Determination of the magnetostrictive atomic enviroments in FeCoB alloys

The atomic environments of Fe and Co involved in the magnetostriction effect in FeCoB alloys have been identified by differential extended x-ray fine structure (DiffEXAFS) spectroscopy. The study, done in amorphous and polycrystalline FeCoB films, demonstrates that the alloys are heterogeneous and that boron plays a crucial role in the origin of their magnetostrictive properties. The analysis of DiffEXAFS in the polycrystalline and amorphous alloys indicates that boron activates magnetostriction when entering as an impurity into octahedral interstitial sites of the Fe bcc lattice, causing its tetragonal distortion. Magnetostriction would be explained then by the relative change in volume when the tetragonal axis of the site is reoriented under an externally applied magnetic field. The experiment demonstrates the extreme sensitivity of DiffEXAFS to characterize magnetostrictive environments that are undetectable in their related EXAFS spectra.

Perturbed angular correlation study of Ta-181-doped PbTi1-xHfxO3 compounds

In this work, the hyperfine quadrupole interaction at Ta-doped PbTi1-xHfxO3 polycrystalline samples is studied for the first time. Powders with x=0.25, 0.50 and 0.75 were prepared and characterized by X-ray diffraction analysis. Perturbed Angular Correlation (PAC) analyses were done as a function of temperature, using low concentration Ta-181 nuclei as probes. In the ferroelectric and paraelectric phases of these compounds two sites were occupied by the probes. For each site the quadrupole frequency, asymmetry and relative distribution width parameters were obtained as a function of temperature above and below the Curie temperature (T-C). One of these sites was assigned to the regular Ti-Hf site, while the other one was assigned to some kind of defect. The behavior of the hyperfine parameters as a function of temperature was analyzed in terms of a recent published phase diagram and the presence of disorder below and above T-C. For the three compositions measured, the obtained hyperfine parameters present discontinuities which correspond to the ferroelectric-paraelectric phase transition. In both phases it was found broad frequency distributed interactions. The disorder in the electronic distribution would be responsible for the broad line width of the hyperfine interaction. (C) 2012 Elsevier B.V. All rights reserved.

Scaling of the coercivity with the geometrical parameters in epitaxial Fe antidot arrays

We studied a series of square lattice antidot arrays, with diameter and lattice parameter from hundreds of nanometers to some microns, fabricated using two lithography techniques in epitaxial Fe(001) films. The coercivity increase of each array with respect to its base film can be scaled to a simple geometric parameter, irrespective of the lithography technique employed. Magnetic transmission x-ray microscopy studies, in arrays fabricated on polycrystalline Fe films deposited on silicon nitride membranes, evidenced the propagation of reversed domains from the edges of the arrays, in agreement with the coercivity analysis of the epitaxial arrays and with micromagnetic models.

Effect of substrate-target distance and sputtering pressure in the synthesis of AlN thin films

In this work, we analyze the influence of the processing pressure and the substrate–target distance on the synthesis by reactive sputtering of c-axis oriented polycrystalline aluminum nitride thin films deposited on Si(100) wafers. The crystalline quality of AlN has been characterized by high-resolution X-ray diffraction (HR-XRD). The films exhibited a very high degree of c-axis orientation especially when a low process pressure was used. After growth, residual stress measurements obtained indirectly from radius of curvature measurements of the wafer prior and after deposition are also provided. Two different techniques are used to determine the curvature—an optically levered laser beam and a method based on X-ray diffraction. There is a transition from compressive to tensile stress at a processing pressure around 2 mTorr. The transition occurs at different pressures for thin films of different thickness. The degree of c-axis orientation was not affected by the target–substrate distance as it was varied in between 30 and 70 mm.

Grain size gradient length scale in ballistic properties optimization of functionally graded nanocrystalline steel plates

The last few years have highlighted the existence of two relevant length scales in the quest to ultrahigh-strength polycrystalline metals. Whereas the microstructural length scale – e.g. grain or twin size – has mainly be linked to the well-established Hall–Petch relationship, the sample length scale – e.g. nanopillar size – has also proven to be at least as relevant, especially in microscale structures. In this letter, a series of ballistic tests on functionally graded nanocrystalline plates are used as a basis for the justification of a “grain size gradient length scale” as an additional ballistic properties optimization parameter.

Experimental and numerical study of cw green laser crystallization of a-Si:H thin films

Crystallization and grain growth technique of thin film silicon are among the most promising methods for improving efficiency and lowering cost of solar cells. A major advantage of laser crystallization and annealing over conventional heating methods is its ability to limit rapid heating and cooling to thin surface layers. Laser energy is used to heat the amorphous silicon thin film, melting it and changing the microstructure to polycrystalline silicon (poly-Si) as it cools. Depending on the laser density, the vaporization temperature can be reached at the center of the irradiated area. In these cases ablation effects are expected and the annealing process becomes ineffective. The heating process in the a-Si thin film is governed by the general heat transfer equation. The two dimensional non-linear heat transfer equation with a moving heat source is solve numerically using the finite element method (FEM), particularly COMSOL Multiphysics. The numerical model help to establish the density and the process speed range needed to assure the melting and crystallization without damage or ablation of the silicon surface. The samples of a-Si obtained by physical vapour deposition were irradiated with a cw-green laser source (Millennia Prime from Newport-Spectra) that delivers up to 15 W of average power. The morphology of the irradiated area was characterized by confocal laser scanning microscopy (Leica DCM3D) and Scanning Electron Microscopy (SEM Hitachi 3000N). The structural properties were studied by micro-Raman spectroscopy (Renishaw, inVia Raman microscope).

Continuum models of the mechanical behavior of rolled and die-cast magnesium alloys

En los últimos años ha habido una fuerte tendencia a disminuir las emisiones de CO2 y su negativo impacto medioambiental. En la industria del transporte, reducir el peso de los vehículos aparece como la mejor opción para alcanzar este objetivo. Las aleaciones de Mg constituyen un material con gran potencial para el ahorro de peso. Durante la última década se han realizado muchos esfuerzos encaminados a entender los mecanismos de deformación que gobiernan la plasticidad de estos materiales y así, las aleaciones de Mg de colada inyectadas a alta presión y forjadas son todavía objeto de intensas campañas de investigación. Es ahora necesario desarrollar modelos que contemplen la complejidad inherente de los procesos de deformación de éstos. Esta tesis doctoral constituye un intento de entender mejor la relación entre la microestructura y el comportamiento mecánico de aleaciones de Mg, y dará como resultado modelos de policristales capaces de predecir propiedades macro- y microscópicas. La deformación plástica de las aleaciones de Mg está gobernada por una combinación de mecanismos de deformación característicos de la estructura cristalina hexagonal, que incluye el deslizamiento cristalográfico en planos basales, prismáticos y piramidales, así como el maclado. Las aleaciones de Mg de forja presentan texturas fuertes y por tanto los mecanismos de deformación activos dependen de la orientación de la carga aplicada. En este trabajo se ha desarrollado un modelo de plasticidad cristalina por elementos finitos con el objetivo de entender el comportamiento macro- y micromecánico de la aleación de Mg laminada AZ31 (Mg-3wt.%Al-1wt.%Zn). Este modelo, que incorpora el maclado y tiene en cuenta el endurecimiento por deformación debido a las interacciones dislocación-dislocación, dislocación-macla y macla-macla, predice exitosamente las actividades de los distintos mecanismos de deformación y la evolución de la textura con la deformación. Además, se ha llevado a cabo un estudio que combina difracción de electrones retrodispersados en tres dimensiones y modelización para investigar el efecto de los límites de grano en la propagación del maclado en el mismo material. Ambos, experimentos y simulaciones, confirman que el ángulo de desorientación tiene una influencia decisiva en la propagación del maclado. Se ha observado que los efectos no-Schmid, esto es, eventos de deformación plástica que no cumplen la ley de Schmid con respecto a la carga aplicada, no tienen lugar en la vecindad de los límites de baja desorientación y se hacen más frecuentes a medida que la desorientación aumenta. Esta investigación también prueba que la morfología de las maclas está altamente influenciada por su factor de Schmid. Es conocido que los procesos de colada suelen dar lugar a la formación de microestructuras con una microporosidad elevada, lo cuál afecta negativamente a sus propiedades mecánicas. La aplicación de presión hidrostática después de la colada puede reducir la porosidad y mejorar las propiedades aunque es poco conocido su efecto en el tamaño y morfología de los poros. En este trabajo se ha utilizado un enfoque mixto experimentalcomputacional, basado en tomografía de rayos X, análisis de imagen y análisis por elementos finitos, para la determinación de la distribución tridimensional (3D) de la porosidad y de la evolución de ésta con la presión hidrostática en la aleación de Mg AZ91 (Mg- 9wt.%Al-1wt.%Zn) colada por inyección a alta presión. La distribución real de los poros en 3D obtenida por tomografía se utilizó como input para las simulaciones por elementos finitos. Los resultados revelan que la aplicación de presión tiene una influencia significativa tanto en el cambio de volumen como en el cambio de forma de los poros que han sido cuantificados con precisión. Se ha observado que la reducción del tamaño de éstos está íntimamente ligada con su volumen inicial. En conclusión, el modelo de plasticidad cristalina propuesto en este trabajo describe con éxito los mecanismos intrínsecos de la deformación de las aleaciones de Mg a escalas meso- y microscópica. Más especificamente, es capaz de capturar las activadades del deslizamiento cristalográfico y maclado, sus interacciones, así como los efectos en la porosidad derivados de los procesos de colada. ---ABSTRACT--- The last few years have seen a growing effort to reduce CO2 emissions and their negative environmental impact. In the transport industry more specifically, vehicle weight reduction appears as the most straightforward option to achieve this objective. To this end, Mg alloys constitute a significant weight saving material alternative. Many efforts have been devoted over the last decade to understand the main mechanisms governing the plasticity of these materials and, despite being already widely used, high pressure die-casting and wrought Mg alloys are still the subject of intense research campaigns. Developing models that can contemplate the complexity inherent to the deformation of Mg alloys is now timely. This PhD thesis constitutes an attempt to better understand the relationship between the microstructure and the mechanical behavior of Mg alloys, as it will result in the design of polycrystalline models that successfully predict macro- and microscopic properties. Plastic deformation of Mg alloys is driven by a combination of deformation mechanisms specific to their hexagonal crystal structure, namely, basal, prismatic and pyramidal dislocation slip as well as twinning. Wrought Mg alloys present strong textures and thus specific deformation mechanisms are preferentially activated depending on the orientation of the applied load. In this work a crystal plasticity finite element model has been developed in order to understand the macro- and micromechanical behavior of a rolled Mg AZ31 alloy (Mg-3wt.%Al-1wt.%Zn). The model includes twinning and accounts for slip-slip, slip-twin and twin-twin hardening interactions. Upon calibration and validation against experiments, the model successfully predicts the activity of the various deformation mechanisms and the evolution of the texture at different deformation stages. Furthermore, a combined three-dimensional electron backscatter diffraction and modeling approach has been adopted to investigate the effect of grain boundaries on twin propagation in the same material. Both experiments and simulations confirm that the misorientation angle has a critical influence on twin propagation. Non-Schmid effects, i.e. plastic deformation events that do not comply with the Schmid law with respect to the applied stress, are absent in the vicinity of low misorientation boundaries and become more abundant as misorientation angle increases. This research also proves that twin morphology is highly influenced by the Schmid factor. Finally, casting processes usually lead to the formation of significant amounts of gas and shrinkage microporosity, which adversely affect the mechanical properties. The application of hydrostatic pressure after casting can reduce the porosity and improve the properties but little is known about the effects on the casting’s pores size and morphology. In this work, an experimental-computational approach based on X-ray computed tomography, image analysis and finite element analysis is utilized for the determination of the 3D porosity distribution and its evolution with hydrostatic pressure in a high pressure diecast Mg AZ91 alloy (Mg-9wt.%Al-1wt.%Zn). The real 3D pore distribution obtained by tomography is used as input for the finite element simulations using an isotropic hardening law. The model is calibrated and validated against experimental stress-strain curves. The results reveal that the pressure treatment has a significant influence both on the volume and shape changes of individuals pores, which have been precisely quantified, and which are found to be related to the initial pore volume. In conclusion, the crystal plasticity model proposed in this work successfully describes the intrinsic deformation mechanisms of Mg alloys both at the mesoscale and the microscale. More specifically, it can capture slip and twin activities, their interactions, as well as the potential porosity effects arising from casting processes.

Microstructure-based numerical modeling of the mechanical behavior of Mg alloys

Dentro de los materiales estructurales, el magnesio y sus aleaciones están siendo el foco de una de profunda investigación. Esta investigación está dirigida a comprender la relación existente entre la microestructura de las aleaciones de Mg y su comportamiento mecánico. El objetivo es optimizar las aleaciones actuales de magnesio a partir de su microestructura y diseñar nuevas aleaciones. Sin embargo, el efecto de los factores microestructurales (como la forma, el tamaño, la orientación de los precipitados y la morfología de los granos) en el comportamiento mecánico de estas aleaciones está todavía por descubrir. Para conocer mejor de la relación entre la microestructura y el comportamiento mecánico, es necesaria la combinación de técnicas avanzadas de caracterización experimental como de simulación numérica, a diferentes longitudes de escala. En lo que respecta a las técnicas de simulación numérica, la homogeneización policristalina es una herramienta muy útil para predecir la respuesta macroscópica a partir de la microestructura de un policristal (caracterizada por el tamaño, la forma y la distribución de orientaciones de los granos) y el comportamiento del monocristal. La descripción de la microestructura se lleva a cabo mediante modernas técnicas de caracterización (difracción de rayos X, difracción de electrones retrodispersados, así como con microscopia óptica y electrónica). Sin embargo, el comportamiento del cristal sigue siendo difícil de medir, especialmente en aleaciones de Mg, donde es muy complicado conocer el valor de los parámetros que controlan el comportamiento mecánico de los diferentes modos de deslizamiento y maclado. En la presente tesis se ha desarrollado una estrategia de homogeneización computacional para predecir el comportamiento de aleaciones de magnesio. El comportamiento de los policristales ha sido obtenido mediante la simulación por elementos finitos de un volumen representativo (RVE) de la microestructura, considerando la distribución real de formas y orientaciones de los granos. El comportamiento del cristal se ha simulado mediante un modelo de plasticidad cristalina que tiene en cuenta los diferentes mecanismos físicos de deformación, como el deslizamiento y el maclado. Finalmente, la obtención de los parámetros que controlan el comportamiento del cristal (tensiones críticas resueltas (CRSS) así como las tasas de endurecimiento para todos los modos de maclado y deslizamiento) se ha resuelto mediante la implementación de una metodología de optimización inversa, una de las principales aportaciones originales de este trabajo. La metodología inversa pretende, por medio del algoritmo de optimización de Levenberg-Marquardt, obtener el conjunto de parámetros que definen el comportamiento del monocristal y que mejor ajustan a un conjunto de ensayos macroscópicos independientes. Además de la implementación de la técnica, se han estudiado tanto la objetividad del metodología como la unicidad de la solución en función de la información experimental. La estrategia de optimización inversa se usó inicialmente para obtener el comportamiento cristalino de la aleación AZ31 de Mg, obtenida por laminado. Esta aleación tiene una marcada textura basal y una gran anisotropía plástica. El comportamiento de cada grano incluyó cuatro mecanismos de deformación diferentes: deslizamiento en los planos basal, prismático, piramidal hc+ai, junto con el maclado en tracción. La validez de los parámetros resultantes se validó mediante la capacidad del modelo policristalino para predecir ensayos macroscópicos independientes en diferentes direcciones. En segundo lugar se estudió mediante la misma estrategia, la influencia del contenido de Neodimio (Nd) en las propiedades de una aleación de Mg-Mn-Nd, obtenida por extrusión. Se encontró que la adición de Nd produce una progresiva isotropización del comportamiento macroscópico. El modelo mostró que este incremento de la isotropía macroscópica era debido tanto a la aleatoriedad de la textura inicial como al incremento de la isotropía del comportamiento del cristal, con valores similares de las CRSSs de los diferentes modos de deformación. Finalmente, el modelo se empleó para analizar el efecto de la temperatura en el comportamiento del cristal de la aleación de Mg-Mn-Nd. La introducción en el modelo de los efectos non-Schmid sobre el modo de deslizamiento piramidal hc+ai permitió capturar el comportamiento mecánico a temperaturas superiores a 150_C. Esta es la primera vez, de acuerdo con el conocimiento del autor, que los efectos non-Schmid han sido observados en una aleación de Magnesio. The study of Magnesium and its alloys is a hot research topic in structural materials. In particular, special attention is being paid in understanding the relationship between microstructure and mechanical behavior in order to optimize the current alloy microstructures and guide the design of new alloys. However, the particular effect of several microstructural factors (precipitate shape, size and orientation, grain morphology distribution, etc.) in the mechanical performance of a Mg alloy is still under study. The combination of advanced characterization techniques and modeling at several length scales is necessary to improve the understanding of the relation microstructure and mechanical behavior. Respect to the simulation techniques, polycrystalline homogenization is a very useful tool to predict the macroscopic response from polycrystalline microstructure (grain size, shape and orientation distributions) and crystal behavior. The microstructure description is fully covered with modern characterization techniques (X-ray diffraction, EBSD, optical and electronic microscopy). However, the mechanical behaviour of single crystals is not well-known, especially in Mg alloys where the correct parameterization of the mechanical behavior of the different slip/twin modes is a very difficult task. A computational homogenization framework for predicting the behavior of Magnesium alloys has been developed in this thesis. The polycrystalline behavior was obtained by means of the finite element simulation of a representative volume element (RVE) of the microstructure including the actual grain shape and orientation distributions. The crystal behavior for the grains was accounted for a crystal plasticity model which took into account the physical deformation mechanisms, e.g. slip and twinning. Finally, the problem of the parametrization of the crystal behavior (critical resolved shear stresses (CRSS) and strain hardening rates of all the slip and twinning modes) was obtained by the development of an inverse optimization methodology, one of the main original contributions of this thesis. The inverse methodology aims at finding, by means of the Levenberg-Marquardt optimization algorithm, the set of parameters defining crystal behavior that best fit a set of independent macroscopic tests. The objectivity of the method and the uniqueness of solution as function of the input information has been numerically studied. The inverse optimization strategy was first used to obtain the crystal behavior of a rolled polycrystalline AZ31 Mg alloy that showed a marked basal texture and a strong plastic anisotropy. Four different deformation mechanisms: basal, prismatic and pyramidal hc+ai slip, together with tensile twinning were included to characterize the single crystal behavior. The validity of the resulting parameters was proved by the ability of the polycrystalline model to predict independent macroscopic tests on different directions. Secondly, the influence of Neodymium (Nd) content on an extruded polycrystalline Mg-Mn-Nd alloy was studied using the same homogenization and optimization framework. The effect of Nd addition was a progressive isotropization of the macroscopic behavior. The model showed that this increase in the macroscopic isotropy was due to a randomization of the initial texture and also to an increase of the crystal behavior isotropy (similar values of the CRSSs of the different modes). Finally, the model was used to analyze the effect of temperature on the crystal behaviour of a Mg-Mn-Nd alloy. The introduction in the model of non-Schmid effects on the pyramidal hc+ai slip allowed to capture the inverse strength differential that appeared, between the tension and compression, above 150_C. This is the first time, to the author's knowledge, that non-Schmid effects have been reported for Mg alloys.

Design, Technology and Characterization of Micromechanised Sensors and Actuators for Harsh Environments

Los sistemas micro electro mecánicos (MEMS) han demostrado ser una exitosa familia de dispositivos que pueden usarse como plataforma para el desarrollo de dispositivos con aplicaciones en óptica, comunicaciones, procesado de señal y sensorización. Los dispositivos MEMS estándar suelen estar fabricados usando tecnología de silicio. Sin embargo, el rendimiento de estos MEMS se puede mejorar si se usan otros materiales. Por ejemplo, el diamante nanocristalino (NCD) ofrece unas excelentes propiedades mecánicas, transparencia y una superficie fácil de funcionalizar. Por otro lado, el sistema de materiales (In; Ga; Al)N, los materiales IIIN, se pueden usar para producir estructuras monocristalinas con alta sensibilidad mecánica y química. Además, el AlN se puede depositar por pulverización catódica reactiva sobre varios substratos, incluyendo NCD, para formar capas policristalinas orientadas con alta respuesta piezoeléctrica. Adicionalmente, tanto el NCD como los materiales III-N muestran una gran estabilidad térmica y química, lo que los hace una elección idónea para desarrollar dispositivos para aplicaciones para alta temperatura, ambientes agresivos e incluso para aplicaciones biocompatibles. En esta tesis se han usado estos materiales para el diseño y medición de demostradores tecnológicos. Se han perseguido tres objetivos principales: _ Desarrollo de unos procesos de fabricación apropiados. _ Medición de las propiedades mecánicas de los materiales y de los factores que limitan el rendimiento de los dispositivos. _ Usar los datos medidos para desarrollar dispositivos demostradores complejos. En la primera parte de esta tesis se han estudiado varias técnicas de fabricación. La estabilidad de estos materiales impide el ataque y dificulta la producción de estructuras suspendidas. Los primeros capítulos de esta disertación se dedican al desarrollo de unos procesos de transferencia de patrones por ataque seco y a la optimización del ataque húmedo sacrificial de varios substratos propuestos. Los resultados de los procedimientos de ataque se presentan y se describe la optimización de las técnicas para la fabricación de estructuras suspendidas de NCD y materiales III-N. En un capítulo posterior se estudia el crecimiento de AlN por pulverización catódica. Como se ha calculado en esta disertación para obtener una actuación eficiente de MEMS, las capas de AlN han de ser finas, típicamente d < 200 nm, lo que supone serias dificultades para la obtención de capas orientadas con respuesta piezoeléctrica. Las condiciones de depósito se han mapeado para identificar las fronteras que proporcionan el crecimiento de material orientado desde los primeros pasos del proceso. Además, durante la optimización de los procesos de ataque se estudió un procedimiento para fabricar películas de GaN nanoporoso. Estas capas porosas pueden servir como capas sacrificiales para la fabricación de estructuras suspendidas de GaN con baja tensión residual o como capas para mejorar la funcionalización superficial de sensores químicos o biológicos. El proceso de inducción de poros se discutirá y también se presentarán experimentos de ataque y funcionalización. En segundo lugar, se han determinado las propiedades mecánicas del NCD y de los materiales III-N. Se han fabricado varias estructuras suspendidas para la medición del módulo de Young y de la tensión residual. Además, las estructuras de NCD se midieron en resonancia para calcular el rendimiento de los dispositivos en términos de frecuencia y factor de calidad. Se identificaron los factores intrínsecos y extrínsecos que limitan ambas figuras de mérito y se han desarrollado modelos para considerar estas imperfecciones en las etapas de diseño de los dispositivos. Por otra parte, los materiales III-N normalmente presentan grandes gradientes de deformación residual que causan la deformación de las estructuras al ser liberadas. Se han medido y modelado estos efectos para los tres materiales binarios del sistema para proporcionar puntos de interpolación que permitan predecir las características de las aleaciones del sistema III-N. Por último, los datos recabados se han usado para desarrollar modelos analíticos y numéricos para el diseño de varios dispositivos. Se han estudiado las propiedades de transducción y se proporcionan topologías optimizadas. En el último capítulo de esta disertación se presentan diseños optimizados de los siguientes dispositivos: _ Traviesas y voladizos de AlN=NCD con actuación piezoeléctrica aplicados a nanoconmutadores de RF para señales de alta potencia. _ Membranas circulares de AlN=NCD con actuación piezoeléctrica aplicadas a lentes sintonizables. _ Filtros ópticos Fabry-Pérot basados en cavidades aéreas y membranas de GaN actuadas electrostáticamente. En resumen, se han desarrollado unos nuevos procedimientos optimizados para la fabricación de estructuras de NCD y materiales III-N. Estas técnicas se han usado para producir estructuras que llevaron a la determinación de las principales propiedades mecánicas y de los parámetros de los dispositivos necesarios para el diseño de MEMS. Finalmente, los datos obtenidos se han usado para el diseño optimizado de varios dispositivos demostradores. ABSTRACT Micro Electro Mechanical Systems (MEMS) have proven to be a successful family of devices that can be used as a platform for the development of devices with applications in optics, communications, signal processing and sensorics. Standard MEMS devices are usually fabricated using silicon based materials. However, the performance of these MEMS can be improved if other material systems are used. For instance, nanocrystalline diamond (NCD) offers excellent mechanical properties, optical transparency and ease of surface functionalization. On the other hand, the (In; Ga; Al)N material system, the III-N materials, can be used to produce single crystal structures with high mechanical and chemical sensitivity. Also, AlN can be deposited by reactive sputtering on various substrates, including NCD, to form oriented polycrystalline layers with high piezoelectric response. In addition, both NCD and III-N materials exhibit high thermal and chemical stability, which makes these material the perfect choice for the development of devices for high temperatures, harsh environments and even biocompatible applications. In this thesis these materials have been used for the design and measurement of technological demonstrators. Three main objectives have been pursued: _ Development of suitable fabrication processes. _ Measurement of the material mechanical properties and device performance limiting factors. _ Use the gathered data to design complex demonstrator devices. In a first part of the thesis several fabrication processes have been addressed. The stability of these materials hinders the etching of the layers and hampers the production of free standing structures. The first chapters of this dissertation are devoted to the development of a dry patterning etching process and to sacrificial etching optimization of several proposed substrates. The results of the etching processes are presented and the optimization of the technique for the manufacturing of NCD and III-N free standing structures is described. In a later chapter, sputtering growth of thin AlN layers is studied. As calculated in this dissertation, for efficient MEMS piezoelectric actuation the AlN layers have to be very thin, typically d < 200 nm, which poses serious difficulties to the production of c-axis oriented material with piezoelectric response. The deposition conditions have been mapped in order to identify the boundaries that give rise to the growth of c-axis oriented material from the first deposition stages. Additionally, during the etching optimization a procedure for fabricating nanoporous GaN layers was also studied. Such porous layers can serve as a sacrificial layer for the release of low stressed GaN devices or as a functionalization enhancement layer for chemical and biological sensors. The pore induction process will be discussed and etching and functionalization trials are presented. Secondly, the mechanical properties of NCD and III-N materials have been determined. Several free standing structures were fabricated for the measurement of the material Young’s modulus and residual stress. In addition, NCD structures were measured under resonance in order to calculate the device performance in terms of frequency and quality factor. Intrinsic and extrinsic limiting factors for both figures were identified and models have been developed in order to take into account these imperfections in the device design stages. On the other hand, III-N materials usually present large strain gradients that lead to device deformation after release. These effects have been measured and modeled for the three binary materials of the system in order to provide the interpolation points for predicting the behavior of the III-N alloys. Finally, the gathered data has been used for developing analytic and numeric models for the design of various devices. The transduction properties are studied and optimized topologies are provided. Optimized design of the following devices is presented at the last chapter of this dissertation: _ AlN=NCD piezoelectrically actuated beams applied to RF nanoswitches for large power signals. _ AlN=NCD piezoelectrically actuated circular membranes applied to tunable lenses. _ GaN based air gap tunable optical Fabry-Pérot filters with electrostatic actuation. On the whole, new optimized fabrication processes has been developed for the fabrication of NCD and III-N MEMS structures. These processing techniques was used to produce structures that led to the determination of the main mechanical properties and device parameters needed for MEMS design. Lastly, the gathered data was used for the design of various optimized demonstrator devices.

Coupled Nonlinear Ginzburg-Landau and Mechanics Model for Martensitic Transformations in Polycrystals

Las transformaciones martensíticas (MT) se definen como un cambio en la estructura del cristal para formar una fase coherente o estructuras de dominio multivariante, a partir de la fase inicial con la misma composición, debido a pequeños intercambios o movimientos atómicos cooperativos. En el siglo pasado se han descubierto MT en diferentes materiales partiendo desde los aceros hasta las aleaciones con memoria de forma, materiales cerámicos y materiales inteligentes. Todos muestran propiedades destacables como alta resistencia mecánica, memoria de forma, efectos de superelasticidad o funcionalidades ferroicas como la piezoelectricidad, electro y magneto-estricción etc. Varios modelos/teorías se han desarrollado en sinergia con el desarrollo de la física del estado sólido para entender por qué las MT generan microstructuras muy variadas y ricas que muestran propiedades muy interesantes. Entre las teorías mejor aceptadas se encuentra la Teoría Fenomenológica de la Cristalografía Martensítica (PTMC, por sus siglas en inglés) que predice el plano de hábito y las relaciones de orientación entre la austenita y la martensita. La reinterpretación de la teoría PTMC en un entorno de mecánica del continuo (CM-PTMC) explica la formación de los dominios de estructuras multivariantes, mientras que la teoría de Landau con dinámica de inercia desentraña los mecanismos físicos de los precursores y otros comportamientos dinámicos. La dinámica de red cristalina desvela la reducción de la dureza acústica de las ondas de tensión de red que da lugar a transformaciones débiles de primer orden en el desplazamiento. A pesar de las diferencias entre las teorías estáticas y dinámicas dado su origen en diversas ramas de la física (por ejemplo mecánica continua o dinámica de la red cristalina), estas teorías deben estar inherentemente conectadas entre sí y mostrar ciertos elementos en común en una perspectiva unificada de la física. No obstante las conexiones físicas y diferencias entre las teorías/modelos no se han tratado hasta la fecha, aun siendo de importancia crítica para la mejora de modelos de MT y para el desarrollo integrado de modelos de transformaciones acopladas de desplazamiento-difusión. Por lo tanto, esta tesis comenzó con dos objetivos claros. El primero fue encontrar las conexiones físicas y las diferencias entre los modelos de MT mediante un análisis teórico detallado y simulaciones numéricas. El segundo objetivo fue expandir el modelo de Landau para ser capaz de estudiar MT en policristales, en el caso de transformaciones acopladas de desplazamiento-difusión, y en presencia de dislocaciones. Comenzando con un resumen de los antecedente, en este trabajo se presentan las bases físicas de los modelos actuales de MT. Su capacidad para predecir MT se clarifica mediante el ansis teórico y las simulaciones de la evolución microstructural de MT de cúbicoatetragonal y cúbicoatrigonal en 3D. Este análisis revela que el modelo de Landau con representación irreducible de la deformación transformada es equivalente a la teoría CM-PTMC y al modelo de microelasticidad para predecir los rasgos estáticos durante la MT, pero proporciona una mejor interpretación de los comportamientos dinámicos. Sin embargo, las aplicaciones del modelo de Landau en materiales estructurales están limitadas por su complejidad. Por tanto, el primer resultado de esta tesis es el desarrollo del modelo de Landau nolineal con representación irreducible de deformaciones y de la dinámica de inercia para policristales. La simulación demuestra que el modelo propuesto es consistente fcamente con el CM-PTMC en la descripción estática, y también permite una predicción del diagrama de fases con la clásica forma ’en C’ de los modos de nucleación martensítica activados por la combinación de temperaturas de enfriamiento y las condiciones de tensión aplicada correlacionadas con la transformación de energía de Landau. Posteriomente, el modelo de Landau de MT es integrado con un modelo de transformación de difusión cuantitativa para elucidar la relajación atómica y la difusión de corto alcance de los elementos durante la MT en acero. El modelo de transformaciones de desplazamiento y difusión incluye los efectos de la relajación en borde de grano para la nucleación heterogenea y la evolución espacio-temporal de potenciales de difusión y movilidades químicas mediante el acoplamiento de herramientas de cálculo y bases de datos termo-cinéticos de tipo CALPHAD. El modelo se aplica para estudiar la evolución microstructural de aceros al carbono policristalinos procesados por enfriamiento y partición (Q&P) en 2D. La microstructura y la composición obtenida mediante la simulación se comparan con los datos experimentales disponibles. Los resultados muestran el importante papel jugado por las diferencias en movilidad de difusión entre la fase austenita y martensita en la distibución de carbono en las aceros. Finalmente, un modelo multi-campo es propuesto mediante la incorporación del modelo de dislocación en grano-grueso al modelo desarrollado de Landau para incluir las diferencias morfológicas entre aceros y aleaciones con memoria de forma con la misma ruptura de simetría. La nucleación de dislocaciones, la formación de la martensita ’butterfly’, y la redistribución del carbono después del revenido son bien representadas en las simulaciones 2D del estudio de la evolución de la microstructura en aceros representativos. Con dicha simulación demostramos que incluyendo las dislocaciones obtenemos para dichos aceros, una buena comparación frente a los datos experimentales de la morfología de los bordes de macla, la existencia de austenita retenida dentro de la martensita, etc. Por tanto, basado en un modelo integral y en el desarrollo de códigos durante esta tesis, se ha creado una herramienta de modelización multiescala y multi-campo. Dicha herramienta acopla la termodinámica y la mecánica del continuo en la macroescala con la cinética de difusión y los modelos de campo de fase/Landau en la mesoescala, y también incluye los principios de la cristalografía y de la dinámica de red cristalina en la microescala. ABSTRACT Martensitic transformation (MT), in a narrow sense, is defined as the change of the crystal structure to form a coherent phase, or multi-variant domain structures out from a parent phase with the same composition, by small shuffles or co-operative movements of atoms. Over the past century, MTs have been discovered in different materials from steels to shape memory alloys, ceramics, and smart materials. They lead to remarkable properties such as high strength, shape memory/superelasticity effects or ferroic functionalities including piezoelectricity, electro- and magneto-striction, etc. Various theories/models have been developed, in synergy with development of solid state physics, to understand why MT can generate these rich microstructures and give rise to intriguing properties. Among the well-established theories, the Phenomenological Theory of Martensitic Crystallography (PTMC) is able to predict the habit plane and the orientation relationship between austenite and martensite. The re-interpretation of the PTMC theory within a continuum mechanics framework (CM-PTMC) explains the formation of the multivariant domain structures, while the Landau theory with inertial dynamics unravels the physical origins of precursors and other dynamic behaviors. The crystal lattice dynamics unveils the acoustic softening of the lattice strain waves leading to the weak first-order displacive transformation, etc. Though differing in statics or dynamics due to their origins in different branches of physics (e.g. continuum mechanics or crystal lattice dynamics), these theories should be inherently connected with each other and show certain elements in common within a unified perspective of physics. However, the physical connections and distinctions among the theories/models have not been addressed yet, although they are critical to further improving the models of MTs and to develop integrated models for more complex displacivediffusive coupled transformations. Therefore, this thesis started with two objectives. The first one was to reveal the physical connections and distinctions among the models of MT by means of detailed theoretical analyses and numerical simulations. The second objective was to expand the Landau model to be able to study MTs in polycrystals, in the case of displacive-diffusive coupled transformations, and in the presence of the dislocations. Starting with a comprehensive review, the physical kernels of the current models of MTs are presented. Their ability to predict MTs is clarified by means of theoretical analyses and simulations of the microstructure evolution of cubic-to-tetragonal and cubic-to-trigonal MTs in 3D. This analysis reveals that the Landau model with irreducible representation of the transformed strain is equivalent to the CM-PTMC theory and microelasticity model to predict the static features during MTs but provides better interpretation of the dynamic behaviors. However, the applications of the Landau model in structural materials are limited due its the complexity. Thus, the first result of this thesis is the development of a nonlinear Landau model with irreducible representation of strains and the inertial dynamics for polycrystals. The simulation demonstrates that the updated model is physically consistent with the CM-PTMC in statics, and also permits a prediction of a classical ’C shaped’ phase diagram of martensitic nucleation modes activated by the combination of quenching temperature and applied stress conditions interplaying with Landau transformation energy. Next, the Landau model of MT is further integrated with a quantitative diffusional transformation model to elucidate atomic relaxation and short range diffusion of elements during the MT in steel. The model for displacive-diffusive transformations includes the effects of grain boundary relaxation for heterogeneous nucleation and the spatio-temporal evolution of diffusion potentials and chemical mobility by means of coupling with a CALPHAD-type thermo-kinetic calculation engine and database. The model is applied to study for the microstructure evolution of polycrystalline carbon steels processed by the Quenching and Partitioning (Q&P) process in 2D. The simulated mixed microstructure and composition distribution are compared with available experimental data. The results show that the important role played by the differences in diffusion mobility between austenite and martensite to the partitioning in carbon steels. Finally, a multi-field model is proposed by incorporating the coarse-grained dislocation model to the developed Landau model to account for the morphological difference between steels and shape memory alloys with same symmetry breaking. The dislocation nucleation, the formation of the ’butterfly’ martensite, and the redistribution of carbon after tempering are well represented in the 2D simulations for the microstructure evolution of the representative steels. With the simulation, we demonstrate that the dislocations account for the experimental observation of rough twin boundaries, retained austenite within martensite, etc. in steels. Thus, based on the integrated model and the in-house codes developed in thesis, a preliminary multi-field, multiscale modeling tool is built up. The new tool couples thermodynamics and continuum mechanics at the macroscale with diffusion kinetics and phase field/Landau model at the mesoscale, and also includes the essentials of crystallography and crystal lattice dynamics at microscale.

Strategies to unblock the n-GaAs surface when electrodepositing Bi from acidic solutions

Bismuth ultra-thin films grown on n-GaAs electrodes via electrodeposition are porous due to a blockade of the electrode surface caused by adsorbed hydrogen when using acidic electrolytes. In this study, we discuss the existence of two sources of hydrogen adsorption and we propose different routes to unblock the n-GaAs surface in order to improve Bi films compactness. Firstly, we demonstrate that increasing the electrolyte temperature provides compact yet polycrystalline Bi films. Cyclic voltammetry scans indicate that this low crystal quality might be a result of the incorporation of Bi hydroxides within the Bi film as a result of the temperature increase. Secondly, we have illuminated the semiconductor surface to take advantage of photogenerated holes. These photocarriers oxidize the adsorbed hydrogen unblocking the surface, but also create pits at the substrate surface that degrade the Bi/GaAs interface and prevent an epitaxial growth. Finally, we show that performing a cyclic voltammetry scan before electrodeposition enables the growth of compact Bi ultra-thin films of high crystallinity on semiconductor substrates with a doping level low enough to perform transport measurements.

Supercondutividade em ligas de Ta1-xZrx

No presente estudo, amostras policristalinas ricas em Ta e com estequiometrias Ta1-xZrx; x < 0.15; foram preparadas através da mistura apropriada dos elementos metálicos, os quais foram fundidos em forno a arco elétrico sobre uma placa de cobre refrigerada a água e sob atmosfera de argônio de alta pureza. Os padrões de difração de raios-X das ligas, como fundidas (as cast) e tratadas termicamente a 850 °C por 24 h, revelaram a ocorrência de uma estrutura cristalina cúbica de corpo centrada bcc, tipo W, e parâmetros de rede que aumentam suavemente com o aumento do teor de Zr nas ligas. Medidas de susceptibilidade magnética dc, conduzidas nas condições de resfriamento da amostra em campo zero (ZFC) e do resfriamento com o campo magnético aplicado (FC), indicaram que supercondutividade volumétrica é observada abaixo de ~ 5.8, 6.9, 7.0 K em amostras com x = 0.05, 0.08, e 0.10, respectivamente. Essas temperaturas críticas supercondutoras são bastante superiores àquela observada no Ta elementar ~ 4.45 K. Medidas de resistividade elétrica na presença de campos magnéticos aplicados de até 9 T confirmaram a temperatura crítica supercondutora das amostras estudadas. O campo crítico superior Hc2 e o comprimento de coerência E foram estimados a partir dos dados de magnetorresistência. Os valores estimados de Hc2 foram de ~ 0.46, 1.78, 3.85 e 3.97 T, resultando em valores de E ~ 26.0, 13.6, 9.2 e 9.1 nm para as ligas as cast com x = 0.00, 0.05, 0.08 e 0.10, respectivamente. A partir dos dados experimentais do calor específico Cp das ligas, magnitudes estimadas do salto em Cp nas vizinhanças das transições supercondutoras indicaram valores maiores que o previsto pela teoria BCS. Utilizando as equações analíticas derivadas da teoria do acoplamento forte da supercondutividade foi então proposto que o aumento da temperatura de transição supercondutora nas ligas devido a substituição parcial do Ta por Zr está intimamente relacionado ao aumento do acoplamento elétron-fônon, visto que a densidade de estados eletrônicos no nível de Fermi foi estimada ser essencialmente constante através da série Ta1-xZrx com x < 0.10.

Ultrasound-assisted selective hydrogenation of C-5 acetylene alcohols with Lindlar catalysts

The selective hydrogenation of 2-methyl-3-butyn-2-ol (MBY) was performed in the presence of Lindlar catalyst, comparing conventional stirring with sonication at different frequencies of 40, 380 and 850 kHz. Under conventional stirring, the reaction rates were limited by intrinsic kinetics, while in the case of sonication, the reaction rates were 50–90% slower. However, the apparent reaction rates were found to be significantly frequency dependent with the highest rate observed at 40 kHz. The original and the recovered catalysts after the hydrogenation reaction were compared using bulk elemental analysis, powder X-ray diffraction and scanning and transmission electron microscopy coupled with energy-dispersive X-ray analysis. The studies showed that sonication led to the frequency-dependent fracturing of polycrystalline support particles with the highest impact caused by 40 kHz sonication, while monocrystals were undamaged. In contrast, the leaching of Pd/Pb particles did not depend on the frequency, which suggests that sonication removed only loosely-bound catalyst particles.

Detrital zircon geochronology data, petrographic point count data and paleocurrent indicator data of Triassic turbidites in the Nanpanjiang Basin, South China

Triassic turbidites of the Nanpanjiang basin of south China represent the most expansive and voluminous siliciclastic turbidite accumulation in south China. The Nanpanjiang basin occurs at a critical junction between the southern margin of the south China plate and the Indochina, Siamo and Sibumasu plates to the south and southwest. The Triassic Yangtze carbonate shelf and isolated carbonated platforms in the basin have been extensively studied, but silicilastic turbidites in the basin have received relatively little attention. Deciphering the facies, paleocurrent indicators and provenance of the Triassic turbidites is important for several reasons: it promises to help resolve the timing of plate collisions along suture zones bordering the basin to the south and southwest, it will enable evaluation of which suture zones and Precambrian massifs were source areas, and it will allow an evaluation of the impact of the siliciclastic flux on carbonate platform evolution within the basin. Turbidites in the basin include the Early Triassic Shipao Formation and the Middle-Late Triassic Baifeng, Xinyuan, Lanmu Bianyang and Laishike formations. Each ranges upward of 700 m and the thickest is nearly 3 km. The turbidites contain very-fine sand in the northern part of the basin whereas the central and southern parts of the basin also commonly contain fine and rarely medium sand size. Coarser sand sizes occur where paleocurrents are from the south, and in this area some turbidites exhibit complete bouma sequences with graded A divisions. Successions contain numerous alternations between mud-rich and sand-rich intervals with thickness trends corresponding to proximal/ distal fan components. Spectacularly preserved sedimentary structures enable robust evaluation of turbidite systems and paleocurrent analyses. Analysis of paleocurrent measurements indicates two major directions of sediment fill. The northern part of the basin was sourced primarily by the Jiangnan massif in the northeast, and the central and southern parts of the basin were sourced primarily from suture zones and the Yunkai massif to the south and southeast respectively. Sandstones of the Lower Triassic Shipao Fm. have volcaniclastic composition including embayed quartz and glass shards. Middle Triassic sandstones are moderately mature, matrix-rich, lithic wackes. The average QFL ratio from all point count samples is 54.1/18.1/27.8% and the QmFLt ratio is 37.8/ 18.1/ 44.1%. Lithic fragments are dominantly claystone and siltstone clasts and metasedimentary clasts such as quartz mica tectonite. Volcanic lithics are rare. Most samples fall in the recycled orogen field of QmFLt plots, indicating a relatively quartz and lithic rich composition consistent with derivation from Precambrian massifs such as the Jiangnan, and Yunkai. A few samples from the southwest part of the basin fall into the dissected arc field, indicating a somewhat more lithic and feldspar-rich composition consistent with derivation from a suture zone Analysis of detrial zircon populations from 17 samples collected across the basin indicate: (1) Several samples contain zircons with concordant ages greater than 3000 Ma, (2) there are widespread peaks across the basin at 1800 Ma and 2500, (3) a widespread 900 Ma population, (3) a widespread population of zircons at 440 Ma, and (5) a larger population of younger zircons about 250 Ma in the southwestern part which is replaced to the north and northwest by a somewhat older population around 260-290 Ma. The 900 Ma provenance fits derivation from the Jiangnan Massif, the 2500, 1800, and 440 Ma provenance fits the Yunkai massif, and the 250 Ma is consistent with convergence and arc development in suture zones bordering the basin on the south or southwest. Early siliciclastic turbidite flux, proximal to source areas impacted carbonate platform evolution by infilling the basin, reducing accommodation space, stabilizing carbonate platform margins and promoting margin progradation. Late arrival, in areas far from source areas caused margin aggradation over a starved basin, development of high relief aggradational escarpments and unstable scalloped margins.

Composition of Aleutian forearc sediments

The ultimate composition of any sandstone is affected by a host of primary and secondary factors, including the lithologies present in source terranes, climate, depositional environment and diagenesis. In the case of a subduction complex, however, unequivocal identification of detrital provenance may be impossible because of the cumulative effects of tectonic and sedimentary transport. Long-distance sedimentary transport (> 1000 km) is common within trenches, and abyssal-plain turbidites can be tectonically transported for long distances as the underlying oceanic basement drifts towards a subduction front. Post-accretionary displacement can occur as a consequence of strike-slip faulting, and the total distance of tectonic dislocation may reach several thousand kilometers. The present-day Aleutian forearc region (North Pacific Ocean) illustrates many of the "problems" which typify subduction zones. Several petrologic suites can be identified, and there are significant variations in detrital modes in both time and space. The Aleutian region serves as a sobering modern analog for accreted rock units such as the Franciscan Complex of California, where intercalations of discrete sandstone suites have been noted. In the absence of paleomagnetic control, interpretations of sediment provenance within ancient subduction complexes probably should be restricted to the generic level.