Modelling of the kinetics of municipal solid waste composting in full-scale mechanical-biological treatment plants

A thesis submitted in fulfilment of the requirements for the Degree of Doctor of Philosophy in Sanitary Engineering in the Faculty of Sciences and Technology of the New University of Lisbon

Mechanical properties of chemically modified portuguese pinewood

To turn wood into a construction material with enhanced properties, many methods of chemical modification have been developed in the last few decades. In this work, mechanical properties of pine wood were chemically modified, compared and evaluated. Maritime pine wood (Pinus pinaster) was modified with four chemical processes: 1,3-dimethylol-4,5- dihydroxyethyleneurea, N-methylol melamine formaldehyde, tetra-alkoxysilane and wax. The following mechanical properties were assessed experimentally: Modulus of elasticity measured statically, stiffness stabilization efficiency in different climates (30 and 87% of relative humidity), modulus of rupture, work maximum load, impact bending strength, compression, tensile and shear strength at indoor conditions (65% of relative humidity). In both types of active principle of modification, cell wall or lumen fill, no significant changes on the bending stiffness (modulus of elasticity) were found. In the remaining properties analysed significant changes in the modified wood-material took place compared to unmodified wood control: - Cell wall modification was the most effective method to achieve high stiffness stabilization efficiency (up to 60%) and also increased compression strength (up to 230%). However, modulus of rupture, tensile, shear and the impact bending strength were reduced by both resins, but in a varying extent, where the N-methylol melamine formaldehyde endured less reduction than 1,3-dimethylol-4,5-dihydroxyethyleneurea resin. In the latter, reduction up to 60% can take place. - In the lumen fill modification: tetra-alkoxysilane has no effect in the mechanical properties. Although, a slight increase in shear strength parallel to the grain was found. Wax specimens have shown a slight increase in bending strength, compression, tensile and shear strength as well as in the absorption energy capacity.

Experimental characterization of the out-of-plane performance of regular stone masonry walls, including test setups and axial load influence

Stone masonry is one of the oldest and most worldwide used building techniques. Nevertheless, the structural response of masonry structures is complex and the effective knowledge about their mechanical behaviour is still limited. This fact is particularly notorious when dealing with the description of their out-of-plane behaviour under horizontal loadings, as is the case of the earthquake action. In this context, this paper describes an experimental program, conducted in laboratory environment, aiming at characterizing the out-of-plane behaviour of traditional unreinforced stone masonry walls. In the scope of this campaign, six full-scale sacco stone masonry specimens were fully characterised regarding their most important mechanic, geometric and dynamic features and were tested resorting to two different loading techniques under three distinct vertical pre-compression states; three of the specimens were subjected to an out-of-plane surface load by means of a system of airbags and the remaining were subjected to an out-of-plane horizontal line-load at the top. From the experiments it was possible to observe that both test setups were able to globally mobilize the out-of-plane response of the walls, which presented substantial displacement capacity, with ratios of ultimate displacement to the wall thickness ranging between 26 and 45 %, as well as good energy dissipation capacity. Finally, very interesting results were also obtained from a simple analytical model used herein to compute a set of experimental-based ratios, namely between the maximum stability displacement and the wall thickness for which a mean value of about 60 % was found.

Caraterização das propriedades mecânicas de um adesivo estrutural de alta ductilidade

A tecnologia de ligação por adesivos estruturais tem vindo a ser utilizada ao longo de várias décadas, permitindo solucionar diversos problemas associados a técnicas chamadas "tradicionais" de ligação, como a soldadura, a rebitagem ou a ligação aparafusada. Esta é uma alternativa viável para substituir as ligações mecânicas, devido a diversos fatores como o menor peso estrutural, menor custo de fabricação e capacidade de união de diferentes materiais. O crescente recurso a materiais compósitos em diversas indústrias, nomeadamente a aeronáutica e naval, levaram ao consequente aumento da aplicação de ligações adesivas, por serem indicadas como forma de união destes materiais, onde é de enaltecer a sua elevada resistência à fadiga. Uma junta adesiva está maioritariamente sujeita a esforços de corte e arrancamento e portanto o conhecimento dos módulos de elasticidade à tração (E) ou corte (G) do adesivo, e ainda as resistências máximas à tração e ao corte, não é suficiente quando se pretende prever o comportamento da mesma. Na verdade, torna-se necessário abranger na análise a plastificação progressiva verificada nas juntas adesivas antes da rotura, sendo necessário o conhecimento de parâmetros tais como a taxa crítica de libertação de energia de deformação à tração (GIc) e corte (GIIc). Este trabalho pretende estudar um adesivo estrutural recentemente lançado no mercado, carecendo portanto da sua caracterização, para facilitar a previsão da resistência de estruturas adesivas ligadas com o mesmo. São 4 os ensaios a realizar: ensaios à tração de provetes em bruto, ensaios ao corte com a geometria Thick Adherend Shear Test (TAST), ensaios Double-Cantilever Beam (DCB) e ensaios End-Notched Flexure (ENF). Com a realização dos ensaios referidos, serão determinadas as propriedades mecânicas e de fratura à tração e ao corte, e serão fornecidos os parâmetros para a previsão da resistência de juntas adesivas com este adesivo por uma variedade de métodos, desde métodos analíticos mais expeditos até aos métodos numéricos mais avançados existentes atualmente. Os resultados foram de encontro aos disponibilizados pelo fabricante, sempre que estes se encontravam disponíveis, obtendo-se discrepâncias bastante reduzidas nos diversos parâmetros determinados.

A constructive technology assessment of stationary energy storage systems: prospective life cycle orientated analysis

Based on the presentation and discussion at the 3rd Winter School on Technology Assessment, December 2012, Universidade Nova de Lisboa (Portugal), Caparica Campus, PhD programme on Technology Assessment

Lime mortars with ceramic wastes: characterization of components and their influence on the mechanical behaviour

Considering the fundamental importance of preserving the built heritage and of ensuring the good performance achieved by incorporating ceramic particles in lime mortars in ancient times, it is important to study solutions that use materials the available today, in order to produce mortars intended to repair and replace the old ones. Solutions incorporating industrial ceramic waste might be profitable for several reasons, namely for economic, environmental and technical aspects. In this paper, seven ceramic waste products collected from ceramics factories are characterized. Their mineralogy, dimensional features and pozzolanicity were determined. Three of these products, with different particle size fractions (obtained directly from milling, dust only and fragment fractions only), were selected, incorporated into air lime mortars, and their mechanical strength was determined. In the present work, evidence of mechanical efficiency, when common sand or air lime were partially replaced by ceramic wastes, was made clear, drawing attention to the sustainability of this type of mortars, hence, encouraging further research.

Development and efficiency optimizing of the human body energy converters

Nowadays it is known that the human body is continuous source of many types of energy and the devices used for collecting energy taken from the environment also have the required capabilities for the collection of the energy produced by the Human body (HB), but very limited and with very low efficiency. Low power and high yield converters are particularly needed in these cases of collecting energy from human activity and its movements due to the small amount of energy generated this way. But this situation can be improved. Enhancing or focusing the human movements by using mechanical amplifiers applied to the piezoelectric element. By doing so the input of energy in the element increases. As such increasing its output, therefore producing more energy.

Thermo-hydro-mechanical analysis of CO2 injection into deep aquifers

One of the biggest challenges for humanity is global warming and consequently, climate changes. Even though there has been increasing public awareness and investments from numerous countries concerning renewable energies, fossil fuels are and will continue to be in the near future, the main source of energy. Carbon capture and storage (CCS) is believed to be a serious measure to mitigate CO2 concentration. CCS briefly consists of capturing CO2 from the atmosphere or stationary emission sources and transporting and storing it via mineral carbonation, in oceans or geological media. The latter is referred to as carbon capture and geological storage (CCGS) and is considered to be the most promising of all solutions. Generally it consists of a storage (e.g. depleted oil reservoirs and deep saline aquifers) and sealing (commonly termed caprock in the oil industry) formations. The present study concerns the injection of CO2 into deep aquifers and regardless injection conditions, temperature gradients between carbon dioxide and the storage formation are likely to occur. Should the CO2 temperature be lower than the storage formation, a contractive behaviour of the reservoir and caprock is expected. The latter can result in the opening of new paths or re-opening of fractures, favouring leakage and compromising the CCGS project. During CO2 injection, coupled thermo-hydro-mechanical phenomena occur, which due to their complexity, hamper the assessment of each relative influence. For this purpose, several analyses were carried out in order to evaluate their influences but focusing on the thermal contractive behaviour. It was finally concluded that depending on mechanical and thermal properties of the pair aquifer-seal, the sealing caprock can undergo significant decreases in effective stress.

Influence of the molecular weight in mechanical properties and degradation kinetics of chitosan inverted colloidal crystals

Tissue engineering arises from the need to regenerate organs and tissues, requiring the development of scaffolds, which can provide an optimum environment for tissue growth. In this work, chitosan with different molecular weights was used to develop biodegradable 3D inverted colloidal crystals (ICC) structures for bone regeneration, exhibiting uniform pore size and interconnected network. Moreover, in vitro tests were conducted by studying the influence of the molecular weight in the degradation kinetics and mechanical properties. The production of ICC included four major stages: fabrication of microspheres; assembly into a cohesive structure, polymeric solution infiltration and microsphere removal. Chitosan’s degree of deacetylation was determined by infrared spectroscopy and molecular weight was obtained via capillary viscometry. In order to understand the effect of the molecular weight in ICC structures, the mass loss and mechanical properties were analyzed after degradation with lysozyme. Structure morphology observation before and after degradation was performed by scanning electron microscopy. Cellular adhesion and proliferation tests were carried out to evaluate ICC in vitro response. Overall, medium molecular weight ICC revealed the best balance in terms of mechanical properties, degradation rate, morphology and biological behaviour.

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.

Functional characterization and directed engineering of redox proteins for a rational improvement of Bioelectrochemical systems

In recent years, new methods of clean and environmentally friendly energy production have been the focus of intense research efforts. Microbial fuel cells (MFCs) are devices that utilize naturally occurring microorganisms that feed on organic matter, like waste water, while producing electrical energy. The natural habitats of bacteria thriving in microbial fuel cells are usually marine and freshwater sediments. These microorganisms are called dissimilatory metal reducing bacteria (DMRB), but in addition to metals like iron and manganese, they can use organic compounds like DMSO or TMAO, radionuclides and electrodes as terminal electron acceptors in their metabolic pathways.(...)

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.

Advancing tendon regeneration through the development of bio-stimulating tissue engineering approaches

Tendon tissue engineering (TE) requires tailoring scaffolds designs and properties to the anatomical and functional requirements of tendons located in different regions of the body. Cell sourcing is also of utmost importance as tendon cells are scarce. Recently, we have found that it is possible to direct the tenogenic differentiation of Amniotic fluid and Adipose tissue derived stem cells (hAFSCs and hASCs), and also that there are hASCs subpopulations that might be more prone to tenogenic differentiation. Nevertheless, biochemical stimulation may not be enough to develop functional TE substitutes for a tissue that is known to be highly dependent on mechanical loading.

Compact saloplastic membranes of natural polysaccharides for soft tissue engineering

The regeneration of soft biological tissues requires new substitutes that exhibit mechanical properties similar to the native tissue. Herein, thin saloplastic membranes with tunable physical properties are prepared by complexation of chitosan and alginate solutions containing different concentrations of sodium chloride. Polyelectrolyte complexes (PECs) are transferred to flat Petri dishes for compaction into membrane shapes by sedimentation and solvent evaporation. All membranes are resistant to degradation by lysozyme and are stable in solutions with pH values between 1 and 13. Immersing the different membranes in new doping solutions of increasing salt concentrations triggers the typical saloplastic behavior, with a high water absorption and decrease of the rigidity and ultimate tensile strength. The range of such variations is tuned by the sodium chloride amount used in the synthesis: high salt concentrations increase water uptake and tensile moduli, while decreasing the ultimate strength. Cellular assays demonstrate high proliferation rates and viability of L929 fibroblasts seeded onto the most rigid membranes. The results validate the use of saloplastic membranes as soft tissue substitutes for future biomedical applications.