Phase diagrams of binary mixtures of patchy colloids with distinct numbers and types of patches: Theempty fluid regime

We investigate the effect of distinct bonding energies on the onset of criticality of low functionality fluid mixtures. We focus on mixtures ofparticles with two and three patches as this includes the mixture where "empty" fluids were originally reported. In addition to the number of patches, thespecies differ in the type of patches or bonding sites. For simplicity, we consider that the patches on each species are identical: one species has threepatches of type A and the other has two patches of type B. We have found a rich phase behavior with closed miscibility gaps, liquid-liquid demixing, and negative azeotropes. Liquid-liquid demixing was found to pre-empt the "empty" fluid regime, of these mixtures, when the AB bonds are weaker than the AA or BB bonds. By contrast, mixtures in this class exhibit "empty" fluid behavior when the AB bonds are stronger than at least one of the other two. Mixtureswith bonding energies epsilon(BB) = epsilon(AB) and epsilon(AA) < epsilon(BB), were found to exhibit an unusual negative azeotrope. (C) 2011 American Institute of Physics. [doi:10.1063/1.3561396]

Computing the phase diagram of binary mixtures: A patchy particle case study

We investigate the phase behaviour of 2D mixtures of bi-functional and three-functional patchy particles and 3D mixtures of bi-functional and tetra-functional patchy particles by means of Monte Carlo simulations and Wertheim theory. We start by computing the critical points of the pure systems and then we investigate how the critical parameters change upon lowering the temperature. We extend the successive umbrella sampling method to mixtures to make it possible to extract information about the phase behaviour of the system at a fixed temperature for the whole range of densities and compositions of interest. (C) 2013 AIP Publishing LLC.

Asphalt rubber mixtures in Portugal: fatigue resistance

This paper presents a study concerning the fatigue behaviour of asphalt mixtures with bitumen modified with high content of crumb rubber used in Portugal. For assessing the fatigue behaviour of this type of mixtures, four asphalt mixtures with high content of crumb rubber were used: two field bituminous mixtures – an open-graded and a gap-graded – both with granite aggregates; and two laboratory manufactured bituminous mixtures – an open-graded mixture with granite aggregates and a gap-graded mixture with crushed gravel aggregates. Since this type of mixtures are mainly applied in wearing courses, the effect of ageing in the fatigue behaviour of one of the studied asphalt rubber mixtures was also assessed through laboratory testing. The paper presents the main results achieved so far concerning the fatigue resistance and it could be concluded that all the materials have exhibited a good behaviour, in agreement with others previous studies. In the case of the aged gap-graded material, it was observed a slight reduction on the fatigue life comparatively to the un-aged one.

Hydroisomerization of n-decane over SAPO-11 catalysts synthesized with methylamine as co-template

The present work deals with preliminary studies concerning a new synthesis approach to prepare SAPO materials with AEL structure and evaluate their catalytic behavior in the hydroisomerization of long paraffins. The new SAPO-11 catalysts were synthesized with the help of a small amine (methylamine, MA) added during the preparation of the initial gel. As MA incorporates into the structure of the final materials, it contributes, together with DPA (dipropylamine), to an increase in Si incorporation as isolated species, which results in Bronsted acid sites. Thus, this new and original synthesis strategy allows to obtain materials with enhanced Bronsted acidity when compared with free MA materials. The catalysts were tested in n-decane hydroisomerization (n-decane was used as a model molecule) and confirmed the effect of MA on the acidic properties of the catalysts. The samples synthesized with MA present a higher number of acid sites that increase the catalytic conversion but have a negative effect in the isomerization selectivity, i.e. a more significant amount of cracking products is formed.

Caracterização mecânica de misturas betuminosas a aplicar em infra-estruturas de transportes

A maioria das infra-estruturas de transportes, nomeadamente os pavimentos rodoviários e aeroportuários, são constituídas por misturas betuminosas, o que permite um bom desempenho e uma adequada durabilidade, nas condições usuais de serviço. As misturas betuminosas são ainda amplamente utilizadas na construção de zonas de estacionamento de veículos, tendo-se verificado recentemente a sua aplicação também em infra-estruturas ferroviárias. Face à necessidade de melhorar o desempenho das vias-férreas, permitindo uma concepção mais durável de linhas de alta velocidade e uma redução dos custos da sua manutenção, tem-se vindo a desenvolver diversos estudos para promover a utilização de novos materiais, principalmente através da incorporação de misturas betuminosas. O presente trabalho tem como objectivo a caracterização do comportamento mecânico de misturas betuminosas a aplicar em infra-estruturas de transportes. Como metodologia para o estudo do comportamento mecânico das misturas betuminosas foram realizados em laboratório ensaios de cargas repetidas, nomeadamente, ensaios de flexão em quatro pontos para determinação da rigidez e da resistência à fadiga e ensaios de compressão triaxiais cíclicos para avaliação do comportamento à deformação permanente. A resistência à fadiga das misturas betuminosas em estudo foi avaliada através do ensaio de flexão em quatro pontos, com extensão controlada, e aplicação de um carregamento sinusoidal com diferentes frequências, de acordo com o procedimento de ensaio da norma europeia EN 12697-24 (2004 + A1: 2007). A resistência à deformação permanente das misturas betuminosas foi analisada através de ensaios de compressão triaxiais cíclicos, submetendo-as a uma tensão de confinamento estática pela aplicação parcial de vácuo e a uma pressão axial cíclica sob a forma rectangular, de acordo com a norma europeia EN 12697-25 (2004). O conhecimento destas propriedades mecânicas assume particular importância ao nível da formulação das misturas betuminosas, do dimensionamento de uma estrutura ou do estabelecimento de uma adequada solução para uma obra de reabilitação duma infra-estrutura de transportes. Para este estudo foi utilizado um modelo físico construído numa fossa no LNEC, com o propósito de serem testadas três substruturas ferroviárias não convencionais, utilizando sub-balastro betuminoso. A selecção das substruturas foi efectuada após uma análise de várias secções de estruturas já testadas e aplicadas noutros países, de forma a proporcionar comparações fiáveis entre elas. Os resultados obtidos mostraram que a mistura betuminosa AC20 base 50/70 (MB) aplicada na camada de sub-balastro é adequada para ser aplicada nas infra-estruturas de transportes pois apresenta um bom desempenho à fadiga e à deformação permanente. Através dos ensaios efectuados foi ainda possível entender a importante influência das características volumétricas, principalmente da porosidade para o bom comportamento da mistura betuminosa.

Variation of magnetic properties in sedimentary rocks hosting the Foum Zguid dyke (southern Morocco): Combined effects of re-crystallization and Fe-metasomatism

The effects of dyke intrusion on the magnetic properties of host sedimentary rocks are still poorly understood. Therefore, we have evaluated bulk magnetic parameters of standard palaeomagnetic samples collected along several sections across the sediments hosting the Foum Zguid dyke in southern Morocco. The study has been completed with the evaluation of the magnetic fabric after laboratory application of sequential heating experiments. The present study shows that: (1) close to Fourn Zguid dykes, the variations of the bulk magnetic parameters and of the magnetic fabric is strongly related with re-crystallization and Fe-metasomatism intensity. (2) The thermal experiments on AMS of samples collected farther from the dyke and, thus, less affected by heating during dyke emplacement, indicate that 300-400 degrees C is the minimum experimental temperature necessary to trigger appreciable transformations of the pre-existing magnetic fabrics. For temperatures higher than ca. 580 degrees C, the magnetic fabric transformations are fully realized, with complete transposition of the initial fabric to a fabric similar to that of samples collected close to the dyke. Therefore, measured variations of the magnetic fabric can be used to evaluate re-crystallization temperatures experienced by the host sedimentary rock during dyke emplacement. The distinct magnetic behaviour observed along the cross-sections strongly suggests that samples collected farther from the dyke margins did not experience thermal episodes with temperatures higher than 300 degrees C after dyke emplacement. (3) AMS data shows a gradual variation of the magnetic fabric with distance from the dyke margin, from sub-horizontal K-3 away from the dyke to vertical K3 close to the dyke. Experimental heating shows that heat alone can be responsible for this strong variation. Therefore, such orientation changes should not be unequivocally interpreted as the result of a stress field (resulting from the emplacement of the dyke, for instance). (4) Magnetic studies prove to be a very sensitive tool to assess rock magnetic transformations, thermally and chemically induced by dyke intrusion in hosting sediments.

Simulation of default events in a CDX and estimation of the spread

The portfolio generating the iTraxx EUR index is modeled by coupled Markov chains. Each of the industries of the portfolio evolves according to its own Markov transition matrix. Using a variant of the method of moments, the model parameters are estimated from a data set of Standard and Poor's. Swap spreads are evaluated by Monte-Carlo simulations. Along with an actuarially fair spread, at least squares spread is considered.

Estudo da utilização de fibras em misturas betuminosas

A presente dissertação tem como objectivo principal aprofundar os conhecimentos sobre a incorporação de fibras em misturas betuminosas, em particular, sobre as misturas do tipo Stone Mastic Asphalt (SMA). Para este tipo de mistura betuminosa existe uma norma de produto europeia, a EN 13108-5:2006. Os ensaios tipo iniciais para efeitos de certificação CE das misturas estão contemplados na norma portuguesa NP EN 13108-20:2008, onde também são estipuladas as condições de ensaio. São descritos diversos tipos de fibras passíveis de serem utilizadas no fabrico da mistura betuminosa do tipo SMA, dando especial enfoque às misturas fabricadas com fibras celulósicas, uma vez que este tipo específico de mistura é frequentemente aplicado em camada de desgaste noutros países, com reconhecidas vantagens em termos de durabilidade e desempenho do pavimento. As misturas do tipo SMA são descritas, analisando-se métodos de formulação e métodos para a sua caracterização. Posteriormente, são apresentados e discutidos os trabalhos experimentais levados a cabo para um caso concreto. Os ensaios realizados permitiram caracterizar a mistura quanto à sensibilidade à água, ao seu módulo de rigidez e resistência à deformação permanente. Conclui-se que a mistura do tipo SMA com a incorporação de fibras analisada, apresenta bom comportamento à deformação permanente e boa resistência á acção da água, comparativamente às misturas betuminosas tradicionais aplicadas em camada de desgaste.

Femtosecond laser ablation of dentin

The surface morphology, structure and composition of human dentin treated with a femtosecond infrared laser (pulse duration 500 fs, wavelength 1030 nm, fluences ranging from 1 to 3 J cm(-2)) was studied by scanning electron microscopy, x-ray diffraction, x-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The average dentin ablation threshold under these conditions was 0.6 +/- 0.2 J cm(-2) and the ablation rate achieved in the range 1 to 2 mu m/pulse for an average fluence of 3 J cm(-2). The ablation surfaces present an irregular and rugged appearance, with no significant traces of melting, deformation, cracking or carbonization. The smear layer was entirely removed by the laser treatment. For fluences only slightly higher than the ablation threshold the morphology of the laser-treated surfaces was very similar to the dentin fracture surfaces and the dentinal tubules remained open. For higher fluences, the surface was more porous and the dentin structure was partially concealed by ablation debris and a few resolidified droplets. Independently on the laser processing parameters and laser processing method used no sub-superficial cracking was observed. The dentin constitution and chemical composition was not significantly modified by the laser treatment in the processing parameter range used. In particular, the organic matter is not preferentially removed from the surface and no traces of high temperature phosphates, such as the beta-tricalcium phosphate, were observed. The achieved results are compatible with an electrostatic ablation mechanism. In conclusion, the high beam quality and short pulse duration of the ultrafast laser used should allow the accurate preparation of cavities, with negligible damage of the underlying material.

Catalytic combustion of toluene on Pt zeolite coated cordierite foams

The catalytic properties of Pt based cordierite foam catalysts have been evaluated in catalytic combustion of toluene (800 ppm in air). The catalysts contain identical Pt content (0.1%) which was introduced by three different ways: Pt ion exchange on MFI zeolite and then coating on the foam; Pt ion exchange after zeolite coating and finally Pt directly wet impregnated on the cordierite foam. The catalytic behaviour of Pt foam based catalysts was compared with that of PtMFI zeolite under powder form. Pt exchanged MFI supported on the cordierite foams present an improvement of activity for toluene combustion of about 50 degrees C on the light off temperature (T-50%). The enhanced performance of the structured catalysts is due not only to the open structure of foams and homogeneous thin layers catalyst deposited on their cell walls, but also to the fact that the size and location of Pt particles present in MFI zeolite are changed during the dipping step. Indeed, as prepared Pt samples and those used in the preparation of the slurry were observed by transmission electron microscopy revealing that the chemical interaction of PtMFI zeolite with the binder and detergent, both present in the slurry, leads to an increase of Pt particles size which were found to migrate from internal pores to the external surface of zeolite crystallites thereby increasing catalytic activity. (C) 2011 Elsevier B.V. All rights reserved.

Incorporation of niobium in SAPO-11 materials: Synthesis and characterization

The present work concerns a new synthesis approach to prepare niobium based SAPO materials with AEL structure and the characterization ofNb species incorporated within the inorganic matrixes. The SAPO-11 materials were synthesized with or without the help of a small amine, methylamine (MA) as co-template, while Nb was added directly during the preparation of the initial gel. Structural, textural and acidic properties of the different supports were evaluated by XRD, TPR, UV-Vis spectroscopy, pyridine adsorption followed by IR spectroscopy and thermal analyses. Pure and well crystalline Nb based SAPO-11 materials were obtained, either with or without MA, using in the initial gel a low Si content of about 0.6. Increasing the Si content of the gel up to 0.9 led to an important decrease of the samples crystallinity. Niobium was found to incorporate the AEL pores support as small Nb2O5 oxide particles and also as extra framework cationic species (Nb5+), compensating the negative charges from the matrix and generating new Lewis acid sites. (C) 2011 Elsevier Inc. All rights reserved.

Synthesis of optimization of [11C] Pittsburgh compound B by the captive solvent method

Mestrado em Medicina Nuclear.

Arrow Plot: a new graphical tool for selecting up and down regulated genes and genes differentially expressed on samples subgroups

Background: A common task in analyzing microarray data is to determine which genes are differentially expressed across two (or more) kind of tissue samples or samples submitted under experimental conditions. Several statistical methods have been proposed to accomplish this goal, generally based on measures of distance between classes. It is well known that biological samples are heterogeneous because of factors such as molecular subtypes or genetic background that are often unknown to the experimenter. For instance, in experiments which involve molecular classification of tumors it is important to identify significant subtypes of cancer. Bimodal or multimodal distributions often reflect the presence of subsamples mixtures. Consequently, there can be genes differentially expressed on sample subgroups which are missed if usual statistical approaches are used. In this paper we propose a new graphical tool which not only identifies genes with up and down regulations, but also genes with differential expression in different subclasses, that are usually missed if current statistical methods are used. This tool is based on two measures of distance between samples, namely the overlapping coefficient (OVL) between two densities and the area under the receiver operating characteristic (ROC) curve. The methodology proposed here was implemented in the open-source R software. Results: This method was applied to a publicly available dataset, as well as to a simulated dataset. We compared our results with the ones obtained using some of the standard methods for detecting differentially expressed genes, namely Welch t-statistic, fold change (FC), rank products (RP), average difference (AD), weighted average difference (WAD), moderated t-statistic (modT), intensity-based moderated t-statistic (ibmT), significance analysis of microarrays (samT) and area under the ROC curve (AUC). On both datasets all differentially expressed genes with bimodal or multimodal distributions were not selected by all standard selection procedures. We also compared our results with (i) area between ROC curve and rising area (ABCR) and (ii) the test for not proper ROC curves (TNRC). We found our methodology more comprehensive, because it detects both bimodal and multimodal distributions and different variances can be considered on both samples. Another advantage of our method is that we can analyze graphically the behavior of different kinds of differentially expressed genes. Conclusion: Our results indicate that the arrow plot represents a new flexible and useful tool for the analysis of gene expression profiles from microarrays.

Assessment of saccharide fractionation by ultrafiltration and nanofiltration

This paper addresses the investigation of the fractionation of saccharide mixtures and saccharide mixtures with calcium using ultrafiltration (UF) and nanofiltration (NF). A set of cellulose acetate membranes covered a wide range of molecular weight cut-off (MWCO) ranging from 250 to 46,000 Da and the total feed concentration of saccharides mixtures varied from 1550 to 4700 ppm with the ratio of the two saccharides-solutes (glucose to raffinose) being kept constant at the value of 1.8. The evolution pattern of the saccharide concentration ratio in the UF/NF permeate streams displayed a dependence on the membrane MWCO, on the total sugar concentration and on the presence of calcium ions. For the highest total sugar content, the membranes with MWCO from 2000 to 7000 Da showed saccharide fractionation capability that was enhanced in the presence of calcium. The Steric Pore Flow Model was used to predict individual solute permeation behaviours and to assess the deviations to steric hindered transport of the solutes in multi-component saccharide solutions. (C) 2008 Elsevier B.V. All rights reserved.

Towards the detection of deception in interactive multimedia environments

A classical application of biosignal analysis has been the psychophysiological detection of deception, also known as the polygraph test, which is currently a part of standard practices of law enforcement agencies and several other institutions worldwide. Although its validity is far from gathering consensus, the underlying psychophysiological principles are still an interesting add-on for more informal applications. In this paper we present an experimental off-the-person hardware setup, propose a set of feature extraction criteria and provide a comparison of two classification approaches, targeting the detection of deception in the context of a role-playing interactive multimedia environment. Our work is primarily targeted at recreational use in the context of a science exhibition, where the main goal is to present basic concepts related with knowledge discovery, biosignal analysis and psychophysiology in an educational way, using techniques that are simple enough to be understood by children of different ages. Nonetheless, this setting will also allow us to build a significant data corpus, annotated with ground-truth information, and collected with non-intrusive sensors, enabling more advanced research on the topic. Experimental results have shown interesting findings and provided useful guidelines for future work. Pattern Recognition