[EN] Different strategies were used to improve physical properties of corn starch based films, with glycerol (30%) as plasticizer, based on increasing their hydrophobic character in order to reduce the materials' water sensitivity. Starch was blended with different components (surfactants and more hydrophobic polymers), with and without compatibilizers, to obtain blend films through different processing techniques (casting, melt blending, compression molding and extrusion). Bilayer film formation by compression molding with starch and poly(e-caprolactone) (PCL) was also studied. The addition of surfactants to starch films obtained by casting gave rise to a decrease in water vapor permeability (WVP), but an increase in the film fragility was observed. Surfactants with lower hydrophilic-lipophilic balance (HLB), solid at room temperature, promoted a fine microstructure in the matrix with smaller lipid particle, which enhanced water vapor barrier properties. Thermo-processing was used to obtain the other films due to its broader industrial application. Starch blends with hydroxypropyl methylcellulose (HPMC) showed an HPMC dispersed phase in the starch matrix and better water barrier properties, but they were more permeable to oxygen, especially when they contained citric acid (CA) as compatibilizer. CA induced cross-linking in the polymeric matrix, thus slightly increasing film hardness, but decreasing its extensibility. The incorporation of PCL in different ratios to starch films obtained by compression molding gave rise to polymer phase separation, although a small PCL miscibility in the starch rich phase was detected, which reduced the glass transition temperature of the starch phase. The structural heterogeneity and lack of interfacial adhesion between polymers gave rise to fragile films. Nevertheless, small amounts of PCL (10%) reinforced the matrix (increase in the elastic modulus). When the PCL ratio increased, WVP was reduced but oxygen permeability increased. The incorporation of CA as compatibilizer of these blends provoked an increase in the water solubility of the films, by hydrolysis, and improved the mechanical properties of the films when PCL ratio was low (10%), but it did not affect the film barrier properties. The incorporation of polyethylene glycol (PEG 4000) to the blends with a low proportion of PCL did not imply an improvement in the film properties, since it promoted phase separation. Starch-PCL blends with 1:0.05 mass ratio, without compatibilizer, were quite homogenous and exhibited good mechanical properties and stability. In order to incorporate greater amounts of PCL, thus improving film hydrophobicity and stability, PCL was chemically modified by grafting glycidyl methacrylate or glycidyl methacrylate and maleic anhydride (PCL-g), to be used as compatibilizers. Films with 20 % PCL and 2.5 or 5 % of PCL-g showed very good mechanical and barrier properties and stability, inhibiting starch retrogradation. Their barrier properties met the food packaging requirements for a wide number of food products. Bilayer films obtained by compression molding of starch (or starch with 5% PCL) and PCL layers showed very low WVP and oxygen permeability and adequate mechanical properties. The adhesion of bilayers was greatly improved by the application of ascorbic acid and, especially, potassium sorbate, as aqueous solutions, at the interface before compression molding. These compounds, in turn, imparted antioxidant and antimicrobial properties, respectively, to the films, thus improving their potential use as active packaging material for food uses. / [ES] Se han utilizado diversas estrategias para mejorar las propiedades físicas de films a base de almidón de maíz, con glicerol (30 %) como plastificante, basadas en el incremento de su carácter hidrofóbico, para reducir su sensibilidad al agua. El almidón se mezcló con diferentes compuestos (surfactantes y polímeros más hidrofóbicos), con y sin compatilizadores, para la obtención de films mixtos por diferentes técnicas de procesado (casting, mezclado en fundido, moldeo por compresión y extrusión). Se estudió también la formación de films bicapa almidón-poli-e-caprolactona (PCL) mediante moldeo por compresión. La adición de surfactantes a los films de almidón elaborados por casting dio lugar a una disminución de su permeabilidad al vapor de agua (WVP), pero aumentó su fragilidad. Los surfactantes con menor balance hidrófilo-lipófilo (HLB), y sólidos a temperatura ambiente, proporcionaron una microestructura de los films con menor tamaño de partícula, que potenció las propiedades barrera al vapor de agua. Por su mayor aplicabilidad industrial, se emplearon técnicas de termo-procesado para la obtención del resto de films estudiados. Los obtenidos por mezcla con hidroxipropil metilcelulosa (HPMC) presentaron una fase dispersa de HPMC en la matriz de almidón y mejores propiedades barrera al vapor de agua, pero fueron algo más permeables al oxígeno, sobre todo cuando se incorporó ácido cítrico (CA) como compatibilizador. Este provocó entrecruzamiento en la matriz polimérica, incrementado ligeramente su dureza y reduciendo su extensibilidad. La incorporación de PCL en diferentes proporciones a los films de almidón obtenidos por termo-compresión, dio lugar a la separación de fases polímericas, detectándose una pequeña miscibilidad de la PCL en la fase rica en almidón que redujo la temperatura de transición vítrea de la fase amilácea. La heterogeneidad de su estructura y la falta de adhesión entre fases dio lugar a films demasiado frágiles, aunque en pequeña proporción (10%), la PCL reforzó la matriz (aumentó el módulo de elasticidad). Al aumentar la proporción de PCL, disminuyó la WVP de los films, pero aumentó la permeabilidad al oxígeno. La incorporación de CA como compatibilizador de estas mezclas aumentó la solubilidad en agua de los films por efecto de hidrólisis y supuso una mejora en las propiedades mecánicas de los films con baja proporción de PCL (10 %), pero no afectó a sus propiedades barrera. La incorporación de polietilenglicol (PEG 4000) a las mezclas con baja proporción de PCL no mejoró las propiedades de los films, potenciando la separación de fases. Las mezclas almidón:PCL con proporción másica 1:0.05, sin compatibilizador, fueron bastante homogéneas y exhibieron buen comportamiento mecánico y estabilidad. Para incorporar una mayor proporción de PCL, y mejorar la hidrofobicidad y estabilidad de los films, se modificó la PCL por reacción con glicidil metacrilato o anhídrido maleico y glicidil metacrilato (PCL-g), para su uso como compatibilizadores. Los films con 20% de PCL y 2.5 y 5 % de los PCL-g presentaron muy buenas propiedades mecánicas y de barrera al vapor de agua y a los gases y buena estabilidad al inhibir la retrogradación del almidón. Sus propiedades de barrera cumplieron con los requisitos de envasado de un número importante de productos alimentarios. La obtención de films bicapa por termo-compresión a partir de almidón (o almidón con 5% PCL) y PCL proporcionó un material con muy baja permeabilidad al vapor de agua y al oxígeno y buenas propiedades mecánicas. La adhesión entre las capas mejoró en gran medida con la incorporación de ácido ascórbico, y sobre todo de sorbato potásico, en la interfase en forma de disolución acuosa antes de la termo-compresión. Estos compuestos impartieron, a su vez, propiedades antioxidantes y antimicrobianas, respectivamente, a los films, mejorando su uso potencial para el envasad / [CAT] S'han utilitzat diverses estratègies per a millorar les propietats físiques de films a base de midó de dacsa, amb glicerol (30 %) com plastificant, basades en l'increment del seu caràcter hidrofòbic, per a reduir la seua sensibilitat a l'aigüa. El midó es va mesclar amb diferents compostos (surfactants i polímers més hidrofòbics), amb i sense compatibilitzadors, per l'obtenció de films mixtos mitjançant diferents tècniques de processat (càsting, mesclat en fos, modelatge per compressió i extrusió). Es va estudiar també la formació de films bicapa midó-poli-e-caprolactona (PCL) mitjançant modelatge per compressió. L'addició de surfactants als films de midó elaborats per càsting va donar lloc a una disminució de la seua permeabilitat al vapor d'aigüa (WVP), però va augmentar la seua fragilitat. Els surfactants amb menor balanç hidròfil-lipòfil (HLB), i sòlids a temperatura ambient, varen proporcionar una microestructura dels films amb menor grandària de partícula, que varen potenciar les propietats barrera al vapor d'aigüa. Per la seua major aplicabilitat industrial, es van emprar tècniques de termo-processat per l'obtenció de la resta de films estudiats. Aquells obtinguts per mescla amb hidroxipropil-metilcellulosa (HPMC) varen presentar una fase dispersa de HPMC en la matriu de midó i millors propietats barrera al vapor d'aigüa, però varen ser un poc més permeables a l'oxigen, sobretot quan es va incorporar àcid cítric (CA) com compatibilitzador. Aquest va provocar entrecreuament en la matriu polimérica, incrementant lleugerament la seua duresa i reduïnt la seua extensibilitat. La incorporació de PCL en diferents proporcions als films de midó obtinguts per termo-compressió, va donar lloc a la separació de fases polimèriques, detectant-se una xicoteta miscibilitat de la PCL en la fase rica en midó que va reduir la temperatura de transició vítria de la fase amilàcea. L'heterogeneïtat de la seua estructura i la falta d'adhesió entre fases va donar lloc a films massa fràgils, encara que en xicoteta proporció (10%), la PCL va reforçar la matriu (augmentant el mòdul d'elasticitat). Al augmentar la proporció de PCL, va disminuir la WVP dels films, però va augmentar la permeabilitat a l'oxigen. La incorporació de CA com compatibilitzador d'aquestes mescles va augmentar la solubilitat en aigüa dels films per efecte d'hidròlisi i va suposar una millora en les propietats mecàniques dels films amb baixa proporció de PCL (10 %), però no va afectar les propietats barrera. La incorporació de polietilenglicol (PEG 4000) a les mescles amb baixa proporció de PCL no va millorar les propietats dels films, potenciant la separació de fases. Les mescles midó:PCL amb proporció màssica 1:0.05, sense compatibilitzador, varen ser prou homogènies i varen exhibir un bon comportament mecànic i una bona estabilitat. Per a incorporar una major proporció de PCL i millorar l'hidrofobicitat i estabilitat dels films, es va modificar la PCL per reacció amb glicidil metacrilat o anhídrid maleic i glicidil metacrilat (PCL-g), per al seu ús com compatibilitzadors. Els films amb 20% de PCL i 2.5 i 5 % dels PCL-g varen presentar molt bones propietats mecàniques i de barrera al vapor d'aigüa i als gasos i bona estabilitat al inhibir la retrogradació del midó. Les seues propietats de barrera varen complir amb els requisits d'envasament d'un nombre important de productes alimentaris. L'obtenció de films bicapa per termo-compressió a partir de midó (o midó amb 5% PCL) i PCL va proporcionar un material amb molt baixa permeabilitat al vapor d'aigüa i al oxigen i bones propietats mecàniques. L'adhesió entre les capes va millorar en gran mesura amb l'incorporació d'àcid ascòrbic, i sobretot de sorbat de potassi, en la interfase en forma de dissolució aquosa abans de la termocompressió. Aquestos compostos varen impartir, a la vegada, propietats antioxidants i antimicrobianes, respec / Ortega Toro, R. (2015). DESARROLLO Y CARACTERIZACION DE PELÍCULAS DE ALMIDÓN DE MAÍZ POR MEZCLADO CON COMPUESTOS MÁS HIDROFÓBICOS [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/52521 / TESIS

Le présent travail s'articule autour de l'élaboration du matériau binaire In2S3 en couches minces en tant qu'alternative crédible au composé CdS, dans les cellules solaires à base de CuInS2. Nous avons utilisé la technique de dépôt chimique en solution (Chemical Bath Deposition ou CBD) qui est une technique non coûteuse, non toxique et facile à manipuler. Les couches fabriquées sont caractérisées de différents points de vue et à différentes échelles : caractérisations structurale par diffraction de rayons X (DRX), morphologique par Microscopie Electronique à Balayage (MEB), composition chimique par spectroscopie en dispersion d'énergie (EDS), propriétés optiques par spectrophotométrie, et électriques par la méthode du courant thermiquement stimulé (TSC) et par cartographie de courant localisé. L'objectif de ce travail est l'étude systématique des effets du dopage à l'aluminium et à l'étain, et du traitement thermique des films minces de In2S3 déposés sur verre et sur SnO2. Nous avons réalisé tout d'abord par CBD une multicouche d'In2S3 :4%Al formée par trois dépôts successifs sur des substrats verre et SnO2:F. La comparaison des caractéristiques physicochimiques est faite avec la couche non dopée en tant que caractéristiques de référence. L'étude par DRX faite pour différentes concentrations en Al, montre que ce binaire cristallise selon la structure cubique d'orientation préférentielle (400). Une meilleure cristallisation est obtenue pour une concentration en aluminium dans la solution y = [Al]/[In] = 4%. L'analyse optique montre que le gap est direct, il varie de 2,3 à 2,9 eV; la plus large bande optique est obtenue pour y = 4%. C'est une bonne valeur pour l'utilisation du composé β-In2-xAlxS3 comme fenêtre optique dans les dispositifs photovoltaïques. L'étude de l'effet du dopage à l'étain des multicouches d'In2S3, nous a permis de déduire qu'une meilleure cristallinité, une faible rugosité de la morphologie de surface et un gap optique plus proche de l'optimum théorique, sont obtenus pour des films croissants sur le substrat Pyrex avec une concentration d'étain égale à 2‰. L'analyse effectuée par MEB sur la tranche a montré que l'épaisseur moyenne des couches diminue avec l'augmentation de la concentration d'étain. La présence de l'étain, même en très petites quantités induit des changements importants dans le processus de croissance du film. L'étude TSC montre que l'augmentation de la concentration de l'étain au-delà 2 ‰ conduit à une diminution de courant thermiquement stimulé. Le recuit à différentes températures sous azote est appliqué aux couches dopées et non dopées étudiées précédemment. Le traitement thermique sous azote à 400°C provoque une augmentation nette de la taille des cristallites pour pratiquement tous les films minces dopés ou non dopés déposés sur verre ou sur SnO2. L'analyse par diffraction des rayons X a révélé une conversion de la phase cubique (400) à la phase tétragonale (109) pour l'In2S3:4%. Le changement de la forme des cristallites observé par AFM, met également en évidence l'existence d'une autre phase. Les analyses électriques par TSC montrent particulièrement le comportement électrique de type semiconducteur pour les films minces dopés à 4% Al, et recuit à 400°C, ainsi que pour les films minces dopés à l'étain après recuit à 200°C. L'analyse locale du courant de conduction dans la couche de In2S3 fait apparaître des inhomogénéités plus grandes après traitement thermique. Cependant les bons résultats macroscopiques permettent d'envisager sereinement la fabrication de cellules solaires incluant ces couches. / The present work focuses on the development of binary material In2S3 thin films as an alternative to CdS in thin film solar cells based on CuInS2. We used the technique of Chemical Bath Deposition (CBD) as it is non-expensive, non-toxic and easy to handle. Layers produced are characterized at different levels and scales: cristalline structure by X-ray diffraction (XRD), surface morphology by Scanning Electron Microscopy (SEM), chemical composition by energy dispersive spectroscopy (EDS), optical properties by spectrophotometry and electrical conduction by thermally stimulated currents (TSC) and local mapping of currents. The objective of this work is the systematic study of the effects of aluminum or tin doping, and heat treatment of In2S3 thin films deposited on glass and SnO2. We achieved first a multilayer of CBD In2S3:Al(4%) formed by three successive deposits on glass and SnO2 substrates. Comparison of physicochemical characteristics is made with the undoped layer as reference features. The XRD study done for different Al concentrations, shows that In2S3:Al crystallizes in the cubic structure with preferential orientation (400). Better crystallization is obtained for a concentration of aluminum in the solution y = [Al] / [In] = 4%. The analysis shows that the optical gap is direct, it varies from 2.3 to 2.9 eV, the largest optical band is obtained for y = 4%. It is a good value for the use of the compound β-In2-xAlxS3 as optical window in photovoltaic devices. The effect of tin doping in In2S3 multilayers induces a better crystallinity, low roughness of the surface morphology and optical gap closer to the theoretical optimum, obtained for films grown on Pyrex substrate with a tin concentration equal to 2 ‰. Analysis by SEM on the wafer cleaved-edge showed that the average thickness of the layers decreases with increasing the concentration of tin. The presence of tin, even in very small quantities induced significant changes in the growth process of the film. The TSC study shows that increasing concentration of tin beyond 2‰ leads to a reduction of thermally stimulated current.Annealing at different temperatures under nitrogen is applied to doped and undoped layers studied previously. Heat treatment under nitrogen at 400 ° C causes a net increase of crystallite size for virtually all thin films doped or undoped deposited on glass or SnO2. The analysis by XRD showed a conversion of the cubic phase (400) to the tetragonal phase (109) for In2S3:Al(4%). Change the shape of the crystallites observed by AFM, also highlights the existence of another phase. The TSC analyzes show particular electrical behavior close to semiconductor type for the thin films doped with 4% Al and annealed at 400°C, as well as thin films doped with tin after annealing at 200°C. The local analysis of the conduction current in the layer of In2S3 shows inhomogeneities larger after heat treatment. However, good macroscopic results should allow to fabricate promising solar cells incorporating these layers.

The aim of master thesis was to study structural and transport properties of PVA films modified with method of semi-IPN with suitable polyectrolytes and plasticizers. The first important step was optimalization of PVA films preparation, when time of heating was set at 90 °C for 1 hour. Drying was set at 50 °C for 24 hours. Molecular weight of PVA was chosen 85–124 kDa in concentration 10 wt.%. For preparation of PVA-based semi-IPN thin films polyelectrolytes (polyglutamic acid, DEAE-dextran hydrochloride) and plasticizer (glycerol) were selected. Basic characterization of prepared materials was performed with FTIR, TGA, SEM and specific surface analysis. The difference between modified PVA films was in the chargé of individual functional groups carried by used polyelectrolytes. Surfaces of all the PVA films were smooth without visible defects. Transport properties were characterized with the method of horizontal diffusion cell with methylen blue used as a probe. Diffusion coefficients of methylen blue through PVA films were determined. It was found, that the fastest pass was throw PVA film without additives. The slowest diffusion was observed through PVA/DEAE-dextran film, because of the same charge of the film with a probe. PVA/PGA reacted with methylen blue to form a complex. Plasticizer effect on the diffusion was only minor; it caused a slight decrease of diffusion coefficient. These films were easier to handle.

La restauration des peintures d'art consiste à restaurer la lisibilité d'une œuvre d'art et à préserver son intégrité. La plupart des techniques consiste à déposer des solvants juste en surface afin de ne dissoudre que la couche de vernis. Cependant, les couches sous-jacentes risquent d'être endommagées par la pénétration de ces solvants, causant éventuellement un gonflement ou un craquèlement de ces dernières. Du fait de la complexité physico- chimique de la couche picturale, nous proposons d'étudier la pénétration de solvants dans un nanoporeux modèle issu du séchage contrôlé de dispersions aqueuses de nanoparticules de silice. Le séchage et la consolidation de ces dispersions colloïdales jusqu'à l'apparition de craquelures de séchage sont étudiés. La réflectivité de neutrons et la diffusion de neutrons aux petits angles permettent d'accéder à la structuration des systèmes en surface et en volume, respectivement, au cours du séchage. L’étude expérimentale des ouvertures de craquelures dues au séchage, associée à un modèle de poroélasticité que nous développons, renseigne sur les propriétés mécaniques des systèmes consolidés et du tableau « Jeanne d'Arc en prison » (1824) du peintre français Louis Crignier (1790-1824). La caractérisation du milieu poreux formé après la consolidation est réalisée par imagerie de neutrons et permet de déterminer la perméabilité et les porosités des milieux. Enfin, nous présentons la dynamique d'imprégnation d'une goutte sessile de solvant dans plusieurs milieux poreux, qui diffèrent de par leur taille de pores. Notre montage expérimental permet une quantification précise et directe des écoulements au-dessus et à l'intérieur du milieu poreux. Des mesures de propriétés mécaniques sont réalisées avant et après imprégnation par micro-indentation. / Art painting restoration aims to restore the readability of a painting and to preserve its integrity. Most of the techniques consist of depositing solvents on the surface of the painting to dissolve the varnish layer. However, the sublayers can be damaged by the penetration of the solvent, possibly resulting in swelling or cracking processes. Due to the physical and chemical complexity of the pictorial layer, we propose to study solvent penetration in model nano porous media obtained by controlled drying of aqueous silica nanoparticles dispersions. Drying and the consolidation process of these colloidal dispersions are studied until drying cracks appear. Neutron reflectivity and small angle neutron scattering provide structural information on particles near the interface between the dispersion and the air and in the bulk, respectively, during drying. The experimental study of drying cracks, associated to a poroelastic model, inform on mechanical properties of consolidated model systems and of the painting “Jeanne d'Arc en prison” (1824) by the French painter Louis Crignier (1790-1824). Characterization of the porous media obtained after consolidation is carried out with neutron imaging to determine the permeability and the porosities of the porous media. Finally, we present the dynamics of imbibition of sessile solvent drops on several porous media with different pore sizes. Our experimental set-up provides a precise and a direct quantification of the different flows outside and through the porous media. Mechanical properties are performed before and after solvent imbibition, by micro-indentation testing.

Solid state approaches to structural properties like diffraction or microscopy techniques often cannot be applied to biomolecular systems, at least not without special postpreparation which often corrupts the desired properties of the pristine systems. In this work the capabilities of synchrotron-based, soft X-ray spectroscopies as an alternative way to unravel structural properties of such systems are tested. To this end, three exemplary systems were investigated each with the focus on another facet and characteristic length scale. The first example are DNA-alkanethiol self-assembled monolayers, also known as DNA microarrays or DNA chips, for which a way to monitor and controllably tune the structural composition on the mesoscopic scale of many thousands of molecules was sought for. The second example focuses on the single-molecule and submolecular scale in metalprotein hybrid compounds with the aim to identify the binding site of metal atoms or ions within protein molecules and the underlying interaction mechanisms. The most fundamental structural scale, the level of single bonds and molecular orbitals, is addressed in the last example where it was tried to elaborate an approach to map the topology of molecular orbitals based upon X-ray absorption properties. This approach was put to the practical test for the characteristic pi*peptide orbitals in protein backbones. For all three investigated examples, spectroscopies using soft X-ray synchrotron radiation were able to extract the desired information, thus confirming that they may grant alternative access to structural properties of soft-matter systems in cases where standard approaches fail. / Klassische Festkörpertechniken zur Strukturuntersuchung, wie Streu- oder Mikroskopiemethoden, können häufig nicht auf Biomolekülsysteme angewandt werden, zumindest nicht ohne spezielle Postpräparation, die die ursprünglichen Eigenschaften dieser Systeme oft verfälscht. In dieser Arbeit soll untersucht werden, inwieweit Röntgenspektroskopien basierend auf Synchrotronstrahlung einen alternativen Zugang zu Struktureigenschaften solcher Systeme bieten. Dazu wurden drei Systeme exemplarisch untersucht, jeweils mit Schwerpunkt auf einen anderen Aspekt und charakteristischen Längenbereich. Für selbstorganisierende DNA-Alkanthiol-Schichten, sogenannte DNA-Chips, wurde nach eine Weg gesucht, ihre strukturelle Zusammensetzung auf der mesoskopischen Ebene vieler tausend Moleküle zu bestimmen und kontrolliert zu modifizieren. Metallisierte Proteinstrukturen wurden auf Einzelmolekül- bzw. submolekularer Ebene untersucht, mit dem Ziel, die Orte der Metallanlagerung innerhalb des Proteins und die zugrundeliegenden Wechselwirkungsmechanismen zu identifizieren. Die unterste strukturelle Ebene, der Bereich einzelne Bindungen und Molekülorbitale, wurde adressiert am Beispiel der pi*peptide Orbitale des Proteinrückrats. Dafür wurde eine Methode zur Kartographierung einzelner Orbitale anhand von Röntgenabsorptionseigentschaften herausgearbeitet und praktisch getestet. In allen drei Fällen konnten Röntgenspektroskopien die nötigen Informationen liefern und damit ihr Potential für Strukturuntersuchungen in weicher Materie unter Beweis stellen.

<p>A first-principles theory of plasticity in metals currently does not exist. While many plasticity models make reference to rules based on heuristic arguments regarding dislocations (the fundamental mediators of plastic deformation in crystals), the scientific community still does not have a theory of dislocation dynamics which can recover even basic features of plasticity theory. Discrete dislocation dynamics, though a valuable tool for understanding fundamentals topics in dislocation plasticity, becomes unusable beyond ~1.5\% strain due to the line length multiplication inherent in deformation. As a result, it is necessary to develop continuum theories of dislocation dynamics which treat dislocation densities rather than individual dislocations. This thesis examines the foundations of one such continuum theory: line bundle continuum dislocation dynamics, which assumes that dislocations are roughly parallel at every point. First, this assumption is given definite meaning and it is shown from discrete dislocation dynamics data that to be appropriate when modelling dislocation densities on fine length scales (resolving densities on lengths less than 100 nm). Second, it is found that an additional driving force, the correlation stress, emerges from coarse-graining the line bundle dynamics. This correction to the dislocation interactions is dependent on tensorial dislocation correlation functions describing the short-range errors in the products of dislocation densities lying on two slip systems. The full set of these dislocation correlation functions are evaluated from discrete density data with the aid of a novel left-and-right handed classification of slip system interactions in FCC crystals. Lastly, a study of the correlation stress in a representative dislocation system suggests that these stresses are roughly one tenth the magnitude of the mean-field dislocation interaction stress. Taken together, this thesis bridges discrete and continuum models of dislocation dynamics and provides a foundation for future work on a first-principles theory of metal plasticity. </p>

[pt] Esta dissertação teve como objetivo estudar as propriedades estruturais, mecânicas dos filmes de silício carbono nitrogenado amorfo (a-SiC:N) e a viabilidade do seu uso como camada adesiva entre filmes finos de carbono amorfo hidrogenado e aço inoxidável 316L. Os filmes de a-SiC:N foram crescidos pela técnica de deposição química na fase vapor assistida por plasma (PECVD) utilizando como precursor hexametildissilazano (HMDSN) sobre chapas de aço inoxidável 316L e lâminas de silício cristalino 100. Para a deposição foram variados os parâmetros de tensão de autopolarização (de -150V até -450V) e a temperatura de deposição (25 Graus Celsius, 200 Graus Celsius e 300 Graus Celsius). Os filmes foram caracterizados por técnicas de perfilometria, onde pudemos obter a taxa de deposição, a tensão interna dos filmes, análises por espectroscopia de fotoelétrons induzidos por raios-x (XPS) e espectroscopia de infravermelho onde identificamos a presença de ligações entre os átomos de silício, carbono e nitrogênio. Com a espectroscopia Raman observamos a presença das bandas D e G com características de filmes de carbono amorfo. As análises de nanoindentação determinaram que a dureza variou entre 8 e 12 GPa. A microscopia de força atômica evidenciou a presença de nanoestruturas sobre a superfície dos filmes. E por fim, obtivemos sucesso na deposição de filmes de carbono amorfo hidrogenado e carbono amorfo fluorado sobre chapas de aço inoxidável empregando filmes finos de a-SiC:N como camada adesiva. / [en] The objective of this dissertation has been to study the structural and mechanical properties of amorphous SiC:N thin films and the viability of their use as adhesive layer between amorphous C:N thin films and 316L stainless steel. The a-SiC:N films were grown via Plasma-Enhanced Chemical Vapor Deposition (PECVD), using Hexamethyldisilazane (HMDSN) as precursor on 316L stainless steel and crystalline silicon substrates 100. For the deposition, the parameters changed were the self-bias (from -150V to -450V) and the deposition temperature (25 Degree Celsius, 200 Degree Celsius and 300 Degree Celius). The characterization of the films was accomplished by using profilometry techniques, used to obtain the deposition rate and the internal stress of the films, x-ray photoelectron spectroscopy (XPS) and infrared spectroscopy used to identify the presence of bonding between the Silicon, Carbon and Nitrogen atoms. The Raman spectroscopy was employed to observe the presence of the D and G bands with characteristics of amorphous carbon films. The nanoindentation analysis determined that the hardness varied between 8 and 12GPa. Atomic force microscopy (AFM) evidenced the presence of nanostructures on the surface of the films. Finally, we were able to perform deposition of hydrogenated amorphous carbon and of fluorinated amorphous carbon thin films on stainless steel substrates using a-SiC:N thin films as adhesive layer.

We derive the amplitude expansion for a phase-field-crystal (APFC) model that captures the basic physics of magneto-structural interactions. The symmetry breaking due to magnetization is demonstrated, and the characterization of the magnetic anisotropy for a bcc crystal is provided. This model enables a convenient coarse-grained description of crystalline structures, in particular when considering the features of the APFC model combined with numerical methods featuring inhomogeneous spatial resolution. This is shown by addressing the shrinkage of a spherical grainwithin amatrix, chosen as a prototypical system to demonstrate the influence of different magnetizations. These simulations serve as a proof of concept for the modeling of manipulation of dislocation networks and microstructures in ferromagnetic materials within the APFC model.

<p dir="ltr">Since the discovery of graphene in 2004, numerous other materials with intriguing electronic, optical, and magnetic properties have been found to be layered and exfoliatable down to atomic thickness. Owing to their weak interlayer coupling, mediated only by van der Waals forces, this new class of 2-dimensional materials, also known as van der Waals (vdW) materials, allows layer-by-layer stacking, overcoming some of the limitations of growth techniques. In particular, the growing inventory of vdW materials has expanded to include magnetic materials, further broadening the possibilities of novel devices based on stacked heterostructures. These magnetic heterostructures can find applications in spintronics and memory devices and may be combined with other vdW materials with optical properties for applications in optoelectronics. In this thesis, we assembled heterostructures via mechanical transfer or growth to modify the magnetism in these vdW materials. We used various optical and electrical techniques to probe the modified magnetism or its effects on the novel heterostructure. Thus, we observed the emergence of the magnetic proximity effect on the topological insulator BiSbTeSe₂ after dry transferring a thin flake of Cr₂Ge₂Te₆ on top, taking steps towards the observation of novel topological phases, such as the quantum Hall insulator. Additionally, we demonstrated an increased Curie temperature and magnetic anisotropy, effectively enhancing the magnetism, in thin flakes of Cr₂Ge₂Te₆ and Cr₂Si₂Te₆ after sputtering NiO or MgO. Finally, noting that the effect of modified magnetism in Cr2Ge2Te6 after sputtering NiO or MgO is induced due to wrinkle formation and strain, we further reproduce similar wrinkle formation on other 2D materials such as hBN, graphite, and 2D antiferromagnets (XPS₃, (X= Mn, Fe, Ni), CrSBr, RuCl₃). We used polarized Raman spectroscopy to characterize the induced biaxial strain in hBN and showed that such wrinkle formation can lead to moderately (up to 1.4% strain) spatially inhomogeneous and anisotropic strain profiles. These efforts demonstrate the versatility of tailoring the properties of these vdW materials.</p>

Dans cette thèse, plusieurs concepts importants liés à la théorie de la réalisation des modèles linéaires à paramètres variants (LPV) sont étudiés.Tout d’abord, nous abordons le problème de l’identifiabilité des modèles LPV affines (ALPV). Une nouvelle condition suffisante et nécessaire est introduite afin de garantir l’identifiabilité structurelle pour les paramétrages ALPV. L’identifiabilité de cette classe de paramétrages est liée à l’absence d’isomorphismes liant deux représentations d’état LPV lorsque deux modèles LPV correspondant à différentes valeurs des variables de séquencement sont considérés. Nous présentons ainsi une condition suffisante et nécessaire pour l’identifiabilité structurelle locale, et une condition suffisante pour l’identifiabilité structurelle (globale) qui sont toutes deux fonction du rang d’une matrice définie par l’utilisateur. Ces dernières conditions permettent la vérification de l’identifiabilité structurelle des modèles ALPV.Ensuite, étant donné que les techniques d’identification dites locales sont parfois inévitables, nous fournissons une expression analytique de la borne supérieure de l’erreur de comportements entrées-sorties de deux modèles LPV équivalents localement. Cette erreur se révèle être une fonction de (i) la vitesse de changement du signal de séquencement et (ii) l’écart entre les bases cohérentes de deux modèles LPV. En particulier, la différence entre les sorties des deux modèles peut être arbitrairement réduite en choisissant un signal de séquencement qui varie assez lentement.Enfin, nous présentons et étudions des propriétés importantes de la transformation des représentations d’état ALPV en Représentations Linéaires Fractionnelles (LFR). Plus précisément, nous montrons que (i) les représentations ALPV minimales conduisent à des LFR minimales, et vice versa, (ii) le comportement entrée-sortie de la représentation ALPV détermine de manière unique le comportement entrée-sortie de la LFR résultante, (iii) les modèles ALPV structurellement identifiables fournissent des LFRs structurellement identifiables et vice versa. Nous caractérisons ensuite les LFRs qui correspondent á des modèles ALPV équivalents basés sur leurs applications entrées-sorties. Comme illustré tout au long du manuscrit, ces résultats ont des conséquences importantes pour l’identification et la commande des systèmes LPV. / In this thesis, important concepts related to the identification of Linear Parameter-Varying (LPV) systems are studied.First, we tackle the problem of identifiability of Affine-LPV (ALPV) state-space parametrizations. A new sufficient and necessary condition is introduced in order to guarantee the structural identifiability for ALPV parameterizations. The identifiability of this class of parameterizations is related to the lack of state-space isomorphisms between any two models corresponding to different scheduling parameter values. In addition, we present a sufficient and necessary condition for local structural identifiability, and a sufficient condition for (global) structural identifiability which are both based on the rank of a model-based matrix. These latter conditions allow systematic verification of structural identifiability of ALPV models. Moreover, since local identification techniques are inevitable in certain applications, it is thus a priority to study the discrepancy between different LPV models obtained using different local techniques. We provide an analytic error bound on the difference between the input-output behaviors of any two LPV models which are frozen equivalent. This error bound turns out to be a function of both (i) the speed of the change of the scheduling signal and (ii) the discrepancy between the coherent bases of the two LPV models. In particular, the difference between the outputs of the two models can be made arbitrarily small by choosing a scheduling signal which changes slowly enough.Finally, we introduce and study important properties of the transformation of ALPV statespace representations into Linear Fractional Representations (LFRs). More precisely, we show that (i) state minimal ALPV representations yield minimal LFRs, and vice versa, (ii) the inputoutput behavior of the ALPV representation determines uniquely the input-output behavior of theresulting LFR, (iii) structurally identifiable ALPV models yield structurally identifiable LFRs, and vice versa. We then characterize LFRs which correspond to equivalent ALPV models based on their input-output maps. As illustrated all along the manuscript, these results have important consequences for identification and control of LPV systems.