Rainfall interception is a primary control over the moisture input to a forested ecosystem through the partitioning of precipitation into throughfall, stemflow, and an evaporated component (i.e. the interception loss). Rainfall interception is a spatially and temporally varying process at multiple scales, but heterogeneity in interception processes are poorly understood and poorly described in the literature. We need to know how net precipitation varies in ecosystems because natural systems are driven by non-linear ecohydrological processes where mean values cannot capture localized effects or the cumulative consequences associated with an extremely heterogeneous input. In this thesis, we present two studies that investigate the heterogeneity of interception loss and throughfall in a forested catchment in the western Cascades range of Oregon. In one study, we examined the spatio-temporal patterns among point measurements of throughfall depth and isotopic composition to determine the cause of isotopic differences between throughfall and rainfall. Our results indicated that the residual moisture retained on the canopy from previous events plays a major role in determining the isotopic composition of the next event's throughfall. Differences between the isotopic composition of throughfall samples could indicate further partitioning of throughfall into various flow-paths from the canopy. The second project examined the question of how vegetation variability and terrain complexity drive interception loss heterogeneity at the whole-catchment scale. We applied a simple interception model to a watershed gridded at a 50 m resolution to investigate the relative importance of topographic and vegetative controls over the spatial variability of interception loss. We found that storm characteristics are crucial regarding the impact of spatial heterogeneities in vegetation and evaporation rates. In the Pacific Northwest climate, interception loss is not highly variable for the majority of the year because the annual precipitation is dominated by large storms with low interception losses. However, the net precipitation input to a watershed becomes extremely heterogeneous in the summer due to high interception loss variability. Summer interception loss could be an important control over the spatial variability of the availability of moisture, coinciding with when vegetation is most water-limited. / Graduation date: 2013

CdSe thin films were deposited by thermal evaporation and e-beam evaporation techniques on to well cleaned glass substrates. Low dose of boron have been implanted on a group of samples. EDAX and X-ray patterns revealed that almost stoichiometric polycrystalline films have been deposited in (002) preferred orientation. An analysis of optical measurements revealed a sharp increase in absorption coefficient below 700 nm and existence of a direct allowed transition. The calculated band gap was around 1.7 eV. The room temperature conductivity values of the samples were found to be between 9.4 and 7.5x10-4 (&amp / #937 / -cm)-1 and 1.6x10-6 and 5.7x10-7 (&amp / #937 / -cm)-1for the thermally evaporated and e-beam evaporated samples respectively. After B implantation conductivity of these films increased 5 and 8 times respectively. Hall mobility measurements could be performed only on the thermally evaporated and B-implanted e-beam evaporated samples and found to be between 8.8 and 86.8 (cm2/V.s). The dominant conduction mechanism were determined to be thermionic emission above 250 K for all samples. Tunneling and v variable range hopping mechanisms have been observed between 150-240 K and 80- 140 K respectively. Photoconductivity &amp / #8211 / illumination intensity plots indicated two recombination centers dominating at the low and high regions of studied temperature range of 80-400 K. Photoresponse measurements have corrected optical band gap measurements by giving peak value at 1.72 eV.

Les effets capillaires sont très courant dans la Nature. Dans le contexte du séchage de milieux poreux dont la taille de pore est dans la gamme micromètre-millimètre, ils jouent un effet dominant en contrôlant la répartition des phases (liquide-vapeur) dans l’espace poral, au fur et a` mesure que le séchage se produit. L’idée du présent travail est d’étudier le séchage d’un fluide pur et mouillant dans des micromodèles, c’est-à-dire des milieux poreux modèles quasi-2D et micro-fabriqués. Nous présentons des résultats obtenus pour différentes géométries. Typiquement, les micromodèles utilisés sont constitués de réseaux de cylindres pris en sandwich entre deux plaques. La distribution des phases et le taux d’évaporation dans de tels micromodèles peuvent être aisément mesurés par visualisation directe puis traitement d’images.En jouant sur l’arrangement spatial des cylindres, on obtient dans un premier temps des micromodèles pour lesquels le taux de séchage est quasi-constant, depuis le début de l’expérience de séchage jusqu’à l’évaporation totale du liquide saturant initialement le système. Typiquement, cette situation est obtenue quand la taille des pores décroît en allant du centre du micromodèle vers sa périphérie (les micromodèles sont axisymmétriques). Au contraire, quand la taille des pores croît du centre vers la périphérie, l’invasion d’un front de séchage stable est observée, d’ou` un temps de séchage total bien supérieur.Nous avons aussi réalisé un autre type de microsystèmes, au sein duquel les cylindres sont arrangés en spirale de Fibonacci, en nous inspirant de motifs observés en phillotaxie. Dans de tels systèmes, des films liquides épais se développent le long des spirales, au cours du séchage, et jouent un rôle crucial dans la cinétique d’évaporation. Cette situation rappelle celle déjà étudiée par Chauvet dans des tubes capillaires de section carrée. Cependant, elle est plus complexe, de par la nature poreuse du micromodèle (alors qu’un tube capillaire, tel qu’étudié par Chauvet, peut être vu comme un pore unique) et parce que les films liquides y ont une forme plus complexe. Pour de tels systèmes, nous présentons des résultats expérimentaux quantifiant l’effet des films liquides sur la cinétique de séchage, en lien avec des prédictions théoriques issues d’un modèle de séchage visco-capillaire. Un tel modèle nécessite l’utilisation du logiciel Surface Evolver pour modéliser la forme des films liquides, couplée avec des simulations directes de l’écoulement de Stokes dans les films liquides, pour y calculer la résistance visqueuse a` l’écoulement induit par l’évaporation.Enfin, dans un dernier chapitre, plusieurs expériences d’évaporation sont conduites sur des micromodèles déformables. Des effets élasto-capillaires peuvent en effet induire des changements de géométrie de l’espace poral en cours d’évaporation, ce qui, comme vu précédemment, peut affecter la distribution des phases et la cinétique de séchage. / Capillarity is a common phenomenon encountered in Nature. In the context of the drying of porous media with pore size in the micrometer-millimeter size range, capillary effects play a dominant role in controlling the phases (liquid or vapor) distribution in the pore space as drying occurs. The basic idea of the present work is to study the drying of pure, wetting fluids in micro-fabricated, quasi-2D, model porous media (hereafter called micromodels). We present results obtained for different micromodel geometries. Typically, the micromodels used consist of arrangements of cylinders sandwiched between a top and bottom plate. Phases distribution and evaporation rates in such micromodels can easily be measured by direct visualizations and subsequent image processing.By tuning the cylinders pattern, one can first obtain micromodels for which the drying rate is almost constant, from the beginning of the drying experiment to the total evaporation of the liquid initially filling the system. Typically, this situation is obtained when the pores size decreases from the micromodel center to the periphery (the micromodels are axisymmetric). On the contrary, when the pores size increases from the center to the periphery, invasion of a stable drying front is observed, resulting in a much longer total drying time.We also designed another type of micromodel where the cylinders are arranged in a Fibonacci spiral pattern, a design inspired by phyllotaxic structure. In such systems, thick liquid films develop along the spirals during drying and play a key role in the drying kinetics. This situation is reminiscent of that already studied by Chauvet in capillary tubes with square cross-sections. However, it is more complex because of the porous nature of the micromodel (whereas a single capillary tube, as studied by Chauvet, can be viewed as a unique pore), and because of the much more complex liquid films shapes. For such systems, we present some experimental results on the liquid films effects on the drying kinetics, together with theoretical prediction, based on a visco-capillary drying model. Such a modelling requires the use of the Surface Evolver software to model the film shape, coupled with DNS simulations of the Stokes flow within the liquid films to compute the viscous resistance to the evaporation-induced flow.Finally, as a last part of this thesis, several evaporation experiments performed on deformable micromodels are presented. This preliminary work aims at reaching a situation where elasto-capillary effects modify the pore space geometry during evaporation. This, as seen above, should in turn alter the phase distribution during evaporation and the drying kinetics.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Worldwide, the agricultural sector is the largest consumer of water, reaching about 69% of total water derived from rivers, lakes and underground aquifers. Because of this huge consumption of water by agriculture and the scarcity of water in various parts of the world there is a social and environmental pressure very big, mainly on irrigated agriculture in order to improve the efficiency of the use of water. This study aimed to quantify the loss of water from the soil by evaporation, in the early stages of development of the corn crop sown in cultivation from no-tillage system and conventional tillage. The work was developed in Experimental Area of the Department of Rural Engineering of the Federal University of Santa Maria (UFSM), RS. The experiment was conducted in the period from October 28, 2006 to December 10, 2006 and consisted of four treatments: (i) direct maize sowing in bare soil (PD0), (ii) direct sowing of corn with 3,0 Mg ha-1 of straw on the soil surface (PD3), (iii) direct sowing of corn with 6,0 Mg ha-1 of straw on the soil surface (PD6), and (iv) conventional tillage of the soil without coverage of straw on the surface (PC). The loss of water from the soil were determined in four cycles of dry soil during the first 38 days after the emergence of culture, holding up the water balance in soil layers from 0 to 10 cm and 10 to 30 cm, from data of volumetric soil moisture determined with a TDR at intervals of 15 minutes. It was also determined, for the first cycle of drying soil coefficients of evaporation(K) and reducing of water evaporation from the soil (Kr), as the methodology of Kc Dual. For the short duration of the cycles of drying of the soil, growth and development of plants were not affected by the system of cultivation of the soil in the early stages of development of the corn crop. In layer from 0 to 10 cm depth for the first cycle of drying of the soil, 3,0 Mg ha-1 of straw on the surface provided a reduction in the loss of water by evaporation of 24,6% and 19,9% in relation to the PC and PD0, respectively. With 6.0 Mg ha-1 of straw, the reduction was 50,7% and 47,6%, respectively. In the first 30 cm of the soil profile, the reduction in losses of water was 18.2% and 23% respectively to 3.0 Mg ha-1 of straw. Increasing to 6.0 Mg ha-1 reduction was 38,3% and 42,0% respectively. With the growth of culture, the increase in the loss of water in the soil was due to the bigger development of plants with increasing participation of transpiration in water consumption by culture, by shading the surface at the higher leaf area index of the plants. Treatments with PC and PD0 show Ke higher, reaching 1,32 and 1,17, respectively. With the presence of straw, the maximum value of K was reduced to approximately 50% compared with the treatments without straw on the surface reaching values of 0,70 and 0,44, respectively, when EToac was 10,0 mm. The treatments of PC and PD0 showed a fast reduction in the coefficient of reduction of water evaporation from soil, after 6,5 mm of EToac. The lowest value of Kr at the end of the cycle of drying, 0,47, was observed for the treatment PD0. The PD6 has remained longer in the first stage of evaporation, reducing the Kr when EToac exceeded 20,0 mm. / Mundialmente, o setor agrícola é o maior consumidor de água, alcançando cerca de 69% do total de água derivada de rios, lagos e aqüíferos subterrâneos. Em função deste grande consumo de água pela agricultura e pela escassez de água em várias partes do mundo, há uma pressão social e ambiental muito grande, principalmente sobre a agricultura irrigada, a fim de melhorar a eficiência do uso da água. Este estudo teve como objetivo quantificar as perdas de água do solo por evaporação, nos estádios iniciais de desenvolvimento da cultura do milho semeada em sistema de cultivo direto e preparo convencional. O trabalho foi desenvolvido em Área Experimental do Departamento de Engenharia Rural da Universidade Federal de Santa Maria (UFSM), RS. O experimento foi conduzido no período de 28 de outubro de 2006 a 10 de dezembro de 2006 e constituiu-se de quatro tratamentos: (i) semeadura direta do milho em solo desnudo (PD0); (ii) semeadura direta do milho com 3,0 Mg ha-1 de palha na superfície do solo (PD3); (iii) semeadura direta do milho com 6,0 Mg ha-1 de palha na superfície do solo (PD6) e, (iv) preparo convencional do solo, sem cobertura de palha na superfície (PC). As perdas de água do solo foram determinadas em quatro ciclos de secagem do solo durante os primeiros 38 dias após a emergência da cultura, realizando-se o balanço hídrico do solo nas camadas de 0 a 10 cm e de 10 a 30 cm, a partir dos dados de umidade volumétrica do solo determinada com um TDR em intervalos de 15 minutos. Determinou-se também, para o primeiro ciclo de secagem do solo os coeficientes de evaporação (Ke) e de redução da evaporação da água do solo (Kr), conforme a metodologia do Kc Dual de cultivo. Pela curta duração dos ciclos de secagem do solo, o crescimento e o desenvolvimento das plantas não foram influenciados pelo sistema de cultivo do solo nas fases iniciais de desenvolvimento da cultura do milho. Na camada de 0 a 10 cm de profundidade, para o primeiro ciclo de secagem do solo, 3,0 Mg ha-1 de palha na superfície proporcionou uma redução nas perdas de água por evaporação de 24,6% e 19,9% em relação ao PC e PD0, respectivamente. Com 6,0 Mg ha-1 de palha, a redução foi de 50,7% e 47,6%,respectivamente. Nos primeiros 30 cm do perfil do solo, a redução nas perdas de água foi de 18,2% e 23%, respectivamente com 3,0 Mg ha-1 de palha. Aumentando para 6,0 Mg ha-1 a redução foi de 38,3% e 42% respectivamente. Com o crescimento da cultura, o aumento nas perdas de água do solo foi devido ao maior desenvolvimento das plantas com aumento da participação da transpiração no consumo de água pela cultura, pelo sombreamento da superfície pelo maior índice de área foliar das plantas. Os tratamentos com PC e PD0 apresentam Ke mais elevado, chegando a 1,32 e 1,17, respectivamente. Com a presença de palha, o máximo valor de Ke foi reduzido para aproximadamente 50% comparados com os tratamentos sem palha na superfície atingindo valores de 0,70 e 0,44, respectivamente, quando EToac era de 10,0 mm. Os tratamentos de PC e PD0 apresentaram uma rápida redução no coeficiente de redução da evaporação da água do solo, após 6,5 mm de EToac. O menor valor de Kr no final do ciclo de secagem, 0,47, foi observado para o tratamento PD0. O PD6 manteve-se por mais tempo no primeiro estagio da evaporação, reduzindo o Kr quando a EToac superou 20,0 mm.

Les aciers inoxydables ferritiques sont actuellement les meilleurs candidats pour répondre au cahier des charges des matériaux destinés aux interconnexions de piles à combustibles à oxyde solide (SOFC acronyme anglo-saxon pour Solid Oxide Fuel Cell). Cependant, du coté du compartiment cathodique de ces piles, le phénomène de sublimation du chrome à haute température conduit à des dégradations importantes, réduisant ainsi la durée de vie en service des SOFC. Les objectifs de ce travail de thèse sont (i) d'étudier le phénomène de sublimation du chrome sur l'acier inoxydable ferritique AISI 441 et (ii) de rechercher le ou les moyen(s) d'atténuer cette même sublimation. Sur le deuxième point, des méthodes de protection ont été mises en œuvre, en particulier avec le dépôt de films minces de spinelle Mn-Co obtenues via un procédé de galvanoplastie ou bien encore en procédant à des pré-oxydations des alliages dans des atmosphères contrôlées de type argon impur ou mélanges gazeux équimolaires CO / CO2 (250 ° C et 850 ° C, pour une durée totale de 3 h).Concernant l'étude de la sublimation du chrome, des essais d'oxydation simulant les conditions de service ont été conduites dans des mélanges gazeux : 5% de O2 dans H2O à 800 °C pendant 96 h. A vitesse de gaz oxydants faible, de 1 à 3 cm / s, la sublimation du chrome est limitée par un phénomène de diffusion dans la phase gazeuse de l'espèce volatile oxo-hydroxyde de chrome. A vitesse plus élevée, de 3 à 10 cm / s, la sublimation du chrome semble limitée par un phénomène interfacial. La vitesse de sublimation apparait indépendante de la rugosité de surface des échantillons, elle même variant selon la préparation des échantillons. Du point de vue de la caractérisation morphologique des couches d'oxydation thermiques obtenues, sur les surfaces de plus forte rugosité (surface industrielle), nous avons noté le développement de nodules riches en titane et en niobium avec une partie externe et une autre interne. Dans le substrat, des phases de lave de type Fe2Nb ont été observées le long des joints de grain métalliques.Dans une deuxième partie, la sublimation du chrome a été étudiée sur échantillons revêtus ou pré-oxydés. Les films minces de spinelle Mn-Co ne conduisent pas à l'abaissement de la vitesse de sublimation du chrome et sont donc pas protecteurs. L'adhérence de ces revêtements est de mauvaise qualité. Les couches présentent de nombreuses fissures. La pré-oxydation conduit quant à elle à une réduction considérable (jusqu'à un facteur 10) de la vitesse de sublimation du chrome (sauf dans le cas de la pré-oxydation dans l'argon à 850 °C). La formation d'un film riche en fer obtenu à basse température (250 °C) peut expliquer cette réduction par l'établissement d'une barrière de diffusion. Cette même réduction est cependant surprenante sur les films riches en chrome obtenus par pré-oxydation à 850 °C dans CO / CO2. Nous proposons dans ce travail une interprétation originale basée sur les différences de nature semi-conductrice des films de chromine formées à haute pression d'oxygène (proche de l'atmosphère) et identifiés comme étant de type p par rapport à ceux obtenus à basse pression (dans CO/CO2) qui sont connu pour être de type n. Après l'oxydation à haute température de 96 heures, tous les échantillons préalablement pré-oxydés ont été observés comme étant composés d'oxyde de chrome et d'un spinelle Mn-Cr.Au terme de ce travail de thèse, il peut être conclu que la pré-oxydation de l'alliage 441 à basse température (250 °C) dans l'argon ou le mélange CO/CO2 ou encore à plus haute température (850 °C) dans le mélange CO/CO2 sont des traitements qui conduisent à l'abaissement de la vitesse de sublimation du chrome et par voie de conséquence à l'amélioration de la tenue de cet alliage en condition d'oxydation dans le compartiment cathodique des SOFC. / Ferritic stainless steels are the most attractive materials that are able to fulfil SOFC(Solid Oxide Fuel Cell) interconnect properties. However, in cathodic SOFC condition, Crvolatilisation from ferritic steels leads to degradations of interconnect and cathode materialsand shorter service lifetime of SOFC. The objectives of this work are (i) to study Crvolatilisation from AISI 441 ferritic stainless steel and (ii) to find the way out to suppress Crvolatilisation. The Cr volatilisation protective methods used in this work were coating withMn-Co spinel by an electroplating method and preoxidation in the condition of Ar or CO/CO2at either 250°C or 850°C, for 3 h. Cr volatilisation experiments were performed in 5%H2O inO2 at 800°C for 96 h. According to the results, it can be concluded that the preoxidation ofthe AISI 441 in Ar or CO/CO2 at low temperature (250°C) or in the CO/CO2 at a highertemperature (850°C) are treatments that lead to lowering the sublimation rate of the Cr andimprovement in the oxidation resistance of this alloy in the cathodic compartment of theSOFC.

L'évaporation d'une goutte reposant sur un support plat semble être un système relativement simple à étudier et a fait l'objet d'études scientifiques depuis plus d'un siècle. Cependant, l'étude de l'évaporation de gouttes sessiles est toujours d'actualité aujourd'hui avec l'essor de nouvelles techniques de visualisation ou de l'apparition de nouveaux types de fluides complexes.Cette étude expérimentale sera focalisée sur deux aspects distincts :- L'étude sur l'évaporation de fluides purs permettra d'étudier la dynamique d'évaporation et les ondes hydrothermales qui apparaissent dans les gouttes de fluides volatils lors du changement de phase. L'influence du type de fluide (différents alcools et alcanes) et du niveau de gravité (terrestre, lunaire et martienne) seront étudiés. De plus, l'utilisation de différents niveaux de gravité permet de développer un modèle empirique afin de prendre en compte dans le modèle quasi-stationnaire limité par diffusion de la vapeur la convection naturelle qui augmente fortement le débit d'évaporation.- Si les fluides complexes présentent une dynamique de séchage similaire à celle des fluides purs, d'autres mécanismes entrent en jeux, comme la gélification, l'organisation des particules et l'apparition de craquelures (voir Figure 2). Le mouillage et les différents groupes fonctionnels graphés sur les particules seront étudiés en regard du motif final de craquelures. / Sessile droplets are widely found in day to day life: it might be a coffee spilt, rain onto a waterproof raincoat or again, water falling onto a cooking plate. However, despite the vast number of studies devoted to droplets for almost half a century, the fundamental phenomenon of the evaporation of sessile droplets is still a field that attracts a high level of interest due to its wide applicability and the development of new visualisation techniques or new types of complex fluids. This experimental study is focused two distinct aspects:- The evaporation of pure fluids has allow to study hydrothermal waves that appear in the droplets of volatile fluids during phase change. The influence of the type of fluid ---different alcohols and alkanes--- and the gravity levels ---Terrestrial, Lunar and Martian--- is investigated to have a better understanding of the flow motion inside droplet. Moreover, the use of different gravity levels allows to experimentally evidence the contribution of the atmospheric convective transport to sessile droplet evaporation. This investigation has allowed to develop an empirical model to take account of natural convection which greatly increases the evaporation rate in the quasi-steady diffusion-controlled evaporation model.- If complex fluids exhibit an evaporation dynamic similar to pure fluid, other mechanisms come into play, such as gelation, particles organisation and cracks formation. Wetting and different functional groups on the particles graphs will be studied in relation to the final pattern of cracks.

This thesis investigates lead oxides as photovoltaic materials. Vacuum deposition methods and ex-situ annealing are used to produce different stoichiometries of lead oxide. The relationship between structure and the optoelectronic properties is then investigated. Following this, a number of photovoltaic devices are prototyped and a Kelvin probe used to determine and understand the band structure of devices. Thin films of PbO produced via air annealing of thermally evaporated lead consist of a mixture of two phases, orthorhombic and tetragonal, that determine the materials properties and effectiveness as absorber layer in a Schottky device. Films of higher tetragonal content are more photoactive, showing lower series resistance. Kelvin probe reveals that with an increasing work function of the PbO with increasing duration of the annealing, the Schottky barrier between PbO and Al increases, which results in a higher VOC. This trend is inverted when the Fermi level of PbO drops below that of ITO, creating an opposing junction. Reactively sputtered PbO2 films are highly conductive degenerate semiconductors. Increasing oxygen flow rate during deposition leads to increased resistivity and decreased mobility, resulting from a decrease in grain size. Alongside this an increase in carrier concentration is observed as the material gets less ordered at higher oxygen flow rates, which results in an increase in Fermi level. Due to its high conductivity the material is not photoactive, and the high work function between -5.6 and -5.8 eV does not allow the formation of a Schottky junction or a p-n junction with the evaporated p- type PbO. Post deposition annealing of the sputtered films leads to the formation of the more resistive Pb3O4 phase. This material shows lower carrier concentration and mobility, however, work functions are similarly high. The changes induced by the heat treatment are not substantial enough to be able to create a junction between the as-deposited and the annealed material, as is revealed by Kelvin probe and Hall Effect measurements. Heterojunctions between P3HT and Pb3O4 were made to test predictions made by KP measurements. A heat treatment on P3HT improved its electronic properties and raised the Fermi level, resulting in the transformation of a diode in to a photovoltaic device and a decrease in dark current.

Various techniques of fabricating surface patterns of small scales have been widely studied due to the potential applications of surface patterns in a variety of areas. It is a challenge to fabricate well-ordered surface area efficiently and economically. Evaporation-induced surface patterning is a promising approach to fabricate well-ordered surface patterns over a large area at low cost. In this study, the evaporation-induced surface patterns with controllable geometrical characteristics have been constructed. The dewetting kinetics on deformable substrate is also investigated. Using simple templates to control the geometry and the evaporation behavior of a droplet of volatile solvent, various gradient surface patterns, such as concentric rings, multiple straight stripes formed with a straight copper wire, etc. have been constructed on PMMA films. The wavelength and amplitude are found to decreases with the decrease of the distance to the objects used in templates. There is also a nearly linear relation between the amplitude and wavelength. The effects of several experimental parameters on the geometrical characteristics of the surface structures are studied, i.e. dimensions of the template, film thickness (solution concentration), substrate temperature, etc. The wavelength and amplitude increase with the increase of the film thickness (solution concentration), with the increase of the dimension of the template. However with the increase of the substrate temperature, the wavelength increases, while the amplitude decrease. Hexagonal network in pre-cast PMMA film have been fabricated by a “breath figure” approach at low humidity and low substrate temperature. The dimensions of the hexagonal holes are dependent on the template size and film thickness. The kinetics of the evaporative dewetting of a liquid (toluene) film on a deformable substrate (PMMA film) with the confinement of a circular copper ring is also studied. The liquid film first dewets from the outside towards the copper ring. When a critical volume is reached, an internal contact line appears, which dewets from the center to the copper ring smoothly with a constant velocity, then switches to a “stick-slip” motion. The average velocity of the smooth motion increases with the increase of the copper ring size and film thickness.

Self-assembled nonionic alkyl glycoside surfactants are of interest for creating functional adsorption and catalytic sites at the surface of mesoporous metal oxides, but they typically impart poor long-range order when used as pore templates. Improved order and control over the functional site density may be achieved by mixing them with a cationic surfactant. To confirm this hypothesis, we investigate the lyotropic liquid crystalline (LLC) phase behavior of aqueous solutions of the functional nonionic surfactant n-dodecyl β-D-maltoside (C12G2) and cationic cetyltrimethylammonium bromide (C16TAB). A ternary phase diagram of the C16TAB-C12G2-water system is developed at 50 °C. By replacing the volume of water in the phase diagram with an equivalent volume of silica, ordered mesoporous materials are prepared by nanocasting with variable C12G2/C16TAB ratios. Metal oxide mesophases can almost always be predicted from the ternary phase diagram, except that silica prepared with high C12G2/C16TAB ratios are very weakly ordered, perhaps due to differences in hydrogen bonding or rate of assembly. Based on the ternary phase diagram of the system, a systematic approach is taken to the incorporation of titania sites via complexation to the maltoside headgroup of C12G2. Complexation to a saccharide is expected not only to guide titanium to the pore surface, but also to prevent uncontrolled hydrolysis and condensation of the (usually quite reactive) titanium precursor. Tetrahedrally coordinated titanium atoms incorporated into a silica network are believed to be the active oxidation sites required for heterogeneous silica-supported titania oxidation catalysts. To promote well-ordered materials and to allow control over titania site density, the mixed C12G2 / C16TAB system is used for pore templating. Series of Si-Ti mixed oxide thin films and bulk materials are synthesized with different amounts of titanium loading by utilizing pre-complexation between C12G2 and titanium isopropoxide. The degrees of homogeneity (indicated by tetracoordinated Ti) in these films are superior to those of films synthesized with the same loading of titanium but without C12G2 or without pre-complexation. Transition metal-carbohydrate complexation provides highly dispersed, tetrahedrally coordinated titanium atoms rather than the octahedral sites found without saccharide complexation.

No description available.