Implementação da análise dos modos de falha e seus efeitos no processo de fabricação de peças em material compósito

Dissertação para obtenção do Grau de Mestre em Engenharia e Gestão Industrial

Gestão soft da manutenção de automotoras UQE-S3500: aplicação de modelos de risco proporcionais

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia e Gestão Industrial.

O Mobiliário do Antigo Egipto no Império Novo. Análise Material e Simbólica

A presente dissertação reflecte a compilação de um estudo essencialmente bibliográfico e iconográfico de doze peças de mobiliário do antigo Egipto, Império Novo. É primeiramente apresentado um breve estudo sobre materiais usados para a construção dos diversos objectos produzidos no referido período histórico e analisados os seus aspectos simbólicos. São também apresentadas sucintamente algumas técnicas de construção adoptadas durante as dinastias XVIII-XX para a construção de mobiliário doméstico e ritual. De seguida estes objectos são analisados material e simbolicamente em dois capítulos tendo como base a investigação efectuada. Colocam-se ao longo deste trabalho diversas questões, sendo as mais prementes “se terá havido transferência de mobiliário doméstico para o contexto funerário” e “Terão tido os espólios funerários mobiliário feito exclusivamente para esse fim”. As conclusões revelam dados comparativos do universo de peças de mobiliário recolhidas e apresentam algumas hipóteses explicativas sobre o assunto abordado.

Application of NMR RDC’s, relaxation and self-diffusion for the study of dynamic processes of small molecules in solution

Spin-lattice Relaxation, self-Diffusion coefficients and Residual Dipolar Couplings (RDC’s) are the basis of well established Nuclear Magnetic Resonance techniques for the physicochemical study of small molecules (typically organic compounds and natural products with MW < 1000 Da), as they proved to be a powerful and complementary source of information about structural dynamic processes in solution. The work developed in this thesis consists in the application of the earlier-mentioned NMR techniques to explore, analyze and systematize patterns of the molecular dynamic behavior of selected small molecules in particular experimental conditions. Two systems were chosen to investigate molecular dynamic behavior by these techniques: the dynamics of ion-pair formation and ion interaction in ionic liquids (IL) and the dynamics of molecular reorientation when molecules are placed in oriented phases (alignment media). The application of NMR spin-lattice relaxation and self-diffusion measurements was applied to study the rotational and translational molecular dynamics of the IL: 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4]. The study of the cation-anion dynamics in neat and IL-water mixtures was systematically investigated by a combination of multinuclear NMR relaxation techniques with diffusion data (using by H1, C13 and F19 NMR spectroscopy). Spin-lattice relaxation time (T1), self-diffusion coefficients and nuclear Overhauser effect experiments were combined to determine the conditions that favor the formation of long lived [BMIM][BF4] ion-pairs in water. For this purpose and using the self-diffusion coefficients of cation and anion as a probe, different IL-water compositions were screened (from neat IL to infinite dilution) to find the conditions where both cation and anion present equal diffusion coefficients (8% water fraction at 25 ºC). This condition as well as the neat IL and the infinite dilution were then further studied by 13C NMR relaxation in order to determine correlation times (c) for the molecular reorientational motion using a mathematical iterative procedure and experimental data obtained in a temperature range between 273 and 353 K. The behavior of self-diffusion and relaxation data obtained in our experiments point at the combining parameters of molar fraction 8 % and temperature 298 K as the most favorable condition for the formation of long lived ion-pairs. When molecules are subjected to soft anisotropic motion by being placed in some special media, Residual Dipolar Couplings (RDCs), can be measured, because of the partial alignment induced by this media. RDCs are emerging as a powerful routine tool employed in conformational analysis, as it complements and even outperforms the approaches based on the classical NMR NOE or J3 couplings. In this work, three different alignment media have been characterized and evaluated in terms of integrity using 2H and 1H 1D-NMR spectroscopy, namely the stretched and compressed gel PMMA, and the lyotropic liquid crystals CpCl/n-hexanol/brine and cromolyn/water. The influence that different media and degrees of alignment have on the dynamic properties of several molecules was explored. Different sized sugars were used and their self-diffusion was determined as well as conformation features using RDCs. The results obtained indicate that no influence is felt by the small molecules diffusion and conformational features studied within the alignment degree range studied, which was the 3, 5 and 6 % CpCl/n-hexanol/brine for diffusion, and 5 and 7.5 % CpCl/n-hexanol/brine for conformation. It was also possible to determine that the small molecules diffusion verified in the alignment media presented close values to the ones observed in water, reinforcing the idea of no conditioning of molecular properties in such media.

Avaliações in vitro da utilização da gelatina como material de suporte à regeneração de tecidos

Neste trabalho foram produzidas matrizes de nanofibras de gelatina de porco e de gelatina de peixe através da técnica de electrofiação. Estas matrizes têm uma estrutura morfológica e química interessantes para o desenvolvimento de scaffolds no âmbito da Engenharia de Tecidos mas a sua instabilidade em água compromete essa aplicação. Assim, as matrizes foram reticuladas recorrendo a dois processos diferentes: um físico (tratamento desidrotérmico - DHT) e outro químico (exposição a vapor de glutaraldeído - GTA). Os resultados obtidos permitiram verificar que a gelatina de porco reticulou mais facilmente que a gelatina de peixe, provavelmente devido a uma maior presença de grupos funcionais capazes de reagir com os processos de reticulação. Foram analisados possíveis efeitos citotóxicos das matrizes reticuladas em culturas de células Vero. Os extratos das matrizes não revelaram ser tóxicos mas o tratamento com GTA comprometeu a adesão das células às matrizes indicando acarretar um certo risco de toxicidade. O uso da glicina revelou-se eficaz na redução dessa toxicidade. Para além das matrizes de fibras sem orientação preferencial (depositadas num coletor plano), foram depositadas fibras paralelamente alinhadas recorrendo a um coletor cilíndrico rotatório. Marcações fluorescentes de células semeadas nos dois tipos de fibras revelaram que o citoesqueleto das células semeadas nas fibras alinhadas se organiza na direção do alinhamento.

Analysis, testing and development of safe cleaning methods of rusted stone material

Three different treatments were applied on several specimens of dolomitic and calcitic marble, properly stained with rust to mimic real situations (the stone specimens were exposed to the natural environment for about six months in contact with rusted iron). Thirty six marble specimens, eighteen calcitic and eighteen dolomitic, were characterized before and after treatment and monitored throughout the cleaning tests. The specimens were characterized by SEM-EDS (Scanning Electron Microscopy coupled with Energy Dispersion System), XRD (XRay Diffraction), XRF (X-Ray Fluorescence), FTIR (Fourier Transform Infrared Spectroscopy) and color measurements. It was also made a microscopic and macroscopic analysis of the stone surface along with the tests of short and long term capillary absorption. A series of test trials were conducted in order to understand which concentrations and contact times best suits to this purpose, to confirm what had been written to date in the literature. We sought to develop new methods of treatment application, skipping the usual methods of applying chemical treatments on stone substrates, with the use of cellulose poultice, resorting to the agar, a gel already used in many other areas, being something new in this area, which possesses great applicability in the field of conservation of stone materials. After the application of the best methodology for cleaning, specimens were characterized again in order to understand which treatment was more effective and less harmful, both for the operator and the stone material. Very briefly conclusions were that for a very intense and deep penetration into the stone, a solution of 3.5% of SDT buffered with ammonium carbonate to pH around 7 applied with agar support would be indicated. For rust stains in its initial state, the use of Ammonium citrate at a concentration of 5% buffered with ammonium to pH 7 could be applied more than once until satisfactory results appear.

Cellulose nanorods in liquid crystalline elastomers for improved actuators

Nanotechnology plays a central role in ‘tailoring’ materials’ properties and thus improving its performances for a wide range of applications. Coupling nature nano-objects with nanotechnology results in materials with enhanced functionalities. The main objective of this master thesis was the synthesis of nanocrystalline cellulose (NCCs) and its further incorporation in a cellulosic matrix, in order to produce a stimuli-responsive material to moisture. The induced behaviour (bending/unbending) of the samples was deeply investigated, in order to determine relationships between structure/properties. Using microcrystalline cellulose as a starting material, acid hydrolysis was performed and the NCC was obtained. Anisotropic aqueous solutions of HPC and NCC were prepared and films with thicknesses ranging from 22μm to 61μm were achieved, by using a shear casting technique. Microscopic and spectroscopic techniques as well as mechanical and rheological essays were used to characterize the transparent and flexible films produced. Upon the application of a stimulus (moisture), the bending/unbending response times were measured. The use of NCC allowed obtaining films with response times in the order of 6 seconds for the bending and 5 seconds for the unbending, improving the results previously reported. These promising results open new horizons for building up improved soft steam engines.

Soft biomaterials as a substitute for the Nucleus Pulposus

One of the largest health problems faced worldwide, when evaluated by direct (clinical) as well indirect cost (absenteeism), is the degeneration of the intervertebral disc (IVD) that leads to back pain and, potentially disability and individual´s quality of life decreasing. The intervertebral disc is a mechanical and biological complex structure, formed by a tough outer layer of fibrocartilage called Annulus Fibrosus (AF),which surrounds a soft, elastic and gelatinous core called Nucleus Pulposus (NP). These two structures are completed by two upper and lower encasing layer called Vertebral Endplates (VEP). The degeneration of the IVD is marked by the dehydration of the Nucleus Pulposus, reducing the hydrostatic pressure inside the nucleus, resulting in a loss of capability to support compressive forces, during the active period, and to regain height during the resting period. This situation will compromise the role of shock absorber by the NP and transfers these forces to the AF. This transfer will result in cracks on the AF, deteriorating the IVD, allowing the ingrowth of vessels and nerves. This project was based on the developing a protocol to test suitable NP replacements, in hope to future assessment of discrete mechanical values and characteristics for an NP replacement. For this, Nucleus pulposus samples from goat, encapsulated Hydromed gel denominated “Raviolis” and Chitosan gels, produced via wet route using an ammonium environment, were confined compressed. Chitosan was rheologically tested and swelling capability of all the three type of materials was assessed. Results showed that the Nucleus Pulposus and “Raviolis” have similar mechanical behavior, being able to swell and “build up” hydrostatic pressure after a compression stage, while the Chitosan gel did not showed that ability. Therefore, “Raviolis” are a more suitable candidate to replace the NP than Chitosan gels. It was also observed that confined compression is the key test to perform on any possible candidate to replace the NP.

Evaluation of mechanical soft-abrasive blasting and chemical cleaning methods on alkyd-paint graffiti made on carbonate stones

In the context of this dissertation several studies were developed resulting in submission and publication “Evaluation of mechanical soft-abrasive blasting and chemical cleaning methods on alkyd-paint graffiti made on calcareous stones” to Journal of Cultural Heritage. (http://dx.doi.org/10.101 /j.culher.2014.10.004)

Produção de misturas betuminosas a quente com incorporação de material fresado

A incorporação de materiais reciclados na construção de estradas, como substituição de materiais virgens é percebida como uma oportunidade de economizar recursos, e evitar o impacto associado à sua extração e transporte. Desta forma, a incorporação de material fresado (do termo inglês RAP - Reclaimed Asphalt Pavement) em misturas betuminosas produzidas a quente em central tem sido uma alternativa satisfatória. Neste trabalho, foram estudadas três misturas betuminosas do tipo macadame betuminoso (AC 20 base 35/50), tradicional e com taxas de incorporação de RAP de 10% e 20%, com o objetivo de efetuar uma análise comparativa do seu comportamento. Começou-se por realizar um estudo Marshall de forma a determinar a percentagem ótima de betume a usar em cada mistura e, posteriormente, a composição foi transposta para central para o seu fabrico. No final foram realizados ensaios de caracterização mecânica sobre as misturas para avaliar o seu desempenho, através de ensaios de sensibilidade à água, módulo de rigidez, resistência à fadiga e à deformação permanente. Esta dissertação teve o apoio da empresa Tecnovia – Sociedade de Empreitadas S.A., com a disponibilização de instalações e materiais para o trabalho experimental. De acordo com os resultados obtidos, é possível concluir que as misturas recicladas apresentaram um comportamento satisfatório, quando comparado com as misturas tradicionais.

Conservar depois da catástrofe. O caso dos documentos queimados do antigo Arquivo Histórico do Museu Bocage: caracterização material e proposta de um protocolo de intervenção

Tendo como caso de estudo um conjunto documental do Arquivo Histórico dos Museus da Universidade de Lisboa (AHMUL) – Museu Nacional de História Natural e da Ciência (MUHNAC), anteriormente fazendo parte do antigo Arquivo Histórico do Museu Bocage – fortemente atingido por um incêndio em 1978, o objectivo principal desta investigação é dar início à pesquisa e explorar a possibilidade de aplicação de métodos não invasivos de restauro digital, como a técnica de digitalização volumétrica (volumetric scanning), para a recuperação da informação escrita na parte mais deteriorada do arquivo; e propor métodos de estabilização/recuperação do seu suporte físico, usando técnicas tradicionais de conservação e restauro. Assim, o objectivo deste estudo não é apenas rever métodos de recuperação da informação para estes documentos tidos como perdidos, mas também propor uma forma de recuperar, tanto quanto possível, o seu suporte original. Será realizada a caracterização material da colecção, com recurso a métodos de exame e análise e o diagnóstico de conservação da parte da colecção mais deteriorada, bem como uma contextualização histórica sobre o arquivo e as condições do incêndio. Como conclusões principais salienta-se a confirmação da possibilidade de aplicação de técnicas de digitalização, os resultados promissores de outras técnicas como a fotografia de infravermelho com recurso adicional a software de processamento da imagem e o uso da imagem multiespectral em documentos carbonizados, além do estabelecimento de uma proposta de protocolo de intervenção para documentos queimados, com recurso a dois éteres de celulose, com diferentes solventes (água e etanol) de acordo com a solubilidade dos meios de escrita. Pretendeu-se ainda com este estudo contribuir para a divulgação da existência deste fundo do AHMUL em específico, tendo sido fundamental a realização, após 37 anos, do primeiro registo e compilação de fontes documentais sobre o incêndio de 18 de março de 1978, um facto tão relevante para a Memória do MUHNAC e dos Museus de Portugal.

AS COSTUREIRAS, AS QUEENS E OS SEUS MANTOS: DESTERRITORIALIZAÇÃO, CULTURA MATERIAL E CONSTRUÇÃO DO LUGAR

Durante as décadas de 1980 e de 1990 a noção de lugar foi, na literatura antropológica, sujeita a uma abordagem crítica que debateu as dimensões metodológicas e conceptuais envolvidas na sua construção. No seguimento dessa abordagem, surgiram propostas de trabalho que, de maneiras muito diversas, conseguiram ultrapassar as limitações das concepções mais clássicas da figura do lugar. Essas propostas revelaram, no entanto, que mesmo quando estamos face a uma lógica de desterritorialização, a figura do lugar pode reaparecer (embora obviamente transmutada, visto construir-se no interior de outras lógicas sociais, culturais e económicas). Partindo de uma etnografia realizada na Ilha do Pico, o texto explora algumas das inovações, provenientes dos EUA no início do século XX, que foram introduzidas nas Festas do Espírito Santo. A principal inovação prende-se com a emergência de novos personagens: as rainhas (“queens”) coroadas durante o ritual, seguidas pelas costureiras indispensáveis à confecção dos seus vestidos e mantos. Centrado nos processos de feitura dos mantos, o texto pretende mostrar como a cultura material local se constrói e se transforma no interior de um movimento transcontinental constante de pessoas, rituais, coisas e técnicas. Num contexto transnacional, a mobilidade das pessoas pode objetificar-se em coisas que são feitas localmente, participando assim a desterritorialização na construção do lugar.

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.