>Magister Scientiae - MSc / The main aim of this study is to investigate theelectrochemical determination of two beneficial (selenium and zinc) and two toxic (chromium and vanadium) metals in the potable water within the City of Cape Town's distribution area. The Water Laboratory of the City's Scientific Services Branch analyses for these metals in their elemental state, using the Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES). This is a standard method used for the detection of trace metals. The most sensitive voltammetric method for determining these metals is by adsorptive stripping voltammetry, using a thin mercury film electrode with a glassy carbon support. This voltammetric method is used for quantitative determination of specific ionic species. Because of mercury's toxicity it is not really favoured for trace metals anymore. Many other possibilities are under investigation, e.g. bismuth-film, modified glassy carbon and antimony electrodes. The boron-doped diamond (BDD) electrode has distinct advantages when used to determine metal concentrations. Advantages of BDD electrodes include lower detection limit, speciation and wider potential window. In this study cyclic voltammetry (CV) was used to determine the copper, cadmium and lead concentrations in potable water by means of square wave voltammetry (SWV) and a bare glassy carbon electrode (GCE). Furthermore, a boron-doped diamond electrode (BDDE) was used to investigate the possibilities of determining selenium, chromium and vanadium by SWV. Real samples (potable water samples) were analysed electrochemically to qualify and quantify these metals and determine whether they comply with the SANS 241:2006 drinking water guidelines.The copper, cadmium, lead and selenium peaks appear very close to the theoretical values, which indicate that these metals can be detected by SWV method, but further analysis with more samples is advised. Even though responses were observed for vanadium and chromium, it was not reliable and requires further investigation. Further studies into the analyses of zinc are also advised.

Abstract In this thesis work, crystal and phase structure, chemical composition and gas sensing properties of pulsed laser deposited vanadium oxide thin films were studied. Pulsed laser deposition was used to manufacture vanadium oxide thin films with various crystal structures, film morphologies and phase compositions. Both the well-known vanadium pentoxide V2O5, and a totally new stable phase in a solid-state thin-film form, V7O16, was produced. The existence of these phases was proven by several different characterization methods such as, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. The resistive gas sensing measurements of the films with pure V2O5 composition, and mixed phase compositions of V2O5 and V7O16, showed that behaviour of the electrical response to different gases at various measurement temperatures was dependent on the phase composition of the thin films. It was proved that in certain conditions the mixed phase films show p-type semiconducting gas sensing behaviour, instead of the pure n-type behaviour of V2O5. Both types of film compositions were shown to be highly sensitive to ammonia gas, down to 40 ppb-level. The mixed phase composition showed a higher response to ammonia compared to the pure V2O5 phase; however the pure V2O5 showed better long-term stability. Both sensing layer types also showed high selectivity to ammonia in comparison to NO and CO gases. Nanostructured pure V2O5 layers were successfully deposited on commercial microheater platforms and then used as a gas sensor. The V2O5 nanostructures were proven to be very promising candidates as gas sensor material to control the Selective Catalytic Reduction process used in the reduction of NOx gas emissions. The surface valence states of the thin film structures with various phase compositions were studied spectroscopically, and a clear connection between the valence states of the film surfaces and gas sensing properties was found. It was concluded that the pure V2O5 films also had some V4+ ions in the surface, and in the mixed phase thin films, the amount V4+ ions was already quite high, indicating a higher amount of oxygen vacancies in the thin film surface – another proof of the existence of V7O16 phase in the film composition. It is also suggested that the particular quantity of oxygen vacancies is one of the reasons for the high gas-sensing response of the thin films. / Tiivistelmä Tässä työssä tutkittiin pulssilaserkasvatettujen vanadiinioksidiohutkalvojen kide- ja faasirakenteita sekä ominaisuuksia kaasuantureina. Vanadiinioksidiohutkalvoja, jotka omaavat erilaiset kide- ja faasirakenteet, sekä erilaiset morfologiat valmistettiin pulssilaserkasvatuksella. Tunnetun V2O5 -faasin lisäksi myös V7O16 -faasi onnistuttiin valmistamaan ensimmäistä kertaa kiinteän aineen epäorgaanisena faasina ohutkalvorakenteeseen. Näiden erilaisten faasirakenteiden olemassaolo todistettiin käyttämällä useita menetelmiä kuten röntgendiffraktiota, Raman spektroskopiaa ja röntgenfotoelektronispektroskopiaa. Sekä ainoastaan V2O5 -faasia sisältäviä ohutkalvoja, että V2O5 ja V7O16 sekafaasirakenteen omaavia ohutkalvoja tutkittiin kaasuanturina, ja mittaustulokset osoittivat erilaisten kalvojen sähköisten kaasuanturivasteiden ominaisuuksien voimakkaan riippuvuuden kalvojen faasirakenteesta. Havaittiin myös, että sekafaasirakenne omaa tietyissä olosuhteissa p-tyyppisen puolijohteen sähkönjohtavuusmekanismin, toisin kuin puhdas V2O5-rakenne, joka on täysin n-tyyppinen. Molemmat ohutkalvotyypit todennettiin olevan erityisen herkkiä ammoniakki (NH3) kaasulle, jopa 40 miljardisosatasolle. Kalvo, jossa oli sekafaasirakenne, omasi korkeamman sähköisen kaasuvasteen kuin puhtaasta V2O5 faasista koostuva ohutkalvo, joka taas toisaalta omasi paremman stabiiliuden pidemmällä aikavälillä. Molemmat kaasuanturimateriaalit havaittiin selektiiviseksi NH3 -kaasulle verrattuna NO- ja CO-kaasuihin. Puhdas V2O5 nanorakenne onnistuttiin myös kasvattamaan kaupalliselle anturialustalle, ja käyttämään menestyksekkäästi herkkänä NH3- kaasuanturina. Lisäksi puhtaan V2O5 nanorakenteen todennettiin olevan erittäin lupaava kaasuanturimateriaali hyödynnettäväksi NOx-kaasupäästöjen vähentämiseen käytettävän SCR-katalyysiprosessin (Selective Catalytic Reduction) ohjauksessa. Ohutkalvotyyppien pinnan sähköistä rakennetta tutkittiin röntgenspektroskopiamenetelmillä, ja selvä yhteys materiaalien pintojen valenssitilojen ja kaasuanturiominaisuuksien välillä havaittiin. Huomattiin, että myös puhdas V2O5 ohutkalvo omaa pinnallaan pienen määrän V4+ -ioneja, ja että ohutkalvossa, jossa on sekafaasirakenne, V4+ -ionien määrä on suuri, ollen yksi todiste lisää V7O16 faasin olemassaoloon kalvon rakenteessa. Tästä johtuva happivakanssien olemassaolo on yksi syy näiden ohutkalvojen korkeaan kaasuherkkyyteen.

Submitted by Edileide Reis (leyde-landy@hotmail.com) on 2013-04-23T13:14:32Z No. of bitstreams: 1 Raphael Holt.pdf: 5449117 bytes, checksum: 052b88f3a4242aebdef5fdf978a8b5ce (MD5) / Made available in DSpace on 2013-04-23T13:14:32Z (GMT). No. of bitstreams: 1 Raphael Holt.pdf: 5449117 bytes, checksum: 052b88f3a4242aebdef5fdf978a8b5ce (MD5) Previous issue date: 2008 / A principal rota utilizada industrialmente para a produção de estireno é a desidrogenação catalítica do etilbenzeno, responsável por mais de 90% da produção mundial de estireno. O processo industrial é operado na faixa de temperatura de 550-700 oC, em excesso de vapor d’água aquecido, sobre catalisadores de óxido de ferro promovidos com potássio e cromo, que são tóxicos e possuem vida útil limitada a 2 anos. Neste contexto, existe a demanda por catalisadores que sejam ativos e seletivos nessa reação e que apresentem elevada vida útil, além de não serem tóxicos. Na busca de sistemas alternativos, neste trabalho foram desenvolvidos catalisadores de vanádio e magnésio suportados em carvão ativado obtido pela pirólise do copolímero estireno-divinilbenzeno, em atmosfera não oxidativa. Os catalisadores foram caracterizados pela medida da área superficial específica e de porosidade, difração de raios X, termogravimetria, análise térmica diferencial, espectrofotometria de absorção atômica, microscopia eletrônica de varredura acoplada ao sistema de quantificação por energia dispersiva. Os catalisadores foram avaliados na desidrogenação do etilbenzeno em ausência de vapor d’água, a 530 oC e 1 atm, para a produção de estireno. Verificou-se a presença de trióxido de vanádio e de aglomerados de vanádio e magnésio de diferentes tamanhos, nos sólidos. Os materiais apresentaram isotermas de adsorção e dessorção de nitrogênio do Tipo II ou IV, que são típicas de sólidos meso e macroporos com microporos associados, e uma histerese do Tipo H I, característica de materiais com poros cilíndricos. Estes sólidos apresentaram áreas superficiais específicas entre 378 e 611 m2/g. Os catalisadores com vanádio e magnésio apresentaram menor perda da área superficial específica que o carvão ativado, durante a desidrogenação do etilbenzeno. A adição de magnésio e vanádio provocou um aumento da atividade catalítica do carvão ativado e da seletividade ao estireno. Todos catalisadores foram mais ativos que uma amostra de catalisador comercial. O catalisador contendo 5 % de vanádio foi o mais promissor. Esta amostra conduziu, em ausência de vapor d’água, 35% de conversão do etilbenzeno, que é cerca de três vezes o valor obtido com uma amostra de catalisador comercial em presença de vapor d’água. Isto foi atribuído à ação catalítica do vanádio e à presença de grupos oxigenados na superfície do carvão que possuem atividade na desidrogenação do etilbenzeno. / Salvador

Orientador: Prof. Dr. Mauro Coelho dos Santos / Dissertação (mestrado) - Universidade Federal do ABC. Programa de Pós-Graduação em Ciência e Tecnologia/Química, 2015. / No presente trabalho foram desenvolvidos eletrocatalisadores de materiais nanoestruturados à base de V/C (vanádio/carbono) para estudo da Reação de Redução de Oxigênio (RRO) por dois métodos: o Método dos Precursores Poliméricos (MPP) e o Método Sol-Gel (MSG). Estes materiais foram preparados com variação da proporção em massa de vanádio de 1%, 3%, 5% 7%, 10% e 13% em suporte de carbono Vulcan XC 72R. Para cada método foi comparada a diferença da atividade catalítica no que se refere à formação do peróxido de hidrogênio (H2O2) pela RRO via dois elétrons tendo como referência os resultados de corrente de anel obtidos nos testes dos materiais, utilizando-se a técnica de eletrodo de disco-anel rotatório. Os materiais mais promissores referentes a cada metodologia de síntese apresentaram resultados bastante semelhantes. O eletrocatalisador nanoestruturado com 3 % de vanádio em suporte de carbono produzido pelo MSG mostrou maior eficiência em relação ao Vulcan XC 72R, com a transferência de 2,2 elétrons e eletrogeração de 89% de H2O2 na RRO. Utilizando o MPP, o eletrocatalisador nanoestruturado com 7% de vanádio em carbono apresentou maior atividade catalítica, transferindo 2,2 elétrons e eletrogerando 91% de H2O2 na RRO. Os materiais foram caracterizados fisicamente por Difratometria de 10 Raios X (DRX), que indicou principalmente a formação de V2O5 na superfície do suporte, sendo que seu caráter ácido pode facilitar a formação de H2O2. As imagens obtidas por Microscopia Eletrônica de Transmissão (MET) sugerem que os materiais são amorfos e com tamanho de partículas sub-microscópicos. As proporções de vanádio que obtiveram melhores resultados para cada método foram caracterizadas por Espectroscopia Fotoeletrônica de Raios-X (XPS: X-Ray Photoelectron Spectroscopy), sendo possível determinar a composição química da estrutura superficial da camada, confirmando a presença do V2O5 na superfície dos mesmos, bem como das espécies oxigenadas ácidas. Este fator contribuiu para o aumento da hidrofilicidade, facilitando a adsorção de gás oxigênio na superfície do eletrocatalisador, e potencializando a formação de H2O2. Ambos os materiais também foram avaliados quanto ao seu ângulo de contato e molhabilidade em relação ao carbono Vulcan XC 72R, mostrando que a adição do vanádio na superfície do carbono, em ambos os métodos, aumentou sua hidrofilicidade, e favorece a eletrogeração do H2O2. / In this work were developed electrocatalysts of nanostructured materials based on V/C (vanadium/carbon) prepared by two methods, Polymeric Precursors Method (PPM) and the Sol-Gel Method (SGM), to study the oxygen reduction reaction (ORR). These materials were prepared with 1%, 3%, 5%, 7%, 10% and 13% of vanadium load on carbon Vulcan XC 72R support. For each method, the difference on catalytic activity was compared with regard to the hydrogen peroxide (H2O2) formation by ORR via two electrons. Similar results on H2O2 electrogeneration were obtained for both methods. The catalytic activity for ORR was studied using a rotating ring-disk electrode. The nanostructured electrocatalyst with 3% of vanadium on carbon produced by SGM showed greater efficacy compared to Vulcan XC 72R, with transfer of 2.2 electrons and 89% of H2O2 electrogeneration in ORR. Related to PPM, the nanostructured electrocatalyst with 7% vanadium on carbon showed higher catalytic activity, transferring 2.2 electrons and electrogenerating 91% of H2O2 in ORR. The materials were characterized physically by X-ray diffractometry (XRD), which indicated mainly the formation of V2O5 on the support surface, and its acidic character assists to the H2O2 formation. The images obtained by Transmission Electron Microscopy (TEM) suggest that the materials are amorphous and present 12 sub-microscopic particles size. The vanadium loads which presented the best results for each method were characterized by X-Ray Photoelectron Spectroscopy (XPS), it being possible to determine the chemical composition of the surperficial layer structure, confirming the presence of V2O5 on the surface thereof, and the oxygenated acid species. This factor contributes to the increased hydrophilicity, facilitating the adsorption of oxygen gas on the electrocatalyst surface, and enhancing the H2O2 formation. These materials were also evaluated from the contact angle and wettability, indicating that the addition of vanadium on the carbon surface increases the hydrophilicity and promotes the increase in H2O2 electrogeneration, for both methods.

Este trabalho, realizado em cooperação com a Gerdau Riograndense, tem por finalidade avaliar o comportamento do aço GG1013-M, um aço baixo teor de carbono microligado com vanádio e manganês, na laminação a quente no que tange a sua resistência à deformação, possibilitando assim a tomada de decisão em relação a modificações no processo. Foram realizados testes em simulador termomecânico Gleeble™ para determinação das temperaturas a serem usadas no teste prático no laminador, onde testou-se lotes que cobrissem toda a amplitude da faixa de composição química da qualidade do aço em estudo. No teste prático no laminador, foram retiradas amostras para os ensaios mecânicos, onde identificou-se, por intermédio do tratamento de dados em software estatístico, a influência da variação dentro da faixa da composição química sobre os limites de escoamento e resistência. Como resultado, conseguiu-se determinar a faixa de temperatura mais provável, onde a resistência a deformação a quente é menor, minimizando ou eliminando as conseqüências da redução de ductilidade a quente por conta do endurecimento da matriz por precipitação dos elementos de liga em forma de compostos. / This work was conducted in cooperation with Gerdau Riograndense aiming at the evaluation of the hot rolling behavior of a low carbon steel microalloyed with manganese and vanadium (internally GG1013-M steel).The deformation resistance was evaluated, allowing for the decision in relation to changes in the process. A thermomechanical simulator GleebleTM was used to determine the temperatures to be used in practical tests in the rolling mill, where it was tested different material batches covering the large range of chemical compositions for this kind of steel. Mechanical tests were performed on samples taken from the practical tests in the rolling mill. From this tests the influence of chemical composition variation on the yeld strength and maximum stress was studied. As a result, we were able to determine the most likely range of temperatures for a minimization of hot strentgh, therefore also minimizing or eliminating the consequences of the reduction in the hot ductility due precipitation hardening of the matrix.

abstract: Arsenic (As) is a naturally occurring element that poses a health risk when continually consumed at levels exceeding the Environmental Protection Agencies (EPA) maximum contaminant level (MCL) of 10 ppb. With the Arizona Department of Water Resources considering reliance on other sources of water other than just solely surface water, groundwater proves a reliable, supplemental source. The Salt River Project (SRP) wants to effectively treat their noncompliance groundwater sources to meet EPA compliance. Rapid small-scale column tests (RSSCTs) of two SRP controlled groundwater wells along the Eastern Canal and Consolidated Canal were designed to assist SRP in selection and future design of full-scale packed bed adsorbent media. Main concerns for column choice is effectiveness, design space at groundwater wells, and simplicity. Two adsorbent media types were tested for effective treatment of As to below the MCL: a synthetic iron oxide, Bayoxide E33, and a strong base anion exchange resin, SBG-1. Both media have high affinity toward As and prove effective at treating As from these groundwater sources. Bayoxide E33 RSSCT performance indicated that As treatment lasted to near 60,000 bed volumes (BV) in both water sources and still showed As adsorption extending past this operation ranging from several months to a year. SBG-1 RSSCT performance indicated As, treatment lasted to 500 BV, with the added benefit of being regenerated. At 5%, 13%, and 25% brine regeneration concentrations, regeneration showed that 5% brine is effective, yet would complicate overall design and footprint. Bayoxide E33 was selected as the best adsorbent media for SRP use in full-scale columns at groundwater wells due to its simplistic design and high efficiency. / Dissertation/Thesis / Masters Thesis Civil and Environmental Engineering 2015

[pt] A cromatografia líquida de alta eficiência hifenada por injeção em fluxo com espectrometria de massa com plasma indutivamente acoplado (HPLC-FI-ICP-MS) foi utilizada para investigar vanádio ligado a porfirinas presente em frações de óleo cru. Em primeiro lugar, a amostra de óleo cru foi submetida a um fracionamento por meio de cromatografia líquida preparativa com detecção em UV-Vis, no comprimento de onda da banda Soret da porfirina (400 nm). As frações de porfirina obtidas foram então separadas numa coluna única de 250 mm, no HPLC e eluídas com fases móveis diferentes, metanol ou metanol:tolueno (80:20; v:v). A quantificação de V-porfirinas nas frações eluídas do HPLC foi feita pela medida do isótopo 51V no ICP-MS, usando-se soluções-padrão de octaetil-porfirina de vanádio (VO-OEP), preparados no mesmo solvente usado na fase móvel, e injetados pós-coluna diretamente no plasma. Um padrão de Ge em metanol (20 microgramas L−1) foi utilizado como padrão interno para minimizar interferências não-espectrais, tais como oscilações devido à injeção. O tratamento matemático do sinal com base no algoritmo de suavização do tipo Transformada Rápida de Fourier (FFT) foi utilizado para melhorar a precisão. As concentrações de V como V-porfirinas foram entre 2,7 e 11 mg kg-1 nas frações, valores próximos à concentração total de V nas frações de óleo cru estudadas. / [en] High performance liquid chromatography hyphenated by flow injection to inductively coupled plasma mass spectrometry (HPLC–FI–ICP-MS) was used to investigate vanadium linked to porphyrins present in fractions of crude oil. First, the crude oil sample was submitted to fractionation by preparative liquid chromatography with UV-Vis detection, at the porphyrin Soret band wavelength (400 nm). The obtained porphyrin fractions were then separated in a 250 mm single column, in the HPLC, and eluted with different mobile phases, methanol or methanol:toluene (80:20; v:v). The quantification of V-porphyrins in the fractions eluted from HPLC was carried out by online measuring the 51V isotope in the ICP-MS, against vanadyl octaethylporphine standard solutions (VO-OEP), prepared in the same solvent as the mobile phase, and injected post-column directly into the plasma. A 20 micrograms L−1 Ge in methanol was used as internal standard for minimizing non-spectral interference, such as short-term variations due to injection. The mathematical treatment of the signal based on Fast Fourier Transform (FFT) smoothing algorithm was employed to improve the precision. The concentrations of V as V-porphyrins were between 2.7 and 11 mg kg−1 in the fractions, which were close to the total concentration of V in the fractions of the studied crude oil.

The estimated global production of red mud, a by-product of alumina production, is ~120 million t per year. Little is known about the long-term chemical, physical and ecological responses in aquatic ecosystems following pollution with red mud. To date, no whole-lake assessment of the impact of red mud and recovery trajectories has been conducted. Kinghorn Loch, Fife, Scotland, is an important example of a red mud polluted aquatic ecosystem. This is due mainly to the availability of long-term data documenting changes in the lake during the pollution and recovery following diversion of red mud leachate in 1983 to date. Long-term data were assessed to determine the time scale of recovery for a range of specific pollutants in the surface waters of Kinghorn Loch, and field surveys and a laboratory controlled experiment were conducted to investigate lake sediment-pollutant interactions and arsenic (As) species bioaccumulation in aquatic plants. Results showed recovery of the lake water column, with a significant decrease of pH and the concentrations of all red mud constituents in surface water since the cessation of pollution. Using generalised additive models the chemical recovery period was 5 years for pH and from 22 to 26 years for As, vanadium (V) and phosphorus (P), with aluminium (Al) still not reaching the end-point recovery following this period. A 12- month field survey showed that concentrations of phosphate (PO4-P), total phosphorus (TP), dissolved and total As and V in lake water varied significantly throughout the year, with depth of overlying water contributing to variation in P concentrations in water above sediment. A range of physico-chemical factors, including dissolved oxygen (DO), pH and concentrations of pollutant binding element controlled seasonal and spatial variations in water column contaminant concentrations. The behaviour of V differed from As and P concentrations in water, with maximum V concentrations occurring in spring and the highest concentrations of As and P in surface water and dissolved As and PO4-P in water above sediment observed in summer. With the exception of V in deeper layers of the water column in spring and winter, observed total As and V concentrations met standards for Protection of Aquatic Life in the UK (50 and 20 μg L-1, respectively). Sediment in Kinghorn Loch is still contaminated 30 years into the lake recovery period. The highest seasonal mean concentrations in the upper (0-4 cm) sediment layer were 231 mg kg-1 for V and 185 mg kg-1 for As, the latter considerably exceeding Canadian Sediment Quality Guidelines for the Protection of Aquatic Life for As (17 mg kg-1). Evidence from the laboratory experiment and the field observations suggests that the lake still processes red mud contaminants, with seasonal mobilisation of As and P from lake sediment under reducing conditions. In contrast, release of V from sediment into overlying water appeared not to be driven predominantly by redox conditions, but instead by interactions between pH, competitive ion concentrations and DO. Higher pollutant concentrations observed throughout the year in deeper layers of the water column compared to surface water indicated that the impact of sediment on the water column is generally confined to the bottom waters of the lake. Macrophytes in Kinghorn Loch contained relatively high concentrations of As, predominantly in the inorganic form which is most toxic to organisms. The highest As content measured in roots of Persicaria amphibia (L.) Gray (40.4 – 218 mg kg-1) greatly exceeded the 3 – 10 mg kg-1 range suggested as a potential phytotoxic level. Accumulation of toxic As species by plants suggested toxicological risk to higher organisms in the food web and indicated that ecological recovery of the lake is still in progress. The results of this research at Kinghorn Loch will help water resource managers to understand not only the environmental and human health effects of multiple pressures related to red mud pollution, but also the likely recovery time scales in relation to water quality targets.

Submitted by Bruna Carolina Costa (prabrunah@hotmail.com) on 2018-06-17T15:27:22Z No. of bitstreams: 1 Tese Final - CostaBC.pdf: 9813307 bytes, checksum: 06e43540e98bad04c9faaccaa3e9e5c9 (MD5) / Approved for entry into archive by Lucilene Cordeiro da Silva Messias null (lubiblio@bauru.unesp.br) on 2018-06-18T18:45:24Z (GMT) No. of bitstreams: 1 costa_bc_dr_bauru.pdf: 9671307 bytes, checksum: b57db2112606e04abdeb6cef0449e963 (MD5) / Made available in DSpace on 2018-06-18T18:45:25Z (GMT). No. of bitstreams: 1 costa_bc_dr_bauru.pdf: 9671307 bytes, checksum: b57db2112606e04abdeb6cef0449e963 (MD5) Previous issue date: 2018-04-20 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Dentre os biomateriais metálicos, largamente empregados pela indústria biomédica, o titânio (Ti) e suas ligas, principalmente o sistema Ti-6Al-4V (responsável por 45% da produção total de titânio como biomaterial) representam a principal escolha para a confecção de implantes ortopédicos e dentários. No entanto, processos de degradação (corrosão, desgaste e tribocorrosão) atuantes sobre estas ligas podem ocasionar a liberação de partículas e íons metálicos (comumente referidos produtos de desgaste ou debris), o que pode representar uma situação perigosa in vivo. Neste contexto, as propriedades físico-químicas dos produtos de desgaste irão influenciar fortemente o tipo e intensidade das respostas de um organismo vivo após sua exposição aos mesmos. De forma geral, a interação de tais produtos com as células dos tecidos adjacentes ao implante e do sistema imune pode desencadear processos de sinalização, nomeadamente em termos da produção e liberação de citocinas pró-inflamatórias, conduzindo a osteólise (reabsorção óssea) e consequente falha do implante. Ademais, muitas preocupações têm sido levantadas com relação à liberação de partículas e íons compostos pelos elementos alumínio e vanádio. Alternativamente, novas ligas de titânio isentas da adição destes elementos têm sido propostas nos últimos anos, dentre as quais podemos citar, por exemplo, a liga Ti-15Zr-15Mo. Neste trabalho, foram avaliados (in vitro), a partir de um modelo de células de camundongo, os possíveis efeitos relacionados à exposição de íons vanádio às células dos tecidos ósseo e conjuntivo (fibroblastos e osteoblastos). Ademais, a especiação iônica para determinação dos íons vanádio predominantemente relacionados aos resultados obtidos também foi realizada. Complementarmente, a avaliação do comportamento com relação à tribocorrosão para duas ligas de titânio (Ti-6Al-4V e Ti-15Zr-15Mo), a produção e caracterização de partículas de desgaste a partir destas ligas e avaliação dos efeitos relacionados à exposição de tais partículas às células do tecido ósseo (osteoblastos) humano, nomeadamente em termos de viabilidade celular e produção de citocinas pró-inflamatórias, também foram propostas. De acordo com os resultados obtidos, foi possível verificar que as espécies iônicas de vanádio predominantemente dissolvidas nos meios de cultura utilizados para os experimentos in vitro com os osteoblastos e fibroblastos de camundongo foram essencialmente vanadatos, nomeadamente H2VO4- e HVO42-. Verificou-se também que a interação destas espécies iônicas com as células das linhagens celulares testadas, principalmente fibroblastos, pode causar uma diminuição significativa em viabilidade para concentrações próximas aquela possível ser encontrada in vivo em pacientes que apresentam mau funcionamento de seu dispositivo médico baseado na liga Ti-6Al-4V. Para as partículas de desgaste geradas a partir de ensaios de tribocorrosão sobre as ligas Ti-6Al-4V e Ti-15Zr-15Mo foram verificadas características semelhantes com relação à morfologia e a capacidade de preservar a composição e estrutura cristalina do material a partir do qual são geradas. No entanto, diferenças significativas em termos de tamanho foram observadas. Por fim, verificou-se também que a interação das partículas de desgaste obtidas (ambas as composições) com células do tecido ósseo humano, in vitro, pode provocar a diminuição da viabilidade ou (possivelmente) alterações no metabolismo celular, além de conduzir a um aumento na produção das citocinas pró-inflamatórias interleucina-6 e prostaglandina E2. / Among the metallic biomaterials, widely used in the biomedical industry, titanium (Ti) and its alloys, mainly the Ti-6Al-4V system (responsible for 45% of the total titanium production as biomaterial) represent the main choice for orthopedic and dental implants’ manufacturing. However, degradation processes (corrosion, wear and tribocorrosion) acting on these alloys may lead the release of metallic particles and/or ions (also referred as wear products or debris), and this may represent a dangerous situation in vivo. In this context, the wear products’ physical-chemical properties will strongly influence the type and intensity of the living organism responses after their exposure to them. In general, these products’ interaction with the implants’ surrounding tissues and immune system cells may trigger signaling processes, particularly in terms of the proinflammatory cytokines production and release, leading to osteolysis (bone resorption) and consequent implant loosening. Additionally, many concerns have been raised regarding the release of particles and ions composed by aluminum and vanadium. Alternatively, new vanadium and aluminum-free titanium alloys have been proposed in recent years, among which it is possible to mention, for example, the Ti-15Zr-15Mo alloy. In this work, the possible effects related to the vanadium ions exposure to bone and connective tissue cells (fibroblasts and osteoblasts) were evaluated (in vitro), from a mouse cells’ model. Also, ionic speciation analyzes were also performed in order to determine the vanadium ions related to the obtained results. Complementarily, the tribocorrosion behavior evaluation of two titanium alloys (Ti-6Al-4V and Ti-15Zr-15Mo), the production and characterization of wear particles generated from these alloys and the evaluation of the possible effects related to these particles exposure to human osteoblasts (particularly in terms of cell viability and proinflammatory cytokines production) were also proposed. According to the obtained results, it was possible to verify that the vanadium ionic species predominantly dissolved in the culture media used for the in vitro experiments with mouse osteoblasts and fibroblasts were essentially vanadates, namely H2VO4- and HVO42-. It has also been found that the interaction of such ionic species with the tested cells lines, mainly fibroblasts, may lead to a significant decrease in cell viability at concentrations close to that possible to be found in vivo for patients who present malfunctioning of their medical device based on Ti-6Al-4V alloy. Regarding the wear particles generated from tribocorrosion assays on Ti-6Al-4V and Ti-15Zr-15Mo alloys, similar characteristics were verified, mainly in morphology and the ability to preserve the chemical composition and crystal structure of the material from which are generated. However, significant differences in size were observed. Finally, it has also been found that the interaction of the obtained wear particles (both compositions) with human bone tissue cells, in vitro, may be related to decreased viability or (possibly) changes in cellular metabolism, in addition to leading to an increased production of the interleukin-6 and prostaglandin E2 proinflammatory cytokines / 88887.122946/2016-00

Made available in DSpace on 2014-06-11T19:27:21Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-11-08Bitstream added on 2014-06-13T19:55:53Z : No. of bitstreams: 1 vasconcellos_a_me_sjrp.pdf: 3559439 bytes, checksum: 7626ad7d7fb3ecc2909ae46dc06812db (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Os principais objetivos do presente trabalho de pesquisa são a síntese de novos catalisadores zeolíticos, a avaliação de seus usos como possíveis matrizes para imobilização enzimática, e o uso desse complexo zeólita/enzima como catalisador para produção de biodiesel. Inicialmente foram sintetizadas duas classes de zeólitas: faujasita (FAU) e gismondina (GIS), em suas formas sódicas, e estas zeólitas foram convertidas para as formas Cu2+, Ni2+ e Zn2+ por troca iônica. Na sequência foi avaliado o potencial desses materiais zeolíticos para imobilização e atividade lipolítica da enzima (Lipase de Rhizomucor miehei) na reação de hidrólise do p-nitrofenil palmitato (pNPP) a p-nitrofenol (pNP). Os estudos de imobilização foram feitos variando os parâmetros térmicos do pré-tratamento do suporte zeolítico e o meio catiônico dominante. Os resultados obtidos mostraram que dos 16 suportes avaliados para imobilização enzimática, todos se mostraram capazes de imobilizar a enzima em questão e produzir atividade catalítica, no entanto, o melhor compromisso entre imobilização e atividade enzimática foi obtido pelo complexo LIPASE/GIS/Ni2+ pré-tratada a 200ºC. Este complexo que imobilizou 11,2 ± 0,6% da quantidade de enzima da solução e obteve uma atividade de 13,278 U/mg-suporte. Para as reações de transesterificação foram usados como catalisadores as zeólitas puras (GIS/Ni2+ e GIS/Zn2+), enzimas livres (Lipases de Rhizomucor miehei) e enzimas imobilizadas sobre as zeólitas (LIPASE/GIS/Ni2+ e LIPASE/GIS/Zn2+) para a produção de biodiesel a partir do óleo vegetal (óleo de soja). Os resultados obtidos indicaram que os dois complexos produziram biodiesel, no entanto, o teor de ésteres metílicos de 56,2% produzidos pelo suporte LIPASE/GIS/Ni2+ mostrou que houve... / The main goals of this research work are the syntheses of new zeolitic catalysts and their use as possible solid matrices for enzyme immobilization, and the study this complex zeolite/enzyme as a catalyst for biodiesel production. Initially, two different zeolites were synthesized: faujasite (FAU) and gismondine (GIS). The two zeolites were first prepared in their sodic forms and thereafter they were submitted to an ion exchange process in order to the replace the extra-framework Na+ by Cu2+, Ni2+ and Zn2+. The potential of these zeolitic materials for immobilization and lipolytic activity of the enzyme (Lipase from Rhizomucor miehei) was evaluated through the hydrolysis reaction from p-nitrophenyl palmitate (pNPP) to p-nitrophenol (pNP). Several immobilization studies were performed and two main parameters were singled out for this study: the thermal parameters or thermal stability of the zeolitic support and the main dominant cationic medium. The results showed that all of the 16 prepared zeolitic supports were not only able to immobilize the enzyme, but also they were able to show significant catalytic activity. However, the best compromise between immobilization and enzymatic activity was obtained with the complex LIPASE/GIS/Ni2+ pre-treated at 200°C, since it was able to immobilize 11.2 ± 0.6% of the amount of enzymes in solution and an activity of 13.278 U/mg-support. The transesterification reactions for the production of biodiesel from vegetable oils (soybean oil) were performed with the following catalysts: zeolite pure (GIS/Zn2+ and GIS/Ni2+), free enzymes (Lipases from Rhizomucor miehei) and immobilized enzymes on zeolites (LIPASE/GIS/Zn2+ and LIPASE/GIS/Ni2+). The results indicated that two zeolite/enzyme complexes were able to produce biodiesel, but the content... (Complete abstract click electronic access below)