Compósitos CNTs/biocerâmico para a estimulação elétrica óssea in situ

The present thesis aims to develop a biocompatible and electroconductor bone graft containing carbon nanotubes (CNTs) that allows the in situ regeneration of bone cells by applying pulsed external electrical stimuli. The CNTs were produced by chemical vapor deposition (CVD) by a semi-continuous method with a yield of ~500 mg/day. The deposition parameters were optimised to obtain high pure CNTs ~99.96% with controlled morphologies, fundamental requisites for the biomedical application under study. The chemical functionalisation of CNTs was also optimised to maximise their processability and biocompatibility. The CNTs were functionalised by the Diels-Alder cycloaddition of 1,3-butadiene. The biological behaviour of the functionalised CNTs was evaluated in vitro with the osteoblastic cells line MG63 and in vivo, by subcutaneous implantation in rats. The materials did not induce an expressed inflammatory response, but the functionalised CNTs showed a superior in vitro and in vivo biocompatibility than the non-functionalised ones. Composites of ceramic matrix, of bioglass (Glass) and hydroxyapatite (HA), reinforced with carbon nanotubes (CNT/Glass/HA) were processed by a wet approach. The incorporation of just 4.4 vol% of CNTs allowed the increase of 10 orders of magnitude of the electrical conductivity of the matrix. In vitro studies with MG63 cells show that the CNT/Glass/HA composites guarantee the adhesion and proliferation of bone cells, and stimulate their phenotype expression, namely the alkaline phosphate (ALP). The interactions between the composite materials and the culture medium (α-MEM), under an applied electrical external field, were studied by scanning vibrating electrode technique. An increase of the culture medium electrical conductivity and the electrical field confinement in the presence of the conductive samples submerged in the medium was demonstrated. The in vitro electrical stimulation of MG63 cells on the conductive composites promotes the increase of the cell metabolic activity and DNA content by 130% and 60%, relatively to the non-stimulated condition, after only 3 days of daily stimulation of 15 μA for 15 min. Moreover, the osteoblastic gene expression for Runx2, osteocalcin (OC) and ALP was enhanced by 80%, 50% and 25%, after 5 days of stimulation. Instead, for dielectric materials, the stimulus delivering was less efficient, giving an equal or lower cellular response than the non-stimulated condition. The proposed electroconductive bone grafts offer exciting possibilities in bone regeneration strategies by delivering in situ electrical stimulus to cells and consequent control of the new bone tissue formation rate. It is expected that conductive smart biomaterials might turn the selective bone electrotherapy of clinical relevance by decreasing the postoperative healing times.

Contaminated soil exposure assessment in Portugal and in the EU

Este estudo baseou-se na análise dos mecanismos de transferência de elementos potencialmente tóxicos (PTE’s) entre o solo, a solução do solo e as plantas como forma de realizar uma avaliação mais eficaz do risco em áreas agrícolas. Foram aplicados conceitos recentemente desenvolvidos para a avaliação da reactividade biogeoquímica de contaminantes no solo e da sua partição sólido:solução recorrendo-se a modelos empíricos (tipo Freundlich). Estes modelos permitiram analisar a transferência de PTE’s ao longo da cadeia alimentar e avaliar o impacto da contaminação do solo na qualidade da alimentação animal (forragens) e Humana (vegetais e carne) em Portugal. Os modelos empíricos de transferência solo-planta de PTE’s foram utilizadas para obter limites críticos para estes elementos em solos agrícolas em Portugal, a partir dos seus limites legais nos alimentos para animais e teores máximos nos géneros alimentícios. Simultaneamente, modelos de exposição Humana a contaminantes do solo, desenvolvidos noutros países da UE foram analisados e foi proposto um modelo de exposição para Portugal. Este trabalho é uma contribuição para o desenvolvimento de critérios de qualidade de solos para áreas agrícolas em Portugal, tendo em vista a protecção da saúde animal e Humana. Contribuiu também para o desenvolvimento de uma estratégia de harmonização de políticas de protecção do solo (nomeadamente no que diz respeito aos problemas de contaminação) na União Europeia.

Laser assisted directional solidification of zirconia-based eutectics

Directionally solidified zirconia-based eutectic (DSE) fibres were obtained using the laser floating zone (LFZ) method. Two systems were investigated: zirconia-barium zirconate and zirconia-mullite. The purpose was to take advantage of zirconia properties, particularly as an ionic conductor and a mechanical rein-forcement phase. The influence of processing conditions in the structural and microstructural characteristics and their consequences on the electrical and mechanical behaviour were the focus of this thesis. The novel zirconia-barium zirconate eutectic materials were developed in order to combine oxygen ionic conduction through zirconia with protonic conduction from barium zirconate, promoting mixed ionic conduction behaviour. The mi-crostructure of the fibres comprises two alternated regions: bands having coarser zirconia-rich microstructure; and inter-band regions changing from a homogeneous coupled eutectic, at the lowest pulling rate, to columnar colony microstructure, for the faster grown fibres. The bands inter-distance increases with the growth rate and, at 300 mm/h, zirconia dendrites develop enclosed in a fine-interpenetrated network of 50 vol.% ZrO2-50 vol.% BaZrO3. Both phases display contiguity without interphase boundaries, according to impedance spec-troscopy data. Yttria-rich compositions were considered in order to promote the yttrium incorporation in both phases, as revealed by Raman spectroscopy and corroborated by the elemental chemical analysis in energy dispersive spectros-copy. This is a mandatory condition to attain simultaneous contribution to the mixed ionic conduction. Such results are supported by impedance spectrosco-py measurements, which clearly disclose an increase of total ionic conduction for lower temperatures in wet/reduction atmospheres (activation energies of 35 kJ/mol in N2+H2 and 48 kJ/mol in air, in the range of 320-500 ºC) compared to the dry/oxidizing conditions (attaining values close to 90 kJ/mol, above 500 ºC). At high temperatures, the proton incorporation into the barium zirconate is un-favourable, so oxygen ion conduction through zirconia prevails, in dry and oxi-dizing environments, reaching a maximum of 1.3x10-2 S/cm in dry air, at ~1000 ºC. The ionic conduction of zirconia was alternatively combined with another high temperature oxygen ion conductor, as mullite, in order to obtain a broad elec-trolytic domain. The growth rate has a huge influence in the amount of phases and microstructure of the directionally solidified zirconia-mullite fibres. Their microstructure changes from planar coupled eutectic to dendritic eutectic mor-phology, when the growth rate rises from 1 to 500 mm/h, along with an incre-ment of tetragonal zirconia content. Furthermore, high growth rates lead to the development of Al-Si-Y glassy phase, and thus less mullite amount, which is found to considerably reduce the total ionic conduction of as-grown fibres. The reduction of the glassy phase content after annealing (10h; 1400 ºC) promotes an increase of the total ionic conduction (≥0.01 S/cm at 1370 °C), raising the mullite and tetragonal zirconia contents and leading to microstructural differ-ences, namely the distribution and size of the zirconia constituent. This has important consequences in conductivity by improving the percolation pathways. A notable increase in hardness is observed from 11.3 GPa for the 10 mm/h pulled fibre to 21.2 GPa for the fibre grown at 500 mm/h. The ultra-fine eutectic morphology of the 500 mm/h fibres results in a maximum value of 534 MPa for room temperature bending strength, which decreases to about one-fourth of this value at high temperature testing (1400 ºC) due to the soft nature of the glassy-matrix.

Materials and concepts for CO2 lean ironmaking by pyroelectrolysis

The main purpose of this PhD thesis was to provide convincing demonstration for a breakthrough concept of pyroelectrolysis at laboratory scale. One attempted to identify fundamental objections and/or the most critical constraints, to propose workable concepts for the overall process and for feasible electrodes, and to establish the main requirements on a clearer basis. The main effort was dedicated to studying suitable anode materials to be developed for large scale industrial units with molten silicate electrolyte. This concept relies on consumable anodes based on iron oxides, and a liquid Fe cathode, separated from the refractory materials by a freeze lining (solid) layer. In addition, one assessed an alternative concept of pyroelectrolysis with electron blocking membranes, and developed a prototype at small laboratory scale. The main composition of the molten electrolyte was based on a magnesium aluminosilicate composition, with minimum liquidus temperature, and with different additions of iron oxide. One studied the dynamics of devitrification of these melts, crystallization of iron oxides or other phases, and Fe2+/Fe3+ redox changes under laser zone melting, at different pulling rates. These studies were intended to provide guidelines for dissolution of raw materials (iron oxides) in the molten electrolyte, to assess compatibility with magnetite based consumable anodes, and to account for thermal gradients or insufficient thermal management in large scale cells. Several laboratory scale prototype cells were used to demonstrate the concept of pyroelectrolysis with electron blocking, and to identify the most critical issues and challenges. Operation with and without electron blocking provided useful information on transport properties of the molten electrolyte (i.e., ionic and electronic conductivities), their expected dependence on anodic and cathodic overpotentials, limitations in faradaic efficiency, and onset of side electrochemical reactions. The concept of consumable anodes was based on magnetite and derived spinel compositions, for their expected redox stability at high temperatures, even under oxidising conditions. Spinel compositions were designed for prospective gains in refractoriness and redox stability in wider ranges of conditions (T, pO2 and anodic overpotentials), without excessive penalty for electrical conductivity, thermomechanical stability or other requirements. Composition changes were also mainly based on components of the molten aluminosilicate melt, to avoid undue contamination and to minimize the dissolution rate of consumable anodes. Additional changes in composition were intended for prospective pyroelectrolysis of Fe alloys, with additions of different elements (Cr, Mn, Ni, Ti).

Valorização de resíduos provenientes da atividade no setor avícola: aplicação do processo de compostagem

O setor avícola, como setor em constante crescimento está associado à produção de elevadas quantidades de resíduos sólidos orgânicos. A crescente taxa de produção de resíduos avícolas leva à necessidade de lhes dar um destino adequado podendo a valorização orgânica, nomeadamente a compostagem, ser uma opção. O presente estudo pretende dar um contributo para o projeto de uma unidade de compostagem numa empresa portuguesa do setor, com valorização dos resíduos produzidos pela mesma, avaliando o potencial de aplicação desta operação de tratamento de resíduos e a qualidade do produto final. Como primeiro passo foi realizada uma caracterização dos resíduos a utilizar de forma a perceber a sua possível influência no processo de degradação. Os ensaios de compostagem foram realizados à escala laboratorial, numa gama de temperatura de 50 a 55ᵒC, utilizando como substrato base uma mistura dos resíduos avícolas, de acordo com os seus quantitativos de produção. Vários potenciais agentes estruturantes foram também testados, como adição ao substrato. A monitorização do processo foi feita com base em análises das fases gasosa (gases de exaustão), sólida (substrato em decomposição) e líquida (lixiviado). A avaliação do processo foi ainda complementada com a caracterização dos produtos finais obtidos, os quais foram ainda sujeitos a testes de fitotoxicidade. Foram observados graus de conversão de matéria orgânica relativamente altos (40-50%), comprovando a aplicabilidade desta operação de tratamento de resíduos. Embora a diferença entre ensaios tenha sido pouco notória, a utilização de uma combinação de cama de aviário e mato destroçado e compostado aparenta ser ligeiramente mais eficiente, enquanto a utilização de casca de eucalipto produziu os piores resultados. Perdas de humidade e de azoto foram as duas situações mais críticas observadas para os vários ensaios, tendo influência tanto sobre o processo como sobre o produto final. Os compostos obtidos revelam baixa qualidade, exibindo valores elevados de pH e condutividade elétrica e elevadas concentrações de metais pesados, tais como cobre e zinco. Supõe-se que as características adversas verificadas estejam associadas à aplicação de quantidades demasiado elevadas de cinza nos substratos, levando à necessidade de redução deste material; estudos adicionais seriam necessários a fim de avaliar as possibilidades de ajuste das quantidades a utilizar, dos diferentes materiais, com o intuito de produzir um produto final com qualidade, respeitando os requisitos legais.