Supporting real-time distributed computer-controlled systems with multi-hop P-NET networks

Fieldbus communication networks aim to interconnect sensors, actuators and controllers within process control applications. Therefore, they constitute the foundation upon which real-time distributed computer-controlled systems can be implemented. P-NET is a fieldbus communication standard, which uses a virtual token-passing medium-access-control mechanism. In this paper pre-run-time schedulability conditions for supporting real-time traffic with P-NET networks are established. Essentially, formulae to evaluate the upper bound of the end-to-end communication delay in P-NET messages are provided. Using this upper bound, a feasibility test is then provided to check the timing requirements for accessing remote process variables. This paper also shows how P-NET network segmentation can significantly reduce the end-to-end communication delays for messages with stringent timing requirements.

Hybrid wired/wireless PROFIBUS networks supported by bridges/routers

Fieldbus networks are becoming increasingly popular in industrial computer-controlled systems. More recently, there has been the desire to extend the capabilities of fieldbuses to cover functionalities not previously considered in such networks, with particular emphasis on industrial wireless communications. Thinking about wireless means considering hybrid wired/wireless solutions capable of interoperating with legacy (wired) systems. One possible solution is to use intermediate systems (IS) acting as repeaters to interconnect the wired and wireless parts. In contrast, we analyze a solution where intermediate systems are implemented as bridges/routers. We detail the main advantages in terms of dependability and timeliness, and propose mechanisms to manage message transactions and intercell mobility.

Fieldbus networks: real-time from the perspective of the application tasks

Fieldbus communication networks aim to interconnect sensors, actuators and controllers within distributed computer-controlled systems. Therefore they constitute the foundation upon which real-time applications are to be implemented. A potential leap towards the use of fieldbus in such time-critical applications lies in the evaluation of its temporal behaviour. In the past few years several research works have been performed on a number of fieldbuses. However, these have mostly focused on the message passing mechanisms, without taking into account the communicating application tasks running in those distributed systems. The main contribution of this paper is to provide an approach for engineering real-time fieldbus systems where the schedulability analysis of the distributed system integrates both the characteristics of the application tasks and the characteristics of the message transactions performed by these tasks. In particular, we address the case of system where the Process-Pascal multitasking language is used to develop P-NET based distributed applications

Non pre-emptive scheduling of messages on SMTV token-passing networks

Fieldbus communication networks aim to interconnect sensors, actuators and controllers within distributed computer-controlled systems. Therefore, they constitute the foundation upon which real-time applications are to be implemented. A specific class of fieldbus communication networks is based on a simplified version of token-passing protocols, where each station may transfer, at most, a single message per token visit (SMTV). In this paper, we establish an analogy between non-preemptive task scheduling in single processors and the scheduling of messages on SMTV token-passing networks. Moreover, we clearly show that concepts such as blocking and interference in non-preemptive task scheduling have their counterparts in the scheduling of messages on SMTV token-passing networks. Based on this task/message scheduling analogy, we provide pre-run-time schedulability conditions for supporting real-time messages with SMTV token-passing networks. We provide both utilisation-based and response time tests to perform the pre-run-time schedulability analysis of real-time messages on SMTV token-passing networks, considering RM/DM (rate monotonic/deadline monotonic) and EDF (earliest deadline first) priority assignment schemes

Transport mechanism in ionic liquid membranes and the study of thiomersal biodegradation

The initial goal of this work was the development of a supported liquid membrane (SLM) bioreactor for the remediation of vaccine production effluents contaminated with a highly toxic organomercurial – thiomersal. Therefore, two main aspects were focused on: 1) the development of a stable supported liquid membrane – using room temperature ionic liquids (RTILs) – for the selective transport of thiomersal from the wastewater to a biological compartment, 2) study of the biodegradation kinetics of thiomersal to metallic mercury by a Pseudomonas putida strain. The first part of the work focused on the evaluation of the physicochemical properties of ionic liquids and on the SLMs’ operational stability. The results obtained showed that, although it is possible to obtain a SLM with a high stability, water possesses nonnegligible solubility in the RTILs studied. The formation of water clusters inside the hydrophobic ionic liquid was identified and found to regulate the transport of water and small ions. In practical terms, this meant that, although it was possible to transport thiomersal from the vaccine effluent to the biological compartment, complete isolation of the microbial culture could not be guaranteed and the membrane might ultimately be permeable to other species present in the aqueous vaccine wastewater. It was therefore decided not to operate the initially targeted integrated system but, instead, the biological system by itself. Additionally, attention was given to the development of a thorough understanding of the transport mechanisms involved in the solubilisation and transport of water through supported liquid membranes with RTILs as well as to the evaluation of the effect of water uptake by the SLM in the transport mechanisms of water-soluble solutes and its effect on SLM performance. The results obtained highlighted the determinant role played by water – solubilised inside the ionic liquids – on the transport mechanism. It became clear that the transport mechanism of water and water-soluble solutes through SLMs with [CnMIM][PF6] RTILs was regulated by the dynamics of water clusters inside the RTIL, rather than by molecular diffusion through the bulk of the ionic liquid. Although the stability tests vi performed showed that there were no significant losses of organic phase from the membrane pores, the formation of water clusters inside the ionic liquid, which constitute new, non-selective environments for solute transport, leads to a clear deterioration of SLM performance and selectivity. Nevertheless, electrical impedance spectroscopy characterisation of the SLMs showed that the formation of water clusters did not seem to have a detrimental effect on the SLMs’ electrical characteristics and highlighted the potential of using this type of membranes in electrochemical applications with low resistance requirements. The second part of the work studied the kinetics of thiomersal degradation by a pure culture of P. putida spi3 strain, in batch culture and using a synthe tic wastewater. A continuous ly stirred tank reactor fed with the synthetic wastewater was also operated and the bioreactor’s performance and robustness, when exposed to thiomersal shock loads, were evaluated. Finally, a bioreactor for the biological treatment of a real va ccine production effluent was set up and operated at different dilution rates. Thus it was possible to treat a real thiomersal-contaminated effluent, lowering the outlet mercury concentration to values below the European limit for mercury effluent discharges.

Experimental study of proton induced nuclear reactions in 6,7 Li

This work presents the results of the experimental study of proton induced nuclear reactions in lithium, namely the 7Li(p,α) 4He, 6Li(p,α) 3He and 7Li(p,p)7Li reactions. The amount of 7Li and 6Li identified as primordial and observed in very old stars of the Milky Way galactic halo strongly deviates from the predictions of primordial nucleosynthesis and stellar evolution models which depend, among other factors, on the cross sections of reactions like 7Li(p,α) 4He and 6Li(p,α) 3He. These discrepancies have triggered a large amount of research in the fields of stellar evolution, cosmology, pre-galactic evolution and low energy nuclear reactions. Focusing on nuclear reactions, this work has measured the 7Li(p,α) 4He and 6Li(p,α) 3He reactions cross sections (expressed in terms of the astrophysical S -factor) with higher accuracy, and the electron screening effects in these reactions for different environments (insulators and metallic targets). The 7Li(p,α) 4He angular distributions were also measured. These measurementstook place in two laboratory facilities, in the framework of the LUNA (Laboratory for Undergroud Nuclear Astrophysics) international collaboration, namely the Laboratorio ´ de Feixe de Ioes ˜ in ITN (Instituto Tecnologico ´ e Nuclear) Sacavem, ´ Portugal, and the Dynamitron-TandemLaboratorium in Ruhr-Universitat¨ Bochum, Germany. The ITN target chamber was modified to measure these nuclear reactions, with the design and construction of new components, the addition of one turbomolecular pump and a cold finger. The 7Li(p,α) 4He and 6Li(p,α) 3He reactions were measured concurrently with seven and four targets, respectively. These targets were produced in order to obtain adequate and stable lithium depth profiles. In metallic environments, the measured electron screening potential energies are much higher than the predictions of atomic-physics models. The Debye screening model applied to the metallic conduction electrons is able to explain these high values. It is a simple model, but also very robust. Concerning primordial nucleosynthesis and stellar evolution models, these results are very important as they show that laboratory measurements are well controlled, and the model inputs from these cross sections are therefore correct. In this work the 7Li(p,p)7Li differential cross section was also measured, which is useful to describe the 7Li(p,α) 4He entrance channel.

A vision of cyber-physical internet

When the Internet was born, the purpose was to interconnect computers to share digital data at large-scale. On the other hand, when embedded systems were born, the objective was to control system components under real-time constraints through sensing devices, typically at small to medium scales. With the great evolution of the Information and Communication Technology (ICT), the tendency is to enable ubiquitous and pervasive computing to control everything (physical processes and physical objects) anytime and at a large-scale. This new vision gave recently rise to the paradigm of Cyber-Physical Systems (CPS). In this position paper, we provide a realistic vision to the concept of the Cyber-Physical Internet (CPI), discuss its design requirements and present the limitations of the current networking abstractions to fulfill these requirements. We also debate whether it is more productive to adopt a system integration approach or a radical design approach for building large-scale CPS. Finally, we present a sample of realtime challenges that must be considered in the design of the Cyber-Physical Internet.

Periplasmic nitrate reductases: structural and spectroscopic studies

Dissertação apresentada para obtenção do grau de Doutor em Bioquímica, especialidade Bioquímica-Física, pela Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa

Emissions of nanoparticles during friction stir welding (FSW) of aluminium alloys

Friction stir welding (FSW) is now well established as a welding process capable of joining some different types of metallic materials, as it was (1) found to be a reliable and economical way of producing high quality welds, and (2) considered a "clean" welding process that does not involve fusion of metal, as is the case with other traditional welding processes. The aim of this study was to determine whether the emission of particles during FSW in the nanorange of the most commonly used aluminum (Al) alloys, AA 5083 and AA 6082, originated from the Al alloy itself due to friction of the welding tool against the item that was being welded. Another goal was to measure Al alloys in the alveolar deposited surface area during FSW. Nanoparticles dimensions were predominantly in the 40- and 70-nm range. This study demonstrated that microparticles were also emitted during FSW but due to tool wear. However, the biological relevance and toxic manifestations of these microparticles remain to be determined.

Homo-and heteropolymetallic 3-(2-pyridyl)pyrazolate manganese and rhenium complexes

fac-[MBr(CO)(3)(pypzH)] (M = Mn, Re; pypzH = (3-(2-pyridyl) pyrazole) complexes are prepared from fac[ MBr(CO)(3)(NCMe)(2)] and pypzH. The result of their deprotonation depends on the metallic substrate: the rhenium complex affords cleanly the bimetallic compound [fac-{Re(CO)(3)(mu(2)-pypz)}] 2 (mu(2)-pypz = mu(2)-3-(2pyridyl-. 1N) pyrazolate-2. 1N), which was crystallographically characterized, whereas a similar manganese complex was not detected. When two equivalents of pyridylpyrazolate are used, polymetallic species [fac-M(CO) 3(mu(2)-pypz)(mu(3)-pypz) M'] (mu(3)-pypz = mu(3)-3-(2-pyridyl-kappa N-1) pyrazolate-1 kappa 2N, N: 2. 1N:; M = Mn, M' = Li, Na, K; M = Re, M' = Na) are obtained. The crystal structures of the manganese carbonylate complexes were determined. The lithium complex is a monomer containing one manganese and one lithium atom, whereas the sodium and potassium complexes are dimers and reveal an unprecedented coordination mode for the bridging 3-(2-pyridyl) pyrazolate ligand, where the nitrogen of the pyridyl fragment and the nitrogen-1 of pyrazolate are chelated to manganese atoms, and each nitrogen-2 of pyrazolate is coordinated to two alkaline atoms. The polymetallic carbonylate complexes are unstable in solution and evolve spontaneously to [fac-{Re(CO) 3(mu(2)-pypz)}](2) or to the trimetallic paramagnetic species [MnII(mu(2)-pypz) 2{fac-{MnI(CO) 3(mu(2)-pypz)}(2)}]. The related complex cis-[MnCl2(pypzH)(2)] was also synthesized and structurally characterized. The electrochemical behavior of the new homo-and heteropolymetallic 3-(2-pyridyl) pyrazolate complexes has been studied and details of their redox properties are reported.

Anti-Corrosion performance of a new silane coating for corrosion protection of AZ31 Magnesium alloy in Hank’s solution

Mg alloys can be used as bioresorsable metallic implants. However, the high corrosion rate of magnesium alloys has limited their biomedical applications. Although Mg ions are essential to the human body, an excess may cause undesirable health effects. Therefore, surface treatments are required to enhance the corrosion resistance of magnesium parts, decreasing its rate to biocompatible levels and allowing its safe application as bioresorbable metallic implants. The application of biocompatible silane coatings is envisaged as a suitable strategy for retarding the corrosion process of magnesium alloys. In the current work, a new glycidoxypropyltrimethoxysilane (GPTMS) based coating was tested on AZ31 magnesium substrates subjected to different surface conditioning procedures before coating deposition. The surface conditioning included a short etching with hydrofluoric acid (HF) or a dc polarisation in alkaline electrolyte. The silane coated samples were immersed in Hank's solution and the protective performance of the coating was studied through electrochemical impedance spectroscopy (EIS). The EIS data was treated by new equivalent circuit models and the results revealed that the surface conditioning process plays a key role in the effectiveness of the silane coating. The HF treated samples led to the highest impedance values and delayed the coating degradation, compared to the mechanically polished samples or to those submitted to dc polarisation.

Mechanical properties of stent-graft materials

An aneurysm is a localized blood-filled dilatation of an artery whose consequences can be deadly. One of its current treatments is endovascular aneurysm repair, a minimally invasive procedure in which an endoprosthesis, called a stent-graft, is placed transluminally to prevent wall rupture. Early stent-grafts were custom designed for the patient through the assembling of off-the-shelf components by the operating surgeon. However, nowadays, stent-grafts have become a commercial product. The existing endoprostheses differ in several aspects, such as shape design and materials, but they have in common a metallic scaffold with a polymeric covering membrane. This article aims to gather relevant information for those who wish to understand the principles of stent-grafts and even to develop new devices. Hence, a stent-graft classification based on different characteristics is presented and the desired features for an ideal device are pointed out. Additionally, the materials currently in use to fabricate this type of endoprosthesis are reviewed and new materials are suggested.

Molybdenum – and tungsten(II) monometallic 3-(2-pyridyl)pyrazole and bimetallic 3-(2-pyridyl)pyrazolate complexes

Molybdenum and tungsten complexes containing the pypzH (3-(2-pyridyl)pyrazole) ligand as a chelating bidentate are prepared: [Mo(CO)(4)(pypzH)], cis-[MoBr(eta(3)-allyl)(CO)(2)(pypzH)], cis-[MoCl(eta(3)-methallyl)(CO)(2)(pypzH)], [MI2(CO)(3)(pypzH)] (M = Mo, W) from [Mo(CO)(4)(NBD)] or the adequate bis(acetonitrile) complexes. The deprotonation of the molybdenum allyl or methallyl complexes affords the bimetallic complexes [cis-{Mo(eta(3)-allyl)(CO)(2)(mu(2)-pypz)}](2) or [cis-{Mo(eta(3)-methallyl)(CO)(2)(mu(2)-pypz)}](2) (mu(2)-pypz = mu(2)-3-(2-pyridyl-kappa N-1) pyrazolate-2 kappa N-1). The allyl complex was subjected to an electrochemical study, which shows a marked connection between both metallic centres through the bridging pyridylpyrazolates.

Pt/Carbon materials as Bi-Functional catalysts for N-decane hydroisomerization

The activity and selectivity of bi-functional carbon-supported platinum catalysts for the hydroisomerization of n-alkanes have been studied. The influence of the properties of the carbon support on the performance of the catalysts were investigated by incorporating the metallic function on a series of carbons with varied porosity (microporous: GL-50 from Norit, and mesoporous: CMK-3) and surface chemistry (modified by wet oxidation). The characterization results achieved with H-2 chemisorption and TEM showed differences in surface metal concentrations and metal-support interactions depending on the support composition. The highest metal dispersion was achieved after oxidation of the carbon matrix in concentrated nitric acid, suggesting that the presence of surface functional sites distributed in inner and outer surface favors a homogeneous metal distribution. On the other hand, the higher hydrogenating activity of the catalysts prepared with the mesoporous carbon pointed out that a fast molecular traffic inside the pores plays an important role in the catalysts performance. For n-decane hydroisomerization of long chain n-alkanes, higher activities were obtained for the catalysts with an optimized acidity and metal dispersion along with adequate porosity, pointing out the importance of the support properties in the performance of the catalysts.

Desenvolvimento de métodos rápidos para deteção de drogas no meio aquático

A vasta aplicação de antibióticos em sistemas de aquacultura tem conduzido ao aparecimento de espécies microbianas resistentes, devendo ser evitada ou, se possível, minimizada. A minimização implica um controlo muito rigoroso das doses aplicadas, algo que só pode ser realizado se todo o processo analítico for simples, barato e puder ser implementado no local. O presente trabalho descreve para este efeito um sistema sensor constituído por papel quimicamente modificado, cujo procedimento analítico foi semelhante à monitorização de pH através das conhecidas tiras indicadoras de pH universal. O papel foi modificado com base em reacções de monocamadas e assumiu uma coloração típica após contacto com o antibiótico. A intensidade da coloração estava também relacionada com a concentração desse antibiótico. Como prova deste conceito, o sensor proposto foi desenhado tendo em vista a monitorização de oxitetraciclina, um dos antibióticos utilizados neste contexto com elevada frequência. A modificação do papel foi baseada na alteração química das unidades de glucose na matriz sólida por reacção covalente com reagentes apropriados. Foram utilizadas duas estratégias diferentes para este efeito: uma foi baseada em reacções de tipo sol-gel e a outra em reacção de adição nucleófila. Posteriormente, o papel foi modificado com espécies metálicas capazes de mudar de cor na presença da oxitetraciclina. Estas modificações químicas foram avaliadas e optimizadas relativamente a vários parâmetros, no sentido de promover uma variação de cor intensa face à concentração de antibiótico. Procedeu-se ainda ao controlo desta modificação por técnicas de espectroscopia de infravermelho. A variação de cor foi avaliada por comparação visual, mas registada por imagem digital. Os materiais sensores preparados foram ainda caracterizados do ponto de vista do seu desempenho analítico. Incluíram-se aqui a identificação de uma relação linear entre coordenadas de cor e concentração, a atribuição de uma gama de concentrações capaz de fornecer uma resposta previsível e resposta cruzada face a outros antibióticos. Procedeu-se ainda à aplicação dos sensores numa amostra de água ambiental dopada com antibiótico. De uma forma geral, foi possível estabelecer um processo simples de modificação de papel capaz de aferir a presença e a quantidade de tetraciclinas, mais concretamente a oxitetraciclina. O processo aqui estabelecido é promissor, antevendo a concretização de uma metodologia simples, barata e local para a monitorização de anitbióticos em águas.