Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2007.

The determination of the atmospheric aerosol size distribution is an inverse illposed problem. The shape and the material composition of the air-carried particles are two substantial model parameters. Present evaluation algorithms only used an approximation with spherical homogeneous particles. In this paper we propose a new numerically efficient recursive algorithm for inhomogeneous multilayered coated and absorbing particles. Numerical results of real existing particles show that the influence of the two parameters on the model is very important and therefore cannot be ignored.

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. 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. 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.

This study focuses on the analysis of atmospheric particles sampled from two different field campaigns: the field study at a cattle feeding facility in the summer from 2005 to 2008 and the Indirect and Semi-Direct Aerosol Campaign (ISDAC) in 2008. A ground site field study at a representative large cattle feeding facility in the Texas Panhandle was conducted to characterize the particle size distributions, hygroscopicity, and chemical composition of agricultural aerosols. Here, a first comprehensive dataset is reported for these physical and chemical properties of agricultural aerosols appropriate for use in a site-specific emission inventory. The emission rate and transport of the aerosols are also discussed. In addition, mixing ratios of total and gaseous ammonia were measured at the same field in 2007 and 2008. Measurements such as these provide a means to determine whether the fugitive dust emitted from a typical large feedlot represents a health concern for employees of the feeding operation and the nearby community. Detailed chemical composition of aircraft-sampled particles collected during ISDAC was studied. Filter samples were collected under a variety of conditions in and out of mixed phase and ice clouds in the Arctic. Specifically, particles were sampled from a mixed-phase cloud during a period of observed high concentrations of ice nuclei (IN), a biomass plume, and under relatively clean ambient conditions. Composition of particles was studied on a particle-by-particle basis using several microspectroscopy techniques. Based on the elemental composition analysis, more magnesium was found in Arctic cloud residues relative to ambient air. Likewise, based on the carbon speciation analysis, high IN samples contained coated inorganics, carbonate, and black or brown carbon particles. In the samples collected during a flight through a biomass burning plume, water-soluble organic carbon was the dominant overall composition. Due to their hygroscopic nature, these organics may preferably act as cloud condensation nuclei (CCN) rather than IN. Other ambient samples contained relatively higher fractions of organic and inorganic mixtures and less purely water-soluble organics than found in the biomass particles. The most likely source of inorganics would be sea salt. When present, sea salt may further enhance ice nucleation.

Volcanogenic lightning has a long documented history in the scientific field, though its origins are still poorly understood. The interactions leading to electrification of ash plumes is essentially a function of the microphysics controlling and affecting ash particle collisions. This thesis presents measurements made on charged particle interactions in a fluidized bed, with large-scale applications to the phenomenon of volcanogenic lightning and charged particle dynamics in volcanic plumes. Using a fluidized bed of ash samples taken from Ecuador's Volcán Tungurahua, particles are introduced to a collisional environment, where they acquire an associated polarity. A charged copper plate is used to collect particles of a given polarity, and particle size distributions are obtained for different weight fractions of the ash. It is observed that relatively smaller particles acquire a net negative charge, while larger particles in the sample charge positively. This is a well-documented occurrence with perfectly spherical, chemically identical samples, but this work represents one of the first applications of the principle to volcanic ash. Image analysis is preformed to determine the size distribution associated with specific polarities, and the associated minimum charge on each particle is calculated based on the plate collection height and particle size. We also present results that demonstrate the relationship between particle collisions and the amount of charge exchanged. Using techniques developed to examine the collision rate within a flow, combined with the charging rates determined from this experiment, we determine a maximum charge exchange rate of 1.28±0.23 electrons transferred per collision.

<p>Fatigue and ductility properties in various tool steels, produced by powder metallurgy, spray forming or conventionally ingot casting, have been analysed experimentally and successfully compared to developed models. The models are able to predict the fatigue limit and cause for fatigue fracture, and strain- and stress-development until fracture during the ductile fracture process respectively. Total fracture in a tool steel component, both in fatigue and ductility testing, is caused by a propagating crack initiated by particles, i.e. carbides or non-metallic inclusions. The models are based on experimentally observed size distributions.</p><p>The axial fatigue strength at two million cycles was determined for various tool steels. The fracture surface of each test bar broken was examined in SEM to determine the cause for fatigue failure, i.e. a single carbide or inclusion particle or a cluster of carbides, and the size of the particle. The particles act as stress concentrators where a crack is easily initiated when the material is subjected to alternating stresses. The developed models calculate the probability that at least one particle will be present in the material which is larger than the threshold level for crack initiation at a certain stress range.</p><p>The ductility testing was performed on various tool steels by four-point bending under static load. The load and displacement until total fracture were recorded and the maximum strain and stress acting in the material were calculated. The fracture surface of each broken test bar was examined in SEM, though the crack initiating area appears different compared to a fatigue failure. Ductile fracture is caused by a crack emanating from voids nucleated around many particles in a joint process and then linked together. By finite element modelling of void initiation and propagation in 2D of an experimentally observed carbide microstructure for each tool steel, successful comparisons with experiments were performed. Carbides were modelled as cracked when larger than a certain size, based on fracture surface observations, and the matrix cracked above a pre-defined plastic deformation level. The stresses and strains at total failure were in good agreement between model and experiments when evaluated.</p><p>The use of these developed models could be a powerful tool for optimisation of fatigue and ductility properties for tool steels. With good fatigue and ductility properties normal failures appearing during operation of a tool steel product could be minimised. By theoretical tests in the developed models of various carbide microstructures the optimum mechanical properties could be achieved with a minimum of experiments performed.</p>

Για τον προσδιορισμό της πορομετρικής καμπύλης των γεωυφασμάτων διατίθενται σήμερα τρία πρότυπα (ASTM D6767, EN ISO 12956 και ASTM D4751) που θεωρούνται “διεθνούς” αποδοχής. Το πιο πρόσφατο από αυτά (ASTM D6767) εγκρίθηκε το 2002, ορίζει μέθοδο με βάση τη ροή σε τριχοειδή και αποτελεί το κύριο αντικείμενο της παρούσας διατριβής. Ελέγχθηκαν 52 μη υφασμένα γεωυφάσματα κατασκευασμένα από ίνες πολυπροπυλενίου τόσο κατά ASTM D6767 όσο και κατά EN ISO 12956 (υγρό κοσκίνισμα) και ASTM D4751 (ξηρό κοσκίνισμα). Τα αποτελέσματα που προέκυψαν συγκρίθηκαν τόσο μεταξύ τους όσο και με φυσικές ιδιότητες των γεωυφασμάτων, με τιμές μεγεθών που παρέχουν οι κατασκευαστές αυτών των προϊόντων και με τιμές μεγεθών που υπολογίζονται θεωρητικά. Τα μεγέθη πόρων και οι πορομετρικές καμπύλες που προκύπτουν εργαστηριακά με εφαρμογή κάθε μίας από τις τρεις μεθόδους είναι διαφορετικά. Αυτό οφείλεται στις διαφορετικές παραδοχές ή υποθέσεις κάθε μεθόδου αλλά και στις διαδικασίες που προβλέπει η κάθε μέθοδος. Ειδικότερα, οι δύο βασικές υποθέσεις του προτύπου ASTM D6767 αφορούν τη γωνία επαφής, θ, μεταξύ ρευστού και στερεού (τίθεται ίση με μηδέν) και τη μορφή της διατομής των πόρων των γεωυφασμάτων (κυλινδρική). Λόγω της δομής των μη υφασμένων γεωυφασμάτων οι δύο παραπάνω υποθέσεις δεν είναι δυνατόν να επαληθευθούν. Για τον λόγο αυτό στην εξίσωση προσδιορισμού των μεγεθών πόρων του προτύπου ASTM D6767 εισάγεται διορθωτικός συντελεστής. Από την επεξεργασία των αποτελεσμάτων της παρούσας διατριβής προέκυψε ότι ο συντελεστής αυτός πρέπει να έχει τιμή ίση με 1/3 (για τη συγκεκριμένη συσκευή που χρησιμοποιήθηκε και τις διαδικασίες που εφαρμόστηκαν για την εκτέλεση των δοκιμών) ώστε τα αποτελέσματα να προσεγγίζουν ικανοποιητικά αυτά της δοκιμής κατά EN ISO 12956. / Three internationally accepted standards (ASTM D6767, EN ISO 12956 and ASTM D4751) are available today for determing the pore size distribution of geotextiles. The most recently approved standard (2002) is ASTM D6767 which defines a method based on capillary flow. Laboratory testing according to this standard is the main subject of this thesis. Fifty two nonwoven geotextiles, made of polypropylene fibers, were tested according to the three standardized methods (ASTM D6767, EN ISO 12956 – wet sieving and ASTM D4751 – dry sieving). Comparisons were made between the results obtained from each standardized method as well as between measured pore sizes and geotextile physical properties, manufacturer provided pore sizes and values obtained theoretically. Different pore sizes and pore size distribution curves are obtained when different laboratory standard methods are applied. This is due to the different assumptions on which each method is based and also due to the procedures that each method specifies. The two main assumptions of the Standard ASTM D6767 concern the contact angle, θ, between liquid and solid (equal to zero) and the pore shapes of the geotextiles (cylindrical). Due to the structure of the nonwoven geotextiles the effect of these assumptions is different to quantify. Accordingly, the computation of pore sizes according standard ASTM D6767 is based on the introduction of a correction coefficient in the pertinent equation. The results obtained during this correction coefficient should have a value equal to 1/3 for the particular device used and the procedures applied. Use of this correction coefficient fields results that approximate very well the results obtained from wet sieving tests according to Standard EN ISO 12956.

科学研究費補助金 研究種目:一般研究(C) 課題番号:04640413 研究代表者:藤吉 康志 研究期間:1992-1993年度

Recent research has shown that secondary organic aerosols (SOA) are major contributors to ultrafine particle growth to climatically relevant sizes, increasing global cloud condensation nuclei (CCN) concentrations within the continental boundary layer (BL). This thesis contains two separate studies investigating SOA characteristics and the implications of SOA on global climate. The first study investigates two critical, but uncertain, characteristics of SOA: (1) the amount of SOA available to condense and (2) the volatility or condensational behavior of SOA. The second study investigates the effect of biological volatile organic compound (BVOC) emission changes on SOA formation from preindustrial to present day, and the effect on CCN concentrations using BVOC emission estimates over the last millennium.

Pheroid is a patented system comprising of a unique submicron emulsion type formulation. Pheroid vesicles consist mainly of plant and essential fatty acids and can entrap, transport and deliver pharmacologically active compounds and other useful molecules. The aim of this study was to show that a modulation of components and parameters is necessary to obtain the optimum formula to be used in pharmaceutical preparations. Non-optimal or non-predictable stability properties of emulsions can be limiting for the applications of emulsions (Bjerregaard et al., 2001:23). Careful consideration was given to the apparatus used during the processing along with the ratios of the various components added to the formulation and the storage conditions of the Pheroid vesicles. A preliminary study was performed to optimize the most accurate processing parameters during emulsification. The effect of emulsification rate and time, the temperature of the aqueous phase, the number of days the water phase were gassed, the concentration of the surfactant, cremophor® RH 40, used and the concentration of Vitamin F Ethyl Ester CLR added to the oil phase of the o/w emulsion has been studied. Quantification of the mean particle size, zeta potential, turbidity, pH and current values were used to characterize the emulsions. The samples were characterised after 1, 2, 3, 7, 14, 21 and 28 days of storage. The emulsions were also characterised with confocal laser scanning microscopy (CLSM) to measure the number and size and size distribution of the vesicles. After determination of the processing variables influencing the emulsion stability an accelerated stability test was conducted on a final formula. In the present study, accelerated stability testing employing elevated temperatures and relative humidity were used with good accuracy to predict long-term stability of an o/w emulsion kept at both 5 and 25 OC with 60 % relative humidity and 40 OC with 75 % relative humidity. The results of the stability tests were presented in histograms of the physical properties 24 hours, 1 month, 2 months and 3 months after preparation of the emulsion. It was concluded that Pheroid vesicles demonstrate much potential as a drug delivery system. The high stability of this formula allows its use in a wide variety of applications in the pharmaceutical industry. / Thesis (M.Sc. (Pharmaceutics))--North-West University, Potchefstroom Campus, 2007.