Dissertations / Theses on the topic 'Extended surface'

Thesis (Degree of Mechanical Engineering) Naval Postgraduate School, Dec. 2000.
Thesis advisor, Shin, Young S. "December 2000." Includes bibliographical references (p. 87-88). Also available in print.

In general, the stability of suspension can be studied using two methods. One is to directly measure the forces between two interacting surfaces in media. The other is to study the interfacial surface free energies of the particles in suspension. Direct surface force measurements were conducted between silica surfaces in octadecyltrimetylammonium chloride (C₁₈TACl) solutions using an Atomic Force Microscope (AFM). The results showed that the hydrophobic force existed in both air-saturated and degassed C₁₈TACl solutions. The attraction decreased with NaCl addition, and was the strongest at the point of charge neutralization (p.c.n.) of silica substrate. The force measurement results obtained in C_nTACl solutions showed that the attractions decayed exponentially and became the maximum at the p.c.n.'s. The decay lengths (D) increased with surfactant chain length. The measured forces were fitted to a charged-patch model of Miklavic et al. (1994) with rather large patch sizes. It was also found that the decay length decreased linearly with the effective concentration of the CH2/CH3 groups raised to the power of -1/2. This finding is in line with the model of Eriksson et al. (1989). It suggested that the long-range attractions are hydrophobic forces originating from the changes in water structure across a hydrophobic surface-solution interface. For the TiO₂/water/TiO₂ system, the Hamaker constant was found to be 4±1×10^-20 J. The force curves obtained in the TiO₂/C_nTACl system showed a repulsion-attraction-repulsion transition with increasing surfactant concentration. The long-range attraction observed between TiO₂ surfaces in C_nTACl solutions reached maximum at the p.c.n., and the decay length increased with chain length. In present work, the thin-layer wicking technique was used to determine the surface free energy (γ_s) and its components of talc samples. The results showed that the basal surfaces of talc are weakly basic while the edge surfaces are acidic. The effect of chemicals on the surface free energies of talc was systemically studied. The results showed that CMC (carboxymethyl cellulose sodium salt) and EO/PO (ethylene oxide/propylene oxide) co-polymers made talc surface hydrophilic by increasing the surface free energies, especially γ^LW and γ ^-. SOPA (sodium polyacrylate) increased greatly the zeta-potentials instead of the surface free energies.
Ph. D.

Approved for public release; distribution is unlimited
Heat sinks consisting of individual fins and arrays of fins are used extensively throughout the Navy and industry. The fins serve to increase the surface area thorough which heat is transferred to the surrounding environment by natural convection. Extended surfaces or fins are commonly found on electronic components ranging from power supplies to transformers. The dissipation and subsequent rejection of potentially destructive self produced heat is an important aspect of electronic equipment design. Fin design theory is examined starting with the optimization of individual fin dimensions. The insights obtained are utilized in an investigation of the optimal number and spacing of elements in an array of fins. The results are implemented in a computer program written in ADA and compiled for use on IBM compatible machines. The program takes as inputs thermal and physical data and outputs an optimized fin configuration. Menu driven, the program is easily employed without any amplifying documentation. The program serves to greatly simplify and accelerate the fin design process and should be an invaluable tool to electronic component designers, especially those with a limited background in heat transfer and fin optimization theory.

The combination of capillary electrophoresis (CE) and mass spectrometry (MS) constitutes a powerful microanalytical system in the fields of biology, medicine and chemistry. This thesis describes the development of three novel capillary coatings and demonstrates how these extend the utility of CE as a high-efficiency separation technique in protein analysis and biopharmaceutical drug screening.

Due to the rapidly growing interest in characterizing the human proteome, there is an increased need for rapid protein separations. The use of CE in protein analysis is, however, nontrivial due to problems with protein adsorption to the fused-silica capillary walls. In this thesis, this problem was addressed by developing two novel, physically adsorbed, cationic polymer surface coatings, denoted PolyE-323 and Q-agarose. By using simple rinsing protocols, highly reproducible coatings, stable over a wide range of pH 2-11 were generated. Successful protein separations using cationic-coated capillaries in CE-MS, equipped with either electrospray ionization (ESI) or matrix-assisted laser desorption/ionization (MALDI), has been demonstrated.

In the pharmaceutical industry, favorable pharmacokinetic properties of a candidate drug, such as high bioavailability after oral administration, are crucial for a high success rate in clinical development. Tools for prediction of biopharmaceutically relevant drug properties are important in order to identify and discard poor candidate drugs as soon as possible. In this thesis, a membrane mimetic coating was developed by electrostatically immobilizing liposomes to the capillary wall, via an anchoring sublayer of Q-agarose. The liposome-coated capillaries were demonstrated in on-line CE-MS for prediction of drug membrane permeability.

Reflector design stemmed from the need to shape the light emitted by candles or lamps. Over 2,000 years ago people realized that a mirror shaped as a parabola can concentrate light, and thus significantly boosts its intensity, to the point where objects can be set afire. Nowadays many applications require an accurate control of light, such as automotive headlights, streetlights, projection displays, and medical illuminators. In all cases light emitted from a light source can be shaped into a desired target distribution with a reflective surface. Design methods for systems with rotational and translational symmetry were devised in the 1930s. However, the freeform reflector shapes required to illuminate targets with no such symmetries proved to be much more challenging to design. Even when the source is assumed to be a point, the reflector shape is governed by a set of second-order partial non-linear differential equations that cannot be solved with standard numerical integration techniques. An iterative approach to solve the problem for a discrete target, known as the method of supporting ellipsoids, was recently proposed by Oliker. In this research we report several efficient implementations of the method of supporting ellipsoids, based on the point source approximation, and we propose new reflector design techniques that take into account the extent of the source. More specifically, this work has led to three major achievements. First, a thorough analysis of the method of supporting ellipsoids was performed that resulted in two alternative implementations of the algorithm, which enable a fast generation of freeform reflector shapes within the point source approximation. We tailored the algorithm in order to provide control over the parameters of interest to the designers, such as the reflector scale and geometry. Second, the shape generation algorithm was used to analyze how source flux can be mapped onto the target. We derived the condition under which a given source-target mapping can be achieved with a smooth continuous surface, referred as the integrability condition. We proposed a method to derive mappings that satisfy the integrability condition. We then use these mappings to quickly generate reflector shapes that create continuous target distributions as opposed to reflectors generated with the method of supporting ellipsoids that create discrete sets of points on the target. We also show how mappings that do not satisfy the integrability condition can be achieved by introducing step discontinuities in the reflector surface. Third, we investigated two methods to design reflectors with extended sources. The first method uses a compensation approach where the prescribed target distribution is adjusted iteratively. This method is effective for compact sources and systems with rotational or translational symmetry. The second method tiles the source images created by a reflector designed with the method of supporting ellipsoids and then blends the source images together using scattering in order to obtain a continuous target distribution. This latter method is effective for freeform reflectors and target distributions with no sharp variations. Finally, several case studies illustrate how these methods can be successfully applied to design reflectors for general illumination applications such as street lighting or luminaires. We show that the proposed design methods can ease the design of freeform reflectors and provide efficient, cost-effective solutions that avoid unnecessary energy consumption and light pollution.
Ph.D.
Optics and Photonics
Optics and Photonics
Optics PhD

Thesis (M.S. in Operations Research) Naval Postgraduate School, September 1998.
"September 1998." Thesis advisor(s): Donald P. Gaver. Includes bibliographical references (p. 105). Also Available online.

This work is a string of essays that aesthetically frames estrangement as the quintessential experience of modern culture. Accordingly, detachment and distance are themes that persist throughout these essays. They weave their way through the cultural, social, psychological, and spatial dimensions of modern life, but at a tentative remove. Such a level of generality precludes any claims of the work to be a methodical dissection of the subject matter. Neither is it a series of literature reviews or response letters to canonical essays. It is, primarily, a literary reflection on the matter; an assemblage of evocative rhetoric that dramatizes the experience of modern estrangement. Each passage is written as a commentary that insecurely hovers between the categories listed above. What all these evasions enable in turn is a text that mirrors the attitude of the dilettante, comfortably flitting between passages that trail off from the lingering mood of one essay to the next. The work of a handful of German cultural theorists of the early 20th century supply the primary sources to this reflection, and what I have tried to draw from a selection of their writings is a mental state that tries to peer through the opacity of the metropolitan spectacle. The mood that is meant to be evoked here is the obverse of the glamour and excitement associated with the imagined social life of the big city. Urban is a word that has seen its definition drowned out by the associative imagery around it; in other words, its connotations overwhelm what the term is meant to denote. The psychological counter-pole to such imagery is the characteristically urban disposition that is marked by a refusal to be dazzled. This sort of disinterestedness directly feeds into the endless pursuit of the new, and the compulsion to seek a lost sense of wonderment. In what is to follow, I have tried to find resonance with the notion of the urban on such a note of resignation.

Hydrophobic interaction plays an important role in biology, daily lives, and a variety of industrial processes such as flotation. While the mechanisms of hydrophobic interactions at molecular scale, as in self-assembly and micellization, is relatively well understood, the mechanisms of macroscopic hydrophobic interactions have been controversial. It is, therefore, the objective of the present work to study the mechanisms of interactions between macroscopic hydrophobic surfaces in H-bonding liquids, including water, ethanol, and water-ethanol mixtures. The first part of the present study involves the measurement of the hydrophobic forces in the thin liquid films (TLFs) confined between two identical hydrophobic surfaces of contact angle 95.3o using an atomic force microscope (AFM). The measurements are conducted in pure water, pure ethanol, and ethanol-water mixtures of varying mole fractions. The results show that strong attractive forces, not considered in the classical DLVO theory, are present in the colloid films formed with all of the H-bonding liquids tested. When an H-bonding liquid is confined between two hydrophobic surfaces, the vicinal liquid molecules form clusters in the TLFs and give rise to an attractive force. The cluster formation is a way to minimize free energy for the molecules denied of H-bonding with the substrates. Thus, solvophobic forces are the result of the antipathy between the CH2- and CH3-coated surface and H-bonding liquid confined in the film. A thermodynamic analysis of the solvophobic forces measured at different temperatures support this mechanism, in which solvophobic interactions entail decreases in the excess film enthalpy and entropy. The former represents the energy gained by building clusters, while the latter represents loss of entropy due to structure building. Thus, hydrophobic interaction may be a subset of solvophobic interaction. The solvophobic forces are strongest in pure water and pure ethanol, and decrease when one is added to the other. Adding a very small amount of ethanol to water sharply reduced the solvophobic force due to the adsorption of the former with an inverse orientation. An exposure of the OH-group toward the aqueous phase decreases the antipathy between the surface and H-bonding liquid and hence causes the hydrophobic (or solvophobic) forces to decrease. The second part of the study involves the measurement of the hydrophobic forces in the wetting films of water using the force apparatus for deformable surfaces (FADS). This new instrument recently developed at Virginia Tech is designed to monitor the deformation of bubbles to determine the surface forces in wetting films. In effect, an air bubble is used a force sensor. The measurements have been conducted with gold, chalcopyrite, and galena as substrates. The results obtained with all three minerals show that hydrophobic force increases with increasing water contact angle, suggesting that hydrophobic forces are inherent properties of hydrophobic surfaces rather than created from artifacts such as preexisting nanobubbles and/or cavitation. A utility of the intrinsic relationship between hydrophobic force and contact angle is to predict flotation kinetics from the hydrophobicity of the minerals of interest.
Ph. D.

The use of registered intra-operative to pre-operative imaging has been proposed for many medical interventions, with the goal of providing more informed guidance to the physician. The registration may be difficult to carry out in real-time.Therefore, it is often necessary to track the motion of the anatomy of interest in order to maintain a registration. In this work, a surface based Extended Kalman Filter (EKF) framework is proposed to track a tissue surface based on temporal correspondences of 3D features extracted from the tissue surface. Specifically, an initial 3D surface feature map is generated based on stereo matched Scale Invariant Feature Transform (SIFT) feature pairs extracted from the targeted surface. For each consecutive frame, the proposed EKF framework is used to provide 2D temporal matching guidance in both stereo channels for each feature in the surface map. The 2D feature matching is carried out based on the Binary Robust Independent Elementary Feature (BRIEF) descriptor. If the temporal match is successful in both stereo channels, the stereo feature pair can be used to reconstruct the feature location in 3D. The newly measured 3D locations drive the EKF update to simultaneously estimate the current camera motion states and the feature locations of the 3D surface map. The framework is validated on ex vivo porcine tissue surface and in vivo prostate surface during a da Vinci radical prostatectomy. The peak and mean fiducial errors are 2.5 mm and 1.6 mm respectively. Compared to other methods, the surface based EKF framework can provide a reliable 2D feature matching guidance for each feature in the 3D surface map. This maintains a chance to relocate a feature that was lost for a significant period of time. Such a surface based framework provides persistent feature tracking over time, which is crucial to drift free surface tracking. With implementation on a Graphic Unit Processor (GPU), real time performance is achieved.

As the mission field for autonomous vehicles expands into a larger variety of territories, the development of autonomous surface vehicles (ASVs) becomes increasingly important. ASVs have the potential to travel for long periods of time in areas that cannot be reached by aerial, ground, or underwater autonomous vehicles. ASVs are useful for a variety of missions, including bathymetric mapping, communication with other autonomous vehicles, military reconnaissance and surveillance, and environmental data collecting. Critical to an ASV's ability to maneuver without human intervention is its ability to detect obstacles, including the shoreline. Prior topological knowledge of the environment is not always available or, in dynamic environments, reliable. While many existing obstacle detection systems can only detect 3D obstacles at close range via a laser or radar signal, vision systems have the potential to detect obstacles both near and far, including "flat" obstacles such as the shoreline. The challenge lies in processing the images acquired by the vision system and extracting useful information. While this thesis does not address the issue of processing the images to locate the pixel positions of the obstacles, we assume that we have these processed images available. We present an algorithm that takes these processed images and, by incorporating the kinematic model of the ASV, maps the pixel locations of the obstacles into a global coordinate system. An Extended Kalman Filter is used to localize the ASV and the surrounding obstacles.
Master of Science

The prediction of settlements in infrastructural design puts high demands on the numerical analysis of the subsoil and the associated constitutive model: complex installation processes and the repetitive character of live loads pose considerable challenges. Although in this context the main focus is on the analytical requirements of a geotechnical problem in order to realistically capture soil behaviour, the needs of engineering practice should not be neglected in constitutive modelling. Along these lines, a new soil model for non-cohesive soils has been developed in the theoretical framework of elastoplasticity. Based on the concept of bounding surface plasticity according to Manzari and Dafalias (1997), soil properties such as strength, stiffness and dilatancy depend on the distance between the current stress state and a corresponding model surface in stress space. This way the multi surface model correctly reproduces elementary behavioural patterns of soil, including for example shear related phenomena such as hardening/softening, contraction/dilation and attainment of critical state (constant volume shear strength). Moreover, the model captures the state dependence of soil behaviour (barotropy and pycnotropy). Thus, with only one set of material parameters, the mechanical behaviour of a wide range of initial soil states with respect to stress and void ratio can be simulated (unified modelling). The kinematic hardening mechanism of the conical yield surface contributes to a realistic stiffness evolution in un- and reloading and is hence essential for stress or strain accumulation due to load reversals. Since the chosen modelling framework is suitable for further development, the original formulation has been extended to adapt the model to the defined needs. In order to adequately simulate geotechnically relevant stress paths of low and higher complexity, first of all, a cap shaped yield surface was added to allow for plastic straining not only in shear, but also in constant stress ratio loading (e. g. isotropic or oedometric compression). When it comes to stress paths of unconventional orientation, to load reversals or composed stress paths with changes in loading direction, a supplementary stiffness increase at small strains and its subsequent strain dependent degradation have proven valuable. Furthermore, an additional mechanism accounts for a regressive accumulation of stresses or strains with increasing number of load cycles (in terms of dissipated energy). In view of its suitability for practical use, all model extensions are structured in a modular fashion, so that the complexity of the model (and hence the amount of parameters) can be adapted to the complexity of the geotechnical problem by activating or deactivating certain features. Most model parameters can be determined by conventional laboratory testing. An internal routine optionally facilitates the parameter choice by calibrating certain bounding surface related parameters from an alternative user input, which is more oriented towards experimental outcome. Since a good understanding of a material model is crucial for its reasonable and responsible use, the present thesis aims at offering a sound documentation. Thus, the first part gives an outline of the underlying bounding surface concept and describes the innovations on the constitutive level with reference to theoretical considerations. It is followed by a detailed analysis of capabilities and limitations of the extended model. The next part is dedicated to the numerical implementation of the soil model and its calibration procedure on the basis of laboratory test results. Moreover, the embedded calibration routine including the applied optimisation algorithm is presented. The subsequent section serves model validation: by means of element test simulations, generation of response envelopes as well as the reproduction of more general (e. g. composed) stress paths the performance of the extended bounding surface model is demonstrated. Finally, the last chapter draws conclusions and discloses potential future perspectives.:1 Introduction 1.1 General aspects on constitutive modelling 1.2 Motivation and outline of the thesis 1.3 Basic assumptions and terminology 2 Literature review 2.1 From elastoplasticity to bounding surface plasticity 2.1.1 Bounding surface model according to Manzari and Dafalias (1997) 2.2 Further development of the original model 2.2.1 Papadimitriou and Bouckovalas (2002) 2.2.2 Taiebat and Dafalias (2008) 2.3 Small strain stiffness 2.3.1 Observations 2.3.2 Micromechanical considerations 2.3.3 Very small strain shear modulus G0 2.3.4 Constitutive modelling approaches 2.4 Dilatancy 3 The extended bounding surface model 3.1 Fundamental capabilities of the bounding surface concept 3.1.1 Elastic region 3.1.2 Critical state 3.1.3 Shear strength 3.1.4 Shear stiffness (monotonic) 3.1.5 Contractancy and dilatancy 3.1.6 Barotropy and pycnotropy 3.1.7 Compressive stiffness 3.1.8 Shear stiffness in reversed loading 3.1.9 Additional features 3.2 New features of the extended bounding surface model 3.2.1 Minor modifications 3.2.2 Dilatancy formulation 3.2.3 Cap yield surface 3.2.4 Small strain stiffness mechanism 3.2.5 Cyclic loading mechanism 3.2.6 Summary 3.3 Limitations of the bounding surface model 3.3.1 Intrinsic insuffciencies of the bounding surface concept 3.3.2 Remaining shortcomings of the advanced model version 3.3.3 Newly introduced deficiencies 4 The numerical model and its calibration procedure 4.1 Octave implementation of an element test programme 4.2 Calibration procedure 4.2.1 Sands for calibration 4.2.2 Calibration of basic parameters 4.2.3 Calibration of extended model parameters 4.3 User friendly calibration routine 4.3.1 Conceptual background 4.3.2 Optimisation algorithm 5 Performance of the extended bounding surface model 5.1 Model performance in element tests 5.1.1 Monotonic drained triaxial compression test 5.1.2 Monotonic undrained triaxial compression test 5.1.3 Monotonic eta-constant tests 5.2 Model performance in non-standard triaxial testing 5.2.1 Concept of response envelopes 5.2.2 Simulation of response envelopes 5.3 Model performance on general stress paths 5.3.1 Triaxial compression at small strains 5.3.2 Cyclic triaxial loading 6 Conclusions and perspectives 6.1 Conclusions 6.2 Future perspectives Bibliography Appendices A Mathematical background A.1 Fundamental equations of elastoplasticity A.2 Compilation of major constitutive equations (multiaxial formulation) A.3 Elastoplastic stiffness matrix for singular yield surfaces A.4 Coefficient matrices S and E for loading constraints A.5 Derivation of Mcap and Hcap A.6 Intergranular strain adjustment A.7 Intergranular strain correlation B Details on particle swarm optimisation C Compilation of simulation results C.1 Monotonic triaxial loading C.1.1 Toyoura sand C.1.2 Sacramento River sand C.1.3 Hostun sand C.2 Monotonic eta-constant loading C.2.1 Sacramento River sand C.2.2 Hostun sand C.3 Cyclic triaxial loading
Die Prognose von Setzungen für die Bemessung von Infrastrukturbauwerken stellt hohe Anforderungen an die numerische Untersuchung des Baugrunds und das damit verbundene Stoffgesetz: komplexe Herstellungsprozesse und zyklisch wiederkehrende Verkehrslasten stellen beachtliche Herausforderungen dar. Während das Hauptaugenmerk zumeist auf der realitätsnahen Abbildung des Bodenverhaltens liegt und damit die analytischen Anforderungen des geotechnischen Problems im Fokus stehen, sollten die Bedürfnisse der Ingenieurspraxis in der Stoffgesetzmodellierung nicht außer Acht gelassen werden. In diesem Sinne wurde im Rahmen der Elastoplastizität ein neues Materialmodell für nichtbindige Böden entwickelt. Auf dem Konzept der Bounding Surface Plastizität nach Manzari und Dafalias (1997) beruhend, sind Eigenschaften wie Festigkeit, Steifigkeit und Dilatanz Funktion des Abstands zwischen aktuellem Spannungszustand und einer zugeordneten Modellfläche im Spannungsraum. Auf diese Weise bildet das Mehrflächenmodell fundamentale Verhaltensmuster von Boden korrekt ab, einschließlich beispielsweise scherbezogener Phänomene wie Ver- und Entfestigung, Kontraktanz und Dilatanz oder das Erreichen des kritischen Zustands (Scherfestigkeit bei konstantem Volumen). Des Weiteren erfasst das Modell die Zustandsabhängigkeit des Bodenverhaltens (Barotropie und Pyknotropie). So kann mit nur einem Parametersatz das mechanische Verhalten einer großen Spannweite unterschiedlicher Anfangszustände hinsichtlich Spannung und Lagerungsdichte simuliert werden. Der kinematische Verfestigungsmechanismus der konusförmigen Fließfläche trägt bei Ent- und Wiederbelastungen zu einer realistischeren Steifigkeitsentwicklung bei und ist damit von essenzieller Bedeutung für die Akkumulation von Spannungen oder Verformungen infolge von Lastwechseln. Da sich der gewählte konstitutive Rahmen für Weiterentwicklungen eignet, wurde die ursprüngliche Formulierung des Stoffgesetzes erweitert, um das Modell an die definierten Anforderungen anzupassen. Um geotechnisch relevante Spannungspfade niedriger und höherer Komplexität adäquat reproduzieren zu können, wurde zunächst eine kappenförmige Fließfläche ergänzt. So können irreversible Verformungen nicht nur bei Scherung, sondern auch bei Belastungen ohne Änderung des Spannungsverhältnisses, wie z. B. bei isotroper oder ödometrischer Kompression, auftreten. Bei Spannungspfaden ungewöhnlicher Orientierung, bei Lastwechseln oder zusammengesetzten Spannungspfaden mit Änderung der Belastungsrichtung hat sich eine erhöhte Steifigkeit bei kleinen Dehnungen mit anschließendem dehnungsabhängigen Abfall als nützlich erwiesen. Darüber hinaus berücksichtigt ein zusätzlicher Mechanismus die rückläufige Akkumulation von Spannung oder Verformung mit zunehmender Zyklenanzahl (mittels dissipierter Energie). Im Hinblick auf die Eignung des Stoffgesetzes für die Praxis ist das Modell modular aufgebaut. So kann die Komplexität des Modells (und damit die Anzahl der Parameter) durch Ein- und Ausschalten bestimmter Erweiterungen an die Komplexität des geotechnischen Problems angepasst werden. Die Mehrzahl der Modellparameter wird mit Hilfe konventioneller Laborversuche bestimmt. Eine interne Routine erleichtert durch die Kalibrierung bestimmter Bounding Surface bezogener Größen anhand eines alternativen, stärker an Versuchsergebnissen orientierten User-Inputs bei Bedarf die Parameterwahl. Da die Kenntnis eines Stoffgesetzes entscheidend ist für dessen vernünftigen und verantwortungsvollen Einsatz, soll die vorliegende Arbeit eine fundierte und umfassende Dokumentation bieten. Der erste Teil vermittelt daher zunächst einen Überblick über das zugrunde liegende Bounding Surface Konzept und beschreibt die Neuerungen auf konstitutiver Ebene mit Bezug auf theoretische Hintergründe. Er wird gefolgt von einer detaillierten Darlegung von Potenzialen und Einschränkungen für die Nutzung des erweiterten Modells. Der nächste Abschnitt widmet sich der numerischen Implementierung des Stoffgesetzes und seiner Kalibrierung auf Basis von Versuchsergebnissen. Des Weiteren wird die Kalibrierungsroutine einschließlich des verwendeten Optimierungsalgorithmus präsentiert. Der nachfolgende Teil dient der Modellvalidierung: durch die Simulation von Elementversuchen, die Erzeugung von Antwortellipsen sowie die Abbildung allgemeinerer (beispielsweise zusammengesetzter) Spannungspfade wird die Leistungsfähigkeit des erweiterten Bounding Surface Modells demonstriert. Abschließend werden Schlussfolgerungen gezogen und potenzielle Perspektiven aufgezeigt.:1 Introduction 1.1 General aspects on constitutive modelling 1.2 Motivation and outline of the thesis 1.3 Basic assumptions and terminology 2 Literature review 2.1 From elastoplasticity to bounding surface plasticity 2.1.1 Bounding surface model according to Manzari and Dafalias (1997) 2.2 Further development of the original model 2.2.1 Papadimitriou and Bouckovalas (2002) 2.2.2 Taiebat and Dafalias (2008) 2.3 Small strain stiffness 2.3.1 Observations 2.3.2 Micromechanical considerations 2.3.3 Very small strain shear modulus G0 2.3.4 Constitutive modelling approaches 2.4 Dilatancy 3 The extended bounding surface model 3.1 Fundamental capabilities of the bounding surface concept 3.1.1 Elastic region 3.1.2 Critical state 3.1.3 Shear strength 3.1.4 Shear stiffness (monotonic) 3.1.5 Contractancy and dilatancy 3.1.6 Barotropy and pycnotropy 3.1.7 Compressive stiffness 3.1.8 Shear stiffness in reversed loading 3.1.9 Additional features 3.2 New features of the extended bounding surface model 3.2.1 Minor modifications 3.2.2 Dilatancy formulation 3.2.3 Cap yield surface 3.2.4 Small strain stiffness mechanism 3.2.5 Cyclic loading mechanism 3.2.6 Summary 3.3 Limitations of the bounding surface model 3.3.1 Intrinsic insuffciencies of the bounding surface concept 3.3.2 Remaining shortcomings of the advanced model version 3.3.3 Newly introduced deficiencies 4 The numerical model and its calibration procedure 4.1 Octave implementation of an element test programme 4.2 Calibration procedure 4.2.1 Sands for calibration 4.2.2 Calibration of basic parameters 4.2.3 Calibration of extended model parameters 4.3 User friendly calibration routine 4.3.1 Conceptual background 4.3.2 Optimisation algorithm 5 Performance of the extended bounding surface model 5.1 Model performance in element tests 5.1.1 Monotonic drained triaxial compression test 5.1.2 Monotonic undrained triaxial compression test 5.1.3 Monotonic eta-constant tests 5.2 Model performance in non-standard triaxial testing 5.2.1 Concept of response envelopes 5.2.2 Simulation of response envelopes 5.3 Model performance on general stress paths 5.3.1 Triaxial compression at small strains 5.3.2 Cyclic triaxial loading 6 Conclusions and perspectives 6.1 Conclusions 6.2 Future perspectives Bibliography Appendices A Mathematical background A.1 Fundamental equations of elastoplasticity A.2 Compilation of major constitutive equations (multiaxial formulation) A.3 Elastoplastic stiffness matrix for singular yield surfaces A.4 Coefficient matrices S and E for loading constraints A.5 Derivation of Mcap and Hcap A.6 Intergranular strain adjustment A.7 Intergranular strain correlation B Details on particle swarm optimisation C Compilation of simulation results C.1 Monotonic triaxial loading C.1.1 Toyoura sand C.1.2 Sacramento River sand C.1.3 Hostun sand C.2 Monotonic eta-constant loading C.2.1 Sacramento River sand C.2.2 Hostun sand C.3 Cyclic triaxial loading

Orientador: Konstantin Georgiev Kostov
Resumo: Nos últimos anos, tem intensificado o emprego de plasmas em pressão atmosférica para diferentes aplicações. Com o desenvolvimento dos jatos de plasma em pressão atmosférica, alguns tratamentos precisos, como no campo biomédico ou em específicos processamentos de superfícies, tornaram-se mais frequentes. No entanto, a aplicação de plasma à objetos irregulares, dentro de tubos ou mesmo dentro de órgãos ocos é limitada quando se utilizam configurações convencionais de jatos de plasma. Portanto, essas limitações podem ser superadas com o desenvolvimento de jatos de plasma alongados ou gerados remotamente. Neste trabalho, duas configurações de jato de plasma longo visando diferentes campos de aplicação foram aperfeiçoadas e caracterizadas. Inicialmente foi desenvolvido um jato de plasma endoscópico (plasma endoscope) operando em configuração de descarga por barreira dielétrica (DBD) com dimensões milimétricas, versátil ao acoplamento em endoscópios típicos. Este jato de plasma pode operar com hélio ou neônio e conta com um canal externo e concêntrico de gás que permite a introdução de uma cortina de gás eletronegativo ao redor da pluma de plasma. A cortina de proteção a gás preserva a forma do jato de plasma quando operado dentro de cavidades fechadas. As dificuldades advindas do desenvolvimento deste foram investigadas quando diferentes gases foram testados como cortina de proteção dele, dentre estes, o dióxido de carbono se mostrou uma boa opção evitando a formação de descargas ... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: The use of atmospheric pressure plasmas for different purposes has increased in recent years. With the development of atmospheric pressure plasma jets, some precise treatments such as in the biomedical field or specific surface processing became more often. However, the delivery of plasma to irregular shaped objects, inside tubes or even hollow organs is limited with the use of conventional plasma jet configurations. Therefore, those limitations can be surpassed with the development of elongated or remotely generated plasma jets. In this work, two extended plasma jet configurations aiming at different application fields were further developed and characterized. Firstly, an endoscopic plasma jet (plasma endoscope) operating with a dielectric barrier discharge (DBD) configuration in millimeter dimensions that can be coupled to a typical endoscope was developed. This plasma jet can operate with helium or neon and counts with an external concentric shielding gas channel that provides the introduction of an electronegative gas curtain around the plasma plume. The shielding gas allows the preservation of the plasma jet shape when operated inside closed cavities. The construction difficulties arisen from the use of different feed and shielding gases were explored. Carbon dioxide was proven to be a good option for the curtain gas around the plasma plume avoiding the formation of parasitic discharges inside the shielding gas tube and the endoscopic housing. When operated with neon, th... (Complete abstract click electronic access below)
Doutor

This thesis paper presents a simultaneous 3D mapping and geolocation of road surface technique that combines local road surface mapping and global camera localization. The local road surface is generated by structure from motion (SFM) with multiple views and optimized by Bundle Adjustment (BA). A system is developed for the global reconstruction of 3D road surface. Using the system, the proposed technique globally reconstructs 3D road surface by estimating the global camera pose using the Adaptive Extended Kalman Filter (AEKF) and integrates it with local road surface reconstruction techniques. The proposed AEKF-based technique uses image shift as prior. And the camera pose was corrected with the sparse low-accuracy Global Positioning System (GPS) data and digital elevation map (DEM). The AEKF adaptively updates the covariance of uncertainties such that the estimation works well in environment with varying uncertainties. The image capturing system is designed with the camera frame rate being dynamically controlled by vehicle speed read from on-board diagnostics (OBD) for capturing continuous data and helping to remove the effects of moving vehicle shadow from the images with a Random Sample and Consensus (RANSAC) algorithm. The proposed technique is tested in both simulation and field experiment, and compared with similar previous work. The results show that the proposed technique achieves better accuracy than conventional Extended Kalman Filter (EKF) method and achieves smaller translation error than other similar other works.
Master of Science
This thesis paper presents a simultaneous three dimensional (3D) mapping and geolocation of road surface technique that combines local road surface mapping and global camera localization. The local road surface is reconstructed by image processing technique with optimization. And the designed system globally reconstructs 3D road surface by estimating the global camera poses using the proposed Adaptive Extended Kalman Filter (AEKF)-based method and integrates with local road surface reconstructing technique. The camera pose uses image shift as prior, and is corrected with the sparse low-accuracy Global Positioning System (GPS) data and digital elevation map (DEM). The final 3D road surface map with geolocation is generated by combining both local road surface mapping and global localization results. The proposed technique is tested in both simulation and field experiment, and compared with similar previous work. The results show that the proposed technique achieves better accuracy than conventional Extended Kalman Filter (EKF) method and achieves smaller translation error than other similar other works.

Placement and compaction of the backfill behind an earth retaining wall may induce a vertical shear force at the soil-to-wall interface. This vertical shear force, or downdrag, is beneficial for the stability of the structure. A significant reduction in construction costs may result if the downdrag is accounted for during design. This potential reduction in costs is particularly interesting in the case of U.S. Army Corps of Engineers lock walls. A simplified procedure is available in the literature for estimating the downdrag force developed at the wall-backfill interface during backfilling of a retaining wall. However, finite element analyses of typical U.S. Army Corps of Engineers lock walls have shown that the magnitude of the downdrag force may decrease during operation of the lock with a rise in the water table in the backfill. They have also shown that pre- and post-construction stress paths followed by interface elements often involve simultaneous changes in shear and normal stresses and unloading-reloading. The hyperbolic formulation for interfaces (Clough and Duncan 1971) is accurate for modeling the interface response in the primary loading stage under constant normal stress. However, it has not been extended to model simultaneous changes in shear and normal stresses or unloading-reloading of the interface. The purpose of this research was to develop an interface model capable of giving accurate predictions of the interface response under field loading conditions, and to implement this model in a finite element program. In order to develop the necessary experimental data, a series of tests were performed on interfaces between concrete and two different types of sand. The tests included initial loading, staged shear, unloading-reloading, and shearing along complex stress paths. An extended hyperbolic model for interfaces was developed based on the results of the tests. The model is based on Clough and Duncan (1971) hyperbolic formulation, which has been extended to model the interface response to a variety of stress paths. Comparisons between model calculations and tests results showed that the model provides accurate estimates of the response of interfaces along complex stress paths. The extended hyperbolic model was implemented in the finite element program SOILSTRUCT-ALPHA, used by the U.S. Army Corps of Engineers for analyses of lock walls. A pilot-scale test was performed in the Instrumented Retaining Wall (IRW) at Virginia Tech that simulated construction and operation of a lock wall. SOILSTRUCT-ALPHA analyses of the IRW provided accurate estimates of the downdrag magnitude throughout inundation of the backfill. It is concluded that the extended hyperbolic model as implemented in SOILSTRUCT-ALPHA is adequate for routine analyses of lock walls.
Ph. D.

This thesis reports on the findings of an investigation into the dosimetry resulting from the abutment of en face 6 MeV electron and 6 MV photon beams as applied to the clinical challenge of radiation therapy treatments to head and neck cancer sites. Particular concern is given to the use of multi-leaf collimator (MLC) technology for photon beam definition when abutted to extended source-to-surface (SSD) electron beams. We made dosimetric comparison between MLC and Cerrobend® shielding for use in an abutment situation. The effects of extending the SSD of the electron beam were also assessed. We checked the ability of a Pinnacle3 v7.6 treatment planning system (TPS) to correctly model the dosimetry resulting from this extended electron beam SSD. Volumetric simulations of composite dosimetry resulting in water were conducted in MATLAB® for variations of surface abutment gap, and photon beam shielding type and angle. Visualization Toolkit (VTK) script was developed to visualise the resulting dosimetry. The effect of extending the SSD of the electron beam increases the beam penumbra significantly, exacerbating the challenge of matching this field to a photon beam edge. Furthermore, the TPS was shown to inaccurately model the electron beam penumbra for the extended SSD conditions. The employment of MLC shielding provides for some advantages over Cerrobend® in terms of overall composite hotspot volumes and coldspot magnitudes, though introduces detrimental dosimetric inhomogeneities in the underlying volume. Distinctly, no combination of abutment gap and shielding variables resulted in dosimetry in the range of 90% to 110% at the depth of dmax for the beam energies considered here. We provided tabulated data across these variables to outline the trade-offs present, and aid clinical decisions regarding this challenging dosimetric

A prestudy indicated superior accuracy and convergence properties of apseudo-spectral method compared to a spline-based method implemented byCòrdoba et al. in 2005 when solving the α-patches problem. In this thesis wefurther investigate the numerical properties of the pseudo-spectral method and makeit more robust by implementing the Nonequispaced Fast Fourier Transform. Wepresent a more detailed overview and analysis of the pseudo-spectral method and theα-patches problem in general and conclude that the pseudo-spectral method issuperior in regards to accuracy in periodic settings.

In many applications, it is necessary to simulate wave scattering from surfaces that have small radii of curvature relative to the incident wavelength. Surface features smaller than an electromagnetic wavelength are known to create diffracted fields over a wide range of scattering angles. In this thesis, the significance of such effects at low grazing angles with the presence of an extended planar surface is considered. The magnetic field integral equation (MFIE) describing the currents on such surfaces is used to solve for the bistatic scattered fields. The integral equations are discretized using the moment method and solved using the Method of Ordered Multiple Interactions (MOMI) iterative procedure. This thesis will concentrate on normal incidence and low grazing angle (LGA) incidence, specifically an incident angle of 80 degrees. The surface used in the analysis is a one-dimensional, perfectly-conducting wedge-on-a-plane with a varying radius of curvature at the wedge tip and Gaussian tails that smoothly extend the wedge to the plane surface. This surface displays continuous first and second derivatives over the entire surface. The radius of curvature at the wedge tip is varied between 0.0125 wavelengths and 8 wavelengths. The form of the bistatic scattered fields will be investigated for three different wedge height to wedge width geometries. The surface scattering mechanisms and their respective location and form in the scattered field will be discussed. The dependence of the scattered field pattern on the radius of curvature at the wedge tip and the beam width of the incident field will be considered. The difficulties associated with using a numerical technique on extended surfaces where a significant source of diffracted energy is present will also be examined. This includes the issue of sampling a surface that contains areas of small radii of curvature and the issue of surface truncation when significant currents due to tip diffraction are produced well outside the illuminated area. Both TE (VV) and TM (HH) polarization will be considered. This thesis also analyzes the scattered fields for a perfect electric conducting (PEC) ridge and well in the presence of an extended planar surface for an incident angle of 70 degrees. The dual-surface magnetic field integral equation (DMFIE) formulation for a one-dimensional extended surface will be used to solve for the unknown currents on the surface of the scatterer. The DMFIE formulation leads to a second kind integral equation that can be solved via the MOMI series with the proper choice of the parameters appearing in the DMFIE formulation. The bistatic scattered fields for several ridge and well geometries are examined for both TE and TM polarization.
Master of Science

Surface force measurements previously conducted with thiolated gold surfaces showed a decrease in excess film entropy (£GSf), suggesting that hydrophobic force originates from changes in the structure of the medium (water) confined between hydrophobic surfaces. As a follow-up to the previous study, surface force measurements have been conducted using an atomic force microscope (AFM) with hydrophobic silica surfaces at temperatures in the range of 10 to 40¢XC. The silica sphere and silica plate were treated by both chemisorption of octadecyltrichlorosilane (OTS) and physical adsorption of octadecyltrimethylammonium chloride (C18TACl). A thermodynamic analysis of the results show similar results for both of the samples, that both ""Sf and excess film enthalpy ("Hf) become more negative with decreasing thickness of the water layer between the hydrophobic surfaces and decreasing temperature. |"Hf | > |T"Sf| represents a necessary condition for the excess free energy change ("Gf ) to be negative and the hydrophobic interaction to be attractive. Thus, the results obtained with both the silylated and C18TACl-adosrbed silica surfaces in the present work and the thiolated gold suefaces reported before show hydrophobic forces originate from structural changes in the medium. Thermodynamic analysis of SFA force measurements obtained at various temperatures revealed that "Sf were much more negative in the shorter hydrophobic force ranges than in the longer ranges, indicating a more significant degree of structuring in the water film when the two hydrophobic surfaces are closer together.

It is believed that the water molecules in the thin liquid films (TLFs) of water form clusters as a means to reduce their free energy when they cannot form H-bonds to neighboring hydrophobic surfaces. Dissolved gas molecules should enhance the stability of structured cluster due to the van der Waals force between the entrapped gas molecules and the surrounding water molecules1, which may enhance the strength of the hydrophobic force. Weaker long-range attractive forces detected in degassed water than in air-equilibrated water was found in the present work by means of AFM force measurements, supporting the effect of dissolved gas on the structuring of water. At last, temperature effects on hydrophobic interactions measured in ethanol and the thermodynamic analysis revealed similar results as those found in water, indicating that the hydrophobic force originates from H-bond propagated structuring in the mediums. •

Ph. D.

In the context of 2D persistent homology a new metric has been recently introduced, the coherent matching distance. In order to study this metric, the filtering function is required to present particular “regularity” properties, based on a geometrical construction of the real plane, called extended Pareto grid. This dissertation shows a new result for modifying the extended Pareto grid associated to a filtering function defined on a smooth closed surface, with values in the real plane. In future, the technical result presented here could be used to prove the genericity of the regularity conditions assumed for the filtering function.

This thesis presents a new template for multidisciplinary habitat mapping that combines the analyses of seafloor geomorphology, oceanographic proxies and modelling of associated biologic features. High resolution swath bathymetry of the Faial and western Pico shelves is used to present the first state-of-the-art geomorphologic assessment of submerged island shelves in the Azores. Solid seafloor structures are described in previously unreported detail together with associated volcanic, tectonic and erosion processes. The large sedimentary expanses identified in the area are also investigated and the large bedforms identified are discussed in view of new data on the local hydrodynamic conditions. Coarse-sediment zones of types hitherto unreported for volcanic island shelves are described using swath data and in situ imagery together with sub-bottom profiles and grainsize information. The hydrodynamic and geological processes producing these features are discussed. New oceanographic information extracted from satellite imagery is presented including yearly and seasonal sea surface temperature and chlorophyll-a concentration fields. These are used as proxies to understand the spatio-temporal variability of water temperature and primary productivity in the immediate island vicinity. The patterns observed are discussed, including onshore-offshore gradients and the prevalence of colder/more productive waters in the Faial-Pico passage and shelf areas in general. Furthermore, oceanographic proxies for swell exposure and tidal currents are derived from GIS analyses and shallow-water hydrographic modelling. Finally, environmental variables that potentially regulate the distribution of benthic organisms (seafloor nature, depth, slope, sea surface temperature, chlorophyll-a concentration, swell exposure and maximum tidal currents) are brought together and used to develop innovative statistical models of the distribution of six macroalgae taxa dominant in the infralittoral (articulated Corallinaceae, Codium elisabethae, Dictyota spp., Halopteris filicina, Padina pavonica and Zonaria tournefortii). Predictive distributions of these macroalgae are spatialized around Faial island using ordered logistic regression equations and raster fields of the explanatory variables found to be statistically significant. This new approach represents a potentially highly significant step forward in modelling benthic communities not only in the Azores but also in other oceanic island shelves where the management of benthic species and biotopes is critical to preserve ecosystem health.

L'extraction des paramètres de surface est une activité essentielle des Sciences de la vie et de la Terre. Ce mémoire propose une nouvelle méthodologie pour l'analyse des paramètres biophysiques et géophysiques, appelée Réalité Terrain Étendue, et qui mêle les avantages des relevés terrain et de la télédétection. Nous nous sommes en particulier attachés aux avantages de la télédétection basse altitude et d'un système micro-drone multi-caméras pour la cartographie de la dynamique de la végétation à l'échelle des individus. Cette problématique pose de nombreuses contraintes sur notre système car l'identification des arbrisseaux nécessite des capteurs innovants et une adaptation aux cycles phénologiques pour améliorer leur capacité de discrimination. La télédétection basse altitude semble être une solution intéressante en terme de résolution spatiale et de souplesse opérationnelle, et le développement des micro-drones civils permet des outils d'autant plus performants et fiables pour les missions terrain. Nous avons donc mis en place un système complet de drone avec une charge utile spécifique emportant simultanément trois appareils photographiques pour l'acquisition à la demande d'images obliques, stéréoscopiques ou multispectrales et permettant le développement de nouvelles méthodes d'identification de la végétation. Enfin, en participant à un relevé terrain du Muséum national d'Histoire naturelle, nous avons validé l'intérêt de notre système pour la cartographie de la dynamique de la végétation. Ce travail s'ouvre sur de nombreuses applications et perspectives de recherche, comme l'extraction de paramètres biophysiques par stéréo-restitution et l'agriculture de précision

Thesis (Ph. D.) -- University of Maryland, College Park, 2007.
Thesis research directed by: Dept. of Mechanical Engineering. Title from t.p. of PDF. Includes bibliographical references. Published by UMI Dissertation Services, Ann Arbor, Mich. Also available in paper.

Cette thèse est consacrée à l’étude mathématique de la propagation d’ondes bi-dimensionnelles à la surface d’un fluide non visqueux irrotationnel et incompressible dont la surface libre n’agit que par la gravité et la tension superficielle dans un régime fortement non linéaire. La thèse est séparée en deux parties d’égale importance. Dans la première partie, nous justifions des modèles d’approximation plus précis du point de vue mathématique pour le problème des vagues, couramment utilisés en océanographie côtière pour décrire la propagation des ondes de surface de grande amplitude. On obtient un nouveau modèle asymptotique en eaux peu profondes du type Green-Naghdil incorporant les termes dispersifs d’ordre supérieur arbitraire tout en préservant la non-linéarité totale. Un résultat sur le caractère bien posé et une propriété de stabilité sont alors établis pour le cas unidimensionnel lorsque le fond est plat et non plat en tenant compte d’une faible tension de surface. Dans la deuxième partie, un résultat de stabilité orbitale est montré pour le peakon de Degasperis-Procesi dans le cas de perturbations ayant une densité de quantité de mouvement d’abord négative, puis positive. Ceci conduit à la stabilité orbitale du profil antipeakon- peakon vis-à-vis de telles perturbations et plus généralement d’un train de antipeakon-peakon bien ordonnés
This thesis is devoted to the mathematical study of the water-waves problem concerning two- dimensional motion of an irrotational and incompressible inviscid liquid with a free surface acted only by gravity and surface tension in a highly nonlinear regime. The thesis is separated into two parts of equal importance. In the first part, we justify mathematically more accurate approximation models for the water wave problem that are commonly used in coastal oceanography to describe the propagation of large amplitude surface waves. A new two-dimensional asymptotic shallow-water extended Green-Naghdi system is derived which incorporates the arbitrary higher-order dispersive terms while preserving the full nonlinearity. A well-posedness result and a stability property is then ensured for the one-dimensional case when the bottom is flat and not flat taking into consid- eration a small e

Le développement des énergies renouvelables, telles que le solaire photovoltaïque ou l’éolien, est fortement conditionné par la nature intermittente de ces sources d’énergie. Cette intermittence se traduit par un décalage entre pics de production et de consommation. Le stockage de l’énergie électrique revêt donc un caractère primordial dans la gestion de ce décalage. Pour accomplir cette tâche, la technologie lithium-ion est une bonne candidate parmi les technologies de stockage électrochimique de l’énergie. Mais les applications visées exigent des durées de vie bien supérieures à celles requises pour l’électronique portable ou pour les véhicules électriques. En effet les performances des batteries, notamment en termes de capacité, doivent être préservées pendant des durées de 15 à 20 ans. Cette thèse a alors pour but l’étude des mécanismes de vieillissement à long terme d’accumulateurs Li-ion composés d’oxydes lamellaires Li(NixMnyCo1 x y)O2 à l’électrode positive et de graphite à l’électrode négative, en se focalisant sur les interfaces électrode/électrolyte qui sont le lieu privilégié des mécanismes de vieillissement. Ce travail a été réalisé à l'aide de la spectroscopie photoélectronique à rayonnement X (XPS) et de la spectroscopie d’impédance électrochimique (EIS), deux techniques complémentaires particulièrement bien adaptées à l’étude des interfaces, l'une permettant de sonder les environnements chimiques en extrême surface, l'autre donnant la réponse d’un système à une sollicitation électrique sinusoïdale de fréquence variable. La contrainte importante induite par les durées de vie visées (20 ans) ont conduit à simuler le vieillissement à long terme des batteries en leur faisant subir des sollicitations électrochimiques beaucoup plus importantes que lors d’une utilisation normale Les caractérisations par XPS et EIS ont été systématiquement mises en relation avec l’évolution des performances électrochimiques des batteries considérées. Cette étude a permis d'apporter des améliorations aux batteries pour apporter une meilleure réponse à ces phénomènes de vieillissement en termes de maintien des performances: modification de la formulation des électrodes, des électrolytes, de la nature des matériaux actifs, etc
Development of renewable energy sources such as photovoltaic or wind energy is limited by the intermittent nature of these energy sources. This intermittent nature results in the mismatch between production and consumption peaks. As a result, the storage of electrical energy plays an essential role to manage this mismatch. To this aim, lithium-ion technology appears as a good candidate among other ways of electrochemical storage of energy. However the targeted applications require much greater life span than those commonly admitted for portable electronics or electric vehicles. Battery performances, e.g. rechargeable capacity, should be preserved over 15 or 20 years. This PhD thesis aims at studying the long-term aging mechanisms of Li-ion batteries made up of lamellar oxides Li(NixMnyCo1 x y)O2 at the positive electrode and graphite at the negative electrode. We focused on the electrode/electrolyte interfaces which are the major place of aging processes. The work has been performed by X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS), two complementary techniques especially adapted to the study of interfaces, the former giving access to the chemical environments of atoms at the surface, the latter giving the answer of a system to a sinusoidal electric current with various frequencies. An important technical constraint was the difference between the targeted life span for the application (20 years) and the duration of the thesis (3 years). In order to simulate long-term aging the batteries were submitted to electrochemical stress in much harder conditions than in normal use. XPS and EIS characterizations were constantly related to evolution of electrochemical performances of batteries. This study allowed us during the duration of the project to bring improvements to batteries in order to obtain a better response to aging mechanisms regarding retention of electrochemical performances: e.g. change of electrodes or electrolyte formulation, change of active materials composition, etc

Motivated by the structure of the normal surface stress of the extended Hertzian approach [1] given due to terms of the form r^2n*(a^2-r^2)^(1/2) (n=0, 2, 4, 6…) it seems attractive to evaluate the complete elastic field also for shear loadings of this form. The reason for this lays in the demand for analytical tools for the description of mixed loading conditions as they appear for example in scratch experiments. [1] N. Schwarzer, "Elastic Surface Deformation due to Indenters with Arbitrary symmetry of revolution", J. Phys. D: Appl. Phys., 37 (2004) 2761-2772

To date, the cost of high platinum loadings in polymer electrolyte fuel cells (PEFCs) remains one of the main deterrents preventing their broad commercialisation. The reaction of interest in this work is the oxygen reduction reaction (ORR) occurring at the cathode side of the PEFC. The ORR has been studied at great length owing to the sluggish kinetics of this reaction and thus the necessity of the higher platinum loadings required on the cathode side of the PEFC. Platinum particle size and surface morphology are thought to be directly related to the catalytic activity of platinum towards the ORR (Mayrhofer et al., 2005) A better understanding of the effects of platinum particle size and surface morphology on the mechanism and kinetics of the ORR is critical if platinum loadings are to be reduced whilst maintaining the US Department of Energy (DoE) target performance levels (Schwanitz et al., 2012). This study focuses on the effects of platinum surface morphology on ORR activity by the development of platinum supported carbon electrodes. The surface morphology was modified by varying the platinum loading, such that the surface was taken from isolated nanoparticles to an extended surface. The effects of the changes in surface morphology and particle size on the ORR were then investigated. First a model electrode system was developed by magnetron sputter deposition of platinum onto a carbon black (VulcanXC72) surface supported on a glassy carbon electrode. The model system was then translated into a practical system, whereby platinum supported on carbon catalysts were prepared by metal-organic chemical vapour deposition (MOCVD) with increasing weight percentages of platinum. Similar trends were observed for the MOCVD catalyst system and the model electrode system. The trends of particular interest were the effects of platinum loading on hydrogen peroxide formation during the ORR and the double voltammeric CO oxidation peak observed with increased platinum loading during CO stripping voltammetry experiments. Hydrogen peroxide formation was observed at potentials below 0.8 V vs. SHE/RHE and it was found that hydrogen peroxide formation was predominant on dispersed platinum nanoparticles compared with platinum agglomerates. This is most likely related to peroxide species, a partial reduction product from oxygen to water, being able to desorb from the active surface without being further reduced to water on an adjacent site as the inter-particle distance is greater for the low loading samples relative to the higher loading samples in both systems. A clear indication of differing surface morphology between the low and high loading samples was observed by the double voltammeric peak detected during CO stripping voltammetry experiments. The low potential peak attributed to platinum agglomerates was seen to increase in amplitude as platinum loading increased. The corresponding high potential peak attributed to isolated nanoparticles, decreased in amplitude with increasing platinum loading. This observation alludes to an increase in particle agglomeration with platinum loading, and physical characterisation methods such as TEM and XRD showed an increase in the average particle size with increasing platinum loading, which supports the CO stripping voltammetry findings. The findings indicate a profound dependence of the ORR on platinum particle size and surface morphology. A better insight into these properties could assist in improved catalyst design and the enhancement of platinum utilisation and ORR activity of platinum.

Extended Hückel methods are known to be a useful tool in understanding surface phenomena. Important quantities about atoms and chemical bonds can be obtained from this computationally simple method, although caution must be exercised in interpreting the results. Application of Extended Hückel calculations to large metal clusters reveals the role of d orbitals in solids. Basic ideas of constructing model compounds have been developed. Several model systems for surface chemisorption processes are constructed in order to understand the surface catalyzed oxidative degradation of polyperfluoroethers. The activation of oxygen molecules can be explained. The Lewis acid character of the iron fluoride surface can be predicted. Based on these results, mechanisms of the degradation processes are discussed.

La recherche actuelle dans le domaine des nanosciences, l’assemblage supramoléculaire d’atomes métalliques et de molécules sur des surfaces ouvre la voie à des composants fonctionnels, utiles dans une multitude d’applications comme l’Optoélectronique, le magnétisme et la catalyse. Il a été démontré que dans certains cas, l’état de Spin Haut et une forte anisotropie magnétique apparaissent suite à un transfert d’électron entre ligands, surface et atome métallique. Le but de cette thèse porte sur l’auto-assemblage des 1,2,4,5-Tetracyanobenzene (TCNB) et des coordinations nanostructurelles des Fe-TCNB sur une surface d’Au(111). La formation de ces structures est conduite par les interactions non-covalentes. La spectroscopie à effet tunnel (STS) révèle que la molécule de TCNB est physisorbée sur la surface d’Au(111). Une analyse détaillée des spectres dI/dV effectués sur une monocouche de TCNB sur une surface d’Au(111) montre que la molécule de TCNB a un transfert de charge négligeable sur ce substrat avec une énergie d’adsorption de 0,5 eV par molécule. Les mesures STS révèlent un gap HOMO-LUMO de 3 eV, comme le prédit la théorie. En contrôlant les paramètres de fabrication, des composants nanostructurels avec différentes compositions chimiques ou des arrangements moléculaires ont été synthétisés. Les propriétés électroniques ont été caractérisées par une analyse spectroscopique dI/dV locale sur les centres métalliques à différentes étapes de formation des complexes Fe-(TCNB)x (x=4, 2). La déposition à très basse température forme un état intermédiaire métastable. Les données STM montrent que l’angle que forment le trièdre Fe-N-C est de 120°. La spectroscopie tunnel révèle que le Fe et la molécule de TCNB gardent leur identité spectroscopique, le Fe garde ses états de surface de la même façon que s’il avait été déposé seul sur une surface d’Au(111). Ceci indique que les molécules de TCNB sont virtuellement dans le même état électronique qu’avant la déposition du Fe. La situation change lorsque ce dépôt est effectué à température ambiante. Une augmentation de température agit sur l’interaction des composants transformant ainsi la formation en un complexe monomère de Fe(TCNB)4 avec un angle Fe-N-C de 180°. La spectroscopie STS sur ce complexe suggère fortement que la liaison de coordination est formée entre le Fe et la molécule de TCNB. Les calculs DFT soutiennent ces conclusions. Plus loin, une structure a été réalisée par la synthèse d’un réseau Fe(TCNB)2. Ce réseau a une structure carrée avec une séparation régulière entre les atomes de Fe. Les informations électroniques de la structure sont données par la molécule de FePc (où Pc représente la molécule de Phthalocyanine) pour identifier les pics de résonnance du spectre du réseau de Fe(TCNB)2. Une similitude apparait dans les spectres dI/dV effectués sur l’atome de Fe et sur les ligands dans les deux systèmes, indiquant que le Fe ressent un environnement similaire quand il est entouré de TCNB ou quand il est à l’intérieur d’une Phthalocyanine. Une analyse plus détaillée basée sur la formation des liaisons métal-ligands a été discutée
In the bottom up approach of today’s nanoscience, the supramolecular assembly of metal atoms and molecules on surfaces is leading to functional compounds, relevant to many applications in optoelectronics, magnetism, and catalysis. It has been found that in some cases high magnetic spin states and strong magnetic anisotropy appear as a result of electron transfer between ligands, surface and metal atom. The focus of this thesis lies on the self assembling of 1,2,4,5-Tetracyanobenzene (TCNB) and Fe-TCNB coordination nanostructures on the Au(111) surface. The structural formation is directed by the non covalent interactions. Scanning tunneling spectroscopy (STS) reveal that the TCNB molecules are physisorbed on Au(111) surface. By detail analysis of the dI/dV spectra above the TCNB monolayer on the Au(111) surface, we found that the TCNB molecules on Au(111) shows a negligible charge transfer with Au(111) substrate and a small adsorption energy of 0.5 eV per TCNB molecules. STS measurement provide a HOMO-LUMO gap of 3 eV in agreement with DFT calculations. By controlling the fabrication parameters, surface coordination nanostructures with different chemical composition or molecular packing have been synthesized. The electronic properties have been characterized by the local dI/dV analysis of the metal centers at different steps of a Fe-(TCNB)x (x=4, 2) complexes formation. At low temperature deposition, first form an ordered metastable intermediate. STM data yield the bond angle between the Fe-N-C is 120°. The scanning tunneling spectroscopy reveal that Fe atoms and the TCNB molecules keep their identity while the Fe atoms localize the surface-state electrons similar to what they do on the bare Au(111) surface. This result indicates that the TCNB molecules are virtually in the same electronic state as before the Fe adsorption. The situations are different when the deposition performance at room temperature. When the temperature is changed, to room temperature, the original entities transform into the Fe(TCNB)4 monomer complexes with 180° Fe-N-C bond angles. The STS above the Fe(TCNB)4 complex strongly suggest that the coordination bond had been formed between the Fe atom and the TCNB ligands. DFT calculations support the conclusions and drawn from experimental studies and assist the interpretations of experiment. Further structural complexation is achieved by the synthesis of Fe(TCNB)2 network. The network has a square structure with a regular separation of the magnetic Fe atoms in the network. The electronic information is gathered from the spectroscopic labeling of FePc to identify some of the resonances of the Fe(TCNB)2 network. There are similar features are found in the dI/dV spectra above the Fe atoms and ligand in both system, indicating that the Fe somehow feels a similar environment from the TCNB ligands in the network and in the FePc molecules. Further analysis of this feature have been disused by means of metal-ligand bond formation

This thesis is in two distinct sections. In the first section, novel diketopiperazines are synthesised and incorporated as chain extenders into thermoplastic polyurethane elastomers and the resulting mechanical, thermal and degradative properties are analysed. In the second section, hyperbranched chain terminating agents are synthesised from 1,1’-carbonyldiimidazole in a one-pot process and the potential applications of fluorinated hyperbranched chain terminating agents are investigated. Chapter 1 has three parts. First, the synthesis and applications of polyurethanes are introduced and the current market trends and growth projections are discussed. Secondly, an overview of current literature covering biodegradable polymers focusing on the incorporation of amino acids into polyurethanes and their potential applications is presented. Thirdly, hyperbranched polymers are introduced and a focus is made on the synthesis of isocyanate and non-isocyanate polyurethanes and polyureas. In chapter 2, the use of the dipeptides of tyrosine and glutamic acid as chain extenders in polyurethane synthesis is explored. The dipeptide of glutamic acid is modified to incorporate a higher content of ester and amide degradable linkages with aromatic character that form comparable chain extenders to tyrosine dipeptide. Their use in the organocatalysed step-growth polymerisation of novel thermoplastic polyurethane elastomers is described. In chapter 3, the resulting tyrosine and glutamic acid-derived thermoplastic polyurethane elastomers are utilised to explore the variation of thermal, mechanical and degradative properties of a range of polymer compositions. In chapter 4, the synthesis of novel hyperbranched materials polymerised in a one-pot, temperature-controlled sequential synthesis incorporating aromatic or fluorinated functional chain ends from both carbonylbiscaprolactam and 1,1’-carbonyldiimidazole precursors is described. In chapter 5, 1,1’-carbonyldiimidazole derived hyperbranched polymers are incorporated into an existing thermoplastic polyurethane formulation and the surface properties are studied by varying polymer composition. In chapter 6, the significant findings and conclusions are summarised. In chapter 7, the experimental methods used are set out.