Formulação teórica dos fundamentos da otimização global topográfica com análise de desempenho e aplicações à estabilidade de fases de misturas termodinâmicas

Métodos de otimização que utilizam condições de otimalidade de primeira e/ou segunda ordem são conhecidos por serem eficientes. Comumente, esses métodos iterativos são desenvolvidos e analisados à luz da análise matemática do espaço euclidiano n-dimensional, cuja natureza é de caráter local. Consequentemente, esses métodos levam a algoritmos iterativos que executam apenas as buscas locais. Assim, a aplicação de tais algoritmos para o cálculo de minimizadores globais de uma função não linear,especialmente não-convexas e multimodais, depende fortemente da localização dos pontos de partida. O método de Otimização Global Topográfico é um algoritmo de agrupamento, que utiliza uma abordagem baseada em conceitos elementares da teoria dos grafos, a fim de gerar bons pontos de partida para os métodos de busca local, a partir de pontos distribuídos de modo uniforme no interior da região viável. Este trabalho tem dois objetivos. O primeiro é realizar uma nova abordagem sobre método de Otimização Global Topográfica, onde, pela primeira vez, seus fundamentos são formalmente descritos e suas propriedades básicas são matematicamente comprovadas. Neste contexto, propõe-se uma fórmula semi-empírica para calcular o parâmetro chave deste algoritmo de agrupamento, e, usando um método robusto e eficiente de direções viáveis por pontos-interiores, estendemos o uso do método de Otimização Global Topográfica a problemas com restrições de desigualdade. O segundo objetivo é a aplicação deste método para a análise de estabilidade de fase em misturas termodinâmicas,o qual consiste em determinar se uma dada mistura se apresenta em uma ou mais fases. A solução deste problema de otimização global é necessária para o cálculo do equilíbrio de fases, que é um problema de grande importância em processos da engenharia, como, por exemplo, na separação por destilação, em processos de extração e simulação da recuperação terciária de petróleo, entre outros. Além disso, afim de ter uma avaliação inicial do potencial dessa técnica, primeiro vamos resolver 70 problemas testes, e então comparar o desempenho do método proposto aqui com o solver MIDACO, um poderoso software recentemente introduzido no campo da otimização global.

Biossorção de lantânio por Sargassum sp.: ensaios em batelada e contínuos

Diante dos avanços tecnológicos, pesquisadores têm intensificado a busca por métodos de remoção de metais, que tragam bons resultados de captação a partir de efluentes contaminados, aliados a um baixo custo. A utilização de materiais biológicos como algas marinhas, fungos e bactérias vem se destacando e se tornando uma solução atrativa quando comparados com os tratamentos químicos convencionais; essa técnica é denominada biossorção. A biossorção é um processo de captação de íons metálicos de uma solução, a partir de interações entre o metal e determinados sítios ativos presentes na parede celular da biomassa. Existe também um crescente interesse pelo estudo dos elementos de terras raras (TR) por possuirem alto valor agregado, acarretado por processos caros e de alta complexidade na sua separação e purificação. Desta forma, este trabalho teve como objetivo descrever o potencial de biossorção de lantânio - um representante dos TR - pela macroalga Sargassum sp., a partir de soluções aquosas. Para isso foram realizados estudos em batelada, aplicando modelos cinéticos e de equilíbrio, e estudos em regime contínuo de biossorção dos íons de lantânio (III), além de um sistema contínuo bimetálico, no qual houve a adição do metal cério, outro TR. As determinações analíticas foram realizadas por espectrometria de emissão ótica por plasma indutivamente acoplado. Os ensaios cinéticos foram realizados nas concentrações metálicas de 10 e 100 mg.L-1 e em duas concentrações distintas de biomassa 2 e 5 g.L-1 na temperatura de 301C. Dois modelos cinéticos foram testados, pseudo-primeira ordem e segunda ordem, tendo o modelo de segunda ordem apresentado melhor ajuste dos dados, com r2 igual a 0,9697. No ensaio de equilíbrio foi construída a isoterma que apresentou um perfil crescente na captação no entanto não alcançou a remoção máxima. Os modelos de Langmuir e Freundlich foram utilizados para ajustar os dados da isoterma, sendo verificado maior correlação dos dados com o modelo de Langmuir; resultando num valor de captação máxima calculado pelo modelo de 3,55 mmol.g-1. No ensaio dinâmico foram realizados dois experimentos, 1 e 2. O Experimento 1 foi realizado com três colunas interligadas e recheadas com 20g de biomassa cada, sendo bombeada uma solução aquosa de lantânio na concentração de 1,41mmol.L-1. O Experimento 2 foi constituido de uma solução contendo lantânio e cério ambos na mesma concentração anterior de 1,41 mmol.L-1, sendo bombeada somente para uma única coluna recheada com 20g de biomassa. Os resultados demonstraram que o ponto de saturação não foi atingido dentro das 8 horas em que se deu o processo, o que indica a alta afinidade da Sargassum sp. pelo lantânio e que a presença do cério associada a redução da vazão prejudicou a captação do lantânio

Aplicação da equação de Poisson-Boltzmann modificada em sistemas biológicos: análise da partição iônica em um eritrócito

Neste trabalho, a partição iônica e o potencial de membrana em um eritrócito são analisados via equação de Poisson-Boltzmann modificada, considerando as interações não eletrostáticas presentes entre os íons e macromoléculas, assim como, o potencial β. Este potencial é atribuído à diferença de potencial químico de referência entre os meios intracelular e extracelular e ao transporte ativo de íons. O potencial de Gibbs-Donnan via equação de Poisson-Boltzmann na presença de carga fixa em um sistema contendo uma membrana semipermeável também é estudado. O método de aproximação paraboloide em elementos finitos em um sistema estacionário e unidimensionalé aplicado para resolver a equação de Poisson-Boltzmann em coordenadas cartesianas e esféricas. O parâmetro de dispersão relativo às interações não eletrostáticas écalculado via teoria de Lifshitz. Os resultados em relação ao potencial de Gibbs-Donnan mostram-se adequados, podendo ser calculado pela equação de Poisson-Boltzmann. No sistema contendo um eritrócito, quando o potencial β é considerado igual a zero, não se verifica a diferença iônica observada experimentalmente entre os meios intracelular e extracelular. Dessa forma, os potenciais não eletrostáticos calculados via teoria de Lifshitz têm apenas uma pequena influência no que se refere à alta concentração de íon K+ no meio intracelular em relação ao íon Na+

Interesse e virtude: a sociologia modernista dos anos 30

O objeto de estudo desta tese é a sociologia modernista brasileira da década de 1930. Em primeiro lugar, se adentra nas configurações gerais do termo sociologia modernista em relação à sua inserção na história e desenvolvimento das ciências sociais no Brasil. Em segundo lugar, se discute o suporte de escrita que este tipo de interpretação privilegiou, o ensaio. Em terceiro lugar, se relacionou os mundos da cultura e política no contexto da formação do modernismo brasileiro e sua imbricação direta com as florações da sociologia modernista. E por fim, se estabeleceu uma interpretação dos principais temas e dos argumentos expostos e debatidos pela sociologia modernista dos anos 1930. Nestes termos, este trabalho diz respeito: a constituição de uma tradição sociológica periférica em relação ao sistema-mundo; a proposição da constituição de uma história da sociologia brasileira, múltipla e dinâmica, que leva em conta as diferentes imersões propostas por cada estilo de pensamento; a constituição do ensaio como suporte de escrita e modo de apresentação das ideias conectados à posição e experiência intelectual latino-americana em geral e brasileira em particular; a uma ampliação do conceito de modernismo e sua relação com a teoria social periférica; ao processo de modernização brasileiro e suas íntimas relações com o modernismo; à construção de uma interpretação de segunda ordem, que possibilite interpretar a teoria social advinda da sociologia modernista a partir da dupla perspectiva do cronótopo constituído: o tempo e o espaço; a caracterização da sociologia modernista a partir da concepção de cartografia semântica e figuração, como permeáveis à análise dos textos abordados.

Otimização global topográfica aplicada a problemas de otimização com restrições de igualdade e desigualdade

Os métodos de otimização que adotam condições de otimalidade de primeira e/ou segunda ordem são eficientes e normalmente esses métodos iterativos são desenvolvidos e analisados através da análise matemática do espaço euclidiano n-dimensional, o qual tem caráter local. Esses métodos levam a algoritmos iterativos que são usados para o cálculo de minimizadores globais de uma função não linear, principalmente não-convexas e multimodais, dependendo da posição dos pontos de partida. Método de Otimização Global Topográfico é um algoritmo de agrupamento, o qual é fundamentado nos conceitos elementares da teoria dos grafos, com a finalidade de gerar bons pontos de partida para os métodos de busca local, com base nos pontos distribuídos de modo uniforme no interior da região viável. Este trabalho tem como objetivo a aplicação do método de Otimização Global Topográfica junto com um método robusto e eficaz de direções viáveis por pontos-interiores a problemas de otimização que tem restrições de igualdade e/ou desigualdade lineares e/ou não lineares, que constituem conjuntos viáveis com interiores não vazios. Para cada um destes problemas, é representado também um hiper-retângulo compreendendo cada conjunto viável, onde os pontos amostrais são gerados.

A comparison of methods for the coupled analysis of floating structures

The dynamic analysis of a deepwater floating platform and the associated mooring/riser system should ideally be fully coupled to ensure a reliable response prediction. It is generally held that a time domain analysis is the only means of capturing the various coupling and nonlinear effects accurately. However, in recent work it has been found that for an ultra-deepwater floating system (2000m water depth), the highly efficient frequency domain approach can provide highly accurate response predictions. One reason for this is the accuracy of the drag linearization procedure over both first and second order motions, another reason is the minimal geometric nonlinearity displayed by the mooring lines in deepwater. In this paper, the aim is to develop an efficient analysis method for intermediate water depths, where both mooring/vessel coupling and geometric nonlinearity are of importance. It is found that the standard frequency domain approach is not so accurate for this case and two alternative methods are investigated. In the first, an enhanced frequency domain approach is adopted, in which line nonlinearities are linearized in a systematic way. In the second, a hybrid approach is adopted in which the low frequency motion is solved in the time domain while the high frequency motion is solved in the frequency domain; the two analyses are coupled by the fact that (i) the low frequency motion affects the mooring line geometry for the high frequency motion, and (ii) the high frequency motion affects the drag forces which damp the low frequency motion. The accuracy and efficiency of each of the methods are systematically compared. Copyright © 2007 by ASME.

Metal Retention Experiments for the Design of Soil-Mix Technology Permeable Reactive Barriers

Soil-mix technology is effective for the construction of permeable reactive barriers (PRBs) for in situ groundwater treatment. The objective of this study was to perform initial experiments for the design of soil-mix technology PRBs according to (i) sorption isotherm, (ii) reaction kinetics and (iii) mass balance of the contaminants. The four tested reactive systems were: (i) a granular zeolite (clinoptilolite-GZ), (ii) a granular organoclay (GO), (iii) a 1:1-mixture GZ and model sandy clayey soil and (iv) a 1:1:1-mixture of GZ, GO and model soil. The laboratory experiments consisted of batch tests (volume 900mL and sorbent mass 18g) with a multimetal solution of Pb, Cu, Zn, Cd and Ni. For the adsorption experiment, the initial concentrations ranged from 0.01 to 0.5mM (2.5 to 30mg/L). The maximum metal retention was measured in a batch test (300mg/L for each metal, volume 900mL, sorbent mass 90-4.5g). The reactive material efficiency order was found to be GZ>GZ-soil mix>GZ-soil-GO mix>GO. Langmuir isotherms modelled the adsorption, even in presence of a mixed cations solution. Adsorption was energetically favourable and spontaneous in all cases. Metals were removed according to the second order reaction kinetics; GZ and the 1:1-mix were very similar. The maximum retention capacity was 0.1-0.2mmol/g for Pb in the presence of clinoptilolite; for Cu, Zn, Cd and Ni, it was below 0.05mmol/g for the four reactive systems. Mixing granular zeolite, organoclay and model soil increased the chemisorption. Providing that GZ is reactive enough for the specific conditions, GZ can be mixed to obtain the required sorption. Granular clinoptilolite addition to soil is recommended for PRBs for metal contaminated groundwater. The laboratory experiments consisted of batch tests with a multimetal solution of Pb, Cu, Zn, Cd and Ni. The four reactive materials chosen were granular zeolite, clinoptilolite and model sandy clayey soil, granular organoclay and a mix of clinoptilolite, model soil and organoclay. The reactive material efficiency order was found to be granular clinoptilolite>clinoptilolite-soil mix>clinoptilolite-soil-organoclay mix>granular organoclay. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Measurement-Integrated simulations and Kalman filter applied to a co-flowing jet

This paper deals with the experimental evaluation of a flow analysis system based on the integration between an under-resolved Navier-Stokes simulation and experimental measurements with the mechanism of feedback (referred to as Measurement-Integrated simulation), applied to the case of a planar turbulent co-flowing jet. The experiments are performed with inner-to-outer-jet velocity ratio around 2 and the Reynolds number based on the inner-jet heights about 10000. The measurement system is a high-speed PIV, which provides time-resolved data of the flow-field, on a field of view which extends to 20 jet heights downstream the jet outlet. The experimental data can thus be used both for providing the feedback data for the simulations and for validation of the MI-simulations over a wide region. The effect of reduced data-rate and spatial extent of the feedback (i.e. measurements are not available at each simulation time-step or discretization point) was investigated. At first simulations were run with full information in order to obtain an upper limit of the MI-simulations performance. The results show the potential of this methodology of reproducing first and second order statistics of the turbulent flow with good accuracy. Then, to deal with the reduced data different feedback strategies were tested. It was found that for small data-rate reduction the results are basically equivalent to the case of full-information feedback but as the feedback data-rate is reduced further the error increases and tend to be localized in regions of high turbulent activity. Moreover, it is found that the spatial distribution of the error looks qualitatively different for different feedback strategies. Feedback gain distributions calculated by optimal control theory are presented and proposed as a mean to make it possible to perform MI-simulations based on localized measurements only. So far, we have not been able to low error between measurements and simulations by using these gain distributions.

On the use of combined compact scheme for numerical solution of the two-layer oceanic shallow water equations

Many types of oceanic physical phenomena have a wide range in both space and time. In general, simplified models, such as shallow water model, are used to describe these oceanic motions. The shallow water equations are widely applied in various oceanic and atmospheric extents. By using the two-layer shallow water equations, the stratification effects can be considered too. In this research, the sixth-order combined compact method is investigated and numerically implemented as a high-order method to solve the two-layer shallow water equations. The second-order centered, fourth-order compact and sixth-order super compact finite difference methods are also used to spatial differencing of the equations. The first part of the present work is devoted to accuracy assessment of the sixth-order super compact finite difference method (SCFDM) and the sixth-order combined compact finite difference method (CCFDM) for spatial differencing of the linearized two-layer shallow water equations on the Arakawa's A-E and Randall's Z numerical grids. Two general discrete dispersion relations on different numerical grids, for inertia-gravity and Rossby waves, are derived. These general relations can be used for evaluation of the performance of any desired numerical scheme. For both inertia-gravity and Rossby waves, minimum error generally occurs on Z grid using either the sixth-order SCFDM or CCFDM methods. For the Randall's Z grid, the sixth-order CCFDM exhibits a substantial improvement , for the frequency of the barotropic and baroclinic modes of the linear inertia-gravity waves of the two layer shallow water model, over the sixth-order SCFDM. For the Rossby waves, the sixth-order SCFDM shows improvement, for the barotropic and baroclinic modes, over the sixth-order CCFDM method except on Arakawa's C grid. In the second part of the present work, the sixth-order CCFDM method is used to solve the one-layer and two-layer shallow water equations in their nonlinear form. In one-layer model with periodic boundaries, the performance of the methods for mass conservation is compared. The results show high accuracy of the sixth-order CCFDM method to simulate a complex flow field. Furthermore, to evaluate the performance of the method in a non-periodic domain the sixth-order CCFDM is applied to spatial differencing of vorticity-divergence-mass representation of one-layer shallow water equations to solve a wind-driven current problem with no-slip boundary conditions. The results show good agreement with published works. Finally, the performance of different schemes for spatial differencing of two-layer shallow water equations on Z grid with periodic boundaries is investigated. Results illustrate the high accuracy of combined compact method.

A study of capacitance-voltage characteristics of lead zirconate titanate ferroelectric thin films and their usage to investigate polarization and coercive field.

Capacitance-voltage (C-V) characteristics of lead zirconate titanate (PZT) thin films with a thickness of 130 nm were measured between 300 and 533 K. The transition between ferroelectric and paraelectric phases was revealed to be of second order in our case, with a Curie temperature at around 450 K. A linear relationship was found between the measured capacitance and the inverse square root of the applied voltage. It was shown that such a relationship could be fitted well by a universal expression of C/A = k(V+V(0))(-1/2) and that this expression could be derived by expanding the Landau-Devonshire free energy at an effective equilibrium position of the Ti/Zr ion in a PZT unit cell. By using the derived equations in this work, the free energy parameters for an individual material can be obtained solely from the corresponding C-V data, and the temperature dependences of both remnant polarization and coercive voltage are shown to be in quantitative agreement with the experimental data.

Psychometric evaluation and experimental validation of the statistics anxiety rating scale.

The Statistics Anxiety Rating Scale (STARS) was adapted into German to examine its psychometric properties (n = 400). Two validation studies (n = 66, n = 96) were conducted to examine its criterion-related validity. The psychometric properties of the questionnaire were very similar to those previously reported for the original English version in various countries and other language versions. Confirmatory factor analysis indicated 2 second-order factors: One was more closely related to anxiety and the other was more closely related to negative attitudes toward statistics. Predictive validity of the STARS was shown both in an experimental exam-like situation in the laboratory and during a real examination situation. Taken together, the findings indicate that statistics anxiety as assessed by the STARS is a useful construct that is more than just an expression of a more general disposition to anxiety.

Explosion pressure prediction via polynomial mathematical correlation based on advanced CFD Modelling

Computational Fluid Dynamics CFD can be used as a powerful tool supporting engineers throughout the steps of the design. The combination of CFD with response surface methodology can play an important role in such cases. During the conceptual engineering design phase, a quick response is always a matter of urgency. During this phase even a sketch of the geometrical model is rare. Therefore, the utilisation of typical response surface developed for congested and confined environment rather than CFD can be an important tool to help the decision making process, when the geometrical model is not available, provided that similarities can be considered when taking into account the characteristic of the geometry in which the response surface was developed. The present work investigates how three different types of response surfaces behave when predicting overpressure in accidental scenarios based on CFD input. First order, partial second order and complete second order polynomial expressions are investigated. The predicted results are compared with CFD findings for a classical offshore experiment conducted by British Gas on behalf of Mobil and good agreement is observed for higher order response surfaces. The higher order response surface calculations are also compared with CFD calculations for a typical offshore module and good agreement is also observed. © 2011 Elsevier Ltd.

The non-local nature of structure functions

Kolmogorov's two-thirds, ((Δv) 2) ∼ e 2/ 3r 2/ 3, and five-thirds, E ∼ e 2/ 3k -5/ 3, laws are formally equivalent in the limit of vanishing viscosity, v → 0. However, for most Reynolds numbers encountered in laboratory scale experiments, or numerical simulations, it is invariably easier to observe the five-thirds law. By creating artificial fields of isotropic turbulence composed of a random sea of Gaussian eddies whose size and energy distribution can be controlled, we show why this is the case. The energy of eddies of scale, s, is shown to vary as s 2/ 3, in accordance with Kolmogorov's 1941 law, and we vary the range of scales, γ = s max/s min, in any one realisation from γ = 25 to γ = 800. This is equivalent to varying the Reynolds number in an experiment from R λ = 60 to R λ = 600. While there is some evidence of a five-thirds law for g > 50 (R λ > 100), the two-thirds law only starts to become apparent when g approaches 200 (R λ ∼ 240). The reason for this discrepancy is that the second-order structure function is a poor filter, mixing information about energy and enstrophy, and from scales larger and smaller than r. In particular, in the inertial range, ((Δv) 2) takes the form of a mixed power-law, a 1+a 2r 2+a 3r 2/ 3, where a 2r 2 tracks the variation in enstrophy and a 3r 2/ 3 the variation in energy. These findings are shown to be consistent with experimental data where the polution of the r 2/ 3 law by the enstrophy contribution, a 2r 2, is clearly evident. We show that higherorder structure functions (of even order) suffer from a similar deficiency.

Spatial correlation of heat release rate and sound emission from turbulent premixed flames

The two-point spatial correlation of the rate of change of fluctuating heat release rate is central to the sound emission from open turbulent flames, and a few attempts have been made to address this correlation in recent studies. In this paper, the two-point correlation and its role in combustion noise are studied by analysing direct numerical simulation (DNS) data of statistically multi-dimensional turbulent premixed flames. The results suggest that this correlation function depends on the separation distance and direction but, not on the positions inside the flame brush. This correlation can be modelled using a combination of Hermite-Gaussian functions of zero and second order, i.e. functions of the form (1-Ax2)e-Bx2 for constants A and B, to include its possible negative values. The integral correlation volume obtained using this model is about 0.2δL3 with the length scale obtained from its cube root being about 0.6δ L, where δ L is the laminar flame thermal thickness. Both of the values are slightly larger than the values reported in an earlier study because of the anisotropy observed for the correlation. This model together with the turbulence-dependent parameter K, the ratio of the root-mean-square (RMS) value of the rate of change of reaction rate to the mean reaction rate, derived from the DNS data is applied to predict the far-field sound emitted from open flames. The calculated noise levels agree well with recently reported measurements and show a sensitivity to K values. © 2012 The Combustion Institute.

2D PIV measurements in the near field of grid turbulence using stitched fields from multiple cameras

We present measurements of grid turbulence using 2D particle image velocimetry taken immediately downstream from the grid at a Reynolds number of Re M = 16500 where M is the rod spacing. A long field of view of 14M x 4M in the down- and cross-stream directions was achieved by stitching multiple cameras together. Two uniform biplanar grids were selected to have the same M and pressure drop but different rod diameter D and crosssection. A large data set (10 4 vector fields) was obtained to ensure good convergence of second-order statistics. Estimations of the dissipation rate ε of turbulent kinetic energy (TKE) were found to be sensitive to the number of meansquared velocity gradient terms included and not whether the turbulence was assumed to adhere to isotropy or axisymmetry. The resolution dependency of different turbulence statistics was assessed with a procedure that does not rely on the dissipation scale η. The streamwise evolution of the TKE components and ε was found to collapse across grids when the rod diameter was included in the normalisation. We argue that this should be the case between all regular grids when the other relevant dimensionless quantities are matched and the flow has become homogeneous across the stream. Two-point space correlation functions at x/M = 1 show evidence of complex wake interactions which exhibit a strong Reynolds number dependence. However, these changes in initial conditions disappear indicating rapid cross-stream homogenisation. On the other hand, isotropy was, as expected, not found to be established by x/M = 12 for any case studied. © Springer-Verlag 2012.