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No Rio Grande do Sul opera uma planta piloto que incinera resíduos do setor coureirocalçadista; o processo de gaseificação e combustão gera uma cinza contendo alto teor de cromo (~55% Cr2O3). O objetivo do presente trabalho foi avaliar a possibilidade de aproveitamento do cromo da “cinza de couro” na produção de aço inoxidável (no reator Forno Elétrico a Arco), utilizando-se como ferramenta a Termodinâmica Computacional. Inicialmente fez-se um estudo sobre os fundamentos termodinâmicos dos sistemas envolvidos. Partiu-se de sistemas simples, com grau crescente de complexidade, avaliando-se a possibilidade de redução do Cr2O3(s) presente na cinza. Após esse estudo, foram realizadas simulações. Nas proporções analisadas, os resultados mostram que não acontece incorporação de cromo ao banho com a adição da cinza, na temperatura de 1600 ºC, pois a escória é saturada em cromo. Na temperatura de 1700 ºC é possível a adição de certa quantidade de cinza, mas, no entanto, sob condições muito especiais, e com baixo rendimento (no melhor resultado obtido, apenas 6% do cromo adicionado através da cinza de couro é incorporado à fase banho). Verificou-se ainda que variar a basicidade da escória causa efeito bastante significativo no retorno de cromo ao banho. Se a cinza de couro for adicionada a um sistema escória-banho que inicialmente contém pouco cromo (é o caso de aços baixa liga), a maior parte do cromo adicionado é incorporada ao banho. Ou seja, adicionar Cr2O3(s) em escória de aços que tem como especificação baixos teores de cromo resulta em melhor aproveitamento do cromo da cinza. Quanto ao sistema CaO-SiO2-CrOx-MgO , verificou-se que a existência de magnésio leva à formação de picrocromita (MgO.Cr2O3), fase de difícil redução pelo silício. Adicionando-se ainda alumina a esse sistema, não se observaram mudanças significativas. / In Rio Grande do Sul State (Brazil) has been working a pilot plant that burns footwear leather waste. The gasification/combustion process generates an ash with high chromium content (~55% Cr2O3). The aim of this work was to evaluate the possibility of using the “leather ash” in the stainless steel production (in the Eletric Arc Furnace), with the aid of computational thermodynamics. The thermodynamic fundamentals of the involved systems were investigated. The possibility of reduction of the Cr2O3(s) present in the ash was evaluated starting at simpler systems, with increasing degree of complexity. After this preliminary study was done, the simulations were carried through. The results showed that incorporation of chromium to the bath by ash addition does not happen in the temperature of 1600ºC, since the slag is saturated in chromium. In the temperature of 1700ºC, it is possible the addition of certain amount of ash, however with low income (in the best result, only 6% of chromium added through the leather ash was incorporated to the bath). It was showed that slag basicity causes a significant effect in the return of chromium to the bath. If the leather ash is added to a slag-metal system which does not contain chromium, or which contains only a low quantity of chromium, the majority of the added chromium will be incorporated to the bath. Thus, Cr2O3(s) addition can be carried out for the production of another kinds of steel (with lower chromium content). It has been verified that magnesium leads to the picrochromite (MgO.Cr2O3) formation; for this phase, the reduction by silicon is not possible. Adding aluminium to the slags results in no significant changes observed.

No Rio Grande do Sul opera uma planta piloto que incinera resíduos do setor coureirocalçadista; o processo de gaseificação e combustão gera uma cinza contendo alto teor de cromo (~55% Cr2O3). O objetivo do presente trabalho foi avaliar a possibilidade de aproveitamento do cromo da “cinza de couro” na produção de aço inoxidável (no reator Forno Elétrico a Arco), utilizando-se como ferramenta a Termodinâmica Computacional. Inicialmente fez-se um estudo sobre os fundamentos termodinâmicos dos sistemas envolvidos. Partiu-se de sistemas simples, com grau crescente de complexidade, avaliando-se a possibilidade de redução do Cr2O3(s) presente na cinza. Após esse estudo, foram realizadas simulações. Nas proporções analisadas, os resultados mostram que não acontece incorporação de cromo ao banho com a adição da cinza, na temperatura de 1600 ºC, pois a escória é saturada em cromo. Na temperatura de 1700 ºC é possível a adição de certa quantidade de cinza, mas, no entanto, sob condições muito especiais, e com baixo rendimento (no melhor resultado obtido, apenas 6% do cromo adicionado através da cinza de couro é incorporado à fase banho). Verificou-se ainda que variar a basicidade da escória causa efeito bastante significativo no retorno de cromo ao banho. Se a cinza de couro for adicionada a um sistema escória-banho que inicialmente contém pouco cromo (é o caso de aços baixa liga), a maior parte do cromo adicionado é incorporada ao banho. Ou seja, adicionar Cr2O3(s) em escória de aços que tem como especificação baixos teores de cromo resulta em melhor aproveitamento do cromo da cinza. Quanto ao sistema CaO-SiO2-CrOx-MgO , verificou-se que a existência de magnésio leva à formação de picrocromita (MgO.Cr2O3), fase de difícil redução pelo silício. Adicionando-se ainda alumina a esse sistema, não se observaram mudanças significativas. / In Rio Grande do Sul State (Brazil) has been working a pilot plant that burns footwear leather waste. The gasification/combustion process generates an ash with high chromium content (~55% Cr2O3). The aim of this work was to evaluate the possibility of using the “leather ash” in the stainless steel production (in the Eletric Arc Furnace), with the aid of computational thermodynamics. The thermodynamic fundamentals of the involved systems were investigated. The possibility of reduction of the Cr2O3(s) present in the ash was evaluated starting at simpler systems, with increasing degree of complexity. After this preliminary study was done, the simulations were carried through. The results showed that incorporation of chromium to the bath by ash addition does not happen in the temperature of 1600ºC, since the slag is saturated in chromium. In the temperature of 1700ºC, it is possible the addition of certain amount of ash, however with low income (in the best result, only 6% of chromium added through the leather ash was incorporated to the bath). It was showed that slag basicity causes a significant effect in the return of chromium to the bath. If the leather ash is added to a slag-metal system which does not contain chromium, or which contains only a low quantity of chromium, the majority of the added chromium will be incorporated to the bath. Thus, Cr2O3(s) addition can be carried out for the production of another kinds of steel (with lower chromium content). It has been verified that magnesium leads to the picrochromite (MgO.Cr2O3) formation; for this phase, the reduction by silicon is not possible. Adding aluminium to the slags results in no significant changes observed.

No Rio Grande do Sul opera uma planta piloto que incinera resíduos do setor coureirocalçadista; o processo de gaseificação e combustão gera uma cinza contendo alto teor de cromo (~55% Cr2O3). O objetivo do presente trabalho foi avaliar a possibilidade de aproveitamento do cromo da “cinza de couro” na produção de aço inoxidável (no reator Forno Elétrico a Arco), utilizando-se como ferramenta a Termodinâmica Computacional. Inicialmente fez-se um estudo sobre os fundamentos termodinâmicos dos sistemas envolvidos. Partiu-se de sistemas simples, com grau crescente de complexidade, avaliando-se a possibilidade de redução do Cr2O3(s) presente na cinza. Após esse estudo, foram realizadas simulações. Nas proporções analisadas, os resultados mostram que não acontece incorporação de cromo ao banho com a adição da cinza, na temperatura de 1600 ºC, pois a escória é saturada em cromo. Na temperatura de 1700 ºC é possível a adição de certa quantidade de cinza, mas, no entanto, sob condições muito especiais, e com baixo rendimento (no melhor resultado obtido, apenas 6% do cromo adicionado através da cinza de couro é incorporado à fase banho). Verificou-se ainda que variar a basicidade da escória causa efeito bastante significativo no retorno de cromo ao banho. Se a cinza de couro for adicionada a um sistema escória-banho que inicialmente contém pouco cromo (é o caso de aços baixa liga), a maior parte do cromo adicionado é incorporada ao banho. Ou seja, adicionar Cr2O3(s) em escória de aços que tem como especificação baixos teores de cromo resulta em melhor aproveitamento do cromo da cinza. Quanto ao sistema CaO-SiO2-CrOx-MgO , verificou-se que a existência de magnésio leva à formação de picrocromita (MgO.Cr2O3), fase de difícil redução pelo silício. Adicionando-se ainda alumina a esse sistema, não se observaram mudanças significativas. / In Rio Grande do Sul State (Brazil) has been working a pilot plant that burns footwear leather waste. The gasification/combustion process generates an ash with high chromium content (~55% Cr2O3). The aim of this work was to evaluate the possibility of using the “leather ash” in the stainless steel production (in the Eletric Arc Furnace), with the aid of computational thermodynamics. The thermodynamic fundamentals of the involved systems were investigated. The possibility of reduction of the Cr2O3(s) present in the ash was evaluated starting at simpler systems, with increasing degree of complexity. After this preliminary study was done, the simulations were carried through. The results showed that incorporation of chromium to the bath by ash addition does not happen in the temperature of 1600ºC, since the slag is saturated in chromium. In the temperature of 1700ºC, it is possible the addition of certain amount of ash, however with low income (in the best result, only 6% of chromium added through the leather ash was incorporated to the bath). It was showed that slag basicity causes a significant effect in the return of chromium to the bath. If the leather ash is added to a slag-metal system which does not contain chromium, or which contains only a low quantity of chromium, the majority of the added chromium will be incorporated to the bath. Thus, Cr2O3(s) addition can be carried out for the production of another kinds of steel (with lower chromium content). It has been verified that magnesium leads to the picrochromite (MgO.Cr2O3) formation; for this phase, the reduction by silicon is not possible. Adding aluminium to the slags results in no significant changes observed.

The influence of basicity, heat treatment as well as different oxygen partial pressures on the phase relationships in the CaO-MgO-SiO2-Cr2O3 slags was studied with a view to control the precipitation of Cr-spinel in the slag phase. The equilibrium phases in CaO-MgO-SiO2-Cr2O3 slag system in the range on 1673-1873 K have been investigated under low oxygen partial pressure as well as in as air atmosphere. In low oxygen partial pressure experiments, a suitable mixture of CO and CO2 was used to control the oxygen partial pressure. The oxygen partial pressure was kept at 10-4 Pa. The Cr2O3 and MgO contents in the slag were fixed to be 6 and 8wt% respectively. The basicity (CaO/ SiO2) of the slag was varied in the range 1.0-2.0. Gas/slag equilibrium technique was adopted to synthesize the slag at a suitable temperature above the liquidus point. One heat treatment procedure is that the samples were heated to and soaked at 1873 K for 24h in order to achieve the equilibrium state and subsequently quenched in water. The other is that the samples were heated to and soaked at 1873 K for 24h, then slow cooled to 1673 K and soaked at this temperature for additional 24h in order to achieve the equilibrium state at lower temperature before quenching in water. The chromium distribution and phase compositions in the quenched slag were studied using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction techniques (XRD). FACTsage software was used for the phase equilibrium calculations. The experimental results obtained from the present work are compared with the calculation results from FACTsage software as well as with results from samples directly quenched after soaking at 1873K. It is found that the spinel formation at 1873 K in air atmosphere is favored in the slag basicity range of 1.0 to 1.6. The size of spinel crystals increased drastically after slow cooling followed by annealing compared to samples being quenched after soaking at 1873 K. The amount of foreign elements dissolved in the spinel phase, and matrix phases decreased after slow cooling followed by annealing at lower temperature, resulting in purer phases with less defects. It was found that the amount of foreign elements in the spinel phase, and other phases decreased after soaking at very low PO2. The size of the spinel crystals was found to be larger in samples with low basicity. Spinel phase precipitation has improved in the samples with higher basicities compared to the results obtained in air. / QC 20111208

L'acier inoxydable est utilisé dans de nombreuses applications biomédicales. Au contact d'un environnement biologique, des protéines s'adsorbent à la surface des aciers inoxydables. La maîtrise de la biocompatibilité nécessite la connaissance à l'échelle moléculaire de l'interaction biomolécule- surface. Nous développons une approche " bottom up " de cette interaction déclinée selon 3 axes : Complexification de la surface : Les films passifs en surface des aciers inoxydables sont composés à la fois d'oxydes de chrome et de fer et la surface α-Cr2O3 (0001) représente un modèle pertinent de ce film passif. Nous avons tout d'abord étudié l'adsorption des acides aminés (AA) sur une surface de Cr2O3 anhydre. Les acides aminés acides et basiques interagissent le plus fortement avec Cr2O3. Nous avons mis en évidence une différence de réactivité entre Cr2O3, Fe2O3 et un film de Cr2O3 enrichi en Fer en extrême surface, imputable à la structure électronique des cations Cr3+ et Fe3+. Activité de l'eau : Elle a été prise en compte en modélisant une surface hydroxylée et en extrapolant à l'interface solide liquide. L'étude de l'adsorption des AA sur une surface hydroxylée (en sphère externe) et en substitution de groupements -OH de surface a montré que seuls les acides aminés acides (Glu, Asp) peuvent s'adsorber en sphère interne. La formation de couches auto-assemblées de sphère externe est favorisée pour les acides aminés hydrophobes. Taille de la biomolécule : Dans cet optique nous avons développé une nouvelle méthodologie pour l'étude de l'adsorption de peptides sur des surfaces bien définies. Cette méthodologie est appliquée à l'exemple de l'adsorption du dipeptide de l'acide glutamique Glu2 sur Cr2O3. Une adsorption par multi-ancrage des résidus, de type sphère interne, est calculée.

La croissance de couches minces d'oxydes sur les alliages métalliques et les métaux purs est un phénomène ayant fait l'objet d'un grand nombre d'études expérimentales. Les structures des couches d'oxydes sont bien connues, ainsi que les modèles mathématiques servant à modéliser les aspects macroscopiques de la croissance. Cependant, les détails des mécanismes de germination de la couche d'oxyde dans les premiers stades de la corrosion ainsi que sa croissance ultérieure demeurent peu ou mal connus. La simulation atomistique apparaît comme une alternative pour évaluer les différents mécanismes proposés et appréhender l'influence des différents paramètres physico-chimiques. Le développement d'un tel outil de simulation a démarré au LPCS avec la thèse de M. Legrand. En se basant sur l'exemple de l'alliage FeCr, un modèle informatique tridimensionnel dit "modèle de Legrand", permettant de simuler la dissolution sélective et la passivation des alliages binaires a été réalisé. L'évolution dynamique est basée sur une technique de type Monte Carlo classique. Le logiciel permet de simuler l'évolution d'un alliage quelconque, d'une composition et d'une structure cristallographique donnée. Il prend en compte la diffusion des atomes sur la surface, leur dissolution et le blocage de la dissolution par formation d'une couche de passivation. Cet outil était adapté pour la simulation des premiers stades de la corrosion. L'objectif de ce travail est d'améliorer ce modèle existant, afin de simuler l'évolution de la couche passive sur une échelle de temps plus longue. A l'issue de ce travail, de nombreux apports ont été effectués. Ainsi, l'introduction d'un champ de force MEAM (Modified Embedded Atom Method) pour le calcul des barrières de diffusion et de dissolution, a permis de remplacer les probabilités de diffusion empiriques par des probabilités calculées, et de mettre en évidence la diffusion préférentielle des Cr vers leurs semblables. L'introduction d'une dynamique de simulation Monte Carlo Cinétique (KMC) a permis une prise en compte réaliste de l'évolution cinétique du modèle avec des temps de simulation reliés au temps réel. Enfin Un second réseau cristallographique RVO (réseau virtuel d'oxyde) tridimensionnel, correspondant à celui de la couche passive (Cr2O3) a été implémenté, ainsi qu'une interface graphique pour un meilleur suivi de la simulation. Les résultats obtenus lors des simulations sont en accord avec les observations expérimentales: passivation totale à partir du Fe-16Cr, enrichissement en Cr de la couche passive, allures des courbes cinétiques, influence du champ électrique, mise en évidence l'apparition de cavités sous la couche passive.

Content: Tannery effluent with high salinity and chromium have a serious environmental impact. The traditional chrome tannage that involved the use of sodium chloride, acid and chromium is one of the main origins of salt and chromium pollution. In this study, a non-pickling, low-chrome tanning technology was developed. The novel Chrome-free agent SL can be directly employed to tan bated cattle pelts and the wet white was obtained. Then the shaved wet white was pre-treated by Poly-carboxylate auxiliary agent and tanned by chrome powder. It was tested that the shrinkage temperature of the wet white, the initial pH of chrome tanning, the consumption of chrome powder, the shrinkage temperature of the chrome-tanned leather, the content of Cr2O3 in effluent, the absorption of chromium and the other properties of the chrome-tanned leather. It was found that the shrinkage temperature of the wet white tanned by SL reached over 80oC, the optimal consumption of Poly-carboxylate auxiliary agent was 2wt% based on the weight of the shaved wet white, the better low-chrome tanning conditions were that the wet white was tanned by 4wt% chromium powder for 150～180min at room temperature when the initial pH value was 3.5. The next processes were same as traditional chrome tannage. Meanwhile, the shrinkage temperature of the leather tanned by the low-chrome tannage reached more than 95oC, the absorption of chromium was 96%, the content of Cr2O3 in the effluent was under 200mg/L. For the low-chrome tanned leather, the absorption of dyestuff, fat-liquor reached 99.5%, 82.5% respectively. Compared with the traditional chrome tanned process, not only the conventional pickling process was eliminated, the process was been shorten and reduce the pollution of sodium chloride, but it can reduce 50% of the consumption of Chrome powder, improve the absorption of chromium and can reduce content of Cr2O3 in effluent. Take-Away: 1. LUO JIAN-XUN, LI JING, LIAO XUE-PIN,etc.Cleaner Chrome Tanning – A Non-Pickling Process Using an Aliphatic Aldehyde as Pre-tanning Agent. J. Soc. Leather. Technol.Chem. 2012,96 (1):21-26. 2.LUO JIAN-XUN,FENG YANJUAN.Cleaner Processing of Bovine Wet-white: Synthesis and Application of a Novel Chrome-free Tanning Agent Based on an Amphoteric Organic Compound. J. Soc. Leather. Technol.Chem. 2015,99 (4):190-195. 3.XU JIA-LI, LUO JIAN-XUN.Synthesis and application of a polycarboxylate auxiliary agent. China Leather.2017,46(3):35-41.