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.

As atividades agrícolas no Estado de São Paulo, foram responsáveis pela supressão da cobertura vegetal original do solo e, sua conseqüente degradação. A vegetação nativa foi gradativamente substituída por culturas como café, pastagem, citros e cana-de-açúcar, durante séculos de ocupação e uso da terra. A recomposição da cobertura florestal auxilia na prevenção da erosão do solo e na redução dos impactos causados. A floresta ripária retém os sedimentos resultantes do desprendimento do solo à montante e transportados pela enxurrada. A deposição de sedimentos na zona ripária está relacionada à pluviosidade, às feições geomorfológicas, ao material de origem e manejo da área à montante. O padrão de distribuição de sedimentos na zona ripária reflete a dinâmica da deposição e os prováveis processos ocorridos. Para inferir sobre os processos de deposição ocorridos, foram realizadas análises macro e micromorfológicas e, também análises granulométricas apoiadas na interpretação estatística dos parâmetros de Folk & Ward (1957). As amostras de solo foram dispersas em Hexametafosfato de Sódio e também em água, para simular as condições de campo, seguindo a metodologia de Camargo (1986). Os resultados obtidos através da análise granulométrica, foram reforçados pelas análises de imagens e porosidade em amostras indeformadas. Os atributos do solo enterrado e dos sedimentos depositados, evidenciam um padrão de deposição irregular e desuniforme, que sugere a ocorrência de eventos erosivos de grande intensidade (fluxo turbulento). Essa irregularidade e desuniformidade da deposição está relacionada à alteração do uso da terra. A implantação do reflorestamento na zona ripária de Iracema B deslocou a deposição de sedimentos, 25m à montante na encosta. / Agricultural pratices in the state of São Paulo - Brazil, are directly responsible for the suppression of the natural vegetation cover and soil degradation. The natural vegetation was substituted by coffee, pastures, citrus and sugar-cane crops, over centuries of occupation and land use. The native forest recuperation prevents soil erosion and reduces environmental impacts. Riparian forest traps sediments transported by \"splash\" and runoff. Sediments deposition in riparian zone depends on rainfall, geomorphology, original soil characteristics and management. Sediment distribution paths in riparian zones reflect the deposition dynamics and the type of deposition event. In order to study the deposition processes in a riparian forest located in the county of Iracemapolis-state of São Paulo, macro and micromorphological analyses, as well as particle size distribution using Folk & Ward (1957) parameters, were done. Soil samples were dispersed with sodium hexametaphosphate and water. This last technique was done to simulate field transport conditions. The particle size distribution results together with the field and laboratory morphological analyses showed an irregular and non-uniform sediment deposition. This deposition process suggests the occurrence of high intensity erosive events that produce high amount of sediments and runoff characterized by a turbulent flow. Land use changes significantly affect this type of deposition. The recuperation of the natural forest dislocated sediment deposition inside the riparian forest 25 m upslope.

As atividades agrícolas no Estado de São Paulo, foram responsáveis pela supressão da cobertura vegetal original do solo e, sua conseqüente degradação. A vegetação nativa foi gradativamente substituída por culturas como café, pastagem, citros e cana-de-açúcar, durante séculos de ocupação e uso da terra. A recomposição da cobertura florestal auxilia na prevenção da erosão do solo e na redução dos impactos causados. A floresta ripária retém os sedimentos resultantes do desprendimento do solo à montante e transportados pela enxurrada. A deposição de sedimentos na zona ripária está relacionada à pluviosidade, às feições geomorfológicas, ao material de origem e manejo da área à montante. O padrão de distribuição de sedimentos na zona ripária reflete a dinâmica da deposição e os prováveis processos ocorridos. Para inferir sobre os processos de deposição ocorridos, foram realizadas análises macro e micromorfológicas e, também análises granulométricas apoiadas na interpretação estatística dos parâmetros de Folk & Ward (1957). As amostras de solo foram dispersas em Hexametafosfato de Sódio e também em água, para simular as condições de campo, seguindo a metodologia de Camargo (1986). Os resultados obtidos através da análise granulométrica, foram reforçados pelas análises de imagens e porosidade em amostras indeformadas. Os atributos do solo enterrado e dos sedimentos depositados, evidenciam um padrão de deposição irregular e desuniforme, que sugere a ocorrência de eventos erosivos de grande intensidade (fluxo turbulento). Essa irregularidade e desuniformidade da deposição está relacionada à alteração do uso da terra. A implantação do reflorestamento na zona ripária de Iracema B deslocou a deposição de sedimentos, 25m à montante na encosta. / Agricultural pratices in the state of São Paulo - Brazil, are directly responsible for the suppression of the natural vegetation cover and soil degradation. The natural vegetation was substituted by coffee, pastures, citrus and sugar-cane crops, over centuries of occupation and land use. The native forest recuperation prevents soil erosion and reduces environmental impacts. Riparian forest traps sediments transported by \"splash\" and runoff. Sediments deposition in riparian zone depends on rainfall, geomorphology, original soil characteristics and management. Sediment distribution paths in riparian zones reflect the deposition dynamics and the type of deposition event. In order to study the deposition processes in a riparian forest located in the county of Iracemapolis-state of São Paulo, macro and micromorphological analyses, as well as particle size distribution using Folk & Ward (1957) parameters, were done. Soil samples were dispersed with sodium hexametaphosphate and water. This last technique was done to simulate field transport conditions. The particle size distribution results together with the field and laboratory morphological analyses showed an irregular and non-uniform sediment deposition. This deposition process suggests the occurrence of high intensity erosive events that produce high amount of sediments and runoff characterized by a turbulent flow. Land use changes significantly affect this type of deposition. The recuperation of the natural forest dislocated sediment deposition inside the riparian forest 25 m upslope.

Lime has been used in construction for millennia, and its value, especially in the field of conservation architecture, has only recently been rediscovered. Lime mortars harden through carbonation, and this thesis is a study of that process. The research conducted has resulted in the development of two novel techniques for the measurement and detection of carbonation. The first technique is a method of thermogravimetric analysis which allows the carbonation profile to be measured within an acceptable time-frame. The second technique is the use of drilling resistance measurement to visualise the carbonation profile. The potential of elemental analysis to measure the carbonation profile has also been identified. It has been demonstrated that the lime/water ratio has less impact on the compressive strength of air lime mortars than had previously been supposed. The change in the pore size distribution of air lime mortars caused by carbonation has been studied, and a theory has been proposed to explain this phenomenon. Five different forms of air lime binder were studied. The impact of these on the structural performance of the resultant mortars has been assessed. It was concluded that mortars made with lime putties perform better than mortars made with dry lime hydrate. Mortars made with dispersed hydrated lime appear to perform as well as mortars made with lime putties, but at a slower rate of strength growth. The use of extra mature lime putty does not appear to confer structural performance benefits when compared with ordinary lime putty. It has been shown that the use of calcitic aggregates can produce air lime mortars which perform as well as moderately hydraulic lime mortars. It is theorised that this phenomenon is not directly related to carbonation, but rather to a complex interaction of the granulometry, mineralogy, chemistry and porosity of the aggregate with the binder.

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.

L'exposition aux particules fines et ultrafines, pouvant contenir des éléments métalliques, est un sujet de préoccupation sanitaire majeure, notamment dans les zones fortement industrialisées. Cette thèse a consisté à mieux caractériser la fraction métallique des particules fines et ultrafines émises dans un contexte industrialo-urbain (Littoral dunkerquois) et à déterminer leur bioaccessibilité pulmonaire, en lien avec l'impact sanitaire. Des particules ont été collectées selon leur granulométrie dans des environnements très contrastés : (i) en milieu urbain sous l'influence du trafic automobile et d'émissions industrielles et (ii) à proximité immédiate et à la source même d'une usine de ferromanganèse (Glencore), caractéristique de l'activité industrielle du dunkerquois. La bioaccessibilité pulmonaire des éléménts métalliques a été déterminée par une extraction avec un fluide pulmonaire synthétique (solution "Gamble") et comparée avec une méthode d'extraction séquentielle. En milieu urbain, les concentrations élémentaires dans les particules ultrafines sont principalement liées aux sources locales (issues d'émissions de véhicules ou de chauffage). Les particules submicroniques (< 1µm) sont elles, principalement affectées par les sources industrielles, notamment la métallurgie, principale émettrice de métaux particulaires de la zone industrielle. Les autres sources identifiées par les traceurs métalliques sont la pétrochimie, la combustion des fiouls lourds et des charbons et les sources naturelles (terrigène et marine). Une variabilité temporelle importante des concentrations en masse des particules fines et ultrafines et de leurs teneurs en éléments métalliques a été observée, en cheminée et en champ proche de l'usine de ferromanganèse. Les fortes concentrations en particules ultrafines (PM₀,₁ : 60% de la masse des PM₂,₅), enrichies en métaux de cheminée, diminuent rapidement à proximité immédiate de l'usine, dû au changement rapide des conditions de température et d'humidité induisant des transformations précoces de la matière particulaire. Ce travail a permis par ailleurs de montrer que la bioaccessibilité des métaux associés aux particules est variable selon les propriétés physicochimiques des particules (spéciation chimique des métaux et distribution granulométrique), en lien avec leurs origines et leurs processus de formation. La bioaccessibilité des métaux peut aussi être affectée par des transformations physico-chimiques (mélange/agglomération, agrégation, oxydoréduction...) des particules fines durant leur transport atmosphérique. L'estimation in-vitro de la bioaccessibilité permet de mieux comprendre la biodosponibilité des métaux dans l'organiqme et donc de mieux appréhender l'impact sanitaire des métaux toxiques. / Exposure to metals from fine and ultrafine particles is of major health concern, especially in heavily industrialized areas. This thesis aims to better characterize the metal fraction of fine and ultrafine particles emitted in an industrial-marked urban context (Dunkirk harbour) and to determine their lung bioaccessibility, in relation with their health impact. Particles were collected according to their size in specific environments : (i) in an urban area influenced by traffic and industrial emissions and (ii) at the stacks and in the vicinity of a ferromanganese plant (Glencore), characteristic of the industrial activity in Dunkirk. Pulmonary bioaccessibility of metals was determined using a synthetic lung fluid (Gamble solution), and compared to a sequential extraction method. In the urban area, the elemental concentrations in ultrafine particles are primarily related to lacal sources (traffic and housse heating), while submicronic particles (< 1µm) are mainly affected by industrial sources, especially metallurgical plants, the main source of particulate metals in the industrial area. The other sources identified are petrochemistry, coal and heavy-fuels burning and natural sources (sea salts and crustal particles). A high temporal variability of fine and ultrafine particles mass concentrations and of their metal contents was observed at the stacks and in the close environment of the ferromanganese plant. The high concentrations of ultrafine particles (PM₀,₁ : 60% of the total PM₂,₅ mass), enriched in metals, as observed in stack flues, decrease rapidly in the vicinity of the plant, due to the changes in temperatureand humidity, inducing rapid transformations. The metal bioaccessibility varies according to the particle properties (metals chemical speciation and particle size distribution), depending on their origin and formation processes. This metal bioaccessibility may also be affected by physicochemical transformations of fine particles occuring during atmospheric transport (mixing/agglomeration, aggregation, oxidation or reduction processes). The in-vitro bioaccessibility assessment is of interest to better understand the metal bioavailability and thus for a better appreciation of the health impact of toxic metals.

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.

Measurements of gas volume fraction, bubble velocity, chord length and bubble size distributions were performed in the research vessel Athena II operating in Saint Andrew Bay in the gulf coast near Panama City, FL. Double tipped sapphire optical local phase-detection probes were used to acquire indicator functions downstream of the breaking bow wave, behind the masker and at the stern. These indicator functions were also taken at different depths, distances from the hull, operating speeds and headings respect to the waves. The data processing includes the computation of velocity of individual bubbles and chord lengths, resulting in chord length distributions. These chord length distributions are used to obtain bubble size distributions using a novel procedure described in detail. Uncertainty analysis is performed for gas volume fraction, average bubble velocity and chord length. The results indicate that air entrainment increases with ship speed and sailing against the waves at all positions. The bow wave exhibits unsteady breaking that creates bubble clouds, which were characterized and identified by signal processing. At the stern a very strong dependence of bubble size with depth was found, with evidence that bubbles smaller than 500 micrometers are transported through the bottom of the hull and reach the transom. The roller present at the transom, the associated strong unsteadiness and bubble entrainment are well captured, as indicated by the stern results, showing the frothy nature of the upper layer.

Emulsion explosives have become the preferred choice as blasting agents for numerous industries including mining, agriculture, and construction. One of the most important components in such an emulsion is an emulsifier, which controls the emulsification properties of the explosive. The present study involves the production of one such emulsifier, which is produced by reacting two immiscible liquids, PIBSA (polyisobutylene succinic anhydride) and MEA (monoethanolamine). The study examines the effect of design variable such as the impeller speed, impeller type and the dispersed phase volume fraction on interfacial area. Experiments were carried out in a 0.15 m diameter fully baffled stirred tank using a 6-bladed Rushton turbine impeller and a marine propeller. Drop size was determined using a microscope with a video camera and image processing system. The transient concentration of PIBSA was determined using FTIR analysis and used to estimate the volume fraction of the dispersed phase (ƒÖ). The effective interfacial area was calculated using the Sauter mean drop diameter, d32 and ƒÖ. Impeller speeds ranging from 150 to 600 rpm and dispersed phase volume fractions, ƒÖ ranging from 0.01 to 0.028 were examined in the experimental study. It was found that that the evolution of Sauter mean drop diameter, d32 has four different trends depending on ƒÖ and impeller speed. At high impeller speeds and high ƒÖ, d32 values decrease initially and reach constant values after a long period of time. This trend is consistent with the findings in previous investigations. Under certain operating conditions, d32 values increase initially with stirring time to reach a maximum value and then decrease to reach a steady state value. The presence of these trends has been attributed to the effect of changing physical properties of the system as a result of chemical reaction. Results indicate that, in general, Sauter mean drop diameter d32 decreases with an increase in agitation intensity. However a decrease in the dispersed phase volume fraction is found to increase d32. These trends are found to be the same for both impeller types studied. Comparing the drop size results produced by the two impellers, it appears that low-power number propeller produces s ignificantly smaller drops than the Rushton turbine. It was found that the concentrations of reactants decrease with time for all impeller speeds thereby leading to a decrease in interfacial area with the progress of the reaction. Interfacial area values obtained at higher impeller speeds are found to be lower in spite of lower d32 values at these speeds. Also, these values decrease with time and become zero in a shorter duration indicating the rapid depletion of MEA. The interfacial area values obtained with the propeller at a given impeller speed are lower as compared to those for Rushton turbine. They also decrease and become zero in a shorter duration as compared to those for Rushton turbine suggesting propeller¡¦s performance is better in enhancing the reaction rate.

<p>Due to the small dimensions, nanoparticles and materials consisting of nano-sized building blocks exhibit unique — mostly superior — properties, well differing from their bulk counterpart. Most of the novel properties of nanoparticles (and nanomaterials) are size-dependent, while the majority of the common gasphase methods used for generation of nanopowders result in different, usually wide, size-dispersions. Further understanding of the fundamental processes leading to particle formation is therefore required, leading to better control of size and distribution of the nanoparticles, thus allowing engineering of the desired properties for both nanoparticles and nanomaterials.</p><p>In this present thesis, nanoparticles were produced by two different gasphase techniques activated by lasers, namely laser chemical vapor deposition (LCVD) and pulsed laser ablation (PLA). Optical emission spectroscopy (OES) was performed on thermal (blackbody-like) radiation originating from laser-excited particles during LCVD and coupled to measured size-distributions. In-situ monitoring of size-distributions by a differential mobility analyzer (DMA) was employed during PLA. In addition, deposited nanoparticles were characterized by a variety of standard techniques.</p><p>Different cooling mechanisms of the laser-excited gasphase particles were identified based on temperature and emitted intensity data extracted from OES measurements. The strong evaporation at elevated temperatures also allowed direct size manipulation of the particles. By monitoring the intensity of the emitted thermal radiation and the scattered laser line, strong indications about the so called coagulation limit, where a broadening of the size-distribution occurred, was obtained. The DMA monitoring, supported by modeling, gave information about different mechanisms (thermal and photochemical) of the ablation process, and particle condensation well below the ablation threshold was also found.</p>