Metalworking fluids (MWFs) are petroleum emulsions employed for metal machining processes as coolants and lubricants. To date, they have been irreplaceable in modern heavy and manufacturing industries, with annual usage exceeding two billion litres worldwide. However, the large amount of MWFs, the highly concentrated complex recalcitrant and toxic petroleum components contained in them continue to cause significant concern in terms of sustainable routes of end-of-life treatment and disposal. Compared with other treatment methods, the anaerobic treatment method has significant advantages, such as the low capital, operating and maintenance costs and energy recovery. This latter factor has the potential benefit of generating bio-energy from waste organic matter whilst aerobic route leads to CO₂ emission. However, the bio-toxicity of MWFs is a huge challenge in terms of employing bio-treatment of waste MWFs. In this study, the anaerobic biodegradability of a typical MWF was investigated employing an activated sludge experimental system. Furthermore, the toxic effects of the MWF on the anaerobic ecosystem, particularly on methanogen species, were investigated using bio-molecular analytical methods and a biosensor. In order to overcome its toxicity, the indigenous anaerobic bacteria isolated from spent MWFs were employed in the treatment of the MWF since they were assumed to be acclimated to the conditions. The major findings include: (1) approximately 80% of the MWF (5,000mgCOD/L) was found to be anaerobically biodegradable, with around 35% of the biodegraded COD could be converted to methane; (2) the MWF appeared to be toxic to the anaerobic ecosystem, especially to methanogen species; and (3) however, treatment employing the anaerobic bacteria successfully reduced the toxicity of the MWF and enhanced the methane production in the process.

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This work characterized burn-off emissions from automobiles. After an exhaustive literature review, engine temperatures were determined to reach a maximum temperature of approximately 110oC, while exhaust system components reached a maximum temperature around 600oC. Metal-drawing fluids were used to bend the exhaust system components during manufacturing. Because these components were not rinsed prior to incorporation into a vehicle, residues could be left on the surfaces. An experimental test chamber was constructed to conduct controlled testing of three metalworking fluids of various types to mimic real-world conditions. Real-time particle number measurements were made using a condensation particle counter and an optical particle counter. The temperature at which burn-off begins to occur was found to be around 120 to 150oC. This burn-off was found to be an evaporation-condensation phenomenon when metalworking fluid residues vaporize and condense forming fine (0.1µm to 2.5µm) and ultrafine (<0.1µm) aerosols. The temperature dependency of this phenomenon was observed to follow the Clausius-Clapeyron equation that states as temperature increases, vapor pressure increases. Most aerosol particles were observed to be in the range of less than 0.01µm to approximately 2.0µm.

The biological treatment of metalworking fluids (MWFs) is a cost effective alternative to conventional waste disposal processes. While research has proven that this process is capable of treating large volumes of wastes with high organic concentrations, there are uncertainties about the mechanisms by which the treatment occurs, and there are limitations that must be overcome. There is a need to understand the importance of the mechanisms by which carbon (and hence COD) is removed from the wastewater. This will allow for waste practitioners to make better decisions for optimizing the process, and for disposing of waste (i.e sludge) that is generated. The biological treatment process is also susceptible to biocides present within formulations. These compounds either need to be removed before the treatment process, or the bioreactors need to be made more resistant to them to ensure that their presence does not hinder the reactor functioning. This study aims to answer the uncertainties about the carbon removal mechanisms involved in the treatment of oil-containing MWFs. In the first experimental chapter, it is shown that the predominant mechanism of carbon removal is oil/water separation induced by emulsifier degradation, and hence the bioprocess treatment rate is significantly affected by the biodegradability of surfactants and by the presence of cations found naturally in the water that used to prepare the emulsions. The study then provides insights into the potential that coagulation and coalescence has for removing inhibitory components commonly found in MWFs. Coagulation and coalescence is shown to effectively remove biocides with low aqueous solubility (iodopropynyl butylcarbamate) and those that partition themselves into the oil phase (o-phenyl phenate and its sodium salt). Finally, to improve the resistance of reactors to inhibitory compounds, factors influencing the development of fixed-film reactors are investigated. A micro-cosmic system is used to study the both physico-chemical effects and nutritional factors on the development of biofilm reactors. It is shown that biofilm yields can be controlled through pH adjustment, and that these yields are maximized with phosphate stimulation and ammonium limitation. It is then shown that fixed-film reactors are able to treat metalworking fluids even under conditions deemed to be inhibitory. In summary, this project provides insights into further understanding and enhancing the biological treatment of MWFs.

Monitoring of emulsion properties is important in many applications, like in foods and pharmaceutical products, or in emulsion polymerization processes, since aged and broken emulsions perform worse and may affect product quality. In machining processes, special types of emulsions called metalworking fluids (MWF) are widely used, because of its combined characteristics of cooling and lubrication, increasing the productivity, enabling the use of higher cutting speeds, decreasing the amount of power consumed and increasing tool life. Even though emulsion quality monitoring is a key issue in manufacturing processes, traditional methods are far from accurate and generally fail in providing the tools for determining the optimal useful life of these emulsions, with high impact in costs. The present study is dedicated to the application of a spectroscopic sensor to monitor MWF emulsion destabilization, which is related to changes in its droplet size distribution. Rapeseed oil emulsions, artificially aged MWF and MWF in machining application were evaluated, using optical measurements and multivariate calibration by neural networks, for developing a new method for emulsion destabilization monitoring. The technique has shown good accuracy in rebuilding the droplet size distribution of emulsions for monomodal and bimodal distributions and different proportions of each droplet population, from the spectroscopic measurements, indicating the viability of this method for monitoring such emulsions. This study is part of a joint project between the University of São Paulo and the University of Bremen, within the BRAGECRIM program (Brazilian German Cooperative Research Initiative in Manufacturing) and is financially supported by FAPESP, CAPES, FINEP and CNPq (Brazil), and DFG (Germany). / Sem resumo em português.

O monitoramento de emulsões utilizadas na indústria metalmecânica compõe uma importante atividade para o controle da qualidade das peças trabalhadas, proporcionando também o aumento da vida útil de ferramentas e maquinários utilizados neste setor através da lubrificação e refrigeração da região de corte. Em grande parte dos casos, estas emulsões são preparadas pela diluição de um fluido de corte em meio aquoso, constituindo assim um conjunto de gotículas estabilizadas em um meio contínuo devido à presença de compostos emulsificantes, estando constantemente sujeitas a ciclos de aquecimento e resfriamento durante os processos de usinagem. Apesar do acompanhamento deste material ser realizado através de análises periódicas usuais, não há um método eficiente estabelecido para verificar sua qualidade em tempo real e em linha de processo. Neste contexto, torna-se possível aplicar técnicas relacionadas à espectroscopia UV-Vis para se obterem informações sobre a estabilidade destes sistemas, correlacionando intensidades de espalhamento de luz com as dimensões das gotas presentes no meio. Dessa forma, tornou-se possível o estudo da desestabilização térmica de emulsões de um fluido de corte comercial, a qual mostrou-se, através do acompanhamento do cálculo do expoente do comprimento de onda, dependente do tempo de exposição ao aquecimento e de sua temperatura média temporal, não sendo influenciada pela perda de meio contínuo por processos evaporativos ou sua posterior reposição. Também se verificou que parâmetros típicos do processo de preparo de emulsões, como a temperatura do meio dispersante e o tempo de repouso do fluido de corte sobre a superfície do mesmo, apresentam fundamental importância para a definição do tamanho médio de gota inicial destes sistemas, o que forneceu evidência da possibilidade de se relacionar a área sob espectros de extinção de luz com tamanhos médios de gota. / The monitoring of emulsions used in the metal-mechanical industry comprise an important activity to the quality control of the products manufectured, also providing an increase in the working life of the tools and machinery employed in this sector through the lubrication and refrigeration of the cutting zone. In the majority of cases, these emulsions are prepared diluting a metalworking fluid in an aqueous media, constituting a collection of particles stabilized by emulsifiers and undergoing heating and cooling cycles during metalworking processes. Currently, monitoring routines are based on regular analyses of samples taken from the process fluid, and an effective in-line method is not available to monitor emulsion quality in real time. In this context, it is possible to apply techniques related to UV-Vis spectrocopy in order to obtain information concerning the stability of those systems, correlating light scattering intensities to the droplet dimensions. In this study, it was possible to investigate the thermal destabilisation of a commercial metalworking fluid emulsion, which showed, through the evaluation of the wavelength exponent, to be dependant on the exposure time to heating and its time-averaged temperature. It was also noted that the loss of continuous phase by evaporation and its reposition do not affect the emulsion stability. Moreover, it was observed that important emulsion preparation parameters, such as continuous phase temperature and the time span between the addition of the metalworking fluid on the water surface and the stirring, have fundamental roles in defining the initial average droplet size, which made possible to correlate the area under the light extinction spectra with average droplet sizes.

O monitoramento de emulsões utilizadas na indústria metalmecânica compõe uma importante atividade para o controle da qualidade das peças trabalhadas, proporcionando também o aumento da vida útil de ferramentas e maquinários utilizados neste setor através da lubrificação e refrigeração da região de corte. Em grande parte dos casos, estas emulsões são preparadas pela diluição de um fluido de corte em meio aquoso, constituindo assim um conjunto de gotículas estabilizadas em um meio contínuo devido à presença de compostos emulsificantes, estando constantemente sujeitas a ciclos de aquecimento e resfriamento durante os processos de usinagem. Apesar do acompanhamento deste material ser realizado através de análises periódicas usuais, não há um método eficiente estabelecido para verificar sua qualidade em tempo real e em linha de processo. Neste contexto, torna-se possível aplicar técnicas relacionadas à espectroscopia UV-Vis para se obterem informações sobre a estabilidade destes sistemas, correlacionando intensidades de espalhamento de luz com as dimensões das gotas presentes no meio. Dessa forma, tornou-se possível o estudo da desestabilização térmica de emulsões de um fluido de corte comercial, a qual mostrou-se, através do acompanhamento do cálculo do expoente do comprimento de onda, dependente do tempo de exposição ao aquecimento e de sua temperatura média temporal, não sendo influenciada pela perda de meio contínuo por processos evaporativos ou sua posterior reposição. Também se verificou que parâmetros típicos do processo de preparo de emulsões, como a temperatura do meio dispersante e o tempo de repouso do fluido de corte sobre a superfície do mesmo, apresentam fundamental importância para a definição do tamanho médio de gota inicial destes sistemas, o que forneceu evidência da possibilidade de se relacionar a área sob espectros de extinção de luz com tamanhos médios de gota. / The monitoring of emulsions used in the metal-mechanical industry comprise an important activity to the quality control of the products manufectured, also providing an increase in the working life of the tools and machinery employed in this sector through the lubrication and refrigeration of the cutting zone. In the majority of cases, these emulsions are prepared diluting a metalworking fluid in an aqueous media, constituting a collection of particles stabilized by emulsifiers and undergoing heating and cooling cycles during metalworking processes. Currently, monitoring routines are based on regular analyses of samples taken from the process fluid, and an effective in-line method is not available to monitor emulsion quality in real time. In this context, it is possible to apply techniques related to UV-Vis spectrocopy in order to obtain information concerning the stability of those systems, correlating light scattering intensities to the droplet dimensions. In this study, it was possible to investigate the thermal destabilisation of a commercial metalworking fluid emulsion, which showed, through the evaluation of the wavelength exponent, to be dependant on the exposure time to heating and its time-averaged temperature. It was also noted that the loss of continuous phase by evaporation and its reposition do not affect the emulsion stability. Moreover, it was observed that important emulsion preparation parameters, such as continuous phase temperature and the time span between the addition of the metalworking fluid on the water surface and the stirring, have fundamental roles in defining the initial average droplet size, which made possible to correlate the area under the light extinction spectra with average droplet sizes.

Monitoring of emulsion properties is important in many applications, like in foods and pharmaceutical products, or in emulsion polymerization processes, since aged and broken emulsions perform worse and may affect product quality. In machining processes, special types of emulsions called metalworking fluids (MWF) are widely used, because of its combined characteristics of cooling and lubrication, increasing the productivity, enabling the use of higher cutting speeds, decreasing the amount of power consumed and increasing tool life. Even though emulsion quality monitoring is a key issue in manufacturing processes, traditional methods are far from accurate and generally fail in providing the tools for determining the optimal useful life of these emulsions, with high impact in costs. The present study is dedicated to the application of a spectroscopic sensor to monitor MWF emulsion destabilization, which is related to changes in its droplet size distribution. Rapeseed oil emulsions, artificially aged MWF and MWF in machining application were evaluated, using optical measurements and multivariate calibration by neural networks, for developing a new method for emulsion destabilization monitoring. The technique has shown good accuracy in rebuilding the droplet size distribution of emulsions for monomodal and bimodal distributions and different proportions of each droplet population, from the spectroscopic measurements, indicating the viability of this method for monitoring such emulsions. This study is part of a joint project between the University of São Paulo and the University of Bremen, within the BRAGECRIM program (Brazilian German Cooperative Research Initiative in Manufacturing) and is financially supported by FAPESP, CAPES, FINEP and CNPq (Brazil), and DFG (Germany). / Sem resumo em português.

In case of metalworking operations, the purpose of lubrication is served by a complex mixture of two or more phases, these mixtures are known as metalworking fluids (MWFs). For many decades oil-in-water emulsions have been used as metalworking fluids. The particular advantage of using oil-in-water emulsion in metalworking operations is that it combines the cooling property of water and the lubrication property of the oil. To explain the lubrication mechanism for oil-in-water emulsions as metalworking fluids a variety of models and theories has been proposed. To understand the lubrication mechanism, the role of each ingredient in the tribological process needs to be studied. In the present study a model for lubrication which determines force and proximity regimes of droplets based on the droplet size distribution is proposed. Dynamic light scattering (DLS) is used to characterize the emulsions. The small droplets are found to be the ones which enhance lubricity. DLVO (Derjaguin-Landau-Verwey-Overbeek) theory is used to validate the results. The concentration and type of surfactant is found to be the performance controlling parameter. A further analysis of the three interfacial energetics; oil/water, oil/substrate, water/substrate, is studied in the presence and absence of surfactants with the help of a Goniometer, Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM). Such energetics reflects the rate at which the excess surfactant molecules accumulate at the water/oil interface and desorb into the phases. The tribological response is recorded using AFM and the nanotribometer (NTR). Frictional response of the chemisorbed self-assembled monolayer of surfactant (sodium oleate) on the steel substrate reflects that a tribofilm helps in lubricating the contact under boundary lubrication by creating a low shear strength material. Water being the continuous phase in oil/water emulsion a thin water layer adjacent to steel substrate is always present. This thin layer on the solid substrate acts as a barrier to the lubricating oil droplets to reach the metal surface. The focus of the present work is also to investigate conditions which permit the disjoining of the water film to allow the oil to lubricate the metal substrate. AFM is used to study the interaction force between an oil droplet and the steel substrate through water. An oil encapsulated SiO2 colloidal probe used to simulate the oil droplet. The charge regulatory status of the substrates and interfaces are found to be critical in mapping the force characteristics when DLVO interaction is considered. The condition for activation of non-DLVO (hydration, hydrophobic, capillary) forces are also identified and found to be dependent on the physical states of surfaces. Disjoining of the thin film can be controlled by selecting surfactants based on interfacial energetics and attractive force characteristic can be achieved to facilitate lubrication.