Geochemistry and resonance ionization of platinum-group elements

Experimental studies were conducted with the goals of 1) determining the origin of Pt- group element (PGE) alloys and associated mineral assemblages in refractory inclusions from meteorites and 2) developing a new ultrasensitive method for the in situ chemical and isotopic analysis of PGE. A general review of the geochemistry and cosmochemistry of the PGE is given, and specific research contributions are presented within the context of this broad framework.

An important step toward understanding the cosmochemistry of the PGE is the determination of the origin of POE-rich metallic phases (most commonly εRu-Fe) that are found in Ca, AJ-rich refractory inclusions (CAI) in C3V meteorites. These metals occur along with γNi-Fe metals, Ni-Fe sulfides and Fe oxides in multiphase opaque assemblages. Laboratory experiments were used to show that the mineral assemblages and textures observed in opaque assemblages could be produced by sulfidation and oxidation of once homogeneous Ni-Fe-PGE metals. Phase equilibria, partitioning and diffusion kinetics were studied in the Ni-Fe-Ru system in order to quantify the conditions of opaque assemblage formation. Phase boundaries and tie lines in the Ni-Fe-Ru system were determined at 1273, 1073 and 873K using an experimental technique that allowed the investigation of a large portion of the Ni-Fe-Ru system with a single experiment at each temperature by establishing a concentration gradient within which local equilibrium between coexisting phases was maintained. A wide miscibility gap was found to be present at each temperature, separating a hexagonal close-packed εRu-Fe phase from a face-centered cubic γNi-Fe phase. Phase equilibria determined here for the Ni-Fe-Ru system, and phase equilibria from the literature for the Ni-Fe-S and Ni-Fe-O systems, were compared with analyses of minerals from opaque assemblages to estimate the temperature and chemical conditions of opaque assemblage formation. It was determined that opaque assemblages equilibrated at a temperature of ~770K, a sulfur fugacity 10 times higher than an equilibrium solar gas, and an oxygen fugacity 10⁶ times higher than an equilibrium solar gas.

Diffusion rates between -γNi-Fe and εRu-Fe metal play a critical role in determining the time (with respect to CAI petrogenesis) and duration of the opaque assemblage equilibration process. The diffusion coefficient for Ru in Ni (D^Ru_Ni) was determined as an analog for the Ni-Fe-Ru system by the thin-film diffusion method in the temperature range of 1073 to 1673K and is given by the expression:

D^Ru_Ni (cm² sec^-1) = 5.0(±0.7) x 10^-3 exp(-2.3(±0.1) x 10¹² erg mole^-1/RT) where R is the gas constant and T is the temperature in K. Based on the rates of dissolution and exsolution of metallic phases in the Ni-Fe-Ru system it is suggested that opaque assemblages equilibrated after the melting and crystallization of host CAI during a metamorphic event of ≥ 10³ years duration. It is inferred that opaque assemblages originated as immiscible metallic liquid droplets in the CAI silicate liquid. The bulk compositions of PGE in these precursor alloys reflects an early stage of condensation from the solar nebula and the partitioning of V between the precursor alloys and CAI silicate liquid reflects the reducing nebular conditions under which CAI were melted. The individual mineral phases now observed in opaque assemblages do not preserve an independent history prior to CAI melting and crystallization, but instead provide important information on the post-accretionary history of C3V meteorites and allow the quantification of the temperature, sulfur fugacity and oxygen fugacity of cooling planetary environments. This contrasts with previous models that called upon the formation of opaque assemblages by aggregation of phases that formed independently under highly variable conditions in the solar nebula prior to the crystallization of CAI.

Analytical studies were carried out on PGE-rich phases from meteorites and the products of synthetic experiments using traditional electron microprobe x-ray analytical techniques. The concentrations of PGE in common minerals from meteorites and terrestrial rocks are far below the ~100 ppm detection limit of the electron microprobe. This has limited the scope of analytical studies to the very few cases where PGE are unusually enriched. To study the distribution of PGE in common minerals will require an in situ analytical technique with much lower detection limits than any methods currently in use. To overcome this limitation, resonance ionization of sputtered atoms was investigated for use as an ultrasensitive in situ analytical technique for the analysis of PGE. The mass spectrometric analysis of Os and Re was investigated using a pulsed primary Ar⁺ ion beam to provide sputtered atoms for resonance ionization mass spectrometry. An ionization scheme for Os that utilizes three resonant energy levels (including an autoionizing energy level) was investigated and found to have superior sensitivity and selectivity compared to nonresonant and one and two energy level resonant ionization schemes. An elemental selectivity for Os over Re of ≥ 10³ was demonstrated. It was found that detuning the ionizing laser from the autoionizing energy level to an arbitrary region in the ionization continuum resulted in a five-fold decrease in signal intensity and a ten-fold decrease in elemental selectivity. Osmium concentrations in synthetic metals and iron meteorites were measured to demonstrate the analytical capabilities of the technique. A linear correlation between Os⁺ signal intensity and the known Os concentration was observed over a range of nearly 10⁴ in Os concentration with an accuracy of ~ ±10%, a millimum detection limit of 7 parts per billion atomic, and a useful yield of 1%. Resonance ionization of sputtered atoms samples the dominant neutral-fraction of sputtered atoms and utilizes multiphoton resonance ionization to achieve high sensitivity and to eliminate atomic and molecular interferences. Matrix effects should be small compared to secondary ion mass spectrometry because ionization occurs in the gas phase and is largely independent of the physical properties of the matrix material. Resonance ionization of sputtered atoms can be applied to in situ chemical analysis of most high ionization potential elements (including all of the PGE) in a wide range of natural and synthetic materials. The high useful yield and elemental selectivity of this method should eventually allow the in situ measurement of Os isotope ratios in some natural samples and in sample extracts enriched in PGE by fire assay fusion.

Phase equilibria and diffusion experiments have provided the basis for a reinterpretation of the origin of opaque assemblages in CAI and have yielded quantitative information on conditions in the primitive solar nebula and cooling planetary environments. Development of the method of resonance ionization of sputtered atoms for the analysis of Os has shown that this technique has wide applications in geochemistry and will for the first time allow in situ studies of the distribution of PGE at the low concentration levels at which they occur in common minerals.

The abundances of ultraheavy elements in the cosmic radiation

Analysis of the data from the Heavy Nuclei Experiment on the HEAO-3 spacecraft has yielded the cosmic ray abundances of odd-even element pairs with atomic number, Z, in the range 33 ≤ Z ≤60, and the abundances of broad element groups in the range 62 ≤ Z ≤83, relative to iron. These data show that the cosmic ray source composition in this charge range is quite similar to that of the solar system provided an allowance is made for a source fractionation based on first ionization potential. The observations are inconsistent with a source composition which is dominated by either r-process or s-process material, whether or not an allowance is made for first ionization potential. Although the observations do not exclude a source containing the same mixture of r- and s-process material as in the solar system. the data are best fit by a source having an r- to s-process ratio of 1.22^(+0.25)_(0.21), relative to the solar system The abundances of secondary elements are consistent with the leaky box model of galactic propagation, implying a pathlength distribution similar to that which explains the abundances of nuclei with Z<29.

The energy spectra of the even elements in the range 38 ≤ Z ≤ 60 are found to have a deficiency of particles in the range ~1.5 to 3 GeV/amu, compared to iron. This deficiency may result from ionization energy loss in the interstellar medium, and is not predicted by propagation models which ignore such losses. ln addition, the energy spectra of secondary elements are found to be different to those of the primary elements. Such effects are consistent with observations of lighter nuclei, and are in qualitative agreement with galactic propagation models using a rigidity dependent escape length. The energy spectra of secondaries arising from the platinum group are found to be much steeper than those of lower Z. This effect may result from energy dependent fragmentation cross sections.

BLOG: da Internet à sala de aula

Os diários de escrita íntima constituem tipo de texto do domínio confessional. Apresentam narrativas pessoais com características específicas ao gênero, como datação, marcas de subjetividade, escrita informal e coloquialidade. Durante muitos anos, eram escritos em cadernos e guardados a sete chaves por seus autores para que não fossem lidos por outras pessoas. Por volta dos anos 80, surgiram as agendas de adolescentes. Aproveitando o modelo pré-definido industrialmente, as agendas eram preenchidas dia a dia, como um diário, mas com a novidade do acréscimo de elementos semióticos, como fotos, papéis de bala, recortes de revistas, entre outros. Além disso, traziam como diferencial a presença de um leitor participativo: os textos eram compartilhados com amigos, e bilhetes e comentários eram escritos nas páginas das agendas. Com o advento da Internet, o diário e a agenda se fundem no blog que aproveita os recursos do suporte virtual para tornar o gênero interativo, hipertextual e multimídia, acentuando o processo de leitura e de escrita nos jovens produtores de blogs. Paralelamente, a escrita se torna grande ferramenta de comunicação no ambiente virtual, adquirindo características peculiares em função da rapidez na comunicação e da economia de digitação. A partir da teoria de Bakthin sobre gêneros do discurso e do conceito de gêneros digitais de Marcuschi, a pesquisa apresenta como objeto perceber e elencar categorias pertinentes aos gêneros diário e blog para analisá-las e compará-las, na intenção de mapear um possível percurso dos diários aos blogs de adolescentes, discutindo o contraste público-privado na escrita íntima, bem como suas principais marcas linguísticas, percebendo vantagens e desvantagens de sua utilização como ferramenta auxiliar no processo de aprendizagem da escrita e da leitura de Língua Portuguesa. A pesquisa foi motivada pela discussão de que a escrita digital pode prejudicar o desenvolvimento da produção textual de jovens em formação, o que não se confirmou, visto que a estrutura sintática da língua se mantém, e que a variação acontece apenas no nível vocabular, não interferindo na comunicação. Os resultados apontam para a utilização de blogs na educação como complementação do material pedagógico e como incentivo à leitura, à escrita, à construção da argumentação e do posicionamento crítico, aproximando a escola da vida cotidiana dos estudantes

Phase transitions from the solid state of monatomic elements

The principle aims of this thesis include the development of models of sublimation and melting from first principles and the application of these models to the rare gases.

A simple physical model is constructed to represent the sublimation of monatomic elements. According to this model, the solid and gas phases are two states of a single physical system. The nature of the phase transition is clearly revealed, and the relations between the vapor pressure, the latent heat, and the transition temperature are derived. The resulting theory is applied to argon, krypton, and xenon, and good agreement with experiment is found.

For the melting transition, the solid is represented by an anharmonic model and the liquid is described by the Percus-Yevick approximation. The behavior of the liquid at high densities is studied on the isotherms kT/∈ = 1.3, 1.8, and 2.0, where k is Boltzmann's constant, T is the temperature, and e is the well depth of the Lennard-Jones 12-6 pair potential. No solutions of the PercusYevick equation were found for ρσ³ above 1.3, where ρ is the particle density and σ is the radial parameter of the Lennard-Jones potential. The liquid structure is found to be very different from the solid structure near the melting line. The liquid pressures are about 50 percent low for experimental melting densities of argon. This discrepancy gives rise to melting pressures up to twice the experimental values.

Transgressive elements in The Monk: social taboos

A presente dissertação tem como objetivo mostrar como a literatura gótica pode ser atemporal, subvertendo as mentes e conceitos de seus leitores. Partindo do contexto histórico e cultural em que The Monk se inseriu, esse trabalho visa levantar as questões e elementos tão fortemente reprimidos em nossa sociedade desde o final do século XVIII, como as idéias de mal, abjeção e expressão do eu, em um diálogo permanente com a teoria de Michel Foucault, David Punter, Julia Kristeva, entre outros. Desta forma, a análise do romance se dá paralelamente a uma crítica social, visto que a obra gótica tem por um de seus fins denunciar e deslocar a realidade social. Em última instância, será feita a análise algumas personagens do romance e sua respectiva importância na obra

SteelConverter and Caltech VirtualShaker: Rapid Nonlinear Cloud-Based Structural Model Conversion and Analysis

STEEL, the Caltech created nonlinear large displacement analysis software, is currently used by a large number of researchers at Caltech. However, due to its complexity, lack of visualization tools (such as pre- and post-processing capabilities) rapid creation and analysis of models using this software was difficult. SteelConverter was created as a means to facilitate model creation through the use of the industry standard finite element solver ETABS. This software allows users to create models in ETABS and intelligently convert model information such as geometry, loading, releases, fixity, etc., into a format that STEEL understands. Models that would take several days to create and verify now take several hours or less. The productivity of the researcher as well as the level of confidence in the model being analyzed is greatly increased.

It has always been a major goal of Caltech to spread the knowledge created here to other universities. However, due to the complexity of STEEL it was difficult for researchers or engineers from other universities to conduct analyses. While SteelConverter did help researchers at Caltech improve their research, sending SteelConverter and its documentation to other universities was less than ideal. Issues of version control, individual computer requirements, and the difficulty of releasing updates made a more centralized solution preferred. This is where the idea for Caltech VirtualShaker was born. Through the creation of a centralized website where users could log in, submit, analyze, and process models in the cloud, all of the major concerns associated with the utilization of SteelConverter were eliminated. Caltech VirtualShaker allows users to create profiles where defaults associated with their most commonly run models are saved, and allows them to submit multiple jobs to an online virtual server to be analyzed and post-processed. The creation of this website not only allowed for more rapid distribution of this tool, but also created a means for engineers and researchers with no access to powerful computer clusters to run computationally intensive analyses without the excessive cost of building and maintaining a computer cluster.

In order to increase confidence in the use of STEEL as an analysis system, as well as verify the conversion tools, a series of comparisons were done between STEEL and ETABS. Six models of increasing complexity, ranging from a cantilever column to a twenty-story moment frame, were analyzed to determine the ability of STEEL to accurately calculate basic model properties such as elastic stiffness and damping through a free vibration analysis as well as more complex structural properties such as overall structural capacity through a pushover analysis. These analyses showed a very strong agreement between the two softwares on every aspect of each analysis. However, these analyses also showed the ability of the STEEL analysis algorithm to converge at significantly larger drifts than ETABS when using the more computationally expensive and structurally realistic fiber hinges. Following the ETABS analysis, it was decided to repeat the comparisons in a software more capable of conducting highly nonlinear analysis, called Perform. These analyses again showed a very strong agreement between the two softwares in every aspect of each analysis through instability. However, due to some limitations in Perform, free vibration analyses for the three story one bay chevron brace frame, two bay chevron brace frame, and twenty story moment frame could not be conducted. With the current trend towards ultimate capacity analysis, the ability to use fiber based models allows engineers to gain a better understanding of a building’s behavior under these extreme load scenarios.

Following this, a final study was done on Hall’s U20 structure [1] where the structure was analyzed in all three softwares and their results compared. The pushover curves from each software were compared and the differences caused by variations in software implementation explained. From this, conclusions can be drawn on the effectiveness of each analysis tool when attempting to analyze structures through the point of geometric instability. The analyses show that while ETABS was capable of accurately determining the elastic stiffness of the model, following the onset of inelastic behavior the analysis tool failed to converge. However, for the small number of time steps the ETABS analysis was converging, its results exactly matched those of STEEL, leading to the conclusion that ETABS is not an appropriate analysis package for analyzing a structure through the point of collapse when using fiber elements throughout the model. The analyses also showed that while Perform was capable of calculating the response of the structure accurately, restrictions in the material model resulted in a pushover curve that did not match that of STEEL exactly, particularly post collapse. However, such problems could be alleviated by choosing a more simplistic material model.

I. Baryon-antibaryon phase transition at high temperature. II. Inclusive virtual photon-hadron reactions in the parton model

Part I

Present experimental data on nucleon-antinucleon scattering allow a study of the possibility of a phase transition in a nucleon-antinucleon gas at high temperature. Estimates can be made of the general behavior of the elastic phase shifts without resorting to theoretical derivation. A phase transition which separates nucleons from antinucleons is found at about 280 MeV in the approximation of the second virial coefficient to the free energy of the gas.

Part II

The parton model is used to derive scaling laws for the hadrons observed in deep inelastic electron-nucleon scattering which lie in the fragmentation region of the virtual photon. Scaling relations are obtained in the Bjorken and Regge regions. It is proposed that the distribution functions become independent of both q² and ν where the Bjorken and Regge regions overlap. The quark density functions are discussed in the limit x→1 for the nucleon octet and the pseudoscalar mesons. Under certain plausible assumptions it is found that only one or two quarks of the six types of quarks and antiquarks have an appreciable density function in the limit x→1. This has implications for the quark fragmentation functions near the large momentum boundary of their fragmentation region. These results are used to propose a method of measuring the proton and neutron quark density functions for all x by making measurements on inclusively produced hadrons in electroproduction only. Implications are also discussed for the hadrons produced in electron-positron annihilation.

Leitura virtual em língua espanhola: a intervenção dos elementos linguísticos presentes em blogs de professores

Esta dissertação tem como objetivo analisar a intervenção de elementos linguísticos no processo leitor em espanhol como língua estrangeira (E/LE) ,em ambiente virtual, de docente desse idioma. A partir desse objetivo macro, estabelecemos um recorte e nos focamos na análise de como/se elementos linguísticos mais característicos de uma linguagem coloquial podem afetar mais a leitura de um docente de E/LE que teve na sua formação e na sua atividade profissional um contato maior com a língua formal. Nesse contexto, escolhemos o blog como o suporte virtual dos textos a serem lidos pelo sujeito por apresentar uma linguagem mais coloquial. No que se refere ao aporte teórico, esta pesquisa tem com principais bases a Linguística Textual (KOCH, 2009, 2002, 2007; KOCH ; TRAVAGLIA, 1996, 2000) e a leitura sócio-interacional (KATO, 1986, 2007; KLEIMAN, 1993, 1996, 2008; NUNES, 2005; VERGNANO-JUNGER, 2009). Também utilizamos alguns elementos da Análise do Discurso de base enunciativa em pontos nos quais ela dialoga com a perspectiva sócio-interacional, como, por exemplo, na noção de gênero do discurso (MAINGUENEAU, 1996, 2003; BAKTHIN, 2003). A Sociolinguística (MORENO FERNANDÉZ, 1996; ALKMIN, 2001) contribuiu para estabelecer os parâmetros da língua coloquial e formal. Quanto à leitura em ambiente virtual, seguimos Ribeiro (2005), Marcuschi (2007), Santaella (2008) e Vergnano-Junger (2009). Para a elaboração deste trabalho, utilizamos uma metodologia híbrida composta de uma parte documental e de um estudo de caso. A fase documental teve como metas classificar os blogs de docentes de E/LE e selecionar dois para a elaboração de atividades de leitura guiada. O estudo de caso realizado com um docente de E/LE, por sua vez, teve como etapas uma leitura livre, duas guiadas e uma entrevista. Objetivou observar e discutir o perfil e o processo leitor do sujeito, com foco na intervenção de elementos linguísticos. Dos resultados obtidos, podemos destacar uma proposta de classificação dos blogs de professores de E/LE. Com base no estudo de caso, duas considerações merecem destaque: (a) uma maior dificuldade de leitura do texto coloquial, ao que tudo indica, gerada pela variedade lexical e (b) uma tendência do sujeito à leitura linear em ambiente virtual, com atenção voltada, frequentemente, para os aspectos de vocabulário e como esses afetavam a compreensão, demonstrando uma tendência à leitura decodificadora

Geodiversidad de la franja litoral Deba-Zumaia. Un paseo geológico virtual

El tramo litoral entre Deba y Zumaia constituye una de las zonas más conocidas y mejor estudiadas de todo el ámbito geológico de los Pirineos y, más particularmente, de su porción más occidental: la denominada cuenca o Región Vasco Cantábrica. Tal circunstancia deriva de los atributos particulares de su registro geológico: un potente conjunto de rocas sedimentarias de persistente estratificación, formadas en un antiguo fondo marino que, a pesar de grandes semejanzas, era muy distinto a los fondos marinos actuales. A este potente conjunto de rocas sedimentarias se le conoce bajo la denominación genérica de “flysch”, término de amplia raigambre geológica, cuya concepción y uso han cambiado considerablemente con el tiempo y el avance del conocimiento.

Elements of Decision under Uncertainty with Applications

This work presents the basic elements for the analysis of decision under uncertainty: Expected Utility Theory and its citicisms and risk aversion and its measurement. The concepts of certainty equivalent, risk premium, absolute risk aversion and relative risk aversion, and the "more risk averse than" relation are discussed. The work is completed with several applications of decision making under uncertainty to different economic problems: investment in risky assets and portfolio selection, risk sharing, investment to reduce risk, insurance, taxes and income underreporting, deposit insurance and the value of information.

Desarrollo de una herramienta virtual destinada al diseño de una plataforma robótica reconfigurable.

[ES]Este proyecto tiene como objeto aumentar el conocimiento concerniente a mecanismos robóticos reconfigurables, así como ponerlo en práctica. Estos mecanismos pueden lograr rápidas transiciones y son capaces de adaptarse a sí mismos a muchos entornos diferentes, conduciendo a una reducción de costes y requerimientos de espacio. Para ello, se estudia el estado del arte, de manera que se pueda reunir información sobre las principales aplicaciones y oportunidades que este campo ofrece en diferentes áreas. A continuación, se requiere llevar a cabo un análisis cinemático de un robot específico, y junto a métodos de planificación de trayectorias, su implementación en un software gráfico para simular su movimiento. La herramienta de software “Matlab” va a ser la que permitirá llevar a cabo toda la programación y representación a lo largo de todo el proyecto.