This thesis is to study on the preparation of iron nano-particles by electrochemical method in aqueous solution. The resultant particles are stabilized as a colloidal suspension by the use of cationic surfactants. The advantages include those high yield, low cost, and simple control of particle size by adjustment of the current density. It is revealed that current density, distance between electrodes, temperature, and surfactant concentration of aqueous solution play important roles on the preparation of nano-particles. The morphology, structure, composition, and optical properties of nano-particles are studied by Ultraviolet-Visible spectrophotometer (UV/Vis spectrophotometer), transmission electron microscopy (TEM), and X-ray diffraction (XRD). The effect of particle size on the magnetic properties of nano-particles has been studied using superconducting quantum interference device (SQUID). According to the experimental results, the greater imposed current density is applied, the smaller the particle size is obtained. The absorption spectra of the particles exhibit that the characteristic peak of surface plasmon band is at 264 nm. The maghemite (£^-Fe2O3) phase is clearly confirmed by X-ray diffraction and TEM analysis. From the hysteresis loop studies, particles are paramagnetic at room temperature and they exhibited super-paramagnetic phenomenon. They become ferromagnetic at low temperature. The increase of the coercive force is due to the reduction of thermal vibration.

O diabetes mellitus não é uma doença única, mas um conjunto de doenças que exibem como características a intolerância à glicose, resultante da deficiência na secreção ou na ação do hormônio pancreático, a insulina, produzindo severas anormalidades no metabolismo. As dosagens bioquímicas de alguns metabólitos específicos no sangue e urina são indicadores importantes do estado metabólico do indivíduo diabético e, são usadas tanto no diagnóstico da doença como na avaliação do tratamento. Métodos analíticos para alguns metabólitos de controle do diabetes mellitus, entre eles sódio, potássio, cloreto, bicarbonato, acetoacetato, lactato, β-hidroxibutirato em soro humano e hemoglobina glicada em sangue total, foram desenvolvidos utilizando a eletroforese capilar como técnica única de análise. Os métodos para a análise simultânea de sódio e potássio, cloreto e bicarbonato, acetoacetato, lactato, e β-hidroxibutirato foram desenvolvidos por eletroforese capilar em solução livre e detecção indireta. Estudos de seletividade, sensibilidade, linearidade, precisão, exatidão recuperação e aplicação dos métodos a amostras reais foram realizadas. Os resultados mostraram a possibilidade de aplicação dos métodos a amostras de soro humano, com resultados analíticos equivalentes a métodos de referência para os metabólitos sódio, potássio, cloreto e lactato. A focalização isoelétrica capilar foi utilizada no desenvolvimento do método de análise para a hemoglobina glicada. O método desenvolvido foi aplicado à análise de 31 amostras de hemolisado e os resultados comparados a um método de referência que utiliza cromatografia líquida de alta eficiência. A comparação de métodos apresentou boa correlação, e estudos estatísticos indicaram boa precisão inter e intra-ensaio e estabilidade na preservação da amostra. Resolução completa de hemoglobinas com diferença de ponto isoelétrico de 0,03 foi obtida, além da possibilidade de análise de hemoglobinas variantes, como a S e C. / Diabetes Mellitus is considered a class of diseases that exhibits a sole characteristic: intolerance to glucose. This condition results from a deficiency in the secretion or action of a pancreatic hormone, the insulin, causing severe metabolic disorders. Typically, high levels of glucose are found in blood, in addition to excessive production of the so called ketonic bodies (pyruvic, acetoacetic acids, acetone and the reduced forms: lactic and β-hidroxybutyric acids). The increase in production of ketonic bodies causes an imbalance in the anion gap, given by the expression: [Na+] + [K+] [Cl-] [HCO3-]. In addition to these metabolites, an amount of glicosilated hemoglobin (HbA1C) is formed. HbA1C can be used as indicative of the glucose concentration in the blood during the period of time red cells have been exposed to. For clinical diagnostics, each of the ions of the anion gap, the ketonic bodies and HbA1c are determined by isolated methodologies. In this work, capillary electrophoresis was explored as a single analytical technique for the evaluation of sodium, potassium chloride, bicarbonate, acetoacetate, lactate, β-hidroxybutyrate and HbA1C. The ionic species were determined by free solution capillary electrophoresis with indirect detection while HbA1C was evaluated by capillary isoeletric focusing. The proposed methodologies were validated for sodium, potassium, chloride and lactate, with respect to the following parameters: selectivity, sensitivity, linearity, precision and accuracy showing equivalent results when compared to standard methods applied to control samples. All proposed methodologies were applied to the quantitative analysis of real samples (serum and hemolisate of diabetic and non-diabetic individuals). In addition, HbA1C determinations were contrasted to a chromatographic procedure adopted in a clinical laboratory, showing good correlation (31 samples). Baseline resolution of hemoglobins with pl differing by 0.03 units was achieved, and the possibility of simultaneous analysis of variant hemoglobins, such as S and C was also demonstrated.

O diabetes mellitus não é uma doença única, mas um conjunto de doenças que exibem como características a intolerância à glicose, resultante da deficiência na secreção ou na ação do hormônio pancreático, a insulina, produzindo severas anormalidades no metabolismo. As dosagens bioquímicas de alguns metabólitos específicos no sangue e urina são indicadores importantes do estado metabólico do indivíduo diabético e, são usadas tanto no diagnóstico da doença como na avaliação do tratamento. Métodos analíticos para alguns metabólitos de controle do diabetes mellitus, entre eles sódio, potássio, cloreto, bicarbonato, acetoacetato, lactato, β-hidroxibutirato em soro humano e hemoglobina glicada em sangue total, foram desenvolvidos utilizando a eletroforese capilar como técnica única de análise. Os métodos para a análise simultânea de sódio e potássio, cloreto e bicarbonato, acetoacetato, lactato, e β-hidroxibutirato foram desenvolvidos por eletroforese capilar em solução livre e detecção indireta. Estudos de seletividade, sensibilidade, linearidade, precisão, exatidão recuperação e aplicação dos métodos a amostras reais foram realizadas. Os resultados mostraram a possibilidade de aplicação dos métodos a amostras de soro humano, com resultados analíticos equivalentes a métodos de referência para os metabólitos sódio, potássio, cloreto e lactato. A focalização isoelétrica capilar foi utilizada no desenvolvimento do método de análise para a hemoglobina glicada. O método desenvolvido foi aplicado à análise de 31 amostras de hemolisado e os resultados comparados a um método de referência que utiliza cromatografia líquida de alta eficiência. A comparação de métodos apresentou boa correlação, e estudos estatísticos indicaram boa precisão inter e intra-ensaio e estabilidade na preservação da amostra. Resolução completa de hemoglobinas com diferença de ponto isoelétrico de 0,03 foi obtida, além da possibilidade de análise de hemoglobinas variantes, como a S e C. / Diabetes Mellitus is considered a class of diseases that exhibits a sole characteristic: intolerance to glucose. This condition results from a deficiency in the secretion or action of a pancreatic hormone, the insulin, causing severe metabolic disorders. Typically, high levels of glucose are found in blood, in addition to excessive production of the so called ketonic bodies (pyruvic, acetoacetic acids, acetone and the reduced forms: lactic and β-hidroxybutyric acids). The increase in production of ketonic bodies causes an imbalance in the anion gap, given by the expression: [Na+] + [K+] [Cl-] [HCO3-]. In addition to these metabolites, an amount of glicosilated hemoglobin (HbA1C) is formed. HbA1C can be used as indicative of the glucose concentration in the blood during the period of time red cells have been exposed to. For clinical diagnostics, each of the ions of the anion gap, the ketonic bodies and HbA1c are determined by isolated methodologies. In this work, capillary electrophoresis was explored as a single analytical technique for the evaluation of sodium, potassium chloride, bicarbonate, acetoacetate, lactate, β-hidroxybutyrate and HbA1C. The ionic species were determined by free solution capillary electrophoresis with indirect detection while HbA1C was evaluated by capillary isoeletric focusing. The proposed methodologies were validated for sodium, potassium, chloride and lactate, with respect to the following parameters: selectivity, sensitivity, linearity, precision and accuracy showing equivalent results when compared to standard methods applied to control samples. All proposed methodologies were applied to the quantitative analysis of real samples (serum and hemolisate of diabetic and non-diabetic individuals). In addition, HbA1C determinations were contrasted to a chromatographic procedure adopted in a clinical laboratory, showing good correlation (31 samples). Baseline resolution of hemoglobins with pl differing by 0.03 units was achieved, and the possibility of simultaneous analysis of variant hemoglobins, such as S and C was also demonstrated.

O presente trabalho versa sobre a modificação de eletrodos de carbono vítreo por óxidos de molibdênio e estudos referentes à catálise de redução de oxiânions, bem como o emprego do sensor assim preparado para análise de bromato e iodato em amostras sintéticas e naturais. Estudos executados em solução contendo Mo (VI) na faixa de pH de 1,8 a 3,0 indicaram que em meios mais ácidos a resposta catalítica é muito maior, envolvendo a participação de prótons na abstração de oxigênio ao reduzir o substrato. Os resultados dos experimentos voltamétricos realizados com eletrodo de carbono vítreo modificado demonstraram que iodeto é gerado na eletroredução de iodato. O processo de modificação do eletrodo consistiu na execução de experimentos voltamétricos sucessivos com o eletrodo de carbono vítreo em solução contendo Mo (VI), em pH ajustado para otimização da formação do filme e minimização das perdas de depósito por solubilização ácida. O material imobilizado assim obtido foi analisado por técnicas espectrais e microscópicas, observando-se a existência de centros preferenciais de formação de depósito (grumos) ao qual foi atribuída a fórmula mínima de MoO2,78. O óxido de valência mista mostrou grande potencialidade de catálise na redução de oxiânions oxidantes, observando-se antecipação do potencial de redução do iodato, acompanhada de grande intensificação no sinal de corrente. Trabalhando-se em condições de convecção forçada regida pela rotação do eletrodo de trabalho, foram observadas anomalias nos sinais de corrente durante o decorrer dos experimentos eletroquímicos. Explicações para tal fato foram associadas à formação de diferentes fases de óxidos de molibdênio com atividades catalíticas distintas. O sensor desenvolvido para determinação de iodato foi utilizado em sistema em fluxo após otimização de parâmetros como pH do transportador e da amostra, bem como condições relacionadas à modificação do eletrodo (espessura do filme). Amostras de sal de cozinha foram analisadas pelo método proposto e os resultados obtidos foram concordantes com aqueles oriundos do emprego de metodologia padrão. / The electroreduction of both iodate and bromate at glassy carbon discs modified by molybdenum oxide films in sulfuric acid medium is discussed. Studies carried out at the 1.8 - 3.0 pH range with Mo(VI) in solution show that at more acidic conditions the catalytic response is much larger since protons participate in the oxygen abstraction step when the substrate is reduced. The results of voltammetric experiments carried out with a glassy carbon electrode coated by the molybdenum oxide layer established that iodide is generated in the electroreduction of iodate. The electrochemical modification of the glassy carbon electrode was carried out by cycling consecutively the potential in a solution containing Mo(VI) at a convenient pH. At the optimal condition an adherent film is obtained and the acidic solubilisation is minimised. The immobilised material was analysed by spectral techniques and scanning electronics microscopy, indicating the existence of preferential centres of deposition of material whose formula was calculated to be MoO2,78. The electroreduction of the analyte occurs at a glassy carbon disc modified electrode, the film acting as an efficient electrocatalyst for the mass transport controlled reduction. Rotating disc experiments performed in solutions containing both Mo(VI) and iodate at pH 1.8 confirmed that an immobilised form of molybdenum is responsible for the reduction of the substrate, even though at more acidic solutions the film is partially solubilised. The response from chronoamperometric experiments shows unexpected results explained by the existence of different catalytic species in equilibrium as two distinct phases with different catalytical activity. A method for the amperometric determination of iodate with the modified electrode in a flow injection configuration was described and the sensor was applied to the determination of iodate in commercial salt samples in a wall-jet cell coupled to a flow injection apparatus after convenient desoxygenation of the carrier solution.

This thesis studied on the research of how conducting polymer polyaniline can be used in the buffer layer of organic solar cell. There are two methods used.¡]1¡^Using spin-coating to make film of polyaniline solution.¡]2¡^Polymerizing aniline on the substrate directly by electrochemical polymerization. The electrochemical method is separated into cyclic voltammetry and potentiostatic method respectively. The latter method which improved the disadvantage of infractable thick film and low electric conductivity of polyaniline for spin-coating is chosen as the preparation method for polyaniline films. We discuss of the photoelectric characteristics and surface morphologies of polyaniline film and to make a solar cell base on Poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester measured with AM 1.5G 100 mW/cm2 solar light simulation. This research combine above-mentioned results to use potentiostatic method to polymerize polyaniline on the PEDOT¡GPSS into a compound electrode and to replace currently popular ITO positive pole in a organic solar component. The structure is PEDOT¡GPSS/PANI/P3HT¡GPCBM/Al. By electroplating polyaniline, it can enhance the electric conductivity of the film of PEDOT¡GPSS from 1 S/cm to 154 S/cm, furthermore, to reach 1.06% of photoelectric conversion efficiency and creates a new possibility of preparing a flexible organic solar cell.

O presente trabalho versa sobre a modificação de eletrodos de carbono vítreo por óxidos de molibdênio e estudos referentes à catálise de redução de oxiânions, bem como o emprego do sensor assim preparado para análise de bromato e iodato em amostras sintéticas e naturais. Estudos executados em solução contendo Mo (VI) na faixa de pH de 1,8 a 3,0 indicaram que em meios mais ácidos a resposta catalítica é muito maior, envolvendo a participação de prótons na abstração de oxigênio ao reduzir o substrato. Os resultados dos experimentos voltamétricos realizados com eletrodo de carbono vítreo modificado demonstraram que iodeto é gerado na eletroredução de iodato. O processo de modificação do eletrodo consistiu na execução de experimentos voltamétricos sucessivos com o eletrodo de carbono vítreo em solução contendo Mo (VI), em pH ajustado para otimização da formação do filme e minimização das perdas de depósito por solubilização ácida. O material imobilizado assim obtido foi analisado por técnicas espectrais e microscópicas, observando-se a existência de centros preferenciais de formação de depósito (grumos) ao qual foi atribuída a fórmula mínima de MoO2,78. O óxido de valência mista mostrou grande potencialidade de catálise na redução de oxiânions oxidantes, observando-se antecipação do potencial de redução do iodato, acompanhada de grande intensificação no sinal de corrente. Trabalhando-se em condições de convecção forçada regida pela rotação do eletrodo de trabalho, foram observadas anomalias nos sinais de corrente durante o decorrer dos experimentos eletroquímicos. Explicações para tal fato foram associadas à formação de diferentes fases de óxidos de molibdênio com atividades catalíticas distintas. O sensor desenvolvido para determinação de iodato foi utilizado em sistema em fluxo após otimização de parâmetros como pH do transportador e da amostra, bem como condições relacionadas à modificação do eletrodo (espessura do filme). Amostras de sal de cozinha foram analisadas pelo método proposto e os resultados obtidos foram concordantes com aqueles oriundos do emprego de metodologia padrão. / The electroreduction of both iodate and bromate at glassy carbon discs modified by molybdenum oxide films in sulfuric acid medium is discussed. Studies carried out at the 1.8 - 3.0 pH range with Mo(VI) in solution show that at more acidic conditions the catalytic response is much larger since protons participate in the oxygen abstraction step when the substrate is reduced. The results of voltammetric experiments carried out with a glassy carbon electrode coated by the molybdenum oxide layer established that iodide is generated in the electroreduction of iodate. The electrochemical modification of the glassy carbon electrode was carried out by cycling consecutively the potential in a solution containing Mo(VI) at a convenient pH. At the optimal condition an adherent film is obtained and the acidic solubilisation is minimised. The immobilised material was analysed by spectral techniques and scanning electronics microscopy, indicating the existence of preferential centres of deposition of material whose formula was calculated to be MoO2,78. The electroreduction of the analyte occurs at a glassy carbon disc modified electrode, the film acting as an efficient electrocatalyst for the mass transport controlled reduction. Rotating disc experiments performed in solutions containing both Mo(VI) and iodate at pH 1.8 confirmed that an immobilised form of molybdenum is responsible for the reduction of the substrate, even though at more acidic solutions the film is partially solubilised. The response from chronoamperometric experiments shows unexpected results explained by the existence of different catalytic species in equilibrium as two distinct phases with different catalytical activity. A method for the amperometric determination of iodate with the modified electrode in a flow injection configuration was described and the sensor was applied to the determination of iodate in commercial salt samples in a wall-jet cell coupled to a flow injection apparatus after convenient desoxygenation of the carrier solution.

In this work, a comparative electrochemical study has been performed to evaluate corrosion inhibition property of several film-forming corrosion inhibitors provide by Akzo Nobel on carbon steel in a chloride solution. For carbon steel exposed to 1 M NaCl solution with and without added inhibitor, electrochemical measurements including electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR) at different exposure time intervals, and potentiodynamic polarization at the termination of the exposure, have been performed to investigate the film forming process and to evaluate corrosion inhibition efficiency of the inhibitors, as well as its evolution with time. The corrosion resistance data obtained from the EIS and LPR measurements are in good agreement. The results indicate different inhibition properties of the inhibitors tested. The inhibition effect of SSF CI-1 is negligible in the first hour of exposure, but it increases steadily with time for 1 day, and then remains the same level during the exposure up to one week. SSF CI-2 exhibits a good inhibition effect in the first hour, but the effect decreases with time to a low level after 8 hours, and then increases again with prolonged exposure. SSF CI-4 shows a low inhibition effect during the first day, and then increases to a maximum level after three days’ exposure. For SSF CI-5 and SSF CI-6, the inhibition effect within 8 hours is relative low but higher than that of SSF CI-4, and the effect increases with time during prolonged exposure. The SSF CI-5 seems to be better than SSF CI-6 because of a more stable inhibition effect. The EIS results indicate that most of the inhibitors form a resistive surface film on carbon steel, which becomes more resistive and protective after several days’ of exposure. However, in the initial stage of exposure, the SSF CI-6 does not show an effect of formation of a resistive film on the surface. The potentiodynamic polarization measurements suggest that, SSF CI-1 and SSF CI-2 are anodic type inhibitor, SSF CI-4 is cathodic type inhibitor, and SSF CI-5 and SSF CI-6 are mix type inhibitor. Moreover, the inhibitors tested show a similar corrosion inhibition effect as mussel adhesive protein (MAP) at the low dosage level.

Com o objetivo de implementar um procedimento eletroquímico rápido para determinar urânio em diferentes matrizes, desenvolveu-se um método eletroanalítico simples e de baixo custo operacional, mas com características analíticas desejáveis tais como: rapidez de análise, boa exatidão, reprodutível e suficientemente sensível. Recorreu-se para isto, à bem conhecida redução catalítica do íon nitrato (em excesso), por U(III) que é gerado eletroquimicamente no eletrodo de gota pendente de mercúrio (EGPM), após a redução de U(IV) em meio ácido (pH ≈ 2,5). A reação catalítica entre urânio/nitrato, é capaz de aumentar a sensibilidade de um método voltamétrico quando comparado ao obtido com uma reação de caráter meramente difusional. A Amperometria, cuja potencialidade analítica parecia estar estagnada voltou a ressurgir nas últimas décadas devido ao rápido desenvolvimento de sistemas analíticos automáticos. Esta técnica mostrou-se adequada ao desenvolvimento de um método analítico baseado no processo catalítico entre urânio/nitrato no EGPM sob condições de fluxo. Diante disso, diversos parâmetros experimentais foram investigados visando melhores condições de análise. A melhor combinação de ácido e eletrólito (gerador de nitrato) necessários ao processo catalítico foi conseguida com a mistura de 10 mM de HNO3 e 10 mM de LiNO3 ou 10 mM de NaNO3. A disponibilidade de um eficiente método de desgaseificação em fluxo permitiu a adaptação do método amperométrico para medidas em fluxo. Entretanto, esta adaptação só foi conseguida após a modificação na célula voltamétrica convencional desenhada para sistemas em batelada (batch). Desta maneira, construiu-se um dispositivo para tornar a célula voltamétrica apta a realizar medidas em fluxo a partir de um pequeno bloco de acrílico usinado e adaptado na ponta do EGPM. O limite de detecção determinado para este método foi de 3 x 10-9 M, porém a possibilidade de expandir este limite uma unidade de grandeza é perfeitamente viável recorrendo a uma nova combinação de parâmetros experimentais principalmente no que diz respeito ao sincronismo no descarte e geração da gota de mercúrio e a redução ou minimização da corrente residual. O método amperométrico em fluxo desenvolvido foi aplicado a soluções padrão, amostras reais e amostras certificadas. Para determinar urânio em matrizes complexas, foram efetuados procedimentos usuais de separação química por extração líquido-líquido. As amostras sólidas foram mineralizadas por incidência de radiação de microondas associado ao ataque ácido. Utilizou-se para isso, um forno de microondas apropriado para digestão em vasos de PTFE, devidamente selados e sob controle de temperatura e pressão. Procedimentos de decomposição \"on line\" da matéria orgânica dissolvida em águas naturais (MOD), foram efetuados com um sistema de radiação ultravioleta. Além disso, procedimentos de extração líquido-líquido também foram testadas para amostras de água do mar. Os resultados para amostras reais e certificadas de rochas e solos apresentaram resultados concordantes com os conseguidos por outras técnicas analíticas. Os resultados para amostras de água do mar e água mineral também foram concordantes com os resultados esperados. / With the aim of implementing an electrochemical method for determination of uranium in different matrices, a simple electroanalytical method was developed with low operational cost, but with such desirable analytic characteristics: fast analysis, good accuracy, reproducibility and sufficiently sensitivity. The method was based on the catalytic reduction of the nitrate ion (in excess) by U(III) (electrochemically generated on the hanging mercury drop electrode, HMDE), after reduction of U(IV) in acid solutions (pH ≈ 2,5). The catalytic reaction between uranium/nitrate allows the increase of the sensibility of the voltammetric method when compared to the obtained from a reaction of a merely diffusional process. Amperommetry, of which analytic potentiality seemed to have been stagnated, carne back again in the last decades due to the fast development of automatic analytic systems. This technique seemed to be appropriate to the development of an analytic method based on the catalytic process among uranium/nitrate on HMDE under flow conditions. Therefore, some experimental parameters were investigated in order to provide better conditions of analysis. The best combination of acid and electrolyte (generator of nitrate) needed to the catalytic process was obtained with the mixture of 10 mM of HNO3 and 10 mM of LiNO3 or 10 mM NaNO3. The availability of an efficient degassing method in flow allowed the adaptation of the amperometric method for measures in flow. However, this adaptation was gotten only after modification was made in the conventional voltammetric batch cell designed for systems on batches. This way, a cell for measures in flow was built, from a little block of acrylic and adapted to the tip of HMDE. The detection limit determined for this method was of 3 nM, but the possibility of that limit expansion is perfectly viable, falling back upon a new combination of experimental parameters, mainly on the subject of synchronism on mercury drop discarding and generation, and also the reduction of residual current. The amperometric method on flowing was applied to standard solutions, real samples and certified samples. To determine uranium in complex matrices, usual procedures of chemical separation were taken by liquid-liquid extraction. The solid samples were mineralized by incidence of microwaves radiation combined with acid digestion. An appropriate microwaves oven (with controlled temperature and pressure) was used for digestion samples in PTFE vessels properly closed e duly sealed. Procedures of \"on line\" decomposition of the dissolved organic matter (DOM), in natural waters were home made by ultraviolet radiation system. Besides, liquid-liquid extraction procedures were tested for seawater samples as well. The results for real and certified rocks and soils samples, showed agreement when compared by other analytic techniques. The results for seawater and fresh water samples were also in agreement with the expected result.

Made available in DSpace on 2014-12-17T14:07:23Z (GMT). No. of bitstreams: 1 MariadasVitoriasVAS.pdf: 9409036 bytes, checksum: 998170be52f9e25917324f5a0f7e8bba (MD5) Previous issue date: 2006-12-28 / The construction industry is one of the largest consumers of natural raw materials, and concrete is considered today the most used material wide. This accentuated consumption of natural resources has generated concern with the preservation of the environment, and has motivated various studies related to the use of resid ues, which can partially or entirely substitute, with satisfactory performance, some materials such as the aggregate, and in so doing, decrease the impact on the environment caused by the produced residues. Research has been done to better understand and improve the microstructure of concrete, as well as to understand the mechanism of corrosion in reinforced steel. In this context, this work was developed aiming at discovering the influence of the substitution of natural sand by artificial sand, with rega rd to mechanical resistance, microstructure, and durability. To obtain the electrochemical parameters, an adaptation was made to the galvanostatic electrochemical method to study the corrosion in reinforced steel. Concretes of categories 20 MPa and 40 MPa were produced, containing natural sand, and concretes of the same categories were produced with artificial sand substituting the natural sand, and with the addition of sodium nitrate and sodium chloride. Due to the use of rock dust reject (artificial sand), an evaluation was made of its environmental risk. The results indicate that the concretes of category 20 MPa present a better performance than the concrete made with natural sand, thus making it a viable substitute. For the category 40 MPa, the better performance is from the concrete containing natural sand. The adaptation of the galvanostatic electrochemical technique to the study of the corrosion of reinforced steel within concrete proved to be valid for obtaining electrochemical parameters with a high degree of reliability, considering the number of degrees of freedom / A constru??o civil ? um dos maiores consumidores de mat?rias-primas naturais, sendo o concreto considerado hoje, o material mais utilizado em todo o mundo. Esse acentuado consumo de recursos naturais tem gerado preocupa??o com a preserva??o do meio ambiente, motivado v?rios estudos relativos ? utiliza??o de res?duos, que possam substituir, na sua totalidade ou parcialmente, com desempenho satisfat?rio, alguns materiais, como, por exemplo, o agregado, diminuindo assim o impacto ambiental causado pelos res?duos gerados. Pesquisas t?m sido realizadas, buscando conhecer e melhorar a microestrutura do concreto, bem como conhecer o mecanismo de corros?o das armaduras. Nesse contexto, esse trabalho foi desenvolvido visando conhecer a influ?ncia da substitui??o da areia natural pelo p? de pedra, quanto ? resist?ncia mec?nica, ? microestrutura e quanto ? sua durabilidade. Para obten??o dos par?metros eletroqu?micos, foi feita uma adapta??o do m?todo eletroqu?mico galvanost?tico ao estudo da corros?o das armaduras. Foram produzidos concretos com categorias de 20 MPa e 40 MPa, contendo areia natural, e concretos de mesma categoria, contendo p? de pedra, em substitui??o da areia natural, e os aditivos: nitrito de s?dio e cloreto de s?dio. Devido a utiliza??o do rejeito p? de pedra, foi feita a avalia??o do risco ambiental do mesmo. Os resultados indicam que os concretos de categoria 20 MPa apresentam melhor desempenho do que o concreto contendo areia natural, sendo vi?vel a sua substitui??o. Para a categoria de 40 MPa, o melhor desempenho ? o do concreto contendo areia natural. A adapta??o da t?cnica eletroqu?mica galvanost?tica ao estudo da corros?o das armaduras, mostrou-se v?lida para obten??o dos par?metros eletroqu?micos com grau de confian?a alto, considerando-se o n?mero de graus de liberdade

The main aim of the work reported is the design of proof-of-concept of at point-of-use hydrogen peroxide electrogeneration from air. The experimental work discussed within this thesis explores five major areas: the kinetics of electrocatalysis, ion-pairing, change of solvent media, the electrode surface modication by a redox mediator, and the electrochemical reduction of oxygen within enhanced mass transport systems. The electrocatalytic rates and mass transport of two oxygen reduction redox meditors, viz. anthraquinone and methyl viologen, are studied in aqueous solutions. The investigation is facilitated through the use of a boron-doped diamond electrode, allowing the catalytic response to be clearly delineated from that of the direct oxygen reduction process. The use of simulation software is highlighted in combination with experimental voltammograms to extract kinetic data. Specifically, the voltammetric features, such as the `reverse' peak and the `split waves', are given particular attention. Consequently, it is possible to deconvolute the electrocatalytic reaction mechanisms. The reactivity of the viologen radical cation is comparable to the semiquinone radical anion in aqueous solution ((4.8~6)x10^9 M^-1 s^-1), but over a far wider pH range (pH 2.5 - pH 8.5). The change of local proton concentration, and sequential electron transfers play key roles here. Moreover, the reduced reactivity of semiquinone is observed upon formation of ion-pairs with tetrabutylammonium cations in alkaline solutions. The electro-reduction of oxygen and its mediated pathways are also investigated in non-aqueous media; in particular the thermodynamics, the kinetics, and mass transport involved in these processes. Through a variable temperature study in electrolytic acetonitrile solution, the oxygen dissolution is quantitatively shown to be an endothermic process. Moreover, the diffusion coeficients and concentration of oxygen upon change of acetonitrile mole fraction is also explored in water-acetonitrile mixtures. The rates of bimolecular reactions are extracted from simulation programs, involving semiquinone in anhydrous acetonitrile and viologen radical cation in ethanol, and show a 3 - 4 orders of magnitude reduction compared to that in aqueous solution. Although the solubility of oxygen is ca. 6 - 8 times larger in non-aqueous solvents, the much reduced homogeneous rates limit the electrogeneration of hydrogen peroxide in pure organic media. Novel surface modification methodologies for graphitic surfaces with covalently attached anthraquinonyl groups are studied and characterised. The anthraquinonyl-modified carbon surfaces show much reduced overpotentials required for oxygen reduction. In the final chapter, utilising the new surface modification methodology and novel designs, two gravity-feed flow cells for electrochemical reduction of oxygen in aqueous solutions are proposed and characterised, one based upon the tubular electrode geometry. The other exhibits much enhanced current conversion by using a porous reticulated vitreous carbon electrode. The latter may provide a prototype hydrodynamic system to produce dilute hydrogen peroxide solution at point-of-use.