Η παρούσα διπλωματική εργασία εστιάζει στη μελέτη των πετρωμάτων που φιλοξενούν τη μεταλλοφορία ψευδαργύρου, αργύρου και μολύβδου στην ευρύτερη περιοχή των Μολάων Λακωνίας. Οι κύριοι σχηματισμοί που εντοπίζονται στην υπό μελέτη περιοχή είναι η ενότητα της Άρνας και τα στρώματα του Τυρού. Σκοπός της εργασίας αυτής είναι η πετρογραφική και γεωχημική μελέτη των δύο προαναφερθέντων σχηματισμών, ώστε να καταστούν κατανοητές οι συνθήκες σχηματισμού. Πραγματοποιήθηκαν 9 χημικές αναλύσεις σε ηφαιστειακά πετρώματα των στρωμάτων του Τυρού για κύρια στοιχεία, ιχνοστοιχεία και σπάνιες γαίες, παράλληλα μελετήθηκαν και 15 πετρογραφικές λεπτές τομές των ηφαιστειτών αυτών. Τα δεδομένα συμπληρώθηκαν με 14 χημικές αναλύσεις κύριων στοιχείων και 9 χημικές αναλύσεις ιχνοστοιχείων των πετρωμάτων της ενότητας της Άρνας από βιβλιογραφική πηγή. Τα ηφαιστειακά πετρώματα των στρωμάτων του Τυρού αποτελούν ηφαιστείτες με εύρος συστάσεων από ανδεσιτικό βασάλτη έως δακίτη. Φέρουν ασβεσταλκαλικό χαρακτήρα με ελαφρά θολεϊτική τάση. Επίσης, προβάλλονται στα πεδία των θολεϊτών ηφαιστειακού τόξου, καθώς και σε ζώνη καταβύθισης των λιθοσφαιρικών πλακών. Ορισμένα εκ των δειγμάτων έχουν μεταμορφωθεί σε πρασινοσχιστολιθική φάση, ενώ στην πλειοψηφία των φέρουν έντονη εξαλλοίωση. Τα πετρώματα της ενότητας της Άρνας αποτελούν μεταηφαιστειακά πετρώματα βασαλτικής σύστασης. Φέρουν σαφή θολεϊτικό χαρακτήρα και προβάλλονται στο πεδίο των βασαλτών μεσωκεάνιας ράχης. / This thesis focuses on the study of the rocks that host the metalliferous of zinc, silver and lead in the wider area of Molai, Laconia. The main formations, which are spotted in the under study area, are the section of Arna Units and the Tyros Beds. The purpose of this work is the petrographic and geochemical study of the two formations mentioned above, so that the conditions of the formation become comprehensible. Nine chemical analysis were carried out in volcanic rocks of Tyros Beds for main elements, trace elements and rare earth elements, while at the same time fifteen petrographic thin sections of those volcanic rocks were studied. The data was complete with fourteen chemical analysis of main elements and nine chemical analysis of trace elements of the Arna Units from a bibliographical source. The volcanic rocks of Tyros Beds are volcanic rocks with amplitude of composition from andesitic basalt to dacite. They have calc-alcaline nature with a slight tholeitic tendency. Also, they are displayed / projected in the fields of the volcanic arc’s tholeites as well as in the zone of the lithospheric plates’ submersion. Some of the samples have been transformed into a greenschist phase, while the majority has an intense alteration. The rocks of Arna Units are metavolcanic rocks with basaltic composition. They have a clear tholeitic nature and they are displayed in the field of the basalts of the mid ocean ridge.

Trois systèmes ternaires (SAS, BAS et ZAS) ont été étudiés dans le cadre de la thèse. Les principaux objectifs étaient l’élaboration et la caractérisation de verres aluminosilicatés de Sr, Ba et Zn peu étudiés auparavant. Une étude systématique a été réalisée sur des aluminosilicates vitreux et dans certains cas sur des aluminosilicates fondus avec différents rapports MO/Al₂O₃ (M = Sr, Ba, Zn) et SiO₂/Al₂O₃. Les compositions étudiées couvrent une partie significative des diagrammes ternaires (des silicates aux verres peralumineux, des compositions pauvres en silice à celles riches en silice). Cela a permis d'accroître nos connaissances sur les domaines de vitrification de ces systèmes. Afin d’obtenir des informations sur la structure et les propriétés macroscopiques des verres SAS, BAS et ZAS, une approche multi-technique a été mise en place. Une telle approche permet d’avoir une vue d’ensemble sur les systèmes étudiés et de trouver des origines nano- à microscopiques aux propriétés macroscopiques. La spectroscopie de résonance magnétique nucléaire, la diffractométrie de neutrons et la spectroscopie Raman ont été utilisées au cours de la thèse afin de sonder l'échelle à courte et à moyenne distance. Les propriétés macroscopiques mesurées ont été : la densité, la viscosité et la température de transition vitreuse. Les données issues de cette thèse permettent une meilleure compréhension des changements de structures et des propriétés macroscopiques des verres aluminosilicatés produits par les variations de MO/Al₂O₃ ou SiO₂/Al₂O₃, ou par la nature des cations non-formateurs de réseau. / Three ternary systems (SAS, BAS and ZAS) have been investigated within the framework of the PhD thesis. The main goals were the elaboration and characterization of previously poorly studied Sr, Ba and Zn aluminosilicate glasses. A systematic study has been carried out on glasses and in some cases on melts with various MO/Al₂O₃ (M = Sr, Ba, Zn) and SiO₂/Al₂O₃ ratios. The compositions studied cover a significant part of the ternary diagrams (from silicates to peraluminous glasses, from silica-poor to silica-rich compositions). This allowed expanding our knowledge of the vitrification domains in these systems. In order to obtain information on the structure and macroscopic properties of SAS, BAS and ZAS glasses, a multi-technique approach has been implemented. Such approach allows having a broad view on the systems and finding nano- to microscopic origins of macroscopic properties. The techniques used during the thesis probe short- (NMR, ND) to medium-range (Raman) scale and among the properties studied were density, viscosity and glass transition temperature. The data resulting from this thesis provides a better understanding of the changes in the structure and macroscopic properties of the aluminosilicate glasses produced by variations in MO/Al₂O₃ or SiO₂/Al₂O₃, or by the nature of non-network forming cation.

The effect of individual additions of calcium oxide (CaO), Gd, Nd and Y was investigated on the microstructure, mechanical properties and corrosion resistance of the as-cast ZK40 alloy. The microstructural features were analised using optical, scanning and transmission electron microscopy, X-ray diffraction and Scanning Kelvin Atomic Probe Force Microscopy. The compressive and tensile behaviours of the as-cast alloys at room temperature were investigated. Electrochemical Impedance Spectroscopy, hydrogen evolution and weight loss under immersion in 0.5 wt.% NaCl solution were used to evaluate the corrosion behaviour. The results of the mechanical and corrosion tests were correlated with the microstructures. The 2 wt.% Gd addition enhanced the ductility, while the Nd addition resulted in deterioration in mechanical properties. The addition of 2 wt.% Gd and 1 wt.% Y resulted in the improvement of the ductility. The addition of CaO did not affect the mechanical properties while the 2 wt.% Nd deteriorate it. The 1 wt.% Y addition enhanced the ductility. The CaO addition did not caused enhancement in mechanical properties. The corrosion behaviour was enhanced with the addition of CaO and Gd. The modification of ZK40 with Gd opens up new perspectives in the development of Mg-Zn based alloys. / O efeito da adição individual de óxido de cálcio (CaO), Gd, Nd e Y foi investigado na microestrutura, propriedades mecânicas e resistência à corrosão de ligas ZK40 fundidas. As características microestruturais foram analisadas via microscopia óptica, microscopia eletrônica de varredura, microscopia eletrônica de transmissão, difração de Raios-X e \"Scanning Kelvin Atomic Probe Force Microscopy\". O comportamento à compressão e à tração das ligas à temperatura ambiente foi investigado. Espectroscopia eletroquímica de impedância, evolução de hidrogênio e ensaios de imersão em solução de 0.5% em peso de NaCl foram utilizados para avaliar a resistência à corrosão. Os resultados dos ensaios mecânicos e corrosão foram relacionados com a microestrutura. A adição de 2% em peso de Gd melhorou a ductilidade, ao passo que a adição de Nd resultou na piora das propriedades mecânicas. A adição de 2% em peso de Gd e 1% em peso de Y resultou na melhora da ductilidade. A adição de 1% em peso de Y causou uma melhora na ductilidade e a adição de CaO não teve impacto benéfico nas propriedades mecânicas. A resistência à corrosão foi melhorada com a adição de CaO e Gd. A modificação da liga ZK40 com a adição de Gd abre novas perspectivas no desenvolvimento de ligas Mg-Zn.

Les travaux décrits dans ce manuscrit s’intéressent au contrôle du mouvement moléculaire. Après une introduction dédiée à l’état de l’art des machines moléculaires, le premier chapitre s’intéresse à la conception de tourniquets moléculaires à base de complexes porphyriniques de P(V). Le mouvement moléculaire a pu être contrôlé de manière réversible soit par l’utilisation des sites de coordination présents à la périphérie du système soit par des variations de pH. Le deuxième chapitre s’intéresse aux propriétés photophysiques des porphyrines de P(V) obtenues et plus particulièrement à leur capacité à générer de l’oxygène singulet avec une application potentielle en Thérapie Photodynamique (PDT).Le troisième chapitre concerne l’élaboration d’un complexe contenant deux porphyrines de Zn(II) dont le mouvement relatif a pu être bloqué réversiblement par l’utilisation des positions axiales des cations métalliques. / The manuscript focuses on molecular machines and the control of their movement. Two different devices have been designed, synthetized and characterized. Moreover, a series of new potential photosensitizer was obtained.The introduction gives a general overview on molecular machines, reported during the past 20 years. The first chapter describes the synthesis of molecular turnstiles based on P(V) porphyrins. The molecular motion was controlled reversibly using either coordination chemistry or by changing the pH. The second part is dedicated to the study of the photophysical properties of P(V) porphyrins and especially their capacity to generate singlet oxygen under irradiation., making them potential photosensitizers that can be use in Photodynamic Therapy (PDT) or as catalyst. The third chapter is devoted to the study of a molecular break based on a Zn (II) porphyrin dimer. The control of the movement was performed using the coordination of a bidentate ligand in the axial position of the metal cations.

Nous étudions la fragilisation par l'hydrogène de l'alliage d'aluminium 7108. Une technique expérimentale spécifique a été développée : Un pré-chargement en hydrogène des échantillons, à travers un dépôt de nickel de quelques dizaines de microns, qui empêche la dissolution du substrat d'aluminium, est utilisé. Il permet la comparaison de la résistance à la fragilisation de différentes microstructures modèles. Nous étudions l'effet du traitement thermique et de la précipitation sur la sensibilité à l'hydrogène pour des vitesses de déformation macroscopiques imposées variables. Différents modes de rupture sont observés ainsi que des transitions entre eux. Au moyen de simulations numériques à l'échelle mésoscopique, l'effet de taille des précipités intergranulaires pré-fragilisés sur la ténacité des joints de grains est estimé, en utilisant un modèle de zone cohésive. Nous analysons la compétition entre la diffusion de l'hydrogène vers la pointe de la fissure et la vitesse de fissuration par un couplage mécanique - diffusion basé sur la diffusion de l'hydrogène assistée par la contrainte hydrostatique. Une vitesse critique au-delà de laquelle l'hydrogène ne peut plus suivre la fissure, est mise en évidence. L'influence de la microstructure du joint de grains sur cette vitesse est analysée. La valeur est comparée à une estimation des vitesses de propagation expérimentales obtenues pour différentes vitesses de déformation macroscopiques. Nous analysons l'effet du piégeage de l'hydrogène par les précipités intergranulaires et la désorption sur la répartition de l'hydrogène le long du joint de grains en imposant un flux au niveau de l'interface précipités - matrice. / We study the hydrogen embrittlement of the 7108 aluminum alloy. A specific experimental technique was developed : A hydrogen pre-charging, through few tens of microns of deposit of nickel, which prevents the dissolution of the aluminum substrate is used. It allows a comparison of the resistance to embrittlement of different model microstructures. We study the effect of heat treatment and intergranular precipitation on the susceptibility to hydrogen embrittlement for several macroscopic strain rates. Different failure modes and transitions between them are observed. Through numerical simulations, at the mesoscopic scale, the effect of the size of pre-weakened intergranular precipitates on the grain boundary toughness is estimated using a cohesive zone model. We further analyze the competition between the hydrogen diffusion toward the crack tip and crack velocity. For this purpose, a mechanical – diffusion coupling based on the hydrogen diffusion assisted by hydrostatic stress is elaborated. A critical crack velocity, beyond which hydrogen can no longer follow the crack, is highlighted. The influence of the grain boundary microstructure on this critical crack velocity is evaluated and its value is compared with an estimate of velocities obtained for different experimental macroscopic strain rates. We analyze the effect of hydrogen trapping by intergranular precipitates and hydrogen desorption by imposing a flux at the precipitates – matrix interfaces.

O cinturão Fíngoè é uma unidade tectônica do Supercontinente Gondwana Oeste composta por rochas supracrustais formadas há aproximadamente 1.33 Ga. Essas rochas são portadoras de mineralizações de Au, Cu, Zn, Pb e Fe. Com cerca de 150 km de comprimento, e orientado WSW-ENE, este cinturão estende-se desde o Monte Atchiza a oeste até cerca de 30 km para leste da vila de Fíngoè no norte de Moçambique e consiste de uma extensa variedade de rochas metassedimentares e metavulcânicas. O cinturão Fíngoè apresenta especialização metalogenética para Au e Cu, que já foram explotados no passado em diversos locais. Muitos destes registros estão associados com magnetita e malaquita. Atualmente trabalhos de prospecção e pesquisa mineral têm sido realizados pela empresa de mineração African Queen Mines Ltda, através do projeto denominado de King Solomons, localizado na parte central do mesmo. A geologia da área abrangida pelo prospecto Mankombiti, mostra uma predominância de rochas carbonáticas, granitos e gabros. As rochas carbonáticas são consideradas importantes na gênese de depósitos tipo skarn e depósitos de substituição de metais de base e Au devido à sua natureza fortemente reativa. Os dados geocronológicos realizados neste trabalho indicaram uma idade precisa para a rocha intrusiva granítica associada à mineralização de 1079,1 ± 8,2 Ma, que poderia ser a idade da formação do skarn e consequentemente desta mineralização. Entretanto a idade obtida para o processo de alteração hidrotermal que afetou o gabro, na ordem de 657 ± 36 Ma e a idade modelo Pb-Pb sugerida pelo modelo de Stacey e Kramers (1975) para a calcopirita da mineralização principal de 725 Ma, sugerem que a mineralização, do prospecto Mankombiti é neoproterozóica. Para melhor entendimento dos processos que estiveram envolvidos na formação deste depósito skarn, duas hipóteses são consideradas: (i) poderia ser admitida a presença de corpos graníticos intrusivos em 700 Ma, situados em profundidade, que não foram ainda caracterizados, como responsáveis pela fonte de calor necessária, (ii) pode ser admitida ocorrência de um evento distensional em 700 Ma que produziria um adelgaçamento da litosfera e a consequente ascensão da astenosfera, produzindo uma elevação do fluxo térmico gerando os fluidos mineralizantes necessários. / The Fíngoè belt is a tectonic unit of West Gondwana Supercontinent, comprised of supracrustal rocks formed at approximately 1.33 Ga. These rocks are carriers of Au, Cu, Zn, Pb and Fe mineralization. With about 150 km long and oriented WSW- ENE, this belt extends from west of the Atchiza Mount to about 30 km east of the Fíngoè village in the north Mozambique, and consists of an extensive variety of metasedimentary and metavolcanic rocks. The Fíngoè metallogenic belt provides specialization for Au and Cu, which have been exploited in the past in various locations. Many of these records are associated with magnetite and malachite. Currently, the prospecting and mineral exploration have been conducted by the African Queen Mines Ltd mining company, through a project called the King Solomons, located in the central part of it. The geology of the studied area shows a predominance of carbonate rocks, granites and gabbros. The carbonate rocks are considered important in the genesis of the skarn deposits type and deposits of replacement for base metals and Au due to its highly reactive nature. The geochronological data performed in this work indicate a precise age of the 1079.1 ± 8.2 Ma for the intrusive granitic rock associated with mineralization, which could be interpreted as the age of the skarn and consequently of the mineralization. However the age obtained for the hydrothermal alteration that affected the gabbro at about 657 ± 36 Ma and the Pb-Pb model age suggested by the model of Stacey and Kramers (1975) for primary chalcopyrite mineralization at 725 Ma, suggesting that the mineralization of the Mankombiti prospectus was developed during the Neoproterozoic time. For understanding the processes that were involved in the skarn-type mineralization processes, two hypotheses are here considered: (i) could be admitted the presence of i ntrusive granitic rocks at 700 Ma, situated in depth, which have not yet been characterized, as responsible for the heat source required, (ii) may be admitted occurrence of an extensional event at 700 Ma to produce a thinning of the lithosphere and the uplift of the asthenosphere, producing high thermal flows generating the mineralization fluids.

V práci je zkoumán vliv podmínek na průběh hydrolýzy alkoxidů titanu a vlastností připravovaných nanočástic oxidu titaničitého s důrazem na teplotu a množství vody přítomné v systému. Připravované hydrolyzáty alkoxidů titanu a nanočástice oxidu titaničitého připravené z hydrolyzátů jsou studovány metodami XRD, DTA – TGA, SEM – EDS, BET a PCCS. Nanočástice magnetitu byly syntetizovány pomocí precipitační reakce z roztoku Mohrovy soli a jejich krystalová struktura, velikost a povrchové vlastnosti byly sledovány s vyhodnocením vlivu teploty a při modifikaci povrchu polykarboxyletherovým superplastifikátorem. Pro upevnění TiO2 na povrch magnetitu byla použita kombinovaná metoda aplikace vybraných nanočástic TiO2 s hydrolýzou TiO2 pomocí alkoxidů titanu za účelem přípravy fotokatalyticky aktivního core-shell práškového katalyzátoru s vylepšenými vlastnostmi adsorpce na povrchu. Studovány byly možnosti aplikace TiO2 na povrch Mn-Zn feritu, kdy byl studován vliv depozice tenkých vrstev C a Au na morfologii povrchu. Fotokatalytická aktivita vybraných připravených materiálů byla studována pomocí dekompozice methylenové modři v roztoku a par isopropanolu a ethanolu rozkládaných pomocí Mn-Zn feritu v experimentálním chemickém reaktoru s magnetickým polem stabilizovaným ložem nosiče katalyzátoru.

Recently, Zn-XAl-YMg coatings have emerged as lighter-weight substitutes for traditional Zn-based coatings for the corrosion protection of steels; however, little is currently known concerning the interactions between the oxides present on advanced high strength steel (AHSS) surfaces and the Zn-Al-Mg bath. In the current contri- bution, the selective oxidation and reactive wetting of a series of C-Mn AHSS were determined with the objective of providing a quantitative description of this pro- cess. The process atmosphere pO2 was varied using dew points of −50◦C, −30◦C and −5◦C. The surface oxide chemistry and morphology were analysed by means of SEM and XPS techniques. Reactive wetting of the selectively oxidized surfaces using a Zn-1.6 wt.% Al-1.6 wt.% Mg bath was monitored as a function of annealing time at 60 s, 100 s and 140 s at 800◦C. The resulting bare spot defects in the Zn-1.6 wt.% Al-1.6 wt.% Mg coating were assessed by means of SAM-AES and FIB, while coating adhesion was analysed by 180◦ bend tests. Annealing the steel substrates resulted in the formation of surface MnO, which varied based on pO2 and Mn alloy content, and that this MnO greatly reduced the wettability of the steel by the Zn-1.6 wt.% Al- 1.6 wt.% Mg bath, resulting in bare spot defects. It was determined that the reactive wetting of the steel substrate was dependant on the oxide morphology and oxidation mode, which was a function of both alloying content of Mn in the steel and annealing pO2 process atmosphere (dew point). Finally, it was concluded that the bare spot area percentage on the coated panels was statistically invariant for annealing times of between 60 s and 140 s at 800◦C. / Thesis / Master of Applied Science (MASc) / Metallic coatings are applied to steels that are not naturally corrosion resistant. The aim of this research was to determine how well a coating containing zinc, aluminum and magnesium adhered to high strength automotive steel. It was deter- mined that manganese oxides formed on the steel during heating prior to applying the metallic coating. The manganese oxides prevented good adhesion between the steel and the coating, resulting in bare spot defects in the coating. The bare spot defects are undesirable as they leave the steel exposed and therefore susceptible to corrosion and are unsightly when painted.

The anode-free battery concept is proposed to pursue the aspiration of energy-dense, rechargeable metal batteries, but this has not been achieved with dual-ion batteries. Herein, the first anode-free Zn–graphite battery enabled by efficient Zn plating–stripping onto a silver-coated Cu substrate is demonstrated. The silver coating guides uniform Zn deposition without dendrite formation or side reaction over a wide range of electrolyte concentrations, enabling the construction of anode-free Zn cells. In addition, the graphite cathode operates efficiently under reversible bis(trifluoromethanesulfonyl)imide anion (TFSI−) intercalation without anodic corrosion. An extra high-potential TFSI− intercalation plateau is recognized at 2.75 V, contributing to the high capacity of graphite cathode. Thanks to efficient Zn plating–stripping and TFSI− intercalation–deintercalation, an anode-free Zn–graphite dual-ion battery that exhibits impressive cycling stability with 82% capacity retention after 1000 cycles is constructed. At the same time, a specific energy of 79 Wh kg−1 based on the mass of cathode and electrolyte is achieved, which is over two times higher than conventional Zn–graphite batteries (<30 Wh kg−1).

Doctor of Philosophy / Department of Agronomy / Gary M. Pierzynski / The bioavailability of Pb and Zn is linked to the solubility of solid phases and other soil chemical characteristics, which is associated with their environmental risk, suggesting that in situ stabilization of these elements can be accomplished by influencing their chemistry. However, more research is needed to investigate the effectiveness of different soil amendments on reducing Pb and Zn bioavailability. A lab study was conducted to evaluate the effects of five different P amendments and time on Pb/Zn speciation in a contaminated soil using synchrotron-based techniques, while a field investigation studied the effects of composted beef manure on plant biomass production and the influence on microbial function, size, and community shifts. In the lab study, the Pb-phosphate mineral plumbogummite was found as an intermediate phase of pyromorphite formation, which has not been documented until now. Additionally, all fluid and granular P sources were able to induce Pb-phosphate formation, but fluid phosphoric acid (PA) was the most effective with time and distance from the treatment. However, acidity from PA increased the prescence of soluble Zn species, which can have negative environmental consequences. Granular phosphate rock (PR) and triple super phosphate (TSP) reacted to generate both Pb- and Zn-phosphates, with TSP being more effective at greater distances than PR. In the field study, compost additions of 269 Mg ha[superscript]1 significantly decreased bioavailable Zn, while increasing estimated available water, plant nutrients, and plant biomass as compared to a contaminated control and low addition of compost (45 Mg ha[superscript]1) over three years. Additionally, compost additions of 269 Mg ha[superscript]1 significantly increased microbial enzyme activities, nitrification, and microbial biomass over the contaminated control through the duration of the study. Increases in microbial activity and biomass are related to increases in total C, available water, and extractable P, while negative relationships were found with electrical conductivity and with bioavailable Zn. The addition of lime or lime plus bentonite with compost did not further reduce metal availability, increase plant biomass, or improve the size or function of microbial communities. High compost additions caused a slight shift in microbial community structure according to phospholipids fatty acid analysis. Increases in the mole percents of both Gram-positive (Gm[superscript]+) and Gram negative (Gm[superscript]-) bacteria were found depending on site. Microbial biomass of Gm[superscript]+, Gm[superscript]-, and fungi were also increased by high compost additions. Results indicate that large additions of compost are needed to increase microbial biomass, improve microbial activity, and re-establish a healthy vegetative community. This study proposes that organic matter and P amendments can be used to stabilize and reduce the bioavailability of heavy metals in soils and mine waste materials, but must be managed carefully and intelligently.