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<p> A brief review of the theoretical and experimental aspects of liquid droplet nucleation from vapours and of crystal nucleation from aqueous solution is presented. In order to study the nucleation and crystal growth of several analytically important metal chelates, methods were developed to measure the size distribution of crystals growing in a supersaturated solution. These methods involved rapid mixing techniques followed by measurement of the size distribution of the precipitated particles using a Coulter counter and multichannel analyser. The size distributions were dumped from the analyser onto magnetic tape and recovered using computer methods. The mixing and counting techniques were calibrated and tested using barium sulphate and spheres of known size distribution. </p> <p> From the size distributions obtained for the metal chelates, conclusions were made regarding the nucleation step, and the parameters important in the classical Volmer-Weber-Becker-Doring theory of nucleation were calculated. The validity of the values were evaluated and comparisons made with values obtained by other workers. </p> <p> The laws controlling the crystal growth of the metal chelates and their importance in elucidating the type of nucleation process were also investigated. </p> / Thesis / Doctor of Philosophy (PhD)

Traditional occupational hygiene assessment of occupational exposures to organic gases and vapours rely on low flow (<200 ml/min) NIOSH sorbent tubes. This work investigates 3M charcoal filter media (JK50 and JK40, 3M, Inc.) for collection and analysis of organic vapours across 0.1-5 l/min. To enable this work, a custom exposure facility was constructed and validated within which organic analyte gas/vapour concentrations could be introduced at known concentrations while controlling environmental variables such as temperature and humidity and other variables. This facility enabled experiments designed to investigate collection and desorption efficiencies across a range of sample flow rates, temperature and humidity conditions for both NIOSH sorbent tubes (e.g. SKC tube) and 3M charcoal filter media. As a result of the investigations described in this thesis, the following conclusions are drawn. Performance of the 3M charcoal filter media for collection and desorption efficiencies for loading, storage time, humidity and breakthrough at low flow rates (<0.5 l/min) were found comparable to the SKC sorbent tube. It is concluded that 3M charcoal media (JK50 and JK40) are suitable for sampling and analyses of hydrocarbons at flow rates <0.5 l/min. The collection efficiencies of the 3M charcoal filter media were investigated at high flow rates (>0.5l/min) for the same parameters, i.e., loading, temperature and humidity. It is concluded that 3M charcoal filter media can be used with confidence in sampling and analysis of airborne hydrocarbons up to 5 l/min. The Wheeler-Jonas model was found to satisfactorily predict the adsorption kinetics of the 3M charcoal filter media at different loading values of hydrocarbons. It was therefore concluded that the model can be applied to determine the suitable amount of 3M charcoal filter media prior to sampling for a given loading.

Activated carbons have been modif fed using reactive chemicals to produce adsorbents of enhanced hydrophobic character which will also be resistant to surface oxidation that results from exposure to humid air ("ageing"). The intention was that modification would not disrupt the carbon pore structure. The adsorptive properties of the modified carbons have been investigated using probe molecules Including nitrogen, water, hexane, and chloropicrin, and the ageing characteristics of the carbons, and the factors controlling the adsorption of a model hydrophobic vapour from high humidity air have been studied. Directly fluorinated carbons were unstable, probably due to weakly adsorbed fluorine. Treatment of these adsorbents with other chemicals indicated the potential of the technique for Introducing specific functional groups onto the carbon surface. Carbons modified using selective fluorinating reagents (hexafluoropropene and 1,1-difluoroethene) were more hydrophobic, and adsorbed hydrophobic vapours more efficiently from humid air in comparison to controls. These adsorbents aged, but at a reduced rate in comparison to control carbon. Carbons modified using chlorinating reagents (carbonyl chloride and chlorine) and treated with solvents to remove adsorbed reagent and/or reaction products were of improved hydrophobic character, and adsorbed hydrophobic vapours from humid air at least as efficiently as the control samples. More importantly, these carbons offered resistance to ageing effects. A study of the factors controlling the efficiency with which hydrophobic vapours; are adsorbed from humid air revealed that the surface chemistry of the carbon is important, but that under typical conditions of use, filter performance was limited by the rate at which water displaced by the organic vapour could be carried away by the airstream. The results illustrate that filters containing chemically modified activated carbon offer advantages when volatile hydrophobic contaminant vapours are present, and where ageing effects are an important mechanism by which filtration efficiency is degraded.

Traditional occupational hygiene assessment of occupational exposures to organic gases and vapours rely on low flow (<200 ml/min) NIOSH sorbent tubes. This work investigates 3M charcoal filter media (JK50 and JK40, 3M, Inc.) for collection and analysis of organic vapours across 0.1 ¿ 5 l/min. To enable this work, a custom exposure facility was constructed and validated within which organic analyte gas/vapour concentrations could be introduced at known concentrations while controlling environmental variables such as temperature and humidity and other variables. This facility enabled experiments designed to investigate collection and desorption efficiencies across a range of sample flow rates, temperature and humidity conditions for both NIOSH sorbent tubes (e.g. SKC tube) and 3M charcoal filter media. As a result of the investigations described in this thesis, the following conclusions are drawn. Performance of the 3M charcoal filter media for collection and desorption efficiencies for loading, storage time, humidity and breakthrough at low flow rates (<0.5 l/min) were found comparable to the SKC sorbent tube. It is concluded that 3M charcoal media (JK50 and JK40) are suitable for sampling and analyses of hydrocarbons at flow rates <0.5 l/min. The collection efficiencies of the 3M charcoal filter media were investigated at high flow rates (>0.5l/min) for the same parameters, i.e., loading, temperature and humidity. It is concluded that 3M charcoal filter media can be used with confidence in sampling and analysis of airborne hydrocarbons up to 5 l/min. The Wheeler-Jonas model was found to satisfactorily predict the adsorption kinetics of the 3M charcoal filter media at different loading values of hydrocarbons. It was therefore concluded that the model can be applied to determine the suitable amount of 3M charcoal filter media prior to sampling for a given loading.

Durant les régimes de fonctionnement transitoires à froid des technologies d’Injection Directe Essence, des films liquides peuvent se former sur les parois du cylindre moteur. L’interaction entre le gradient de fraction de vapeur, résultant de l’évaporation de ces films avec le front de flamme, est responsable de la majorité des émissions d’hydrocarbures imbrulés (HC). Dans ces travaux, une configuration expérimentale simplifiée a été développée de façon à générer un gradient de fraction de vapeur par évaporation, dans un contexte d’écoulement réactif confiné, mais préservé des complexités inhérentes aux configurations industrielles. L’étude porte sur les influences de la vitesse de l’écoulement et de la température de l’interface de changement de phase sur les intensités des transferts de masse et de chaleur ainsi que sur l’établissement de la stratification de vapeur. Dans un premier temps, les flux de vapeur et de chaleur provenant d’une paroi poreuse saturée en liquide volatil ont été mesurés et évalués. Dans un second temps, le gradient de fraction de vapeur à proximité de la paroi poreuse a été caractérisé par un diagnostic de Fluorescence Induite par Laser (FIL). L’approche globale a confirmé que le flux de chaleur consommé par le changement de phase représente une part importante du flux de chaleur total échangé. De plus, les résultats de mesures de FIL ont montré l’existence de différents types de distributions et comportements provenant du lien étroit entre la forte densité du mélange gazeux et la formation de la couche de vapeur. / During cold start and warm up engine regimes for Gasoline Direct Injection (GDI) technology, fuel liquid films may accumulate on the cylinder walls. The interaction between the mass fraction gradient, witch is resulting from its evaporation, and the front flame, manages to produce the majority of Unburnt HydroCarbon (UHC) emissions. In order to reproduce the conditions found in internal combustion without the industrial setup complexity, an academic experimental configuration has been developed to generate a mass fraction gradient by evaporation. This study focuses on the influence of the air stream velocity and the influence of the phase change interface temperature. First, mass and heat fluxes from the phase change surface have been measured and calculated near a porous wall saturated with volatile liquid. Then, the mass fraction gradient near the porous wall has been characterised by a Laser Induced Fluorescence (LIF) diagnostic. The global approach has confirmed that latent heat flux represents a major part of the total heat transfer flux exchange. Moreover, LIF results have shown different global behaviours that link the high density of the gas mixture to the vapour layer formation.

Um dos primeiros requisitos para utilização de lasers de diodo em espectroscopia é sua estabilização térmica. Neste trabalho desenvolvemos um sistema de controle de temperatura para laser de diodo que permite estabilização melhor que 0.01&#176C. O controle é feito através de um sistema sensor e um elemento Peltier como atuador. Lasers somente estabilizados em temperatura (estabilização primária) foram utilizados para realização de espectroscopia de vapores atômicos de Rb e Cs. / One of the first requisites for utilization of diode lasers in spectroscopy is its thermal stabilization. In this work, we develop a diode laser temperature controlling system, which yields stabilization better than 0.01&#176C. The controlling is obtained by means of a sensor system and a Peltier element as actuator. Lasers stabilized in temperature only (primary stabilizations) were utilized in the spectroscopy of atomic vapors of Rb and Cs.

Objectives: The aim of this study was to determine if exposure to volatile organic compounds can lead to DNA damage and impaired DNA repair capacity. Nail cosmetics is a fast growing industry around the world where employees and clients are subjected to various chemical substances which may be harmful to their health: such as formaldehyde, toluene, acetone, xylene, ethylmethacrylate, methylmethacrylate and n–buthyl acetate. These chemicals have the potential to be harmful to their health and exposure to these chemicals should be actively controlled. Formaldehyde is classified as a human carcinogen by the IARC, whereas, toluene and xylene are group three carcinogens, classified in 1999 (not classified as carcinogenic to humans), and various studies have linked DNA damage and impaired DNA repair to the above mentioned substances. Methods: Fifteen nail technicians were monitored by means of personal air sampling, measuring formaldehyde, toluene, xylene, acetone and ethylmethacrylate exposure. Fifteen unexposed subjects were chosen and matched for age and smoking habits with the exposed group. Heparinised blood samples were obtained from each test subject with which the Comet Assay was performed on lymphocytes to determine DNA damage and repair ability. Results: Exposure to ethylmethacrylates and methylmethacrylates leads to DNA damage. Methylmethacrylate causes DNA damage by specifically targeting pyrimidine (fpg) bases. N–buthyl acetate, xylene and acetone exposure impaired DNA repair capacity. The exposed group showed signs of Class III and Class IV DNA damage, whereas the control group had little Class III damage and no indication of Class IV damage. The overall DNA repair ability of the nail technicians was slightly impaired when compared to that of the control group, which is in concurrence with previous studies. Smoking habits and age did not show significant influences on the level of DNA damage and repair when compared with the control group. Conclusion: Exposure to volatile organic compounds such as ethylmethacryale and methylmethacrylate may lead to DNA damage and altered DNA repair in some individuals, although further studies are recommended. / Thesis (M.Sc. (Occupational Hygiene))--North-West University, Potchefstroom Campus, 2011.