Thesis (Ph. D.)--University of Liverpool, 1977. / Includes bibliographical references (leaves 245-261).

Waste oil emulsions are generated in several manufacturing processes. Such emulsions not only affect the efficacy of wastewater treatment but also influence the water quality of the effluent. Therefore, these waste oil emulsions that have to be treated before being released into the environment. Many processes have been developed for demulsifying such materials and microwave irradiation has been shown to be most effective in this respect. It does not require the addition of chemicals and the oil recovered from the emulsion can be reused. With microwave irradiation, there are two main mechanisms occurring simultaneously. One is the rapid increase of temperature which reduces the viscosity of the emulsion. The other is molecular rotation, which neutralizes the Zeta potential because of the rearrangement of electrical charges surrounding the water droplets. Hence, water droplets coalesce and result in the separation of the emulsion. Addition of inorganic salts has also been shown to improve the efficiency of microwave irradiation in demulsification owing to an increase in solvent conductivity, which accelerates the heating rate. This process is termed salt-assisted microwave irradiation. In the present study, we propose that NaCl and artificial seawater can be an economical source of cations required in salt-assisted microwave demulsification. Our experiments included batch tests of emulsion characteristics and the effects of microwave operating conditions on demulsification rate and separation efficiency of three oil-in-water (O/W) emulsions (mineral oil, vegetable oil, and mineral-oil/vegetable-oil mix). First study was aimed to examine the demulsification of an O/W cutting oil emulsion with the addition of NaCl under microwave irradiation. This work investigates the effect of a set of operating variables, including irradiation time, irradiation power, dosage of NaCl, settling time, pH and the initial oil concentration, on the separation efficiency in the treatment of an oil in water (O/W) type cutting oil emulsion by microwave assisted demulsification. As a result of a series of batch demulsification tests a set of optimum operating conditions was found, consisting of 2 min of microwave irradiation at 280 W, the addition of 14 g/L of NaCl, 60 min settling time, and at a pH of 9.5. A separation efficiency of 93.8% was obtained with these conditions for 50 mL of cutting oil emulsion with an initial oil content of 10 g/L. The objective of the second study was to examine the demulsification of an O/W cutting oil emulsion, an olive oil emulsion, and a 1:1 cutting-oil/olive-oil emulsion mix, using a proposed process termed as seawater-assisted microwave irradiation demulsification. We conducted batch demulsification tests on 50-mL aliquots with an initial oil content of 10 g/L, and found that the separation efficiencies of a cutting oil emulsion, an olive oil emulsion, and a cutting-oil/olive-oil mix reached 93.1%, 92.6%, and 93.2%, respectively, using our optimum operating conditions, which were 40 sec of microwave irradiation at 700 W, a 60 min settling time, and addition of 12%, 32%, and 20% (all v/v) of artificial seawater, respectively. Using this set of operating conditions, a decrease in solution pH was found to significantly increase the demulsification efficiency after addition of inorganic acid, whereas an increase in the concentration of surfactant, sodium dodecyl sulfate (SDS), resulted in a decrease in efficiency. In addition, our test data were explored using a stepwise regression method, yielding a multi-variable equation. This empirical equation was able to describe separation efficiency rather well, after exclusion of tests showing separation efficiency below 40% and temperature higher than the boiling point. This study could provide essential information related to O/W emulsions using salt-assisted microwave demulsification.

Inibidores de corrosão são substâncias que quando adicionadas a um meio agressivo, diminuem ou previnem a reação de oxidação de um metal com este meio e/ou as reações de redução de espécies presentes no meio. Para a inibição da corrosão de cobre e suas ligas em meios ácidos ou neutros, o inibidor mais empregado é o benzotriazol (BTAH), o qual forma complexos com os íons Cu (I) e Cu (II) na superfície do metal, diminuindo o processo corrosivo. A preocupação com a preservação ambiental e a toxicidade de inibidores de corrosão vem sendo discutida na literatura. Vários estudos têm-se intensificado usando aminoácidos, como proposta para substituição ao BTAH, considerado tóxico. Entre os aminoácidos estudados, dois apresentavam enxofre em suas moléculas (cisteína e metionina) e um outro sem heteroátomo na cadeira lateral (glicina). As concentrações variaram entre 10-2 a 10-4 mol/L e pH da solução entre 7,2 e 8,4. Foram realizadas medidas gravimétricas (ensaios de imersão total) e técnicas eletroquímicas, tais como polarização potenciodinâmica e espectroscopia de impedância eletroquímica. A caracterização morfológica da superfície do substrato após os ensaios de imersão total (743 horas) foi feita por meio de microscopia eletrônica de varredura (MEV), espectroscopia de raios X por dispersão de energia (EDS ou EDX) e difração de raios X (DRX). Embora os resultados com aminoácidos tenham sido sempre muito inferiores àqueles obtidos na presença de BTAH, comportamentos semelhantes em função da concentração dos aminoácidos puderam ser observados pelos diagramas de Nyquist. Contudo, com exceção dos resultados verificados para o meio contendo cisteína 10-2 mol/L, todas as eficiências de inibição para os meios contendo aminoácidos, obtidas pelos ensaios de imersão total, foram negativas, mostrando que o tempo de exposição também pode ser relevante para o desempenho destes inibidores. Entre todos os aminoácidos testados, os meios contendo glicina apresentaram os piores desempenhos anticorrosivos, inclusive acelerando o processo de dissolução anódica do cobre. Esse resultado pode estar relacionado à faixa de pH das soluções testadas e à solubilidade dos complexos de cobre formados com os aminoácidos, mostrando que uma faixa ótima de pH também deve ser assegurada para aprimorar a ação destes aminoácidos como inibidores de corrosão / Corrosion inhibitors are substances that, when added to an aggressive medium reduce or prevent the oxidation reaction of a metal with such medium and / or the reduction reactions of specimens present in the medium. For inhibiting the corrosion of copper and copper alloys in acidic or neutral media, the most widely used inhibitor is benzotriazole (BTAH), which forms complexes with the Cu (I) and Cu (II) ions on the metal surface, decreasing the corrosive process. The concern for environmental preservation and the toxicity of corrosion inhibitors have been discussed in the literature. Several studies havebeen intensified using amino acids as a proposal to replace the BTAH, which is considered toxic. Among the amino acids studied, two presented sulfur in their molecules (cysteine and methionine) and another without heteroatom in the side chair (glycine). The concentrations ranged from 10-2 to 10-4mol/L and the pH of the solution variedbetween 7,2 and 8,4. Gravimetric measurements (total immersion tests) and electrochemical techniques, such as potentiodynamic polarization and electrochemical impedance spectroscopy, were performed. The morphological characterization of the substrate surface after the immersion tests (743 hours) was made by means of scanning electron microscopy (SEM), X-rays spectroscopy energy dispersive (EDS or EDX) and X-rays diffraction (XRD ).This effect was probably due to the increased concentration of molecules adsorbed on the metal surface. Although the results with amino acids were always lower than those obtained in the presence of BTAH, similar behaviorsas a function of the amino acid concentration could be observed for the Nyquist diagrams. However, except for the results observed for the cysteine medium containing 10-2mol/L, all the inhibition efficiencies of the media containing amino acids, obtained by total immersion tests, were negative, showing that exposure time may also be relevant to the performance of these inhibitors. Among all amino acids tested, the medium containing glycine showed the worst corrosion performance, accelerating the process of anodic dissolution of copper. This result may be related to the pH range of tested solutions and to the solubility of the copper complexes formed with amino acids, showing that an optimal range of pH must also be provided to enhance the action of these amino acids as corrosion inhibitors

Inibidores de corrosão são substâncias que quando adicionadas a um meio agressivo, diminuem ou previnem a reação de oxidação de um metal com este meio e/ou as reações de redução de espécies presentes no meio. Para a inibição da corrosão de cobre e suas ligas em meios ácidos ou neutros, o inibidor mais empregado é o benzotriazol (BTAH), o qual forma complexos com os íons Cu (I) e Cu (II) na superfície do metal, diminuindo o processo corrosivo. A preocupação com a preservação ambiental e a toxicidade de inibidores de corrosão vem sendo discutida na literatura. Vários estudos têm-se intensificado usando aminoácidos, como proposta para substituição ao BTAH, considerado tóxico. Entre os aminoácidos estudados, dois apresentavam enxofre em suas moléculas (cisteína e metionina) e um outro sem heteroátomo na cadeira lateral (glicina). As concentrações variaram entre 10-2 a 10-4 mol/L e pH da solução entre 7,2 e 8,4. Foram realizadas medidas gravimétricas (ensaios de imersão total) e técnicas eletroquímicas, tais como polarização potenciodinâmica e espectroscopia de impedância eletroquímica. A caracterização morfológica da superfície do substrato após os ensaios de imersão total (743 horas) foi feita por meio de microscopia eletrônica de varredura (MEV), espectroscopia de raios X por dispersão de energia (EDS ou EDX) e difração de raios X (DRX). Embora os resultados com aminoácidos tenham sido sempre muito inferiores àqueles obtidos na presença de BTAH, comportamentos semelhantes em função da concentração dos aminoácidos puderam ser observados pelos diagramas de Nyquist. Contudo, com exceção dos resultados verificados para o meio contendo cisteína 10-2 mol/L, todas as eficiências de inibição para os meios contendo aminoácidos, obtidas pelos ensaios de imersão total, foram negativas, mostrando que o tempo de exposição também pode ser relevante para o desempenho destes inibidores. Entre todos os aminoácidos testados, os meios contendo glicina apresentaram os piores desempenhos anticorrosivos, inclusive acelerando o processo de dissolução anódica do cobre. Esse resultado pode estar relacionado à faixa de pH das soluções testadas e à solubilidade dos complexos de cobre formados com os aminoácidos, mostrando que uma faixa ótima de pH também deve ser assegurada para aprimorar a ação destes aminoácidos como inibidores de corrosão / Corrosion inhibitors are substances that, when added to an aggressive medium reduce or prevent the oxidation reaction of a metal with such medium and / or the reduction reactions of specimens present in the medium. For inhibiting the corrosion of copper and copper alloys in acidic or neutral media, the most widely used inhibitor is benzotriazole (BTAH), which forms complexes with the Cu (I) and Cu (II) ions on the metal surface, decreasing the corrosive process. The concern for environmental preservation and the toxicity of corrosion inhibitors have been discussed in the literature. Several studies havebeen intensified using amino acids as a proposal to replace the BTAH, which is considered toxic. Among the amino acids studied, two presented sulfur in their molecules (cysteine and methionine) and another without heteroatom in the side chair (glycine). The concentrations ranged from 10-2 to 10-4mol/L and the pH of the solution variedbetween 7,2 and 8,4. Gravimetric measurements (total immersion tests) and electrochemical techniques, such as potentiodynamic polarization and electrochemical impedance spectroscopy, were performed. The morphological characterization of the substrate surface after the immersion tests (743 hours) was made by means of scanning electron microscopy (SEM), X-rays spectroscopy energy dispersive (EDS or EDX) and X-rays diffraction (XRD ).This effect was probably due to the increased concentration of molecules adsorbed on the metal surface. Although the results with amino acids were always lower than those obtained in the presence of BTAH, similar behaviorsas a function of the amino acid concentration could be observed for the Nyquist diagrams. However, except for the results observed for the cysteine medium containing 10-2mol/L, all the inhibition efficiencies of the media containing amino acids, obtained by total immersion tests, were negative, showing that exposure time may also be relevant to the performance of these inhibitors. Among all amino acids tested, the medium containing glycine showed the worst corrosion performance, accelerating the process of anodic dissolution of copper. This result may be related to the pH range of tested solutions and to the solubility of the copper complexes formed with amino acids, showing that an optimal range of pH must also be provided to enhance the action of these amino acids as corrosion inhibitors