Tesis sobre el tema "Chromace"

Les matériaux utilisés industriellement sont de plus en plus sollicités dans des conditions extrêmes, exigeant résistance à l’usure et à la corrosion. A ces performances techniques s’ajoutent désormais des contraintes environnementales de plus en plus fortes nécessitant la recherche de traitements de surface alternatifs. L’objet de cette thèse est de remplacer le chromage dur électrolytique par des traitements par voie sèche, en garantissant performances techniques et environnementales par analyse du cycle de vie des dépôts. Afin de corriger certains défauts des dépôts obtenus par projection thermique, et de se rapprocher des qualités des dépôts obtenus par rechargement laser, procédé performant mais beaucoup plus lent, un procédé hybride innovant de refusion laser in situ a été utilisé. La refusion de dépôts NiCrBSi - matériau sélectionné pour ses bonnes performances environnementales - a mis en évidence une répartition homogène de carbures et de borures dans une structure plus dense, sans porosité, entraînant une amélioration des propriétés mécaniques. Le traitement hybride permet d’architecturer différemment les dépôts en remplaçant la microstructure lamellaire par une microstructure dendritique, multiphasique, plus adaptée aux sollicitations mécaniques et chimiques. Les modes de dégradation tribologique, comme les mécanismes de corrosion, diffèrent. Le dépôt d’alliage NiCrBSi par refusion laser in situ, au bilan environnemental acceptable, appliqué avec une densité d’énergie laser suffisante, pourrait être une solution de choix au remplacement des dépôts électrolytiques de chrome dur
Materials used industrially are more and more applied under extreme conditions, implementing wear and/or corrosion resistance. In addition, environmental regulations are nowadays effective. Thus, it seems necessary to find surface coatings with justified environmental behaviour, implementing life cycle assessment of the processes. This Ph. D. Thesis aims to replace electrolytic hard chromium plating by dry coatings. In order to improve some well-known drawbacks of thermal spraying, laser remelting was combined to thermal spraying. Remelting of NiCrBSi deposit, which was selected for its good environmental behaviour, shows a homogeneous carbides and borides distribution in the coating layer and an improvement of the mechanical properties compared to the as-sprayed sample. The hybrid process changes structure from lamellar to dendritic and produces denser coatings with finer structures, without porosity, which improves chemical and mechanical properties. Results are closely linked to laser cladding, except that there are obtained with a very high process velocity. Whereas hard chromium plating is affected by its characteristic microcrack structure, and APS by surface fatigue, laser coatings show an adhesive wear mechanism corresponding to a wear by oxidation in case of laser remelting. If the corrosion kinetics are comparable according to the selected process, mechanisms change. In case of as-sprayed sample, porosity lets the electrolyte reach the substrate, while the in situ remelted sample substrate is not reached. Concerning hard chromium replacement, laser in situ remelted NiCrBSi could be a good solution

This investigation has been geared towards several aspects of chromone chemistry. Selected 2-(N,N-dimethylarnino)chromones have been synthesized via 2-hydroxyacetophenone boron difluoride complex intermediates, and potentiometric analysis of these compounds in ethanolwater has been used to determine the influence of substituents on their basicity. The pKa values have been found to lie within a narrow range (1.92 - 2.52), and the observed substituent effects have been rationalized with the aid of semi-empirical and ab initio molecular orbital calculations. An efficient route has been developed for the synthesis of the naturally-occurring chromone, "granulosin" [7,8-(methylenedioxy)-2-propylchromone], and several C-2 side chain analogues in good yields, by condensing 2'-hydroxy-3',4'-(methylenedioxy)acetophenone with a range of ethyl carboxylate esters. These compounds show significant cytotoxic activity against the brine shrimp, Artemia salina, and two of them, the 2-ethyl and 2-benzyl derivatives also show 100% activity as pesticides on Beet army worms (BAW). Another naturally-occurring chromone derivative, 5-hydroxy-2-isopropyl-7-methoxychromone, and four C-2 side chain analogues have been prepared in moderate yields. These compounds also show significant cytotoxic activity against the brine shrimp, Artemia salina, and it is apparent that the presence of the hydroxyl group at C-5 is critical for such activity. The electronimpact mass spectra of both series of chromone derivatives have been investigated, permitting the elucidation of characteristic fragmentation patterns. In work directed towards the synthesis of potential HIV -1 protease inhibitors, five novel chromone-containing analogues of the clinically useful drug, ritonavir, have been synthesized. The design strategy has involved the coupling of substituted chromone-2- carboxylic acids with a specially prepared, hydroxyethylene dipeptide isostere to afford ritonavir analogues containing chromone termini. An interactive docking procedure has been used to explore the docking of ritonavir and the novel chromone-containing analogues into ' the active site of the enzyme, and has indicated the capacity of the ritonavir analogues to form hydrogen-bonds with the HJV-l enzyme receptor. Various substituted cbromone-3-carbaldehydes, which have been synthesized from the corresponding o-hyclroxyacetophenones using Vilsmeier-Haack methodology, have been examined as substrates for Morita-Baylis-Hillman reactions, using 3-hyclroxyquinuclidine as the catalyst and arcylonitrile and methyl acrylate as the activated alkenes. Optimization of the reaction conditions has permitted efficient conversion of the cbromone-3-carbaldehydes to the Morita-Baylis-Hillman products and, in some cases, dimeric products, within 24 h. Heating of the Morita-Baylis-Hillman products, arising from reactions with methyl acrylate, at 80 ºC for 3 h in the presence of DABCO as catalyst, has been shown to effect transformation to the corresponding dimers in good yield.

L’addition nucléophile des réactifs de Grignard sur les nitriles conduit généralement aux cétones après hydrolyse acide. La double addition, menant à des carbinamines tertiaires après traitement, est beaucoup plus difficile et ne s’effectue habituellement qu’avec les organomagnésiens allyliques. Dans ce contexte, nous avons découvert que les organomagnésiens peuvent effectuer une double addition sur la fonction nitrile des acylcyanhydrines, pour fournir des hydroxyamides. Cette réaction est originale par le fait qu’une large gamme d’organomagnésiens peut être utilisée, dans des conditions particulièrement douces. Cette réaction a été appliquée à la synthèse de différents acides α-aminés α,α-disubstitués, par oxydation de la fonction alcool et hydrolyse du motif amide. La divinylglycine a notamment pu être préparée avec un bon rendement. L’addition successive de deux organomagnésiens différents a aussi pu être réalisée, après optimisation des conditions de réaction, pour accéder à des hydroxyamides disymétriques, précurseurs d’acides aminés quaternaires chiraux. Enfin, l’addition des réactifs de Grignard sur les 3-cyano iminocoumarines N-éthoxycarbonylées a été étudiée. Malgré la présence de nombreux sites électrophiles, la réaction est très chimiosélective, et des chromènes originaux substitués en position 4 ont été obtenus. Les propriétés antifongiques et antibactériennes de ces derniers ont été évaluées
The nucleophilic addition of Grignard reagents on nitriles generally leads to ketones after acidic hydrolysis. The double addition, providing tertiary carbinamines after work-up, is more difficult and usually occurs only with allylic Grignard reagents. In this context, we discovered that Grignard reagents can perform a double addition on the nitrile function of acyl cyanohydrins, to provide hydroxyamides. This reaction is original by the fact that a wide range of Grignard reagents can be used, in particularly mild conditions. This reaction has been applied to the synthesis of different α,α-disubstituted α-aminoacids, by oxidation of the alcohol functionality and hydrolysis of the amide moiety. Especially, divinylglycine has been prepared in good yield. The successive addition of two different Grignard reagents was also carried out, after optimization of reaction conditions, to access unsymmetrical hydroxyamides, which are precursors of chiral quaternary aminoacids. Finally, the addition of the Grignard reagents on N-ethoxycarbonyl 3-cyano-iminocoumarines was studied. Despite the presence of several electrophilic centers, the reaction is highly chemoselective, and novel chromenes displaying substituent on position 4 were obtained. The antifungal and antibacterial properties of these compounds have been evaluated

Les catalyseurs employes pour la fluoration en phase gazeuse par le fluorure d'hydrogene (hf) du 1,1,1-trifluoro 2-chloroethane (f133a) en 1,1,1,2-tetrafluoroethane (f134a), utilise dans les systemes de refrigeration en remplacement du dichlorodifluoromethane (cfc 12) responsable du trou d'ozone stratospherique, sont a base d'oxydes de chrome. Les chromites de metaux de transition (nickel, cobalt, cuivre) et de zinc et magnesium, prepares par combustion, cristallisent sous forme spinelle, mcr#2o#4, et presentent superficiellement du chrome vi qui contribue en partie a l'activite catalytique. La conversion du f133a, obtenue avec ces oxydes mixtes de surfaces specifiques inferieures a 20 m#2/g, est relativement faible et est maximale pour le chromite de nickel dont l'activite catalytique ramenee a l'unite de surface est alors comparable a celle d'un sesquioxyde de chrome non-stchiometrique microcristallise. Ces chromites ont l'avantage d'etre stables sous hf et de peu se fluorer, a la difference des chromates correspondants, qui se decomposent en oxyfluorures de chrome volatils et en fluorure de metal divalent, rendant impossible toute exploitation industrielle. Par ailleurs,. . . .

The magnesia-chromite refractory composites are the best candidates for the lining of non-ferrous metal smelting and refining furnaces, due to their high melting temperature, chemical inertness, and excellent thermal shock resistance. However, their high sintering temperatures (>1700°C) increase the processing complexity and costs. In this investigation, the primary goal was to study the sintering of these composites, with the long-term engineering goal to reduce their sintering temperature to <1500°C in air. The materials were synthesized via chemical methods using nitrates to assure chemical homogeneity. Al₂O₃, Fe₂O₃, and SnO₂ affected the kinetics of the MgCr₂O₄ formation and increased the density of MgCr₂O₄ in the order Fe₂O₃>Al₂O₃>SnO₂. The enhanced MgCr₂O₄ densification was attributed to the cation distribution in spinel structure (inversion phenomenon), caused by the inherent affinity of Fe⁺³ and Al⁺³ to tetrahedral sites. Fe₂O₃ and Al₂O₃ showed to form inverted spinel, while SnO₂ resulted in the formation of normal spinel solid solutions. Twelve magnesia-chromite composites were synthesized to study the effects of Al₂O₃, Fe₂O₃ and Cr₂O₃ on their sintering conditions; Cr₂O₃ decreased the density, while Fe₂O₃ and Al₂O₃ enhanced the densification of composites. The microstructural studies revealed that Fe₂O₃ and Al₂O₃ reduced the dihedral angle between MgO and spinel, while Cr₂O₃ increased it. The increased densification by Fe₂O₃ and Al₂O₃ was attributed to the decreased dihedral angle and formation of inverted solid solutions. The optimized composition [MgO6.9Cr₂O₃6.9Al₂O₃2.7Fe₂O₃]mol% (MK) reached nearly full density in air at 1475°C for 70minutes; 1700°C is currently used for magnesia-chromite refractories. In order to study the effects of the particle size on densification, magnesia-chromite composites (NMK) with average particle size of ~20 nm were synthesized via Pechini's method. Reducing the particle size from 1.2 um for MK to 20 nm for NMK reduced the onset sintering temperature by 200°C to 1000°C. The densification results were evaluated using master sintering curve theory for the first time for this kind of composites. The sintering activation energy was 443.7 and 302.6 kJ/mol for MK and NMK respectively. It was hypothesized that the oxygen diffusion through lattice and grain boundaries was rate controlling mechanism for MK and NMK respectively.

A range of natural chrome ores, containing iron in two valence states, have been investigated using the technique of Mossbauer spectroscopy. The instrumentation required to cry out the technique was studied and an additional item of equipment was designed and constructed to extend the temperature range over which the effect could be observed. All the chrome ores yielded a complex spectra which could be attributed to a combination of octahedrally and tetrahedrally co-ordinated Fe2+ and Fe3+ quadrupole doublets. A model for fitting the spectra was devised assuming the presence of octahedrally co-ordinated Fe3+ and tetrahedrally co-ordinated Fe2+. The inhomogeneous nature of the samples caused a broadening of the tetrahedral Fe2+ contribution which was fitted as a distribution of three doublets. The Mossbauer parameters obtained were compared with those of pure compounds of a similar structure. Spectra recorded from 12K to 600K enabled effective Debye temperatures to be calculated. Second order Doppler shift (S.O.D.S.) calculations gave values for theta[D] of 385K and 658K for the Fe2+ and Fe3+ contributions respectively. Absorption area data gave similar values. An examination of the temperature dependence of the quadrupole splitting of the Fe2+ contributions appeared to confirm the validity of the proposed fitting model. Estimations of the Fe2+ / Fe3+ ratio were made using the data obtained and yielded values of 1.6 - 3.6.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 2006.
This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.
Includes bibliographical references.
While chromated copper arsenate (CCA) has proven to be exceptionally effective in protecting wood from rot and infestation, its toxic nature has led to the problem of disposal of CCA-treated lumber and remediation of waters and soils contaminated by process wastes. The active ions in water-based CCA are hexavalent chromium, divalent copper, and pentavalent arsenic. The objective of this study was to develop the underlying engineering science for remediation of aqueous CCA wastes via electrolytic deposition of neutral arsenic, chromium, and copper in order to evaluate the technical feasibility of this process. The specific approach focused on electrochemical stability analysis of the metals; development and testing of a copper sulfate reference electrode (CSE); electrolytic deposition of arsenic, chromium, and copper from model aqueous CCA wastes; and characterization of the resulting deposits. The electrochemical stability analysis of the individual components, As, Cr, and Cu, in an aqueous system was used to determined the most thermodynamically stable forms of the metals as a function of pH and electrochemical potential. This analysis predicted that under the conditions of codeposition of all three metals, hydrogen and arsine would also be produced.
(cont.) A robust and accurate CSE was designed, constructed, developed and used as a reference electrode for the electrolytic deposition experiments in this study. The potential of the CSE as a function of temperature over the range of 5 to 45 °C was measured and related to the normal hydrogen electrode potential (317 mV at 25°C, slope of 0.17 mV/°C). Electrolytic deposition was performed using working and reference electrodes specially designed and fabricated for this study. Despite the results of the electrochemical stability analysis, conditions were found experimentally where arsenic, chromium, and copper were deposited from model aqueous CCA type-C solutions over a range of concentrations without the formation of arsine or hydrogen. Three different types of deposits were observed. One type contained a ratio of metal concentrations similar to that of CCA type-C and is a good candidate for use in CCA remediation and recycling processes. This study indicated that CCA remediation via electrolytic deposition is probably feasible from an engineering perspective.
by Heather A.G. Stern.
Ph.D.

Various chromone derivatives have been used in asthma therapy, and their biological activity is apparently related to certain chemical features which include conformation and acidity. In the present study, substituent effects on conformation and acidity have been explored in chromone systems with potential biological activity. A range of variously substituted symmetrical chromone-2-carboxamides (including a series of N,N-dimethylchromone-2-carboxamides) have been prepared via chromone-2-carboxylic acids, which, in turn, were prepared from the corresponding o-hydroxyacetophenones. The N,N-dimethylchromone-2-carboxamides were prepared by reacting the appropriate chromone-2-carbonyl chlorides with dimethylammonium chloride in pyridine, in an approach which resolved various problems encountered in the preparation of these compounds. Substituent effects on the conformation of chromone-2-carboxamides have been explored using dynamic NMR spectroscopy, and the observed splitting of the N-alkyl signals has been attributed to slow site-exchange of the N-alkyl substituents. Dynamic NMR frequency separations and coalescence temperatures have been used to calculate rotational energy barriers, and substituent effects on these rotational energy barriers have been analysed. The possible implication of ring-opening of chromones in chromone pharmacology has also been examined. A range of 3-(2-hydroxybenzoyl)acrylamides has been prepared via the dimethylamine-mediated ring-opening of N,N-dimethylchromone-2-carboxamides and the E-double-bond configuration of the ring-opened products has been unambiguously established by single crystal analysis of the parent system. The configuration and conformation of the crystal structure of the parent system have been shown, using IR and NMR spectroscopic, and molecular graphics techniques, to be maintained in solution and to characterise the whole series. ¹H and ¹³C NMR spectroscopy have also been used to study the dimethylamine-mediated ring-opening of disodium cromoglycate. The kinetics of the dimethylamine-mediated ring-opening of N,N-dimethylchromone-2-carboxamides have been studied using UV spectroscopy. These reactions have been shown to follow third-order kinetics overall and a mechanism accommodating the observed third-order kinetics has been proposed. Substituent effects have been further investigated by the potentiometric determination of the pKa (pK [subscript a]) values for a series of chromone-2-carboxylic acids. The relationship between acidity and the observed rate constants has been explored and has verified that the observed rate constants are sensitive to the influence of meta-substituents on the stability of the phenoxide ion "leaving group" rather than C-2 electrophilicity.

A number of biologically active chromones occur in plants (eg. Khellin) and research in this field has eventually led to the discovery of chromoglycic acid, which is widely used as a sodium salt in asthma therapy. Since biological activity may be related to acidity, a range of chromone-2-carboxylic acids have been prepared via Claisen acylation of substituted o- hydroxyacetophenones and their acid dissociation constants determined potentiometrically to explore substituent effects. From this study it has been found that introduction of certain groups does have a marked effect on acidity. A variety of acrylamide derivatives have been prepared via the dimethylamine-mediated ring opening of chromone-2-carboxamides which, in turn, were prepared from the chromone-2- carboxylic acids via the corresponding acid chlorides. Variable temperature NMR spectroscopy was employed to examine the effect of substituents on the rotational barriers and it has been found that for the acrylamides examined, ring substituents have little effect on the rotational barriers. A combination of low resolution, high resolution and meta-stable peak analysis has been used to study mass fragmentation patterns for a series of acrylamide derivatives. The proposed fragmentation pathways for selected peaks have been found to be common to all the spectra examined when differences in the atomic masses of substituents were taken into account.

Chromite belongs to the spinel group with the general chemical formula XY2O4, where X and Y represent divalent and trivalent metal ions, respectively. Four types of chromite ore deposits occur as either lode or secondary deposits. Lode chromite ore deposits comprise stratiform and podiform deposits, whereas secondary chromite ore deposits comprise laterite and placer deposits. Chromite is an important industrial mineral used in the refractory industry. Moreover it is the only industrial source of chromium for chemical and metallurgical industries and to be marketed as a valuable commodity it requires very demanding quality parameters that differ according to the kind of application. Chromite ore cannot be usually sold as it is and, therefore, some kind of ore beneficiation is required in order to separate chromite from gangue minerals. The most commonly used beneficiation methods for chromite ores are the gravity methods, such as the shaking table, jig, spiral and Reichert cone methods. The present work deals with the geologic studies that, coming after prospection, lead to the evaluation of the chromite ore quality and to planning and/or improvement of beneficiation plants. The quality of chromite ore deposits, in order to rank them for possible exploitation, was studied in five deposits of Madagascar (Andriamena, Antanimbary, North Befandriana, North Belobaka and North Toamasina), in collaboration with UT Group s.r.l., for the development of chromite mining in the country. The basic geological, mineralogical and geochemical study of the deposits led to the reconstruction of genetic models for each of them. This was the starting point for a more detailed study on the quality of the chromite ore. The five most important chromite ore localities, investigated for this work, are all characterized by outcropping chromitite bodies hosted within mafic/ultramafic intrusions of probable Neoproterozoic to Cambrian age. Metamorphism and alteration affected, at different degrees, all chromitites, but never completely obliterate their primary characters. Chromitite host rocks are peridotite, orthopyroxenite or orthoamphibolite, while primary gangue phases are orthopyroxene, olivine, rare plagioclase, ilmenite, rutile, pyrrhotite and pentlandite. Secondary assemblage comprises serpentine, talc, Cr-chlorite, tremolitic to actinolitic amphibole and magnetite. Geologic, textural, mineralogical and mineral chemistry data are compatible with an ophiolite origin for North Befandriana chromitites and a layered intrusion origin for Andriamena, North Toamasina, North Belobaka and Antanimbary chromitites. These latter show differences that can be related to a different position of the chromitite bodies within the stratigraphic sequence of a layered intrusion. North Befandriana is a high quality deposit that could be exploited without any beneficiation of the ore, Andriamena needs beneficiation to reach market standard, Antanimbary and North Belobaka is low quality for metallurgical or chemical use but could be a good prospect for refractory market. Finally North Toamasina chromite ore is not suitable for any market even after beneficiation. An innovative study of geologic processes that can affect chromite ore beneficiation was applied to Vavdos chromite deposit (Greece) hosted in the Vavdos ultramafic massif belonging to the Halkidiki ophiolite of the Circum-Rhodope orogenic belt. Here metamorphic modification of chromite led to redistribution of Cr2O3 from chromite to silicates. The effect of the redistribution is to lower the efficiency of gravity plants as Cr2O3 contained in silicate phases will be preferentially discharged into the tailing during enrichment. The influence of this process that is widespread in chromite ores, on chromite enrichment was evaluated quantitatively. Generally accepted assumption that chromite ores do host Cr only in chromite is misleading as metamorphosed chromite ores host significative amounts of Cr in gangue phases and especially in Cr-chlorite. This study, of a completely metasomatized chromite ore, shows that about 3 wt% of total Cr2O3 in the rock is hosted in Cr-chlorite; while only about 0.2 wt% of total Cr2O3 is hosted in serpentine. As Cr-chlorite can host even more Cr2O3 than at Vavdos, and as the deepest alteration of chromite due to metasomatism occurs for ores containing about 34% chromite, the amount of Cr2O3 redistributed within the gangue can be even higher than at Vavdos, especially in low grade disseminated ores, where probably about 5-6% of Cr2O3 can be hosted in the gangue, a value that could rise to 7-8 wt% for high Cr2O3 Cr-chlorite. The effect of this wrong assumption is a mistake in the calculation of plant efficiency that will be overestimated. Mistakes due to redistribution of Cr2O3 during metamorphism can be easily avoided through mineralogical analysis that can detect the presence of Cr-chlorite in the ore. Planning of beneficiation in Cr-chlorite-bearing chromite ores requires additional investigation, concerning Cr2O3 content in Cr-chlorite and Cr-chlorite amount in the ore. A procedure to evaluate efficiency and results of gravity chromite enrichment plants was tested on Brieville enrichment plant (Madagascar), which belongs to Kraomita Malagasy mining company. Here a detailed study of chromite sand quality parameters at each step within the plant together with the measuring of all sand flow rates led to the reconstruction of separation efficiency at each step of chromite processing. The results of grain size, XRD, XRF, EMP and grain counting analyses together with separation efficiency (SE) and liberation degree (LD) evaluation allow to conclude that Brieville plant does not properly work due to the low sorting of sands feeding shaking tables that negatively affects their separation efficiency. Moreover the low degree of liberation of chromite, especially in the coarsest grain sizes, negatively affects the re-cycling process of mix materials. Plant efficiency and quality of final product can be improved by: moving the Cr2O3-enriched mixes to the concentrate and the Cr2O3-depleted mixes to the waste; grinding to finer grain size the overall feed of shaking tables and the mixes that will be re-cycled and substituting hydrosizers with screens. The first change, that does not involve any additional operational cost, has been effectively applied to the plant just after publication of the present study. The other changes involve additional operational costs and require a detailed economic analysis before being applied to the plant. Finally a completely new technology for high performance beneficiation of chromite sand that leads to the production of chromite refractory sands was tested. For this work chromite concentrate sand from Krasta enrichment plant (Albania) was used. The innovative beneficiation plant of Omega Foundry Machinery LTD. comprises a drum magnet and the new Inclined Fluidised Separator that uses an air cushion as the fluidizing agent during gravity driven grain separation. Refractory chromite sand chemical and technical requirements are the most demanding in chromite market and no chromite ore can attain them by simple crushing and grinding. On the other hand usual enrichment methodologies either cannot meet the required parameters or have a very low refractory sand recovery. The combination of drum magnet and Inclined Fluidised Separator in the Omega Foundry Machinery LTD. pilot plant not only produces a good quality refractory sand, but the result is reached with a high recovery, making of this plant an optimal solution for the production of refractory chromite sand. The Inclined Fluidised Separator is particularly performing as it combines a very high recovery of silica in the waste with an increase of the grain size of concentrate.

Content: Chrome tanning is the commonest tanning agent in leather manufacture, and the discard of chrome tanned leather goods inevitably leads to chrome discharge that might have potential environmental risks. In this study, the kinetic behaviors of the release of chrome and organics were investigated by ICP-OES and TOC analyzers respectively. Deionized water was used as medium, and leaching tests were proceed at solid liquid ratio 1:20 as well as rotational speed 60 r/min to simulate the release of chrome tanned leather under natural conditions. The effect of temperature on the behavior kinetics was further explored. The results showed that the release of chrome and organics could be well fitted by the second-order kinetic equation, and the rate constant for the release process indicated the release of organics was faster than chrome. Then Tenax model was used to illustrate the release kinetics experiments of chrome to obtain the three release compartments (fast, slow and very slow). The results could provide the theoretical parameters for the assessment of risks of chrome-tanned leather. Take-Away: The second-order kinetic equation could describe the release of chrome and organics from chrome tanned leather under natural environment. The activation energy of the release of chrome and organics from leather could be obtained. The fast, slow and very slow compartments of chrome release could be obtained.

Ce travail de these a pour objectif d'obtenir des depots de chrome par electrolyse des sels de chrome en bains de sels fondus. Dans ce but une etude fondamentale a ete developpee, qui comprend d'une part la determination des proprietes thermodynamiques des solutions de chrome et d'autre part l'examen des mecanismes reactionnels conduisant au depot de chrome. A partir des mesures de la f. E. M. De la pile de formation chrome-chlore on obtient les caracteristiques thermodynamiques des solutions (enthalpie libre, entropie et enthalpie), ainsi que la solubilite des sels de chrome. L'utilisation des methodes impulsionnelle a permis de determiner la cinetique des differentes etapes des reactions elctrochimiques en donnant acces aux coefficients de diffusion des especes electroactives, c'est-a-dire des ions chrome 2 et chrome 3. En outre ces techniques permettent de mettre en evidence l'influence de phenomenes d'adsorption et d'un controle par transfert de charge. Un modele theorique a ete developpe pour prendre en consideration ces differents parametres. Enfin, des travaux d'elaboration de depot ont ete effectues en examinant principalement le role de complexants et des caracteristiques de l'electrolyse en utilisant en particulier les courants pulses