Long-term characterization of air lime mortars with ceramic waste

Due to their exposure to environmental conditions, outer coatings composed by render and painting system are usually the first construction elements to deteriorate and require intervention. A correct conservation and rehabilitation of these materials is fundamental once they provide protection to other façade materials. It is known that old mortar renders were essentially air lime based mortars. To maintain the integrity of the whole wall-render elements, the image of the building and to avoid accelerated degradation, conservation and rehabilitation must be implemented with compatible mortars. As that, lime based mortars would be preferable. It was also common, in ancient renders, the incorporation of ceramic residues, which is, nowadays, an abundant material, especially in Central Region of Portugal. The reuse of these materials has great relevance once their landfilling causes serious environmental issues. In an attempt to combine the environmental and technical advantages of the use of ceramic waste in mortars’ production for rehabilitation purposes, a research has been developed at the University of Coimbra, in cooperation with Nova University of Lisbon, on the long term behaviour of air lime mortars with ceramic residues. In this paper the most significant up to one year results of an experimental campaign with air lime mortars with 1:3 and 1:2 volumetric proportions and ceramic residues are presented.

Characterization of molecular damage induced by UV photons and carbon ions on biomimetic heterostructures

The study of the effect of radiation on living tissues is a rather complex task to address mainly because they are made of a set of complex functional biological structures and interfaces. Particularly if one is looking for where damage is taking place in a first stage and what are the underlying reaction mechanisms. In this work a new approach is addressed to study the effect of radiation by making use of well identified molecular hetero-structures samples which mimic the biological environment. These were obtained by assembling onto a solid support deoxyribonucleic acid (DNA) and phospholipids together with a soft water-containing polyelectrolyte precursor in layered structures and by producing lipid layers at liquid/air interface with DNA as subphase. The effects of both ultraviolet (UV) radiation and carbon ions beams were systematically investigated in these heterostructures, namely damage on DNA by means vacuum ultraviolet (VUV), infrared (IR), X-Ray Photoelectron (XPS) and impedance spectroscopy. Experimental results revealed that UV affects furanose, PO2-, thymines, cytosines and adenines groups. The XPS spectrometry carried out on the samples allowed validate the VUV and IR results and to conclude that ionized phosphate groups, surrounded by the sodium counterions, congregate hydration water molecules which play a role of UV protection. The ac electrical conductivity measurements revealed that the DNA electrical conduction is arising from DNA chain electron hopping between base-pairs and phosphate groups, with the hopping distance equal to the distance between DNA base-pairs and is strongly dependent on UV radiation exposure, due loss of phosphate groups. Characterization of DNA samples exposed to a 4 keV C3+ ions beam revealed also carbon-oxygen bonds break, phosphate groups damage and formation of new species. Results from radiation induced damage carried out on biomimetic heterostructures having different compositions revealed that damage is dependent on sample composition, with respect to functional targeted groups and extent of damage. Conversely, LbL films of 1,2-dipalmitoyl-sn-Glycero-3-[Phospho-rac-(1-glycerol)] (Sodium Salt) (DPPG) liposomes, alternated with poly(allylamine hydrochloride) (PAH) revealed to be unaffected, even by prolonged UV irradiation exposure, in the absence of water molecules. However, DPPG molecules were damaged by the UV radiation in presence of water with cleavage of C-O, C=O and –PO2- bonds. Finally, the study of DNA interaction with the ionic lipids at liquid/air interfaces revealed that electrical charge of the lipid influences the interaction of phospholipid with DNA. In the presence of DNA in the subphase, the effects from UV irrladiation were seen to be smaller, which means that ionic products from biomolecules degradation stabilize the intact DPPG molecules. This mechanism may explain why UV irradiation does not cause immediate cell collapse, thus providing time for the cellular machinery to repair elements damaged by UV.

On and off air: an ethnographic exploration of minority radio in Portugal

Taking a Media Anthropology’s approach to dynamics of mediated selfrepresentation in migratory contexts, this thesis starts by mapping radio initiatives produced by, for and/or with migrants in Portugal. To further explore dynamics of support of initial settlement in the country, community-making, cultural reproduction, and transnational connectivity - found both in the mapping stage and the minority media literature (e.g. Kosnick, 2007; Rigoni & Saitta, 2012; Silverstone & Georgiou, 2005) - a case study was selected: the station awarded with the first bilingual license in Portugal. The station in question caters largely to the British population presenting themselves as “expats” and residing in the Algarve. The ethnographic strategy to research it consisted of “following the radio” (Marcus, 1995) beyond the station and into the events and establishments it announces on air, so as to relate production and consumption realms. The leading research question asks how does locally produced radio play into “expats” processes of management of cultural identity – and what are the specificities of its role? Drawing on conceptualizations of lifestyle migration (Benson & O’Reilly, 2009), production of locality (Appadurai 1996) and the public sphere (Butsch, 2007; Calhoun & et al, 1992; Dahlgren, 2006), this thesis contributes to valuing radio as a productive gateway to research migrants’ construction of belonging, to inscribe a counterpoint in the field of minority media, and to debate conceptualizations of migratory categories and flows. Specifically, this thesis argues that the station fulfills similar roles to other minority radio initiatives but in ways that are specific to the population being catered to. Namely, unlike other minority stations, radio facilitates the process of transitioning between categories along on a continuum linking tourists and migrants. It also reflects and participates in strategies of reterritorialization that rest on functional and partial modes of incorporation. While contributing to sustain a translocality (Appadurai, 1996) it indexes and fosters a stance of connection that is symbolically and materially connected to the UK and other “neighborhoods” but is, simultaneously, oriented to engaging with the Algarve as “home”. Yet, besides reifying a British cultural identity, radio’s oral, repetitive and ephemeral discourse particularly trivializes the reproduction of an ambivalent stance of connection with place that is shared by other “expats”. This dynamic is related to migratory projects driven by social imaginaries fostered by international media that stimulate the search for idealized ways of living, which the radio associates with the Algarve. While recurrently localizing and validating the narrative projecting an idealized “good life”, radio amplifies dynamics among migrants that seem to reaffirm the migratory move as a good choice.

Reactive electron scattering from biomolecules and technologically relevant molecules

The role of a set of gases relevant within the context of biomolecules and technologically relevant molecules under the interaction of low-energy electrons was studied in an effort to contribute to the understanding of the underlying processes yielding negative ion formation. The results are relevant within the context of damage to living material exposed to energetic radiation, to the role of dopants in the ion-molecule chemistry processes, to Electron Beam Induced Deposition (EBID) and Ion Beam Induced Deposition (IBID) techniques. The research described in this thesis addresses dissociative electron attachment (DEA) and electron transfer studies involving experimental setups from the University of Innsbruck, Austria and Universidade Nova de Lisboa, Portugal, respectively. This thesis presents DEA studies, obtained by a double focusing mass spectrometer, of dimethyl disulphide (C2H6S2), two isomers, enflurane and isoflurane (C3F5Cl5) and two chlorinated ethanes, pentachloroethane (C2HCl5) and hexachloroethane (C2Cl6), along with quantum chemical calculations providing information on the molecular orbitals as well as thermochemical thresholds of anion formation for enflurane, isoflurane, pentachloroethane and hexachloroethane. The experiments represent the most accurate DEA studies to these molecules, with significant differences from previous work reported in the literature. As far as electron transfer studies are concerned, negative ion formation in collisions of neutral potassium atoms with N1 and N3 methylated pyrimidine molecules were obtained by time-of-flight mass spectrometry (TOF). The results obtained allowed to propose concerted mechanisms for site and bond selective excision of bonds.

Ion-beam sources based on superionic solid electrolytes

An ion emitter consisting of a sharp silver tip covered in RbAg4I5 solid electrolyte film has been developed and studied. An accelerating potential is applied and Ag+ ions are emitted from the tip’s apex by field evaporation. The emitted ions are collected by a Faraday cup, producing a current on the pico/nanoampere level which is read by an electrometer. The tips were produced mechanically by sandpaper polishing. The sharpest tip produced had a 2:4 m apex radius. Two deposition methods were studied: thermal vacuum and pulsed laser deposition. The best tip produced a peak current value of 96nA at 180oC, and a quasi-stable 4nA emission current at 160oC, both using an extraction potential of 10kV . The emission dependence on time, temperature and accelerating potential has been studied. Deposited films were characterized by X-ray diffraction (XRD), profilometry, optical and Scanning Electron Microscope (SEM) and Secondary Ion Mass Spectroscopy (SIMS) measurements. Several ion emitters were developed, the latter ones were all able to maintain stable high ion emissions for long periods of time. This investigation was a continuation of an ongoing project backed by the European Space Agency, with the objective of making a proof of concept of this kind of ion emitter with potential application on ion thrusters for orbiting satellites. Going forward, it would be interesting to make a finer analysis of the electrolyte’s conductivity at high temperatures, explore Wien Effect-based emission and to further develop a multi-tip ion emitter prototype.