[pt] Concentrado minerais sulfetados são uma importante fonte de matérias-primas nos processos de extração de metais não-ferrosos. No que diz respeito ao cobre, estes são usualmente processados segundo um fluxograma contemplando as etapas de ustulação, fusão mática, conversão e refino. Todavia, algumas características dos concentrados podem limitar a sua aceitação nas plantas de processamento tais como: baixo teor de cobre assim como a presença de elementos ditos deletérios, como, por exemplo, o flúor e seus efeitos corrosivos sobre materiais refratários após a transformação e ácido fluorídrico; ainda que o material possua um teor do metal de interesse elevado. Dentro desse contexto, o presente trabalho tem por objetivo avaliar o processamento químico de concentrados sulfetados de cobre com essas características a fim de entender o seu comportamento nos processos de ustulação, visando à identificação de condições que minimizem os efeitos danosos do flúor, no caso de concentrados de alto, assim como determinar uma janela operacional que possibilite a obtenção seletiva de CuSO4, no caso de concentrados de baixo teor. Para atender a esses objetivos, foi levado a efeito um estudo teórico incluindo uma breve revisão da literatura e uma apreciação termodinâmica das reações químicas mais relevantes em cada sistema reacional. O estudo experimental foi conduzido através da avaliação do efeito de variáveis específicas para cada sistema reacional. No caso particular de concentrados de alto teor contendo flúor, os experimentos contemplaram a presença, ou não, de água na atmosfera reacional ao passo que nos ensaios envolvendo concentrados de baixo teor de cobre foram levados a efeito variando a temperatura e a composição química da atmosfera reacional a partir da recirculação de parte dos produtos gasosos, como, por exemplo, o SO2. Os materiais envolvidos foram caracterizados por meio de microscopia eletrônica de varredura e difração de raios-x. As previsões teóricas de ambos os sistemas reacionais puderam ser confirmadas na caracterização dos produtos reacionais obtidos após o processamento químico dos concentrados sulfetados de alto e baixo teor de cobre. No que tange o primeiro destes, observou-se que o flúor tende a permanecer estável na forma de fluorita quando na ausência de umidade no sistema reacional. Por outro lado, no que diz respeito ao último destes materiais, verificou-se que o reciclo de parte dos produtos gasosos do processo é responsável por uma melhora de desempenho da reação química de ustulação visando à formação seletiva de sulfato de cobre e óxido de ferro. / [en] Sulfide minerals concentrates are an important source of raw materials for non-ferrous metals extraction processes. For copper, these are usually processed through a flowchart containing the operations of roasting, matte smelting, conversion and refining. However, some concentrates characteristics may limit its acceptance in processing plants such as low copper content and the presence of deleterious elements, such as fluorine and its corrosive effects as result of its transformation into hydrofluoric acid; even if the metal content is this material is high. Within this context, this study aims to evaluate the chemical processing of sulfide concentrates with these characteristics in order to understand their roasting behavior, in order to identify conditions that minimize the fluorine harmful effects for concentrate with high copper content, and determine an operating window that allows the selective obtainment of CuSO4, for low grade concentrates. To meet these objectives, it was carried out a theoretical study including a brief review of the literature and a thermodynamics assessment of the most important chemical reactions in each reaction system. The experimental study was conducted evaluating the effect of specific variables for each reaction system. In the case of concentrates of high grade containing fluorine, the experiments contemplate the presence or absence of water in the reaction atmosphere while the tests involving the concentrate with low copper content were carried out by varying the temperature and the chemical composition of the atmosphere, recirculating part of the gaseous products, like SO2. The materials were characterized by scanning electron microscopy and x-ray diffraction. The theoretical predictions of both reaction systems could be confirmed in the characterization of the reaction products obtained after the chemical processing of sulfide concentrates of high and low copper content. In what touches the former, it was observed that fluorine tends to remain stable as fluorite in the absence of moisture within the reaction system. On the other hand, regarding the latter material, it was found that the part of recycled gaseous products of the process are responsible for a performance improvement of the roasting reaction focused on the selective formation of copper sulfate and iron oxide.

Ce travail de recherche porte sur l'élaboration de céramiques transparentes de CaLa₂S₄ pour la réalisation d'optiques MWIR et LWIR. Différentes méthodes de synthèse de poudres ont été explorées afin d'élaborer des poudres céramiques de grande pureté, cubiques et de morphologie adaptée à la densification. Il en a résulté le développement d'une méthode combustion comme nouvelle voie de synthèse de ce matériau. Différentes techniques de frittage ont été explorées : le SPS, le pressage à chaud (HP) et le frittage sous sulfure d'hydrogène (H₂S) suivi d'un post-frittage HIP. Le pressage à chaud permet d'élaborer des céramiques transparentes dans l'IR. Cependant leurs propriétés optiques sont dégradées par la présence de bandes d'absorption et par un noircissement important dû à l'interaction du matériau avec le graphite. Ces deux problématiques ont été résolues en combinant frittage naturel et compaction isostatique à chaud. La transmission des céramiques obtenues par ce procédé atteint à 13µm la transmission théorique de 68%. / This work focuses on the elaboration of CaLa₂S₄ transparent ceramics for IR optical applications in the MWIR and LWIR atmospheric windows. Various synthesis methods were explored for the elaboration of high purity cubic ceramic powders with adequate morphology for densification. As a result, we developed an innovative combustion method of this material. Different sintering techniques were investigated: Spark Plasma Sintering (SPS), Hot Pressing (HP) and Sintering in sulfurizing atmosphere (H₂S) combined to Hot Isostatic Pressing (HIP). Hot Pressing produces IR transparent ceramics. However, their optical properties are affected by the presence of absorption bands and significant blackening due to the interaction of the material with the graphite. These two issues have been solved by using sintering coupled to post-HIP. Transmission of the optics obtained by this process reaches the theoretical transmission of 68 % at 13μm.

Abstract The metamorphosed Palaeoproterozoic Orivesi gold deposit in southern Finland is located within the Tampere Schist Belt, which belongs to the Svecofennian domain. The Orivesi mine, run by Outokumpu Mining Oy, was in production from 1994 to 2003, during which time a total of approximately 1.7 million tons of ore was extracted, with an Au content of 9.31 g/t, implying a total output 13.115 tons of gold in concentrate. The hydrothermal alteration halo can be divided successively into chlorite-dominant, sericite-dominant and quartz-dominant rocks from the outer zone inwards. The host rocks of the ore are quartz rocks with andalusite-rich quartz rocks. Topaz-bearing rocks also occur in the inner part of the alteration halo. In addition to Au, the elements Ag, Te, Bi, Sb, S, As, Se, Cu, Zn, Pb, Sn and Mo are enriched to varying degrees within the alteration halo. The main ore minerals include base metal sulphides, sulphosalts and tellurides. Pyrite is the most common sulphide. The sulphosalts are represented by tetrahedrite, bournonite, boulangerite and meneghinite. The most common gold, gold-silver and silver tellurides are calaverite, montbrayite, petzite, kostovite, sylvanite and hessite. Other known tellurides include tellurobismuthite, altaite, melonite, frohbergite, tsumoite, tetradymite and rucklidgeite. Gold occurs mostly in fine-grained native grains containing an average of 5% Ag. The native gold is usually of very small grain size, generally < 20 µm. Most of the gold grains in the deposit occur as intergrowths with tellurides. The adjacent hypabyssal intrusion is an obvious source of both hydrothermal fluids and metals. A comb quartz layering has been discovered in the transition zone between the intrusion and the alteration halo. The Orivesi deposit is thought to belong to the high-sulphidation epithermal type. Soon after its formation the deposit encountered deformation and metamorphism that amounted to lower amphibolite facies conditions. The subsequent retrograde metamorphism caused the reappearance of some hydrothermal minerals typical of high-sulphidation epithermal deposits.

Electron confinement due to the two-dimensional (2D) nature of layered materials accounts for their fascinating electronic properties and for their applications in new-generation electronic devices. Moreover, the large specific surface area of 2D materials also enables their use in surface-related applications, such as catalysis and adsorption. In addition, these 2D materials are promising photocatalysts thanks to the shorter migration distance of photogenerated electrons and of electron holes. The research reported in this thesis aimed to provide atomistic insight into 2D layered materials, particularly into their structures, electronic properties and potential applications in the field of catalysis, photocatalysis and alkali metal ion batteries. Our findings are not only theoretically relevant but also open new research avenues for our experimental collaborators to improve specific properties and activities of their materials. The main results from this thesis, for five different classes of 2D materials, are summarized below. 2D covalent organic frameworks (COFs). CTF-type COFs with similar topology but different nitrogen-to-carbon ratios were investigated for their potential in photocatalytic water splitting. More specifically, torsion and bending effects on structure stability were investigated in...

Unsaturated sugars constitute as an important category of carbohydrate precursors in synthesis. Specifically, 1,2- and 2,3-unsaturated glycosides are excellent intermediates to derivatize monosaccharides and as building blocks in organic synthesis. For example, a major utility of 1,2-unsaturated sugars, namely glycals, is the addition reactions to afford 2-deoxy glycosides under acidic conditions and rearrangement reactions to produce 2,3-unsaturated glycosides. Lewis acids favour the formation of 2,3-unsaturated glycosides, whereas, Brønsted acids lead to normal addition products. A mixture of both the product is obtained often, depending on the nucleophiles and the stereochemistry of glycal. Chapter 1 of the thesis describes (i) reactivities of glycals under acidic condition and (ii) a general survey of reactions involving on C2-C3 carbons of monosaccharides. Glycals are useful precursors to derive a number of functionalized monosaccharide derivatives. A well-known acid catalyzed reaction of glycals is their conversion to 2,3¬unsaturated glycosides, known as the Ferrier products. In a research programme, reactivity switching and selective activation of C-1 or C-3 of 2,3-unsaturated thioglycosides under acid catalyzed condition was undertaken. Thioglycosides are excellent glycosyl donors and can be activated easily. In identifying the reactivities of 2,3-unsaturated thioglycosides, obtained through Ce(IV)-mediated reaction of a glycal, it was intended to study the glycosylation reaction and also the reactivity control of C1-C3 carbons during a glycosylation reaction. Experiments showed that a reactivity switching was possible through activation of either C-1 or C-3. Thus, C-1 glycosylation with alcohol acceptors occurred in the presence of NIS/TfOH, without the acceptors reacting at C-3. On the other hand, reaction of 2,3-unsaturated thioglycosides with alcohols mediated by triflic acid alone led to a transposition of C-1 ethylthio-moiety to C-3 intramolecularly, to form 3-ethylthio-glycals. Resulting glycals underwent glycosylation with alcohols to afford 3-ethylthio-2-deoxy glycosides. However, when thiol was used as an acceptor, only a stereoselective addition at C-3 resulted, so as to form C-1, C-3 dithio-substituted 2-deoxypyranosides. Oxocarbenium ion is the reactive intermediate during activation of a glycosyl donor, and in the case of a 2,3-unsaturated thioglycosides, the oxocarbenium ion may stabilize further by the presence of a C2-C3 unsaturation. Reaction of a nucleophile with allylic oxocarbenium ion may lead to two regio-isomers. Initially, NIS/TfOH was attempted on 2,3–unsaturated sugar with various alcohols and it was found that C-1 was the preferred reactive centre (Scheme 1) Scheme 1 In order to optimize the reaction for selective nucleophilic attack at C-3, further study was continued by using stoichiometric TfOH, in presence of acceptors alcohols with the intension to activate the double bond. The reaction led to the formation of 2-deoxy O-glycosides with the concomitant transposition of C-1 ethylthio-moiety to C-3 (Scheme 2). Scheme 2 An important observation was that the transposition of thioethyl group from C-1 to C-3 was highly regioselective. For example, with thiocresol as the nucleophile, there was an addition across the C-2-C-3 double bond to afford C-1, C-3-dithio derivative (Scheme 2). Thus, hard-soft nature of the nucleophiles, as well as, carbon centres helped to rationalize the reactivites. It was also observed that the intramolecular transposition of thioethyl group is highly stereo-controlled by equatorial C-4 acetoxy group. Thus, thioethyl nucleophile approached selectively at C-3 and afforded trans-diequatorial products. This rationalization was further confirmed through (i) reaction of benzyl protected 2,3-unsaturated thioglycoside, wherein a C-3 epimeric mixture was observed in 1:1 ratio; (ii) galactosyl derivative under similar reaction condition afforded anomeric mixture of 3-(4-methylphenylthio)-O-glycosides, with trans-diaxial orientation of substituent at C-3 (Scheme 3). Scheme 3 These reactions confirmed the role of C-4 substituent on the carbocation at C-3, through the presence or absence of a neighbouring group participation. In summary, in Chapter 2 the selective activation of either anomeric carbon or C-3 with proper choice of activation and reactivity control at each carbon will be described. Thioglycosides are excellent glyosyl donor and their glycosylation reactions were well explored. Upon indentifying the intramolecular transposition of thioalkyl/aryl functionality from C-1 to C-3, further investigations was undertaken to utilize the newly formed carbon sulfur bonds at C-3. Realizing a potential for such 3-alkyl/aryl thio 2-deoxy sugar, the Pummerer rearrangement was investigated. For this purpose, the thioalkyl/aryl moiety at C-3 was oxidized first to a sulfoxide. The resulting sulfoxide was allowed to undergo Pummerer rearrangement to afford vinyl sulfide (Scheme 4), resulting from the elimination of HOAc in the thioacetal formed in situ. Having implemented Pummerer rearrangement on a sugar substrate, synthetic utility of the rearrangement product, namely vinyl sulfide was undertaken. An effort to implement conjugate addition reaction was undertaken, which required the conversion of vinyl sulfide to vinyl sulfoxide in the first step. The conjugate addition reactions were first conducted with alkoxide nucleophiles. The reaction showed that addition of nucleophiles occurred from axial face to furnish manno-configured derivatives as a single diastereomer at sulfinyl sulfur in a moderate yield along with O-deacetylated product. It was also found that O-benzyl protected sugar vinyl sulfoxide was totally resistant to the conjugate addition reaction (Scheme 4). Scheme 4 In order to find the influence of the substituents in sulfoxide moiety in the addition of nucleophiles, additional study was conducted in which a less hindered thioethyl moiety was installed in place of p-tolylthio moiety. To install ethylthio moiety, a similar sequence of reaction was undertaken as described previously in Scheme 4. Conjugate addition reaction with alkoxide nucleophiles was conducted and analysis of the reaction showed that the addition of alkoxides remained similar, leading to the formation of manno-configuration of substituents (Scheme 5). Scheme 5 The configuration of the Michael adducts were ascertained from 1H NMR, as well as 2D NMR spectroscopies. H-1 of all adducts appeared as an apparent singlet, consistent with very small J1,2 values. Aryl vinyl sulfoxide afforded conjugate addition product at much higher ratio than corresponding alkyl vinyl sulfoxide. Thus, among aryl and alkyl vinyl sulfoxides, conjugate addition occurred better with the aryl vinyl sulfoxide, indicating a strong electronic effect of aryl group in stabilizing the conjugate anion which would form in situ during nucleophilic addition with vinyl sulfoxide. Therefore, p-tolylthio substituted vinyl sulfoxide served as a more efficient Michael acceptor when compared to the thioethyl substituted vinyl sulfoxide. Asymmetric environment of vinyl sulfoxides play a vital role during the reaction. Vinyl sulfoxides can exist in two stereochemically distinct conformation which makes the vinyl group electronically dissimilar. In one of the conformer S-O and C-C bonds are coplanar, whereas in the other conformation, these two bonds are opposite to each other. It is agreed generally that vinyl sulfoxides generally try to adopt the most reactive conformer during the reaction in which the C-C and S-O bonds are syn to each other. Thus, the preference for an axial attack would originate from a face anti to the lone pair of electrons on the sulfur of sulfoxide functionality, leading to the formation of the product with manno-configuration. As O-deacetylated vinyl sulfoxide was obtained along with the Michael adducts, it was assumed that one of the epimers of vinyl sulfoxide appeared to be more reactive when compared to the other. Chapter 3 describes implementation of a Pummerer rearrangement in order to synthesize a sugar vinyl sulfoxide and its conjugate addition reactions with alkoxide nucleophiles. The nucleophilic addition reactions of vinyl sulfoxide with other nucleophiles were studied further. The effect of the substituents of chiral sulfoxides in conjugate addition reactions was also incorporated in the course of reactions. Reactions of amines, carbon and sulfur nucleophiles were undertaken with p-tolylthio-substituted vinyl sulfoxides. The reactions showed formation of the addition-elimination products (Scheme 6). All primary amines, carbon and sulfur nucleophiles afforded C-2 axial epimer, namely, threo-epimer exclusively, wherein secondary amines furnished the equatorial vs axial epimer in 3:1 ratio. Scheme 6 In order to assess the course of the reaction, vinyl sulfoxide presenting a p-cumenethio¬moiety was installed in place of p-tolylthio moiety. Conjugate addition reactions were performed with both primary as well as secondary amines that showed formation of the C-2 epimeric mixtures. With both the primary and secondary amines C-2 equatorial epimer was found to be as the major product (Scheme 7). Scheme 7 In conjugate addition of vinyl sulfoxides, nucleophiles approach the olefinic face preferentially, which is anti to the electron rich sulfur lone pair of electrons and syn to the bulky aryl group. Therefore, C-2 axial epimer was observed as most favourable product. However, secondary amines remarkably influenced the pattern as well as selectivity of the reaction. Steric considerations were likely to dictate the overall reactivity with secondary amines which was even more pronounced when using p-cumenethio-substituted vinyl sulfoxide. Chapter 4 describes the conjugate additions as well as remote effect of aryl substituent on the selectivity of addition of amines on sugar sulfoxide In summary, the Thesis establishes: A new reactivity of switching and a selective activation of 2,3-unsaturated thioglycoside; A Pummerer rearrangement route in order to synthesize sugar vinyl sulfide for the first time, which on selective oxidation furnish a sugar vinyl sulfoxide, a useful precursor for conjugate addition reactions; An assessment of the stereoelectronic, as well as, steric effect of the chiral vinyl sulfoxide with various nucleophiles in conjugate addition reactions; Influence of the protecting groups were also studied in conjugate addition reactions. Overall the study presented in the Thesis provides a new insight to unsaturated sugars. The salient features of the present findings also showed that the intermediates such as C-3 substituted thioalkyl/aryl glycosides, vinyl sulfides, a variety of new C-2 substituted vinyl sulfoxides are also the potential sites for many types of modifications in monosaccharides. (For structural formula pl see the pdf file)

L’objectif de cette thèse était d’utiliser les propriétés magnétiques des roches (paléomagnétisme, anisotropie de la susceptibilité magnétique (ASM) et différentes techniques d’analyse de la minéralogie magnétique), complété par d’autres méthodes classiques (microscopie pétrographique et électronique, goniométrie de texture, spectroscopie Raman, statistiques d’orientation préférentielle de forme et cathodoluminescence) pour aborder des thématiques récurrentes relatives à la formation des gisements métalliques. Cette approche a été appliquée à deux problèmes métallogéniques : (i) le traçage de la circulation du fluide ayant produit la métasomatose ferrifère des carbonates de La Florida (Cantabrie, Nord de l’Espagne) et la mise en place des minéralisations à Pb–Zn associées (MVT) ; et (ii) l’étude de la structuration des gossans et le décryptage de l’histoire de l'altération des amas sulfurés de la Ceinture Pyriteuse Sud Ibérique (CPSI, Andalousie, Sud de l’Espagne). Dans le premier cas, nous avons pu démontrer expérimentalement que la circulation des fluides produit une anisotropie de forme dont on peut retrouver l’empreinte dans le signal de l’ASM. Cette propriété nous a permis de définir une direction NE–SW de circulation du fluide métasomatique à La Florida. Dans le deuxième cas, le couplage entre l’ASM et le paléomagnétisme nous a permis de définir deux fabriques magnétiques dans les gossans primaires ; (i) une fabrique, d’âge ancien, de « compaction », caractéristique des parties supérieures des gossans, probablement associé au réchauffement de l’Oligocène supérieur et (ii) une fabrique de « mélange », plus récente, localisée dans les parties inférieures des gossans, formée probablement lors de l’événement messinien. La fabrique de « compaction » refléterait donc une altération plus mâture comparée à la fabrique de « mélange ». Par ailleurs, l’analyse de la minéralogie magnétique des gossans et des terrasses de la CPSI a révélé la présence « inhabituelle » de la pyrrhotite, une présence que nous avons attribué à l’activité de bactéries sulfato-réductrices dans des microdomaines réducteurs, disséminés dans un environnement globalement oxydant et très acide. / The purpose of this PhD thesis was to use the magnetic properties of rocks (paleomagnetism, anisotropy of the magnetic susceptibility (ASM) and various techniques of magnetic mineralogy analysis), supplemented by some traditional methods (petrographic and electronic microscopy, texture goniometry, Raman spectroscopy, shape preferential orientation statistics and cathodoluminescence) to study the formation of metal deposits. This approach was applied to two metallogenic studies: (i) the track of fluid circulation that produced the iron-bearing metasomatism of the carbonates of La Florida mining district (Cantabria, Northern Spain), and the Pb–Zn mineralization deposits (MVT); and (ii) the study of the internal structures of the gossans and the alteration history of the massive sulphides of the Iberian Pyrite Belt (IPB, Andalusia, Southern Spain). In the first case, we showed experimentally that the fluid circulation produces a shape anisotropy, recorded in the form of a magnetic anisotropy. This property enabled us to define a NE–SW direction of the circulation of the metasomatic fluid in the La Florida district mining. In the second case, the coupling of AMS and paleomagnetism enabled us to define two magnetic fabrics in the primary gossans; (i) a “compaction” fabric in the upper parts of the gossans, associated to an old age, and probably caused by the Late Oligocene Warming Event, and (ii) a “mixture” fabric, more recent, located in the lower parts of the gossans and probably formed during the Messinian Salinity Crisis. The “compaction” fabric would reflect an alteration stage more mature than the “mixture” fabric. In addition, the magnetic mineralogical analysis of the gossans and the associated terraces of the CPSI revealed the “curious” occurrence of the pyrrhotite, which was attributed to the sulfato-reducing bacteria activity in some reducing microdomains, disseminated in an environment globally oxidant and highly acid.