Development of lithium disilicate based glass-ceramics

O principal objectivo deste estudo foi o desenvolvimento de vitrocerâmicos à base de dissilicato de lítio no sistema Li2O-K2O-Al2O3-SiO2 contendo uma razão molar SiO2/Li2O muito afastada da do dissilicato de lítio (Li2Si2O5) usando composições simples e a técnica tradicional de fusão-vazamento de vidro de forma a obter materiais com propriedades mecânicas, térmicas, químicas e eléctricas superiores que permitam a utilização destes materiais em diversas aplicações funcionais. Investigou-se o fenómeno de separação de fases, a cristalização e as relações estrutura-propriedades de vidros nos sistemas Li2O-SiO2, Li2O-Al2O3-SiO2 e Li2O-K2O-Al2O3-SiO2. Os vidros nos sistemas Li2O-SiO2 e Li2O-Al2O3-SiO2 apresentaram fraca densificação e resultaram em materiais frágeis, contrastando com a boa sinterização dos vidros no sistema Li2O-K2O-Al2O3-SiO2. Pequenas adições de Al2O3 e K2O ao sistema Li2O-SiO2 permitiram controlar a separação de fases devido à formação de espécies de Al(IV) que confirmaram o papel de Al2O3 como formador de rede. Os compactos de pó de vidro das composições contendo Al2O3 e K2O tratados termicamente resultaram em vitrocerâmicos bem densificados, apresentando dissilicato de lítio como a principal fase cristalina, e valores de resistência mecânica à flexão, resistência química e condutividade eléctrica (173-224 MPa, 25-50 mg/cm2 e ~2´10-18 S/cm, respectivamente) que possibilitam a utilização destes materiais em diversas aplicações funcionais. A adição de P2O5, TiO2 e ZrO2 ao sistema Li2O-K2O-Al2O3-SiO2 como agentes nucleantes revelou que os vidros contendo apresentaram cristalização em volume, com a formação de metassilicato de lítio a temperaturas mais baixas e dissilicato de lítio para as temperaturas mais elevadas, enquanto a adição de zircónia reduz o grau de segregação, aumenta a polimerização da matriz vítrea e desloca o valor de Tg para temperaturas superiores, inibindo a cristalização.

Lanthanide-organic frameworks for optical and catalytic applications

Este projecto de doutoramento tem como objetivo isolar e caracterizar sistematicamente novos polímeros de coordenação, no estado sólido. A presença de grupos rígidos possuindo, em particular, átomos de oxigénio e de azoto, deverá induzir interessantes propriedades fotoluminescentes (rendimentos quânticos e tempos de vida elevados, assim como vias de transferência de energia eficientes), que poderão permitir a utilização dos compostos poliméricos na produção de dispositivos funcionais. As diferentes abordagens sintéticas foram ajustadas para cada material e basearam-se, preferencialmente, nas sínteses hidrotérmicas e nas assistidas por radiação de microondas. A estrutura dos materiais foi elucidada a partir de métodos de difracção de raios X (de cristal único ou de pós) em conjunto com outras técnicas, tais como RMN de estado sólido, microscopia eletrónica, análises térmicas, espectroscopia vibracional e estudos de composição elementar. Os compostos microcristalinos foram sistematicamente estudados a fim de investigar outras propriedades além das de fotoluminescência. Alguns dos materiais revelaram multifuncionalidade apresentando simultaneamente tempos de vida na ordem dos milisegundos, elevados rendimentos quânticos e elevado desempenho como catalisadores heterogéneos. As propriedades magnéticas de um composto baseado em érbio foram igualmente estudadas, assim como as de adsorpção e permuta de solvente de uma estrutura porosa baseada em cério.

Hydrological and photochemical influence on dynamics of estuarine bacteria

Os estuários são ecossistemas complexos, onde os processos físicos, químicos e biológicos estão intimamente ligados. A dinâmica bacteriana num estuário reflete a interação e a elevada variação temporal e espacial desses processos. Este trabalho teve como objetivo elucidar as interações entre os processos físicos, fotoquímicos e microbiológicos no sistema estuarino da Ria de Aveiro (Portugal). Para tal, foi realizada uma abordagem inicial no campo, durante a qual as comunidades bacterianas na coluna de água foram caracterizadas em termos de abundância e atividade ao longo de 2 anos. O estudo foi realizado em dois locais distintos, escolhidos por tipificarem as características marinhas e salobras do estuário. Estes locais possuem diferentes hidrodinâmicas, influências fluviais e, quantidade e composição de matéria orgânica. Numa perspectiva mecanicista, foram realizadas simulações laboratoriais no sentido de elucidar a resposta das bactérias à matéria orgânica foto-transformada. As comunidades bacterianas no estuário adaptam-se a diferentes regimes de água doce, desenvolvendo padrões de abundância e atividade distintos nas zonas marinha e salobra. Os elevados caudais dos rios induzem estratificação vertical na zona marinha, promovendo o fluxo de fitoplâncton do mar para o estuário, do bacterioplâncton do estuário para o mar, e estimulam a importação de bactérias aderentes a partículas na zona salobra. O transporte advectivo e os processos de ressuspensão contribuem para aumentar 3 vezes o número de bactérias aderentes a partículas durante os períodos de intensas descargas fluviais. Adicionalmente, a atividade bacteriana no estuário é controlada pela concentração de azoto inerente à variações de água doce. O fornecimento de azoto em associação com a fonte dos substratos bacterianos induzem alterações significativas na produtividade. O padrão de variação vertical de comunidades bacterianas foi distinto nas duas zonas do estuário. Na zona marinha, as bactérias na microcamada superficial (SML) apresentaram taxas de hidrólise mais elevadas, mas menores taxas de incorporação de monómeros e produção de biomassa que na água subjacente (UW), enquanto na zona salobra, as taxas de hidrólise e incorporação foram similares nos dois compartimentos, mas a produtividade foi significativamente mais elevada na SML. Apesar da abundância bacteriana ter sido semelhante na SML e UW, a fração de células aderentes a partículas foi significativamente maior na SML (2-3 vezes), em ambas as zonas do estuário. A integração dos resultados microbiológicos com as variáveis ambientais e hidrológicos mostraram que fortes correntes na zona marinha promovem a mistura vertical, inibindo o estabelecimento de uma comunidade bacteriana na SML distinta da UW. Em contraste, na zona de água salobra, a menor velocidades das correntes fornece as condições adequadas ao aumento da atividade bacteriana na SML. Características específicas do local, tais como a hidrodinâmica e as fontes e composição da matéria orgânica, conduzem também a diferentes graus de enriquecimento superficial de matéria orgânica e inorgânica, influenciando a sua transformação. Em geral, o ambiente da SML estuarina favorece a hidrólise de polímeros, mas inibe a utilização de monómeros, comparativamente com água subjacente. No entanto, as diferenças entre as duas comunidades tendem a atenuar-se com o aumento da atividade heterotrófica na zona salobra. A matéria orgânica dissolvida cromófora (CDOM) das duas zonas do estuário possui diferentes características espectrais, com maior aromaticidade e peso molecular médio (HMW) na zona de água salobra, em comparação com a zona marinha. Nesta zona, a abundância bacteriana correlacionou-se com a350 e a254, sugerindo uma contribuição indireta das bactéria para HMW CDOM. A irradiação do DOM resultou numa diminuição dos valores de a254 e a350, e, em um aumento do declive S275-295 e dos rácios E2:E3 (a250/a365) e SR. No entanto, a extensão de transformações foto-induzidas e as respostas microbianas são dependentes das características iniciais CDOM, inferidas a partir das suas propriedades ópticas. A dinâmica estuarina influencia claramente as atividades heterotróficas e a distribuição dos microorganismos na coluna de água. A entrada de água doce influencia a dinâmica e os principais reguladores das comunidades bacterianas no estuário. Os processos fotoquímicos e microbianos produzem alterações nas propriedades ópticas da CDOM e a combinação desses processos determina o resultado global e o destino da CDOM nos sistemas estuarinos com influência na produtividade nas áreas costeiras adjacente.

Fiber optic sensors for the biomechanical study of the intervertebral disc

O presente trabalho teve como objetivo principal estudar o comportamento mecânico do disco intervertebral recorrendo a sensores em fibra ótica. Na expetativa de efetuar o melhor enquadramento do tema foi efetuada uma revisão exaustiva das várias configurações de sensores em fibra ótica que têm vindo a ser utilizadas em aplicações biomédicas e biomecânicas, nomeadamente para medição de temperatura, deformação, força e pressão. Nesse âmbito, procurou-se destacar as potencialidades dos sensores em fibra ótica e apresentá-los como uma tecnologia alternativa ou até de substituição das tecnologias associadas a sensores convencionais. Tendo em vista a aplicação de sensores em fibra ótica no estudo do comportamento do disco intervertebral efetuou-se também uma revisão exaustiva da coluna vertebral e, particularmente, do conceito de unidade funcional. A par de uma descrição anatómica e funcional centrada no disco intervertebral, vértebras adjacentes e ligamentos espinais foram ainda destacadas as suas propriedades mecânicas e descritos os procedimentos mais usuais no estudo dessas propriedades. A componente experimental do presente trabalho descreve um conjunto de experiências efetuadas com unidades funcionais cadavéricas utilizando sensores convencionais e sensores em fibra ótica com vista à medição da deformação do disco intervertebral sob cargas compressivas uniaxiais. Inclui ainda a medição in vivo da pressão intradiscal num disco lombar de uma ovelha sob efeito de anestesia. Para esse efeito utilizou-se um sensor comercial em fibra ótica e desenvolveu-se a respetiva unidade de interrogação. Finalmente apresenta-se os resultados da investigação em curso que tem como objetivo propor e desenvolver protótipos de sensores em fibra ótica para aplicações biomédicas e biomecânicas. Nesse sentido, são apresentadas duas soluções de sensores interferométricos para medição da pressão em fluídos corporais.

Synthesis of new Aβ-ligands useful in diagnosis of Alzheimer's disease

Alzheimer’s disease is a chronic progressive neurodegenerative disease and is the most common form of dementia (estimated 50−60% of all cases), associated with loss of memory (in particular episodic memory), cognitive decline, and behavioural and physical disability, ultimately leading to death. Alzheimer’s disease is a complex disease, mostly occurring sporadically with no apparent inheritance and being the age the main risk factor. The production and accumulation of amyloid-beta peptide in the central nervous system is a key event in the development of Alzheimer’s disease. This project is devoted to the synthesis of amyloid-beta ligands, fluorophores and blood brain barrier-transporters for diagnosis and therapy of Alzheimer’s disease. Different amyloid-beta ligands will be synthesized and their ability to interact with amyloid-beta plaques will be studied with nuclear magnetic resonance techniques and a process of lead optimization will be performed. Many natural and synthetic compounds able to interact as amyloid-beta ligands have been identified. Among them, a set of small molecules in which aromatic moieties seem to play a key role to inhibit amyloid-beta aggregation, in particular heteroaromatic polycyclic compounds such as tetracyclines. Nevertheless tetracyclines suffer from chemical instability, low water solubility and possess, in this contest, undesired anti-bacterial activity. In order to overcome these limitations, one of our goals is to synthesize tetracyclines analogues bearing a polycyclic structure with improved chemical stability and water solubility, possibly lacking antibacterial activity but conserving the ability to interact with amyloid-beta peptides. Known tetracyclines have in common a fourth cycle without an aromatic character and with different functionalisations. We aim to synthesize derivatives in which this cycle is represented by a sugar moiety, thus bearing different derivatisable positions or create derivatives in which we will increase or decrease the number of fused rings. In order to generate a potential drug-tool candidate, these molecules should also possess the correct chemical-physical characteristics. The glycidic moiety, not being directly involved in the binding, it assures further possible derivatizations, such as conjugation to others molecular entities (nanoparticles, polymeric supports, etc.), and functionalization with chemical groups able to modulate the hydro/lipophilicity. In order to be useful such compounds should perform their action within the brain, therefore they have to be able to cross the blood brain barrier, and to be somehow detected for diagnostic purposes.

Modelling the Minho river plume intrusion into the rias baixas

The Minho River, situated 30 km south of the Rias Baixas is the most important freshwater source flowing into the Western Galician Coast (NW of the Iberian Peninsula). This discharge is important to determine the hydrological patterns adjacent to its mouth, particularly close to the Galician coastal region. The buoyancy generated by the Minho plume can flood the Rias Baixas for long periods, reversing the normal estuarine density gradients. Thus, it becomes important to analyse its dynamics as well as the thermohaline patterns of the areas affected by the freshwater spreading. Thus, the main aim of this work was to study the propagation of the Minho estuarine plume to the Rias Baixas, establishing the conditions in which this plume affects the circulation and hydrographic features of these coastal systems, through the development and application of the numerical model MOHID. For this purpose, the hydrographic features of the Rias Baixas mouths were studied. It was observed that at the northern mouths, due to their shallowness, the heat fluxes between the atmosphere and ocean are the major forcing, influencing the water temperature, while at the southern mouths the influence of the upwelling events and the Minho River discharge were more frequent. The salinity increases from south to north, revealing that the observed low values may be caused by the Minho River freshwater discharge. An assessment of wind data along the Galician coast was carried out, in order to evaluate the applicability of the study to the dispersal of the Minho estuarine plume. Firstly, a comparative analysis between winds obtained from land meteorological stations and offshore QuikSCAT satellite were performed. This comparison revealed that satellite data constitute a good approach to study wind induced coastal phenomena. However, since the numerical model MOHID requires wind data with high spatial and temporal resolution close to the coast, results of the forecasted model WRF were added to the previous study. The analyses revealed that the WRF model data is a consistent tool to obtain representative wind data near the coast, showing good results when comparing with in situ wind observations from oceanographic buoys. To study the influence of the Minho buoyant discharge influence on the Rias Baixas, a set of three one-way nested models was developed and implemented, using the numerical model MOHID. The first model domain is a barotropic model and includes the whole Iberian Peninsula coast. The second and third domains are baroclinic models, where the second domain is a coarse representation of the Rias Baixas and adjacent coastal area, while the third includes the same area with a higher resolution. A bi-dimensional model was also implemented in the Minho estuary, in order to quantify the flow (and its properties) that the estuary injects into the ocean. The chosen period for the Minho estuarine plume propagation validation was the spring of 1998, since a high Minho River discharge was reported, as well as favourable wind patterns to advect the estuarine plume towards the Rias Baixas, and there was field data available to compare with the model predictions. The obtained results show that the adopted nesting methodology was successful implemented. Model predictions reproduce accurately the hydrodynamics and thermohaline patterns on the Minho estuary and Rias Baixas. The importance of the Minho river discharge and the wind forcing in the event of May 1998 was also studied. The model results showed that a continuous moderate Minho River discharge combined with southerly winds is enough to reverse the Rias Baixas circulation pattern, reducing the importance of the occurrence of specific events of high runoff values. The conditions in which the estuarine plume Minho affects circulation and hydrography of the Rias Baixas were evaluated. The numerical results revealed that the Minho estuarine plume responds rapidly to wind variations and is also influenced by the bathymetry and morphology of the coastline. Without wind forcing, the plume expands offshore, creating a bulge in front of the river mouth. When the wind blows southwards, the main feature is the offshore extension of the plume. Otherwise, northward wind spreads the river plume towards the Rias Baixas. The plume is confined close to the coast, reaching the Rias Baixas after 1.5 days. However, for Minho River discharges higher than 800 m3 s-1, the Minho estuarine plume reverses the circulation patterns in the Rias Baixas. It was also observed that the wind stress and Minho River discharge are the most important factors influencing the size and shape of the Minho estuarine plume. Under the same conditions, the water exchange between Rias Baixas was analysed following the trajectories particles released close to the Minho River mouth. Over 5 days, under Minho River discharges higher than 2100 m3 s-1 combined with southerly winds of 6 m s-1, an intense water exchange between Rias was observed. However, only 20% of the particles found in Ria de Pontevedra come directly from the Minho River. In summary, the model application developed in this study contributed to the characterization and understanding of the influence of the Minho River on the Rias Baixas circulation and hydrography, highlighting that this methodology can be replicated to other coastal systems.

Novas dispersões aquosas com morfologia controlada para revestimentos

O objetivo desta dissertação foi o desenvolvimento de dispersões poliméricas acrílicas, passíveis de serem usadas como ligantes em esmaltes aquosos que sejam capazes de conferir características especiais como elevada resistência ao empilhamento e à nódoa, assim como reduzir o impacto no ambiente quer através da utilização de matérias-primas de fontes renováveis, quer pela substituição de esmaltes de base solvente por esmaltes de base aquosa. Depois de uma introdução em que se contextualiza o conhecimento e as práticas nas áreas de polimerização em emulsão e revestimentos decorativos, são descritos e discutidos os resultados das várias etapas de desenvolvimento efetuadas ao longo do qual foram exploradas diferentes vias: - Funcionalização de polímeros acrílicos procurando melhorar as propriedades de superfície através da introdução de monómeros com grupos funcionais amina, epóxido e acetoacetoxilo; - Formulação de dispersões poliméricas com partículas de morfologia heterogénea, otimizando-se as suas propriedades de superfície em função da variação da composição monomérica das diferentes fases, da partição entre as duas fases poliméricas e diferentes níveis de monómero funcional. Complementaram-se os resultados com seleções afinadas baseadas em ensaios delineados através de planeamento de experiências. - Modificação dos produtos obtidos para melhoria de propriedades de resistência à nódoa, através da adição de aditivos específicos; - Teste de emulsionantes com origem em fontes renováveis quer aniónicos, quer não-iónicos. Todas as dispersões aquosas foram caracterizadas de acordo com as suas características mais relevantes entre as quais a temperatura mínima de formação de filme, o tamanho médio de partícula e a formação de grumos. As formulações mais promissoras foram também caracterizadas por 1H - NMR, FTIR, DSC, STEM e AFM). Seguidamente com essas dispersões foram preparados esmaltes com as dispersões aquosas mais promissoras que foram caracterizados exaustivamente em termos de propriedades de relevo para a aplicação decorativa em madeira. Os objetivos principais do trabalho foram atingidos, tendo sido desenvolvido um produto com morfologia heterogénea que apresenta elevada resistência ao empilhamento e propriedades antinódoa aceitáveis capaz de substituir os esmaltes de base solvente. A sua produção foi validada através do fabrico industrial (scale-up) e introdução no mercado. Relativamente à utilização de matérias-primas de fontes renováveis, esta carece ainda de otimizações futuras.

Characterization of water-soluble organic matter from urban aerosols

Water-soluble organic matter (WSOM) from atmospheric particles comprises a complex array of molecular structures that play an important role on the physic-chemical properties of atmospheric particles and, therefore, are linked to several global-relevant atmospheric processes which impact the climate and public health. Due to the large variety of sources and formation processes, adequate knowledge on WSOM composition and its effects on the properties of atmospheric aerosol are still limited. Therefore, this thesis aims at providing new insights on the molecular composition of WSOM from fine atmospheric aerosols typical of an urban area (Aveiro, Portugal). In a first step, adsorption phenomena of semivolatile organic compounds on quartz fibre filters employed in the collection of atmospheric aerosols were assessed. Afterwards, atmospheric aerosol samples were collected during fifteen months, on a weekly basis. A mass balance of aerosol samples was performed in order to set the relative contribution of elemental carbon, WSOM and water-insoluble organic matter to the aerosol mass collected at the urban area of Aveiro, with a special focus on the assessment of the influence of different meteorological conditions. In order to assess the chemical complexity of the WSOM from urban aerosols, their structural characteristics were studied by means of Fourier transform infrared infrared - Attenuated Total Reflectance (FTIR-ATR) and solid-state cross polarization with magic angle spinning 13C nuclear magnetic resonance (CPMAS 13C NMR) spectroscopies, as well as their elemental composition. The structural characterization of aerosol WSOM samples collected in the urban area highlighted a highly complex mixture of functional groups. It was concluded that aliphatic and aromatic structures, hydroxyl groups and carboxyl groups are characteristic to all samples. The semi-quantitative assessment of the CPMAS 13C NMR data showed different distributions of the various functional groups between the aerosol samples collected at different seasons. Moreover, the presence of signals typical of lignin-derived structures in both CPMAS 13C NMR and FTIR-ATR spectra of the WSOM samples from the colder seasons, highlights the major contribution of biomass burning processes in domestic fireplaces, during low temperature conditions, into the bulk chemical properties of WSOM from urban aerosols. A comprehensive two-dimensional liquid chromatography (LC x LC) method, on-line coupled to a diode array, fluorescence, and evaporative light scattering detectors, was employed for resolving the chemical heterogeneity of the aerosol WSOM samples and, simultaneously, to map the hydrophobicity versus the molecular weight distribution of the samples. The LC x LC method employed a mixed-mode hydrophilic interaction column operating under aqueous reversed phase mode in the first dimension, and a size-exclusion column in the second dimension, which was found to be useful for separating the aerosol WSOM samples into various fractions with distinct molecular weight and hydrophobic features. The estimative of the average molecular weight (Mw) distribution of the urban aerosol WSOM samples ranged from 48 to 942 Da and from 45 to 1241 Da in terms of UV absorption and fluorescence detection, respectively. Findings suggest that smaller Mw group fractions seem to be related to a more hydrophobic nature.

Alkali-free bioactive glasses for bone regeneration

Bioactive glasses and glass-ceramics are a class of third generation biomaterials which elicit a special response on their surface when in contact with biological fluids, leading to strong bonding to living tissues. The purpose of the present study was to develop diopside based alkali-free bioactive glasses in order to achieve good sintering behaviour, high bioactivity, and a dissolution/ degradation rates compatible with the target applications in bone regeneration and tissue engineering. Another aim was to understand the structure-property relationships in the investigated bioactive glasses. In this quest, various glass compositions within the Diopside (CaMgSi2O6) – Fluorapatite (Ca5(PO4)3F) – Tricalcium phosphate (3CaO•P2O5) system have been investigated. All the glasses were prepared by melt-quenching technique and characterized by a wide array of complementary characterization techniques. The glass-ceramics were produced by sintering of glass powders compacts followed by a suitable heat treatment to promote the nucleation and crystallization phenomena. Furthermore, selected parent glass compositions were doped with several functional ions and an attempt to understand their effects on the glass structure, sintering ability and on the in vitro bio-degradation and biomineralization behaviours of the glasses was made. The effects of the same variables on the devitrification (nucleation and crystallization) behaviour of glasses to form bioactive glass-ceramics were also investigated. Some of the glasses exhibited high bio-mineralization rates, expressed by the formation of a surface hydroxyapatite layer within 1–12 h of immersion in a simulated body fluid (SBF) solution. All the glasses showed relatively lower degradation rates in comparison to that of 45S5 Bioglass®. Some of the glasses showed very good in vitro behaviour and the glasses co-doped with zinc and strontium showed an in vitro dose dependent behaviour. The as-designed bioactive glasses and glass–ceramic materials are excellent candidates for applications in bone regeneration and for the fabrication of scaffolds for tissue engineering.

Sustainable viticulture in Bairrada appellation: vineyard and harvest year effects on grapes oenological potential

The sustainable viticulture of a region passes, among other aspects, for maximizing the varieties potential minimizing subsequent interventions during winemaking, which should contribute to the production of quality wines maintaining their typicity and rationalizing costs. The detailed knowledge of each Appellation specificities, namely vineyard parcel (soil type and topographical peculiarities) and harvest climatic conditions is crucial for sustainability in this sector. Thus, in line with this current trend, the starting point for the development of this PhD thesis was to evaluate the oenological potential of different varieties cultivated throughout Bairrada Appellation (Portugal). During maturation several changes in grape varieties occur, namely berries become sweeter, less acidic, and they develop flavour, aroma and colour properties. The development of these characteristics is essential to define grapes oenological potential, i.e. to estimate the possibility of their usage to produce specific wines. A three years sampling plan was designed to evaluate the effect of harvest year and parcel characteristics on V. vinifera cv. Arinto, Bical, Sauvignon Blanc, Baga, Castelão, Touriga Nacional, and Sousão grapes composition. For each variety, 3 parcels with different characteristics were selected. Several physicochemical parameters were evaluated, during maturation: berry weight, pH, titratable acidity, sugar and phenolic contents, antiradical activity, and volatile composition (free fraction). Special attention was devoted to grapes at technologic maturity, since, besides these parameters, glycosidically-linked fraction was also considered. By using the results obtained at technologic maturity, a comprehensive approach was applied to identify the significance of harvest and parcel characteristics effects on each variety composition. Considering all the parameters under study, it may be highlighted some significant differences. According to the obtained results determined during maturation, it was possible to conclude that Arinto, Bical and Sauvignon Blanc grapes from parcels with clay-sandy and clay-calcareous soils have higher phenolic content and antiradical activity. Otherwise, Sauvignon Blanc presented similar volatile composition for grapes cultivated in the 3 parcels, while Arinto and Bical exhibited higher volatile content in grapes from claysandy and clay-calcareous soils. For Baga, Castelão and Touriga Nacional red varieties, grapes with higher phenolic content, antiradical activity, and volatile content were obtained from clayey and clay-calcareous soils. Furthermore, for Touriga Nacional, parcels altitude seems also to modulate grapes composition. Beyond parcel effect, harvest year conditions also influence grapes composition: 2011 harvest was related with lower phenolic and volatile contents, as well as lower antiradical activity.For grapes collected at technologic maturity, analysis of variance-simultaneous component analysis (ASCA) was applied combining all the parameters under study, in order to assess the influence of harvest and parcel characteristics on each variety oenological potential. The results obtained using this comprehensive approach is closely related with those observed during maturation and revealed that harvest was the main factor that influenced grapes composition (53% to 68% of the total data set variance) followed by parcel characteristics, explaining ca. 15-19% of the total data set variance. The oenological potential of each variety may be different from one parcel to another, i.e., clay-sandy and clay-calcareous related-environments seem to favour Arinto and Bical white grapes composition, but for the red varieties, grapes composition was favoured by clayey and clay-calcareous soils. Besides, also higher altitude seems to favour Touriga Nacional grapes composition. Sauvignon Blanc seems to be a variety well adapted to the different parcel characteristics. In order to go forward in the valuation of these varieties, the aroma properties of 6 monovarietal wines were studied based on an aroma network-approach, linking molecular data related to volatile composition and aroma data about the key odor active molecules. This approach allowed to identify different wine aroma properties and to infer about the consumer’s sensory perception. It was found that aroma properties differ from one wine variety to another: while Arinto and Sauvignon Blanc wine exhibited higher tree fruity, sweety and flowery aromas, related essentially with ester compounds and C13 norisoprenoids, the opposite was obtained for Bical wine, corroborating the aroma sensory perceptions of the trained panel. Sauvignon Blanc also exhibited higher toasted aromas (related with thiols, mainly with 2-methyl-3-furanthiol). Touriga Nacional red wine exhibited higher tree, tropical, and berry fruits notes (sensory described as sweet fruits), toasted and flowery aromas, while these are similar for the other red wines under study. Besides Portuguese Bairrada wines, this aroma network approach is a tool that can be used to explain the aroma properties of wines worldwide. The grape and wine data generated under the present PhD thesis, in the context of Bairrada Appellation, shows the unique character of each variety, and may be used by growers and wine producers as a support for decisionmaking based on objective criteria, increasing the sustainability in this sector. For instance, it is possible to take advantage of the natural resources and produce products with different characteristics obtained from the same variety, minimizing costs during the winemaking process.

Ferroelectric : CNTs structures fabrication for advanced functional nano devices

This work is about the combination of functional ferroelectric oxides with Multiwall Carbon Nanotubes for microelectronic applications, as for example potential 3 Dimensional (3D) Non Volatile Ferroelectric Random Access Memories (NVFeRAM). Miniaturized electronics are ubiquitous now. The drive to downsize electronics has been spurred by needs of more performance into smaller packages at lower costs. But the trend of electronics miniaturization challenges board assembly materials, processes, and reliability. Semiconductor device and integrated circuit technology, coupled with its associated electronic packaging, forms the backbone of high-performance miniaturized electronic systems. However, as size decreases and functionalization increases in the modern electronics further size reduction is getting difficult; below a size limit the signal reliability and device performance deteriorate. Hence miniaturization of siliconbased electronics has limitations. On this background the Road Map for Semiconductor Industry (ITRS) suggests since 2011 alternative technologies, designated as More than Moore; being one of them based on carbon (carbon nanotubes (CNTs) and graphene) [1]. CNTs with their unique performance and three dimensionality at the nano-scale have been regarded as promising elements for miniaturized electronics [2]. CNTs are tubular in geometry and possess a unique set of properties, including ballistic electron transportation and a huge current caring capacity, which make them of great interest for future microelectronics [2]. Indeed CNTs might have a key role in the miniaturization of Non Volatile Ferroelectric Random Access Memories (NVFeRAM). Moving from a traditional two dimensional (2D) design (as is the case of thin films) to a 3D structure (based on a tridimensional arrangement of unidimensional structures) will result in the high reliability and sensing of the signals due to the large contribution from the bottom electrode. One way to achieve this 3D design is by using CNTs. Ferroelectrics (FE) are spontaneously polarized and can have high dielectric constants and interesting pyroelectric, piezoelectric, and electrooptic properties, being a key application of FE electronic memories. However, combining CNTs with FE functional oxides is challenging. It starts with materials compatibility, since crystallization temperature of FE and oxidation temperature of CNTs may overlap. In this case low temperature processing of FE is fundamental. Within this context in this work a systematic study on the fabrication of CNTs - FE structures using low cost low temperature methods was carried out. The FE under study are comprised of lead zirconate titanate (Pb1-xZrxTiO3, PZT), barium titanate (BaTiO3, BT) and bismuth ferrite (BiFeO3, BFO). The various aspects related to the fabrication, such as effect on thermal stability of MWCNTs, FE phase formation in presence of MWCNTs and interfaces between the CNTs/FE are addressed in this work. The ferroelectric response locally measured by Piezoresponse Force Microscopy (PFM) clearly evidenced that even at low processing temperatures FE on CNTs retain its ferroelectric nature. The work started by verifying the thermal decomposition behavior under different conditions of the multiwall CNTs (MWCNTs) used in this work. It was verified that purified MWCNTs are stable up to 420 ºC in air, as no weight loss occurs under non isothermal conditions, but morphology changes were observed for isothermal conditions at 400 ºC by Raman spectroscopy and Transmission Electron Microscopy (TEM). In oxygen-rich atmosphere MWCNTs started to oxidized at 200 ºC. However in argon-rich one and under a high heating rate MWCNTs remain stable up to 1300 ºC with a minimum sublimation. The activation energy for the decomposition of MWCNTs in air was calculated to lie between 80 and 108 kJ/mol. These results are relevant for the fabrication of MWCNTs – FE structures. Indeed we demonstrate that PZT can be deposited by sol gel at low temperatures on MWCNTs. And particularly interesting we prove that MWCNTs decrease the temperature and time for formation of PZT by ~100 ºC commensurate with a decrease in activation energy from 68±15 kJ/mol to 27±2 kJ/mol. As a consequence, monophasic PZT was obtained at 575 ºC for MWCNTs - PZT whereas for pure PZT traces of pyrochlore were still present at 650 ºC, where PZT phase formed due to homogeneous nucleation. The piezoelectric nature of MWCNTs - PZT synthesised at 500 ºC for 1 h was proved by PFM. In the continuation of this work we developed a low cost methodology of coating MWCNTs using a hybrid sol-gel / hydrothermal method. In this case the FE used as a proof of concept was BT. BT is a well-known lead free perovskite used in many microelectronic applications. However, synthesis by solid state reaction is typically performed around 1100 to 1300 ºC what jeopardizes the combination with MWCNTs. We also illustrate the ineffectiveness of conventional hydrothermal synthesis in this process due the formation of carbonates, namely BaCO3. The grown MWCNTs - BT structures are ferroelectric and exhibit an electromechanical response (15 pm/V). These results have broad implications since this strategy can also be extended to other compounds of materials with high crystallization temperatures. In addition the coverage of MWCNTs with FE can be optimized, in this case with non covalent functionalization of the tubes, namely with sodium dodecyl sulfate (SDS). MWCNTs were used as templates to grow, in this case single phase multiferroic BFO nanorods. This work shows that the use of nitric solvent results in severe damages of the MWCNTs layers that results in the early oxidation of the tubes during the annealing treatment. It was also observed that the use of nitric solvent results in the partial filling of MWCNTs with BFO due to the low surface tension (<119 mN/m) of the nitric solution. The opening of the caps and filling of the tubes occurs simultaneously during the refluxing step. Furthermore we verified that MWCNTs have a critical role in the fabrication of monophasic BFO; i.e. the oxidation of CNTs during the annealing process causes an oxygen deficient atmosphere that restrains the formation of Bi2O3 and monophasic BFO can be obtained. The morphology of the obtained BFO nano structures indicates that MWCNTs act as template to grow 1D structure of BFO. Magnetic measurements on these BFO nanostructures revealed a week ferromagnetic hysteresis loop with a coercive field of 956 Oe at 5 K. We also exploited the possible use of vertically-aligned multiwall carbon nanotubes (VA-MWCNTs) as bottom electrodes for microelectronics, for example for memory applications. As a proof of concept BiFeO3 (BFO) films were in-situ deposited on the surface of VA-MWCNTs by RF (Radio Frequency) magnetron sputtering. For in situ deposition temperature of 400 ºC and deposition time up to 2 h, BFO films cover the VA-MWCNTs and no damage occurs either in the film or MWCNTs. In spite of the macroscopic lossy polarization behaviour, the ferroelectric nature, domain structure and switching of these conformal BFO films was verified by PFM. A week ferromagnetic ordering loop was proved for BFO films on VA-MWCNTs having a coercive field of 700 Oe. Our systematic work is a significant step forward in the development of 3D memory cells; it clearly demonstrates that CNTs can be combined with FE oxides and can be used, for example, as the next 3D generation of FERAMs, not excluding however other different applications in microelectronics.

Ecological quality assessment in transitional systems

Estuaries are poles of attraction for human settlement which is a source of pressures to surface water bodies. The implementation of the European Water Framework Directive (WDF, 2000/60/EC) has increased the investigation in order to develop methodologies to assess the Ecological Quality Status (EQS) of aquatic ecosystems. Transitional systems are naturally stressed and characterized by highly dynamic physical, chemical and hydro-morphologic conditions and by species with a higher level of tolerance to change, being more difficult to develop suitable quality indicators for these systems. The general purpose of this study is to test the ability of synthesis descriptors, including primary (S, taxa richness) and derived biological variable (H’, Shannon-Wiener diversity), biotic indices (AMBI and M-AMBI), body size properties (abundance distribution by body size classes, length, weight and length-weight relationships) and non-taxonomic indices (ISS), as well as functional indicators related to the decomposition rates of various experimental substrates, a macrophyte (Phragmites australis) and an alga (Fucus vesiculosus), to evaluate the environmental quality in transitional systems. This study was carried out in one of the most pristine channels of the Ria the Aveiro, Mira Channel, along a full salinity gradient and in a metals and metalloid sediment contamination area, the Estarreja Channel, and two reference channels (Canelas and Salreu). In this study were used different sampling techniques, the leaf-bag technique and a hand-held corer. In Mira Channel, the alga and the macrophyte presented an opposite trend in the decomposition rate along the salinity gradient, with the decomposition rates of the alga always higher than those of the macrophyte. The decomposition rates of the macrophyte and the alga were higher in the mid estuary and in higher salinity areas, respectively, corresponding to the preferencial distribution areas of each species. The macrobenthic fauna associated with the decaying and an artificial substrate (control) showed equally well the benthic succession from the marine to the freshwater areas and, despite the strong differences in the decay rates, no significant differences were found between the benthic communities associated with the alga and the macrophyte. The body size properties of the macrobenthic fauna associated with the P. australis leaf-bag (1mm and 5mm) and corer samples were studied along the full salinity gradient. The dominant species of the sub-set of measured specimens were not the same of the original macrobenthic fauna sampled but, despite that, the sub-set of measured specimens was also able to show the benthic succession from the marine to the freshwater areas. The body size abundance distribution of the benthic macroinvertebrates according to the ISS size classes did not show a particular trend in any sampler along the salinity gradient. Significant differences were found in the length, weight and length-weight relationships of Annelids, , Molluscs and even some species along the salinity gradient. No significant differences were found in the AMBI, M-AMBI and ISS values along the salinity gradient for all the samplers. The EQS of the corer samples obtained using the M-AMBI was lower than that of the leaf-bags. The EQS obtained with the ISS was higher than that obtained with the M-AMBI in the leaf-bags but not in the corer samples. The ecological effects of contaminated sediments associated with the industrial chemical effluents discharged in the Estarreja Channel were studied a decade after ceasing the emissions, using the Sediment Quality Triad approach and two reference channels. The results showed that despite the emissions ceased in 2004, the sediment remains polluted with high levels of metals and metalloid, available to bioaccumulation and with severe consequences at the community level. The sediment contamination problem was also studied using the leaf-bag technique with a macrophyte, an alga and a control substrate. The results showed that the decay rates, the associated macrofauna and the application of the AMBI, M-AMBI and ISS indices to the mesh-bag samples were not able to identify the sediment contamination. Contrarily to the AMBI, the M-AMBI and the ISS showed significant differences between the contaminated and the reference channels for the corer samples. Although such statistical significance, the interest of using these complex biotic indices could be questioned, when much simple ones, like the S and H’ allow to reach the same conclusions.

Propriedades de lamas de salinas de Aveiro, tendo em vista aplicações dermoterapêuticas e dermocosméticas

Desde tempos históricos que diferentes tipos de lama são utilizados para aplicações externas no corpo humano, para fins terapêuticos e cosméticos. As lamas cuja beneficiação e caracterização físico-química são apresentadas nesta dissertação são formadas no ambiente hipersalino que existe nas salinas da Troncalhada e de São Tiago da Fonte, localizadas no estuário do rio Vouga, em Aveiro, Portugal. As salinas são constituídas por uma sequência de tanques onde, no período de verão, da água do mar e por evaporação natural, se produz sal marinho que precipita no último tanque (o cristalizador) do qual é extraído. Na base dos tanques ocorrem lamas que correspondem a sedimentos constituídos por material argiloso de cor preto-cinzento e que incorporam argila, silte, areia, bioclastos, sal, matéria orgânica e gás. A componente inorgânica da lama extraída do cristalizador foi estudada por Difracção de Raios-X (DRX) e Fluorescência de Raios-X (FRX), enquanto a componente orgânica da mesma lama foi estudada por Cromatografia de Gás- Espectrometria de Massa (GC-MS). Os estudos efectuados incidiram sobre amostras representativas de lama, obtidas antes e após refinação e beneficiação a que foi submetida a lama tal-qual colhida nas salinas. Foram utilizados métodos geofísicos para caracterizar e distinguir as lamas depositadas na época de safra e no período de interregno. Para o efeito, foram cravados tubos amostradores no sedimento que reveste o fundo dos tanques, tubos que seguidamente foram transportados para o laboratório para medição da condutividade eléctrica do topo até à base da coluna de sedimento amostrado. A refinação foi efectuada por elutriação de suspensões aquosas de lama utilizando um equipamento desenvolvido para o efeito e que permitiu concentrar a lama fina no overflow. Após floculação, sifonagem da água sobrenadante, dessalinização e centrifugação a lama refinada e beneficiada pôde ser incorporada em formulações com objectivos terapêuticos e cosméticos. O estudo microbiológico efectuado nas amostras de lama com sal e sem sal e na água das salinas permitiu identificar diversos tipos de bactérias e colónias presentes na lama e avaliar também os processos de esterilização testados. Concluiu-se que a lama hipersalina ou dessalinizada resultante do processamento a que foram submetidas, não deve ser aplicada ou incorporada em formulações tal-qual, pelo facto de em ambas terem sido identificadas bactérias como é o caso de Clostridium perfringens. Não obstante, se submetidas a esterilização utilizando autoclave a lama salina refinada e beneficiada poderá ser aplicada como peloide extemporâneo. Assim sendo foram desenvolvidas formulações dermoterapêuticas e dermocosméticas contendo lama beneficiada e dessalinizada e esterilizada termicamente.

Micro/nanoreservoirs for controlled release of active species in smart functional coatings

This work reports one possible way to develop new functional coatings used to increase the life time of metallic structures. The functionalities selected and attributed to model coatings in the frame of this work were corrosion protection, self-sensing and prevention of fouling (antifouling). The way used to confer those functionalities to coatings was based on the encapsulation of active compounds (corrosion inhibitors, pH indicators and biocides) in micro and nanocontainers followed by their incorporation into the coating matrices. To confer active corrosion protection, one corrosion inhibitor (2-mercaptobenzothiazole, MBT) was encapsulated in two different containers, firstly in silica nanocapsules (SiNC) and in polyurea microcapsules (PU-MC). The incorporation of both containers in different models coatings shows a significant improvement in the corrosion protection of aluminum alloy 2024 (AA2024). Following the same approach, SiNC and PU-MC were also used for the encapsulation of phenolphthalein (one well known pH indicator) to introduce sensing properties in polymeric coatings. SiNC and PU-MC containing phenolphthalein acted as corrosion sensor, showing a pink coloration due to the beginning of cathodic reaction, resulting in a pH increase identified by those capsules. Their sensing performance was proved in suspension and when integrated in coatings for aluminium alloy 2024 and magnesium alloy AZ31. In a similar way, the biocide activity (antifouling) was assigned to two polymeric matrices using SiNC for encapsulation of one biocide (Dichloro-2-octyl-2H-isothiazol-3-one, DCOIT) and also SiNC-MBT was tested as biocide. The antifouling activity of those two encapsulated compounds was assessed through inhibition and consequent decrease in the bioluminescence of modified E. coli. That effect was verified in suspension and when incorporated in coatings for AISI 1008 carbon steel. The developed micro and nanocontainers presented the desired performance, allowing the introduction of new functionalities to model coatings, showing potential to be used as functional additives in the next generation of multifunctional coatings.

Propriedades intrínsecas e de processamento de termoplásticos elastoméricos incorporando borracha de pneu reciclada

O trabalho apresentado tem por objetivo contribuir para a valorização da borracha proveniente de pneus em fim de vida, assente em princípios de sustentabilidade ambiental. A abordagem adotada para a concretização deste objetivo consiste na incorporação de borracha de pneus em formulações de base termoplástica e elastomérica (TPE), adequadas ao processo de moldação por injeção. São desenvolvidos estudos sobre a morfologia, propriedades mecânicas, térmicas e reológicas das ligas poliméricas à base de granulado de borracha de pneu (GTR). A falta de adesão entre o GTR e a matriz polimérica leva à degradação das propriedades mecânicas dos materiais obtidos. A estratégia explorada passa pela utilização de um elastómero para promover o encapsulamento do GTR e, desta forma, procurar obter ligas com propriedades mecânicas características de um TPE. São analisadas ligas ternárias (TPEGTR) compostas por polipropileno (PP) de elevada fluidez, GTR e elastómero virgem. O efeito da presença de diferentes elastómeros nas ligas é analisado neste trabalho: um elastómero de etilenopropileno- dieno (EPDM), e um novo elastómero de etileno-propileno (EPR) obtido por catálise metalocénica. O estudo da morfologia das ligas obtidas mostra haver interação entre os materiais, sendo possível inferir a viabilidade da estratégia adotada para promover a adesão do GTR. A incorporação de elastómero promove o aumento da resistência ao impacto e da extensão na rotura nas ligas, o que é atribuído, fundamentalmente, ao encapsulamento do GTR e ao aumento da tenacidade da matriz termoplástica. Com o objetivo de avaliar a influência da estrutura cristalina das ligas TPEGTR no seu comportamento mecânico, procede-se à análise do processo de cristalização sob condições isotérmicas e não isotérmicas. Neste estudo, é avaliado o efeito da presença dos materiais que constituem a fase elastomérica na cinética de cristalização. Para cada uma das ligas desenvolvidas, recorre-se ao modelo de Avrami para avaliar o efeito da temperatura no mecanismo de nucleação, na morfologia das estruturas cristalinas e na taxa de cristalização. Recorre-se à reometria capilar para estudar, sob condições estacionárias, o comportamento reológico das ligas TPEGTR. O modelo de Cross-WLF é utilizado para avaliar o comportamento reológico de todos os materiais, obtendo-se resultados similares àqueles obtidos experimentalmente. O comportamento reológico dos polímeros PP, EPR e EPDM é do tipo reofluidificante, tendo o EPR um comportamento reológico similar ao do PP e o EPDM um comportamento reo-fluidificante mais pronunciado. Em todas as ligas analisadas o comportamento reológico revela-se do tipo reo-fluidificante, sendo que a presença de GTR promove o aumento da viscosidade. Os parâmetros obtidos do modelo de Cross-WLF são utilizados para realizar a simulação da etapa de injeção recorrendo a um software comercial. Os resultados obtidos são validados experimentalmente pelo processo de moldação por injeção, evidenciando uma boa adequabilidade da aplicação deste modelo a estas ligas. O trabalho desenvolvido sobre ligas TPEGTR, constitui um contributo para a valorização da borracha proveniente de pneus em fim de vida, assente em princípios de sustentabilidade ambiental.