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Phase-field modeling of surface-energy driven processesAsp Grönhagen, Klara January 2009 (has links)
Surface energy plays a major role in many phenomena that are important in technological and industrial processes, for example in wetting, grain growth and sintering. In this thesis, such surface-energy driven processes are studied by means of the phase-field method. The phase-field method is often used to model mesoscale microstructural evolution in materials. It is a diffuse interface method, i.e., it considers the surface or phase boundary between two bulk phases to have a non-zero width with a gradual variation in physical properties such as energy density, composition and crystalline structure. Neck formation and coarsening are two important diffusion-controlled features in solid-state sintering and are studied using our multiphase phase-field method. Inclusion of Navier-Stokes equation with surface-tension forces and convective phase-field equations into the model, enables simulation of reactive wetting and liquid-phase sintering. Analysis of a spreading liquid on a surface is investigated and is shown to follow the dynamics of a known hydrodynamic theory. Analysis of important capillary phenomena with wetting and motion of two particles connected by a liquid bridge are studied in view of important parameters such as contact angles and volume ratios between the liquid and solid particles. The interaction between solute atoms and migrating grain boundaries affects the rate of recrystallization and grain growth. The phenomena is studied using a phase-field method with a concentration dependent double-well potential over the phase boundary. We will show that with a simple phase-field model it is possible to model the dynamics of grain-boundary segregation to a stationary boundary as well as solute drag on a moving boundary. Another important issue in phase-field modeling has been to develop an effective coupling of the phase-field and CALPHAD methods. Such coulping makes use of CALPHAD's thermodynamic information with Gibbs energy function in the phase-field method. With the appropriate thermodynamic and kinetic information from CALPHAD databases, the phase-field method can predict mictrostructural evolution in multicomponent multiphase alloys. A phase-field model coupled with a TQ-interface available from Thermo-Calc is developed to study spinodal decomposition in FeCr, FeCrNi and TiC-ZrC alloys. / QC 20100622
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Surface Energy Budget Over A Land Surface In The TropicsArunchandra, S C 04 1900 (has links)
Atmospheric convection is sensitive to the nature of the surface and its temperature. Both dry (without cloud) and moist (with cloud) convections depend on the surface temperature. Surface temperature is of critical importance in several practical applications like human comfort and crop cultivation. In the climate change scenario too, variations in the surface temperature take the center stage. Therefore, prediction of surface temperature is important. The evolution of the temperature is governed by the energy equation and the surface temperature by the surface energy balance. Important components of the surface energy balance are radiation (incoming solar radiation, reflected solar radiation, incoming and outgoing longwave radiation), sensible and latent heat fluxes and heat flux into the ground (called ground heat flux). A large number of individual and collective observations have been carried out in the past to understand the atmospheric boundary layer and the surface energy budgets. However a major share of the observations is from mid-latitudes. There have been few experiments carried out in India, for example, MONTBLEX, LASPEX, etc. One common drawback among these experiments is that the data time series is discontinuous and continuous measurements covering an entire season are lacking. Moreover these measurements were not comprehensive and hence did not allowed to calculate complete surface energy balance – in some cases radiation data is not available while in some humidity data. Therefore, continuous time series of sufficient duration and covering all variables needed to look at the seasonal energy balance based on measurements alone is missing in the Indian context. New programmes with the main objective of predicting convection are being planned in India. For example, PROWNAM (Prediction of Regional Weather with Observational Meso-Network and Atmospheric Modeling) is aimed at predicting the short term weather at SHAR and STORM (Severe Thunderstorms – Observations and Regional Modeling) aims to predict the occurrence of severe thunderstorms in the northeastern India. In both these programmes, measurement of all components of surface energy balance is one of the main objectives. However, the minimum configuration and data accuracy requirements for the flux towers, sensitivity of computed fluxes on data accuracy have not been carefully evaluated. This thesis is aimed at filling this gap.
As a part of my work, a 10 m high micrometeorological tower was installed in an open area within the Indian Institute of Science (IISc) Air Field. Temperature, relative humidity and wind speed and direction instruments were mounted at two levels, 2 m and 8 m. All components of radiation were measured. Data, sampled every 5 s and averaged for 2 minutes were continuously stored, starting May 2006 onwards. Soil temperature was measured at 4 depths, 5 cm, 10 cm, 15 cm and 20 cm. In addition, a sonic anemometer capable of measuring 3 components of velocity and air temperature was installed at 2 m height, and data was collected for more than a month to enable the calculation of momentum and buoyancy fluxes using the Eddy correlation method (ECM).
The present work evaluated the sensitivity of the fluxes for small calibration errors and quantified the minimum data accuracies and configuration needed for flux measurement with the Profile method (PM). After applying corrections, the comparison of fluxes from PM and ECM are in good agreement. The complete long-term surface energy balances is calculated in terms of source and sink. One aspect that emerges from the observation is that the seasonal variation in the sink term is relatively small (150-170 Wm-2) whereas the source term shows much larger variation from 180-250 Wm-2. A method has been implemented by which the ground surface temperature can be estimated by using the subsurface temperature timeseries by the method of Fourier decomposition and using the Fourier heat conduction equation. In addition we can compute the thermal diffusivity of the soil by using the amplitude and phase information of the sub-surface soil time series. The estimated temperatures from this method and one that estimated from radiation method are in good agreement with the maximum difference being less than 0º C.
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Film Formation and Surface Tension Studies of Powder CoatingsAdler, Jeanette January 2005 (has links)
<p>In industrial use of paint systems a swift processing is crucial. Another very important issue is to improve the quality of the final coating. This report investigates the film formation process of powder coatings, specially the spreading of individual powder particles. The obtained results can be used to understand and control the film formation process. In this way the desired levelling can be achieved and thus the desired gloss or other surface characteristics that may be required. This means that the method could be used when evaluating different polymer and additive combinations that could be used to change film formation behaviour or curing time for powder coating systems to suit various substrates. It makes it possible to avoid and minimize different surface defects as orange peel or cratering in the powder coated film.</p><p>We used a reflection optical microscope to better understand the film formation process and especially the spreading of a powder melt on surfaces with various surface energies. The obtained data were: the particle diameter, the area, area ratio and the contact angle of the powder particle as a function of time and temperature. This information can be used to derive the surface tension of any powder melt.</p><p>In this report we evaluate the dependencies of temperature, heat rate and surface energy for powder coatings on different substrates. The method provides information that can be used to optimize the film formation of a specific powder coating/substrate combination. This method can be used to evaluate the powder spreading and levelling on different substrates from a surface tension point of view.</p><p>We found, as expected, that the powder flows out on a hydrophilic surface and is inhibited by a hydrophobic. The increase of the area ratio on a hydrophilic surface was about five times as the initial area coverage and on a hydrophobic surface only two times the initial area coverage. The contact angle between the melted powder particle on the different surface types could be calculated. The melt surface tension could be calculated since three substrates surfaces with various surface energies were used. The melt surface tension was found to be about 18.5 mN/m.</p> / <p>Sammanfattning</p><p>Vid industriell användning av ett färgsystem är det viktigt med en snabb och smidig målningsprocess. En viktig del är att förbättra kvaliteten på den färdiga ytan. Denna rapport undersöker filmbildningsprocessen för pulverfärg, närmare bestämt spridningen av individuella pulverpartiklar. Resultaten från utvärderingen av denna metod kan användas för att bättre förstå och få kontroll över filmbildningsprocessen. Med denna undersökningsmetod kan den önskade utslätningen uppnås och därmed den önskade glansen eller annan yteffekt som kan vara önskvärd.</p><p>Metoden kan användas för att utvärdera olika polymer- och additivkombinationer som kan användas för att ändra filmbildningens uppförande eller bestämma härdningstiden för en pulverfärg att passa ett visst substrat. Metoden gör det möjligt att förhindra och minska olika ytdefekter såsom apelsinskals- eller kratereffekter i pulverfärgens yta.</p><p>Ett optiskt reflectionsmikroskop användes för att bättre kunna förstå filmbildningsprocessen och särskilt spridningen av smält pulver på substrat med olika ytenergier. De mätdata vi fick var partikeldiameter, area, areaförändring och kontaktvinkeln för pulverpartiklar som funktion av tid och temperatur. Ur denna information kunde pulversmältans ytenergier härledas.</p><p>I denna rapport utvärderas pulvrets beroende av temperatur, uppvärmning och ytenergi på olika substrat. Denna metod ger information som kan användas för att optimera filmbildningen av en specifik kombination av pulverfärg och substrat. Denna metod kan också användas för att utvärdera pulverspridning och utjämning av färgfilmen på olika substrat med avseende på ytenergierna.</p><p>Som förväntat flyter pulvret ut på hydrofila ytor och utflytningen ändras på en hydrofob yta. På en hydrofil yta sprider sig partikeln till fem gånger den ursprungliga arean över substratet och motsvarande två gånger för en hydrofob yta. Kontaktvinkeln mellan en smält pulverpartikel på olika sorters substrat från utförda mätningar beräknas utifrån utförda mätningar. Kontaktvinklar mellan pulver och olika substrat kan användas för att beräkna smältans ytspänning. Smältans ytspänning kan beräknas då experiment gjorts på tre sorters ytor med olika kända ytenergier. Smältans ytspänning var 18,5 mN/m.</p><p>Slutsatsen är att det går att observera och utvärdera resultaten av utsmältningsförloppet för pulverfärg med denna metod.</p>
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Synchrotron X-ray diffraction studies of phase transitions and mechanical properties of nanocrystalline materials at high pressurePrilliman, Gerald Stephen January 2003 (has links)
Thesis (Ph.D.); Submitted to The University of California at Berkeley, Berkeley, CA (US); 1 Sep 2003. / Published through the Information Bridge: DOE Scientific and Technical Information. "LBNL--55022" Prilliman, Gerald Stephen. USDOE Director. Office of Science. Office of Basic Energy Sciences (US) 09/01/2003. Report is also available in paper and microfiche from NTIS.
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Evolution du bilan de masse de surface Antarctique par régionalisation physique et contribution aux variations du niveau des mers / Evolution of Antarctic surface mass balance by high-resolution downscaling and impact on sea-level changesAgosta, Cécile 15 June 2012 (has links)
Le Bilan de Masse de Surface (BMS, c'est-à-dire les précipitations de neige auxquelles est retranchée l'ablation par sublimation, ruissellement ou érosion) de la calotte polaire Antarctique représente une contribution majeure et encore mal connue à l'évolution actuelle du niveau des mers. Le stockage d'eau douce par accumulation de neige sur la calotte posée est supposé s'intensifier au cours du 21eme siècle, modérant l'élévation du niveau des mers et modifiant la dynamique glaciaire. Les trois-quarts du bilan de masse de surface Antarctique sont concentrés au dessous de 2000 m d'altitude alors que cette zone ne représente que 40% de la surface de la calotte posée. Les précipitations orographiques sont une contribution majeure à l'accumulation dans cette région, il est donc crucial d'estimer précisément ce terme. La modélisation de ce processus est fortement dépendant de la résolution des modèles, car les pentes de la calotte influencent l'intensité des précipitations orographiques. La sublimation et la fonte de la neige sont eux aussi fortement dépendant de l'élévation. Bien qu'ils contribuent actuellement peu au bilan de masse de surface de l'Antarctique, ils sont susceptibles de subir des changements importants au cours des prochains siècles. Les modèles atmosphériques de climat, globaux ou régionaux, ne peuvent pas atteindre une résolution allant au delà de 40 km sur l'Antarctique pour des simulations à l'échelle du siècle du fait de coûts de calcul importants. A ces résolutions, la topographie des zones côtières Antarctique n'est pas correctement représentée. C'est pourquoi nous avons développé le modèle de régionalisation SMHiL (Surface Mass balance High-resolution downscaLing) qui permet d'estimer les composantes du bilan de masse de surface Antarctique à haute résolution (~15 km) à partir de champs atmosphériques de plus grande échelle. Nous calculons l'effet de la topographie fine sur les précipitations orographiques et sur les processus de couche limite menant à la sublimation, la fonte et le regel. SMHiL est validé pour la période actuelle à partir d'un jeu de données inédit constitué de plus de 2700 observations de qualité contrôlée. Cependant, les observations représentatives du BMS de la zone côtière Antarctique y sont sous-représentées. Dans ce contexte, nous montrons que la ligne de balise mise en place par l'observatoire GLACIOCLIM-SAMBA en bordure de calotte constitue une référence pour estimer les performances des modèles. Enfin, nous utilisons SMHiL à l'aval du modèle de circulation générale LMDZ4 pour évaluer les variations de BMS au cours du 21eme et du 22eme siècles. Le BMS à haute résolution est significativement différent de celui de LMDZ4 et est plus proche du BMS observé pour la période actuelle. Les résultats suggèrent que les précédentes estimations d'augmentation du BMS au cours du prochain siècle étaient sous-estimées de près de 30% par LMDZ4. Les changements de BMS à faible élévation résulteront d'une compétition entre l'augmentation d'accumulation de neige et de ruissellement. SMHiL est un outil destiné à être appliqué à l'aval d'autres modèles de climat, globaux ou régionaux, pour une meilleure estimation des variations futures du niveau des mers. / The Antarctic Surface Mass Balance (SMB, i.e. the snow accumulation from which we subtract ablation by sublimation, run-off or erosion) is a major yet badly known contribution to changes in the present-day sea level. Water storage by snow accumulation on the Antarctic continent is expected to increase in the 21st century, which would moderate the rise in sea level and impact the ice dynamic response of the ice sheet. Three-quarters of the Antarctic SMB are concentrated below 2000 m above sea level whereas this area represents only 40% of the grounded ice sheet area. Orographic precipitation is a major contributor to snow accumulation in this region, which is why a better estimation of this term is important. The representation of this process by models depends to a great extent on the resolution of the model, since precipitation amounts depend on the ice sheet slopes. Sublimation and snowmelt also depend on elevation, and although they are presently minor contributors to the Antarctic SMB, their role is expected to become more important in the coming centuries. Global and regional atmospheric climate models are unable to achieve a 40-km resolution over Antarctica at a century time scale, due to their computing cost. At this resolution, the Antarctic coastal area is still badly represented. This is why we developed the downscaling model SMHiL (Surface mass balance high-resolution downscaling) to estimate the Antarctic SMB components at a high resolution (~15 km) from large-scale atmospheric forcings. We computed the impact of the high-resolution topography on orographic precipitation amounts and the boundary layer processes that lead to sublimation, melting and refreezing. SMHiL has been validated for the present period with a dataset composed of more than 2700 quality-controlled observations. However, very few of these observations are representative of the Antarctic coastal area. In this context, we show that the GLACIOCLIM-SAMBA stake lines located on the ice sheet coast-to-plateau area is an appropriate reference to evaluate model performance. Finally, we used SMHiL to estimate the SMB changes during the 21st and 22nd centuries, by downscaling the atmospheric global climate model LMDZ4. The high-resolution SMB is significantly different from the SMB given by LMDZ4 and is closer to the observed one for the present period. Our results suggest that previous studies using the LMDZ4 models underestimated the future increase in SMB in Antarctica by about 30%. Future changes in the Antarctic SMB at low elevations will result from the conflict between higher snow accumulation and runoff. The downscaling model is a powerful tool that can be applied to climate models for a better assessment of a future rise in sea level.
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Propriedades estruturais e eletrônicas de filmes finos de β-PbO2 / Structural and electronic properties of fine films of β-PbO2Alves, Arilson Costa [UNESP] 03 November 2016 (has links)
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Previous issue date: 2016-11-03 / O chumbo, em função de sua alta resistividade é mau condutor de eletricidade, sendo classificado como um metal semicondutor. Já os seus óxidos são muito utilizados na confecção de baterias automotivas, pelo seu comportamento condutor. Dos vários óxidos de chumbo que existem, o dióxido de chumbo (PbO2) é um dos que mais se destacam devido a suas aplicações. O β-PbO2 é um semicondutor com band gap estreito, que recebeu uma grande atenção ultimamente devido à sua potencial utilização como óxidos condutores transparentes (TCO). Os TCO são compostos que combinam as propriedades normalmente mutuamente excludentes da transparência e da condutividade. O desempenho óptico e elétrico dos TCO está intimamente ligado à estrutura de bandas e, desta forma, a distribuição periódica de potencial em um cristal. Neste trabalho procura-se compreender os fundamentos das propriedades elétricas macroscópicas do material β-PbO2 na forma de filmes finos. Para tanto, adotou-se abordagem da mecânica quântica baseada na Teoria do Funcional Densidade (DFT), com potencial híbrido B3LYP, implementada no código CRYSTAL09. Cálculos de estrutura de bandas e densidade de estados mostram que o band gap de filmes de β-PbO2 tendem para o gap do material na forma de bulk e cálculos de energia de superfície permitem concluir que sua face mais estável é a (110). / Lead, due to its high resistivity, is a poor conductor of electricity and is classified as a semiconductor. On the other hand their oxides are widely used in the manufacture of automotive batteries, because of its conductivity. β-PbO2 is a narrow band gap semiconductor which received great attention lately due to their potential use as a transparent conducting oxide (TCO). The TCO are compounds which combine transparency and conductivity, properties that normally do not coexist. The optical and electrical performance of the TCO are intimately connected to the band structure and thus the potential distribution in a periodic crystal. This work, seeks to contribute for understanding the fundamentals of macroscopic electrical properties of β-PbO2 material in the form of thin films. Therefore, it was adopted the quantum mechanics approach based on Density Functional Theory (DFT), with B3LYP hybrid potential, implemented in the CRYSTAL09 code. Band structure and density of states calculation show that the band gap of β-PbO2 films tend to the bulk band gapsurface energy calculations permit conclude that its most stable face is the (110).
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Land use and land cover changes in South East Asia: The effects of land transformations on biophysical variables in IndonesiaSabajo, Clifton Ralph 22 June 2018 (has links)
Au cours des dernières décennies, l'Indonésie a connu des transformations spectaculaires des terres avec une expansion des plantations de palmiers à huile au détriment des forêts tropicales. L'Indonésie est actuellement l'une des régions ayant le plus haut taux de transformation de la surface terrestre dans le monde à cause de l'expansion des plantations de palmiers à huile et d'autres agricultures qui remplacent les forêts à grande échelle. Comme la végétation est un modificateur du climat près du sol, ces transformations à grande échelle ont des impacts majeurs sur les variables biophysiques de surface telles que la température de surface, l'albédo, les indices de végétation (NDVI), sur le bilan énergétique de surface et le partitionnement énergétique.
Ce travail de thèse vise à quantifier les impacts des changements d’usage des terres en Indonésie sur les variables biophysiques de surface. Pour évaluer ces changements à l'échelle régionale, des données de télédétection sont nécessaires.
Étant une variable clé de nombreuses fonctions écologiques, la température de surface (LST) est directement affectée par les changements de la couverture terrestre. Nous avons analysé la LST à partir de la bande thermique d'une image Landsat et produit une carte de température de surface avec une haute résolution (30m) pour les basses terres de la province de Jambi à Sumatra (Indonésie), une région qui a subi de grandes transformations au cours des dernières décennies. La comparaison des LST, albédo, NDVI et évapotranspiration (ET) entre sept différents types de couverture terrestre (forêts, zones urbaines, terres incultes, plantations de palmiers à huile jeunes et matures, plantations d'acacias et de caoutchouc) montre que les forêts ont des températures de surface inférieures à celles des autres types de couvert végétal, ce qui indique un effet de réchauffement local après la conversion des forêts vers des plantations. Les différences de LST atteignaient 10,1 ± 2,6 ºC (moyenne ± écart-type) entre les forêts et les terres déforestées. Les différences de températures de surface s'expliquent par un effet de refroidissement évaporatif des forêts, qui compense l'effet de réchauffement de l'albédo.
Basé sur des différences observées dans les variables biophysiques entre les plantations de palmiers à huile jeunes et matures, nous avons analysé trois images Landsat couvrant une chronoséquence de plantations de palmiers à huile pour étudier la dynamique des variables biophysiques de surface pendant le cycle de rotation de 20-25 ans des plantations de palmiers à huile.
Nos résultats montrent que les différences entre les plantations de palmiers à huile à différents stades du cycle de rotation du palmier à huile se reflètent dans les différences du bilan énergétique de surface, du partitionnement énergétique et des variables biophysiques. Au cours du cycle de rotation des plantations de palmiers à huile, les différences de température à la surface diminuent graduellement et se rapprochent de zéro autour du stade mature de la plantation de palmiers à huile de 10 ans. Parallèlement, le NDVI augmente et l'albédo diminue à proximité des valeurs typiques des forêts. Le bilan énergétique de surface et le partitionnement énergétique montrent des tendances de développement liés aux variables biophysiques et à l'âge des plantations de palmiers à huile. Les nouvelles plantations et les jeunes plantations (<5 ans) ont un rayonnement net plus faible que les plantations de palmiers à huile matures, mais ont des températures de surface plus élevées que les plantations de palmiers à huile matures.
Les changements dans les variables biophysiques, le bilan énergétique et la répartition de l'énergie au cours du cycle d’une rotation du palmier à huile peuvent s'expliquer par l'effet de refroidissement évaporatif précédemment identifié dans les forêts, qui compense l'effet de réchauffement de l'albédo. L'un des principaux déterminants de ce mécanisme est la couverture végétale au cours des différentes phases du cycle de rotation du palmier à huile. Le NDVI en tant qu'indicateur du couvert végétal a montré une relation inverse cohérente avec LST de différentes plantations de palmiers à huile âgés, une tendance qui est également observée pour différents types d'utilisation des terres dans cette étude.
Une analyse régionale et à plus long terme de la tendance LST entre 2000 et 2015 basée sur les données MODIS montre que dans la journée la température moyenne de Jambi a augmenté de 1,05 ºC, suivant la tendance des changements observés et dépassant les effets du réchauffement climatique.
Afin d'évaluer les effets de l'expansion du palmier à huile sur le climat, le bilan énergétique de surface, le partitionnement énergétique et les processus biophysiques jouent un rôle important et le cycle complet de rotation des plantations de palmiers à huile doit être envisagé. Basé sur nos résultats, nous construisons le cycle de rotation des plantations de palmiers à huile et les changements qui se produisent au cours du développement de la végétation de palmiers à huile.
Cette étude fournit des preuves que l'expansion des plantations de palmiers à huile et d'autres cultures commerciales entraîne des changements dans les variables biophysiques, réchauffant la surface du sol et augmentant ainsi l'augmentation de la température de l'air à cause du changement climatique. En utilisant des données Landsat à haute résolution, nous avons pu inclure les effets du changement d'utilisation des terres sur les variables biophysiques. Comprendre les effets du changement de la couverture terrestre sur les variables biophysiques peut soutenir des politiques concernant la conservation des forêts existantes, la planification et l'expansion des plantations de palmiers à huile et les mesures de boisement possibles. La connaissance des variables biophysiques, du bilan radiatif et de la répartition énergétique au cours du cycle de rotation du palmier à huile peut inclure de nouvelles pratiques de gestion susceptibles de réduire les conditions environnementales et microclimatiques extrêmes dans la phase initiale des plantations de palmiers à huile.
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Modificação da energia de superfície em nano-óxidos do sistema SnO2-TiO2 preparados por síntese química. / Surface energy modification of nano-oxides of the SnO₂-TiO₂ system prepared by chemical synthesis.Joice Miagava 21 July 2015 (has links)
Devido à elevada razão superfície/volume dos nanomateriais, estes apresentam propriedades únicas que são consequência das propriedades de suas superfícies. Para estabilizar as nanopartículas, as quais tendem ao crescimento para reduzir o excesso de energia, uma estratégia é a introdução de aditivos que segreguem na superfície e reduzam a energia de superfície. Neste trabalho, o sistema de importância tecnológica SnO2-TiO2 foi estudado. Nanopartículas de Sn1-xTixO2 (0,00 x 1,00) foram sintetizadas pelo método dos precursores poliméricos. Difratogramas de raios X mostram que uma solução sólida com estrutura do tipo rutilo é obtida para x 0,90. A evolução dos parâmetros de rede, os espectros obtidos por perda de energia de elétrons (EELS) e os espectros no infravermelho coletados no modo de refletância difusa (DRIFT) sugerem a segregação do Ti4+ na superfície, que justifica a elevada solubilidade do Ti4+ no SnO2. Os espectros Raman são coerentes com a segregação, mostrando que, mesmo sem a formação de segunda fase, ocorrem regiões ricas em Ti. A segregação está relacionada também à redução do tamanho de cristalito e ao aumento da área de superfície específica devido à redução da energia de superfície (de 1,40 Jm-2 em x = 0,00 até 1,08 Jm-2 em x = 0,50) determinada por calorimetria de adsorção de água e coerente com os dados da calorimetria de dissolução. Para x 0,90, ocorre a formação da fase anatásio além do rutilo e os fenômenos de estabilização dos polimorfos podem ser explicados pela modificação da energia de superfície. Com base na caracterização feita, as atividades fotocatalíticas das nanopartículas foram avaliadas e foi verificado um aumento da eficiência devido à superior área de superfície das amostras aditivadas em relação às amostras puras. / Due to the high surface/volume ratio, nanomaterials have unique properties as a consequence of their surface properties. In order to stabilize the nanoparticles, which tend to grow to reduce their excess energy, one can introduce additives that are prone to segregate at the surfaces and reduce the surface energy. In this work, the technologically relevant SnO2-TiO2 system was studied. Sn1-xTixO2 (0.00 x 1.00) nanoparticles were synthesized by polymeric precursors method. X-ray diffraction patterns show that a rutile-structured solid solution is formed for x 0.90. Lattice parameters evolution, electron energy loss spectra (EELS) and diffuse reflectance infrared spectra (DRIFT) suggest a Ti4+ surface segregation, which explains the high Ti4+ solubility in SnO2. Raman spectra are in accord with the segregation, showing Ti-rich sites in the absence of a second crystalline phase. The segregation is also related to a decrease in the crystallite size and an increase in the surface area due to a decrease in the surface energy (from 1.40 Jm-2 for x = 0.00 to 1.08 Jm-2 for x = 0.50) determined by water adsorption calorimetry and consistent with drop solution calorimetry data. For x 0.90, the formation of anatase occurs in addition to rutile, and the polymorphic stability can be explained according to the surface energy modification. Based on these results, photocatalytic activity of the samples were evaluated, and an increase in the efficiency due to a higher surface area was observed for the samples containing additive compared to pure samples.
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Influencia da adesão particula-suspensão durante o processo de recobrimento em leito de jorro com atomização na base / The influence of adhesion winth the particle-suspension during the coating process in a spouted bed with bottom-sprayMarques, Aline Maria Manrique 26 February 2007 (has links)
Orientador: Sandra Cristina dos Santos Rocha / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-09T14:53:14Z (GMT). No. of bitstreams: 1
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Previous issue date: 2007 / Resumo: O objetivo de estudo deste trabalho consistiu na análise do recobrimento de partículas em leito de jorro com atomização na base do equipamento. Estudou-se o comportamento fluidodinâmico, as propriedades de adesão entre partícula-suspensão, o crescimento da partícula e a eficiência do processo. Os ensaios foram realizados em equipamento de escala laboratorial e ângulo de base de 60º, sendo utilizados núcleos, como: vidro, ABS®, polipropileno (PP) e poliestireno (PS). Todos foram objeto de análise e classificação quanto à forma, tamanho, esfericidade, densidades absoluta e aparente, porosidade, ângulo de repouso e escoabilidade. Quanto às suspensões, foram utilizadas as poliméricas aquosas, tendo como polímero base o hidroxietilcelulose (HEC), caracterizadas pela densidade, tensão superficial, ângulo de contato e reologia. Em termos de fluidodinâmica do processo, foram avaliados parâmetros como a queda de pressão no leito, a vazão do ar de entrada, a velocidade de circulação dos sólidos e a altura da fonte. Observou-se a ocorrência de dois processos distintos: o recobrimento das partículas e a secagem da suspensão, dependendo do par úcleo-suspensão utilizado. No recobrimento das partículas, a velocidade de circulação e a queda de pressão no leito aumentam com o aumento da vazão de ar de jorro, já que se adotou como procedimento manter a altura do leito constante através do aumento da vazão de ar para que o regime de jorro permanecesse estável. Já na secagem, a velocidade de circulação das partículas diminui em função da retenção de sólidos no leito e a queda de pressão mantémse praticamente constante com o aumento do ar de jorro. A ocorrência do processo de recobrimento ou secagem é determinada pelas propriedades de adesão entre a partícula-suspensão. Ao atomizar-se as diferentes suspensões sobre os núcleos, visualizou-se que a energia superficial do sólido e a tensão superficial da suspensão influenciam a eficiência dos processos. Partículas com alta energia superficial (vidro e ABS®) foram recobertas pela suspensão, enquanto que a secagem ocorreu quando foram utilizadas partículas com menores energias superficiais (PP e PS). Sendo importante ressaltar que a tensão superficial da suspensão influencia diretamente a eficiência do recobrimento e, para a secagem, a quantidade de pó coletado no leito / Abstract: The aim of this work is to analyze the coating process in a spouted bed with bottom-spray, where parameters like fluid-dynamic behavior, properties of adhesion between the particles and the suspensions, the particles growth and the process efficiency were studied. The experiments were realized in a conventional spouted bed of laboratory scale, with base angle of 60º. Inert particles, such as glass beads, ABS®, polypropylene (PP) and polystyrene (PS), were analyzed and classified by size, shape, sphericity, absolute and apparent densities, porosity, angle of repose and flow ability. The polymeric suspension was characterized by density, surface tension and rheology. In terms of fluid-dynamic, values of bed pressure drop, spout air flow rate, solids circulation velocity and fountain height, were analyzed. The occurrence of two distinct process: the coating of the particles or the suspension drying, was observed depending on the particles-suspensions characteristics. During the particles coating, the particles circulation velocity and the bed pressure drop increased with the spout air flow rate increase. For the drying process, the particles circulation velocity decreased with the solids retention in the bed and the bed pressure drop maintained practically constant increasing the spout air flow rate. The occurrence of coating or drying process is influenced by the adhesion properties between the particle and the suspension. Atomizing the three suspensions on the four particles, it was observed that the solid surface energy and the surface tension cause some influence on the process efficiency. Particles with higher surface energy (glass beads and ABS®) were coated by the suspension, while the drying of the suspension occurred when the bed was filled with inert particles with lower surface energy (PP and PS). The suspension surface tension influences directly the coating efficiency and the quantity of powder collected in the cyclone / Mestrado / Engenharia de Processos / Mestre em Engenharia Química
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Electromouillage et fiabilité : investigation de matériaux diélectriques et de couches minces hydrophobes / Electrowetting and reliability : investigation of dielectric materials and hydrophobic thin filmsBonfante, Gwenaël 14 December 2017 (has links)
Dans le but d'améliorer la fiabilité des technologies utilisant l'électromouillage, l'objectif de cette thèse est d'étudier les mécanismes de vieillissement de matériaux diélectriques et hydrophobes utilisés en électromouillage et d'appliquer ensuite le protocole de caractérisation établi, à de nouveaux matériaux. Cette thèse s'articule en trois parties. Dans une première partie, afin de caractériser finement les propriétés d'hydrophobie de surfaces et de déterminer plus particulièrement leur polarité, nous avons mis au point une méthode de mesure de la polarité de surface basée sur le mouillage de deux liquides sur une surface, ce qui apporte une précision accrue avec un minimum de mesures. Dans une deuxième partie, nous avons étudié différents revêtements utilisés en électromouillage avant et après vieillissement. Nous nous sommes plus particulièrement intéressés aux films hydrophobes largement utilisés dans les systèmes optiques et de micro-laboratoires comme le Fluoropel©, le Cytop© et le parylène C. Cette étude montre une altération non négligeable des performances des matériaux de manière reproductible. L'hystérésis de mouillage, l'angle de contact au repos ainsi que les propriétés de cohésion des couches ont été étudiés afin de mettre en évidence les paramètres critiques à la durée de vie.Dans la dernière partie, nous avons cherché à mettre au point une méthode de dépôt d'un nouveau matériau hydrophobe par deux techniques de synthèse ; la voie sol-gel et la pulvérisation cathodique (PVD). Ainsi, un sol de précurseur à base du métal applicable pour la préparation de couches minces de son oxyde a été élaboré. La solution est obtenue à partir d'un précurseur synthétisé au laboratoire et stabilisée par des chélatants (acétylacétone). La stabilité de la solution ainsi que la procédure de dépôt sont présentées et les revêtements recuits déposés par sol-gel et PVD sont caractérisés par DRX et d'un point de vue morphologique (MEB, microscope optique…). Si, il fut possible de préparer par la méthode sol-gel des films de 300nm couvrants, leur forte rugosité n'a pas permis de les tester en électromouillage. Par la méthode PVD, nous avons pu réaliser des couches de 400 nm d'épaisseur, très lisses et utilisables en électromouillage. Ces films donnent de très bons résultats en électromouillage sur substrats plans et en lentilles liquides / In order to increase the technologies reliability using electrowetting, this work aims to study the mechanisms of ageing on dielectric and hydrophobic materials used in electrowetting as well and to apply this study to new materials. This thesis is composed of three parts.First, to be able to characterize precisely the hydrophobic properties of these surfaces and especially their surface polarity, we established a method to measure the surface polarity based on wettability of two liquids on a surface permitting a better precision with less measurements. In a second part, we studied different films used in electrowetting before and after ageing around 90°C for one week in order to simulate a long term ageing at an ambient temperature. Widely used hydrophobic coating used in optical systems and lab-on-chip will be mainly characterized such as Fluoropel©, Cytop© and parylène C. This work shows the visible alteration of material performances in a reproducible way. Wetting hysteresis and natural contact angle with the cohesive properties of the coatings are studied in order to establish critical parameters for the life time.Finally, we tried to establish a method to deposit a hydrophobic metal oxide coating by two ways, sol-gel technic with dip-coating deposition and by PVD. A precursor sol made of the metal usable to deposit its oxide thin films has been elaborated. The solution is prepared from the synthesized precursor and stabilized by chelatant (acetylacetone). The solution stability as well as the deposition method used are presented and the annealed coatings deposited by sol-gel and PVD are characterized by XRD and morphologically (SEM, optic microscope …). By the sol-gel method, covering coatings of about 300nm have been made. However, because of the roughness, no electrowetting experiments could have been achieved. By PVD, we have deposited coatings of 400nm thickness, very smooth and usable in electrowetting. These coatings give very good results in electrowetting on plane substrates and liquid lenses
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