A class of singular first order differential equations with applications in reaction-diffusion

Agências Financiadoras: FCT e MIUR

Travelling wave profiles in some models with nonlinear diffusion

We study some properties of the monotone solutions of the boundary value problem (p(u'))' - cu' + f(u) = 0, u(-infinity) = 0, u(+infinity) = 1, where f is a continuous function, positive in (0, 1) and taking the value zero at 0 and 1, and P may be an increasing homeomorphism of (0, 1) or (0, +infinity) onto [0, +infinity). This problem arises when we look for travelling waves for the reaction diffusion equation partial derivative u/partial derivative t = partial derivative/partial derivative x [p(partial derivative u/partial derivative x)] + f(u) with the parameter c representing the wave speed. A possible model for the nonlinear diffusion is the relativistic curvature operator p(nu)= nu/root 1-nu(2). The same ideas apply when P is given by the one- dimensional p- Laplacian P(v) = |v|(p-2)v. In this case, an advection term is also considered. We show that, as for the classical Fisher- Kolmogorov- Petrovski- Piskounov equations, there is an interval of admissible speeds c and we give characterisations of the critical speed c. We also present some examples of exact solutions. (C) 2014 Elsevier Inc. All rights reserved.

Completion problems for real matrices, II

Thirty years ago, G.N. de Oliveira has proposed the following completion problems: Describe the possible characteristic polynomials of [C-ij], i,j is an element of {1, 2}, where C-1,C-1 and C-2,C-2 are square submatrices, when some of the blocks C-ij are fixed and the others vary. Several of these problems remain unsolved. This paper gives the solution, over the field of real numbers, of Oliveira's problem where the blocks C-1,C-1, C-2,C-2 are fixed and the others vary.

Coordination Chemistry of the (eta(6)-p-Cymene)ruthenium(II) Fragment with Bis-, Tris-, andTetrakis(pyrazol-1-yl)borate Ligands: Synthesis, Structural, Electrochemical, and CatalyticDiastereoselective Nitroaldol Reaction Studies

Novel [Ru(eta(6)-p-cymene)(kappa(2)-L)X] and [Ru(eta(6)-p-cymene)(kappa(3)-L)]X center dot nH(2)O complexes (L = bis-, tris-, or tetrakis-pyrazolylborate; X = Cl, N-3, PF6, or CF3SO3) are prepared by treatment of [Ru(eta(6)-p-cymene)Cl-2](2) with poly-(pyrazolyl)borate derivatives [M(L)] (L in general; in detail L = Ph(2)Bp = diphenylbis-(pyrazol-1-yl)borate; L = Tp = hydrotris(pyrazol-1-yl)borate; L = pzTp = tetrakis(pyrazol-1-yl)borate; L = Tp(4Bo) = hydrotris(indazol-1-yl)borate, L = T-p4Bo,T-5Me = (5-methylindazol-1-yl)borate; L = Tp(Bn,4Ph) = hydrotris(3-benzyl-4-phenylpyrazol-1-yl)borate; M = Na, K, or TI) and characterized by analytical and spectral data (IR, ESIMS, H-1 and C-13 NMR). The structures of [Ru(eta(6)-p-cymene)(Ph(2)Bp)Cl] (1) and [Ru(eta(6)-p-cymene)(Tp)Cl] (3) have been established by single-crystal X-ray diffraction analysis. Electrochemical studies allowed comparing the electron-donor characters of Tp and related ligands and estimating the corresponding values of the Lever E-L ligand parameter. The complexes [Ru(eta(6)-p-cymene)-(kappa(2)-L)X] and [Ru(eta(6)-p-cymene)(kappa(3)-L)]X center dot nH(2)O act as catalyst precursors for the diastereoselective nitroaldol reaction of benzaldehyde and nitroethane to the corresponding beta-nitroalkanol (up to 82% yield, at room temperature) with diastereoselectivity toward the formation of the threo isomer.

Positive solutions of fourth order problems with clamped beam boundary conditions

n this paper we make an exhaustive study of the fourth order linear operator u((4)) + M u coupled with the clamped beam conditions u(0) = u(1) = u'(0) = u'(1) = 0. We obtain the exact values on the real parameter M for which this operator satisfies an anti-maximum principle. Such a property is equivalent to the fact that the related Green's function is nonnegative in [0, 1] x [0, 1]. When M < 0 we obtain the best estimate by means of the spectral theory and for M > 0 we attain the optimal value by studying the oscillation properties of the solutions of the homogeneous equation u((4)) + M u = 0. By using the method of lower and upper solutions we deduce the existence of solutions for nonlinear problems coupled with this boundary conditions. (C) 2011 Elsevier Ltd. All rights reserved.

Study on the glycerolysis reaction of high free fatty acid oils for use as biodiesel feedstock

Biodiesel is the main alternative to fossil diesel and it may be produced from different feedstocks such as semi-refined vegetable oils, waste frying oils or animal fats. However, these feedstocks usually contain significant amounts of free fatty acids (FFA) that make them inadequate for the direct base catalyzed transesterification reaction (where the FFA content should be lower than 4%). The present work describes a possible method for the pre-treatment of oils with a high content of FFA (20 to 50%) by esterification with glycerol. In order to reduce the FFA content, the reaction between these FFA and an esterification agent is carried out before the transesterification reaction. The reaction kinetics was studied in terms of its main factors such astemperature, % of glycerin excess, % of catalyst used, stirring velocity and type of catalyst used. The results showed that glycerolysis is a promising pretreatment to acidic oils or fats (> 20%) as they led to the production of an intermediary material with a low content of FFA that can be used directly in thetransesterification reaction for the production of biodiesel. (C) 2011 Elsevier B.V. All rights reserved.

Efeito da incorporação de resíduos da indústria petrolífera na durabilidade de argamassas de reparação de estruturas de betão

Na presente dissertação, o trabalho desenvolvido teve como objetivo, a avaliação de alguns parâmetros de durabilidade de argamassas com incorporação de catalisador exausto de FCC (do inglês “Fluid Catalytic Cracking”) para serem utilizadas na reparação de estruturas de betão. O catalisador exausto de FCC é um resíduo da indústria petrolífera e o utilizado neste estudo é proveniente da refinaria da Petrogal, S.A. em Sines. A presente investigação baseou-se na preparação, e avaliação de propriedades, de duas séries distintas de argamassas: a série que se denominou “RAS” e a série que se denominou “Durabilidade”, nas quais se substituiu, parcialmente entre 5, 10 e 15%, em massa de cimento por resíduo exausto de FCC. As argamassas de ambas as séries diferenciam-se entre si, sobretudo, pela utilização de areia reativa nas argamassas da série RAS e de areia inerte no caso das argamassas da série durabilidade. Nas argamassas estudadas foram realizados ensaios no estado fresco e ensaios no estado endurecido. Os ensaios no estado fresco incluíram a determinação da consistência por espalhamento, da massa volúmica e do teor de ar. Nos ensaios no estado endurecido foram avaliadas, no caso das argamassas da série RAS a extensão da reação àlcalis-sílica e no caso das argamassas da série Durabilidade as resistências mecânicas - à flexão e à compressão, a resistência à carbonatação acelerada, o módulo de elasticidade à compressão, a absorção capilar, a permeabilidade ao oxigénio, a difusão de cloretos em regime não estacionário. O trabalho desenvolvido nesta dissertação demonstrou que a incorporação de catalisador exausto de FCC, em argamassas à base de cimento, minimiza o efeito de expansão das reações álcalis-sílica, bem como contribui para reduzir a absorção capilar e coeficiente de difusão de cloretos. No entanto, este resíduo quando incorporados em argamassas contribui para a diminuição da resistência à carbonatação acelerada e para o aumento da permeabilidade ao oxigénio.

Hexanuclear and undecanuclear iron(III) carboxylates as catalyst precursors for cyclohexane oxidation

Two multinuclear complexes [Fe-6(mu(3)-O)(2)(mu(4)-O-2)L-10(OAc)(2)(H2O)(2)]center dot 2.625Et(2)O center dot 2.375H(2)O (1) and [(Fe11Cl)-Cl-III-(mu(4)-O)(3)(mu(3)-O)(5)L-16(dmf)(2.5)(H2O)(0.5)]center dot Et2O center dot 1.25dmf center dot 3.8H(2)O (2), where HL = 3,4,5-trimethoxybenzoic acid and dmf = dimethylformamide, have been prepared from trinuclear iron(III) carboxylates via their structural rearrangement in dimethylformamide or diethyl ether-dimethylformamide 9:1, respectively, and slow vapor diffusion of diethyl ether into the reaction mixture. Both compounds have been characterized by X-ray diffraction, optical, Mossbauer spectroscopy, and magnetic measurements. Complex 1 possesses a hexanuclear ferric peroxido-dioxido {Fe-6(O-2)(O)(2)}(12+) core unit, which adopts a recliner conformation, while complex 2 contains an unprecedented {Fe11O8Cl}(16+) core, in which 9 ferric ions are six-coordinate and the remaining two are five-coordinate. Another structural feature of note of the undecanuclear core is the presence of a deformed cubane entity {Fe-4(mu(3)-O)(mu(4)-O)(3)}(4+). Both complexes act as catalyst precursors for the oxidation of cyclohexane to cyclohexanol and cyclohexanone with aqueous H2O2, in the presence of pyrazinecarboxylic acid. Remarkable TONs and TOFs (the latter mainly for 1) with concomitant quite good yields have been achieved under mild conditions. Moreover, 1 exhibits remarkably high activity in an exceptionally short reaction time (45 min), being unprecedented for any metal catalyzed alkane oxidation by H2O2. The catalytic reactions proceed via Fenton type chemistry.

Water quality issues in rivers, lakes and reservoirs in Asian countries: an approach to the problems and the methodologies

Water covers over 70% of the Earth's surface, and is vital for all known forms of life. But only 3% of the Earth's water is fresh water, and less than 0.3% of all freshwater is in rivers, lakes, reservoirs and the atmosphere. However, rivers and lakes are an important part of fresh surface water, amounting to about 89%. In this Master Thesis dissertation, the focus is on three types of water bodies – rivers, lakes and reservoirs, and their water quality issues in Asian countries. The surface water quality in a region is largely determined both by the natural processes such as climate or geographic conditions, and the anthropogenic influences such as industrial and agricultural activities or land use conversion. The quality of the water can be affected by pollutants discharge from a specific point through a sewer pipe and also by extensive drainage from agriculture/urban areas and within basin. Hence, water pollutant sources can be divided into two categories: Point source pollution and Non-point source (NPS) pollution. Seasonal variations in precipitation and surface run-off have a strong effect on river discharge and the concentration of pollutants in water bodies. For example, in the rainy season, heavy and persistent rain wash off the ground, the runoff flow increases and may contain various kinds of pollutants and, eventually, enters the water bodies. In some cases, especially in confined water bodies, the quality may be positive related with rainfall in the wet season, because this confined type of fresh water systems allows high dilution of pollutants, decreasing their possible impacts. During the dry season, the quality of water is largely related to industrialization and urbanization pollution. The aim of this study is to identify the most common water quality problems in Asian countries and to enumerate and analyze the methodologies used for assessment of water quality conditions of both rivers and confined water bodies (lakes and reservoirs). Based on the evaluation of a sample of 57 papers, dated between 2000 and 2012, it was found that over the past decade, the water quality of rivers, lakes, and reservoirs in developing countries is being degraded. Water pollution and destruction of aquatic ecosystems have caused massive damage to the functions and integrity of water resources. The most widespread NPS in Asian countries and those which have the greatest spatial impacts are urban runoff and agriculture. Locally, mine waste runoff and rice paddy are serious NPS problems. The most relevant point pollution sources are the effluents from factories, sewage treatment plant, and public or household facilities. It was found that the most used methodology was unquestionably the monitoring activity, used in 49 of analyzed studies, accounting for 86%. Sometimes, data from historical databases were used as well. It can be seen that taking samples from the water body and then carry on laboratory work (chemical analyses) is important because it can give an understanding of the water quality. 6 papers (11%) used a method that combined monitoring data and modeling. 6 papers (11%) just applied a model to estimate the quality of water. Modeling is a useful resource when there is limited budget since some models are of free download and use. In particular, several of used models come from the U.S.A, but they have their own purposes and features, meaning that a careful application of the models to other countries and a critical discussion of the results are crucial. 5 papers (9%) focus on a method combining monitoring data and statistical analysis. When there is a huge data matrix, the researchers need an efficient way of interpretation of the information which is provided by statistics. 3 papers (5%) used a method combining monitoring data, statistical analysis and modeling. These different methods are all valuable to evaluate the water quality. It was also found that the evaluation of water quality was made as well by using other types of sampling different than water itself, and they also provide useful information to understand the condition of the water body. These additional monitoring activities are: Air sampling, sediment sampling, phytoplankton sampling and aquatic animal tissues sampling. Despite considerable progress in developing and applying control regulations to point and NPS pollution, the pollution status of rivers, lakes, and reservoirs in Asian countries is not improving. In fact, this reflects the slow pace of investment in new infrastructure for pollution control and growing population pressures. Water laws or regulations and public involvement in enforcement can play a constructive and indispensable role in environmental protection. In the near future, in order to protect water from further contamination, rapid action is highly needed to control the various kinds of effluents in one region. Environmental remediation and treatment of industrial effluent and municipal wastewaters is essential. It is also important to prevent the direct input of agricultural and mine site runoff. Finally, stricter environmental regulation for water quality is required to support protection and management strategies. It would have been possible to get further information based in the 57 sample of papers. For instance, it would have been interesting to compare the level of concentrations of some pollutants in the diferente Asian countries. However the limit of three months duration for this study prevented further work to take place. In spite of this, the study objectives were achieved: the work provided an overview of the most relevant water quality problems in rivers, lakes and reservoirs in Asian countries, and also listed and analyzed the most common methodologies.

Influence of network effects on the diffusion of information systems: the case of open source

Doutoramento em Gestão

Action, reaction and protest by publishers in 1960s Portugal: books and other publications in the Catholic opposition

The authoritarian regime of the Portuguese Estado Novo (New State), the longest dictatorship in twentieth-century Western Europe, suffered one of its most serious threats during the late 1950s and the whole of the following decade. An array of events and dynamics of opposition to the regime and condemnation of the political and social situation in Portugal appeared at that time. One of the core groups that displayed their dissidence in the 1960s, with the awakening of their critical conscience, originated in Catholic sectors that rallied the laity and the clergy to express their disagreement or even break with the government of Salazar (and, later, Marcelo Caetano). This article aims to establish the role of print culture and, in particular, publishing in the opposition’s mobilisation of Catholics who criticised the Estado Novo. It will also closely examine the contribution of certain publishers to the formulation of the terms of this mobilisation, in publishing new authors and topics and creating new printed forums (e.g. periodicals) for discussion and reflection. The most detailed case will be that of the publishing house Livraria Moraes Editora, under the command of the publisher António Alçada Baptista.

NiII, CuII and ZnII complexes with a sterically hindered scorpionate ligand (TpmsPh) and catalytic application in the diasteroselective nitroaldol (Henry) reaction

The Ni-II and Zn-II complexes [MCl(Tpms(Ph))] (Tpms(Ph) = SO3C(pz(Ph))(3), pz = pyrazolyl; M = Ni 2 or Zn 3) and the Cu-II complex [CuCl(Tpms(Ph))(H2O)] (4) have been prepared by treatment of the lithium salt of the sterically demanding and coordination flexible tris(3-phenyl-1-pyrazolyl)methanesulfonate (Tpms(Ph))(-) (1) with the respective metal chlorides. The (Tpms(Ph))(-) ligand shows the N-3 or N2O coordination modes in 2 and 3 or in 4, respectively. Upon reaction of 2 and 3 with Ag(CF3SO3) in acetonitrile the complexes [M(Tpms(Ph))-(MeCN)](CF3SO3) (M = Ni 5 or Zn 6, respectively) were formed. The compounds were obtained in good yields and characterized by analytic and spectral (IR, H-1 and C-13{H-1} NMR, ESI-MS) data, density functional theory (DFT) methods and {for 4 and [(Bu4N)-Bu-n](Tpms(Ph)) (7), the tatter obtained upon Li+ replacement by [(Bu4N)-Bu-n](+) in Li(Tpms(Ph))} by single crystal X-ray diffraction analysis. The Zn-II and Cu-II complexes (3 and 4, respectively) act as efficient catalyst precursors for the diastereoselective nitroaldol reaction of benzaldehydes and nitroethane to the corresponding beta-nitroalkanols (up to 99% yield, at room temperature) with diastereoselectivity towards the formation of the anti isomer, whereas the Ni-II complex 2 only shows a modest catalytic activity.

Phex: a computational tool for plate heat exchanges design problems

This paper presents a computational tool (PHEx) developed in Excel VBA for solving sizing and rating design problems involving Chevron type plate heat exchangers (PHE) with 1-pass-1-pass configuration. The rating methodology procedure used in the program is outlined, and a case study is presented with the purpose to show how the program can be used to develop sensitivity analysis to several dimensional parameters of PHE and to observe their effect on transferred heat and pressure drop.

Modifications of MCM-22 zeolite through sequential post-synthesis treatments. Implications on the acidic and catalytic behaviour

Desilication and a combination of alkaline followed by acid treatment were applied to MCM-22 zeolite using two different base concentrations. The samples were characterised by powder X-ray diffraction, Al-27 and Si-29 MAS-NMR spectroscopy, SEM, TEM and low temperature N-2 adsorption. The acidity of the samples was study through pyridine adsorption followed by FTIR spectroscopy and by the analyses of the hydroxyl region. The catalytic behaviour, anticipated by the effect of post-synthesis treatments on the acidity and space available inside the two internal pore systems was evaluated by using the model reaction of m-xylene transformation. The generation of mesoporosity was achieved upon alkaline treatment with 0.05 M NaOH solution and practically no additional gain was obtained when the more concentrate solution, 0.1 M, was used. Instead, Al extraction takes place along with Si, as shown by Si-29 and Al-27 MAS-NMR data, followed by Al deposition as extraframework species. Samples submitted to alkaline plus acid treatments present distinct behaviour. When the lowest NaOH solution was used no relevant effect was observed on the textural characteristics. Additionally, when the acid treatment was performed on an already fragilized MCM-22 structure, due to previous desilication with 0.1 M NaOH solution, the extraction of Al from both internal pore systems promotes their interconnection, evolving from a 2-D to a 3-D porous structure. This transformation has a marked effect in the catalytic behaviour, allowing an increase of m-xylene conversion as a consequence of an easier and faster molecular traffic in the 3-D structure. On the other hand, the continuous deposition of extraframework Al species inside the pores leads to a shape selective effect that privileges the formation of the more valuable isomer p-xylene.

Catálise de hydrocraking baseado em zeólitos

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química