953 resultados para first-order kinetics


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The problem of uncertainty propagation in composite laminate structures is studied. An approach based on the optimal design of composite structures to achieve a target reliability level is proposed. Using the Uniform Design Method (UDM), a set of design points is generated over a design domain centred at mean values of random variables, aimed at studying the space variability. The most critical Tsai number, the structural reliability index and the sensitivities are obtained for each UDM design point, using the maximum load obtained from optimal design search. Using the UDM design points as input/output patterns, an Artificial Neural Network (ANN) is developed based on supervised evolutionary learning. Finally, using the developed ANN a Monte Carlo simulation procedure is implemented and the variability of the structural response based on global sensitivity analysis (GSA) is studied. The GSA is based on the first order Sobol indices and relative sensitivities. An appropriate GSA algorithm aiming to obtain Sobol indices is proposed. The most important sources of uncertainty are identified.

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Trabalho de Projeto para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização em Estruturas

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This article describes a finite element-based formulation for the statistical analysis of the response of stochastic structural composite systems whose material properties are described by random fields. A first-order technique is used to obtain the second-order statistics for the structural response considering means and variances of the displacement and stress fields of plate or shell composite structures. Propagation of uncertainties depends on sensitivities taken as measurement of variation effects. The adjoint variable method is used to obtain the sensitivity matrix. This method is appropriated for composite structures due to the large number of random input parameters. Dominant effects on the stochastic characteristics are studied analyzing the influence of different random parameters. In particular, a study of the anisotropy influence on uncertainties propagation of angle-ply composites is carried out based on the proposed approach.

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The influence of uncertainties of input parameters on output response of composite structures is investigated in this paper. In particular, the effects of deviations in mechanical properties, ply angles, ply thickness and on applied loads are studied. The uncertainty propagation and the importance measure of input parameters are analysed using three different approaches: a first-order local method, a Global Sensitivity Analysis (GSA) supported by a variance-based method and an extension of local variance to estimate the global variance over the domain of inputs. Sample results are shown for a shell composite laminated structure built with different composite systems including multi-materials. The importance measures of input parameters on structural response based on numerical results are established and discussed as a function of the anisotropy of composite materials. Needs for global variance methods are discussed by comparing the results obtained from different proposed methodologies. The objective of this paper is to contribute for the use of GSA techniques together with low expensive local importance measures.

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Renders are an important item in historical buildings and the need for their periodical re-application is a basic conservation procedure. In modern times there has been a trend towards the replacement of traditional pure lime mortars by new formulations including Portland cement or hydraulic lime. Apart from those interventions on specific and very important monuments, in which the use oftraditional non-hydraulic mortars can be enforced, in most of the projects involving less than first order magnitude heritage the use of some sort of hydraulic components is becoming the rule rather than the exception. The present paper describes and analyses the results of an experimental study with ten formulations of current mortars - including some that can hardly be considered as adequate conservation procedures - allowing a direct comparison in terms of some of the most relevant characteristics.

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Dual-phase functionally graded materials are a particular type of composite materials whose properties are tailored to vary continuously, depending on its two constituent's composition distribution, and which use is increasing on the most diverse application fields. These materials are known to provide superior thermal and mechanical performances when compared to the traditional laminated composites, exactly because of this continuous properties variation characteristic, which enables among other advantages smoother stresses distribution profile. In this paper we study the influence of different homogenization schemes, namely the schemes due to Voigt, Hashin-Shtrikman and Mod-Tanaka, which can be used to obtain bounds estimates for the material properties of particulate composite structures. To achieve this goal we also use a set of finite element models based on higher order shear deformation theories and also on first order theory. From the studies carried out, on linear static analyses and on free vibration analyses, it is shown that the bounds estimates are as important as the deformation kinematics basis assumed to analyse these types of multifunctional structures. Concerning to the homogenization schemes studied, it is shown that Mori-Tanaka and Hashin-Shtrikman estimates lead to less conservative results when compared to Voigt rule of mixtures.

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Treatment of a dichloromethane solution of trans-[Mo(NCN){NCNC(O)R}(dppe)(2)]Cl [R = Me (1a), Et (1b)] (dppe = Ph2PCH2CH2PPh2) with HBF4, [Et3O][BF4] or EtC(O)Cl gives trans-[Mo(NCN)Cl-(dppe)(2)]X [X = BF4 (2a) or Cl (2b)] and the corresponding acylcyanamides NCN(R')C(O)Et (R' = H, Et or C(O)Et). X-ray diffraction analysis of 2a (X = BF4) reveals a multiple-bond coordination of the cyanoimide ligand. Compounds 1 convert to the bis(cyanoimide) trans-[Mo(NCN)(2)(dppe)(2)] complex upon reaction with an excess of NaOMe (with formation of the respective ester). In an aprotic medium and at a Pt electrode, compounds 1 (R = Me, Et or Ph) undergo a cathodically induced isomerization. Full quantitative kinetic analysis of the voltammetric behaviour is presented and allows the determination of the first-order rate constants and the equilibrium constant of the trans to cis isomerization reaction. The mechanisms of electrophilic addition (protonation) to complexes 1 and the precursor trans[Mo(NCN)(2)(dppe)(2)], as well as the electronic structures, nature of the coordination bonds and electrochemical behaviour of these species are investigated in detail by theoretical methods which indicate that the most probable sites of the proton attack are the oxygen atom of the acyl group and the terminal nitrogen atom, respectively.

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Remote Laboratories or WebLabs constitute a first-order didactic resource in engineering faculties. However, in many cases, they lack a proper software design, both in the client and server side, which degrades their quality and academic usefulness. This paper presents the main characteristics of a Remote Laboratory, analyzes the software technologies to implement the client and server sides in a WebLab, and correlates these technologies with the characteristics to facilitate the selection of a technology to implement a WebLab. The results obtained suggest the adoption of a Service Oriented Laboratory Architecture-based approach for the design of future Remote Laboratories so that client-agnostic Remote Laboratories and Remote Laboratory composition are enabled. The experience with the real Remote Laboratory, WebLab-Deusto, is also presented.

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Hierarchical wrinkling on elastomeric Janus spheres is permanently imprinted by swelling, for different lengths of time, followed by drying the particles in an appropriate solvent. First-order buckling with a spatial periodicity (lambda(11)) of the order of a few microns and hierarchical structures comprising of 2nd order buckling with a spatial periodicity (lambda(12)) of the order of hundreds of nanometers have been obtained. The 2nd order buckling features result from a Grinfeld surface instability due to the diffusion of the solvent and the presence of sol molecules.

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We investigate the behavior of a patchy particle model close to a hard-wall via Monte Carlo simulation and density functional theory (DFT). Two DFT approaches, based on the homogeneous and inhomogeneous versions of Wertheim's first order perturbation theory for the association free energy are used. We evaluate, by simulation and theory, the equilibrium bulk phase diagram of the fluid and analyze the surface properties for two isochores, one of which is close to the liquid side of the gas-liquid coexistence curve. We find that the density profile near the wall crosses over from a typical high-temperature adsorption profile to a low-temperature desorption one, for the isochore close to coexistence. We relate this behavior to the properties of the bulk network liquid and find that the theoretical descriptions are reasonably accurate in this regime. At very low temperatures, however, an almost fully bonded network is formed, and the simulations reveal a second adsorption regime which is not captured by DFT. We trace this failure to the neglect of orientational correlations of the particles, which are found to exhibit surface induced orientational order in this regime.

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We generalize Wertheim's first order perturbation theory to account for the effect in the thermodynamics of the self-assembly of rings characterized by two energy scales. The theory is applied to a lattice model of patchy particles and tested against Monte Carlo simulations on a fcc lattice. These particles have 2 patches of type A and 10 patches of type B, which may form bonds AA or AB that decrease the energy by epsilon(AA) and by epsilon(AB) = r epsilon(AA), respectively. The angle theta between the 2 A-patches on each particle is fixed at 601, 90 degrees or 120 degrees. For values of r below 1/2 and above a threshold r(th)(theta) the models exhibit a phase diagram with two critical points. Both theory and simulation predict that rth increases when theta decreases. We show that the mechanism that prevents phase separation for models with decreasing values of theta is related to the formation of loops containing AB bonds. Moreover, we show that by including the free energy of B-rings ( loops containing one AB bond), the theory describes the trends observed in the simulation results, but that for the lowest values of theta, the theoretical description deteriorates due to the increasing number of loops containing more than one AB bond.

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We investigate the liquid-vapor interface of a model of patchy colloids. This model consists of hard spheres decorated with short-ranged attractive sites ("patches") of different types on their surfaces. We focus on a one-component fluid with two patches of type A and nine patches of type B (2A9B colloids), which has been found to exhibit reentrant liquid-vapor coexistence curves and very low-density liquid phases. We have used the density-functional theory form of Wertheim's first-order perturbation theory of association, as implemented by Yu and Wu [J. Chem. Phys. 116, 7094 (2002)], to calculate the surface tension, and the density and degree of association profiles, at the liquid-vapor interface of our model. In reentrant systems, where AB bonds dominate, an unusual thickening of the interface is observed at low temperatures. Furthermore, the surface tension versus temperature curve reaches a maximum, in agreement with Bernardino and Telo da Gama's mesoscopic Landau-Safran theory [Phys. Rev. Lett. 109, 116103 (2012)]. If BB attractions are also present, competition between AB and BB bonds gradually restores the monotonic temperature dependence of the surface tension. Lastly, the interface is "hairy," i.e., it contains a region where the average chain length is close to that in the bulk liquid, but where the density is that of the vapor. Sufficiently strong BB attractions remove these features, and the system reverts to the behavior seen in atomic fluids.

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Corrosion of reinforcement bars in concrete structures is the most significant deterioration mechanism in these structures. Corrosion is extremely difficult to predict and, consequently, can be regarded as an unpredictable event. Following this, robustness assessment methods can be employed to define the susceptibility of a structure to corrosion. In this work, robustness is measured in terms of the remaining safety of a deteriorated structure. The proposed methodology is illustrated by means of a reinforced concrete (RC) slab subjected to dead and live loads. The performance of the corroded slab is evaluated using non-linear analysis. The reliability index is adopted to assess the safety of the deteriorated structure. To compute the reliability index a strategy combining the First Order Reliability Method (FORM) and the Response Surface Method (RSM) is used.

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Na tentativa de se otimizar o processo de fabrico associado a uma tinta base aquosa (TBA), para minimizar os desvios de viscosidade final verificados, e de desenvolver um novo adjuvante plastificante para betão, recorreu-se a métodos e ferramentas estatísticas para a concretização do projeto. Relativamente à TBA, procedeu-se numa primeira fase a um acompanhamento do processo de fabrico, a fim de se obter todos os dados mais relevantes que poderiam influenciar a viscosidade final da tinta. Através de uma análise de capacidade ao parâmetro viscosidade, verificou-se que esta não estava sempre dentro das especificações do cliente, sendo o cpk do processo inferior a 1. O acompanhamento do processo resultou na escolha de 4 fatores, que culminou na realização de um plano fatorial 24. Após a realização dos ensaios, efetuou-se uma análise de regressão a um modelo de primeira ordem, não tendo sido esta significativa, o que implicou a realização de mais 8 ensaios nos pontos axiais. Com arealização de uma regressão passo-a-passo, obteve-se uma aproximação viável a um modelo de segunda ordem, que culminou na obtenção dos melhores níveis para os 4 fatores que garantem que a resposta viscosidade se situa no ponto médio do intervalo de especificação (1400 mPa.s). Quanto ao adjuvante para betão, o objetivo é o uso de polímeros SIKA ao invés da matériaprima comum neste tipo de produtos, tendo em conta o custo final da formulação. Escolheram-se 3 fatores importantes na formulação do produto (mistura de polímeros, mistura de hidrocarbonetos e % de sólidos), que resultou numa matriz fatorial 23. Os ensaios foram realizados em triplicado, em pasta de cimento, um para cada tipo de cimento mais utilizado em Portugal. Ao efetuar-se a análise estatística de dados obtiveram-se modelos de primeira ordem para cada tipo de cimento. O processo de otimização consistiu em otimizar uma função custo associada à formulação, garantindo sempre uma resposta superior à observada pelo produto considerado padrão. Os resultados foram animadores uma vez que se obteve para os 3 tipos de cimentocustos abaixo do requerido e espalhamento acima do observado pelo padrão.

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Dissertação para obtenção do Grau de Doutor em Matemática