Submitted by Marlene Santos (marlene.bc.ufg@gmail.com) on 2016-04-20T18:45:25Z No. of bitstreams: 2 Dissertaçao - Leandro Rezende Franco- 2016.pdf: 12911790 bytes, checksum: 424add978f6ebc12f99143d7bb1c924f (MD5) license_rdf: 19874 bytes, checksum: 38cb62ef53e6f513db2fb7e337df6485 (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2016-04-25T14:29:50Z (GMT) No. of bitstreams: 2 Dissertaçao - Leandro Rezende Franco- 2016.pdf: 12911790 bytes, checksum: 424add978f6ebc12f99143d7bb1c924f (MD5) license_rdf: 19874 bytes, checksum: 38cb62ef53e6f513db2fb7e337df6485 (MD5) / Made available in DSpace on 2016-04-25T14:29:50Z (GMT). No. of bitstreams: 2 Dissertaçao - Leandro Rezende Franco- 2016.pdf: 12911790 bytes, checksum: 424add978f6ebc12f99143d7bb1c924f (MD5) license_rdf: 19874 bytes, checksum: 38cb62ef53e6f513db2fb7e337df6485 (MD5) Previous issue date: 2016-02-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The combined use of the Sequential QM/MM method with the ASEC mean field approximation [1] and the Free Energy Gradient method [2] has been very successful in describing the electronic structure of molecules in solution [3]. The advantage of this combination is that it permits the usage of an atomic- level modeling of the whole system, in contrast to continuum models, and, at the same time, it is less computationally expensive than ab initio or QM/MM simulations, even allowing the employment of more sophisticated electronic structure methods. In this context, the present work deals with the study of conformational and electronic structure, in solvent medium, of two organic compounds, DMACA and Phenol Blue, which have in common the characteristic of having acceptor-donor groups. The study is conducted in the presence of nonpolar, polar protic and polar aprotic solvents. It is adopted as basic methodology the ASEC-FEG, but also it is made a study with a continuum method, namely PCM. The results show that the solvent effect causes a significant geometric distortion of the molecules of interest while causing an internal charge displacement from donor group to acceptor group. Both effects are more pronounced in protic and aprotic solvents but mainly in protic solvents, in which hydrogen bonds lead to a greater solute polarization. The absorption spectra of these molecules, calculated by TD-DFT (CAM-B3LYP), directly reflect these changes. For all solvents, the absolute values of electronic transitions and their respective solvatochromic shifts are in good agreement with the experimental results. / O uso combinado de métodos QM/MM sequencial com uma aproximação de campo médio (ASEC) [1] e o método do Gradiente de Energia Livre [2] tem tido sucesso na descrição da estrutura eletrônica de moléculas em solução [3]. Uma das vantagens dessa combinação é que ela permite o tratamento do sistema soluto-solvente em um nível atomístico, em contraste com modelos contínuos, e tem a vantagem de, ao mesmo tempo, ser uma metodologia menos cara computacionalmente do que simulações QM/MM ab initio [4]. Nesse contexto, o presente trabalho versa sobre o estudo da estrutura conformacional e eletrônica, em meio, de dois compostos orgânicos, DMACA e Phenol Blue, que tem em comum a característica de possuir grupos aceitador e doador de elétrons. O estudo é realizado na presença de solventes apolares, polares apróticos e polares próticos. Adota-se como metodologia básica o método QM/MM sequencial utilizando o ASEC, mas faz-se também um estudo com um método contínuo conhecido, o PCM. Os resultados mostram que o efeito de solvente provoca uma signifativa reestruturação geométrica das moléculas de interesse, ao mesmo tempo em que causa um deslocamento interno de carga do grupo doador para o grupo aceitador. Os dois efeitos são mais pronuciados em solventes apróticos e próticos, mas principalmente nos solventes próticos, em que as ligações de hidrogênio levam a uma maior polarização do soluto. Essas mudanças refletem diretamente no espectro de absorção, calculado por TD-DFT (CAM-B3LYP), dessas moléculas. Dos meios apolares, passando pelos polares apróticos, indo até os polares próticos, os valores absolutos das transições eletrônicas e seus respectivos deslocamentos solvatocrômicos encontram-se em bom acordo com os resultados experimentais.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Ao analisar a Educação Básica nos dias atuais, observa-se que no Ensino Médio o estudo dos problemas sobre máximos e mínimos é realizado de forma limitada e superficial, resumindo-se basicamente a algumas aplicações de funções quadráticas. A resolução de problemas de otimização de índole geométrica constitui um campo fértil para trabalhar a formação matemática dos alunos nesse nível e contribuir com o aperfeiçoamento da qualidade do ensino da Matemática. Esta categoria de problemas pode ser de utilidade na preparação de alunos para as Olimpíadas de Matemática. Este trabalho aborda o estudo e descrição de métodos de solução de problemas de otimização em geometria euclidana, apresentando uma catalogação devida a Andreescu, junto a vários exemplos resolvidos. / Looking over the Basic Education nowadays, it becomes aware that in high school the study of maxima and minimas problems is carry out in a limited and superficial way. In general, the resolution of these problems lessened to some application of quadratic functions. However, Geometric optimizations problems may be a fecund area to contribute for improving the quality of math education at this level and to develop the mathematical mind of students. That category of problems is also useful for training students for the Math Olympics. This masters dissertation deals with the study of resolutions methods of optimization problems in Euclidean Plane Geometry, presenting a cataloging, according to Andreescu, and some several solved illustrative examples.

As a clean, abundant, and renewable source of energy with a strategic location in close proximity to global population regions, ocean wave energy shows major promise. Although much wave energy converter development has focused on large-scale power generation, there is also increasing interest in small-scale applications for powering the blue economy. In this thesis, the objective was to optimize the performance of small-sized, portable, oscillating-body wave energy converters (WECs). Two types of oscillating body WECs were studied: bottom hinged and two-body attenuator. For the bottom-hinged device, the goal was to show the feasibility of an oscillating surge WEC and desalination system using numerical modeling to estimate the system performance. For a 5-day test period, the model estimated 517 L of freshwater production with 711 ppm concentration and showed effective brine discharge, agreeing well with preliminary experimental results. The objective for the two-body attenuator was to develop a method of power maximization through resonance tuning and numerical simulation. Three different geometries of body cross sections were used for the study with four different drag coefficients for each geometry. Power generation was maximized by adjusting body dimensions to match the natural frequency with the wave frequency. Based on the time domain simulation results, there was not a significant difference in power between the geometries when variation in drag was not considered, but the elliptical geometry had the highest power when using approximate drag coefficients. Using the two degree-of-freedom (2DOF) model with approximate drag coefficients, the elliptical cross section had a max power of 27.1 W and 7.36% capture width ratio (CWR) for regular waves and a max power of 8.32 W and 2.26% CWR for irregular waves. Using the three degree-of-freedom (3DOF) model with approximate drag coefficients, the elliptical cross section had a max power of 22.5 W and 6.12% CWR for regular waves and 6.18 W and 1.68% CWR for irregular waves. A mooring stiffness study was performed with the 3DOF model, showing that mooring stiffness can be increased to increase relative motion and therefore increase power. / Master of Science / As a clean, abundant, and renewable source of energy with a strategic location in close proximity to global population centers, ocean wave energy shows major promise. Although much wave energy converter development has focused on large-scale power generation, there is also increasing interest in small-scale applications for powering the blue economy. There are many situations where large-scale wave energy converter (WEC) devices are not necessary or practical, but easily-portable, small-sized WECs are suitable, including navigation signs, illumination, sensors, survival kits, electronics charging, and portable desalination. In this thesis, the objective was to optimize the performance of small-sized, oscillating body wave energy converters. Oscillating body WECs function by converting a device's wave-driven oscillating motion into useful power. Two types of oscillating body WECs were studied: bottom hinged and two-body attenuator. For the bottom-hinged device, the goal was to show the feasibility of a WEC and desalination system using numerical modeling to estimate the system performance. Based on the model results, the system will produce desirable amounts of fresh water with suitably low concentration and be effective at discharging brine. The objective for the two-body attenuator was to develop a method of power maximization through resonance tuning and numerical simulation. Based on the two- and three-degree-of-freedom model results with approximate drag coefficients, the elliptical cross section had the largest power absorption out of three different geometries of body cross sections. A mooring stiffness study with the three-degree-of-freedom model showed that mooring stiffness can be increased to increase power absorption.

<p>A systematic study of trends in band gap and lattice energies for bare zinc oxide nanoparticles were performed by means of quantum chemical density functional theory (DFT) calculations and density of states (DOS) calculations. The geometry of the optimized structures and the appearance of their frontier orbitals were also studied. The particles studied varied in sizes from (ZnO)₆ up to (ZnO)₁₉₂.The functionalization of bare and hydroxylated ZnO surfaces with MPTMS was studied with emphasis on the adsorption energies for adsorption to different surfaces and the effects on the band gap for such adsorptions.</p>

A systematic study of trends in band gap and lattice energies for bare zinc oxide nanoparticles were performed by means of quantum chemical density functional theory (DFT) calculations and density of states (DOS) calculations. The geometry of the optimized structures and the appearance of their frontier orbitals were also studied. The particles studied varied in sizes from (ZnO)6 up to (ZnO)192.The functionalization of bare and hydroxylated ZnO surfaces with MPTMS was studied with emphasis on the adsorption energies for adsorption to different surfaces and the effects on the band gap for such adsorptions.

Pjezoelektriniai keitikliai naudojami įvairiuose įrenginiuose, kur reikalingas itin didelis tikslumas, greitaveika ir nanometrų eilės matmenys. Šiame darbe pristatomas nanometrinės skyros cilindrinio pjezokeitiklio, naudojamo palydovo kameros pozicionavimui, tyrimas. Pirmame skyriuje aptartos fizikinės pjezokeraminių medžiagų savybės, pjezokeitiklių konstrukcijos, tvirtinimo sąlygos bei baigtinių elementų metodas. Antrame skyriuje pateikta išsami publikacijų, susijusių su cilindriniais pjezokeitikliais apžvalga. Trečiame skyriuje sprendžiamas cilindrinio pjezokeitiklio matmenų ir elektrodų schemos parinkimo uždavinys. Baigtinių elementų metodas naudojamas sprendžiant cilindrinio pjezokeitiklio savųjų reikšmių ir harmoninės analizės uždavinius. Cilindrinio pjezokeitiklio skaitinis modeliavimas atliktas naudojant ANSYS programinę įrangą. / Piezoelectric actuators are used in various devices where great precision, speed and nanometric scaling are needed. In this paper a nanometric scale piezoelectric actuator used for satellite camera's positioning is presented. In the first chapter physical properties of piezoeletric materials, piezoelectric constructions, support conditions and finite element method are presented. In the second chapter a wide review of literature related to cylindrical piezoelectric actuators is given. In the third chapter a problem of geometrical parameters and electrode schemes selection of cylindrical piezoelectric actuator is investigated. Finite element method is used for determining eigenfrequencies and performing harmonic analysis. Numerical modeling of piezoelectric actuator is carried out using ANSYS software.

The nature of the ground state and the first (lowest) singlet excited state geometrical conformations and electronic transitions in the aromatic five-membered heterocyclic oligomers &ndash / oligothiophenes (nT), oligofurans (nF), and oligopyrroles (nP)- containing up to six monomer units (total of 18 molecules) were explored using several computational methodologies. Geometry optimizations were carried out at Austin Model 1 (AM1), Restricted Hartree-Fock (RHF/6-31G*), and Density Functional Theory (DFT, B3LYP/6-31G*) levels for the ground-state conformations of these structurally well-defined heterocyclic oligomers. The Configuration Interaction Singles (CIS) method with the 6-31G* basis set was chosen in computation of the optimal geometry of the lowest singlet excited state. Lowest singlet excitation S1&szlig / S0 energies were calculated using the Zerner&rsquo / s Intermediate Neglect of Differential Overlap for Spectroscopy (ZINDO/S), CIS (CIS/6-31G*), and Time-Dependent DFT (TDDFT/6-31G* and TDDFT/6-31+G*) methods. In computation of the emission S1&agrave / S0 energies, we have employed all methods above except ZINDO/S. In investigation of geometries of the ground and lowest singlet excited state, we compared the bond length alternation (BLA) parameters, Dri in the conjugated backbone of the oligomers. Saturation of the geometrical parameters at the center of oligomers was observed after a certain chain length. Among all methodologies used in computation of excitation (S1&szlig / S0) and emission (S1&agrave / S0) energies, TDDFT results showed the best agreement with experimental data. Fits of computed and experimental excitation energies to an exponential function using the least squares method enabled us to predict Effective Conjugation Length (ECL) values. We obtained the ECLs of 17 (17), 16 (15), and 14 (13) monomer units for polythiophene (PTh), polyfuran (PFu), and polypyrrole (PPr), which have very good agreement with the results obtained from the fits of experimental data (the values in parentheses).

Este trabalho trata da aplicação do método Design Construtal para investigar a transferência de calor através de caminhos de alta condutividade térmica com geometrias definidas. O objetivo é obter a configuração que reduz a temperatura máxima em excesso do sistema considerando que as áreas ocupadas pelos materiais de alta e baixa condutividade são tratadas como constantes. Assim, o objeto de estudo é um volume de área finita onde ocorre a geração de calor. O escoamento da energia térmica para fora do volume é feito através de um caminho condutor de alta condutividade térmica. O trabalho considerou a resistência térmica de contato entre o elemento condutivo e o corpo gerador de calor, onde um terceiro material com resistência térmica equivalente à resistência de contato é interposto entre os dois primeiros. Na solução da equação da difusão do calor, foi realizado um tratamento numérico através de um código baseado em elementos finitos e utilizando o toolbox PDETool, Partial Differential Equations Tool, que pertence ao aplicativo comercial MatLab®. O tratamento numérico foi realizado considerando-se caminhos condutivos com geometrias em forma de "I" e em forma de "T", mantendo-se as frações de área constantes e variando-se os comprimentos dos materiais de alta condutividade e os da resistência térmica de contato. A otimização geométrica foi feita considerando-se os graus de liberdade existentes para cada geometria, onde os valores otimizados para a situação ideal, ou de acoplamento térmico perfeito, foram comparados para os resultados envolvendo a resistência térmica de contato (RTC). Os resultados indicam que a RTC pode aumentar a temperatura máxima em excesso, assim como tem efeito significativo sobre as ótimas configurações calculadas quando a resistência de contato é levada em consideração para ambas as configurações "I" e "T" estudadas. / This work applies Constructal Design to investigate the heat transfer through high conductive pathways with defined geometries. The objective is to find the configuration which reduces the maximal excess of temperature considering the areas with high and low thermal conductivity are constants. Thus, the object studied here is a volume with a finite area and heat generation. The outside heat flux is conducted through a high thermal conductive pathway. Here, special attention is given to the thermal contact resistance between the high conductive pathway and the solid body, where a third material with a thermal resistance equivalent to the thermal contact resistance is inserted between them. A numerical treatment was given in order to solve the heat diffusive equation. It was used a numerical code based on finite elements and the toolbox – PDETool, Partial Differential Equations Tool, which is part of the MatLab® applicative. The numerical treatment was achieved considering "I" and "T" geometries for the high conductive pathways keeping the areas fraction constants and varying the lengths of both high conductive and the equivalent thermal contact layer materials. The optimization was performed considering the degrees of freedom of each geometry, where the optimized values for the ideal situation, i.e., perfect thermal contact were compared with the results considering the thermal contact resistance. The results indicate that the thermal contact resistance can increase the excess of temperature, as well as it has a significant effect on the optimal configurations when using perfect thermal contact or taking into account the thermal contact resistance for "I" and "T" shaped geometries.

Este trabalho trata da aplicação do método Design Construtal para investigar a transferência de calor através de caminhos de alta condutividade térmica com geometrias definidas. O objetivo é obter a configuração que reduz a temperatura máxima em excesso do sistema considerando que as áreas ocupadas pelos materiais de alta e baixa condutividade são tratadas como constantes. Assim, o objeto de estudo é um volume de área finita onde ocorre a geração de calor. O escoamento da energia térmica para fora do volume é feito através de um caminho condutor de alta condutividade térmica. O trabalho considerou a resistência térmica de contato entre o elemento condutivo e o corpo gerador de calor, onde um terceiro material com resistência térmica equivalente à resistência de contato é interposto entre os dois primeiros. Na solução da equação da difusão do calor, foi realizado um tratamento numérico através de um código baseado em elementos finitos e utilizando o toolbox PDETool, Partial Differential Equations Tool, que pertence ao aplicativo comercial MatLab®. O tratamento numérico foi realizado considerando-se caminhos condutivos com geometrias em forma de "I" e em forma de "T", mantendo-se as frações de área constantes e variando-se os comprimentos dos materiais de alta condutividade e os da resistência térmica de contato. A otimização geométrica foi feita considerando-se os graus de liberdade existentes para cada geometria, onde os valores otimizados para a situação ideal, ou de acoplamento térmico perfeito, foram comparados para os resultados envolvendo a resistência térmica de contato (RTC). Os resultados indicam que a RTC pode aumentar a temperatura máxima em excesso, assim como tem efeito significativo sobre as ótimas configurações calculadas quando a resistência de contato é levada em consideração para ambas as configurações "I" e "T" estudadas. / This work applies Constructal Design to investigate the heat transfer through high conductive pathways with defined geometries. The objective is to find the configuration which reduces the maximal excess of temperature considering the areas with high and low thermal conductivity are constants. Thus, the object studied here is a volume with a finite area and heat generation. The outside heat flux is conducted through a high thermal conductive pathway. Here, special attention is given to the thermal contact resistance between the high conductive pathway and the solid body, where a third material with a thermal resistance equivalent to the thermal contact resistance is inserted between them. A numerical treatment was given in order to solve the heat diffusive equation. It was used a numerical code based on finite elements and the toolbox – PDETool, Partial Differential Equations Tool, which is part of the MatLab® applicative. The numerical treatment was achieved considering "I" and "T" geometries for the high conductive pathways keeping the areas fraction constants and varying the lengths of both high conductive and the equivalent thermal contact layer materials. The optimization was performed considering the degrees of freedom of each geometry, where the optimized values for the ideal situation, i.e., perfect thermal contact were compared with the results considering the thermal contact resistance. The results indicate that the thermal contact resistance can increase the excess of temperature, as well as it has a significant effect on the optimal configurations when using perfect thermal contact or taking into account the thermal contact resistance for "I" and "T" shaped geometries.

Este trabalho trata da aplicação do método Design Construtal para investigar a transferência de calor através de caminhos de alta condutividade térmica com geometrias definidas. O objetivo é obter a configuração que reduz a temperatura máxima em excesso do sistema considerando que as áreas ocupadas pelos materiais de alta e baixa condutividade são tratadas como constantes. Assim, o objeto de estudo é um volume de área finita onde ocorre a geração de calor. O escoamento da energia térmica para fora do volume é feito através de um caminho condutor de alta condutividade térmica. O trabalho considerou a resistência térmica de contato entre o elemento condutivo e o corpo gerador de calor, onde um terceiro material com resistência térmica equivalente à resistência de contato é interposto entre os dois primeiros. Na solução da equação da difusão do calor, foi realizado um tratamento numérico através de um código baseado em elementos finitos e utilizando o toolbox PDETool, Partial Differential Equations Tool, que pertence ao aplicativo comercial MatLab®. O tratamento numérico foi realizado considerando-se caminhos condutivos com geometrias em forma de "I" e em forma de "T", mantendo-se as frações de área constantes e variando-se os comprimentos dos materiais de alta condutividade e os da resistência térmica de contato. A otimização geométrica foi feita considerando-se os graus de liberdade existentes para cada geometria, onde os valores otimizados para a situação ideal, ou de acoplamento térmico perfeito, foram comparados para os resultados envolvendo a resistência térmica de contato (RTC). Os resultados indicam que a RTC pode aumentar a temperatura máxima em excesso, assim como tem efeito significativo sobre as ótimas configurações calculadas quando a resistência de contato é levada em consideração para ambas as configurações "I" e "T" estudadas. / This work applies Constructal Design to investigate the heat transfer through high conductive pathways with defined geometries. The objective is to find the configuration which reduces the maximal excess of temperature considering the areas with high and low thermal conductivity are constants. Thus, the object studied here is a volume with a finite area and heat generation. The outside heat flux is conducted through a high thermal conductive pathway. Here, special attention is given to the thermal contact resistance between the high conductive pathway and the solid body, where a third material with a thermal resistance equivalent to the thermal contact resistance is inserted between them. A numerical treatment was given in order to solve the heat diffusive equation. It was used a numerical code based on finite elements and the toolbox – PDETool, Partial Differential Equations Tool, which is part of the MatLab® applicative. The numerical treatment was achieved considering "I" and "T" geometries for the high conductive pathways keeping the areas fraction constants and varying the lengths of both high conductive and the equivalent thermal contact layer materials. The optimization was performed considering the degrees of freedom of each geometry, where the optimized values for the ideal situation, i.e., perfect thermal contact were compared with the results considering the thermal contact resistance. The results indicate that the thermal contact resistance can increase the excess of temperature, as well as it has a significant effect on the optimal configurations when using perfect thermal contact or taking into account the thermal contact resistance for "I" and "T" shaped geometries.