Writing/erasing 3D micro and nano wrinkles in flexible elastomers for volatile organic compounds sensor

Micro/nano wrinkled patterns on cross-linked urethane/urea polymeric flexible free standing films with two soft segments, polypropylene oxide and polybutadiene, can be induced by UV-irradiation. The ability to write/erase these 3D structures, in a controlled manner, is the main focus of this work. The imprinting of the wrinkled structures was accomplished by swelling in an appropriate solvent followed by drying the membranes after the cross-linking process and UV irradiation. The surface tailoring of the elastomeric membranes was imaged by optical microscopy, scanning electronic microscopy and by atomic force microscopy. To erase the wrinkled structures the elastomers were swollen. The swelling as well as the sol/gel fraction and the UV radiation were tuned in order to control the wrinkles characteristics. It was found that the wrinkles wavelength, in the order of microns (1±0,25μm), was stamped by the UV radiation intensity and exposure time while the wrinkles' amplitude, in the order of nanometers (150-450 nm), was highly dependent on the swelling and sol/gel fraction. A prototype for volatile organic compounds detection was developed taking advantage of the unique 3D micro/nano wrinkles features.

Ageing on commercial automotive catalysts, a structure reactivity study

Increasingly stringed regulations for diesel engine emissions have a significant impact on the required efficiency of DOC. Lowered DOC oxidation efficiency due to thermal aging effects influences the efficiency of the exhaust aftertreatment systems downstream of the DOC. In this work carried out in the Jean Le Rond d’Alembert Institute the effect of hydrothermal aging on the reactivity and structure of a commercial DOC was investigated. The characterization of the catalytic performance was carried out on a synthetic gas bench using carrots catalyst under conditions close to the realistic conditions i.e. using a synthetic gas mixture, representative of the exhaust gases from diesel engines. Different structural characterization techniques were performed: textural and morphological proprieties were analyzed by BET and TEM, the characterization of the presented crystallographic phases was performed by DRX and the determination of the number of reducible species was possible by TPR. TEM results shown, an increase of the metal particle size with the aging caused by the agglomeration of metal particles, revealing the presence of metal sintering. DRX results also suggest the presence of support sintering. Furthermore, DRX and BET results unexpectedly reveal that the most drastic aging conditions used actually activated the catalyst surface. As expected, the aging affected negatively the catalyst performance on the oxidation of methane and CO, however an improvement of the NO oxidation performance with the aging was observed. Nevertheless, for the aging conditions used, catalytic activity results show that the influence of aging in DOC performance was not significant, and therefore, more drastic aging conditions must be used.

Cellulose nanorods in liquid crystalline elastomers for improved actuators

Nanotechnology plays a central role in ‘tailoring’ materials’ properties and thus improving its performances for a wide range of applications. Coupling nature nano-objects with nanotechnology results in materials with enhanced functionalities. The main objective of this master thesis was the synthesis of nanocrystalline cellulose (NCCs) and its further incorporation in a cellulosic matrix, in order to produce a stimuli-responsive material to moisture. The induced behaviour (bending/unbending) of the samples was deeply investigated, in order to determine relationships between structure/properties. Using microcrystalline cellulose as a starting material, acid hydrolysis was performed and the NCC was obtained. Anisotropic aqueous solutions of HPC and NCC were prepared and films with thicknesses ranging from 22μm to 61μm were achieved, by using a shear casting technique. Microscopic and spectroscopic techniques as well as mechanical and rheological essays were used to characterize the transparent and flexible films produced. Upon the application of a stimulus (moisture), the bending/unbending response times were measured. The use of NCC allowed obtaining films with response times in the order of 6 seconds for the bending and 5 seconds for the unbending, improving the results previously reported. These promising results open new horizons for building up improved soft steam engines.

UAV - based imagery processing using structure from motion and remote sensing technology

With the recent advances in technology and miniaturization of devices such as GPS or IMU, Unmanned Aerial Vehicles became a feasible platform for a Remote Sensing applications. The use of UAVs compared to the conventional aerial platforms provides a set of advantages such as higher spatial resolution of the derived products. UAV - based imagery obtained by a user grade cameras introduces a set of problems which have to be solved, e. g. rotational or angular differences or unknown or insufficiently precise IO and EO camera parameters. In this work, UAV - based imagery of RGB and CIR type was processed using two different workflows based on PhotoScan and VisualSfM software solutions resulting in the DSM and orthophoto products. Feature detection and matching parameters influence on the result quality as well as a processing time was examined and the optimal parameter setup was presented. Products of the both workflows were compared in terms of a quality and a spatial accuracy. Both workflows were compared by presenting the processing times and quality of the results. Finally, the obtained products were used in order to demonstrate vegetation classification. Contribution of the IHS transformations was examined with respect to the classification accuracy.

Nanostructuring silicon probes via electrodeposition: characterization of electrode coatings for acute in vivo neural recordings

Understanding how the brain works will require tools capable of measuring neuron elec-trical activity at a network scale. However, considerable progress is still necessary to reliably increase the number of neurons that are recorded and identified simultaneously with existing mi-croelectrode arrays. This project aims to evaluate how different materials can modify the effi-ciency of signal transfer from the neural tissue to the electrode. Therefore, various coating materials (gold, PEDOT, tungsten oxide and carbon nano-tubes) are characterized in terms of their underlying electrochemical processes and recording ef-ficacy. Iridium electrodes (177-706 μm2) are coated using galvanostatic deposition under different charge densities. By performing electrochemical impedance spectroscopy in phosphate buffered saline it is determined that the impedance modulus at 1 kHz depends on the coating material and decreased up to a maximum of two orders of magnitude for PEDOT (from 1 MΩ to 25 kΩ). The electrodes are furthermore characterized by cyclic voltammetry showing that charge storage capacity is im-proved by one order of magnitude reaching a maximum of 84.1 mC/cm2 for the PEDOT: gold nanoparticles composite (38 times the capacity of the pristine). Neural recording of spontaneous activity within the cortex was performed in anesthetized rodents to evaluate electrode coating performance.

How do current term structure model behave beyond the last liquid point?: A comparison of the DNS and Smith-Wilson methods

A Work Project, presented as part of the requirements for the Award of a Master’s Double Degree in Finance from Maastricht University and NOVA – School of Business and Economics

Design and characterization of novel biopolymeric structure using biocompatible ionic liquids

The main objective of this thesis was the development of polymeric structures from the dissolution of FucoPol, a bacterial exopolysaccharide (EPS), in a biocompatible ionic liquid, choline acetate. The FucoPol was produced by the bacteria Enterobacter A47 using glycerol as carbon source at controlled temperature and pH (30ºC and 7, respectively). At the end of 3 days it was produced 7 g/L of FucoPol. The net yield of Fucopol in glycerol (YP/S) was 0.22 g/g and the maximum productivity 2.37 g/L.d This polymer was characterized about its composition in sugars and acyl groups (by High-Performance Liquid Chromatography - HPLC), containing fucose (35 % mol), galactose (21 % mol), glucose (29 % mol), rhamnose (3% mol) and glucuronic acid (12% mol) as well as acetate (14.28 % mol), pyruvate (2.15 % mol) and succinate (1.80 % mol). Its content of water and ash was 15% p/p and 2% p/p, respectively, and the chemical bonds (determined by Infrared Spectroscopy - FT-IR) are consistent to the literature reports. However, due to limitations in Differential Scanning Calorimetry (DSC) equipment it was not possible to determine the glass transition temperature. In turn, the ionic liquid showed the typical behavior of a Newtonian fluid, glass transition temperature (determined by DSC) -98.03ºC and density 1.1031 g/cm3. The study of chemical bonds by FT-IR showed that amount of water (8.80%) influenced the visualization of the bands predicted to in view of their chemical structure. After the dissolution of the FucoPol in the ionic liquid at different temperatures (50, 60, 80 and 100 ° C) it was promoted the removal of this by the phase inversion method using deionized water as a solvent, followed by drying in an oven at 70 ° C. The mixtures before and after the phase inversion method were characterized through the studies mentioned above. In order to explore possible application field’s biocompatibility assays and collage on balsa wood tests were performed. It was found that the process of washing with water by the phase inversion method was not totally effective in removing the biocompatible ionic liquid, since all FucoPol – IL mixtures still contained ionic liquid in their composition as can be seen by the DSC results and FT-IR. In addition, washing the mixtures with water significantly altered the composition of FucoPol. However, these mixtures, that developed a viscous behavior typical of a non-Newtonian fluid (shear-thinning), have the potential to be applied in the biomedical field as well as biological glues.

Does ownership structure matter? Three essays in finance

Management

The Multidimensional and Centred Structure of Our Interested Perception in Hierocles

O objectivo desta dissertação é identificar a estrutura da percepção tal como ela é desenhada por Hiérocles nos <,(#= >1!(?$%&'(). Para alcançar este objectivo focar-me-ei na análise que o filósofo estóico leva a cabo em torno da percepção. O foco começa por incindir sobre a distinção entre percepção de si e percepção do exterior, com todas as suas subtilezas. Tal análise implicará então a consideração da importância da não-indiferença nessa estrutura de percepção. O objectivo é compreender como a percepção é sempre relacional e interessada. . Centrar-me-ei então na noção de !"#$%&'(), tentanto explorar a complexidade e multiplicidade do fenómeno em causa. Será também estabalecida a relação com o fragmento de Estobeu (6.671), que é, a par da obra, a fonte mais importante do pensamento de Hiérocles. Através desta relação introduzir-se-á a estrutura circular e concêntrica de uma percepção relacional e interessada. Toda esta dissertação será levada a cabo focando-se principalmente nos textos do próprio Hiérocles.

Inovcity- Structure of trials evaluation

In 2007, the UK government commissioned the Energy Demand Research Project to conduct a large scale experiment of smart metering technologies to test the impacts from many different forms of feedback to residential consumers. A full evaluation of the results was completed in 2011. In Portugal, EDP is also conducting smart meter trials in a project called InovCity in the city of Évora whose results will be evaluated during 2012. In this work, the case of Great Britain is studied as a reference on how an evaluation of trial results should be conducted. I also discuss potential limitations of the experiments, implications for national roll-out decisions, and finally draw some lessons that can be applied to the Portuguese case.

Impact of chromossomal structure on the evolution of Schizosaccharomyces pombe undergoing Mutation Accumulation

Large chromosomal rearrangements are common in natural populations and thought to be involved in speciation events. In this project, we used experimental evolution to determine how the speed of evolution and the type of accumulated mutations depend on the ancestral chromosomal structure and genotype. We utilized two Wild Type strains and a set of genetically engineered Schizosaccharomyces pombe strains, different solely in the presence of a certain type of chromosomal variant (inversions or translocations), along with respective controls. Previous research has shown that these chromosomal variants have different fitness levels in several environments, probably due to changes in the gene expression along the genome. These strains were propagated in the laboratory at very low population sizes, in which we expect natural selection to be less efficient at purging deleterious mutations. We then measured these strains’ changes in fitness throughout this accumulation of deleterious mutations, comparing the evolutionary trajectories in the different rearrangements to understand if the chromosomal structure affected the speed of evolution. We also tested these mutations for possible epistatic effects and estimated their parameters: the number of arising deleterious mutations per generation (Ud) and each one’s mean effect (sd).

Damage propagation in composite Materials meso-mechanical models

Composite materials have a complex behavior, which is difficult to predict under different types of loads. In the course of this dissertation a methodology was developed to predict failure and damage propagation of composite material specimens. This methodology uses finite element numerical models created with Ansys and Matlab softwares. The methodology is able to perform an incremental-iterative analysis, which increases, gradually, the load applied to the specimen. Several structural failure phenomena are considered, such as fiber and/or matrix failure, delamination or shear plasticity. Failure criteria based on element stresses were implemented and a procedure to reduce the stiffness of the failed elements was prepared. The material used in this dissertation consist of a spread tow carbon fabric with a 0°/90° arrangement and the main numerical model analyzed is a 26-plies specimen under compression loads. Numerical results were compared with the results of specimens tested experimentally, whose mechanical properties are unknown, knowing only the geometry of the specimen. The material properties of the numerical model were adjusted in the course of this dissertation, in order to find the lowest difference between the numerical and experimental results with an error lower than 5% (it was performed the numerical model identification based on the experimental results).

Orthogonal models, structure crossing, nesting and inference

We intend to study the algebraic structure of the simple orthogonal models to use them, through binary operations as building blocks in the construction of more complex orthogonal models. We start by presenting some matrix results considering Commutative Jordan Algebras of symmetric matrices, CJAs. Next, we use these results to study the algebraic structure of orthogonal models, obtained by crossing and nesting simpler ones. Then, we study the normal models with OBS, which can also be orthogonal models. We intend to study normal models with OBS (Orthogonal Block Structure), NOBS (Normal Orthogonal Block Structure), obtaining condition for having complete and suffcient statistics, having UMVUE, is unbiased estimators with minimal covariance matrices whatever the variance components. Lastly, see ([Pereira et al. (2014)]), we study the algebraic structure of orthogonal models, mixed models whose variance covariance matrices are all positive semi definite, linear combinations of known orthogonal pairwise orthogonal projection matrices, OPOPM, and whose least square estimators, LSE, of estimable vectors are best linear unbiased estimator, BLUE, whatever the variance components, so they are uniformly BLUE, UBLUE. From the results of the algebraic structure we will get explicit expressions for the LSE of these models.

Garland, since 1776- a unique ownership structure

The case is based on Garland, a 240 years old Portuguese family business, now owned by the Dawson family. It focuses on a decision made 50 years ago, aligned with what had been the company’s history, about the ownership rules for family members, which influences the ownership structure of the firm. It addresses the main issues about ownership in family businesses, and tackles the problem of succession planning and fair process. It contains a teaching note to support the utilization of the case in a classroom context, with learning objectives, target audience, a teaching plan, questions and proposed answers, and theory that relates to the case. It is also complemented with an epilogue and an overview of the case.

Does the existing Corporate Governance structure and strict Legal Framework, affect the strategic decisionmaking of CEOs?

This thesis is a case study on Corporate Governance and Business Ethics, using the Portuguese Corporate Law as a general setting. The thesis was conducted in Portugal with illustrations on past cases under the Business Judgment Rule of the State of Delaware, U.SA along with illustrations on current cases in Portugal under the Portuguese Judicial setting, along with a comparative analysis between both. A debate is being considered among scholars and executives; a debate on best practices within corporate governance and corporate law, associated with recent discoveries of unlawful investments that lead to the bankruptcy of leading institutions and an aggravation of the crisis in Portugal. The study aimed at learning possible reasons and causes for the current situation of the country’s corporations along with attempts to discover the best way to move forward. From the interviews and analysis conducted, this paper concluded that the corporate governance structure and legal frameworks in Portugal were not the sole influencers behind the actions and decisions of Corporate Executives, nor were they the main triggers for the recent corporate mishaps. But it is rather a combination of different factors that played a significant role, such as cultural and ethical aspects, individual personalities, and others all of which created gray areas beyond the legal structure, which in turn accelerated and aggravated the corporate governance crisis in the country.