L’essor des matériaux composites à matrice céramique dans les domaines de l’aéronautique, du spatial et du nucléaire force le développement de nouveaux matériaux et procédés associés afin de répondre à l’exigence toujours plus poussée de ces secteurs d’activité. La course à la réduction des coûts de fabrication a notamment contribué à ces développements. Dans cet objectif, le LCTS contribue à développer un moyen original et alternatif pour la synthèse d’interphases et de matrices des CMC par densification du renfort fibreux : le procédé dit « de caléfaction ». Ces travaux de recherche ont pour principal objectif l’étude de précurseurs originaux pour l’élaboration de matériaux pyrocarbone (pyC) et Si-O-C par ce procédé. Ce mémoire s’articule ainsi autour de 2parties expérimentales que sont i) l’élaboration de revêtements pyC à partir de précurseurs alcools et ii)l’élaboration de revêtements Si-O-C à partir de précurseurs organosilylés.Les diverses techniques de caractérisation physico-chimique utilisées, couplées aux nombreuses expériences réalisées dans ces travaux ont permis de relier la structure et/ou la composition chimique des revêtements obtenus aux paramètres expérimentaux utilisés (précurseurs, températures et durées d’élaboration). Des conditions optimales de préparation de PyC de très haute qualité à partir d’alcools ont été obtenues. Quant au système Si-O-C, il est montré que la structure et la composition des dépôts dépendent des conditions. / The growth of ceramic matrix composite (CMC) in the fields of aeronautic, spatial and nuclear pushes the development of new material and associated processes in order to answer to the tough requirements in this business sectors. Fabrication cost savings, in particular, has helped these improvements. In this aim, the LTCS has contributed to develop an original and alternative device for the synthesis of CMC’s interphases and matrices : the “film boiling densification”.This PhD as for key objective the study of original precursors for PyC and Si-O-C fabrication using this process. This manuscript is divided into two experimental parts dedicated to : i) the fabrication of carbon coatings from alcohols and ii) the fabrication of Si-O-C coatings from silylated precursors.The diverse characterization technics coupled to the numerous experiments permitted to connect the coatings structure and/or the chemical composition to the experimental parameters (precursor, temperature,duration). Optimal conditions were found for the preparation of high quality PyC from alcohols.For Si-O-C system, it is show that structure and chemical composition depends on experimental conditions.

This thesis presents the results of a study focussed on the elucidation of the mechanisms responsible for determining the structural integrity of carbon coatings on ductile substrates. Through elucidation of these mechanisms, two different coating systems are designed; a multilayered coating and a functionally graded coating. While concentrating upon carbon coatings, the findings of this study are applicable to a broad range of hard coatings on ductile substrates. The thesis concludes with a chapter outlining a brief study of the effects of gold coatings on silicon under contact load at moderate temperatures to complement the major part of the thesis. Carbon coatings with differing mechanical properties were deposited using plasma enhanced chemical vapour deposition (PECVD), filtered assisted deposition (FAD) and magnetron sputtering deposition methods. Combinations of these techniques plus variation of deposition parameters enabled composite multilayered and functionally-graded coatings to also be deposited. Substrates were ductile metals; stainless steel and aluminium. Characterisation of the coating mechanical properties was undertaken using nanoindentation and nano-scratch tests. The same techniques were used to induce fracture within the coatings to allow subsequent analysis of the fracture mechanism. These were ascertained with the assistance of cross-sectional imaging of indents prepared using a focussed ion beam (FIB) mill and transmission electron microscopy (TEM) using specimen preparation techniques also utilising the focussed ion beam mill. A two dimensional axisymmetric finite element model (FEM) was built of the coating systems using the commercial software package, ANSYS. Substrate elastic-plastic properties were ascertained by calibrating load-displacement curves on substrate materials with the finite element model results. Utilising the simulation of spherical indentation, the distribution of stresses and the locations for fracture initiation were ascertained using finite element models. This enabled determination of the influence such factors as substrate mechanical properties, residual stresses in the coatings and importantly the variation of elastic properties of the different coating materials. Based upon the studies of monolithic coatings, simulations were undertaken on multilayer and functionally-graded coatings to optimise design of these coating types. Based on the results of the modelling, multilayered and functionally graded coatings were then deposited and mechanical testing undertaken to confirm the models. Three major crack types were observed to occur as the result of the spherical nanoindentation on the coatings; ring, radial and lateral cracks. Ring cracks were found to initiate from the top surface of the film, usually at some distance from the edge of the spherical contact. Radial cracks usually initiated from the interface between the coating and the substrate directly under the symmetry axis of indentation and propagated outwards in a non symmetrical star-like fashion. Lateral cracks formed either between layers in the multilayer coatings or at the interface with substrate. Ring and radial cracks were found to form upon loading whereas lateral cracks formed upon both loading and unloading depending upon the crack driving mechanism. Pop-in events in the load displacement indentation curve were found to be indicative of the formation of ring cracks, while the formation of the other types of cracks was not signified by pop-ins but rather by variations in the slope of the curve. The substrate yield strength was found to influence the initiation of all crack systems while compressive stresses in the coating were seen to only influence the formation of ring and radial cracks. However, it was also noted that the initiation of one form of crack tended to then hinder the subsequent formation of others. In multilayer coatings, the lateral cracks were suppressed, as opposed to the monolayer coating system, but a ring crack was observed. This drawback in the multilayer system was successfully addressed by the design of a graded coating having the highest Young??s modulus at the middle of the film thickness. In this coating, due to the graded nature of the elastic modulus, the stresses at the deleterious locations (top surface and interface) were guided toward the middle of coating and hence increased the load bearing capabilities. The effect of substrate roughness upon the subsequent surface roughness of the coating and also upon the fracture process of the coating during indentation was also investigated. For the coatings deposited on rough substrates, the radial cracks were observed to form initially and this eventfully delayed the initiation of ring cracks. Also the number of radial cracks observed at the interface was found to be proportional to the distribution of the interfacial asperities. In summary, the study elucidated the fracture mechanisms of monolayer, multilayer and graded carbon coatings on ductile substrates under uniaxial and sliding contact loading. The effects of the yield strength, surface roughness of the substrate, along with the residual stress and elastic modulus of the coatings on the fracture of coatings were investigated. The study utilised finite element modelling to explain the experiments observations and to design coating systems.

Uncoated defects in hot dip metal-coated steel products result from non-wetting of the steel surface by the molten alloy. The occurrence of uncoated defects is highly detrimental to product quality and production efficiency; uncoated defects compromise the appearance and anti-corrosion performance of hot dip metal-coated steel products and causes time delays in the application of subsequent surface treatments. Although many studies have been directed towards evaluating the effect of steel pre-heat temperature and oxidation on the formation of uncoated defects, fewer investigations have analysed how oil-derived residues remaining on steel surface following the cold rolling and furnace cleaning processes impact upon hot dip metallic coating quality. Furthermore, although a considerable amount of research has focussed on the process of deposit formation in lubricants used in other applications, the composition of oily residues remaining after the continuous annealing process, and the origins of these residues in the original rolling oil formulation, are poorly understood. The primary focus of the present work has been to gain an improved understanding of relationships between cold rolling oil composition, oil residue-formation characteristics and the occurrence of uncoated defects in 55Al-43.4Zn-1.6Si hot dip metallic coatings. Several key classes of rolling oil ingredients which decompose to leave high levels of thermally-stable residue have been identified. The thermal decomposition processes undergone by a variety ingredients within these classes have been studied under both oxidising and reducing conditions using Thermogravimetric Analysis (TGA) and Pressure Differential Scanning Calorimetry (PDSC) techniques, with chemical characterisation of the decomposition process and the resultant thermally-stable residue by infrared spectroscopy. Model blends of each ingredient in a typical cold rolling oil base ester have also been evaluated by TGA and PDSC to identify the impact of ingredient concentration and chemical structure on the amount of oily residue formed. The results of these investigations have been related to the impact of the ingredients on 55Al-43.4Zn-1.6Si hot dip metallic coating quality through the performance of industrial-scale hot dipping trials and hot dip simulation studies. In order to translate these results into a context more closely aligned with industrial conditions, the effect of processing variables, including furnace atmosphere and the availability/concentration of iron in contact with the rolling oil at the steel surface, on the decomposition process of a fully-formulated commercial cold rolling oil has also been investigated. The information gained can potentially be used to tailor operating conditions within the cold rolling/continuous hot dip metallic coating processes to enhance steel surface cleanliness. Finally, the deposit-forming tendencies of an array of different commercial cold rolling oils have been evaluated, leading to the development of a thermal analysis-based test for screening cold rolling oils with respect to their likely impact upon 55Al-43.4Zn-1.6Si hot dip metallic coating quality. This test, together with the understanding obtained on the effect of different rolling oil ingredients on hot dip metallic coating quality, can be used within the industry to formulate improved cold rolling oils.

Thesis (M.S.)--State University of New York at Binghamton, Thomas J. Watson School of Engineering and Applied Science, Materials Science and Engineering Program, 2006. / Includes bibliographical references.

Cette étude se place dans le contexte de réalisation de nouveaux matériaux à bas coût pour l'optique non linéaire. Pour cela, nous avons développé une approche nanocomposite, basée sur la fabrication de films Laponite/ LiIO3. Ces films sont réalisés à l'aide d'une technologie issue du procédé sol-gel puis recuits pour cristalliser LiIO3, matériau optiquement non linéaire, et ils présentent de bonnes potentialités en raison d'une concentration en nanocristaux actifs importante. De plus, la possibilité d'orienter les nanocristaux pendant la cristallisation par l'application d'un champ électrique permet d'obtenir un matériau présentant des propriétés optiques non linéaires comparables à celles des matériaux usuels de ce domaine.<br /><br />Au cours de ce travail, nous avons tout d'abord affiné le modèle de structure des films composites en mettant en évidence l'absence d'intercalation du LiIO3 dans l'espace interplaquette. Par la suite, nous avons optimisé le processus de dépôt des films. En particulier, nous avons amélioré sa reproductibilité en déterminant les principaux paramètres intervenant durant le process : pH, viscosité, température de recuit, champ électrique d'orientation. Par ailleurs, nous avons montré que le vieillissement des films, une limitation importante de ce procédé, pouvait être ralenti par le dépôt d'un film protecteur. Nous sommes ainsi parvenus à définir un ensemble de critères permettant la réalisation de films nanocomposites aux propriétés optiques linéaires et non linéaires satisfaisantes.<br /><br />Dans une seconde partie, nous nous sommes attachés à caractériser et modéliser les propriétés optiques linéaires et non linéaires des films nanocomposites Laponite/LiIO3. Nous avons cherché à établir le lien entre ces propriétés et la structure des films, et nous avons observé l'influence de la distribution d'orientation des nanocristaux d'iodate de lithium au sein de la matrice de Laponite sur les propriétés optiques non linéaire et pour le guidage. Cette étude, au caractère plus fondamental, a permis de construire des modèles adaptés à ce type de matériaux composites permettant d'interpréter les résultats expérimentaux et de prévoir les indices de réfraction et les propriétés optiques non linéaires de ce type de matériau.

La pérennisation de la valorisation agricole des boues résiduaires passe par une optimisation des techniques d'épandage. Dans le cas présent, nous nous sommes focalisés sur les phénomènes intervenant sur les disques qui constituent la table d'épandage, en tenant compte à la fois des caractéristiques rhéologiques du matériau à épandre et des réglages mécaniques du matériel. On montre d'abord par des expériences de rhéométrie qu'aux faibles contraintes, les boues ne peuvent s'écouler de manière stable: la déformation totale du matériau résulte d'une compétition entre la restructuration pendant la phase de repos précédant le cisaillement et la déstructuration due au cisaillement. De plus, lors du cisaillement avec une surface lisse, un glissement apparaît dans la même gamme de contrainte, à partir d'une déformation critique. Il se forme une fine couche de liquide newtonien entre la surface qui induit le cisaillement et le reste du matériau dans l'entrefer. Au delà d'une contrainte critique, l'écoulement devient homogène, quelque soit la nature de la surface, lisse ou rugueuse. A partir de travaux sur maquette, nous avons analysé la déformation d'un échantillon de fluide à seuil engendrée par l'application d'une force centrifuge d'intensité croissante, en accélérant progressivement la vitesse de rotation du disque. On montre que la dynamique de l'étalement se résume en trois phases distinctes. Aux faibles vitesses de rotation, le matériau se comporte comme un solide viscoélastique et subit de faibles déformations élongationnelles. Quand la vitesse de rotation dépasse une valeur critique, la déformation n'est plus homogène: le matériau se comporte comme un liquide en périphérie, et comme un solide au centre de l'échantillon. Seule la partie liquide s'étale en formant un bourrelet. On montre ainsi que les paramètres viscoélastiques du matériau et l'initiation de l'écoulement sont étroitement liés: plus le seuil de contrainte est élevé, plus la vitesse critique est grande. Enfin, l'étalement se localise au sein de digitations qui se forment à partir du bourrelet. Finalement, on montre qu'au cours de l'épandage les paquets de boues arrivant sur la table d'épandage ne sont pas cisaillés sous l'action de la force centrifuge, mais ils subissent une élongation puis une fragmentation avant d'être projeté à la sortie du disque. On démontre au passage que les pâles n'ont aucune utilité sur le procédé d'émiettement.

Les diodes électroluminescentes hybrides organiques-inorganiques ou Quantum Dot- Light-Emitting Diodes (QD-LED) sont le parangon de dispositifs qui associeraient les propriétés semi-conductrices des matériaux organiques conjugués, ainsi que leur facilité de mise en oeuvre en couche mince, aux propriétés exceptionnelles (couleur accordable par la taille, bon rendement quantique de photoluminescence) des nanoparticules nanométriques de semi-conducteurs inorganiques, telles que CdSe/ZnS (TOPO). Diverses approches ont été explorées pour optimiser les QD-LEDs ; elles reposent sur la réalisation d'architectures diverses (uni, bi, tri couches) combinant matériaux organiques et QDs (en couche compacte ou dispersés dans une matrice), obtenues par diverses méthodes de dépôt (spin coating, tampon, impression jet d'encre). Dans ce travail de thèse, nous avons d'abord réalisé une structure originale sous forme de diodes comportant une couche hybride nanocomposite, obtenue en incorporant les QDs dans une matrice diélectrique de PMMA. Le but était de contrôler les flux de porteurs pour maximiser leur recombinaison sur les QDs. Les mesures des caractéristiques électriques, d'électro- et photoluminescence sont discutées, conjointement à des études de la morphologie des dépôts par AFM qui ont montré comment la microstructure dépendait des caractéristiques du, ou des, solvant(s) utilisé(s) pour le spin coating. D'une façon générale, les nanoparticules sont agrégées et la couche apparait inhomogène et rugueuse, ce qui permet des contacts entre les couches de transport. La faible électroluminescence résulterait de transferts d'excitation à partir d'états excités produits par les recombinaisons à ces endroits. Dans une seconde partie, nous avons déposé les QDs par spin coating à partir de solutions dans l'heptane, un solvant qui ne perturbe pas les couches organiques préalablement déposées. Les morphologies observées sont celles d'ilots compacts, avec des taux de couverture allant de 0 à 100%. La diminution, puis la disparition, de l'électroluminescence aux fortes couvertures confirme que l'émission des QDs provient exclusivement de transferts d'excitation à partir d'espèces excitées générées à l'interface organique-organique, en fonction de la nature des matériaux organiques. Les mécanismes d'injection des porteurs à la cathode, dépendant de la nature de celle-ci et de la couche de transport d'électrons, sont variables eux-aussi.

<p>The thesis describes an investigation into the interaction between the conducting polymer and cellulosic materials, and the preparation of electroconductive paper. The adsorption behavior of the conducting polymer onto cellulosic materials was characterized. Poly(3,4-ethylenedioxythiophene) doped with poly(4-styrene sulfonate) (PEDOT:PSS) was used as conducting polymer because of its attractive properties in terms of conductivity, water solubility, and environmental stability. The model substrate used for adsorption was microcrystalline cellulose (MCC). Various pH levels and salt concentrations were explored to completely understand the adsorption behavior of PEDOT:PSS. The variation in surface charge characteristics when the pH and salt concentration were changed was monitored by polyelectrolyte titration and zeta potential measurement. The adsorption isotherm showed a broad molecular distribution of the conducting polymer and considerable interaction between the polymer and MCC. As the pH of the solution was increased, the adsorbed amount decreased. With varying salt concentrations, the adsorption passed through a maximum. The extent of deposition of PEDOT:PSS on the surface of cellulosic fibers was investigated using X-ray Photoelectron Spectroscopy (XPS) with a commercial base paper as substrate. XPS analysis of dip-coated paper samples showed PEDOT enrichment on the surface. The degree of washing the dip-coated paper with acidic water did not significantly affect the PEDOT enrichment on the surface.</p><p> </p><p>A base paper was coated with PEDOT:PSS blends to produce electroconductive papers. The bulk conductivities (σ_dc) of the coated papers were measured using a four-probe technique and impedance spectroscopy. One-side and two-side coating gave comparable conductivity levels. Various organic solvents added to the PEDOT:PSS dispersion at different concentrations showed various effects on the bulk conductivity of the coated paper. Blends containing sorbitol and isopropanol did not enhance the bulk conductivity of the coated paper, and at high concentrations these organic solvents lowered the conductivity. Paper samples coated with a PEDOT:PSS blend containing N-methylpyrrolidinone (NMP) and dimethyl sulfoxide (DMSO) exhibited a higher conductivity than when coated with pure PEDOT:PSS, due to conformational changes and their plasticizing effect. The effect of calendering was investigated and only the sample subjected to 174 kN/m line load after coating showed significant conductivity enhancement. The addition of TiO₂ pigment lowered the bulk conductivity of the paper. Contact angle measurements were made to monitor the effect of coating the paper with PEDOT:PSS blends on the hydrophilicity of the paper samples. The amount of PEDOT:PSS deposited in the fiber network was determined using total sulfur analysis. Thus, this study makes use of conventional paper surface treatment as method for achieving bulk conductivity of paper in the semi-conductor range without significantly decreasing the paper strength.</p> / Printed Polymer Electronics

<p>Inkjet is a digital printing process where the ink is ejected directly onto a substrate from a jet device driven by an electronic signal. Most inkjet inks have a low viscosity and a low surface tension, which put high demands on the coating layer’s porosity and absorbency characteristics.</p><p>The aim of this study has been to gain an increased knowledge of the mechanisms that control the sorption and fixation of inkjet inks on coated papers. The focus has been on printability aspects of high print quality (although not photographic quality) laboratory-coated inkjet papers for printers using aqueous-based inks.</p><p>Papers coated solely with polyvinyl alcohol (PVOH) and starch presented excellent gamut values and good print sharpness over the uncoated substrate, due to good film-forming characteristics observed by light microscopy and ESCA. ESEM analyses showed the complexity and variation of PVOH surface structures, which has probably explained the wide scatter in the colour-to-colour bleed results. Pure PVOH coatings also gave a surface with high gloss variations (2-8 times greater than that of commercial inkjet papers), prolonged ink drying time, and cracked prints when using pigmented inks. When an amorphous silica gel pigment (with broad pore size distribution) was used in combination with binder, a new structure was formed with large pores in and between the pigments and a macro-roughness generated by the large particles. The inkjet ink droplets could quickly penetrate into the large pores and the time for surface wicking was reduced, which was beneficial for the blurriness. However, the macro-roughness promoted bulk spreading in the coarse surface structure, and this tended to increase the line width. Finally, when the ink ends up within the coating, the colorant is partly shielded by the particles, and this reduced the gamut area to some extent. The binder demand of the silica pigments was strongly related to their pore size distributions. Silica gel required two to three times the amount of binder compared to novel surfactant-templated mesoporous silica pigments (with small pores and narrow pore size distribution). This finding was attributed to the significant penetration of PVOH binder into the pores in the silica gel, thereby, increasing its binder demand. Furthermore, this binder penetration reduced the effective internal pore volume available for rapid drainage of the ink vehicle. Consequently, the surfactant-templated pigments required significantly lower amounts of binder, and gave improvements in print quality relative to the commercial pigment.</p>

The chemistry of hafnium oxide based and materials are described in the context of ion exchange and lithography. HafSOx, represented by the composition HfO₂₋[subscript x](SO₄)x, is described to possess a significant capacity towards ion exchange in acidic and basic solutions, enabling films of HafSOx to be cleanly and readily be converted to oxide films by neutralization. The optical properties, composition and morphology of these oxide films are characterized. The fabrication of mixed metal oxide films is demonstrated via solution and ion exchange routes. This thesis also explores the photoresist chemistry of HafSOx resists. A photoreaction mechanism based on the decomposition of peroxide is proposed. In addition, the patterning of HafSOx films by 193 nm, extreme ultraviolet (EUV) and electron beam radiation is described, and the influence of composition on its photoresist properties is studied. / Graduation date: 2012