variáveis analisadas foram: resistência insulínica, perfil lipídico, composição corporal, marcadores de inflamação e de estresse oxidativo. Resultados: Os participantes tinham idade (média ± DP) de 47,09 ± 8,15 anos. A composição corporal e os marcadores de inflamação e estresse oxidativo não sofreram alterações após intervenção. Glicemia, insulina, triglicerídeos e o colesterol total e frações, também, não sofreram alterações significativas após 3 meses de suplementação com cromo. No entanto, os participantes que apresentam LDL colesterol alterado (>= 130mg/dL), a suplementação com cromo foi capaz de reduzir 31,2 mg/dL (p = 0,049, de 176,6 (43,2) mg/dL para 145,4 (32,10) mg/dL). Apesar de não significativo (p = 0,27, de 244,1 (47,1) mg/dL para 220,8 (32,5) mg/dL), a média do colesterol total reduziu 23,8 mg/dL no grupo cromo com colesterol alterado (CT > 200mg/dL). Conclusão: A suplementação de cromo por 3 meses reduziu os níveis de LDL colesterol nos voluntários com hiperlipidemia. Esses resultados sugerem que o tratamento com cromo pode beneficiar indivíduos HIV-positivo com lipodistrofia, sobretudo, aqueles com LDL colesterol aumentado.Introduction: Antiretroviral therapy (HAART) leads to the development of metabolic changes, including dyslipidemia, glucose intolerance, insulin resistance, hypertension and lipodystrophy, associated with an increased risk of cardiovascular diseases. Chromium is an essential mineral involved in the metabolism of carbohydrates and lipids. The role of chromium is associated to the improvement of insulin sensitivity, metabolic abnormalities and body composition. Objective: Evaluate the effect of chromium supplementation in HIVpositive peoples with lipodystrophy on HAART in glucose metabolism, lipid metabolism, inflammation and oxidative stress markers. Materials and Methods: The current study is a randomized, double-blind, placebo-controlled trial, with subjects receiving 200 ?g / day of chromium (Cr3+) chelate 10% or placebo for 3 months. Forty-one (n = 41) HIV-positive 41 HIV-positive volunteers with lipodystrophy on HAART were randomized into 02 groups, placebo (n = 19) and Chromium (n = 22). Before and after intervention, all volunteers were submitted to clinical, nutritional and biochemical evaluations. Analyzed variables: insulin resistance, lipid profile, body composition, markers of inflammation and oxidative stress. Results: The volunteers\' average age were 47.09 ± 8.15 (mean ± SD) years. Body composition, inflammatory and oxidative stress markers did not change by the intervention. In addition, glycemia, insulin, triglycerides and total cholesterol and fractions did not change after 3 months of chromium supplementation. Although, in subjects with altered LDL cholesterol (>= 130 mg/dL), chromium supplementation were able to reduce 31.2 mg / dL (P = 0.049, from 176.6 (43.2) mg/dL to 145, 4 (32.10) mg/dL). Even if not significant, mean total cholesterol (p = 0.27, from 244.1 (47.1) mg/dL to 220.8 (32.5) mg/dL) decreased 23.8 mg/dL Chromium group with altered cholesterol (TC > 200 mg/dL). Conclusion: Chromium supplementation for 3 months reduced LDL cholesterol levels in subjects with hyperlipidemia. These results suggest that chromium treatment may benefit HIV-positive individuals with lipodystrophy, especially those with increased LDL cholesterol.
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Delaunay, François. „Etude de l'influence des éléments mineurs d'addition sur l'oxydation à haute température d'alliages base nickel“. Rouen, 1997. http://www.theses.fr/1997ROUES029.
Annotation:
La compréhension des phénomènes d'oxydation à haute température des alliages base nickel revêt un intérêt particulier pour l'industrie nucléaire. Les performances de ces alliages, tout comme celles des aciers, sont fortement influencées par les différents éléments mineurs d'addition. Six alliages commerciaux ont été traités entre 800°C et 1000°C sous air et étudiés à l'aide des méthodes d'analyse complémentaires suivantes : spectroscopie de photoélectrons induits par un rayonnement X, spectroscopie infrarouge à transformée de Fourier, diffraction des rayons X et microscopie électronique à balayage couplée avec un système d'analyse en énergie des rayons X émis. Les résultats obtenus mettent en évidence le rôle très important des éléments mineurs d'addition que sont le manganèse, le silicium, le titane, l'aluminium et le niobium sur les mécanismes d'oxydation. La diffusion rapide du manganèse et du titane à travers la phase rhomboédrique formée initialement, conduit à la formation d'une couche d'oxydes de structure duplex. L'oxydation intergranulaire du titane et de l'aluminium est substantielle et peut être corrélée avec l'épaisseur de la zone affectée par la déplétion en chrome dans l'alliage sous-jacent. Le silicium favorise la formation du chromite de manganèse, cependant, le développement d'une couche continue de silice à l'interface oxyde-alliage ralentit la cinétique d'oxydation. La présence de niobium semble également avoir un effet bénéfique sur la résistance à l'oxydation. La comparaison de ces résultats avec ceux obtenus sur des aciers ferritiques et austénitiques étudiés au laboratoire et avec ceux issus de la littérature permet d'apporter des informations qualitatives concernant la vitesse de diffusion des différents éléments en fonction de la matrice. Ainsi, dans les aciers ferritiques, ou les vitesses de diffusion sont plus élevées que dans les matrices austénitiques, la diffusion du titane est plus rapide que celle du manganèse. Dans les aciers austénitiques, ces deux éléments diffusent à des vitesses comparables alors que dans les alliages base nickel, le manganèse diffuse plus vite que le titane.
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Alexiou, Amanda Elton. „The effects of chromia coatings on the oxidation characteristics on Ni and Ni-20Cr“. Thesis, Georgia Institute of Technology, 1998. http://hdl.handle.net/1853/15046.
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Karamullaoglu, Gulsun. „Dynamic And Steady-state Analysis Of Oxidative Dehydrogenation Of Ethane“. Phd thesis, METU, 2005. http://etd.lib.metu.edu.tr/upload/12606269/index.pdf.
Annotation:
In this research, oxidative dehydrogenation of ethane to ethylene was studied over Cr-O and Cr-V-O mixed oxide catalysts through steady-state and dynamic experiments. The catalysts were prepared by the complexation method. By XRD, presence of Cr2O3 phase in Cr-Oand the small Cr2O3 and V2O4 phases of Cr-V-O were revealed. In H2-TPR, both catalysts showed reduction behaviour. From XPS the likely presence of Cr+6 on fresh Cr-O was found. On Cr-V-O, the possible reduction of V+5 and Cr+6 forms of the fresh sample to V+4, V+3 and Cr+3 states by TPR was discovered through XPS. With an O2/C2H6 feed ratio of 0.17, Cr-O exhibited the highest total conversion value of about 0.20 at 447°
C with an ethylene selectivity of 0.82. Maximum ethylene selectivity with Cr-O was obtained as 0.91 at 250°
C. An ethylene selectivity of 0.93 was reached with the Cr-V-O at 400°
C. In the experiments performed by using CO2 as the mild oxidant, a yield value of 0.15 was achieved at 449°
C on Cr-O catalyst. In dynamic experiments performed over Cr-O, with C2H6 pulses injected into O2-He flow, the possible occurrence of two reaction sites for the formation of CO2 and H2O was detected. By Gaussian fits to H2O curves, the presence of at least three production ways was thought to be probable. Different from Cr-O, no CO2 formation was observed on Cr-V-O during pulsing C2H6 to O2-He flow. In the runs performed by O2 pulses into C2H6-He flow over Cr-V-O, formation of CO rather than C2H4 was favored.
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Gheno, Thomas. „Oxydation et carburation d'alliages modèles chromino-formeurs dans le dioxyde de carbone“. Thesis, Toulouse, INPT, 2012. http://www.theses.fr/2012INPT0060/document.
Annotation:
La capture du carbone de combustion implique le transport de gaz riches en CO2 a haute temperature. Cette etude vise a preciser les facteurs controlant l'oxydation d'alliages chromino-formeurs dans ces environnements. Des alliages modeles Fe–Cr et Fe–Cr–Ni ont ainsi ete exposes a des melanges Ar–CO2–H2O a 650 et 800 °C, et les produits de reaction examines a l'aide de techniques de metallographie conventionnelles. La precipitation de carbures sous des couches d'oxyde indique une sursaturation en carbone a l'interface metal/oxyde, par rapport a l'atmosphere exterieure. Sur la base d'un modele d'equilibre thermodynamique local, les vitesses de carburation et fractions volumiques de precipites mesurees sont utilisees pour evaluer l'influence de la composition de l'oxyde et de la presence d'H2O dans le gaz sur le transport du carbone. En analysant la depletion en chrome dans l'alliage sous-jacent, nous montrons que la carburation limitee sous une couche de chromine n'altere pas la stabilite de l'oxyde. L'evolution morphologique des nodules d'oxydes riches en fer formes a la suite de la rupture localisee de la chromine est mise en relation avec la capacite de l'alliage a fournir du chrome a l'interface metal/oxyde. L'application de modeles de germination-croissance aux cinetiques de developement de nodules permet d'evaluer la resistance des couches de chromine via des frequences de germination determinees a partir des taux de recouvrement de nodules et des gains de masse des echantillons. Nous examinons enfin l'importance relative de la germination et de la croissance des nodules dans le controle de la performance globale des alliages en fonction de la temperature de reactionMaterials to convey hot CO2-rich gases are needed in carbon capture technologies currently being developed. This work is aimed at investigating the factors controlling the oxidation of chromia-forming alloys in these atmospheres. To do so, model Fe–Cr and Fe–Cr–Ni alloys were exposed to Ar–CO2–H2O gas mixtures at 650 and 800 °C,and the reaction products examined using conventional metallography techniques. Carbide precipitation beneath oxide scales reflects a carbon supersaturation at the metal/oxide interface relative to the external atmosphere: as a gradient of oxygen potential is established across the growing scale, an elevated carbon activity results at the interface if the scale transmits carbon. On the basis of a local equilibrium model, measured carburisation rates and precipitate volume fractions were used to evaluate the influence of oxide composition and of the presence of H2O in the gas on carbon uptake/transport in the scales. Limited carburisation beneath Cr2O3 scales was shown by means of an analysis of subscale chromium depletion not to alter the oxide stability. The morphological evolution of Fe-rich oxide nodules formed as a result of localised Cr2O3 failure was studied in relation to the alloy ability to supply chromium to the metal/oxide interface. Application of nucleation-growth models to the kinetics of nodule development allowed the resistance of Cr2O3 scales to be evaluated in terms of nodule nucleation rates determined from experimental nodule surface coverages and specimen weight gains. The relative importance of nodule nucleation and growth in determining the overall alloy performance as a function of reaction temperature is discussed