Polioxometalatos: dos agregados moleculares a redes e materiais

Esta dissertação teve como objectivo principal a preparação de novos materiais luminescentes contendo lantanopolioxometalatos. Foram utilizados polioxometalatos (POMs) do tipo Keggin, Wells-Dawson e [Ln(M5O18)2]9- com M (VI) = W, Mo contendo diferentes iões lantanídeo. Foram sintetizados materiais híbridos orgânico-inorgânicos com base em lantanopolioxometalatos e ligandos orgânicos. O efeito da coordenação destes ligandos orgânicos na luminescência dos iões lantanídeo (efeito de antena) foi investigado para os ácidos picolínico e 3-hidroxipicolínico. Os estudos de fotoluminescência destes materiais permitiram mostrar a existência de um processo de sensitização da emissão dos iões lantanídeo através de fenómenos de transferência de energia dos ligandos e do POM para o centro emissor. No caso particular dos materiais híbridos contendo POMs do tipo Wells-Dawson, a introdução do ligando orgânico levou à intensificação da absorção de energia através do POM, a qual era praticamente inexistente nos correspondentes lantanopolioxometalatos. Prepararam-se nanocompósitos do tipo “core/shell” contendo POMs e híbridos orgânico-inorgânicos como núcleo rodeados por uma camada de sílica. Os nanocompósitos preparados apresentam uma estrutura “core/shell” bem definida com um diâmetro médio de aproximadamente 35 nm. As técnicas de microscopia electrónica, nomeadamente o mapeamento por EDX, permitiram confirmar a presença dos POMs no núcleo das nanopartículas de sílica. A biofuncionalização destes nanocompósitos com um anticorpo foi estudada, com vista à potencial aplicação destes sistemas como biomarcadores ópticos. Os estudos de microscopia de fluorescência permitiram observar a emissão do Eu3+ presente nas nanopartículas biofuncionalizadas com o anticorpo, utilizando excitação na zona do ultravioleta. Estes resultados reforçam a viabilidade da aplicação destes sistemas como marcadores celulares em alternativa a “quantum dots” e corantes orgânicos. No âmbito dos nanomateriais, foi também preparado um material constituído por partículas de Na9[Eu(W5O18)2] de dimensões nanométricas, utilizando micelas invertidas como nanoreactores, de forma a limitar o tamanho das partículas. Foi realizada a preparação de novos materiais lamelares luminescentes por intercalação de POMs e respectivos materiais híbridos em argilas aniónicas de zinco e alumínio. A intercalação foi realizada através de um método de troca aniónica directa usando uma argila contendo nitrato como anião precursor. O estudo por difracção de raios-X revelou-se uma técnica fundamental na caracterização destes materiais, nomeadamente através da determinação da altura de galeria. A partir deste parâmetro foi possível verificar a orientação da espécie intercalada na argila. No caso da intercalação do anião do tipo Keggin, o estudo por RMN de 31P MAS permitiu identificar a espécie intercalada na argila. As propriedades de luminescência foram estudadas para a generalidade dos novos materiais preparados.

O vidro como material plástico: transparência, luz, cor e expressão

A presente tese de doutoramento procura focar o vidro como material plástico para a concepção de obras de arte. Os seus alicerces caracterizam-se pelo estudo técnico sobre o uso do vidro e a sua aplicação na realização de obras com pressupostos estéticos e artísticos. Hoje a arte em vidro apresenta-se inovadora e contemporânea, procurando uma componente ligada à pesquisa e à experimentação. Portugal possui uma ampla história ligada à tradição do vidro, em especial ao vitral. No que concerne à sua aplicação na arte contemporânea, assistimos a um renovado interesse por parte de vários artistas. No entanto, quando se trabalha com o vidro, é necessário o artista conhecer e dominar a técnica que utiliza, para assim compreender as potencialidades que o material oferece e empregá-las de acordo com o seu modus operandi. Cria-se uma relação entre a ciência e a arte, uma descoberta e utilização de novos conhecimentos, em que se pretende manter uma relação estreita entre o cientista e o artista através do desenvolvimento de novos materiais, nomeadamente os vidros e esmaltes luminescentes e a adição de óxidos de metais de transição 3d na sua composição. Neste sentido foram desenvolvidos estudos minuciosos sobre a técnica de kilncasting onde se utilizou o vidro sonoro superior produzido no CRISFORM (Centro de Formação Profissional para o Sector da Cristalaria), na Marinha Grande. Assim, verifica-se que as premissas desta tese podem ser divididas em três vertentes: a) Uma contextualização histórica e teórica do panorama artístico do vidro em Portugal; b) Uma componente teórica/prática do estudo do vidro: a ciência do vidro, a sua composição, com a preocupação de utilizar esses conhecimentos para a elaboração de amostras práticas, onde a componente técnica é fundamental para a produção de futuras obras de arte; c) A idealização de obras de arte e a utilização do vidro como material plástico para a sua realização. Na elaboração destas obras procurou-se focar a dicotomia entre transparência versus opacidade, os efeitos cromáticos produzidos por diferentes espessuras e texturas do vidro, assim como da monocromia versus policromia, esta última através do vidro e esmaltes luminescentes. Em suma, na complementaridade laboratório/ateliê, os segredos da matéria abrem novas fronteiras à criatividade estética.

Piñatex, the design development of a new sustainable material

This is a research project by practice, which firstly develops a new material invention derived from natural fibres extracted from waste pineapple leaves; secondly it articulates the contemporary designer’s role in facilitating sustainable solutions through: Insights from my own material invention, PiñatexTM, which integrates the materiality of design with the immateriality of concepts and values Developing a visual model of mapping I began with these questions: ‘What are the challenges in seeking to make a new and sustainable material from the waste products of pineapple agriculture in the Philippines?’ and ‘How can a design practice link elements of materiality (artifacts) with immaterial elements (value systems) in order to improve sustainable social and economic development?’ Significant influences have been the work of Papanek1 (2003), Hawken2 (1999) and Abouleish3 (2008) and in particular the ethical business model initiated by McDonough and Braungart in Cradle to Cradle®4 (2002). My own research project is inspired by the Cradle to Cradle® model. It proposes the development of a new material, PiñatexTM which is derived from natural fibres extracted from waste pineapple leaves and could be used in a wide variety of products that are currently fabricated in leather or petroleum-based materials. The methods have comprised: Contextual reviews; case studies (SEKEM, Cradle to Cradle® and Gawad Kalinga); practical experiments in the field of natural fibres, chemistry, product development, manufacturing and prototyping, leading to an invention and a theoretical model of mapping. In addition, collaboration has taken place across scientific, technological, social, ecological, academic and business fields. The outcome is a new material based on the synchronicity between the pineapple fibres, polymers, resins and coatings specially formulated. The invention of the new material that I developed as a central part of this research by practice has a patent in the national phase (PCT/GB 2011/000802) and is in the first stages of manufacturing, commercial testing and further design input (Summer 2014). The contribution to knowledge is firstly the material, PiñatexTM, which exhibits certain key qualities, namely environmentally non-toxic, biodegradable, income-generating potential and marketability. This is alongside its intrinsic qualities as a textile product: aesthetic potential, durability and stability, which will make it suitable for the accessories, interiors and furnishing markets. The theoretical mapping system Upstream and Downstream forms a secondary contribution.

Mid-Century Molecular: The Material Culture of X-ray Crystallographic Visualisation across Postwar British Science and Industrial Design

This thesis investigates the use and significance of X-ray crystallographic visualisations of molecular structures in postwar British material culture across scientific practice and industrial design. It is based on research into artefacts from three areas: X-ray crystallographers’ postwar practices of visualising molecular structures using models and diagrams; the Festival Pattern Group scheme for the 1951 Festival of Britain, in which crystallographic visualisations formed the aesthetic basis of patterns for domestic objects; and postwar furnishings with a ‘ball-and-rod’ form and construction reminiscent of those of molecular models. A key component of the project is methodological. The research brings together subjects, themes and questions traditionally covered separately by two disciplines, the history of design and history of science. This focus necessitated developing an interdisciplinary set of methods, which results in the reassessment of disciplinary borders and productive cross-disciplinary methodological applications. This thesis also identifies new territory for shared methods: it employs network models to examine cross-disciplinary interaction between practitioners in crystallography and design, and a biographical approach to designed objects that over time became mediators of historical narratives about science. Artefact-based, archival and oral interviewing methods illuminate the production, use and circulation of the objects examined in this research. This interdisciplinary approach underpins the generation of new historical narratives in this thesis. It revises existing histories of the cultural transmissions between X-ray crystallography and the production and reception of designed objects in postwar Britain. I argue that these transmissions were more complex than has been acknowledged by historians: they were contingent upon postwar scientific and design practices, material conditions in postwar Britain and the dynamics of historical memory, both scholarly and popular. This thesis comprises four chapters. Chapter one explores X-ray crystallographers’ visualisation practices, conceived here as a form of craft. Chapter two builds on this, demonstrating that the Festival Pattern Group witnesses the encounter between crystallographic practice, design practice and aesthetic ideologies operating within social networks associated with postwar modernisms. Chapters three and four focus on ball-and-rod furnishings in postwar and present-day Britain, respectively. I contend that strong relationships between these designed objects and crystallographic visualisations, for example the appellation ‘atomic design’, have been largely realised through historical narratives active today in the consumption of ‘retro’ and ‘mid-century modern’ artefacts. The attention to contemporary historical narratives necessitates this dual historical focus: the research is rooted in the period from the end of the Second World War until the early 1960s, but extends to the history of now. This thesis responds to the need for practical research on methods for studying cross-disciplinary interactions and their histories. It reveals the effects of submitting historical subjects that are situated on disciplinary boundaries to interdisciplinary interpretation. Old models, such as that of unidirectional ‘influence’, subside and the resulting picture is a refracted one: this study demonstrates that the material form and meaning of crystallographic visualisations, within scientific practice and across their use and echoes in designed objects, are multiple and contingent.

Bio-synthesis of nanosized semiconductors using mine wastes as material sources

This work describes the synthesis of nanosized metal sulfides and respective SiO2 and/or TiO2 composites in high yield via a straightforward process, under ambient conditions (temperature and pressure), by adding to aqueous metals a nutrient solution containing biologically generated sulfide from sulfate-reducing bacteria (SRB). The nanoparticles‘ (NPs) morphological properties were shown not to be markedly altered by the SRB growth media composition neither by the presence of bacterial cells. We further extended the work carried out, using the effluent of a bioremediation system previously established. The process results in the synthesis of added value products obtained from metal rich effluents, such as Acid Mine Drainage (AMD), when associated with the bioremediation process. Precipitation of metals using sulfide allows for the possibility of selective recovery, as different metal sulfides possess different solubilities. We have evaluated the selective precipitation of CuS, ZnS and FeS as nanosized metal sulfides. Again, we have also tested the precipitation of these metal sulfides in the presence of support structures, such as SiO2. Studies were carried out using both artificial and real solutions in a continuous bioremediation system. We found that this method allowed for a highly selective precipitation of copper and a lower selectivity in the precipitation of zinc and iron, though all metals were efficiently removed (>93% removal). This research has also demonstrated the potential of ZnS-TiO2 nanocomposites as catalysts in the photodegradation of organic pollutants using the cationic dye, Safranin-T, as a model contaminant. The influence of the catalyst amount, initial pH and dye concentration were also evaluated. Finally, the efficiency of the precipitates as catalysts in sunlight mediated photodegradation was investigated, using different volumes of dye-contaminated water (150 mL and 10 L). This work demonstrates that all tested composites have the potential to be used as photocatalysts for the degradation of Safranin-T.

Preserving southern history material : an address before the Southern Club of Columbia University, July 31, 1923

This publication is a short address made by William H. Kilpatrick to the Southern Club of Columbia University calling on Southerners to gather and preserve their own history.

As coisas da casa: cultura material, migrações e memórias familiares

Este livro corresponde, no essencial, à investigação que realizei no âmbito do doutoramento em Antropologia Social e Cultural da Universidade Nova de Lisboa e que terminei em 2007. Publicar um trabalho desta natureza quase dez anos após a sua conclusão foi uma tarefa simultaneamente complexa e entusiasmante. Por um lado, obrigou a revisões intensas e cortes substanciais, bem como à leitura de materiais que não tinham sido usados aquando da primeira redação e à consulta de trabalhos que entretanto foram sendo publicados sobre temas afins. Por outro, permitiu descobrir aspetos originais e olhar para detalhes que tinham passado despercebidos na primeira versão do trabalho e reforçaram a argumentação desenvolvida.

Interrupting the courtroom organism: screaming bodies, material affects and the theatre of cruelty

This article offers a method of reading the courtroom which produces an alternative mapping of the space. My method combines a reading of Antonin Artaud’s Theatre of Cruelty with a Deleuzian theoretical analysis. I suggest that this is a useful method since it allows examination of the spatial praxes of the courtroom which pulsate with a power to organize, terrorize and to judge. This method is also able to conceptualize the presence of ‘‘screaming’’ bodies and living matter which are appropriated to build, as well as feed the presence and functioning of the courtroom space, or organism. By using a method that articulates the cry of these bodies in the shadow of the organism, it becomes clear that this cry is both unwelcome and suppressed by the courtroom. The howl of anxious bodies enduring the process and space of the law can be materialized through interruptions to the courtroom, such as when bodies stand when they should not and when they speak when they should be silent. These vociferous actualizations of the scream serve only to feed the organism they seek to disturb, yet if the scream is listened to before it disrupts, the interruption becomes-imperceptible to the courtroom. Through my Artaudian/Deleuzian reading, I give a voice to the corporeal gasp that lingers before the cry, which is embedded within the embodied multiplicity from which it is possible to draw a creative line of flight. The creative momentum of this line of flight produces a sustainable interruption to the courtroom process, which instead of being consumed by the system, has the potential to produce new courtroom alignments. My text therefore offers an alternative reading of the courtroom, and in doing so also offers a refined understanding of how to productively ‘‘interrupt’’ the courtroom process.

Flesh of the Law: Material Metaphors

Existing legal metaphors, even the predominantly spatial and corporeal ones, paradoxically perpetuate a dematerialized impression of the law. This is because they depict the law as universal, adversarial, and court-based, thus ignoring alternative legalities. Instead, there is a need to employ more radically material metaphors, in line with the material turn in law and other disciplines, in order to allow law's materiality to come forth. I explore the connection between language and matter (the ‘flesh’ of the law) through legal, linguistic, and art theory, and conclude by suggesting four characteristics of material legal metaphors.

Introduction: The ‘material turn’ in migration studies

This introduction firstly discusses the ongoing paradigm shift in the study of transnational migration, in particular the emergent interest in the convergence of migration and material culture as the starting point of our investigation. Then it highlights three aspects that this Special Issue could further in the current study of migration and materialities: namely, historical consciousness in materialising migration experiences and the notion of generational transmission; the everyday experience of body as the site for mutual constitution between subject and object; and the unique value of a language-based, interdisciplinary-oriented approach for migration studies. In the final part, it summarizes the four articles that follow, highlighting the contribution that each makes to our overall objective of making a ‘material turn’ in migration studies, and discusses some ways it could be further developed.

Contribuição para o conhecimento sobre o efeito da utilização de material pozolânico no fabrico de betão

O presente trabalho, realizado no âmbito da Tese de Mestrado, tem como principal objectivo estudar as características pozolânicas dos materiais da zona de Arganil para substituição parcial do cimento Portland com o objectivo de intensificar certas qualidades devido à diminuição da porosidade do betão. Estas qualidades são interessantes quando se procura maior durabilidade. Para tal, foram realizados diversos ensaios para a caracterização física, química e mineralógica dos produtos. Os metacaulinos utilizados foram obtidos de amostras de argila submetidas a calcinação (750oC, durante uma hora), processo que permitiu a desidroxilação quase total da matéria-prima, transformando esta numa fase amorfa e irreversível, com propriedades pozolânicas. São apresentados os resultados dos ensaios de caracterização da matéria-prima, das condições de calcinação e do produto resultante da desidroxilação, nomeadamente a determinação da pozolanicidade e superfície específica e das características fundamentais para a aplicabilidade do produto. Descreve ainda o emprego do metacaulino em betões de resistência convencional. Estudou-se a influência do emprego do metacaulino (15% de substituição de cimento, em massa) na resistência à flexão e à compressão (aos 28 dias) em argamassas e o emprego de metacaulino (10%, 15% e 20% de substituição de cimento, em massa) na resistência à compressão (3, 7 e 28 dias) no betão.

Aço em varão para betão armado: caracterização do material e enquadramento atual

Dissertação para obtenção do grau de Mestre em Engenharia Civil

Role of abrasive material on micro-abrasion wear tests

Micro-abrasion wear tests with ball-cratering configuration are widely used. Sources of variability are already studied by different authors and conditions for testing are parameterized by BS EN 1071-6: 2007 standard which refers silicon carbide as abrasive. However, the use of other abrasives is possible and allowed. In this work, ball-cratering wear tests were performed using four different abrasive particles of three dissimilar materials: diamond, alumina and silicon carbide. Tests were carried out under the same conditions on a steel plate provided with TiB2 hard coating. For each abrasive, five different test durations were used allowing understanding the initial wear phenomena. Composition and shape of abrasive particles were investigated by SEM and EDS. Scar areas were observed by optical and electronic microscopy in order to understand the wear effects caused by each of them. Scar geometry and grooves were analyzed and compared. Wear coefficient was calculated for each situation. It was observed that diamond particles produce well-defined and circular wear scars. Different silicon carbide particles presented dissimilar results as consequence of distinct particle shape and size distribution.