Compósitos de nanocelulose / PHBV: manta microfibrilica por eletrofiação

Pós-graduação em Engenharia Mecânica - FEG

Otimização dos parâmetros para obtenção de nanotubos em Ti-Cp por anodização eletroquímica e aplicação na liga experimental Ti-35Nb-7Zr

Pós-graduação em Engenharia Mecânica - FEG

Simulación de maniobras de buques con sistemas de propulsión no convencional en aguas poco profundas

Los requisitos cada vez más exigentes en cuanto a misiones, limitaciones operacionales y ambientales así como nuevas tecnologías, imponen permanentemente retos a los arquitectos navales para generar alternativas de buques y valorar su bondad en las primeras etapas del proyecto. Este es el caso de los Buques Patrulleros de Apoyo Fluvial Pesados PAF-P, que por requerimiento de la Armada Nacional de Colombia ha diseñado y construido COTECMAR. Los PAF-P, son buques fluviales cuya relación Manga-Calado excede la mayoría de los buques existentes (B/T=9,5), debido principalmente a las restricciones en el calado a consecuencia de la escasa profundidad de los ríos. Estos buques están equipados con sistemas de propulsión acimutales tipo “Pum-Jet”. Las particularidades del buque y del ambiente operacional, caracterizado por ríos tropicales con una variabilidad de profundidad dependiente del régimen de lluvias y sequía, así como la falta de canalización y la corriente, hacen que la maniobrabilidad y controlabilidad sean fundamentales para el cumplimiento de su misión; adicionalmente, no existen modelos matemáticos validados que permitan predecir en las primeras etapas del diseño la maniobrabilidad de este tipo de buques con los efectos asociados por profundidad. La presente tesis doctoral aborda el desarrollo de un modelo matemático para simulación de maniobrabilidad en aguas poco profundas de buques con relación manga-calado alta y con propulsores acimutales tipo “Pump-Jet”, cuyo chorro además de entregar el empuje necesario para el avance del buque, genera la fuerza de gobierno en función del ángulo de orientación del mismo, eliminando la necesidad de timones. El modelo matemático ha sido validado mediante los resultados obtenidos en las pruebas de maniobrabilidad a escala real del PAF-P, a través de la comparación de trayectorias, series temporales de las variables de estado más significativas y parámetros del círculo evolutivo como son diámetro de giro, diámetro táctico, avance y transferencia. El plan de pruebas se basó en técnicas de Diseño de Experimentos “DOE” para racionalizar el número de corridas en diferentes condiciones de profundidad, velocidad y orientación del chorro (ángulo de timón). En el marco de la presente investigación y para minimizar los errores por efectos ambientales y por inexactitud en los instrumentos de medición, se desarrolló un sistema de adquisición y procesamiento de datos de acuerdo con los lineamientos de ITTC. La literatura existente describe los efectos negativos de la profundidad en los parámetros de maniobrabilidad de buques convencionales (Efecto tipo S), principalmente las trayectorias descritas en los círculos evolutivos aumentan en la medida que disminuye la profundidad; no obstante, en buques de alta relación manga-calado, B/T=7,51 (Yoshimura, y otros, 1.988) y B/T=6,38 (Yasukawa, y otros, 1.995) ha sido reportado el efecto contrario (Efecto tipo NS Non Standart). Este último efecto sin embargo, ha sido observado mediante experimentación con modelos a escala pero no ha sido validado en pruebas de buques a escala real. El efecto tipo NS en buques dotados con hélice y timones, se atribuye al mayor incremento de la fuerza del timón comparativamente con las fuerzas del casco en la medida que disminuye la profundidad; en el caso de estudio, el fenómeno está asociado a la mejor eficiencia de la bomba de agua “Pump-Jet”, debido a la resistencia añadida en el casco por efecto de la disminución de la profundidad. Los resultados de las pruebas con buque a escala real validan el excelente desempeño de esta clase de buques, cumpliendo en exceso los criterios de maniobrabilidad existentes y muestran que el diámetro de giro y otras características de maniobrabilidad mejoran con la disminución de la profundidad en buques con alta relación manga-calado. ABSTRACT The increasingly demanding requirements in terms of missions, operational and environmental constraints as well as new technologies, constantly impose challenges to naval architects to generate alternatives and asses their performance in the early stages of design. That is the case of Riverine Support Patrol Vessel (RSPV), designed and built by COTECMAR for the Colombian Navy. RSPV are riverine ships with a Beam-Draft ratio exceeding most of existing ships (B/T=9,5), mainly due to the restrictions in draft as a result of shallow water environment. The ships are equipped with azimuthal propulsion system of the “Pump-Jet” type. The peculiarities of the ship and the operational environment, characterized by tropical rivers of variable depth depending on the rain and dry seasons, as well as the lack channels and the effect of water current, make manoeuvrability and controllability fundamental to fulfill its mission; on the other hand, there are not validated mathematical models available to predict the manoeuvrability of such ships with the associated water depth effects in the early stages of design. This dissertation addresses the development of a mathematical model for shallow waters’ manoeuvrability simulation of ships with high Beam-Draft ratio and azimuthal propulsion systems type “Pump-Jet”, whose stream generates the thrust required by the ship to advance and also the steering force depending on the orientation angle, eliminating the need of rudders. The mathematical model has been validated with the results of RSPV’s full scale manoeuvring tests, through a comparison of paths, time series of state variables and other parameters taken from turning tests, such as turning diameter, tactical diameter, advance and transfer. The test plan was developed applying techniques of Design of Experiments “DOE”, in order to rationalize the number of runs in different conditions of water depth, ship speed and jet stream orientation (rudder angle). A data acquisition and processing system was developed, following the guidelines of ITTC, as part of this research effort, in order to minimize errors by environmental effects and inaccuracy in measurement instruments, The negative effects of depth on manoeuvrability parameters for conventional ships (Effect Type S: the path described by the ship during turning test increase with decrease of water depth), has been documented in the open literature; however for wide-beam ships, B/T=7,51 (Yoshimura, y otros, 1.988) and B/T=6,38 (Yasukawa, y otros, 1.995) has been reported the opposite effect (Type NS). The latter effect has been observed thru model testing but until now had not been validated with full-scale results. In ships with propellers and rudders, type NS effect is due to the fact that increment of rudder force becomes larger than hull force with decrease of water depth; in the study case, the phenomenon is associated with better efficiency of the Pump-Jet once the vessel speed becomes lower, due to hull added resistance by the effect of the decrease of water depth. The results of full scale tests validates the excellent performance of this class of ships, fulfilling the manoeuvrability criteria in excess and showing that turning diameter and other parameters in high beam-draft ratio vessels do improve with the decrease of depth.

Electricity price forecasting accounting for renewable energies: optimal combined forecasts

Electricity price forecasting is an interesting problem for all the agents involved in electricity market operation. For instance, every profit maximisation strategy is based on the computation of accurate one-day-ahead forecasts, which is why electricity price forecasting has been a growing field of research in recent years. In addition, the increasing concern about environmental issues has led to a high penetration of renewable energies, particularly wind. In some European countries such as Spain, Germany and Denmark, renewable energy is having a deep impact on the local power markets. In this paper, we propose an optimal model from the perspective of forecasting accuracy, and it consists of a combination of several univariate and multivariate time series methods that account for the amount of energy produced with clean energies, particularly wind and hydro, which are the most relevant renewable energy sources in the Iberian Market. This market is used to illustrate the proposed methodology, as it is one of those markets in which wind power production is more relevant in terms of its percentage of the total demand, but of course our method can be applied to any other liberalised power market. As far as our contribution is concerned, first, the methodology proposed by García-Martos et al(2007 and 2012) is generalised twofold: we allow the incorporation of wind power production and hydro reservoirs, and we do not impose the restriction of using the same model for 24h. A computational experiment and a Design of Experiments (DOE) are performed for this purpose. Then, for those hours in which there are two or more models without statistically significant differences in terms of their forecasting accuracy, a combination of forecasts is proposed by weighting the best models(according to the DOE) and minimising the Mean Absolute Percentage Error (MAPE). The MAPE is the most popular accuracy metric for comparing electricity price forecasting models. We construct the combi nation of forecasts by solving several nonlinear optimisation problems that allow computation of the optimal weights for building the combination of forecasts. The results are obtained by a large computational experiment that entails calculating out-of-sample forecasts for every hour in every day in the period from January 2007 to Decem ber 2009. In addition, to reinforce the value of our methodology, we compare our results with those that appear in recent published works in the field. This comparison shows the superiority of our methodology in terms of forecasting accuracy.

Improving recombinant human adenosine A2A receptor production in yeast

Over 50% of clinically-marketed drugs target membrane proteins; in particular G protein-coupled receptors (GPCRs). GPCRs are vital to living cells, performing an active role in many processes, making them integral to drug development. In nature, GPCRs are not sufficiently abundant for research and their structural integrity is often lost during extraction from cell membranes. The objectives of this thesis were to increase recombinant yield of the GPCR, human adenosine A2A receptor (hA2AR) by investigating bioprocess conditions in large-scale Pichia pastoris and small-scale Saccharomyces cerevisiae cultivations. Extraction of hA2AR from membranes using novel polymers was also investigated. An increased yield of hA2AR from P. pastoris was achieved by investigating the methanol feeding regime. Slow, exponential feed during induction (μlow) was compared to a faster, exponential feed (μhigh) in 35 L pilot-scale bioreactors. Overall hA2AR yields were increased for the μlow cultivation (536.4pmol g-1) compared to the μhigh148.1 pmol g-1. hA2AR levels were maintained in cytotoxic methanol conditions and unexpectedly, pre-induction levels of hA2AR were detected. Small-scale bioreactor work showed that Design of Experiments (DoE) could be applied to screen for bioprocess conditions to give optimal hA2AR yields. Optimal conditions were retrieved for S. cerevisiae using a d-optimal screen and response surface methodology. The conditions were 22°C, pH 6.0, 30% DO without dimethyl sulphoxide. A polynomial equation was generated to predict hA2AR yields if conditions varied. Regarding the extraction, poly (maleic anhydride-styrene) or PMAS was successful in solubilising hA2AR from P. pastoris membranes compared with dodcecyl-β-D-maltoside (DDM) detergent. Variants of PMAS worked well as solubilising agents with either 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) or cholesteryl hemisuccinate (CHS). Moreover, esterification of PMAS improved solubilisation, suggesting that increased hydrophobicity stabilises hA2AR during extraction. Overall, hA2AR yields were improved in both, P. pastoris and S. cerevisiae and the use of novel polymers for efficient extraction was achieved.

Síntese enzimática de ésteres de açúcar: surfactantes e polímeros como novos materiais ambientalmente seguros

Sugar esters are substances which possess surfactant, antifungical and bactericidal actions and can be obtained through two renewable sources of raw materials: sugars and vegetable oils. Their excellent biodegradability, allied to lhe fact that they are non toxic, insipid, inodorous, biocompatible, no-ionic, digestible and because they can resist to adverse conditions of temperature, pH and salinity, explain lhe crescent use of these substances in several sections of lhe industry. The objective of this thesis was to synthesize and characterize surfactants and polymers containing sugar branched in their structures, through enzymatic transesterification of vinyl esters and sugars, using alkaline protease from Bacillus subtilis as catalyst, in organic medium (DMF).Three types of sugars were used: L-arabinose, D-glucose and sucrose and two types of vinyl esters: vinyl laurate and vinyl adipate. Aiming to reach high conversions from substrates to products for a possible future large scale industrial production, a serie of variables was optimized, through Design of Experiments (DOE), using Response Surface Methodology (RSM).The investigated variables were: (1) enzyme concentration; (2) molar reason of substrates; (3) water/solvent rale; (4) temperature and (5) time. We obtained six distinct sugar esters: 5-0-lauroyl L-arabinose, 6-0-lauroyl D-glucose, 1'-O-lauroyl sucrose, 5-0-vinyladipoyl L-arabinose, 6-0-vinyladipoyl D-glucose and 1 '-O-vinyladipoyl sucrose, being lhe last three polymerizable. The progress of lhe reaction was monitored by HPLC analysis, through lhe decrease of sugar concentration in comparison to lhe blank. Qualitative analysis by TLC confirmed lhe formation of lhe products. In lhe purification step, two methodologies were adopted: (1) chromatographic column and (2) extraction with hot acetone. The acylation position and lhe chemical structure were determined by 13C-RMN. The polymerization of lhe three vinyl sugar esters was possible, through chemical catalysis, using H2O2 and K2S2O8 as initiators, at 60°C, for 24 hours. IR spectra of lhe monomers and respective polymers were compared revealing lhe disappearance of lhe vinyl group in lhe polymer spectra. The molar weights of lhe polymers were determined by GPC and presented lhe following results: poly (5-0-vinyladipoyl L-arabinose): Mw = 7.2 X 104; PD = 2.48; poly (6-0-vinyladipoyl D-glucose): Mw = 2.7 X 103; PD = 1.75 and poly (1'-O-vinyladipoyl sucrose): Mw = 4.2 X 104; PD = 6.57. The six sugar esters were submitted to superficial tension tests for determination of the critical micelle concentrations (CMC), which varied from 122 to 167 ppm. Finally, a study of applicability of these sugar esters, as lubricants for completion fluids of petroleum wells was' accomplished through comparative analysis of lhe efficiency of these sugar esters, in relation to three commercial lubricants. The products synthesized in this thesis presented equivalent or superior action to lhe tested commercial products

On the design of peer punishment experiments

We discuss how technologies of peer punishment might bias the results that are observed in experiments. A crucial parameter is the “fine-to-fee” ratio, which describes by how much the punished subjects income is reduced relatively to the fee the punishing subject has to pay to inflict punishment. We show that a punishment technology commonly used in experiments embeds a variable fine-to-fee ratio and show that it confounds the empirical findings about why, whom, and how much subjects punish.

On the use of Cramér-Rao minimum variance bounds for the design of magnetic resonance spectroscopy experiments

Localized Magnetic Resonance Spectroscopy (MRS) is in widespread use for clinical brain research. Standard acquisition sequences to obtain one-dimensional spectra suffer from substantial overlap of spectral contributions from many metabolites. Therefore, specially tuned editing sequences or two-dimensional acquisition schemes are applied to extend the information content. Tuning specific acquisition parameters allows to make the sequences more efficient or more specific for certain target metabolites. Cramér-Rao bounds have been used in other fields for optimization of experiments and are now shown to be very useful as design criteria for localized MRS sequence optimization. The principle is illustrated for one- and two-dimensional MRS, in particular the 2D separation experiment, where the usual restriction to equidistant echo time spacings and equal acquisition times per echo time can be abolished. Particular emphasis is placed on optimizing experiments for quantification of GABA and glutamate. The basic principles are verified by Monte Carlo simulations and in vivo for repeated acquisitions of generalized two-dimensional separation brain spectra obtained from healthy subjects and expanded by bootstrapping for better definition of the quantification uncertainties.

Some results on the design of field experiments for comparing unreplicated treatments

In early generation variety trials, large numbers of new breeders' lines need to be compared, and usually there is little seed available for each new line. A so-called unreplicated trial has each new line on just one plot at a site, but includes several (often around five) replicated check or control (or standard) varieties. The total proportion of check plots is usually between 10% and 20%. The aim of the trial is to choose some good performing lines (usually around 1/3 of those tested) to go on for further testing, rather than precise estimation of their mean yield. Now that spatial analyses of data from field experiments are becoming more common, there is interest in an efficient layout of an experiment given a proposed spatial analysis. Some possible design criteria are discussed, and efficient layouts under spatial dependence are considered.

Design of improved membrane protein production experiments:quantitation of the host response

Eukaryotic membrane proteins cannot be produced in a reliable manner for structural analysis. Consequently, researchers still rely on trial-and-error approaches, which most often yield insufficient amounts. This means that membrane protein production is recognized by biologists as the primary bottleneck in contemporary structural genomics programs. Here, we describe a study to examine the reasons for successes and failures in recombinant membrane protein production in yeast, at the level of the host cell, by systematically quantifying cultures in high-performance bioreactors under tightlydefined growth regimes. Our data show that the most rapid growth conditions of those chosen are not the optimal production conditions. Furthermore, the growth phase at which the cells are harvested is critical: We show that it is crucial to grow cells under tightly-controlled conditions and to harvest them prior to glucose exhaustion, just before the diauxic shift. The differences in membrane protein yields that we observe under different culture conditions are not reflected in corresponding changes in mRNA levels of FPS1, but rather can be related to the differential expression of genes involved in membrane protein secretion and yeast cellular physiology. Copyright © 2005 The Protein Society.

Mix design process of polyester polymer mortars modified with recycled GFRP waste materials

In this study, the effect of incorporation of recycled glass fibre reinforced plastics (GFRP) waste materials, obtained by means of shredding and milling processes, on mechanical behaviour of polyester polymer mortars (PM) was assessed. For this purpose, different contents of GFRP recyclates, between 4% up to 12% in weight, were incorporated into polyester PM materials as sand aggregates and filler replacements. The effect of the addition of a silane coupling agent to resin binder was also evaluated. Applied waste material was proceeding from the shredding of the leftovers resultant from the cutting and assembly processes of GFRP pultrusion profiles. Currently, these leftovers as well as non-conform products and scrap resulting from pultrusion manufacturing process are landfilled, with additional costs to producers and suppliers. Hence, besides the evident environmental benefits, a viable and feasible solution for these wastes would also conduct to significant economic advantages. Design of experiments and data treatment were accomplish by means of full factorial design approach and analysis of variance ANOVA. Experimental results were promising toward the recyclability of GFRP waste materials as partial replacement of aggregates and reinforcement for PM materials, with significant improvements on mechanical properties of resultant mortars with regards to waste-free formulations.

Optimization process of polyester polymer mortars modified with recycled GFRP waste aggregates – application of factorial experiment design-

Glass fibre-reinforced plastics (GFRP), nowadays commonly used in the construction, transportation and automobile sectors, have been considered inherently difficult to recycle due to both: cross-linked nature of thermoset resins, which cannot be remolded, and complex composition of the composite itself, which includes glass fibres, matrix and different types of inorganic fillers. Presently, most of the GFRP waste is landfilled leading to negative environmental impacts and supplementary added costs. With an increasing awareness of environmental matters and the subsequent desire to save resources, recycling would convert an expensive waste disposal into a profitable reusable material. There are several methods to recycle GFR thermostable materials: (a) incineration, with partial energy recovery due to the heat generated during organic part combustion; (b) thermal and/or chemical recycling, such as solvolysis, pyrolisis and similar thermal decomposition processes, with glass fibre recovering; and (c) mechanical recycling or size reduction, in which the material is subjected to a milling process in order to obtain a specific grain size that makes the material suitable as reinforcement in new formulations. This last method has important advantages over the previous ones: there is no atmospheric pollution by gas emission, a much simpler equipment is required as compared with ovens necessary for thermal recycling processes, and does not require the use of chemical solvents with subsequent environmental impacts. In this study the effect of incorporation of recycled GFRP waste materials, obtained by means of milling processes, on mechanical behavior of polyester polymer mortars was assessed. For this purpose, different contents of recycled GFRP waste materials, with distinct size gradings, were incorporated into polyester polymer mortars as sand aggregates and filler replacements. The effect of GFRP waste treatment with silane coupling agent was also assessed. Design of experiments and data treatment were accomplish by means of factorial design and analysis of variance ANOVA. The use of factorial experiment design, instead of the one factor at-a-time method is efficient at allowing the evaluation of the effects and possible interactions of the different material factors involved. Experimental results were promising toward the recyclability of GFRP waste materials as polymer mortar aggregates, without significant loss of mechanical properties with regard to non-modified polymer mortars.

A New Approach in the Design of Air Stripping Columns for the Treatment of Groundwater Contaminated With Volatile Organic Compounds

Volatile organic compounds are a common source of groundwater contamination that can be easily removed by air stripping in columns with random packing and using a counter-current flow between the phases. This work proposes a new methodology for column design for any type of packing and contaminant which avoids the necessity of an arbitrary chosen diameter. It also avoids the employment of the usual graphical Eckert correlations for pressure drop. The hydraulic features are previously chosen as a project criterion. The design procedure was translated into a convenient algorithm in C++ language. A column was built in order to test the design, the theoretical steady-state and dynamic behaviour. The experiments were conducted using a solution of chloroform in distilled water. The results allowed for a correction in the theoretical global mass transfer coefficient previously estimated by the Onda correlations, which depend on several parameters that are not easy to control in experiments. For best describe the column behaviour in stationary and dynamic conditions, an original mathematical model was developed. It consists in a system of two partial non linear differential equations (distributed parameters). Nevertheless, when flows are steady, the system became linear, although there is not an evident solution in analytical terms. In steady state the resulting ODE can be solved by analytical methods, and in dynamic state the discretization of the PDE by finite differences allows for the overcoming of this difficulty. To estimate the contaminant concentrations in both phases in the column, a numerical algorithm was used. The high number of resulting algebraic equations and the impossibility of generating a recursive procedure did not allow the construction of a generalized programme. But an iterative procedure developed in an electronic worksheet allowed for the simulation. The solution is stable only for similar discretizations values. If different values for time/space discretization parameters are used, the solution easily becomes unstable. The system dynamic behaviour was simulated for the common liquid phase perturbations: step, impulse, rectangular pulse and sinusoidal. The final results do not configure strange or non-predictable behaviours.