Production and characterization of electrospun composite fibers: confinement of thermosensitive microgels

Materials engineering focuses on the assembly of materials´ properties to design new products with the best performance. By using sub-micrometer size materials in the production of composites, it is possible to obtain objects with properties that none of their compounds show individually. Once three-dimensional materials can be easily customized to obtain desired properties, much interest has been paid to nanostructured poly-mers in order to build biocompatible devices. Over the past years, the thermosensitive microgels have become more common in the framework of bio-materials with potential applicability in therapy and/or diagnostics. In addition, high aspect ratio biopolymers fibers have been produced using the cost-effective method called electrospinning. Taking advantage of both microgels and electrospun fibers, surfaces with enhanced functionalities can be obtained and, therefore employed in a wide range of applications. This dissertation reports on the confinement of stimuli-responsive microgels through the colloidal electro-spinning process. The process mainly depends on the composition, properties and patterning of the precur-sor materials within the polymer jet. Microgels as well as the electrospun non-woven mats were investigated to correlate the starting materials with the final morphology of the composite fibers. PNIPAAm and PNIPAAm/Chitosan thermosensitive microgels with different compositions were obtained via surfactant free emulsion polymerization (SFEP) and characterized in terms of chemical structure, morphology, thermal sta-bility, swelling properties and thermosensitivity. Finally, the colloidal electrospinning method was carried out from spinning solutions composed of the stable microgel dispersions (up to a concentration of about 35 wt. % microgels) and a polymer solution of PEO/water/ethanol mixture acting as fiber template solution. The confinement of microgels was confirmed by Scanning Electron Microscopy (SEM). The electrospinning process was statistically analysed providing the optimum set of parameters aimed to minimize the fiber diameter, which give rise to electrospun nanofibers of PNIPAAm microgels/PEO with a mean fiber diameter of 63 ± 25 nm.

Geopolymers as infill material for conservation of azulejos

The restoration materials currently used to fill gaps in architectural historical azulejos (e.g. lime or organic resin pastes) usually show serious drawbacks in terms of compatibility, effectiveness and durability. The existing solutions do not fully protect azulejos in outdoor conditions and frequently result in further deterioration. Geopolymers can be a potential solution for azulejo lacunae infill given the chemical-mineralogical similitude to the ceramic body, and also the durability and versatile range of physical properties that can be obtained through the manipulation of their formulation and curing conditions. This work presents and discusses the viability of the use of geopolymeric pastes to fill lacunae in azulejos or to act as “cold” cast ceramic tile surrogates reproducing missing azulejo fragments. The formulation of geopolymers, namely the type of activators, the aluminosilicate source, the amount of water (to meet adequate workability requirements) and curing conditions were studied. The need for post-curing desalination was also considered envisaging their application in the restoration of outdoor architectural historical azulejos frequently exposed to adverse environmental conditions. The possible advantages and disadvantages of the use of geopolymers in the conservation of azulejos are also discussed. Several techniques were used to study the chemical and physical behavior of geopolymers, namely FT-IR, XRD, MIP, SEM-EDS, WDXRF, electrical conductivity, open porosity, bending strength, adhesion strength, water vapour permeability, thermal expansion and hydric expansion. The results indicate that geopolymers are a promising material for restoration of azulejos, exhibiting some properties, such as adhesion to the ceramic substrate, higher than inorganic materials used nowadays, such as aerial lime based pastes.

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.

Torrefação de biomassa de Arundo donax L. e de Phoenix canariensis com vista à sua valorização energética ou material

A torrefação é vista como um pré-tratamento térmico que introduz modificações na biomassa, ou em resíduos de biomassa, que facilitam o seu processamento mecânico e aumentam a sua estabilidade e densidade energética, potenciando, assim, uma valorização posterior. Neste trabalho, estudou-se o impacte da torrefação na gama de 200 a 350 ºC e tempos de residência entre 15 e 90 min nas propriedades da biomassa proveniente da herbácea Arundo donax L. e das palmeiras Phoenix canariensis, espécies muito abundantes em vários locais do país, tendo em vista a sua posterior valorização. A proliferação descontrolada do arundo e a praga do escaravelho das palmeiras leva a que estas espécies sejam alvo de frequentes operações de remoção. A sua estrutura altamente fibrosa dificulta e encarece estas operações, que acarretam custos significativos para as câmaras municipais, e não se conhecem medidas para a sua valorização material ou energética. A torrefação foi também aplicada a peletes de resíduos de pinheiro, na gama de 200 a 250 ºC e com tempos de residência de 30 e 60 min, para averiguar o seu impacte na qualidade desse biocombustível sólido. A torrefação permitiu obter peletes mais resistentes à biodegradação, devido à redução do teor de humidade para valores residuais, sem aumentar significativamente o seu teor de cinzas e sem afetar de forma relevante a sua durabilidade, o teor de finos ou a densidade aparente. Com a biomassa de arundo e de palmeira obtiveram-se produtos com maior poder calorífico e com melhor moabilidade. No entanto, a acentuada diminuição dos rendimentos mássico e energético e o elevado teor de cinzas constrangem a sua utilização como biocombustíveis sólidos. Desta forma, optou-se por testar a sua valorização como adsorventes do corante azul de metileno, bastante comum, por exemplo, na indústria têxtil, nos curtumes ou nas industrias do papel. Os estudos de adsorção revelaram maior afinidade pelo corante por parte da biomassa sujeita a torrefação mais ligeira, com eficiências de remoção muito próximas das do carvão ativado comercial, para concentrações iniciais de corante até 200 mg/L. As isotérmicas foram melhor ajustadas ao modelo de Langmuir, que revelou capacidades máximas de adsorção na monocamada entre 59,92 e 92,68 mg/g, tendo as curvas de cinética sido melhor descritas pelo modelo de pseudo-segunda ordem. A adsorção é bastante rápida nos primeiros minutos, essencialmente devido a atrações eletrostáticas, sendo inicialmente controlada pela difusão no filme e depois pela difusão nos poros. Os adsorventes revelaram seletividade por um corante catiónico e permitiram dessorção de corante, ao contrário do verificado com o carvão ativado comercial, o que é um aspeto da maior relevância tendo em mente a regeneração do adsorvente e a recuperação do corante.

Material Zoológico depositado nas coleções sistemáticas de entomologia do INPA, resultante do "Projeto INPA/MAX-PLANK" (Convênio CNPq/MGP)

As coleções de Entomolologia Sistemática do Instituto nacional de Pesquisas da Amazônia (INPA) em Manaus, Brasil, no momento, contém aproximadamente 16.350 exemplares de invertebrados e vertebrados identificados, representando 330a espécies e incluindo 692 tipos que foram depositados entre 1940 e 1982 por pesquisadores e associados do Instituto Max-Planck de Limnologia em Plön, Alemanha Ocidental.

O âmbito de aplicação material da legislação de proteção de dados pessoais e o tratamento de imagem por pessoa singular

Images have gained a never before seen importance. Technological changes have given the Information Society extraordinary means to capture, treat and transmit images, wheter your own or those of others, with or without a commercial purpose, with no boundaries of time or country, without “any kind of eraser”. From the several different ways natural persons may engage in image processing with no commercial purpose, the cases of sharing pictures through social networks and video surveillance assume particular relevance. Consequently there are growing legitimate concerns with the protection of one's image, since its processing may sometimes generate situations of privacy invasion or put at risk other fundamental rights. With this in mind, the present thesis arises from the question: what are the existent legal instruments in Portuguese Law that enable citizens to protect themselves from the abusive usage of their own pictures, whether because that image have been captured by a smartphone or some video surveillance camera, whether because it was massively shared through a blog or some social network? There is no question the one's right to not having his or her image used in an abusive way is protected by the Portuguese constitution, through the article 26th CRP, as well as personally right, under the article 79th of the Civil Code, and finally through criminal law, articles 192nd and 193rd of the Criminal Code. The question arises in the personal data protection context, considering that one's picture, given certain conditions, is personal data. Both the Directive 95/46/CE dated from 1995 as well as the LPD from 1998 are applicable to the processing of personal data, but both exclude situations of natural persons doing so in the pursuit of activities strictly personal or family-related. These laws demand complex procedures to natural persons, such as the preemptive formal authorisation request to the Data Protection National Commission. Failing to do so a natural person may result in the application of fines as high as €2.500,00 or even criminal charges. Consequently, the present thesis aims to study if the image processing with no commercial purposes by a natural person in the context of social networks or through video surveillance belongs to the domain of the existent personal data protection law. To that effect, it was made general considerations regarding the concept of video surveillance, what is its regimen, in a way that it may be distinguishable from Steve Mann's definition of sousveillance, and what are the associated obligations in order to better understand the concept's essence. The application of the existent laws on personal data protection to images processing by natural persons has been analysed taking into account the Directive 95/46/CE, the LPD and the General Regulation. From this analysis it is concluded that the regimen from 1995 to 1998 is out of touch with reality creating an absence of legal shielding in the personal data protection law, a flaw that doesn't exist because compensated by the right to image as a right to personality, that anyway reveals the inability of the Portuguese legislator to face the new technological challenges. It is urgent to legislate. A contrary interpretation will evidence the unconstitutionality of several rules on the LPD due to the obligations natural persons are bound to that violate the right to the freedom of speech and information, which would be inadequate and disproportionate. Considering the recently approved General Regulation and in the case it becomes the final version, the use for natural person of video surveillance of private spaces, Google Glass (in public and private places) and other similar gadgets used to recreational purposes, as well as social networks are subject to its regulation only if the images are shared without limits or existing commercial purposes. Video surveillance of public spaces in all situations is subject to General Regulation provisions.

Enraizamento de estacas de material juvenil de Pau-rosa (Aniba rosaeodora Ducke - Lauraceae)

RESUMOO presente, trabalho teve como objetivo o enraizamento de estacas de material juvenil ramos laterais e terminais) de pau-rosa, através do uso das concentrações de 2000 ppm, 4000 ppm e 6000 ppm de ácido indol-3-butírico (AIB) na forma líquida. Αs condições do enraizamento αs estacas foram oferecidas mediante o uso de ncbulização intermitente, regulada em 20 segundos para espécies com intervalos de 20 minutos. O substrato utilizado foi terriço + areia, na proporção de 4:1. Semanalmente foram feitas aplicações de fertilizante foliar. Aos 210 dias do plantio, as estacas foram retiradas, do substrato e avaliados os seguintes parâmetros: porcentagem de enraizamento, porcentagem de sobrevivência, tamanho das raízes e Peso da matéria fresca das raízes. Os resultados obtidos mostram que a emissão de raízes das estacas de material juvenil, possivelmente independe do uso do ácido indol-3-butírico (AIB).

Sources to study Antiquity: Between texts and material culture. Abstract Book

FCT

Estratégias pedagógicas na aprendizagem da emissão de som no clarinete: respiração, material e metodologias de estudo

Relatório de estágio de mestrado em Ensino de Música

Produtos têxteis inteligentes incorporando filamentos compósitos com nanotubos de carbono

Programa Doutoral em Engenharia Têxtil.

Thin panels of cement composites reinforced with recycled fibres for the shear strengthening of reinforced concrete elements

A new technique was developed for producing thin panels of a cement based material reinforced with relatively high content of steel fibres originated from the industry of tyre recycling. Flexural tests with notched and un-notched specimens were carried out to characterize the mechanical properties of this Fibre Reinforced Cement Composite (FRCC) and the results are presented and discussed. The values of the fracture mode I parameters of the developed FRCC were determined by performing inverse analysis with test results obtained in three point notched beam bending tests. To appraise the potentialities of these FRCC panels for the increase of the shear capacity of reinforced (RC) beams, numerical research was performed on the use of developed FRCC panel for shear reinforcement by applying the panels in the lateral faces of RC beams deficiently reinforced in shear.

Design formula for the flexural strengthening of RC beams using prestressed CFRP reinforcement

Applying a certain prestress level to the carbon fiber reinforced polymer (CFRP) reinforcement according to either externally bonded reinforcing (EBR) or near surface mounted (NSM) techniques can mobilize the strengthening potentialities of this high tensile strength composite material. For the prediction of the flexural behavior of reinforced concrete (RC) structures strengthened with prestressed EBR or NSM CFRPs, however, simplified analytical and design formulations still need to be developed as a guidance for engineers to design this type of strengthened structures by hand calculation without any programming help. Hence, the current work aims to briefly explain a developed simplified analytical approach, with a design framework, to predict the flexural behavior of RC beams flexurally strengthened with either prestressed EBR or NSM CFRP reinforcements. Moreover, an upper limit for the prestress level is proposed in order to optimize the ductility performance of the NSM prestressing technique. The good predictive performance of the analytical approaches was appraised by simulating the results of experimental programs composed of RC beams strengthened with prestressed NSM CFRP reinforcements.

Embedded Through-Section shear strengthening technique using steel and CFRP bars in RC beams of different percentage of existing stirrups

The Embedded Through-Section (ETS) technique is a promising technique for the shear strengthening of existing (RC) elements. According to this technique, holes are drilled through the beam section, and bars of steel or FRP material are introduced into these holes and bonded to the concrete with adhesive materials. An experimental program was carried out with RC T-cross section beams strengthened in shear using the ETS steel bars and ETS CFRP rods. The research is focused on the evaluation of the ETS efficiency on beams with different percentage of existing internal transverse reinforcement (ρsw=0.0%, ρsw=0.1% and ρsw=0.17%). The effectiveness of different ETS strengthening configurations was also investigated. The good bond between the strengthening ETS bars and the surrounding concrete allowed the yield initiation of the ETS steel bars and the attainment of high tensile strains in the ETS CFPR rods, leading to significant increase of shear capacity, whose level was strongly influenced by the inclination of the ETS bars and the percentage of internal transverse reinforcement.

Shear strengthening of damaged reinforced concrete beams with hybrid composite plates

This paper aims to evaluate experimentally the potentialities of Hybrid Composite Plates (HCPs) technique for the shear strengthening of reinforced concrete (RC) beams that were previously subjected to intense damage in shear. HCP is a thin plate of Strain Hardening Cementitious Composite (SHCC) reinforced with Carbon Fiber Reinforced Polymer (CFRP) laminates. For this purpose, an experimental program composed of two series of beams (rectangular and T cross section) was executed to assess the strengthening efficiency of this technique. In the first step of this experimental program, the control beams, without steel stirrups, were loaded up to their shear failure, and fully unloaded. Then, these pre-damaged beams were shear strengthened by applying HCPs to their lateral faces by using a combination of epoxy adhesive and mechanical anchors. The bolts were applied with a certain torque in order to increase the concrete confinement. The obtained results showed that the increase of load carrying capacity of the damaged strengthened beams when HCPs were applied with epoxy adhesive and mechanical anchors was 2 and 2.5 times of the load carrying capacity of the corresponding reference beams (without HCPs) for the rectangular and T cross section beam series, respectively. To further explore the potentialities of the HCPs technique for the shear strengthening, the experimental tests were simulated using an advanced numerical model by a FEM-based computer program. After demonstration the good predictive performance of the numerical model, a parametric study was executed to highlight the influence of SHCC as an alternative for mortar, as well as the influence of torque level applied to the mechanical anchors, on the load carrying capacity of beams strengthened with the proposed technique.