Dissertations / Theses on the topic 'Metallic lithium'

Lithium borohydride (LiBH4) has been shown great interest as a hydrogen storage material owing to its large hydrogen storage capacity of 18.5 wt%, but unfortunately to release the vast majority of the stored hydrogen requires temperatures in excess of 600 °c. To improve the temperature at which LiBH4 decomposes, and to improve its poor reversibility, a process known as thermodynamic tuning can be used. Thermodynamic tuning involves creating new, more favourable reaction pathways and in this work the addition of nickel, silicon, iron and cobalt were investigated. The addition of nickel in the LiBH4:2Ni system was shown to be the most effective in reducing the decomposition temperature to occur below 300 °c while also improving reversibility to occur in the solid state at temperatures of 250 °c or lower. The addition of silicon was found to not be effective in reducing the decomposition temperature of LiBH4 even though it was thermodynamically predicted to do so. Attempts to improve the kinetics of the system with a titanium catalyst only showed an improvement when large quantities of the catalyst were used implying that the reaction with the catalyst was the driving force. Addition of both cobalt and iron were also effective in reducing the temperature of LiBH4 decomposition, in a similar reaction to the nickel systems by forming borides. The mass loss in the solid state (< 300 °c) was, however, inferior to the addition of nickel.

Thesis (Ph. D.)--State University of New York at Binghamton, Materials Science, 2005.
Numerals in chemical formula in title are "subscript" in t.p. of printed version. Includes bibliographical references.

Thesis: S.M., Massachusetts Institute of Technology, Department of Mechanical Engineering, 2015.
Cataloged from PDF version of thesis.
Includes bibliographical references (pages 37-39).
Aluminum 1235-H18 foils with sub-micron grain dimensions are often used as current collectors in Li-ion batteries. Due to their contribution to the structural integrity of batteries under impact loading, their plastic and fracture response is investigated in detail. Using a novel micro-tensile testing device with a piezoelectric actuator, dogbone specimens with a 1.25 mm wide and 5.7 mm long gage section are tested for three different in-plane material orientations and for strain rates ranging from 10-5/s to 10-2/s. It was found that the stress at a proof strain of 2% increased by about 25% from 160MPa to 200MPa within this range of strain rates. Furthermore, pronounced inplane anisotropy is observed as reflected by Lankford ratios variations from 0.2 to 1.5 .A material model is proposed which borrows elements of the anisotropic Yld2000-2d plasticity model and integrates these into a basic viscoplasticity framework that assumes the multiplicative decomposition of the equivalent stress into a strain and strain rate dependent contributions. The an isotropic fracture response is characterized for a strain rate of 10-3 /s using notched tension and Hasek punch experiments. It is found that a simple stress state independent version of the anisotropic MMC fracture initiation model provides a reasonable approximation of the observed experimental results.
by Colin Bonatti.
S.M.

L'amélioration continue des performances des batteries Li-ion au cours des deux dernières décennies a permis l'introduction de nombreuses automobiles électriques sur le marché. Cependant, les demandes concernant la sécurité, l'autonomie et la charge rapide des véhicules nécessitent le développement de nouvelles technologies plus performantes.C'est dans cette optique qu'a été fondé le projet RAISE 2024 dans lequel s'inscrit cette thèse. Cette collaboration entre SAFT, ARKEMA et l'université de Pau et des pays de l'Adour vise à développer une batterie à électrolyte solide. Le développement d'un tel système possède un objectif double, à savoir le renforcement de la sécurité lors du fonctionnement des batteries, et l'utilisation de nouveaux matériaux d'électrode de plus forte capacité comme le lithium métal.Pour atteindre cet objectif, deux électrolytes ont été étudiés dans cette thèse. Le premier est constitué d'un électrolyte polymère gélifié obtenu par la réticulation d'un polymère mélangé à un électrolyte liquide. Il permet d'obtenir de bonnes performances en matière de conductivité ionique à température ambiante (10-3 S/cm) et son utilisation en batterie a permis de réaliser plus de 700 cycles avec une rétention de capacité supérieure à 80%. L'impact de la matrice polymère sur les performances a été étudié à travers une série de tests électrochimiques et d'analyse de surface (XPS). Enfin, les tests de sécurité effectués sur des cellules contenant cet électrolyte permettent de mettre en évidence une diminution significative de la quantité d'énergie libérée.Enfin, un deuxième système conducteur ionique a été étudié. Il se présente sous la forme d'une membrane polymère, plastifiée avec un liquide ionique et un solvant. Cette membrane permet d'obtenir une conductivité ionique supérieure à 10-4 S/cm à température ambiante. Couplée à un électrolyte gélifié dans les électrodes pour favoriser le contact au niveau des interfaces, la membrane présente une résistance élevée à la formation de dendrites de lithium. Son utilisation dans une cellule composée d'une électrode positive de NMC 811 et d'une électrode négative de lithium métal a permis de réaliser plus de 200 cycles à un régime de C/5, D/2 avant de perdre 20% de la capacité initiale
Improvements in the performances of Li-ion batteries in the past two decades, has enabled the introduction of many electric cars on the market. However, demands regarding the safety, autonomy, and fast charging require the development of new and more efficient technologies.It was in this context that the RAISE 2024 project, in which this thesis is part of, was founded. This collaboration between ARKEMA, SAFT and the University of Pau and Adour Countries aims to develop a lithium ion battery with a solid electrolyte. The development of such a system has a double objective: the reinforcement of safety during operation, and the use of new electrode materials with higher capacity such as metallic lithium.To achieve this objective, two electrolytes were studied in this thesis. The first consists of a gelled electrolyte obtained by crosslinking of a polymer matrix. It provides good performance in terms of ionic conductivity at room temperature (10-3 S/cm). More than 700 cycles were achieved with this electrolyte in a battery cell before reaching 80% of initial capacity. The impact of polymer matrix on performance was studied through a series of electrochemical tests and surface analysis (XPS). Finally, safety tests (nail penetration) carried out on cells filled with this electrolyte show a significant reduction of energy released.Finally, a second ionic conductor was studied. It comes in the form of a polymer membrane, plasticized with an ionic liquid and a solvent. This membrane exhibits ionic conductivity above 10-4 S/cm at room temperature. Coupled with a gel electrolyte in electrodes to improve interfacial contact, the membrane shows a high resistance to lithium dendrites. A cell using this electrolyte and composed of NMC 811 as positive electrode and lithium metal as negative electrode performed 200 cycles at a rate of C/5, D/2 before losing 20% of its initial capacity

Thesis (Ph. D.)--Chemical and Biomolecular Engineering, Georgia Institute of Technology, 2007.
Teja, Amyn, Committee Chair ; Kohl, Paul, Committee Member ; Liu, Meilin, Committee Member ; Nair,Sankar, Committee Member ; Rousseau, Ronald, Committee Member.

Le développement de méthodes de synthèse asymétriques a largement été exploré au cours des vingt dernières années et en particulier par le biais de réactifs organométalliques. Bien que ces processus mènent à d’excellents résultats en terme d’énantiodiscrimination, l’objectif de cette thèse a été de développer de nouveaux outils de synthèse peu onéreux, respectueux des fonctions sensibles environantes et permettant l’accès aux composés attendus avec de bons rendements et excès énantiomériques. Dans cet optique, des triorganozincates de lithium chiraux ont été étudiés. Des méthodes d’alkylation et d’arylation 1,2 énantiosélectives d’aldéhydes, comportant comme partenaire chiral la (R)-N-(2-iso-butoxybenzyl)-1- phenyléthanamine, ont ainsi été développées et mises en application sur divers aldéhydes. Les alcools secondaires correspondants ont été obtenus avec de bons rendements (jusqu'à 83%) et d’excellents excès énantiomériques (jusqu'à 99%). Ces procédures ont ensuite été appliquées à la synthèse asymétrique de produits naturels et/ou bioactifs tels que la Spiromastilactone A, la (R)-Néobénodine et la (R)-Orphénadrine. Par ailleurs, la synthèse de nouveaux ligands de type amino-alcool a été développée dans le but ultime de désymétriser des substrats de type imines cycliques
The development of new asymetric methodologies have been widely explored during the last twenty years and in particular through organometallic reagents. Although these processes lead to excellent results in terms of enantiodiscrimination, the goal of this thesis was to develop new tools: cheap, chemoselective and allowing the access to the desired compounds with high yields and enantiomeric excesses. In this context, chiral lithium triorganozincates have been studied. Enantioselective nucleophilic 1,2 alkylation and arylation of aldehydes reactions, including (R)-N-(2-iso-butoxybenzyl)-1-phenylethanamine as the chiral ligand, have been optimized toward various aldehydes. The expected secondary chiral alcohols have been obtained with good yields (up to 83%) and high enantiomeric excesses (up to 99%).These processes have been then applied to the asymmetric synthesis of naturals and/or bioactive compounds as Spiromastilactone A, (R)-Neobenodine and (R)-Orphenadrine. Finally, the access to new amino-alcohols have been developed with the ultimate goal to engage those species as the chiral partner when reacting chiral lithium zincates with imines

The experimental data and results demonstrated here illustrate the preparation and application of mesoporous metal oxides in energy storage, adsorption, and catalysis. First, a new method of controlling the pore size and wall thickness of mesoporous silica was developed by controlling the calcination temperature. A series of such silica were used as hard templates to prepare the mesoporous metal oxide Co₃O₄. Using other methods, such as varying the silica template hydrothermal treatment temperature, using colloid silica, varying the materials ratio etc., a series of mesoporous β-MnO₂ with different pore size and wall thickness were prepared. By using these materials it has been possible to explore the influence of pore size and wall thickness on the rate of lithium intercalation into mesoporous electrode. There is intense interest in lithium intercalation into titanates due to their potential advantages (safety, rate) replacing graphite for new generation Li-ion battery. After the preparation of an ordered 3D mesoporous anatase the lithium intercalation as anode material has been investigated. To the best of our knowledge, there are no reports of ordered crystalline mesoporous metal oxides with microporous walls. Here, for the first time, the preparation and characterization of three dimensional ordered crystalline mesoporous α-MnO₂ with microporous wall was described, in which K+ and KIT-6 mesoporous silica act to template the micropores and mesopores, respectively. It was used as a cathode material for Li-ion battery. Its adsorption behavior and magnetic property was also surveyed. Following this we described the preparation and characterization of mesoporous CuO and reduced Cu[subscript(x)]O, and demonstrated their application in NO adsorption and delivery. Finally a series of crystalline mesoporous metal oxides were prepared and evaluated as catalysts for the CO oxidation.

Les mécanismes de lithiation électrochimique, de passivation et de vieillissement de sulfures métalliques (Fe1-xS (0≤x≤0. 07), Ni3S2 et Cu2S) ont éte�� étudiés par spectroscopie de surface (XPS et ToF-SIMS) couplée à des mesures électrochimiques. Une approche modèle des matériaux d’électrode négative de type conversion pour les batteries Li-ion a été développée. Elle repose sur l’élaboration de films minces de sulfure par croissance en milieu H2S sur substrat métallique. Le substrat sert de collecteur de courant. Les résultats montrent que la conversion/déconversion avec le lithium est réversible mais incomplète. La décharge conduit à la passivation de la surface du matériau avec formation d’une couche interfaciale (SEI) dont la composition, la stabilité et l’épaisseur ont été suivies durant le premier cycle puis en cyclage répété. Le gonflement/rétrécissement, typique des matériaux de type conversion, génère des modifications morphologiques (fissures et trous) amplifiées par cyclage répété. Un modèle mécanistique des modifications de l’électrode incluant l’influence de l’électrolyte est proposé
Surface analytical techniques were combined to study the electrochemical lithiation, passivation and ageing mechanisms of transition metal sulfides (Fe1-xS (0≤x≤0. 07), Ni3S2 and Cu2S) as conversion-type negative electrode materials for Li-ion batteries. A thin film approach was applied by thermal sulfidation of metal substrate used as current collector. The results show reversible but incomplete conversion/deconversion with lithium. Discharge leads to surface passivation with formation of the solid electrolyte interphase (SEI) layer whose chemical composition, stability and thickness were followed during the first cycle and with repeated cycling. Swelling/shrinkage, typical for conversion-type materials, causes irreversible morphological modifications (cracks and pinholes) amplified by multi-cycling. A mechanistic model of the induced thin film electrode modifications including the electrolyte influence is proposed

L’étain est une alternative privilégiée en remplacement du carbone graphite comme matériau d’électrode négative dans les batteries Li-ion en raison de son importante capacité théorique spécifique massique de 993 mAh.g-1. Toutefois son expansion volumique lors sa lithiation conduit à sa dégradation au cours du cyclage, diminuant la durée de vie du matériau. Pour pallier à sa pulvérisation, l’utilisation de l’espace inter-granulaire via la nanostructuration du matériau est complétée par l’adjonction d’une matrice carbonée ou d’un autre élément inactif vis-à-vis de la lithiation (utilisation d’alliages intermétalliques). L’objectif de ce travail porte sur l’élaboration de nouveaux procédés de synthèse de nanoparticules d’étain et d’alliage étain-cuivre en milieu liquide ionique. Des nanoparticules de Sn de taille variant de 7 à 45 nm, selon la combinaison cation-anion du liquide ionique et à partir de différents sels métalliques, ont été synthétisées, ainsi qu’un nano-alliage, le composé Cu6Sn5. La taille des nanoparticules est liée à la nature de l’anion bien que le cation présente une interaction privilégiée avec la surface métallique des nanoparticules. Isolées du liquide ionique, les nanoparticules de Sn et Cu6Sn5 montrent une architecture de type cœur-coquille avec un cœur cristallin métallique ou intermétallique et une coquille amorphe d’oxydes d’étain. Les nanoparticules de type Sn@SnOx présentent une capacité spécifique élevée supérieure à 950 mAh.g-1, mettant en lumière un mécanisme de conversion réversible du SnOx surfacique, et celle du nano-alliage Sn-Cu@SnOx est proche de la capacité attendue pour un mécanisme d’alliage, à plus de 530 mAh.g-1
Tin is a promising alternative to replace graphite carbon as a negative electrode material in Li-ion batteries due to its high specific theoretical mass capacity of 993 mAh.g-1. However, change in volume during lithiation leads to its mechanical degradation during the cycling, and consequently very short life of the material. To overcome this issue, the use of the intergranular space via the nanostructuration of the material combined by the addition of a carbon matrix or other inactive element vs. lithium (intermetallic alloys), which buffers drastically the volume expansion during the lithium alloying process, is employed. The aim of this work is to develop new processes for the synthesis of tin nanoparticles and tin-copper alloys in ionic liquid medium. Sn nanoparticles varying in size from 7 to 45 nm were synthesized, according to the cation-anion combination of the ionic liquid and from different metallic salts, as well as a nano-alloy compound, Cu6Sn5. The size of the nanoparticles is directly related to the nature of the anion although the cation has a privileged interaction with the metal surface of the nanoparticles. Once isolated from the ionic liquid, Sn and Cu6Sn5 nanoparticles have a core-shell architecture with a metallic or intermetallic crystalline core and an amorphous shell of tin oxides. A reversible conversion mechanism of the SnOx from the shell is highlighted for Sn@SnOx nanoparticles, with a high specific capacity of approximately 950 mAh.g-1. Sn-Cu@SnOx nano-alloys have a capacity close to the theoretical for an alloy mechanism at more than 530 mAh.g-1

The topological diversity of lithium-boron imidazolates LiB(imid)4 was studied by combining topological enumeration and ab initio DFT calculations. The structures based on zeolitic rho, gme and fau nets are shown to be stable and have high total hydrogen uptake (6.9–7.8 wt.%) comparable with that of MOF-177
Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich

The topological diversity of lithium-boron imidazolates LiB(imid)4 was studied by combining topological enumeration and ab initio DFT calculations. The structures based on zeolitic rho, gme and fau nets are shown to be stable and have high total hydrogen uptake (6.9–7.8 wt.%) comparable with that of MOF-177.
Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Lithium Cesium Tantalum (LCT) pegmatites are important resources for rare metals like Cesium, Lithium or Tantalum, whose demand increased markedly during the past decade. At present, Cs is known to occur in economic quantities only from the two LCT pegmatite deposits at Bikita located in Zimbabwe and Tanco in Canada. Host for this Cs mineralisation is the extreme rare zeolite group mineral pollucite. However, at Bikita and Tanco, pollucite forms huge massive, lensoid shaped and almost monomineralic pollucite mineralisations that occur within the upper portions of the pegmatite. In addition, both pegmatite deposits have a comparable regional geological background as they are hosted within greenstone belts and yield a Neoarchean age of about 2,600 Ma. Furthermore, at present the genesis of these massive pollucite mineralisations was not yet investigated in detail. Major portions of Western Australia consist of Meso- to Neoarchean crustal units (e.g., Yilgarn Craton, Pilbara Craton) that are known to host a large number of LCT pegmatite systems. Among them are the LCT pegmatite deposits Greenbushes (Li, Ta) and Wodgina (Ta, Sn). In addition, small amounts of pollucite were recovered from one single diamond drill core at the Londonderry pegmatite field. Despite that, no systematic investigations and/or exploration studies were conducted for the mode of occurrence of Cs and especially that of pollucite in Western Australia. In the course of the present study nineteen individual pegmatites and pegmatite fields located on the Yilgarn Craton, Pilbara Craton and Kimberley province have been visited and inspected for the occurrence of the Cs mineral pollucite. However, no pollucite could be detected in any of the investigated pegmatites. Four of the inspected LCT-pegmatite systems, namely the Londonderry pegmatite field, the Mount Deans pegmatite field, the Cattlin Creek LCT pegmatite deposit (Yilgarn Craton) and the Wodgina LCT pegmatite deposit (Pilbara Craton) was sampled and investigated in detail. In addition, samples from the Bikita pegmatite field (Zimbabwe Craton) were included into the present study in order to compare the Western Australian pegmatites with a massive pollucite mineralisation bearing LCT pegmatite system. This thesis presents new petrographical, mineralogical, mineralchemical, geochemical, geochronological, fluid inclusion and stable and radiogenic isotope data. The careful interpretation of this data enhances the understanding of the LCT pegmatite systems in Western Australia and Zimbabwe. All of the four investigated LCT pegmatite systems in Western Australia, crop out in similar geological settings, exhibit comparable internal structures, geochemistry and mineralogy to that of the Bikita pegmatite field in Zimbabwe. Furthermore, in all LCT pegmatite systems evidences for late stage hydrothermal processes (e.g., replacement of feldspars) and associated Cs enrichment (e.g., Cs enriched rims on mica, beryl and tourmaline) is documented. With the exception of the Wodgina LCT pegmatite deposit, that yield a Mesoarchean crystallisation age (approx. 2,850 Ma), all other LCT pegmatite systems gave comparable Neoarchean ages of 2,630 Ma to 2,600 Ma. The almost identical ages of the LCT pegmatite systems of the Yilgarn and Zimbabwe cratons suggests, that the process of LCT pegmatite formation at the end of the Neoarchean was active worldwide. Nevertheless, essential distinguishing feature of the Bikita pegmatite field is the presence of massive pollucite mineralisations that resulted from a process that is not part of the general development of LCT pegmatites and is associated with the extreme enrichment of Cs. The new findings of the present study obtained from the Bikita pegmatite field and the Western Australian LCT pegmatite systems significantly improve the knowledge of Cs behaviour in LCT pegmatite systems. Therefore, it is now possible to suggest a genetical model for the formation of massive pollucite mineralisations within LCT pegmatite systems. LCT pegmatites are generally granitic in composition and are interpreted to represent highly fractionated and geochemically specialised derivates from granitic melts. Massive pollucite mineralisation bearing LCT pegmatites evolve from large and voluminous pegmatite melts that intrude as single body along structures within an extensional tectonic setting. After emplacement, initial crystallisation will develop the border and wall zone of the pegmatites, while due to fractionated crystallisation immobile elements (i.e., Cs, Rb) become enriched within the remaining melt and associated hydrothermal fluids. Following this initial crystallisation, a relatively small portion (0.5–1 vol.%) of immiscible melt or fluid will separate during cooling. This immiscible partial melt/fluid is enriched in Al2O3 and Na2O, as well as depleted in SiO2 and will crystallise as analcime. In addition, this melt might allready contains up to 1–2 wt.% Cs2O. However, due to the effects of fluxing components (e.g., H2O, F, B) this analcime melt becomes undercooled which prevents crystallisation of the analcime as intergranular grains. Since this analcime melt exhibits a lower relative gravity when compared to the remaining pegmatite melt the less dense analcime melt will start to ascent gravitationally and accumulate within the upper portion of the pegmatite sheet. At the same time, the remaining melt will start to crystallise separately and form the inner portions of the pegmatite. This crystallisation is characterised by still ongoing fractionation and enrichment of incompatible elements (i.e., Cs, Rb) within the last crystallising minerals (e.g., lepidolite) or concentration of these incompatible elements within exsolving hydrothermal fluids. As analcime and pollucite form a continuous solid solution series, the analcime melt is able to incorporate any available Cs from the melt and/or associated hydrothermal fluids and crystallise as Cs-analcime in the upper portion of the pegmatite sheet. Continuing hydrothermal activity and ongoing substitution of Cs will then start to shift the composition from Cs-analcime composition towards Na-pollucite composition. In addition, if analcime is cooled below 400 °C it is subjected to a negative thermal expansion of about 1 vol.%. This contraction results in the formation of a prominent network of cracks that is filled by late stage minerals (e.g., lepidolite, quartz, feldspar and petalite). Certainly, prior to filling, this network of cracks enhances the available conduits for late stage hydrothermal fluids and the Cs substitution mechanism within the massive pollucite mineralisation. Furthermore, during cooling of the pegmatite, prominent late stage mineral replacement reactions (e.g., replacement of K-feldspar by lepidolite, cleavelandite, and quartz) as well as subsolidus self organisation processes in feldspars take place. These processes are suggested to release additional incompatible elements (e.g., Cs, Rb) into late stage hydrothermal fluids. As feldspar forms large portions of pegmatite a considerable amount of Cs is released and transported via the hydrothermal fluids towards the massive pollucite mineralisation in the upper portion of the pegmatite. Consequently, the initial analcime can accumulate enough Cs in order to shift its composition from the Cs-analcime member (>2 wt.% Cs2O) towards the Na-pollucite member (23–43 wt.% Cs2O) of the solid solution series. The timing of this late stage Cs enrichment is interpreted to be quasi contemporaneous or immediately after the complete crystallisation of the pegmatite melt. However, much younger hydrothermal events that overprint the pegmatite are also interpreted to cause similar results. Hence, it has been demonstrated that the combination of this magmatic and hydrothermal processes is capable to generate an extreme enrichment in Cs in order to explain the formation of massive pollucite mineralisations within LCT pegmatite systems. This genetic model can now be applied to evaluate the potential for occurrences of massive pollucite mineralisations within LCT pegmatite systems in Western Australia and worldwide
Lithium-Caesium-Tantal-(LCT) Pegmatite repräsentieren eine bedeutende Quelle für seltene Metalle, deren Bedarf im letzten Jahrzehnt beträchtlich angestiegen ist. Im Falle von Caesium sind zurzeit weltweit nur zwei LCT-Pegmatitlagerstätten bekannt, die abbauwürdige Vorräte an Cs enthalten. Dies sind die LCT-Pegmatitlagerstätten Bikita in Simbabwe und Tanco in Kanada. Das Wirtsmineral für diese Cs-Mineralisation ist das extrem selten auftretende Zeolith-Gruppen-Mineral Pollucit. In den Lagerstätten Bikita und Tanco bildet Pollucit dagegen massive, linsenförmige und fast monomineralische Pollucitmineralisationen, die in den oberen Bereichen der Pegmatitkörper anstehen. Zusätzlich befinden sich beide Lagerstätten in geologisch vergleichbaren Einheiten. Die Nebengesteine sind Grünsteingürtel die ein neoarchaisches Alter von ca. 2,600 Ma aufweisen. Die Bildung derartiger massiver Pollucitmineralisationen ist bis jetzt noch nicht detailliert untersucht worden. Große Bereiche von Westaustralien werden von meso- bis neoarchaischen Krusteneinheiten (z.B. Yilgarn Kraton, Pilbara Kraton) aufgebaut, von denen auch eine große Anzahl an LCT-Pegmatitsystemen bekannt sind. Darunter befinden sich unter anderem die LCT-Pegmatitlagerstätten Greenbushes (Li, Ta) und Wodgina (Ta, Sn). Zusätzlich wurden kleine Mengen an Pollucit in einer einzigen Kernbohrung im Londonderry Pegmatitfeld angetroffen. Ungeachtet dessen, wurden in Westaustralien bis jetzt keine systematischen Untersuchungen und/oder Explorationskampagnen auf Vorkommen von Cs und speziell der von Pollucit durchgeführt. Im Verlauf dieser Studie wurden insgesamt neunzehn verschiedene Pegmatitvorkommen und Pegmatitfelder des Yilgarn Kratons, Pilbara Kratons und der Kimberley Provinz auf das Vorkommen des Minerals Pollucit untersucht. Allerdings konnte in keinem der untersuchten LCT-Pegmatitsystemen Pollucit nachgewiesen werden. Von vier der untersuchten LCT-Pegmatitsystemen, dem Londonderry Pegmatitfeld, dem Mount Deans Pegmatitfeld, der Cattlin Creek LCT-Pegmatitlagerstätte (Yilgarn Kraton) und der Wodgina LCT-Pegmatitlagerstätte (Pilbara Kraton) wurden detailliert Proben entnommen und weitergehend untersucht. Zusätzlich wurden die massiven Pollucitmineralisationen im Bikita Pegmatitfeld beprobt und in die detailierten Untersuchungen einbezogen. Der Probensatz aus dem Bikita Pegmatitfeld dient als Referenzmaterial mit dem die Pegmatitproben aus Westaustralien verglichen werden. Die vorliegende Arbeit fasst die wesentlichen Ergebnisse der petrographischen, mineralogischen, mineralchemischen, geochemischen und geochronologischen Untersuchungen sowie der Flüssigkeitseinschlussuntersuchungen und stabilen und radiogenen Isotopenzusammensetzungen zusammen. Alle vier der in Westaustralien untersuchten LCT-Pegmatitsysteme kommen in geologisch ähnlichen Rahmengesteinen vor, weisen einen vergleichbaren internen Aufbau, geochemische Zusammensetzung und Mineralogie zu dem des Bikita Pegmatitfeldes in Simbabwe auf. Weiterhin konnten in allen LCT-Pegmatitsystemen Hinweise für späte hydrothermale Prozesse (z.B. Verdrängung von Feldspat) nachgewiesen werden, die einhergehend mit einer Anreicherung von Cs verbunden sind (z.B. Cs-angereicherte Säume um Glimmer, Beryll und Turmalin). Mit der Ausnahme der Wodgina LCT-Pegmatitlagerstätte, in der ein mesoarchaisches Kristallisationsalter (ca. 2,850 Ma) nachgewiesen wurde, lieferten die Altersdatierungen in den anderen LCT-Pegmatitsystemen übereinstimmende neoarchaische Alter von 2,630 Ma bis 2,600 Ma. Diese fast identischen Alter der LCT-Pegmatitsysteme des Yilgarn und Zimbabwe Kratons suggerieren, dass die Prozesse, die zur LCT-Pegmatitbildung am Ende des Neoarchaikums führten, weltweit aktiv waren. Ungeachtet dessen stellt das Vorhandensein von massiver Pollucitmineralisation das Alleinstellungsmerkmal des Bikita Pegmatitfeldes dar, welche sich infolge eines Prozesses gebildet haben der nicht Bestandteil der üblichen LCT-Pegmatitentwicklung ist und sich durch eine extreme Anreicherung an Cs unterscheidet. Die neuen Ergebnisse die in dieser Studie von den Bikita Pegmatitfeld und den Westaustralischen LCT-Pegmatitsystemen gewonnen wurden, verbessern das Verständnis des Verhaltens von Cs in LCT-Pegmatitsystemen deutlich. Somit ist es nun möglich, ein genetisches Modell für die Bildung von massiven Pollucitmineralisationen in LCT-Pegmatitsystemen vorzustellen. LCT-Pegmatite weisen im Allgemeinen eine granitische Zusammensetzung auf und werden als Kristallisat von hoch fraktionierten und geochemisch spezialisierten granitischen Restschmelzen interpretiert. Die Bildung von massiven Pollucitmineralisationen ist nur aus großen und voluminösen Pegmatitschmelzen, die als einzelner Körper entlang von Störungen in extensionalen Stressregimen intrudieren möglich. Nach Platznahme der Schmelze bildet die beginnende Kristallisation zunächst die Kontakt- und Randzone des Pegmatits, wobei infolge von fraktionierter Kristallisation die immobilen Elemente (v.a. Cs, Rb) in der verbleibenden Restschmelze angereichert werden. Im Anschluss an diese erste Kristallisation entmischt sich nach Abkühlung eine sehr kleine Menge (0.5–1 vol.%) Schmelze und/oder Fluid von der Restschmelze. Diese nicht mischbare Teilschmelze/-fluid ist angereichert an Al2O3 und Na2O sowie verarmt an SiO2 und kristallisiert als Analcim. Zusätzlich kann diese Schmelze bereits mit 1–2 wt.% Cs2O angereichert sein. Aufgrund der Auswirkung von Flussmitteln (z.B. H2O, F, B) wird allerdings der Schmelzpunkt dieser Analcimschmelze herabgesetzt und so die Kristallisation des Analcims als intergranulare Körner verhindert. Da diese Analcimschmelze im Vergleich zu der restlichen Schmelze eine geringere relative Dichte besitzt, beginnt sie gravitativ aufzusteigen und sich in den oberen Bereichen des Pegmatitkörpers zu akkumulieren. Währenddessen beginnt die restliche Schmelze separat zu kristallisieren und die inneren Bereiche des Pegmatits zu bilden. Diese Kristallisation ist einhergehend mit fortschreitender Fraktionierung und der Anreicherung von inkompatiblen Elementen (v.a. Cs, Rb) in den sich als letztes bildenden Mineralphasen (z.B. Lepidolit) oder der Konzentration der inkompatiblen Element in die sich entmischenden hydrothermalen Fluiden. Da Analcim und Pollucit eine lückenlose Mischungsreihe bilden, ist die Analcimschmelze in der Lage, alles verfügbare Cs von der Restschmelze und/oder assoziierten hydrothermalen Fluiden an sich zu binden und als Cs-Analcim im oberen Bereich des Pegmatitkörpers zu kristallisieren. Fortschreitende hydrothermale Aktivität und Substitution von Cs verschiebt dann die Zusammensetzung des Analcims von der Cs-Analcim- zu Na-Pollucitzusammensetzung. Zusätzlich erfährt der Analcim bei Abkühlung unter 400 °C eine negative thermische Expansion von ca. 1 vol.%. Diese Kontraktion führt zu der Bildung des markanten Rissnetzwerkes das durch späte Mineralphasen (z.B. Lepidolit, Quarz, Feldspat und Petalit) gefüllt wird. Vor der Mineralisation allerdings, erhöht dieses Netzwerk an Rissen die verfügbaren Wegsamkeiten für die späten hydrothermalen Fluide und begünstigt somit den Cs-Substitutionsmechanismus in der massiven Pollucitmineralisation. Weiterhin kommt es bei der Abkühlung des Pegmatits zu späten Mineralverdrängungsreaktionen (z.B. Verdrängung von K-Feldspat durch Lepidolit, Cleavelandit und Quarz), sowie zu Subsolidus-Selbstordnungsprozessen in Feldspäten. Diese Prozesse werden weiterhin interpretiert inkompatible Elemente (z.B. Cs, Rb) in die späten hydrothermalen Fluide freizusetzen. Da Feldspäte große Teile der Pegmatite bilden, kann somit eine beträchtliche Menge an Cs freigeben werden und durch die späten hydrothermalen Fluide in die massive Pollucitmineralisation in den oberen Bereichen des Pegmatitkörpers transportiert werden. Infolgedessen ist es möglich, dass genügend Cs frei gesetzt werden kann, um die Zusammensetzung innerhalb der Mischkristallreihe von Cs-Analcim (>2 wt.% Cs2O) zu Na-Pollucit (23–43 wt.% Cs2O) zu verschieben. Die zeitliche Einordnung dieser späten Cs-Anreicherung wird als quasi zeitgleich oder im direkten Anschluss an die vollständige Kristallisation der Pegmatitschmelze interpretiert. Es kann allerdings nicht vernachlässigt werden, dass auch jüngere hydrothermale Ereignisse, die den Pegmatitkörper nachträglich überprägen, ähnliche hydrothermale Prozesse hervorrufen können. Somit konnte gezeigt werden, dass es durch Kombination dieser magmatischen und hydrothermalen Prozessen möglich ist, genügend Cs anzureichern, um die Bildung von massiven Pollucitmineralisationen in LCT-Pegmatitsystemen zu ermöglichen. Dieses genetische Modell kann nun dazu genutzt werden, um das Potential von Vorkommen von massiven Pollucitmineralisationen in LCT-Pegmatitsystemen in Westaustralien und weltweit besser einzuschätzen

Aluminum based amorphous metallic glass powders were produced and tested as the anode materials for the lithium ion rechargeable batteries. Ground Al₈₀Ni₁₀La₁₀ was found to have a low first cycle capacity of about 100 Ah/Kg. The considerable amount of intermetallic formed in the amorphous glass makes the aluminum inactive towards the lithium. The ball milled Al₈₈Ni₉Y₃ powders contain pure aluminum crystalline particles in the amorphous matrix and have first cycle capacity of about 500 Ah/Kg. Nevertheless, polarization was caused by oxidation introduced by the ball-milling process. The electrochemical performances of these amorphous metallic glasses need to be further investigated. Their full lithium insertion capacities cannot be confirmed until the compositions and particle size inside the metallic glass anodes, the conformation of the electrodes and the mechanical milling processes are optimized.
Singapore-MIT Alliance (SMA)

by Li, Tsui Kiu = 納米鋁酸鋰網絡增強的鋁基複合材料的製造和表徵 / 李翠翹.
Thesis (M.Phil.)--Chinese University of Hong Kong, 2006.
Includes bibliographical references.
Text in English; abstracts in English and Chinese.
by Li, Tsui Kiu = Na mi lü suan li wang luo zeng qiang de lü ji fu he cai liao de zhi zao he biao zheng / Li Cuiqiao.
Acknowledgement --- p.i
Abstract --- p.ii
摘要 --- p.iv
Table of contents --- p.vi
List of tables --- p.ix
List of figures --- p.xii
Chapter Chapter 1. --- Introduction
Chapter 1.1. --- Metal matrix composites (MMCs) --- p.1-2
Chapter 1.1.1. --- Introduction --- p.1-2
Chapter 1.1.2. --- Aluminum-based metal matrix composites (Al-MMCs) --- p.1-2
Chapter 1.1.3. --- Applications of MMCs --- p.1-3
Chapter 1.1.3.1. --- Automotive applications --- p.1-3
Chapter 1.1.3.2. --- Aerospace applications --- p.1-4
Chapter 1.1.4. --- Fabrication methods of metal matrix composites --- p.1-5
Chapter 1.1.4.1. --- Stir casting --- p.1-5
Chapter 1.1.4.2. --- Liquid metal infiltration --- p.1-5
Chapter 1.1.4.3. --- Powder metallurgy --- p.1-6
Chapter 1.1.4.4. --- The ex-situ sintering method --- p.6
Chapter 1.1.4.5. --- The in-situ sintering method --- p.1-7
Chapter 1.2. --- The Al-γ-LiA102 MMC --- p.1-7
Chapter 1.2.1. --- Lithium aluminate (LiA102) --- p.1-8
Chapter 1.2.2. --- Applications ofγ-LiA102 --- p.1-8
Chapter 1.2.2.1. --- Ceramic matrices in molten carbonate fuel cell (MCFC) --- p.1-8
Chapter 1.2.2.2. --- Tritium breeder materials in nuclear fusion reactors --- p.1-9
Chapter 1.2.3. --- Fabrication methods ofγ-LiA102 --- p.1-10
Chapter 1.2.3.1. --- Solid state reaction methods --- p.1-10
Chapter 1.2.3.2. --- Sol-gel methods --- p.1-11
Chapter 1.2.3.3. --- Hydrothermal treatment --- p.1-13
Chapter 1.2.3.4. --- Ultrasonic Spray Pyrolysis --- p.1-13
Chapter 1.2.3.5. --- The templated wet-chemical process --- p.1-13
Chapter 1.2.3.6. --- Tape-casting --- p.1-14
Chapter 1.2.3.7. --- Combustion Synthesis --- p.1-14
Chapter 1.3. --- Previous works --- p.1-15
Chapter 1.4. --- Current works --- p.1-16
Chapter 1.5. --- Thesis layout --- p.1-17
References
Chapter Chapter 2. --- Methodology and Instrumentation
Chapter 2.1. --- Introduction --- p.2-2
Chapter 2.2. --- Powder Metallurgy --- p.2-2
Chapter 2.3. --- Fabrication methods --- p.2-3
Chapter 2.3.1. --- Tube furnace sintering --- p.2-3
Chapter 2.3.2. --- Arc melting --- p.2-4
Chapter 2.3.3. --- Annealing --- p.2-5
Chapter 2.3.4. --- Sodium hydroxide etching --- p.2-5
Chapter 2.4. --- Characterization methods --- p.2-6
Chapter 2.4.1. --- Thermal analysis - Differential thermal analysis (DTA) --- p.2-6
Chapter 2.4.2. --- Physical property analysis - Thermomechanical analyzer (TMA) --- p.2-6
Chapter 2.4.3. --- Physical property analysis - The Archimedes' method --- p.2-7
Chapter 2.4.4. --- Physical property analysis-Surface area and porosimetry analyzer --- p.2-8
Chapter 2.4.5. --- Physical property analysis - Microhardness test --- p.2-9
Chapter 2.4.6. --- Microstructural analysis - Scanning electron Microscopy (SEM) --- p.2-9
Chapter 2.4.7. --- Surface morphology analysis - Atomic Force Microscopy (AFM) --- p.2-10
Chapter 2.4.8. --- Phase determination - X-ray Diffractometry (XRD) --- p.2-11
References
Chapter Chapter 3. --- Al-y-LiA102 MMC samples prepared by arc-melting
Chapter 3.1. --- Introduction --- p.3-2
Chapter 3.2. --- Experimental details --- p.3-3
Chapter 3.3. --- XRD analysis --- p.3-4
Chapter 3.4. --- Microstructures --- p.3-5
Chapter 3.5. --- NaOH etching time effects --- p.3-5
Chapter 3.6. --- The 2-minute-etched sample --- p.3-6
Chapter 3.7. --- Physical properties analysis --- p.3-7
Chapter 3.7.1. --- Apparent density --- p.3-7
Chapter 3.7.2. --- Microhardness --- p.3-7
Chapter 3.7.3. --- BET analysis --- p.3-8
Chapter 3.8. --- Formation mechanism ofγ-LiA102 network --- p.3-9
Chapter 3.9. --- Effects ofLi20 contents --- p.3-10
Chapter 3.9.1. --- Effects of Li2O contents on structure and compositions of MMCs --- p.3-10
Chapter 3.9.2. --- Effects of Li2O- contents on coefficient of thermal expansion (CTE) --- p.3-11
Chapter 3.10. --- Conclusions --- p.3-12
References
Chapter Chapter 4. --- Al-y-LiAlO2 MMCs samples prepared by furnace sintering
Chapter 4.1. --- Introduction --- p.4-2
Chapter 4.2. --- Experimental details --- p.4-2
Chapter 4.3. --- The effects of sintering temperature --- p.4-3
Chapter 4.3.1. --- Microstructures --- p.4-3
Chapter 4.3.2. --- XRD analysis --- p.4-4
Chapter 4.4. --- Prolonged NaOH etching --- p.4-5
Chapter 4.5. --- Effects of annealing temperature --- p.4-7
Chapter 4.6. --- DTA analysis of over-etched sample --- p.4-7
Chapter 4.7. --- Thermal stability of the as-synthesized γ-LiA1O2 powders --- p.4-8
Chapter 4.8. --- Conclusions --- p.4-9
References
Chapter Chapter 5. --- Y-LiA1O2 pellets
Chapter 5.1. --- Introduction --- p.5-2
Chapter 5.2. --- Experimental details --- p.5-2
Chapter 5.3. --- Pellets fabricated by method 1 --- p.5-3
Chapter 5.4. --- CTE and volume fraction of MMCs --- p.5-4
Chapter 5.5. --- Pellets fabricated by method II --- p.5-5
Chapter 5.6. --- Comparisons of γ-LiA1O2 fabricated by method I and method II --- p.5-6
Chapter 5.7. --- Conclusions --- p.5-7
References
Chapter Chapter 6. --- Conclusions and future works
Chapter 6.1. --- Conclusions --- p.6-2
Chapter 6.2. --- Suggestions for future work --- p.6-3
Chapter 6.2.1. --- Stability test of y-LiA1O2 in molten carbonates --- p.6-3
Chapter 6.2.2. --- Investigation of the pore size distribution of γ-LiAIO2 network --- p.6-4
Chapter 6.2.3. --- Fabrication of Al-γ-LiA1O2 MMC by hot isotatic pressing --- p.6-4
Chapter 6.2.4. --- Mechanical tests --- p.6-4
Chapter 6.2.5. --- Development of gas sensors --- p.6-5
References

abstract: A distinct characteristic of ferroelectric materials is the existence of a reversible spontaneous polarization with the application of an electric field. The relevant properties ferroelectric lithium niobate surfaces include a low density of defects and external screening of the bound polarization charge. These properties result in unique surface electric field distribution with a strong electric field in the vicinity of domain boundaries, while away from the boundaries, the field decreases rapidly. In this work, ferroelectric lithium niobate (LN) is used as a template to direct the assembly of metallic nanostructures via photo-induced reduction and a substrate for deposition of ZnO semiconducting thin films via plasma enhanced atomic layer deposition (PE-ALD). To understand the mechanism the photo-induced deposition process the following effects were considered: the illumination photon energy and intensity, the polarization screening mechanism of the lithium niobate template and the chemical concentration. Depending on the UV wavelength, variation of Ag deposition rate and boundary nanowire formation are observed and attributed to the unique surface electric field distribution of the polarity patterned template and the penetration depth of UV light. Oxygen implantation is employed to transition the surface from external screening to internal screening, which results in depressed boundary nanowire formation. The ratio of the photon flux and Ag ion flux to the surface determine the deposition pattern. Domain boundary deposition is enhanced with a high photon/Ag ion flux ratio while domain boundary deposition is depressed with a low photon/Ag ion flux ratio. These results also support the photo-induced deposition model where the process is limited by carrier generation, and the cation reduction occurs at the surface. These findings will provide a foundational understanding to employ ferroelectric templates for assembly and patterning of inorganic, organic, biological, and integrated structures. ZnO films deposited on positive and negative domain surfaces of LN demonstrate different I-V curve behavior at different temperatures. At room temperature, ZnO deposited on positive domains exhibits almost two orders of magnitude greater conductance than on negative domains. The conductance of ZnO on positive domains decreases with increasing temperature while the conductance of ZnO on negative domains increases with increasing temperature. The observations are interpreted in terms of the downward or upward band bending at the ZnO/LN interface which is induced by the ferroelectric polarization charge. Possible application of this effect in non-volatile memory devices is proposed for future work.
Dissertation/Thesis
Ph.D. Physics 2011

We have investigated the use of aluminum based amorphous metallic glass as the anode in lithium ion rechargeable batteries. Amorphous metallic glasses have no long-range ordered microstructure; the atoms are less closely packed compared to the crystalline alloys of the same compositions; they usually have higher ionic conductivity than crystalline materials, which make rapid lithium diffusion possible. Many metallic systems have higher theoretical capacity for lithium than graphite/carbon; in addition irreversible capacity loss can be avoided in metallic systems. With careful processing, we are able to obtain nano-crystalline phases dispersed in the amorphous metallic glass matrix. These crystalline regions may form the active centers with which lithium reacts. The surrounding matrix can respond very well to the volume changes as these nano-size regions take up lithium. A comparison study of various kinds of anode materials for lithium rechargeable batteries is carried out.
Singapore-MIT Alliance (SMA)

博士
國立成功大學
材料科學及工程學系碩博士班
95
Li+ conductors are key materials for technological applications as all- solid-state lithium batteries. Unfortunately, many crystalline phases having high Li+ conductivity are unstable in the presence of a metallic lithium anode. Although interfacial reactions between such conductors and the lithium anode are always inferred, very little effort has been devoted to studying this interfacial instability, which is usually examined by observing the coloration of sample with the naked eye. The scope of our study is, therefore, focused on the detailed reaction mechanism and its suppression. Among the various ceramic Li+ conductors, we employed a perovskite-type La2/3–xLi3xTiO3 as a model material for our fundamental study into the interfacial instability. This selection stems from the availability of the crystal structure and the easily comprehensible ion-transport mechanism. In this study, we found that when this La0.56Li0.33TiO3 sample and lithium were placed in contact at room temperature for 24 h, the results of X-ray photoelectron spectrometry (XPS) indicate that 12% of the tetravalent Ti4+ ions were converted into trivalent Ti3+ ions and the valence conversion and degree of conversion were limited by the structural rigidity of the host crystal. The secondary ion mass spectrometry (SIMS) analyses suggests the existence of a local electric field near the contact surface and indicates that the 6Li+ isotope ions were inserted into the specimen through the effect of this field. The mechanism of the lithium-activated RT interfacial reaction is associated with the reduction of Ti4+ transition metal ions from tetravalent to trivalent states, which resulted in the increase of electronic conductivity, and the local-electric-field-induced Li+ insertion into La3+/Li+-site vacancies of La0.56Li0.33TiO3. Moreover, although this metallic-lithium- activated donor doping process semiconductorized the sample on its surface, the ionic conduction of bulk sample was altered to mixed ionic/electronic conduction, which includes a spontaneous electronic transition without directly depending on the interfacial instability. Through our identification, this transition is the lithium-ion- motion dependent electron hopping process. As a result, it was roughly found that the phenomena mentioned above were caused by the presence of Ti4+–transition metal ions and the highly vacant structure in La2/3–xLi3xTiO3 system. Thus, La0.50Li0.50TiO3 has higher reaction inhibition against metallic lithium, and we also found that the perovskite-type LaAlO3 can be incorporated into La0.50Li0.50TiO3 to form a xLaAlO3–(1–x)La0.50Li0.50TiO3 solid solution (0.0 ≤ x ≤ 1.0; i.e., La0.50+0.50xLi0.50–0.50x - Ti1–xAlxO3), indicating that the Al3+ ions can be completely substituted for the Ti4+ ions. However, the samples with 0–40 mol % LaAlO3 have the Li+ ion conduction properties to be used as solid electrolytes of electrochemical devices. After measuring its electrical transition by using metallic lithium electrodes and digital multimeter, the altered process indicate that the sample’s electron concentration decreased with the incorporated amount of LaAlO3, in accordance with the decrease in the resulting electronic conductivity form 1.23× 10–2 S cm–1 to 4.33×10–4 S cm–1. Consequently, Al3+ ions substituted for the Ti4+ ions can assist La0.50Li0.50TiO3 to suppress the interfacial reaction between solid electrolyte and metallic lithium.

Utilization of amorphous metallic alloy has received much attention for use in numerous microelectronic and electrochemical devices since they provide unique electrical, thermal conductivity, and magnetic properties. To develop these functional properties, it is essential to understand the amorphous structure and the property relationships. First principles calculations provide insight into the structure, thermodynamic stability, electronic and magnetic properties of amorphous alloys. For Ru- and Co-based alloys, the thermodynamic stability was examined by calculating the mixing energy along with those of crystalline counterparts. The amorphous RuP, CoP, RuB, and CoB alloys, become energetically more favorable than their crystalline counterparts at moderate P(B) content. The atomistic structures have well-defined local structures depending on the atomic size ratio and electronic interactions between constituent elements. Their local ordering is attributed to strong p-d hybridization, which contributes to stabilizing the Ru(Co)-P(B) alloys. Surface segregation of P(B) and interfacial adhesion with copper were also studied. Li-X (X: Si, Ge, and Sn) were examined when 1 or 2 Li atoms are inserted into the interstitial sites. Li insertion in the tetrahedral site, which is the most preferable site in the diamond matrix, causes outward displacement and charge localization around the X neighbors, thereby weakening of the covalent bonds leading to destabilization of the host matrix. We present the energetics, structure, electronic and mechanical properties of crystalline and amorphous Li-X (X: Si, Ge, Sn, and Si+Sn) alloys. Our calculations show that the incorporation of Li leads to disintegration of the tetrahedrally-bonded X network into small clusters of various shapes. Electronic structure analysis highlights that the charge transfer leads to weakening or breaking of X bonds with the growing splitting between s and p states, and consequently the Li-X alloys softens with increasing Li content.
text

Al based alloy powders (Al₈₅Ni₅Y₆Co₂Fe₂) are produced by spray atomization method. High energy ball milling is done to modify the surface topology and particle size for better electrochemical performance. X ray diffraction (XRD), differential scanning calorimeter (DSC), scanning electron microscope (SEM) and transmission electron microscope (TEM) were conducted to characterize the microstructure of the alloys after ball milling. It is found that 5 hours ball milling gives the minimum crystallization and structure change. Thin film sample is also deposited on stainless steel substrate by pulsed laser deposition (PLD) method for electrochemical test. The capacity and reversibility for different samples are compared and discussed. A capacity of 200mAh/g is obtained for the battery with thin film sample as anode and a capacity of 140mAh/g is obtained for that with electrode from powder sample. Both of the batteries give up to 94% capacity retention after 20 cycles.
Singapore-MIT Alliance (SMA)

碩士
國立臺灣科技大學
材料科學與工程系
104
Lithium bis(trifluoromethane sulfonyl) imide (LiTFSI) salt is claimed to be a potential alternative to lithium hexafluorophosphate (LiPF6) since it has greater electrochemical properties such as chemical and thermal stability which may provide benefits of higher safety and longer lifetime of lithium ion batteries (LIBs).

Many material properties depend on specific details of microstructure and both optimal material performance and material reliability often correlate directly to microstructure. In nano- and micro-systems, the material's microstructure has a characteristic length scale that approaches that of the device in which it is used. Fundamental understanding and prediction of material behavior in nano- and micro-systems depend critically on methods for computing the effect of microstructure. Methods for including the physics and spatial attributes of microstructures are presented for a number of materials applications in devices. The research in our group includes applications of computation of macroscopic response of material microstructures, the development of methods for calculating microstructural evolution, and the morphological stability of structures. In this review, research highlights are presented for particular methods for computing the response in: 1) rechargeable lithium ion battery microstructures, 2) photonic composites with anisotropic particulate morphologies, 3) crack deflection in partially devitrified metallic glasses.
Singapore-MIT Alliance (SMA)

Thesis (Ph. D.)--University of Wisconsin--Madison, 1988.
Typescript. Vita. 2. Investigation of chelation-controlled lithium-metalloid exchange. eContent provider-neutral record in process. Description based on print version record. Includes bibliographies.

Lithium Cesium Tantalum (LCT) pegmatites are important resources for rare metals like Cesium, Lithium or Tantalum, whose demand increased markedly during the past decade. At present, Cs is known to occur in economic quantities only from the two LCT pegmatite deposits at Bikita located in Zimbabwe and Tanco in Canada. Host for this Cs mineralisation is the extreme rare zeolite group mineral pollucite. However, at Bikita and Tanco, pollucite forms huge massive, lensoid shaped and almost monomineralic pollucite mineralisations that occur within the upper portions of the pegmatite. In addition, both pegmatite deposits have a comparable regional geological background as they are hosted within greenstone belts and yield a Neoarchean age of about 2,600 Ma. Furthermore, at present the genesis of these massive pollucite mineralisations was not yet investigated in detail. Major portions of Western Australia consist of Meso- to Neoarchean crustal units (e.g., Yilgarn Craton, Pilbara Craton) that are known to host a large number of LCT pegmatite systems. Among them are the LCT pegmatite deposits Greenbushes (Li, Ta) and Wodgina (Ta, Sn). In addition, small amounts of pollucite were recovered from one single diamond drill core at the Londonderry pegmatite field. Despite that, no systematic investigations and/or exploration studies were conducted for the mode of occurrence of Cs and especially that of pollucite in Western Australia. In the course of the present study nineteen individual pegmatites and pegmatite fields located on the Yilgarn Craton, Pilbara Craton and Kimberley province have been visited and inspected for the occurrence of the Cs mineral pollucite. However, no pollucite could be detected in any of the investigated pegmatites. Four of the inspected LCT-pegmatite systems, namely the Londonderry pegmatite field, the Mount Deans pegmatite field, the Cattlin Creek LCT pegmatite deposit (Yilgarn Craton) and the Wodgina LCT pegmatite deposit (Pilbara Craton) was sampled and investigated in detail. In addition, samples from the Bikita pegmatite field (Zimbabwe Craton) were included into the present study in order to compare the Western Australian pegmatites with a massive pollucite mineralisation bearing LCT pegmatite system. This thesis presents new petrographical, mineralogical, mineralchemical, geochemical, geochronological, fluid inclusion and stable and radiogenic isotope data. The careful interpretation of this data enhances the understanding of the LCT pegmatite systems in Western Australia and Zimbabwe. All of the four investigated LCT pegmatite systems in Western Australia, crop out in similar geological settings, exhibit comparable internal structures, geochemistry and mineralogy to that of the Bikita pegmatite field in Zimbabwe. Furthermore, in all LCT pegmatite systems evidences for late stage hydrothermal processes (e.g., replacement of feldspars) and associated Cs enrichment (e.g., Cs enriched rims on mica, beryl and tourmaline) is documented. With the exception of the Wodgina LCT pegmatite deposit, that yield a Mesoarchean crystallisation age (approx. 2,850 Ma), all other LCT pegmatite systems gave comparable Neoarchean ages of 2,630 Ma to 2,600 Ma. The almost identical ages of the LCT pegmatite systems of the Yilgarn and Zimbabwe cratons suggests, that the process of LCT pegmatite formation at the end of the Neoarchean was active worldwide. Nevertheless, essential distinguishing feature of the Bikita pegmatite field is the presence of massive pollucite mineralisations that resulted from a process that is not part of the general development of LCT pegmatites and is associated with the extreme enrichment of Cs. The new findings of the present study obtained from the Bikita pegmatite field and the Western Australian LCT pegmatite systems significantly improve the knowledge of Cs behaviour in LCT pegmatite systems. Therefore, it is now possible to suggest a genetical model for the formation of massive pollucite mineralisations within LCT pegmatite systems. LCT pegmatites are generally granitic in composition and are interpreted to represent highly fractionated and geochemically specialised derivates from granitic melts. Massive pollucite mineralisation bearing LCT pegmatites evolve from large and voluminous pegmatite melts that intrude as single body along structures within an extensional tectonic setting. After emplacement, initial crystallisation will develop the border and wall zone of the pegmatites, while due to fractionated crystallisation immobile elements (i.e., Cs, Rb) become enriched within the remaining melt and associated hydrothermal fluids. Following this initial crystallisation, a relatively small portion (0.5–1 vol.%) of immiscible melt or fluid will separate during cooling. This immiscible partial melt/fluid is enriched in Al2O3 and Na2O, as well as depleted in SiO2 and will crystallise as analcime. In addition, this melt might allready contains up to 1–2 wt.% Cs2O. However, due to the effects of fluxing components (e.g., H2O, F, B) this analcime melt becomes undercooled which prevents crystallisation of the analcime as intergranular grains. Since this analcime melt exhibits a lower relative gravity when compared to the remaining pegmatite melt the less dense analcime melt will start to ascent gravitationally and accumulate within the upper portion of the pegmatite sheet. At the same time, the remaining melt will start to crystallise separately and form the inner portions of the pegmatite. This crystallisation is characterised by still ongoing fractionation and enrichment of incompatible elements (i.e., Cs, Rb) within the last crystallising minerals (e.g., lepidolite) or concentration of these incompatible elements within exsolving hydrothermal fluids. As analcime and pollucite form a continuous solid solution series, the analcime melt is able to incorporate any available Cs from the melt and/or associated hydrothermal fluids and crystallise as Cs-analcime in the upper portion of the pegmatite sheet. Continuing hydrothermal activity and ongoing substitution of Cs will then start to shift the composition from Cs-analcime composition towards Na-pollucite composition. In addition, if analcime is cooled below 400 °C it is subjected to a negative thermal expansion of about 1 vol.%. This contraction results in the formation of a prominent network of cracks that is filled by late stage minerals (e.g., lepidolite, quartz, feldspar and petalite). Certainly, prior to filling, this network of cracks enhances the available conduits for late stage hydrothermal fluids and the Cs substitution mechanism within the massive pollucite mineralisation. Furthermore, during cooling of the pegmatite, prominent late stage mineral replacement reactions (e.g., replacement of K-feldspar by lepidolite, cleavelandite, and quartz) as well as subsolidus self organisation processes in feldspars take place. These processes are suggested to release additional incompatible elements (e.g., Cs, Rb) into late stage hydrothermal fluids. As feldspar forms large portions of pegmatite a considerable amount of Cs is released and transported via the hydrothermal fluids towards the massive pollucite mineralisation in the upper portion of the pegmatite. Consequently, the initial analcime can accumulate enough Cs in order to shift its composition from the Cs-analcime member (>2 wt.% Cs2O) towards the Na-pollucite member (23–43 wt.% Cs2O) of the solid solution series. The timing of this late stage Cs enrichment is interpreted to be quasi contemporaneous or immediately after the complete crystallisation of the pegmatite melt. However, much younger hydrothermal events that overprint the pegmatite are also interpreted to cause similar results. Hence, it has been demonstrated that the combination of this magmatic and hydrothermal processes is capable to generate an extreme enrichment in Cs in order to explain the formation of massive pollucite mineralisations within LCT pegmatite systems. This genetic model can now be applied to evaluate the potential for occurrences of massive pollucite mineralisations within LCT pegmatite systems in Western Australia and worldwide.:Contents Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii Zusammenfassung . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v Versicherung . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix Contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi 1. Introduction 1 1.1. Motivation and Scope of the Thesis . . . . . . . . . . . . . . . . . . . . . . . . 1 1.2. Structure of the Thesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2. Fundamentals 7 2.1. The Alkali Metal Cesium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.1.1. Distribution of Cesium . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.1.2. Mineralogy of Cesium . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 2.1.3. Geochemical Behaviour of Cesium . . . . . . . . . . . . . . . . . . . . 13 2.1.4. Economy of Cesium . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 2.2. Pollucite – (Cs,Na)2Al2Si4O12×H2O . . . . . . . . . . . . . . . . . . . . . . . . 16 2.2.1. Crystal Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 2.2.2. Analcime–Pollucite–Series . . . . . . . . . . . . . . . . . . . . . . . . . 17 2.2.3. Formation of Pollucite . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 2.2.4. Pollucite Occurences . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 2.3. Pegmatites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 2.3.1. General Characteristics of Pegmatites . . . . . . . . . . . . . . . . . . 34 2.3.2. Controls on Pegmatite Formation and Evolution . . . . . . . . . . . . . 40 2.3.3. Pegmatite Age Distribution and Continental Crust Formation . . . . . . 43 3. Geological Settings of Archean Cratons 47 3.1. Zimbabwe Craton . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47 3.1.1. Tectonostratigraphic Subdivision . . . . . . . . . . . . . . . . . . . . . 48 3.1.2. Tectonometamorphic Evolution of the Northern Limpopo Thrust Zone . 49 3.1.3. Pegmatites within the Zimbabwe Craton . . . . . . . . . . . . . . . . . 52 3.1.4. Masvingo Greenstone Belt . . . . . . . . . . . . . . . . . . . . . . . . . 53 3.1.5. Geological Setting of the Bikita Pegmatite District . . . . . . . . . . . . 58 3.2. Yilgarn Craton . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 3.2.1. Tectonostratigraphic Framework and Geological Development . . . . . 62 3.2.2. Tectonic Models for the Development . . . . . . . . . . . . . . . . . . . 70 3.2.3. Pegmatites within the Yilgarn Craton . . . . . . . . . . . . . . . . . . . 76 3.2.4. Geological setting of the Londonderry Pegmatite Field . . . . . . . . . . 76 3.2.5. Geological Setting of the Mount Deans Pegmatite Field . . . . . . . . . 85 3.2.6. Geological Setting of the Cattlin Creek Pegmatite Deposit . . . . . . . . 91 3.3. Pilbara Craton . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99 3.3.1. Tectonostratigraphic Framework and Geological Development . . . . . 99 3.3.2. Tectonic Model for the Development . . . . . . . . . . . . . . . . . . . 101 3.3.3. Pegmatites within the Pilbara Craton . . . . . . . . . . . . . . . . . . . 105 3.3.4. Geological Setting of the Wodgina Pegmatite District . . . . . . . . . . 106 4. Fieldwork and Sampling of Selected Pegmatites and Pegmatite Fields 115 4.1. Bikita Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115 4.2. Londonderry Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115 4.2.1. Londonderry Feldspar Quarry Pegmatite . . . . . . . . . . . . . . . . . 115 4.2.2. Lepidolite Hill Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . 117 4.2.3. Tantalite Hill Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . 118 4.3. Mount Deans Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . 118 4.3.1. Type I – Flat Lying Pegmatites . . . . . . . . . . . . . . . . . . . . . . . 118 4.3.2. Type II – Steeply Dipping Pegmatites . . . . . . . . . . . . . . . . . . . 120 4.4. Cattlin Creek Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120 4.5. Wodgina LCT-Pegmatite Deposit . . . . . . . . . . . . . . . . . . . . . . . . . . 121 4.5.1. Mount Tinstone Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . 123 4.5.2. Mount Cassiterite Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . 123 5. Petrography and Mineralogy 139 5.1. Quantitative Mineralogy by Means of Mineral Liberation Analysis . . . . . . . . 141 5.2. Mineralogical and Petrographical Characteristics of Individual Mineral Groups . 141 5.2.1. Feldspar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141 5.2.2. Quartz . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144 5.2.3. Mica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146 5.2.4. Pollucite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147 5.2.5. Petalite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149 5.2.6. Spodumene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149 5.2.7. Beryl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154 5.2.8. Tourmaline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155 5.2.9. Apatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157 5.2.10. Ta-, Nb- and Sn-oxides . . . . . . . . . . . . . . . . . . . . . . . . . . 157 5.3. Reconstruction of the General Crystallisation Sequence . . . . . . . . . . . . . 162 6. Geochemistry 165 6.1. Major Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165 6.2. Selected Minor and Trace Elements . . . . . . . . . . . . . . . . . . . . . . . . 174 6.3. Fractionation Indicators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175 6.4. Rare Earth Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185 7. Geochronology 193 7.1. 40Ar/39Ar-Method on Mica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193 7.1.1. Bikita Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . 194 7.1.2. Mount Deans Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . 195 7.1.3. Londonderry Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . 195 7.1.4. Cattlin Creek Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . 195 7.1.5. Wodgina Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198 7.2. Th-U-Total Pb Monazite Dating . . . . . . . . . . . . . . . . . . . . . . . . . . . 201 7.2.1. Monazite Ages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201 7.3. U/Pb Dating of Selected Ta-, Nb- and Sn-Oxide Minerals . . . . . . . . . . . . 203 7.3.1. Bikita Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . 203 7.3.2. Londonderry Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . 203 7.3.3. Mount Deans Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . 206 7.3.4. Cattlin Creek Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . 206 7.3.5. Wodgina Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207 8. Fluid Inclusion Study 211 8.1. Bikita Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211 8.2. Wodgina Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211 8.3. Carbon Isotope Analysis on Fluid Inclusion Gas of Selected Mineral Phases . . 212 9. Stable and Radiogenic Isotopes 217 9.1. Whole Rock Sm/Nd-Isotopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217 9.1.1. New Whole Rock Sm/Nd Data . . . . . . . . . . . . . . . . . . . . . . 217 9.2. Lithium Isotope Analysis on Selected Mineral Phases . . . . . . . . . . . . . . . 220 9.2.1. New Lithium Isotope Data . . . . . . . . . . . . . . . . . . . . . . . . . 220 10.Discussion 227 10.1. Regional Geological and Tectonomagmatic Development . . . . . . . . . . . . 227 10.1.1. Constraints from Field Evidence . . . . . . . . . . . . . . . . . . . . . . 227 10.1.2. Petrographical and Mineralogical Constraints . . . . . . . . . . . . . . 229 10.1.3. Geochemical Constraints . . . . . . . . . . . . . . . . . . . . . . . . . 230 10.1.4. Isotopic Constraints . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232 10.1.5. Constraints from Fluid Inclusion Data . . . . . . . . . . . . . . . . . . . 233 10.1.6. Geochronological Constrains . . . . . . . . . . . . . . . . . . . . . . . 233 10.2. Massive Pollucite Mineralisations . . . . . . . . . . . . . . . . . . . . . . . . . . 243 10.2.1. Unique Characteristics of Massive Pollucite Mineralisations . . . . . . . 243 10.2.2. New Concepts for the Formation of Massive Pollucite Mineralisations . . 252 10.3. Genetic Model for the Formation of Massive Pollucite Mineralisations within LCT Pegmatite Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264 11.Summary and Conclusions 267 References 273 Lists of Abbreviations 309 General Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309 Mineral Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310 List of Figures 311 List of Tables 315 Appendix 317 A. Legend for Topographic Maps 319 B. Sample List 323 C. Methodology 331 C.1. Quantitative Mineralogy by Means of Mineral Liberation Analysis . . . . . . . . 331 C.2. Geochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331 C.3. 40Ar/39Ar-Method on Mica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335 C.4. Th-U-Total Pb Monazite Dating . . . . . . . . . . . . . . . . . . . . . . . . . . . 335 C.5. U/Pb Dating of Selected Ta-, Nb- and Sn-Oxide Minerals . . . . . . . . . . . . 336 C.6. Fluid Inclusion Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337 C.7. Whole Rock Sm/Nd-Isotopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338 C.8. Lithium Isotope Analysis on Selected Mineral Phases . . . . . . . . . . . . . . . 338 D. Data – Mineral Liberation Analysis 341 E. Data – Geochemistry 345 F. Data – Geochronology 349 G. Data – Stable and Radiogenic Isotopes 353
Lithium-Caesium-Tantal-(LCT) Pegmatite repräsentieren eine bedeutende Quelle für seltene Metalle, deren Bedarf im letzten Jahrzehnt beträchtlich angestiegen ist. Im Falle von Caesium sind zurzeit weltweit nur zwei LCT-Pegmatitlagerstätten bekannt, die abbauwürdige Vorräte an Cs enthalten. Dies sind die LCT-Pegmatitlagerstätten Bikita in Simbabwe und Tanco in Kanada. Das Wirtsmineral für diese Cs-Mineralisation ist das extrem selten auftretende Zeolith-Gruppen-Mineral Pollucit. In den Lagerstätten Bikita und Tanco bildet Pollucit dagegen massive, linsenförmige und fast monomineralische Pollucitmineralisationen, die in den oberen Bereichen der Pegmatitkörper anstehen. Zusätzlich befinden sich beide Lagerstätten in geologisch vergleichbaren Einheiten. Die Nebengesteine sind Grünsteingürtel die ein neoarchaisches Alter von ca. 2,600 Ma aufweisen. Die Bildung derartiger massiver Pollucitmineralisationen ist bis jetzt noch nicht detailliert untersucht worden. Große Bereiche von Westaustralien werden von meso- bis neoarchaischen Krusteneinheiten (z.B. Yilgarn Kraton, Pilbara Kraton) aufgebaut, von denen auch eine große Anzahl an LCT-Pegmatitsystemen bekannt sind. Darunter befinden sich unter anderem die LCT-Pegmatitlagerstätten Greenbushes (Li, Ta) und Wodgina (Ta, Sn). Zusätzlich wurden kleine Mengen an Pollucit in einer einzigen Kernbohrung im Londonderry Pegmatitfeld angetroffen. Ungeachtet dessen, wurden in Westaustralien bis jetzt keine systematischen Untersuchungen und/oder Explorationskampagnen auf Vorkommen von Cs und speziell der von Pollucit durchgeführt. Im Verlauf dieser Studie wurden insgesamt neunzehn verschiedene Pegmatitvorkommen und Pegmatitfelder des Yilgarn Kratons, Pilbara Kratons und der Kimberley Provinz auf das Vorkommen des Minerals Pollucit untersucht. Allerdings konnte in keinem der untersuchten LCT-Pegmatitsystemen Pollucit nachgewiesen werden. Von vier der untersuchten LCT-Pegmatitsystemen, dem Londonderry Pegmatitfeld, dem Mount Deans Pegmatitfeld, der Cattlin Creek LCT-Pegmatitlagerstätte (Yilgarn Kraton) und der Wodgina LCT-Pegmatitlagerstätte (Pilbara Kraton) wurden detailliert Proben entnommen und weitergehend untersucht. Zusätzlich wurden die massiven Pollucitmineralisationen im Bikita Pegmatitfeld beprobt und in die detailierten Untersuchungen einbezogen. Der Probensatz aus dem Bikita Pegmatitfeld dient als Referenzmaterial mit dem die Pegmatitproben aus Westaustralien verglichen werden. Die vorliegende Arbeit fasst die wesentlichen Ergebnisse der petrographischen, mineralogischen, mineralchemischen, geochemischen und geochronologischen Untersuchungen sowie der Flüssigkeitseinschlussuntersuchungen und stabilen und radiogenen Isotopenzusammensetzungen zusammen. Alle vier der in Westaustralien untersuchten LCT-Pegmatitsysteme kommen in geologisch ähnlichen Rahmengesteinen vor, weisen einen vergleichbaren internen Aufbau, geochemische Zusammensetzung und Mineralogie zu dem des Bikita Pegmatitfeldes in Simbabwe auf. Weiterhin konnten in allen LCT-Pegmatitsystemen Hinweise für späte hydrothermale Prozesse (z.B. Verdrängung von Feldspat) nachgewiesen werden, die einhergehend mit einer Anreicherung von Cs verbunden sind (z.B. Cs-angereicherte Säume um Glimmer, Beryll und Turmalin). Mit der Ausnahme der Wodgina LCT-Pegmatitlagerstätte, in der ein mesoarchaisches Kristallisationsalter (ca. 2,850 Ma) nachgewiesen wurde, lieferten die Altersdatierungen in den anderen LCT-Pegmatitsystemen übereinstimmende neoarchaische Alter von 2,630 Ma bis 2,600 Ma. Diese fast identischen Alter der LCT-Pegmatitsysteme des Yilgarn und Zimbabwe Kratons suggerieren, dass die Prozesse, die zur LCT-Pegmatitbildung am Ende des Neoarchaikums führten, weltweit aktiv waren. Ungeachtet dessen stellt das Vorhandensein von massiver Pollucitmineralisation das Alleinstellungsmerkmal des Bikita Pegmatitfeldes dar, welche sich infolge eines Prozesses gebildet haben der nicht Bestandteil der üblichen LCT-Pegmatitentwicklung ist und sich durch eine extreme Anreicherung an Cs unterscheidet. Die neuen Ergebnisse die in dieser Studie von den Bikita Pegmatitfeld und den Westaustralischen LCT-Pegmatitsystemen gewonnen wurden, verbessern das Verständnis des Verhaltens von Cs in LCT-Pegmatitsystemen deutlich. Somit ist es nun möglich, ein genetisches Modell für die Bildung von massiven Pollucitmineralisationen in LCT-Pegmatitsystemen vorzustellen. LCT-Pegmatite weisen im Allgemeinen eine granitische Zusammensetzung auf und werden als Kristallisat von hoch fraktionierten und geochemisch spezialisierten granitischen Restschmelzen interpretiert. Die Bildung von massiven Pollucitmineralisationen ist nur aus großen und voluminösen Pegmatitschmelzen, die als einzelner Körper entlang von Störungen in extensionalen Stressregimen intrudieren möglich. Nach Platznahme der Schmelze bildet die beginnende Kristallisation zunächst die Kontakt- und Randzone des Pegmatits, wobei infolge von fraktionierter Kristallisation die immobilen Elemente (v.a. Cs, Rb) in der verbleibenden Restschmelze angereichert werden. Im Anschluss an diese erste Kristallisation entmischt sich nach Abkühlung eine sehr kleine Menge (0.5–1 vol.%) Schmelze und/oder Fluid von der Restschmelze. Diese nicht mischbare Teilschmelze/-fluid ist angereichert an Al2O3 und Na2O sowie verarmt an SiO2 und kristallisiert als Analcim. Zusätzlich kann diese Schmelze bereits mit 1–2 wt.% Cs2O angereichert sein. Aufgrund der Auswirkung von Flussmitteln (z.B. H2O, F, B) wird allerdings der Schmelzpunkt dieser Analcimschmelze herabgesetzt und so die Kristallisation des Analcims als intergranulare Körner verhindert. Da diese Analcimschmelze im Vergleich zu der restlichen Schmelze eine geringere relative Dichte besitzt, beginnt sie gravitativ aufzusteigen und sich in den oberen Bereichen des Pegmatitkörpers zu akkumulieren. Währenddessen beginnt die restliche Schmelze separat zu kristallisieren und die inneren Bereiche des Pegmatits zu bilden. Diese Kristallisation ist einhergehend mit fortschreitender Fraktionierung und der Anreicherung von inkompatiblen Elementen (v.a. Cs, Rb) in den sich als letztes bildenden Mineralphasen (z.B. Lepidolit) oder der Konzentration der inkompatiblen Element in die sich entmischenden hydrothermalen Fluiden. Da Analcim und Pollucit eine lückenlose Mischungsreihe bilden, ist die Analcimschmelze in der Lage, alles verfügbare Cs von der Restschmelze und/oder assoziierten hydrothermalen Fluiden an sich zu binden und als Cs-Analcim im oberen Bereich des Pegmatitkörpers zu kristallisieren. Fortschreitende hydrothermale Aktivität und Substitution von Cs verschiebt dann die Zusammensetzung des Analcims von der Cs-Analcim- zu Na-Pollucitzusammensetzung. Zusätzlich erfährt der Analcim bei Abkühlung unter 400 °C eine negative thermische Expansion von ca. 1 vol.%. Diese Kontraktion führt zu der Bildung des markanten Rissnetzwerkes das durch späte Mineralphasen (z.B. Lepidolit, Quarz, Feldspat und Petalit) gefüllt wird. Vor der Mineralisation allerdings, erhöht dieses Netzwerk an Rissen die verfügbaren Wegsamkeiten für die späten hydrothermalen Fluide und begünstigt somit den Cs-Substitutionsmechanismus in der massiven Pollucitmineralisation. Weiterhin kommt es bei der Abkühlung des Pegmatits zu späten Mineralverdrängungsreaktionen (z.B. Verdrängung von K-Feldspat durch Lepidolit, Cleavelandit und Quarz), sowie zu Subsolidus-Selbstordnungsprozessen in Feldspäten. Diese Prozesse werden weiterhin interpretiert inkompatible Elemente (z.B. Cs, Rb) in die späten hydrothermalen Fluide freizusetzen. Da Feldspäte große Teile der Pegmatite bilden, kann somit eine beträchtliche Menge an Cs freigeben werden und durch die späten hydrothermalen Fluide in die massive Pollucitmineralisation in den oberen Bereichen des Pegmatitkörpers transportiert werden. Infolgedessen ist es möglich, dass genügend Cs frei gesetzt werden kann, um die Zusammensetzung innerhalb der Mischkristallreihe von Cs-Analcim (>2 wt.% Cs2O) zu Na-Pollucit (23–43 wt.% Cs2O) zu verschieben. Die zeitliche Einordnung dieser späten Cs-Anreicherung wird als quasi zeitgleich oder im direkten Anschluss an die vollständige Kristallisation der Pegmatitschmelze interpretiert. Es kann allerdings nicht vernachlässigt werden, dass auch jüngere hydrothermale Ereignisse, die den Pegmatitkörper nachträglich überprägen, ähnliche hydrothermale Prozesse hervorrufen können. Somit konnte gezeigt werden, dass es durch Kombination dieser magmatischen und hydrothermalen Prozessen möglich ist, genügend Cs anzureichern, um die Bildung von massiven Pollucitmineralisationen in LCT-Pegmatitsystemen zu ermöglichen. Dieses genetische Modell kann nun dazu genutzt werden, um das Potential von Vorkommen von massiven Pollucitmineralisationen in LCT-Pegmatitsystemen in Westaustralien und weltweit besser einzuschätzen.:Contents Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii Zusammenfassung . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v Versicherung . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix Contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi 1. Introduction 1 1.1. Motivation and Scope of the Thesis . . . . . . . . . . . . . . . . . . . . . . . . 1 1.2. Structure of the Thesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2. Fundamentals 7 2.1. The Alkali Metal Cesium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.1.1. Distribution of Cesium . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2.1.2. Mineralogy of Cesium . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 2.1.3. Geochemical Behaviour of Cesium . . . . . . . . . . . . . . . . . . . . 13 2.1.4. Economy of Cesium . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 2.2. Pollucite – (Cs,Na)2Al2Si4O12×H2O . . . . . . . . . . . . . . . . . . . . . . . . 16 2.2.1. Crystal Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 2.2.2. Analcime–Pollucite–Series . . . . . . . . . . . . . . . . . . . . . . . . . 17 2.2.3. Formation of Pollucite . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 2.2.4. Pollucite Occurences . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 2.3. Pegmatites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 2.3.1. General Characteristics of Pegmatites . . . . . . . . . . . . . . . . . . 34 2.3.2. Controls on Pegmatite Formation and Evolution . . . . . . . . . . . . . 40 2.3.3. Pegmatite Age Distribution and Continental Crust Formation . . . . . . 43 3. Geological Settings of Archean Cratons 47 3.1. Zimbabwe Craton . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47 3.1.1. Tectonostratigraphic Subdivision . . . . . . . . . . . . . . . . . . . . . 48 3.1.2. Tectonometamorphic Evolution of the Northern Limpopo Thrust Zone . 49 3.1.3. Pegmatites within the Zimbabwe Craton . . . . . . . . . . . . . . . . . 52 3.1.4. Masvingo Greenstone Belt . . . . . . . . . . . . . . . . . . . . . . . . . 53 3.1.5. Geological Setting of the Bikita Pegmatite District . . . . . . . . . . . . 58 3.2. Yilgarn Craton . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 3.2.1. Tectonostratigraphic Framework and Geological Development . . . . . 62 3.2.2. Tectonic Models for the Development . . . . . . . . . . . . . . . . . . . 70 3.2.3. Pegmatites within the Yilgarn Craton . . . . . . . . . . . . . . . . . . . 76 3.2.4. Geological setting of the Londonderry Pegmatite Field . . . . . . . . . . 76 3.2.5. Geological Setting of the Mount Deans Pegmatite Field . . . . . . . . . 85 3.2.6. Geological Setting of the Cattlin Creek Pegmatite Deposit . . . . . . . . 91 3.3. Pilbara Craton . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99 3.3.1. Tectonostratigraphic Framework and Geological Development . . . . . 99 3.3.2. Tectonic Model for the Development . . . . . . . . . . . . . . . . . . . 101 3.3.3. Pegmatites within the Pilbara Craton . . . . . . . . . . . . . . . . . . . 105 3.3.4. Geological Setting of the Wodgina Pegmatite District . . . . . . . . . . 106 4. Fieldwork and Sampling of Selected Pegmatites and Pegmatite Fields 115 4.1. Bikita Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115 4.2. Londonderry Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115 4.2.1. Londonderry Feldspar Quarry Pegmatite . . . . . . . . . . . . . . . . . 115 4.2.2. Lepidolite Hill Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . 117 4.2.3. Tantalite Hill Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . 118 4.3. Mount Deans Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . 118 4.3.1. Type I – Flat Lying Pegmatites . . . . . . . . . . . . . . . . . . . . . . . 118 4.3.2. Type II – Steeply Dipping Pegmatites . . . . . . . . . . . . . . . . . . . 120 4.4. Cattlin Creek Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120 4.5. Wodgina LCT-Pegmatite Deposit . . . . . . . . . . . . . . . . . . . . . . . . . . 121 4.5.1. Mount Tinstone Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . 123 4.5.2. Mount Cassiterite Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . 123 5. Petrography and Mineralogy 139 5.1. Quantitative Mineralogy by Means of Mineral Liberation Analysis . . . . . . . . 141 5.2. Mineralogical and Petrographical Characteristics of Individual Mineral Groups . 141 5.2.1. Feldspar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141 5.2.2. Quartz . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144 5.2.3. Mica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146 5.2.4. Pollucite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147 5.2.5. Petalite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149 5.2.6. Spodumene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149 5.2.7. Beryl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154 5.2.8. Tourmaline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155 5.2.9. Apatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157 5.2.10. Ta-, Nb- and Sn-oxides . . . . . . . . . . . . . . . . . . . . . . . . . . 157 5.3. Reconstruction of the General Crystallisation Sequence . . . . . . . . . . . . . 162 6. Geochemistry 165 6.1. Major Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165 6.2. Selected Minor and Trace Elements . . . . . . . . . . . . . . . . . . . . . . . . 174 6.3. Fractionation Indicators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175 6.4. Rare Earth Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185 7. Geochronology 193 7.1. 40Ar/39Ar-Method on Mica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193 7.1.1. Bikita Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . 194 7.1.2. Mount Deans Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . 195 7.1.3. Londonderry Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . 195 7.1.4. Cattlin Creek Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . 195 7.1.5. Wodgina Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198 7.2. Th-U-Total Pb Monazite Dating . . . . . . . . . . . . . . . . . . . . . . . . . . . 201 7.2.1. Monazite Ages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201 7.3. U/Pb Dating of Selected Ta-, Nb- and Sn-Oxide Minerals . . . . . . . . . . . . 203 7.3.1. Bikita Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . 203 7.3.2. Londonderry Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . 203 7.3.3. Mount Deans Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . 206 7.3.4. Cattlin Creek Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . 206 7.3.5. Wodgina Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207 8. Fluid Inclusion Study 211 8.1. Bikita Pegmatite Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211 8.2. Wodgina Pegmatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211 8.3. Carbon Isotope Analysis on Fluid Inclusion Gas of Selected Mineral Phases . . 212 9. Stable and Radiogenic Isotopes 217 9.1. Whole Rock Sm/Nd-Isotopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217 9.1.1. New Whole Rock Sm/Nd Data . . . . . . . . . . . . . . . . . . . . . . 217 9.2. Lithium Isotope Analysis on Selected Mineral Phases . . . . . . . . . . . . . . . 220 9.2.1. New Lithium Isotope Data . . . . . . . . . . . . . . . . . . . . . . . . . 220 10.Discussion 227 10.1. Regional Geological and Tectonomagmatic Development . . . . . . . . . . . . 227 10.1.1. Constraints from Field Evidence . . . . . . . . . . . . . . . . . . . . . . 227 10.1.2. Petrographical and Mineralogical Constraints . . . . . . . . . . . . . . 229 10.1.3. Geochemical Constraints . . . . . . . . . . . . . . . . . . . . . . . . . 230 10.1.4. Isotopic Constraints . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232 10.1.5. Constraints from Fluid Inclusion Data . . . . . . . . . . . . . . . . . . . 233 10.1.6. Geochronological Constrains . . . . . . . . . . . . . . . . . . . . . . . 233 10.2. Massive Pollucite Mineralisations . . . . . . . . . . . . . . . . . . . . . . . . . . 243 10.2.1. Unique Characteristics of Massive Pollucite Mineralisations . . . . . . . 243 10.2.2. New Concepts for the Formation of Massive Pollucite Mineralisations . . 252 10.3. Genetic Model for the Formation of Massive Pollucite Mineralisations within LCT Pegmatite Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264 11.Summary and Conclusions 267 References 273 Lists of Abbreviations 309 General Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309 Mineral Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310 List of Figures 311 List of Tables 315 Appendix 317 A. Legend for Topographic Maps 319 B. Sample List 323 C. Methodology 331 C.1. Quantitative Mineralogy by Means of Mineral Liberation Analysis . . . . . . . . 331 C.2. Geochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331 C.3. 40Ar/39Ar-Method on Mica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335 C.4. Th-U-Total Pb Monazite Dating . . . . . . . . . . . . . . . . . . . . . . . . . . . 335 C.5. U/Pb Dating of Selected Ta-, Nb- and Sn-Oxide Minerals . . . . . . . . . . . . 336 C.6. Fluid Inclusion Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337 C.7. Whole Rock Sm/Nd-Isotopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338 C.8. Lithium Isotope Analysis on Selected Mineral Phases . . . . . . . . . . . . . . . 338 D. Data – Mineral Liberation Analysis 341 E. Data – Geochemistry 345 F. Data – Geochronology 349 G. Data – Stable and Radiogenic Isotopes 353