Lime mortars with brick dust and grounded particles for ancient masonry: development and evaluation

HMC08 - 1st Historical Mortars Conference: Characterization, Diagnosis, Conservation, Repair and Compatibilit, LNEC, Lisbon, 24-26 September 2008

Influência do teor em pozolana na reatividade e nas características mecânicas de argamassas

Dissertação para obtenção do Grau de Mestre em Engenharia Civil – Perfil de Construção

Smart macroporous structures for the purification of viral particles

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

Experimental high-throughput adsorption unit for multi-evaluation of adsorbents for gas capture, storage and separation applications

Dissertação para obtenção do grau de Mestre em Engenharia Química e Bioquímica

Molecular simulation of gas adsorption equilibria in nanoporous materials

This work is divided into two distinct parts. The first part consists of the study of the metal organic framework UiO-66Zr, where the aim was to determine the force field that best describes the adsorption equilibrium properties of two different gases, methane and carbon dioxide. The other part of the work focuses on the study of the single wall carbon nanotube topology for ethane adsorption; the aim was to simplify as much as possible the solid-fluid force field model to increase the computational efficiency of the Monte Carlo simulations. The choice of both adsorbents relies on their potential use in adsorption processes, such as the capture and storage of carbon dioxide, natural gas storage, separation of components of biogas, and olefin/paraffin separations. The adsorption studies on the two porous materials were performed by molecular simulation using the grand canonical Monte Carlo (μ,V,T) method, over the temperature range of 298-343 K and pressure range 0.06-70 bar. The calibration curves of pressure and density as a function of chemical potential and temperature for the three adsorbates under study, were obtained Monte Carlo simulation in the canonical ensemble (N,V,T); polynomial fit and interpolation of the obtained data allowed to determine the pressure and gas density at any chemical potential. The adsorption equilibria of methane and carbon dioxide in UiO-66Zr were simulated and compared with the experimental data obtained by Jasmina H. Cavka et al. The results show that the best force field for both gases is a chargeless united-atom force field based on the TraPPE model. Using this validated force field it was possible to estimate the isosteric heats of adsorption and the Henry constants. In the Grand-Canonical Monte Carlo simulations of carbon nanotubes, we conclude that the fastest type of run is obtained with a force field that approximates the nanotube as a smooth cylinder; this approximation gives execution times that are 1.6 times faster than the typical atomistic runs.

Transístores de óxidos semicondutores com óxido de alumínio produzido por solução

A integração da camada dieléctrica de AlOx em TFTs com ZTO, também produzido por solução, originou uma publicação científica que foi recentemente aceite numa revista da especialidade: R. Branquinho, D. Salgueiro, A. Santa, A. Kiazadeh, P. Barquinha, L. Pereira, R. Martins and E. Fortunato, Towards environmental friendly solution-based ZTO/AlOx TFTs, Semiconductor Science and Technology, in press.

40 K Neon liquid energy storage unit

Cryocoolers have been progressively replacing the use of the stored cryogens in cryogenic chains used for detector cooling, thanks to their higher and higher reliability. However, the mechanical vibrations, the electromagnetic interferences and the temperature fluctuations inherent to their functioning could reduce the sensor’s sensitivity. In order to minimize this problem, compact thermal energy storage units (ESU) are studied, devices able to store thermal energy without significant temperature increase. These devices can be used as a temporary cold source making it possible to turn the cryocooler OFF providing a proper environment for the sensor. A heat switch is responsible for the thermal decoupling of the ESU from the cryocooler’s temperature that increases when turned OFF. In this work, several prototypes working around 40 K were designed, built and characterized. They consist in a low temperature cell that contains the liquid neon connected to an expansion volume at room temperature for gas storage during the liquid evaporation phase. To turn this system insensitive to the gravity direction, the liquid is retained in the low temperature cell by capillary effect in a porous material. Thanks to pressure regulation of the liquid neon bath, 900 J were stored at 40K. The higher latent heat of the liquid and the inexistence of triple point transitions at 40 K turn the pressure control during the evaporation a versatile and compact alternative to an ESU working at the triple point transitions. A quite compact second prototype ESU directly connected to the cryocooler cold finger was tested as a temperature stabilizer. This device was able to stabilize the cryocooler temperature ((≈ 40K ±1 K) despite sudden heat bursts corresponding to twice the cooling power of the cryocooler. This thesis describes the construction of these devices as well as the tests performed. It is also shown that the thermal model developed to predict the thermal behaviour of these devices, implemented as a software,describes quite well the experimental results. Solutions to improve these devices are also proposed.

40 K neon liquid energy storage unit

Cryocoolers have been progressively replacing the use of the stored cryogens in cryogenic chains used for detector cooling, thanks to their higher and higher reliability. However, the mechanical vibrations, the electromagnetic interferences and the temperature fluctuations inherent to their functioning could reduce the sensor’s sensitivity. In order to minimize this problem, compact thermal energy storage units (ESU) are studied, devices able to store thermal energy without significant temperature increase. These devices can be used as a temporary cold source making it possible to turn the cryocooler OFF providing a proper environment for the sensor. A heat switch is responsible for the thermal decoupling of the ESU from the cryocooler’s temperature that increases when turned OFF. In this work, several prototypes working around 40 K were designed, built and characterized. They consist in a low temperature cell that contains the liquid neon connected to an expansion volume at room temperature for gas storage during the liquid evaporation phase. To turn this system insensitive to the gravity direction, the liquid is retained in the low temperature cell by capillary effect in a porous material. Thanks to pressure regulation of the liquid neon bath, 900 J were stored at 40K. The higher latent heat of the liquid and the inexistence of triple point transitions at 40 K turn the pressure control during the evaporation a versatile and compact alternative to an ESU working at the triple point transitions. A quite compact second prototype ESU directly connected to the cryocooler cold finger was tested as a temperature stabilizer. This device was able to stabilize the cryocooler temperature ((≈ 40K ±1 K) despite sudden heat bursts corresponding to twice the cooling power of the cryocooler. This thesis describes the construction of these devices as well as the tests performed. It is also shown that the thermal model developed to predict the thermal behaviour of these devices,implemented as a software, describes quite well the experimental results. Solutions to improve these devices are also proposed.

Maritime Security in the Gulf of Guinea: Issues and Solutions for the 21st Century

A producer of 5.4 M bbl/d, totalling almost half of the consumption of the entire European Union, the Gulf of Guinea is a fundamental lifeline and maritime link between Europe, the Americas and Africa. Geographically positioned as a staging post for transit originating in Latin America and coupled with its relatively porous borders, the region is also the perfect stepping stone for contraband heading to European shores. While blessed with an enviable wealth of marine and mineral resources, the region is also plagued by an ever-increasing spectre of maritime piracy; accounting for around 30% of incidents in African waters from 2003 to 2011. It is for these reasons that this research centres around the issues of maritime security in the Gulf of Guinea, with a particular focus on the first two decades of the 21st century. This research looks to examine the overall picture of the present state of play in the area, before going on to provide an analysis of potential regional developments in maritime security. This research begins with the analysis of concepts/phenomena that have played a notable role in the shaping of the field of maritime security, namely Globalisation and security issues in the post-Cold War era. The ensuing chapter then focuses in on the Gulf of Guinea and the issues dominating the field of maritime security in the region. The penultimate chapter presents a SWOT analysis, undertaken as part of this research with the aim of correlating opinions from a variety of sectors/professions regarding maritime security in the Gulf of Guinea. The final chapter builds upon the results obtained from the abovementioned SWOT analysis, presenting a series of potential proposals/strategies that can contribute to the field of maritime security in the region over the coming years. This research draws to a close with the presentation of conclusions taken from this particular investigation, as well as a final overview of the earlier presented proposals applicable to the field of maritime security during the second decade of the 21st century.

Numerical prediction of diffusion and electric field-induced iron nanoparticle transport

Zero valent iron nanoparticles (nZVI) are considered very promising for the remediation of contaminated soils and groundwaters. However, an important issue related to their limited mobility remains unsolved. Direct current can be used to enhance the nanoparticles transport, based on the same principles of electrokinetic remediation. In this work, a generalized physicochemical model was developed and solved numerically to describe the nZVI transport through porous media under electric field, and with different electrolytes (with different ionic strengths). The model consists of the Nernst–Planck coupled system of equations, which accounts for the mass balance of ionic species in a fluid medium, when both the diffusion and electromigration of the ions are considered. The diffusion and electrophoretic transport of the negatively charged nZVI particles were also considered in the system. The contribution of electroosmotic flow to the overall mass transport was included in the model for all cases. The nZVI effective mobility values in the porous medium are very low (10−7–10−4 cm2 V−1 s−1), due to the counterbalance between the positive electroosmotic flow and the electrophoretic transport of the negatively charged nanoparticles. The higher the nZVI concentration is in the matrix, the higher the aggregation; therefore, low concentration of nZVI suspensions must be used for successful field application.

Efeito do teor em Y2O3 nos catalisadores suportados de 8%Ni/α-Al2O3 durante a reação de oxidação parcial do Metano para produção de Hidrogénio

Neste trabalho avaliou-se o desempenho de cinco catalisadores de Níquel suportados em α-Alumina, com diferentes teores em Ítria, durante a reação de Oxidação Parcial do Metano para a produção de Hidrogénio: 8%Ni/α-Al2O3, 8%Ni/2%Y2O3.α-Al2O3, 8%Ni/2,5%Y2O3.α-Al2O3, 8%Ni/5%Y2O3.α-Al2O3 e 8%Ni/Y2O3. Foram realizados testes catalíticos numa Unidade de Reação acoplada a um equipamento de análise, microGC. A reação decorreu à temperatura de 800 °C, num reator laboratorial de quartzo, durante 18 horas, com uma mistura pura de CH4 e O2 (Condição Concentrada). Os resultados demonstraram um aumento de atividade para os catalisadores de suporte misto com maior teor em Y2O3. Usando o mesmo procedimento, a reação de OPM foi realizada também para outra mistura reacional de CH4 e O2, mas agora diluída em Hélio (Condição Diluída). Estes resultados permitiram avaliar a velocidade de reação e a atividade dos catalisadores (TOF), para diferentes valores de temperatura, numa situação inicial de ausência de coque. Numa segunda etapa, avaliou-se o desempenho dos mesmos materiais durante 2 horas de reação à temperatura constante de 800 ℃. Finalmente, através da técnica de caraterização de XPS, identificaram-se as espécies presentes na superfície dos catalisadores. Os resultados sugerem que há formação de um composto intermediário NiYO3 formado entre o metal e o promotor Y2O3, conferindo atividade e estabilidade aos catalisadores e reduzindo a deposição de coque. O catalisador com maior teor em Y2O3 (8%Ni/5%Y2O3.α-Al2O3) foi o mais beneficiado com a adição do promotor, demonstrando melhor desempenho para a produção de H2 na Reação de Oxidação Parcial do Metano.

Can body traits, other than wings, reflect the flight ability of Triatominae bugs?

Abstract: INTRODUCTION : Insects of the subfamily Triatominae are vectors of Trypanosoma cruzi , the Chagas disease parasite, and their flying behavior has epidemiological importance. The flying capacity is strikingly different across and within Triatominae species, as well as between sexes or individuals. Many Triatoma infestans individuals have wings but no flying muscles. In other Triatominae species, no clear relationships were found between wing length and flying behavior. If wing presence or size is not reflective of the flying behavior, which other parts of the body could be considered as reliable markers of this important function? METHODS : The genus Mepraia has exceptional characteristics with invariably wingless females and wingless or winged males. We calculated the porous surface exposed to odorant molecules to estimate the olfactory capacity of Mepraia spinolai . The head shape and thorax size were estimated using the geometric morphometric approach and traditional morphometric techniques, respectively. RESULTS : Alary polymorphism in M. spinolai was significantly associated with consistent modification of the thorax size, head shape, and notable change in the estimated olfactory capacity. The macropterous individuals had a larger olfactory surface and thorax size and significantly different head shape compared to those of the micropterous individuals. CONCLUSIONS: We concluded that these structural changes could be associated with the flying potential of Triatominae. Thus, morphological attributes not found on wings could help determine the likely flying potential of the bugs.

Potencial do Sienito Nefelínico de Monchique para incorporação na indústria cerâmica

A procura de novos materiais aumenta dia após dia, obrigando o Homem a procurar e encontrar novas soluções, tendo sempre como critério decisivo, uma exploração económica e ambiental sustentável. É neste âmbito que surge o tema desta dissertação. O objetivo é tirar um maior proveito do sienito nefelínico de Monchique (Portugal), à semelhança de países como a Rússia, Canadá e Noruega, que utilizam esta rocha a nível industrial. Neste trabalho, a investigação foi no sentido de estudar o potencial da rocha portuguesa para a indústria cerâmica. O elevado teor de alumina e álcalis que o sienito nefelínico apresenta na sua constituição, serve de substituto aos minerais atualmente utilizados neste sector, os feldspatos isolados. A alumina serve de estabilizador, promovendo a durabilidade dos materiais pelo aumento da resistência e o conteúdo em álcalis funciona como fundente, diminuindo a temperatura de queima. Desta forma, o Maciço de Monchique ganha uma nova importância económica, sendo uma mais-valia para o país. Para tal, elaboraram-se provetes cerâmicos constituídos por 0, 20, 40 e 60% em peso de sienito nefelínico em mistura com argila. Posteriormente, sujeitaram-se os provetes a três temperaturas diferentes, 900 °C, 1000 °C e 1100 °C e submeteram-se cada um deles a ensaios físicos e mecânicos, para determinar o potencial da incorporação do sienito de Monchique na indústria cerâmica. Os resultados indicaram que a adição de sienito nefelínico melhora as propriedades físicas da argila. Relativamente às propriedades mecânicas, o ensaio de resistência à flexão indicou que, dos vários teores testados, o mais positivo encontra-se na percentagem de 20% de sienito nefelínico, apresentando valores próximos da argila pura utilizada como referência.

Historical reconstructions of raw materials based on a blue smalt coating applied to a seventeenth-century altarpiece

Based on samples cross-sections from the Main Altarpiece of the Coimbra Old Cathedral, where a blue coating performed in 1685 is observed (that was partly covered with a Prussian blue-containing overpaint), the raw materials present in this coating were reproduced and studied. Blue areas were painted with smalt in oil, according to the contract signed by Manoel da Costa Pereira in 1684 and the analysis by Le Gac in 2009. Based on these, three batches of cobalt-based glasses (S1, S2 and S3) were heated and melted in alumina crucibles in the kiln. S1 contained 6.03 % of cobalt oxide, S2 contained 2.10 %, with the addition of 1.49 % of magnesium oxide, and S3 contained 6.82 % of cobalt oxide, with the addition of 4.63% of antimony trioxide. These batches were ground mechanically with water and manually with different vehicles stated in recipes. The results were studied by means of OM, SEM-EDS, X-Ray CT, Colorimetry and Vickers HT. Different binders were also produced and analyzed by means of μ-FTIR, in order to perform their characterization and obtain Standard Spectra. Since anhydrite was identified in the ground layers, gypsum from Óbidos was also characterized by XRD. The main goal of this thesis was to study all the raw materials present in the 1685-blue coating, in order to allow the historically accurate reconstruction of the layers build-up in the next future.

Engineering bio-based polymers using alternative solvents and processes

The work presented in this thesis explores novel routes for the processing of bio-based polymers, developing a sustainable approach based on the use of alternative solvents such as supercritical carbon dioxide (scCO2), ionic liquids (ILs) and deep eutectic solvents (DES). The feasibility to produce polymeric foams via supercritical fluid (SCF) foaming, combined with these solvents was assessed, in order to replace conventional foaming techniques that use toxic and harmful solvents. A polymer processing methodology is presented, based on SCF foaming and using scCO2 as a foaming agent. The SCF foaming of different starch based polymeric blends was performed, namely starch/poly(lactic acid) (SPLA) and starch/poly(ε-caprolactone) (SPCL). The foaming process is based on the fact that CO2 molecules can dissolve in the polymer, changing their mechanical properties and after suitable depressurization, are able to create a foamed (porous) material. In these polymer blends, CO2 presents limited solubility and in order to enhance the foaming effect, two different imidazolium based ILs (IBILs) were combined with this process, by doping the blends with IL. The use of ILs proved useful and improved the foaming effect in these starch-based polymer blends. Infrared spectroscopy (FTIR-ATR) proved the existence of interactions between the polymer blend SPLA and ILs, which in turn diminish the forces that hold the polymeric structure. This is directly related with the ability of ILs to dissolve more CO2. This is also clear from the sorption experiments results, where the obtained apparent sorption coefficients in presence of IL are higher compared to the ones of the blend SPLA without IL. The doping of SPCL with ILs was also performed. The foaming of the blend was achieved and resulted in porous materials with conductivity values close to the ones of pure ILs. This can open doors to applications as self-supported conductive materials. A different type of solvents were also used in the previously presented processing method. If different applications of the bio-based polymers are envisaged, replacing ILs must be considered, especially due to the poor sustainability of some ILs and the fact that there is not a well-established toxicity profile. In this work natural DES – NADES – were the solvents of choice. They present some advantages relatively to ILs since they are easy to produce, cheaper, biodegradable and often biocompatible, mainly due to the fact that they are composed of primary metabolites such as sugars, carboxylic acids and amino-acids. NADES were prepared and their physicochemical properties were assessed, namely the thermal behavior, conductivity, density, viscosity and polarity. With this study, it became clear that these properties can vary with the composition of NADES, as well as with their initial water content. The use of NADES in the SCF foaming of SPCL, acting as foaming agent, was also performed and proved successful. The SPCL structure obtained after SCF foaming presented enhanced characteristics (such as porosity) when compared with the ones obtained using ILs as foaming enhancers. DES constituted by therapeutic compounds (THEDES) were also prepared. The combination of choline chloride-mandelic acid, and menthol-ibuprofen, resulted in THEDES with thermal behavior very distinct from the one of their components. The foaming of SPCL with THEDES was successful, and the impregnation of THEDES in SPCL matrices via SCF foaming was successful, and a controlled release system was obtained in the case of menthol-ibuprofen THEDES.