Pressurized metered dose inhalers (pMDIs) are widely utilized to manage diseases of the lungs, such as asthma and chronic obstructive pulmonary disease. They can be formulated such that the drug and/or nonvolatile excipients are dissolved or dispersed in the formulation, rendering a solution or suspension formulation, respectively. While the formulation process for solution pMDIs is well defined, the formulation process of pMDIs with any type of suspended entity can be lengthy and empirical. The use of suspended drug or the addition of a second drug or excipient in a suspension pMDI formulation may non-linearly impact the product performance of the drug of interest in the formulation; this requires iterative testing of a series of pMDIs in order to identify a formulation with the most potential for success. One of the primary attributes used to characterize the product performance and quality control of inhaled medications is the residual aerodynamic particle size distribution (APSD) of the aerosolized drug. Along with clinical factors, formulation and device parameters have a significant impact on APSD. In this study, a computational model was developed using the principles of statistics and physical chemistry to predict the residual APSD generated by suspension pMDIs based on formulation, device, and raw drug or excipient substance considerations. The formulations modeled and experimentally evaluated consist of a suspended drug or excipient with/without a dissolved drug or excipient in a cosolvent-propellant system. The in silico model enables modeling a process that is difficult to delineate experimentally and contributes to understanding the link between pMDI formulation and device to product performance. The ability to identify and understand the variables that affect atomization and/or aerosol disposition , such as initial droplet size, suspended micronized drug or excipient size, and drug or excipient concentration, facilitates defining the design space for suspension pMDIs during development and improves recognizing the sensitive of the APSD is on each hardware and formulation variable. This model can later be applied to limit batch-to-batch variation in the manufacturing process and selecting plausible suspension pMDI formulations with quality design as the end goal.

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Athabasca asphaltenes were characterized using small-angle X-ray scattering (SAXS) with synchrotron radiation. Two methods were used to separate asphaltenes from Athabasca bitumen. Conventional chemical separation by precipitation with n-pentane, and physical separation realized by passing bitumen through a zirconia membrane with a 20 nm average pore size. The Athabasca permeates and chemically separated samples were dispersed in 1-methylnaphtalene and n-dodecane, with temperature and asphaltene concentration ranges of 50-310 C and 1-8 wt. %, respectively. Two approaches were also taken in the analysis of the SAXS emissions. A model-independent approach provided radii of gyration and scattering coefficients. A model-dependent fit provided size distributions for asphaltenes aggregates assuming that they are dense and spherical. Physically and chemically separated asphaltenes showed significant differences in nominal size and structure, and their structural properties exhibited different temperature dependencies. The results challenge the merits of using chemically separated asphaltene properties as a basis for asphaltene property prediction in crude oil/bitumen.

Com a crescente diminuição de recursos minerais e o alto custo envolvido na construção da estrutura de uma mina, a recuperação máxima possível de uma jazida vem se tornando fundamental. Para isso além da escolha do método de lavra ter a necessidade de ser feito cautelosamente, é possível lançar mão de métodos adicionais de recuperação, como por exemplo, a recuperação de pilares. Essa pesquisa foi baseada na determinação da caracterização do enchimento (backfill cimentado) utilizado nas câmaras vazias que possibilita a posterior recuperação dos pilares. A caracterização do enchimento é composta da determinação da resistência simples do backfill necessária para que o enchimento cumpra com seu objetivo, desenvolvimento da classificação granulométrica ótima para os agregados e dosagem de cimento e água para alcançar a resistência proposta. A metodologia desenvolvida para obter a nova caracterização é composta de várias etapas que incluem pesquisas em campo e trabalhos em laboratório. Primeiramente, foram obtidos através de análise em campo os parâmetros de dosagem de cimento e classificação granulométrica dos agregados já utilizados na planta de fabricação do enchimento, bem como sua resistência correspondente. Em seguida definições teóricas da dosagem de cimento ideal e classificação granulométrica ótima foram realizadas com base na resistência à compressão simples que foi identificada como necessária para cumprir com as solicitações geomecânicas do maciço rochoso, então posteriormente, a nova caracterização definida teoricamente foi posta à prova através da confecção de corpos de prova de backfill, seguido de execuções de ensaios de compressão. Durante a primeira etapa da metodologia, já se pôde identificar que os agregados possuíam um alto índice de partículas tamanho argila que estavam afetando os resultados de resistência obtidos com a caracterização empregada inicialmente. A partir disso se optou por construir a curva granulométrica ótima sem essa fração. A resistência à compressão simples calculada de 2,69 MPa, foi obtida com base no planejamento de longo prazo que prevê a total recuperação dos pilares existentes na mina. Dessa maneira toda a área que será minerada foi considerada como um único bloco. Finalmente, foi identificada a dosagem de cimento sendo de 4% em peso, que juntamente com a granulometria ótima é capaz de alcançar os valores esperados de resistência. Para que o planejamento da produção da mina durante os próximos anos de vida útil seja efetivamente cumprido, o enchimento deverá prover à mina estabilidade geomecânica local a nível de câmaras abertas com paredes verticais de backfill estáveis e também estabilidade global a nível de contato entre níveis e galerias de acesso. Isso somente será alcançado se a nova caracterização for corretamente aplicada. / As a consequence of the ongoing reduction of mineral resources and the high cost involved in the construction of a mine, the maximum recovery of a mineral deposit becomes a fundamental issue. Therefore, besides the need of caution on the choice of the mining method, it is possible to make use of additional recovery methods, such as the recovery of pillars. This research was based on the determination of the characterization of the fill (cemented backfill) used in avoid stopes that allows the subsequent recovery of adjacent pillars. The characterization of the fill consists of determining the uniaxial compressive strength of the backfill required for an efficient filling, developing an optimal particle-size distribution for the aggregates and finding the cement-water ratio necessary to reach the desired resistance. The methodology developed to obtain the new characterization is comprised of several steps which include field work and laboratory tests. First, cement dosing parameters and particle size of the aggregates (already used at the filling manufacturing plant), as well as their corresponding strength, were obtained through analyses in the field work. Then, theoretical definitions of the ideal cement dosing and optimal particle-size analysis were carried out based on the uniaxial compressive strength that has been identified as necessary to comply with the geomechanical requests from the rock mass, and then later, the new theoretical characterization was tested by making backfill samples, followed by execution of compression tests. During the first stage of this methodology, it has been identified a high proportion of clay particle size for the aggregates, that have affected the strength results obtained from the characterization used initially. From this point, we decided to build the optimal particle-size curve without this fraction. Uniaxial compressive strength, calculated as 2.69 MPa, was obtained from the long-term planning that determines the full recovery of the existing pillars in the mine. In this way, the entire area to be mined was considered as a single block. Finally, the cement dosing has been identified as 4% by weight, which together with the optimal particle size, is able to achieve the expected strength values. In order to effectively fulfill the mine production planning over the next years of lifespan, the filling should provide the mine local geomechanical stability at open stopes level, with vertical walls of stable backfill, and also global stability at the contacts between levels and access galleries. This will only be achieved if the new characterization is correctly applied.

Com a crescente diminuição de recursos minerais e o alto custo envolvido na construção da estrutura de uma mina, a recuperação máxima possível de uma jazida vem se tornando fundamental. Para isso além da escolha do método de lavra ter a necessidade de ser feito cautelosamente, é possível lançar mão de métodos adicionais de recuperação, como por exemplo, a recuperação de pilares. Essa pesquisa foi baseada na determinação da caracterização do enchimento (backfill cimentado) utilizado nas câmaras vazias que possibilita a posterior recuperação dos pilares. A caracterização do enchimento é composta da determinação da resistência simples do backfill necessária para que o enchimento cumpra com seu objetivo, desenvolvimento da classificação granulométrica ótima para os agregados e dosagem de cimento e água para alcançar a resistência proposta. A metodologia desenvolvida para obter a nova caracterização é composta de várias etapas que incluem pesquisas em campo e trabalhos em laboratório. Primeiramente, foram obtidos através de análise em campo os parâmetros de dosagem de cimento e classificação granulométrica dos agregados já utilizados na planta de fabricação do enchimento, bem como sua resistência correspondente. Em seguida definições teóricas da dosagem de cimento ideal e classificação granulométrica ótima foram realizadas com base na resistência à compressão simples que foi identificada como necessária para cumprir com as solicitações geomecânicas do maciço rochoso, então posteriormente, a nova caracterização definida teoricamente foi posta à prova através da confecção de corpos de prova de backfill, seguido de execuções de ensaios de compressão. Durante a primeira etapa da metodologia, já se pôde identificar que os agregados possuíam um alto índice de partículas tamanho argila que estavam afetando os resultados de resistência obtidos com a caracterização empregada inicialmente. A partir disso se optou por construir a curva granulométrica ótima sem essa fração. A resistência à compressão simples calculada de 2,69 MPa, foi obtida com base no planejamento de longo prazo que prevê a total recuperação dos pilares existentes na mina. Dessa maneira toda a área que será minerada foi considerada como um único bloco. Finalmente, foi identificada a dosagem de cimento sendo de 4% em peso, que juntamente com a granulometria ótima é capaz de alcançar os valores esperados de resistência. Para que o planejamento da produção da mina durante os próximos anos de vida útil seja efetivamente cumprido, o enchimento deverá prover à mina estabilidade geomecânica local a nível de câmaras abertas com paredes verticais de backfill estáveis e também estabilidade global a nível de contato entre níveis e galerias de acesso. Isso somente será alcançado se a nova caracterização for corretamente aplicada. / As a consequence of the ongoing reduction of mineral resources and the high cost involved in the construction of a mine, the maximum recovery of a mineral deposit becomes a fundamental issue. Therefore, besides the need of caution on the choice of the mining method, it is possible to make use of additional recovery methods, such as the recovery of pillars. This research was based on the determination of the characterization of the fill (cemented backfill) used in avoid stopes that allows the subsequent recovery of adjacent pillars. The characterization of the fill consists of determining the uniaxial compressive strength of the backfill required for an efficient filling, developing an optimal particle-size distribution for the aggregates and finding the cement-water ratio necessary to reach the desired resistance. The methodology developed to obtain the new characterization is comprised of several steps which include field work and laboratory tests. First, cement dosing parameters and particle size of the aggregates (already used at the filling manufacturing plant), as well as their corresponding strength, were obtained through analyses in the field work. Then, theoretical definitions of the ideal cement dosing and optimal particle-size analysis were carried out based on the uniaxial compressive strength that has been identified as necessary to comply with the geomechanical requests from the rock mass, and then later, the new theoretical characterization was tested by making backfill samples, followed by execution of compression tests. During the first stage of this methodology, it has been identified a high proportion of clay particle size for the aggregates, that have affected the strength results obtained from the characterization used initially. From this point, we decided to build the optimal particle-size curve without this fraction. Uniaxial compressive strength, calculated as 2.69 MPa, was obtained from the long-term planning that determines the full recovery of the existing pillars in the mine. In this way, the entire area to be mined was considered as a single block. Finally, the cement dosing has been identified as 4% by weight, which together with the optimal particle size, is able to achieve the expected strength values. In order to effectively fulfill the mine production planning over the next years of lifespan, the filling should provide the mine local geomechanical stability at open stopes level, with vertical walls of stable backfill, and also global stability at the contacts between levels and access galleries. This will only be achieved if the new characterization is correctly applied.

Due to its prevalence over large, densely populated areas, ammonium nitrate is an important chemical species in aerosol research. However, due to its volatility at ambient temperatures and over low temperature gradients, ammonium nitrate can be a difficult species to accurately measure. The volatility of ammonium nitrate is known to be dependent on temperature, relative humidity, the internal mixing state of the particle, and availability of the precursor gas constituents. The particle's physical state affects the equilibrium constant value of the ammonium nitrate - nitric acid / ammonia exchange and helps determine the dissociation rate. For indoor aerosol research, the outdoor originating aerosol particles' exposure to the new physical conditions indoors, such as changes in temperature, humidity, and particle-surface reactions within the microenvironment all accelerate ammonium nitrate dissociation. This increased rate of partitioning can generate artifacts on datasets, increase indoor particle formation, and accelerate the corrosion of cultural antiquities through acidification. The magnitude of these impacts is uncertain due to the current lack of knowledge on particle transformation processes when outdoor originating particles migrate indoors. To address this gap in knowledge, this thesis...

The separation of solids from biological wastewater treatment is an important step in the treatment process, as it has a significant impact on effluent water quality. The moving bed biofilm reactor (MBBR) technology is a proven upgrade or replacement wastewater treatment system for carbon and nitrogen removal. However, a challenge of this technology is the characteristics of the effluent solids that results in their poor settlement; with settling being the common method of solids removal. The main objective of this research is to understand and expand the current knowledge on the settling characteristics of MBBR produced solids and the parameters that influence them. In particular, in this dissertation, the impacts are studied of carrier types, biofilm thickness restraint design of carriers, and varying carbonaceous loading rates on MBBR performance, biofilm morphology, biofilm thickness, biofilm mass, biofilm density, biofilm detachment rate, solids production, particle size distribution (PSD) and particle settling velocity distribution (PSVD). With this aim, three MBBR reactors housing three different carrier types were operated with varying loading rates. In order to investigate the effect of carrier geometrical properties on the MBBR system, the conventional, cylindrically-shaped, flat AnoxK™ K5 carrier with protected voids was compared to two newly-designed, saddle-shaped Z-carriers with the fully exposed surface area. Moreover, the AnoxK™ Z-200 carrier was compared to the AnoxK™ Z-400 carrier to evaluate the biofilm thickness restraint design of these carriers, where the Z-200 carrier is designed for greater biofilm thickness-restraint. The Z-200 carrier is designed to limit the biofilm thickness to the level of 200 µm as opposed to 400 µm for the Z-400 carrier. Finally, to investigate the effects of varying carbonaceous loading rates on system removal performance, biofilm characteristics and solids characteristics, further analyses were performed at three different loading rates of 1.5 to 2.5 and 6.0 g-sBOD/m2·d in steady-state conditions. The PSD and the PSVD analyses were combined to relate these two properties. A settling velocity distribution analytical method, the ViCAs, was applied in combination with microscopy imaging and micro-flow imaging to investigate the relation of PSD and settling behaviour of MBBR produced particles. The obtained results have indicated that the carrier type significantly impacted the MBBR performance, biofilm, and particle characteristics. As such, the K5 carrier MBBR system demonstrated a statistically significantly higher carbonaceous removal rate and efficiency (3.8 ± 0.3 g-sBOD/m2·d and 59.9 ± 3.0% sBOD removal), higher biofilm thickness (281.1 ± 8.7 μm), higher biofilm mass per carrier (43.9 ± 1.0 mg), lower biofilm density (65.0 ± 1.5 kg/m3), lower biofilm detachment rate (1.7 ± 0.7 g-TSS/ m2·d) and hence lower solids production (0.7 ± 0.3 g-TSS/d) compared to the two Z-carriers. The Z-carriers' different shape exposes the biofilm to additional shear stress, which could explain why the Z-carriers have thinner and denser biofilm, resulting in higher solids production and lower system performance in comparison with K5. Moreover, the carrier type was also observed to impact the particle characteristics significantly. PSD analysis demonstrated a higher percentage of small particles in the Z-carrier system effluent and hence a significantly lower solids settling efficiency. Therefore, the solids produced in the K5 reactor have shown enhanced settling behaviour, consisting of larger particles with faster settling velocities compared to Z-carriers. This dissertation also investigated the effects of restraint biofilm thickness on MBBR performance by comparing the Z-200 biofilm thickness-restraint carrier to the Z-400 carrier. No significant difference was observed in removal efficiency, biofilm morphology, biofilm density, biofilm detachment rate, and solids production between the Z-200 to the Z-400 carriers. The PSD and the PSVD analyses did not illustrate any significant difference in the particles’ settling behaviour for these two biofilm thickness restraint carriers, indicating that the biofilm thickness-restraint carrier design was not a controlling factor in the settling potential of MBBR produced solids. Finally, this research studied the effect of varying loading rates and demonstrated a positive, strong linear correlation between the measured sBOD loading rate and the removal rate, indicating first-order BOD removal kinetics. The biofilm thickness, biofilm density and biofilm mass decreased when the surface area loading rate (SALR) was increased from 2.5 to 6.0 g-sBOD/m2·d. The solids retention time (SRT) was also shown to decrease by increasing the SALR, where the lowest SRT (1.7 ± 0.1 days) was observed at the highest SALR, with the highest cell viability (81.8 ± 1.7%). Significantly higher biofilm detachment rate and yield were observed at SALR 2.5, with the thickest biofilm and a higher percentage of dead cells. Consequently, a higher fraction of larger and rapidly settling particles was observed at SALR of 2.5 g-sBOD/m2·d, which leads to a significantly better settling behaviour of the MBBR effluent solids. This study expands the current knowledge of MBBR-produced particle characteristics and settling behaviour. A comprehensive understanding of the MBBR system performance and the potential influencing factors on the MBBR produced solids, particle characteristics, and their settleability will lead to optimized MBBR design for future pilot- and full-scale applications of the MBBR.

This project deals with the mixed micellar and interfacial properties of mixtures of three surfactants [sodium dodecyl sulphate (SDS), cetyltrimethylammonium bromide (CTAB), and tetraethylene glycol monododecyl ether (C12E4)] with ABA symmetrical triblock copolymer (Pluronic F127), which has many industrial applications. Evidence of F127 micellisation and interaction with surfactants in the aqueous phase is inferred through interfacial tension measurements. The solution containing diluted monomeric F127 showed complex formation with surfactants before the latter self-aggregate as pure micelles. The simultaneous presence of ionic surfactants and micellar F127 in solutions displayed a decrease of interfacial activity and led to the conclusion of F127 micelles disruption. C12E4 was found to interact differently with micellar F127 in forming mixed micelles, and no loss of interfacial activity was recorded. This “association-dissociation” behaviour of F127 and surfactants was leveraged to understand the stability of mineral oil in water emulsions formulated with them in the presence of sodium phosphate (Na3PO4). The mechanisms of emulsions breakdown were found to rely on aggregation behaviour and complex structure of F127 and surfactants mixtures in solution. Laser diffraction showed that unlike SDS and CTAB, mixed-emulsifier systems containing C12E4 are stable to both flocculation, Ostwald ripening and coalescence. Due to electrostatic repulsion between its head group and F127 hydrophilic block, and also because of the combined effect of Ostwald ripening and coalescence, CTAB emulsifier containing systems displayed quicker instability than SDS. SDS containing systems showed a progressive shifting of droplets size distributions to bimodality as SDS concentration was increased and heat exposure pursued, revealing the activity of two distinct population of droplets in the emulsions. More insight on the mechanisms underlying the stability of the three mixed emulsifier systems was gained in performing optical microscopy and rheology measurements; the results were found to be consistent with particle size distribution. / Dissertation (MSc (Applied Science: Chemical Technology))--University of Pretoria, 2020. / Chemical Engineering / MSc (Applied Science: Chemical Technology) / Unrestricted

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21096号 / 工博第4460号 / 新制||工||1693(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 高岡 昌輝, 教授 田中 宏明, 准教授 大下 和徹 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM