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Sphalerite is, apart from being the main global source of zinc (Zn), also one of the main source for the critical elements indium (In), gallium (Ga) and germanium (Ge), which can be extracted as by-products during Zn mining. In the westernmost part of the Palaeoproterozoic Bergslagen ore province, Sweden, In-anomalies have been reported from sulphide mineralizations. These In-anomalies can be attributed to either pre-ore formation crustal processes manifested by the local (Svecofennian, c. 1.87-1.89 Ga) syn-volcanic mineralisations, or to epigenetic metasomatic events primarily related to younger (c. 1.80-1.79 Ga) granitoids. In this study, sphalerite samples from 19 different mineralisations in westernmost Bergslagen were examined by both electron probe microanalyzer (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), in order to firstly, measure trace element concentrations, and especially those of the critical element In, Ga and Ge, and secondly, to apply this information to gain new information on the trace element inventory and incorporation mechanisms of sphalerite. The dataset also allows for testing the ore-formation process models, not least in cases of elevated In-contents. Utilization of these two analytical methods also provided the opportunity for a direct spot-to-spot comparison of their performance in detecting trace element concentrations in sphalerite. The results verify the In-enrichment of the area, whereas Ga and Ge only follow crustal abundancies. The concentrations of the other trace elements vary significantly, even at a sample scale. The compositional variation shows several patterns between certain elements, suggesting that their incorporation in the sphalerite lattice was allowed via substitution mechanisms (e.g. In3++(Cu+,Ag+)↔2Zn2+; Fe2++Cd2++Mn2+↔3Zn2+; Cu++Mn2++In3+↔3Zn2+). In contrast, some measured high Cd, Ag and Pb concentrations are attributed to nano (or micro) inclusions of primarily galena. Other elements such as As, Sn, Sb, Se, Au, Tl, Ni, Te and Mo yielded, in almost all the samples, concentrations below the detection limit for both analytical methods. Discrimination methods based on trace element concentrations and distribution of the In-enriched mineralizations suggest that the In-anomalies are most likely related to Svecofennian volcanic to subvolcanic hydrothermal processes, forming mineralisations that were later modified during the Svecokarelian orogeny. Finally, the direct comparison of EPMA results to that of LA-ICP-MS, showed the significantly better performance of the latter method in detecting trace-level concentrations, provided that a proper calibration procedure has been followed. / Sulfidmineralet zinkblände är, förutom att vara den huvudsakliga globala källan för zink (Zn), också ett av de viktigaste värdmineralen för de kritiska metallerna indium (In), gallium (Ga) och germanium (Ge), vilka kan utvinnas som viktiga biprodukter vid zinkbrytning. I den västligaste delen av malmprovinsen Bergslagen i Mellansverige har In-anomalier rapporterats från flera mineraliseringar. Dessa lokala In-anrikningar kan tillskrivas antingen processer verksamma innan och under den vulkaniska aktiviteten, eller senare geologiska händelser relaterade till yngre graniter. I denna studie har zinkblände från 19 olika mineraliseringar i västra Bergslagen karakteriserats med två olika system för mikrokemisk analys; elektronmikrosond (EPMA) och laserablativ induktivt kopplad plasma-masspektrometri (LA-ICP-MS). Detta har gjorts för att mäta spårelementhalter, och särskilt då för de kritiska metallerna In, Ga och Ge. Genom att använda dessa två metoder parallellt gavs också möjligheten till direkta jämförelser mellan dem vad gäller deras kapacitet för spårelementanalys av zinkblände. Resultaten verifierar att detta område är anomalt In-anrikat, medan halterna av Ga och Ge är låga och endast följer genomsnittshalterna för kontinental jordskorpa. Halterna av de övriga spårelementen varierar avsevärt, även på individuell provskala, och visar i flera fall systematiska mönster mellan vissa element. Dessa mönster tyder på att deras införlivande i zinkbländestrukturen gått via flera specifika utbytes-(substitutions-)mekanismer (t.ex. In3++ (Cu+, Ag+) ↔2Zn2+; Fe2+ + Cd2++ Mn2+ ↔3Zn2+, Cu++ Mn2++ In3+ ↔3Zn2+). Däremot kan förhöjda halter av Cd, Ag och Pd tillskrivas nano- (eller mikro-) inneslutningar av framförallt blyglans. Andra element, som As, Sn, Sb, Se, Au, TI, Ni, Te och Mo uppvisade halter under detektionsgränserna för båda analysmetoderna i nästan alla undersökta prov. Bildningsmässiga (genetiska) diskrimineringsmetoder baserade på spårelementhalter kombinerat med de geologiska och spatiella relationerna för de In-anrikade mineraliseringarna tyder på att de senare bildades genom svekofenniska vulkanisk-hydrotermala processer och därefter modifierats under svekokarelsk bergskedjebildning. Slutligen, i den direkta jämförelsen av EPMA gentemot LA-ICP-MS, visade den senare metoden signifikant bättre kapacitet för spårämnesanalys, förutsatt att ett korrekt kalibreringsprotokoll har följts.

I detta arbete har polerprov framställts för att därefter undersökas med malm- och svepelektronmikroskopi (SEM) med energidispersiv röntgenspektroskopisk analys (EDS). Med dessa metoder har mineralsammansättning, strukturer och texturer identifierats och undersökts. De undersökta proverna kommer från borrkärnor genom malmzonen i Lovisagruvan i Bergslagen, södra Mellansverige. Malmen är en tabulär, silverförande Zn-Pb-sulfidmineralisering.  De kombinerade undersökningarna av polerproven visar att de huvudsakligen består av zinkblände, blyglans, kvarts, mikroklin, granat, amfibol och pyrit, vilka karakteriseras av texturer som visar på omkristallisation, heterogen deformation och lokal remobilisering. De uppvisar småskaliga texturer som sannolikt är direkt relaterade till uppkomsten av s.k. kulmalmstextur. De ingående mineralens inbördes relationer tyder på att blyglans och zinkblände bildades samtidigt och därefter, under regionalmetamorfa förhållanden, tillväxte pyrit och granat som porfyroblaster. Majoriteten av texturerna och strukturerna är sekundära och visar på en kraftig senare överprägling av malmen genom metamorfos och flerfasig deformation under olika tryck- och temperaturförhållanden. / In this project polished sections have been prepared for study by means of ore and scanning electron microscopy (SEM) with energy dispersive x-ray spectroscopy (EDS). The application of these methods allows mineralogy, structures and textures to be characterized. This was done within the EU H2020-funded project X-Mine. The studied samples are from drill cores transecting the ore zone of the Lovisa mine (Lovisagruvan), which is located in Örebro County in the Bergslagen ore province, south central Sweden. Here, a tabular, stratiform silver-bearing Zn-Pb sulphide ore is mined.  Studies of the polished ore sections show that the samples mainly contain sphalerite, galena, quartz, microcline, garnet, amphibole and pyrite, characterized by textures of recrystallisation, heterogeneous deformation and localized remobilization.  The studied samples from the main ore and exhibit textures directly related to the formation off the so-called ball ore. The textural interrelationships of the major minerals indicate that galena and sphalerite formed penecontemporaneously, and then under regional metamorphic conditions, pyrite and garnet formed as porphyroblasts. The majority of the present textures and structures are secondary, representing different stages of metamorphism and deformation under variable P-T-conditions, post-dating original ore formation. / Real-Time Mineral X-Ray Analysis for Efficient and Sustainable Mining, H2020 X-Mine, Projekt-id: 730270

<p> The "B" horizon at Tilt Cove occurs in subaqueous mafic volcanics near the base of the Silurian Cape St. John Group. It is 3 metres below a well-banded oxide iron formation ("A" horizon). </p> <p> Mineralization in the "B" horizon is analogous to that of the East Mine in that it is volcanogenic and has resulted in extensive chloritization of the footwall rocks, and in the deposition of banded sulphides or the replacement of the existing mafic volcanics by sulphides. There are differences in the geochemistry mineral textures and mineral types. The East Mine host volcanics are alkali depleted basaltic komatiites to magnesium theleiites. The horizon host volcanics are spillitized magnesium tholeiites. Samples of ore from the East Mine show well-developed colloform and framboidal textures. Pyrite, magnetite, hematite and chalcopyrite are the dominant minerals with minor sphalerite and accessory covellite. Samples from the horizon show relict colloform textures and framboids with less internal structure due to overgrowths. Atoll textures indicating extensive replacement are common. Pyrite is the dominant sulphide followed by sphalerite, chalcopyrite, accessory covellite and gold. The chalcopyrite occurs both as replacement of pyrite and exsolution in sphalerite. The most significant difference between samples from the East Mine and "B" horizon is the greater abundance of gold in the "B" horizon and its correlation with sphalerite. </p> / Thesis / Bachelor of Science (BSc)

Ce travail présente les résultats dune étude menée sur la dépollution des tailings de Kipushi (RD Congo) par la valorisation des métaux contenus. Ce sont les rejets anciens dun concentrateur. Ils contiennent de la pyrite et des sulfures résiduels de cuivre et de zinc. Du fait du stockage à lair libre pendant plus de 40 ans, ces sulfures sont partiellement oxydés. Ces tailings présentent une certaine instabilité physique et chimique qui est à la base de la dégradation des milieux environnants les plus proches (rivières naturelles, sols sous-jacents, nappes souterraines, etc.) suite à la migration et à la dispersion dETM (éléments traces métalliques) tels que larsenic, le cadmium, le cobalt, le cuivre, le plomb, le zinc, Linstabilité physique se manifeste par des phénomènes dérosion par les eaux de ruissellement pendant la saison des pluies et par des phénomènes dérosion éolienne pendant la saison sèche. Leur stockage en surface saccompagne dune lente oxydation des sulfures avec production deaux acides qui dans leur neutralisation par la dolomie présente dans les rejets et celle des formations géologiques sur lesquelles ils reposent, contribuent à laccroissement des réseaux karstiques, au durcissement des eaux des nappes et parfois provoquent des phénomènes daffaissements, voire même deffondrements de terrains. Pour réduire les impacts environnementaux majeurs de ces tailings, nous avons effectué ce travail en recherchant un traitement qui combinerait dune part la dépollution par la réduction des ETM et du soufre sulfure et dautre part la valorisation du cuivre et du zinc contenus. Les deux voies qui ont été testées commencent par une flottation globale de tous les sulfures (désulfuration environnementale). Les résultats de nos expérimentations montrent quon peut obtenir un nouveau rejet de flottation dans lequel une majeure partie des ETM facilement mobilisables dans lenvironnement est éliminée ainsi que presque tout le soufre (95 %), ce qui écarte donc tout risque de DMA. Nous avons démontré que pour atteindre ces résultats, il suffit de ne broyer que la fraction la moins libérée de dimension supérieure à 75 μm et dactiver par un prétraitement à pH 6 les sulfures dont la collection par le xanthate est sinon inhibée par laltération superficielle avec formation doxydes ou par les complexes cyanométalliques formés lors de la flottation avec dépression de la pyrite par les ions cyanures ayant produit les tailings étudiés. Nous avons tenté denrichir le concentré global de la désulfuration environnementale par une flottation différentielle avec dépression de la pyrite à pH 11. Cet enrichissement est difficile à réaliser à cause de la finesse des grains et des caractéristiques minéralogiques du concentré global qui contient beaucoup de grains mixtes. Les essais ont alors porté sur la lixiviation chimique acide oxydante (avec Fe3+) et la lixiviation bactérienne du concentré global après son enrichissement en cuivre et en zinc dans un circuit de flottation avec deux finissages. Une étude approfondie des paramètres qui influencent le mécanisme des biolixiviations a été effectuée et les conditions de leur mise en pratique industrielle ont été déterminées. La lixiviation chimique doit être réalisée à des températures élevées (98°C) pour fragiliser la couche de passivation de soufre élémentaire qui se forme à la surface des grains et qui tend à freiner la diffusion des réactifs et des produits de la réaction. Par contre, la biolixiviation donne de bons résultats à température modérée. Elle est techniquement applicable aux tailings de Kipushi. Nous proposons de réaliser la biolixiviation en deux étapes successives, la première avec des bactéries thermophiles modérées (55°C) à une densité de pulpe de 15 % (poids/volume) et la deuxième avec des bactéries mésophiles (33°C) sur des pulpes à 4 % de solides. Dans ces conditions, on réussit à produire deux solutions de lixiviation (PLS : pregnant leach solution), lune à 3 g/l de cuivre et 7 g/l de zinc et lautre à 0,2 g/l de cuivre et 7 g/l de zinc, quon purifie et concentre facilement dans un circuit dextraction par solvant. Lextraction par solvant du cuivre est réalisée avec le LIX984N directement sans modifier le pH des PLS (1,7-1,9) et le zinc est extrait par le D2EHPA après précipitation dions Fe3+ du raffinat cuivre à des pH entre 3 et 3,5. On obtient ainsi des solutions aqueuses de cuivre et de zinc convenant aux installations délectrolyse industrielle. Nous avons proposé un schéma de traitement des tailings de Kipushi qui pourrait fonctionner pendant 20 ans avec les 36 684 600 tonnes sèches de rejets stockés à la digue 1 et 2. Le traitement produirait un nouveau rejet plus ou moins dépollué qui représente 66 % en poids des tailings traités, 80 950 tonnes de cuivre et 631 750 tonnes de zinc. The work present results from research study devoted to de-pollution of the stocked tailings in Kipushi (DR Congo) via valorization of the metals contained in the tailings. Pyrite and copper and zinc sulfides present the principal mineral composition of the laid down tailings from the concentrator. Due to the fact that the sulphides have been stocked during more than 40 years, they are partly oxidized. These tailings present a constant risk from physical instability and spillage, which reflects in the deterioration of the surrounding environment (rivers, soil, underground water table, etc). Moreover the migration and dispersion of TEM (trace metal elements) such as arsenic, cadmium, cobalt, copper, lead, zinc, is leading to erosion and mine run-off phenomena during wet season and generate air-borne particles during dry season. The stocking of the tailings is accompanied by slow oxidation of the sulfides with concomitant production of acidic waters which are neutralized by the dolomite present, which finally reflects in hardening of the underground waters and even provoke soil subsidence and ground collapses. In order to reduce the major environmental impacts from the tailings, we have performed a study for their post-treatment which encompasses the cleanup from one side and the reduction of TEMs and sulphur on the other side. Apart from this, the aim was to economically extract the remaining non-ferrous metals, notably Zn and Cu. The approach which has been chosen to accomplish this task has been to re-float by bulk flotation the majority of the sulphides and thus by elimination of the nearly total sulphur (95 %) to eliminate the risk of AMD generation and metals immobilization. We have shown that this is possible to be achieved via grinding the 75 μm oversize fraction in order to facilitate minerals liberation, following by subsequent activation at pH 6 before flotation. Without this pretreatment step, the flotation by use of xanthates is impossible, due to the surface coatings of the grains, which are either of oxide nature or are cyano-metallic complexes formed from the use of potassium cyanide as pyrite depressor in the flotation circuit practiced at the times when the concentrator was operational. The further attempts to produce monometallic flotation concentrates via selective flotation with depression of the pyrite at pH 11 have been unsuccessful due to reasons of complex mineralogy. Therefore chemical (Fe3+) and bacterial leaching of the bulk concentrate enriched in Cu and Zn via two cleaning flotation circuits have been envisaged. The technological parameters for the both leaching options have been studied and the mechanisms of the bioleaching taking place have been proposed in view industrial scale up of the process. It has been found that the chemical leaching should be conducted at very high temperatures (98°C) in order to breakdown the passivation coatings (sulphur). In contrast, the bioleaching has shown good results at moderate temperatures. It has been found that bioleaching is technically feasible to the tailings of Kipushi. We have suggested a bioleaching in two successive stages: the first one with moderate thermophilic microorganisms (55 °C) at pulp density 15 % (weight / volume) and the second one with mesophilic microorganisms (33 °C) at pulp density of 4 % (w/v). Under these conditions two principal PLSs (pregnant leach solution) can be obtained - a one with 3 g/l Cu and 7 g/ l Zn and other one in 0.2 g/l Cu and 7 g/l Zn. The both PLSs could be further processed via solvent extraction. The solvent extraction of Cu is accomplished with LIX984N without modifying the pH of the PLS (1.7 - 1.9), while Zn is extracted using a D2EHPA at pH between 3 and 3,5, after elimination of the iron from the copper raffinate. The aqueous solutions thus obtained are suitable for Cu and Zn electrowinning. Finally, a flow sheet for re-treatment of the Kipushi tailings which could operate during 20 years has been proposed. It could treat about 37 mln tones of dry tailings stocked in the tailing ponds 1 and 2. Preliminary calculations estimate that such treatment would produce new tailings with low environmental risk which will represent about 66 % in weight of the original treated tailings and will yield about 80 950 tons of Cu and 631 750 tons of Zn.

<p> The BAR CLAIM GROUP is located on the western margin of the Selwyn Basin geologic province in south central Yukon. The rock sequence is eugeosynclinal in nature, belonging to the Englishman's Group of the Mississippian. Chronologically, these rocks include massive limestone, white to red chert breccia, dark grey chert breccia, chert pebble conglomerate, lithic wacke, massive barite, grey green chert, and hornblende microdiorite. The elastic units in particular appear to be correlative with the units on the eastern margin of the Selwyn Basin. </p> <p> The barite is light grey, bedded, massive, and contains rare relic rosette structures. Associated minerals include pyrite, galena and minor sphalerite. Extensive recrystallisation and mobilization has occurred, probably as a result of regional compression and faulting. The barite may have had an exhalative origin along fault or extensional zones; however, sedimentogenic sources, such as the redistribution of pre-existing barite, cannot be precluded. </p> / Thesis / Bachelor of Science (BSc)

<p> The existence of significant and consistent fractionation of sulfur isotopes in natural coexisting sulfide mineral pairs is demonstrated. Such fractionations are shown to depend exclusively on the mineralogy of the assemblage and temperature of equilibration, consistent with a process of fractionation during equilibrium exchange of sulfur isotopes between the sulfide phases . The fractionation of sulfur isotopes between galena, sphalerite and pyrite has been determined experimentally over the temperature range 300-725°C . The fractionation for each mineral pair is shown to vary as T^(-2) so that three isotope geothermometer s have been calibrated. Experi mental results are applied to natural sulfide assemblages to determine the temperature of equilibration and extent to which isotopic equilibriurn has b een attained. </p> / Thesis / Doctor of Philosophy (PhD)

Abstract Polymetallic (Pb-Zn-Cu-Ag-Au-Sb-As-Bi-Cd-Te-Se-Ge…) quartz veins occur in an area from Eidsvoll in southeastern Norway to west of LakeVänern in southwestern Sweden. They most likely formed during the waning stage of the c. 1 Ga Sveconorwegian orogeny. In Värmskog parish, Värmland county, several mineralized quartz veins of different types are known. Of these, three of the larger vein deposits, Vegerbol, Karlsbol and Södra Gärdsjön, have been investigated. Despite a history of mining activities (mostly for silver) and exploration from the mid-1800s up until the present day, details about their ore mineralogy have remained essentially unknown. In order to classify and characterize them better, the present study was undertaken. The main ore minerals in the veins are galena, sphalerite, chalcopyrite, tetrahedrite sensu lato and pyrite. Additionally, this investigation showed the occurrence of an array of silver-bearing phases such as argentian tetrahedrite to freibergite, native silver, polybasite, pyrargyrite, jalpaite, aguilarite, cervelleite, hessite and matildite. These are the main and accessory silver carriers in the studied deposits. Gold (argentiferous) was also found, as well as the nickel-cobalt sulphide siegenite.    The silver contents of the tetrahedrites may vary within one deposit, ranging from tetrahedrite sensu stricto to freibergite. A weak positive correlation occurs between silver and iron in the tetrahedrites. Cadmium was found both in the tetrahedrites and in the sphalerites. Many sphalerites, however, are very pure ZnS. The complex accessory ore mineralogy, including native gold as well as tellurium and selenium-bearing phases (Vegerbol), makes these vein deposits comparable to mineralized veins to the west and southwest of the Värmskog area.    Combining mineralogical and textural observations with previous studies, the vein mineralizations most likely formed during a change in tectonic regime, in recurrently active brittle structures, at temperatures ranging from c. 350 down to below 100°C. The occurrence of pyrite and hematite and the lack of pyrrhotite and magnetite points to an oxidizing ore-forming environment with relatively high sulphur activity.    Finally, in order to assess the possibility of connecting two of the mined vein systems, VLF (Very Low Frequency) electromagnetic measurements were performed across the strike of a possible continuation between the Vegerbol and Karlsbol deposits. The VLF survey showed a significant anomaly where such a continuation was to be expected, thus indicating an overall strike length of at least 1 km for that vein system. / Sammanfattning Polymetalliska (Pb-Zn-Cu-Ag-Au-Sb-As-Bi-Cd-Te-Se-Ge…) kvartsgångar förekom­mer inom ett område från Eidsvoll, Norge i norr, till sydväst om Vänern i Sverige. De tros ha bildats under den svekonorvegiska orogenesens (ca 1 Ga) slutskede. I Värmskogs socken, Värmland, förekommer mineraliserade kvartsgångar av flera olika typer. Bland dessa har tre undersökts med avseende på malmmineralogi. Dessa kallas för Vegerbol, Karlsbol och Södra Gärdsjön, och de har brutits i huvudsak på silver. Trots att brytning och prospekteringsarbeten pågått från 1800-talet fram till i dag har det saknats detaljerade mineralogiska beskrivningar över fyndigheterna. Denna studie har genomförts för att bättre kunna karakterisera och klassificera dessa mineralis­eringar. Huvudmalmmineral vid dessa förekomster är blyglans, zinkblände, koppar­kis, pyrit och för Södra Gärdsjön även tetraedrit. Denna undersökning har påvisat förekomsten av silverförande faser som silverhaltig tetraedrit till freibergit, gediget silver, polybasit, jalpait, aguilarit, cervelleit, hessit och matildit, vilka utgör både huvudsakliga och accessoriska silverbärare i de undersökta förekomsterna. Guld (silverhaltigt) har också hittats, samt ett Ni-Co-förande mineral, siegenit.    Silverinnehållet i tetraedriterna varierar inom en och samma förekomst, några analyser har givit freibergitsammansättningar. En svag positiv korrelation finns mellan silver och järnhalt i tetraedrit. Kadmium förekommer både i tetraedrit och i zinkblände. Många zinkbländen består dock av rent ZnS. Förekomsten av relativt komplexa accessoriska mineral inklusive guld och Se-Te-faser (Vegerbol) visar att dessa gångar är jämförbara med liknande förekomster väster och sydväst om Värmskogs­området.    Genom att sammanföra data från denna undersökning med sådana från tidigare studier gjorda på gångarna kan man anta att de bildats vid vid en förändring av den tektoniska miljön, i upprepat aktiva spröda strukturer och vid temperaturer mellan ungefär 350 till under 100 °C. Förekomsten av pyrit och hematit samt avsaknad av magnetkis och magnetit tyder på att malmbildningen skett under oxiderade förhållan­den och relativt hög svavelaktivitet.      Elektromagnetiska mätningar i VLF-bandet (Very Low Frequency) utfördes tvärs över den förmodade strykningsriktningen för en möjlig fortsättning av gången mellan Karlsbol och Vegerbol. Mätningarna gav en tydlig anomali där en sådan fortsättning kan förväntas vilket skulle kunna betyda att det finns en sammanhängande mineralisering med ca 1 kilometers längd.

In the present work, novel dewatering aids and a novel centrifuge configuration were developed and applied for the purpose of dewatering fine particles. Three different types dewatering reagents were tested in different filtration and centrifugation units. These chemicals included low-HLB surfactants, naturally occurring lipids, and modified lipids. Most of these reagents are insoluble in water; therefore, they were used in solutions of appropriate solvents, such as light hydrocarbon oils and short-chain alcohols. The role of these reagents was to increase the hydrophobicity of the coal and selected mineral particles (chalcopyrite, sphalerite, galena, talc, clay, phosphate, PCC and silica) for the dewatering. In the presence of these reagents, the water contact angles on the coal samples were increased up to 90o. According to the Laplace equation, an increase in contact angle with the surfactant addition should decrease the capillary pressure in a filter cake, which should in turn increase the rate of dewatering and help reduce the cake moisture. The use of the novel dewatering aids causes a decrease in the surface tension of water and an increase in the porosity of the cake, both of which also contribute to improved dewatering. A series of batch-scale dewatering tests were conducted on a variety of the coal and mineral samples using the novel dewatering aids. The results obtained with a Buchner funnel and air pressure filters showed that cake moistures could be reduced substantially, the extent of which depends on the particle size, cake thickness, drying time, reagent dosage, conditioning time, reagent type, sample aging, water chemistry, etc. It was determined that use of the novel dewatering aids could reduce the cake formation time by a significant degree due to the increased kinetics of dewatering. At the same time, the use of the dewatering aids reduced the cake moistures by allowing the water trapped in smaller capillaries of the filter cake. It was found that final cake moistures could be reduced by 50% of what can be normally achieved without using the reagents. However, the moisture reduction becomes difficult with increasing cake thickness. This problem can be minimized by applying a mechanical vibration to the cake, spraying a short-chain alcohol on the cake and by adding a small amount of an appropriate coagulant, such as alum and CaCl2 to the coal and mineral slurries. The novel dewatering aids were also tested using several different continuous filters, including a drum filter, disc filter and horizontal belt filter (HBF). The results obtained with these continuous filtration devices were consistent with those obtained from the batch filters. Depending on the coal and mineral samples and the type of the reagent, 40 to 60% reductions in moisture were readily achieved. When using vacuum disc filters, the cake thickness increased substantially in the presence of the novel dewatering aids, which could be attributed to the increased kinetics of dewatering. A dual vacuum system was developed in the present work in order to be able to control the cake thickness, which was necessary to achieve lower cake moistures. It was based on using a lower vacuum pressure during the cake formation time, while a full vacuum pressure was used during the drying cycle time. Thus, use of the dual vacuum system allowed the disc filter to be used in conjunction with the novel dewatering aids. Its performance was similar to that of HBF, which is designed to control cake thickness and cake formation time independently. The effectiveness of using the novel dewatering aids were also tested in a full-continuous pilot plant, in which coal samples were cleaned by a flotation column before the flotation product was subjected to the disc filter. The tests were conducted with and without using novel dewatering aids. These results were consistent with those obtained from the laboratory and batch-scale tests. The novel centrifuge developed in the present work was a unit, which combined a gravity force and air pressure. The new centrifuge was based on increasing the pressure drop across the filter cake formed on the surface of the medium (centrifuge wall). This provision made it possible to take advantage of Darcy s law and improve the removal of capillary water, which should help lower the cake moisture. A series of tests were conducted on several fine coal and mineral particles and obtained more than 50% moisture reduction even at very fine particle size (2 mm x 0). Based on the test results obtained in the present work, two proof-of-concept (POC) plants have been designed. The first was for the recovery of cyclone overflows that are currently being discarded in Virginia, and the other was for the recovery of fines from a pond in southern West Virginia. The former was designed based on the results of the plant tests conducted in the present work. Cost vs. benefit analyses were conducted on the two POC plants. The results showed very favorable internal rates of return when using the novel dewatering aids. Surface chemistry studies were conducted on the coal samples based on the results obtained in the present investigation. These consisted mainly of the surface characterization of the coal samples (surface mineral composition, surface area, zeta potential, x-ray photoelectron microscopy (XPS)), acid-base interactions of the solids and liquids, dewatering kinetic tests, contact angle measurements of the coal samples and surface force measurements using AFM. In addition, carbon coating on a silica plate using palsed laser deposition (PLD) and Langmuir-Blodgett (LB) film deposition tests were conducted on the sample to better understand the surfactant adsorption and dewatering processes. The test results showed that the moisture reductions on the fine particles agree well with the surface chemistry results. / Ph. D.

Ziel der Arbeit war die Synthese von ZnS, welches strukturell natürlichen Sphalerit imitieren und für die Untersuchung und Optimierung von biologischen Laugungsexperimenten genutzt werden soll. Zur Herstellung von chemisch reinem sowie mit den Wertelementen Indium, Kupfer und Eisen dotierten ZnS wurden vier verschiedene Synthesemethoden getestet: Ofentempern, chemische Gasphasentransportreaktion (CVT), feldunterstütztes Sintern (SPS) und die Hochdruck-Hochtemperatur-Synthese (HP/HT). Es folgte die Charakterisierung der synthetisierten Produkte hinsichtlich der Realstruktur und chemischen Reinheit mittels XANES, REM, XRD, EPMA und nasschemischer Verfahren. Abschließend wurden die Synthesemethoden nach ihrer Effizienz evaluiert. Das Ziel, defektfreies kubisches ZnS zu erzeugen, wurde nur mittels CVT und HP/HT erreicht. In dieser Arbeit konnte weiterhin gezeigt werden, dass der Einbau von Indium ohne gleichzeitige Aufnahme von Kupfer bis zu 1 Ma-% möglich ist.:Abbildungsverzeichnis VII Tabellenverzeichnis XI Abkürzungen, Akronyme und Symbole XII Einheiten XV 1 Einleitung 1 2 Forschungsstand zur Synthese von Zinksulfid 6 2.1 Kristallographie von ZnS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 2.2 p-T -Phasendiagramm von ZnS . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 3 Synthesematerial 15 3.1 Gefälltes ZnS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 3.2 Dotierungsmaterialien . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 3.3 Recherche zu kommerziellen Metallsulfiden . . . . . . . . . . . . . . . . . . . . 18 4 Synthesemethoden 21 4.1 Ofentempern . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 4.2 FAST-SPS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 4.3 CVT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 4.4 HP/HT-Synthese . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 4.4.1 Toroid-Zelle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 4.4.2 HP/HT-Experimentalaufbau und -ablauf . . . . . . . . . . . . . . . . . 27 4.4.3 HP/HT-Kalibrierung . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 5 Analysemethoden 42 5.1 ICP-MS & ICP-OES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 5.2 XRD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44 5.3 UV-VIS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55 5.4 REM-EDX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55 5.5 EBSD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56 5.6 EPMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57 5.7 XANES Spektroskopie . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58 5.8 Ramanspektroskopie . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61 5.9 Dichtebestimmung . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 5.10 BET-Messung . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 6 Ergebnisse 63 6.1 Charakterisierung industriell verfügbarer Materialien und natürlicher Proben . 63 6.1.1 Synthetische, industriell verfügbare Materialien . . . . . . . . . . . . . . 63 6.1.2 Referenzspektren für XANES-Analysen . . . . . . . . . . . . . . . . . . 65 6.2 Charakterisierung der Synthesematerialien . . . . . . . . . . . . . . . . . . . . 74 6.2.1 ZnS der Leuchtstoffwerke Breitungen GmbH (LWB) . . . . . . . . . . . 74 6.2.2 Dotierungsmaterialien In, Cu und Fe . . . . . . . . . . . . . . . . . . . . 77 6.3 Charakterisierung der synthetisierten Produkte . . . . . . . . . . . . . . . . . . 80 6.3.1 Einkristalle (CVT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80 6.3.2 Polykristalline Produkte (Ofentempern, FAST-SPS und HP/HT) . . . . 112 6.4 Bestimmung des Stapelfehleranteils mittels Ramanspektroskopie? . . . . . . . . 152 7 Diskussion 155 7.1 Synthesematerialien und industriell verfügbare Materialien . . . . . . . . . . . 155 7.2 Syntheseprodukte . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160 7.2.1 Syntheseprodukte: Einkristalle (CVT) . . . . . . . . . . . . . . . . . . . 160 7.2.2 Syntheseprodukte: Polykristalline Produkte (Ofentempern, FAST-SPS und HP/HT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183 7.2.3 Vergleich der Syntheseprodukte: Einkristalle und Polykristalline Produkte 202 8 Laugungsexperimente: Zusammenfassung und Schlussfolgerung 213 9 Schlussfolgerung 220 10 Zusammenfassung 221 Literaturverzeichnis 225 Anhang A Ergebnispräsentation auf internationalen Fachtagungen 247 B Pulver vs. Kompaktprobe-Diffraktometrie 249 C ZnSdis.str-Datei 252 D Bestimmung der Bandlücke 254 E Messpunkte EPMA 256 F Einwaagen der Synthese 258 G Texturfaktoren der Röntgenbeugung X-Ray Diffraction (XRD)-Analyse 260