Formulação teórica dos fundamentos da otimização global topográfica com análise de desempenho e aplicações à estabilidade de fases de misturas termodinâmicas

Métodos de otimização que utilizam condições de otimalidade de primeira e/ou segunda ordem são conhecidos por serem eficientes. Comumente, esses métodos iterativos são desenvolvidos e analisados à luz da análise matemática do espaço euclidiano n-dimensional, cuja natureza é de caráter local. Consequentemente, esses métodos levam a algoritmos iterativos que executam apenas as buscas locais. Assim, a aplicação de tais algoritmos para o cálculo de minimizadores globais de uma função não linear,especialmente não-convexas e multimodais, depende fortemente da localização dos pontos de partida. O método de Otimização Global Topográfico é um algoritmo de agrupamento, que utiliza uma abordagem baseada em conceitos elementares da teoria dos grafos, a fim de gerar bons pontos de partida para os métodos de busca local, a partir de pontos distribuídos de modo uniforme no interior da região viável. Este trabalho tem dois objetivos. O primeiro é realizar uma nova abordagem sobre método de Otimização Global Topográfica, onde, pela primeira vez, seus fundamentos são formalmente descritos e suas propriedades básicas são matematicamente comprovadas. Neste contexto, propõe-se uma fórmula semi-empírica para calcular o parâmetro chave deste algoritmo de agrupamento, e, usando um método robusto e eficiente de direções viáveis por pontos-interiores, estendemos o uso do método de Otimização Global Topográfica a problemas com restrições de desigualdade. O segundo objetivo é a aplicação deste método para a análise de estabilidade de fase em misturas termodinâmicas,o qual consiste em determinar se uma dada mistura se apresenta em uma ou mais fases. A solução deste problema de otimização global é necessária para o cálculo do equilíbrio de fases, que é um problema de grande importância em processos da engenharia, como, por exemplo, na separação por destilação, em processos de extração e simulação da recuperação terciária de petróleo, entre outros. Além disso, afim de ter uma avaliação inicial do potencial dessa técnica, primeiro vamos resolver 70 problemas testes, e então comparar o desempenho do método proposto aqui com o solver MIDACO, um poderoso software recentemente introduzido no campo da otimização global.

Computation of high-stability DC balancing scheme for ferroelectric liquid crystal on silicon holograms using graphics processing units.

Spatial light modulators based around liquid crystal on silicon have found use in a variety of telecommunications applications, including the optimization of multimode fibers, free-space communications, and wavelength selective switching. Ferroelectric liquid crystals are attractive in these areas due to their fast switching times and high phase stability, but the necessity for the liquid crystal to spend equal time in each of its two possible states is an issue of practical concern. Using the highly parallel nature of a graphics processing unit architecture, it is possible to calculate DC balancing schemes of exceptional quality and stability.

Thin Ta films: growth, stability, and diffusion studied by molecular-dynamics simulations

We report results of classical molecular-dynamics simulations of bcc and beta-Ta thin films. Thermal PVD film growth, surface roughness, argon ion bombardment, phase stability and transformation, vacancy and adatom diffusion, and thermal relaxation kinetics are discussed. Distinct differences between the two structures are observed, including a complex vacancy diffusion mechanism in beta-Ta. Embedded atom method potentials, which were fitted to bcc properties, have been used to model the Ta-Ta interactions. In order to verify the application of these potentials to the more complex beta-Ta structure, we have also performed density functional theory calculations. Results and implications of these calculations are discussed.

Near Field Enhancement and Subwavelength Imaging Using Resonantly Loaded Apertures

It is demonstrated that the electromagnetic (EM) transmission through a subwavelength or non-resonant aperture in a conductive screen can be dramatically enhanced by loading it with folded metallic strips exhibiting resonant properties. When illuminated by an EM plane wave these loaded apertures enable very tight, subwavelength, collimation of the EM power in the near field zone. We propose planar and quasi-planar resonant insertion geometries that should allow, for the first time, two-dimensional dual-polarization subwavelength field confinement along with ability to focus both electric and magnetic fields. The proposed technique for resonance transmission enhancement and near field confinement forms a basis for a new class of microwave near field imaging probe with subwavelength resolution capable of operating over a wide range of imaging distances (0.05–$0.25lambda$). Measurement results demonstrate the possibility of high contrast (more than 3 dB in amplitude and 40 degrees in phase) near field subwavelength imaging of 2D and 3D resonant and non-resonant metallic and dielectric targets in free space and in moderately lossy layered media.

Structural stability of the synthetic thermoelectric ternary and nickel-substituted tetrahedrite phases

The purity and structural stability of the high thermoelectric performance Cu12Sb4S13 and Cu10.4Ni1.6Sb4S13 tetrahedrite phases, synthesized by solid–liquid–vapor reaction and Spark Plasma Sintering, were studied at high temperature by Rietveld refinement using high resolution X-ray powder diffraction data, DSC/TG measurements and high resolution transmission electron microscopy. In a complementary study, the crystal structure of Cu10.5Ni1.5Sb4S13 as a function of temperature was investigated by powder neutron diffraction. The temperature dependence of the structural stability of ternary Cu12Sb4S13 is markedly different to that of the nickel-substituted phases, providing clear evidence for the significant and beneficial role of nickel substitution on both sample purity and stability of the tetrahedrite phase. Moreover, kinetic effects on the phase stability/decomposition have been identified and discussed in order to determine the maximum operating temperature for thermoelectric applications. The thermoelectric properties of these compounds have been determined for high density samples (>98%) prepared by Spark Plasma Sintering and therefore can be used as reference values for tetrahedrite samples. The maximum ZT of 0.8 was found for Cu10.4Ni1.6Sb4S13 at 700 K.

Structural phase transformations of Mg3N2 at high pressure : experimental and theoretical studies

The structural behavior of Mg₃N₂ has been investigated up to 40.7 GPa at room temperature by means of angle-dispersive X-ray diffraction. A reversible, first-order structural phase transition from the ambient cubic phase (Ia3̅) to a high-pressure monoclinic phase (C2/m) is found to start at ~ 20.6 GPa and complete at ~ 32.5 GPa for the first time. The equation of state determined from our experiments yields bulk moduli of 110.7(2) and 171.5(1) GPa for the cubic and monoclinic phases, respectively, indicating higher incompressibility of the high-pressure phase of Mg₃N₂. First-principles calculations reproduced the phase stability and transition pressure determined in our experiment. In addition, a second phase transition from the monoclinic phase to a hexagonal phase (P3̅m₁) was predicted around 67 GPa for Mg₃N₂. The electronic band structures of three phases of Mg₃N₂ are also calculated and discussed.

Phase morphology, thermomechanical, and crystallization behavior of uncompatibilized and PP-g-MAH compatibilized polypropylene/polystyrene blends

In this article, we discuss the phase morphology, thermal, mechanical, and crystallization properties of uncompatibilized and compatibilized polypropylene/polystyrene (PP/PS) blends. It is observed that the Young's modulus increases, but other mechanical properties such as tensile strength, flexural strength, elongation at break, and impact strength decrease by blending PS to PP. The tensile strength and Young's modulus of PP/PS blends were compared with various theoretical models. The thermal stability, melting, and crystallization temperatures and percentage crystallinity of semicrystalline PP in the blends were marginally decreased by the addition of amorphous PS. The presence of maleic anhydride-grafted polypropylene (compatibilizer) increases the phase stability of 90/10 and 80/20 blends by preventing the coalescence. Hence, finer and more uniform droplets of PS dispersed phases are observed. The compatibilizer induced some improvement in impact strength for the blends with PP matrix phase, however fluctuations in modulus, strength and ductility were observed with respect to the uncompatibilized blend. The thermal stability was not much affected by the addition of the compatibilizer for the PP rich blends but shows some decrease in the thermal stability of the blends, where PS forms the matrix. On the other hand, the % crystallinity was increased by the addition of compatibilizer, irrespective of the blend concentration.

Investigation of thermal, mechanical and magnetic behaviors of the Cu-11%Al alloy with Ag and Mn additions

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Size-dependent phase transitions in nanostructured zirconia-scandia solid solutions

The dependences of phase stability and solid state phase transitions on the crystallite size in ZrO2-10, 12 and 14 mol% Sc2O3 nanopowders are investigated by X-ray powder diffraction using a synchrotron source (S-XPD). The average crystallite sizes lie within the range of 35 to 100 nm, approximately. At room temperature these solid solutions were previously characterised as mixtures of a cubic phase and one or two rhombohedral phases, beta and gamma, with their fractions depending on composition and average crystallite sizes. In this study, it is shown that at high temperatures these solid solutions become cubic single-phased. The size-dependent temperatures of the transitions from the rhombohedral phases to the cubic phase at high temperature are determined through the analyses of a number of S-XPD patterns. These transitions were studied on cooling and on heating, exhibiting hysteresis effects whose relevant features are size and composition dependent.

Magnetic Properties of Liquid-Phase Sintered CoFe2O4 for Application in Magnetoelastic and Magnetoelectric Transducers

Cobalt ferrite is a ferrimagnetic magnetostrictive ceramic that has potential application in magnetoelastic and magnetoelectric transducers. In this work, CoFe2O4 was obtained using a conventional ceramic method and Bi2O3 was used as additive in order to obtain liquid-phase sintered samples. Bi2O3 was added to the ferrite in amounts ranging from 0.25 mol% to 0.45 mol% and samples were sintered at 900 degrees C and 950 degrees C. It was observed the presence of Bi-containing particles in the microstructure of the sintered samples and the magnetostriction results indicated microstructural anisotropy. It was verified that it is possible to get dense cobalt ferrites, liquid-phase sintered, with relative densities higher than 90% and with magnetostriction values very close to samples sintered without additives.

Size-dependent phase transitions in nanostructured zirconia-scandia solid solutions.

Size effects on phase stability and phase transitions in technologically relevant materials have received growing attention. Several works reported that metastable phases can be retained at room temperature in nanomaterials, these phases generally corresponding to the high-temperature polymorph of the same material in bulk state. Additionally, size-dependent shifts in solubility limits and/or in the transition temperatures for on heating or on cooling cycles have been observed. ZrO2-Sc2O3 (zirconia-scandia) solid solutions are known to exhibit very high oxygen ion conductivity provided their structure is composed of cubic and/or pseudocubic tetragonal phases. Unfortunately, for solid zirconia-scandia polycrystalline samples with typical micrometrical average crystal sizes, the high-conductivity cubic phase is only stable above 600°C. Depending on composition, three low-conductivity rhombo-hedral phases (β, γ and δ) are stable below 600°C down to room temperature, within the compositional range of interest for SOFCs. In previous investigations, we showed that the rhombohedral phases can be avoided in nanopowders with average crystallite size lower than 35 nm.

Constraints on mantle melting from major and trace element systematics in residual abyssal peridotites

ZusammenfassungDie Bildung von mittelozeanischen Rückenbasalten (MORB) ist einer der wichtigsten Stoffflüsse der Erde. Jährlich wird entlang der 75.000 km langen mittelozeanischen Rücken mehr als 20 km3 neue magmatische Kruste gebildet, das sind etwa 90 Prozent der globalen Magmenproduktion. Obwohl ozeanische Rücken und MORB zu den am meisten untersuchten geologischen Themenbereichen gehören, existieren weiterhin einige Streit-fragen. Zu den wichtigsten zählt die Rolle von geodynamischen Rahmenbedingungen, wie etwa Divergenzrate oder die Nähe zu Hotspots oder Transformstörungen, sowie der absolute Aufschmelzgrad, oder die Tiefe, in der die Aufschmelzung unter den Rücken beginnt. Diese Dissertation widmet sich diesen Themen auf der Basis von Haupt- und Spurenelementzusammensetzungen in Mineralen ozeanischer Mantelgesteine.Geochemische Charakteristika von MORB deuten darauf hin, dass der ozeanische Mantel im Stabilitätsfeld von Granatperidotit zu schmelzen beginnt. Neuere Experimente zeigen jedoch, dass die schweren Seltenerdelemente (SEE) kompatibel im Klinopyroxen (Cpx) sind. Aufgrund dieser granatähnlichen Eigenschaft von Cpx wird Granat nicht mehr zur Erklärung der MORB Daten benötigt, wodurch sich der Beginn der Aufschmelzung zu geringeren Drucken verschiebt. Aus diesem Grund ist es wichtig zu überprüfen, ob diese Hypothese mit Daten von abyssalen Peridotiten in Einklang zu bringen ist. Diese am Ozeanboden aufgeschlossenen Mantelfragmente stellen die Residuen des Aufschmelz-prozesses dar, und ihr Mineralchemismus enthält Information über die Bildungs-bedingungen der Magmen. Haupt- und Spurenelementzusammensetzungen von Peridotit-proben des Zentralindischen Rückens (CIR) wurden mit Mikrosonde und Ionensonde bestimmt, und mit veröffentlichten Daten verglichen. Cpx der CIR Peridotite weisen niedrige Verhältnisse von mittleren zu schweren SEE und hohe absolute Konzentrationen der schweren SEE auf. Aufschmelzmodelle eines Spinellperidotits unter Anwendung von üblichen, inkompatiblen Verteilungskoeffizienten (Kd's) können die gemessenen Fraktionierungen von mittleren zu schweren SEE nicht reproduzieren. Die Anwendung der neuen Kd's, die kompatibles Verhalten der schweren SEE im Cpx vorhersagen, ergibt zwar bessere Resultate, kann jedoch nicht die am stärksten fraktionierten Proben erklären. Darüber hinaus werden sehr hohe Aufschmelzgrade benötigt, was nicht mit Hauptelementdaten in Einklang zu bringen ist. Niedrige (~3-5%) Aufschmelzgrade im Stabilitätsfeld von Granatperidotit, gefolgt von weiterer Aufschmelzung von Spinellperidotit kann jedoch die Beobachtungen weitgehend erklären. Aus diesem Grund muss Granat weiterhin als wichtige Phase bei der Genese von MORB betrachtet werden (Kapitel 1).Eine weitere Hürde zum quantitativen Verständnis von Aufschmelzprozessen unter mittelozeanischen Rücken ist die fehlende Korrelation zwischen Haupt- und Spuren-elementen in residuellen abyssalen Peridotiten. Das Cr/(Cr+Al) Verhältnis (Cr#) in Spinell wird im Allgemeinen als guter qualitativer Indikator für den Aufschmelzgrad betrachtet. Die Mineralchemie der CIR Peridotite und publizierte Daten von anderen abyssalen Peridotiten zeigen, dass die schweren SEE sehr gut (r2 ~ 0.9) mit Cr# der koexistierenden Spinelle korreliert. Die Auswertung dieser Korrelation ergibt einen quantitativen Aufschmelz-indikator für Residuen, welcher auf dem Spinellchemismus basiert. Damit kann der Schmelzgrad als Funktion von Cr# in Spinell ausgedrückt werden: F = 0.10×ln(Cr#) + 0.24 (Hellebrand et al., Nature, in review; Kapitel 2). Die Anwendung dieses Indikators auf Mantelproben, für die keine Ionensondendaten verfügbar sind, ermöglicht es, geochemische und geophysikalischen Daten zu verbinden. Aus geodynamischer Perspektive ist der Gakkel Rücken im Arktischen Ozean von großer Bedeutung für das Verständnis von Aufschmelzprozessen, da er weltweit die niedrigste Divergenzrate aufweist und große Transformstörungen fehlen. Publizierte Basaltdaten deuten auf einen extrem niedrigen Aufschmelzgrad hin, was mit globalen Korrelationen im Einklang steht. Stark alterierte Mantelperidotite einer Lokalität entlang des kaum beprobten Gakkel Rückens wurden deshalb auf Primärminerale untersucht. Nur in einer Probe sind oxidierte Spinellpseudomorphosen mit Spuren primärer Spinelle erhalten geblieben. Ihre Cr# ist signifikant höher als die einiger Peridotite von schneller divergierenden Rücken und ihr Schmelzgrad ist damit höher als aufgrund der Basaltzusammensetzungen vermutet. Der unter Anwendung des oben erwähnten Indikators ermittelte Schmelzgrad ermöglicht die Berechnung der Krustenmächtigkeit am Gakkel Rücken. Diese ist wesentlich größer als die aus Schweredaten ermittelte Mächtigkeit, oder die aus der globalen Korrelation zwischen Divergenzrate und mittels Seismik erhaltene Krustendicke. Dieses unerwartete Ergebnis kann möglicherweise auf kompositionelle Heterogenitäten bei niedrigen Schmelzgraden, oder auf eine insgesamt größere Verarmung des Mantels unter dem Gakkel Rücken zurückgeführt werden (Hellebrand et al., Chem.Geol., in review; Kapitel 3).Zusätzliche Informationen zur Modellierung und Analytik sind im Anhang A-C aufgeführt

GRAIL gravity field determination using the Celestial Mechanics Approach

The NASA mission GRAIL (Gravity Recovery and Interior Laboratory) inherited its concept from the GRACE (Gravity Recovery and Climate Experiment) mission to determine the gravity field of the Moon. We present lunar gravity fields based on the data of GRAIL’s primary mission phase. Gravity field recovery is realized in the framework of the Celestial Mechanics Approach, using a development version of the Bernese GNSS Software along with Ka-band range-rate data series as observations and the GNI1B positions provided by NASA JPL as pseudo-observations. By comparing our results with the official level-2 GRAIL gravity field models we show that the lunar gravity field can be recovered with a high quality by adapting the Celestial Mechanics Approach, even when using pre-GRAIL gravity field models as a priori fields and when replacing sophisticated models of non-gravitational accelerations by appropriately spaced pseudo-stochastic pulses (i.e., instantaneous velocity changes). We present and evaluate two lunar gravity field solutions up to degree and order 200 – AIUB-GRL200A and AIUB-GRL200B. While the first solution uses no gravity field information beyond degree 200, the second is obtained by using the official GRAIL field GRGM900C up to degree and order 660 as a priori information. This reduces the omission errors and demonstrates the potential quality of our solution if we resolved the gravity field to higher degree.

Gas-phase fragmentation and conformation of the sugar-modified antisense oligonucleotide tcDNA

Tricyclo-DNA (tcDNA) is a sugar- and backbone-modified analogue of DNA that is currently tested as antisense oligonucleotide for the treatment of Duchenne muscular dystrophy. The name tricyclo-DNA is derived from the modified sugar-moiety: the deoxyribose is extended to a three-membered ring system. This modification is designed to limit the flexibility of the structure, thus giving rise to entropically stabilized hybrid duplexes formed between tcDNA and complementary DNA or RNA oligonucleotides. While the structural modifications increase the biostability of the therapeutic agent, they also render the oligonucleotide inaccessible to enzyme-based sequencing methods. Tandem mass spectrometry constitutes an alternative sequencing technique for partially and fully modified oligonucleotides. For reliable sequencing, the fragmentation mechanism of the structure in question must be understood. Therefore, the presented work evaluates the effect of the modified sugar-moiety on the gas-phase dissociation of single stranded tcDNA. Moreover, our experiments reflect the exceptional gas-phase stability of hybrid duplexes that is most noticeable in the formation of truncated duplex ions upon collision-induced dissociation. The stability of the duplex arises from the modified sugar-moiety, as the rigid structure of the tcDNA single strand minimizes the change of the entropy for the annealing. Moreover, the tc-modification gives rise to extended conformations of the nucleic acids in the gas-phase, which was studied by ion mobility spectrometry-mass spectrometry.

Major element concentrations in spinel, olivine and pyroxene from peridotites of ODP Hole 210-1277 of the Newfoundland margin

Serpentinized spinel peridotites of the Newfoundland margin drilled during ODP Leg 210 at Site 1277 have preserved, relic mineral compositions similar to the most depleted abyssal peridotites worldwide and different from those of the conjugate Iberian margin. The samples are derived from mass flows containing clasts of peridotite and gabbro and from in-situ basement, and are mostly mylonitic cpx-poor spinel harzburgites with Cr-rich spinels (Cr#0.35-0.66). Melting of the Newfoundland mantle occurred in the spinel peridotite field and probably exceeded the cpx-out phase boundary for some samples. Using proposed spinel peridotite melting models and experimentally derived phase diagrams, the Newfoundland harzburgites can be modeled as a residue after extraction of 14 to 20-25% melting. Basalts that are interleaved with mass flow deposits on top of the peridotite basement resemble normal to transitional mid-ocean ridge basalt. This, together with the unusually high Cr# of some spinel harzburgites suggest that the formation of basalts and partial melting of the underlying peridotite are not cogenetic. Among mantle samples some of the Newfoundland harzburgites approach mineral compositions of the Bay of island ophiolite and ophiolites from Japan that represent peridotites formed in an arc-setting. Thus, the peridotites drilled at Site 1277 may represent inherited (Caledonian or older) subarc mantle that was exhumed close to the ocean floor during the rifting evolution of the Atlantic. Compared to the spinel harzburgites from Newfoundland, the peridotites from the conjugate Iberian margin are, on average, less depleted and provide evidence for local equilibration in the plagioclase stability field. This can either be explained by an inherited, primary, Ca-richer composition of the Iberia peridotite, or, alternatively, by local melt impregnation and stagnation during continental rifting, and thus refertilizing previously depleted (arc-related) peridotite.