Made available in DSpace on 2014-10-09T12:55:24Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:07:13Z (GMT). No. of bitstreams: 0 / Este trabalho trata da avaliação da compressibilidade de misturas de pós de nióbio e alumínio, previamente ativadas por moagem de bolas de alta energia. Foram variados o tempo de moagem e a quantidade de ácido esteárico, adicionado como agente controlador de processo (ACP), assim como o tamanho médio de partícula do pó de alumínio. Os pós de partida e as misturas moídas foram caracterizados por microscopia eletrônica de varredura (forma das partículas) e por difração de raios laser (distribuição granulométrica). Uma máquina universal de ensaios foi utilizada nos testes de compressibilidade mediante compactação das amostras numa matriz cilíndrica de aço-ferramenta. Os dados de compressibilidade foram comparados graficamente segundo curvas de densidade (relativa) versus pressão. As diferenças de comportamento na compactação das amostras foram correlacionadas com as diferentes condições de moagem. Houve um decréscimo da compressibilidade com o aumento do tempo de moagem e da quantidade de ACP. Menos compressíveis foram também as misturas provenientes do pó de alumínio com maior tamanho de partícula. Uma nova equação de compactação foi ainda proposta, cujo ajuste aos dados deste trabalho foi superior aos verificados nas equações de modelos anteriormente publicados. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

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Orientador: Paulo Mazzafera / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Biologia / Made available in DSpace on 2018-08-13T02:41:43Z (GMT). No. of bitstreams: 1 Bottcher_Alexandra_M.pdf: 1074089 bytes, checksum: 5190092093a682d1c16cfe9c85d37e3f (MD5) Previous issue date: 2009 / Resumo: A ferritina é uma proteína que armazena átomos de ferro (Fe) em uma forma não tóxica, controlando o nível desse metal nas células. Em humanos, a ferritina também é capaz de se ligar ao alumínio (Al), evitando sua toxicidade. Como o cafeeiro consegue crescer adequadamente em solos ácidos, com níveis elevados de Al, e células em suspensão tratadas com esse mesmo metal têm expressão aumentada de genes que codificam para ferritina, há a possibilidade dessa proteína se complexar ao Al também em plantas. Na indução da síntese da ferritina em suspensões celulares de Coffea arabica cv. Mundo Novo com 300 e 1.200 µmol/L de sulfato ferroso observou-se um aumento de 8,9 e 18,2 vezes, respectivamente, do RNAm CaFer1 da ferritina, em relação ao controle. Já o tratamento com 5 mmol/L de sulfato de alumínio-potássio resultou na diminuição de 4,57 vezes na expressão desse gene, em relação ao controle. Para Coffea arabica cv. Icatu, todos os tratamentos resultaram na queda da expressão de CaFer1, sendo que essa diminuição foi de 29,0 e 6,3 vezes para as células tratadas com 300 e 1.200 µmol/L de sulfato ferroso, respectivamente, e de 98,0 vezes para o tratamento com 5 mmol/L de sulfato de alumínio-potássio, em relação ao controle. Esses mesmos tratamentos não induziram, em ambas as cultivares, expressão diferencial significativa de outro gene da ferritina analisado, o CaFer2. Os resultados do Western Blot mostraram certa concordância com esses resultados. Assim como em outras plantas, a ferritina de células em suspensão de cafeeiro responde à presença do Fe, entretanto, devido ao não acúmulo dessa proteína nas células submetidas ao tratamento com 5 mmol/L de sulfato de alumínio-potássio, provavelmente, a ferritina não esteja envolvida na complexação desse metal no cafeeiro ou a concentração utilizada foi elevada, o que pode ter causado danos nos ácidos nucléicos ou impedido a transcrição normal dos genes. Nas análises in silico utilizando CaFer1 e CaFer2 de C. arabica e os genes da ferritina de C. canephora e C. racemosa, observaram-se alta similaridade entre CaFer1 e a ferritina de C. canephora e entre CaFer2 e a ferritina de C. racemosa. Por fim, os ensaios com as enzimas antioxidantes superóxido dismutase (SOD), catalase (CAT), glutationa S-transferase (GST), glutationa redutase (GR) e guaiacol peroxidase (GPOX) revelaram que as culturas celulares de Mundo Novo foram mais responsivas aos tratamentos aplicados, exceto em relação à GST, que foi a enzima que apresentou atividade mais acentuada para Icatu. Além disso, observou-se que a resposta enzimática foi dose dependente e que as duas cultivares utilizaram vias distintas para defesa celular contra espécies ativas de oxigênio. / Abstract: Ferritin is a protein capable to store iron (Fe) atoms in a nontoxic form, controlling the level of this metal in the cells. In humans, ferritin is able to accommodate aluminium (Al) atoms, avoiding its toxicity. Considering that Coffea arabica plants are able to grow well in acidic soils with high Al and suspension cells treated with this same metal showed high ferritin gene expression, it is possible that this protein is also able to complex Al atoms in planta. The induction of ferritin synthesis in suspension cells of C. arabica cv. Mundo Novo with 300 and 1.200 µmol/L of ferrous sulphate revealed an increase of 8,9 and 18,2 times, respectively, of transcripts of ferritin gene CaFer1, as compared with the control. The treatment with 5 mmol/L of aluminium-potassium sulphate resulted in the reduction of 4,57 times the expression of this gene, as compared with the control. In cells from the Icatu cultivar all treatments resulted in reduction of the expression of CaFer1. This decrease was about 29,0 and 6,3 times in cells treated with 300 and 1.200 µmol/L of ferrous sulphate, respectively, and 98,02 times in the treatment with 5 mmol/L of aluminium-potassium sulphate, as compared with the control. For both varieties, these same treatments did not result in significant differential expression of the other ferritin gene analyzed, CaFer2. Western Blots data were in agreement with this observation. Therefore, ferritin expression in suspension cells of Coffea plants responds to Fe, as shown for other plants, however, on account of the no accumulation of ferritin in both cultivars treated with 5 mmol/L of aluminium-potassium sulphate, possibly this protein is not involved with Al complexation in C. arabica plants or the level of Al used was sufficiently high to provoke damages in the nucleic acids or to impair the normal transcription of the genes. An in silico analysis carried out with CaFer1 and CaFer2 from C. arabica and with ferritin genes of the Coffea canephora and Coffea racemosa revealed high similarity between CaFer1 and C. canephora ferritin, and CaFer2 with C. racemosa ferritin. Finally, assays of the antioxidant enzymes superoxide dismutase (SOD), catalase (CAT), glutathione S-transferase (GST), glutathione reductase (GR), and guaiacol peroxidase (GPOX) revealed that cell cultures of the Mundo Novo variety are more responsive to the treatments with the metals, except for GST, wich was the only enzyme with higher activity in cells from the Icatu cultivar. Furthermore, it was observed that enzymatic response was dose dependent and that Mundo Novo and Icatu used distinct mechanisms to protect cells against reactive oxygen species. / Mestrado / Mestre em Biologia Vegetal

This research work studies the influence of zinc on surface treatments such as mechanical polishing, anodic alkaline etching, alkaline etching and electropolishing. Solid-solution binary alloys containing 0.6, 1.0 and 1.9at.%Zn were investigated using scanning and transmission electron microscopies and ion beam analysis. Initially, the near-surface composition of the surface pretreated aluminium alloys were determined using Rutherford backscattering spectroscopy (RBS), medium energy ion scattering (MEIS) and glow discharge optical spectroscopy (GDOES). Subsequently, the surface morphologies of the pretreated specimens were characterized by secondary electron microscopy (SEM) and atomic force microscopy (AFM). Further related work was undertaken on the effect of the employed surface treatments on the anodic behaviour of aluminium-zinc alloys. A final analysis was carried out on the influence of grain orientation on zinc enrichment and surface morphologies of aluminium-zinc alloys developed during alkaline etching.The results reveal that surface pretreatments of aluminium-zinc alloys lead to zinc enrichment at the alloy/film interface. The number of zinc atoms contained in the enriched layer depends upon the employed surface pretreatment and the alloy composition. Surface pretreatments influence the topography of Al-Zn alloys. In particular, for electropolishing, alkaline etching and anodic alkaline etching, the resultant surface morphologies were associated with the oxidation-dissolution-precipitation mechanisms occurring at the alloy/film interface and at the film/solution interface. Anodizing of Al-Zn alloys shows that the anodic films growth on Al-Zn alloys in rolled condition and after surface treatment becomes detached from the substrate independently of the surface treatment employed, although detachment of the anodic film occur earlier on surface pre-treated Al-Zn alloys that developed zinc enrichment. The final studies correlated the mechanisms of oxidation and dissolution with the grain orientation. The result revealed that the (111) grain dissolves faster than other grains, while the higher number of zinc enriched atoms were measured on the (001) grain.

The effect of microstructure on corrosion resistance and anodising behaviour of a 3rd generation lithium-containing aluminium alloy, AA 2099-T8, has been studied. Microstructural characterisation of the alloy has shown elongated grains with high angle grain boundaries and approximately equiaxed subgrains with low angle grain boundaries. Two types of constituent particles of high and reduced contents of copper were found, which are present individually or in the form of multiphase particles. The alloy also contains rod-like Al-Cu-Mn-Li and spherical (Al3Zr) dispersoids, and fine age hardening precipitates of T1 (Al2CuLi), (Al3Li) and (Al2Cu).Immersion testing in a chloride-containing solution revealed two types of localised corrosion sites: one was initiated from intermetallics and quickly became passivated; the other lasted for the course of testing, with extensive boundary attack. The latter has been correlated to grains and subgrains with relatively high stored energy.Alkaline etching removed intermetallics from alloy surface; generated a copper-enriched layer in the alloy matrix immediately beneath the residual alumina film; and gradually developed a surface nanotexture. The surface nanotexture has been correlated to the formation of copper-rich nanoparticles within the copper-enriched layer.Anodising the alloy in tartaric-sulphuric acid disclosed that copper in the alloy matrix could be occluded in the anodic film material as copper-rich nanoparticles or be oxidized and incorporated into the film material as copper ions, depending on the anodising voltage. In the latter case, the process was accompanied by oxygen gas generation within the film material, forming anodic films with lateral porosity. Intermetallics of different compositions behaved differently during anodising, leading to modification of the morphology and composition of anodic films. Concerning the effect of alkaline etching on anodising behaviour of the alloy, the removal of intermetallics increased anodising efficiency; the pre-developed copper-enriched layer advanced the establishment of the steady-state film/alloy interface. Variation of copper-enriched layer structure is revealed by the detection of copper-rich nanoparticles in the copper-enriched layer. The copper-rich nanoparticles have structures consistent with either θ", θ' or θ phases. Machining damage can be detected not only by chromic acid anodising (CAA) but also by tartaric-sulphuric acid anodising (TSAA). Neither CAA nor TSAA can be used for detecting shallow corrosion pits.

Carbon dioxide emissions must be dramatically reduced to avoid the potentially dangerous effects of climate change. The steel and aluminium industries produce large amounts of carbon dioxide, accounting for 6% of anthropogenic emissions. Previous studies have shown that in these industries there is limited scope for further improvements in energy efficiency. Material efficiency strategies can, however, further reduce emissions. This thesis focuses on materially efficient reuse without melting. A scoping study of current reuse found three opportunities, an examination of which forms the basis of this thesis: reusing components at end of product life; extending the lifespan of products; and reusing manufacturing scrap. The opportunity to reuse components has received little attention to date and there is no clearly defined set of strategies or barriers to enable assessment of appropriate component reuse; neither is it possible to predict future levels of reuse. This thesis presents a global assessment of the potential for reusing steel and aluminium components. A combination of top-down and bottom-up analyses is used to allocate the final destinations of current global steel and aluminium production to final products. A substantial catalogue has been compiled for these products characterizing key features of steel and aluminium components including design specifications, requirements in use, and current reuse patterns. To estimate the fraction of end-of-life metal components that could be reused for each product, the catalogue formed the basis of a set of semi-structured interviews with industrial experts. The results suggest that approximately 30% of steel and aluminium used in current products could be reused. Barriers against reuse are examined, prompting recommendations for redesign that would facilitate future reuse. In order to understand how product lifespans can be extended it must first be understood why products are replaced. A simple framework with which to analyse failure is applied to the products that dominate steel use, finding that they are often replaced because a component/sub-assembly becomes degraded, inferior, unsuitable or worthless. In light of this, four products, which are representative of high steel content products in general, are analysed at the component level, determining profiles of cumulative steel mass over the lifespan of each product. The results show that the majority of the steel components are underexploited – still functioning when the product is discarded. In particular, the potential lifespan of the steel-rich structure is typically much greater than its actual lifespan. Evidence from twelve case studies, in which product or component life has been increased, is used to tailor life-extension strategies to each reason for product failure, providing practical guidelines for designers. There is currently no commercial method of reusing small manufacturing scrap; however, previous research has demonstrated that extruded profiles can be created from small clean aluminium scrap, the scrap fragments solid-state welding together when extruded. In order to evaluate potential applications for these profiles four case studies are conducted in collaboration with aluminium producers and product manufacturers. It was found that strong and formable profiles could be produced from scrap. However, contaminated scrap sources, unreliable bonding and poor surface quality limited their potential for commercial use. No model exists for solid-state weld strength that is applicable to scrap extrusion. This prevents optimisation of the existing extrusion process and the development of new, potentially better, processes. Subsequently, this thesis presents a new model of weld strength as a function of relevant deformation parameters. The model is evaluated using a new experiment in which the deformation conditions can be varied independently. The experiments establish the basic relationships between deformation parameters and weld strength. The model correctly predicts these trends with predicted weld strengths typically lying within the experimental error range. The technical assessment of reuse presented in this thesis demonstrates the scope of potential change. If implemented, the opportunities presented would greatly increase the reuse of steel and aluminium, reducing the emissions emitted from liquid metal production in conventional recycling.

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