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Modelagem NumÃrico-AnalÃtica da ContaminaÃÃo de AqÃÃferos Utilizando o MÃtodo de ColocaÃÃo RBF Livre de Malha / Numerical Analytical Modeling of Aquifer Contamination Using The RBF Meshfree Collocation MethodGermana Cavalcante Menescal 30 April 2008 (has links)
CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / O aumento da capacidade dos computadores nessas trÃs ultimas dÃcadas tem tornado possÃvel a soluÃÃo de problemas de engenharia cada vez mais complexos. Essa ampliaÃÃo na possibilidade de soluÃÃo de tais problemas à resultado do avanÃo nos mÃtodos numÃricos e do desenvolvimento de algoritmos eficientes. Entretanto, estes mÃtodos numÃricos sÃo baseados na construÃÃo de malhas de discretizaÃÃo e a geraÃÃo de malhas ainda representa o maior desafio desses mÃtodos. Por esse motivo, nos Ãltimos anos o foco dos estudos de modelagem de problemas relacionados Ãs Ãguas subterrÃneas està voltado para o desenvolvimento de âmÃtodos livres de malhasâ ( meslhess ou meshfree methods) que tÃm como objetivo eliminar ou, pelo menos aliviar os problemas associados à construÃÃo e/ou reconstruÃÃo de malhas. Em problemas transientes, nos mÃtodos numÃricos tradicionais, o espaÃo à discretizado e em seguida à feita uma nova discretizaÃÃo para o tempo que requer a escolha de uma relaÃÃo Ãtima entre o intervalo de tempo escolhido e a discretizaÃÃo do espaÃo. Esta tese propÃe o desenvolvimento de um modelo numÃrico-analÃtico para problemas transientes de fluxo e contaminaÃÃo de Ãgua subterrÃnea. à um mÃtodo numÃrico com relaÃÃo à descriÃÃo do espaÃo, onde serà utilizado o mÃtodo RBF livre de malha e à analÃtico com relaÃÃo ao tempo, onde serÃo geradas expressÃes matemÃticas para a parte transiente. TrÃs configuraÃÃes de problemas unidimensionais de Ãgua subterrÃnea foram modeladas pelo mÃtodo RBF livre de malha e pelo mÃtodo numÃrico-analÃtico (MNA), utilizando o MAPLE e ( versÃo 10.0) como linguagem de programaÃÃo. Nos trÃs casos estudados, o meio poroso à homogÃneo e saturado. Os resultados apresentados mostram a validaÃÃo de fÃsica do MNA, mas possuem algumas restriÃÃes em sua aplicaÃÃo, tais como domÃnios poucos discretizados e a escolha de um fator de forma Ãtimo. O presente trabalho mostra tambÃm que o modelo proposto acomoda condiÃÃes de contorno que variam com o tempo. / Improvements in computer capabilities in the last three decades make it possible to solve more and more complex engineering problems. The increase in possibilities for
solving such problems has been due to advances in numerical methods and development of efficient algorithms. Nevertheless, these numerical methods are based on mesh discretization and it is widely acknowledged that mesh generation remains one of the biggest challenges in mesh-based methods. During recent years, groundwater problems modeling studies are focused on the development of meshless or mesh-free methods. The aim of the so-called mesh-free methods is to eliminate or at least minimize the problems associated with meshing and/or remeshing. Traditional numerical methods discretize space and then discretize time in order to solve transient problems. This procedure requires na optimal relationship between space and time discretizations. This work proposes the development of a numerical-analytical model for flow and contaminant transport groundwater transient problems. It is a numerical method with respect to space, with RBF meshfree method and it is analytical with respect to time, with mathematical expressions. Three onedimensional problems configurations were teste using RBF meshless method and numerical-analytical (MNA) method, in MAPLE program. In all three cases, porous media is homogeneous and saturated. Results show MNAâs physical validation, but
there are some restrictions to its use, such as domain discretization, PÃclet number and optimal shape parameter. The present work also shows that MNA accommodates well varying boundary conditions.
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Avaliação pré-clínica em roedores do perfil farmacocinético de novo candidato a Leishmanicida lassbio-1736Moraes, Barbra Katyúscya Sanches 29 May 2015 (has links)
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Previous issue date: 2015-05-29 / Neste estudo, um método de CLAE-DAD foi desenvolvido e validado para a determinação de LASSBio-1736 em plasma de rato usando diclofenaco de sódio como padrão interno (PI). Extração líquido-líquido com acetonitrila foi utilizado para extrair LASSBio-1736. A separação cromatográfica foi realizada com coluna Waters Spherisorb®S5 ODS2 C18 (150 mm x 4,6 mm, 5μm), fase móvel isocrática composta por Trietilamina 0,3% (pH 4), metanol e acetonitrila (45:15:40, v/v/v) com vazão de 1 mL/min. Ambos LASSBio-1736 e PI foram eluídos em 4,2 e 5 min, respectivamente. O limite inferior de quantificação foi de 0,2 μg/mL e linearidade entre 0,2 - 4 μg/mL, com um r2> 0,99. A exatidão do método foi > 90,5%. Os desvios padrão relativos intra e inter-dias foram < 6,19 e < 7,83%, respectivamente. O método mostrou sensibilidade, linearidade, precisão, exatidão e seletividade necessária para quantificar LASSBio-1736 em estudos farmacocinéticos pré-clínicos O presente trabalho também investigou a farmacocinética plasmática e a distribuição do LASSBio-1736 em ratos Wistar. A farmacocinética de LASSBio-1736 foi investigada após a administração de dose intravenosa (3,2 mg/kg), por via oral e intraperitoneal (12,6 mg/kg).. A distribuição nos tecidos foi avaliada após administração de dose i.v. bolus. Os resultados para a via intravenosa indicam longo tempo meia-vida (24,3 ± 8,2 h), depuração de 49,3 ± 9,8 mL/Kg*h e volume de distribuição de 1,16 ± 0,3 L/kg. Para a via oral o tempo meia-vida foi de 28,6 ± 4,6 h, depuração de 49,7 ± 13 mL/Kg*h e volume de distribuição de 1,47 ± 0,34 L/kgforam semelhantes e biodisponibilidade de 12%. Para a via intraperitoneal o tempo meia-vida foi de 26 ± 8,9 h, depuração de 58 ± 19,6 mL/Kg*h e volume de distribuição de 1,8 ± 0,8 L/kg e biodisponibilidade de 38%. O LASSBio-1736 demonstrou penetração tecidual adequada no fígado, baço e pele. Com base nas características farmacocinéticas de outros fármacos leishmanicidas e a proposição de decisão para estudos farmacocinéticos visando a descoberta de candidatos a fármacos e a continuidade dos estudos, o LASSBio-1736 possui características farmacocinéticas apropriadas para um medicamento leishmanicida e novos estudos devem ser realizados para o escalonamento interespécies, além de estudos farmacológicos e toxicológicos complementares. / In this study, a method was developed and validated for HPLC-PDA determination LASSBio-1736 in rat plasma using diclofenac sodium as internal standard (IS). Liquid-liquid extraction was used to extract acetonitrile LASSBio-1736. The chromatographic separation was performed with Waters Spherisorb®S5 ODS2 C18 column (150 mm x 4.6 mm, 5μm), isocratic mobile phase consisting of Triethylamine 0.3% (pH 4), methanol and acetonitrile (45:15:40, v / v / v) with a flow rate of 1 mL/min. Both LASSBio-1736 and IS were eluted at 4.2 and 5 min, respectively. The lower limit of quantification was 0.2 μg/mL and linearity between 0.2 - 4 μg/mL, with r2> 0.99. The accuracy was > 90.5%. The relative standard deviation within and between days were < 6.19 and < 7.83%, respectively. The method showed sensitivity, linearity, precision, accuracy and selectivity needed to quantify LASSBio-1736 in preclinical pharmacokinetic studies. This study also investigated the plasma pharmacokinetics and distribution of LASSBio-1736 in Wistar rats. The pharmacokinetic LASSBio-1736 was investigated after intravenous dose administration (3.2 mg/kg) intraperitoneally and orally (12.6 mg/kg). The tissue distribution was evaluated after iv bolus dose administration. The results indicated an intravenous long half-life (24.3 ± 8.2 h) clearance 49.3 ± 9.8 mL/kg*h and the volume of distribution 1.16 ± 0.3 L/ kg. The oral route the half-life was 28.6 ± 4.6 h, clearance 49.7 ± 13 mL/kg*h and volume of distribution 1.47 ± 0.34 L/kg and bioavailability of 12%. The intraperitoneally half-life was 26 ± 8.9 h, clearance 58 ± 19.6 mL/kg*h and the volume of distribution 1.8 ± 0.8 L/kg and bioavailability of 38%were similar. The LASSBio-1736 showed adequate tissue penetration for liver, spleen and skin. Based on the pharmacokinetic characteristics of other antileishmanial drugs and the decision proposition for pharmacokinetic studies for the discovery of drug candidates and continuing studies, the LASSBio-1736 has pharmacokinetic characteristics appropriate for a leishmanicide and new drug studies should be conducted to the interspecies scaling, and additional pharmacological and toxicological studies.
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Προσεγγιστικά αναλυτικά μοντέλα για τη μελέτη της απόδοσης πολυβάθμιων διασυνδεμένων δικτύων μεταγωγήςΣτεργίου, Ελευθέριος 05 January 2011 (has links)
H παρούσα ερευνητική εργασία αφορά την εκτίμηση της απόδοσης πολυβάθμιων διασυνδεδεμένων δικτύων μεταγωγής. Για την εκτίμηση της απόδοσης αναπτύχθηκαν προσεγγιστικά αναλυτικά μοντέλα τα οποία και παρουσιάζονται στην εργασία αυτή. Πιο συγκεκριμένα:
1. Παρουσιάζεται μια πρωτότυπη ολοκληρωμένη μεθοδολογία εύρεσης της απόδοσης αυτό-δρομολογούμενων απλών πολυβάθμιων διασυνδεδεμένων δικτύων (πχ κλασσικά δίκτυα banyan) τα οποία συγκροτούνται από συμμετρικά στοιχειώδη συστήματα μεταγωγής (πχ 2x2 Switch Element). Το μοντέλο που δημιουργήθηκε βασίστηκε στην λειτουργία και την συμπεριφορά μιας τυχαίας μνήμης (ουράς) ενός στοιχειώδους συστήματος μεταγωγής. Βασιζόμενοι στην ανάλυση, η οποία συμπεριλαμβάνει έναν επαναληπτικό αλγόριθμο ο οποίος συγκλίνει σε πολύ λίγες επαναλήψεις, υπολογίζουμε την Χρησιμοποίηση των ουρών του συστήματος. Στην συνεχεία προσδιορίζουμε τους λοιπούς δείκτες απόδοσης.
2. Παρουσιάζεται διαδικασία εκτίμησης της απόδοσης πολυβάθμιων διασυνδεδεμένων δικτύων μεταγωγής, τα οποία έχουν την ικανότητα να εξυπηρετούν φορτίο με δύο οι περισσότερες προτεραιότητες. Προτάθηκε ένα στοιχειώδες σύστημα μεταγωγής (SE- Switch Element) το οποίο διαθέτει παράλληλες μνήμες σε κάθε είσοδο, μία για κάθε υποστηριζόμενη προτεραιότητα φορτίου, και το οποίο μοντελοποιήθηκε με την βοήθεια ουρών. Βασιζόμενοι στην ανάλυση του μοντέλου αυτού και με την βοήθεια σχετικού επαναληπτικού αλγορίθμου ο οποίος συγκλίνει με λίγες επαναλήψεις, υπολογίστηκαν με ακρίβεια όλοι οι δείκτες απόδοσης.
3. Επιπρόσθετα, αναπτύσσεται μια ακόμη πρωτότυπη αναλυτική προσέγγιση η οποία παρέχει την εκτίμηση της απόδοσης πολυβάθμιων διασυνδεδεμένων δικτύων μεταγωγής με ένα ή περισσότερα επίπεδα τα οποία εφαρμόζουν ως τεχνική εκπομπής πακέτων την τεχνική ‘full multicast’, όταν τα δίκτυα αυτά εξυπηρετούν φορτίο απλής και πολλαπλής εκπομπής (multicast). Δημιουργήθηκε σχετικό μοντέλο για την μελέτη των δικτύων αυτών. Απεδείχθη ότι τα διασυνδεδεμένα δίκτυα τα οποία διαθέτουν περιορισμένο αριθμό επιπέδων, υποστηρίζουν με εξαιρετική αποτελεσματικότητα φορτίο απλής και πολλαπλής εκπομπής (multicast).
4. Αναπτύσσεται και άλλη αναλυτική μελέτη η οποία παρέχει την εκτίμηση της απόδοσης πολυβάθμιων διασυνδεδεμένων δικτύων μεταγωγής με ένα ή περισσότερα επίπεδα τα οποία όμως εφαρμόζουν ως τεχνική εκπομπής πακέτων την τεχνική ‘partial multicast’.
5. Παρουσιάζεται αναλυτική προσέγγιση απόδοσης η οποία αφορά αυτο-δρομολoγούμενα πολυβάθμια συστήματα με περιορισμένα επίπεδα τα οποία όμως εφαρμόζουν ταυτόχρονα δύο διαφορετικές πολιτικές εκπομπής πακέτων, μία σε κάθε τμήμα τους. Και πάλι ακολουθώντας παρόμοια διαδικασία προσδιορίστηκαν όλοι οι δείκτες απόδοσης των πολυβάθμιων δικτύων αυτών
6. Για διευκόλυνση των μελετητών, ορίστηκε ένας γενικός συντελεστής απόδοσης (CPF) του συστήματος ο οποίος εκφράζει την γενική απόδοση μιας πολυβάθμιας συσκευής μεταγωγής πακέτων, λαμβάνοντας υπ όψιν όλους τους ανεξάρτητους δείκτες, με βάση συγκεκριμένα κριτήρια.
Αξιοσημείωτο είναι ότι όλες οι αναλυτικές μέθοδοι παρέχουν αναλυτικά αποτελέσματα για όλα τα ενδιάμεσα στάδια. Όλα τα αποτελέσματα τα οποία προέκυψαν από εφαρμογή των αναλυτικών μεθόδων επιβεβαιώθηκαν με προσομοιώσεις που δημιουργήθηκαν γι αυτό τον σκοπό.
Επίσης τα αποτελέσματα τα οποία ελήφθησαν από τις αναλυτικές μεθόδους, συγκρίθηκαν με αποτελέσματα από παλαιότερες εργασίες. Η σύγκριση αναδεικνύει την μεγαλύτερη ακρίβεια και ταχύτητα των αναλυτικών μεθόδων που παρουσιάζονται στην παρούσα εργασία έναντι όλων των παλαιοτέρων ερευνητικών τεχνικών.
Εξετάζοντας τις σχετική ερευνητική βιβλιογραφία καθίσταται πρόδηλο ότι υπάρχει ανεπάρκεια αναλυτικών μελετών οι οποίες να καλύπτουν θέματα εκτίμησης απόδοσης συγχρόνων δικτύων μεταγωγής, όπως πχ είναι τα πολυεπίπεδα δίκτυα.
Οι παραπάνω αναλυτικές προσεγγίσεις αναμένεται να είναι ένα χρήσιμο εργαλείο για τους σχεδιαστές και κατασκευαστές δικτυακών συστημάτων στην προσπάθειά τους να πετύχουν κατασκευή δικτύων με καλύτερη ποιότητα εξυπηρέτησης (QoS). / This research work concerns the performance evaluation of multistage, interconnected switching networks. To assess the performance, approximated analytical models are developed and presented. In particular:
1. A novel integrated methodology for assessing the performance of simple, self-routing, multistage, interconnected networks (e.g. banyan networks), which are formed by symmetrical switch elements, is presented. The model that is created is based on the function and behaviour of a random simple multistage switch system in a memory level (queue). Based on analysis, which includes a repetitive algorithm that converges within a small number of iterations, the queue's’ utilisation is estimated. Subsequently, other performance indicators are determined.
2. A performance evaluation process for multistage interconnection networks, which has the ability to service traffic with two or more classes of priorities, is presented. Particularly, a new switch element which has parallel memories in each entry is proposed to ensure effective servicing of multi-priority traffic. This switch element has one memory for each supported class of priority, and is modelled by means of queues. Based on the analysis provided by this model, and in conjunction with the application of a repetitive algorithm which converges with few iterations, all performance indicators were precisely calculated.
3. In addition, a novel analytical approach was developed that provides a performance evaluation of multistage interconnection networks that have one or more levels which apply the packet transmission ‘full multicast’ method when these networks serve unicast and multicast traffic. A relevant study model for those networks was created. It appears that the interconnected networks which have a limited number of levels lend excellent support with effective unicast and multicast traffic.
4. The study provides a performance evaluation of multistage interconnection networks with one or more levels, and uses a technical transmission packet technique for multicast traffic, the ‘partial multicast’ operation.
5. Also is presented an analytical approach that estimates a performance evaluation of self-routing, multistage interconnection networks (which have a limited number of levels) that apply two different transmission packet techniques in each segment. By application of a similar procedure, all the performance indicators of multistage networks are identified.
6. To assist designers, a compound performance factor (CPF) is defined which expresses the overall performance evaluation of multistage interconnection network devices (taking into account all the individual performance factors, according to a specific set of criteria).
It is noteworthy that all of the analytical methods provide detailed results for all intermediate stages. All of the results obtained by application of analytical methods are confirmed by simulations.
The results garnered by analytical methods are also compared with the results from previous work. The comparison highlights the greater accuracy and speed that these analytical methods have over older research techniques. Examination of the relevant research literature makes it evident that there is an insufficient number of analytical studies which cover the performance evaluation issue relating to modern switched networks; for example, multi-layered networks. This gap in the field of research is completed by this work.
These analytical approaches will be useful tools for designers and manufacturers of network systems in their efforts to provide better quality of service (QoS).
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Método analítico para análise da estabilidade do gerador assíncrono através do monitoramento da tensão /Zamperin, Joao Luiz Bergamo. January 2011 (has links)
Orientador: Laurence Duarte Colvara / Banca: Dionizio Paschoareli Junior / Banca: Walmir de Freitas Filho / Resumo: Propõe-se neste trabalho o desenvolvimento de uma metodologia analítica para análise do desempenho dinâmico/transitório dos geradores de indução conectados ao sistema de energia elétrica. O método proposto para o estudo da estabilidade das máquinas de indução baseia-se no monitoramento da tensão interna E' durante o período transitório do sistema, a qual pode comprometer a capacidade de transmissão de potência na linha, com consequente colapso da estabilidade da máquina. Deste modo, faz-se a análise do desempenho transitório da máquina pela observação da grandeza em que efetivamente reside a causa da instabilidade. O método desenvolvido foi validado por meio de simulações digitais, em duas configurações do sistema: o primeiro caso, desprezando o suporte de potência reativa, para efeito de análise nos estudos de estabilidade transitória. No segundo, é realizada a compensação dinâmica de potência reativa via SVC (Static Var Compensator). Neste caso, mesmo na presença do compensador variável de reativo, o método da tensão interna revelou-se capaz de avaliar novos limites de estabilidade para o sistema. Considerados os resultados obtidos, observa-se que o método proposto apresenta resultados suficientemente precisos para avaliar o comportamento dos geradores de indução conectados à rede elétrica / Abstract: This dissertation proposes the development of an analytical methodology for analysis of dynamic/transient performance of an induction generator connected to a bulk power system. The proposed method for studying the stability of induction machines is based on monitoring the internal voltage named E' since during the transient system, its magnitude may decrease and so causing degeneration of the transmission system capability, with consequent collapse of machine stability. Thus it is the analysis of transient performance of the machine by observing the variable that is actually the cause of instability. The analytical method was validated by means of digital simulations, in two system configurations: in the first case, no reactive support is considered, and the purpose is to analyse the machine transient stability itself. In the second, a reactive support is provided by means of the dynamic reactive compensation via SVC (Static Var Compensator). In this case, even in the presence of variable reactive compensator, the method of internal voltage proved to be able to properly assess new stability limits. The results so obtained lead to the indication that the proposed method results are accurate enough in order to evaluate the behavior of induction generators, connected to the power grid
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Simulation numérique d’un assemblage métal / composite thermoplastique par CMT pins / Numerical simulation of a metal / thermoplastic assembly by CMT pinsParoissien, Simon 14 November 2016 (has links)
Une méthode est proposée pour la modélisation d’unassemblage multimatériaux innovant visant des applicationsdans l’allègement structurel des véhicules. Dans cetassemblage une partie composite thermoplastique, est fixée àune plaque acier texturée par la technologie CMT pins.L’interface est particulièrement complexe et non linéaire : unereprésentation fine du comportement local serait extrêmementpénalisante en temps de calcul. Dans cette optique il a étéchoisi d’orienter la méthodologie vers une modélisation la plussimple possible tout en conservant de bons résultats globaux.Pour ce faire, en s’inspirant de l’état de l’art existant sur lesmultimatériaux, une campagne expérimentale a été menée surdes éprouvettes longitudinales à double recouvrement afin decaractériser cette interface. Une fois les mécanismes locauxinvestigués, deux modèles sont proposés. Le premiernumérique basé sur la méthode des éléments finis etl’introduction d’éléments cohésifs nous permet de valider leshypothèses de modélisation tout en quantifiant la répartitiondes efforts entre les picots. Le deuxième se base sur le calcullocal d’un Volume Élémentaire Représentatif pour établiranalytiquement la loi de comportement de l’interface. Cette loiest ensuite introduite sous la forme d’un ressort non linéaire ausein d’un modèle numérique simplifié de l’éprouvette. Pourfinir ces approches sont appliquées au cas d’étude industriel etles résultats sont validés par une deuxième campagneexpérimentale. / A method is proposed to simulate an innovative multimaterialassembly which has applications in structural lightweight forvehicles. In this assembly, a thermoplastic composite part isfixed on a steel plate, textured by the CMT pins technology.This is an especially complex and nonlinear interface: a finerepresentation of local behaviour would be extremely costlyfor calculation. So, it has been chosen to investigate a model assimple as possible which still demonstrates accurate globalresults.An experimental campaign on double lap shear specimen,inspired by existing state of the art on multimaterial has beenset up to characterize this interface. Once local mechanismshave been understood, two models are proposed and compared.The first is numerical and based on finite elements method andcohesive elements. It allows us to validate the modelhypotheses while describing the effort repartition between thepins. The second one is based on a Representative VolumeElement. It establishes analytically the behaviour law of theinterface. This law is then inserted inside a simplifiednumerical model of the specimen by means of a nonlinearspring. To conclude, these approaches are applied to theindustrial case of study and the result have been validated by asecond experimental campaign.
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Simulação de escoamentos viscosos utilizando mapeamentos entre equações / Viscous flow simulations using diferential equation mappingsSantiago, Gustavo Fuhr January 2007 (has links)
Este trabalho faz uma nova proposta de método para solucionar a equação advectivodifusiva tridimensional que descreve os escoamentos viscosos incompressíveis. Este método usa um esquema analítico baseado em split seguido de gênese de equações diferenciais. A solução do problema é efetuada em duas etapas distintas. A primeira etapa consiste na aplicação de um split não-homogêneo sobre as Equações de Navier-Stokes, no qual uma das equações do sistema resultante contém a derivada temporal e o termo viscoso, constituindo uma equação diferencial linear não-homogênea. A solução dessa equação é obtida via mapeamento em uma equação de primeira ordem, fornecendo o formato do campo de velocidades. A partir deste se obtém o formato da função corrente para fins de gênese. Desta forma faz-se com que simulações possam ser obtidas usando computadores portáteis e, mesmo assim, requeiram tempo de processamento pequeno para a solução de problemas ditos de engenharia. Estas vantagens podem ser diretamente traduzidas em aplicações práticas de simulação como, por exemplo, a possibilidade de tomada de decisão em tempo real sobre o controle de um processo em andamento numa planta industrial, respostas transientes num escoamento turbulento ou na previsão da dispersão de poluentes em rios e mananciais críticos à saúde da população. / This work proposes a new method to solve the three-dimensional advective-diffusive equation which describes incompressible viscous flows. The proposed solution uses an analytical method based in the split of the original equation, followed by a genesis of differential equa tions. The problem is solved in two distinct steps. The first step consists of applying a nonhomogeneous split on the Navier-Stokes equations, which results in one non-homogeneous partial differential equation containing the time derivative and the viscous term. This equation is solved by mapping it into a first order equation that provides the velocity field format. Using this result we are able to obtain the stream function format, which will be used in the following genesis. This sequence allows the use of portable computers to achieve simulation results for engineering problems in small enough processing time. These advantages can be used in applications such as real- time decision making about industrial processes variables, transient turbulent flow calculations or pollution dispersion simulations in rivers or other water sources critical to the population.
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The physical chemistry of pMDI formulations derived from hydrofluoroalkane propellants : a study of the physical behaviour of poorly soluble active pharmaceutical ingredients : bespoke analytical method development leading to novel formulation approaches for product developmentTelford, Richard January 2013 (has links)
Active Pharmaceutical Ingredients (APIs) are frequently prepared for delivery to the lung for local topical treatment of diseases such as Chronic Obstructive Pulmonary Disease (COPD) and asthma, or for systemic delivery. One of the most commonly used devices for this purpose is the pressurised metered dose inhaler (pMDI) whereby drugs are formulated in a volatile propellant held under pressure. The compound is aerosolised to a respirably sized dose on actuation, subsequently breathed in by the user. The use of hydrofluoroalkanes (HFAs) in pMDIs since the Montreal Protocol initiated a move away from chlorofluorocarbon (CFC) based devices has resulted in better performing products, with increased lung deposition and a concomitant reduction in oropharyngeal deposition. The physical properties of HFA propellants are however poorly understood and their capacity for solubilising inhaled pharmaceutical products (IPPs) and excipients used historically in CFCs differ significantly. There is therefore a drive to establish methodologies to study these systems in-situ and post actuation to adequately direct formulation strategies for the production of stable and efficacious suspension and solution based products. Characterisation methods have been applied to pMDI dosage systems to gain insight into solubility in HFAs and to determine forms of solid deposits after actuation. A novel quantitative nuclear magnetic resonance method to investigate the physical chemistry of IPPs in these preparations has formed the centrepiece to these studies, accessing solubility data in-situ and at pressure for the first time in HFA propellants. Variable temperature NMR has provided thermodynamic data through van’t Hoff approaches. The methods have been developed and validated using budesonide to provide limits of determination as low as 1 μg/mL and extended to 11 IPPs chosen to represent currently prescribed inhaled corticosteroids (ICS), β2-adrenoagonists and antimuscarinic bronchodilators, and have highlighted solubility variations between the classes of compounds with lipophilic ICSs showing the highest, and hydrophilic β2- agonist/antimuscarinics showing the lowest solubilities from the compounds under study. To determine solid forms on deposition, a series of methods are also described using modified impaction methods in combination with analytical approaches including spectroscopy (μ-Raman), X-ray diffraction, SEM, chromatography and thermal analysis. Their application has ascertained (i) physical form/morphology data on commercial pMDI formulations of the ICS beclomethasone dipropionate (QVAR®/Sanasthmax®, Chiesi) and (ii) distribution assessment in-vitro of ICS/β2-agonist compounds from combination pMDIs confirming co-deposition (Seretide®/Symbicort®, GlaxoSmithKline/AstraZeneca). In combination, these methods provide a platform for development of new formulations based on HFA propellants. The methods have been applied to a number of ‘real’ systems incorporating derivatised cyclodextrins and the co-solvent ethanol, and provide a basis for a comprehensive study of solubilisation of the ICS budesonide in HFA134a using two approaches: mixed solvents and complexation. These new systems provide a novel approach to deliver to the lung, with reduced aerodynamic particle size distribution (APSD) potentially accessing areas suitable for delivery to peripheral areas of the lung (ICS) or to promote systemic delivery.
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Simulação de escoamentos viscosos utilizando mapeamentos entre equações / Viscous flow simulations using diferential equation mappingsSantiago, Gustavo Fuhr January 2007 (has links)
Este trabalho faz uma nova proposta de método para solucionar a equação advectivodifusiva tridimensional que descreve os escoamentos viscosos incompressíveis. Este método usa um esquema analítico baseado em split seguido de gênese de equações diferenciais. A solução do problema é efetuada em duas etapas distintas. A primeira etapa consiste na aplicação de um split não-homogêneo sobre as Equações de Navier-Stokes, no qual uma das equações do sistema resultante contém a derivada temporal e o termo viscoso, constituindo uma equação diferencial linear não-homogênea. A solução dessa equação é obtida via mapeamento em uma equação de primeira ordem, fornecendo o formato do campo de velocidades. A partir deste se obtém o formato da função corrente para fins de gênese. Desta forma faz-se com que simulações possam ser obtidas usando computadores portáteis e, mesmo assim, requeiram tempo de processamento pequeno para a solução de problemas ditos de engenharia. Estas vantagens podem ser diretamente traduzidas em aplicações práticas de simulação como, por exemplo, a possibilidade de tomada de decisão em tempo real sobre o controle de um processo em andamento numa planta industrial, respostas transientes num escoamento turbulento ou na previsão da dispersão de poluentes em rios e mananciais críticos à saúde da população. / This work proposes a new method to solve the three-dimensional advective-diffusive equation which describes incompressible viscous flows. The proposed solution uses an analytical method based in the split of the original equation, followed by a genesis of differential equa tions. The problem is solved in two distinct steps. The first step consists of applying a nonhomogeneous split on the Navier-Stokes equations, which results in one non-homogeneous partial differential equation containing the time derivative and the viscous term. This equation is solved by mapping it into a first order equation that provides the velocity field format. Using this result we are able to obtain the stream function format, which will be used in the following genesis. This sequence allows the use of portable computers to achieve simulation results for engineering problems in small enough processing time. These advantages can be used in applications such as real- time decision making about industrial processes variables, transient turbulent flow calculations or pollution dispersion simulations in rivers or other water sources critical to the population.
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Absorção de água em compósitos poliméricos reforçados por fibras da folha do abacaxi: modelagem e simulação.MELO, João Baptista da Costa Agra de. 12 December 2017 (has links)
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Previous issue date: 2014-08-29 / Neste trabalho de pesquisa, buscou-se determinar através de um modelo matemático, utilizando-se da equação da Segunda Lei de FICK, que trata do fenômeno de difusão para predizer a umidade absorvida por compósitos de matriz poliéster insaturado, reforçado por fibras da folha de abacaxi nas condições de variação do volume de fibras, variação dos comprimentos das fibras, variação no tempo de tratamento das fibras em solução de NaOH a 10% e tratamento das fibras por Plasma a frio.Para a solução da formulação matemática, utilizou-se método analítico considerando-se um sólido tridimensional, isotrópico, simétrico, condição de contorno convectiva de superfície, e regime transiente. Para a obtenção dos valores analíticos dos coeficientes de difusão de massa, umidade e umidade média utilizou-se um código computacional desenvolvido na plataforma do software Mathematica versão sete. Foi observado que os valores dos coeficientes de difusão para o modelo tridimensional crescem conforme o aumento do volume de fibra e que para o comprimento das fibras, este coeficiente apresenta um
aumento até o comprimento de 55 mm, voltando a diminuir para comprimento de fibras maiores. Analisaram-se também os valores de umidade e umidade média comparando-se os valores experimentais e os analíticos. Os resultados obtidos comparativamente entre dados experimentais e analíticos demonstraram que o modelo proposto pode predizer a umidade absorvida para as condições adotadas, em qualquer tempo com uma precisão de mais de 95%. / In this research, we sought to determine by a mathematical model, using the Fick's Second Law that explores the phenomenon of diffusion to predict the moisture absorbed by unsaturated polyester composite matrix, reinforced by fibers of pineapple leaf in conditions of variation of fiber volume, variation of the lengths of the fibers, variation in treatment time of the fibers in a solution of 10% NaOH and fiber treatment by cold plasma. For the solution of the mathematical formulation, it was used analytical method considering a solid three-dimensional, isotropic, and symmetric, with boundary condition convective surface and transient. To obtain the analytical values of the diffusion coefficients of mass, moisture and average moisture, it we used a computer code developed at the software platform Mathematica7. It was observed that the values
of the diffusion coefficients for the three-dimensional model increases with increasing of fiber volume and forthe fiber length this ratio has increased to a length of 55 mm, decreasing again to greater fiber length. Was analized the values of moisture and average moisture comparing the experimental and analytical values. The results compared between experimental and analytical data demonstrated that the proposed model can predict the absorbed moisture conditions adopted for conditions at any time with an accuracy of over 95%.
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Simulação de escoamentos viscosos utilizando mapeamentos entre equações / Viscous flow simulations using diferential equation mappingsSantiago, Gustavo Fuhr January 2007 (has links)
Este trabalho faz uma nova proposta de método para solucionar a equação advectivodifusiva tridimensional que descreve os escoamentos viscosos incompressíveis. Este método usa um esquema analítico baseado em split seguido de gênese de equações diferenciais. A solução do problema é efetuada em duas etapas distintas. A primeira etapa consiste na aplicação de um split não-homogêneo sobre as Equações de Navier-Stokes, no qual uma das equações do sistema resultante contém a derivada temporal e o termo viscoso, constituindo uma equação diferencial linear não-homogênea. A solução dessa equação é obtida via mapeamento em uma equação de primeira ordem, fornecendo o formato do campo de velocidades. A partir deste se obtém o formato da função corrente para fins de gênese. Desta forma faz-se com que simulações possam ser obtidas usando computadores portáteis e, mesmo assim, requeiram tempo de processamento pequeno para a solução de problemas ditos de engenharia. Estas vantagens podem ser diretamente traduzidas em aplicações práticas de simulação como, por exemplo, a possibilidade de tomada de decisão em tempo real sobre o controle de um processo em andamento numa planta industrial, respostas transientes num escoamento turbulento ou na previsão da dispersão de poluentes em rios e mananciais críticos à saúde da população. / This work proposes a new method to solve the three-dimensional advective-diffusive equation which describes incompressible viscous flows. The proposed solution uses an analytical method based in the split of the original equation, followed by a genesis of differential equa tions. The problem is solved in two distinct steps. The first step consists of applying a nonhomogeneous split on the Navier-Stokes equations, which results in one non-homogeneous partial differential equation containing the time derivative and the viscous term. This equation is solved by mapping it into a first order equation that provides the velocity field format. Using this result we are able to obtain the stream function format, which will be used in the following genesis. This sequence allows the use of portable computers to achieve simulation results for engineering problems in small enough processing time. These advantages can be used in applications such as real- time decision making about industrial processes variables, transient turbulent flow calculations or pollution dispersion simulations in rivers or other water sources critical to the population.
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