Wetting behaviour of femtosecond laser textured Ti-6Al-4V surfaces

The aim of the present work was to investigate the wetting behaviour of biomedical grade Ti-6Al-4V alloy surfaces textured by a femtosecond laser treatment. The material was treated in ambient atmosphere using an Yb: KYW chirped-pulse-regenerative amplification laser with a wavelength of 1030 nm and a pulse duration of 500 fs. Four main types of surface textures were obtained depending on the processing parameters and laser treatment method. These textures consist of: (1) nanoscale laser-induced periodic surface structures (LIPSS); (2) nanopillars; (3) a bimodal roughness distribution texture formed of LIPSS overlapping microcolumns; (4) a complex texture formed of LIPSS overlapping microcolumns with a periodic variation of the columns size in the laser scanning direction. The wettability of the surfaces was evaluated by the sessile drop method using distilled-deionized (DD) water and Hank's balanced salt solution (HBSS) as testing liquids. The laser treated surfaces present a hydrophilic behaviour as well as a high affinity for the saline solution, with equilibrium contact angles in the ranges 24.1-76.2. for DD water and 8.4-61.8. for HBSS. The wetting behaviour is anisotropic, reflecting the anisotropy of the surface textures. (c) 2012 Elsevier B.V. All rights reserved.

Measuring spatial interaction behavior in team sports using superimposed Voronoi diagrams

In team sports, the spatial distribution of players on the field is determined by the interaction behavior established at both player and team levels. The distribution patterns observed during a game emerge from specific technical and tactical methods adopted by the teams, and from individual, environmental and task constraints that influence players' behaviour. By understanding how specific patterns of spatial interaction are formed, one can characterize the behavior of the respective teams and players. Thus, in the present work we suggest a novel spatial method for describing teams' spatial interaction behaviour, which results from superimposing the Voronoi diagrams of two competing teams. We considered theoretical patterns of spatial distribution in a well-defined scenario (5 vs 4+ GK played in a field of 20x20m) in order to generate reference values of the variables derived from the superimposed Voronoi diagrams (SVD). These variables were tested in a formal application to empirical data collected from 19 Futsal trials with identical playing settings. Results suggest that it is possible to identify a number of characteristics that can be used to describe players' spatial behavior at different levels, namely the defensive methods adopted by the players.

Temporal patterns of TV watching for Portuguese viewers

Audiometer systems provide enormous amounts of detailed TV watching data. Several relevant and interdependent factors may influence TV viewers' behavior. In this work we focus on the time factor and derive Temporal Patterns of TV watching, based on panel data. Clustering base attributes are originated from 1440 binary minute-related attributes, capturing the TV watching status (watch/not watch). Since there are around 2500 panel viewers a data reduction procedure is first performed. K-Means algorithm is used to obtain daily clusters of viewers. Weekly patterns are then derived which rely on daily patterns. The obtained solutions are tested for consistency and stability. Temporal TV watching patterns provide new insights concerning Portuguese TV viewers' behavior.

Análise técnica dos principais índices bolsistas europeus

Mestrado em Controlo e Gestão e dos Negócios

Convective patterns under the Indo-Atlantic << box >>

Using fluid mechanics, we reinterpret the mantle images obtained from global and regional tomography together with geochemical, geological and paleomagnetic observations, and attempt to unravel the pattern of convection in the Indo-Atlantic "box" and its temporal evolution over the last 260 Myr. The << box >> presently contains a) a broad slow seismic anomaly at the CMB which has a shape similar to Pangea 250 Myr ago, and which divides into several branches higher in the lower mantle, b) a "superswell, centered on the western edge of South Africa, c) at least 6 "primary hotspots" with long tracks related to traps, and d) numerous smaller hotspots. In the last 260 Myr, this mantle box has undergone 10 trap events, 7 of them related to continental breakup. Several of these past events are spatially correlated with present-day seismic anomalies and/or upwellings. Laboratory experiments show that superswells, long-lived hotspot tracks and traps may represent three evolutionary stages of the same phenomenon, i.e. episodic destabilization of a hot, chemically heterogeneous thermal boundary layer, close to the bottom of the mantle. When scaled to the Earth's mantle, its recurrence time is on the order of 100-200 Myr. At any given time, the Indo-Atlantic box should contain 3 to 9 of these instabilities at different stages of their development, in agreement with observations. The return flow of the downwelling slabs, although confined to two main << boxes >> (Indo-Atlantic and Pacific) by subduction zone geometry, may therefore not be passive, but rather take the form of active thermochemical instabilities. (c) 2005 Elsevier B.V. All rights reserved.

Shear-induced lamellar phase of an ionic liquid crystal at room temperature

The phase behaviour of a number of N-alkylimidazolium salts was studied using polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction. Two of these compounds exhibit lamellar mesophases at temperatures above 50 degrees C. In these systems, the liquid crystalline behaviour may be induced at room temperature by shear. Sheared films of these materials, observed between crossed polarisers, have a morphology that is typical of (wet) liquid foams: they partition into dark domains separated by brighter (birefringent) walls, which are approximately arcs of circle and meet at "Plateau borders" with three or more sides. Where walls meet three at a time, they do so at approximately 120 degrees angles. These patterns coarsen with time and both T1 and T2 processes have been observed, as in foams. The time evolution of domains is also consistent with von Neumann's law. We conjecture that the bright walls are regions of high concentration of defects produced by shear, and that the system is dominated by the interfacial tension between these walls and the uniform domains. The control of self-organised monodomains, as observed in these systems, is expected to play an important role in potential applications.

How foam-like is the shear-induced lamellar phase of an ionic liquid crystal?

Philosophical Magazine Letters Volume 88, Issue 9-10, 2008 Special Issue: Solid and Liquid Foams. In commemoration of Manuel Amaral Fortes

Generalizing repeating patterns: a study with children aged four

This paper presents part of a study that aimed to understand how the emergence of algebraic thinking takes place in a group of four-year-old children, as well as its relationship to the exploration of children‘s literature. To further deepen and guide this study the following research questions were formulated: (1) How can children's literature help preschoolers identify patterns?; (2) What strategies and thinking processes do children use to create, analyze and generalize repeating and growing patterns?; (3) What strategies do children use to identify the unit of repeat of a pattern? and (4) What factors influence the identification of patterns? The paper focuses only on the strategies and thinking processes that children use to create, analyze and generalize repeating patterns. The present study was developed with a group of 14 preschoolers in a private school in Lisbon, and it was carried out with all children. In order to develop the research, a qualitative research methodology under the interpretive paradigm was chosen, emphasizing meanings and processes. The researcher took the dual role of teacher-researcher, conducting the study with her own group and in her own natural environment. Participant observation and document analysis (audio and video recordings, photos and children productions) were used as data collection methods. Data collection took place from October 2013 to April 2014. The results of the study indicate that children master the concept of repeating patterns, and they are able to identify the unit of repeat, create and analyze various repeating patterns, evolving from simpler to more complex forms.

Especulação em mercado bolsista : análise técnica : o caso Nasdaq-100 perante a crise subprime

Mestrado em Controlo de Gestão e dos Negócios

Assessing the behaviour of RC beams subject to significant gravity loads under cyclic loads

Gravity loads can affect a reinforced concrete structure's response to seismic actions, however, traditional procedures for testing the beam behaviour do not take this effect into consideration. An experimental campaign was carried out in order to assess the influence of the gravity load on RC beam connection to the column subjected to cyclic loading. The experiments included the imposition of a conventional quasi-static test protocol based on the imposition of a reverse cyclic displacement history and of an alternative cyclic test procedure starting from the gravity load effects. The test results are presented, compared and analysed in this paper. The imposition of a cyclic test procedure that included the gravity loads effects on the RC beam ends reproduces the demands on the beams' critical zones more realistically than the traditional procedure. The consideration of the vertical load effects in the test procedure led to an accumulation of negative (hogging) deformation. This phenomenon is sustained with the behaviour of a portal frame system under cyclic loads subject to a significant level of the vertical load, leading to the formation of unidirectional plastic hinges. In addition, the hysteretic behaviour of the RC beam ends tested was simulated numerically using the nonlinear structural analysis software - OpenSees. The beam-column model simulates the global element behaviour very well, as there is a reasonable approximation to the hysteretic loops obtained experimentally. (C) 2013 Elsevier Ltd. All rights reserved.

Mu-Chlorido-Bridged Dimanganese(II) complexes of the schiff base derived from [2+2] condensation of 2,6-diformyl-4-methylphenol and 1,3-bis(3-aminopropyl)tetramethyldisloxane: structure, magnetismo, electrochemical behaviour, and catalytic oxidation of secondary alcohols

The reaction of 2,6-diformyl-4-methylphenol with 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the presence of MnCl2 in a 1:1:2 molar ratio in methanol afforded a dinuclear -chlorido-bridged manganese(II) complex of the macrocyclic [2+2] condensation product (H2L), namely, [Mn2Cl2(H2L)(HL)]Cl center dot 3H(2)O (1). The latter afforded a new compound, namely, [Mn2Cl2(H2L)(2)][MnCl4]center dot 4CH(3)CN center dot 0.5CHCl(3 center dot)0.4H(2)O (2), after recrystallisation from 1:1 CHCl3/CH3CN. The co-existence of the free and complexed azomethine groups, phenolato donors, mu-chlorido bridges, and the disiloxane unit were well evidenced by ESI mass spectrometry and FTIR spectroscopy and confirmed by X-ray crystallography. The magnetic measurements revealed an antiferromagnetic interaction between the two high-spin (S = 5/2, g = 2) manganese(II) ions through the mu-chlorido bridging ligands. The electrochemical behaviour of 1 and 2 has been studied, and details of their redox properties are reported. Both compounds act as catalysts or catalyst precursors in the solvent-free low-power microwave-assisted oxidation of selected secondary alcohols, for example, 1-phenylethanol, cyclohexanol, 2- and 3-octanol, to the corresponding ketones in the absence of solvent. The highest yield of 72% was achieved for 1-phenylethanol by using a maximum of 1% molar ratio of catalyst relative to substrate.

The solvation and electrochemical behaviour of Copper acetylacetonate complexes in ionic liquids

The behavior of copper(II) complexes of pentane-2,4-dione and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, [Cu(acac)(2) (1) and [Cu(HFacac)(2)(H2O)] (2), in ionic liquids and molecular organic solvents, was studied by spectroscopic and electrochemical techniques. The electron paramagnetic resonance characterization (EPR) showed well-resolved spectra in most solvents. In general the EPR spectra of [Cu(acac)(2)] show higher g(z) values and lower hyperfine coupling constants, A(z), in ionic liquids than in organic solvents, in agreement with longer Cu-O bond lengths and higher electron charge in the copper ion in the ionic liquids, suggesting coordination of the ionic liquid anions. For [Cu(HFacac)(2)(H2O)] the opposite was observed suggesting that in ionic liquids there is no coordination of the anions and that the complex is tetrahedrically distorted. The redox properties of the Cu(II) complexes were investigated by cyclic voltammetry (CV) at a Pt electrode (d = 1 mm), in bmimBF(4) and bmimNTf(2) ionic liquids and, for comparative purposes, in neat organic solvents. The neutral copper(II) complexes undergo irreversible reductions to Cu(I) and Cu(0) species in both ILs and common organic solvents (CH2Cl2 or acetonitrile), but, in ILs, they are usually more easier to reduce (less cathodic reduction potential) than in the organic solvents. Moreover, 1 and 2 are easier to reduce in bmimNTf(2) than in bmimBF(4) ionic liquid. (C) 2013 Elsevier B.V. All rights reserved.

The solvation and redox behaviour of mixed ligand COPPER(II) complexes of acetylacetonate and aromatic dimines in ionic liquids

The behavior of two cationic copper complexes of acetylacetonate and 2,2'-bipyridine or 1,10-phenanthroline, [Cu(acac)(bipy)]Cl (1) and [Cu(acac)(phen)]Cl (2), in organic solvents and ionic liquids, was studied by spectroscopic and electrochemical techniques. Both complexes showed solvatochromism in ionic liquids although no correlation with solvent parameters could be obtained. By EPR spectroscopy rhombic spectra with well-resolved superhyperfine structure were obtained in most ionic liquids. The spin Hamiltonian parameters suggest a square pyramidal geometry with coordination of the ionic liquid anion. The redox properties of the complexes were investigated by cyclic voltammetry at a Pt electrode (d = 1 mm) in bmimBF(4) and bmimNTf(2) ionic liquids. Both complexes 1 and 2 are electrochemically reduced in these ionic media at more negative potentials than when using organic solvents. This is in agreement with the EPR characterization, which shows lower A(z) and higher g(z) values for the complexes dissolved in ionic liquids, than in organic solvents, due to higher electron density at the copper center. The anion basicity order obtained by EPR is NTf2-, N(CN)(2)(-), MeSO4- and Me2PO4-, which agrees with previous determinations. (C) 2013 Elsevier B.V. All rights reserved.

µ-Chlorido-bridged dimanganese(II) complexes of the schiff base derived from [2+2] condensation of 2,6-diformyl-4-methylphenol and 1,3-bis(3-aminopropyl)tetramethyldisiloxane: structure, magnetismo, electrochemical behaviour, and catalytic oxidation of secondary alcohols

The reaction of 2,6-diformyl-4-methylphenol with 1,3-bis(3-aminopropyl)tetramethyldisiloxane in the presence of MnCl2 in a 1:1:2 molar ratio in methanol afforded a dinuclear -chlorido-bridged manganese(II) complex of the macrocyclic [2+2] condensation product (H2L), namely, [Mn2Cl2(H2L)(HL)]Cl center dot 3H(2)O (1). The latter afforded a new compound, namely, [Mn2Cl2(H2L)(2)][MnCl4]center dot 4CH(3)CN center dot 0.5CHCl(3 center dot)0.4H(2)O (2), after recrystallisation from 1:1 CHCl3/CH3CN. The co-existence of the free and complexed azomethine groups, phenolato donors, mu-chlorido bridges, and the disiloxane unit were well evidenced by ESI mass spectrometry and FTIR spectroscopy and confirmed by X-ray crystallography. The magnetic measurements revealed an antiferromagnetic interaction between the two high-spin (S = 5/2, g = 2) manganese(II) ions through the mu-chlorido bridging ligands. The electrochemical behaviour of 1 and 2 has been studied, and details of their redox properties are reported. Both compounds act as catalysts or catalyst precursors in the solvent-free low-power microwave-assisted oxidation of selected secondary alcohols, for example, 1-phenylethanol, cyclohexanol, 2- and 3-octanol, to the corresponding ketones in the absence of solvent. The highest yield of 72% was achieved for 1-phenylethanol by using a maximum of 1% molar ratio of catalyst relative to substrate.

A magnanimidade da teoria: interpretar a ética em teoria da literatura

Tese de doutoramento, Teoria da Literatura, Universidade de Lisboa, Faculdade de Letras, 2003