Thermal degradation of diamond compacts: a TEM investigation
- Authors: Westraadt, Johan Ewald
- Date: 2011
- Subjects: Materials -- Thermal properties Chemical weathering
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/10829 , vital:26827
- Description: Diamond compacts consist of fine diamond grains bonded together by using high pressure and high temperature. In this study transmission electron microscopy (TEM)was used to study thermal degradation of diamond compacts. Three different types of diamond compacts – namely cobalt polycrystalline diamond (PCD), calcium carbonate PCD, and diamond-SiC composites – were investigated with TEM to understand the processes that occur during synthesis. These compacts were then heated in inert atmospheres and the chemical changes studied with TEM. It was found that PCD, using cobalt as a bonding agent, will degrade after exposure to temperatures above 750ºC. The cobalt pools contain tungsten in solid solution. During heat treatment above 700ºC the solid solution tungsten combines with cobalt and dissolved carbon to form η-phase particles at the cobalt/diamond interface. At higher temperatures or insufficient tungsten levels the rate of dissolved carbon, into the cobalt pool, is too high and the excess carbon will form as graphite in the cobalt pool. Increased levels of solid solution tungsten, in the cobalt, is expected to delay the onset of graphitization in the diamond compact, thereby increasing the thermal stability of the diamond compact. Non-metallic PCD using calcium carbonate as a bonding agent was successfully sintered in this study. TEM revealed similar micro-structural features as in cobalt based PCD. No signs of thermal degradation were found after exposure to 1200ºC in vacuum for this PCD. Contaminants introduced during processing prevented a detailed study of the binder in this system. The effect of substitutional metal atoms and plastic deformation of diamond on the thermal stability of diamond-SiC composites were investigated. A piston cylinder press was developed and used to synthesize diamond-SiC composites with different levels of plastically deformed diamond. It was concluded that substitutional metal atoms and plastic deformation of diamond grains play no role in the thermal degradation of diamond compacts at 750ºC. The thermal degradation of cobalt PCD is therefore completely determined by the cobalt/diamond interaction at 750ºC.
- Full Text:
- Date Issued: 2011
- Authors: Westraadt, Johan Ewald
- Date: 2011
- Subjects: Materials -- Thermal properties Chemical weathering
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/10829 , vital:26827
- Description: Diamond compacts consist of fine diamond grains bonded together by using high pressure and high temperature. In this study transmission electron microscopy (TEM)was used to study thermal degradation of diamond compacts. Three different types of diamond compacts – namely cobalt polycrystalline diamond (PCD), calcium carbonate PCD, and diamond-SiC composites – were investigated with TEM to understand the processes that occur during synthesis. These compacts were then heated in inert atmospheres and the chemical changes studied with TEM. It was found that PCD, using cobalt as a bonding agent, will degrade after exposure to temperatures above 750ºC. The cobalt pools contain tungsten in solid solution. During heat treatment above 700ºC the solid solution tungsten combines with cobalt and dissolved carbon to form η-phase particles at the cobalt/diamond interface. At higher temperatures or insufficient tungsten levels the rate of dissolved carbon, into the cobalt pool, is too high and the excess carbon will form as graphite in the cobalt pool. Increased levels of solid solution tungsten, in the cobalt, is expected to delay the onset of graphitization in the diamond compact, thereby increasing the thermal stability of the diamond compact. Non-metallic PCD using calcium carbonate as a bonding agent was successfully sintered in this study. TEM revealed similar micro-structural features as in cobalt based PCD. No signs of thermal degradation were found after exposure to 1200ºC in vacuum for this PCD. Contaminants introduced during processing prevented a detailed study of the binder in this system. The effect of substitutional metal atoms and plastic deformation of diamond on the thermal stability of diamond-SiC composites were investigated. A piston cylinder press was developed and used to synthesize diamond-SiC composites with different levels of plastically deformed diamond. It was concluded that substitutional metal atoms and plastic deformation of diamond grains play no role in the thermal degradation of diamond compacts at 750ºC. The thermal degradation of cobalt PCD is therefore completely determined by the cobalt/diamond interaction at 750ºC.
- Full Text:
- Date Issued: 2011
Ecological assessment and biogeography of coastal vegetation and flora in southern Mozambique
- Authors: Massingue, Alice Obed
- Date: 2019
- Subjects: Coastal plants -- Mozambique , Coastal plants Marine biodiversity -- Mozambique Coastal biodiversity -- Mozambique
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/40988 , vital:36280
- Description: This study considered aspects of the vegetation of the coastal zone of southern Mozambique, an area with a rich biodiversity. The vegetation and flora were assessed in their current state including the associated anthropogenic pressures. The environmental conditions that determined the distribution of the vegetation were evaluated. A hierarchical classification, description and ecological interpretation of the vegetation and flora of the coastal zone in southern Mozambique are presented. Analysis was based on 242 sample quadrats that were distributed in a stratified manner throughout the study area. The vegetation could be grouped into six distinct types of vegetation: Dune Forest, Coastal Forest, Coastal Grassland, Coastal Miombo, Coastal Savanna and Coastal Woodland. Species diversity was high for the all the vegetation types, particularly in the woody elements. A total of 673 species in 410 genera was recorded. They represented 104 families with Fabaceae and Rubiaceae being the most common. Of these, 6.6% were endemic or near-endemic to the coastal zone of southern Mozambique with Coastal Forest being the habitat with the greatest endemism. All soils from different vegetation types had poor agricultural potential. Soil properties were the strongest defining environmental feature separating the vegetation types: e.g. pH was high in Dune Forest compared to the others. Results from Maxent modelling suggest that the distribution of endemic species is influenced by a combination of climatic and non-climatic variables. Soil type, temperature annual range and precipitation of the driest month were the most important predictor variables. Overlaying the potential distributions of the seven selected species indicated two areas of abundance of endemic species – these should be given attention for conservation. Endemic species are not well protected in southern Mozambique – their sampled and potential habitats are largely outside protected areas. Hence, additional reserves should be created to improve their protection. Most endemic and near-endemics species were found in the south, from Ponta de Ouro (Matutuine, south of Maputo Province) to Manhica district (north of the Maputo Province) forming part of the Maputaland Centre of Endemism. A second concentration of endemism was found in the Inhambane Province, specifically the Inhassoro and Vilanculos districts. This is proposed to be an Important Plants Area (IPA). Because most endemics and near-endemics are found in the Coastal Forest, their main threat is harvesting for charcoal production, although none of the endemic species are specifically targeted for charcoal production. In Inhambane they are also threatened by the tourism industry, agriculture and settlements. The impact of the habitat destruction on endemic species is expected to cause severe declines in the near future. The tourism industry and harvesting of trees for charcoal production and over-frequent fires are the main drivers of vegetation loss in this region. Shifting agriculture, harvesting for firewood and construction materials, cattle grazing (at a minor scale) are also impacts, but these were only observed in a small area of Maputo Province. Although the study was done in coastal zone of southern Mozambique, effective management of whole coastal zone of the country will be required to maintain a functioning and diverse ecosystem. Priorities for management are to ensure that forests are protected, in particular, Dune Forest. Actions are required to minimise degradation of coastal vegetation. Further research on Coastal Forest restoration should be planned, as field observations in this study confirm that forest in the coastal zone of southern Mozambique has resilience.
- Full Text:
- Date Issued: 2019
- Authors: Massingue, Alice Obed
- Date: 2019
- Subjects: Coastal plants -- Mozambique , Coastal plants Marine biodiversity -- Mozambique Coastal biodiversity -- Mozambique
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/40988 , vital:36280
- Description: This study considered aspects of the vegetation of the coastal zone of southern Mozambique, an area with a rich biodiversity. The vegetation and flora were assessed in their current state including the associated anthropogenic pressures. The environmental conditions that determined the distribution of the vegetation were evaluated. A hierarchical classification, description and ecological interpretation of the vegetation and flora of the coastal zone in southern Mozambique are presented. Analysis was based on 242 sample quadrats that were distributed in a stratified manner throughout the study area. The vegetation could be grouped into six distinct types of vegetation: Dune Forest, Coastal Forest, Coastal Grassland, Coastal Miombo, Coastal Savanna and Coastal Woodland. Species diversity was high for the all the vegetation types, particularly in the woody elements. A total of 673 species in 410 genera was recorded. They represented 104 families with Fabaceae and Rubiaceae being the most common. Of these, 6.6% were endemic or near-endemic to the coastal zone of southern Mozambique with Coastal Forest being the habitat with the greatest endemism. All soils from different vegetation types had poor agricultural potential. Soil properties were the strongest defining environmental feature separating the vegetation types: e.g. pH was high in Dune Forest compared to the others. Results from Maxent modelling suggest that the distribution of endemic species is influenced by a combination of climatic and non-climatic variables. Soil type, temperature annual range and precipitation of the driest month were the most important predictor variables. Overlaying the potential distributions of the seven selected species indicated two areas of abundance of endemic species – these should be given attention for conservation. Endemic species are not well protected in southern Mozambique – their sampled and potential habitats are largely outside protected areas. Hence, additional reserves should be created to improve their protection. Most endemic and near-endemics species were found in the south, from Ponta de Ouro (Matutuine, south of Maputo Province) to Manhica district (north of the Maputo Province) forming part of the Maputaland Centre of Endemism. A second concentration of endemism was found in the Inhambane Province, specifically the Inhassoro and Vilanculos districts. This is proposed to be an Important Plants Area (IPA). Because most endemics and near-endemics are found in the Coastal Forest, their main threat is harvesting for charcoal production, although none of the endemic species are specifically targeted for charcoal production. In Inhambane they are also threatened by the tourism industry, agriculture and settlements. The impact of the habitat destruction on endemic species is expected to cause severe declines in the near future. The tourism industry and harvesting of trees for charcoal production and over-frequent fires are the main drivers of vegetation loss in this region. Shifting agriculture, harvesting for firewood and construction materials, cattle grazing (at a minor scale) are also impacts, but these were only observed in a small area of Maputo Province. Although the study was done in coastal zone of southern Mozambique, effective management of whole coastal zone of the country will be required to maintain a functioning and diverse ecosystem. Priorities for management are to ensure that forests are protected, in particular, Dune Forest. Actions are required to minimise degradation of coastal vegetation. Further research on Coastal Forest restoration should be planned, as field observations in this study confirm that forest in the coastal zone of southern Mozambique has resilience.
- Full Text:
- Date Issued: 2019
Ecology of key cerithioidean gastropods in the mangroves of the iSimangaliso Wetland Park, KwaZulu-Natal South Africa
- Authors: Raw, Jacqueline Leoni
- Date: 2017
- Subjects: Gastropoda -- South Africa -- KwaZulu-Natal Mangrove ecology -- South Africa -- KwaZulu-Natal
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/11942 , vital:27009
- Description: Gastropods are one of the most diverse species groups in mangrove habitats, however, many of their specific roles in relation to ecological patterns and processes are currently largely unknown. The overall aim of this research project was to provide basic ecological information for key gastropod species from subtropical mangroves within a protected area. South African mangroves cover relatively small areas and are restricted to estuaries, these habitats therefore present unique opportunities and challenges to the species that occur in them. Three gastropod species, Terebralia palustris, Cerithidea decollata, and Melanoides tuberculata, all occur at their natural southernmost range limit within South Africa and were selected based on their prominence and occurrence in mangrove habitats of the iSimangaliso Wetland Park, a UNESCO World Heritage Site. Trophic linkages and resource partitioning, resource utilization rates, and ecological resilience were investigated respectively using: 1) a stable isotope (δ15N and δ13C) approach; 2) an experimental approach to quantify feeding dynamics (ingestion rate, consumption/digestion efficiency and grazing impact); and 3) a mixed-effects modelling approach to relate population responses to environmental variables. The diet of T. palustris was seasonally variable and a number of sources were incorporated by different sized snails, but their grazing impact on microphytobenthos was not significant. The results also indicated an ontogenetic shift in the dietary niche for T. palustris through robust partitioning of resources between different size classes. The diets of C. decollata and M. tuberculata were dominated by different primary resources as a function of where they occurred in the mangroves. Melanoides tuberculata consumed a wide variety of primary resources, a typical trait of an opportunistic generalist species. The ingestion rate of M. tuberculata was not dependent on the availability of microphytobenthos, and was highest when conditions were oligotrophic. The resilience of C. decollata was related to the tree-climbing behaviour of this species and its occurrence was best explained by sediment conductivity. These responses were considered in conjunction to what has previously been reported on the resilience of the mangrove trees. The results of this research project have provided new basic ecological information for all three gastropod species in this data-deficient subtropical region. This information can potentially be used in comparative studies for these species in other regions or in broader scale ecological studies. Terebralia palustris has recently experienced a range contraction along the South African coastline. This research project has shown that the diet of this species is highly variable and that food limitation and competition for resources should be considered as potential drivers of the local decline. Cerithidea decollata has in contrast expanded its distributional range in this region. This research project has shown that this species has a generalist diet and exhibits traits in relation to tolerance that are expected to have facilitated its expansion into temperate saltmarsh habitats that occur in dynamic estuaries. Melanoides tuberculata is a globally invasive species, and as South African populations are within its native range, ecological information from this region is valuable as it can be used to investigate the potential ecological effects following introduction into new habitats beyond the native range. Biological drivers have a significant impact on mangrove ecosystem functioning, particularly in relation to recycling and the retention of organic carbon generated through primary productivity. Understanding the ecological linkages that maintain ecological functioning and stability is therefore an important step towards conserving and sustainably managing threatened ecosystems such as mangrove forests.
- Full Text:
- Date Issued: 2017
- Authors: Raw, Jacqueline Leoni
- Date: 2017
- Subjects: Gastropoda -- South Africa -- KwaZulu-Natal Mangrove ecology -- South Africa -- KwaZulu-Natal
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/11942 , vital:27009
- Description: Gastropods are one of the most diverse species groups in mangrove habitats, however, many of their specific roles in relation to ecological patterns and processes are currently largely unknown. The overall aim of this research project was to provide basic ecological information for key gastropod species from subtropical mangroves within a protected area. South African mangroves cover relatively small areas and are restricted to estuaries, these habitats therefore present unique opportunities and challenges to the species that occur in them. Three gastropod species, Terebralia palustris, Cerithidea decollata, and Melanoides tuberculata, all occur at their natural southernmost range limit within South Africa and were selected based on their prominence and occurrence in mangrove habitats of the iSimangaliso Wetland Park, a UNESCO World Heritage Site. Trophic linkages and resource partitioning, resource utilization rates, and ecological resilience were investigated respectively using: 1) a stable isotope (δ15N and δ13C) approach; 2) an experimental approach to quantify feeding dynamics (ingestion rate, consumption/digestion efficiency and grazing impact); and 3) a mixed-effects modelling approach to relate population responses to environmental variables. The diet of T. palustris was seasonally variable and a number of sources were incorporated by different sized snails, but their grazing impact on microphytobenthos was not significant. The results also indicated an ontogenetic shift in the dietary niche for T. palustris through robust partitioning of resources between different size classes. The diets of C. decollata and M. tuberculata were dominated by different primary resources as a function of where they occurred in the mangroves. Melanoides tuberculata consumed a wide variety of primary resources, a typical trait of an opportunistic generalist species. The ingestion rate of M. tuberculata was not dependent on the availability of microphytobenthos, and was highest when conditions were oligotrophic. The resilience of C. decollata was related to the tree-climbing behaviour of this species and its occurrence was best explained by sediment conductivity. These responses were considered in conjunction to what has previously been reported on the resilience of the mangrove trees. The results of this research project have provided new basic ecological information for all three gastropod species in this data-deficient subtropical region. This information can potentially be used in comparative studies for these species in other regions or in broader scale ecological studies. Terebralia palustris has recently experienced a range contraction along the South African coastline. This research project has shown that the diet of this species is highly variable and that food limitation and competition for resources should be considered as potential drivers of the local decline. Cerithidea decollata has in contrast expanded its distributional range in this region. This research project has shown that this species has a generalist diet and exhibits traits in relation to tolerance that are expected to have facilitated its expansion into temperate saltmarsh habitats that occur in dynamic estuaries. Melanoides tuberculata is a globally invasive species, and as South African populations are within its native range, ecological information from this region is valuable as it can be used to investigate the potential ecological effects following introduction into new habitats beyond the native range. Biological drivers have a significant impact on mangrove ecosystem functioning, particularly in relation to recycling and the retention of organic carbon generated through primary productivity. Understanding the ecological linkages that maintain ecological functioning and stability is therefore an important step towards conserving and sustainably managing threatened ecosystems such as mangrove forests.
- Full Text:
- Date Issued: 2017
Beta-N-methylamino-L-alanine in South African fresh water cyanobacteria : incidence, prevalence, ecotoxicological considerations and human exposure risk
- Authors: Esterhuizen-Londt, Maranda
- Date: 2010
- Subjects: Cyanobacteria , Bioaccumulation , Chromatographic analysis , Neurotoxic agents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10306 , http://hdl.handle.net/10948/1473 , Cyanobacteria , Bioaccumulation , Chromatographic analysis , Neurotoxic agents
- Description: β-N-methylamino-L-alanine (BMAA) is a non-proteinogenic amino acid associated with human neurodegenerative disease. Due to the cosmopolitan nature of cyanobacteria, detection of BMAA in cyanobacteria has caused concerns about human exposure risk. This study was therefore based on the hypothesis that BMAA poses a health risk to humans either by direct ingestion or by indirect exposure to BMAA from a cyanobacterial source via a freshwater food chain. A validated gas chromatography-mass spectrometry (GC-MS) BMAA analysis method and a confirmatory liquid chromatography-mass spectrometry (LC-MS) method, with improved sensitivity, were developed in addition to a LC-MS/MS method for analyte confirmation. These methods were used to quantify BMAA in South African cyanobacteria, isolated from various potable water reservoirs. The majority of the isolates tested, contained BMAA. Possible human exposure by direct consumption of BMAA released from cyanobacterial blooms was investigated by the development of a robust solid phase extraction (SPE) method used for BMAA concentration and quantification in raw and treated tap water. Despite the use of the SPE method that facilitated the concentration of BMAA from large quantities of water, no free dissolved BMAA was detected in raw or processed fresh water. The fate of exogenous BMAA was therefore investigated firstly by evaluating the efficacy of standard water treatment processes employed in South Africa and secondly by investigating the possibility of BMAA bioaccumulation and biomagnification in aquatic food chains. Standard water treatment processes proved highly efficient at removing free dissolved BMAA, explaining the absence of BMAA in treated tap water. However, the cause of the BMAA absence in raw potable water remained unknown. Uptake of BMAA by model aquatic organisms was investigated in controlled experiments. BMAA uptake was documented in both Ceratophyllum demersum and Daphnia magna, however, BMAA-protein association and biomagnification were not observed in D. magna. BMAA had an inhibitory effect on the oxidative stress enzyme acitivties of both organisms tested (as well as human S9 extracts), resulting in accumulation of detrimental reactive oxygen species (ROS) in the cells. Exposure of crop plants to BMAA in controlled experiments resulted in BMAA uptake, protein association, and subsequent inhibition of the antioxidative enzyme activities. However, BMAA was detected in neither free nor protein-associated form in natural crop plants irrigated with known BMAA-containing bloom water. Post-mortem liver samples of Clarias gariepinus (Catfish) and Crocodylus niloticus (Crocodile), from a natural fresh water ecosystem that experienced frequent cyanobacterial blooms, contained both free and protein-associated BMAA. Higher BMAA concentrations were found in crocodile liver samples compared to fish liver samples, strongly suggesting biomagnification from one trophic level to the next. BMAA concentrations corresponded to crocodile age. This is the first report of bioaccumulation and biomagnification in two trophic levels in a fresh water ecosystem. These findings strongly suggest possible human exposure via aquatic food chains of cyanobacterial origin. Direct BMAA exposure via drinking water is not plausible due to the efficiency of standard water treatment processes to remove BMAA. The use of raw water for agricultural and recreational use, however, remains a problem. The development of management strategies as well as daily tolerable levels for BMAA is urgently required.
- Full Text:
- Date Issued: 2010
- Authors: Esterhuizen-Londt, Maranda
- Date: 2010
- Subjects: Cyanobacteria , Bioaccumulation , Chromatographic analysis , Neurotoxic agents
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10306 , http://hdl.handle.net/10948/1473 , Cyanobacteria , Bioaccumulation , Chromatographic analysis , Neurotoxic agents
- Description: β-N-methylamino-L-alanine (BMAA) is a non-proteinogenic amino acid associated with human neurodegenerative disease. Due to the cosmopolitan nature of cyanobacteria, detection of BMAA in cyanobacteria has caused concerns about human exposure risk. This study was therefore based on the hypothesis that BMAA poses a health risk to humans either by direct ingestion or by indirect exposure to BMAA from a cyanobacterial source via a freshwater food chain. A validated gas chromatography-mass spectrometry (GC-MS) BMAA analysis method and a confirmatory liquid chromatography-mass spectrometry (LC-MS) method, with improved sensitivity, were developed in addition to a LC-MS/MS method for analyte confirmation. These methods were used to quantify BMAA in South African cyanobacteria, isolated from various potable water reservoirs. The majority of the isolates tested, contained BMAA. Possible human exposure by direct consumption of BMAA released from cyanobacterial blooms was investigated by the development of a robust solid phase extraction (SPE) method used for BMAA concentration and quantification in raw and treated tap water. Despite the use of the SPE method that facilitated the concentration of BMAA from large quantities of water, no free dissolved BMAA was detected in raw or processed fresh water. The fate of exogenous BMAA was therefore investigated firstly by evaluating the efficacy of standard water treatment processes employed in South Africa and secondly by investigating the possibility of BMAA bioaccumulation and biomagnification in aquatic food chains. Standard water treatment processes proved highly efficient at removing free dissolved BMAA, explaining the absence of BMAA in treated tap water. However, the cause of the BMAA absence in raw potable water remained unknown. Uptake of BMAA by model aquatic organisms was investigated in controlled experiments. BMAA uptake was documented in both Ceratophyllum demersum and Daphnia magna, however, BMAA-protein association and biomagnification were not observed in D. magna. BMAA had an inhibitory effect on the oxidative stress enzyme acitivties of both organisms tested (as well as human S9 extracts), resulting in accumulation of detrimental reactive oxygen species (ROS) in the cells. Exposure of crop plants to BMAA in controlled experiments resulted in BMAA uptake, protein association, and subsequent inhibition of the antioxidative enzyme activities. However, BMAA was detected in neither free nor protein-associated form in natural crop plants irrigated with known BMAA-containing bloom water. Post-mortem liver samples of Clarias gariepinus (Catfish) and Crocodylus niloticus (Crocodile), from a natural fresh water ecosystem that experienced frequent cyanobacterial blooms, contained both free and protein-associated BMAA. Higher BMAA concentrations were found in crocodile liver samples compared to fish liver samples, strongly suggesting biomagnification from one trophic level to the next. BMAA concentrations corresponded to crocodile age. This is the first report of bioaccumulation and biomagnification in two trophic levels in a fresh water ecosystem. These findings strongly suggest possible human exposure via aquatic food chains of cyanobacterial origin. Direct BMAA exposure via drinking water is not plausible due to the efficiency of standard water treatment processes to remove BMAA. The use of raw water for agricultural and recreational use, however, remains a problem. The development of management strategies as well as daily tolerable levels for BMAA is urgently required.
- Full Text:
- Date Issued: 2010
A framework for grain commodity trading decision support in South Africa
- Authors: Ayankoya, Kayode Anthony
- Date: 2016
- Subjects: Grain trade -- South Africa Commodity exchanges -- South Africa Food industry and trade -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/11437 , vital:26925
- Description: In several countries around the world, grain commodities are traded as assets on stock exchanges. This indicate that the market and effectively the prices of the grain commodities in such countries, are controlled by several local and international economic, political and social factors that are rapidly changing. As a result, the prices of some grain commodities are volatile and trading in such commodities are prone to price-related risks. There are different trading strategies for minimising price-related risks and maximising profits. But empirical research suggests that making the right decision for effective grain commodities trading has been a difficult task for stakeholders due to high volatility of grain commodities prices. Studies have shown that this is more challenging among grain commodities farmers because of their lack of skills and the time to sift through and make sense of the datasets on the plethora of factors that influence the grain commodities market. This thesis focused on providing an answer for the main research problem that grain farmers in South Africa do not take full advantage of all the available strategies for trading their grain commodities because of the complexities associated with monitoring the large datasets that influence the grain commodities market. The main objective set by this study is to design a framework that can be followed to collect, integrate and analyse datasets that influence trading decisions of grain farmers in South Africa about grain commodities. This study takes advantage of the developments in Big Data and Data Science to achieve the set objective using the Design Science Research (DSR) methodology. The prediction of future prices of grain commodities for the different trading strategies was identified as an important factor for making better decisions when trading grain commodities and the key factors that influence the prices were identified. This was followed by a critical review of the literature to determine how the concepts of Big Data and Data Science can be leveraged for an effective grain commodities trading decision support. This resulted in a proposed framework for grain commodities trading. The proposed framework suggested an investigation of the factors that influence the prices of grain commodities as the basis for acquiring the relevant datasets. The proposed framework suggested the adoption of the Big Data approach in acquiring, preparing and integrating relevant datasets from several sources. Furthermore, it was suggested that algorithmic models for predicting grain commodities prices can be developed on top of the data layer of the proposed framework to provide real-time decision support. The proposed framework suggests the need for a carefully designed visualisation of the result and the collected data that promotes user experience. Lastly, the proposed framework included a technology consideration component to support the Big Data and Data Science approach of the framework. To demonstrate that the proposed framework addressed the main problem of this research, datasets from several sources on trading white maize in South Africa and the factors that influence market were streamed, integrated and analysed. Backpropagation Neural Network algorithm was used for modelling the prices of white maize for spot and futures trading strategies were predicted. There are other modelling techniques such as the Box-Jenkins statistical time series analysis methodology. But, Neural Networks was identified as more suitable for time series data with complex patterns and relationships. A demonstration system was setup to provide effective decision support by using near real-time data to provide a dynamic predictive analytics for the spot and December futures contract prices of white maize in South Africa. Comparative analysis of predictions made using the model from the proposed framework to actual data indicated a significant degree of accuracy. A further evaluation was carried out by asking experienced traders to make predictions for the spot and December futures contract prices of white maize. The result of the exercise indicated that the predictions from the developed model were much closer to the actual prices. This indicated that the proposed framework is technically capable and generally useful. It also shows that the proposed framework can be used to provide decision support about trading grain commodities to stakeholders with lesser skills, experience and resources. The practical contribution of this thesis is that relevant datasets from several sources can be streamed into an integrated data source in real-time, which can be used as input for a real-time learning algorithmic model for predicting grain commodities prices. This will make it possible for a predictive analytics that responds to market volatility thereby providing an effective decision support for grain commodities trading. Another practical contribution of this thesis is a proposed framework that can be followed for developing a Decision Support System for trading in grain commodities. This thesis made theoretical contributions by building on the information processing theory and the decision making theory. The theoretical contribution of this thesis consists of the identification of Big Data approach, tools and techniques for eradicating uncertainty and equivocality in grain commodities trading decision making process.
- Full Text:
- Date Issued: 2016
- Authors: Ayankoya, Kayode Anthony
- Date: 2016
- Subjects: Grain trade -- South Africa Commodity exchanges -- South Africa Food industry and trade -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/11437 , vital:26925
- Description: In several countries around the world, grain commodities are traded as assets on stock exchanges. This indicate that the market and effectively the prices of the grain commodities in such countries, are controlled by several local and international economic, political and social factors that are rapidly changing. As a result, the prices of some grain commodities are volatile and trading in such commodities are prone to price-related risks. There are different trading strategies for minimising price-related risks and maximising profits. But empirical research suggests that making the right decision for effective grain commodities trading has been a difficult task for stakeholders due to high volatility of grain commodities prices. Studies have shown that this is more challenging among grain commodities farmers because of their lack of skills and the time to sift through and make sense of the datasets on the plethora of factors that influence the grain commodities market. This thesis focused on providing an answer for the main research problem that grain farmers in South Africa do not take full advantage of all the available strategies for trading their grain commodities because of the complexities associated with monitoring the large datasets that influence the grain commodities market. The main objective set by this study is to design a framework that can be followed to collect, integrate and analyse datasets that influence trading decisions of grain farmers in South Africa about grain commodities. This study takes advantage of the developments in Big Data and Data Science to achieve the set objective using the Design Science Research (DSR) methodology. The prediction of future prices of grain commodities for the different trading strategies was identified as an important factor for making better decisions when trading grain commodities and the key factors that influence the prices were identified. This was followed by a critical review of the literature to determine how the concepts of Big Data and Data Science can be leveraged for an effective grain commodities trading decision support. This resulted in a proposed framework for grain commodities trading. The proposed framework suggested an investigation of the factors that influence the prices of grain commodities as the basis for acquiring the relevant datasets. The proposed framework suggested the adoption of the Big Data approach in acquiring, preparing and integrating relevant datasets from several sources. Furthermore, it was suggested that algorithmic models for predicting grain commodities prices can be developed on top of the data layer of the proposed framework to provide real-time decision support. The proposed framework suggests the need for a carefully designed visualisation of the result and the collected data that promotes user experience. Lastly, the proposed framework included a technology consideration component to support the Big Data and Data Science approach of the framework. To demonstrate that the proposed framework addressed the main problem of this research, datasets from several sources on trading white maize in South Africa and the factors that influence market were streamed, integrated and analysed. Backpropagation Neural Network algorithm was used for modelling the prices of white maize for spot and futures trading strategies were predicted. There are other modelling techniques such as the Box-Jenkins statistical time series analysis methodology. But, Neural Networks was identified as more suitable for time series data with complex patterns and relationships. A demonstration system was setup to provide effective decision support by using near real-time data to provide a dynamic predictive analytics for the spot and December futures contract prices of white maize in South Africa. Comparative analysis of predictions made using the model from the proposed framework to actual data indicated a significant degree of accuracy. A further evaluation was carried out by asking experienced traders to make predictions for the spot and December futures contract prices of white maize. The result of the exercise indicated that the predictions from the developed model were much closer to the actual prices. This indicated that the proposed framework is technically capable and generally useful. It also shows that the proposed framework can be used to provide decision support about trading grain commodities to stakeholders with lesser skills, experience and resources. The practical contribution of this thesis is that relevant datasets from several sources can be streamed into an integrated data source in real-time, which can be used as input for a real-time learning algorithmic model for predicting grain commodities prices. This will make it possible for a predictive analytics that responds to market volatility thereby providing an effective decision support for grain commodities trading. Another practical contribution of this thesis is a proposed framework that can be followed for developing a Decision Support System for trading in grain commodities. This thesis made theoretical contributions by building on the information processing theory and the decision making theory. The theoretical contribution of this thesis consists of the identification of Big Data approach, tools and techniques for eradicating uncertainty and equivocality in grain commodities trading decision making process.
- Full Text:
- Date Issued: 2016
Novel camphor derivatives as potential asymmetric alkylation auxiliaries
- Authors: Skiti-Mama, Neliswa
- Date: 2008
- Subjects: Alkylation , Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10372 , http://hdl.handle.net/10948/1077 , Alkylation , Chemistry, Organic
- Description: The investigation has been focussed on the synthesis and characterisation of camphor-derived chiral auxiliaries that incorporate two camphor skeletons and an evaluation of their stereodirecting potential in ester α-benzylation reactions. Two regioisomeric camphorquinone-derived monoketals were synthesised and identified by 1D- and 2D-NMR, and X-ray crystallography. The stereo-directing potential of the alcohols that resulted from reduction of these ketones as chiral auxiliaries in the alkylation of carboxylate ester derivatives has been studied. The diastereoselectivities shown by NMR spectroscopy range from 14- 30 % d.e. for (1R,2 S, 3R) -2 ,2-[ (1R, 2 S, 3R) -bornane-2,3-dioxy] - bornan-3-ol and 68-74 % d.e. for (1R, 2S ,3R) -3 ,3-[ (1R, 2S ,3R) - bornane-2, 3 -dioxy]bornan-2-ol with selectivities that correlate with the size of the alkyl group in the ester moiety. Trapping of the enolates generated from (1R, 2S ,3R)-2, 2 -[(1R,2 S, 3R) -bornane- 2,3-dioxy]bornan-3-yl propanoate afforded both E- and Z-silyl ketene acetal derivatives in the ratio of 64:36 confirming the formation of both possible enolate structures during enolization. Chiral auxiliaries containing a hemiaminal ether blocking group as well as two chiral alcohols containing monothio-ketal blocking groups have also been synthesised. α-Benzylation of their corresponding propanoate esters afforded the alkylated product with disappointingly low diastereos electivities. Asymmetric reduction of α-keto esters attached to (1R, 2 S, 3R) - 2,2- [ (1R,2 S, 3R) -bornane-2, 3 -dioxy]bornan-3-ol and (1R, 2S ,3R) - 3,3- [ (1R,2 S, 3R) -bornane-2, 3 -dioxy]bornan-2-ol with metal hydrides proceeded with selectivities of up to 30 % d.e. Modelling of the keto ester derivatives at DFT levels provided useful insights into possible conformations adopted by the two α-keto esters and hence the preferred face of attack by metal hydride during reduction.
- Full Text:
- Date Issued: 2008
- Authors: Skiti-Mama, Neliswa
- Date: 2008
- Subjects: Alkylation , Chemistry, Organic
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10372 , http://hdl.handle.net/10948/1077 , Alkylation , Chemistry, Organic
- Description: The investigation has been focussed on the synthesis and characterisation of camphor-derived chiral auxiliaries that incorporate two camphor skeletons and an evaluation of their stereodirecting potential in ester α-benzylation reactions. Two regioisomeric camphorquinone-derived monoketals were synthesised and identified by 1D- and 2D-NMR, and X-ray crystallography. The stereo-directing potential of the alcohols that resulted from reduction of these ketones as chiral auxiliaries in the alkylation of carboxylate ester derivatives has been studied. The diastereoselectivities shown by NMR spectroscopy range from 14- 30 % d.e. for (1R,2 S, 3R) -2 ,2-[ (1R, 2 S, 3R) -bornane-2,3-dioxy] - bornan-3-ol and 68-74 % d.e. for (1R, 2S ,3R) -3 ,3-[ (1R, 2S ,3R) - bornane-2, 3 -dioxy]bornan-2-ol with selectivities that correlate with the size of the alkyl group in the ester moiety. Trapping of the enolates generated from (1R, 2S ,3R)-2, 2 -[(1R,2 S, 3R) -bornane- 2,3-dioxy]bornan-3-yl propanoate afforded both E- and Z-silyl ketene acetal derivatives in the ratio of 64:36 confirming the formation of both possible enolate structures during enolization. Chiral auxiliaries containing a hemiaminal ether blocking group as well as two chiral alcohols containing monothio-ketal blocking groups have also been synthesised. α-Benzylation of their corresponding propanoate esters afforded the alkylated product with disappointingly low diastereos electivities. Asymmetric reduction of α-keto esters attached to (1R, 2 S, 3R) - 2,2- [ (1R,2 S, 3R) -bornane-2, 3 -dioxy]bornan-3-ol and (1R, 2S ,3R) - 3,3- [ (1R,2 S, 3R) -bornane-2, 3 -dioxy]bornan-2-ol with metal hydrides proceeded with selectivities of up to 30 % d.e. Modelling of the keto ester derivatives at DFT levels provided useful insights into possible conformations adopted by the two α-keto esters and hence the preferred face of attack by metal hydride during reduction.
- Full Text:
- Date Issued: 2008
Investigating the fitness of sea turtles nesting in South Africa
- Le Gouvello du Timat, Diane Z M
- Authors: Le Gouvello du Timat, Diane Z M
- Date: 2020
- Subjects: Sea turtles -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/48445 , vital:40877
- Description: The South African rookeries of the South Western Indian Ocean (SWIO) loggerhead and leatherback regional management units have been continuously monitored for more than 5 decades, representing one of the longest-running sea turtle beach protection and monitoring programmes in the world. Although such conservation has been successful in protecting adults on land when they come to nest, it might not be enough to ensure population recovery if survival is not ensured across all life stages. Sea turtles are particularly vulnerable to direct threats and changing environmental conditions because they are long-lived, slow maturing, and have low survival rates at early life stages, making them conservation-dependent. These characteristics also render them difficult to conserve as a consequence of their wide geographic distributions, spanning multiple jurisdictions and legislative systems with different conservation targets, and a complex life cycle with changes in habitats and diets at different life stages. Sea turtle populations have been severely depleted as a result of historical over-exploitation and current threats including fisheries bycatch, direct harvest, habitat loss, pollution and pathogens, and climate change. In many cases however, population declines have been reversed by a variety of effective conservation measures such as beach protection programs, and marine protected areas, enabling successful population recovery around the world. Despite protection and apparent increase in abundance, indirect pressures can still affect turtle populations. Therefore, it is fundamental to evaluate the effectiveness of conservation measures (using fitness traits such as female and hatchling sizes) and examine underlying trends. The aim of this thesis was thus to evaluate the fitness of loggerhead and leatherback sea turtles nesting in South Africa. Long-term female size trends over time were evaluated and the populations were split between first-time nesters and experienced nesters. As sea turtle reproductive output (clutch size only) is correlated with female size and evidence is showing that in some populations individual female size is decreasing, the effects of maternal body size on reproductive output and hatchling fitness were investigated for both species. Crawling and swimming speeds were used as proxies of hatchling fitness, because these two traits positively influence their survival. An oceanic model was further used in combination with a particle tracking framework to estimate, for the first time, post-hatchling dispersal of loggerhead and leatherback turtles in the SWIO. I investigated whether the trend in female size for loggerhead turtles nesting in South Africa is a result of their foraging strategy to determine if there is a foraging dichotomy (neritic and oceanic). Despite an apparent increasing population, a significant 3.7 and 3.6 cm decrease in the size of both recruit and remingrant female loggerhead turtles, but a stable mean size of leatherbacks for both age groups was observed. I hypothesise that these contradictory effects are attributable to the very distinct foraging ecologies of the two turtle species and speculate that these variations in carapace length may be driven by environmental change. The reproductive strategy of both loggerhead and leatherback turtles nesting in South Africa supports the optimal egg size theory with larger turtles producing larger clutches but not larger eggs. Egg size was thus constant irrespective of maternal length. Hatchlings with longer carapaces and flippers had higher swimming speed, suggesting that larger hatchlings are fitter (potentially higher survival) than smaller ones by spending less time in high predation risk areas (i.e. beach and nearshore). The model revealed that dispersal trajectories of both loggerhead and leatherback sea turtle hatchlings were very similar and simulations indicated that initial active swimming (frenzy) as well as variability in oceanic conditions strongly influenced dispersal of virtual hatchlings. The trends observed in this study emphasize the importance of long-term monitoring, examining not only abundance but also individual size, to understand population dynamics, support recovery planning and prioritize future conservation practices. Furthermore, the findings of this study have important implications for overall population growth if smaller hatchlings of lower fitness are produced as a result of climate change and thus have decreased dispersal abilities and lower likelihood of survival.
- Full Text:
- Date Issued: 2020
- Authors: Le Gouvello du Timat, Diane Z M
- Date: 2020
- Subjects: Sea turtles -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/48445 , vital:40877
- Description: The South African rookeries of the South Western Indian Ocean (SWIO) loggerhead and leatherback regional management units have been continuously monitored for more than 5 decades, representing one of the longest-running sea turtle beach protection and monitoring programmes in the world. Although such conservation has been successful in protecting adults on land when they come to nest, it might not be enough to ensure population recovery if survival is not ensured across all life stages. Sea turtles are particularly vulnerable to direct threats and changing environmental conditions because they are long-lived, slow maturing, and have low survival rates at early life stages, making them conservation-dependent. These characteristics also render them difficult to conserve as a consequence of their wide geographic distributions, spanning multiple jurisdictions and legislative systems with different conservation targets, and a complex life cycle with changes in habitats and diets at different life stages. Sea turtle populations have been severely depleted as a result of historical over-exploitation and current threats including fisheries bycatch, direct harvest, habitat loss, pollution and pathogens, and climate change. In many cases however, population declines have been reversed by a variety of effective conservation measures such as beach protection programs, and marine protected areas, enabling successful population recovery around the world. Despite protection and apparent increase in abundance, indirect pressures can still affect turtle populations. Therefore, it is fundamental to evaluate the effectiveness of conservation measures (using fitness traits such as female and hatchling sizes) and examine underlying trends. The aim of this thesis was thus to evaluate the fitness of loggerhead and leatherback sea turtles nesting in South Africa. Long-term female size trends over time were evaluated and the populations were split between first-time nesters and experienced nesters. As sea turtle reproductive output (clutch size only) is correlated with female size and evidence is showing that in some populations individual female size is decreasing, the effects of maternal body size on reproductive output and hatchling fitness were investigated for both species. Crawling and swimming speeds were used as proxies of hatchling fitness, because these two traits positively influence their survival. An oceanic model was further used in combination with a particle tracking framework to estimate, for the first time, post-hatchling dispersal of loggerhead and leatherback turtles in the SWIO. I investigated whether the trend in female size for loggerhead turtles nesting in South Africa is a result of their foraging strategy to determine if there is a foraging dichotomy (neritic and oceanic). Despite an apparent increasing population, a significant 3.7 and 3.6 cm decrease in the size of both recruit and remingrant female loggerhead turtles, but a stable mean size of leatherbacks for both age groups was observed. I hypothesise that these contradictory effects are attributable to the very distinct foraging ecologies of the two turtle species and speculate that these variations in carapace length may be driven by environmental change. The reproductive strategy of both loggerhead and leatherback turtles nesting in South Africa supports the optimal egg size theory with larger turtles producing larger clutches but not larger eggs. Egg size was thus constant irrespective of maternal length. Hatchlings with longer carapaces and flippers had higher swimming speed, suggesting that larger hatchlings are fitter (potentially higher survival) than smaller ones by spending less time in high predation risk areas (i.e. beach and nearshore). The model revealed that dispersal trajectories of both loggerhead and leatherback sea turtle hatchlings were very similar and simulations indicated that initial active swimming (frenzy) as well as variability in oceanic conditions strongly influenced dispersal of virtual hatchlings. The trends observed in this study emphasize the importance of long-term monitoring, examining not only abundance but also individual size, to understand population dynamics, support recovery planning and prioritize future conservation practices. Furthermore, the findings of this study have important implications for overall population growth if smaller hatchlings of lower fitness are produced as a result of climate change and thus have decreased dispersal abilities and lower likelihood of survival.
- Full Text:
- Date Issued: 2020
Separation of rhodium (III) and iridium (IV) using functional polymeric materials
- Authors: Majavu, Avela
- Date: 2014
- Subjects: Rhodium -- Separation , Iridium -- Separation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/6576 , vital:21116
- Description: Poly(vinylbenzylchloride) (PVBC) nanofibers were fabricated by the electrospinning process. The Merrifield micropheres, silica microsparticles and PVBC nanofibers were functionalised with different quaternary diammonium groups derived from ethylenediamine (EDA), tetramethylenediamine (TMDA), hexamethylenediamine (HMDA), 1,8-diaminooctane (OMDA), 1,10-diaminodecane (DMDA) and 1,12-diaminododecane (DDMDA) and investigated for separation of [RhCl5(H2O)]2- and [IrCl6]2-. The sorbent materials were characterised by means of FTIR, XPS, SEM, BET surface area, thermogravimetric analysis and elemental analysis, and characterization results showed that the functionalization of the sorbent materials was successful. Batch equilibrium studies were carried out to assess the efficiency of these different anion exchangers using single metal aqueous solutions. The adsorption isotherms and kinetics of both [RhCl5(H2O)]2- and [IrCl6]2- adsorption onto the sorbent materials are presented. The isothermal batch adsorption studies fitted the Freundlich model indicating heterogeneous surface adsorption. The Freundlich isotherm confirmed multilayer adsorption and the Freundlich constant (kf) displayed the following ascending order for nanofibers (F-QUAT EDA, F-QUAT TMDA, F-QUAT HMDA, F-QUAT OMDA and F-QUAT DMDA), silica microparticles (Si-QUAT EDA, Si-QUAT TMDA, Si-QUAT HMDA, Si-QUAT OMDA and Si-QUAT DMDA) and microspheres (B-QUAT EDA, B-QUAT TMDA, B-QUAT HMDA, B-QUAT OMDA and B-QUAT DMDA) and a decrease in kf for F-QUAT DDMDA, Si-QUAT DDMDA and B-QUAT DDMDA has been observed. The pseudo second-order model was found to be the best fit to describe the adsorption kinetics of both metal ions complexes onto all the sorbent materials. K2 value in pseudo second-order kinetics showed that the rate constant for adsorption of [IrCl6]2- onto nanofibers was larger than for silica microparticles and Merrifield microspheres. Column sorption of [IrCl6]2- and [RhCl5(H2O)]2- was carried out and the loading capacities of [IrCl6]2- were obtained, and they showed dependence on the length of the methylene spacer between the two diammonium centres. [RhCl5(H2O)]2- was not adsorbed by the sorbent materials while [IrCl6]2- was loaded onto the column. The highest iridium loading capacities for all the sorbent materials for the diamines with decylene spacer, and were found to be 32.94 mg/g, 29.35 mg/g, and 27.09 mg/g for F-QUAT DMDA, Si-QUAT DMDA and B-QUAT DMDA respectively. It was also observed on the derivatives of DMDA supported on nanofibers that F-QUAT ethyl loading capacity for iridium (19.89 mg/g) reduced which may be due to the electron-donating nature of the ethyl group and the increase of hydrophobicity whereas F-QUAT benzyl loading capacity (244.64 mg/g) increased dramatically due to increase in the size of the cation which lowers the positive charge density of the quaternary diammonium center. The charge delocalizing ability of the benzyl group resulted in the best interaction of the diammonium group derived from this quaternizing agent, yielding the highest loading capacity for [IrCl6]2-. Reusability was conducted and the results showed that the all the sorbent materials can be used repeatedly without decreasing their adsorption capacity significantly. The neat diammonium salts were also synthesized and interacted with the chorido metal complex anions to form ion-pairs which were then studied for their solubility. The synthesis of the quaternary salts was rather challenging and resulted in some interesting species when impurities of the iodide form of the salts were present in the process of converting them to the iodide form. Some of these include I52+, which was confirmed preliminarily by X-ray structural analysis, potentiometry and cyclic voltammetry. Molecular modeling studies were also conducted to explain the interaction of the chlorido anions with the cationic diammonium centres, and to quantify these interactions by thermodynamic parameters, partial charge calculations, dipole moments and electrostatic potentials, and there was good agreement between theory and experiment. This thesis presents iridium-specific materials that could be applied in solutions of secondary PMGs sources containing rhodium and iridium as well as in feed solutions from ore processing.
- Full Text:
- Date Issued: 2014
- Authors: Majavu, Avela
- Date: 2014
- Subjects: Rhodium -- Separation , Iridium -- Separation
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/6576 , vital:21116
- Description: Poly(vinylbenzylchloride) (PVBC) nanofibers were fabricated by the electrospinning process. The Merrifield micropheres, silica microsparticles and PVBC nanofibers were functionalised with different quaternary diammonium groups derived from ethylenediamine (EDA), tetramethylenediamine (TMDA), hexamethylenediamine (HMDA), 1,8-diaminooctane (OMDA), 1,10-diaminodecane (DMDA) and 1,12-diaminododecane (DDMDA) and investigated for separation of [RhCl5(H2O)]2- and [IrCl6]2-. The sorbent materials were characterised by means of FTIR, XPS, SEM, BET surface area, thermogravimetric analysis and elemental analysis, and characterization results showed that the functionalization of the sorbent materials was successful. Batch equilibrium studies were carried out to assess the efficiency of these different anion exchangers using single metal aqueous solutions. The adsorption isotherms and kinetics of both [RhCl5(H2O)]2- and [IrCl6]2- adsorption onto the sorbent materials are presented. The isothermal batch adsorption studies fitted the Freundlich model indicating heterogeneous surface adsorption. The Freundlich isotherm confirmed multilayer adsorption and the Freundlich constant (kf) displayed the following ascending order for nanofibers (F-QUAT EDA, F-QUAT TMDA, F-QUAT HMDA, F-QUAT OMDA and F-QUAT DMDA), silica microparticles (Si-QUAT EDA, Si-QUAT TMDA, Si-QUAT HMDA, Si-QUAT OMDA and Si-QUAT DMDA) and microspheres (B-QUAT EDA, B-QUAT TMDA, B-QUAT HMDA, B-QUAT OMDA and B-QUAT DMDA) and a decrease in kf for F-QUAT DDMDA, Si-QUAT DDMDA and B-QUAT DDMDA has been observed. The pseudo second-order model was found to be the best fit to describe the adsorption kinetics of both metal ions complexes onto all the sorbent materials. K2 value in pseudo second-order kinetics showed that the rate constant for adsorption of [IrCl6]2- onto nanofibers was larger than for silica microparticles and Merrifield microspheres. Column sorption of [IrCl6]2- and [RhCl5(H2O)]2- was carried out and the loading capacities of [IrCl6]2- were obtained, and they showed dependence on the length of the methylene spacer between the two diammonium centres. [RhCl5(H2O)]2- was not adsorbed by the sorbent materials while [IrCl6]2- was loaded onto the column. The highest iridium loading capacities for all the sorbent materials for the diamines with decylene spacer, and were found to be 32.94 mg/g, 29.35 mg/g, and 27.09 mg/g for F-QUAT DMDA, Si-QUAT DMDA and B-QUAT DMDA respectively. It was also observed on the derivatives of DMDA supported on nanofibers that F-QUAT ethyl loading capacity for iridium (19.89 mg/g) reduced which may be due to the electron-donating nature of the ethyl group and the increase of hydrophobicity whereas F-QUAT benzyl loading capacity (244.64 mg/g) increased dramatically due to increase in the size of the cation which lowers the positive charge density of the quaternary diammonium center. The charge delocalizing ability of the benzyl group resulted in the best interaction of the diammonium group derived from this quaternizing agent, yielding the highest loading capacity for [IrCl6]2-. Reusability was conducted and the results showed that the all the sorbent materials can be used repeatedly without decreasing their adsorption capacity significantly. The neat diammonium salts were also synthesized and interacted with the chorido metal complex anions to form ion-pairs which were then studied for their solubility. The synthesis of the quaternary salts was rather challenging and resulted in some interesting species when impurities of the iodide form of the salts were present in the process of converting them to the iodide form. Some of these include I52+, which was confirmed preliminarily by X-ray structural analysis, potentiometry and cyclic voltammetry. Molecular modeling studies were also conducted to explain the interaction of the chlorido anions with the cationic diammonium centres, and to quantify these interactions by thermodynamic parameters, partial charge calculations, dipole moments and electrostatic potentials, and there was good agreement between theory and experiment. This thesis presents iridium-specific materials that could be applied in solutions of secondary PMGs sources containing rhodium and iridium as well as in feed solutions from ore processing.
- Full Text:
- Date Issued: 2014
On the growth and characterisation of AIGaN alloys for optoelectronic applications
- Authors: James, Grant Robert
- Date: 2005
- Subjects: Gallium nitride -- Electric properties , Photoluminescence
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/8824 , vital:26433
- Description: In this study the growth and characterisation of undoped and Si-doped AlxGa1-xN has been performed. The layers were grown using low-pressure metalorganic vapour phase deposition (MOCVD) on sapphire substrates. The optical and electrical properties of the AlxGa1-xN layers were studied using variable temperature Hall effect and photoluminescence measurements. AlxGa1-xN layers were grown over the entire composition range. Room temperature ultraviolet (UV) transmission measurements showed that the material quality was very good for layers with an Al content, x, of 0 _ x _ 0.5. However, the quality of layers of higher composition was seen to rapidly decrease with increasing x. The electrical and optical properties of AlxGa1-xN with x < 0.5 were also good, comparable to those reported on in literature. The study of the Si-doping of AlxGa1-xN was performed in two parts; firstly a series of Al0.23Ga0.77N samples was grown in which the doping level was increased from zero to n _ 3 × 1018 cm-3. A similar, albeit a less rigorous, study was performed for Al0.41Ga0.59N and Al0.5Ga0.5N. A second series of samples was then grown in which the doping level was kept constant, while the Al content was incrementally increased. Room temperature Hall effect measurements performed on Si-doped Al0.23Ga0.77N showed that the electron concentration did not scale linearly with the silane flow, as was the case in GaN. It was also seen that the electron mobility of the layers increased with slight Si-doping, possibly due to an improvement in the crystalline quality and/or a change in the conduction mechanism. It was also found that at higher compositions (x = 0.41 and 0.50) an increase in the doping level resulted in an increase in the mobility. Variable temperature Hall effect and photoluminescence measurements, performed on the Al0.23Ga0.77N samples, revealed a good correlation between the first PL activation energy E1 and the donor activation energy ED, prompting the conclusion that the first PL recombination channel in AlxGa1-xN is due to the delocalisation of excitons bound at neutral Si donors. Furthermore, E1 and ED were seen to decrease with n1/3, as is the case for GaN and other semiconductor materials. It was also observed that strong exciton localisation occurs in slightly Si-doped material, with the amount of localization becoming less at higher doping levels. Possible mechanisms responsible for the second PL recombination channel of activation energy E2 were also proposed. The electrical and optical properties of the second set of AlxGa1-xN samples was then studied. The PL properties of undoped AlxGa1-xN were typical of a homogeneous alloy system, with the increase in the PL FWHM and exciton localisation energies with x following the trend predicted by alloy disorder theory. The variation of the band gap energy with the Al content could not, however, be fitted over the entire composition range using a single bowing parameter. It was proposed that this was due either to an effect of the 9 7 valence band crossover, or due to exciton localisation at alloy disorder and/or impurities. As was the case for GaN and Al0.23Ga0.77N, all undoped material was highly resistive. As was mentioned earlier, the exciton localisation energies increased according to alloy disorder theory in undoped AlxGa1-xN. In the doped samples, however, a large increase in the donor localisation energy was measured for x > 0.3. The possibility that Si could become a DX-centre in AlxGa1-xN was then investigated. However, Hall effect measurements showed that the Si activation energy increased in good agreement with the model of a shallow effective mass state donor, with no sudden increase in ED being observed up to x = 0.4. It was then suggested that the increase in the E1 and E2 activation energies, as well as the exciton localisation energies, could be due to the 9 7 valence band crossover, which occurs at roughly the same composition. However, due to the scarcity of reports on the valence band structure in AlxGa1-xN no conclusions could be made at this stage as to the effect of the 9 7 valence band crossover on the PL properties of AlxGa1-xN.
- Full Text:
- Date Issued: 2005
- Authors: James, Grant Robert
- Date: 2005
- Subjects: Gallium nitride -- Electric properties , Photoluminescence
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/8824 , vital:26433
- Description: In this study the growth and characterisation of undoped and Si-doped AlxGa1-xN has been performed. The layers were grown using low-pressure metalorganic vapour phase deposition (MOCVD) on sapphire substrates. The optical and electrical properties of the AlxGa1-xN layers were studied using variable temperature Hall effect and photoluminescence measurements. AlxGa1-xN layers were grown over the entire composition range. Room temperature ultraviolet (UV) transmission measurements showed that the material quality was very good for layers with an Al content, x, of 0 _ x _ 0.5. However, the quality of layers of higher composition was seen to rapidly decrease with increasing x. The electrical and optical properties of AlxGa1-xN with x < 0.5 were also good, comparable to those reported on in literature. The study of the Si-doping of AlxGa1-xN was performed in two parts; firstly a series of Al0.23Ga0.77N samples was grown in which the doping level was increased from zero to n _ 3 × 1018 cm-3. A similar, albeit a less rigorous, study was performed for Al0.41Ga0.59N and Al0.5Ga0.5N. A second series of samples was then grown in which the doping level was kept constant, while the Al content was incrementally increased. Room temperature Hall effect measurements performed on Si-doped Al0.23Ga0.77N showed that the electron concentration did not scale linearly with the silane flow, as was the case in GaN. It was also seen that the electron mobility of the layers increased with slight Si-doping, possibly due to an improvement in the crystalline quality and/or a change in the conduction mechanism. It was also found that at higher compositions (x = 0.41 and 0.50) an increase in the doping level resulted in an increase in the mobility. Variable temperature Hall effect and photoluminescence measurements, performed on the Al0.23Ga0.77N samples, revealed a good correlation between the first PL activation energy E1 and the donor activation energy ED, prompting the conclusion that the first PL recombination channel in AlxGa1-xN is due to the delocalisation of excitons bound at neutral Si donors. Furthermore, E1 and ED were seen to decrease with n1/3, as is the case for GaN and other semiconductor materials. It was also observed that strong exciton localisation occurs in slightly Si-doped material, with the amount of localization becoming less at higher doping levels. Possible mechanisms responsible for the second PL recombination channel of activation energy E2 were also proposed. The electrical and optical properties of the second set of AlxGa1-xN samples was then studied. The PL properties of undoped AlxGa1-xN were typical of a homogeneous alloy system, with the increase in the PL FWHM and exciton localisation energies with x following the trend predicted by alloy disorder theory. The variation of the band gap energy with the Al content could not, however, be fitted over the entire composition range using a single bowing parameter. It was proposed that this was due either to an effect of the 9 7 valence band crossover, or due to exciton localisation at alloy disorder and/or impurities. As was the case for GaN and Al0.23Ga0.77N, all undoped material was highly resistive. As was mentioned earlier, the exciton localisation energies increased according to alloy disorder theory in undoped AlxGa1-xN. In the doped samples, however, a large increase in the donor localisation energy was measured for x > 0.3. The possibility that Si could become a DX-centre in AlxGa1-xN was then investigated. However, Hall effect measurements showed that the Si activation energy increased in good agreement with the model of a shallow effective mass state donor, with no sudden increase in ED being observed up to x = 0.4. It was then suggested that the increase in the E1 and E2 activation energies, as well as the exciton localisation energies, could be due to the 9 7 valence band crossover, which occurs at roughly the same composition. However, due to the scarcity of reports on the valence band structure in AlxGa1-xN no conclusions could be made at this stage as to the effect of the 9 7 valence band crossover on the PL properties of AlxGa1-xN.
- Full Text:
- Date Issued: 2005
Analysis of temporal and spatial variations in water storage by means of gravimetric and hydrologic methods in the region around the South African gravimetric observation station
- Authors: Mahed, Gaathier
- Date: 2013
- Subjects: Ground water -- South Africa , Geology -- South Africa , Hydrogeology -- South Africa , Water-supply -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/6714 , vital:21137
- Description: This work examines the use of gravity data and its application to subsurface water reservoirs in the immediate vicinity of the South African Geodynamic Observatory, Sutherland (SAGOS), situated in a semi-arid region of the Karoo region of South Africa, and underlain by the Karoo sedimentary rocks intruded by dolerite dykes and sills. SAGOS houses the only supergravity metre (SG) in Africa, and this thesis sets out to test its use in monitoring groundwater dynamics using hydrological and gravity data. The main aim of this work is the application of the SG data, in conjunction with hydrological data, to better understand episodic recharge of subsurface reservoirs. The importance of water as a resource, globally and specifically the Karoo, is reviewed in conjunction with supply and demand of water. This is to contextualise the socio-economic, technical as well as policy issues related to water resource management. Applicable technologies for water resource management and efficient water use are highlighted and the application of gravity to hydrology is introduced, including satellite as well as ground based tools. In addition, arid zone hydrology as well as recharge and its mechanisms are analysed in order to better understand these processes when examined from gravity measurements. Issues related to understanding flow within the vadose zone as well as in secondary aquifers are examined, and gravity residuals and subsurface hydrology are highlighted. Thereafter, a conceptual groundwater flow modelof the study area is developed using multiple tools. First, the geology around SAGOS was mapped using SPOT 5 imagery and then ground truthed. Second, stable isotopes and water chemistry analysis was undertaken on water samples from selected boreholes. The results allude to preferential flow acting as the main mechanism for groundwater recharge. Follow-up pump-tests illustrate that fracture connectivity is greatest at close proximity to the dyke. Soil mapping, using aerial photography was also undertaken. Duplex soils, enriched with clay at depth, dominate the study area. Using in-situ infiltration tests, it is shown that the alluvium, which lines the river beds, has a higher hydraulic conductivity than the other soils, confirming that these streams act as preferential conduits for subsurface recharge. Precipitation events were correlated against gravity residuals at 4 wells, over different time periods. The results are examined using time series analyses. Gravity residuals from well SA BK07, over a period of 24 hours after the rainfall event, delineate instances of negative correlations, as well as strong positive correlations (of up to 0.9). On the whole however, correlations between gravity and groundwater at SA BK07 are variable and weak, and in conjunction with water level measurements and water chemistry, the data suggest that this well is located in a dynamic conduit (throughflow) and not in a permanent groundwater reservoir. By contrast, other wells show strong positive correlations between gravity residuals and water levels following episodic recharge events for a later time series. Correlations between the water levels and gravity residuals in wells SA BK04, SA BK05 and SA BK 01 are in excess of 0.7 for specific rainfall events. In summary, the results suggests that gravity is an excellent tool for measuring episodic groundwater recharge within the immediate vicinity of the SAGOS. This implies that gravity can aid in monitoring groundwater losses/gains in arid and semi-arid areas. Recommendations for future work are highlighted at the end; these include the possible use of hydrological modelling of reservoirs at various scales and then comparing these results to the SG as well as GOCE and GRACE satellites data, and then improving numerical modelling of the groundwater dynamics for sites like Sutherland and the surrounding arid Karoo region, where sparse water shortages, and potential pollution related to fracking for shale-gas, are likely to compete with established water needs for farming and human consumption. It is also suggested that the gravity modelling be examined to better understand site specific scenarios and thus aid in improving the processing of the gravity signal.
- Full Text:
- Date Issued: 2013
- Authors: Mahed, Gaathier
- Date: 2013
- Subjects: Ground water -- South Africa , Geology -- South Africa , Hydrogeology -- South Africa , Water-supply -- South Africa
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/6714 , vital:21137
- Description: This work examines the use of gravity data and its application to subsurface water reservoirs in the immediate vicinity of the South African Geodynamic Observatory, Sutherland (SAGOS), situated in a semi-arid region of the Karoo region of South Africa, and underlain by the Karoo sedimentary rocks intruded by dolerite dykes and sills. SAGOS houses the only supergravity metre (SG) in Africa, and this thesis sets out to test its use in monitoring groundwater dynamics using hydrological and gravity data. The main aim of this work is the application of the SG data, in conjunction with hydrological data, to better understand episodic recharge of subsurface reservoirs. The importance of water as a resource, globally and specifically the Karoo, is reviewed in conjunction with supply and demand of water. This is to contextualise the socio-economic, technical as well as policy issues related to water resource management. Applicable technologies for water resource management and efficient water use are highlighted and the application of gravity to hydrology is introduced, including satellite as well as ground based tools. In addition, arid zone hydrology as well as recharge and its mechanisms are analysed in order to better understand these processes when examined from gravity measurements. Issues related to understanding flow within the vadose zone as well as in secondary aquifers are examined, and gravity residuals and subsurface hydrology are highlighted. Thereafter, a conceptual groundwater flow modelof the study area is developed using multiple tools. First, the geology around SAGOS was mapped using SPOT 5 imagery and then ground truthed. Second, stable isotopes and water chemistry analysis was undertaken on water samples from selected boreholes. The results allude to preferential flow acting as the main mechanism for groundwater recharge. Follow-up pump-tests illustrate that fracture connectivity is greatest at close proximity to the dyke. Soil mapping, using aerial photography was also undertaken. Duplex soils, enriched with clay at depth, dominate the study area. Using in-situ infiltration tests, it is shown that the alluvium, which lines the river beds, has a higher hydraulic conductivity than the other soils, confirming that these streams act as preferential conduits for subsurface recharge. Precipitation events were correlated against gravity residuals at 4 wells, over different time periods. The results are examined using time series analyses. Gravity residuals from well SA BK07, over a period of 24 hours after the rainfall event, delineate instances of negative correlations, as well as strong positive correlations (of up to 0.9). On the whole however, correlations between gravity and groundwater at SA BK07 are variable and weak, and in conjunction with water level measurements and water chemistry, the data suggest that this well is located in a dynamic conduit (throughflow) and not in a permanent groundwater reservoir. By contrast, other wells show strong positive correlations between gravity residuals and water levels following episodic recharge events for a later time series. Correlations between the water levels and gravity residuals in wells SA BK04, SA BK05 and SA BK 01 are in excess of 0.7 for specific rainfall events. In summary, the results suggests that gravity is an excellent tool for measuring episodic groundwater recharge within the immediate vicinity of the SAGOS. This implies that gravity can aid in monitoring groundwater losses/gains in arid and semi-arid areas. Recommendations for future work are highlighted at the end; these include the possible use of hydrological modelling of reservoirs at various scales and then comparing these results to the SG as well as GOCE and GRACE satellites data, and then improving numerical modelling of the groundwater dynamics for sites like Sutherland and the surrounding arid Karoo region, where sparse water shortages, and potential pollution related to fracking for shale-gas, are likely to compete with established water needs for farming and human consumption. It is also suggested that the gravity modelling be examined to better understand site specific scenarios and thus aid in improving the processing of the gravity signal.
- Full Text:
- Date Issued: 2013
Megaherbivores in succulent thicket: resource use and implications
- Authors: Landman, Marietjie
- Date: 2012
- Subjects: Elephants , African elephant , Black rhinoceros , Succulent plants
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10689 , http://hdl.handle.net/10948/d1007956 , Elephants , African elephant , Black rhinoceros , Succulent plants
- Description: This study aims to develop a predictive understanding of the resource use, impacts and interactions of elephant Loxodonta africana and black rhinoceros Diceros bicornis in the succulent thickets of the Eastern Cape, South Africa. While these megaherbivores typically dominate the biomass, elephant are more abundant, such that their impacts off-set that of all other herbivores. Consequently, this thesis has three main foci: first, developing a mechanistic understanding of the influences of elephant; second, developing predictive insights into elephant impacts on plant communities; finally, an understanding of the knockon-effects of the impacts for coexisting rhinoceros. Thus, by documenting the diet and dietary preferences of elephant, I firstly show that only about 18 percent of the species previously thought vulnerable to herbivory, occur in the diet. This refutes the generally held belief that elephant herbivory is the primary driver of decline among plants, and emphasizes the likely contribution of other mechanisms (e.g. trampling, knock-on-effects, etc.). Thus, the accurate prediction of the impacts caused by elephant requires an understanding of previously marginalized mechanisms. From here, I quantify >50 years of impacts on the thicket shrub community and test their spatial and temporal extent near water. I confirm the vulnerability of thicket to transformation (particularly near water) as the accumulated influences of elephant reduce community composition and structure, and predict that these impacts will eventually bring about landscape-level degradation and a significant loss of biodiversity. Importantly, results show an uneven distribution of effects between elements of this community: from community composition and structure, to the structure of individual canopy species and ecological functioning. While these findings confound our interpretation of the extent of the impacts, it demonstrates the importance of explicitly recognizing biodiversity and heterogeneity for the conservation management of elephant. Finally, I test the consequences of the impacts for coexisting rhinoceros. While I show that this causes rhinoceros to change their foraging strategies in the presence of elephant at high densities, I also show that elephant may facilitate access to food for rhinoceros at reduced densities. These findings indicate the importance of elephant in driving the structure and composition of the thicket shrub community and the consequences of this for coexisting large herbivores. Thus, developing a predictive understanding of the spatial and temporal variations of elephant impacts between elements of biodiversity and the mechanisms driving these changes are key to their management. This implies that the effective conservation management of elephant can only be achieved through the careful, scientific design of monitoring programmes.
- Full Text:
- Date Issued: 2012
- Authors: Landman, Marietjie
- Date: 2012
- Subjects: Elephants , African elephant , Black rhinoceros , Succulent plants
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10689 , http://hdl.handle.net/10948/d1007956 , Elephants , African elephant , Black rhinoceros , Succulent plants
- Description: This study aims to develop a predictive understanding of the resource use, impacts and interactions of elephant Loxodonta africana and black rhinoceros Diceros bicornis in the succulent thickets of the Eastern Cape, South Africa. While these megaherbivores typically dominate the biomass, elephant are more abundant, such that their impacts off-set that of all other herbivores. Consequently, this thesis has three main foci: first, developing a mechanistic understanding of the influences of elephant; second, developing predictive insights into elephant impacts on plant communities; finally, an understanding of the knockon-effects of the impacts for coexisting rhinoceros. Thus, by documenting the diet and dietary preferences of elephant, I firstly show that only about 18 percent of the species previously thought vulnerable to herbivory, occur in the diet. This refutes the generally held belief that elephant herbivory is the primary driver of decline among plants, and emphasizes the likely contribution of other mechanisms (e.g. trampling, knock-on-effects, etc.). Thus, the accurate prediction of the impacts caused by elephant requires an understanding of previously marginalized mechanisms. From here, I quantify >50 years of impacts on the thicket shrub community and test their spatial and temporal extent near water. I confirm the vulnerability of thicket to transformation (particularly near water) as the accumulated influences of elephant reduce community composition and structure, and predict that these impacts will eventually bring about landscape-level degradation and a significant loss of biodiversity. Importantly, results show an uneven distribution of effects between elements of this community: from community composition and structure, to the structure of individual canopy species and ecological functioning. While these findings confound our interpretation of the extent of the impacts, it demonstrates the importance of explicitly recognizing biodiversity and heterogeneity for the conservation management of elephant. Finally, I test the consequences of the impacts for coexisting rhinoceros. While I show that this causes rhinoceros to change their foraging strategies in the presence of elephant at high densities, I also show that elephant may facilitate access to food for rhinoceros at reduced densities. These findings indicate the importance of elephant in driving the structure and composition of the thicket shrub community and the consequences of this for coexisting large herbivores. Thus, developing a predictive understanding of the spatial and temporal variations of elephant impacts between elements of biodiversity and the mechanisms driving these changes are key to their management. This implies that the effective conservation management of elephant can only be achieved through the careful, scientific design of monitoring programmes.
- Full Text:
- Date Issued: 2012
The FAST fabric objective measurement properties of commercial worsted apparel fabrics available in South Africa
- Authors: Das, Sweta
- Date: 2018
- Subjects: Textile fabrics -- Testing , Textile fabrics -- Measurement , Textile fibers -- Testing , Textile design
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/17814 , vital:28458
- Description: In the last few decades, there has been a shift globally towards the objective measurement of these textile fibre, yarn and fabric properties which determine processing performance and product quality. This shift is also very apparent in the objective measurement of fabric properties, particularly those relating to handle and making-up into a garment. This study was motivated by the fact that the adoption of fabric objective measurement (FOM), specifically the FAST system, will benefit the South African worsted apparel sector, as it has done in various other countries which produce high quality worsted apparel fabrics and garments. FAST is robust and portable, yet inexpensive. The main objective of the study was to develop a FAST referencing system which can be used for benchmarking by the local apparel industry and, as a basis for encouraging and persuading the industry to adopt this system of fabric quality measurement and assurance and thereby improve their product quality and international competitiveness. To achieve the main objective, involved sourcing and FAST testing a representative cross-section of commercial worsted apparel fabrics with the emphasis on wool and wool blends from the local fabric and clothing manufacturing industry, and determining how the various FAST properties were affected by factors such as fabric weave, fibre blend and weight, since this could impact on the specific nature and validity of the referencing system. A total of some 394 worsted type commercial fabrics, mainly in wool and wool blends, were sourced from, and with the inputs of, local apparel fabric and clothing manufacturers so as to ensure the local fabric and garment representative of the sample population and after which the fabrics were tested on the FAST system. ANOVA (regression analysis) was carried out on each of the FAST parameters in order to determine whether fabric weight, weave, thickness and fibre composition (pure wool and wool blends) had a statistically significant effect on them, since this is an important aspect which needs to be clarified prior to the development of a envisaged meaningful FAST system.
- Full Text:
- Date Issued: 2018
- Authors: Das, Sweta
- Date: 2018
- Subjects: Textile fabrics -- Testing , Textile fabrics -- Measurement , Textile fibers -- Testing , Textile design
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/17814 , vital:28458
- Description: In the last few decades, there has been a shift globally towards the objective measurement of these textile fibre, yarn and fabric properties which determine processing performance and product quality. This shift is also very apparent in the objective measurement of fabric properties, particularly those relating to handle and making-up into a garment. This study was motivated by the fact that the adoption of fabric objective measurement (FOM), specifically the FAST system, will benefit the South African worsted apparel sector, as it has done in various other countries which produce high quality worsted apparel fabrics and garments. FAST is robust and portable, yet inexpensive. The main objective of the study was to develop a FAST referencing system which can be used for benchmarking by the local apparel industry and, as a basis for encouraging and persuading the industry to adopt this system of fabric quality measurement and assurance and thereby improve their product quality and international competitiveness. To achieve the main objective, involved sourcing and FAST testing a representative cross-section of commercial worsted apparel fabrics with the emphasis on wool and wool blends from the local fabric and clothing manufacturing industry, and determining how the various FAST properties were affected by factors such as fabric weave, fibre blend and weight, since this could impact on the specific nature and validity of the referencing system. A total of some 394 worsted type commercial fabrics, mainly in wool and wool blends, were sourced from, and with the inputs of, local apparel fabric and clothing manufacturers so as to ensure the local fabric and garment representative of the sample population and after which the fabrics were tested on the FAST system. ANOVA (regression analysis) was carried out on each of the FAST parameters in order to determine whether fabric weight, weave, thickness and fibre composition (pure wool and wool blends) had a statistically significant effect on them, since this is an important aspect which needs to be clarified prior to the development of a envisaged meaningful FAST system.
- Full Text:
- Date Issued: 2018
The separation of platinum and gold from an industrial feed solution
- Authors: Louw, Talana
- Date: 2008
- Subjects: Platinum -- Separation , Gold , Separation -- Technology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10400 , http://hdl.handle.net/10948/731 , Platinum -- Separation , Gold , Separation -- Technology
- Description: In this thesis, the aim was to develop resins which are platinum and gold specific to be utilized for the early removal of these metals from the industrial feed. Efforts were therefore directed towards the synthesis of silica based resins with active centra which were designed for platinum and gold specificity respectively. The large chlorometallate ions in the feed stream were characterized in terms of physical parameters relevant to phase distribution namely distortability (RD), charge density, softness (σ) etc. Matching cations for each of the types were investigated. In order to attempt the design of platinum specific resins different structural amines were used to aminate the silicone precursor and subsequently to fix these onto the silica framework. Two different solvents i.e. alcohol and dmf were used for this process, resulting in two sets of resins with different properties. For gold specific resins, various polyethers were attached to a different type of silicone precursor, which was attached to the silica framework. The design was based on previous experience with these ions with reference to their behaviour towards different types of cations. The platinum species PtCl6 2- and PtCl4 2-, the gold species AuCl4 -, as well as the most important contaminants in the feed stream were typified bearing in mind size, charge, charge density and distortability. Different types of cationic centra having differences in charge density, stereochemical crowding and extent of hydrophobicity were synthesized and tested both as solvent extractants (where possible) and silica based resins. The results indicated that partly screened secondary ammonium cationic resin species, which could be regarded as “intermediate”, proved to be satisfactory both in their high percentage extraction for PtCl4 2- and rejection of contaminants like chlororhodates, chloroiridates(III) and FeCl4 -. It was, however, necessary to work at a redox potential where iridium(IV) in the form of IrCl6 2- is absent. Various 2-aminoalkane resins were prepared with variation in the length of alkane group and synthesized in the two different solvents. The latter resulted in two sets of resins with different compactness also having significantly different properties with reference to platinum specificity, HCl effect and stripping potential. The 2- aminobutane and 2-aminoheptane resins both proved to be very satisfactory platinum specific resins with respect to selectivity, platinum capacity and stripping potential. The various physical parameters could be utilized to accommodate the chemical behaviour. To obtain gold specific resins, experiments were performed with resins having oxygen-donor atoms which can readily be protonated to form onium type cations for example amides and ether oxygen atoms. In the case of the latter, various polyethers with a different number of ether groups (polyether groups linked by ethylene and propylene groups) and variations of hydrophobicity (by substitution) have also been studied. Linked to the polyether groups were alkane and aryl groups. Those having 8 to 10 ether groups and aromatic tail ends proved to be moderately successful in terms of gold capacity and sharp breakthrough curves of their columns, however, platinum could not be very effectively rejected.
- Full Text:
- Date Issued: 2008
- Authors: Louw, Talana
- Date: 2008
- Subjects: Platinum -- Separation , Gold , Separation -- Technology
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10400 , http://hdl.handle.net/10948/731 , Platinum -- Separation , Gold , Separation -- Technology
- Description: In this thesis, the aim was to develop resins which are platinum and gold specific to be utilized for the early removal of these metals from the industrial feed. Efforts were therefore directed towards the synthesis of silica based resins with active centra which were designed for platinum and gold specificity respectively. The large chlorometallate ions in the feed stream were characterized in terms of physical parameters relevant to phase distribution namely distortability (RD), charge density, softness (σ) etc. Matching cations for each of the types were investigated. In order to attempt the design of platinum specific resins different structural amines were used to aminate the silicone precursor and subsequently to fix these onto the silica framework. Two different solvents i.e. alcohol and dmf were used for this process, resulting in two sets of resins with different properties. For gold specific resins, various polyethers were attached to a different type of silicone precursor, which was attached to the silica framework. The design was based on previous experience with these ions with reference to their behaviour towards different types of cations. The platinum species PtCl6 2- and PtCl4 2-, the gold species AuCl4 -, as well as the most important contaminants in the feed stream were typified bearing in mind size, charge, charge density and distortability. Different types of cationic centra having differences in charge density, stereochemical crowding and extent of hydrophobicity were synthesized and tested both as solvent extractants (where possible) and silica based resins. The results indicated that partly screened secondary ammonium cationic resin species, which could be regarded as “intermediate”, proved to be satisfactory both in their high percentage extraction for PtCl4 2- and rejection of contaminants like chlororhodates, chloroiridates(III) and FeCl4 -. It was, however, necessary to work at a redox potential where iridium(IV) in the form of IrCl6 2- is absent. Various 2-aminoalkane resins were prepared with variation in the length of alkane group and synthesized in the two different solvents. The latter resulted in two sets of resins with different compactness also having significantly different properties with reference to platinum specificity, HCl effect and stripping potential. The 2- aminobutane and 2-aminoheptane resins both proved to be very satisfactory platinum specific resins with respect to selectivity, platinum capacity and stripping potential. The various physical parameters could be utilized to accommodate the chemical behaviour. To obtain gold specific resins, experiments were performed with resins having oxygen-donor atoms which can readily be protonated to form onium type cations for example amides and ether oxygen atoms. In the case of the latter, various polyethers with a different number of ether groups (polyether groups linked by ethylene and propylene groups) and variations of hydrophobicity (by substitution) have also been studied. Linked to the polyether groups were alkane and aryl groups. Those having 8 to 10 ether groups and aromatic tail ends proved to be moderately successful in terms of gold capacity and sharp breakthrough curves of their columns, however, platinum could not be very effectively rejected.
- Full Text:
- Date Issued: 2008
Development of a small production platform for citronellal processing
- Mafu, Lubabalo Rowan, Zeelie, Ben
- Authors: Mafu, Lubabalo Rowan , Zeelie, Ben
- Date: 2016
- Subjects: Organic compounds -- Synthesis , Plasticizers
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/8488 , vital:26370
- Description: The aim of the project was to develop a small production platform for citronellal processing. The objective of the study was to develop a single continuous flow reactor system for the synthesis of novel derivatives of citronellal and isopulegol. The first step was to develop a continuous flow reactor system for the isopulegol synthesis. The stainless steel tubular fixed-bed reactor equipped with a reaction column (I.D: 9.53 mm and length: 120 mm) was used for the study. The reactor column was packed with H-ZMS-5 zeolite extrusion catalyst. The solvent-free cyclisation reaction of citronellal was investigated and at optimum conditions, 100% of citronellal conversion and almost 100% selectivity towards isopulegol was achieved. A good catalytic performance was observed from the H-ZSM-5 catalyst and proved to be stable for a prolonged reaction time. The second reaction step was to develop a continuous flow reactor system for the synthesis of isopulegyl-ether derivatives. A UniQsis FlowSyn reactor system equipped with a stainless steel reactor column was used for the study. The reactor column was packed with amberlyst-15 dry catalyst. Wherein, n-propanol was employed as a model etherifying agent and as a reaction solvent. At optimum reaction condition, only 30% selectivity of isopulegyl propoxy-ether was achieved. The reaction was found to depend highly on temperature and residence time. The increase of these parameters was found to increase the side reactions and reduced the selectivity of the desired product. Other heterogeneous catalysts such as H-beta zeolite, aluminium pillared clay, Aluminium oxide and H-ZSM-5 were also evaluated in the reaction. Among these catalysts, a catalytic activity was observed with H-beta zeolite (19%) and aluminium pillared clay (5%). Based on these results, none of the evaluated catalysts provided the desired selectivity (greater than 70%) towards the isopulegyl propoxy-ether, therefore the process was not investigated further. In light of this, the isopulegol etherification synthetic route was terminated. Consequently, another analogue of citronellal was used as an alternative intermediate in place of isopulegol, namely para-menthane-3,8-diol (PMD). The initial studies for the synthesis of the novel PMD di-esters from isopulegol were performed in the batch-scale reactor. In a solvent-free reaction, acetic anhydride was initially used as a model acetylating agent. The reaction was performed using polymer-bound scandium triflate (PS-Sc(OTf)3) catalyst. The effect of reaction parameters such as temperature, molar ratio, and reaction time were studied towards the PMD conversion and di-esters selectivity. At optimum reaction conditions, PMD conversion of 70% and di-acetate selectivity of 67% were observed. The reaction was found to follow the zeroth-order kinetics with respect to PMD conversion and obeyed the Arrhenius equation. Other types of di-ester derivatives were synthesized from PMD by varying the carbon chain length of the acetylating agent. The prepared compounds were separated from the product mixtures by vacuum distillation, purified on a column chromatography and characterised by FT-IR, GC-MS, and 1H-NMR, 13C-NMR. The developed methodology was optimised in flow by using an ArrheniumOne microwave-assisted continuous-flow fixed-bed reactor system. A detailed experimental design was used to carry-out the reactions. The reaction parameters such as temperature and flow-rate were studied towards the PMD conversion and di-ester selectivity. From the experimental design analysis, the di-ester selectivity was found to depend highly on the residence time (flow-rate) and significantly on temperature. The PMD conversion and di-ester selectivity were found to increase with decrease in the flow-rate. The conversion and selectivity achieved in the continuous flow process were significantly higher than the achieved in the batch-scale process with respect to the residence time.
- Full Text:
- Date Issued: 2016
- Authors: Mafu, Lubabalo Rowan , Zeelie, Ben
- Date: 2016
- Subjects: Organic compounds -- Synthesis , Plasticizers
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/8488 , vital:26370
- Description: The aim of the project was to develop a small production platform for citronellal processing. The objective of the study was to develop a single continuous flow reactor system for the synthesis of novel derivatives of citronellal and isopulegol. The first step was to develop a continuous flow reactor system for the isopulegol synthesis. The stainless steel tubular fixed-bed reactor equipped with a reaction column (I.D: 9.53 mm and length: 120 mm) was used for the study. The reactor column was packed with H-ZMS-5 zeolite extrusion catalyst. The solvent-free cyclisation reaction of citronellal was investigated and at optimum conditions, 100% of citronellal conversion and almost 100% selectivity towards isopulegol was achieved. A good catalytic performance was observed from the H-ZSM-5 catalyst and proved to be stable for a prolonged reaction time. The second reaction step was to develop a continuous flow reactor system for the synthesis of isopulegyl-ether derivatives. A UniQsis FlowSyn reactor system equipped with a stainless steel reactor column was used for the study. The reactor column was packed with amberlyst-15 dry catalyst. Wherein, n-propanol was employed as a model etherifying agent and as a reaction solvent. At optimum reaction condition, only 30% selectivity of isopulegyl propoxy-ether was achieved. The reaction was found to depend highly on temperature and residence time. The increase of these parameters was found to increase the side reactions and reduced the selectivity of the desired product. Other heterogeneous catalysts such as H-beta zeolite, aluminium pillared clay, Aluminium oxide and H-ZSM-5 were also evaluated in the reaction. Among these catalysts, a catalytic activity was observed with H-beta zeolite (19%) and aluminium pillared clay (5%). Based on these results, none of the evaluated catalysts provided the desired selectivity (greater than 70%) towards the isopulegyl propoxy-ether, therefore the process was not investigated further. In light of this, the isopulegol etherification synthetic route was terminated. Consequently, another analogue of citronellal was used as an alternative intermediate in place of isopulegol, namely para-menthane-3,8-diol (PMD). The initial studies for the synthesis of the novel PMD di-esters from isopulegol were performed in the batch-scale reactor. In a solvent-free reaction, acetic anhydride was initially used as a model acetylating agent. The reaction was performed using polymer-bound scandium triflate (PS-Sc(OTf)3) catalyst. The effect of reaction parameters such as temperature, molar ratio, and reaction time were studied towards the PMD conversion and di-esters selectivity. At optimum reaction conditions, PMD conversion of 70% and di-acetate selectivity of 67% were observed. The reaction was found to follow the zeroth-order kinetics with respect to PMD conversion and obeyed the Arrhenius equation. Other types of di-ester derivatives were synthesized from PMD by varying the carbon chain length of the acetylating agent. The prepared compounds were separated from the product mixtures by vacuum distillation, purified on a column chromatography and characterised by FT-IR, GC-MS, and 1H-NMR, 13C-NMR. The developed methodology was optimised in flow by using an ArrheniumOne microwave-assisted continuous-flow fixed-bed reactor system. A detailed experimental design was used to carry-out the reactions. The reaction parameters such as temperature and flow-rate were studied towards the PMD conversion and di-ester selectivity. From the experimental design analysis, the di-ester selectivity was found to depend highly on the residence time (flow-rate) and significantly on temperature. The PMD conversion and di-ester selectivity were found to increase with decrease in the flow-rate. The conversion and selectivity achieved in the continuous flow process were significantly higher than the achieved in the batch-scale process with respect to the residence time.
- Full Text:
- Date Issued: 2016
A multiscale remote sensing assessment of subtropical indigenous forests along the wild coast, South Africa
- Authors: Blessing, Sithole Vhusomuzi
- Date: 2015
- Subjects: Forests and forestry -- South Africa -- Remote sensing , Forest conservation , Remote sensing , Geographic information systems
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10677 , http://hdl.handle.net/10948/d1021169
- Description: The subtropical forests located along South Africa’s Wild Coast region, declared as one of the biodiversity hotspots, provide benefits to the local and national economy. However, there is evidence of increased pressure exerted on the forests by growing population and reduced income from activities not related to forest products. The ability of remote sensing to quantify subtropical forest changes over time, perform species discrimination (using field spectroscopy) and integrating field spectral and multispectral data were all assessed in this study. Investigations were conducted at pixel, leaf and sub-pixel levels. Both per-pixel and sub-pixel classification methods were used for improved forest characterisation. Using SPOT 6 imagery for 2013, the study determined the best classification algorithm for mapping sub-tropical forest and other land cover types to be the maximum likelihood classifier. Maximum likelihood outperformed minimum distance, spectral angle mapper and spectral information divergence algorithms, based on overall accuracy and Kappa coefficient values. Forest change analysis was made based on spectral measurements made at top of the atmosphere (TOC) level. When applied to the 2005 and 2009 SPOT 5 images, subtropical forest changes between 2005-2009 and 2009-2013 were quantified. A temporal analysis of forest cover trends in the periods 2005-2009 and 2009-2013 identified a decreasing trend of -3648.42 and -946.98 ha respectively, which translated to 7.81 percent and 2.20 percent decrease. Although there is evidence of a trend towards decreased rates of forest loss, more conservation efforts are required to protect the Wild Coast ecosystem. Using field spectral measurements data, the hierarchical method (comprising One-way ANOVA with Bonferroni correction, Classification and Regression Trees (CART) and Jeffries Matusita method) successfully selected optimal wavelengths for species discrimination at leaf level. Only 17 out of 2150 wavelengths were identified, thereby reducing the complexities related to data dimensionality. The optimal 17 wavelength bands were noted in the visible (438, 442, 512 and 695 nm), near infrared (724, 729, 750, 758, 856, 936, 1179, 1507 and 1673 nm) and mid-infrared (2220, 2465, 2469 and 2482 nm) portions of the electromagnetic spectrum. The Jeffries-Matusita (JM) distance method confirmed the separability of the selected wavelength bands. Using these 17 wavelengths, linear discriminant analysis (LDA) classified subtropical species at leaf level more accurately than partial least squares discriminant analysis (PLSDA) and random forest (RF). In addition, the study integrated field-collected canopy spectral and multispectral data to discriminate proportions of semi-deciduous and evergreen subtropical forests at sub-pixel level. By using the 2013 land cover (using MLC) to mask non-forested portions before sub-pixel classification (using MTMF), the proportional maps were a product of two classifiers. The proportional maps show higher proportions of evergreen forests along the coast while semi-deciduous subtropical forest species were mainly on inland parts of the Wild Coast. These maps had high accuracy, thereby proving the ability of an integration of field spectral and multispectral data in mapping semi-deciduous and evergreen forest species. Overall, the study has demonstrated the importance of the MLC and LDA and served to integrate field spectral and multispectral data in subtropical forest characterisation at both leaf and top-of-atmosphere levels. The success of both the MLC and LDA further highlighted how essential parametric classifiers are in remote sensing forestry applications. Main subtropical characteristics highlighted in this study were species discrimination at leaf level, quantifying forest change at pixel level and discriminating semi-deciduous and evergreen forests at sub-pixel level.
- Full Text:
- Date Issued: 2015
- Authors: Blessing, Sithole Vhusomuzi
- Date: 2015
- Subjects: Forests and forestry -- South Africa -- Remote sensing , Forest conservation , Remote sensing , Geographic information systems
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10677 , http://hdl.handle.net/10948/d1021169
- Description: The subtropical forests located along South Africa’s Wild Coast region, declared as one of the biodiversity hotspots, provide benefits to the local and national economy. However, there is evidence of increased pressure exerted on the forests by growing population and reduced income from activities not related to forest products. The ability of remote sensing to quantify subtropical forest changes over time, perform species discrimination (using field spectroscopy) and integrating field spectral and multispectral data were all assessed in this study. Investigations were conducted at pixel, leaf and sub-pixel levels. Both per-pixel and sub-pixel classification methods were used for improved forest characterisation. Using SPOT 6 imagery for 2013, the study determined the best classification algorithm for mapping sub-tropical forest and other land cover types to be the maximum likelihood classifier. Maximum likelihood outperformed minimum distance, spectral angle mapper and spectral information divergence algorithms, based on overall accuracy and Kappa coefficient values. Forest change analysis was made based on spectral measurements made at top of the atmosphere (TOC) level. When applied to the 2005 and 2009 SPOT 5 images, subtropical forest changes between 2005-2009 and 2009-2013 were quantified. A temporal analysis of forest cover trends in the periods 2005-2009 and 2009-2013 identified a decreasing trend of -3648.42 and -946.98 ha respectively, which translated to 7.81 percent and 2.20 percent decrease. Although there is evidence of a trend towards decreased rates of forest loss, more conservation efforts are required to protect the Wild Coast ecosystem. Using field spectral measurements data, the hierarchical method (comprising One-way ANOVA with Bonferroni correction, Classification and Regression Trees (CART) and Jeffries Matusita method) successfully selected optimal wavelengths for species discrimination at leaf level. Only 17 out of 2150 wavelengths were identified, thereby reducing the complexities related to data dimensionality. The optimal 17 wavelength bands were noted in the visible (438, 442, 512 and 695 nm), near infrared (724, 729, 750, 758, 856, 936, 1179, 1507 and 1673 nm) and mid-infrared (2220, 2465, 2469 and 2482 nm) portions of the electromagnetic spectrum. The Jeffries-Matusita (JM) distance method confirmed the separability of the selected wavelength bands. Using these 17 wavelengths, linear discriminant analysis (LDA) classified subtropical species at leaf level more accurately than partial least squares discriminant analysis (PLSDA) and random forest (RF). In addition, the study integrated field-collected canopy spectral and multispectral data to discriminate proportions of semi-deciduous and evergreen subtropical forests at sub-pixel level. By using the 2013 land cover (using MLC) to mask non-forested portions before sub-pixel classification (using MTMF), the proportional maps were a product of two classifiers. The proportional maps show higher proportions of evergreen forests along the coast while semi-deciduous subtropical forest species were mainly on inland parts of the Wild Coast. These maps had high accuracy, thereby proving the ability of an integration of field spectral and multispectral data in mapping semi-deciduous and evergreen forest species. Overall, the study has demonstrated the importance of the MLC and LDA and served to integrate field spectral and multispectral data in subtropical forest characterisation at both leaf and top-of-atmosphere levels. The success of both the MLC and LDA further highlighted how essential parametric classifiers are in remote sensing forestry applications. Main subtropical characteristics highlighted in this study were species discrimination at leaf level, quantifying forest change at pixel level and discriminating semi-deciduous and evergreen forests at sub-pixel level.
- Full Text:
- Date Issued: 2015
Phytoplankton of the Southern Agulhas Large Marine Ecosystem (sACLME)
- Authors: Sonnekus, Martinus Jakobus
- Date: 2020
- Subjects: Botanical chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/47646 , vital:40261
- Description: The southern Agulhas Large Marine Ecosystem (sACLME) consists of the greater Agulhas Current system, including the areas influenced by the Agulhas Current, the Agulhas Shelf, Agulhas Bank, Agulhas Retroflection as well as the Agulhas Return Current. Four biogeographical regions were identified within the sACLME and the composition of the phytoplankton communities and the associated physico-chemical variables in each were investigated. Water temperature and nitrate concentration were found to be the main drivers of the sACLME phytoplankton community. A total of 215 phytoplankton taxa were identified that were separated into two groups: the Agulhas Current group and the Southwest Indian Ocean Ridge group. The structure of the phytoplankton community was consistently homogeneous throughout the sACLME. Nutrient concentrations of the water varied, but nitrate was the most abundant source of nitrogen, especially in regions that were subjected to the upwelling of cold nutrient-rich water. The phytoplankton communities were significantly influenced by the availability and stoichiometry of the macronutrients nitrogen; phosphorus and silicon. The low mean N:P ratio of 5.5 is an indication that the waters of the sACLME are generally nitrogen limited, as is typical of oceanic systems. There is a change in phytoplankton cell size and functional groups within in the various water masses that are specific to certain biogeographical regions within the Agulhas Current system. It is clear that frontal systems may form barriers between phytoplankton communities.
- Full Text:
- Date Issued: 2020
- Authors: Sonnekus, Martinus Jakobus
- Date: 2020
- Subjects: Botanical chemistry
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/47646 , vital:40261
- Description: The southern Agulhas Large Marine Ecosystem (sACLME) consists of the greater Agulhas Current system, including the areas influenced by the Agulhas Current, the Agulhas Shelf, Agulhas Bank, Agulhas Retroflection as well as the Agulhas Return Current. Four biogeographical regions were identified within the sACLME and the composition of the phytoplankton communities and the associated physico-chemical variables in each were investigated. Water temperature and nitrate concentration were found to be the main drivers of the sACLME phytoplankton community. A total of 215 phytoplankton taxa were identified that were separated into two groups: the Agulhas Current group and the Southwest Indian Ocean Ridge group. The structure of the phytoplankton community was consistently homogeneous throughout the sACLME. Nutrient concentrations of the water varied, but nitrate was the most abundant source of nitrogen, especially in regions that were subjected to the upwelling of cold nutrient-rich water. The phytoplankton communities were significantly influenced by the availability and stoichiometry of the macronutrients nitrogen; phosphorus and silicon. The low mean N:P ratio of 5.5 is an indication that the waters of the sACLME are generally nitrogen limited, as is typical of oceanic systems. There is a change in phytoplankton cell size and functional groups within in the various water masses that are specific to certain biogeographical regions within the Agulhas Current system. It is clear that frontal systems may form barriers between phytoplankton communities.
- Full Text:
- Date Issued: 2020
Bush clumps as indicators of thresholds of change in Arid Thicket mosaic piospheres
- Authors: Schmidt, Anton George
- Date: 2017
- Subjects: Biodiversity conservation Ecological processes
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/20811 , vital:29403
- Description: In the literature, Arid Thicket transformation by domestic meso-herbivores is purported to follow a state-and-transition model, whereby the ecosystem is initially resilient to herbivory until some threshold is crossed, where after there is a rapid shift to a new alternative stable state. My study represents a first attempt to verify this hypothesis by searching for evidence of stable ecosystem states separated by structural, functional and degradation thresholds in Pruim-Spekboomveld, a variation of Arid Thicket found in the southern Cape of South Africa. In this variation, thicket bush clumps ranging in size from approximately 1 m2 to 100 m2 are interspersed in a matrix of Succulent Karoo vegetation. I correlate structural and functional attributes of the thicket bush clumps and the soil environment beneath them (indicators of ecosystem function) to distance from artificial watering points in four piosphere treatments that have had a different rangeland management history. I mostly fit linear, exponential and sigmoid regression models to my data and use Akaike’s Information Criterion to select the best fitting model. When analysing data on changes in the variation of vegetation production with distance from water using the Normalized Difference Vegetation Index, I additionally fit Generalized Additive Models to the data to take into account more complex predicted patterns of change. Furthermore, I compare the end regions of my data in the piosphere treatments to each other and to similar data collected in a transformed and untransformed reference site. I use both the pattern and extent of transformation within and between the treatments and the reference sites, to verify the existence of stable states and structural, functional and degradation thresholds. I also subject my entire dataset to multivariate analysis using ordination and permutation procedures, in an attempt to corroborate my results from the univariate analysis and to assess the response of bush clump community composition to herbivory. My results indicate that at the scale of a bush clump, a threshold reduction in species richness, functional type diversity, succulent shrub redundancy and cover, palatable shrub cover and bush clump leaf mass below 1.5 m occurs in regions intensively used by domestic meso-herbivores. Furthermore, at the landscape scale there is a threshold reduction in canopy tree cover and bush clump density. In addition to these structural threshold changes, results from a Landscape Function Analysis indicate that soil nutrient cycling, soil water infiltration and soil stability thresholds are crossed at the landscape scale. The soil nutrient cycling threshold is affirmed by soil chemical analyses which indicate that the most rested treatment in the study area has low carbon and nitrogen levels. Furthermore, the keystone species, Portulacaria afra, is unable to re-establish itself in any of the treatments. High pH and potassium levels in all the treatments, relative to the untransformed reference site, indicate that Portulacaria afra (which prefers moderate soil conditions) is unlikely to re-establish in the study area. This finding suggests that all my treatments have crossed a degradation threshold and therefore represent an alternative stable state to the untransformed reference site. My multivariate analysis supports this finding and further indicates that the sampling zones within 25 m of the watering points in the most utilized treatments have crossed a second degradation threshold. This finding is supported by my results that indicate that structural and function thresholds (related to the size, density and ability of bush clumps to capture and retain soil resources) have been crossed. Furthermore, excessively high concentrations of base cations in these sampling zones, relative to the untransformed reference site, affirm the crossing of a degradation threshold. My results on the changes in the variation of vegetation production with distance from water using the Normalized Difference Vegetation Index, support the growing body of evidence in the literature that suggests that increases in the variance of ecosystem processes and services are important indicators of impending ecological thresholds. In general, my findings support the prediction in the literature that domestic meso-herbivore induced transformation of Arid Mosaic Thicket will follow a state-andtransition model.
- Full Text:
- Date Issued: 2017
- Authors: Schmidt, Anton George
- Date: 2017
- Subjects: Biodiversity conservation Ecological processes
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/20811 , vital:29403
- Description: In the literature, Arid Thicket transformation by domestic meso-herbivores is purported to follow a state-and-transition model, whereby the ecosystem is initially resilient to herbivory until some threshold is crossed, where after there is a rapid shift to a new alternative stable state. My study represents a first attempt to verify this hypothesis by searching for evidence of stable ecosystem states separated by structural, functional and degradation thresholds in Pruim-Spekboomveld, a variation of Arid Thicket found in the southern Cape of South Africa. In this variation, thicket bush clumps ranging in size from approximately 1 m2 to 100 m2 are interspersed in a matrix of Succulent Karoo vegetation. I correlate structural and functional attributes of the thicket bush clumps and the soil environment beneath them (indicators of ecosystem function) to distance from artificial watering points in four piosphere treatments that have had a different rangeland management history. I mostly fit linear, exponential and sigmoid regression models to my data and use Akaike’s Information Criterion to select the best fitting model. When analysing data on changes in the variation of vegetation production with distance from water using the Normalized Difference Vegetation Index, I additionally fit Generalized Additive Models to the data to take into account more complex predicted patterns of change. Furthermore, I compare the end regions of my data in the piosphere treatments to each other and to similar data collected in a transformed and untransformed reference site. I use both the pattern and extent of transformation within and between the treatments and the reference sites, to verify the existence of stable states and structural, functional and degradation thresholds. I also subject my entire dataset to multivariate analysis using ordination and permutation procedures, in an attempt to corroborate my results from the univariate analysis and to assess the response of bush clump community composition to herbivory. My results indicate that at the scale of a bush clump, a threshold reduction in species richness, functional type diversity, succulent shrub redundancy and cover, palatable shrub cover and bush clump leaf mass below 1.5 m occurs in regions intensively used by domestic meso-herbivores. Furthermore, at the landscape scale there is a threshold reduction in canopy tree cover and bush clump density. In addition to these structural threshold changes, results from a Landscape Function Analysis indicate that soil nutrient cycling, soil water infiltration and soil stability thresholds are crossed at the landscape scale. The soil nutrient cycling threshold is affirmed by soil chemical analyses which indicate that the most rested treatment in the study area has low carbon and nitrogen levels. Furthermore, the keystone species, Portulacaria afra, is unable to re-establish itself in any of the treatments. High pH and potassium levels in all the treatments, relative to the untransformed reference site, indicate that Portulacaria afra (which prefers moderate soil conditions) is unlikely to re-establish in the study area. This finding suggests that all my treatments have crossed a degradation threshold and therefore represent an alternative stable state to the untransformed reference site. My multivariate analysis supports this finding and further indicates that the sampling zones within 25 m of the watering points in the most utilized treatments have crossed a second degradation threshold. This finding is supported by my results that indicate that structural and function thresholds (related to the size, density and ability of bush clumps to capture and retain soil resources) have been crossed. Furthermore, excessively high concentrations of base cations in these sampling zones, relative to the untransformed reference site, affirm the crossing of a degradation threshold. My results on the changes in the variation of vegetation production with distance from water using the Normalized Difference Vegetation Index, support the growing body of evidence in the literature that suggests that increases in the variance of ecosystem processes and services are important indicators of impending ecological thresholds. In general, my findings support the prediction in the literature that domestic meso-herbivore induced transformation of Arid Mosaic Thicket will follow a state-andtransition model.
- Full Text:
- Date Issued: 2017
A contribution to the theory of prime modules
- Authors: Ssevviiri, David
- Date: 2013
- Subjects: Modules (Algebra) , Radical theory , Rings (Algebra)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10510 , http://hdl.handle.net/10948/d1019923
- Description: This thesis is aimed at generalizing notions of rings to modules. In par-ticular, notions of completely prime ideals, s-prime ideals, 2-primal rings and nilpotency of elements of rings are respectively generalized to completely prime submodules and classical completely prime submodules, s-prime submodules, 2-primal modules and nilpotency of elements of modules. Properties and rad-icals that arise from each of these notions are studied.
- Full Text:
- Date Issued: 2013
- Authors: Ssevviiri, David
- Date: 2013
- Subjects: Modules (Algebra) , Radical theory , Rings (Algebra)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10510 , http://hdl.handle.net/10948/d1019923
- Description: This thesis is aimed at generalizing notions of rings to modules. In par-ticular, notions of completely prime ideals, s-prime ideals, 2-primal rings and nilpotency of elements of rings are respectively generalized to completely prime submodules and classical completely prime submodules, s-prime submodules, 2-primal modules and nilpotency of elements of modules. Properties and rad-icals that arise from each of these notions are studied.
- Full Text:
- Date Issued: 2013
A context-aware model to improve usability of information presented on mobile devices
- Authors: Ntawanga, Felix Fred
- Date: 2014
- Subjects: Context-aware computing , Online information services
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10495 , http://hdl.handle.net/10948/d1020768
- Description: Online information access on mobile devices is increasing as a result of the growth in the use of Internet-enabled handheld (or pocket-size) devices. The combined influence of recent enabling technologies such as Web 2.0, mobile app stores and improved wireless networks have driven the increase in online applications that allow users to access various types of information on mobile devices regardless of time and location. Examples of such applications (usually shortened to app) include: social media, such as FacebookTM App and TwitterTM App, banking applications such as (Standard Bank South Africa)TM Mobile Banking App and First National Bank (FNB) BankingTM App, and news application such as news 24TM App and BBCTM News App. Online businesses involved in buying, selling and business transaction processing activities via the Internet have exploited the opportunity to extend electronic commerce (e-commerce) initiatives into mobile commerce (m-commerce). Online businesses that interact with end user customers implement business to consumer (B2C) m-commerce applications that enable customers to access and browse product catalogue information on mobile devices, anytime, anywhere. Customers accessing electronic product catalogue information on a mobile device face a number of challenges such as a long list of products presented on a small screen and a longer information download time. These challenges mainly originate from the limiting and dynamic nature of the mobile apps operating environment, for example, dynamic location, bandwidth fluctuations and, diverse and limited device features, collectively referred to as context. The goal of this research was to design and implement a context-aware model that can be incorporated into an m-commerce application in order to improve the presentation of product catalogue information on m-commerce storefronts. The motivation for selecting product catalogue is prompted by literature which indicates that improved presentation of information in m-commerce (and e-commerce) applications has a positive impact on usability of the websites. Usable m-commerce (and e-commerce) websites improve efficiency in consumer behaviour that impacts sales, profits and business growth. The context-aware model aimed at collecting context information within the user environment and utilising it to determine optimal retrieval and presentation of product catalogue in m-commerce. An integrated logical context sensor and Mathematical algorithms were implemented in the context-aware model. The integrated logical context sensor was responsible for the collection of different types of predetermined context information such as device specification or capabilities, connection bandwidth, location and time of the day as well as the user profile. The algorithms transformed the collected context information into usable formats and enabled optimal retrieval and presentation of product catalogue data on a specific mobile device. Open-source implementation tools were utilised to implement components of the model including: HTML5, PhP, JavaScript and MySQL database. The context-aware model was incorporated into an existing m-commerce application. Two user evaluation studies were conducted during the course of the research. The first evaluation was to evaluate the accuracy of information collected by the context sensor component of the model. This survey was conducted with a sample of 30 users from different countries across the world. In-between the context sensor and main evaluation surveys, a pilot study was conducted with a sample of 19 users with great experience in mobile application development and use from SAP Next Business and Technology, Africa. Finally an overall user evaluation study was conducted with a sample of 30 users from a remote area called Kgautswane in Limpopo Province, South Africa. The results obtained indicate that the context-aware model was able to determine accurate context information in real-time and effectively determine how much product information should be retrieved and how the information should be presented on a mobile device interface. Two main contributions emerged from the research, first the research contributed to the field of mobile Human Computer Interaction. During the research, techniques of evaluating and improving usability of mobile applications were demonstrated. Secondly, the research made a significant contribution to the upcoming field of context-aware computing. The research brought clarity with regard to context-aware computing which is lacking in existing, current research despite the field’s proven impact of improving usability of applications. Researchers can utilise contributions made in this research to develop further techniques and usable context-aware solutions.
- Full Text:
- Date Issued: 2014
- Authors: Ntawanga, Felix Fred
- Date: 2014
- Subjects: Context-aware computing , Online information services
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: vital:10495 , http://hdl.handle.net/10948/d1020768
- Description: Online information access on mobile devices is increasing as a result of the growth in the use of Internet-enabled handheld (or pocket-size) devices. The combined influence of recent enabling technologies such as Web 2.0, mobile app stores and improved wireless networks have driven the increase in online applications that allow users to access various types of information on mobile devices regardless of time and location. Examples of such applications (usually shortened to app) include: social media, such as FacebookTM App and TwitterTM App, banking applications such as (Standard Bank South Africa)TM Mobile Banking App and First National Bank (FNB) BankingTM App, and news application such as news 24TM App and BBCTM News App. Online businesses involved in buying, selling and business transaction processing activities via the Internet have exploited the opportunity to extend electronic commerce (e-commerce) initiatives into mobile commerce (m-commerce). Online businesses that interact with end user customers implement business to consumer (B2C) m-commerce applications that enable customers to access and browse product catalogue information on mobile devices, anytime, anywhere. Customers accessing electronic product catalogue information on a mobile device face a number of challenges such as a long list of products presented on a small screen and a longer information download time. These challenges mainly originate from the limiting and dynamic nature of the mobile apps operating environment, for example, dynamic location, bandwidth fluctuations and, diverse and limited device features, collectively referred to as context. The goal of this research was to design and implement a context-aware model that can be incorporated into an m-commerce application in order to improve the presentation of product catalogue information on m-commerce storefronts. The motivation for selecting product catalogue is prompted by literature which indicates that improved presentation of information in m-commerce (and e-commerce) applications has a positive impact on usability of the websites. Usable m-commerce (and e-commerce) websites improve efficiency in consumer behaviour that impacts sales, profits and business growth. The context-aware model aimed at collecting context information within the user environment and utilising it to determine optimal retrieval and presentation of product catalogue in m-commerce. An integrated logical context sensor and Mathematical algorithms were implemented in the context-aware model. The integrated logical context sensor was responsible for the collection of different types of predetermined context information such as device specification or capabilities, connection bandwidth, location and time of the day as well as the user profile. The algorithms transformed the collected context information into usable formats and enabled optimal retrieval and presentation of product catalogue data on a specific mobile device. Open-source implementation tools were utilised to implement components of the model including: HTML5, PhP, JavaScript and MySQL database. The context-aware model was incorporated into an existing m-commerce application. Two user evaluation studies were conducted during the course of the research. The first evaluation was to evaluate the accuracy of information collected by the context sensor component of the model. This survey was conducted with a sample of 30 users from different countries across the world. In-between the context sensor and main evaluation surveys, a pilot study was conducted with a sample of 19 users with great experience in mobile application development and use from SAP Next Business and Technology, Africa. Finally an overall user evaluation study was conducted with a sample of 30 users from a remote area called Kgautswane in Limpopo Province, South Africa. The results obtained indicate that the context-aware model was able to determine accurate context information in real-time and effectively determine how much product information should be retrieved and how the information should be presented on a mobile device interface. Two main contributions emerged from the research, first the research contributed to the field of mobile Human Computer Interaction. During the research, techniques of evaluating and improving usability of mobile applications were demonstrated. Secondly, the research made a significant contribution to the upcoming field of context-aware computing. The research brought clarity with regard to context-aware computing which is lacking in existing, current research despite the field’s proven impact of improving usability of applications. Researchers can utilise contributions made in this research to develop further techniques and usable context-aware solutions.
- Full Text:
- Date Issued: 2014
A comparative study of artificial neural networks and physics models as simulators in evolutionary robotics
- Pretorius, Christiaan Johannes
- Authors: Pretorius, Christiaan Johannes
- Date: 2019
- Subjects: Neural networks (Computer science)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/30789 , vital:31131
- Description: The Evolutionary Robotics (ER) process is a technique that applies evolutionary optimization algorithms to the task of automatically developing, or evolving, robotic control programs. These control programs, or simply controllers, are evolved in order to allow a robot to perform a required task. During the ER process, use is often made of robotic simulators to evaluate the performance of candidate controllers that are produced in the course of the controller evolution process. Such simulators accelerate and otherwise simplify the controller evolution process, as opposed to the more arduous process of evaluating controllers in the real world without use of simulation. To date, the vast majority of simulators that have been applied in ER are physics- based models which are constructed by taking into account the underlying physics governing the operation of the robotic system in question. An alternative approach to simulator implementation in ER is the usage of Artificial Neural Networks (ANNs) as simulators in the ER process. Such simulators are referred to as Simulator Neural Networks (SNNs). Previous studies have indicated that SNNs can successfully be used as an alter- native to physics-based simulators in the ER process on various robotic platforms. At the commencement of the current study it was not, however, known how this relatively new method of simulation would compare to traditional physics-based simulation approaches in ER. The study presented in this thesis thus endeavoured to quantitatively compare SNNs and physics-based models as simulators in the ER process. In order to con- duct this comparative study, both SNNs and physics simulators were constructed for the modelling of three different robotic platforms: a differentially-steered robot, a wheeled inverted pendulum robot and a hexapod robot. Each of these two types of simulation was then used in simulation-based evolution processes to evolve con- trollers for each robotic platform. During these controller evolution processes, the SNNs and physics models were compared in terms of their accuracy in making pre- dictions of robotic behaviour, their computational efficiency in arriving at these predictions, the human effort required to construct each simulator and, most im- portantly, the real-world performance of controllers evolved by making use of each simulator. The results obtained in this study illustrated experimentally that SNNs were, in the majority of cases, able to make more accurate predictions than the physics- based models and these SNNs were arguably simpler to construct than the physics simulators. Additionally, SNNs were also shown to be a computationally efficient alternative to physics-based simulators in ER and, again in the majority of cases, these SNNs were able to produce controllers which outperformed those evolved in the physics-based simulators, when these controllers were uploaded to the real-world robots. The results of this thesis thus suggest that SNNs are a viable alternative to more commonly-used physics simulators in ER and further investigation of the potential of this simulation technique appears warranted.
- Full Text:
- Date Issued: 2019
- Authors: Pretorius, Christiaan Johannes
- Date: 2019
- Subjects: Neural networks (Computer science)
- Language: English
- Type: Thesis , Doctoral , PhD
- Identifier: http://hdl.handle.net/10948/30789 , vital:31131
- Description: The Evolutionary Robotics (ER) process is a technique that applies evolutionary optimization algorithms to the task of automatically developing, or evolving, robotic control programs. These control programs, or simply controllers, are evolved in order to allow a robot to perform a required task. During the ER process, use is often made of robotic simulators to evaluate the performance of candidate controllers that are produced in the course of the controller evolution process. Such simulators accelerate and otherwise simplify the controller evolution process, as opposed to the more arduous process of evaluating controllers in the real world without use of simulation. To date, the vast majority of simulators that have been applied in ER are physics- based models which are constructed by taking into account the underlying physics governing the operation of the robotic system in question. An alternative approach to simulator implementation in ER is the usage of Artificial Neural Networks (ANNs) as simulators in the ER process. Such simulators are referred to as Simulator Neural Networks (SNNs). Previous studies have indicated that SNNs can successfully be used as an alter- native to physics-based simulators in the ER process on various robotic platforms. At the commencement of the current study it was not, however, known how this relatively new method of simulation would compare to traditional physics-based simulation approaches in ER. The study presented in this thesis thus endeavoured to quantitatively compare SNNs and physics-based models as simulators in the ER process. In order to con- duct this comparative study, both SNNs and physics simulators were constructed for the modelling of three different robotic platforms: a differentially-steered robot, a wheeled inverted pendulum robot and a hexapod robot. Each of these two types of simulation was then used in simulation-based evolution processes to evolve con- trollers for each robotic platform. During these controller evolution processes, the SNNs and physics models were compared in terms of their accuracy in making pre- dictions of robotic behaviour, their computational efficiency in arriving at these predictions, the human effort required to construct each simulator and, most im- portantly, the real-world performance of controllers evolved by making use of each simulator. The results obtained in this study illustrated experimentally that SNNs were, in the majority of cases, able to make more accurate predictions than the physics- based models and these SNNs were arguably simpler to construct than the physics simulators. Additionally, SNNs were also shown to be a computationally efficient alternative to physics-based simulators in ER and, again in the majority of cases, these SNNs were able to produce controllers which outperformed those evolved in the physics-based simulators, when these controllers were uploaded to the real-world robots. The results of this thesis thus suggest that SNNs are a viable alternative to more commonly-used physics simulators in ER and further investigation of the potential of this simulation technique appears warranted.
- Full Text:
- Date Issued: 2019