The work presented in this thesis concerns surface energy modification and patterning of the surfaces of conjugated polymers. Goniometry and Wilhelmy Balance techniques were used to evaluate the surface energy or wettability of a polymer’s surface; infrared reflectionabsorption spectroscopy (IRAS) was used to analyse the residuals on the surface as modified by a bare elastomeric stamp poly(dimethylsiloxane) (PDMS). The stamp was found to be capable of modifying a polymer surface. Patterning of a single and/or double layer of conjugated polymers on the surface can be achieved by surface energy controlled dewetting. Modification of a conjugated polymer film can also be carried out when a sample is subjected to electrochemical doping in an aqueous electrolyte. The dynamic surface energy changes during the process were monitored in-situ using the Wilhelmy balance method. This thesis also concerns studies of conjugated polymer-based optoelectronics, including light-emitting diodes (PLEDs), that generate light by injecting charge into the active polymer layer, and solar cells (PSCs), that create electrical power by absorbing and then converting solar photons into electron/hole pairs. A phosphorescent metal complex was doped into polythiophene to fabricate PLEDs. The energy transfer from the host polymer to the guest phosphorescent metal (iridium and platinum) complex was studied using photoluminescence and electroluminescence measurements performed at room temperature and at liquid nitrogen temperature. PSCs were prepared using low-bandgap polyfluorene copolymers as an electron donor blended with several fullerene derivatives acting as electron acceptors. Energetic match is the main issue affecting efficient charge transfer at the interface between the polymers and the fullerene derivatives, and therefore the performance of the PSCs. Photoluminescence, luminescence quenching and the lowest unoccupied molecular orbital (LUMO) together with the highest occupied molecular orbital (HOMO) of the active materials in the devices were studied. A newly synthesized fullerene, that could match the low-bandgap polymers, was selected and used as electron acceptor in the PSCs. Photovoltaic properties of these PSCs were characterised, demonstrating one of the most efficient polymer:fullerene SCs that generate photocurrent at 1 μm. / On the day of the defence the status of article number III was Manuscript and article VII was Accepted.

El conocimiento de las interacciones entre célula/proteína/biomaterial es fundamental para la ingeniería de superficies debido a las numerosas aplicaciones biomédicas y biotecnológicas que se están desarrollando así como al éxito clínico que han alcanzado muchos implantes. La respuesta biológica final inducida por los implantes está fuertemente influenciada por las interacciones superficiales entre los componentes biológicos y el material sintético. Las propiedades físicas y químicas de la superficie de un biomaterial, en lugar de las propiedades en su masa, influyen directamente en la capa de proteínas que se adsorben sobre el biomaterial y, como consecuencia de ello, en la respuesta celular a la misma, tanto in vitro como in vivo.El objetivo de esta tesis doctoral es profundizar en el conocimiento de las interacciones material-biosistema, con el énfasis en el descubrimiento de relaciones entre las propiedades superficiales de las superficies de titanio y su respuesta biológica in vitro.El titanio comercialmente puro (Ti c.p.) está siendo ampliamente utilizado con éxito durante muchos años como biomaterial para implantes en cirugía ósea. Su excelente biocompatibilidad se basa en sus adecuadas propiedades mecánicas y, con mayor importancia, en su excelente resistencia a la corrosión. Esta última se debe principalmente a la formación espontanea de una fina película de óxido de titanio que le confiere protección natural contra los ataques degradativos. La modificación de la topografía de la superficie del titanio ha sido objeto de investigación en el pasado con el fin de mejorar la osteointegración. El granallado de partículas es una de las tecnologías más utilizadas para conferir rugosidad a las superficies del titanio. La rugosidad óptima y el tipo de partículas abrasivas del granallado para una respuesta óptima in vitro e in vivo fue previamente determinada en nuestro laboratorio. Sin embargo, todavía están por determinar cuáles son las causas últimas que llevan al biomaterial a su exitosa respuesta biológica.En este trabajo se han estudiado superficies pulidas y rugosas de Ti c.p. obtenidas mediante el granallado con partículas abrasivas de diferente composición química(Al2O3 y SiC) y diferentes tamaños (212-300μm; 425-600μm; 1000-1400μm). La completa caracterización de las propiedades física y química de la superficie, incluyendo la rugosidad, la composición química, la mojabilidad/energía libre y la carga eléctrica de las superficies ensayadas ha llevado a una serie de relevantes conclusiones. Entre ellas, cabe destacar que a) la composición química de las partículas de granallado, así como el método de esterilización fueron los principales factores que influyeron en la mojabilidad y la energía libre superficial de las superficies de titanio estudiadas, b) el método de esterilización cambió en la energía superficial el carácter de donante de electrones de las superficies mediante el cambio de la cantidad y la naturaleza de las sustancias adsorbidas, y c) la composición química de las partículas de granallado no influyó en la carga eléctrica a pH fisiológico ni en el punto isoeléctrico de las superficies.Un segundo paso consistió en el uso de una microbalanza de cristal de cuarzo con monitorización de la energía de disipación, para el estudio de la cinética de adsorción (cantidad y conformación) y de los procesos de adsorción competitiva de tres proteínas de especial interés en los procesos de curación del hueso - la albúmina de suero bovino (BSA), el fibrinógeno (Fbg), y la fibronectina (Fn)- en sensores lisos recubiertos de TiO2. Se determinaron diferentes modelos de procesos de adsorción con una, dos o múltiples pasos distinguibles en función de las proteínas en solución. La capa adsorbida de BSA mostró los cambios más significativos en sus propiedades mecánicas, de conformación y de incorporación de agua hasta que se alcanzaron las condiciones estables de adsorción de proteínas. La BSA, la más pequeña de las proteínas ensayadas, desplazó la Fn y el Fbg cuando se ensayó en condiciones de la competencia por la adsorción, indicando su mayor afinidad por las superficies de TiO2. También se emplearon técnicas de marcaje fluorescente para el estudio de la adsorción proteica en superficies rugosas granalladas. En este estudio, por un parte, se pudo determinar que la cantidad de Fn y BSA adsorbidas en las superficies granalladas está directamente correlacionada con su energía superficial. Por otra parte, se visualizó la adsorción de fibronectina en solución sobre muestras granalladas rugosas de Ti. La Fn formó un patrón irregular de adsorción con una mayor cantidad de proteína adsorbida en los picos que en los valles de la topografía.También se evaluó la organización espacial de la matriz extracelular de los osteoblastos, ECM, sobre superficies de Ti lisas y rugosas por medio de la visualización de las fibrillas de Fn teñidas con marcador fluorescente. Las células osteoblásticas depositaron las fibrillas de Fn con un determinado patrón organizado dentro de la matriz total secretada. Aparecen como una película que cubre la parte superior de las diferentes superficies rugosas de titanio. Un resultado relevante es que el espesor de esta capa aumentó con la rugosidad de la topografía subyacente. Sin embargo no más de la mitad de la máxima distancia pico-valle se cubrió con la proteína secretada y/o reorganizada.Por último, teniendo en cuenta las diferencias en la organización de la ECM y laadsorción de Fn en las superficies ensayadas de Ti, se realizó un estudio de qRT-PCR para determinar la influencia de las propiedades superficiales del titanio, con y sin preadsorción de Fn, en la respuesta osteoblástica. La expresión génica de la subunidad 5 de la integrina celular, como marcador de la adhesión celular, se incrementó en las superficies granalladas con SiC en comparación con las granalladas con alúmina. Este resultado fue correlacionado con la mayor cantidad de Fn adsorbida debido a la mayor energía superficial de las superficies granalladas con SiC. El aumento de la rugosidad, así como la presencia de partículas de alúmina en las superficies rugosas incrementó la actividad de ALP y la expresión génica de ALP mRNA por los osteoblastos, y por lo tanto su diferenciación. / The understanding of cell/protein/biomaterial interactions is critical to the engineering of substrates for numerous biomedical and biotechnological applications and to the clinical success of implants. The final biological response induced by implants is strongly influenced by the biological-components/synthetic-material surface interactions. It is well accepted that the physical and chemical surface properties of a biomaterial rather than its bulk properties will influence the protein adlayer and then the cell response to it, both in vitro and in vivo.The aim of this PhD thesis is to gain an increased understanding of the materialbiosystem interactions, with an emphasis on establishing correlations between surface properties of titanium surfaces and its in vitro biological response.Commercially pure titanium (c.p. Ti) is being widely and successfully used implant biomaterial in bone surgery over many years. Its excellent biocompatibility is based in its appropriate mechanical properties and, more importantly, in its excellent corrosion resistance, which is mainly due to the presence of a naturally-occurring thin protective titanium oxide film. Modification of titanium surface topography has been a subject of research in the past with the purpose of improving its osseointegration. Grit blasting is one of the most used technologies to roughen titanium surfaces for this purpose. The optimal roughness and type of abrasive blasting-particles for a better in vitro and in vivo response was previously determined in our lab. However, which and how different relevant surface properties of the blasted titanium surfaces induce that optimal biological behavior is still poorly understood.Smooth/polished and rough c.p. Ti surfaces obtained by blasting with abrasiveparticles of different chemical composition (Al2O3 and SiC) and different sizes (212-300μm; 425-600μm; 1000-1400μm) were studied. The comprehensive characterization of physical and chemical surface properties, including roughness, chemical composition, wettability/free energy and electrical charge of the tested surfaces led to a series of relevant conclusions. Among them, it is worth noting that a) the chemical composition of the grit-blasting particles as well as the method of sterilization were found the main factors influencing wettability and surface free energy of the titanium surfaces; b) the sterilization method changed the electron donor character of the surfaces by changing the amount/nature of physisorbed substances on the surfaces, and c) the chemical composition of the blasting particles did not influence on the electrical charge at physiological pH and the isoelectric point of the surfaces.A second step consisted in the use of a quartz crystal microbalance with monitoring of the energy dissipation to study the adsorption kinetics (amount and conformation) and adsorption competition processes of three proteins of special interest in the healing processes of bone -bovine serum albumin (BSA), fibrinogen (Fbg), and fibronectin (Fn)-on smooth TiO2-coated sensors. Different patterns of adsorption with processes in one, two or multiple distinguishable steps were determined depending of the protein in solution. The BSA adlayers showed the most significant changes in their mechanical properties/conformation/incorporation of water until steady protein-adsorption conditions were reached. BSA, the smallest of the tested proteins, displaced Fn and Fbg when in competition for adsorption, which is an indication of its higher affinity for TiO2 surfaces. Fluorescent labelling techniques where used to study protein adsorption on blasted rough surfaces. Most significantly, the amount of Fn and BSA adsorbed on blasted surfaces was positively correlated with their surface energy. The adsorption of fibronectin from solution on shot-blasted rough titanium surfaces resulted in an irregular pattern of adsorption with a higher amount of protein adsorbed on peaks than on valleys of the topography.Further, the spatial organization of the osteoblast extracellular matrix, ECM, on smooth and rough Ti surfaces was evaluated by visualizing fluorescently-stained Fn-fibrils. Osteoblast-like cells deposited Fn- fibrils in a specific facet-like pattern that was organized within the secreted total matrix. It appeared as a film overlying the top of the different rough titanium surfaces. Interestingly, the thickness of this layer increased with the roughness of the underlying topography, but no more than half of the total maximum peak-to-alley distance was covered.Finally, taking into consideration the differences in ECM organization and Fn adsorption on the tested Ti surfaces a qRT-PCR study was carried out to elucidate the influence of titanium surface properties with and without Fn-precoatings on the osteoblast response. The expression of 5 integrin subunit gene, as a marker for cell adhesion, was increased in SiC-blasted surfaces compared to alumina-blasted surfaces. This was related to the higher amount of adhesive-protein Fn adsorbed caused by the higher surface energy of SiC-blasted surfaces. The increase of roughness as well as the presence of alumina particles on blasted surfaces increased ALP activity and ALP mRNA gene expression by osteoblasts, and so their differentiation.This research work contribute to increase our knowledge on the interactions taking place at the bio/non-bio interface between different biological components -water, proteins, cells- and materials of clinical relevance, such as rough titanium. Theintertwined effects of the different properties of the synthetic surfaces appear as a challenge to unravel the ultimate causes that determine the fate of cells on synthetic biomaterials.

Interfacial adhesion and friction are significant factors in determining the reliability of small-scale mechanical devices such as with MEMS and the computer head/disk interface (HDI). As the interface spacing becomes smaller, operational failure via stiction has become a growing concern in these systems. Fundamentally, interface failure is related to mechanical instability of the interface caused by capillary effects. When liquid is present in a small-scale interface, large concave meniscus curvatures often develop at the liquid-vapor interface, leading to negative pressures in the liquid film and large tensile forces on the surfaces. When the elastic restoring force cannot balance the capillary force, the interface will lose its stability and collapse into intimate contact (jump-on). In addition, when the elastic bodies are then pulled away from contact, separation may occur suddenly and is related to another form of instability (jump-off). The jump-on and jump-off behaviors determine the strength of interfacial adhesion. In this study, the interaction between two elastic bodies coupled via a small liquid bridge was investigated. Geometries of two half-spaces and two sphere contact were considered. Stable equilibrium configurations were determined, and the mechanical stability of the interface was examined. Jump-on and jump-off conditions were given out. Then the theory was applied to study the approach and detachment processes of two elastic spheres in the presence of a liquid bridge. Critical values of the control variables at jump-on and jump-off were found. The pull-off force was calculated as a measure of interfacial adhesion. The results provide insight on some experimental data in the literature.

Phosphonic acids are known to bind strongly to a variety of metal oxide surfaces. Phosphonic acids were designed in order to impart specific properties to the surface of a range of metal oxides upon formation of a monolayer. A large number of novel phosphonic acids were synthesized and fully characterized. The binding of phosphonic acids to the surface of several metal oxides, such as indium tin oxide (ITO) and barium titanate, was studied in detail and determined to be a mixture of bidentate and tridentate binding modes. The modification of several key surface properties of ITO by phosphonic acid modification was also studied. The work function of ITO could be increased or decreased with respect to unmodified ITO by controlling the dipole of phosphonic acids bound to the surface. Additionally, the surface energy could be substantially lowered by attaching phosphonic acids with non-polar terminal functional groups to the ITO surface. The ability to control these surface properties resulted in organic light-emitting diodes (OLEDs) which showed superior lifetimes and stability with respect to OLEDs incorporating ITO without a phosphonic acid monolayer. In addition, the binding of phosphonic acids to a number of other oxides, such as zinc oxide and zeolites, was also studied.

The mechanisms by which hydrates deposit in a petroleum production-line are likely to be related to pipeline surface properties, e.g. pipeline material, surface energy and roughness. In this work, the wettability alteration of pipeline surfaces from contact with oil, as well as the adhesion energy between water and solid in the presence of oil is investigated. Contact angles are determined as a function of solid material and oil composition, for both model oils and crude oils. Although contact angles in oil/brine/solid systems have been extensively reported in the literature, the variety of solids that may mimic a pipeline is limited. In this study, we include various metal surfaces in addition to glass and a coating. Initial results from using near infrared imaging for collecting contact angle data in non-translucent systems are also presented.

abstract: The role of environmental factors that influence atmospheric propagation of sound originating from freeway noise sources is studied with a combination of field experiments and numerical simulations. Acoustic propagation models are developed and adapted for refractive index depending upon meteorological conditions. A high-resolution multi-nested environmental forecasting model forced by coarse global analysis is applied to predict real meteorological profiles at fine scales. These profiles are then used as input for the acoustic models. Numerical methods for producing higher resolution acoustic refractive index fields are proposed. These include spatial and temporal nested meteorological simulations with vertical grid refinement. It is shown that vertical nesting can improve the prediction of finer structures in near-ground temperature and velocity profiles, such as morning temperature inversions and low level jet-like features. Accurate representation of these features is shown to be important for modeling sound refraction phenomena and for enabling accurate noise assessment. Comparisons are made using the acoustic model for predictions with profiles derived from meteorological simulations and from field experiment observations in Phoenix, Arizona. The challenges faced in simulating accurate meteorological profiles at high resolution for sound propagation applications are highlighted and areas for possible improvement are discussed. A detailed evaluation of the environmental forecast is conducted by investigating the Surface Energy Balance (SEB) obtained from observations made with an eddy-covariance flux tower compared with SEB from simulations using several physical parameterizations of urban effects and planetary boundary layer schemes. Diurnal variation in SEB constituent fluxes are examined in relation to surface layer stability and modeled diagnostic variables. Improvement is found when adapting parameterizations for Phoenix with reduced errors in the SEB components. Finer model resolution (to 333 m) is seen to have insignificant ($<1\sigma$) influence on mean absolute percent difference of 30-minute diurnal mean SEB terms. A new method of representing inhomogeneous urban development density derived from observations of impervious surfaces with sub-grid scale resolution is then proposed for mesoscale applications. This method was implemented and evaluated within the environmental modeling framework. Finally, a new semi-implicit scheme based on Leapfrog and a fourth-order implicit time-filter is developed. / Dissertation/Thesis / Doctoral Dissertation Mechanical Engineering 2014

Neste trabalho investigou-se a influência da adição dos ânions cloreto, fluoreto e sulfato nas propriedades físico-químicas de nanopós de zircônia sintetizada pelo método Pechini. Análises de fluorescência de Raios-X, difração de Raios-X, espectroscopia no infravermelho, área de superfície específica, espectroscopia Raman, microscopia eletrônica de varredura, análise termogravimétrica, calorimetria diferencial por varredura, amplitude sônica eletrocinética e dilatometria foram realizadas para caracterizar os pós sintetizados. Os resultados obtidos mostraram que o tratamento térmico realizado para a obtenção dos pós retirou os ânions cloreto e fluoreto da composição química final da zircônia enquanto o ânion sulfato permaneceu. Mesmo sendo retirados os ânions cloreto e fluoreto influenciaram no processo de cristalização da zircônia modificando o tamanho de cristalito obtido. A permanência do ânion sulfato na composição química da zircônia se deve à maior energia de ligação com o cátion Zr 4+ assim, observou-se uma maior influência deste ânion no processo de cristalização. Isso permitiu a formação de cristalitos menores e a estabilização da fase tetragonal da zircônia. Em todos os casos, as análises mostraram que a influência dos ânions se deu por segregação dos mesmos na superfície da zircônia o que, principalmente no caso do ânion sulfato, tende a reduzir a energia da superfície da zircônia através do aumento da área de superfície específica. Verificou-se também que o ânion sulfato pode ser retirado da superfície da zircônia através da lavagem do pó em meio básico. Esse procedimento permitiu aumentar a área de superfície específica e tende a melhorar sua sinterabilidade. / In this study was investigated the influence of the addition of the chloride, fluoride and sulfate anions in the physico-chemical properties of zirconia nanopowders synthesized by the Pechini method. Analyses of X-ray fluorescence, X-ray diffraction, infrared spectroscopy, specific surface area, Raman spectroscopy, scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry, electrokinetic sonic amplitude and dilatometry were performed to characterize the synthesized powders. The results showed that the heat treatment performed to obtain the powders removed the chloride and fluoride anions from the final chemical composition of the zirconium whereas the sulfate anion anion remained. Despite the chloride and fluoride anions removal, they influenced the crystallization process of the zirconium, modifying the size of the crystallite obtained. The permanence of the sulfate anion in the chemical composition of the zirconia is due to the higher binding energy with the Zr 4 + cation, thus it was observed a greater influence of that anion in the crystallization process. That allowed the formation of smaller crystallites and the stabilization of the tetragonal phase of the zirconia. In all of the cases, the analyses showed that the influence of the anions occurred by their segregation on the surface of the zirconia which, particularly in the case of the sulfate anion, tends to reduce the surface energy of the zirconium by increasing the specific surface area. It was also found that the sulfate anion can be removed from the surface of the zirconia by washing the powder in a basic medium. That procedure increased the specific surface area and it tends to improve its sinterability.

As aplicações do ZrO2 dependem das suas fases cristalinas e muitos estudos têm sido realizados sobre suas transições e os aditivos empregados no seu controle. No entanto, os mecanismos atuantes em tais processos são explicados com base exclusivamente cinética desconsiderando a contribuição termodinâmica que os aditivos exercem sobre as energias dos polimorfos e suas superfícies. Neste trabalho, o efeito termodinâmico do MgO sobre as transformações de fases é estudado para pós de ZrO2 preparados por uma rota química derivada do método Pechini. Análises de picnometria, área de superfície específica, difração de raios X, espectroscopias de infravermelho, Raman e de fotoelétrons excitados por raios X, além de amplitude sônica eletrocinética foram empregadas para caracterizar a evolução das fases formadas. Verifica-se que quantidades crescentes de MgO desestabilizam a fase monoclínica e tornam a fase tetragonal estável. A fase cúbica é encontrada para grandes quantidades de MgO. As transformações de fases marcam descontinuidades em características como área de superfície específica devido a alteração de simetria cristalina. O MgO, na forma de periclásio, não foi observado para quantidades inferiores a 40 % molar. Levando-se em conta a baixa solubilidade do MgO no ZrO2 conclui-se que o controle das fases observadas possui pouca contribuição de processos cinéticos associados à formação de defeitos puntiformes. Resultados de XPS mostram que o íon Mg2+ localiza-se tanto na rede cristalina quanto na superfície do ZrO2. A sua segregação é atribuída a um efeito termodinâmico que resulta na diminuição da energia de superfície do ZrO2 promovendo o desenvolvimento de um excesso de superfície, confirmado pelas medidas de área de superfície específica, com a conseqüente diminuição do tamanho de partícula. Tais conclusões implicam que ambos os efeitos termodinâmicos e cinéticos devem ser considerados no controle do polimorfismo do ZrO2. / The applications of ZrO2 depend on its cristalline phases and several studies have been carried out about its transitions and the additives used to control it. However, the active mechanisms in such processes are explained with an exclusively kinetic basis disregarding the thermodynamic contribution that the additives exert over the polimorphs and surface energies. In this work, the thermodynamic effect of MgO on phase transformation is reported for ZrO2 powders prepared by a chemical route derived from Pechini\'s method. Picnometric, specific surface area, X-ray diffraction, infrared, Raman and X-ray photoelectron spectroscopies, besides electrokinetic sonic amplitude experiments were performed to characterize the evolution of the formed phases. It is verified that crescent amounts of MgO desestabilize the monoclinic phase and make stable the tetragonal. The cubic phase is found for large amounts of MgO. The phase transformations appoint descontinuities as the specific surface area due to crystalline simmetry change. The MgO, in the periclase form, wasn?t observed for amounts lower than 40 molar %. Taking into account the low solubility of MgO into ZrO2 it is concluded that the control of the observed phases has a low contribution to kinetic processes associated to point defects formation. XPS data show that Mg2+ ion is located onto the bulk as far as the ZrO2 surface. Its segregation is assigned to a thermodynamic effect resulting in a decrease of ZrO2 surface energy, which promotes the development of a surface excess, upholded by specific surface area measurements, with the consequent decrease of particle size. Such conclusions impose that both thermodynamic and kinetic effects must be considered on the control of ZrO2 polimorphism.

Esta tese está dividida em duas partes. Na Parte I, blendas de polietileno maleado (M-PE) e butirato acetato de celulose (CAB) (5-50% em massa) e compósitos de polietileno (PE) ou M-PE e 20% em massa de celulose, acetato de celulose (CA), propionato acetato de celulose (CAP) ou CAB foram preparados em um misturador. As estruturas e propriedades das misturas foram estudadas através de ensaios mecânicos, calorimetria exploratória diferencial, microscopia eletrônica de varredura, extração com solvente seletivo seguida de espectroscopia FTIR e difração de raios-X (XRD). As blendas M-PE/CAB e os compósitos PE/polissacarídeo e M-PE/polissacarídeo não apresentaram mudanças significativas nos valores da temperatura de fusão (Tm) quando comparados aos valores de Tm do PE e do M-PE. Dados de XRD mostraram que a adição das cargas não causou mudança na estrutura cristalina do PE ou M-PE, mas aumentou a região amorfa dos materiais, indicado que a miscibilidade ocorre na parte amorfa do PE. Compósitos preparados com M-PE apresentaram tensão no escoamento e elongação superiores do que os preparados com PE, evidenciando o efeito compatibilizante do anidrido maléico. Na parte II, o efeito de dois bons solventes, acetona e acetato de etila, nas características e propriedades superficiais dos filmes finos (50nm&#60;espessura<200nm) e ultrafinos (espessura<6nm) de CA, CAP ou CAB preparados por revestimento rotacional ou adsorção, respectivamente, foram caracterizados por elipsometria, microscopia de força atômica (AFM) e medidas de ângulo de contato. Os resultados foram discutidos baseados na taxa de evaporação do solvente e na energia de interação substrato-solvente. Os efeitos do recozimento e do tipo de éster de celulose na espessura, morfologia e molhabilidade da superfície foram investigados. Após o recozimento, os filmes ultrafinos de ésteres de celulose tornam-se hidrofóbicos, indicando uma reorientação molecular na interface sólido-ar. Os filmes ultrafinos preparados a partir de soluções de acetona são estáveis, enquanto que os preparados a partir de soluções de acetato de etila apresentaram dewetting. A estabilidade dos filmes foi monitorada por AFM e explicada pelos valores da constante de Hamaker, determinados pela primeira vez para estes materiais. A imobilização de lipase sobre os filmes ultrafinos estáveis de CA, CAP e CAB com e sem recozimento foi quantificada para avaliar a possibilidade de aplicação destes filmes como substratos para biomoléculas. A adsorção de lipase sobre os filmes de CA e CAP com recozimento foi mais pronunciada do que nos mesmos filmes sem recozimento. A atividade enzimática da lipase foi avaliada com medidas espectrofotométricas do produto formado a partir da hidrólise do para-nitrofenol dodecanoato. A lipase imobilizada sobre os filmes mais hidrofóbicos apresentou uma atividade maior do que a lipase livre e manteve a atividade alta após três usos. As amostras foram estocadas por até 30 dias. A lipase imobilizada sobre os filmes mais hidrofóbicos manteve 70% da sua atividade, e a lipase imobilizada sobre os filmes mais hidrofílicos manteve apenas 30% da atividade. Estes resultados indicaram que preservação da estrutura conformacional da enzima foi favorecida pela hidrofobicidade do substrato polimérico e interações entre os resíduos polares da lipase e as partes de glucopiranosil dos ésteres de celulose. / This thesis is divided into two parts. In the first part, blends of maleated polyethylene (M-PE) and cellulose acetate butyrate (CAB) (5-50wt%) and composites of polyethylene (PE) or M-PE and 20wt% of cellulose, cellulose acetate (CA) or cellulose acetate propionate (CAP) were prepared in an laboratory mixer. The mixtures structures and properties have been studied by means of tensile testing, differential scanning calorimetry, scanning electron microscopy, X-ray diffraction (XRD) and extraction with a selective solvent followed by Raman spectroscopy. No significant change on the melting temperature (Tm) values obtained for M-PE/CAB blends or PE/polysaccharides or M-PE/polysaccharides composites could be observed, when compared with the Tm values obtained for PE and M-PE. X-ray diffraction showed that the addition of the polysaccharides had no influence on the lattice constants of PE or M-PE, but it increased the PE amorphous region, indicating that the miscibility happens on the amorphous region of the PE. Composites prepared with M-PE presented yield stress and elongation values higher than those prepared with PE, showing the compatibilizer effect of maleic anhydride. In the second part, the effect of two good solvents, acetone and ethyl acetate, on the characteristics and surface properties of thin (30nm&#60;thickness<200nm) and ultrathin (thickness<6nm) cellulose ester films obtained by spin coating or adsorption, respectively, has been investigated by means of ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The results were discussed in the light of solvent evaporation rate and interaction energy between substrate and solvent. The effects of annealing and type of cellulose ester on film thickness, film morphology and surface wettability were also studied. Upon annealing, ultrathin films of cellulose ester became hydrophobic, evidencing molecular re-orientation at the solid-air interface. Ultrathin films prepared from acetone solutions are stable, but the ones prepared from ethyl acetate solutions presented dewetting. Film stability was followed by AFM and explained with basis on the Hamaker constant values, calculated for the first time for CA, CAP and CAB. The adsorption of lipase onto stable ultrathin films of cellulose esters, with and without annealing, was quantified in order to evaluate the possibility of applying such films as support for biomolecules. Lipase adsorption onto annealed CA and CAP films was more pronounced than that onto CA and CAP untreated films. Enzymatic activity was evaluated by the spectrophotometric measurement of the product formed from the hydrolysis of para-nitrophenyl dodecanoate. Lipase immobilized onto more hydrophobic films presented higher activity than free lipase and could be reused three times retaining activity at a high level. The effect of storing time on the activity of immobilized lipase was studied. Lipase immobilized onto more hydrophobic films retained 70% of activity after one month, reaching the same level of activity of free lipase, and lipase immobilized onto more hydrophilic films retained just 30% of activity after 30 days. These results indicated that enzyme preservation was favored by polymeric substrate hydrophobicity and by the interactions between the polar residues of lipase and the glucopyranosyl moieties of cellulose ester.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The following study quantifies the seasonal and annual distribution of energy balance components (sensible heat fluxes, latent, soil, and net radiation) in this flooded irrigated rice ecosystem in Southern Brazil for three different periods (Fallow 1: 22 July 2003 to 24 November 2003; Rice: 25 November 2003 to 04 April 2004 and Fallow 2: 05 April 2004 to 21 July 2004). In addition, it has been applied the Noah Land Surface Model with the objective of estimating the surface energy fluxes. An important challenge is to implement a new version of Noah Land Surface Model applied to flooded agricultural land called Noah-Paddy. The stabilization of the models has been performed using the atmospheric forcing data obtained from South American Land Data Assimilation System (SALDAS) for the period 22 July 2000 to 21 July 2003. The models were simulated using the observed atmospheric forcing from a micrometeorological tower installed on a flooded irrigated rice paddies located in the city of Paraíso do Sul - RS. The initial conditions were obtained from the last time step of the spin-up experiment performed with atmospheric forcing data of SALDAS. The models results were compared with experimental data for surface energy fluxes. From the simulated results generated by the Noah Land Surface Model, it seems that when the rice crop is flooded, the model does not satisfactorily represents the experimental data. However, using the Noah-Paddy model the components of surface energy balance are more realistic for the system surface-water-atmosphere. The most important contribution performed in this research was to describe the diffent physical processes originated by the presence of a body of water between the soil surface and the atmosphere. This physical system occorr always in flooded agricultural crops in wich the rice paddies field are predominant. / No presente trabalho, quantifica-se a distribuição sazonal e anual das componentes do balanço de energia (fluxos de calor sensível, latente, do solo e saldo de radiação) em um ecossistema de arroz irrigado por inundação localizado no Sul do Brasil para três períodos distintos ao longo do ano (Pousio 1: 22Jul2003 a 24Nov2003; Arroz: 25Nov2003 a 04Abr2004 e Pousio 2: 05Abr2004 a 21Jul2004). Além disso, é utilizado o Modelo de Superfície Noah (Noah LSM) com o objetivo de estimar os fluxos de energia superficiais. Um dos desafios mais importantes é a implementação de uma nova versão do Noah LSM aplicado para áreas agrícolas alagáveis chamado Noah-Paddy. A estabilização dos modelos foi realizada utilizando dados de forçantes atmosféricas do South American Land Data Assimilation System (SALDAS) para o período de 22Jul2000 a 21Jul2003. Os modelos foram executados usando dados de forçantes atmosféricas observados obtidos a partir da torre micrometeorológica instalada sobre uma cultura de arroz irrigado por inundação localizada em Paraíso do Sul - RS. As condições iniciais foram obtidas a partir do último passo de tempo do experimento spin-up realizado com os dados de forçantes atmosféricas do SALDAS. O desempenho dos modelos estudados foi comparado com dados experimentais de fluxos de energia superficiais. A partir dos resultados obtidos pela simulação do Noah LSM verifica-se que, quando a cultura do arroz está irrigada, o modelo não representa satisfatoriamente os dados experimentais. Porém, utilizando o Noah-Paddy as trocas de energia superficiais são representadas de forma mais realísticas para o sistema superfície-água-atmosfera. A contribuição mais importante realizada neste trabalho foi a descrição dos diferentes processos físicos originados pela presença de uma massa de água entre a superfície do solo e a atmosfera. Esse sistema físico ocorre sempre em culturas agrícolas alagadas nas quais as plantações de arroz são predominantes.