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Thesis (M.S.)--Indiana University, 2009. / Department of Earth Sciences, Indiana University-Purdue University Indianapolis (IUPUI). Advisor(s): Andrew P. Barth, Gabriel Filippelli, Jeffery Wilson. Includes vitae. Includes bibliographical references (leaves 62-64).

Chapter I: Statement of the Problem The purpose of this investigation was to determine to what extent the reaction between stannous and arsenate ions in silicic acid gels is influenced by temperature. This was to be done by observing (1) the rate of crystal growth; and (2) the appearance of the crystal growth in sets of gels identical in composition but kept at different temperatures throughout the process of crystal growth.

The adsorption behavior of silicic acid and arsenite alone and competitively on goethite over a broad pH range (3-11) at environmentally relevant concentrations was investigated utilizing pH adsorption data and zeta potential measurements. Both addition scenarios (Si before As(III) and As(III) before Si) were examined. The results of the adsorption experiments and zeta potential measurements were then used to model the single ion and competitive ion adsorption on goethite with the CD-MUSIC model implemented in the FITEQL 4.0 computer program. Silicic acid adsorption was reduced by the presence of arsenite for all but one of the adsorption scenarios examined, while in contrast silicic acid had little effect upon arsenite adsorption. However, the presence of silicic acid, regardless of the addition scenario, dramatically increased the arsenite equilibrium solution concentration over the entire pH range investigated. The CD-MUSIC model was able to predict the single ion adsorption behavior of silicic acid and arsenite on goethite. The modeled zeta potential data provided further evidence of the CD-MUSIC model's ability to describe the single anion adsorption on goethite. Our model was also able to collectively describe adsorption and zeta potential data for the low Si-arsenite adsorption scenario quite well however, our model under-predicted silicic acid adsorption for the high Si-arsenite competitive scenario. / Master of Science

Orientador: Luiz Felipe Valandro Soares / Coorientadora: Renata Marques de Melo Marinho / Banca: Marco Antonio Bottino / Banca: Paulo Francisco César / Banca: Estevam Augusto Bonfante / Banca: Lilian Costa Anami / Resumo: O objetivo deste estudo foi avaliar os efeitos de duas técnicas de gradação da zircônia no limite de fadiga de próteses parciais fixas (PPFs) de 03 elementos. Blocos pré-sinterizados de 3Y-TZP (zircônia policristalina parcialmente estabilizada por 3% mol de ítria) foram fresados para obter 69 PPFs, que foram divididas em 3 grupos (n = 23). O grupo controle (CTL) foi sinterizado e glazeado odedecendo os parâmetros usuais. Nos dois grupos experimentais as PPFs receberam sílica/vidro antes da sinterização. O grupo sílica sol-gel (SSG) foi graduado pela rota de processamento sol-gel, enquanto o grupo vidro-zircônia-vidro (GZG) foi graduado pela técnica de suspensão (slurry). Os grupos graduados não receberam a camada de glaze após a sinterização. Todas as PPFs foram cimentadas nos pilares de compósito com cimento resinoso de dupla polimerização, incluídas em poliuretano e armazenadas em água por cinco dias. A carga inicial do teste de fadiga foi calculada com base nos resultados do ensaio monotônico de três amostras de cada grupo. Para determinar o limite de fadiga 20 amostras de cada grupo foram submetidas ao método da escada ou staircase (100.000 ciclos/5 Hz). Os limites de fadiga (em Newton) foram: CTL = 1607,27; SSG = 1824,31; GZG = 2006,57 e o teste de Dixon e Mood indicou diferença estatística entre os grupos (intervalo de confiança de 95%). As infiltrações de sílica e vidro no corpo da zircônia, por dois diferentes métodos de gradação, aumentaram o limite de fadiga de PPFs... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The aim of this study was to evaluate the effects of two grading zirconia techniques on the fatigue limit of 3-unit fixed dental prostheses (FDPs). Presintered blocks of 3YTZP (3 mol% yttria-stabilized tetragonal zirconia polycrystal) were milled to obtain sixty-nine 3-unit FDPs, which were divided into three groups (n = 23). The control group (CTL) was sintered and glazed following the usual parameters. In the two experimental groups presintered FDPs received silica/glass before sintering. Silica sol-gel group (SSG) was graded by the sol-gel processing route, while the glasszirconia-glass group (GZG) was graded by a slurry technique. Graded groups did not receive a glaze layer after sintering. All FDPs were then luted with a dual-curing resin cement on composite abutments, embedded in polyurethane and stored in water for five days. The initial load of the fatigue test was calculated based on the results of the monotonic testing applied on three specimens of each group. To determine the fatigue limit, 20 samples of each group were subjected to staircase testing (100,000 cycles/5 Hz). The fatigue limits (in Newtons) were CT = 1607.27, SSG = 1824.31, and GZG = 2006.57, and the Dixon and Mood test indicated statistically significant differences among groups (95% confidence interval). The infiltration of silica and glass on zirconia bulk, by two different grading methods, increased the fatigue limits of monolithic zirconia FDPs / Doutor

Le comportement rhéologique de suspensions magmatiques synthétiques hydratées a été expérimentalement étudié en déformation coaxiale et en torsion à haute température et haute pression à l’aide d’une presse de type Paterson. Les résultats obtenus illustrent l’influence de la fraction cristalline et de la forme des cristaux sur la rhéologie et le développement des Orientations Préférentielles de Forme (OPF) des particules au sein des suspensions magmatiques. La formation d’une charpente cristalline, associée à une forte hausse de la viscosité, intervient pour des fractions solides comprises entre fs = 0,20 et 0,38 en relation avec le développement de fabriques de type pénétratif. En augmentant la fraction solide (fs = 0,50), le développement d’une fabrique pénétrative, couplé à des bandes de cisaillement bordées de gradients de déformation, engendre un adoucissement de la réponse rhéologique et une hausse moins importante de la viscosité. Pour fs = 0,58, des bandes de cisaillement de type cassant sans gradient de déformation, recoupant une suspension non déformée, apparaissent et contrôlent le fort adoucissement de la réponse rhéologique. La viscosité de la suspension n’augmente plus alors que légèrement. Au-delà de cette fraction cristalline, les suspensions étudiées montrent une forte réduction de la taille et du rapport de forme des cristaux se traduisant par une stabilisation de la réponse rhéologique en fonction de la déformation. Aucune OPF n’a pu être déterminée et une quasistabilisation de la viscosité est observée (comportement mécanique de solide). Toutes les suspensions étudiées se caractérisent par un comportement rhéologique non-Newtonien de type rhéofluidifiant. La dépendance entre le comportement rhéologique des suspensions magmatiques et le développement des microstructures doit être intégrée dans la modélisation de la mécanique des suspensions magmatiques. / The rheological behaviour of synthetic hydrous magmatic suspensions has been experimentally investigated in compression and torsion at high temperatures and pressures in a Paterson press. The results illustrate the influence of the crystal fraction and of the shape of the crystals on the rheology and the Shape Preferred Orientation (SPO) of the particles. A solid particle network, associated with a strong increase of the viscosity, is generated between crystal fractions (fs) of 0.20 and 0.38, with the development of pervasive fabrics. With increasing the crystal fraction (fs = 0.50), shear bands bordered by symmetrical deformation gradients crosscut the pervasive fabric, resulting in a weakening in the rheological behaviour of the suspension. The increase of the viscosity with increasing cristallinity of the suspension becomes less important. At fs = 0.58, brittle shear bands without deformation gradients crosscut an undeformed suspension and lead to a strong weakening of the rheological behaviour which explains the small increase of the viscosity of the suspension with increasing crystal fraction. Above this crystal fraction, suspensions show a strong reduction of the crystal size and shape ratio. No SPO has been determined but the near-stabilisation of the viscosity, coupled with a stabilisation of the stress with strain, is consistent with a solid-like mechanical behaviour at these high crystallinities. All studied suspensions are characterized by a non-Newtonian, shear thinning rheological behaviour. Our results and, in particular, the dependence between the rheological behaviour and the development of crystal microstructures, need to be integrated in mechanical models of magmatic suspensions.

Submitted by Guilherme Felisberto (guilherme.felisberto@hotmail.com) on 2018-11-08T20:20:13Z No. of bitstreams: 1 Tese Guilherme online.pdf: 2892923 bytes, checksum: ad775287d1d705604ffde56540725606 (MD5) / Rejected by Neli Silvia Pereira null (nelisps@fcav.unesp.br), reason: Solicitamos que realize correções na submissão seguindo as orientações abaixo: 1- O agradecimento à CAPES deve ter a seguinte redação: O presente trabalho foi realizado com apoio da Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) - Código de Financiamento 001 2- O título na ficha catalográfica está em caixa alta, segundo as normas, deve estar em letra maiúscula somente a letra inicial do título e os nomes próprios. Agradecemos a compreensão. on 2018-11-09T17:16:20Z (GMT) / Submitted by Guilherme Felisberto (guilherme.felisberto@hotmail.com) on 2018-11-12T09:32:46Z No. of bitstreams: 1 Tese Guilherme online.pdf: 2540417 bytes, checksum: cc06d51bdd9f4e0c02a5806a4459259d (MD5) / Approved for entry into archive by Neli Silvia Pereira null (nelisps@fcav.unesp.br) on 2018-11-12T17:03:26Z (GMT) No. of bitstreams: 1 felisberto_g_dr_jabo.pdf: 2540417 bytes, checksum: cc06d51bdd9f4e0c02a5806a4459259d (MD5) / Made available in DSpace on 2018-11-12T17:03:26Z (GMT). No. of bitstreams: 1 felisberto_g_dr_jabo.pdf: 2540417 bytes, checksum: cc06d51bdd9f4e0c02a5806a4459259d (MD5) Previous issue date: 2018-10-05 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A deficiência de zinco (Zn) leva ao estresse oxidativo, causando prejuízos na produção e qualidade do produto colhido em diversas espécies de plantas cultivadas. O silício (Si) por sua vez é um elemento conhecido por mitigar diversos tipos de estresses, podendo ser uma importante ferramenta na mitigação da deficiência de Zn. Contudo, não há relatos na literatura sobre sua eficácia na mitigação da deficiência do micronutriente em nível de produção, nem se há diferenças entre fornecê-lo via solução nutritiva (radicular) ou via aplicação foliar. Possivelmente em função de que a adoção da aplicação foliar de Si ainda é pequena, justamente por apresentar problemas com a polimerização do Si da calda. Isso se dá possivelmente em função da utilização de concentrações, pH e misturas inadequadas. Para tentar minimizar esses problemas, novas fontes de Si têm sido desenvolvidas, mas pouco se sabe sobre seu comportamento e sua eficácia em relação ao silicato de potássio, considerado fonte padrão nos estudos com Si. Nesse sentido foram realizados dois estudos, sendo o primeiro para avaliar o comportamento e a eficácia de fontes de Si (silicato de potássio, nanosílica, silicato de sódio e potássio estabilizado e ácido silícico estabilizado) e concentrações (0; 0,5; 1,0; 1,5 g L-1 de Si) no crescimento e produção de grãos de soja e de arroz; e o segundo para avaliar o efeito do Si aplicado via foliar ou radicular (via solução nutritiva) na mitigação da deficiência de Zn em soja e em arroz. No primeiro estudo foi obervado que as fontes foram eficientes no fornecimento de Si. Na maioria das variáveis estudadas o silicato de sódio e potássio estabilizado se equiparou ou foi superior o silicato de potássio. A concentração de aproximadamente 1 g L-1 de Si apresentou melhor desempenho para a maioria das variáveis analisadas. No segundo estudo foi observado que o Si fornecido via radicular mitigou a deficiência de Zn da soja por ter diminuído os teores de malondialdeído e mantendo a produção de grãos a níveis semelhantes das plantas sem deficiência. O arroz não teve a deficiência de Zn mitigada pelo Si, embora a atividade da enzima superóxido dismutase tenha aumentado com o fornecimento radicular do elemento benéfico. Contudo independentemente se em condição de suficiência ou deficiência de Zn a aplicação radicular ou foliar de Si, promoveu ganhos na produção em relação à não aplicação de Si. Por fim acredita-se as novas fontes apresentem potencial em fornecer Si eficientemente às plantas sendo uma alternativa ao uso do silicato de potássio e que tanto a aplicação foliar como radicular promova ganhos consideráveis na soja e no arroz, seja sob deficiência de Zn ou não. / Zinc (Zn) deficiency leads to oxidative stress, causing losses in yield and quality of the product harvested in several species of cultivated plants. Silicon (Si) is an element known to mitigate several types of stress, and can be an important tool in the mitigation of Zn deficiency. However, there are no reports in the literature about its effectiveness in mitigating Zn deficiency at yield level, nor whether there are differences between providing it via root or leaf. The adoption of the foliar application of Si is still poor due to problems with the Si polymerization in the solution, much as a result of the inadequate concentrations use, pH and mixtures. Recently new sources of Si have been developed but little is known about their behavior and their efficacy compared to potassium silicate, considered a standard source in studies with Si. In this sense, two studies were carried out. The first one to evaluate behavior and efficacy of Si sources (potassium silicate, nanosilica, stabilized sodium and potassium silicate and stabilized silicic acid) and concentrations (0, 0.5, 1.0, 1.5 g L -1 of Si) in the growth and production of soybeans and rice; and the second to evaluate the effect of Si applied by foliar or root in the mitigation of Zn deficiency in soybean and rice. In the first study, it was observed that the sources were efficient in the supply of Si. In most of the variables studied, the stabilized sodium and potassium silicate was equal or superior to the potassium silicate. The concentration of approximately 1 g L-1 of Si presented better performance for most of the analyzed variables. In the second study it was observed that Si provided by the root mitigated the Zn deficiency of soybean by reducing the MDA levels and maintaining grain production at similar levels of plants without deficiency. Rice did not have the Zn deficiency mitigated by Si, although SOD activity increased with root supply of the beneficial element. However independently if in Zn sufficiency or deficiency condition, the root or leaf application of Si promoted production gains in relation to the non-application of Si. Finally, it is believed that the new sources have potential to provide Si efficiently to plants, being an alternative to the use of potassium silicate and that both foliar and root application promote considerable gains in soybean and rice, whether under Zn deficiency or not.

Orientador: Renato de Mello Prado / Resumo: A deficiência de zinco (Zn) leva ao estresse oxidativo, causando prejuízos na produção e qualidade do produto colhido em diversas espécies de plantas cultivadas. O silício (Si) por sua vez é um elemento conhecido por mitigar diversos tipos de estresses, podendo ser uma importante ferramenta na mitigação da deficiência de Zn. Contudo, não há relatos na literatura sobre sua eficácia na mitigação da deficiência do micronutriente em nível de produção, nem se há diferenças entre fornecê-lo via solução nutritiva (radicular) ou via aplicação foliar. Possivelmente em função de que a adoção da aplicação foliar de Si ainda é pequena, justamente por apresentar problemas com a polimerização do Si da calda. Isso se dá possivelmente em função da utilização de concentrações, pH e misturas inadequadas. Para tentar minimizar esses problemas, novas fontes de Si têm sido desenvolvidas, mas pouco se sabe sobre seu comportamento e sua eficácia em relação ao silicato de potássio, considerado fonte padrão nos estudos com Si. Nesse sentido foram realizados dois estudos, sendo o primeiro para avaliar o comportamento e a eficácia de fontes de Si (silicato de potássio, nanosílica, silicato de sódio e potássio estabilizado e ácido silícico estabilizado) e concentrações (0; 0,5; 1,0; 1,5 g L-1 de Si) no crescimento e produção de grãos de soja e de arroz; e o segundo para avaliar o efeito do Si aplicado via foliar ou radicular (via solução nutritiva) na mitigação da deficiência de Zn em soja e em arroz. N... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Zinc (Zn) deficiency leads to oxidative stress, causing losses in yield and quality of the product harvested in several species of cultivated plants. Silicon (Si) is an element known to mitigate several types of stress, and can be an important tool in the mitigation of Zn deficiency. However, there are no reports in the literature about its effectiveness in mitigating Zn deficiency at yield level, nor whether there are differences between providing it via root or leaf. The adoption of the foliar application of Si is still poor due to problems with the Si polymerization in the solution, much as a result of the inadequate concentrations use, pH and mixtures. Recently new sources of Si have been developed but little is known about their behavior and their efficacy compared to potassium silicate, considered a standard source in studies with Si. In this sense, two studies were carried out. The first one to evaluate behavior and efficacy of Si sources (potassium silicate, nanosilica, stabilized sodium and potassium silicate and stabilized silicic acid) and concentrations (0, 0.5, 1.0, 1.5 g L -1 of Si) in the growth and production of soybeans and rice; and the second to evaluate the effect of Si applied by foliar or root in the mitigation of Zn deficiency in soybean and rice. In the first study, it was observed that the sources were efficient in the supply of Si. In most of the variables studied, the stabilized sodium and potassium silicate was equal or superior to the potassium si... (Complete abstract click electronic access below) / Doutor

During the mid Cenozoic, the Chocolate Mountains region of southeastern California experienced crustal extension slightly before, during, and after the main pulse of magmatism. This combined with mid-late Cenozoic faulting to locally uplift plutonic rocks interpreted to represent the plumbing system(s) for volcanic units, allowing an examination of both the extrusive and intrusive result of magmatism. Zircon U-Pb ages of from six magmatic units yield late Oligocene to early Miocene ages and correlate better with stratigraphic relationships than previously compiled ages. These units are four silicic volcanic units – Quechan volcanic rocks, tuff of Felipe Pass, ignimbrite of Ferguson Wash, and tuff of Black Hills – and two plutonic units – the granites of Mount Barrow and Peter Kane Mountain. Regarding contemporaneous plutonic systems as baseline comparisons, zircons from the volcanic units commonly record plutonic temperatures; interpreted to be solidus or near solidus temperature. Remobilization may be a common process leading to eruption. Quartz and zircon thermometers reveal the ignimbrite of Ferguson Wash and tuff of Black Hills magmatic systems evolved differently. Quartz yields temperatures of 700°C to ~750°C in both units with no core-rim trends. Cores of zircons from the ignimbrite of Ferguson Wash yield temperatures between 750°C and 890°C. Zircon rim temperatures are between 875°C and 950°C. Tuff of Black Hills zircon cores generally record temperatures of ~850°C and zircon rim temperatures are ~700°C. Rims from tuff of Black Hills zircon record the same temperature range as zircons from coeval granites. The temperature increase from core to rim in zircons from the ignimbrite of Ferguson Wash indicates reheating and that zircon grew later than and at higher temperatures than quartz. The low zircon temperatures from tuff of Black Hills reveals a system that was growing quartz and zircon at the same low, nearly solidus temperatures. Reasons for its eruption are not readily apparent in the thermal history of zircon and quartz. These two systems record different thermal histories than previously studied, younger systems like the Bishop tuff, in which quartz records late reheating just prior to eruption and a system that was growing quartz later and at higher temperatures than zircon.

The origin of silicic magma in basalt-dominated oceanic settings is fundamental to our understanding of magmatic processes and formation of the earliest continental crust. Particularly significant is magma-crust interaction that can modify the composition of magma and the dynamics of volcanism. This thesis investigates silicic magma genesis on different scales in two ocean island settings. First, volcanic products from a series of voluminous Neogene silicic centres in northeast Iceland are investigated using rock and mineral geochemistry, U-Pb geochronology, and oxygen isotope analysis. Second, interfacial processes of magma-crust interaction are investigated using geochemistry and 3D X-ray computed microtomography on crustal xenoliths from the 2011-12 El Hierro eruption, Canary Islands. The results from northeast Iceland constrain a rapid outburst of silicic magmatism driven by a flare of the Iceland plume and/or by formation of a new rift zone, causing large volume injection of basaltic magma into hydrated basaltic crust. This promoted crustal recycling by partial melting of the hydrothermally altered Icelandic crust, thereby producing mixed-origin silicic melt pockets that reflect the heterogeneous nature of the crustal protolith with respect to oxygen isotopes. In particular, a previously unrecognised high-δ18O end-member on Iceland was documented, which implies potentially complex multi-component assimilation histories for magmas ascending through the Icelandic crust. Common geochemical traits between Icelandic and Hadean zircon populations strengthen the concept of Iceland as an analogue for early Earth, implying that crustal recycling in emergent rifts was pivotal in generating Earth’s earliest continental silicic crust. Crustal xenoliths from the El Hierro 2011-2012 eruption underline the role of partial melting and assimilation of pre-island sedimentary layers in the early shield-building phase of ocean islands. This phenomenon may contribute to the formation of evolved magmas, and importantly, the release of volatiles from the xenoliths may be sufficient to increase the volatile load of the magma and temporarily alter the character and intensity of an eruption. This thesis sheds new light on the generation of silicic magma in basalt-dominated oceanic settings and emphasises the relevance of magma-crust interaction for magma evolution, silicic crust formation, and eruption style from early Earth to present.