Soft materials and compliant structures often undergo significant deformation without failure, a unique feature making them distinct from classical rigid materials. These substantial deformations provide a means for faster or more energy efficient deformations, which can be achieved by taking advantage of elastic instabilities. We intend to utilize structural instabilities to generate advanced functionality within soft materials. In particular, we use the buckling of thin, flexible plates to control or enhance the flow of fluid in a micro channel. The buckling deformation is created or altered via two different stimuli, first a mechanical strain and then an electrical signal. We investigate the behavior of each system under different conditions experimentally, numerically, or theoretically. We also show that the coupled interaction between fluid and the soft film plays a critical role in the shape of deformation and consequently in the functionality of the mechanism. We first embed a buckled thin film in a fluid channel within a soft device. By applying a mechanical strain to the device, we show both experimentally and numerically that the height of the buckled film changes accordingly as does the flow rate. We then offer an analytical solution by extending the classical lubrication theory to higher-order terms as a means to more accurately describe the flow in a channel with a buckled thin film, and in general, the flow in channels with any constrictions provided the Reynolds number is low. Next, we use an electrical signal to make a confined dielectric film undergo out-of-plane buckling deformation. The thin film is sandwiched between two flexible electrodes and the mechanism is implemented in a microfluidic device to pump the fluid into a micro channel. We show that the critical buckling voltage at which the thin film buckles out of the plane is mainly a function of voltage while the shape of deformation and so the functionality of this mechanism depend considerably on the applied boundary conditions. Finally, we enhance the fluid-soft structure response of the actuating mechanism by substituting flexible electrodes with fluid electrodes, resulting in a significant increase in the actuation frequency as well as a reduction in the critical buckling voltage. / Ph. D.

The hydrogenation of β-ketoesters over chirally modified Ni catalysts is a celebrated and thoroughly researched example of an enantioselective heterogeneous catalytic reaction. Enantioselective heterogeneous processes, although extremely attractive in terms of fewer complications in the separation of products from the catalyst, are hindered in their viability as industrial applications due to the lack of detailed knowledge on how chirality is conferred to the metal surface. Surface science techniques have afforded substantial progress into determining mechanisms between modifier, reactant and catalyst to explain the source of enantioselectivity of the system. In this study, a combination of solution and ultra-high vacuum (UHV)-based experiments allow a more realistic interpretation of the surface chemistry underpinning the catalytic reaction as the key step in achieving enantioselective performance is the adsorption of chiral modifiers from solution. The behaviour of (S)-aspartic acid and (S)-lysine on Ni{111} and their interaction with the prochiral β-ketoester methylacetoacetate is investigated in this study to understand their potential as chiral modifiers for the system. In UHV, scanning tunnelling microscopy (STM), reflection absorption infrared spectroscopy (RAIRS), and temperature programmed desorption (TPD) are used to analyse the conformation and order of the amino acids on the metal, and their thermal stability. Additionally, liquid-solid interface RAIRS and X-ray photoelectron spectroscopy (XPS) are used to examine the modified Ni surface, prepared under aqueous conditions, to give an accurate representation of the catalytic studies. It has been found highly likely that, for (S)-aspartic acid modified Ni{111}, enantioselective sites exist at step or step/kink defects, formed by corrosive leaching of the Ni substrate. Conversely, lysine appears to bind with a high sticking probability to Ni, in the form of lysine islands, and does not appear to etch the Ni chirally. Finally, similar experiments have been carried out on Au{111}, where lysine was found to chiral restructure the surface and form nanofingers, and 2D Ni clusters grown on Au{111} in order to investigate the formation of possible metal-organic frameworks.

Orientador: Jose de Alencar Simoni / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-09T10:02:14Z (GMT). No. of bitstreams: 1 OliveiraJunior_NiltonGeraldode_M.pdf: 625277 bytes, checksum: e5c790f33e89db6dc410ed2f7eeef0d2 (MD5) Previous issue date: 2007 / Resumo: Neste trabalho apresentam-se os aspectos do desenvolvimento de um sistema para dosagem de gás especialmente projetado para a investigação calorimétrica da adsorção de gases em sólidos. Descrevem-se a concepção e a adequação do sistema de dosagem de gás assim como a metodologia experimental adequada à utilização do referido sistema e os resultados que permitem avaliar seu desempenho. O sistema de dosagem construído consiste em uma linha de vácuo acoplada a um sensor de pressão e uma cela de adsorção dimensionada para ser inserida no calorímetro Thermométric modelo 2277. A adsorção do vapor de etanol em sílica-gel foi escolhida como "processo piloto" para os testes do desempenho do dispositivo devido à facilidade de preparação e condicionamento das substâncias e também ao grande número de dados disponíveis na literatura recente, referente às propriedades físico-químicas desse sistema. Os resultados das isotermas calorimétricas diferenciais, assim como a sistemática de condução dos experimentos nesse trabalho, é devidamente discutida comparativamente aos resultados recentes da literatura. Os resultados apontam para o fato de que o dispositivo funciona bem, dentro das expectativas químicas para o sistema piloto de adsorção utilizado / Abstract: This work presents the development aspects of a gas dosage system specially projected for calorimetric investigation of the gases adsorption onto solids. They describe it conception and the adequacy of the system of dosage of gas as well as the experimental methodology adjusted to the use of the related system and the results that allow to evaluate its performance. The constructed dosage system consists of a line of vacuum connected to a pressure sensor and a dimensioned adsorption cell to be inserted in the Thermométric calorimeter model 2277. The adsorption of the ethanol vapor on silica-gel was chosen as "pilot process" for the tests of the device performance due to easiness of preparation and conditioning of substances and also to great number of available data in recente literature, referring to physical-chemistry properties of this system. The differential calorimetric isothems results as well as the systematics of conduction of the experiments in this work, are duly argued comparativily to the recent results of literature. The results show that the device functions well in respect of the chemical expectations for the adsorption pilot process used / Mestrado / Físico-Química / Mestre em Química

付記する学位プログラム名: 充実した健康長寿社会を築く総合医療開発リーダー育成プログラム / 京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21798号 / 工博第4615号 / 新制||工||1719(附属図書館) / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 松田 建児, 教授 杉野目 道紀, 教授 浜地 格 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

For an electronic device well-designed interfaces are critical for the performance. Studies of interfaces down to an atomic level are thus highly motivated both from a fundamental and technological point of view. In this thesis, a surface science approach has been employed to study the formation of interfaces in systems relevant for transistor and solar cell applications. Surface science methodology entails ultra high vacuum environment, single crystalline surfaces, submonolayer control of deposited material, surface sensitive spectroscopy and atomic resolution microscopy. The primary experimental method for characterization is electron spectroscopy. This is a family of very powerful experimental techniques capable of giving information on the atomic level. Additionally, studies have been performed using scanning tunnelling microscopy. Combined these two methods can provide an atomic level characterisation of the geometric and electronic properties of the surface. The emphasis of this work is placed on ultra thin TiO2 and ZrO2 films grown on silicon substrates by means of ultra-high vacuum metal-organic chemical vapour deposition. ZrO2 has also been grown on SiC and FeCrAl. Deposition has been performed with different process parameters. The interface region of each film has been characterised. The band alignment, a most important issue with regard to the development of new transistor devices, for the ZrO2/Si(100) system has been explored. Decomposition pathways of the metal organic precursors have been studied in detail. Changing process parameters is shown to alter both the precursor decomposition pathway and the nature of the interface region, thus opening the possibility to tailor the material function. The titanium dioxide films grown in situ have shown to be excellent models of nanostructured electrode materials. In this spirit, interfaces of model systems for the solid-state dye-sensitized solar cell have been studied. Links between device performance and interface structure have been elucidated.

No / This paper reports on the growth of benzamide crystals in the presence of 2'-aminoacetophenone. The resulting self-replicating intergrowth of benzamide crystals gives rise to ordered crystal aggregates in which individuals share a common c*. This behavior is interpreted using the concept of a motif capper additive which is able to halt the extension of structural motifs at the surface of a growing crystal. In this case the additive was selected to terminate the hydrogen-bonding ribbons, which extend along the b axis of the benzamide structure.

Das grundlegende Verständnis von Selbstorganisationsprozessen auf molekularem Niveau ist von entscheidender Bedeutung für den Fortschritt der Nanotechnologie. In diesem Zusammenhang werden hier Untersuchungen derartiger Prozesse an der Grenzfläche zwischen einer flüssigen Phase (z.B. einer Lösung) und einer kristallinen Festkörperoberfläche durchgeführt. Die Konzentration der Lösung und die Polarität des Lösungsmittels sind von entscheidender Bedeutung für die Kontrolle der durch Selbstorganisation gebildeten Strukturen von Molekülen an den flüssig-fest Grenzflächen zu einem Graphitsubstrat (HOPG). Im Mittelpunkt der vorliegenden Arbeit stehen die Einflüsse dieser beiden Parameter auf die Anordnung der Moleküle. Zunächst wird die Polarität der Lösungsmittel diskutiert. Lösungsmittel mit verschiedenen Polaritäten wie Phenyloctan (unpolar), Fettsäuren (moderat polar) und Fettalkohole (stark polar) wurden verwendet um Trimesinsäure (TMA) zu lösen. TMA bildet keine geordnete Struktur aus wenn es aus Phenyloctan (PO) abgeschieden wird. Ein poröses Muster ("Chicken-wire"-Struktur) entsteht aus der Lösung von TMA in Octansäure, wohingegen aus der Lösung von TMA in Undecanol ein Linienmuster durch Koadsorption von TMA und Undecanol Molekülen gebildet wird. Als nächstes werden die Auswirkungen der Ultraschallbehandlung der Lösungen zur Kontrolle der Konzentration der Lösung und die daraus resultierende unterschiedliche molekulare Packungsdichte und Strukturen beschrieben. Eine selbstassemblierte Struktur aus Zick-Zack-Dimerketten wird bei der TMA-PO Lösung nur beobachtet, wenn die Lösung für 5 Stunden Ultraschall ausgesetzt wurde. Die hoher Packungsdichte in Form der "Flower"-Struktur wird für Lösungen von TMA in Octansäure gefunden, nachdem diese für lange Zeit mit Ultraschall behandelt wurden. Ein weiterer Aspekt der vorliegenden Arbeit ist die entdeckte Veresterungsreaktion an der TMA-undecanol/HOPG Grenzfläche. 1-undecyl Monoester von TMA wurde überraschender Weise an dieser Grenzfläche gefunden, nachdem die TMA-Undecanol Lösungen, für lange Zeit Ultraschall ausgesetzt wurden. Diese Monoestermoleküle bilden sich an der flüssig-fest Grenzfläche allein auf Grund der erhöhten Konzentration von TMA (ohne jegliche externe Katalysatoren). Der physikalische Hintergrund der Prozesse des Lösens und der Ultraschallbehandlung sind der Gegenstand weiterer Untersuchungen. Selbstassemblierte Abscheidung tritt auch bei Verwendung nur der reinen Lösungsmittel (Octansäure beziehungsweise Undecanol) auf, was zu verschiedenen Mustern führt, welche ebenfalls durch Ultraschallbehandlung kontrolliert eingestellt werden können.

La réduction des émissions polluantes et l'amélioration des performances des turboréacteurs nécessitent une connaissance détaillée des phénomènes physiques mis en jeu dans une chambre de combustion. L'atomisation du carburant résulte du cisaillement engendré par un fort écoulement d'air généré dans l'injecteur. La simulation numérique directe d'écoulements avec interface permet de simuler l'ensemble du processus d'atomisation. L'utilisation de maillages Cartésiens permet la réalisation de calculs HPC efficaces et précis. Mais, une des complexités de l'atomisation vient d'une interaction forte entre le comportement de la nappe liquide et l'écoulement gazeux dans les conduites de l'injecteur, rendant impératif la simulation de l'injecteur complet. Ceci étant impossible avec des maillages Cartésiens structurés, l'objectif de cette thèse est de développer une méthode d'interface immergée permettant l'inclusion d'objets solides dans un domaine de calcul, indépendamment du maillage, afin de réaliser des DNS du système d'injection complet. Les équations de Navier-Stokes incompressibles diphasiques sont résolues à l'aide d'un algorithme de projection, l'interface liquide-gaz étant transportée avec une méthode CLSVOF conservative en masse et quantité de mouvement. La présence du solide est prise en compte grâce à la méthode d'interface immergée. Cette méthode a été appliquée à la simulation numérique de nappes liquides cisaillées pour une configuration d'injecteur utilisée en essais à l'ONERA et a permis une meilleure prédiction de la fréquence de battement de la nappe. / The reduction of polluting emissions and improvement of aeronautical engines efficiency depends on the detailed knowledge of the physical phenomena encountered in a combustion chamber. Fuel atomization results from the shearing effect induced by the high velocity airflow generated inside the injector. The Direct Numerical Simulation of interfacial flows allows the simulation of the whole atomization process, while Cartesian structured meshes allows efficient and accurate HPC computations. However, the complexity of atomization comes from a strong interaction between the jet behavior and the injector internal flow, which makes essential to simulate the whole injector system. As that is impossible on Cartesian structured grids, the main objective of this thesis is to develop an Immersed Interface Method (IIM) allowing the inclusion of solid objects in the computational domain, independently of the mesh. The incompressible two-phases Navier-Stokes equations are solved using a projection algorithm with the CLSVOF method, conservative in mass and momentum. The solid presence is taken into account using the IIM. The proposed IIM has been applied to the numerical simulation of sheared liquid sheets corresponding to an ONERA experimental configuration and allows a better prediction of the flapping frequencies of the liquid sheet.

Les processus élémentaires hétérogènes à l’interface gaz-solide présentent un intérêt fondamental dans de nombreux domaines tels que la catalyse hétérogène, la chimie atmosphérique et des milieux interstellaires, la rentrée atmosphérique de véhicules spatiaux ou encore la description des interactions plama-paroi. Cette thèse a pour objet l’étude de la dynamique des processus de collision non réactive de l’azote N2 sur une surface de tungstène W(100) et des processus de recombinaison moléculaire de l’hydrogène H2 sur des surfaces de tungstène W(100) et W(110). Leur dynamique quasi classique est simulée au moyen de surfaces d’énergie potentielle préalablement construites à partir de calculs de théorie de la fonctionnelle de la densité. Un potentiel multi-adsorbats est notamment développé pour tenir compte du taux de couverture de surface afin d’étudier la compétition entre la recombinaison directe, de type Eley-Rideal et la recombinaison par « atomes chauds » après diffusion hyperthermique d’un atome sur la surface. / Heterogeneous elementary processes at the gas-solid interface are ofgreat interest in many domains such as heterogeneous catalysis, atmospheric and interstellar media chemistry, spacecraft atmospheric re-entry and plasma-wall interactions description. This thesis focus on the dynamics of nitrogen, N2, non reactive scattering on a tungsten W(100) surface and hydrogen, H2, recombination processes on tungsten surfaces W(100) and W(110). The quasiclassical dynamics of these processes is simulated using potential energy surfaces based on density functional theory calculations. In particular, a multi-adsorbate potential is developed to include surface coverage in the dynamics simulation in order to scrutinize the interplay between both direct abstraction, the so-called Eley-Rideal recombination,and the Hot-Atom recombination process after hyperthermal diffusion on the surface

La rationalisation des processus chimiques élémentaires aux surfacesest d'intérêt primordial pour de nombreux phénomènes naturels ou d'intérêttechnologique. D'un point de vue fondamental, la façon dont l'énergie, concomitanteà toute réaction chimique, est distribuée parmi les degrés de liberté des moléculesformées et/ou transférée à la surface est loin d'être systématisée. Dans ce travail,des simulations, reposant sur la méthode des trajectoires quasi-classiques (QCT),sont réalisées pour examiner cette problématique lors de recombinaisons demolécules d'hydrogène (H2) et d'azote (N2) résultant de l'abstraction d'atomesadsorbés via collision par un atome provenant de la phase gazeuse sur des surfacesde Tungstène - W(100) et W(110) - à taux de couverture non nul. Ces processussont ici étudiés pour leur intérêt en physique des interactions plasma-paroi. Dessurfaces d'énergie potentielle, construites à partir de calculs de structure électroniquebasés sur la théorie de la fonctionnelle densité (DFT), sont utilisées pour simuler,dans le cadre de la mécanique classique - incluant les corrections semi-classiquespertinentes - les processus ultrarapides dit de "Eley-Rideal" et par "atomes-chauds"(sub-picoseconde). La mise en place de modèle effectifs, pour tenir compte de ladissipation de l'énergie aux phonons de la surface et aux excitations électroniques(paires électron-trou), permet de rationaliser la dynamique non-adiabatique del'abstraction atomique aux surfaces métalliques. / The rationalization of elementary processes at surfaces is of prime importance for numerous natural and technological areas. From a fundamental pointof view, the way the energy concomitant to any chemical reaction is distributed among the desorbing molecules degrees-of-freedom and the surface is far frombeing fully pictured. In this work, quasiclassical molecular dynamics (QCT)simulations have been carried out to investigate this issue for the recombination ofH2 and N2 resulting from atomic adsorbate abstraction by atom scattering off theW(100) and W(110) covered surfaces, these processes being of relevance inplasma-wall interactions. Potential energy surfaces, built from density functional(DFT) theory calculations, have been used to simulate, within the framework ofclassical dynamics (including semi-classical corrections), the subpicosecond Eley-Rideal and Hot-Atom processes. The implementation of effective models to accountfor energy dissipation to surface phonons and electron-hole pair excitations, have allowed to rationalize the non-adidabatic dynamics of atom abstraction at metalsurfaces.