In this thesis, we will discuss the construction of algorithms for solving Constraint Satisfaction Problems (CSPs), and describe two new ways of approaching them. Both approaches are based on the idea that it is sometimes faster to solve a large number of restricted problems than a single, large, problem. One of the strong points of these methods is that the intuition behind them is fairly simple, which is a definite advantage over many techniques currently in use. The first method, the covering method, can be described as follows: We want to solve a CSP with n variables, each having a domain with d elements. We have access to an algorithm which solves problems where the domain has size e < d, and we want to cover the original problem using a number of restricted instances, in such a way that the solution set is preserved. There are two ways of doing this, depending on the amount of work we are willing to invest; either we construct an explicit covering and end up with a deterministic algorithm for the problem, or we use a probabilistic reasoning and end up with a probabilistic algorithm. The second method, called the partitioning method, relaxes the demand on the underlying algorithm. Instead of having a single algorithm for solving problems with domain less than d, we allow an arbitrary number of them, each solving the problem for a different domain size. Thus by splitting, or partitioning, the domain of the large problem, we again solve a large number of smaller problems before arriving at a solution. Armed with these new techniques, we study a number of different problems; the decision problems (d, l)-CSP and k-Colourability, together with their counting counterparts, as well as the optimisation problems Max Ind CSP, Max Value CSP, Max CSP, and Max Hamming CSP. Among the results, we find a very fast, polynomial space algorithm for determining k-colourability of graphs.

Ce mémoire présente une approche pluridisciplinaire (pétrologie, spectroscopie Raman et MET) de l'évolution des microstructures des serpentinites avec les conditions métamorphiques et la déformation afin de préciser leur comportement en contexte de convergence. Expérimentalement, les différentes variétés de serpentines se compriment de façon régulière jusqu'à 10 GPa à température ambiante. L'augmentation de pression est principalement ajustée par réduction de l'espace interfoliaire. Les liaisons hydrogène liant les feuillets ne sont pas renforcées avec la pression. L'analyse d'échantillons de serpentinites de HP-BT provenant de Cuba et des Alpes a confirmé que l'antigorite est la variété stable à haute pression. Les microstructures de ce minéral varient avec le degré métamorphique. Les antigorites de haut degré, au delà du faciès des schistes bleus, ne présentent pas le désordre polysomatique intracristallin qui caractérise les antigorites de bas degré. Une second étape de mise en ordre des microstructures est proposée sous les conditions éclogitiques par l'élimination des défauts microstructuraux. Mais les serpentinites étant très sensibles à toute déformation rétromorphique, cette mise en ordre n'a pu être observée que sous des conditions de préservation exceptionnelle (Cuba) et n'a pas été confirmée dans les échantillons alpins. Dans les serpentinite alpines, la déformation se manifeste à bas degré métamorphique (transition SV-SB) par des structures cassantes à l'échelle du cristal. Sous des conditions PT plus sévères, la déformation est accommodée principalement par des phénomènes de dissolution recristallisation qui semblent persister jusqu'aux stades éclogitiques. Les défauts plans observés dans les antigorites suggèrent aussi une contribution à la déformation par glissement des feuillets le long des plans (001).

Els polímers són una sèrie de compostos que troben un ampli ventall d'aplicacions en la indústria actual. Un exemple són les espumes de poliuretà, estructures de tipus cel·lular obtingudes mitjançant la reacció química entre compostos de tipus isocianat i compostos de tipus poliol (polièters amb diferent nombre de grups hidroxil). És imprescindible l'ús d'additius d'estructura tensioactiva (surfactants de silicona) per estabilitzar el procés d'espumació i per proporcionar una estructura cel·lular ordenada i homogènia en mida i distribució. La síntesis i caracterització de les molècules precursores (polihidrosiloxans i polièters al·lílics), l'estudi de la reacció d'hidrosililació com a via d'obtenció dels diferents surfactants per reacció d'addició entre els polihidrosiloxans i els polièters al·lílics i la caracterització i avaluació en formulacions comercials de poliuretà dels surfactants sintetitzats han constituït els objectius del present treball.MEMÒRIALa Tesi Doctoral ha estat presentada seguint el següent esquema:CAPÍTOL I. INTRODUCCIÓ A LA QUÍMICA DEL POLIURETÀ.Es presenten els principis de la química del poliuretà, fent esment dels recents avenços en la síntesis i caracterització d'aquests compostos polimèrics, així com un apartat concret centrat en els surfactants de silicona. Es presenten les estructures habituals d'aquests compostos comercials i es detallen les reaccions de síntesi i les característiques físiques que aquests compostos proporcionen a les espumes de poliuretà.CAPÍTOL II. OBJECTIUS.1.- Síntesis y caracterització d'una àmplia gamma de poliglicols al·lílics i de polihidrosiloxans amb grups hidrur reactius, ambdós precursors d'estructures polimèriques de tipus surfactant.2.- Estudi de la reacció d'hidrosililació com a via de formació d'enllaços Si-C no hidrolitzables, mitjançant la reacció d'addició entre els substrats al·lílics insaturats i els polisiloxans amb grups hidrur reactius.3.- Caracterització de les estructures polimèriques de tipus surfactant sintetitzades i avaluació d'aquestes en formulacions de poliuretà, a fi de relacionar l'estructura química d'aquests oligómers amb els efectes físics que originen en l'espuma de poliuretà.CAPÍTOL III. SÍNTESI I CARACTERITZACIÓ DE SUBSTRATS AL·LÍLICS INSATURATS DE TIPUS POLIGLICOL.S'han caracteritzat per HPLC-UV una sèrie de polietilenglicols comercials. S'ha estudiat la reacció de derivatització al·lílica sobre els grups hidroxil dels polièters comercials (PEG, PPG i copolímers PEG-PPG) i s'han caracteritzat exhaustivament els productes sintetitzats (1H,13C-RMN, GC, GC-MS, FTIR, ESI-MS, HPLC-UV). S'ha iniciat un estudi de polimerització aniònica sobre nous epòxids amb un punt de diversitat molecular, sintetitzant-se i caracteritzant-se els corresponents nous polièters obtinguts. CAPÍTOL IV. SÍNTESI I CARACTERITZACIÓ DE POLIHIDROSILOXANS REACTIUS.S'estudia la síntesis de polihidrosiloxans amb grups hidrur reactius, mitjançant la reacció de polimerització aniònica d'obertura d'anell ("AROP, anionic ring opening polimerization") i mitjançant la reacció de polimerització per equilibració catiònica. Es presenta una caracterització exhaustiva dels productes sintetitzats i es descriu la naturalesa de la microestructura polimèrica a partir de la distribució bivariant dels copolímers PDMS-co-PHMS (poli(dimetilsiloxà)-co-poli(hidrometilsiloxà)).CAPÍTOL V. ESTUDI SISTEMÀTIC DE LA REACCIÓ D'HIDROSILILACIÓ.S'ha estudiat la reacció d'hidrosililació amb la finalitat de sintetitzar estructures copolimèriques poliglicol-polisiloxà a partir de la reacció de polisiloxans hidrur reactius i polièters al·lílics. S'han provat diferents catalitzadors (Pt/C 5%, cat. de Speier i cat. de Karstedt), s'han sintetitzat diferents estructures tensoactives (lineals i ramificades) i s'ha modelitzat les diferents reaccions secundàries observades, per presentar un estudi mecanístic de la reacció d'hidrosililació aplicada a la síntesis de molècules d'elevat PM a partir de la reacció entre substrats al·lílics insaturats i polihidrosiloxans.CAPÍTOL VI. AVALUACIÓ DELS SURFACTANTS EN FORMULACIONS DE POLIURETÀ.S'ha estudiat la idoneïtat dels surfactants de silicona sintetitzats en diferents formulacions de poliuretà comercials. S'ha relacionat el comportament físic d'aquests surfactants en les espumes de poliuretà amb la seva estructura química a partir de l'anàlisi per microscòpia electrònica de rastreig.CAPÍTOL VII. CONCLUSIONS.S'han esposat les conclusions extretes de cada capítol. / The present review has been structured in three parts, firstly a general introduction to polyurethane chemistry and the specific role that silicone surfactants develop, secondly a memory that contents a concise description of the PhD Thesis structure and finally the presentation of the results obtained and their discussion.1.- INTRODUCTIONPolyurethane is one of the most important polymers used in the industry worldwide. The reaction, discovered in 1937 by Otto Bayer, consists in a polyaddition reaction between hydroxyl compounds and isocyanate groups. This reaction forms the new urethane group (strictly a carbamat group) that provide the chemical structure of the polymer. In the presence of different amounts of water, another reaction is involved, between isocyanate groups and water, in order to obtain urea groups. This reaction is very important because, besides generates new polyurea structures it generates carbon dioxide (CO2), the blowing aggent mostly used in the formulations of polyurethane.Actually, a lot of applications of polyurethane products take advantage on the specific cellular structure that presents, specially flexible foams in mattresses, sofas, seats, rigid foams as insulation panels and semi-rigid foams in the automotive industry. The cellular structure is obtained in the foaming process of the reaction, which involves the generation of a gas (usually CO2 although other compounds like pentane, HCFC's and external CO2 had been used) and the growing of the cell because of the exothermic process. The foaming process is usually an unstable state that needs the participation of a surfactant, a silicone structure that provides the necessary stabilizing capacity in the foaming process. Moreover, another important feature of silicone surfactants is to improve the order and distribution of the cells in the foam.Generally, the chemical structure of silicone surfactants is co polymeric, consisting in an hydrophobic part composed by the polysiloxane group and an hydrophilic part, usually being made up of different types of polyether structures. This different physical behaviour in the same molecule provides the specific characteristics of silicone surfactants. In order to obtain commercially available surfactants, it has been necessary to study the synthesis and the characterization of the components in the surfactant molecule (the polyether and the polysiloxane groups) and to perform a study of the hydrosilylation, the chemical reaction that generates the co polymeric structure by the reaction between the polyether and the polysiloxane constituents.2.- PhD THESIS STRUCTUREThe thesis has been organized in seven chapters, being the first of them the introduction to polyurethane chemistry. In the second chapter are exposed the aims of the work. The third chapter is the synthesis and characterization of polyether type unsaturated substrates, the fourth is the synthesis and characterization of reactive polyhydrosiloxanes and the fifth is the systematic study on the hydrosilylation reaction. The evaluation of surfactants in different polyurethane formulations is described in the sixth chapter whereas the concluding remarks have been reported in the seventh chapter.3.- RESULTS AND DISCUSSIONThe first part of this study details the synthesis and characterization of unsaturated polyethers, substrates of the hydrosilylation reaction. Thus, the allylic modification of commercial monohidroxy polyethers has allowed the synthesis of this unsaturated substrates that can react through hydrosilylation reaction with Si-H bonds. In order to obtain new polyether structures, an investigation about the anionic polymerisation of new epoxies has been developed. These new polyether structures have been extensively characterized to estimate the polymerization degree and their molecular weight.The synthesis and characterization of reactive polysiloxane compounds (containing Si-H bonds in their structure) has been the second aim of this work. In order to obtain these polysiloxane structures, both anionic polymerization of cyclic trisiloxane compounds and cationic polymerization have been studied. Its interesting to emphasize that the results have shown that the microstructure of the copolymeric poly(dimethylsiloxane)-co-poly(hidromethylsiloxane) is statistical in the monomeric distribution (based on MALDI-TOF-MS and 29Si-RMN results), thus the chemical composition along the polymer chain become constant.Little information has been reported in the literature about the hydrosilylation as source of polymer structures. In order to clarify the synthetic behaviour of the reaction between polysiloxanes with Si-H bonds and allylic polyethers, an exhaustive study of the hydrosilylation as been developed. Different catalysts (Speier's, Karstedt's and an heterogeneous Pt/C 5% have been studied), concluding that the Karstedt catalyst has given the better behaviour.Finally, the evaluation of the surfactant structures synthesized in different commercially available polyurethane formulations as allowed obtaining a relation between the chemical structure of the silicone surfactant and the physical behavior in the foaming process. SEM has been the technique of choice to better characterize the otained foams.

L'estudi de la formació de microstructures en processos de solidificació té importants aplicacions científiques i tecnològiques. L'aparició d'aquestes estructures determina les propietats elèctriques i mecàniques del material solidificat, i té per tant un important interès tecnològic. La majoria d'aquestes estructures tenen el seu origen en una desestabilització morfològica de la interfase sòlid-líquid que es produeix a mesura que el front avança. Per aquest motiu, l'estudi del comportament dinàmic de la interfase resulta essencial per entendre els mecanismes que intervenen en la creació d'aquests patrons. Els processos de solidificació solen descriure's mitjançant problemes de contorn mòbil. Aquestes formulacions consten d'equacions per a la difusió del calor i de massa en les fases sòlida i líquida, que s'han de resoldre imposant l'acompliment de diverses condicions de contorn mòbils a la interfase. Els problemes de contorn mòbil, malgrat contenir tots els elements que intervenen en la dinàmica i ser de molta utilitat en l'àmbit de l'enginyeria, requereixen un cost computacional que no permet simular sistemes reals en règims interfacials complexos. Els mètodes de camp de fase (phase-field methods), van aparèixer a principis dels anys vuitanta com una eina computacional que permetia l'estudi de fenòmens interfacials de caire general. Aquests mètodes descriuen la forma de la interfase mitjançant un camp continu que pren valors diferents i constants en les dues fases. La dinàmica d'aquest camp és llavors acoblada al camp de difusió de calor o massa que determina l'avanç del front de solidificació. Un dels avantatges d'aquests mètodes és que la seva simulació no requereix d'algorismes de seguiment de la interfase (front tracking algorithsms). És ben conegut que les característiques principals de les microestructures en solidificació, es determinen durant els transitoris inicials en els que els corrents de massa i calor s'adapten a la evolució dinàmica del front. Un dels objectius en aquesta tesi és el de fer servir mètodes de camp de fase per descriure de forma quantitativa aquests transitoris. Per comprovar la validesa del nostre procediment, es realitza una comparació quantitativa entre els resultats numèrics obtinguts i diferents prediccions analítiques derivades del problema de contorn mòbil. Per un altra banda, la desestabilització del front es veu afectada per la presència de fluctuacions al sistema. Aquestes pertorbacions microscòpiques poden tenir el seu origen a les fluctuacions termodinàmiques internes, o bé ser conseqüència de imperfeccions experimentals que actuen com a font externa de soroll. El segon objectiu d'aquesta tesi és la introducció de fluctuacions en mètodes de camp de fase, de forma que es pugui estudiar l'amplificació dinàmica de les pertorbacions microscòpiques que acaben donant lloc a estructures macroscòpiques. Per finalitzar, analitzem el problema de la selecció en solidificació direccional. Estudiem els règims lineal i no-lineal, tot determinant les condicions, el moment i la forma en que apareixen les estructures dendrítiques i cel·lulars. / Crystal growth is a non-equilibrium process which involves physical mechanisms at very different scales. When a solidification front advances, mass and heat diffusion processes are combined with interfacial phenomena like capillarity or kinetic attachment. A complex interplay between these mechanisms gives rise to complex interfacial structures like snowflakes or cellular patterns. The formation of microstructures in solidification has both a scientific and a technological interest. On one hand, the study of the different interfacial structures constitutes a fundamental problem in the field of non-equilibrium pattern-forming systems. On the other side, from a technological point of view, the presence of microstructures determines the final mechanical and electrical properties of the processed material. Directional solidification is a controlled solidification technique which reproduces the conditions occurring in some important metallurgical processes like material casting or zone melting refining procedures. In a directional solidification experiment, the alloy sample is pulled at a constant velocity towards the cold region of an externally-imposed temperature gradient. Depending on the growth conditions, a morphological destabilization of the solid-liquid interface occurs during early transient stages. These initial transients are associated to a solute redistribution process due to the adaptation of the concentration field to the forced motion of the sample. The main objective of this thesis is to study the dynamical evolution of the morphological deformations of the front from these initial transients to the final stages where the properties of the interfacial pattern are determined. An important point in this process is that the internal fluctuations of the system play the role of an initiation mechanism for the morphological deformations of the front. During the initial transients, some of these microscopic perturbations are amplified by several orders of magnitude, and a range of wavelengths becomes morphologically unstable. The interfacial deformations of the front can be then characterized by means of power spectrum techniques. In order to study the dynamical evolution of the solidification front in directional solidification, we have used both theoretical and computational approaches: The main computational technique used in this thesis is the phase-field approach, which is a powerful method to simulate complex interfacial phenomena. The model equations describe the evolution of a continuous field , which takes different constant values at the solid and liquid bulks of the system. This field is then coupled with equations for the mass diffusion, and allows performing numerical studies without simulating the standard Stefan-like moving boundary problem. The phase-field method provides a diffuse interface description in which the transition from solid to liquid happens in a region of a certain thickness. The interface thickness introduces a new length in the simulations which must be taken into account to recover quantitative results. One major point in this thesis concerns with the introduction of fluctuations in phase-field methods. In the particular case of variational phase-field formulations -in which the model equations can be derived from a single free energy functional for the whole system-, the introduction of fluctuations can be done by applying the Fluctuation-Dissipation theorem. Variational formulations, however, although their appealing structure, present a poor computational efficiency and cannot be used to obtain quantitative results. To this extent, we have derived a general approach which does not relay in the Fluctuation-Dissipation assumption and permits to introduce fluctuations in both variational and non-variational phase-field formulations. Well-established analytical techniques like boundary integral methods for the transient front position and linear stability analysis of the interface during the transient have been used as theoretical predictions for the computational results. The dynamical evolution of the solidification front can be divided in two stages: A linear regime where the initial noise is amplified, and a non-linear coarsening process where the final properties of the interfacial pattern are selected. We have studied these different stages of the solidification process by using the phase-field approach, and good agreement is obtained when comparing with well-established theoretical and experimental predictions.

Binäre Polymerbürsten bestehen aus zwei verschiedenen Polymertypen, die nebeneinander auf dem gleichen Trägermaterial verankert sind. Wenn diese Polymere unterschiedliche Benetzungseigenschaften haben, können damit schaltbare Oberflächen produziert werden. Abhängig vom Lösungsmittel, dem man die binäre Polymerbürste aussetzt, streckt sich entweder das hydrophile oder das hydrophobe Polymer zum Lösungsmittel hin, während die zweite Komponente nahe der Oberfläche verbleibt. Durch diese vertikale Phasenseparation kann temporär eine bestimmte Oberflächeneigenschaft erzeugt werden. Allerdings verschwindet diese sofort wieder, wenn ein anderes Lösungsmittel die binäre Bürste benetzt, sei es durch direkten Kontakt oder über die Gasphase. In der vorliegenden Arbeit wurde untersucht, ob es möglich ist, neuartige schaltbare binäre Polymerbürsten bestehend aus einem hydrophilen und einem hydrophoben Polymer angebunden auf Siliziumwafern herzustellen, deren Schaltfähigkeit durch photochemische Vernetzung unterbunden werden kann. Geprüft worden ist unter anderem, inwiefern sich hydrophober und hydrophiler Zustand der Schicht fixieren lassen und ob daraus resultierend, eine entsprechende Strukturierung der Oberfläche nach Bestrahlung durch eine geeignete Fotomaske oder durch fokussiertes Licht nachweisbar ist. Als hydrophobe Komponente wurden photovernetzbare Styren/2-(4’-Styryl)-inden-Copolymere verwendet, als hydrophile Komponente kam Polyvinylpyridin zum Einsatz. Mit einem speziellen Oberflächeninitiator konnten durch „Grafting from“ binäre Polymerbürsten mit bis zu 300 nm Schichtdicke erzeugt werden. Es ist gelungen, diese schaltbaren Schichten durch selektive photochemische Vernetzung einer der Bürstenkomponenten im hydrophilen oder im hydrophoben Zustand zu fixieren, was durch Kontaktwinkelmessung nachgewiesen werden konnte. Wie beabsichtigt, verlieren dabei die vernetzten Bereiche ihre Schaltfähigkeit. Es ließen sich feine Oberflächenstrukturen mittels Bestrahlung durch eine Fotomaske erzeugen, die sichtbar werden, wenn man sie mit Wasser benetzt bzw. Wasserdampf aussetzt.

In der vorliegenden Arbeit wird ein neues Verfahren zur Dünnschichtverkappung von oberflächennahen Mikrostrukturen vorgestellt. Ausgehend von den speziellen Anforderungen an die Verkappung oberflächennaher Mikrostrukturen, insbesondere von Strukturen mit hohem Aspektverhältnis, wurden die Verwendung eines Fluor-Kohlenstoff-Polymers als Opferschichtmaterial und die Eignung unterschiedlicher Schichtstapel zur Realisierung der Dünnschichtkappe untersucht. Die resultierende Technologie ermöglicht eine durchgehend trockenchemische Prozessierung. Für die Abschätzung der notwendigen Schichtdicken und den geometrischen Entwurf der Kappenstrukturen, wurden auf Basis der Plattentheorie analytische und numerische Modelle erstellt. Verschiedene Materialkombinationen bestehend aus Siliziumoxid, Siliziumnitrid und Aluminium wurden hinsichtlich ihrer mechanischen und thermomechanischen Eigenschaften untersucht und bewertet. Ein weiterer Schwerpunkt lag auf der Entwicklung und Optimierung der Opferschichtprozesse, sowie deren Integration in die Gesamttechnologie. Die Eignung der plasmagestützten Prozesse zur Abscheidung und Strukturierung des Opferpolymers wurde durch die Fertigung von verkapselten Beschleunigungssensoren nachgewiesen. Ein ausreichender hermetischer Verschluss der Dünnschichtkappe konnte durch die Messung der viskosen Dämpfung an Feder-Masse-Schwingern bestätigt werden.

Deformation and partial melting have long been recognized to occur together, but differentiating which actually occurred first has remained enigmatic. Prevailing theories suggest that partial melting typically occurs first, and deformation is localized into melt-rich areas because they are rheologically weak. However, evidence from three different areas, suggests the role of strain has been underestimated in localizing partial melting. The Wet Mountains of central Colorado provide evidence for synchronous partial melting and deformation, with each process enhancing the other. Throughout the Wet Mountains, deformation is concentrated in areas where melt producing reactions occurred, and melt appears to be localized along deformation-related features. Melt microstructures present within the Wet Mountains correlate well with crustal-scale plutons and magmatic bodies and provide a proxy for crustal-scale melt flow. Granitic gneisses from the Llano Uplift, central Texas, provide evidence for partial melting occurring within small-scale shear zones and surrounding country rocks, synchronously. In the field, shear zones appear to contain former melt, whereas the country rock does not provide macroscopic evidence for partial melting. However, detailed microstructural investigation of shear zones and country rocks indicates the same density of melt microstructures, in both rock types. Melt microstructures are important for understanding the full melting history of a rock and without detailed structural and petrographic analysis, erroneous conclusions may be reached. Granulite-facies migmatites of the Albany-Fraser Orogen, southwestern Australia, have undergone partial melting, synchronous with three phases of bidirectional extension. Four major groups of leucosomes, including: foliation-parallel, cross-cutting, boudin neck and jumbled channelway leucosomes and late pegmatites were analyzed via whole-rock geochemistry, and there is evidence for fluid-saturated and -undersaturated biotite- and amphibole-dehydration melting. Migmatites from these three locations contain pseudomorphs of melt along subgrain and grain boundaries, areas of high dislocation density, in quartz and plagioclase. For these rocks that involve multicomponent systems, the primary cause for preferential melting in high strain locations is enhanced diffusion rates along the subgrain boundary because of pipe diffusion or water associated with dislocations. / text

Lithium niobate (LiNbO3) and KTiOPO4 (KTP) are ferroelectric crystals of considerable interest in different fields of optics and optoelectronics. Due to its large values of the nonlinear optical, electro-optic (EO), piezoelectric and acousto-optical coefficients, LiNbO3 is widely used for laser frequency conversion using the quasiphase matching (QPM) approach where the sign of nonlinearity has been periodically modulated by electric field poling (EFP). In the microwave and telecommunication field LiNbO3 is used for surface acoustic devices and integrated optical modulators. KTP and its isomorphs, on the other hand, exhibit slightly lower nonlinear coefficients but have much higher photorefractive damage thresholds, so that it is mainly used in the fabrication of QPM devices for both UV, IR and visible light generation and in high power applications. This thesis focus on different key issues: (1) accurate characterization of specific optical properties of LiNbO3, which are of interest in nonlinear and EO applications; (2) in-situ visualization and characterization of domain reversal by EFP in LiNbO3 and KTP crystals for a through understanding of the ferroelectric domain switching; (3) fabrication of periodic surface structures at sub-micron scale in LiNbO for photonic applications. An interferometric method is used for accurate measurement of ordinary and extraordinary refractive indices in uniaxial crystals, which is of great interest in the proper design of QPM crystals. A digital holography (DH) based method is presented here for 2D characterization of the EO properties of LiNbO , which is considerably interesting in the applications where the proper design of the EO device requires a spatially resolved information about the EO behaviour and the existing pointwise techniques are not sufficient. A DH method for novel in-situ monitoring of domain reversal by EFP in both LiNbO3 and KTP, is also presented here. The technqiue could be used as a tool for high fidelity periodic domain engineering but also provides information about domain kinetics, internal field and crystals defects. 3 3 3 Finally this thesis presents novel results concerning nanoscale periodic surface structuring of congruent LiNbO3. Holographic lithography (HL) is used for sub-micron period resist patterning and electric overpoling for surface domain reversal. Surface structures are obtained by selective etching. Moiré effect is also used in the HL to fabricate complicated structures with multiple periods. The depth compatibility with waveguide implementation allows foreseeing possible applications of these structures for Bragg gratings or innovative photonic crystal devices, exploiting the additional nonlinear and EO properties typical of LiNbO3. / QC 20100824

Micro-electro-mechanical systems (MEMS) technology has had an increasing impact on industry and our society. A wide range of MEMS devices are used in every aspects of our life, from microaccelerators and microgyroscopes to microscale drug-delivery systems. The increasing complexity of microsystems demands diverse microfabrication methods and actuation strategies to realize. Currently, it is challenging for existing microfabrication methods—particularly 3D microfabrication methods—to integrate multiple materials into the same component. This is a particular challenge for some applications, such as microrobotics and microfluidics, where integration of magnetically-responsive materials would be beneficial, because it enables contact-free actuation. In addition, most existing microfabrication methods can only fabricate flat, layered geometries; the few that can fabricate real 3D microstructures are not cost efficient and cannot realize mass production. This dissertation explores two solutions to these microfabrication problems: first, a method for integrating magnetically responsive regions into microstructures using photolithography, and second, a method for creating three-dimensional freestanding microstructures using a modified micromolding technique. The first method is a facile method of producing inexpensive freestanding photopatternable polymer micromagnets composed NdFeB microparticles dispersed in SU-8 photoresist. The microfabrication process is capable of fabricating polymer micromagnets with 3 µm feature resolution and greater than 10:1 aspect ratio. This method was used to demonstrate the creation of freestanding microrobots with an encapsulated magnetic core. A magnetic control system was developed and the magnetic microrobots were moved along a desired path at an average speed of 1.7 mm/s in a fluid environment under the presence of external magnetic field. A microfabrication process using aligned mask micromolding and soft lithography was also developed for creating freestanding microstructures with true 3D geometry. Characterization of this method and resolution limits were demonstrated. The combination of these two microfabrication methods has great potential for integrating several material types into one microstructure for a variety of applications.

Les processus physiques et chimiques activés pendant le cycle sismique déterminent l'évolution des propriétés mécaniques des failles, à court terme (pendant un séisme) comme à long terme (la récupération des propretés élastiques des roches de faille après un seisme). L'étude des roches de faille naturelles est un moyen pour identifier les processus actives pendant les diverses phases des cycle séismique. En cette thèse, échantillons prévenants de deux failles séismiques sont étudiés: la Faille de San Andreas (California, USA), une faille séismique active, et la faille de Gole Larghe (Alpes Méridionales, Italie), une faille séismique exhumée. La Faille de San Andreas a été forée jusqu'à 2.7km de profondeur. Les échantillons montrent une superposition de: pression-dissolution - hydrofracturation - pression dissolution. La succession des évents est compatible avec la formation de sacs de fluides dans zones de basse perméabilité dans la faille, ou la pression de fluides augmente à cause de le progressif compactage de le gouge de faille, jusqu'à la nucléation de une rupture. La faille de Gole Larghe est une faille exhumée, qui a préservé des pseudotachylytes (roches fondues par le chaleur de friction pendant une frottement séismique) formées à 9 - 11 km de profondeur il y a 30 millions d'années. Deux argumentes sont traités: (i) l'évolution des microstructures des cataclasites associées à les pseudotachylytes, pour identifier les processus qui peuvent porter à la formation de instabilités frictionnelles pendant les premières phases de croissance de une faille. (ii) L'origine des fluides en failles séismiques et pendant la fusion pour friction. La formation de un système de failles à cataclasites permit la percolation de un fluide aqueux de profondeur. La composition isotopique des pseudotachylytes (calculé sans la component de hydratation) est proche à celle des pseudotachylytes reproduites en expériences du laboratoire (sans fluides). La principale source de fluides pendant la fusion pour friction est donc la déshydratation des minéraux hydraté des roches autour de la faille.