The Ertsberg-Grasberg Mining District of Papua, Indonesia (Western New Guinea) hosts the Ertsberg Cu-Au Skarn, the giant Grasberg Porphyry Cu-Au deposit, and several other orebodies. Two 1700-meter-long cores beneath the Kucing Liar ore skarn (KL98-10-22) and the Grasberg Igneous Complex (KL98-10-21) contain high concentrations of vein and disseminated molybdenite. KL98-10-22, the focus of this study, intersects two previously unencountered intrusions, the “Tertiary intrusion Kucing Liar” (Tikl) and “Tertiary Pliocene intrusion” (Tpi). An intense dilatational quartz vein stockwork cuts Tikl and Ekmai Sandstone (Kkes) units, predating Tpi intrusion. Prior to these ultradeep cores, which extend almost 3 km below pre-mining surface, molybdenite was rarely observed in the district. Geochemistry and isotopic data indicate that Tikl and Tpi intrusions originated from the same large magmatic system that emplaced other ore-forming Ertsberg-Grasberg district intrusions. Magma in a lower crustal chamber was recharged at least twice, according to Sr-Nd data. Laser-ablation inductively-coupled plasma mass spectrometry of magmatic zircons yields 238U-206Pb ages between 3.40 ± 0.12 Ma (Dalam Andesite) and 2.77 ± 0.15 Ma (Ertsberg intrusion), revealing a shorter period of igneous activity than previously measured by K-Ar and Ar-Ar dating. Analyses include composite ages of 3.28 ± 0.08 Ma for Tikl and 3.18 ± 0.11 Ma for Tpi. Inherited zircon cores indicate Precambrian (mostly Proterozoic) basement. Molybdenite veining beneath the Kucing Liar Skarn and Grasberg Igneous Complex postdates stockwork veining and occurred before the 2.99 ± 0.11 Ma Kali dikes. Only one molybdenite vein was observed cutting Tpi. Molybdenites yielded ~3 Ma Re-Os ages and anomalous >4 Ma and <0.5 Ma ages; anomalous ages were not reproducible in follow-up analyses (this study). Smearing deformation of molybdenite (through fault activity) causes crystal strain, likely leading to annealing recrystallization. Recrystallization possibly redistributes daughter-product Os, resulting in anomalous ages from annealed material. Fluids with high Mo/Cu ratios (which were likely supercritical) precipitated late-stage molybdenite deep in the system. These fluids developed through magma chamber crystallization, which concentrated molybdenum in the melt as an incompatible element, and stripping of Cu from the magma chamber during hydrothermal activity. / text

The Ertsberg-Grasberg Mining District of Papua, Indonesia (Western New Guinea) hosts the Ertsberg Cu-Au Skarn, the giant Grasberg Porphyry Cu-Au deposit, and several other orebodies. Two 1700-meter-long cores beneath the Kucing Liar ore skarn (KL98-10-22) and the Grasberg Igneous Complex (KL98-10-21) contain high concentrations of vein and disseminated molybdenite. KL98-10-22, the focus of this study, intersects two previously unencountered intrusions, the “Tertiary intrusion Kucing Liar” (Tikl) and “Tertiary Pliocene intrusion” (Tpi). An intense dilatational quartz vein stockwork cuts Tikl and Ekmai Sandstone (Kkes) units, predating Tpi intrusion. Prior to these ultradeep cores, which extend almost 3 km below pre-mining surface, molybdenite was rarely observed in the district. Geochemistry and isotopic data indicate that Tikl and Tpi intrusions originated from the same large magmatic system that emplaced other ore-forming Ertsberg-Grasberg district intrusions. Magma in a lower crustal chamber was recharged at least twice, according to Sr-Nd data. Laser-ablation inductively-coupled plasma mass spectrometry of magmatic zircons yields 238U-206Pb ages between 3.40 ± 0.12 Ma (Dalam Andesite) and 2.77 ± 0.15 Ma (Ertsberg intrusion), revealing a shorter period of igneous activity than previously measured by K-Ar and Ar-Ar dating. Analyses include composite ages of 3.28 ± 0.08 Ma for Tikl and 3.18 ± 0.11 Ma for Tpi. Inherited zircon cores indicate Precambrian (mostly Proterozoic) basement. Molybdenite veining beneath the Kucing Liar Skarn and Grasberg Igneous Complex postdates stockwork veining and occurred before the 2.99 ± 0.11 Ma Kali dikes. Only one molybdenite vein was observed cutting Tpi. Molybdenites yielded ~3 Ma Re-Os ages and anomalous >4 Ma and <0.5 Ma ages; anomalous ages were not reproducible in follow-up analyses (this study). Smearing deformation of molybdenite (through fault activity) causes crystal strain, likely leading to annealing recrystallization. Recrystallization possibly redistributes daughter-product Os, resulting in anomalous ages from annealed material. Fluids with high Mo/Cu ratios (which were likely supercritical) precipitated late-stage molybdenite deep in the system. These fluids developed through magma chamber crystallization, which concentrated molybdenum in the melt as an incompatible element, and stripping of Cu from the magma chamber during hydrothermal activity. / text

The Ertsberg-Grasberg Mining District of Papua, Indonesia (Western New Guinea) hosts the Ertsberg Cu-Au Skarn, the giant Grasberg Porphyry Cu-Au deposit, and several other orebodies. Two 1700-meter-long cores beneath the Kucing Liar ore skarn (KL98-10-22) and the Grasberg Igneous Complex (KL98-10-21) contain high concentrations of vein and disseminated molybdenite. KL98-10-22, the focus of this study, intersects two previously unencountered intrusions, the “Tertiary intrusion Kucing Liar” (Tikl) and “Tertiary Pliocene intrusion” (Tpi). An intense dilatational quartz vein stockwork cuts Tikl and Ekmai Sandstone (Kkes) units, predating Tpi intrusion. Prior to these ultradeep cores, which extend almost 3 km below pre-mining surface, molybdenite was rarely observed in the district. Geochemistry and isotopic data indicate that Tikl and Tpi intrusions originated from the same large magmatic system that emplaced other ore-forming Ertsberg-Grasberg district intrusions. Magma in a lower crustal chamber was recharged at least twice, according to Sr-Nd data. Laser-ablation inductively-coupled plasma mass spectrometry of magmatic zircons yields 238U-206Pb ages between 3.40 ± 0.12 Ma (Dalam Andesite) and 2.77 ± 0.15 Ma (Ertsberg intrusion), revealing a shorter period of igneous activity than previously measured by K-Ar and Ar-Ar dating. Analyses include composite ages of 3.28 ± 0.08 Ma for Tikl and 3.18 ± 0.11 Ma for Tpi. Inherited zircon cores indicate Precambrian (mostly Proterozoic) basement. Molybdenite veining beneath the Kucing Liar Skarn and Grasberg Igneous Complex postdates stockwork veining and occurred before the 2.99 ± 0.11 Ma Kali dikes. Only one molybdenite vein was observed cutting Tpi. Molybdenites yielded ~3 Ma Re-Os ages and anomalous >4 Ma and <0.5 Ma ages; anomalous ages were not reproducible in follow-up analyses (this study). Smearing deformation of molybdenite (through fault activity) causes crystal strain, likely leading to annealing recrystallization. Recrystallization possibly redistributes daughter-product Os, resulting in anomalous ages from annealed material. Fluids with high Mo/Cu ratios (which were likely supercritical) precipitated late-stage molybdenite deep in the system. These fluids developed through magma chamber crystallization, which concentrated molybdenum in the melt as an incompatible element, and stripping of Cu from the magma chamber during hydrothermal activity. / text

The effects of intermetallic compound (IMC) formation on reliability of Pb-free Sn-based solders for flip chip and three-dimensional (3D) interconnects were studied. The dissertation is organized into four parts. In the first part, the effect of Sn grain orientation on electromigration (EM) reliability of Pb-free Sn-based flip chip solder joints was studied. The Sn grain microstructure in flip chip solder joints was characterized using the electron backscatter diffraction (EBSD) technique, and wa found to be closely related to the EM failure mechanims. The approach to grain structure optimization for improved EM reliability was also explored. In addition to the experimental work, a kinetic analysis was formulated to investigate the early EM degradation mechanism in Sn-based solder joints with Ni under-bump metallization (UMB). The aforementioned kinetic analysis, the intrinsic diffusion coefficients were not readily available in the literature. In the second part of the work, a Monte Carlo method known as simulated annealing was applied to estimate the unknown diffusion coefficients using a multi-parameter optimization method by fitting to experimental measurements. The intrinsic diffusion coefficients of Ni and Sn in Ni₃Sn₄ between 150 and 200°C, and those of Cu and Sn in Cu₃Sn and Cu₆Sn₅ between 120 and 200°C were estimatd. The activation energies for these diffusion coefficients were also determined. Together, this provides the diffusivity parameters to predict the intermetallic growth as a function of temperature. The third objective focused on the EM reliability of Sn-based microbump joints in 3D interconnects with through-silicon vias (TSVs). No EM-induced bump failure was observed, showing a robust EM reliability in microbumps. High temperature thermal annealing test was also performed on microbumps with three different metallizations in an effort to explore structural and process optimization. Finally, interfacial reaction induced stress in IMC microbumps was investigated. A numerial analysis was formulated to study the concurrent diffusion, phase transformation, and deformation in the process of IMC formation. Stress generation due to unbalanced diffusion rates and volumetric change upon phase transformation was considered. The coupled analysis was applied to investigate Ni₃Sn₄ growth in the Ni-Sn microbumping system. A simulation approach based on finite difference method with moving boundaries was employed to numerically solve stress evolution in Ni₃Sn₄. The equilibrium stress was also investigated using a modified model with a finite thickness of solder. Simulation predictions were found to be in good qualitative agreement with experimental observations. / text

Superconductivity is a remarkable quantum phenomenon in which a macroscopic number of electrons form a condensate of Cooper pairs that can be described by a single quantum wave function. According to the celebrated Bardeen-Cooper-Schrieffer (BCS) theory of superconductivity, there is a minimum length scale (the coherence length) below which the condensate has a rigid quantum phase. The fate of superconductivity in a system with spatial dimensions smaller than [the coherence length] has been the subject of intense interest for decades and recent studies of superconductivity in ultra-thin epitaxial metal films have revealed some surprising behaviors in light of BCS theory. Notably, it was found that superconductivity remains robust in thin lead films with thicknesses orders of magnitude smaller than the coherence length (i.e. in the extreme two dimensional limit). Such studies raise the critical question: what happens to superconductivity as all dimensions are reduced toward the zero dimensional limit? By controlling the lateral size of ultra thin 2D islands, we systematically address this fundamental question with a detailed scanning tunneling microscopy/spectroscopy study. We show that as the lateral dimension is reduced, the strength of the superconducting order parameter is also reduced, at first slowly for dimensions larger than the bulk coherence length, and then dramatically at a critical length scale of ~ 40nm. We find this length scale corresponds to the lateral decay length of the order parameter in an island containing regions of different heights and different superconducting strength. Overall, our results suggest that fluctuation corrections to the BCS theory are important in our samples and may need to be systematically addressed by theory. / text

This study investigates the interplay of linguistic practices, linguistic representations, language ideologies and social inclusion between students in three related research sites in south west Wales;a designated English medium school,a designated Bilingual school and a Youth Club,as a point of contact between students from both schools. It identifies how students experience and interpret the language ideological content of their education. The following questions underpin the current research: 1. How are the institutional arrangements within this community(or locality)understood by the students? Do school students see themselves operating within language ideological structures?!Do students resist or affirm school based ideologies and school based practice? 2. How do students understand, interpret and live out what language policy and planning documents in Wales refer to as ‘true bilingualism’? Is ‘choice’ experienced as such at institutional, individual and community levels? 3. Is the Welsh language accounted to be an obstacle to social integration for young people within the ‘community’ and into the school environment, or a positive resource? Ethnographic research as been carried out in both schools and at the Youth Club,with three principle methods characterising this research; ethnographic observational fieldwork, ethnographic chats, and audio recordings of spontaneous interaction. vi This study sets out to investigate how the young people at two contrasting (and ideologically polarised) secondary schools in an ‘community’ traditionally thought of as a heartland area understand and orient to the language ideological content of their education. In the school based data language choice results in boundaries being put up around language and language users, both inter school and intra school, with students forming language hierarchies, positioning themselves and others as more or less Welsh, English or bilingual, ‘better’ or ‘worse’ at speaking Welsh and/or English, and more or less authentically Welsh. Schools serve to reinforce and reproduce social divisions, leading to issues of social exclusion. Contrastingly,the Youth Club data highlights that,when freed from the ideological constraints of the school, the young people reflect, sometimes critically, on their school based practice and school based ideologies. This study adds to our knowledge about Welsh medium/bilingual education in Wales; it helps us better understand ‘multilingual’Wales.

Pb-free piezoelectric materials have grown in importance through increased environmental concern related to the presence of Pb and the subsequent legislation that has arisen including directives such as Waste Electrical and Electronic Equipment (WEEE) and the Restriction of Hazardous Substances Directive (RoHS). While much progress has been made on producing Pb-free bulk materials, the need to integrate these next generation Pb-free piezoelectric materials with substrates to form functional micro devices has received less attention and raises a number of challenges. With respect to the high temperature mixed oxide synthesis method, a simple, cost effective and robust low temperature molten hydroxide synthesis (MHS) method derived from the molten salt synthesis (MSS) method, has been developed to produce K0.5Na0.5NbO3 (KNN) small grain powders and is a method that lends itself easily to industrial scale up. A powder/sol gel composite ink film forming technique has been used to produce KNN thick films on silicon substrates. Characterisation of the produced films has shown the films to exhibit piezoelectric coefficients for un-doped material in the region of 30pC/N. The work will report on the Na ion favouring mechanism of the MSS and the related mechanism of the MHS. The work will also report on the dielectric and piezoelectric characteristics of initial KNN thick films produced and an investigation into use of dopants and process modification to improve the KNN thick film’s characteristics.

This dissertation research addresses the tectonism of continental crust during ocean basin closure, suturing between continental landmasses, and collisional orogenesis. The new data and insights presented here were gathered through localized geologic investigations of the Tibetan Plateau of central Asia. This area of central Asia is an ideal location to study these fundamental tectonic processes because it has been the locus of numerous Tethyan ocean basins and terminal collisions between continents during Phanerozoic accretion of Gondwana-derived landmasses onto the southern margin of Eurasia. In this work, I propose, in many orogens, that high-pressure (HP) metamorphism of continental rocks may mark the early stages of the suturing process between continental landmasses rather than the culmination of suturing. This insight has been acquired from a geologic-, geochronologic-, and thermochronologic-based investigation of the HP-near ultrahigh-pressure bearing Triassic metasedimentary metamorphic belt in central Tibet. This work shows near synchronous continent-continent collisions between landmass adjacent to the Paleo-Tethys ocean prior to its final closure in Late Triassic time. In addition, this work shows that Mediterranean-style tectonics may be more widespread during accretionary tectonics than previously thought. A comparison between the distribution of the HP bearing metamorphic belt, autochthonous crystalline basement, and geophysical images of Tibet suggests that a Mesozoic tectonic feature may be controlling the structure and distribution of melt within the middle crust of the Tibetan Plateau. This concept underscores the importance of inherited tectonic frameworks on the evolution of orogenic plateaus. Work in southwest Tibet, along the India-Asia suture zone, highlights the complex behavior of continental crust during collisional orogenesis. This work identifies previously undocumented magmatism, crustal antexis, and high-grade metamorphism along the India-Asia suture. In this work I attribute these observations to the initial interactions between Indian, Asian, and subducting Neo-Tethys oceanic lithosphere.

In order to improve our understanding of poorly studied Mexican Porphyry Copper Deposits in the SW regional metallogenetic province, a detailed study of the hydrothermal fluid evolution of La Caridad porphyry copper-molybdenum deposit, and its connection to a high sulfidation epithermal deposit, was performed using oxygen, hydrogen and sulfur stable isotopes combined with fluid inclusion studies. In addition, UPb and Re-Os geochronology from La Caridad, Milpillas and El Arco porphyry deposit were performed to constrain the timing of mineralization and magmatism in northwest Mexico. Uranium-lead zircon ages from La Caridad suggest a short period of magmatism, between 55.5 and 53.0 Ma. Re-Os molybdenite ages from potassic and phyllic hydrothermal veins yielded identical ages within error, 53.6 ± 0.3 Ma and 53.8 ± 0.3 Ma, respectively. Four stages of hypogene alteration and mineralization are recognized at La Caridad porphyry copper deposit. The isotopic composition of the water in equilibrium with hydrothermal alteration minerals is consistent with highly evaporated lacustrine waters mixed with magmatic waters or vapor separated from magmatic fluids, however, sulfur isotopes and fluid inclusions data support the lacustrine-magmatic water hypothesis. Milpillas porphyry copper deposit in the Cananea Mining District, yielded a crystallization age of 63.9 ± 1.3 Ma. Two Re-Os molybdenite ages yielded an identical age of 63.1 ± 0.4 Ma, Suggesting a restricted period of mineralization. Re-Os data indicate that mineralization in Cananea District, spanned ~4 m.y. in three discrete pulses at ~59 Ma, ~61 Ma and ~63Ma. El Arco porphyry copper deposit, Baja California, Mexico, yielded a Middle Jurassic crystallization age (U-Pb) of 164.7 ± 6.7 Ma and a Re-Os mineralization age of 164.1 ± 0.4 Ma and not ~100 Ma as previously determinated. Porphyry copper deposits in Mexico range in age from 164 Ma to 54 Ma and the mineralization in Sonora state occurred in two different periods, but magmatism overlaps in space and time.

Stikinia is a tectonostratigraphic terrane in the Canadian Cordillera comprised of the Early Permian Asitka Group, the Late Triassic Stuhini Group and the Early to Middle Jurassic Hazelton Group. William’s Gold property which coincides with the study area is located on the east-northeast margin of the Stikine terrane within a fault mosaic of Devonian to Permian Asitka Group carbonates and volcanic and sedimentary rocks of the Stuhini Group. The primary purpose of this study is to determine the timing of mineralization and the absolute ages of the intrusions within the Williams west region of the William’s Gold property. This study attempts to correlate mesothermal gold veining and Cu-Au porphyry style mineralization from the study area with mineralization that has occurred approximately 100km southeast at Kemess Mine. U-Pb, Ar-Ar geochronology and Pb isotopic studies were used to determine the ages and isotopic signatures of rocks located within the study area. Four samples of quartz monzonite and one sample of a feldspar porphyry gave U-Pb crystallization ages ranging from 221.4 to 183.6 Ma. Two samples G090062, and G090063 contained cores that cluster between 230 and 260 Ma and 330 and 380 Ma. The oldest gave an age of 420Ma. The presence of older cores suggests that the intrusion passed through older basement rocks, possibly the Paleozic Stikine Assemblage. A sample of alteration sericite from the T-bill prospect that is believed to occur syn-mineralization was dated using the Ar-Ar method and returned an inverse isochron age of 194.6 +/-3.5 Ma. The age of the sericite alteration did not correspond to the ages of the five intrusive units analyzed during this study. This suggests that the mineralization at the T-bill prospect was likely not genetically related to any of the intrusions dated in this study.