The field of Tissue Engineering has developed in response to the shortcomings associated to the replacement of tissues lost to disease or trauma: donor tissue rejection, chronic inflammation, and donor tissue shortages. The driving force behind Tissue Engineering is to avoid these problems by creating biological substitutes capable of replacing the damaged tissue. This is done by combining scaffolds, cells and signals in order to create living, physiological, three-dimensional tissues.Scaffolds are porous biodegradable structures that are meant to be colonised by cells and degrade in time with tissue generation. Scaffold design and development is mainly an engineering challenge, and is the goal of this PhD thesis.The main aim of this thesis is to develop and characterise scaffolds for Tissue Engineering applications. Specifically, its objectives are: 1. To study, optimise and characterise two scaffold processing methods: Solvent Casting and Phase Separation. This is done by experiment design analysis. 2. To characterise the degradation, surface properties, and cellular behaviour of the scaffolds produced. The scaffolds are made of a composite of polylactic acid polymer and a calcium phosphate soluble glass. The comparison of the two processing methods reveals that in general, the solvent cast scaffolds have higher porosities and lower mechanical properties than the phase-separated ones. Two compositions containing 20 weight % and 50 weight % of glass particles were chosen for further characterisations including degradation, surface properties and cellular behaviour. The degradation of the scaffolds was studied for a period of 10 weeks. The evolution of various parameters such as: morphology, weight loss, mechanical properties, thermal transitions and porosity, was monitored. Scaffolds produced via solvent casting were found to be more severely affected by degradation than phase-separated ones. The surface properties of the scaffolds were measured by modelling the scaffold pore walls as thin composite films. The morphology, topography, surface energy and protein adsorption of the films was characterised thoroughly. Again, the processing method was critical in determining scaffold properties. Films made via phase-separation processing had markedly different properties due to extensive coating of the glass particles by the polymer. This made the surfaces rougher and more hydrophobic. When the glass particles are not completely coated with polymer, they increase the material's hydrophilic and protein adsorption properties, thus confirming the potential biological benefits of the inclusion of the calcium phosphate glass.The biological behaviour of the scaffolds was characterised by means of in vitro cell cultures with primary osteoblast stem cells and cells from a stable cell line, under static and dynamic conditions. Their morphology, proliferation and differentiation were monitored. Both types of scaffolds sustained osteblastic cell growth. The solvent cast scaffolds were easily colonised by cells which migrated throughout their structure. The cells on the phase-separated scaffolds, however, tended to form thick layers on the scaffold surface. Finally, an alternative characterisation technique was explored applying Synchrotron X-Ray Microtomography and in-situ micromechanical testing. These experiments allowed for the qualitative and quantitative analysis of the microstructure of the scaffolds both at rest and under strain. A finite element model of the solvent cast scaffolds was developed and a preliminary analysis was performed. This technique could be used to complement and overcome some of the limitations of traditional mechanical characterisation of these highly porous materials.

En aquesta tesi s'estudia la passivació del silici cristal·lí per a la producció de cèl·lules solars d'alta eficiència (> 20%) a baix preu.Actualment la indústria fotovoltaica empra capes de nitrur de silici crescut mitjançant la tècnica PECVD. Com a alternativa, es presenta el carbur de silici amorf (a-SiC), també crescut mitjançant PECVD. Resultats anteriors mostren que la passivacio del silici a partir de carbur de silici amorf son excel·lents quan el material és ric en silici i dopat amb fòsfor. L'alt contingut en silici provoca absorció de la llum a la capa, que no es tradueix en corrent elèctric, fent d'aquesta manera que el material sigui només útil quan s'aplica a la cara no il·luminada de la cèl·lula.L'objectiu d'aquesta tesi és millorar les propietats de passivació del carbur de silici afegint els requisits indispensables en cèl·lules solars: uniformitat, transparència i propietats antireflectants, estabilitat a llarg termini i enfront altes temperatures. A part de les aplicacions tecnològiques també es pretèn entendre millor les propietats fonamentals de passivació.Els principals resultats són: - La passivació millora a mesura que s'incrementa el gruix de la capa de a-SiC, fins arribar a una saturació a partir de 50 nm. El mecanisme responsable es una millor saturació dels defectes de la interficie amb hidrogen. Al contrari del que es pensava a priori, la càrrega el·lèctrica emmagatzemada a la capa es manté constant amb el gruix.- Experiments amb "corona charge" indiquen que l'origen de la càrrega el·lèctrica que produeix la passivació per efecte de camp es troba en la densitat d'estats a la interfície.- No ha estat possible trobar una capa tranparent (rica en carboni) amb bona passivació. La millor aproximació per combinar passivació més transparència és emprar dues capes, una molt prima rica en silici per passivar i l'altra rica en carboni per aconseguir les propietats antireflectants adequades. S'ha optimitzat el gruix de la capa rica en silici per aconseguir un compromís entre la pèrdua de corrent degut a l'absorció de la llum a la capa i les propietats de passivació. Aquesta combinació de doble capa s'ha fet servir per passivar bases tipus p i emissors tipus n amb resultats excel·lents. Finalment, amb la doble capa es va poder fabricar la primera cèl·lula passivada amb carbur de silici amb una eficiencia > 20%.- S'ha desenvolupat un material nou: l'al·leació de silici, carboni i nitrogen dopada amb fòsfor. Aquest material ha donat els millors resultats de passició fins ara obtingut dins el nostre grup en bases tipus p i tipus n i en emissors tipus n. La composició òptima és rica en silici i la combinació de capes dobles amb diferents composicions, com en el cas anterior, torna a donar bons resultats de passivació i transparència. - S'han desenvolupat experiments d'estrès tèrmic a alta temperatura. Les propietats de passivació es veuen fortament afectades desprès de l'estrès si les capes són riques en silici. D'altra banda, les dobles capes mostren una estabilitat molt més alta a l'estrès tèrmic. / The thesis focuses on the study of surface passivation of crystalline silicon to produce high efficiency solar cells (with conversion efficiencies > 20%) at reduced prices. The state of the art in surface passivation is done by thin films of amorphous silicon nitride grown by Plasma Enhanced Chemical Vapour Deposition (PECVD) and it is a very well established material in the photovoltaic field.In this thesis we offer an alternative that is based on amorphous silicon carbide (a-SiC), also grown by PECVD. The passivation properties of silicon carbide have been already studied in our group finding that excellent results can be obtained when the films are rich in silicon, especially for those doped with phosphorus to make a n-type material. Because this feature leads to undesirable absorption of solar light within the films that does not contribute to the photocurrent, silicon carbide would then be relegated to passivate only the rear side of the solar cell.The aim of this work is to improve surface passivation properties developed previously and add compulsory requisites for the application of crystalline solar cells. These requisites are: uniformity, transparency and antireflective properties, stability under long term operation and stability under high temperature steps (allowing screen printing processes). Also it is the willing to provide a better understanding of the fundamental properties.The main results achieved are enumerated hereafter:- Surface passivation improves with the film thickness and then saturates for films thicker than 50 nm. The mechanism responsible for this improvement is not an increase of the electric charge in the film, as in principle could be thought, but a better saturation of defects by the presence of hydrogen. The amount of charge density seems to be independent of the film. - Experiments of corona charge reveal some treats about the nature of the charge density to provide the field effect passivation. The origin of the charge seems to be a continuous density of states at the interface, rather a fixed charge allocated in the film.- None of the attempts using carbon rich films, which are transparent and with antireflective properties, resulted in excellent surface passivation. Such attempts included variation of the deposition parameters, use of remote plasma PECVD with high incorporation of hydrogen, and introduction of nitrogen of in the phosphorus doped a-SiC films. Therefore, up to now it becomes apparent that it is a fundamental property of silicon carbide films the necessity to be rich in silicon to perform surface passivation.- The way to combine surface passivation and antireflective properties was applying stacks of different a-SiC layers: one silicon rich and one carbon rich. The thickness of the silicon rich layer was optimized to reach a trade-off between level of passivation and lost of photocurrent due to the absorption in the film. The stacks were used to passivate p-type bases, with reasonably good results, and n+- type emitters, with very good results. The stacks provided the the first silicon solar a-SiC rear side passivated with efficiency above 20%.- A new material was tested: a ternary alloy of silicon, carbon and nitrogen doped with phosphorus. This material was applied to n- and p-type bases and n+-type emitters, presenting the best results in surface passivation achieved by our group, and comparable to surface passivation record achieved by amorphous silicon carbide. Best composition was rich in silicon, and again stacks of silicon rich and carbon rich films was combined successfully. - Stability against thermal processes was tested on different passivation schemes. After the treatment, the passivation is strongly reduced for single silicon rich films, which were offering good initial results. On the other hand, the stacks with a second carbon rich film maintain reasonably well the surface passivation properties.

La difusión de los materiales cerámicos en muchos campos de la industria es amplia y está en fuerte expansión, debido a las excelentes propiedades de estos materiales, ya sean mecánicas, térmicas, tribológicas o biológicas. Sin embargo, su fragilidad intrínseca y falta de fiabilidad limitan una mayor difusión en esas aplicaciones donde se precisa alta resistencia estructural. La producción de composites multilaminares es un camino prometedor para aumentar la fiabilidad de los cerámicos. Los cerámicos multicapa permiten que las propiedades mecánicas sean mejores que las de los componentes, debido a la presencia en la superficie de tensiones residuales de compresión provocadas diferencias de expansión térmica entre las capas.Las aplicaciones óptimas de estos materiales son las que están relacionadas con las propiedades superficiales; por eso la respuesta a las cargas por contacto son especialmente importantes para caracterizar las propiedades mecánicas y para mejorar el diseño de cerámicos composites avanzados.Las técnicas de indentación Hertziana son herramientas muy útiles para estudiar este tipo de carga, que por otro lado es difícil de caracterizar por ensayos mecánico tradicionales. El daño por contacto en materiales frágiles aparece principalmente como grietas anillo en la superficie, que pueden desarrollarse como grietas cono, características de este tipo de carga. Este agrietamiento es perjudicial para la funcionalidad del material, y puede llevar al fallo de la pieza. Las cerámicas tenaces, por otro lado, pueden presentar un daño, cuasi-plástico, que se genera debajo la superficie en forma de microagrietamento, y que es causa de deformación inelástica.En esta tesis, se caracteriza la resistencia al daño por contacto materiales cerámicos en base alúmina, incluyendo todos los aspectos de ese daño, desde la aparición de fisuras superficiales, a la propagación de grietas frágiles en la primera capa y su influencia sobre la resistencia del material, hasta el fallo inducido por carga de contacto. Se comparan medidas experimentales con análisis a los Elementos Finitos de los parámetros involucrados en cada caso, lo que permite formular pautas para una correcta caracterización y diseño de cerámicas multicapas avanzados.Se vio que la presencia de tensiones residuales es efectiva en mejorar la resistencia a la formación de grieta anillo, sea generada por cargas monotónicas, cíclicas o estáticas.La alta resistencia frente a este último tipo de carga revela que existen mecanismos de puenteo intergranular que se oponen a la formación de grietas, lo que era inesperado por el tamaño de grano fino, y que se atribuye a un efecto de grieta corta, comparada con la microestructura. Ensayos cíclicos de larga duración mostraron, por otro lado, que en los materiales multicapas aparece daño superficial más severo que en los monolíticos, lo que sugiere un cambio del daño predominante hacía una degradación superficial producida por cuasi-plasticidad.Las tensiones residuales afectan tanto la longitud como el ángulo de la grieta cono. Se modeló el problema mediante Elementos Finitos y algoritmos de propagación de grieta, lo que permitió predecir el crecimiento de grieta en función tanto de las tensiones residuales, como de otros parámetros microestructurales, y determinar del ángulo de la grieta cono en materiales policristalinos.La respuesta a cargas remotas de materiales indentados, en otras palabras la degradación de la resistencia, se ve afectada por la geometría de la grieta cono, y por otros factores que son consecuencia de la estructura laminar, tales como las tensiones residuales y la redistribución de carga por el desajuste elástico entre capas. Asimismo, la resistencia por contacto, o sea la resistencia a compresión roma localizada, se ve mejorada en materiales laminares, como consecuencia de las tensiones residuales. Sin embargo, se evidenció que existe el riesgo de que se genere tensión elevada en las capas interiores bajo ambos tipos de carga, y se propusieron consideraciones generales sobre el diseño de materiales laminares.En definitiva, se consiguió una caracterización exhaustiva de las propiedades de contacto mecánico de los materiales estudiados, y se amplió y mejoró el conocimiento de la propagación de grieta en materiales frágiles policristalinos. / The use of ceramic materials in many industrial fields is spread and ever-increasing, for their excellent properties, either mechanical, thermal, tribological or biological. However, their intrinsic brittleness and lack of reliability are obstacles to further spreading these materials in applications where structural resistance is required. To build multilayered composite structures is a promising way which aims to increase the reliability of ceramics. As it is common in composite materials, layered materials allow the mechanical properties to be superior to those of the constituent materials, in the studied case due to the presence of compressive residual stress in the surface.The best applications for such materials are those related to the surface properties; for this reason the response to contact loading is especially important to characterize the mechanical properties and to assist in the design of advanced ceramic composites. Hertzian indentation techniques provide a powerful tool to study such type of loading, which is otherwise difficult to characterize with the traditional mechanical testing methodologies. Contact damage in brittle materials appears mainly as surface ring-cracks, which can develop in a characteristic cone crack. Such fissuration is detrimental to the functionality of the material, and can lead to the failure of the component. Tough ceramics often present another type of damage, the so-called quasi-plasticity, generated as subsurface microcracking and which is cause of inelastic deformation.In this thesis, alumina-based ceramic laminates were characterized in their resistance to contact damage in all its aspects, starting from the appearance of surface fissures, to the propagation of brittle cracks in the first layer and its influence on the material strength, to the contact loadinginduced failure. Experimental measurements were coupled with Finite Element analysis of the involved parameters, which assisted in formulating comprehensive guidelines for the correct characterization and the design of advanced multilayered ceramics. The presence of residual stress in ceramic laminates proved to be effective in improving the material resistance to the ring cracking, generated by monotonic, cyclic and longlasting tests.The better resistance to these latter revealed the existence of grain bridging hindering the crack formation, unexpected in fine-grained alumina and which was related to the small crack character of the ring crack. Longer lasting cyclic tests showed that more severe damage appears in the multilayered materials than in the monolithic one, suggesting a modification of the redominant damage mode to quasi-plastic-derived surface degradation.Propagation of long cone cracks is affected by residual stress in both the length and angle. An automatic Finite Element model of crack propagation allowed to predict crack growth as a function of both the extrinsic residual stresses and of microstructural parameters, which helped address the long-open question of the cone crack angle on polycrystalline materials.The response to remote loading of indented materials, in other words the strength degradation, is conditioned by the cone crack geometry, as well as by other factors deriving from the laminated structure, such as the presence of residual stress itself and the load redistribution due to the elastic mismatch between layers. Similarly, the contact strength, i.e. the resistance to local blunt compression, is improved in the composite materials as a consequence of the residual stresses. Nevertheless, the risk of high stress in the lower tensile layers was highlighted for both types of loading and general consideration on the design of laminated materials were proposed.In the overall, a comprehensive characterization of the contact properties of the studied materials was achieved, and the understanding of crack propagation on brittle polycrystalline materials was broadened and improved.