According to NCHRP Report 493, there are five major left turn signal indications for permitted operations in the United States. They are: Circular Green (CG), Flashing Circular Red (FCR), Flashing Red Arrow (FRA), Flashing Circular Yellow (FCY) and Flashing Yellow Arrow (FYA). The main goal of this thesis is to study the driver behavior and analyze safety of drivers for different left turn indications using a real-time driving simulator. Different signal indications alter driver behavior which influences velocity and acceleration profiles. These profiles influence vehicular emissions and hence need to be studied as well. For this purpose, different scenarios are implemented in the driving simulator. Data is analyzed using Microsoft Excel, JMP Statistical tool and MATLAB. Safety of drivers is analyzed with respect to the parameter "Time to Collision (TTC)" which is directly obtained from simulator data. Vehicular emissions and fuel consumption are calculated using VT-Micro microscopic emissions model. Graphs are plotted for TTC and total emissions. Results indicate that for a day-time scenario, FCY and FYA are the most suitable left-turning indications whereas FCR and FRA are most suitable for a night-time scenario. / Master of Science

Automobile accidents are one of the leading causes of death and claim more than 40,000 lives annually in the US alone. A substantial portion of these accidents occur at road intersections. Stop signs and traffic signals are some of the intersection control devices used to increase safety and prevent collisions. However, these devices themselves can contribute to collisions, are costly, inefficient, and are prone to failure. This thesis proposes an adaptive, decentralized, cooperative collision avoidance (CCA) system that optimizes each vehicle's controls subject to the constraint that no collisions occur. Three major contributions to the field of collision avoidance have resulted from this research. First, a nonlinear 5-state variable vehicle model is expanded from an earlier model developed in [1]. The model accounts for internal engine characteristics and more realistically approximates vehicle behavior in comparison to idealized, linear models. Second, a set of constrained, coupled Extended Kalman Filters (EKF) are used to predict the trajectory of the vehicles approaching an intersection in real-time. The coupled filters support decentralized operation and ensure that the optimization algorithm bases its decisions on good, reliable estimates. Third, a vehicular network based on the new WAVE standard is presented that provides cooperative capabilities by enabling intervehicle communication. The system is simulated against today's common intersection control devices and is shown to be superior in minimizing average vehicle delay. / Master of Science

<p dir="ltr">The field of nanoclusters includes a broad range of sizes and structures that influence both their physical and chemical properties. Scientists use several techniques, such as atom-by-atom substitution, to synthesize atomically precise nanoclusters, and ligand shell mixing to protect nanoclusters from unwanted side reactions, while controlling their reactivity and solubility. These combined techniques can provide stable products, but isomers and structural analogs often remain in the product mixture, complicating the structural characterization of individual nanoclusters. Leading structural characterization techniques in nanocluster research are often limited in their ability to examine both the structure of the metal core and ligand shell in sufficient detail. The primary aim of this research is to systematically characterize the structures and chemical properties of several types of transition metal oxide nanoclusters of interest to applications in energy production, catalysis, and magnetic resonance imaging, without requiring purification. Specifically, this work focuses on 1) Polyoxovanadates (POV) with a mixture of methoxy, ethoxy, and ether ligands, 2) Fe- and W-substituted POV alkoxides, and 3) Octanuclear iron oxide clusters substituted with In atoms. Mass spectrometry techniques enable the structural characterization of individual clusters from multicomponent mixtures without interference. Specifically, we use ion mobility spectrometry to explore how surface ligands affect the metal core in mixed-ligand POV alkoxide species. We examine structure-specific fragments to identify the positions of ligands and heteroatoms within the metal core of mixed-ligand species and W and Fe-substituted POV methoxides. Additionally, we use ion soft-landing to purify W-substituted POV methoxide anions on surfaces for characterization using cyclic voltammetry and infrared spectroscopy. We discovered unique characteristics of each nanocluster including the position of heteroatoms, ligands shell mobilities, structures and collisional cross sections, and provided first insights into the redox properties of W-substituted POV alkoxide. These results highlight the growing influence of mass spectrometry in the field of nanocluster characterization and design.</p>

No description available.

This thesis presents the initial components of an integrated guidance, navigation, and control system for vertical take-off and landing (VTOL) autonomous unmanned aerial vehicles (UAVs) such that they may map complex environments that may be hostile. The first part of this thesis presents an autonomous guidance system. For goal selection, the map is partitioned around the presence of obstacles and whether that area has been explored. To perform this partitioning, the Octree algorithm is implemented. In this thesis, we test this algorithm to find a parameter set that optimizes this algorithm. Having selected goal points, we perform a comparison of the LPA* and A* path planning algorithms with a custom heuristic that enables reckless or tactical maneuvers as the UAV maps the environment. For trajectory planning, the fMPC algorithm is applied to the feedback-linearized equations of motion of a quadcopter. For collision avoidance, standalone versions of 4 different constraint generation algorithms are evaluated to compare their resulting computation times, accuracy, and computed volume on a voxel map that simulates a 2-story house along with fixed paths that vary in length at fixed intervals as basis of tests. The second part of this thesis presents the theory of Model Reference Adaptive Control(MRAC) along with augmentation for output signal tracking and switched-dynamic systems. We then detail the development of longitudinal and lateral controllers a Quad-Rotor Tailsitter(QRBP) style UAV. In order to successfully implement the proposed controller on the QRBP, significant effort was placed upon physical design and testing apparatus. / Master of Science / For an autonomously operated, Unmanned Aerial Vehicle (UAV), to operate, it requires a guidance system to determine where and how to go, and a control system to effectively actuate the guidance system's commands. In this thesis, we detail the characterization and optimization of the algorithms comprising the guidance system. We then delve into the theory of MRAC and apply it toward a control system for a QRBP. We then detail additional tools developed to support the testing of the QRBP.

Au cours des deux dernières décennies, les signaux chaotiques ont été de plusen plus pris en compte dans les télécommunications, traitement du signal ou transmissionssécurisées. De nombreux articles ont été publiés qui étudient la densitéspectrale de puissance (DSP) des signaux générés par des transformations spécifiques.La concentration sur la DSP est due à l’importance de la fréquence dans lestélécommunications et la transmission sécurisée. Grâce au grand nombre de systèmessans fil, la disponibilité des fréquences de transmission et de réception est de plus enplus rare pour les communications sans fil. Aussi, les médias guidés ont des limitationsliées à la bande passante du signal. Dans cette thèse, nous étudions certainespropriétés associées à la bifurcation collision de frontière pour une transformationunidimensionnelle linéaire par morceaux avec trois pentes et deux paramètres. Nouscalculons les expressions analytiques de l’autocorrélation et de la densité spectralede puissance des signaux chaotiques générés par les transformations linéaires parmorceaux. Nous montrons l’existence d’une forte relation entre les différents typesde densité spectrale de puissance (passe-bas, passe-haut ou coupe-bande) et les paramètresde bifurcation. Nous notons également en évidence une relation entre le typede spectre et l’ordre des cycles attractifs. Le type du spectre dépend de l’existencedes orbites périodiques au-delà de la bifurcation de collision de frontière qui a donnénaissance au chaos. Nous utilisons ensuite les transformations chaotiques pour étudierla fonction d’ambiguïté. Nous combinons quelques transformations chaotiquesbien déterminées pour obtenir un spectre large bande avec une bonne fonction d’ambiguïtéqui peut être utilisée en système radar / During the two last decades, chaotic signals have been increasingly consideredin telecommunications, signal processing or secure transmissions. Many papers haveappeared which study the power spectral density (PSD) of signals issued from somespecific maps. This interest in the PSD is due to the importance of frequency in thetelecommunications and transmission security. With the large number of wirelesssystems, the availability of frequencies for transmission and reception is increasinglyuncommon for wireless communications. Also, guided media have limitations relatedto the bandwidth of a signal. In this thesis, we investigate some properties associatedto the border-collision bifurcations in a one-dimensional piecewise-linear map withthree slopes and two parameters. We derive analytical expressions for the autocorrelationsequence, power spectral density of chaotic signals generated by our piecewiselinearmap. We prove the existence of strong relation between different types of thepower spectral density (low-pass, high-pass or band-stop) and the parameters. Wealso find a relation between the type of spectrum and the order of attractive cycleswhich are located after the border collision bifurcation between chaos and cycles.We use the chaotic transformations to study the ambiguity function. We combinesome chaotic transformations well determined to obtain a broadband spectrum witha good ambiguity function that can be used in radar systems

Made available in DSpace on 2016-04-26T20:21:41Z (GMT). No. of bitstreams: 1 celio Pereira Oliveira Neto.pdf: 1507882 bytes, checksum: 7103e8b0600844203d81f93da63c2f69 (MD5) Previous issue date: 2013-06-14 / Although there isn‟t a specific rule in the native law, the application of the non concurrence clause profits from the constitutional protection, which is based on the free initiative, private property, free concurrence, property law, consumer defense and general freedom law. Due to constitutional propagation, it enjoys equally of protection in the general clauses of the objective good faith and social function, besides the lawfulness presumption of the contract. On the other hand, there are some directives that can‟t be disregarded when having to limit the freedom right of the work. Indeed, the economical order must be based on the importance of the human work, as well as the reduction of the social inequalities and in the search of the perfect job. Moreover, the private property is established on the basis of the free exercise of any work, occupation or profession, that is to say, it must be observed the social right of the worker in choosing the developed activity, this means that any act that disrespect the importance of the work can be understood as unconstitutional. There is a clear confront between the non concurrence clause and the freedom work both under the constitutional protection in the articles 5° and 170 of the CF. The solution of this conflict is coped with the principles of proportionality, which it justifies and limits the application of the non concurrence clause. However, to reach such point, it‟s necessary the constitutional passage about the traditional methods of constitutional interpretation getting to the pos-positivist moment, taking care of the constitutional‟s principles of interpretation reading as a leading of the whole arrangement, differing from the rules relating them with the principle of proportionality use and its sub-principles of adequacy, necessity and proportionality in the strict way / Although there isn‟t a specific rule in the native law, the application of the non concurrence clause profits from the constitutional protection, which is based on the free initiative, private property, free concurrence, property law, consumer defense and general freedom law. Due to constitutional propagation, it enjoys equally of protection in the general clauses of the objective good faith and social function, besides the lawfulness presumption of the contract. On the other hand, there are some directives that can‟t be disregarded when having to limit the freedom right of the work. Indeed, the economical order must be based on the importance of the human work, as well as the reduction of the social inequalities and in the search of the perfect job. Moreover, the private property is established on the basis of the free exercise of any work, occupation or profession, that is to say, it must be observed the social right of the worker in choosing the developed activity, this means that any act that disrespect the importance of the work can be understood as unconstitutional. There is a clear confront between the non concurrence clause and the freedom work both under the constitutional protection in the articles 5° and 170 of the CF. The solution of this conflict is coped with the principles of proportionality, which it justifies and limits the application of the non concurrence clause. However, to reach such point, it‟s necessary the constitutional passage about the traditional methods of constitutional interpretation getting to the pos-positivist moment, taking care of the constitutional‟s principles of interpretation reading as a leading of the whole arrangement, differing from the rules relating them with the principle of proportionality use and its sub-principles of adequacy, necessity and proportionality in the strict way / Embora inexista regra específica no direito pátrio, a aplicação da cláusula de não concorrência goza de amparo constitucional, fundado na livre iniciativa, propriedade privada, livre concorrência, direito de propriedade, defesa do consumidor e direito geral de liberdade. Por irradiação constitucional, usufrui igualmente de amparo nas cláusulas gerais da boa-fé objetiva e função social do contrato, além da presunção de licitude do contrato. Por outro lado, há diretrizes que não podem ser desconsideradas quando se trata de limitar o direito de liberdade ao trabalho. Com efeito, a ordem econômica deve ser fundada na valorização do trabalho humano, bem como na redução das desigualdades sociais, e na busca do pleno emprego. Ademais, a propriedade privada é estabelecida com base no livre exercício de qualquer trabalho, ofício ou profissão ou seja, deve ser observado o direito social do trabalhador de escolher a atividade desenvolvida, o que significa que qualquer ato que desrespeite a valorização do trabalho poderá ser entendida como inconstitucional. Há nítido confronto, pois, entre a cláusula de não concorrência e a liberdade ao trabalho ambas com amparo constitucional nos arts. 5º e 170 da CF. A resolução desse conflito é enfrentada à luz do princípio da proporcionalidade, que justifica e limita a aplicação da cláusula de não concorrência. Porém, para se chegar a tal ponto, antes se faz necessária passagem constitucional, acerca dos tradicionais métodos de interpretação constitucional chegando ao momento pós-positivista, cuidando-se da leitura dos princípios de interpretação constitucional como vetores de todo o ordenamento, diferenciando-os das regras, e relacionando-os com o uso do princípio da proporcionalidade e seus subprincípios da adequação, necessidade e proporcionalidade em sentido estrito. Daí se observa que a Constituição Federal preserva ambos os bens, e a interpretação constitucional deve ser levada a efeito de modo a harmonizar o conflito, de sorte que um direito ceda ao outro no caso concreto, sem que isso represente a completa exclusão do direito preterido, conservando-se a unidade do sistema e promovendo-se a concordância prática através da ponderação de bens. O princípio da proporcionalidade passa a ser conceituado e aferido em todas as suas nuances, demonstrando-se os prós e contras de seu uso como critério para resolução de conflitos na sociedade contemporânea. Passa-se à análise do direito contratual contemporâneo, em que a autonomia da vontade é mitigada frente à defesa dos direitos sociais, e a responsabilidade pós-contratual é inserida com fulcro nas cláusulas gerais. Com o uso de todos os fundamentos apontados, torna-se ao debate original, justificando e limitando a cláusula de não concorrência, apresentando as possibilidades de uso da cláusula de não concorrência pós pactum finitum em uma relação de desigualdade como é o caso da relação de emprego, valendo-se do princípio da proporcionalidade e seus subprincípios, indicando-se as posições da doutrina e jurisprudência, sem olvidar do direito estrangeiro / Embora inexista regra específica no direito pátrio, a aplicação da cláusula de não concorrência goza de amparo constitucional, fundado na livre iniciativa, propriedade privada, livre concorrência, direito de propriedade, defesa do consumidor e direito geral de liberdade. Por irradiação constitucional, usufrui igualmente de amparo nas cláusulas gerais da boa-fé objetiva e função social do contrato, além da presunção de licitude do contrato. Por outro lado, há diretrizes que não podem ser desconsideradas quando se trata de limitar o direito de liberdade ao trabalho. Com efeito, a ordem econômica deve ser fundada na valorização do trabalho humano, bem como na redução das desigualdades sociais, e na busca do pleno emprego. Ademais, a propriedade privada é estabelecida com base no livre exercício de qualquer trabalho, ofício ou profissão ou seja, deve ser observado o direito social do trabalhador de escolher a atividade desenvolvida, o que significa que qualquer ato que desrespeite a valorização do trabalho poderá ser entendida como inconstitucional. Há nítido confronto, pois, entre a cláusula de não concorrência e a liberdade ao trabalho ambas com amparo constitucional nos arts. 5º e 170 da CF. A resolução desse conflito é enfrentada à luz do princípio da proporcionalidade, que justifica e limita a aplicação da cláusula de não concorrência. Porém, para se chegar a tal ponto, antes se faz necessária passagem constitucional, acerca dos tradicionais métodos de interpretação constitucional chegando ao momento pós-positivista, cuidando-se da leitura dos princípios de interpretação constitucional como vetores de todo o ordenamento, diferenciando-os das regras, e relacionando-os com o uso do princípio da proporcionalidade e seus subprincípios da adequação, necessidade e proporcionalidade em sentido estrito. Daí se observa que a Constituição Federal preserva ambos os bens, e a interpretação constitucional deve ser levada a efeito de modo a harmonizar o conflito, de sorte que um direito ceda ao outro no caso concreto, sem que isso represente a completa exclusão do direito preterido, conservando-se a unidade do sistema e promovendo-se a concordância prática através da ponderação de bens. O princípio da proporcionalidade passa a ser conceituado e aferido em todas as suas nuances, demonstrando-se os prós e contras de seu uso como critério para resolução de conflitos na sociedade contemporânea. Passa-se à análise do direito contratual contemporâneo, em que a autonomia da vontade é mitigada frente à defesa dos direitos sociais, e a responsabilidade pós-contratual é inserida com fulcro nas cláusulas gerais. Com o uso de todos os fundamentos apontados, torna-se ao debate original, justificando e limitando a cláusula de não concorrência, apresentando as possibilidades de uso da cláusula de não concorrência pós pactum finitum em uma relação de desigualdade como é o caso da relação de emprego, valendo-se do princípio da proporcionalidade e seus subprincípios, indicando-se as posições da doutrina e jurisprudência, sem olvidar do direito estrangeiro

Les orogènes collisionnels sont classiquement décrits comme le résultat de l'accrétion continentale de marges proximales. Cette accrétion conduit à la surrection des reliefs et à l'export important de produits d'érosion dans les bassins d'avant-pays qui les jalonnent. Dans ce schéma géodynamique sont alors uniquement considérés les domaines pré-orogéniques les moins déformés. Pourtant, un nombre croissant d'évidences géologiques de terrain indiquent la conservation voire la réutilisation de structures héritées de la phase extensive précédant la convergence et la collision au coeur des orogènes. À partir de l'étude géo-thermochronométrique de la bordure orientale du domaine hyper-étiré nord-pyrénéen (massif de l'Agly, Zone Nord Pyrénéenne) et de son avant-pays précoce (synclinal de Rennes-les-Bains, Bassin Aquitain), cette thèse a pour objectifs de décrire l'évolution d'une marge distale au cours des premiers stades de convergence, de quantifier les processus source-réceptacle associés et d'apporter des contraintes temporelles et paléogéographiques quant à la création des tout premiers reliefs pyrénéens issus de son inversion. Grâce à l'utilisation du multi-thermochronomètre (U-Th)/He sur zircon et apatite, deux épisodes de refroidissement sont mis en évidence dans le prisme nord-pyrénéen (Campano-Maastrichtien et Eocène), chacun d'eux synchrone d'une phase de subsidence dans le bassin d'avant-pays. J'ai ainsi pu proposer un modèle équilibré d'évolution d'une marge distale hyper-amincie par inversion de structures héritées, chevauchements de socle et sous-placage continental se matérialisant par une signature thermochronologique claire de refroidissement sans érosion au début de la convergence. L'absence d'enregistrement de refroidissement au Paléocène par l'arrêt prématuré de l'inversion précoce dans le prisme nord-pyrénéen indique l'absence significative d'érosion et la position bordière de ce prisme par rapport à un édifice déjà construit plus à l'est à cette époque. Pour caractériser cet édifice aujourd'hui disparu du fait de l'ouverture du Golfe du Lion, j'ai utilisé une approche détritique de double datation in situ (U-Th)/He - U/Pb sur zircon et mis en évidence une histoire de dénudation rapide pendant le Campano-Maastrichtien, caractéristique de la création d'une topographie précoce. Ce travail montre pour la première fois clairement la migration progressive de la déformation d'est en ouest par l'inversion de structures héritées au début de la convergence pyrénéenne, ce qui suggère l'existence d'un domaine ouvert à l'est à la fin de l'épisode extensif précédant la convergence. Cette étude met en avant le rôle de l'architecture des systèmes hyper-amincis dans la formation des orogènes collisionnels et confirme les liens étroits existant entre un orogène et ses bassins d'avant-pays. / Collisional orogens are classically described as the result of continental accretion of proximal margins. This accretion leads to the creation of relief and to the important export of erosion products in the directly adjacent foreland basins. In this geodynamic scheme, only the least deformed pre-orogenic domains are considered. However, a growing number of geological field evidences indicate the preservation or even the reuse of structures inherited from the rifting phase preceding convergence and collision within orogens. By conducting a geo-thermochronometric study of the easternmost, inverted hyperextended Aptian-Cenomanian rift system (Agly massif, North Pyrenean Zone) and the adjacent early retroforeland (Rennes-les-Bains syncline, Aquitaine Basin), this thesis aims to describe the evolution of a distal rifted margin during the first stages of convergence, to quantify the associated source-to-sink processes and to provide temporal and paleogeographic constraints regarding the creation of the very first Pyrenean reliefs resulting from inversion of the margin. Using the zircon and apatite (U-Th)/He multi-thermochronometers, I show that the Pyrenean retro-wedge records two clear phases of orogenic cooling, Late Campanian-Maastrichtian and Ypresian-Bartonian, which I relate to early inversion of the distal rifted margin and main collision, respectively. I have thus been able to propose a crustal-scale sequentially restored model for the tectonic and thermal transition from extension to peak orogenesis in the eastern Pyrenees, which suggests that both thrusting and underplating processes contributed to early inversion of the Aptian-Cenomanian rift system. The absence of Paleocene cooling record indicates little to no erosion of the Pyrenean retro-wedge, suggesting the existence of a more easterly source area supplying early retroforeland sediments at this time. To characterize this eastern edifice, which has since been destroyed by the Oligocene-Miocene opening of the Gulf of Lion, I used in situ (U-Th)/He - U/Pb double dating on detrital zircons and show rapid denudation rates during early convergence, characteristic of early topographic growth. This work shows for the first time clearly the progressive migration of deformation from east to west by inversion of inherited structures at the beginning of Pyrenean convergence. This suggests the existence of an open domain in the east at the end of the rifting phase preceding convergence. This study highlights the role of the architecture of hyper-thinned systems in the formation of collisional orogens and confirms the close links between an orogen and its foreland basins.

Diversas aplicações industriais relevantes envolvem os processos de adsorção, citando como exemplos a purificação de produtos, separação de substâncias, controle de poluição e umidade entre outros. O interesse crescente pelos processos de purificação de biomoléculas deve-se principalmente ao desenvolvimento da biotecnologia e à demanda das indústrias farmacêutica e química por produtos com alto grau de pureza. O leito móvel simulado (LMS) é um processo cromatográfico contínuo que tem sido aplicado para simular o movimento do leito de adsorvente, de forma contracorrente ao movimento do líquido, através da troca periódica das posições das correntes de entrada e saída, sendo operado de forma contínua, sem prejuízo da pureza das correntes de saída. Esta consiste no extrato, rico no componente mais fortemente adsorvido, e no rafinado, rico no componente mais fracamente adsorvido, sendo o processo particularmente adequado a separações binárias. O objetivo desta tese é estudar e avaliar diferentes abordagens utilizando métodos estocásticos de otimização para o problema inverso dos fenômenos envolvidos no processo de separação em LMS. Foram utilizados modelos discretos com diferentes abordagens de transferência de massa, com a vantagem da utilização de um grande número de pratos teóricos em uma coluna de comprimento moderado, neste processo a separação cresce à medida que os solutos fluem através do leito, isto é, ao maior número de vezes que as moléculas interagem entre a fase móvel e a fase estacionária alcançando assim o equilíbrio. A modelagem e a simulação verificadas nestas abordagens permitiram a avaliação e a identificação das principais características de uma unidade de separação do LMS. A aplicação em estudo refere-se à simulação de processos de separação do Baclofen e da Cetamina. Estes compostos foram escolhidos por estarem bem caracterizados na literatura, estando disponíveis em estudos de cinética e de equilíbrio de adsorção nos resultados experimentais. De posse de resultados experimentais avaliou-se o comportamento do problema direto e inverso de uma unidade de separação LMS visando comparar os resultados obtidos com os experimentais, sempre se baseando em critérios de eficiência de separação entre as fases móvel e estacionária. Os métodos estudados foram o GA (Genetic Algorithm) e o PCA (Particle Collision Algorithm) e também foi feita uma hibridização entre o GA e o PCA. Como resultado desta tese analisouse e comparou-se os métodos de otimização em diferentes aspectos relacionados com o mecanismo cinético de transferência de massa por adsorção e dessorção entre as fases sólidas do adsorvente. / Several important industrial applications involving adsorption processes, citing as an example the product purification, separation of substances, pollution control and moisture among others. The growing interest in processes of purification of biomolecules is mainly due to the development of biotechnology and the demand of pharmaceutical and chemical products with high purity. The simulated moving bed (SMB) chromatography is a continuous process that has been applied to simulate the movement of the adsorbent bed, in a countercurrent to the movement of liquid through the periodic exchange of the positions of input and output currents, being operated so continuous, notwithstanding the purity of the outlet streams. This is the extract, rich in the more strongly adsorbed component, and the raffinate, rich in the more weakly adsorbed component, the method being particularly suited to binary separations. The aim of this thesis is to study and evaluate different approaches using stochastic optimization methods for the inverse problem of the phenomena involved in the separation process in LMS. We used discrete models with different approaches to mass transfer. With the benefit of using a large number of theoretical plates in a column of moderate length, in this process the separation increases as the solute flowing through the bed, i.e. as many times as molecules interact between the mobile phase and stationary phase thus achieving the equilibrium. The modeling and simulation verified in these approaches allowed the assessment and identification of the main characteristics of a separation unit LMS. The application under consideration refers to the simulation of the separation of Ketamine and Baclofen. These compounds were chosen because they are well characterized in the literature and are available in kinetic studies and equilibrium adsorption on experimental results. With the results of experiments evaluated the behavior of the direct and inverse problem of a separation unit LMS in order to compare these results, always based on the criteria of separation efficiency between the mobile and stationary phases. The methods studied were the GA (Genetic Algorithm) and PCA (Particle Collision Algorithm) and we also made a hybridization between the GA and PCA. This thesis, we analyzed and compared the optimization methods in different aspects of the kinetic mechanism for mass transfer between the adsorption and desorption of the adsorbent solid phases.

L'étude de l'irradiation dans le système moléculaire à l'échelle du nanomètre est un domaine d'investigation innovant des sciences des radiations. Le Dispositif d'Irradiation d'Agrégats Moléculaires (DIAM) est conçu en vue les conséquences de l'irradiation dans des petits systèmes moléculaires modèles comme les agrégats d'eau protonés. L'irradiation provoque la fragmentation en plusieurs fragments neutres ou chargés. La technique de spectrométrie de masse COINTOF (Correlated Ion and Neutral Time of Flight) permet la détection corrélées des fragments neutres et chargés issus de la dissociation d'un système moléculaire préalablement sélectionné en masse et en vitesse. Les données collectées sont traitées et structurées pour permettre l'analyse statistique des corrélations sur un grand nombre d'événements de fragmentation. Parallèlement à l'identification des canaux de fragmentation, la technique COINTOF permet la mesure de leur rapport de branchement et de leur section efficace. La méthode est présentée pour la dissociation induite par collision sur un atome d'argon, d'agrégats d'eau protonés H+(H2O)n:[2;7], accélérés à 8keV. L'efficacité de détection, information déterminante pour la production de données quantitatives, est mesurée à partir des données et étudiée en fonction de la distribution l'amplitude des signaux de détection. Enfin, un nouveau système de cible constituée de nanogouttes de gaz rares a été développé / The study of irradiation in molecular systems at the nanometer scale is an innovative field of research in radiation sciences. The DIAM set-up (Dispositif d'Irradiation d'Agrégats Moléculaires) is designed in order to observe and to characterize the consequences of radiation action on model molecular nanosystems such as protonated water clusters. Irradiation induces the fragmentation of the nanosystem in several neutral and charged fragments. The COINTOF (Correlated Ion and Neutral fragments Time of Flight) mass spectrometry techniques allows the correlated detection of the neutral and charged fragments resulting from the dissociation of a mass and velocity selected molecular system. The data processing is performed before the statistical analysis of the fragment production over a large number of fragmentation events. In parallel with the fragmentation channel identification, branching ratio and cross sections are measured with the COINTOF technique. The method is presented here for the collision induced dissociation on argon atoms of protonated water clusters H+(H2O)n, n=2-7, accelerated at 8keV. The detection efficiency, key parameter for the production of quantitative results, is measured from the set of data itself and studied as a function of the amplitude distribution of the detection signal. Finally, a new set-up for production of rare-gas nanodroplets target has been developed