Photoelectron spectroscopy of nitrogen containing molecules of biological and industrial interest

A thesis submitted for the degree of Ph. D. in Physics

Fate of nitrogen in bioreactor landfills: lab-scale in situ aeration in well decomposed MSW

Dissertação para obtenção do Grau de Mestre em Engenharia do ambiente, perfil de engenharia sanitária

Dissolved organic nitrogen behaviour during denitrification with suspended and attached biomass

Dissertação para obtenção do Grau de Mestre em Engenharia do Ambiente, perfil Engenharia Sanitária

Experimental Gravimetric Adsorption Equilibrium of n-Alkanes and Alkenes, Carbon Dioxide and Nitrogen in MIL-53(Al) and Zeolite 5A

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

Nitrogen (N) : from science to society. A science communication project

O Azoto (N): da ciência para a sociedade é um projecto de comunicação de ciência que tem por objecNvo consciencializar os jovens para as ameaças que o azoto (N) em excesso traz para a humanidade. Pode ser dividido em duas partes. Uma, de invesNgação, sobre a análise de resultados de uma consulta pública realizada entre professores, usando o método qualitaNvo do focus group, para compreender a sua sensibilidade e propostas de solução para minimizar o excesso de N no ambiente. Os resultados obNdos foram instrumentais para o desenvolvimento da segunda parte. Esta segunda parte é uma proposta de projecto a submeter ao Horizon 2020, no âm-­‐ bito da “Science with and for Society “. Nela se propõe uma abordagem educaNva trans-­‐disciplinar, conseguida através da interacção entre docentes do secundário, e do ensino superior, associação de pais e organizações cívicas não governamentais, com vista à consciencialização dos jovens para as ameaças do N em excesso no meio ambiente, fazendo o enquadramento cien@fico e fornecendo abordagens tecnológi-­‐ cas. A inovação desta proposta baseia-­‐se: (i) no acompanhamento e desenvolvimen-­‐ to profissional dos docentes do secundário, (ii) na moNvação dos estudantes a de-­‐ senvolver o seu próprio estudo e pesquisa com a tutoria dos docentes, da escola e do ensino superior, e (iii) no desenvolvimento de capacidades de comunicação dos jo-­‐ vens para exercer uma cidadania acNva em prol da minimização das ameaças do N.

Control of a white organic light emitting diode’s emission parameters using a single doped RGB active layer

White Color tuning is an attractive feature that Organic Light Emitting Diodes (OLEDs) offer. Up until now, there hasn’t been any report that mix both color tuning abilities with device stability. In this work, White OLEDs (W-OLEDs) based on a single RGB blend composed of a blue emitting N,N′-Di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (NPB) doped with a green emitting Coumarin-153 and a red emitting 4-(Dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM1) dyes were produced. The final device structure was ITO/Blend/Bathocuproine (BCP)/ Tris(8-hydroxyquinolinato)aluminium (Alq3)/Al with an emission area of 0.25 cm2. The effects of the changing in DCM1’s concentration (from 0.5% to 1% wt.) allowed a tuning in the final white color resulting in devices capable of emitting a wide range of tunes – from cool to warm – while also keeping a low device complexity and a high stabilitty. Moreover, an explanation on the optoelectrical behavior of the device is presented. The best electroluminescense (EL) points toward 160 cd/m2 of brightness and 1.1 cd/A of efficiency, both prompted to being enhanced. An Impedance Spectroscopy (IS) analysis allowed to study both the effects of BCP as a Hole Blocking Layer and as an aging probe of the device. Finally, as a proof of concept, the emission was increased 9 and 64 times proving this structure can be effectively applied for general lighting.

Impact of carbon/nitrogen feeding strategy on polyhydroxyalkanoates production using mixed microbial cultures

Polyhydroxyalkanoates (PHA) production using mixed microbial cultures (MMC) requires a multi-stage process involving the microbial selection of PHA-storing microorganisms, typically operated in sequencing batch reactors (SBR), and an accumulation reactor. Since low-cost renewable feedstocks used as process feedstock are often nitrogen-deficient, nutrient supply in the selection stage is required to allow for microbial growth. In this context, the possibility to uncouple nitrogen supply from carbon feeding within the SBR cycle has been investigated in this study. Moreover, three different COD:N ratios (100:3.79, 100:3.03 and 100:2.43) were tested in three different runs which also allowed the study of COD:N ratio on the SBR performance. For each run, a synthetic mixture of acetic and propionic acids at an overall organic load rate of 8.5 gCOD L-1 d-1 was used as carbon feedstock, whereas ammonium sulfate was the nitrogen source in a lab-scale sequence batch reactor (SBR) with 1 L of working volume. Besides, a sludge retention time (SRT) of 1 d was used as well as a 6 h cycle length. The uncoupled feeding strategy significantly enhanced the selective pressure towards PHA-storing microorganisms, resulting in a two-fold increase in the PHA production (up to about 1.3 gCOD L-1). A high storage response was observed for the two runs with the COD:N ratios (gCOD:gN) of 100:3.79 and 100:3.03, whereas the lowest investigated nitrogen load resulted in very poor performance in terms of polymer production. In fact, strong nitrogen limitation caused fungi to grow and a very poor storage ability by microorganisms that thrived in those conditions. The COD:N ratio also affected the polymer composition, indeed the produced poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) showed a variable HV content (1-20 %, w/w) among the three runs, lessening as the COD:N increased. This clearly suggests the possibility to use the COD:N ratio as a tool for tuning polymer properties regardless the composition of the feedstock.

Al-doped ZnO ceramic sputtering targets based on nanocrystalline powders produced by emulsion detonation synthesis – deposition and application as a transparent conductive oxide material

Transparent conducting oxides (TCOs) have been largely used in the optoelectronic industry due to their singular combination of low electrical resistivity and high optical transmittance. They are usually deposited by magnetron sputtering systems being applied in several devices, specifically thin film solar cells (TFSCs). Sputtering targets are crucial components of the sputtering process, with many of the sputtered films properties dependent on the targets characteristics. The present thesis focuses on the development of high quality conductive Al-doped ZnO (AZO) ceramic sputtering targets based on nanostructured powders produced by emulsion detonation synthesis method (EDSM), and their application as a TCO. In this sense, the influence of several processing parameters was investigated from the targets raw-materials synthesis to the application of sputtered films in optoelectronic devices. The optimized manufactured AZO targets present a final density above 99 % with controlled grain size, an homogeneous microstructure with a well dispersed ZnAl2O4 spinel phase, and electrical resistivities of ~4 × 10-4 Ωcm independently on the Al-doping level among 0.5 and 2.0 wt. % Al2O3. Sintering conditions proved to have a great influence on the properties of the targets and their performance as a sputtering target. It was demonstrated that both deposition process and final properties of the films are related with the targets characteristics, which in turn depends on the initial powder properties. In parallel, the influence of several deposition parameters in the film´s properties sputtered from these targets was investigated. The sputtered AZO TCOs showed electrical properties at room temperature that are superior to simple oxides and comparable to a reference TCO – indium tin oxide (ITO), namely low electrical resistivity of 5.45 × 10-4 Ωcm, high carrier mobility (29.4 cm2V-1s-1), and high charge carrier concentration (3.97 × 1020 cm-3), and also average transmittance in the visible region > 80 %. These superior properties allowed their successful application in different optoelectronic devices.