Recuperação de componentes de metal duro por projeção térmica

The main objective of this work is the development of a hardmetal components (WC-6%Co) recovery method by thermal deposition process. The thermal deposition technique used was HVOF (high velocity oxygen-fuel). The HVOF enables depositions of thick coatings (100-500 µm) with low porosity levels, high hardness and excellent adhesion. Before deposition, hardmetal samples with different geometries (plates and cylinders) were finished in order to have different roughness. The influence of these parameters in adhesion was studied. After this step, different re-sintering temperatures were used, in order to determine which one allows to obtain the maxima densification, elements distribution and metallurgical bonding. The re-sintering promotes the densification of the coating, with an increase of its hardness and metallurgical bonding formation. The inclusion of an intermetallic layer was tested along with different layer parameters. In liquid phase sintering (1383 and 1455 ºC) a complete densification of the coating occurred, while a bonding between the substrate and the coating only partially happened. The results of SEM/EDS show low levels of porosity and a complete and uniform distribution of the elements of the alloy. The cylindrical samples without intermetallic layer showed the lowest level of porosity and best metallurgical bonding. When the substrate surface was polished (Ra = 0.05 mm) lower levels of porosity and greater metallurgical bonding were found for both geometries. Taking into account the results obtained in this study, we can conclude that the implementation of this process is appropriate for cylindrical components with a polished surface. In these components the intermetallic layer is unnecessary and punctual defects like pores can be repaired with this process.

Marketing desportivo, envolvimento, lealdade e compromisso psicológico

O presente trabalho pretende estudar a relação existente entre o consumo de ações de marketing desportivo e o envolvimento clubístico, compromisso psicológico e a lealdade clubística. O estudo procura apresentar as ações de marketing desportivo que influenciam a criação e fortalecimento das ligações psicológicas entre os fãs desportivos e os seus clubes favoritos com o objetivo de atingir uma fidelização. Criar uma ampla base de fãs fidelizados é importante para os clubes desportivos, pois tem uma influência direta na sua imagem e receita financeira. Numa primeira fase, foi realizado um levantamento bibliográfico sobre estudos já realizados na área que se pretende estudar. Num segundo momento, realizou-se uma fase experimental através da aplicação de questionários que foram analisados quantativamente, numa amostra de 164 participantes. Os resultados obtidos demonstraram uma forte relação entre as dimensões estudadas (envolvimento, compromisso psicológico e lealdade) e o consumo de ações de marketing desportivo e permitiram ainda concluir que os fãs homens e os fãs jovens são os mais consumidores de ações de marketing desportivo. Os resultados postulam ainda que os estudos realizados nesta área são limitados, de modo que o aprofundamento no assunto aguarda por investigações futuras.

Energy systems analysis of transboundary river basins in a nexus approach: the Sava river basin study case

Resource management policies are frequently designed and planned to target specific needs of particular sectors, without taking into account the interests of other sectors who share the same resources. In a climate of resource depletion, population growth, increase in energy demand and climate change awareness, it is of great importance to promote the assessment of intersectoral linkages and, by doing so, understand their effects and implications. This need is further augmented when common use of resources might not be solely relevant at national level, but also when the distribution of resources ranges over different nations. This dissertation focuses on the study of the energy systems of five south eastern European countries, which share the Sava River Basin, using a water-food(agriculture)-energy nexus approach. In the case of the electricity generation sector, the use of water is essential for the integrity of the energy systems, as the electricity production in the riparian countries relies on two major technologies dependent on water resources: hydro and thermal power plants. For example, in 2012, an average of 37% of the electricity production in the SRB countries was generated by hydropower and 61% in thermal power plants. Focusing on the SRB, in terms of existing installed capacities, the basin accommodates close to a tenth of all hydropower capacity while providing water for cooling to 42% of the net capacity of thermal power currently in operation in the basin. This energy-oriented nexus study explores the dependency on the basin’s water resources of the energy systems in the region for the period between 2015 and 2030. To do so, a multi-country electricity model was developed to provide a quantification ground to the analysis, using the open-source software modelling tool OSeMOSYS. Three main areas are subject to analysis: first, the impact of energy efficiency and renewable energy strategies in the electricity generation mix; secondly, the potential impacts of climate change under a moderate climate change projection scenario; and finally, deriving from the latter point, the cumulative impact of an increase in water demand in the agriculture sector, for irrigation. Additionally, electricity trade dynamics are compared across the different scenarios under scrutiny, as an effort to investigate the implications of the aforementioned factors in the electricity markets in the region.

Modelo de Kuramoto com campos aleatórios em redes complexas

Neste trabalho é estudado o modelo de Kuramoto num grafo completo, em redes scale-free com uma distribuição de ligações P(q) ~ q-Y e na presença de campos aleatórios com magnitude constante e gaussiana. Para tal, foi considerado o método Ott-Antonsen e uma aproximação "annealed network". Num grafo completo, na presença de campos aleatórios gaussianos, e em redes scale-free com 2 < y < 5 na presença de ambos os campos aleatórios referidos, foram encontradas transições de fase contínuas. Considerando a presença de campos aleatórios com magnitude constante num grafo completo e em redes scale-free com y > 5, encontraram-se transições de fase contínua (h < √2) e descontínua (h > √2). Para uma rede SF com y = 3, foi observada uma transição de fase de ordem infinita. Os resultados do modelo de Kuramoto num grafo completo e na presença de campos aleatórios com magnitude constante foram comparados aos de simulações, tendo-se verificado uma boa concordância. Verifica-se que, independentemente da topologia de rede, a constante de acoplamento crítico aumenta com a magnitude do campo considerado. Na topologia de rede scale-free, concluiu-se que o valor do acoplamento crítico diminui à medida que valor de y diminui e que o grau de sincronização aumenta com o aumento do número médio das ligações na rede. A presença de campos aleatórios com magnitude gaussiana num grafo completo e numa rede scale-free com y > 2 não destrói a transição de fase contínua e não altera o comportamento crítico do modelo de Kuramoto.

Bioinformatics analysis of the Pedobacter sp. NL19 genome

The last decades of the 20th century defined the genetic engineering advent, climaxing in the development of techniques, such as PCR and Sanger sequencing. This, permitted the appearance of new techniques to sequencing whole genomes, identified as next-generation sequencing. One of the many applications of these techniques is the in silico search for new secondary metabolites, synthesized by microorganisms exhibiting antimicrobial properties. The peptide antibiotics compounds can be classified in two classes, according to their biosynthesis, in ribosomal or nonribosomal peptides. Lanthipeptides are the most studied ribosomal peptides and are characterized by the presence of lanthionine and methylanthionine that result from posttranslational modifications. Lanthipeptides are divided in four classes, depending on their biosynthetic machinery. In class I, a LanB enzyme dehydrate serine and threonine residues in the C-terminus precursor peptide. Then, these residues undergo a cyclization step performed by a LanC enzyme, forming the lanthionine rings. The cleavage and the transport of the peptide is achieved by the LanP and LanT enzymes, respectively. Although, in class II only one enzyme, LanM, is responsible for the dehydration and cyclization steps and also only one enzyme performs the cleavage and transport, LanT. Pedobacter sp. NL19 is a Gram-negative bacterium, isolated from sludge of an abandon uranium mine, in Viseu (Portugal). Antibacterial activity in vitro was detected against several Gram-positive and Gram-negative bacteria. Sequencing and in silico analysis of NL19 genome revealed the presence of 21 biosynthetic clusters for secondary metabolites, including nonribosomal and ribosomal peptides biosynthetic clusters. Four lanthipeptides clusters were predicted, comprising the precursor peptides, the modifying enzymes (LanB and LanC), and also a bifunctional LanT. This result revealed the hybrid nature of the clusters, comprising characteristics from two distinct classes, which are poorly described in literature. The phylogenetic analysis of their enzymes showed that they clustered within the bacteroidetes clade. Furthermore, hybrid gene clusters were also found in other species of this phylum, revealing that it is a common characteristic in this group. Finally, the analysis of NL19 colonies by MALDI-TOF MS allowed the identification of a 3180 Da mass that corresponds to the predicted mass of a lanthipeptide encoded in one of the clusters. However, this result is not fully conclusive and further experiments are needed to understand the full potential of the compounds encoded in this type of clusters. In conclusion, it was determined that NL19 strain has the potential to produce diverse secondary metabolites, including lanthipeptides that were not functionally characterized so far.

Identificação dos produtos de oxidação de glicosfingolípidos por espectrometria de massa

O stress oxidativo está associado ao envelhecimento e a inúmeras patologias, nomeadamente a doenças neurodegenerativas e cardiovasculares, e a diversos outros fatores. O stress oxidativo leva à oxidação de importantes biomoléculas como os lípidos e, ao contrário da maior parte dos produtos de oxidação de fosfolípidos e ácidos gordos insaturados (PUFAS), os produtos de oxidação de glicosfingolípidos (GSLs) têm sido escassamente estudados. Os glicosfingolípidos são moléculas muito diversificadas estruturalmente e com importantes funções, essencialmente no sistema nervoso central (SNC) onde estão localizados maioritariamente. Deste modo, alterações na estrutura dos GSLs conduzirão a consequente comprometimento das suas funções e ao possível desenvolvimento de patologias. Assim para identificar as modificações oxidativas que ocorrem em glicosfingolípidos e pressupor consequentes efeitos biológicos nas células sob stress oxidativo, prepararamse sistemas modelo biomiméticos com diferentes GSLs os quais foram expostos a radicais hidroxilo gerados sob condições da reação de Fenton (H2O2 e Fe2+) e as reações foram monitorizadas por diferentes metodologia utilizando a espectrometria de massa. Os resultados obtidos com este estudo permitiram-nos identificar vários produtos de oxidação produzidos durante a oxidação desta classe de lípidos. Os produtos de oxidação observados em comum, em todos os GSLs estudados (C16:0GalCer, C24:1GalCer, C24:1LacCer e GM1) foram as suas correspondentes ceramidas. Estas atuam como agentes pro-apoptóticos e podem in vivo promover a neurodegeneração nas células sob stress oxidativo. Também foi possível observar produtos com inserção de oxigénio junto às duplas ligações ou na cadeia de esfingosina (no caso do GM1) ou na cadeia de ácido gordo monoinsaturada (no caso da C24:1GalCer, C24:1LacCer), corroborando o facto de que ácidos gordos saturados não são susceptíveis à oxidação por radicais. Interessantemente em ambos os GSLs de cadeias glicosiladas compostas com mais de um açúcar (C24:1LacCer e GM1) observou-se a despolimerização oxidativa da porção glicosilada por quebra das correspondentes ligações glicosídicas. Esta degradação leva à formação de GlcCer no caso de oxidação de LacCer ou na formação de outros gangliósidos (GM2, GM3, asialoGM1 e asialoGM2) e glicolípidos (LacCer e GlcCer), no caso de oxidação de GM1. A formação por via radicalar não enzimática destes GSLs leva a distúrbios no perfil lipídico. Previamente, em certas doenças, foram observadas variações na concentração do perfil de gangliósidos e de ceramidas. Estes dados permitem sugerir que em células em condições de stress oxidativo, a acumulação de gangliósidos mais simples e ceramidas poderá ter uma contribuição de produtos da degradação oxidativa dos gangliósidos e GSLs mais complexos. Este trabalho contribui assim para uma melhor compreensão das modificações estruturais que ocorrem em alguns glicosfingolípidos em condições de stress oxidativo. Os produtos de oxidação aqui identificados suportam a sua possível futura deteção em sistemas biológicos.

Critical magnetic elds in superconducting systems with semi-metallic bands

In this work, we study the Zeeman splitting effects in the parallel magnetic field versus temperature phase diagram of two-dimensional superconductors with one graphene-like band and the orbital effects of perpendicular magnetic fields in isotropic two-dimensional semi-metallic superconductors. We show that when parallel magnetic fields are applied to graphene and as the intraband interaction decreases to a critical value, the width of the metastability region present in the phase diagram decreases, vanishing completely at that critical value. In the case of two-band superconductors with one graphene-like band, a new critical interaction, associated primarily with the graphene-like band, is required in order for a second metastability region to be present in the phase diagram. For intermediate values of this interaction, a low-temperature first-order transition line bifurcates at an intermediate temperature into a first-order transition between superconducting phases and a second-order transition line between the normal and the superconducting states. In our study on the upper critical fields in generic semi-metallic superconductors, we find that the pair propagator decays faster than that of a superconductor with a metallic band. As result, the zero field band gap equation does not have solution for weak intraband interactions, meaning that there is a critical intraband interaction value in order for a superconducting phase to be present in semi-metallic superconductors. Finally, we show that the out-of-plane critical magnetic field versus temperature phase diagram displays a positive curvature, contrasting with the parabolic-like behaviour typical of metallic superconductors.

Mobility in vehicular networks with multiple access points to the infrastructure

Nowadays there is a huge evolution in the technological world and in the wireless networks. The electronic devices have more capabilities and resources over the years, which makes the users more and more demanding. The necessity of being connected to the global world leads to the arising of wireless access points in the cities to provide internet access to the people in order to keep the constant interaction with the world. Vehicular networks arise to support safety related applications and to improve the traffic flow in the roads; however, nowadays they are also used to provide entertainment to the users present in the vehicles. The best way to increase the utilization of the vehicular networks is to give to the users what they want: a constant connection to the internet. Despite of all the advances in the vehicular networks, there were several issues to be solved. The presence of dedicated infrastructure to vehicular networks is not wide yet, which leads to the need of using the available Wi-Fi hotspots and the cellular networks as access networks. In order to make all the management of the mobility process and to keep the user’s connection and session active, a mobility protocol is needed. Taking into account the huge number of access points present at the range of a vehicle for example in a city, it will be beneficial to take advantage of all available resources in order to improve all the vehicular network, either to the users and to the operators. The concept of multihoming allows to take advantage of all available resources with multiple simultaneous connections. This dissertation has as objectives the integration of a mobility protocol, the Network-Proxy Mobile IPv6 protocol, with a host-multihoming per packet solution in order to increase the performance of the network by using more resources simultaneously, the support of multi-hop communications, either in IPv6 or IPv4, the capability of providing internet access to the users of the network, and the integration of the developed protocol in the vehicular environment, with the WAVE, Wi-Fi and cellular technologies. The performed tests focused on the multihoming features implemented on this dissertation, and on the IPv4 network access for the normal users. The obtained results show that the multihoming addition to the mobility protocol improves the network performance and provides a better resource management. Also, the results show the correct operation of the developed protocol in a vehicular environment.