Magister Commercii - MCom / Political and economic sanctions between 1970 and 1994 isolated the inward-oriented economy of South Africa from global trends. A variety of factors, such as a challenging new global competitive environment, production overcapacity, falling protectionist tariff barriers in a period of liberalisation, world-class manufacture and globalisation, are contributing to the reform of the economy and the automotive industry. The South African automotive industry therefore faces a major reform in trade policy. The South African government introduced the Motor Industry Development Plan (MIDP) in 1995, to create the necessary levels of competitiveness, promote world class manufacture practices, increase levels of investments and exports that would consequently lead to the successful reconstruction and development of this sector of the South African economy. Subsequent research has shown that the successful adoption of world-class manufacture (or lean production) processes in the South African automotive industry is necessary not only for survival, but also for increased competitiveness of the industry and the improved economic performance of automotive firms. However, complicated links exist between the adoption of world-class manufacture for improved levels of operational competitiveness. for firm-level success, on the one hand, and long-term sustainability of the industry, on the other hand. Combined firm level economic success and long-term sustainability of the industry depend on factors such as international trends, connectivity to global value chains, modern technological capabilities, lean production and enterprise systems, substantial investments, increased exports, world-wide quality standards, as well as customer satisfaction, human resource development, advanced education, skills development, worker participation, government policy and institutional support. This is borne out by a recent study of the auto component sector, utilising a lean , production 'market driver' toolkit. The study found that although component manufacturers significantly improved their operational competitiveness, they have not necessarily experienced improved economic performance levels. More important is connectedness and integration into global value chains, via intermediaries, mergers and acquisitions. The changing political economy of automotive value chains is also important in shaping fum-level operational success and industry sustainability. In this research paper, we review global automotive industry trends which influenced the introduction of the government's visionary MIDP. We then discuss their impact on the performance of the South African assembly and component sectors at industry and finn level. This leads to a series of recommendations for improved performance to world-class manufacture, world-wide quality standards and global competitiveness

Magister Commercii - MCom / Political and economic sanctions between 1970 and 1994 isolated the inward-oriented economy of South Africa from global trends. A variety of factors, such as a challenging new global competitive environment, production overcapacity, falling protectionist tariff barriers in a period of liberalisation, world-class manufacture and globalisation, are contributing to the reform of the economy and the automotive industry. The South African automotive industry therefore faces a major reform in trade policy. The South African government introduced the Motor Industry Development Plan (MIDP) in 1995, to create the necessary levels of competitiveness, promote worldclass manufacture practices, increase levels of investments and exports that would consequently lead to the successful reconstruction and development of this sector of the South African economy. Subsequent research has shown that the successful adoption of world-class manufacture (or lean production) processes in the South African automotive industry is necessary not only for survival, but also for increased competitiveness of the industry and the improved economic performance of automotive firms. However, complicated links exist between the adoption of world-class manufacture for improved levels of operational competitiveness. for firm-level success, on the one hand, and long-term sustainability of the industry, on the other hand. Combined firm level economic success and long-term sustainability of the industry depend on factors such as international trends, connectivity to global value chains, modern technological capabilities, lean production and enterprise systems, substantial investments, increased exports, world-wide quality standards, as well as customer satisfaction, human resource development, advanced education, skills development, worker participation, government policy and institutional support. This is borne out by a recent study of the auto component sector, utilising a lean , production 'market driver' toolkit. The study found that although component manufacturers significantly improved their operational competitiveness, they have not necessarily experienced improved economic performance levels. More important is connectedness and integration into global value chains, via intermediaries, mergers and acquisitions. The changing political economy of automotive value chains is also important in shaping fum-level operational success and industry sustainability.

The aim of this work was to find a correlation between the electrical, optical and microstructural properties of thin SiO2 layers containing group IV nanostructures produced by ion beam synthesis. The investigations were focused on two main topics: The electrical properties of Ge- and Si-rich oxide layers were studied in order to check their suitability for non-volatile memory applications. Secondly, photo- and electroluminescence (PL and EL) results of Ge-, Si/C- and Sn-rich SiO2 layers were compared to electrical properties to get a better understanding of the luminescence mechanism.

Die Kenntnisse über die zur Passivierung führenden Wechselwirkungen des Verunreinigungselements Cu mit EL2 und EL6 wurden dahingehend erweitert, dass ein Gültigkeitsbereich für die Messungen zur Bestimmung der konzentrationsproportionalen Messgröße der Defekte festgelegt wurde. Der Defekt EL6 ist das die 0.8 eV-PL-Emission bedingende und die Ladungsträgerlebensdauer determinierende Rekombinationszentrum. Die Lebensdauer wird durch mindestens ein weiteres Zentrum beeinflusst. Die atomare Struktur des EL6 wurde mit AsGa VAs und die des weiteren Zentrums mit Asi bestimmt. Mittels Wärmebehandlung kann die Ladungsträgerlebensdauer gezielt beeinflusst werden. Bei der Bildung und Annihilation sowie der Verteilung der Defekte EL2, EL6, VGa und der As-Ausscheidungen besteht eine wechselseitige Korrelation. Sowohl strukturelle Defekte als auch die Inkorporation von Dotierelementen, deren Atomradien deutlich kleiner sind als Ga und As, stellen beeinflussende Faktoren dar. Das Defekt-Transformations-Modell erklärt die Bildung wachstumsfähiger Keime einer As-Ausscheidung durch EL2 bzw. EL6 mit den sich in der ersten Koordingationssphäre befindenden As-Atomen. Das Gitterrelaxations-Modell ermöglicht die Interpretation der katalytischen Wirkung des Dotierelements C. Die Umsetzung dieser Ergebnisse bedeutet die Anwendung des Defect Engineerings im SI-LEC-GaAs.

Die hochempfindliche Methode der „Microwave Detected Photoconductivity“ (MDP) wird eingesetzt, um technologisch relevante Halbleiterparameter wie die Ladungsträgerlebensdauer, Photoleitfähigkeit und Defektkonzentrationen über viele Größenordnungen der optischen Anregung hinweg zu untersuchen. Durch die Entwicklung und die Anwendung eines neuartigen Modellierungssystems für die Ladungsträgerdynamik in Halbleitern können wichtige Defektparameter quantitativ aus MDP Messungen in Abhängigkeit der Anregungsintensität bestimmt werden. Ein Verfahren zur Charakterisierung von Haftstellen (Konzentration, Energielage, Einfangsquerschnitt) bei konstanter Temperatur wird vorgestellt. Das technologisch relevante Verfahren des quantitativen Eisennachweises in p-dotiertem Silizium wird für die MDP Methode angepasst und entsprechende Messergebnisse mit DLTS Resultaten verglichen. Ein detaillierter Vergleich der gängigsten kontaktlosen Messverfahren QSSPC und MW-PCD mit der MDP zeigt, dass entgegen gängiger Annahmen die unterschiedlichen Anregungsbedingungen zu drastischen Unterschieden in den gemessenen Werten der Ladungsträgerlebensdauer führen. Dies wird sowohl durch theoretische Berechnungen als auch durch praktische Messergebnisse belegt.

Brønsted and Lewis acid sites located within microporous solids catalyze a variety of chemical transformations of oxygenates and hydrocarbons. Such reactions occur in condensed phases in envisioned biomass and shale gas upgrading routes, motivating deeper fundamental understanding of the reactivity-determining interactions among active sites, reactants, and solvents. The crystalline structures of zeolites, which consist of SiO₄ tetrahedra with isomorphously-substituted M⁴⁺ (e.g., Sn⁴⁺, Ti⁴⁺) as Lewis acid sites, or Al³⁺ with charge-compensating extraframework H⁺ as Brønsted acid sites, provide a reasonably well-defined platform to study these interactions within confining voids of molecular dimension. In this work, gas-phase probe reactions that afford independent control of solvent coverages are developed and used to interpret measured rate data in terms of rate and equilibrium constants for elementary steps, which reflect the structure and stability of kinetically relevant transition states and reactive intermediates. The foundational role of quantitative kinetic information enables building molecular insights into the mechanistic and active site requirements of catalytic reactions, when combined with complementary tools including synthetic approaches to prepare active sites and surrounding environments of diverse and intended structure, quantitative methods to characterize and titrate active sites and functional groups in confining environments, and theoretical modeling of putative active site structures and plausible reaction coordinates.<br><div><br></div><div>Bimolecular ethanol dehydration to diethyl ether was developed as a gas-phase catalytic probe reaction for Lewis acid zeolites. A detailed mechanistic understanding of the identities of reactive intermediates and transition states on Sn-Beta zeolites was constructed by combining experimental kinetic measurements with density functional theory treatments. Microkinetic modeling demonstrated that Sn active site configurations undergo equilibrated interconversion during catalysis (404 K, 0.5–35 kPa C₂H₅OH, 0.1–50 kPa H₂O) from hydrolyzed-open configurations ((HO)-Sn-(OSi≡)₃---HO-Si) to predominantly closed configurations (Sn-(OSi≡)₄), and identified the most abundant productive (ethanol-ethanol dimer) and inhibitory (ethanol-water dimer) reactive intermediates and kinetically relevant transition state (S_N2 at closed sites). Mechanism-based interpretations of bimolecular ethanol dehydration turnover rates (per Lewis acidic Sn, quantified by CD₃CN IR) enabled measuring chemically significant differences between samples synthesized to contain high or low densities of residual Si-OH defects (quantified by CD₃CN IR) within microporous environments that confine Sn active sites. Hydrogen-bonding interactions with Si-OH groups located in the vicinity of Sn active sites in high-defect Sn-Beta zeolites stabilize both reactive and inhibitory intermediates, leading to differences in reactivity within polar and non-polar micropores that reflect solely the different coverages of intermediates at active sites. The ability of confining microporous voids to discriminate among reactive intermediates and transition states on the basis of polarity thus provides a strategy to mitigate inhibition by water and to influence turnover rates by designing secondary environments of different polarity via synthetic and post-synthetic techniques. </div><div><br></div><div>Despite the expectation from theory that Sn active sites adopt the same closed configurations after high-temperature (823 K) oxidation treatments, distinct Sn sites can be experimentally identified and quantified by the ν(C≡N) infrared peaks of coordinated CD₃CN molecules, and a subset of these sites are correlated with first-order rate constants of aqueous-phase glucose-fructose isomerization (373 K). In contrast, <i>in situ</i> titration of active sites by pyridine during gas-phase ethanol dehydration catalysis (404 K) on a suite of Sn-zeolites of different topology (Beta, MFI, BEC) quantified the dominant active site to correspond to a different subset of Sn sites than those dominant in glucose-fructose isomerization. An extensive series of synthetic and post-synthetic routes to prepare Sn-zeolites containing Sn sites hosted within diverse local coordination environments identified a subset of Sn sites located in defective environments such as grain boundaries, which are more pronounced in Beta crystallites comprised of intergrowths of two polymorphs than in zeolite frameworks with un-faulted crystal structures. Sn sites in such environments adopt defect-open configurations ((HO)-Sn-(OSi≡)₃) with proximal Si-OH groups that do not permit condensation to closed configurations, which resolves debated spectroscopic assignments to hydrolyzed-open site configurations. Defect-open Sn sites are dominant in glucose-fructose isomerization because their proximal Si-OH groups stabilize kinetically relevant hydride shift transition states, while closed framework Sn sites are dominant in alcohol dehydration because they stabilize S_N2 transition states via Sn site opening in the kinetically relevant step and re-closing as part of the catalytic cycle. The structural diversity of real zeolite materials, whose defects distinguish them from idealized crystal structures and allows hosting Lewis acid sites with distinct local configurations, endows them with the ability to effectively catalyze a broad range of oxygenate reactions.</div><div><br></div><div>During aqueous-phase catalysis, high extra-crystalline water chemical potentials lead to intra-pore stabilization of H₂O molecules, clusters, and extended hydrogen-bonded networks that interact with adsorbed intermediates and transition states at Lewis acid sites. Glucose-fructose isomerization turnover rates (373 K, per defect-open Sn, quantified by CD₃CN IR) are higher when Sn sites are confined within low-defect, non-polar zeolite frameworks that effectively prevent extended water networks from forming; however, increasing exposure to hot (373 K) liquid water generates Si-OH groups via hydrolysis of siloxane bridges and leads to lower turnover rates commensurate with those of high-defect, polar frameworks. Detailed kinetic, spectroscopic, and theoretical studies of polar and non-polar titanosilicate zeolite analogs indicate that extended water networks entropically destabilize glucose-fructose isomerization transition states relative to their bound precursors, rather than influence the competitive adsorption of water and glucose at active sites. Infrared spectra support the stabilization of extended hydrogen-bonded water networks by Si-OH defects located within Si- and Ti-Beta zeolites, consistent with ab initio molecular dynamics simulations that predict formation of distinct thermodynamically stable clustered and extended water phases within Beta zeolites depending on the external water chemical potential and the nature of their chemical functionality (closed vs. hydrolyzed-open Lewis acid site, or silanol nest defect). The structure of water confined within microporous solids is determined by the type and density of intracrystalline polar binding sites, leading to higher reactivity in aqueous media when hydrogen-bonded networks are excluded from hydrophobic micropores.</div><div><br></div><div>Aluminosilicate zeolites adsorb water to form (H₃O⁺)(H₂O)_n clusters that mediate liquid-phase Brønsted acid catalysis, but their relative contributions to the solvation of reactive intermediates and transition states remain unclear. Bimolecular ethanol dehydration turnover rates (per H⁺, quantified by NH₃ temperature-programmed desorption and <i>in situ</i> titrations with 2,6-di-<i>tert</i>-butylpyridine) and transmission infrared spectra measured on Brønsted acid zeolites under conditions approaching intrapore H₂O condensation (373 K, 0.02–75 kPa H₂O) reveal the formation of clustered, solvated (C₂H₅OH)(H⁺)(H₂O)_n intermediates, which are stabilized to greater extents than bimolecular dehydration transition states by extended hydrogen-bonded water networks. Turnover rates deviate sharply below those predicted by kinetic regimes in the absence of extended condensed water networks because non-ideal thermodynamic formalisms are required to account for the different solvation of transition states and MARI. The condensation of liquid-like phases within micropores that stabilize reaction intermediates and transition states to different extents is a general phenomenon for Brønsted acid-catalyzed alcohol dehydration within zeolites of different topology (CHA, AEI, TON, FAU), which governs the initial formation and structure of clustered hydronium-reactant and water-protonated transition state complexes. Systematic control of liquid-phase structures within confined spaces by gas-phase measurements around the point of intrapore condensation enables more detailed mechanistic and structural insights than those afforded by either kinetic measurements in the liquid phase, or structural characterizations of aqueous systems in the absence of reactants.</div>

This thesis has covered the democratic development of Poland and Ukraine from 2010 to 2021. The purpose of this study is to test if Merkel’s theory of embedded and defect democracy together with the addition of Boogaard’s diffusely defect democracy can explain the development in Poland and Ukraine. The questions that will be answered are: Shall Poland and Ukraine be classified as embedded or defect democracies?What are the differences and similarities in these countries’ classifications between 2010 and 2021?Is Merkel’s theory about embedded and defect democracy able to explain the development from 2010 to 2021?Poland and Ukraine were classified as diffusely defect democracies. There are some similarities between Poland and Ukraine regarding the rule of law, but Ukraine is more defect than Poland. Merkel’s theory is a better explanation for Ukraine than Poland due to that Ukraine has had the defects during a longer period.

Mine haul road maintenance is traditionally done at scheduled intervals or after regular inspection. Both these methods can lead to unwarranted expenditure, either through over-maintaining the road, or failure to recognise significant deterioration, resulting in an increase in vehicle operating costs. Predictive maintenance management models for unpaved roads have been developed in recent years. These methods work well in a trivial environment where variables such as traffic volume can be predicted. However, many mining systems are too complex for such models to be effective. This work investigates the possibility of using haul truck response to aid haul road maintenance management. The approach adopted for the study was twofold: Firstly, can truck response data be used to recognise specific road defects, in terms of location, type and size? This is important since different defect types require different road maintenance strategies. Secondly, can road roughness be measured on a qualitative basis? With the emphasis on road defect reconstruction, a mathematical modelling approach was adopted. The truck was characterised in terms of its suspension and tyre properties. Dynamic truck response data was acquired during field measurements in which the vehicle was driven over defects of known dimensions. With these data sets available, mathematical modelling and simulation was possible. Quarter vehicle and seven degree of freedom vehicle models played a vital role in this work by laying a foundation in the use of haul truck response for the purpose of road defect reconstruction. A modelling methodology that is based on dynamic equilibrium of an independent front unsprung mass of the truck is proposed in which the vertical dynamic tyre force and eventually the road geometry is calculated. It is shown that defects can be reconstructed from measured truck response data with an accuracy sufficient to fulfil the requirements of defect recognition for road maintenance management purposes. Secondly, a preliminary investigation into the qualitative assessment of road condition via truck response measurements was conducted. The inherent response properties of the truck pertaining to road roughness measurement were studied and some correlation between measured suspension motion and road roughness measured with a high speed profilometer was found. / Dissertation (MEng (Mechanical))--University of Pretoria, 2005. / Mechanical and Aeronautical Engineering / MEng / Unrestricted

Rare diseases (RD) are a heterogeneous group of diseases that affect about 5% of the world population. RDs represent more than 7.000 different phenotypes and many of them are genetically determined. RDs provide unique biological models for understanding the basic principles of molecular and cellular organization and function of human tissues and organs. Results of studies focused at pathogenesis of RDs are often used to diagnose and treat the affected patients. Significant progress in molecular genetic techniques, specifically the use of the next generation sequencing (NGS) in clinical practice, substantially facilitated and improved efficiency of RD laboratory diagnostics. Moreover, these novel testing algorithms identified the previously unknown molecular causes of many RDs. This thesis demonstrates the utility of NGS techniques and bioinformatics processing of obtained data in studies aimed at understanding molecular basis of selected RDs. These methods led to identification and characterization of causative pathogenic variants in the NDUFAF6 and PLD1 genes among patients affected by the Acadian variant of Fanconi disease and patients with a rare congenital heart defect, respectively. This approach was further used to analyze exomes of a large cohort of patients with different types of...

The purpose of this work and the project under which it was created is to develop, compare and validate several theoretical approaches and computation methods used to calculate the cross sections of dissociative recombination. For the most part it is con- cerned with the indirect dissociative recombination of molecular ions of H+ 2 in the singlet ungerade channels computed with three distinct approaches. First, the fully numerically solvable two-dimensional approach developed at ÚTF MFF UK as a part of my master's thesis. Second, a vibrational frame transformation method based on the work of Chang and Fano [E. S. Chang and U. Fano, Phys. Rev. A 6, 173 (1972)] and then enhanced into a full energy-dependent form by Gao and Greene [H. Gao and C. H. Greene, J. Chem. Phys. 91, 3988 (1989)], [H. Gao and C. H. Greene, Phys. Rev. A 42, 6946 (1990)], fur- ther improved by our own revisions. Third, a two-dimensional R-matrix method based on matching exact 2D solutions from a small interaction region to asymptotic solutions in the non-interacting region. We thoroughly discuss the various advantages and caveats of these methods and, in the later chapters, present our work on employing them for the realistic recombination of HeH+ + e− . Furthermore, we attempt to extend the presented models to the description of the...