Thesis (Ph.D. (Nutrition))--North-West University, Potchefstroom Campus, 2007.

In the first part of this thesis the prices of six non-ferrous metals (aluminum, copper, lead, nickel, tin, and zinc) are used to assess the forecasting performance of GARCH models. We find that the forecasting performances of GARCH, EGARCH, and TGARCH models are similar. However, we suggest the use of the GARCH model because it is more parsimonious and has a slightly better statistical performance than the other two. In the second part, the prices of six non-ferrous metals and the price of crude oil are used to examine the dynamic links between oil and metal returns by using the BEKK specification of the multivariate GARCH model and the Granger causality-in-variance tests. Results of our study agree with the previous studies in that the crude oil market volatility leads all non-ferrous metal markets. In order to move as far away from the effects of 9/11, daily data for the period December 12, 2003 &ndash / December 15, 2008 is used for the data analysis part of the thesis.

Although bacterial leaching of sulphidic minerals is a well-known phenomenon, it is only in the last ten years that full-scale bacterial leaching plants have been commissioned for gold processing. In order for bacterial leaching to compete successfully with other pretreatment processes for refractory ores, particularly with established technologies such as roasting and pressure leaching, it needs to be efficient. This requires the optimization of the parameters affecting the leaching reaction and the growth of bacteria. The entire biotreatment process is agitation leaching, carried out in stirred reactors or Pachuca type reactors. The bacterial oxidation is a complex reaction involving gaseous, liquid and solid phases. The interactions are highly complex, and analysis is complicated by the presence of solids in the leaching medium. Inspite of the amount of research that has been performed, kinetic and process models are underdeveloped. Since kinetic data varies widely with the type and source of concentrate, experimental data should be generated before doing the full-scale reactor design. In sizing reactors for a commercial scale process, it would be useful to have a mathematical model that one could use to predict the amount and rate of release of metal, as a function of the various operating parameters of the system. G.R.Halli arsenical gold sulphide concentrate obtained from Hutti Gold Mines Ltd., Karnataka, was chosen for our study, because of its high refractoriness. An indegenous strain of Thiobacillus ferrooxidans was used for biooxidation. The experiments were conducted in a well-agitated stirred tank reactor under controlled conditions. Sparged air was supplemented with carbon-dioxide for optimized growth. In this work, more than 90% gold and 95% silver could be recovered from the sulphidic gold concentrate when bioleaching was used ahead of cyanidation, compared to 40% and 50% by direct cyanidation. A generalized model, which accounts for both direct bacterial attack and indirect chemical leaching, has been proposed for the biooxidation of refractory gold concentrates. The bacterial balance, therefore, accounts for its growth both on solid substrate and in solution, and for the attachment to and detachment from the surface. The overall process is considered to consist of several sub-processes, each of which can be described in terms of a mechanism and related rate expressions. These sub-processes were studied seperately under kinetically controlled conditions. The key parameters appearing in the rate equations were evaluated using the experimental data. Since the refractory concentrate contains pyrite and arsenopyrite as the major leachable entities, leaching studies have been done on pure pyrite and arsenopyrite as test minerals and the key parameters in the rate equations are evaluated using this data. The model so developed is tested with the leaching kinetics of the concentrate. The growth of bacteria is dependent on the availability of the substrate, ferrous iron, and the dependence is modelled by the widely accepted Monod equation. The effect of carbon dioxide supplementation on the bacterial activity was studied and the optimal concentration for growth was found to be l%(v/v). Studies on indirect chemical leaching showed that the rate is sensitive to surface area of concentrate. Indirect rate constant of arsenopyrite was found to be greater than that of pyrite, since pyrite is more nobler than arsenopyrite. Conditions of direct leaching alone was obtained at high pulp density and using substrate adapted bacteria. The rate constant of arsenopyrite was found to be greater than that of pyrite. The parameters obtained were tested with the overall batch leaching data of the concentrate and favourable comparision was obtained. Thus, it has been possible to isolate the various simultaneous sub-processes occurring during the leaching and propose useful models to describe these processes in some detail. The model has been extended successfully to predict the continuous leaching behaviour using the parameters obtained from the batch data. Studies on the effect of residence time and pulp density on steady state behaviour showed that there is a critical residence time and pulp density below which washout conditions occur. The critical residence time at 10% pulp density was found to be 11 hrs. Operation at pulp densities lower than 5% and residence times lower than 72 hrs is not favourable for efficient leaching. Studies on the effect of initial ferric iron concentration showed that there exists an optimum concentration of ferric iron at which the time required to reach steady state is minimum.

Indirect additive processing of ferrous metals offers the potential to freeform fabricate parts with good surface finish and minimal dimensional variation from the computer solid model. The approach described here is to mix a ferrous powder with a transient binder followed by selective laser sintering (SLS) in a commercial polymer machine to create a “green” part. This part is post-processed to burn off the transient binder and to infiltrate the porous structure with a lower melting point metal/alloy. Commercially available SLSed ferrous components contain copper-based infiltrant in a ferrous preform. The choice of copper alloy infiltrant has led to inferior mechanical properties of these components limiting their use in many non-injection-molding structural applications, particularly at elevated temperature. In the present work, an attempt has been made to replace the copper-based infiltrant considering cast iron as a potential infiltrant because of its fluidity, hardness and stability at comparatively high temperature. A critical consideration is loss of part structural integrity by over-melting after infiltration as chemical diffusion of alloying elements, principally carbon, occurs resulting in a decrease in the melting temperature of tool steel preform. A predictive model was developed which defines the degree of success for infiltration based on final part geometry and depending on the relative density of the preform and infiltration temperature. The processing regime is defined as a function of controllable process parameters. An experimental program was undertaken using commercially available LaserForm[superscript tm] A6 tool steel that was infiltrated with ASTM A532 white cast iron. Guided by Ashby densification maps, pre-sintering of the A6 tool steel SLS part was performed to increase the part initial relative density prior to infiltration. The final infiltrated parts were analyzed for geometry, microstructure and hardness. The model may be extended to other ferrous powder and infiltrant compositions in an effort to optimize the properties and utility of the final infiltrated part. / text

Background: The high prevalence of iron deficiency and anaemia among South African children highlights the need for iron fortification, especially with a highly bioavailable iron compound. Fortification of staple foods is an adequate strategy to provide additional iron to populations at risk. In South Africa it is mandatory to fortify maize meal and wheat flour with iron, as well as other micronutrients. Elemental iron, specifically electrolytic iron, is currently the preferred choice but other compounds that might be more effective in alleviating iron deficiency are under consideration. Objectives: The objective of this study was to provide information about the bioavailability of ferrous fumarate and NaFeEDTA from maize meal porridge in young children, which would assist in selecting a bioavailable alternative to electrolytic iron in the South African National Food Fortification Programme, Methods: A randomized parallel study design was used, with each of the 2 groups further randomised to receive either one of two test regimens in a crossover design in which each child acted as his/her own control. Iron bioavailability was measured with a stable-isotope technique based on erythrocyte incorporation 15 days after intake. Results: The mean absorption of iron from NaFeEDTA and ferrous fumarate from the maize porridge meal was 11.5% and 9.29% respectively. NaFeEDTA and ferrous fumarate are both sufficiently bioavailable from a maize based meal rich in phytates. Conclusion: Both NaFeEDTA and ferrous fumarate would provide a physiologically important amount of iron should they replace electrolytic iron as fortificant in maize flour fortification. The final choice between ferrous fumarate and NaFeEDTA as when it comes to finding the alternative iron fortificant will depend on factors such as technical compatibility, bioavailability, relative cost and organoleptic characteristics. / Thesis (Ph.D. (Nutrition))--North-West University, Potchefstroom Campus, 2007

The use of lignocellulosic materials to replace fossil resources for the industrial production of fuels, chemicals, and materials is increasing. The carbohydrate composition of lignocellulose (i.e. cellulose and hemicellulose) is an abundant source of sugars. However, due to the feedstock recalcitrance, rigid and compact structure of plant cell walls, access to polysaccharides is hindered and release of fermentable sugars has become a bottle-neck. Thus, to overcome the recalcitrant barriers, thermochemical pretreatment with an acid catalyst is usually employed for the physical or chemical disruption of plant cell wall. After pretreatment, enzymatic hydrolysis is the preferred option to produce sugars that can be further converted into liquid fuels (e.g. ethanol) via fermentation by microbial biocatalysts. However, during acid pretreatment, several inhibitory compounds namely furfural, 5-hydroxymethyl furfural, phenols, and aliphatic acids are released from the lignocellulose components. The presence of these compounds can greatly effect both enzymatic hydrolysis and microbial fermentation. For instance, when Avicel cellulose and acid treated spruce wood hydrolysate were mixed, 63% decrease in the enzymatic hydrolysis efficiency was observed compared to when Avicel was hydrolyzed in aqueous citrate buffer. In addition, the acid hydrolysates were essentially non-fermentable. Therefore, the associated problems of lignocellulose conversion can be addressed either by using feedstocks that are less recalcitrant or by developing efficient pretreatment techniques that do not cause formation of inhibitory byproducts and simultaneously give high sugar yields. A variety of lignocellulose materials including woody substrates (spruce, pine, and birch), agricultural residues (sugarcane bagasse and reed canary grass), bark (pine bark), and transgenic aspens were evaluated for their saccharification potential. Apparently, woody substrates were more recalcitrant than the rest of the species and bark was essentially amorphous. However, the saccharification efficiency of these substrates varied based on the pretreatment method used. For instance, untreated reed canary grass was more recalcitrant than woody materials whereas the acid treated reed canary grass gave a higher sugar yield (64%) than the woody substrates (max 34%). Genetic modification of plants was beneficial, since under similar pretreatment and enzymatic hydrolysis conditions, up to 28% higher sugar production was achieved from the transgenic plants compare to the wild type. As an alternative to the commonly used acid catalysed pretreatments (prior to enzymatic hydrolysis) lignocellulose materials were treated with four ionic liquid solvents (ILs): two switchable ILs (SILs) -SO2DBUMEASIL and CO2DBUMEASIL, and two other ILs [Amim][HCO2] and [AMMorp][OAc]. viii After enzymatic hydrolysis of IL treated substrates, a maximum amount of glucan to glucose conversion of between 75% and 97% and a maximum total sugar yields of between 71% and 94% were obtained. When using acid pretreatment these values varied between 13-77% for glucan to glucose conversion and 26-83% for total sugar yield. For woody substrates, the hemicellulose recovery (max 92%) was higher for the IL treated substrates than compared to acid treated samples. However, in case of reed canary grass and pine bark the hemicellulose recovery (90% and 88%, respectively) was significantly higher for the acid treated substrates than the IL treated samples. To overcome the inhibitory problems associated with the lignocellulose hydrolysates, three chemical conditioning methods were used 1. detoxification with ferrous sulfate (FeSO4) and hydrogen peroxide (H2O2) 2. application of reducing agents (sulfite, dithionite, or dithiothreitol) and 3. treatment with alkali: Ca(OH)2, NaOH, and NH4OH. The concentrations of inhibitory compounds were significantly lower after treatments with FeSO4 and H2O2 or alkali. Using reducing agents did not cause any decrease in the concentration of inhibitors, but detoxification of spruce acid hydrolysates resulted in up to 54% improvement of the hydrolysis efficiency (in terms of sugar release) compared to untreated samples. On the other hand, application of detoxification procedures to the aqueous buffer resulted in up to 39% decrease in hydrolysis efficiency, thus confirming that the positive effect of detoxification was due to the chemical alteration of inhibitory compounds. In addition, the fermentability of detoxified hydrolysates were investigated using the yeast Saccharomyces cerevisiae. The detoxified hydrolysates were readily fermented to ethanol yielding a maximum ethanol concentration of 8.3 g/l while the undetoxified hydrolysates were basically non-fermentable.

Background: The high prevalence of iron deficiency and anaemia among South African children highlights the need for iron fortification, especially with a highly bioavailable iron compound. Fortification of staple foods is an adequate strategy to provide additional iron to populations at risk. In South Africa it is mandatory to fortify maize meal and wheat flour with iron, as well as other micronutrients. Elemental iron, specifically electrolytic iron, is currently the preferred choice but other compounds that might be more effective in alleviating iron deficiency are under consideration. Objectives: The objective of this study was to provide information about the bioavailability of ferrous fumarate and NaFeEDTA from maize meal porridge in young children, which would assist in selecting a bioavailable alternative to electrolytic iron in the South African National Food Fortification Programme, Methods: A randomized parallel study design was used, with each of the 2 groups further randomised to receive either one of two test regimens in a crossover design in which each child acted as his/her own control. Iron bioavailability was measured with a stable-isotope technique based on erythrocyte incorporation 15 days after intake. Results: The mean absorption of iron from NaFeEDTA and ferrous fumarate from the maize porridge meal was 11.5% and 9.29% respectively. NaFeEDTA and ferrous fumarate are both sufficiently bioavailable from a maize based meal rich in phytates. Conclusion: Both NaFeEDTA and ferrous fumarate would provide a physiologically important amount of iron should they replace electrolytic iron as fortificant in maize flour fortification. The final choice between ferrous fumarate and NaFeEDTA as when it comes to finding the alternative iron fortificant will depend on factors such as technical compatibility, bioavailability, relative cost and organoleptic characteristics. / Thesis (Ph.D. (Nutrition))--North-West University, Potchefstroom Campus, 2007

Epilepsy is a common neurological disease affecting 6 million people in Europe. Early prevention and accurate diagnosis and treatment are of importance to obtain seizure freedom. In this thesis new applications of carbon-11-labelled tracers in PET and autoradiographic studies were explored in focal epilepsy. Patients with low-grade gliomas often experience epileptic seizures. A retrospective PET-study assessing seizure activity, metabolic rate measured with 11C-methionine and other known prognostic factors was performed in patients with glioma. No correlation was found between seizure activity and uptake of methionine. The presence and termination of early seizures was a favourable prognostic factor. Activation of the neurokinin-1 (NK1) receptor by substance P (SP) induces epileptic activity. PET with the NK1 receptor antagonist GR205171 was performed in patients with temporal lobe epilepsy (TLE) and healthy controls. In TLE patients an increased NK1 receptor availability was found in both hemispheres, most pronounced in anterior cingulate gyrus ipsilateral to seizure onset. A positive correlation between NK1 receptors and seizure frequency was observed in ipsilateral medial structures consistent with an intrinsic network using the NK1-SP receptor system for transmission of seizure activity. The uptake of 18F-fluoro-deoxy-glucose (FDG) is related to cerebral blood flow (CBF). Previously, methods to estimate blood flow from dynamic PET data have been described. A retrospective study was conducted in 15 patients undergoing epilepsy surgery investigation, including PET with 11C-FDG and 11C-Flumazenil (FMZ). The dynamic FMZ dataset and pharmacokinetic modeling with a multilinear reference tissue model were used to determine images of relative CBF. Agreement between data of FDG and CBF was analyzed showing a close association between interictal brain metabolism and relative CBF. Epilepsy often occurs after traumatic brain injuries. Changes in glia and inhibitory neuronal cells contribute to the chain of events leading to seizures. Autoradiography with 11C-PK11195, 11C-L-deprenyl and 11C-Flumazenil in an animal model of posttraumatic epilepsy studied the temporal and spatial distribution of microglia, astrocytes and GABAergic neurons. Results showed an instant increase in microglial activity that subsequently normalized, a late formation of astrogliosis and an instant and prolonged decease in GABA binding. The model can be used to visualize pathophysiological events during the epileptogenesis.

Made available in DSpace on 2016-12-08T15:56:18Z (GMT). No. of bitstreams: 1 Rinaldo Puff.pdf: 11901534 bytes, checksum: 902429cd8bc8c70d6eae9029243c8969 (MD5) Previous issue date: 2015-07-10 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This thesis was motivated by the study of voids and non-metallic inclusions influence on the high cycle fatigue of ferrous materials like steel, powder metal and gray cast iron. A second objective was to obtain simpler parameters, like the ones measured in hardness, static bending or axial tests, to evaluate materials in early phases of projects, in a way to avoid long fatigue tests. Initially the average fatigue strength was obtained for a high carbon steel. The effect of a silicon oxide inclusion near the surface on the performance of heavy-duty Cr-Si spring wire was also analyzed. The evaluation was done in terms of stress concentrating on the inclusion contours, due to the shot peening application on the surface and normal fluctuating loads. Mechanical properties of powder metal and cast iron were revised. Static tests without and with the presence of notches were performed, with the objective of obtaining a static notch sensitivity factor, to correlate with torsion fatigue results. The relation between hardness and torsion fatigue strength was evaluated for the cast iron, and simulations using linear elastic and nonlinear materials were performed to obtain geometric stress concentrating factors. A mesoscale simulation was done in plane stress, making it possible to evaluate local stress concentration in the cast iron matrix. / Esta tese foi motivada pelo estudo da influência de vazios e inclusões não metálicas na fadiga de alto ciclo de materiais ferrosos como aços, materiais obtidos por metalurgia do pó e ferros fundidos cinzentos. Foi objetivo também, avaliar parâmetros de medição mais simples, como os obtidos de ensaios de dureza e de flexão ou tração estáticos, como forma de avaliar materiais em fases iniciais de projeto, evitando-se longos ensaios de fadiga. Inicialmente obteve-se a resistência à fadiga de alto ciclo de um aço de alto teor de carbono. Analisou-se também o efeito da presença de uma inclusão de óxido de silício próximo à superfície de um arame de aço Cr-Si utilizado em molas submetidas a cargas reversas. A análise foi feita em termos de concentração de tensão nos contornos da inclusão, devido à aplicação de shot peening na superfície e também devido às cargas de operação. Uma revisão de propriedades mecânicas de aços obtidos por metalurgia do pó e do ferro fundido foi realizada, assim como ensaios estáticos sem e com entalhe, no intuito de obter um fator de sensibilidade ao entalhe estático, como forma de correlacionar com a sensibilidade ao entalhe na fadiga em torção. Foi avaliada a relação entre a dureza do ferro fundido e a sua resistência à fadiga na torção e realizadas simulações com material linear elástico e não linear para obter um fator de concentração de tensão geométrico. Uma simulação em mesoescala em estado plano de tensão foi realizada, podendo-se determinar a concentração de tensões locais na matriz do ferro fundido.

The protein folding problem involves understanding how the tertiary structure of a protein is related to its primary structure. Hence, understanding the thermodynamics associated with the rate-limiting steps for the formation of the earliest events in folding is most crucial to understanding how proteins adopt native secondary and tertiary structures. In order to elucidate the mechanism and pattern of protein folding, an extensively studied protein, Cytochrome-c (Cc), was chosen as a folding system to obtain detailed time-resolved thermodynamic profiles for the earliest events in the protein folding process. Cytochrome-c is an ideal system for understanding the folding process for several reasons. One being that the system can unfold and refold reversibly without the loss of the covalently attached heme group. A number of studies have shown that under denaturing conditions, ferrous Cc (Fe2+Cc) heme group in the presence of carbon monoxide (CO) results in a disruption of the axial heme Methionine-80 (Met80) bond ultimately unfolding the protein. CO-photolysis of this ferrous species results in the formation of a transient unfolded protein that is poised in a non-equilibrium state with the equilibrium state being that of the native folded Fe2+Cc complex. This allows for the refolding reaction of the protein to be photo-initiated and monitor on ns - ms timescales. While CO cannot bind to the ferric form, nitrogen monoxide (NO) photo-release has been developed to photo-trigger ferric Cc (Fe3+Cc) unfolding under denaturing conditions. Photo-dissociation of NO leaves the Fe3+complex in a conformational state that favors unfolding thus allowing the early unfolding events of Fe3+Cc to be probed. Overall the results presented here involve the use of the ligands CO and NO along with photoacoustic calorimetry (PAC) to photo-trigger the folding/unfolding reaction of Cc (and modified Cc). Thus, obtaining enthalpy and molar volume changes directly associated with the initial folding/unfolding events occurring in the reaction pathways of both Fe2+ and Fe3+Cc systems that are most essential to understanding the driving forces involved in forming the tertiary native conformation. The PAC data shows that folding of proteins results from a hierarchy of events that potentially includes the formation of secondary structures, hydrophobic collapse, and/or reorganization of the tertiary complex occurring over ~ns – tens of µs time ranges. In addition, the PAC kinetic fits presented in this work is the first to report Cc folding exhibiting heterogeneous kinetics (in some cases) by utilizing a stretched exponential decay function.