Thesis (MSc)--Stellenbosch University, 2004 / ENGLISH ABSTRACT: The main aim of this study is to establish a standard procedure for all sedimentary particle size analysis methods specifically for clay minerals and mixtures thereof. Not only will it improve accuracy and reproducibility during clay size analysis, it will also secure comparability between different operators. As a start, all the apparatus-related parameters that can affect the accuracy and reproducibility were determined for the apparatus used, viz. the Sedigraph SOOOD. Thereafter, these parameters were kept constant, and the effects of potential material-related parameters were investigated one-by-one. First to be investigated were those parameters relating specifically to sample preparation. They were: grinding intensity, chemical dissolution of cementing materials, duration of prior soaking, salt content, centrifugal washing with polar organic liquids, deflocculant type and concentration, the effect of pH, ultrasonic time, and stirring during ultrasonic treatment. Then, the influence on accuracy and reproducibility of the physical and chemical parameters related to the suspension was determined. They were: the use of the viscosity and density of water to calibrate the apparatus in stead of those of the suspension liquid, hydrolysis of the deflocculant with suspension-ageing, and the effect of solid concentration on hindered settling. During this investigation a novel method was developed to enable faster and more accurate pycnometric density determinations. Next, the unique characteristics of clays, which can influence the results of sedimentary particle size analyses, were examined. Serious problems are encountered with the accuracy of the analyses of some clay types abundantly found in nature, viz. the smectites and mixed-layered clay minerals. Due to their swelling in water, and variations in the amounts of their crystal layers, they experience unpredictable changes in particle size. The latter is caused by the following external factors: clay type, humidity, type of exchange cation, electrolyte concentration, clay concentration, pH, deflocculant type and concentration, pressure history of the swell-clay suspension, and ageing of the suspension. The effect of each of them on the accuracy and reproducibility of the sedimentary particle size analysis of clays are investigated in detail. Another problem that influences the accuracy of the sedimentary methods is that owing to swelling, the densities of smectites and mixed-layered clays change by varying degrees when suspended in water. It is, however, impossible to pycnometrically determine the density of a swell-clay since it absorbs a part of the water used for its volume determination. To solve this problem, a novel method was devised to calculate swell-clay density. This method makes use of existing Monte Carlo simulations of the swelling mechanism of montmorillonite. During all sedimentary methods, an average clay density is normally used to calculate the particle size distribution of clay mixtures. However, if there is a large enough difference between the calculated average density and that of a component, then inaccurate results will be recorded. The magnitude of this effect was investigated for a few self-made clay mixtures, which consisted of different proportions of kaolinite, illite, and montmorillonite. Based on all the above results, a practical approach to, and a standard methodology for all the sedimentary methods of particle size analysis of clay minerals are presented. Additionally, a condensed summary is provided in table-form, which contains the magnitudes of the errors associated with each of the parameters that were examined. / AFRIKAANSE OPSOMMING: Die doel van hierdie studie is om 'n standaard prosedure daar te stel vir alle sedimentêre metodes van partikelgrootte analise, spesifiek vir gebruik met kleiminerale en mengsels daarvan. So 'n standaard prosedure sal die akkuraatheid en herhaalbaarheid van klei-analises verbeter, en die vergelykbaarheid tussen verskillende operateurs verseker. Aanvanklik is slegs die parameters bepaal wat die akkuraatheid en herhaalbaarheid van die gekose apparaat (Sedigraph 5000D) kan beïnvloed. Daarna is al hierdie parameters konstant gehou, en is die potensiële effekte van die moontlike materiaal-verwante parameters een na die ander ondersoek. Eerstens is die invloed van monstervoorbereiding op akkuraatheid en herhaalbaarheid bepaal. Verskillende parameters nl. maal-intensiteit, chemiese oplossing van sementerende materiale, sentrifugale wassing met polêre organiese vloeistowwe, tipe ontvlokker en konsentrasie, die effek van pH, ultrasoniese tyd en die effek van roer tydens ultrasonikasie is ondersoek. Vervolgens is die invloed op die akkuraatheid en herhaalbaarheid van die fisiese en chemiese parameters verwant aan die suspensie bepaal. Hierdie parameters was nl. die gebruik van die viskositeit en digtheid van water in plaas van dié van die suspensievloeistof, hidrolise van die ontvlokker tydens suspensieveroudering, asook die effek van vastestof-konsentrasie op belemmerde uitsakking. Gedurende hierdie ondersoek is ook 'n nuwe metode ontwikkel wat vinniger, en meer akkurate piknometriese digtheidsbepalings moontlik maak. Die unieke eienskappe van kleie wat die resultate van sedimentêre metodes van partikelgrootte analises kan beïnvloed, is volgende ondersoek. Tydens die analises van party kleie wat baie volop in die natuur voorkom, nl. die smektiete en menglaag-kleie, word ernstige akkuraatheids-probleme ondervind. Hul swelling in water, tesame met variasies in hul aantal kristal-lagies, veroorsaak onvoorspelbare verandering van hul partikelgroottes. Laasgenoemde word deur die volgende eksterne faktore veroorsaak: klei tipe, humiditeit, tipe uitruil-katioon, elektrolietkonsentrasie, kleikonsentrasie, pH, ontvlokker-tipe en konsentrasie, drukgeskiedenis van 'n swelklei-suspensie, en veroudering van die suspensie. Die effek van elk op die akkuraatheid en herhaalbaarheid van die sedimentêre partikelgrootte analises van kleie word in detail bespreek. 'n Verdere probleem wat die akkuraatheid van sedimentêre metodes beïnvloed, is dat wanneer smektiete en menglaag-kleie in water gesuspendeer word, hulle digthede in verskillende mates weens swelling verander. Dit is egter onmoontlik om die digtheid van swelkleie in water piknometries te bepaal, omdat swelklei 'n gedeelte van die water absorbeer wat gebruik moet word om die kleivolume mee te bepaal. Om hierdie probleem op te los, is 'n nuwe metode ontwikkelom die digtheid van swelkleie mee te bereken. Die metode maak gebruik van reedsbestaande Monte Carlo simulasies van die swelling van montmorillonite. Tydens alle sedimentêre metodes word normaalweg van 'n gemiddelde kleidigtheid gebruik gemaak om die partikelgrootte-verspreiding van kleimengsels mee te bereken. Indien die berekende gemiddelde digtheid egter genoegsaam met dié van 'n kleikomponent verskil, sal onakkurate resultate verkry word. Hierdie effek is ondersoek vir 'n paar selfgemaakte kleimengsels wat uit verskillende hoeveelhede kaoliniet, illiet, en montmorilloniet bestaan het. Laastens word 'n praktiese benadering en 'n standaard metode vir alle sedimentêre metodes voorgestel, wat gebaseer is op al die bogenoemde resultate. 'n Verkorte opsomming, met die groottes van die foute geassosieer met elke parameter wat ondersoek is, word laastens in tabelvorm verskaf.

This research explores the nature and extent of training and development (TD) provision, as well as top managers' and TD personnel's attitudes towards the TD function within the medium and large-size private manufacturing organisations of Saudi Arabia. Extensive details of the TD situation are provided and assessed for their adequacy, covering among other elements a descriptive analysis of the main characteristics of the organisations concerned, an evaluation of their TD plans and policies, and a review of their budget allocation and funding. The research then proceeds to describe and discuss the extent to which such organisations are applying a systems approach to TD, both in terms of its design and implementation. Thereafter, the main factors impeding the effectiveness of TD programmes are examined, followed by a consideration of the future challenges that are likely to increase the importance of TD for the organisations in question. The research has adopted a mainly descriptive approach and uses both quantitative and qualitative analytical methods. The required data were gathered through a combination of semi-structural interviews with a number of top managers, and survey questionnaires addressed to the persons responsible for TD within the targeted organisations. The sampling strategy was disproportional stratified random sampling. In total 16 senior executives, 132 medium-size organisations and 94 large-size organisations took part in the study. The findings reveal that although attitudes towards the value of TD are generally favourable, in practice in the majority of cases TD is under-resourced, unplanned and patchy, hardly the ideal features of a systematic model of TD that will enable private manufacturing business to successfully meet the challenges of the future ahead. The research ends with a number of specific and practical recommendations intended to improve the effectiveness of TD in the private manufacturing sector of the Kingdom of Saudi Arabia, as well as a number of suggestions for further research.

The aim of this work is to study the in-vitro aerodynamic performance of a new inhaled theophylline formulation prepared by supercritical fluids technique. For the analysis of the output from the in-vitro tests (and further in-vivo tests) a new, fast, sensitive high performance liquid chromatographic (HPLC) method was developed and validated for the determination of theophylline and other related derivatives in aqueous and urine samples using new packing materials (monolithic columns). These columns achieve efficient separation under lower backpressure and shorter time comparing to other traditionally or newly introduced C18 columns. Solution enhanced dispersion by supercritical fluid (SEDS) process has been applied for the production of anhydrous theophylline as pure crystals in the range 2-5 μm to be used as new inhaled dry powder formulation for asthma. Fifteen theophylline samples have been prepared under different experimental conditions. The drug produced by this method has been subject to a number of solid-phase analytical procedures designed to establish the crystal structure [X-ray powder diffraction (XRPD)], the structure and conformation [(FTIR), Fourier-transform Raman spectroscopy (FT-Raman)], and the morphology and particle size [scanning electron microscope (SEM)]. While, thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC) have been used to monitor any phase transition or polymorphic changes after processing. All these analytical techniques gave a satisfactory indication of the solid-state chemistry of the processed particles and assess the development of new inhalation product. The performance of inhaled SEDS theophylline with or without a carrier was evaluated using the developed HPLC method. Three samples having different particle sizes were selected out of the prepared powders by SEDS technique to be tested. The dose sampling unit and the Anderson Cascade Impactor were used to determine the in-vitro emitted dose and the deposition profiles of SEDS samples, respectively. The effect of different inhalation flows was studied using two different flows 28.3, and 60 L min-1 with 4 L inhalation volume. Different DPI devices were investigated in this study; Easyhaler® and Spinhaler®. The particle size has an important effect on the aerodynamic behaviour and deposition profile of inhaled drug, the smaller the particles the greater the total lung deposition. The presence of a carrier improves the respirable fraction for all the tested formulations.

published_or_final_version / Management Studies / Master / Master of Business Administration

published_or_final_version / Business Administration / Master / Master of Business Administration

published_or_final_version / abstract / Education / Master / Master of Education

published_or_final_version / abstract / Industrial and Manufacturing Systems Engineering / Master / Master of Philosophy

This thesis focuses on a number of aspects governing the transformation of gibbsite, via intermediate phases, to a-alumina. These aspects include the size and morphology of the gibbsite grains, the influence of additions of foreign elements, the effect of a mechanical treatment of the gibbsite prior to calcination, and combinations of these factors. The materials were characterisedb y scanninge lectron microscopy, X-ray diffraction and surfacea rea measurementsF. or someo f the calcined materials an attempt was made to sinter the powders to a dense body to investigate if any of the treatments during calcination had an effect on this process. The literature review covers the current state of understanding of the production of bulk alumina powder by the Bayer process and the phase changes seen on calcination of precursors to the stable a-alumina phase. A detailed description of the phase changes is given and the various routes and conditions necessary for the transformations to occur are considered. The transformations are examined in relation to the morphology of the crystals and the variables controlling the phase transformation route are discussed. Calcination in air showed that the size of the gibbsite grain governs the calcination route taken to reach a-alumina. The standard gibbsites used in this work show a mixed calcination sequence transforming both via the boehmite phase, followed by the y, 8 and 0 phases, and via the x and K phases. The formation of boehmite is attributed to retention of water vapour within the grainDifferences in morphology of the starting materials showed that for the range of materials seen, the morphology of the grain is less important than its size. The super fine material confirmed that a small grain size transforms via the non-boehmite route only, with the other gibbsites taking intermediate routes as for the standard gibbsites. Of the additions made prior to calcination, aluminium fluoride was found to reduce the transformation temperature to a-alumina by approximately 300°C. Other additions had little effect on the transformation temperature although a reduction in grain size was seen with aluminium chloride. It was found that good mixing of the alumina fluoride was essential to obtain reliable and reproducible results. This is due to the small amounts of additive that are needed and the sensitivity of the process to concentration variations. Mineralisation of a range of gibbsites showed that the presence of sodium in the starting material was crucial in reducing the calcination temperature. This led to the conclusion that the sodium and fluoride react to form a liquid phase. The presence of a liquid phase increases the mobility of the aluminium and oxygen atoms resulting in a reduction of the transformation temperature. Fluoride additions to the gibbsites with different morphologies showed that the presence of sodium was the governing factor in reduction of the transformation temperature. Milling of the starting materials showed that there was a small reduction in the transformation temperature between some of the phases. The energy involved in milling leads to activation of the gibbsite. This activation takes the form of a reduction in the grain size and in a reduction of the crystallinity seen in the XRD patternFluoride additions during the calcination of sapphire with a standard gibbsite powder showed preferential grain growth. It was possible to initiate growth of small plate-like crystals on the polished surface of a piece of sapphire parallel to the basal plane. Crystal growth was also seen in scratches on a polished surface perpendicular to the basal plane

To enhance test security of high stakes tests, it is vital to understand the way various exposure control strategies function under various IRT models. To that end the present dissertation focused on the performance of several exposure control strategies under the generalized partial credit model with an item pool of 100 and 200 items. These procedures are relatively easy to implement and have shown promise as an alternative to more complex exposure control strategies. Through unique algorithms these procedures select an item for administration from a subset of items in the item pool. The five procedures examined for efficacy were the modified within .10 logits, restricted modified within .10 logits, randomesque, restricted randomesque, and progressive restricted procedures. The modified within .10 logits, restricted modified within .10 logits, and randomesque, and restricted randomesque procedures select an item for administration from a subset of optimal items. To test the effect of the number of items available for selection in this subset, 3, 6, and 9 items were made available for selection in these procedures. Maximum information item selection was used as a base line, no exposure control, condition. The progressive restricted, restricted randomesque, and restricted modified within .10 logits procedures were found to optimally protect test security while not significantly degrading measurement precision. The restricted forms of the randomesque and modified within .10 logits procedures proved superior to their base procedures, particularly in controlling average maximum exposure rate. The incrementation of item group size in the modified within .10 logits, restricted modified within .10 logits, and randomesque, and restricted randomesque procedures demonstrated that increasing the item group size provided better test security while not significantly degrading measurement precision. Additionally, in general, the increase of the item pool size from 100 to 200 improved measurement precision and test security. Implications towards practical application are discussed and directions for future research are suggested. / text

Trade-offs in resource allocation underlie key life history traits of organisms. My dissertation focuses on the size-number trade-off in clonal broods of offspring using the polyembryonic wasp, Copidosoma bakeri parasitizing immature stages of the moth Agrotis ipsilon. I aim to characterize responses of wasp brood size and individual body mass by manipulating the environments in order to understand the allocation pattern in the size number trade-off. In reviewing the functional forms of trade-off relationships in relation to resource constraints, I distinguish among three main trade-off types based on graphical representations of the relationship between the trade-off variables: linear, convex (inverse), and concave. The size-number trade-off in C. bakeri shows convex relationship. Characteristics of the trade-off are sex specific: female broods have larger body mass but smaller brood size than do male broods. When food intake of the host was increased, the trade-off between wasp body mass and brood size for both sexes shifts toward both higher wasp brood size and higher body mass. When the host has better access to food late in development, the size-number trade-off curve moves up and to the right on the graph. However, the trait combinations shift along the same trade-off curve toward greater wasp body mass but smaller brood size when the host development time is shorter due to more resources in early in development. I also investigate temperature effects on the size-number trade-off. C. bakeri brood size significantly increases with high temperature early in host development. There is no shift in the allocation pattern of the size-number trade-off with temperature. Finally, I test effects of body mass on longevity, fecundity, and mating competitiveness of C. bakeri. Larger body size increases female longevity, and mated females produce more eggs than unmated females. There are no significant relationships between male body mass and longevity or mating competitiveness. Mating reduces male longevity independent of body mass. The different impact of body mass on fitness between male and female wasps suggests the observed sex-specific allocation patterns of the size-number trade-off. Implications of the experiments and possible follow-up work are discussed.