Estudo económico das energias renováveis: o caso português

Dissertação de Mestrado apresentado ao Instituto de Contabilidade e Administração do Porto para a obtenção do grau de Mestre em Empreendedorismo e Internacionalização, sob orientação de Maria Clara Dias Pinto Ribeiro

Desenvolvimento de uma metodologia baseada em redes neuronais para o cálculo da energia produzida por aerogeradores

O uso da energia eólica para a produção de eletricidade apresenta na última década um crescimento apreciável. Monitorizar o desempenho dos aerogeradores torna-se um processo incontornável, quer por motivos financeiros, quer por questões operacionais. Os investimentos despendidos na construção de parques eólicos são muito consideráveis, pelo que é essencial a análise constante dos aspetos preponderantes no retorno do investimento. A maximização da energia produzida por cada aerogerador é o objetivo principal da monitorização dos parques eólicos. Os sistemas Supervisory Control and Data Acquisition (SCADAs) instalados nos parques eólicos permitem uma supervisão em tempo real relativamente ao estado e funcionamento dos aerogeradores, adquirindo uma elevada importância na avaliação dos rendimentos energéticos e anomalias de funcionamento, garantido desta forma melhorias de produtividade. O objetivo deste trabalho é estimar a energia produzida pelos aerogeradores quando ocorrem falhas de comunicação com o seu contador interno ou avaria do mesmo. A ocorrência destas situações não permite a monitorização da energia produzida durante esse período. Foram analisados dados operacionais dos aerogeradores relativos a um parque eólico localizado na zona Norte de Portugal, sendo usados os dados recolhidos pelo sistema SCADA sobre a forma de médias de 10 min referentes ao período de janeiro de 2011 a agosto 2011. O desempenho da rede neuronal depende da qualidade e quantidade do conjunto de dados usados para o treino da rede. Os dados usados devem representar de forma fiel o estado que se pretende para o equipamento. Para a obtenção do objetivo proposto foi fundamental a identificação das grandezas disponíveis a utilizar no método de cálculo da energia produzida. Os resultados obtidos com aplicação das redes neuronais no método de cálculo da energia produzida por aerogeradores demonstram que independentemente do período de indisponibilidade da informação referente à energia produzida é possível estimar o valor da mesma.

Growth and Raman scattering characterization of Cu2ZnSnS4 thin films

In the present work we report the results of the growth, morphological and structural characterization of Cu2ZnSnS4 (CZTS) thin films prepared by sulfurization of DC magnetron sputtered Cu/Zn/Sn precursor layers. The adjustment of the thicknesses and the properties of the precursors were used to control the final composition of the films. Its properties were studied by SEM/EDS, XRD and Raman scattering. The influence of the sulfurization temperature on the morphology, composition and structure of the films has been studied. With the presented method we have been able to prepare CZTS thin films with the kesterite structure.

CuxSnSx+1 (x = 2, 3) thin films grown by sulfurization of metallic precursors deposited by dc magnetron sputtering

We report the results of the growth of Cu-Sn-S ternary chalcogenide compounds by sulfurization of dc magnetron sputtered metallic precursors. Tetragonal Cu2SnS3 forms for a maximum sulfurization temperature of 350 ºC. Cubic Cu2SnS3 is obtained at sulfurization temperatures above 400 ºC. These results are supported by XRD analysis and Raman spectroscopy measurements. The latter analysis shows peaks at 336 cm-1, 351 cm-1 for tetragonal Cu2SnS3, and 303 cm-1, 355 cm-1 for cubic Cu2SnS3. Optical analysis shows that this phase change lowers the band gap from 1.35 eV to 0.98 eV. At higher sulfurization temperatures increased loss of Sn is expected in the sulphide form. As a consequence, higher Cu content ternary compounds like Cu3SnS4 grow. In these conditions, XRD and Raman analysis only detected orthorhombic (Pmn21) phase (petrukite). This compound has Raman peaks at 318 cm-1, 348 cm-1 and 295 cm-1. For a sulfurization temperature of 450 ºC the samples present a multi-phase structure mainly composed by cubic Cu2SnS3 and orthorhombic (Pmn21) Cu3SnS4. For higher temperatures, the samples are single phase and constituted by orthorhombic (Pmn21) Cu3SnS4. Transmittance and reflectance measurements were used to estimate a band gap of 1.60 eV. For comparison we also include the results for Cu2ZnSnS4 obtained using similar growth conditions.

Growth pressure dependence of Cu2ZnSnSe4 properties

In this work, we show a set of growth conditions, for the two step process, with which the growth of CZTSe is successful and reproducible. The properties of the best CTZSe thin films grown by this method were examined by SEM/EDS, XRD, Raman scattering, AFM/EFM, transmittance and reflectance measurements, photoluminescence (PL) measurements and hot point probe. A broad emission band was observed in the photoluminescence spectrum of the CZTSe thin film. The band gap energy was estimated to be around 1.05 eV at room temperature, using the transmittance and reflectance data, and CZTSe samples show p-type conductivity with the hot point probe. The different characterization techniques show that we could grow single phase CZTSe thin films with our optimized process conditions.

Influence of selenization pressure on the growth of Cu2ZnSnSe4 films from stacked metallic layers

Cu2ZnSnSe4 (CZTSe) is a p-type semiconductor with a high absorption coefficient, 104 to 105 cm-1, and is being seen as a possible replacement for Cu(In,Ga)Se2 in thin film solar cells. Yet, there are some fundamental properties of CZTSe that are not well known, one of them is its band gap. In order to resolve its correct value it is necessary to improve the growth conditions to ensure that single phase crystalline thin films are obtained. One of the problems encountered when growing CZTSe is the loss of Sn through evaporation of SnSe. Stoichiometric films are then difficult to obtain and usually there are other phases present. One possible way to overcome this problem is to increase the pressure of growth of CZTSe. This can be done by introducing an atmosphere of an inert gas like Ar or N2. In this work we report the results of morphological, structural and optical studies of the properties of CZTSe thin films grown by selenization of DC magnetron sputtered metallic layers under different Ar pressures. The films are analysed by SEM/EDS, Raman scattering and XRD.

Study of polycrystalline Cu2ZnSnS4 films by Raman scattering

Cu2ZnSnS4 (CZTS) is a p-type semiconductor that has been seen as a possible low-cost replacement for Cu(In,Ga)Se2 in thin film solar cells. So far compound has presented difficulties in its growth, mainly, because of the formation of secondary phases like ZnS, CuxSnSx+1, SnxSy, Cu2−xS and MoS2. X-ray diffraction analysis (XRD), which is mostly used for phase identification cannot resolve some of these phases from the kesterite/stannite CZTS and thus the use of a complementary technique is needed. Raman scattering analysis can help distinguishing these phases not only laterally but also in depth. Knowing the absorption coefficient and using different excitation wavelengths in Raman scattering analysis, one is capable of profiling the different phases present in multi-phase CZTS thin films. This work describes in a concise form the methods used to grow chalcogenide compounds, such as, CZTS, CuxSnSx+1, SnxSy and cubic ZnS based on the sulphurization of stacked metallic precursors. The results of the films’ characterization by XRD, electron backscatter diffraction and scanning electron microscopy/energy dispersive spectroscopy techniques are presented for the CZTS phase. The limitation of XRD to identify some of the possible phases that can remain after the sulphurization process are investigated. The results of the Raman analysis of the phases formed in this growth method and the advantage of using this technique in identifying them are presented. Using different excitation wavelengths it is also analysed the CZTS film in depth showing that this technique can be used as non destructive methods to detect secondary phases.

Growth and characterization of Cu2ZnSn(S,Se)4 thin films for solar cells

Cu2ZnSnS4 (CZTS) and Cu2ZnSnSe4 (CZTSe) with their band gap energies around 1.45 eV and 1.0 eV, respectively, can be used as the absorber layer in thin film solar cells. By using a mixture of both compounds, Cu2ZnSn(S,Se)4 (CZTSSe), a band gap tuning may be possible. The latter material has already shown promising results such as solar cell efficiencies up to 10.1%. In this work, CZTSSe thin films were grown in order to study its structure and to establish the best growth precursors. SEM micrographs reveal an open columnar structure for most samples and EDS composition profiling of the cross sections show different selenium gradients. X-ray diffractograms show different shifts of the kesterite/stannite (1 1 2) peak, which indicate the presence of CZTSSe. From Raman scattering analysis, it was concluded that all samples had traces of CZTS and CZTSSe. The composition of the CZTSSe layer was estimated using X-ray diffraction and Raman scattering and both results were compared. It was concluded that Se diffused more easily in precursors with ternary Cu–Sn–S phases and metallic Zn than in precursors with ZnS and/or CZTS already formed. It was also showed that a combination of X-ray diffraction and Raman scattering can be used to estimate the ratio of S per Se in CZTSSe samples.

Legal and political regulation of higher education in Portugal: an evolutionary perspective on the current policy issues and the problem of order

The higher education system in Europe is currently under stress and the debates over its reform and future are gaining momentum. Now that, for most countries, we are in a time for change, in the overall society and the whole education system, the legal and political dimensions have gained prominence, which has not been followed by a more integrative approach of the problem of order, its reform and the issue of regulation, beyond the typical static and classical cost-benefit analyses. The two classical approaches for studying (and for designing the policy measures of) the problem of the reform of the higher education system - the cost-benefit analysis and the legal scholarship description - have to be integrated. This is the argument of our paper that the very integration of economic and legal approaches, what Warren Samuels called the legal-economic nexus, is meaningful and necessary, especially if we want to address the problem of order (as formulated by Joseph Spengler) and the overall regulation of the system. On the one hand, and without neglecting the interest and insights gained from the cost-benefit analysis, or other approaches of value for money assessment, we will focus our study on the legal, social and political aspects of the regulation of the higher education system and its reform in Portugal. On the other hand, the economic and financial problems have to be taken into account, but in a more inclusive way with regard to the indirect and other socio-economic costs not contemplated in traditional or standard assessments of policies for the tertiary education sector. In the first section of the paper, we will discuss the theoretical and conceptual underpinning of our analysis, focusing on the evolutionary approach, the role of critical institutions, the legal-economic nexus and the problem of order. All these elements are related to the institutional tradition, from Veblen and Commons to Spengler and Samuels. The second section states the problem of regulation in the higher education system and the issue of policy formulation for tackling the problem. The current situation is clearly one of crisis with the expansion of the cohorts of young students coming to an end and the recurrent scandals in private institutions. In the last decade, after a protracted period of extension or expansion of the system, i. e., the continuous growth of students, universities and other institutions are competing harder to gain students and have seen their financial situation at risk. It seems that we are entering a period of radical uncertainty, higher competition and a new configuration that is slowly building up is the growth in intensity, which means upgrading the quality of the higher learning and getting more involvement in vocational training and life-long learning. With this change, and along with other deep ones in the Portuguese society and economy, the current regulation has shown signs of maladjustment. The third section consists of our conclusions on the current issue of regulation and policy challenge. First, we underline the importance of an evolutionary approach to a process of change that is essentially dynamic. A special attention will be given to the issues related to an evolutionary construe of policy analysis and formulation. Second, the integration of law and economics, through the notion of legal economic nexus, allows us to better define the issues of regulation and the concrete problems that the universities are facing. One aspect is the instability of the political measures regarding the public administration and on which the higher education system depends financially, legally and institutionally, to say the least. A corollary is the lack of clear strategy in the policy reforms. Third, our research criticizes several studies, such as the one made by the OECD in late 2006 for the Ministry of Science, Technology and Higher Education, for being too static and neglecting fundamental aspects of regulation such as the logic of actors, groups and organizations who are major players in the system. Finally, simply changing the legal rules will not necessary per se change the behaviors that the authorities want to change. By this, we mean that it is not only remiss of the policy maker to ignore some of the critical issues of regulation, namely the continuous non-respect by academic management and administrative bodies of universities of the legal rules that were once promulgated. Changing the rules does not change the problem, especially without the necessary debates form the different relevant quarters that make up the higher education system. The issues of social interaction remain as intact. Our treatment of the matter will be organized in the following way. In the first section, the theoretical principles are developed in order to be able to study more adequately the higher education transformation with a modest evolutionary theory and a legal and economic nexus of the interactions of the system and the policy challenges. After describing, in the second section, the recent evolution and current working of the higher education in Portugal, we will analyze the legal framework and the current regulatory practices and problems in light of the theoretical framework adopted. We will end with some conclusions on the current problems of regulation and the policy measures that are discusses in recent years.

Enoxacin inhibits growth of prostate cancer cells and effectively restores microRNA processing

Prostate cancer (PCa) is one of the most incident malignancies worldwide. Although efficient therapy is available for early-stage PCa, treatment of advanced disease is mainly ineffective and remains a clinical challenge. microRNA (miRNA) dysregulation is associated with PCa development and progression. In fact, several studies have reported a widespread downregulation of miRNAs in PCa, which highlights the importance of studying compounds capable of restoring the global miRNA expression. The main aim of this study was to define the usefulness of enoxacin as an anti-tumoral agent in PCa, due to its ability to induce miRNA biogenesis in a TRBP-mediated manner. Using a panel of five PCa cell lines, we observed that all of them were wild type for the TARBP2 gene and expressed TRBP protein. Furthermore, primary prostate carcinomas displayed normal levels of TRBP protein. Remarkably, enoxacin was able to decrease cell viability, induce apoptosis, cause cell cycle arrest, and inhibit the invasiveness of cell lines. Enoxacin was also effective in restoring the global expression of miRNAs. This study is the first to show that PCa cells are highly responsive to the anti-tumoral effects of enoxacin. Therefore, enoxacin constitutes a promising therapeutic agent for PCa.

The use of information and interactive processes in growth management

Tese de doutoramento em Engenharia do Ambiente, especialidade em Sistemas Sociais

In-situ X-ray diffraction studies during growth of Ni-Ti shape memory alloy films and their complementary ex-situ characterization

Shape Memory Alloy (SMA) Ni-Ti films have attracted much interest as functional and smart materials due to their unique properties. However, there are still important issues unresolved like formation of film texture and its control as well as substrate effects. Thus, the main challenge is not only the control of the microstructure, including stoichiometry and precipitates, but also the identification and control of the preferential orientation since it is a crucial factor in determining the shape memory behaviour. The aim of this PhD thesis is to study the optimisation of the deposition conditions of films of Ni-Ti in order to obtain the material fully crystallized at the end of the deposition, and to establish a clear relationship between the substrates and texture development. In order to achieve this objective, a two-magnetron sputter deposition chamber has been used allowing to heat and to apply a bias voltage to the substrate. It can be mounted into the six-circle diffractometer of the Rossendorf Beamline (ROBL) at the European Synchrotron Radiation Facility (ESRF), Grenoble, France, enabling an in-situ characterization by X-ray diffraction(XRD) of the films during their growth and annealing. The in-situ studies enable us to identify the different steps of the structural evolution during deposition with a set of parameters as well as to evaluate the effect of changing parameters on the structural characteristics of the deposited film. Besides the in-situ studies, other complementary ex-situ characterization techniques such as XRD at a laboratory source, Rutherford backscattering spectroscopy(RBS), Auger electron spectroscopy (AES), cross-sectional transmission electron microscopy (X-TEM), scanning electron microscopy (SEM), and electrical resistivity (ER) measurements during temperature cycling have been used for a fine structural characterization. In this study, mainly naturally and thermally oxidized Si(100) substrates, TiN buffer layers with different thicknesses (i.e. the TiN topmost layer crystallographic orientation is thickness dependent) and MgO(100) single crystals were used as substrates. The chosen experimental procedure led to a controlled composition and preferential orientation of the films. The type of substrate plays an important role for the texture of the sputtered Ni-Ti films and according to the ER results, the distinct crystallographic orientations of the Ni-Ti films influence their phase transformation characteristics.

Integrated analysis of climate, soil, topography and vegetative growth in Iberian viticultural regions

The Iberian viticultural regions are convened according to the Denomination of Origin (DO) and present different climates, soils, topography and management practices. All these elements influence the vegetative growth of different varieties throughout the peninsula, and are tied to grape quality and wine type. In the current study, an integrated analysis of climate, soil, topography and vegetative growth was performed for the Iberian DO regions, using state-of-the-art datasets. For climatic assessment, a categorized index, accounting for phenological/thermal development, water availability and grape ripening conditions was computed. Soil textural classes were established to distinguish soil types. Elevation and aspect (orientation) were also taken into account, as the leading topographic elements. A spectral vegetation index was used to assess grapevine vegetative growth and an integrated analysis of all variables was performed. The results showed that the integrated climate-soil-topography influence on vine performance is evident. Most Iberian vineyards are grown in temperate dry climates with loamy soils, presenting low vegetative growth. Vineyards in temperate humid conditions tend to show higher vegetative growth. Conversely, in cooler/warmer climates, lower vigour vineyards prevail and other factors, such as soil type and precipitation acquire more important roles in driving vigour. Vines in prevailing loamy soils are grown over a wide climatic diversity, suggesting that precipitation is the primary factor influencing vigour. The present assessment of terroir characteristics allows direct comparison among wine regions and may have great value to viticulturists, particularly under a changing climate.

Critical reappraisal of Late Mesozoic-Cenozoic Central and North Atlantic, Caribbean and Mediterranean evolution

(l) The Pacific basin (Pacific area) may be regarded as moving eastwards like a double zip fastener relative to the continents and their respective plates (Pangaea area): opening in the East and closing in the West. This movement is tracked by a continuous mountain belt, the collision ages of which increase westwards. (2) The relative movements between the Pacific area and the Pangaea area in the W-EfE-W direction are generated by tidal forces (principle of hypocycloid gearing), whereby the lower mantle and the Pacific basin or area (Pacific crust = roof of the lower mantle?) rotate somewhat faster eastwards around the Earth's spin axis relative to the upper mantle/crust system with the continents and their respective plates (Pangaea area) (differential rotation). (3) These relative West to East/East to West displacements produce a perpetually existing sequence of distinct styles of opening and closing oeean basins, exemplified by the present East to West arrangement of ocean basins around the globe (Oceanic or Wilson Cycle: Rift/Red Sea style; Atlantic style; Mediterranean/Caribbean style as eastwards propagating tongue of the Pacific basin; Pacific style; Collision/Himalayas style). This sequence of ocean styles, of which the Pacific ocean is a part, moves eastwards with the lower mantle relative to the continents and the upper-mantle/crust of the Pangaea area. (4) Similarly, the collisional mountain belt extending westwards from the equator to the West of the Pacific and representing a chronological sequence of collision zones (sequential collisions) in the wake of the passing of the Pacific basin double zip fastener, may also be described as recording the history of oceans and their continental margins in the form of successive Wilson Cycles. (5) Every 200 to 250 m.y. the Pacific basin double zip fastener, the sequence of ocean styles of the Wilson Cycle and the eastwards growing collisional mountain belt in their wake complete one lap around the Earth. Two East drift lappings of 400 to 500 m.y. produce a two-lap collisional mountain belt spiral around a supercontinent in one hemisphere (North or South Pangaea). The Earth's history is subdivided into alternating North Pangaea growth/South Pangaea breakup eras and South Pangaea growth/North Pangaea breakup eras. Older North and South Pangaeas and their collisional mountain belt spirals may be reconstructed by rotating back the continents and orogenic fragments of a broken spiral (e.g. South Pangaea, Gondwana) to their previous Pangaea growth era orientations. In the resulting collisional mountain belt spiral, pieced together from orogenic segments and fragments, the collision ages have to increase successively towards the West. (6) With its current western margin orientated in a West-East direction North America must have collided during the Late Cretaceous Laramide orogeny with the northern margin of South America (Caribbean Andes) at the equator to the West of the Late Mesozoic Pacific. During post-Laramide times it must have rotated clockwise into its present orientation. The eastern margin of North America has never been attached to the western margin of North Africa but only to the western margin of Europe. (7) Due to migration eastwards of the sequence of ocean styles of the Wilson Cycle, relative to a distinct plate tectonic setting of an ocean, a continent or continental margin, a future or later evolutionary style at the Earth's surface is always depicted in a setting simultaneously developed further to the West and a past or earlier style in a setting simultaneously occurring further to the East. In consequence, ahigh probability exists that up to the Early Tertiary, Greenland (the ArabiaofSouth America?) occupied a plate tectonic setting which is comparable to the current setting of Arabia (the Greenland of Africa?). The Late Cretaceous/Early Tertiary Eureka collision zone (Eureka orogeny) at the northern margin of the Greenland Plate and on some of the Canadian Arctic Islands is comparable with the Middle to Late Tertiary Taurus-Bitlis-Zagros collision zone at the northern margin of the Arabian Plate.

Proposal of a short-form version of the Brazilian Food Insecurity Scale

OBJECTIVE To propose a short version of the Brazilian Food Insecurity Scale. METHODS Two samples were used to test the results obtained in the analyses in two distinct scenarios. One of the studies was composed of 230 low income families from Pelotas, RS, Southern Brazil, and the other was composed of 15,575 women, whose data were obtained from the 2006 National Survey on Demography and Health. Two models were tested, the first containing seven questions, and the second, the five questions that were considered the most relevant ones in the concordance analysis. The models were compared to the Brazilian Food Insecurity Scale, and the sensitivity, specificity and accuracy parameters were calculated, as well as the kappa agreement test. RESULTS Comparing the prevalence of food insecurity between the Brazilian Food Insecurity Scale and the two models, the differences were around 2 percentage points. In the sensitivity analysis, the short version of seven questions obtained 97.8% and 99.5% in the Pelotas sample and in the National Survey on Demography and Health sample, respectively, while specificity was 100% in both studies. The five-question model showed similar results (sensitivity of 95.7% and 99.5% in the Pelotas sample and in the National Survey on Demography and Health sample, respectively). In the Pelotas sample, the kappa test of the seven-question version totaled 97.0% and that of the five-question version, 95.0%. In the National Survey on Demography and Health sample, the two models presented a 99.0% kappa. CONCLUSIONS We suggest that the model with five questions should be used as the short version of the Brazilian Food Insecurity Scale, as its results were similar to the original scale with a lower number of questions. This version needs to be administered to other populations in Brazil in order to allow for the adequate assessment of the validity parameters.