Production of polyhydroxyalkanoates from oil-containing substrates

Different oil-containing substrates, namely, used cooking oil (UCO), fatty acids-byproduct from biodiesel production (FAB) and olive oil deodorizer distillate (OODD) were tested as inexpensive carbon sources for the production of polyhydroxyalkanoates (PHA) using twelve bacterial strains, in batch experiments. The OODD and FAB were exploited for the first time as alternative substrates for PHA production. Among the tested bacterial strains, Cupriavidus necator and Pseudomonas resinovorans exhibited the most promising results, producing poly-3-hydroxybutyrate, P(3HB), form UCO and OODD and mcl-PHA mainly composed of 3-hydroxyoctanoate (3HO) and 3-hydroxydecanoate (3HD) monomers from OODD, respectively. Afterwards, these bacterial strains were cultivated in bioreactor. C. necator were cultivated in bioreactor using UCO as carbon source. Different feeding strategies were tested for the bioreactor cultivation of C. necator, namely, batch, exponential feeding and DO-stat mode. The highest overall PHA productivity (12.6±0.78 g L-1 day-1) was obtained using DO-stat mode. Apparently, the different feeding regimes had no impact on polymer thermal properties. However, differences in polymer‟s molecular mass distribution were observed. C. necator was also tested in batch and fed-batch modes using a different type of oil-containing substrate, extracted from spent coffee grounds (SCG) by super critical carbon dioxide (sc-CO2). Under fed-batch mode (DO-stat), the overall PHA productivity were 4.7 g L-1 day-1 with a storage yield of 0.77 g g-1. Results showed that SCG can be a bioresource for production of PHA with interesting properties. Furthermore, P. resinovorans was cultivated using OODD as substrate in bioreactor under fed-batch mode (pulse feeding regime). The polymer was highly amorphous, as shown by its low crystallinity of 6±0.2%, with low melting and glass transition temperatures of 36±1.2 and -16±0.8 ºC, respectively. Due to its sticky behavior at room temperature, adhesiveness and mechanical properties were also studied. Its shear bond strength for wood (67±9.4 kPa) and glass (65±7.3 kPa) suggests it may be used for the development of biobased glues. Bioreactor operation and monitoring with oil-containing substrates is very challenging, since this substrate is water immiscible. Thus, near-infrared spectroscopy (NIR) was implemented for online monitoring of the C. necator cultivation with UCO, using a transflectance probe. Partial least squares (PLS) regression was applied to relate NIR spectra with biomass, UCO and PHA concentrations in the broth. The NIR predictions were compared with values obtained by offline reference methods. Prediction errors to these parameters were 1.18 g L-1, 2.37 g L-1 and 1.58 g L-1 for biomass, UCO and PHA, respectively, which indicates the suitability of the NIR spectroscopy method for online monitoring and as a method to assist bioreactor control. UCO and OODD are low cost substrates with potential to be used in PHA batch and fed-batch production. The use of NIR in this bioprocess also opened an opportunity for optimization and control of PHA production process.

Robustness of corroded reinforced concrete structures. A structural performance approach

Structure and Infrastructure Engineering, 1-17

A reliability-based measure of robustness for concrete structures subjected to corrosion

This work is a contribution to the definition and assessment of structural robustness. Special emphasis is given to reliability of reinforced concrete structures under corrosion of longitudinal reinforcement. On this communication several authors’ proposals in order to define and measure structural robustness are analyzed and discussed. The probabilistic based robustness index is defined, considering the reliability index decreasing for all possible damage levels. Damage is considered as the corrosion level of the longitudinal reinforcement in terms of rebar weight loss. Damage produces changes in both cross sectional area of rebar and bond strength. The proposed methodology is illustrated by means of an application example. In order to consider the impact of reinforcement corrosion on failure probability growth, an advanced methodology based on the strong discontinuities approach and an isotropic continuum damage model for concrete is adopted. The methodology consist on a two-step analysis: on the first step an analysis of the cross section is performed in order to capture phenomena such as expansion of the reinforcement due to the corrosion products accumulation and damage and cracking in the reinforcement surrounding concrete; on the second step a 2D deteriorated structural model is built with the results obtained on the first step of the analysis. The referred methodology combined with a Monte Carlo simulation is then used to compute the failure probability and the reliability index of the structure for different corrosion levels. Finally, structural robustness is assessed using the proposed probabilistic index.

Avaliação da injecção de grouts em alvenarias antigas com ensaios não destrutivos

Dissertação para obtenção do Grau de Mestre em Engenharia Civil

Análise da injectabilidade do grout variando o meio poroso ao longo do escoamento

O envelhecimento do património edificado que constitui a maioria dos centros históricos e urbanos, não só em Portugal, como em toda a Europa, é uma realidade. Parcela significativa destes edifícios é constituída por paredes de alvenaria de pedra em mau estado de conservação. A necessidade crescente de intervenção no sentido de optimizar as respectivas condições de segurança destes edifícios é por isso prioritária. Uma das técnicas mais comuns, usadas na consolidação de alvenarias antigas e elementos arquitectónicos danificados, é a injecção de grouts. A utilização desta técnica tem como finalidade, não só o preenchimento de vazios existentes, de modo a aumentar a compacidade e resistência mecânica do núcleo da estrutura, mas também a criação de uma boa ligação com os panos exteriores, permitindo que a alvenaria recupere o seu comportamento monolítico. No entanto, é necessário ter em consideração, antes de qualquer intervenção de reabilitação, a compatibilidade entre os materiais originais e os materiais utilizados na intervenção. Deste modo, optou-se pela utilização de um ligante, cuja as propriedades mecânicas, físicas e químicas mais se assemelham aos materiais originais em alvenarias antigas, caso da cal hidráulica. Outro aspecto de grande importância a ter em conta, na injecção de grouts, é o poder de penetração da mistura. Assim, a necessidade de avaliação da eficiência da injecção em diferentes meios porosos conduziu à criação de modelos com diferentes composições que simulassem, com a maior fiabilidade possível, meios porosos encontrados no pano interior de alvenarias antigas. O presente trabalho incide principalmente na realização de ensaios de injecção, tendo como objectivo a análise da influência da variabilidade do meio poroso ao longo da altura de injecção de grout. Foram ainda realizados, de modo a avaliar a qualidade destas injecções, ensaios de velocidade de propagação de ultra-sons, assim como, a utilização da técnica de tomografia ultra-sónica. A combinação deste ensaio e técnica de análise não-destrutivas revelou-se de grande utilidade na avaliação da morfologia interna dos modelos criados. De forma a conhecer as resistências mecânicas e as respectivas relações com a qualidade de injecção dos meios porosos, realizaram-se ensaios de resistência à tracção por compressão diametral (também designados por Splitting Tensile Strength Test). Por fim, na última parte deste trabalho, de modo a simular os testes de injecção realizados anteriormente em laboratório, foi usado um modelo analítico tendo como ponto de partida a teoria de fluxo laminar viscoso através de meios porosos, com base na lei de Darcy.