Objetivo: Verificar a eficácia da associação do alongamento do tronco com exercícios de estabilização segmentar em pacientes com dor lombar crônica inespecífica (LCI). Métodos: Trinta e quatro indivíduos com diagnóstico de lombalgia crônica inespecífica de ambos os sexos, com idade entre 18 e 65 anos, foram randomizados em dois grupos: Grupo Alongamento Placebo + Estabilização Segmental (GAPES) e Grupo Alongamento + Estabilização Segmentar (GAES). Cada grupo realizou 12 sessões de tratamento de uma hora, duas vezes por semana. Os desfechos primários foram: intensidade da dor (Escala Numérica de Dor-END); avaliação qualitativa da dor (Questionário McGill-QMG); e incapacidade funcional (Questionário de Incapacidade de Rolland e Morris-QRM). Os desfechos secundários foram: percepção do efeito global (PEG); estado emocional (Inventário de Depressão de Beck-IDB e Escala Visual Analógica para Ansiedade-EVA-A); sinais e sintomas adversos; e satisfação do paciente (MedRisk). Cada sujeito foi avaliado no início e no fim do tratamento (seis semanas) e seguido três e seis meses após a intervenção. O nível de significância definido em alfa é igual a 0,05. Resultados: Não houve diferença significativa entre os dois grupos de tratamento na redução da intensidade e na qualidade da dor, na incapacidade funcional, na ansiedade e nos índices emocionais após o término do tratamento e durante o follow up. Conclusão: As duas propostas são efetivas no tratamento de LCI, com resultados estatisticamente significantes nos desfechos estudados. No entanto, a associação de exercícios de alongamento de tronco com os de estabilização segmentar não foi mais efetiva do que o uso isolado de estabilização segmentar lombar (ESL) / Objective: To verify the effectiveness of the association of trunk stretching with segmental stabilization exercises in patients with non-specific chronic low back pain (LCI) Methods: Thirty-four individuals with a diagnosis of non-specific chronic low back pain of both sexes, aged between 18 and 65 years. They were randomized into two groups: Group Stretching Placebo + Segmental Stabilization (GSPSS) and Group Stretching + Segmental Stabilization (GSSS), each group received 12 sessions of one hour, twice a week. The primary outcomes were pain intensity (Numerical Rating Scale-NRS); qualitative pain assessment (McGill Questionnaire); functional disability (Rolland and Morris Questionnaire-RMQ). The secondary outcomes were perception of the overall effect Global Effect; emotional state (Beck Depression Inventory-BDI and Analog Visual Scale for Anxiety-VAS-A); adverse signs and symptoms; and patient satisfaction (MedRisk). Each subject was assessed at the baseline and in the end of treatment (six weeks) and followed up three and six months post-intervention. The significance level set at Alpha = 0.05. Results: There was no significant difference between the two treatment groups in reducing intensity and quality of pain, functional disability, anxiety and emotional indexes after the end of the treatment and during follow up. Conclusion: The two treatment proposals are effective in the treatment of LCI, with statistically significant results in the outcomes studied, but the association of trunk elongation exercises with those of segmental stabilization was not more effective than the isolated use of ESL

L'imagerie par Résonance Magnétique (IRM) cardiaque est un domaine qui nécessite d'adapter la séquence au rythme du coeur, afin d'éviter le flou causé par un temps d'acquisition long devant les constantes de temps du mouvement. Ainsi, les temps séparant les impulsions radio-fréquence (RF) de la séquence sont aussi variables que les durées des cycles cardiaques sur lesquels on synchronise l'acquisition. Cela est cause d'imprécision sur l'image résultante, en particulier dans son caractère quantitatif. L'aimantation des spins n'est effectivement pas dans un état d'équilibre sur toute l'acquisition. La thèse présente deux axes principaux de recherche explorés ; le premier est une étude de l'impact de la variation du rythme cardiaque (présentée en outre dans le manuscrit) sur la mesure quantitative du temps de relaxation transversal T2. L'étude a été menée sur des objets fantômes et sur des volontaires sains. Deux méthodes de correction de la variation du rythme sont proposées, l'une basée sur la correction du signal au centre de l'espace de Fourier, l'autre basée sur une approche de reconstruction généralisée. Les résultats préliminaires sont encourageants, et des travaux ultérieurs seraient à entreprendre pour confirmer l'efficacité de ces méthodes. Ensuite, les variations temporelles du cycle cardiaque sont traitées à l'échelle d'un cycle, et nous proposons une méthode de mise en coïncidence des différents segments de l'électrocardiogramme (ECG) basée sur la déformation de l'ECG dans l'IRM probablement par effet magnétohydrodynamique. Cette méthode est mise au service de l'imagerie dans le cadre d'une séquence cinétique CINE dans laquelle une meilleure mise en correspondance des segments de cycles cardiaques successifs devrait permettre de gagner en qualité d'image, à condition d'avoir des résolutions spatiale et temporelle suffisamment fines. Les résultats apportés au cours de cette thèse sont préliminaires à de futures recherches nécessaires dans le domaine temporel de la séquence, beaucoup moins traité que le mouvement des organes / Cardiac Magnetic Resonance Imaging (MRI) requires to adapt the sequence to heart rate, so as to avoid the blur caused by the acquisition time longer than motion time constants. Thus, times between sequence radiofrequency pulses are as much variable as synchronization cardiac cycles durations. It causes imprecision on the resulting image, particularly for quantification. In fact, spins magnetization is not in a steady state during the acquisition. Two main research axis are presented in this thesis; the first one is a study of the impact of heart rate variation (described in the manuscript) on the transversal relaxation time T2 quantitative measurement. The study was lead on both phantom objects and on healthy volunteers. Two correction methods for heart rate variation are proposed, one based on the correction of the signal of the central line of the k-space, the other one based on a generalized reconstruction approach. First results are encouraging, and further works should be lead to confirm the methods efficacity. Then, heart rate variations are treated inside the cardiac cycle, and we propose a method to match the different segments of the electrocardiogram (ECG), based on the ECG deformation in the MR scanner probably due to by magnetohydrodynamic effect. This method is applied on imaging with a CINE kinetic sequence in which a better successive cardiac cycles segments matching should enable to improve image quality, at the condition to have sharp enough spatial and temporal resolutions. Results brought in this thesis are preliminary to necessary future researches in the sequence time domain, largely less addressed than organ motion

Objetivo: Exercícios de mobilização são aplicados em pacientes com Espondilite Anquilosante (EA) para preservar e restaurar a mobilidade axial, no entanto, não há descrição na literatura, de um programa específico de reabilitação compreendendo apenas exercícios de mobilização com e sem a associação de exercícios com resistência elástica em pacientes com EA. Assim, foram avaliados os efeitos de dois programas de exercícios quanto a mobilidade, capacidade funcional, qualidade de vida e atividade de doença em pacientes com EA. Métodos: Cinquenta e cinco pacientes com EA, sedentários, com Índice Bath de atividade de doença da Espondilite Anquilosante (BASDAI) < 4 foram incluídos no estudo. Os pacientes com EA foram alocados ao acaso em três grupos, um grupo foi prescrito exercícios de mobilização (M), um com o programa de mobilização mais exercícios de resistência elástica (M+R) e um grupo controle sem exercícios (C). As sessões de exercícios foram realizadas em grupos, duas vezes por semana, por 16 semanas, e todas as sessões foram supervisionadas. Os grupos M e M+R realizavam 30 minutos de alongamentos e exercícios de mobilidade para coluna, membros superiores e inferiores. Depois do programa de mobilização, apenas o grupo M+R realizava mais 30 minutos de exercícios com resistência elástica. A mobilidade, qualidade de vida, atividade de doença e parâmetros de atividade funcional foram avaliados no início do programa e depois de 16 semanas por um avaliador cego. Resultados: No início do estudo, a média de idade dos pacientes (DP) era 48,2 anos ( ± 11,7); tempo de doença 18,4( ± 9,9) anos; BASDAI 2,2( ± 1,2); escore global Bath de espondilite anquilosante (BAS-g) de 4,2( ± 2,3) Índice funcional Bath (BASFI) de 3,6( ± 2,4) e Índice de mobilidade Bath (BASMI) de 4,6( ± 2,1). Comparando valores iniciais e após 16 semanas o grupo M mostrou uma melhora significante no Índice BASMI e o grupo M+R apresentou uma melhora significante no BASMI e na expansibilidade torácica. BAS-g, BASDAI e BASMI foram significantemente piores no grupo C. Não houve diferença significante entre os grupos M e M+R, mas foi encontrada diferença estatisticamente significante entre os grupos C e M+R nos índices BASDAI, ASDAS e BASFI a favor do grupo M+R. Conclusão: Os programas de exercícios terapêuticos foram seguros e efetivos. O programa de mobilização promoveu benefícios apenas nos parâmetros de mobilidade articular. Os pacientes que realizaram programa de exercícios com resistência elástica além de apresentarem melhora na mobilidade articular, apresentaram melhora da atividade de doença e função quando comparado aos controles no fim do tratamento / Objective: Mobility exercises are used in Ankylosing Spondylitis (AS) patients to preserve and restore axial mobility, but there are no data regarding a specific rehabilitation program that includes mobility alone and its association with elastic resistance exercises in AS patients with stable disease activity. So, we assessed the effects of two exercise programs in terms of mobility, functional capacity, quality of life and disease activity in AS patients. Methods: Fifty-five sedentary AS patients with a Bath Ankylosing Spondylitis Activity Index (BASDAI) <4 were included. The AS patients were randomly assigned into three groups, to receive a mobility exercise program (M), or mobility plus elastic resistance exercise program (M+R) or no exercise (C). The exercises group sessions were conducted twice per week for 16 weeks. This supervised program comprised 30 minutes of outdoor stretching and mobility exercises for the spine and limbs (M). After the mobility program, M+R group carry out more 30 minutes of elastic resistance exercises. The mobility, disease activity and functional parameters were evaluated at baseline and after 16 weeks, with the evaluator blinded to the treatment group. Results: At study entry, the patients had a mean (SD) age of 48,2 years ( ± 11,7), disease duration of 18,4( ± 9,9) years, BASDAI 2,2( ± 1,2), Bath AS Global score (BAS-g) 4,2( ± 2,3) Bath AS functional Index (BASFI) of 3,6( ± 2,4) and Bath AS Metrology Index (BASMI) of 4,6( ± 2,1). Comparing the baseline to 16 weeks, group M showed a significant improvement in BASMI and M+R group showed significant improvement in BASMI and chest expansion. BAS-g, BASDAI and BASMI was significantly worst in C group. No significant differences between M+R group and M group were perceived but there were significant differences in BASDAI, ASDAS and BASFI scores between C group and M+R group in favor of M+R group. Conclusion: Therapeutic exercises programs were effective and safe. The mobility exercises program promoted benefits only in joint mobility parameters. The exercise program with elastic resistance besides those benefits for joint mobility, also improved function and disease activity comparing to controls at the end of the program

The spectral-element method (SEM) is used to study wall-bounded turbulent flowsin moderately complex geometries. The first part of the thesis is devoted to simulations of canonical flow cases, such as temporal K-type transitionand turbulent channel flow, to investigate general resolution requirements and computational efficiency of the numerical code nek5000. Large-eddy simulation (LES) is further performed of a plane asymmetric diffuser flow with an opening angle of 8.5 degrees, featuring turbulent flow separation. Good agreement with numerical studies of Herbst (2007) is obtained, and it is concluded that the use of a high-order method is advantageous for flows featuring pressure-induced separation. Moreover, it is shown, both a priori on simpler model problems and a posteriori using the full Navier--Stokes equations, that the numerical instability associated with SEM at high Reynolds numbers is cured either by employing over-integration (dealiasing) or a filter-based stabilisation, thus rendering simulations of moderate to high Reynolds number flows possible. The second part of the thesis is devoted to the first direct numerical simulation (DNS) of a truly three-dimensional, turbulent and separated diffuser flow at Re = 10 000 (based on bulk velocity and inflow-duct height), experimentally investigated by Cherry et al. (2008). The massively parallel capabilities of the spectral-element method are exploited by running the simulations on up to 32 768 processors. Very good agreement with experimental mean flow data is obtained and it is thus shown that well-resolved simulations of complex turbulent flows with high accuracy are possible at realistic Reynolds numberseven in complicated geometries. An explanation for the discovered asymmetry of the mean separated flow is provided and itis demonstrated that a large-scale quasi-periodic motion is present in the diffuser. In addition, a new diagnostic measure, based on the maximum vorticity stretching component in every spatial point, is designed and tested in a number of turbulent and transitional flows. Finally, Koopman mode decomposition is performed of a minimal channel flow and compared to classical proper orthogonal decomposition (POD). / QC 20111206

No description available.

Le contrôle de santé structural ou Structural Health Monitoring (SHM) des matériaux constitue une démarche fondamentale pour la maîtrise de la durabilité et de la fiabilité des structures en service. Au-delà des enjeux industriels et humains qui ne cessent de s'accroître en termes de sécurité et de fiabilité, le contrôle de santé doit faire face à des exigences de plus en plus élaborées. Les nouvelles stratégies de contrôle de santé doivent non seulement détecter et identifier l'endommagement mais aussi quantifier les différents phénomènes qui en sont responsables. Pour atteindre cet objectif, il est nécessaire d'accéder à une meilleure connaissance des processus d'endommagement. Par ailleurs, ceux-ci surviennent fréquemment sous l'effet de sollicitations mécaniques et environnementales. Ainsi, il est indispensable, d'une part, d'élaborer des méthodes de traitement des signaux permettant d'estimer les effets des conditions environnementales et opérationnelles, dans un contexte de l'analyse des événements précurseurs des mécanismes d'endommagement, et, d'autre part, de définir les descripteurs d'endommagement les plus adaptés à cette analyse. Cette étude propose donc des méthodes de traitement du signal permettant d'atteindre cet objectif, dans un premier temps, pour l'estimation des effets externes sur les ondes multidiffusées dans un contexte de contrôle de santé actif et, dans un second temps, pour l'extraction d'un indicateur d'endommagement à partir de l'analyse des signaux d'émission acoustique dans un contexte de contrôle de santé passif. Dans la première partie de ce travail, quatre méthodes de traitement du signal sont proposées. Celles-ci permettent de prendre en compte les variations des conditions environnementales dans la structure, qui dans le cadre de cette thèse, se sont limitées au cas particulier du changement de la température. En effet, les variations de température ont pour effet de modifier les propriétés mécaniques du matériau et par conséquent la vitesse de propagation des ondes ultrasonores. Ce phénomène entraîne alors une dilatation temporelle des signaux acoustiques qu'il convient d'estimer afin de suivre les variations de température. Quatre estimateurs de coefficients de dilatation sont alors étudiés : Il s'agit de l'intercorrélation à fenêtre glissante, utilisée comme méthode de référence, la méthode du stretching, l'estimateur à variance minimale et la transformée exponentielle. Les deux premières méthodes ont été déjà validées dans la littérature alors que les deux dernières ont été développées spécifiquement dans le cadre de cette étude. Par la suite, une évaluation statistique de la qualité des estimations est menée grâce à des simulations de Monte-Carlo utilisant des signaux de synthèse. Ces signaux sont basés sur un modèle de signal multidiffusé prenant en compte l'influence de la température. Une estimation sommaire de la complexité algorithmique des méthodes de traitement du signal complète également cette phase d'évaluation. Enfin, la validation expérimentale des méthodes d'estimation est réalisée sur deux types de matériaux : Tout d'abord, dans une plaque d'aluminium, milieu homogène dont les caractéristiques sont connues, puis, dans un second temps dans un milieu fortement hétérogène prenant la forme d'une plaque composite en verre/epoxy. Dans ces expériences, les plaques sont soumises à différentes températures dans un environnement thermique contrôlé. Les estimations de température sont alors confrontées à un modèle analytique décrivant le comportement du matériau. La seconde partie de ce travail concerne la caractérisation in situ des mécanismes d'endommagement par émission acoustique dans des matériaux hétérogènes. Les sources d'émission acoustique génèrent des signaux non stationnaires...

Η παρούσα διδακτορική διατριβή αποτελείται από δύο ξεχωριστές ενότητες οι οποίες έχουν σαν στόχο τη μελέτη τροποποιημένων πολυμερικών μεμβρανών για χρήση σε κυψελίδες καυσίμου αγωγής πρωτονίων και σε εφαρμογές διαχωρισμού αερίων. Στην πρώτη ενότητα έγινε εκτίμηση του μοριακού προσανατολισμού μονοαξονικά εφελκυσμένων πολυμερικών μεμβρανών Nafion-115 με τη βοήθεια πολωμένων φασμάτων UV-Raman. Πειράματα δυναμικής μηχανικής ανάλυσης επαλήθευσαν τις προσδοκίες για βελτίωση των μηχανικών ιδιοτήτων του πολυμερικού ηλεκτρολύτη κατά μήκος της διεύθυνσης εφελκυσμού. Η θερμική ανάλυση των δειγμάτων με τις τεχνικές της διαφορικής θερμιδομετρίας σάρωσης και της θερμοσταθμικής ανάλυσης δεν έδειξε κάποια ιδιαίτερη διαφοροποίηση μεταξύ εφελκυσμένων και μη δοκιμίων Nafion-115, πέραν της βελτίωσης της ικανότητας των τανυσμένων μεμβρανών να συγκρατούν το όποιο νερό υπάρχει στο ιονομερές. Μικρή ήταν η αύξηση της ιοντικής αγωγιμότητας που παρατηρήθηκε στα τανυσμένα δείγματα κατά μήκος της διεύθυνσης εφελκυσμού. Η προσπάθεια τροποποίησης του Nafion® με διαξονικό εφελκυσμό είχε σαν αποτέλεσμα τη λήψη λεπτών πολυμερικών ηλεκτρολυτικών μεμβρανών με αποτελεσματικότερες ιδιότητες στην τάση διέλευσης της μεθανόλης, σε σχέση με τις μη τροποποιημένες μεμβράνες. Επιπρόσθετα, με τον ελεγχόμενο διαξονικό και σταθερού πλάτους μονοαξονικό εφελκυσμό κατέστη δυνατό να επιτευχθεί η εξισορρόπηση των ποσοστών διαστολής κατά το μήκος και πλάτος της επιφάνειας του Nafion, μετά τον εμποτισμό του με νερό. Όσον αφορά στην τροποποίηση του Nafion με εναπόθεση στοιβάδας αγώγιμου πολυμερούς πολυανιλίνης (PAni) ή πολυπυρρόλης (PPy) με ενσωματωμένα αντισταθμιστικά ιόντα SO42- ή Nafion-, η φασματοσκοπική μελέτη, μέσω ATR-FTIR, σε συνδυασμό με τις μικροφωτογραφίες SEM που ελήφθησαν, οδήγησαν στα εξής συμπεράσματα: Για τις σύνθετες μεμβράνες Nafion/PAni που παρασκευάστηκαν με την τεχνική της διάχυσης, από τη μία ελήφθησαν δείγματα με ικανοποιητική συνάφεια μεταξύ του κυρίως όγκου της πολυμερικής μεμβράνης Nafion και της PAni, από την άλλη όμως, υπάρχει και κάποιο ποσοστό μονομερούς ανιλίνης (Ani) που εγκλωβίζεται στο εσωτερικό του Nafion, και μάλιστα σε σημαντικό βαθμό, που εξαρτάται από το χρόνο σύνθεσης. Αντίθετα, οι αντίστοιχες μελέτες στις μεμβράνες Nafion/PPy δε φανερώνουν την ύπαρξη διείσδυσης της PPy ή του μονομερούς στην κύρια μάζα του Nafion, ή τουλάχιστον όχι σε τέτοιο βαθμό που να μπορεί να ανιχνευθεί μέσω της τεχνικής που χρησιμοποιήθηκε. Ιδιαίτερο είναι το ενδιαφέρον που προκύπτει από τις φασματοσκοπικές μετρήσεις στην πλευρά του σύνθετου πολυμερούς όπου εναποτίθετο το πολυμερισμένο αγώγιμο υλικό, καθώς με το χρόνο σύνθεσης παρατηρούνται μετατοπίσεις κορυφών του Nafion προς χαμηλότερες συχνότητες, υποδεικνύοντας ενδεχόμενη αλληλεπίδραση με το αγώγιμο πολυμερές. Στη δεύτερη ενότητα μελετήθηκαν οι σύνθετες (ή “mixed matrix”) πολυμερικές μεμβράνες πολυσουλφόνης (PSF) με ενσωματωμένες φυλλώδεις αργυλοφωσφορικές νανονιφάδες τύπου AlPO. Αρχικά πραγματοποιήθηκε η σύνθεση των νανονιφάδων AlPO. Με στόχο τη βελτίωση της συμβατότητάς τους με την πολυμερική μήτρα έγινε παρεμβόλιση με κατάλληλη επιφανειοδραστική ουσία και χαρακτηρισμός με XRD που έδειξε τη διεύρυνση της απόστασης μεταξύ των διαδοχικών στρωμάτων του κρυστάλλου από 9Å σε 33Å περίπου. Στη συνέχεια παρασκευάσθηκαν οι σύνθετες μεμβράνες με διαφορετικές συγκεντρώσεις της ανόργανης φάσης, με τη μέθοδο του film casting. Με βάση τις εικόνες SEM οι νανονιφάδες φαίνεται να έχουν ικανοποιητική διασπορά στη μάζα της πολυσουλφόνης, ενώ τα φάσματα XRD δείχνουν πως η ενσωμάτωση των παρεμβολισμένων νανονιφάδων στην πολυμερική μήτρα δεν επέφερε κάποια σημαντική αλλαγή στη δομή τους. Οι νανονιφάδες, ακόμα και σε μικρές συγκεντρώσεις, βελτιώνουν σε σημαντικό βαθμό τη διαχωριστική ικανότητα των αμιγώς πολυμερικών μεμβρανών για τα ζεύγη αερίων H2/N2 και Η2/CH4 όχι όμως και για το ζεύγος Η2/CO2. Αντίθετα, η αύξηση του ποσοστού των νανονιφάδων AlPO οδηγεί σε μείωση της διαπερατότητας του H2. Oι σύνθετες μεμβράνες PSF/AlPO δείχνουν μια μικρή βελτίωση του μέτρου ελαστικότητας αποθηκευόμενης ενέργειας σε σχέση με τις πολυμερικές μεμβράνες PSF, εμφανίζουν επίσης ελαφρώς μειωμένη θερμοκρασία υαλώδους μετάβασης και, κατά τη θέρμανσή τους, ακολουθούν τρία στάδια απώλειας μάζας λόγω αποσύνθεσης της επιφανειοδραστικής ουσίας σε συνδυασμό με απώλεια φυσικά και χημικά ροφημένου νερού. / The present thesis consists of two separate parts which focus on the study of modified polymer membranes for use in fuel cells applications and gas separation processes. In the first part, the molecular orientation of uniaxially drawn Nafion-115 membranes was estimated utilizing polarized UV-Raman spectra. Dynamic mechanical analysis revealed the enhanced strength of the drawn samples along the draw axis. Thermal analysis, carried out via differential scanning calorimetry, and thermogravimetric analysis did not show any difference between drawn and undrawn specimens, except from a slight enhanced capability of the drawn membranes to water content retain. Proton conductivity is slightly enhanced along the stretching direction, as well. The attempts for biaxial stretching of Nafion® had as a result the production of very thin polymer electrolyte membranes with lower permeability to methanol than the commercial one. In addition, with biaxial and constant width uniaxial stretching, the swelling of Nafion along and across its surface can be controlled. The process of modifying Nafion by embedding conducting polymer layers of polypyrrole or polyaniline with SO42- or Nafion- incorporated into the film as counter-ions is studied via ATR-FTIR spectroscopy in combination with SEM microphotographs. Nafion/PAni composite membranes synthesized by the diffusion method showed very good adherence between Nafion and PAni layers but it seems that there is some Ani monomer still remaining inside the bulk structure of Nafion, depending on the time of synthesis. In contrast, the corresponding studies on Nafion/PPy membranes show that there is no penetration of PPy or Py inside Nafion, at least not to the extent that it could be traced using ATR-FTIR spectroscopy. The spectroscopic measurements from the conducting polymer side show red-shifts of absorption bands of Nafion revealing possible specific interactions with the conducting polymer. In the second part, composite (or mixed matrix) polymeric membranes with dispersed aluminophosphate nanoflakes were studied. At the beginning AlPO nanoflakes were synthesized. To enhance the compatibility with the polymer matrix conventional AlPO nanoflakes were intercalated using suitable surfactant. XRD characterization showed a further individual layers` separation since the distance between them is increased from 9Å to 33Å. Subsequently, mixed matrix membranes with different nanoflakes loading were synthesized, using film casting method. Based on SEM images nanoflakes seem to be well dispersed in the mass of polysulfone, while XRD graphs implied that the incorporation of intercalated nanoflakes into the polymer matrix did not affect their structural characteristics. Nanoflakes incorporation, even at very low concentrations, improves the H2/N2 and H2/CH4 selectivity and deteriorates the H2/CO2 selectivity compared with the pure polymer. On the other hand, the higher the percentage of the AlPO flakes, the more pronounced the decrease in hydrogen permeability. PSF/AlPO membranes exhibit improved storage modulus, appear to have slightly lower glass transition temperature compared with PSF membranes and during their heating, follow a three steps mass loss due to the surfactant decomposition and the loss of physically and chemically absorbed water.

Orientador: Gabriela Rezende Fernandes / Resumo: Neste trabalho é apresentada uma formulação do MEC (Método dos Elementos de Contorno) considerando-se não-linearidade física para analisar microestruturas de materiais heterogêneos no contexto da análise em multi-escala. A microestrutura, também denominada como EVR (Elemento de Volume Representativo), é modelada como uma chapa em sub-regiões onde vazios ou inclusões podem ser considerados dentro da matriz, sendo diferentes propriedades elásticas e modelos constitutivos definidos para cada sub-região. A equação integral para o deslocamento é obtida a partir do Teorema de Betti, onde para considerar o fenômeno dissipativo, um campo de esforços iniciais é considerado. A equação algébrica da chapa é obtida após a discretização do contorno externo e interface em elementos e do domínio das subregiões em células. Na análise multi-escala cada ponto da estrutura (macrocontínuo) é representado por um EVR, onde o comportamento do material não é definido por um modelo constitutivo, mas através da solução do problema de equilíbrio do EVR quando sujeito à deformação referente ao ponto do macrocontínuo. O problema de equilíbrio do EVR é definido em termos da flutuação dos deslocamentos, sendo o mesmo satisfeito quando seu campo de forças se encontra em equilíbrio. Após a solução do EVR, os deslocamentos no contorno e as forças dissipativas são atualizados e as forças de superfície sobre o contorno recalculadas para se obter a tensão homogeneizada. O custo computacional obtido com a presente... (Resumo completo, clicar acesso eletrônico abaixo) / Mestre

Made available in DSpace on 2016-06-02T20:18:08Z (GMT). No. of bitstreams: 1 TeseMAMO.pdf: 4078900 bytes, checksum: 4421c9cd008941297c1f599867d52654 (MD5) Previous issue date: 2007-06-29 / Stretching by the global postural re-education method (GPR) has been widely used as a physical therapeutic procedure for postural alterations, but its action on the cardio-respiratory system has been little documented. However, scientific evidence is necessary to validate it as an alternative treatment. Within this context, three studies were carried out with the objective of verifying the effect of stretching the respiratory muscle chain in the open-arm, open hip joint angle posture by the GPR method on cardio-respiratory responses. Twenty young (22.7±2.5 years old), healthy, sedentary (VO2max: 30.2±4.3 mL.kg.min-1) men with BMI = 25.3±1.5 kg/m2 were studied, divided at random into two groups of ten: the control group (CG) that did not take part in the stretching and the group submitted to treatment (GPR-G). The intervention consisted of two weekly stretching sessions, each of 30 min, for eight weeks, giving a total of 16 sessions. In the first study, the maximal respiratory pressure and the respiratory coefficient were assessed by way of a manovacuometer and thoracoabdominal cirtometry, respectively. Only the GPR-G presented greater values for inspiratory (IPmax) and expiratory (EPmax) maximal pressures and for axillary, xyphoid and abdominal cirtometry after the intervention period. The results showed that the method caused a beneficial effect on respiratory muscle force and on thoracoabdominal mobility, contributing to an improvement in respiratory mechanics. In the second study, pulmonary function was assessed by spirometry. The manoeuvres of slow vital capacity (SVC), forced vital capacity (FVC) and maximal voluntary ventilation (MVV) were carried out. The results showed there was a significant increase in the values for SVC, inspiratory capacity (IC), FVC, forced expiratory volume in the first second (FEV1) and MVV for the GPR-G after the training period, providing evidence that the proposed stretching was efficient in promoting an increase in pulmonary capacity and volume. In the third study, the effect of stretching on the autonomic modulation of the heart rate (HR) and on the ventilatory and metabolic variables was assessed at rest and during the cardio-pulmonary exercise test respectively. The ventilatory and metabolic variables were captured using an automatic metabolic system and the HR using a one-channel heart monitor. The exercise test was carried out using a cycle ergometer, with 20 to 25 W/min increments up to physical exhaustion. Intervention did not change the variables studied either at rest or during the cardio-pulmonary exercise test, for either of the groups. These results showed that the respiratory muscle chain stretching exercise did not promote any adaptations with respect to HR neither at rest and the ventilatory and metabolic variables during the exercise, which could be attributed to the noninvolvement of the major muscle groups in the type of protocol used. Finally, the results obtained in the three studies gave evidence that stretching the respiratory muscle chain by the GPR method was efficient in promoting an increase in respiratory muscle strength, thoracoabdominal mobility and pulmonary function, reflecting in an increase in respiratory mechanics, this fact being attributable to the specificity of the training. In this way, the findings of the present study, reinforce the importance of the GPR method in the maintenance of the functional capacity of the respiratory chain muscles, suggesting that it could be used as an alternative treatment for dysfunctions of the respiratory mechanics. / O alongamento pelo método de reeducação postural global (RPG) tem sido muito utilizado como conduta fisioterapêutica em alterações posturais, porém, sua ação sobre o sistema cardiorrespiratório é pouco documentada. No entanto, as evidências científicas são necessárias para sua validação como alternativa de tratamento. Dentro desse contexto, foram realizados três estudos com o objetivo de verificar o efeito do alongamento da cadeia muscular respiratória na postura rã no chão com os braços abertos do método de RPG sobre as respostas cardiorrespiratórias. Foram estudados 20 homens jovens (22,7±2,5 anos), saudáveis, sedentários (VO2max: 30,2±4,3 mL.kg.min-1) e com IMC = 25,3±1,5 kg/m2, divididos aleatoriamente em dois grupos de dez: grupo controle (G-C) que não participou do alongamento e grupo submetido ao treinamento (G-RPG). A intervenção consistiu em duas sessões semanais de alongamento de 30 min cada, durante oito semanas, totalizando 16 sessões. No primeiro estudo, foram avaliadas as pressões respiratórias máximas e o coeficiente respiratório, por intermédio da monovacuometria e da cirtometria toracoabdominal, respectivamente. Somente o G-RPG apresentou maiores valores das pressões inspiratórias (PImáx) e expiratórias (PEmáx) máximas e da cirtometria axilar, xifoideana e abdominal após o período de intervenção. Os resultados mostraram que o método teve um efeito benéfico na força muscular respiratória e na mobilidade toracoabdominal, contribuindo para a melhora da mecânica respiratória. No segundo estudo, foi avaliada a função pulmonar por intermédio da espirometria. Foram realizadas as manobras de capacidade vital lenta (CVL), capacidade vital forçada (CVF) e ventilação voluntária máxima (VVM). Os resultados mostraram que houve aumento significativo dos valores da CVL, capacidade inspiratória (CI), CVF, volume expiratório forçado no primeiro segundo (VEF1) e VVM do G-RPG após o período de treinamento, evidenciando que o alongamento proposto foi eficiente para promover aumento dos volumes e capacidades pulmonares. No terceiro estudo, foi avaliado o efeito do alongamento nas variáveis ventilatórias e metabólicas durante o teste de exercício cardiopulmonar e na modulação autonômica da freqüência cardíaca (FC) em repouso. As variáveis ventilatórias e metabólicas foram captadas a partir de um sistema metabólico automático, e a FC a partir de um monitor cardíaco de um canal. O teste de exercício foi realizado em cicloergômetro, com incrementos de 20 a 25 W/min até a exaustão física. A intervenção não modificou as variáveis estudadas em nenhum dos grupos. Esses resultados mostram que o exercício de alongamento da cadeia muscular respiratória não promoveu adaptações na FC e em sua variabilidade em repouso e nas variáveis ventilatórias e metabólicas durante o exercício, o que pode ser atribuído ao não envolvimento de grandes grupos musculares no tipo de protocolo utilizado. Finalizando, os resultados obtidos nos três estudos evidenciaram que o alongamento da cadeia muscular respiratória pelo método de RPG mostrou-se eficiente para promover aumento da força muscular respiratória, mobilidade toracoabdominal e função pulmonar, refletindo na melhora da mecânica respiratória, sendo que tal fato pode ser atribuído à especificidade do treinamento. Desse modo, nossos achados reforçam a importância do método de RPG para manutenção da capacidade funcional dos músculos da cadeia respiratória, sugerindo que a postura utilizada pode ser coadjuvante no tratamento das disfunções da mecânica respiratória.

In this thesis, I have investigated gas phase infrared spectroscopy of environmentally as well as astrophysical important large organic molecules such as naphthalene, methy-lated naphthalene, fluorine, methyalted fluorine etc. which are commonly known as polycyclic aromatic hydrocarbons (PAHs). Depending upon the molecular weight these organic molecules can exist both in gaseous as well as in the particulate state at room temperature hence they are the major environmental pollutants. They are also responsible for the unidentified infrared emission bands in the interstellar medium. Chapter 1 provides a brief introduction to my thesis work. A detailed literature survey on the importance, abundance of the PAHs in the environment as well as various spectroscopic techniques useful for identifying the PAHs has been done. Since the objective of my thesis work is to assign the observed fundamental infrared bands of large organic molecules with the help of high level quantum mechanical calculations, a brief introduction to the various high level quantum mechanical techniques that I have used in assigning the bands have been described in this chapter. In Chapter 2 I have presented the experimental and the theoretical methodologies in details. The chapter begins with a detailed description of the experimental procedure used for recording the infrared spectrum of these molecules followed by the theoretical methodologies used for the assignment of the observed infrared bands as well as for identifying the Fermi resonances. In Chapters 3 and 4, of this thesis I have recorded infrared spectrum of 1-and 2-methylnaphthalene (1-and 2-MN), fluorine (FL), 1-methylfluorene (1-MFL) and 1,8-dimethylfluorene (1,8-DMF) in the gas phase. The observed bands were assigned with the help of scaled harmonic frequency, scaled quantum mechanical harmonic force field (SQMFF) and enharmonic frequency calculations. The first two methods are based on the harmonic approximation, whereas the enharmonic frequency calculation is based on the standard second order perturbation theory. All these calculations gave me a partial fit to the fundamental bands in both aromatic and aliphatic C-H stretching as well as in the non C-H stretching region. At the end of both the chapters an error analysis in fitting the spectrum from all the three different calculations have been presented. Evidently the non linear least square fitting method employed in SQMFF calculation gives much better agreement between the experiment and theory than the other two methods. It has been observed in the experimental spectrum of methylated naphthalene that the band structure near the C-H stretch around 3000 cm−1 is very complicated and many bands and shoulders remain unassigned by the methods described in Chapters 3 and 4. Fermi resonance is one of the potential reason for the complicated band structure in this region. In Chapter 5, I have taken naphthalene and have investigated the Fermi resonance around the C-H stretching region using an effective vibrational hamiltonian (EVH) approach. In this method I have constructed an EVH consisting of 8 C-H stretches and 8 H-C-C in-plane bend overtones and 28 H-C-C in-plane bend combination modes as the basis. Both type 1 (stretch overtone) and type 2 (stretch combination) Fermi resonances were investigated. Calculated frequencies belonging to B1u and B2u irreducible representation were compared with the observed bands. Many bands and shoulders have been assigned as the overtone and combination modes of low frequency H-C-C bend motion obtained from the EVH approach. How-ever some bands remain unassigned in this method. This is perhaps due to the neglect of the carbon framework motion in the construction of the EVH. To improve upon the results obtained from the EVH formalism I included the carbon frame degrees of freedom and have carried out a full variation treatment in curvilinear coordinates. I have considered the 8 C-H stretches and 8 H-C-C in-plane bends of naphthalene as local mode oscillators and 17 coordinates belonging to the carbon framework motion as curvilinear normal mode oscillators. A quartic hamiltonian in a mixed local mode -normal mode basis was constructed including up to three body terms in both kinetic and potential energy part. The hamiltonian was subsequently recast into the ladder operator form and diagonal zed in a symmetry adapted basis with polyad constraints. Frequencies so obtained were compared to the experiment All these findings have been presented in Chapter 6 of this thesis. The concluding remark of the thesis and the future direction is presented in Chapter 7