The Bushveld Igneous Complex (BIC) in South Africa holds approximately three quarters of the world’s viable chromite ore deposits. Most chromite is used for the production of ferrochromium (FeCr), which is a relatively crude alloy. Several chromite seams exist in the BIC. The most economically viable seams are the lower group 6 (LG6), the middle group 1 and 2 (MG1 and 2) and the upper group 2 (UG2) seams. The LG and MG seams are exploited specifically for their chromium content, whereas the UG2 seam is mainly exploited for platinum group minerals (PGM). However, the upgraded UG2 chromite in the PGM tailing is increasingly being used as a feedstock for FeCr production. Many different process variations exist for FeCr production. However, the process option applied in most green and brown field FeCr expansion projects during the last two decades in South Africa has been the oxidative sintered process (also referred to as the Outotec or Outokumpu process). Notwithstanding the common application of the oxidative sintered pelletised feed technology in the South African FeCr industry, and the increased utilisation of beneficiated UG2 ore, a direct comparison of the physical properties of oxidative sintered pellets produced from UG2 with the physical properties of that produced with conventional metallurgical grade chromite ore is currently lacking in the peer-reviewed scientific literature. Therefore, the physical properties of oxidative sintered pellets produced from a typical beneficiated South African UG2 ore were compared with the physical properties of that produced with conventional South African metallurgical grade chromite ore in this study. The results indicated that the case study metallurgical grade chromite ore required 13 kWh/t more energy to mill than the case study UG2 ore prior to pelletisation, which can lead to substantial cost savings. The compressive strength of the oxidative sintered pellets of both case study ores statistically showed that oxidative sintered pellets made from UG2 ore Abstract were the same or better than those prepared from metallurgical grade chromite ore. A comparison of the abrasion strengths of the oxidative sintered pellets of both case study ores indicated that the pellets prepared from UG2 ore were superior compared to the metallurgical grade pellets. The reasons for the superior UG2 pellet strength were investigated with backscatter-, secondary electron- and elemental X-ray mapping scanning electron microscopy (SEM), which indicated that differences in crystalline structures at least partially contributed to the differences observed. Results presented here can be utilised by FeCr producers to better quantify the advantages and disadvantages associated with the use of UG2 ore for FeCr production. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

The Bushveld Igneous Complex (BIC) in South Africa holds approximately three quarters of the world’s viable chromite ore deposits. Most chromite is used for the production of ferrochromium (FeCr), which is a relatively crude alloy. Several chromite seams exist in the BIC. The most economically viable seams are the lower group 6 (LG6), the middle group 1 and 2 (MG1 and 2) and the upper group 2 (UG2) seams. The LG and MG seams are exploited specifically for their chromium content, whereas the UG2 seam is mainly exploited for platinum group minerals (PGM). However, the upgraded UG2 chromite in the PGM tailing is increasingly being used as a feedstock for FeCr production. Many different process variations exist for FeCr production. However, the process option applied in most green and brown field FeCr expansion projects during the last two decades in South Africa has been the oxidative sintered process (also referred to as the Outotec or Outokumpu process). Notwithstanding the common application of the oxidative sintered pelletised feed technology in the South African FeCr industry, and the increased utilisation of beneficiated UG2 ore, a direct comparison of the physical properties of oxidative sintered pellets produced from UG2 with the physical properties of that produced with conventional metallurgical grade chromite ore is currently lacking in the peer-reviewed scientific literature. Therefore, the physical properties of oxidative sintered pellets produced from a typical beneficiated South African UG2 ore were compared with the physical properties of that produced with conventional South African metallurgical grade chromite ore in this study. The results indicated that the case study metallurgical grade chromite ore required 13 kWh/t more energy to mill than the case study UG2 ore prior to pelletisation, which can lead to substantial cost savings. The compressive strength of the oxidative sintered pellets of both case study ores statistically showed that oxidative sintered pellets made from UG2 ore Abstract were the same or better than those prepared from metallurgical grade chromite ore. A comparison of the abrasion strengths of the oxidative sintered pellets of both case study ores indicated that the pellets prepared from UG2 ore were superior compared to the metallurgical grade pellets. The reasons for the superior UG2 pellet strength were investigated with backscatter-, secondary electron- and elemental X-ray mapping scanning electron microscopy (SEM), which indicated that differences in crystalline structures at least partially contributed to the differences observed. Results presented here can be utilised by FeCr producers to better quantify the advantages and disadvantages associated with the use of UG2 ore for FeCr production. / MSc (Chemistry), North-West University, Potchefstroom Campus, 2014

Thesis (MSc (Earth Sciences))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: The Bushveld Complex of South Africa contains three of the most important platinum deposits in the world namely the Merensky Reef, the Upper Group Two (UG2) chromitite reef and the Platreef. These three ore bodies are principally beneficiated by froth flotation. During the beneficiation of chromite hosted PGE’s by froth flotation, chromite represents the principal gangue mineral. This is particularly true for the UG2 main seam. An excess of more than 3% in mass of chromite in the PGM concentrate is known to result in significant problems in the downstream processing and extraction of PGEs. The variability in texture and composition of chromite due to its primary crystallization and subsequent modification by the development of potholes or through IRUP intrusions are thought to influence the flotation behaviour of the UG2 main seam chromitite ore. This study conducted at Waterval Mine investigated the role of mineralogical characteristics of chromites on the flotation performance of three different environments for the UG2 main seam: (1) “normal” UG2 main seam; (2) UG2 main seam affected by pothole formation; and (3) UG2 main seam affected by IRUP intrusion. This was achieved through an extensive petrographic investigation of the chromites from each environment, to individually characterise their primary textures. This was followed by compositional characterisation of the chromite from each environment. Finally the flotation performance of the ore from each environment was investigated, using small scale batch flotation experiments, to establish any linkage between the textures, the composition and the flotation performance of the chromite from different environments. In this study it was found that the UG2 normal reef and the UG2 reef affected by pothole formation are both principally characterised by primary mineralogical features comprising mainly fine‐grained chromite as the cumulate phase and orthopyroxene and plagioclase as intercumulate phases. These two reef types were also found to be identical in the composition of the chromites present. In addition, in both of these almost unaltered reef types it was found that chromite showed small recoveries by flotation. On the other hand, it was found that the UG2 affected by IRUP intrusion was affected by post‐magmatic alteration that had overprinted primary textures and compositional features. This resulted in the replacement of primary minerals by secondary alteration assemblages. Orthopyroxene was iii replaced by serpentine, chlorite, amphibole and talc, while plagioclase is replaced by sericitic alteration. Furthermore, this alteration also resulted in modification of the chromite compositions. The compositional change in the chromites from the IRUP reef type resulted in Fe and Ti enrichment of chromite with increasing magnetic properties, and Cr, Al and Mg depletion. The alteration also resulted in the coarsening of chromite in the IRUP affected main seam reef particularly at the bottom and the top of the main seam. These compositional and textural modifications, principally the post‐magmatic alteration of intercumulate orthopyroxene, resulted in a greater recovery of chromite by flotation in the concentrate from the IRUP affected ore compared to the two other two ore types where there was small amount of chromite recovered. The characterisation of the recovered chromite revealed that the principal reason for chromite flotation was caused by the mineral association of chromite with hydrophobic Si, Mg, Fe rich phases, principally altered orthopyroxene and associated serpentine, chlorite, amphibole and talc. This investigation showed that the difference in mineralogical and flotation performances of chromite from the different UG2 main seam reef types was caused by the postcrystallisation alteration of cumulate and intercumulate phases due to the emplacement of IRUPs. Although IRUP affected UG2 main seam ore is not currently processed, it could be processed much more rapidly than the other two types of UG2 main seam ores because of its softer character resulting in shorter milling times. This is most likely a function of the presence of alteration phases and the presence of coarser chromite grains, as well as already brecciated chromite grains. Savings associated with the shorter milling time of this ore type are perhaps offset by the cost of the higher dosages of depressant required to suppress the floatable chromite in this ore type. However, given the energy cost of longer milling times, the cost of the depressant is likely to be insignificant. Moreover, the processing of the UG2 main seam ore affected by IRUP intrusion would also require a different approach to extraction of the ore to keep it separate from the normal reef ore.

Diversos anodos para célula a combustível de óxido sólido (SOFC) têm sido estudados devido aos problemas de deterioração dos anodos tradicionalmente usados, os compósitos à base de zircônia estabilizada/Ni (YSZ/Ni). Estudos prévios evidenciaram que a perovskita La0,75Sr0,25Cr0,50Mn0,50O3 (LSCM) possui desempenho similar em SOFCs usando hidrogênio e metano como combustível, tornando essa cerâmica um possível substituto dos compósitos à base de níquel. No presente estudo, foram sintetizados compostos La0,75Sr0,25Cr0,50-xMn0,50- yRux,yO3 (LSCM-Ru) pelo método dos precursores poliméricos. Análises termogravimétrica e térmica diferencial (TG/ATD) simultâneas e difração de raios X (DRX) foram utilizadas para monitorar a evolução térmica das resinas precursoras e a formação de fase dos compostos. As propriedades elétricas de amostras sinterizadas foram estudadas pela técnica de 4 pontas de prova dc na faixa de temperatura entre 25 °C e 800 °C. Os resultados experimentais indicaram a formação de fase única dos compostos LSCM-Ru calcinados a ~1200 °C. Os parâmetros de rede, calculados a partir dos dados de DRX, revelaram que a substituição parcial dos íons Cr ou Mn pelo Ru não altera significativamente a estrutura cristalina do LSCM até x,y ~ 0,10; uma característica consistente com os raios iônicos similares dos cátions Cr, Mn e Ru com número de coordenação seis. Medidas de resistividade elétrica ao ar mostraram que o mecanismo de transporte não é alterado e que o efeito da substituição de Ru nas propriedades elétricas do composto depende do íon substituído (Cr ou Mn) de maneira consistente com suas substituições parciais. Os testes de SOFCs unitárias revelaram que células com os anodos constituídos por uma camada coletora de corrente do anodo cerâmico LSCM-Ru e uma camada funcional de YSZ/Ni têm desempenho superior a células contendo apenas o anodo cerâmico. As células contendo os anodos cerâmicos LSCM-Ru foram testadas em hidrogênio e etanol, entre 800 °C e 950 °C, e mostraram desempenho em etanol superior ao em hidrogênio; uma característica que foi associada às propriedades de transporte eletrônico dos compostos LSCM-Ru em atmosfera redutora. Os resultados sugerem que os compostos LSCM com substituição parcial de Ru são anodos promissores para SOFC operando com etanol. / Several anodes for solid oxide fuel cell (SOFC) have been studied because of serious degradation exhibited by the traditionally used yttria-stabilized zirconia/Ni cermets (YSZ/Ni). Previous studies showed that the perovskite La0.75Sr0.25Cr0.50Mn0.50O3 (LSCM) has similar performance in SOFCs running on hydrogen and methane fuels, making such a ceramic a potential alternative to YSZ/Ni cermets. In the present study, compounds La0.75Sr0.25Cr0.50- xMn0.50-yRux,yO3 (LSCM-Ru) were synthesized by the polymeric precursor method. Simultaneous thermogravimetric and differential thermal analysis (TG/DTA) and X-ray diffraction (XRD) were used to monitor the thermal evolution of the precursor resins and the formation of crystalline phases. The electrical properties of sintered samples were studied by the 4-probe dc technique in the temperature range between 25 °C and 800 °C with controlled atmosphere. The experimental results showed the formation of single phase LSCM-Ru compounds after heat treatment at ~ 1200 °C. Lattice parameters, calculated from the XRD data, revealed that the partial substitution of Cr or Mn by Ru has no significant effect on the crystal structure of LSCM up to Ru x,y ~ 0.10; in agreement with the similar ionic radius of Cr, Mn and Ru with coordination number six. Electrical resistivity measurements showed that the transport mechanism is unchanged and that the effect of Ru addition on the electrical properties of the compound depends on the substituted ion (Cr or Mn). Electrochemical tests of SOFCs demonstrated that single cells comprised of a current collector layer of LSCM-Ru ceramic anode and a functional layer for YSZ/Ni have superior performance when compared to single cells with only one layer of the ceramic anode. Single cells with the LSCM-Ru ceramic anode layer were tested under both hydrogen and ethanol fuels, in the 800 °C - 950 °C temperature range. The main results showed that the single fuel cells exhibited higher performance under ethanol than under hydrogen; a feature that was related to the enhanced electronic transport properties of LSCM-Ru in reducing atmosphere. The experimental results suggest that the LSCM-Ru compounds are promising anodes for ethanol fueled SOFCs.

Introduction: Aperçu de la situation géologique et de l'historique des recherches CHAP. I - Physiographie des roches de la chaîne pré-triasique. __ A. Nomenclature. __ B. Méthodes spéciales employées pour la détermination des minéraux __ C. Les types structuraux __ Types 1 Roches ultrabasiques massives __ Types 2 Roches ultrabasiques schisteuses et foliacées __ Types 3 Gabbrodiorites massives (y compris les faciès leucocrates, mélanocrates et pegmatitiques) __ Types 4 Amphibolites feldspathiques foliacées ("Flasergabbros" et "Bänderamphibolite") __ Types 5 Roches cornéo-gneissiques __ Types 6 Quartzites, gneiss et schistes __ Types 7 Roches aphanitiques hémato-potassiques et quartzo chloriteuses de Chamrousse __ Type 8 Filons minéralisateurs de quartz __ Types 9 Paragénèses de minéraux remplissant des fentes __ D. L'association chorismatique des divers types et leur gisement géologique CHAP. II - Composition chimique et caractères provinciaux des roches basiques A. La composition minéralogique virtuelle B. Les relations provinciales des roches basiques CHAP. III - Stratigraphie de la couverture sédimentaire A. La série mésozoïque de la Croix de Chamrousse B. La série de la Balme-Recoin C. Comparaison avec la suite idéalisée du Trias de la zone cristalline externe D. Les spilites intercalés dans les strates du Trias et du Lias inférieur de la zone dauphinoise F. Résumé CHAP. IV - Tectonique A. La tectonique anté-westphalienne B. La tectonique postérieure C. Résumé CHAP. V - Pétrogénèse et orogénèse __ A. Historique __ B. La conception de l'auteur CHAP. VI Remarques sur les formations quaternaires, l'hydrologie et la morphologie __ Bibliographie des ouvrages consultés

In this thesis work, a high grade chromite concentrate obtained from PinarbaSi, Kayseri region of Turkey was reacted with sulfuric acid solution to determine the optimum conditions of leaching of chromite ores. Conventional methods for producing chromium are still valid in industry. The main process in production includes soda melting and taking it into solution in the form of chemical compounds such as sodium dichromate. Three and six valence states of chromium have importance in production. Trivalent chromium, chrome ore or chromite have no harmful effects. However, compounds of hexavalent chromium show toxic, irritating and corrosive action to people and environment. In the mentioned conventional method, main products consist of hexavalent chromium compounds. In this study, only trivalent chromium remained in the leach solution and did not change to hexavalent state. Obtained product after leaching was chromium(III) sulfate. The maximum extraction of chromium in the absence of perchloric acid was 94.1 % under the conditions of 175 &deg / C, 6 hours and 84.6 wt % sulfuric acid. The maximum extraction of chromium in the presence of perchloric acid was 98.7 % under the conditions of 175 &deg / C, 2 hours, 84.6 wt % sulfuric acid and &frac12 / perchloric acid / chromite ratio. The latter one was also the highest recovery value obtained during the experiments. Moreover, in none of the analyzed samples, appreciable amounts of hexavalent chromium was found during analyses.

Στα πλαίσια της παρούσας διατριβής μελετήθηκαν οι διεργασίες κοιτασματογένεσης των χρωμιτιτικών εμφανίσεων των οφιολιθικών συμπλεγμάτων του Βούρινου και της Πίνδου, σε συνδυασμό με τη συνδεόμενη με αυτές μεταλλοφορία των στοιχείων της ομάδας του λευκόχρυσου (PGE). Ιδιαίτερη έμφαση δόθηκε επίσης στην πετρογενετική εξέλιξη των μανδυακών ενοτήτων των δύο οφιολιθικών ακολουθιών, προκειμένου να εξαχθούν γενικότερα συμπεράσματα σχετικά με την προέλευση και τη διαμόρφωση των οφιόλιθων του ΒΑ Ελλαδικού χώρου. Γεωτεκτονικά το οφιολιθικό σύμπλεγμα του Βούρινου τοποθετείται στην Υποπελαγονική ζώνη, ενώ εκείνο της Πίνδου βρίσκεται τεκτονικά επωθημένο επί του Ηωκαινικής ηλικίας φλύσχη της ομόνυμης ισοπικής ζώνης. Αμφότερα τα συμπλέγματα θεωρείται ότι αντιπροσωπεύουν υπολείμματα του ενός ενιαίου ωκεανού, τα οποία σήμερα βρίσκονται επωθημένα επί του δυτικού περιθωρίου της Πελαγονικής μικροπλάκας. Αν και εμφανίζουν έντονα χαρακτηριστικά τεκτονικής καταπόνησης και οι δύο ακολουθίες διατηρούν όλο τους τύπους πετρολογικών ενοτήτων που συνθέτουν το φάσμα ενός πλήρως ανεπτυγμένου οφιολιθικού συμπλέγματος. Όλοι οι σχηματισμοί που μελετήθηκαν στα πλαίσια της παρούσας διατριβής προέρχονται από τις μανδυακές σειρές των δύο οφιολιθικών συμπλεγμάτων. Οι μανδυακοί τεκτονίτες αποτελούν τον κύριο όγκο του συμπλέγματος του Βούρινου, ενώ οι μανδυακής προέλευσης σχηματισμοί στο οφιολιθικό σύμπλεγμα της Πίνδου συνθέτουν την επονομαζόμενη ενότητα της Δραμάλας. Στον Βούρινο η δειγματοληπτική έρευνα κάλυψε τις σημαντικότερες από κοιτασματολογικής άποψης περιοχές του βόρειου και νότιου τμήματός του, ενώ στην Πίνδο δείγματα συλλέχθηκαν από τα κεντρικά και νότια τμήματα της όλης ενότητας της Δραμάλας, καθώς και από μανδυακής προέλευσης, ευμεγέθη, εξωτικά τεμάχη εντός της ενότητας της Αβδέλλας mélange. Η υπαίθρια μελέτη των μανδυακών ενοτήτων και στα δύο συμπλέγματα οδήγησε στις ακόλουθες διαπιστώσεις: α) το βόρειο τμήμα του οφιολιθικού συμπλέγματος του Βούρινου εμφανίζει σαφώς εντονότερα χαρακτηριστικά πλαστικής παραμόρφωσης σε σχέση με το νότιο, στο οποίο επικρατούν χαρακτήρες εύθραυστης-ημιπλαστικής παραμόρφωσης. Μια ανάλογη διάκριση, ασθενέστερα ωστόσο εκπεφρασμένη, θα μπορούσε να ειπωθεί πως ισχύει και όσον αφορά στην διάρθρωση των περιοχών Μηλιάς-Πεύκης, αντίστοιχα, στην Πίνδο. β) Η στατιστική ανάλυση των κινηματικών δεικτών συμφωνεί με μια προς τα ΒΑ διεύθυνση επώθησης για τον βόρειο Βούρινο και τη Μηλιά και με μια ΝΑ διεύθυνση τοποθέτησης για τον νότιο Βούρινο και το υπερβασικό τέμαχος της Πεύκης. γ) Οι χρωμιτιτικές εμφανίσεις φιλοξενούνται από δουνίτες και συγκεκριμένα στην πλειονότητα των θέσεων που παρατηρείται η ανάπτυξη χρωμιτικής μεταλλοφορίας το συνοδό είδος περιδοτίτη είναι ο λεπτοκρυσταλλικός δουνίτης (υγιής ή σερπεντινιωμένος). Πέρα από την σε όρους κοκκομετρικού μεγέθους διαφορά του σε σχέση με τον αντίστοιχο αδροκρυσταλλικό λιθότυπο, μια επιπλέον διαφοροποίησή του από αυτόν είναι η έλλειψη φολιωμένης δομής στον πρώτο. δ) Οι χρωμιτίτες του βόρειου Βούρινου και της Μηλιάς είναι συνήθως θυλακοειδούς μορφής, ασύμφωνα-παρασύμφωνα ανεπτυγμένοι σε σχέση με τους πιο άμεσους προς αυτούς αδροκρυσταλλικούς δουνιτικούς-χαρτσβουργιτικούς περιδοτίτες, ενώ τα χρωμιτικά κοιτάσματα του νότιου Βούρινου και της Πεύκης ακολουθούν στρωματοειδή, σύμφωνη-παρασύμφωνη δομική ανάπτυξη. ε) Οι χρωμιτίτες και των δύο συμπλεγμάτων εμφανίζουν μεγάλη ποικιλία ιστολογικής ανάπτυξης, ωστόσο διαπιστώθηκε μια συστηματική διαφοροποίηση όσον αφορά στο κύριο τύπο ιστού της κάθε χρωμιτικής μεταλλοφορίας. Έτσι στους χρωμιτίτες του βόρειου Βούρινου και της Μηλιάς επικρατεί ο συμπαγής και ο ιστός τύπου λεοπαρδάλεως, ενώ στους χρωμιτίτες του νότιου Βούρινου και της Πεύκης το επικρατέστερο είδος είναι ο ιστός κατά πλάκες. στ) Στο νότιο Βούρινο και στην Πεύκη παρατηρούνται συχνά εναλλασσόμενοι χαρτσβουργιτικοί-δουνιτικοί "πάγκοι", ενδεικτικοί μιας στρωματομένης κατάστασης του υπολειμματικού τμήματος του μανδύα που εκτίθεται επί των συγκεκριμένων περιοχών. Επίσης, ο αριθμός των πυροξενιτικών (ροδινγκιτιωμένων και μη) φλεβών είναι υψηλότερος στις περιοχές αυτές σε σχέση με εκείνων του βόρειου Βούρινου και της Μηλιάς. Στην πλειονότητα των περιπτώσεων οι φλέβες διατέμνουν τα κοιτάσματα χρωμίτη, στοιχείο που υποδεικνύει ότι δεν συνδέονται γενετικά μαζί τους, με μόνη εξαίρεση μια χρωμιτική εμφάνιση που φιλοξενείται σε πυροξενιτική φλέβα στην περιοχή της Πεύκης. ζ) Πάντα κοντά στις περιοχές εμφάνισης των κοιτασμάτων η τυπική λιθολογική διαδοχή προς αυτά είναι η: ±κλινοπυροξενομιγής χαρτσβουργίτης-κανονικός χαρτσβουργίτης-μεταβατικός χαρτσβουργίτης-αδροκρυσταλλικός δουνίτης-λεπτοκρυσταλλικός δουνίτης-χρωμιτίτης. Η οποιαδήποτε απόκλιση από την γενική αυτή διαδοχή είναι σπάνια, ακόμη και σε περιπτώσεις μικρών χρωμιτικών φακών. η) Η συχνή παγίδευση χαρτσβουργιτικών τεμαχών εντός αδροκρυσταλλικών δουνιτών υποδηλώνει την προέλευση των τελευταίων από τους πρώτους, ωστόσο περιπτώσεις αντικατάστασης φολιωμένων χαρτσβουργιτών από λεπτοκρυσταλλικούς δουνίτες υποδεικνύουν ότι κάποιοι λιθότυποι δεν έχουν, όπως αναμένεται, υπολειμματική προέλευση. θ) Η παρουσία κλινοπυροξενομιγών χαρτσβουργιτών είναι πιο συστηματική στην Πίνδο, ενώ στον Βούρινο απαντώνται πιο συχνά στείροι λεπτοκρυσταλλικοί δουνίτες κυρίως υπό τη μορφή φλεβών, πάγκων ή φακών. ι) Το χρωμιτικό κοίτασμα του Κορυδαλλού φιλοξενείται μέσα σε ένα εξωτικό, δουνιτικό τέμαχος, το οποίο περιέχεται εντός της οφιολιθικής mélange της ενότητας της Αβδέλλας που αναπτύσσεται στη συγκεκριμένη περιοχή. Τέλος, η συνολική αξιολόγηση όλων των διαθέσιμων γεωλογικών, ορυκτοχημικών, πετρολογικών και κοιτασματολογικών στοιχείων, υποδηλώνει ότι οι μανδυακές ενότητες και των δύο ακολουθιών γεννήθηκαν σε ένα κέντρο ώριμης διάνοιξης (MOR) και στη συνέχεια αναδιαμορφώθηκαν ως τμήματα ενός περιθωρίου πάνω από μια ζώνη καταβύθισης (SSZ). Η μετάβαση από τον Βούρινο στη Μηλιά και την Πεύκη και εν τέλει στον Κορυδαλλό πιθανά ισοδυναμεί με τη μετάβαση από το περιβάλλον μιας λεκάνης μπροστά από νησιωτικό τόξο στο (χώρο κάτω από το) ίδιο το τόξο και τέλος σε μια μικρών διαστάσεων περιθωρειακή λεκάνη πίσω από αυτό. / In the present thesis the processes of the genesis of the chomitite occurrences of the Vourinos and Pindos ophiolite complexes combined with their content in platinum group elements are studied. Special attention is given to the petrogenetic evolution of the mantle units of both ophiolite sequences in an attempt to understand better the origin and the formation of the ophiolites of the NW Greek area. In geotectonic terms the ophiolite complex of Vourinos belongs to the Ypopelagonic isopic zone, while the Pindos ophiolites are tectonically thrusted onto the Eocenic flysch of the Pindos zone. Both complexes are considered as remnants of a certain ocean, which today are found tectonically thrusted over the west margin of the Pelagonic micro-plate. Beyond the fact that both complexes show characteristics of intense tectonic deformation, they do preserve all the types of the petrologic sequences that compose a complete ophiolite complex. All the formations that have been studied in the present thesis are coming from the mantle units of both complexes. The main part of the Vourinos ophiolite complex is composed of mantle tectonites, while the mantle formations in the Pindos ophiolite complex compose the so-called Dramala unit. In the Vourinos complex the sampling covered the most important ore hosting areas of its northern and southern part, while in the Pindos complex several samples were taken from the central-southern parts of the Dramala unit and from exotic blocks of mantle origin of the Avdella mélange unit. The field investigation in both complexes has led to the following conlusions: a) The northern part of the Vourinos ophiolite complex shows clearly more characteristics of plastic deformation compared to its southern part in which characteristics of brittle to semi-plastic deformation prevail. A similar, but not so well-expressed discrimination can be made as far as concerns the structure of the areas of Milia and Pefki in the Pindos complex. b) The statistical analysis of several motional indicators shows a NE thrust direction for the northern sector of the Vourinos complex and the area of Milia and a SE direction of motion for southern Vourinos and Pefki. c) The chromitites are hosted in dunites and in the majority of the chromitite occurrences the accompanying rock-type is thin-grained dunite (serpentinised or not). In contrast to coarse-grained dunite the thin-grained variety of dunite is not foliated. d) The chromitites of northern Vourinos and Milia are usually of podiform type, discordantly to sub-concordantly developed to their neighbouring thick-grained dunitic to harzburgitic peridotites. The chromite ores of southern Vourinos and Pefki are stratiform, having a concordant to sub-concordant structure. e) Chromitites of both complexes show a great variety of chromite textures, although in each deposit a certain type of texture predominates. In northern Vourinos and Milia the dominant textural type is massive and leopard chromitite, while in southern Vourinos and Pefki the most common texture in chromitite is schlieren. f) In southern Vourinos and Pefki are commonly observed interlayered bodies of harzburgite and dunite, which are indicative of a stratified structure of the residual mantle superimposed on these areas. The number of the pyroxenite dykes (rodingitised or not) is higher in these areas compared to those in northern Vourinos and Milia. In their vast majority these dykes cut chromitite bodies, which indicates that they are not genetically related to the ores, except for one case of a chromitite that is hosted in a pyroxenite dyke in the northern part of the area of Pefki. g) Always in the vicinity of the chromitites the lithology follows the sequence: ±Clinopyroxene-bearing harzburgite, normal harzburgite, transitional harzburgite, coarse-grained dunite, thin-grained dunite, chromitite. A different lithological transition is quite unusual. h) The common entrapment of harzburgite blocks in dunites indicates that the latter comes from the former, although replacements of foliated harzburgites from thin-grained dunite that show no mark of foliation supports the fact that some rocks may not be simply of residual origin. I) The presence of clinopyroxene-bearing harzburgites is more common in the Pindos ophiolite complex, while in the Vourinos ophiolite complex bodies of thin-grained dunite in the form of dykes, layers or lenses are more commonly observed. Finally, taking into account all the available geological, mineral chemistry and petrological data, it can be said that the mantle units of both complexes have been initially formed in a mid-ocean ridge and then have been furtherly affected by the processes that take place in the mantle wedge above a SSZ. Thus the transition from Vourinos to Milia and Pefki and then to Korydallos is obviously equivalent to the "passage" from a fore arc basin to the arc and finally to a small back arc basin.

113 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-04-05T17:38:46Z No. of bitstreams: 1 Dissertação_Raildo Alves Fiuza Junior.pdf: 4123130 bytes, checksum: 5d64b18d9c873984e7609ecb4496b552 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-06-06T15:04:38Z (GMT) No. of bitstreams: 1 Dissertação_Raildo Alves Fiuza Junior.pdf: 4123130 bytes, checksum: 5d64b18d9c873984e7609ecb4496b552 (MD5) / Made available in DSpace on 2013-06-06T15:04:38Z (GMT). No. of bitstreams: 1 Dissertação_Raildo Alves Fiuza Junior.pdf: 4123130 bytes, checksum: 5d64b18d9c873984e7609ecb4496b552 (MD5) Previous issue date: 2012 / CAPES / A conversão catalítica do glicerol em insumos químicos de maior valor agregado é desejável para valorizar a cadeia de produção do biodiesel. O glicerol é obtido principalmente como co-produto do biodiesel, com rendimento de 10% em massa. Uma das vias mais promissoras na valorização do glicerol está na hidrogenólise do glicerol a propilenoglicol (1,2-PD), que é empregado como agente anti-congelante, na produção de polímeros, na indústria de alimentos e cosméticos. Muitos estudos têm relatado a hidrogenólise em fase líquida, que requer altas pressões de hidrogênio e demanda altos custos operacionais. Recentes estudos têm relatado a hidrogenólise do glicerol a 1,2-PDO em fase vapor, utilizando principalmente catalisadores a base de cobre. O principal catalisador empregado na hidrogenólise do glicerol tanto na fase liquida como vapor é a cromita de cobre, CuCr2O4. Neste trabalho, a atividade catalítica da cromita de cobre foi avaliada em fase vapor, estudando três fatores: a estruturação da cromita de cobre por diferentes temperaturas de calcinação (500-800°C); mudanças es truturais provocadas por diferentes métodos de síntese (Combustão e Pechini); e a modificação da estrutura da cromita pela introdução do alumínio em substituição do cromo. Todos os catalisadores foram caracterizados por DRX, FTIR, EDX, BET, TPR-H2 e área metálica do cobre. A hidrogenólise do glicerol em fase vapor se mostrou promissora e os resultados obtidos indicaram que a fase cromita de cobre propicia uma maior estabilidade para a fase ativa o cobre metálico. O aumento da área metálica do cobre é influenciado diretamente pelo método de síntese, maximizando a hidrogenólise. A introdução do alumínio provocou o aumento da seletividade ao propanodiol pela melhora nas propriedades texturais. / Salvador

Ce travail est consacré aux études cinétiques et thermodynamique des processus qui produisent les magmas basaltiques (basalte de dorsale océanique ou MORB et basalte de l'île océaniques ou OIB) dans la lithosphère, notamment lors de l'interaction du magma avec la lithosphère serpentinisée. Dans ce travail, nous avons testé l'hypothèse selon laquelle la genèse des chromitites de la zone de transition entre le manteau et la croute peut être la conséquence de l'interaction du magma basaltique avec le protolite du manteau serpentinisé. Une étude détaillée du corps de chromitites nodulaires dans les dunites hôtes de la région Maqsad de l'ophiolite d'Oman a été réalisée. Dans l'étude pétrologique, nous avons démontré une relation génétique étroite entre les dunites hôtes et les chromitites nodulaires et disséminées lors de la cristallisation sans équilibre des cristaux de chromite à partir de l'étude des inclusions piégées dans la chromite. Les expériences d'équilibre sur la saturation des liquides basaltiques et haplobasaltiques en chromite et en magnesiochromite comme la fonction de la fugacité d'oxygène (de ΔFMQ (-2) à ΔFMQ (+2)) ont été effectuées à une température constante de 1450 ° C et une pression de 0,1 MPa. Pour la première fois, les concentrations de chrome dans les liquides basaltiques saturés en magnesiochromite ont été mesurées. Les teneurs en Cr lors de la saturation en magnesiochromitre est de ~ 6800 ppm à ΔFMQ (-2), ~ 4500 ppm à ΔFMQ et 3500 ppm à ΔFMQ (+2), qui sont plus élevés par rapport à ceux (~ 6300 ppm à ΔFMQ (-2), 2900 ppm à ΔFMQ et 2000 ppm à ΔFMQ (+2)) de saturation en chromite (système contenant du Fe). Ce fait a une implication importante pour l'assimilation du manteau serpentinisé par des magmas basaltiques. Sur la base de toutes les données disponibles sur la saturation des liquides mafiques et ultramafiques en chromite, nous avons créé un nouveau modèle prévisible de solubilité de chromite et magnéstochromite dans les liquides en fonction de la température, de la fugacité d'oxygène et de la basicité optique du liquide : [X liq Cr tot]/[X Chr Cr2O3] = exp(a+b*lambda+c/T)*(1+fO2^(-0.25)*exp(d+k/T+g*lambda)), où [X liq Cr tot] est la fraction molaire du chrome dans le liquide silicaté, [X Chr Cr2O3] est la fraction molaire de l'oxyde de chrome dans le chromite, T est la température en Kelvins et fO2 est la fugacité de l'oxygène (en bars), lambda est la basicité optique du liquide, a (-7.01), b (13.72 ), c (-12404.92), d (24.46), k (24394.65), g (-23.59) sont des constantes. Des expériences cinétiques sur l'interaction serpentinite-basalte ont été effectuées à des températures entre 1200 et 1300 C et la pression de 0,2 à 1,0 GPa. Les données impliquent que la réaction est contrôlée par un mécanisme à plusieurs étapes: (i) une transformation métamorphique prograde de la serpentinite en harzdurgite (Fo92-95 mol. %) à spinelles riches en Cr (ii) la dissolution progressive de l'assemblage de harzburgite avec la formation des liquides basaltique à andésitique et (iii) l'assimilation finale de l'association de harzburgite par le basalte avec la formation du liquide basique hydraté appauvri ('depleted' et enrichi en Mg, Cr) à 0,5 - 1,0 GPa (51% pds de SiO2, 12 à 13% pds de MgO). / This work is devoted to kinetic and thermodynamic investigation of processes happening during basaltic (mid-ocean ridge basalt, MORB and ocean island basalt, OIB) magma genesis and evolution in the lithosphere, in particular, during the magma interaction with the serpentinized lithosphere. In this work, we tested hypothesis that the chromitite genesis at the Moho transition zone may be consequence of interaction of basaltic magma with serpentinized mantle protolith. Detailed field investigation of the nodular chromitites ore body in the host dunite at Maqsad area of the Oman ophiolite has been performed. In the petrologic investigation, we have demonstrated close genetic relationship between the host dunites and the nodular and disseminated chromitites during non-equilibrium crystallization of chromites based on investigation of chromite-hosted inclusions. Equilibrium experiments on chromite and magnesiochromite saturation in basaltic and haplobasaltic melts as function of oxygen fugacity (from ΔFMQ(-2) to ΔFMQ(+2)) were performed at a constant temperature of 1450 C and pressure of 0.1 MPa. For the first time, chromium concentrations in basaltic melts at magnesiochromite saturation were determined. The Cr contents at magnesiochromitre saturation are from ~6800 ppm at FMQ(-2), ~4500 ppm at FMQ and 3500 ppm at ΔFMQ(+2), that are higher compared to those (~ 6300 ppm at ΔFMQ(-2), 2900 ppm at ΔFMQ and 2000 ppm at ΔFMQ(+2)) of chromite saturation in Fe-bearing system. This fact has an important implication for serpentinized mantle assimilation by basaltic magmas. Based on all available data on chromite saturation in mafic and ultramafic melts, we created a new predictable model of chromite and magnesiochromite solubility depending on temperature, oxygen fugacity and the melt optical basicity: [X liq Cr tot]/[X Chr Cr2O3] = exp(a+b*lambda+c/T)*(1+fO2^(-0.25)*exp(d+k/T+g*lambda)), where [X liq Cr tot] is molar fraction of chromium in the silicate liquid, [X Chr Cr2O3] is molar fraction of the chromium oxide in the chromite, T is temperature in Kelvins and fO2 is oxygen fugacity (in bars), lambda is optical basicity, a (-7.01), b (13.72), c (-12404.92), d (24.46), k (24394.65), g (-23.59) are constants. Kinetic experiments on serpentinite-basalt interaction have been performed at temperatures of 1200 - 1300 C and pressure range from 0.2 to 1.0 GPa. The data imply that the reaction is controlled by multi-stage mechanism: (i) prograde metamorphic transformation of serpentinite to Cr-rich spinel-bearing harzdurgite (Fo92-95 mol.%) (ii) progressive dissolution of harzburgite assemblage with formation of hydrous basaltic to andesite melts and (iii) the final assimilation of the harzburgite association by basalt with formation of hydrous depleted basaltic melts at 0.5 - 1.0 GPa (51 wt% of SiO2, 12 - 13 wt.% of MgO contents). We experimentally demonstrate that serpentinite assimilation by basaltic melt at 0.5 - 1.0 GPa happening at average rate of 4.3 × 10-10 m2/s at 1300°C is controlled by silica diffusion in hydrous basaltic melt. Our experimental work provides incontestable evidence that depleted MORB melts, depleted high-Mg-Cr cumulates, and oceanic andesites can be routinely produced from "normal" mid-ocean ridge melts by chemical reaction with serpentinized lithospheric mantle. Our study prevents routine interpretation of depleted and primitive oceanic melts (MORB and OIB) as uniquely derived from a deep mantle. The data obtained in this work confirm that serpentinites, which may have been important constituents of the Hadean crust as a whole were possibly involved in the generation of the first continental crust.

Orientador: Prof. Dr. Daniel Zanetti de Florio / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, 2017. / A obtencao de nanoparticulas por exsolucao e uma tecnica que tem sido extensivamente pesquisada e aprimorada recentemente. As particulas exsolvidas apresentam propriedades superiores quando comparadas as depositadas. O metodo de exsolucao consiste na reducao de ions previamente solubilizados em uma matriz, dando origem a particulas fortemente ligadas ao substrato. Materiais com composicoes (La1-xSrx)z(Cr1-yNiy)O3-¿Â (x e y = 0%, 5%, 10%, 15% e 20%; z = 100% e 80%) foram sintetizados, utilizando o metodo de polimerizacao de complexos. A resina produzida no processo de sintese foi analisada utilizando tecnicas de analise termica, tal que a temperatura de calcinacao foi determinada sendo igual a 900 ¿C. Foi utilizada a tecnica de difracao de raios X para caracterizacao estruturas e identificacao das fases presentes. Todas as amostras foram reduzidas com objetivo de criar, atraves de exsolucao, nanoparticulas de niquel metalico. Analises magneticas foram conduzidas para determinar o comportamento magnetico dos materiais produzidos. Materiais nao estequiometricos foram sintetizados para verificar a influencia de diferentes estequiometrias no processo de exsolucao. O sitio A nao estequiometrico prejudicou a solubilizacao do Ni e Sr na estrutura da cromita de lantanio. Todas as amostras com dopantes apresentaram uma diminuicao da temperatura de Neel da cromita de lantanio. Entretanto, o tratamento de reducao provocou um aumento da temperatura de Neel, se comparado com as amostras oxidadas. Esse e um indicativo da diminuicao de concentracao de niquel em solucao solida, um resultado condizente com o mecanismo de exsolucao. Utilizando as medidas de magnetismo foi possivel verificar o mecanismo de exsolucao e fracao massica de niquel metalico para cada amostra. Utilizando tecnicas de microscopia eletronica foi possivel detectar a presenca de nanoparticulas apos o tratamento de reducao com diametro de aproximadamente 20 nm. Ao realizar uma analise quimica local utilizando um microscopio eletronico de transmissao, foi possivel verificar que as particulas em questao sao de niquel metalico. / The production of nanoparticles by exsolution is a technique that has been extensively researched and improved recently. Exsolved particles have superior properties when compared to deposited particles. The method of exsolution consists in the reduction of previously solubilized ions in a matrix, giving rise to particles strongly attached to the substrate. Materials with compositions (La1-xSrx)z(Cr1-yNiy)O3-ä (x and y = 0%, 5%, 10%, 15% and 20%, z = 100% and 80%) were synthesized using the polymerization of complexes technique. The resin produced in the synthesis process was analysed using thermal analysis and the calcination temperature was determined to be 900 ° C. The X-ray diffraction technique was used to characterize structures and identify the present phases. All samples were reduced in order to create nanoparticles of metallic nickel by exsolution. Magnetic analysis was conducted to determine the magnetic behaviour of the produced materials. Non-stoichiometric materials were synthesized to verify the influence of different stoichiometry in the exsolution process. Non-stoichiometric A site impaired the solubilisation of Ni and Sr in the lanthanum chromite structure. All samples with dopants showed a decrease in the temperature of Neel of the lanthanum chromite. However, the reduction treatment caused an increase in the Neel temperature when compared to the oxidized samples. This is indicative of the decrease in nickel concentration in solid solution, a result consistent with the exsolution mechanism. Using the measurements of magnetism it was possible to verify the mechanism of exsolution and mass fraction of metallic nickel for each sample. Using electron microscopy techniques it was possible to detect the presence of nanoparticles after the reduction treatment with a diameter of approximately 20 nm. When performing a local chemical analysis using a transmission electron microscope, it was possible to verify that the particles in question are of metallic nickel.