A full understanding of chemical reaction dynamics at the gas/organic-surface interface requires knowledge of energy-transfer processes that happen during the initial gas/surface collision. We have examined the influence of mass and rovibrational motion on the energy-transfer dynamics of gas-phase species scattering from model organic surfaces using theory and experiment. Molecular-beam scattering techniques were used to investigate the rare gases, Ne, Ar, Kr, and Xe, and the diatomics, N₂ and CO, in collisions with CH₃- and CF₃-terminated self-assembled monolayer (SAM) surfaces. Complementary molecular-dynamics simulations were employed to gain an atomistic view of the collisions and elucidate mechanistic details not observable with our current experimental apparatus. We developed a systematic approach for obtaining highly accurate analytic intermolecular potential-energy surfaces, derived from high-quality ab initio data, for use in our classical-trajectory simulations. Results of rare gas scattering experiments and simulations indicate mass to be the determining factor in the energy-transfer dynamics, while other aspects of the potential-energy surface play only a minor role. Additionally, electronic-structure calculations were used to correlate features of the potential-energy surface with the energy-transfer behavior of atoms and small molecules scattering from polar and non-polar SAM surfaces. Collisions of diatomic molecules with SAMs are seen to be vibrationally adiabatic, however translational energy transfer to and from rotational modes of the gas species, while relatively weak, is readily apparent. Examination of the alignment and orientation of the final rotational angular momentum of the gas species reveals that the collisions induce a stereodynamic preference for the expected "cartwheel" motion, as well as a surprising propensity for "corkscrew" or "propeller" motion. The calculated stereodynamic trends suggest that the CH₃-SAM is effectively more corrugated than the CF₃-SAM. Finally, the feasibility for collisional-energy promoted, direct gas/organic-surface reactions was interrogated using the 1,3-dipolar azide-alkyne cycloaddition reaction. We found that geometrical constraints prevented the reaction from proceeding at the probed conditions. / Ph. D.

Structural health monitoring systems provide a promising route to real-time data for analyzing the current state of large structures. In the wake of two high-profile bridge collapses due to an aging highway infrastructure, the interest in implementing such systems into fracture-critical and structurally deficient bridges is greater now than at any point in history. Traditionally, these technologies have not been cost-effective as bridges lack existing wiring architecture and the addition of this is cost prohibitive. Modern wireless sensor networks (WSN) now present a viable alternative to traditional networking; however, these systems must incorporate localized power sources capable of decade-long operation with minimal maintenance. To this end, this thesis explores the development of two energy harvesting systems capable of long-term bridge deployment with minimal maintenance. First, an electromagnetic, linear, vibrational energy harvester is explored that utilizes the excitations from passing traffic to induce motion in a translating permanent magnet mass. This motion is then converted to electrical energy using Faraday’s law of induction. This thesis presents a review of vibrational energy harvesting literature before detailing the process of designing, simulating, prototyping, and testing a selected design. Included is an analysis of the effects of frequency, excitation amplitude, load, and damping on the power production potential of the harvester. Second, a solar energy harvester using photovoltaic (PV) panels is explored for powering the critical gateway component of the WSN responsible for data aggregation. As solar energy harvesting is a more mature technology, this thesis focuses on the methodologies for properly sizing a solar harvesting system and experimentally validating the selected design. Fabrication of the prototype system was completed and field testing was performed in Austin, TX. The results validate the selected system’s ability to power the necessary 14 W DC load with a 0° panel azimuth angle (facing direct south) and 45° tilt. / text

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In the present work the effect of a dry friction damper device on the dynamic behavior of vibratory systems is analyzed. Two friction devices are designed consisting of a sphere in contact with a flat steel bar. In the first prototype the normal force on the contact is kept constant. In the second device a piezoelectric actuator is used to vary the intensity of the normal force. An experimental methodology is developed to analyze the dynamic behavior of a vibratory system and to identify the physical properties of the friction damper devices. The mathematical-computational models of the two friction dampers are used to perform simulations with a vibratory system, in order to analyze the influence of the variation of the normal contact force on the behavior of the vibratory system and to evaluate the dissipation of vibrational energy. In the first damper, an experimental methodology is used to identify the behavior of friction force induced on the vibratory system, and also to identify nonlinearities due to friction Frequency response is used to identify the structural frequencies generated by the device, as well the operational band of the damper device with constant normal force. The time domain vibratory system response is used to identify the Coulomb friction model. The second damper is designed by finite element method. Experimental analysis of the device is applied to identify the parameters that define the static and dynamic behavior of the damper with variable normal load, The frequency response is used to identify the structural frequencies generated by the device, as well it s effective operational band.. Another experiment evaluates the effect of the normal contact force variation on the dynamic response of a vibratory structure. The vibratory system response is identified using Coulomb friction models. Finally, numerical simulations are used to evaluate the effect of the normal contact variation, generated by a semi active control, on the vibratory system dynamic behavior. The vibration attenuation and the power demand of the piezoelectric actuator .are evaluated. / Neste trabalho é analisado o efeito de amortecedores de atrito seco sobre o comportamento dinâmico de um sistema vibratório de um grau de liberdade São projetados dois dispositivos de atrito constituídos por uma esfera em contato com um barra plana de aço. No primeiro protótipo a força normal no contato é mantida constante. No segundo dispositivo é utilizado um atuador piezelétrico para variar a intensidade da força normal. É desenvolvida uma metodologia experimental para analisar o comportamento dinâmico do sistema vibratório e identificar as propriedades físicas dos amortecedores de atrito. Os modelos matemáticos-computacionais dos dois amortecedores de atrito são usados para realizar simulações com um sistema vibratório, com a finalidade de analisar a influência da variação da força normal de contato sobre o comportamento do sistema vibratório e avaliar a capacidade de dissipação da energia vibratória. No primeiro amortecedor mediante uma metodologia experimental, é possível identificar o comportamento da força de atrito induzida ao sistema dinâmico, são identificadas também as não linearidades devidas ao atrito. Na resposta em frequência é possível identificar as frequências estruturais geradas pelo dispositivo, assim como a banda de atuação do amortecedor de força normal constante. Por ultimo é identificada a resposta do sistema dinâmico no domínio do tempo, mediante os modelos Coulomb do atrito. Para o segundo amortecedor é apresentado a analise estática dos elementos constituintes via um estudo em elementos finitos. Métodos de analise experimental aplicados para identificar os parâmetros que determinam o comportamento estático e dinâmico do amortecedor de carga normal variável. Na resposta em frequência é possível identificar as frequências estruturais geradas pelo dispositivo, assim como também, a banda de atuação do amortecedor de força normal variável. Em uma segunda fase experimental, avaliam-se os efeitos da variação da força normal no contato, na resposta dinâmica da estrutura vibratória e determina-se o comportamento da força do amortecedor, assim como também se identifica a resposta do sistema, com os modelos de atrito de Coulomb. Finalmente, é avaliada numericamente o efeito do ajuste da força normal do contato, mediante um controle semiativo., Verifica-se a eficiência do controle sobre a vibração da estrutura .e sobre o consumo de potência do atuador piezelétrico. / Mestre em Engenharia Mecânica

In this dissertation we present the main results about the magnetic properties of elastic ferromagnets based on the analysis of different behaviours of the exchange parameter O (or exchange interaction). Firstly, we analyzed the variation of exchange parameter O with H and T , i.e., O vH w , O vT w and O vH,T w , obtaining an additional contribution whitout defined physically origin, vH,T w adic { ´S , which when added to the conventional entropy, conv { ´S , results in the variation of total entropy, total { ´S , obtained by Maxwell¡¦s relation. In what follows, we implement a model that includes a vibrational energy in the Einstein approximation for high temperatures, and an other with a quadratic dependence of the isothermal compressibility with the temperature by means of the relation 2 o T K ­ K y a T , so that obtain an additional contribution with defined physically origin. These additional contributions are obtained by magnetoelastic coupling to rewrite the system in terms of the exchange parameter O x that when applied to the model entropy exchange (proposal by Plaza-Campoy), leads to additional contributions to the { ´S eT curves. In a third approximation, we formulate the O parameter within the RKKY fenomenology, Ë Í o RKKY O ­ O J ç , and analyse the magnetic properties (magnetization, exchange parameter, deformation, magnetic entropy, etc.) for different regions of the RKKY curve. In this fenomenology, the exchange parameter varies in a non linear form as a function of the deformation, although when we get closer to a linear region we verified that the Bean- Rodbell model approximates well the RKKY model. Finally, we start from a generalized exchange Hamiltonian and formulate an generalized exchange energy that inserted in the Gibbs free energy, promotes an additional contribution to the magnetic properties, showing up the importance of the v1 4 w factor in the exchange hamiltonian when the exchange parameter depends on the interatomic distances. / Nesta dissertacao sao apresentados os principais resultados das propriedades magneticas de ferromagnetos elasticos baseados na analise de diferentes comportamentos do parametro de troca O (ou interacao de troca). Primeiramente, analisou-se a variacao do parametro O com H e T , ou seja, O vH w , O vT w e O vH,T w , obtendo-se uma contribuicao adicional sem origem fisica definida, vH,T w adic { ´S , que ao ser somada a entropia convencional, conv { ´S , resulta na variacao de entropia total, total { ´S , obtida a partir da relacao de Maxwell. Em seguida, nos implementamos um modelo que contem uma energia vibracional na aproximacao de Einstein para altas temperaturas, e outro com a dependencia quadratica da compressibilidade isotermica com a temperatura pela relacao v w 2 o T K T ­ K y a T , de forma a obtermos contribuicoes adicionais com uma origem fisica definida. Tais contribuicoes adicionais sao obtidas por meio do acoplamento magnetoelastico ao reescrever o sistema em termos de um parametro de troca O x que ao ser aplicado no modelo da entropia de troca (proposta por Plaza-Campoy), apresentam as contribuicoes adicionais nas curvas de { ´S eT . Em uma terceira aproximacao, formulamos o parametro O na fenomenologia RKKY, Ë Í o RKKY O ­ O J ç , e analisamos as propriedades magneticas (magnetizacao, parametro de troca, deformacao, entropia magnetica) para regioes diferentes da curva oscilatoria da interacao RKKY. Nesta fenomenologia o parametro de troca varia de forma nao linear com a deformacao, porem quando nos aproximamos de uma regiao quase linear verificamos que o modelo de Bean-Rodbell se aproxima bem do modelo RKKY. Por fim, partimos de uma hamiltoniana de troca generalizada e formulamos uma energia de troca generalizada que ao ser inserida na energia livre de Gibbs, promove uma contribuicao adicional nas propriedades magneticas, evidenciando a importancia do fator v1 4 w na hamiltoniana de troca quando o parametro de troca depende das distancias interatomicas.

Chaque fois que se produit un mouvement relatif entre deux systèmes, avec une interface à contact sec, le contact frottant induit des vibrations. La dynamique locale au contact (ruptures et la génération d'ondes) se couple avec la dynamique du système, donnant origine à des vibrations et affectant le comportement frictionnel macroscopique du système. Dans cette thèse, afin de développer une approche globale pour l'investigation des phénomènes multi-physiques, l'énergie a été utilisée comme une caractéristique physique universelle du couplage. La formulation de un bilan énergétique mécanique est utilisé pour identifier deux termes dissipatifs différents, i.e. la dissipation par amortissement matériel/système et la dissipation au contact. Les flux d'énergie, provenant des surfaces en contact et dus aux vibrations induites par frottement, excitent la réponse dynamique du système et, vice versa, l'influence de la réponse dynamique du système sur la dissipation d'énergie locale à l'interface de contact affecte les phénomènes tribologiques connexes. Dans cette thèse, les vibrations induites par le frottement ont été analysées en utilisant: l'approche par éléments finis pour étudier, par l'analyse des flux d'énergie, le couplage entre le contact et la dynamique du système; l'approche expérimentale pour valider les résultats numériques et observer l'influence des phénomènes pas encore inclus dans les modèles numériques; une approche avec une modèle à paramètres concentrés pour évaluer rapidement les effets des paramètres du système. L'analyse numérique par le modèle éléments finis 2D permet une répartition de l’énergie introduite dans le système mécanique entre les deux termes dissipatifs (amortissement matériau et contact), au cours de la réponse transitoire aussi bien en conditions stables qu’instables. En particulier, les vibrations induites par frottement modifient la capacité globale du système à absorber et dissiper l’énergie; une estimation de la puissance dissipée au contact, sans prendre en compte le comportement dynamique du système (flux d’énergie par les vibrations induites par frottement) peut conduire à des erreurs significatives dans la quantification de l’énergie dissipée au contact, ce qui affecte directement plusieurs phénomènes tribologiques. Les mesures expérimentales de crissement montrent comment les mêmes modes instables sont reproduits soit expérimentalement soit numériquement, validant l’utilisation de la simulation 2D transitoires pour l’analyse des vibrations instables induites par le frottement. L’équilibre énergétique a été utilisé sur le modèle à paramétrés concentrés, pour approcher le problème de la surestimation d’instabilité, qui est caractéristique d’une analyse des valeurs propres complexes. Un nouvel indice d’instabilité (MAI) a été défini, par des considérations énergétiques, pour comparer les différents modes instables et pour sélectionner le mode qui devient effectivement instable pendant le crissement. / Whenever relative motion between two system components occurs, through a dry contact interface, vibrations are induced by the frictional contact. The local dynamics at the contact (ruptures and wave generation) couples with the system dynamics, giving origin to vibrations and affecting the macroscopic frictional behavior of the system. In this thesis, in order to develop an overall approach to the investigation of the multi-physic phenomenon, the energy has been pointed out as a coupling physical characteristic among the several phenomena at the different scales. The formulation of a mechanical energy balance is used for distinguishing between two different dissipative terms, i.e. the dissipation by material/system damping and the dissipation at the contact. The energy flows coming from the frictional surfaces, by friction induced vibrations, excites the dynamic response of the system, and vice versa the influence of the system dynamic response on the local energy dissipation at the contact interface affects the related tribological phenomena. The friction-induced vibrations have been analyzed using three different approaches: the finite element approach, to investigate the coupling between the contact and system dynamics by the analysis of the energy flows; the experimental approach to validate the numerical results and observe the influence of phenomena not still included into the numerical model; a lumped parameter model approach to quickly investigate the effects of the system parameters. The numerical analysis by the 2D finite element model allowed investigating the repartition of the energy introduced into the mechanical system between the two dissipative terms (material damping and contact) during both stable and unstable friction-induced vibrations. In particular, it has been shown how the friction-induced vibrations modify the overall capacity of the system to absorb and dissipate energy; an estimation of the power dissipated at the contact, without considering the dynamic behavior of the system (energy flows by friction induced vibrations) can lead to significant error in the quantification of the dissipated energy at the contact, which affects directly several tribological phenomena. The experimental squeal measurements show how the same unstable modes are recovered both experimentally and numerically, validating the use of the 2D transient simulations for the reproduction of the unstable friction-induced vibrations. Once the energy balance formulated, it has been used on the lumped model to approach the instability over-prediction issue characteristic of the complex eigenvalue analysis. By energy considerations, a newer instability index (MAI) has been defined to compare the different unstable modes and to select the mode that becomes effectively unstable during the transient response. The Modal Absorption Index allows quantifying the capability of each mode to exchange energy with the external environment.

En esta tesis desarrollamos métodos híbridos clásico-cuánticos para el estudio de la relajación vibracional de moléculas en disolución. En estos tratamientos se realiza una descripción cuántica de la vibración del soluto, mientras que el resto de grado de libertad se describen clásicamente. Estos métodos superan las limitaciones inherentes a los tratamientos clásicos y permiten el análisis del flujo de energía entre el soluto y el disolvente. Hemos aplicado estas metodologías al estudio de la relajación vibracional de la molécula de yodo en xenón líquido y del ión cianuro en agua, analizando el papel del disolvente en las transiciones vibracionales del soluto. Nuestros resultados para estos sistemas, de naturaleza tan diferente, concuerdan bien con las medidas experimentales, lo que en ausencia de resultados teóricos exactos supone una valiosa prueba de la capacidad de estos métodos para el estudio de los procesos de relajación vibracional en líquidos. / In this thesis we have developed hybrid quantum-classical methods to study vibrational relaxation of molecules in solution. In these treatments a quantum description of solute vibration is done, while the other degrees of freedom are classically described. These methods overcome the inherent limitations of classical treatments and let us the analysis of energy flux between solute and solvent. We have applied these methodologies to study vibrational relaxation of iodine molecule in liquid xenon and cyanide ion in water, analyzing the role of the solvent in the vibrational transitions of the solute. Our results for these systems, of so different kind, agree well with experimental measures, what in absence of exact theoric results is a valious proof of the ability of these methods to study the vibrational relaxation processes in liquids.

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