Development of high capacity lithium-manganese-rich cathode materials xLi2MnO3•(1-x)LiMn0.5Ni0.5O2 for lithium ion batteries
- Authors: Rapulenyane, Nomasonto
- Date: 2018
- Subjects: Lithium ion batteries , Electrochemistry Lithium cells
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/34766 , vital:33442
- Description: In this study, a facile synthesis method was developed to produce layered-layered cathode materials with the formula xLi2MnO3•(1-x)LiMO2 (M= Ni and Mn) referred to as lithium-manganese-rich materials for lithium ion batteries. The prepared materials displayed high capacity ≥200 mAh/g at a current density of 20 mA/g in the voltage range of 2.0 V to 4.8 V. In particular the cathode material prepared at pH 10.0 delivered a high initial discharge capacity of 266 mAh/g at 20 mA/g current density and maintained a discharge capacity ≥220 mAh/g at 50 mA/g after 50 cycles. The synthesis method was used to further investigate the effect of lithium ratio in the layered-layered material. Li1+xMn0.6Ni0.2O2, x= 0.2, 0.25, 0.3 and 0.4 cathode materials were produced respectively. The BET surface area analysis results showed that Li1.3Mn0.6Ni0.2O2 material had comparatively higher surface area to the other cathode materials and also delivered good electrochemical results. XPS showed that the cation distribution is affected by the increase in lithium ratio, the Mn4+ percentages decreased significantly with an increase in lithium ratio. All materials peaks deconvoluted into two peaks namely Mn4+ and Mn3+, Li1.3Mn0.6Ni0.2O2 had the highest percentages of the stable Mn4+ 70.8%. Further investigation focused on the effect of the sintering temperature on the structure and the electrochemical performance of Li1+xMn0.6Ni0.2O2, x= 0.25, 0.3 and 0.4 cathode materials. X-ray diffraction showed the same patterns for all cathode materials sintered at 700˚C, 800˚C and 900˚C. Rietveld refined results however, showed that the increase in the sintering temperature, results in a decrease in the Li2MnO3 component percentage in the layered structures. Scanning electron microscopy images further proved that the particle size increases with increasing temperature. The charge–discharge tests of coin cells demonstrated that the materials sintered at 800˚C delivered higher discharge capacities above 200 mAh/g at 20 mA/g current density when compared to the materials made at the lower temperatures. Lastly the cathode material prepared at pH 10.0 was further evaluated in a cell using lithium titanate oxide Li4Ti5O12 as anode material. The cells delivered an initial discharge capacity of 213 mAh/g at 20 mA/g within a voltage range 3.3V-0.5V. The coin cells developed in this work delivered good cycling performance.
- Full Text:
- Date Issued: 2018
- Authors: Rapulenyane, Nomasonto
- Date: 2018
- Subjects: Lithium ion batteries , Electrochemistry Lithium cells
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/34766 , vital:33442
- Description: In this study, a facile synthesis method was developed to produce layered-layered cathode materials with the formula xLi2MnO3•(1-x)LiMO2 (M= Ni and Mn) referred to as lithium-manganese-rich materials for lithium ion batteries. The prepared materials displayed high capacity ≥200 mAh/g at a current density of 20 mA/g in the voltage range of 2.0 V to 4.8 V. In particular the cathode material prepared at pH 10.0 delivered a high initial discharge capacity of 266 mAh/g at 20 mA/g current density and maintained a discharge capacity ≥220 mAh/g at 50 mA/g after 50 cycles. The synthesis method was used to further investigate the effect of lithium ratio in the layered-layered material. Li1+xMn0.6Ni0.2O2, x= 0.2, 0.25, 0.3 and 0.4 cathode materials were produced respectively. The BET surface area analysis results showed that Li1.3Mn0.6Ni0.2O2 material had comparatively higher surface area to the other cathode materials and also delivered good electrochemical results. XPS showed that the cation distribution is affected by the increase in lithium ratio, the Mn4+ percentages decreased significantly with an increase in lithium ratio. All materials peaks deconvoluted into two peaks namely Mn4+ and Mn3+, Li1.3Mn0.6Ni0.2O2 had the highest percentages of the stable Mn4+ 70.8%. Further investigation focused on the effect of the sintering temperature on the structure and the electrochemical performance of Li1+xMn0.6Ni0.2O2, x= 0.25, 0.3 and 0.4 cathode materials. X-ray diffraction showed the same patterns for all cathode materials sintered at 700˚C, 800˚C and 900˚C. Rietveld refined results however, showed that the increase in the sintering temperature, results in a decrease in the Li2MnO3 component percentage in the layered structures. Scanning electron microscopy images further proved that the particle size increases with increasing temperature. The charge–discharge tests of coin cells demonstrated that the materials sintered at 800˚C delivered higher discharge capacities above 200 mAh/g at 20 mA/g current density when compared to the materials made at the lower temperatures. Lastly the cathode material prepared at pH 10.0 was further evaluated in a cell using lithium titanate oxide Li4Ti5O12 as anode material. The cells delivered an initial discharge capacity of 213 mAh/g at 20 mA/g within a voltage range 3.3V-0.5V. The coin cells developed in this work delivered good cycling performance.
- Full Text:
- Date Issued: 2018
Quantification of greenhouse gas fluxes from soil in agricultural fields
- Authors: Nkongolo, Nsalambi Vakanda
- Date: 2010
- Subjects: Greenhouse gases -- Environmental aspects
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10645 , http://hdl.handle.net/10948/1474 , Greenhouse gases -- Environmental aspects
- Description: Field studies were conducted at Lincoln University of Missouri (USA) and Hokkaido University (Japan) to: (i) study the relationships between greenhouse gases emissions and soil properties, (ii) assess the influence of agricultural practices on greenhouse gas fluxes and soil properties and (iii) improve the quantification of greenhouse gases from soil in agricultural fields using geospatial technologies. Results showed that besides soil temperature (T), soil thermal properties such as thermal conductivity (K), resistivity (R) and diffusivity (D) and soil pore spaces indices such as the pore tortuosity factor and the relative gas diffusion coefficient (Ds/Do) are controlling factors for greenhouse gases emissions. Soil thermal properties correlated with greenhouse gases emissions when soil temperature could not. The study has found that predicted Ds/Do and correlate with greenhouse gas fluxes even when the air-filled porosity and the total porosity from which they are predicted did not. We have also showed that Ds/Do and can be predicted quickly from routine measurements of soil water and air and existing diffusivity models found in the literature. Agricultural practices do seriously impact greenhouse gases emissions as showed by the effect of mechanized tillage operations on soil physical properties and greenhouse gas fluxes in a corn and soybean fields. In fact, our results showed that tractor compaction increased soil resistance to penetration, water, bulk density and pore tortuosity while reducing air-filled porosity, total pore space and the soil gas diffusion coefficient. Changes in soil properties resulted in increased CO2, NO and N2O emissions. Finally, our results also confirmed that greenhouse gas fluxes vary tremendously in space and time. As estimates of greenhouse gas emissions are influenced by the data processing approach, differences between the different calculation approaches leads to uncertainty. Thus, techniques for developing better estimates are needed. We have showed that Geographic Information Systems (GIS), Global Positioning System (GPS), computer mapping and geo-statistics are technologies that can be used to better understand systems containing large amounts of spatial and temporal variability. Our GIS-based approach for quantifying CO2, CH4 and N2O fluxes from soil in agricultural fields showed that estimating (extrapolating) total greenhouse gas fluxes using the “standard” approach – multiplying the average flux value by the total field area – results in biased predictions of field total greenhouse gases emissions. In contrast, the GIS-based approach we developed produces an interpolated map portraying the spatial distribution of gas fluxes across the field from point measurements and later process the interpolated map produced to determine flux zones. Furthermore, processing, classification and modeling enables the computation of field total fluxes as the sum of fluxes in different zones, therefore taking into account the spatial variability of greenhouse gas fluxes.
- Full Text:
- Date Issued: 2010
- Authors: Nkongolo, Nsalambi Vakanda
- Date: 2010
- Subjects: Greenhouse gases -- Environmental aspects
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10645 , http://hdl.handle.net/10948/1474 , Greenhouse gases -- Environmental aspects
- Description: Field studies were conducted at Lincoln University of Missouri (USA) and Hokkaido University (Japan) to: (i) study the relationships between greenhouse gases emissions and soil properties, (ii) assess the influence of agricultural practices on greenhouse gas fluxes and soil properties and (iii) improve the quantification of greenhouse gases from soil in agricultural fields using geospatial technologies. Results showed that besides soil temperature (T), soil thermal properties such as thermal conductivity (K), resistivity (R) and diffusivity (D) and soil pore spaces indices such as the pore tortuosity factor and the relative gas diffusion coefficient (Ds/Do) are controlling factors for greenhouse gases emissions. Soil thermal properties correlated with greenhouse gases emissions when soil temperature could not. The study has found that predicted Ds/Do and correlate with greenhouse gas fluxes even when the air-filled porosity and the total porosity from which they are predicted did not. We have also showed that Ds/Do and can be predicted quickly from routine measurements of soil water and air and existing diffusivity models found in the literature. Agricultural practices do seriously impact greenhouse gases emissions as showed by the effect of mechanized tillage operations on soil physical properties and greenhouse gas fluxes in a corn and soybean fields. In fact, our results showed that tractor compaction increased soil resistance to penetration, water, bulk density and pore tortuosity while reducing air-filled porosity, total pore space and the soil gas diffusion coefficient. Changes in soil properties resulted in increased CO2, NO and N2O emissions. Finally, our results also confirmed that greenhouse gas fluxes vary tremendously in space and time. As estimates of greenhouse gas emissions are influenced by the data processing approach, differences between the different calculation approaches leads to uncertainty. Thus, techniques for developing better estimates are needed. We have showed that Geographic Information Systems (GIS), Global Positioning System (GPS), computer mapping and geo-statistics are technologies that can be used to better understand systems containing large amounts of spatial and temporal variability. Our GIS-based approach for quantifying CO2, CH4 and N2O fluxes from soil in agricultural fields showed that estimating (extrapolating) total greenhouse gas fluxes using the “standard” approach – multiplying the average flux value by the total field area – results in biased predictions of field total greenhouse gases emissions. In contrast, the GIS-based approach we developed produces an interpolated map portraying the spatial distribution of gas fluxes across the field from point measurements and later process the interpolated map produced to determine flux zones. Furthermore, processing, classification and modeling enables the computation of field total fluxes as the sum of fluxes in different zones, therefore taking into account the spatial variability of greenhouse gas fluxes.
- Full Text:
- Date Issued: 2010
The influence of genetic relatedness on sociality and demography of female African elephants
- Authors: Munishi, Linus Kasian
- Date: 2011
- Subjects: African elephant , Wildlife conservation , Elephants -- Africa
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10711 , http://hdl.handle.net/10948/d1011612 , African elephant , Wildlife conservation , Elephants -- Africa
- Description: Many elephant populations across Africa were or are being devastated by poaching and habitat loss, making population and range size for the species important issues of conservation concern in elephant ranging areas, including Tarangire National Park (TNP). Poaching and/or overhunting are known to have direct effects on the demography of elephant populations. The current understanding of the indirect effects of poaching on the sociality and demography of elephant populations is relatively poor, both at the group and an individual level. In this thesis the importance of genetic relatedness (as influenced by poaching) on sociality and demography of the female elephants was studied, using a combination of genetic, observation of behaviour and two decades of demography data collected from the northern subpopulation of TNP. I investigated and characterized the relatedness categories within elephant groups. Using a conceptual model for group size analysis in aggregation economies, I hypothesized that elephant populations subject to social disruptions due to poaching would exhibit characteristics of the free entry model, whereas more stable, closed populations would better fit the group-controlled model. I present a rare quantitative analysis of genetic relatedness and group size patterns among groups of adult female elephants in two wild populations: one in Tarangire National Park (TNP), Tanzania, and another in Addo Elephant National Park (AENP), South Africa. I demonstrate that the group size in African elephant populations is governed by genetic relatedness, and that poaching/overhunting has a significant influence upon the apparent group formation and size in elephants. I then focused on the effect of relatedness on agonistic interactions between adult females. I hypothesized that individual-based aggressive interactions among adult female African elephants would vary according to degree of kinship, with closely related dyads showing less aggression towards each other in resource-limited environments, thereby leading to indirect fitness benefits for individuals. As predicted, females did not show agonistic interactions to their close kin most often, and the frequency and intensity of aggressive interactions was inversely related to the degree of relatedness of the interactants. The effect of group relatedness and structure on reproductive success of individual female African elephant in TNP was also investigated. Adult female reproductive success was significantly influenced by within- group relatedness and structure. Higher reproductive success (with higher frequency of calf production and survival and more female calves produced) were more evident in the closely related groups than groups with low relatedness, suggesting that females from genetically disrupted groups are less likely to be reproductive than those in closely related groups. The possibility of negative effects of poaching on the subsequent generation of poached adult females and the alternative of a positive demographic response through reduced density was assessed by analysing the demographic patterns of the first generation (F1) females of prime-aged adult female African elephants in TNP using within- group relatedness and size. I also compared vital rate (age of first birth and interbirth interval) responses of first generation (F1) cows from Tarangire (poached) elephants with other females from poached (Northern Luangwa National Park, Zambia) and unpoached (Amboseli National Park, Kenya and Addo Elephant National Park, South Africa) populations. Group relatedness had no significant effect on sex ratio of the F1 cows‟ calves. There was a significant difference between the mean age of first birth and interbirth interval of F1 cows from the two (poached, Tarangire and unpoached, Amboseli National Park) elephant populations, suggesting that elephant populations reduced by poaching to low levels show an increase vigour through release from density constraints. Based on these results, the broader implications of secondary effects of poaching on elephant populations are critically evaluated. Also the importance of understanding the consequences of these effects is highlighted in light of other elephant conservation and management approaches. This understanding is useful in making conservation and management decisions for elephants and other biodiversity.
- Full Text:
- Date Issued: 2011
- Authors: Munishi, Linus Kasian
- Date: 2011
- Subjects: African elephant , Wildlife conservation , Elephants -- Africa
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10711 , http://hdl.handle.net/10948/d1011612 , African elephant , Wildlife conservation , Elephants -- Africa
- Description: Many elephant populations across Africa were or are being devastated by poaching and habitat loss, making population and range size for the species important issues of conservation concern in elephant ranging areas, including Tarangire National Park (TNP). Poaching and/or overhunting are known to have direct effects on the demography of elephant populations. The current understanding of the indirect effects of poaching on the sociality and demography of elephant populations is relatively poor, both at the group and an individual level. In this thesis the importance of genetic relatedness (as influenced by poaching) on sociality and demography of the female elephants was studied, using a combination of genetic, observation of behaviour and two decades of demography data collected from the northern subpopulation of TNP. I investigated and characterized the relatedness categories within elephant groups. Using a conceptual model for group size analysis in aggregation economies, I hypothesized that elephant populations subject to social disruptions due to poaching would exhibit characteristics of the free entry model, whereas more stable, closed populations would better fit the group-controlled model. I present a rare quantitative analysis of genetic relatedness and group size patterns among groups of adult female elephants in two wild populations: one in Tarangire National Park (TNP), Tanzania, and another in Addo Elephant National Park (AENP), South Africa. I demonstrate that the group size in African elephant populations is governed by genetic relatedness, and that poaching/overhunting has a significant influence upon the apparent group formation and size in elephants. I then focused on the effect of relatedness on agonistic interactions between adult females. I hypothesized that individual-based aggressive interactions among adult female African elephants would vary according to degree of kinship, with closely related dyads showing less aggression towards each other in resource-limited environments, thereby leading to indirect fitness benefits for individuals. As predicted, females did not show agonistic interactions to their close kin most often, and the frequency and intensity of aggressive interactions was inversely related to the degree of relatedness of the interactants. The effect of group relatedness and structure on reproductive success of individual female African elephant in TNP was also investigated. Adult female reproductive success was significantly influenced by within- group relatedness and structure. Higher reproductive success (with higher frequency of calf production and survival and more female calves produced) were more evident in the closely related groups than groups with low relatedness, suggesting that females from genetically disrupted groups are less likely to be reproductive than those in closely related groups. The possibility of negative effects of poaching on the subsequent generation of poached adult females and the alternative of a positive demographic response through reduced density was assessed by analysing the demographic patterns of the first generation (F1) females of prime-aged adult female African elephants in TNP using within- group relatedness and size. I also compared vital rate (age of first birth and interbirth interval) responses of first generation (F1) cows from Tarangire (poached) elephants with other females from poached (Northern Luangwa National Park, Zambia) and unpoached (Amboseli National Park, Kenya and Addo Elephant National Park, South Africa) populations. Group relatedness had no significant effect on sex ratio of the F1 cows‟ calves. There was a significant difference between the mean age of first birth and interbirth interval of F1 cows from the two (poached, Tarangire and unpoached, Amboseli National Park) elephant populations, suggesting that elephant populations reduced by poaching to low levels show an increase vigour through release from density constraints. Based on these results, the broader implications of secondary effects of poaching on elephant populations are critically evaluated. Also the importance of understanding the consequences of these effects is highlighted in light of other elephant conservation and management approaches. This understanding is useful in making conservation and management decisions for elephants and other biodiversity.
- Full Text:
- Date Issued: 2011
Water balance processes in indigenous and introduced spaces three production system in the Southern Cape region of South Africa
- Authors: Mapeto, Tatenda
- Date: 2020
- Subjects: Hydrology -- Research -- South Africa , Groundwater -- Research -- South Africa Trees -- Breeding Sustainable forestry
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/49325 , vital:41621
- Description: Forests and trees are important modulators of water flow and their position in the landscape impacts the spatial and temporal availability of ground water and surface water resources. As such, the global extent of natural forests is linked to the availability of water. In the circumstances where tree production systems have been introduced and are managed in landscapes previously populated with other forms of vegetation, it is necessary to understand their hydrological impact so as to ensure that the benefits derived from these tree systems do not outweigh the costs of water availability for sustaining human and environmental water requirements.
- Full Text: false
- Date Issued: 2020
- Authors: Mapeto, Tatenda
- Date: 2020
- Subjects: Hydrology -- Research -- South Africa , Groundwater -- Research -- South Africa Trees -- Breeding Sustainable forestry
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/49325 , vital:41621
- Description: Forests and trees are important modulators of water flow and their position in the landscape impacts the spatial and temporal availability of ground water and surface water resources. As such, the global extent of natural forests is linked to the availability of water. In the circumstances where tree production systems have been introduced and are managed in landscapes previously populated with other forms of vegetation, it is necessary to understand their hydrological impact so as to ensure that the benefits derived from these tree systems do not outweigh the costs of water availability for sustaining human and environmental water requirements.
- Full Text: false
- Date Issued: 2020
Investigation of the thermo-chemical behaviour of coal-algae agglomerates
- Authors: Baloyi, Hope
- Date: 2018
- Subjects: Biomass energy , Coal -- South Africa
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/23913 , vital:30642
- Description: There is a growing research interest in the co-processing of biomass and coal, with the aim of addressing the negative attributes associated with the thermal processing of coal alone. Biomass feedstocks are regarded as a clean, renewable source, and the co-utilization of biomass feedstocks with coal is deemed to have a potential to reduce emission of pollutants (i.e. NOx and SOx) and volatile organic compounds (VOC’s). Moreover, biomass are thermally reactive and thus facilitate the conversion of coal during co-processing. Biomass material and coal are two autonomous fuel materials with different chemical characteristics and have a dissimilar thermal behaviour making it difficult to achieve chemical interaction between the two solid fuels to contribute to the formation of products. Coalgae® Technology developed at the Nelson Mandela University, involves the biological treatment of coal fines by adsorbing live microalgae biomass (in slurry form) onto waste coal fines to form coal-microalgae agglomerates. This new innovative approach seeks to integrate bio-based feedstock into coal thermal processing and to improve the utilization and thermal efficiency of coal fines as well as the interaction between the volatile components of biomass and coal during thermal processing (e.g. devolatilization), thereby overcoming some of the challenges that confront the co-processing of coal and biomass. Coal fines are low-ranked coals, generally characterized by high contents of sulphur, high ash yields, low calorific values and poor thermal reactivity, and these attributes limits the thermo-chemical processing of the coal fines. Therefore, this investigation was undertaken to assess the thermo-chemical behaviour of coal-microalgae agglomerates, formed by adsorbing live microalgae slurry at varying ratios onto coal fines. For this purpose, the effects of adsorbing microalgae at varying ratios on the chemical characteristics and thermal behaviour of coal fines under pyrolytic conditions were investigated. The primary aim was to assess whether the thermo-chemical behaviour of coal-microalgae agglomerates, formed by adsorption of live microalgae onto fine coal, is substantively modified compared to a simple additive model of the original coal and pre-dried microalgae biomass samples. Results obtained from the proximate analyses performed on an Eltra Thermo-gravimetric analyzer (TGA) thermostep, have shown that the adsorption of microalgae slurry onto coal fines does not possess greater influence in improving the yield of volatiles and ash in coal fines than can be expected from a simple additive model of the original raw materials. Based on the ultimate analyses results, it was found that the adsorption of microalgae slurry resulted in a systematic reduction in the sulphur content, a notable increase in the hydrogen and oxygen contents, however, no significant disparities were found between the measured ultimate properties of coal-microalgae agglomerates as compared to the theoretically-expected ultimate properties from a simple linear combination of parental coal and microalgae biomass. Assessment of the thermal behaviour of parental samples and coal-microalgae agglomerates involved the use non-isothermal (40-900ºC, 20 K/min) thermogravimetry under inert conditions. It was found that the adsorption of microalgae slurry onto coal fines resulted in an improved thermal reactivity of coal fines, although, did not affect the overall pyrolysis characteristics of the coal fines. Comparison of the thermal profiles (measured and calculated TG/DTG curves), revealed that the yield of volatile products during the pyrolysis of coal-microalgae blends do not exceed the expected volatile yields from a simple combination of coal and microalgae biomass. These results suggest that there was no positive or accelerative synergistic interaction between volatile components of adsorbed microalgae and coal fines during pyrolysis. Mild pyrolysis of raw coal and coal-microalgae performed in a fixed-bed reactor furnace (450ºC), resulted in improved yields of Fossil-Bio crude (FBC) oil (derived from coal-microalgae pyrolysis), at increased biomass ratio compared to coal tar. FBC Oil was found to contain relatively high contents of oxygen, hydrogen, and low sulphur content than coal tar. GC-MS analyses showed the presence of a heterocyclic compounds (i.e. Indole and 2, 6 dimethyl pyridine) in the FBC oil and these were not identified in the coal tar. Furthermore, high boiling compounds such as Flourene, pyrene and pentacosane were identified in the coal tar, however not identified in the FBC oil. Simulated distillation results showed notable differences between the FBC oil and coal tar in terms of the distribution of boiling point fractions particularly, high boing point components. Semi-devolatilized chars derived from coal-microalgae agglomerates showed substantial degree of decarboxylation and dehydrogenation compared to the coal chars.
- Full Text:
- Date Issued: 2018
- Authors: Baloyi, Hope
- Date: 2018
- Subjects: Biomass energy , Coal -- South Africa
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/23913 , vital:30642
- Description: There is a growing research interest in the co-processing of biomass and coal, with the aim of addressing the negative attributes associated with the thermal processing of coal alone. Biomass feedstocks are regarded as a clean, renewable source, and the co-utilization of biomass feedstocks with coal is deemed to have a potential to reduce emission of pollutants (i.e. NOx and SOx) and volatile organic compounds (VOC’s). Moreover, biomass are thermally reactive and thus facilitate the conversion of coal during co-processing. Biomass material and coal are two autonomous fuel materials with different chemical characteristics and have a dissimilar thermal behaviour making it difficult to achieve chemical interaction between the two solid fuels to contribute to the formation of products. Coalgae® Technology developed at the Nelson Mandela University, involves the biological treatment of coal fines by adsorbing live microalgae biomass (in slurry form) onto waste coal fines to form coal-microalgae agglomerates. This new innovative approach seeks to integrate bio-based feedstock into coal thermal processing and to improve the utilization and thermal efficiency of coal fines as well as the interaction between the volatile components of biomass and coal during thermal processing (e.g. devolatilization), thereby overcoming some of the challenges that confront the co-processing of coal and biomass. Coal fines are low-ranked coals, generally characterized by high contents of sulphur, high ash yields, low calorific values and poor thermal reactivity, and these attributes limits the thermo-chemical processing of the coal fines. Therefore, this investigation was undertaken to assess the thermo-chemical behaviour of coal-microalgae agglomerates, formed by adsorbing live microalgae slurry at varying ratios onto coal fines. For this purpose, the effects of adsorbing microalgae at varying ratios on the chemical characteristics and thermal behaviour of coal fines under pyrolytic conditions were investigated. The primary aim was to assess whether the thermo-chemical behaviour of coal-microalgae agglomerates, formed by adsorption of live microalgae onto fine coal, is substantively modified compared to a simple additive model of the original coal and pre-dried microalgae biomass samples. Results obtained from the proximate analyses performed on an Eltra Thermo-gravimetric analyzer (TGA) thermostep, have shown that the adsorption of microalgae slurry onto coal fines does not possess greater influence in improving the yield of volatiles and ash in coal fines than can be expected from a simple additive model of the original raw materials. Based on the ultimate analyses results, it was found that the adsorption of microalgae slurry resulted in a systematic reduction in the sulphur content, a notable increase in the hydrogen and oxygen contents, however, no significant disparities were found between the measured ultimate properties of coal-microalgae agglomerates as compared to the theoretically-expected ultimate properties from a simple linear combination of parental coal and microalgae biomass. Assessment of the thermal behaviour of parental samples and coal-microalgae agglomerates involved the use non-isothermal (40-900ºC, 20 K/min) thermogravimetry under inert conditions. It was found that the adsorption of microalgae slurry onto coal fines resulted in an improved thermal reactivity of coal fines, although, did not affect the overall pyrolysis characteristics of the coal fines. Comparison of the thermal profiles (measured and calculated TG/DTG curves), revealed that the yield of volatile products during the pyrolysis of coal-microalgae blends do not exceed the expected volatile yields from a simple combination of coal and microalgae biomass. These results suggest that there was no positive or accelerative synergistic interaction between volatile components of adsorbed microalgae and coal fines during pyrolysis. Mild pyrolysis of raw coal and coal-microalgae performed in a fixed-bed reactor furnace (450ºC), resulted in improved yields of Fossil-Bio crude (FBC) oil (derived from coal-microalgae pyrolysis), at increased biomass ratio compared to coal tar. FBC Oil was found to contain relatively high contents of oxygen, hydrogen, and low sulphur content than coal tar. GC-MS analyses showed the presence of a heterocyclic compounds (i.e. Indole and 2, 6 dimethyl pyridine) in the FBC oil and these were not identified in the coal tar. Furthermore, high boiling compounds such as Flourene, pyrene and pentacosane were identified in the coal tar, however not identified in the FBC oil. Simulated distillation results showed notable differences between the FBC oil and coal tar in terms of the distribution of boiling point fractions particularly, high boing point components. Semi-devolatilized chars derived from coal-microalgae agglomerates showed substantial degree of decarboxylation and dehydrogenation compared to the coal chars.
- Full Text:
- Date Issued: 2018
The evaluation of a pedagogical-program development environment for Novice programmers : a comparative study
- Authors: Vogts, Dieter
- Date: 2007
- Subjects: Computer programming -- Study and teaching , Programming languages (Electronic computers) , Web site development
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10477 , http://hdl.handle.net/10948/638 , Computer programming -- Study and teaching , Programming languages (Electronic computers) , Web site development
- Description: It is an acknowledged fact that many novice programmers experience difficulty in the process of learning to program. One of the contributing factors to this difficulty is the Program Development Environment (PDE). Professional-PDEs are those developed specifically for professional programmers, but are often used by educational institutions in the instruction of programming. It has long been accepted that such environments are inappropriate in the instruction of programming due to unnecessary complexity and lack of support for novice programmers in the learning process. Numerous pedagogical-PDEs supporting the mechanics of programming have been developed in response to this. A review of literature, however, indicates that very limited empirical studies comparing pedagogical-PDEs and professional-PDEs have been conducted. The current study investigates whether there are measurable benefits to using a pedagogical-PDE supporting the mechanics of programming in the instruction of programming instead of a professional-PDE. A comparative study of this nature requires a representative pedagogical-PDE and representative professional-PDE be compared with one another. The first part of the current study determines a set of requirements that a pedagogical- PDE should adhere to based on literature. A set of representative features for a pedagogical-PDE is derived by examining the features of existing PDEs in conjunction with the set of requirements. Based on these features, a pedagogical-PDE, known as SimplifIDE, is developed that implements the representative set of features and that meets are the requirements for a pedagogical-PDE. The second part of the current study is the specification and administration of an empirical experiment in which SimplifIDE and Borland© DelphiTM are compared with one another. A holistic approach in determining the differences between the PDEs is taken and three main areas are examined, namely academic performance, perceptions and programming behavior.
- Full Text:
- Date Issued: 2007
- Authors: Vogts, Dieter
- Date: 2007
- Subjects: Computer programming -- Study and teaching , Programming languages (Electronic computers) , Web site development
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10477 , http://hdl.handle.net/10948/638 , Computer programming -- Study and teaching , Programming languages (Electronic computers) , Web site development
- Description: It is an acknowledged fact that many novice programmers experience difficulty in the process of learning to program. One of the contributing factors to this difficulty is the Program Development Environment (PDE). Professional-PDEs are those developed specifically for professional programmers, but are often used by educational institutions in the instruction of programming. It has long been accepted that such environments are inappropriate in the instruction of programming due to unnecessary complexity and lack of support for novice programmers in the learning process. Numerous pedagogical-PDEs supporting the mechanics of programming have been developed in response to this. A review of literature, however, indicates that very limited empirical studies comparing pedagogical-PDEs and professional-PDEs have been conducted. The current study investigates whether there are measurable benefits to using a pedagogical-PDE supporting the mechanics of programming in the instruction of programming instead of a professional-PDE. A comparative study of this nature requires a representative pedagogical-PDE and representative professional-PDE be compared with one another. The first part of the current study determines a set of requirements that a pedagogical- PDE should adhere to based on literature. A set of representative features for a pedagogical-PDE is derived by examining the features of existing PDEs in conjunction with the set of requirements. Based on these features, a pedagogical-PDE, known as SimplifIDE, is developed that implements the representative set of features and that meets are the requirements for a pedagogical-PDE. The second part of the current study is the specification and administration of an empirical experiment in which SimplifIDE and Borland© DelphiTM are compared with one another. A holistic approach in determining the differences between the PDEs is taken and three main areas are examined, namely academic performance, perceptions and programming behavior.
- Full Text:
- Date Issued: 2007
Assemblage dynamics of larval fishes associated with various shallow water nursery habitats in Algoa Bay, South Africa
- Authors: Pattrick, Paula
- Date: 2013
- Subjects: Spawning -- South Africa -- Algoa Bay , Fishes -- Larvae -- South Africa -- Algoa Bay
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10727 , http://hdl.handle.net/10948/d1021042
- Description: The success of the larval stage in fishes plays a critical role in structuring adult fish populations. It is well understood that juveniles of many marine fish species are closely associated with nearshore and coastal habitats that serve as nursery areas while adult assemblages are more widely distributed. The larval phase however, particularly pertaining to nursery habitat use, remains poorly understood in South Africa. A mixed-method, larval and juvenile fish study was conducted in the warm-temperate shallow coastal waters of Algoa Bay, South Africa. Two years (2010 – 2012) of seasonal sampling at 27 stations at various habitat types revealed distinct spatio-temporal patterns in larval fish composition and abundance. In total, 164 species from 50 families were collected in the nearshore (<30 m), over reef and sand, in the surf zone and large estuarine habitats in Algoa Bay. Engraulidae dominated the larval fish catch in the nearshore (38.4 percent) and over the selected reef and sand habitats (37.8 percent). Cynoglossidae (28.1 percent) and Sparidae (8.4 percent) were the second and third most abundant fish families in the nearshore. In subtidal reef and sand habitats, Gobiidae (23.4 percent) and Clupeidae (9.2 percent) were the second and third most abundant families respectively. Sparidae dominated (71.4 percent) surf zones followed by Soleidae (10.8 percent) and Mugilidae (5.3 percent), while in the mouth area of two permanently open estuaries in Algoa Bay, Gobiidae (35.9 percent) Sparidae (30.1 percent) and Mugilidae (12.4 percent) dominated. Several species from the Blenniidae, Gobiesocidae, Gobiidae, Scorpaenidae and Tripterygiidae fish families complete their pelagic larval phase in the reef habitats in Algoa Bay. These reef habitats therefore serve as important nursery areas for the larvae of benthic species. The sand and nearshore habitats serve as nursery areas for Clupeidae and Engraulidae. Highest densities of Carangidae, Sciaenidae and Sparidae larvae were observed at the subtidal reef habitats indicating that this area is important for accumulation of the early developmental stages of these fishes. The nearshore serves as an important accumulation habitat for species in the Haemulidae and Soleidae families whose juveniles are known to recruit into estuarine nursery areas. The nearshore therefore is a specific area of presettlement buildup of larvae prior to settlement of larvae or juveniles in estuarine nursery areas. Cynoglossidae larvae are also using the nearshore as an accumulation area prior to settlement and recruitment into adult populations occurring in shallow water habitats. In the surf zone, not only are estuary-dependent fish species utilizing this habitat as a nursery area, but marinespecies whose adults are either associated with rocky shores or surf zones are similarly using these areas as nursery habitats. In addition, estuary-dependent fish species which spawn in the marine environment are actively recruiting into estuarine nursery areas on both tides. Active recruitment against the outgoing ebb tide flow was a conclusive finding in this study. These larvae and juveniles are actively swimming against the ebb tide in the shallower, slower-flowing marginal areas where current flow is reduced. Strong environmental gradients on multiple temporal and spatial scales occur in Algoa Bay. Seasonal patterns were evident in larval densities, richness and diversity. Peaks in density, richness and diversity occurred during spring and summer (September to February) associated with increasing water temperatures and a high productivity providing a good food environment for larval fishes. Thereafter densities declined steadily as a result of natural mortality, settlement or adult spawning activity, until autumn when numbers dropped suddenly as the surviving larvae moved to settlement habitats. The relationship between larval fish and environmental variables provides information useful to determine distributions. Therefore the Bay is particularly suited for modelling larval fish distributions. Using generalized linear models, larval fish density in the nearshore of Algoa Bay responded to different ocean features to varying degrees. Larval fish density responded positively to both upwelling and when warm water plumes, originating from an Agulhas Current meander, entered Algoa Bay. On subtidal reefs, habitat complexity played an important role in determining larval fish composition and diversity. The less structurally complex, reefassociated sand habitats, yielded higher species richness and diversity than the high and low profile reef habitats. Therefore, it is likely that the importance of less structurally complex habitats has been overlooked relative to other habitats in terms of their function for larval fishes. In the surf zone, wave period and wave height, which can be related to exposure, were the most significant environmental factors influencing larval fish assemblages. Greatest species diversity was observed in the surf zone habitats heavily influenced by wave action in the windward sector of Algoa Bay. The identification of spawning areas and the mapping of distributions of early developmental stages of fishes are important in providing data pertaining to the protection of these habitats. This is particularly relevant as a new marine protected area MPA)is planned for the eastern sector of Algoa Bay. Results from retrogressive plots indicate that the spawning locations of several species of coastal and pelagic fishes are occurring outside of the Bay, with the bay therefore serving as an accumulation area. Furthermore, distribution modelling results demonstrate that the early developmental stages of fishes in the shallow coastal habitats of Algoa Bay exhibit high spatial variability in their distributions. Results presented in this thesis help fill the knowledge gaps critical to the understanding of larval fish nursery areas of several economically and ecologically important fish species in Algoa Bay.
- Full Text:
- Date Issued: 2013
- Authors: Pattrick, Paula
- Date: 2013
- Subjects: Spawning -- South Africa -- Algoa Bay , Fishes -- Larvae -- South Africa -- Algoa Bay
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10727 , http://hdl.handle.net/10948/d1021042
- Description: The success of the larval stage in fishes plays a critical role in structuring adult fish populations. It is well understood that juveniles of many marine fish species are closely associated with nearshore and coastal habitats that serve as nursery areas while adult assemblages are more widely distributed. The larval phase however, particularly pertaining to nursery habitat use, remains poorly understood in South Africa. A mixed-method, larval and juvenile fish study was conducted in the warm-temperate shallow coastal waters of Algoa Bay, South Africa. Two years (2010 – 2012) of seasonal sampling at 27 stations at various habitat types revealed distinct spatio-temporal patterns in larval fish composition and abundance. In total, 164 species from 50 families were collected in the nearshore (<30 m), over reef and sand, in the surf zone and large estuarine habitats in Algoa Bay. Engraulidae dominated the larval fish catch in the nearshore (38.4 percent) and over the selected reef and sand habitats (37.8 percent). Cynoglossidae (28.1 percent) and Sparidae (8.4 percent) were the second and third most abundant fish families in the nearshore. In subtidal reef and sand habitats, Gobiidae (23.4 percent) and Clupeidae (9.2 percent) were the second and third most abundant families respectively. Sparidae dominated (71.4 percent) surf zones followed by Soleidae (10.8 percent) and Mugilidae (5.3 percent), while in the mouth area of two permanently open estuaries in Algoa Bay, Gobiidae (35.9 percent) Sparidae (30.1 percent) and Mugilidae (12.4 percent) dominated. Several species from the Blenniidae, Gobiesocidae, Gobiidae, Scorpaenidae and Tripterygiidae fish families complete their pelagic larval phase in the reef habitats in Algoa Bay. These reef habitats therefore serve as important nursery areas for the larvae of benthic species. The sand and nearshore habitats serve as nursery areas for Clupeidae and Engraulidae. Highest densities of Carangidae, Sciaenidae and Sparidae larvae were observed at the subtidal reef habitats indicating that this area is important for accumulation of the early developmental stages of these fishes. The nearshore serves as an important accumulation habitat for species in the Haemulidae and Soleidae families whose juveniles are known to recruit into estuarine nursery areas. The nearshore therefore is a specific area of presettlement buildup of larvae prior to settlement of larvae or juveniles in estuarine nursery areas. Cynoglossidae larvae are also using the nearshore as an accumulation area prior to settlement and recruitment into adult populations occurring in shallow water habitats. In the surf zone, not only are estuary-dependent fish species utilizing this habitat as a nursery area, but marinespecies whose adults are either associated with rocky shores or surf zones are similarly using these areas as nursery habitats. In addition, estuary-dependent fish species which spawn in the marine environment are actively recruiting into estuarine nursery areas on both tides. Active recruitment against the outgoing ebb tide flow was a conclusive finding in this study. These larvae and juveniles are actively swimming against the ebb tide in the shallower, slower-flowing marginal areas where current flow is reduced. Strong environmental gradients on multiple temporal and spatial scales occur in Algoa Bay. Seasonal patterns were evident in larval densities, richness and diversity. Peaks in density, richness and diversity occurred during spring and summer (September to February) associated with increasing water temperatures and a high productivity providing a good food environment for larval fishes. Thereafter densities declined steadily as a result of natural mortality, settlement or adult spawning activity, until autumn when numbers dropped suddenly as the surviving larvae moved to settlement habitats. The relationship between larval fish and environmental variables provides information useful to determine distributions. Therefore the Bay is particularly suited for modelling larval fish distributions. Using generalized linear models, larval fish density in the nearshore of Algoa Bay responded to different ocean features to varying degrees. Larval fish density responded positively to both upwelling and when warm water plumes, originating from an Agulhas Current meander, entered Algoa Bay. On subtidal reefs, habitat complexity played an important role in determining larval fish composition and diversity. The less structurally complex, reefassociated sand habitats, yielded higher species richness and diversity than the high and low profile reef habitats. Therefore, it is likely that the importance of less structurally complex habitats has been overlooked relative to other habitats in terms of their function for larval fishes. In the surf zone, wave period and wave height, which can be related to exposure, were the most significant environmental factors influencing larval fish assemblages. Greatest species diversity was observed in the surf zone habitats heavily influenced by wave action in the windward sector of Algoa Bay. The identification of spawning areas and the mapping of distributions of early developmental stages of fishes are important in providing data pertaining to the protection of these habitats. This is particularly relevant as a new marine protected area MPA)is planned for the eastern sector of Algoa Bay. Results from retrogressive plots indicate that the spawning locations of several species of coastal and pelagic fishes are occurring outside of the Bay, with the bay therefore serving as an accumulation area. Furthermore, distribution modelling results demonstrate that the early developmental stages of fishes in the shallow coastal habitats of Algoa Bay exhibit high spatial variability in their distributions. Results presented in this thesis help fill the knowledge gaps critical to the understanding of larval fish nursery areas of several economically and ecologically important fish species in Algoa Bay.
- Full Text:
- Date Issued: 2013
Foraging ecology of gentoo penguins pygoscelis papua at the Falkland Islands
- Authors: Handley, Jonathan Murray
- Date: 2017
- Subjects: Gentoo penguin -- Food -- Falkland Islands Gentoo penguin -- Ecology
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/14113 , vital:27431
- Description: Marine top predators often occupy broad geographical ranges that encompass varied habitats. Therefore, a pre-requisite towards conserving these animals is to determine the components of their realized niche, and investigate whether a species is a specialist or a generalist. For generalist species, it is also necessary to understand if local specialisation occurs. Uncovering these components can allow us to build models of a species realized niche that may then be used to infer habitat use in unsampled locations. However, fully understanding the components of a marine top predators realized niche is challenging owing to the limited opportunity for in situ observations. Overcoming these limitations is a key step in marine top predator research. It will enhance our understanding of trophic coupling in marine systems, and aid in the development of tools to better study these predators in their dynamic environment. Seabirds, penguins (Spheniscids) in particular, are a group of animals for which investigating their realized niche is of vital importance. This is because numerous species face growing uncertainty in the Anthropocene, and in a time of rapid environmental change there is furthermore a need to better understand the potential use of these birds as indicators of ecosystem health. The aim of this thesis, therefore, is to investigate the foraging ecology of gentoo penguins (Pygoscelis papua) at the Falkland Islands. At the Falkland Islands, limited historical information exists regarding this species foraging ecology, with most information coming from a single location at the Falklands. As the Falkland Islands have the world’s largest population of gentoo penguins, elucidating factors influencing this population will have global relevance. Furthermore, historical information indicated potential competition with fisheries, and with prospecting for hydrocarbons and an inshore fishery, there is a need to understand the distribution of these birds across the islands. Penguins are also well suited to carry biologging devices allowing for in situ observations of inter and intraspecific interactions, as well as habitat specific interactions. In this study, I sampled birds over three breeding seasons, from four breeding colonies - chosen for their varied surrounding at sea habitat - across the Falkland Islands. I investigated the diet with stomach content and stable isotope analysis, the at-sea distribution with GPS and time depth recorders, and how these birds behaved at sea using custom made animal-borne camera loggers. Furthermore, I developed a method to recognise prey encounter events from back mounted accelerometers, using a supervised machine learning approach. As part of the first species specific description of diet at this scale for the Falklands, I revealed six key prey items for the birds: rock cod (Patagonotothen spp.), lobster krill (Munida spp.), Falkland herring (Sprattus fuegensis), Patagonian squid (Doryteuthis gahi), juvenile fish (likely all nototheniids), and southern blue whiting (Micromesistius australis). The use of animal-borne camera loggers verified that not only do gentoo penguins consume a diverse array of prey items, but they adopted various methods to capture and pursue prey, with evidence of birds following optimal foraging theory. Prey composition varied significantly between study sites with the at-sea distribution and habitat use of penguins reflecting that of local prey. Birds from colonies close to gently sloping, shallow waters, foraged primarily in a benthic manner and had larger niche widths. However, those at a colony surrounded by steeply sloping, deeper waters, typically foraged in a pelagic manner. Contrasting diet patterns were also prevalent from stable isotope data, and the niche widths of birds relating to both stomach content and stable isotope data were larger at colonies where benthic foraging was prevalent. Therefore, it was clear that surrounding bathymetry played a key role in shaping this species’ foraging ecology, and that at the population level at the Falkland Islands birds are generalists. However, at individual colonies some specialisation occurs to take advantage of locally available prey. I developed habitat distribution models - via boosted regression trees – which transferred well in time but poorly across space. Reasons for poor model transfer might relate to the generalist foraging nature of these birds and the reduced availability of environmental predictors owing to the limited range of these birds. I furthermore developed a method to identify prey encounter events that can also, to a degree, distinguish between prey items. This method will be a promising approach to refine habitat distribution models in future. These habitat distribution models could potentially contribute to marine spatial planning at the Falkland Islands. Footage from animal-borne camera loggers clearly showed that prey behaviour can significantly influence trophic coupling in marine systems and should be accounted for in studies using marine top predators as samplers of mid to lower trophic level species. Ultimately, flexibility in foraging strategies and inter-colony variation will play a critical role when assessing factors such as interspecific competition or overlap with anthropogenic activities.
- Full Text:
- Date Issued: 2017
- Authors: Handley, Jonathan Murray
- Date: 2017
- Subjects: Gentoo penguin -- Food -- Falkland Islands Gentoo penguin -- Ecology
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/14113 , vital:27431
- Description: Marine top predators often occupy broad geographical ranges that encompass varied habitats. Therefore, a pre-requisite towards conserving these animals is to determine the components of their realized niche, and investigate whether a species is a specialist or a generalist. For generalist species, it is also necessary to understand if local specialisation occurs. Uncovering these components can allow us to build models of a species realized niche that may then be used to infer habitat use in unsampled locations. However, fully understanding the components of a marine top predators realized niche is challenging owing to the limited opportunity for in situ observations. Overcoming these limitations is a key step in marine top predator research. It will enhance our understanding of trophic coupling in marine systems, and aid in the development of tools to better study these predators in their dynamic environment. Seabirds, penguins (Spheniscids) in particular, are a group of animals for which investigating their realized niche is of vital importance. This is because numerous species face growing uncertainty in the Anthropocene, and in a time of rapid environmental change there is furthermore a need to better understand the potential use of these birds as indicators of ecosystem health. The aim of this thesis, therefore, is to investigate the foraging ecology of gentoo penguins (Pygoscelis papua) at the Falkland Islands. At the Falkland Islands, limited historical information exists regarding this species foraging ecology, with most information coming from a single location at the Falklands. As the Falkland Islands have the world’s largest population of gentoo penguins, elucidating factors influencing this population will have global relevance. Furthermore, historical information indicated potential competition with fisheries, and with prospecting for hydrocarbons and an inshore fishery, there is a need to understand the distribution of these birds across the islands. Penguins are also well suited to carry biologging devices allowing for in situ observations of inter and intraspecific interactions, as well as habitat specific interactions. In this study, I sampled birds over three breeding seasons, from four breeding colonies - chosen for their varied surrounding at sea habitat - across the Falkland Islands. I investigated the diet with stomach content and stable isotope analysis, the at-sea distribution with GPS and time depth recorders, and how these birds behaved at sea using custom made animal-borne camera loggers. Furthermore, I developed a method to recognise prey encounter events from back mounted accelerometers, using a supervised machine learning approach. As part of the first species specific description of diet at this scale for the Falklands, I revealed six key prey items for the birds: rock cod (Patagonotothen spp.), lobster krill (Munida spp.), Falkland herring (Sprattus fuegensis), Patagonian squid (Doryteuthis gahi), juvenile fish (likely all nototheniids), and southern blue whiting (Micromesistius australis). The use of animal-borne camera loggers verified that not only do gentoo penguins consume a diverse array of prey items, but they adopted various methods to capture and pursue prey, with evidence of birds following optimal foraging theory. Prey composition varied significantly between study sites with the at-sea distribution and habitat use of penguins reflecting that of local prey. Birds from colonies close to gently sloping, shallow waters, foraged primarily in a benthic manner and had larger niche widths. However, those at a colony surrounded by steeply sloping, deeper waters, typically foraged in a pelagic manner. Contrasting diet patterns were also prevalent from stable isotope data, and the niche widths of birds relating to both stomach content and stable isotope data were larger at colonies where benthic foraging was prevalent. Therefore, it was clear that surrounding bathymetry played a key role in shaping this species’ foraging ecology, and that at the population level at the Falkland Islands birds are generalists. However, at individual colonies some specialisation occurs to take advantage of locally available prey. I developed habitat distribution models - via boosted regression trees – which transferred well in time but poorly across space. Reasons for poor model transfer might relate to the generalist foraging nature of these birds and the reduced availability of environmental predictors owing to the limited range of these birds. I furthermore developed a method to identify prey encounter events that can also, to a degree, distinguish between prey items. This method will be a promising approach to refine habitat distribution models in future. These habitat distribution models could potentially contribute to marine spatial planning at the Falkland Islands. Footage from animal-borne camera loggers clearly showed that prey behaviour can significantly influence trophic coupling in marine systems and should be accounted for in studies using marine top predators as samplers of mid to lower trophic level species. Ultimately, flexibility in foraging strategies and inter-colony variation will play a critical role when assessing factors such as interspecific competition or overlap with anthropogenic activities.
- Full Text:
- Date Issued: 2017
Design of metal ion-selective reagents for recovery of precious metals
- Authors: Moleko-Boyce, Pulleng
- Date: 2019
- Subjects: Bioinorganic chemistry , Metal complexes Speciation (Chemistry)
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/42510 , vital:36664
- Description: The study is divided into two sections; namely, (1) the design of rhodium(III) specific chelating ligands (tridentate bis-benzimidazole derivatives), and (2) the development of iridium(IV)-specific quaternary diammonium cations with electron donating and electron withdrawing groups. Bis-benzimidazole chelating ligands used were bis((1H-benzimidazol-2-yl)methyl)amine (NNN1), bis((1H-benzimidazol-2-yl)ethyl)amine (NNN2), bis((1H-benzimidazol-2-yl)methyl)sulfide (NSN1) and bis((1H-benzimidazol-2-yl)ethyl)sulfide (NSN2). Quaternary diammonium cations used were tetramethylbenzyl-1,10-diammonium chloride (QuatDMDAMeBnz), tetrabenzyl-1,10-diammonium chloride (QuatDMDABnz), tetratrifluoromethylbenzyl-1,10-diammonium chloride (QuatDMDACF3Bnz) and tetranitrobenzyl-1,10-diammonium chloride (QuatDMDANO2Bnz). For both studies, polyvinylbenzylchloride (PVBC) nanofibers were used as support material. The PVBC nanofibers which were functionalised with bis-benzimidazole derivatives and quaternary diammonium cations, respectively, were investigated for the selectivity for Rh(III) over Ir(III), Pt(II), Pd(II) and Ni(II), and for separation of Ir(IV) from Rh(III), respectively. The sorbent materials were characterised by FTIR, SEM, BET surface area, TGA, EDS and elemental analysis, and the results showed that the functionalization of the sorbent materials was successful.The efficiency of bis-benzimidazole derivatives and quaternary diammonium cations, respectively, were investigated in a column study under dynamic flow adsorption conditions. The adsorption kinetics and isotherms were investigated under batch conditions and fitted on pseudo-first-order and pseudo-second-order model, and Freundlich and Langmuir isotherm, respectively. It was observed that the bis-benzimidazole derivatives showed uptake of [RhCl3(H2O)3], and the loading capacities were observed in the following order; NSN1 (181.06 mg/g) > NSN2 (148.55 mg/g) > NNN1 (131.88 mg/g) > NNN2 (75.87 mg/g). The bis-benzimidazole derivatives preference for metal ions was further investigated with a multi-element solution containing Rh(III), Ir(III), Pt(II), Pd(II) and Ni(II). The bis-benzimidazole derivatives showed the following order of loading capacity: NSN1 (47.28 mg/g) > NSN2 (23.89 mg/g) > NNN1 (17.47 mg/g) > NNN2 (14.91 mg/g) for Rh(III); NSN2 (10.64 mg/g) > NNN2 (6.84 mg/g) > NSN1 (5.74 mg/g) > NNN1 (5.02 mg/g) for Ir(III); NNN2 (33.96 mg/g) > NSN1 (30.95 mg/g) > NSN2 (19.95 mg/g) > NNN1 (14.92 mg/g) for Pt(II); NNN1 (47.94 mg/g) > NNN2 (28.90 mg/g) > NSN1 (16.22 mg/g) > NSN2 (15.83 mg/g) for Pd(II). Bis-benzimidazole derivatives showed no uptake of nickel(II) under these conditions. It was observed the ligand-selectivity order for Rh(III) was similar in both single-element and multi-element studies. This order showed that the bis-benzimidazoles containing a sulfur atom showed a high preference for rhodium(III) compared to Pt(II) which had a high preference for NNN2 as well as Pd(II) which had a high preference for NNN1. Ir(III) generally had a lower preference for the ligands presumably due to its higher kinetic inertness compared with Rh(III). Column sorption of [IrCl6]2- and [RhCl5(H2O)]2- on nanofibers functionalized with diammonium cations was carried out and the loading capacities of [IrCl6]2- were obtained. [RhCl5(H2O)]2- was not adsorbed by the sorbent materials while [IrCl6]2- was loaded onto the column. The loading capacities of [IrCl6]2- with the quaternary diammonium sorbent materials increased in the order of F-QuatDMDAMeBnz (60.29 mg/g) < F-QuatDMDABnz (67.61 mg/g) < F-QuatDMDACF3Bnz (107.59 mg/g) < F-QuatDMDANO2Bnz (140.47 mg/g). The loading capacity for Ir(IV) with quaternary diammonium cationic nanofibers increased with an increase in the electron-withdrawing nature of the quaternizing group. The charge delocalizing ability of the nitrobenzyl group resulted in the best interaction of the diammonium cation with [IrCl6]2-. Batch equilibrium studies were carried out to assess the efficiency of bis-benzimidazole chelating derivatives as adsorbents using a multi-metal solution (Rh(III), Ir(III), Pt(II), Pd(II) and Ni(II)) in 0.5 M HCl. The efficiency of the quaternary diammonium cations was tested using a binary metal solution (Ir(IV) and Rh(III)) in 6 M HCl. The isothermal batch adsorption studies of a multi-metal solution with bis-benzimidazoles derivatives fitted the Langmuir isotherm model which confirmed monolayer adsorption onto a homogeneous surface. The Langmuir isotherm parameter (qe (mg/g)), using functionalized nanofibers, showed the order of NNN2 (128.21 mg/g) > NSN1 (99.01 mg/g) > NSN2 (91.74 mg/g) > NNN1 (84.03 mg/g) for Pt(II); NNN1 (66.23 mg/g) > NNN2 (5.89 mg/g) > NSN1 (1.40 mg/g) > NSN2 (0.59 mg/g) for Pd(II); NSN2 (10.64 mg/g) > NNN2 (6.84 mg/g) > NSN1 (5.74 mg/g) > NNN1 (5.02 mg/g) for Ir(III); NSN1 (140.85 mg/g) > NSN2 (109.89 mg/g) > NNN1 (104.17 mg/g) > NNN2 (91.74 mg/g) for Rh(III). The pseudo-first-order kinetics model was found to be the best fit to describe the adsorption kinetics of all metal ions onto all the sorbent materials. K1 (min-1) value in pseudo-first-order kinetics showed the same order of adsorption as observed in the Langmuir isotherms. The isothermal batch adsorption studies of [IrCl6]2- and [RhCl5(H2O)]2- with quaternary diammonium cations fitted the Freundlich isotherm model and confirmed to be effective for multiple-layered adsorption onto a heterogeneous surface. The Freundlich isotherm parameter (kf (mg/g)) using functionalized quaternary diammonium cationic nanofibers increased in the order of F-QuatDMDANO2Bnz (794.33 mg/g) > F-QuatDMDACF3Bnz (185.35 mg/g) > F-QuatDMDABnz (156.32 mg/g) > F-QuatDMDAMeBnz (112.46 mg/g) for Ir(IV) uptake. F-QuatDMDANO2Bnz resin showed the highest adsorption than that of F-QuatDMDAMeBnz, F-QuatDMDABnz and F-QuatDMDACF3Bnz and this order is similar to what was observed in column studies. The quaternary diammonium cations were shown to have the highest adsorption capacity for Ir(IV) compared with Rh(III). The adsorption of Rh(III) was also observed to increase in the order of F-QuatDMDANO2Bnz (177.83 mg/g) > F-QuatDMDACF3Bnz (40.37 mg/g) > F-QuatDMDABnz (36.98 mg/g) > F-QuatDMDAMeBnz (12.71 mg/g). The pseudo-second-order kinetic model was found to be the best fit to describe the adsorption kinetics of both metal ions onto all the sorbent materials. K2 (g.mg-1min-1) value in pseudo-second-order kinetics showed the same order of adsorption as observed in the Freundlich isotherms. The adsorption studies showed adsorption takes place via chemisorption process. This thesis presents PGMs and iridium-specific materials that could be applied in solutions of secondary PGMs sources containing rhodium, platinum and palladium with bis-benzimidazoles as well as in feed solutions from ore processing with diammonium cations for iridium recovery.
- Full Text:
- Date Issued: 2019
- Authors: Moleko-Boyce, Pulleng
- Date: 2019
- Subjects: Bioinorganic chemistry , Metal complexes Speciation (Chemistry)
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/42510 , vital:36664
- Description: The study is divided into two sections; namely, (1) the design of rhodium(III) specific chelating ligands (tridentate bis-benzimidazole derivatives), and (2) the development of iridium(IV)-specific quaternary diammonium cations with electron donating and electron withdrawing groups. Bis-benzimidazole chelating ligands used were bis((1H-benzimidazol-2-yl)methyl)amine (NNN1), bis((1H-benzimidazol-2-yl)ethyl)amine (NNN2), bis((1H-benzimidazol-2-yl)methyl)sulfide (NSN1) and bis((1H-benzimidazol-2-yl)ethyl)sulfide (NSN2). Quaternary diammonium cations used were tetramethylbenzyl-1,10-diammonium chloride (QuatDMDAMeBnz), tetrabenzyl-1,10-diammonium chloride (QuatDMDABnz), tetratrifluoromethylbenzyl-1,10-diammonium chloride (QuatDMDACF3Bnz) and tetranitrobenzyl-1,10-diammonium chloride (QuatDMDANO2Bnz). For both studies, polyvinylbenzylchloride (PVBC) nanofibers were used as support material. The PVBC nanofibers which were functionalised with bis-benzimidazole derivatives and quaternary diammonium cations, respectively, were investigated for the selectivity for Rh(III) over Ir(III), Pt(II), Pd(II) and Ni(II), and for separation of Ir(IV) from Rh(III), respectively. The sorbent materials were characterised by FTIR, SEM, BET surface area, TGA, EDS and elemental analysis, and the results showed that the functionalization of the sorbent materials was successful.The efficiency of bis-benzimidazole derivatives and quaternary diammonium cations, respectively, were investigated in a column study under dynamic flow adsorption conditions. The adsorption kinetics and isotherms were investigated under batch conditions and fitted on pseudo-first-order and pseudo-second-order model, and Freundlich and Langmuir isotherm, respectively. It was observed that the bis-benzimidazole derivatives showed uptake of [RhCl3(H2O)3], and the loading capacities were observed in the following order; NSN1 (181.06 mg/g) > NSN2 (148.55 mg/g) > NNN1 (131.88 mg/g) > NNN2 (75.87 mg/g). The bis-benzimidazole derivatives preference for metal ions was further investigated with a multi-element solution containing Rh(III), Ir(III), Pt(II), Pd(II) and Ni(II). The bis-benzimidazole derivatives showed the following order of loading capacity: NSN1 (47.28 mg/g) > NSN2 (23.89 mg/g) > NNN1 (17.47 mg/g) > NNN2 (14.91 mg/g) for Rh(III); NSN2 (10.64 mg/g) > NNN2 (6.84 mg/g) > NSN1 (5.74 mg/g) > NNN1 (5.02 mg/g) for Ir(III); NNN2 (33.96 mg/g) > NSN1 (30.95 mg/g) > NSN2 (19.95 mg/g) > NNN1 (14.92 mg/g) for Pt(II); NNN1 (47.94 mg/g) > NNN2 (28.90 mg/g) > NSN1 (16.22 mg/g) > NSN2 (15.83 mg/g) for Pd(II). Bis-benzimidazole derivatives showed no uptake of nickel(II) under these conditions. It was observed the ligand-selectivity order for Rh(III) was similar in both single-element and multi-element studies. This order showed that the bis-benzimidazoles containing a sulfur atom showed a high preference for rhodium(III) compared to Pt(II) which had a high preference for NNN2 as well as Pd(II) which had a high preference for NNN1. Ir(III) generally had a lower preference for the ligands presumably due to its higher kinetic inertness compared with Rh(III). Column sorption of [IrCl6]2- and [RhCl5(H2O)]2- on nanofibers functionalized with diammonium cations was carried out and the loading capacities of [IrCl6]2- were obtained. [RhCl5(H2O)]2- was not adsorbed by the sorbent materials while [IrCl6]2- was loaded onto the column. The loading capacities of [IrCl6]2- with the quaternary diammonium sorbent materials increased in the order of F-QuatDMDAMeBnz (60.29 mg/g) < F-QuatDMDABnz (67.61 mg/g) < F-QuatDMDACF3Bnz (107.59 mg/g) < F-QuatDMDANO2Bnz (140.47 mg/g). The loading capacity for Ir(IV) with quaternary diammonium cationic nanofibers increased with an increase in the electron-withdrawing nature of the quaternizing group. The charge delocalizing ability of the nitrobenzyl group resulted in the best interaction of the diammonium cation with [IrCl6]2-. Batch equilibrium studies were carried out to assess the efficiency of bis-benzimidazole chelating derivatives as adsorbents using a multi-metal solution (Rh(III), Ir(III), Pt(II), Pd(II) and Ni(II)) in 0.5 M HCl. The efficiency of the quaternary diammonium cations was tested using a binary metal solution (Ir(IV) and Rh(III)) in 6 M HCl. The isothermal batch adsorption studies of a multi-metal solution with bis-benzimidazoles derivatives fitted the Langmuir isotherm model which confirmed monolayer adsorption onto a homogeneous surface. The Langmuir isotherm parameter (qe (mg/g)), using functionalized nanofibers, showed the order of NNN2 (128.21 mg/g) > NSN1 (99.01 mg/g) > NSN2 (91.74 mg/g) > NNN1 (84.03 mg/g) for Pt(II); NNN1 (66.23 mg/g) > NNN2 (5.89 mg/g) > NSN1 (1.40 mg/g) > NSN2 (0.59 mg/g) for Pd(II); NSN2 (10.64 mg/g) > NNN2 (6.84 mg/g) > NSN1 (5.74 mg/g) > NNN1 (5.02 mg/g) for Ir(III); NSN1 (140.85 mg/g) > NSN2 (109.89 mg/g) > NNN1 (104.17 mg/g) > NNN2 (91.74 mg/g) for Rh(III). The pseudo-first-order kinetics model was found to be the best fit to describe the adsorption kinetics of all metal ions onto all the sorbent materials. K1 (min-1) value in pseudo-first-order kinetics showed the same order of adsorption as observed in the Langmuir isotherms. The isothermal batch adsorption studies of [IrCl6]2- and [RhCl5(H2O)]2- with quaternary diammonium cations fitted the Freundlich isotherm model and confirmed to be effective for multiple-layered adsorption onto a heterogeneous surface. The Freundlich isotherm parameter (kf (mg/g)) using functionalized quaternary diammonium cationic nanofibers increased in the order of F-QuatDMDANO2Bnz (794.33 mg/g) > F-QuatDMDACF3Bnz (185.35 mg/g) > F-QuatDMDABnz (156.32 mg/g) > F-QuatDMDAMeBnz (112.46 mg/g) for Ir(IV) uptake. F-QuatDMDANO2Bnz resin showed the highest adsorption than that of F-QuatDMDAMeBnz, F-QuatDMDABnz and F-QuatDMDACF3Bnz and this order is similar to what was observed in column studies. The quaternary diammonium cations were shown to have the highest adsorption capacity for Ir(IV) compared with Rh(III). The adsorption of Rh(III) was also observed to increase in the order of F-QuatDMDANO2Bnz (177.83 mg/g) > F-QuatDMDACF3Bnz (40.37 mg/g) > F-QuatDMDABnz (36.98 mg/g) > F-QuatDMDAMeBnz (12.71 mg/g). The pseudo-second-order kinetic model was found to be the best fit to describe the adsorption kinetics of both metal ions onto all the sorbent materials. K2 (g.mg-1min-1) value in pseudo-second-order kinetics showed the same order of adsorption as observed in the Freundlich isotherms. The adsorption studies showed adsorption takes place via chemisorption process. This thesis presents PGMs and iridium-specific materials that could be applied in solutions of secondary PGMs sources containing rhodium, platinum and palladium with bis-benzimidazoles as well as in feed solutions from ore processing with diammonium cations for iridium recovery.
- Full Text:
- Date Issued: 2019
The development of novel cancer targeting agents
- Authors: Knoetze, Steyn
- Date: 2011
- Subjects: Cancer -- Research , Cancer -- Treatment
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10397 , http://hdl.handle.net/10948/d1010636 , Cancer -- Research , Cancer -- Treatment
- Description: The search for the cure for cancer is currently a multi-billion dollar industry and the search for the elusive “magic bullet”, i.e. the perfect cancer drug that would interact therapeutically with cancerous tissues while having a minimal effect on healthy cells, is the topic of many research studies in the world today. A large number of novel drugs or drug complexes and conjugates are being synthesized and subjected to rigorous evaluation in the race to find the perfect cure. ECDG (Ethylene diCysteine DeoxyGlucose) seems to have promising cancer targeting ability. Even though this compound has been described in a few publications, we could not find any reference to the current use of ECDG in oncology clinics, either as a therapeutic agent, or as a diagnostic tool for imaging purposes. It was also not possible to purchase pure ECDG anywhere in the world. This prompted us to further investigate ECDG as a possible candidate for cancer targeting research, either as an imaging agent for cancer diagnosis or complexed with an anti-cancer agent for therapeutic purposes. Detailed investigations done in our laboratory can be divided into the following categories: - Development of a synthetic method for ECDG on a multigram scale ; - Purification of prepared ECDG not using the described dialysis method that only allows the purification of small quantities of ECDG (mg scale) ; Detailed investigation of the chemistry involved in the preparation of pure ECDG and its metal complexes ; - Investigation of the stability of ECDG and its metal complexes that is essential data required for any pharmaceutical agent ; - Preparation of ECDG complexes for use as a diagnostic tool, i.e. complexation with 99mTc ; Investigation of the bio distribution of ECDG-ReO complexes ; - Preparation of an ECDG kit as a diagnostic tool for use in oncology clinics. The development of novel aromatic ligands having similar characteristics compared to ECDG, containing an N2S2 chromophore as donor atoms, to further investigate their targeting capabilities, have also been investigated. All intermediates and final compounds were characterized mainly by ESI MS, in some cases IR and NMR whenever available. Successful preparation and purification of ECDG ands its metal complexes was achieved and extensively characterized and evaluated. Efforts directed towards the development of ECDG at NECSA, South Africa, were also rewarded with significant success. Furthermore, significant development regarding the synthesis of two novel compounds with ECDG-like characteristics was also completed.
- Full Text:
- Date Issued: 2011
- Authors: Knoetze, Steyn
- Date: 2011
- Subjects: Cancer -- Research , Cancer -- Treatment
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10397 , http://hdl.handle.net/10948/d1010636 , Cancer -- Research , Cancer -- Treatment
- Description: The search for the cure for cancer is currently a multi-billion dollar industry and the search for the elusive “magic bullet”, i.e. the perfect cancer drug that would interact therapeutically with cancerous tissues while having a minimal effect on healthy cells, is the topic of many research studies in the world today. A large number of novel drugs or drug complexes and conjugates are being synthesized and subjected to rigorous evaluation in the race to find the perfect cure. ECDG (Ethylene diCysteine DeoxyGlucose) seems to have promising cancer targeting ability. Even though this compound has been described in a few publications, we could not find any reference to the current use of ECDG in oncology clinics, either as a therapeutic agent, or as a diagnostic tool for imaging purposes. It was also not possible to purchase pure ECDG anywhere in the world. This prompted us to further investigate ECDG as a possible candidate for cancer targeting research, either as an imaging agent for cancer diagnosis or complexed with an anti-cancer agent for therapeutic purposes. Detailed investigations done in our laboratory can be divided into the following categories: - Development of a synthetic method for ECDG on a multigram scale ; - Purification of prepared ECDG not using the described dialysis method that only allows the purification of small quantities of ECDG (mg scale) ; Detailed investigation of the chemistry involved in the preparation of pure ECDG and its metal complexes ; - Investigation of the stability of ECDG and its metal complexes that is essential data required for any pharmaceutical agent ; - Preparation of ECDG complexes for use as a diagnostic tool, i.e. complexation with 99mTc ; Investigation of the bio distribution of ECDG-ReO complexes ; - Preparation of an ECDG kit as a diagnostic tool for use in oncology clinics. The development of novel aromatic ligands having similar characteristics compared to ECDG, containing an N2S2 chromophore as donor atoms, to further investigate their targeting capabilities, have also been investigated. All intermediates and final compounds were characterized mainly by ESI MS, in some cases IR and NMR whenever available. Successful preparation and purification of ECDG ands its metal complexes was achieved and extensively characterized and evaluated. Efforts directed towards the development of ECDG at NECSA, South Africa, were also rewarded with significant success. Furthermore, significant development regarding the synthesis of two novel compounds with ECDG-like characteristics was also completed.
- Full Text:
- Date Issued: 2011
Foraging in a dynamic environment: movement and stable isotope ecology of marine top predators breeding at the Prince Edward Archipelago
- Authors: Carpenter-Kling, Tegan
- Date: 2020
- Subjects: Marine ecology , Stable isotope tracers , Estuarine ecology
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/49049 , vital:41596
- Description: Marine ecosystems are experiencing rapid changes due to climate change. The associated temporal and spatial changes in resource distribution impacts on the foraging behaviour of marine top predators. If these changes negatively affect the ability of marine predators to forage efficiently, there may be dire consequences for their populations. However, evidence of foraging plasticity during adverse conditions, or generalist foraging behaviour, can allow inference about the resilience of species to environmental change and provide essential knowledge towards effective and proactive conservation measures. I examined plasticity in the trophic ecology of 12 marine predator species breeding on Marion Island, southern Indian Ocean, over three years (2015 – 2018), a period characterized by pronounced environmental variability. Firstly, I correlated behavioural states inferred along the GPS tracks of incubating wandering, grey-headed, sooty and light-mantled albatrosses to environmental variables that are indicative of biologically productive oceanographic features. Secondly, I analysed δ13C and δ15N blood values in 12 marine predator species (the afore-mentioned albatrosses as well as king, gentoo, macaroni and eastern rockhopper penguins, northern and southern giant petrels and Antarctic and sub-Antarctic fur seals) over two seasons: summer and autumn. My results revealed that the foraging behaviour of all the species is, to some degree, either plastic (temporally variable isotopic niche) or general (large isotopic niche which remained similar over time), except for the king penguin (small isotopic niche which remained similar over time), a known foraging specialist. Furthermore, despite their dynamic foraging behaviour, resource partitioning among the predators was maintained over time. Due to the ease and relatively low cost of collecting tissues for stable isotope analysis it has the potential to be a powerful tool to monitor the trophic ecology of marine predators. I thus used my simultaneously collected dataset of GPS tracks with the stable isotope blood compositions to investigate some of the assumptions underlying the inferences made from marine predator δ13C and δ15N blood values. I reconstructed species- and guild- specific δ13C and δ15N isoscapes for eight seabird species. Following this, I coupled individual-based movement models of northern giant petrels with global marine isotope models to explore the sensitivity of tissue δ13C values to a range of extrinsic (environmental) and intrinsic (behavioural, physiological) drivers. My results demonstrate the strong influence of reference isoscapes on the inference of stable isotope compositions of marine predators. Furthermore, I show that caution should be used when using non-species-specific or temporally inaccurate isoscapes. I furthermore demonstrate that biological interactions, such as competition for food resources, either past or present, as well as spatio-temporal distribution of food patches strongly influence the foraging behaviour of marine predators. These findings highlight the importance of integrating biological interactions in species distribution models which are used to predict possible distributional shifts of marine predators in the context of global changes. My thesis further developed previously available methods and presents a novel approach to investigate sources of variance in the stable isotopic composition of animals’ tissues.
- Full Text:
- Date Issued: 2020
- Authors: Carpenter-Kling, Tegan
- Date: 2020
- Subjects: Marine ecology , Stable isotope tracers , Estuarine ecology
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/49049 , vital:41596
- Description: Marine ecosystems are experiencing rapid changes due to climate change. The associated temporal and spatial changes in resource distribution impacts on the foraging behaviour of marine top predators. If these changes negatively affect the ability of marine predators to forage efficiently, there may be dire consequences for their populations. However, evidence of foraging plasticity during adverse conditions, or generalist foraging behaviour, can allow inference about the resilience of species to environmental change and provide essential knowledge towards effective and proactive conservation measures. I examined plasticity in the trophic ecology of 12 marine predator species breeding on Marion Island, southern Indian Ocean, over three years (2015 – 2018), a period characterized by pronounced environmental variability. Firstly, I correlated behavioural states inferred along the GPS tracks of incubating wandering, grey-headed, sooty and light-mantled albatrosses to environmental variables that are indicative of biologically productive oceanographic features. Secondly, I analysed δ13C and δ15N blood values in 12 marine predator species (the afore-mentioned albatrosses as well as king, gentoo, macaroni and eastern rockhopper penguins, northern and southern giant petrels and Antarctic and sub-Antarctic fur seals) over two seasons: summer and autumn. My results revealed that the foraging behaviour of all the species is, to some degree, either plastic (temporally variable isotopic niche) or general (large isotopic niche which remained similar over time), except for the king penguin (small isotopic niche which remained similar over time), a known foraging specialist. Furthermore, despite their dynamic foraging behaviour, resource partitioning among the predators was maintained over time. Due to the ease and relatively low cost of collecting tissues for stable isotope analysis it has the potential to be a powerful tool to monitor the trophic ecology of marine predators. I thus used my simultaneously collected dataset of GPS tracks with the stable isotope blood compositions to investigate some of the assumptions underlying the inferences made from marine predator δ13C and δ15N blood values. I reconstructed species- and guild- specific δ13C and δ15N isoscapes for eight seabird species. Following this, I coupled individual-based movement models of northern giant petrels with global marine isotope models to explore the sensitivity of tissue δ13C values to a range of extrinsic (environmental) and intrinsic (behavioural, physiological) drivers. My results demonstrate the strong influence of reference isoscapes on the inference of stable isotope compositions of marine predators. Furthermore, I show that caution should be used when using non-species-specific or temporally inaccurate isoscapes. I furthermore demonstrate that biological interactions, such as competition for food resources, either past or present, as well as spatio-temporal distribution of food patches strongly influence the foraging behaviour of marine predators. These findings highlight the importance of integrating biological interactions in species distribution models which are used to predict possible distributional shifts of marine predators in the context of global changes. My thesis further developed previously available methods and presents a novel approach to investigate sources of variance in the stable isotopic composition of animals’ tissues.
- Full Text:
- Date Issued: 2020
Development of insulin resistance in a rat model and the effects of sutherlandia frutescens as treatment and prevention
- Authors: Mackenzie, Janine
- Date: 2010
- Subjects: Metabolic syndrome , Insulin resistance -- Animal models , Obesity -- Treatment
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10340 , http://hdl.handle.net/10948/d1016216
- Description: The global number of obese people has reached pandemic proportions. High caloric diets and reduced physical exercise are to blame for this growing epidemic. Obesity has a very complex association with several other metabolic disorders, such as insulin resistance (IR), diabetes mellitus type 2 (DMT2) and cardiovascular disease. This puts a huge burden on health care systems world wide and claims many lives. Sutherlandia frutescens is a traditionally used herb, which is known to have anti-diabetic properties. However, the direct mode of action of S. frutescens still remains to be elucidated. The aim of this study was to investigate the developmental stages of high fat diet (HFD)-induced IR, to illuminate the pathogenesis of IR with a focal point on modifications in the lipid metabolism. Furthermore, the effects of S. frutescens as a treatment or prevention drug for IR and associated metabolic changes were examined. Two sets of experiments were conducted on male Wistar rats. In the first experiment rats, one week post weaning received a low fat diet (LFD), high fat diet (HFD) or HFD supplemented with S. frutescens (50mg/kg BW/d). Rats were sacrificed at week 0, 1, 2, 4, 8 and 12 in the feeding regime. In a second experiment rats were fed with a LFD or a HFD for 12 weeks and treated thereafter with S. frutescens (50mg/kg BW/d), metformin (13mg/kg BW/d) or water (control) for 28 days. Rats in the second experiment were sacrificed at week 12 to confirm IR while concurrently run rats were sacrificed after 28 days of treatment. For all the experiments rats were anaesthetized, blood was removed and rats were dissected. Plasma samples were analyzed for insulin, glucose, blood lipid parameters and cytokines. Liver, muscle and adipose tissue were analyzed for glucose uptake, total lipid content, lipid profile and fatty acid profile. It was shown that the intake of HFD caused IR and hyperinsulinaemia. The developmental stages in experiment one confirmed that an increase in plasma free fatty acids preceeded the onset of IR. Plasma and tissue lipid parameters (free fatty acid-, triglyceride- and cholesterol concentrations) showed pathological modifications in the HFD group. An ectopic accumulation of fat was observed in muscle and liver, as well as a change in membrane fatty acid profile. The results for circulating cytokines were somewhat inconclusive. Rats supplemented with S. frutescens did not develop HFD-induced IR (study one) or IR was reversed (study two). S. frutescens treatment also resulted in positive changes in plasma and tissue lipid parameters. In summary, an animal model for HFD-induced IR was established and the detrimental effect of elevated plasma FFA on glucose and lipid metabolism was observed. A novel discovery suggests that the anti-diabetic mode of action of S. frutescens is through modulation of lipid metabolism. It was also established that S. frutescens has the potential to prevent IR in vivo.
- Full Text:
- Date Issued: 2010
- Authors: Mackenzie, Janine
- Date: 2010
- Subjects: Metabolic syndrome , Insulin resistance -- Animal models , Obesity -- Treatment
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10340 , http://hdl.handle.net/10948/d1016216
- Description: The global number of obese people has reached pandemic proportions. High caloric diets and reduced physical exercise are to blame for this growing epidemic. Obesity has a very complex association with several other metabolic disorders, such as insulin resistance (IR), diabetes mellitus type 2 (DMT2) and cardiovascular disease. This puts a huge burden on health care systems world wide and claims many lives. Sutherlandia frutescens is a traditionally used herb, which is known to have anti-diabetic properties. However, the direct mode of action of S. frutescens still remains to be elucidated. The aim of this study was to investigate the developmental stages of high fat diet (HFD)-induced IR, to illuminate the pathogenesis of IR with a focal point on modifications in the lipid metabolism. Furthermore, the effects of S. frutescens as a treatment or prevention drug for IR and associated metabolic changes were examined. Two sets of experiments were conducted on male Wistar rats. In the first experiment rats, one week post weaning received a low fat diet (LFD), high fat diet (HFD) or HFD supplemented with S. frutescens (50mg/kg BW/d). Rats were sacrificed at week 0, 1, 2, 4, 8 and 12 in the feeding regime. In a second experiment rats were fed with a LFD or a HFD for 12 weeks and treated thereafter with S. frutescens (50mg/kg BW/d), metformin (13mg/kg BW/d) or water (control) for 28 days. Rats in the second experiment were sacrificed at week 12 to confirm IR while concurrently run rats were sacrificed after 28 days of treatment. For all the experiments rats were anaesthetized, blood was removed and rats were dissected. Plasma samples were analyzed for insulin, glucose, blood lipid parameters and cytokines. Liver, muscle and adipose tissue were analyzed for glucose uptake, total lipid content, lipid profile and fatty acid profile. It was shown that the intake of HFD caused IR and hyperinsulinaemia. The developmental stages in experiment one confirmed that an increase in plasma free fatty acids preceeded the onset of IR. Plasma and tissue lipid parameters (free fatty acid-, triglyceride- and cholesterol concentrations) showed pathological modifications in the HFD group. An ectopic accumulation of fat was observed in muscle and liver, as well as a change in membrane fatty acid profile. The results for circulating cytokines were somewhat inconclusive. Rats supplemented with S. frutescens did not develop HFD-induced IR (study one) or IR was reversed (study two). S. frutescens treatment also resulted in positive changes in plasma and tissue lipid parameters. In summary, an animal model for HFD-induced IR was established and the detrimental effect of elevated plasma FFA on glucose and lipid metabolism was observed. A novel discovery suggests that the anti-diabetic mode of action of S. frutescens is through modulation of lipid metabolism. It was also established that S. frutescens has the potential to prevent IR in vivo.
- Full Text:
- Date Issued: 2010
Immobilization of catalyst in a wall-coated micro-structured reactor for gas/liquid oxidation of p-cymene
- Authors: Makgwane, Peter Ramashadi
- Date: 2009
- Subjects: Oxidation , Cymene
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10389 , http://hdl.handle.net/10948/1182 , Oxidation , Cymene
- Description: The selective, liquid phase oxidation of p-cymene is an important synthetic route for the production of p-cresol via the tertiary cymene hydroperoxide (TCHP). The industrial-scale oxidation process is characterised by slow oxidation rates due to limitations in the mass transfer of oxidant (gaseous oxygen) into the liquid phase. However, like all other autoxidation reactions, the oxidation reaction is exothermic, following the typical free radical autoxidation reaction mechanism, which implies that careful temperature control is critical in order to prevent the further reaction of the initially formed hydroperoxide species. In the presence of metal catalysts, the limiting oxidation rate is the transfer of oxygen from the gas to liquid boundary interface. As a result, low product yields and poor productivity space-time yield are typically experienced. At high substrate conversions, by-products resulting from the decomposition of the formed hydroperoxides predominate. For this reason, the conversion of substrate is restricted to preserve the TCHP selectivity. The slow rates in industrial-scale p-cymene oxidations results in long oxidation times, typically 8-12 h. Substrate conversions are typically between 15-20 percent, and the TCHP selectivity ranges between 65-70 percent. The work described in this thesis concerns the oxidation of p-cymene in a microstructured falling film reactor (FFMSR). These reactor systems facilitate chemical reactors to have high mass and heat transfer rates because of high surface area-to-volume ratios. Due to their small internal volumes, these reactors are inherently safe to operate. These properties were exploited to improve the p-cymene oxidation rate and, consequently, the space-time yield. In order to evaluate the suitability of vanadium phosphate oxide (VPO) catalysts for use as supported catalyst in the FFMSR, different catalysts prepared from VOHPO4∙0.5H2O and VO(H2PO4)2 precursors was first evaluated for the oxidation of p-cymene in a well-stirred batch reactor. The results of the two activated catalysts, (VO)2P2O7 and VO(PO3)2 when used as powders in their pure form, showed a significant improvement in p-cymene oxidation rates with conversions up to 40 percent in 3-4 h reaction time with a TCHP selectivity of 75-80 percent. The (VO)2P2O7 catalyst showed better oxidation rates and selectivity when compared to the VO(PO3)2 catalyst obtained from the VO(H2PO4)2 precursor. The (VO)2P2O7 catalyst was supported on a stainless steel plate and the coated plate used to study the long-term stability and catalytic perfornance of the catalyst during p-cymene oxidations in a batch reactor. Comparable oxidation rates and TCHP selectivity were obtained with the stainless steel coated VPO catalyst when compared to the “free powder” (VO)2P2O7 catalyst. The results also showed that the stainless steel coated catalyst displays a slow, yet significant deactivation over extended reaction periods (250 h onstream). Characterization of the exposed (VO)2P2O7 catalyst to p-cymene oxidation conditions by powder XRD, SEM and TGA-MS showed that (VO)2P2O7 phase undergoes structural transformation back to VOHPO4∙0.5H2O phase over time. The (VO)2P2O7/-Al2O3 catalyst was used to coat the micro-channel reaction plates of the FFMSR. Both uncoated and coated micro-channel reaction plates were evaluated in the FFMSR for the oxidation of p-cymene. The FFMSR showed effective improvement of oxidation rates in terms of productivity space-time-yield at comparable batch p-cymene conversions. A Typical 10 percent conversion in catalysed batch oxidations at 1-2 h reaction time was achieved in few seconds (19 s) reaction time in FFMSR. The comparison of uncoated (i.e. uncatalysed) and coated (i.e. catalysed) FFMSR oxidations showed slight differences in oxidation rates. No clear explanation could be established with the present results for the observed same behaviour. However, the insufficient contact time between the gas and liquid reactants with the wall-coated solid catalyst is one of the possible causes for the observed behaviour of the coated and uncoated micro-channel plates. A simple developed kinetic model was used to confirm the obtained batch oxidation results using cumene as probe compound due to its similarity to p-cumene oxidation and extensive studied kinetics. With the estimated K values and available rate constants from literature, it was possible to predict the conversions in a batch reactor at the same typical micro-structured reactor residence time (i.e. of 19 s). The predicted conversions in the batch reactor were less than 0.1 percent even at harsh conditions such as 170 oC when compared to about 10 percent achieved in the micro-structured reactor at the same reaction temperature, reactants concentration and reaction time of 19 s. This difference in the reactor systems performance indicates the unique advantages offered by micro-structured reactors (e.g. improved mass transfer, temperature management and high surface-to-volume ratios) to perform typical gas/liquid mass transfer limited reactions such as cumene and p-cymene autoxidations.
- Full Text:
- Date Issued: 2009
- Authors: Makgwane, Peter Ramashadi
- Date: 2009
- Subjects: Oxidation , Cymene
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:10389 , http://hdl.handle.net/10948/1182 , Oxidation , Cymene
- Description: The selective, liquid phase oxidation of p-cymene is an important synthetic route for the production of p-cresol via the tertiary cymene hydroperoxide (TCHP). The industrial-scale oxidation process is characterised by slow oxidation rates due to limitations in the mass transfer of oxidant (gaseous oxygen) into the liquid phase. However, like all other autoxidation reactions, the oxidation reaction is exothermic, following the typical free radical autoxidation reaction mechanism, which implies that careful temperature control is critical in order to prevent the further reaction of the initially formed hydroperoxide species. In the presence of metal catalysts, the limiting oxidation rate is the transfer of oxygen from the gas to liquid boundary interface. As a result, low product yields and poor productivity space-time yield are typically experienced. At high substrate conversions, by-products resulting from the decomposition of the formed hydroperoxides predominate. For this reason, the conversion of substrate is restricted to preserve the TCHP selectivity. The slow rates in industrial-scale p-cymene oxidations results in long oxidation times, typically 8-12 h. Substrate conversions are typically between 15-20 percent, and the TCHP selectivity ranges between 65-70 percent. The work described in this thesis concerns the oxidation of p-cymene in a microstructured falling film reactor (FFMSR). These reactor systems facilitate chemical reactors to have high mass and heat transfer rates because of high surface area-to-volume ratios. Due to their small internal volumes, these reactors are inherently safe to operate. These properties were exploited to improve the p-cymene oxidation rate and, consequently, the space-time yield. In order to evaluate the suitability of vanadium phosphate oxide (VPO) catalysts for use as supported catalyst in the FFMSR, different catalysts prepared from VOHPO4∙0.5H2O and VO(H2PO4)2 precursors was first evaluated for the oxidation of p-cymene in a well-stirred batch reactor. The results of the two activated catalysts, (VO)2P2O7 and VO(PO3)2 when used as powders in their pure form, showed a significant improvement in p-cymene oxidation rates with conversions up to 40 percent in 3-4 h reaction time with a TCHP selectivity of 75-80 percent. The (VO)2P2O7 catalyst showed better oxidation rates and selectivity when compared to the VO(PO3)2 catalyst obtained from the VO(H2PO4)2 precursor. The (VO)2P2O7 catalyst was supported on a stainless steel plate and the coated plate used to study the long-term stability and catalytic perfornance of the catalyst during p-cymene oxidations in a batch reactor. Comparable oxidation rates and TCHP selectivity were obtained with the stainless steel coated VPO catalyst when compared to the “free powder” (VO)2P2O7 catalyst. The results also showed that the stainless steel coated catalyst displays a slow, yet significant deactivation over extended reaction periods (250 h onstream). Characterization of the exposed (VO)2P2O7 catalyst to p-cymene oxidation conditions by powder XRD, SEM and TGA-MS showed that (VO)2P2O7 phase undergoes structural transformation back to VOHPO4∙0.5H2O phase over time. The (VO)2P2O7/-Al2O3 catalyst was used to coat the micro-channel reaction plates of the FFMSR. Both uncoated and coated micro-channel reaction plates were evaluated in the FFMSR for the oxidation of p-cymene. The FFMSR showed effective improvement of oxidation rates in terms of productivity space-time-yield at comparable batch p-cymene conversions. A Typical 10 percent conversion in catalysed batch oxidations at 1-2 h reaction time was achieved in few seconds (19 s) reaction time in FFMSR. The comparison of uncoated (i.e. uncatalysed) and coated (i.e. catalysed) FFMSR oxidations showed slight differences in oxidation rates. No clear explanation could be established with the present results for the observed same behaviour. However, the insufficient contact time between the gas and liquid reactants with the wall-coated solid catalyst is one of the possible causes for the observed behaviour of the coated and uncoated micro-channel plates. A simple developed kinetic model was used to confirm the obtained batch oxidation results using cumene as probe compound due to its similarity to p-cumene oxidation and extensive studied kinetics. With the estimated K values and available rate constants from literature, it was possible to predict the conversions in a batch reactor at the same typical micro-structured reactor residence time (i.e. of 19 s). The predicted conversions in the batch reactor were less than 0.1 percent even at harsh conditions such as 170 oC when compared to about 10 percent achieved in the micro-structured reactor at the same reaction temperature, reactants concentration and reaction time of 19 s. This difference in the reactor systems performance indicates the unique advantages offered by micro-structured reactors (e.g. improved mass transfer, temperature management and high surface-to-volume ratios) to perform typical gas/liquid mass transfer limited reactions such as cumene and p-cymene autoxidations.
- Full Text:
- Date Issued: 2009
Purification and characterisation of 20S proteasome from ostrich skeletal muscle and its role in meat tenderisation
- Authors: Thomas, Adele René
- Date: 2004
- Subjects: Proteolytic enzymes , Ostrich products industry
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:11081 , http://hdl.handle.net/10948/320 , Proteolytic enzymes , Ostrich products industry
- Description: The proteasome is renowned for its high molecular weight, multisubunit and mulicatalytic nature. One of its many suggested roles is the degradation of myofibrillar proteins, and therefore it has been proposed to play a role in the meat tenderisation process. The aim of this study was therefore to isolate, purify and characterise the 20S proteasome from ostrich skeletal muscle, with a view to ultimately investigating its role in the tenderisation process of ostrich meat. The 20S proteasome was successfully isolated and purified from ostrich skeletal muscle using Toyopearl Super Q-650S, Sephacryl S-300, hydroxylapatite and Mono Q chromatographies. The intact molecule showed a molecular weight of 725 K and a pI of 6.67. The subunits showed a molecular weight range of 22.2-33.5 K and a pI range of 3-9. 2D-PAGE revealed at least 14 polypeptides. The amino acid composition of the intact enzyme and of each of the eight subunits separating on SDSPAGE, as well as the N-terminal sequences of five of the eight subunits, were determined. The trypsinlike (Tr-L), chymotrypsin-like (ChT-L), peptidylglutamyl peptide hydrolase (PGPH) and caseinolytic activities showed pH optima of 11, 9, 7-8 and 10.3, and temperature optima of 40, 60, 70 and 60oC, respectively. The pH stability range for all four activities was 5-12. The ChT-L and PGPH activities showed thermostabilities up to 60oC, whereas the Tr-L and caseinolytic activities were stable up to 40o C. The enzyme showed complex kinetics. It was inhibited by the peptide aldehyde Z-LLL-CHO and cysteine protease inhibitors. Cations had negligible effects on the enzyme, excepting for Ca2+ and Mg2+. Of the detergents tested, SDS had the most potent stimulatory effect, particularly on the PGPH and caseinolytic activities. The fatty acid studies showed that unsaturation enhanced the ChT-L and the caseinolytic activities, while it completely suppressed the Tr-L activity. Heating at 60oC for 1-2 min stimulated the caseinolytic and PGPH activities. The studies on the role of ostrich skeletal muscle 20S proteasome in ostrich meat tenderisation suggested a definite but minor role of this enzyme, based on the fact that it remained active throughout the 12 days of storage of ostrich M. iliofibularis meat at 4oC and that it participated in myofibril degradation of post-mortem muscle, but to a small degree. These results support the proposal that the proteasome comes into play after the calpains have initiated degradation. However, there was a lack of improvement in tenderness values and minimal myofibrillar degradation over the 12-day storage period of the ostrich M. iliofibularis meat, leading to the conclusion that the tenderisation of this meat was incomplete after 12 days.
- Full Text:
- Date Issued: 2004
- Authors: Thomas, Adele René
- Date: 2004
- Subjects: Proteolytic enzymes , Ostrich products industry
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: vital:11081 , http://hdl.handle.net/10948/320 , Proteolytic enzymes , Ostrich products industry
- Description: The proteasome is renowned for its high molecular weight, multisubunit and mulicatalytic nature. One of its many suggested roles is the degradation of myofibrillar proteins, and therefore it has been proposed to play a role in the meat tenderisation process. The aim of this study was therefore to isolate, purify and characterise the 20S proteasome from ostrich skeletal muscle, with a view to ultimately investigating its role in the tenderisation process of ostrich meat. The 20S proteasome was successfully isolated and purified from ostrich skeletal muscle using Toyopearl Super Q-650S, Sephacryl S-300, hydroxylapatite and Mono Q chromatographies. The intact molecule showed a molecular weight of 725 K and a pI of 6.67. The subunits showed a molecular weight range of 22.2-33.5 K and a pI range of 3-9. 2D-PAGE revealed at least 14 polypeptides. The amino acid composition of the intact enzyme and of each of the eight subunits separating on SDSPAGE, as well as the N-terminal sequences of five of the eight subunits, were determined. The trypsinlike (Tr-L), chymotrypsin-like (ChT-L), peptidylglutamyl peptide hydrolase (PGPH) and caseinolytic activities showed pH optima of 11, 9, 7-8 and 10.3, and temperature optima of 40, 60, 70 and 60oC, respectively. The pH stability range for all four activities was 5-12. The ChT-L and PGPH activities showed thermostabilities up to 60oC, whereas the Tr-L and caseinolytic activities were stable up to 40o C. The enzyme showed complex kinetics. It was inhibited by the peptide aldehyde Z-LLL-CHO and cysteine protease inhibitors. Cations had negligible effects on the enzyme, excepting for Ca2+ and Mg2+. Of the detergents tested, SDS had the most potent stimulatory effect, particularly on the PGPH and caseinolytic activities. The fatty acid studies showed that unsaturation enhanced the ChT-L and the caseinolytic activities, while it completely suppressed the Tr-L activity. Heating at 60oC for 1-2 min stimulated the caseinolytic and PGPH activities. The studies on the role of ostrich skeletal muscle 20S proteasome in ostrich meat tenderisation suggested a definite but minor role of this enzyme, based on the fact that it remained active throughout the 12 days of storage of ostrich M. iliofibularis meat at 4oC and that it participated in myofibril degradation of post-mortem muscle, but to a small degree. These results support the proposal that the proteasome comes into play after the calpains have initiated degradation. However, there was a lack of improvement in tenderness values and minimal myofibrillar degradation over the 12-day storage period of the ostrich M. iliofibularis meat, leading to the conclusion that the tenderisation of this meat was incomplete after 12 days.
- Full Text:
- Date Issued: 2004
Development of MOVPE-grown InAsSb for barrier diode applications
- Authors: Dobson, Stephen R
- Date: 2020
- Subjects: Gallium arsenide semiconductors , Electronics
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/49071 , vital:41598
- Description: In this study, layers of GaSb, InAs and InAsSb are grown by metalorganic vapour phase epitaxy and characterised. Growth is conducted using the precursors of trimethylgallium, trimethylindium, trimethylantimony and tertiarybutylarsine. Focus is then placed on the characterisation of the materials, carried out by the techniques of X-ray diffraction, photoluminescence spectroscopy, Hall measurements and photocurrent spectroscopy. It is observed that V/III ratio plays a vital role in the growth of the GaSb and InAsSb layers. Epilayers of GaSb showed best crystalline quality when a V/III ratio of 1.2 was used at a growth temperature of 600 °C and a cell pressure of 600 Torr. Resultant Hall measurements indicated p-type GaSb. The Hall carrier concentrations of the p-type GaSb samples were analyzed considering electrical neutrality conditions and found to be highly compensated with evidence of band impurity conduction at low measurement temperatures. Both the donor and acceptor concentrations were determined to be of the order of 1016 cm−3 for all samples. For low temperature (< 150 K) a monovalent acceptor concentration is calculated to have an activation energy at approximately 20 meV. At high temperature (> 150 K) a divalent acceptor is extracted with an activation energy varying between samples based on compensation in a range of 90 meV to 70 meV. Photoluminescence measurements show four peaks with recombination mechanisms linked to the native acceptor identified in literature as either the gallium antisite and/or vacant gallium site. A fifth peak observed is attributed to the longitudinal phonon of the native acceptor. InAs and InAsSb epilayer are all grown at a temperature of 600 °C and cell pressure of 600 Torr. InAs is grown at a V/III ratio of 9.5 on GaAs substrate. Photoluminescence of the InAs layer shows two distinct peaks, one of which is an extrinsic band to band recombination. The other is attributed to free electron to acceptor or a donor-acceptor pair transition. An additional weak peak is also observed which is assigned to the longitudinal phonon of the band to band. InAsSb growth was conducted under a range of V/III ratios of 4.8 to 5, with a vapour phase composition of 0.4 to 0.435. Structural analysis via X-ray diffraction showed a 6 % to 12 % solid antimony content. Photoluminescence exhibited a single broad peak for all samples, with extended band tails. Temperature and power dependant analysis of luminescence indicated a convolution of extrinsic band to tail and band to band recombinations. Hall measurements indicated the InAsSb was n-type material with an apparent measured maximum mobility at 120 K of 9.5 × 103 cm2/V.s. and a room temperature apparent mobility of 7.5 × 103 cm2/V.s. Analysis of hall results using a two-layer model calculated a true bulk mobility of the epilayer at room temperature with an increased value of 15.4 × 103 cm2/V.s. The two-layer model details the effects of the surface conduction. From photoconductivity measurements and further analysis a resultant effective lifetime, at room temperature, was found to be on same order of magnitude as that of InAs materials. Application of a single Einstein oscillator extrapolated 0 K energy gaps for two samples of solid Sb contents of 6 % and 12 %, of 354 meV and 332 meV, respectively. Finally consideration was given to the growth of aluminium containing compounds, particularly AlGaSb. Multiple phases were observed under scanning electron microscope showing growth of GaSb regions surrounded by amorphous solid aluminium and/or aluminium oxide phases. The failure of the aluminium to incorporate into the desired crystal structure is speculated to be due to impure precursor introducing oxygen into the films. Additionally, the effectiveness of the gallium precursor compared to the aluminium precursor in helping the removal of the methyl groups at the growth surface, could also promote a preference for GaSb growth.
- Full Text:
- Date Issued: 2020
- Authors: Dobson, Stephen R
- Date: 2020
- Subjects: Gallium arsenide semiconductors , Electronics
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/49071 , vital:41598
- Description: In this study, layers of GaSb, InAs and InAsSb are grown by metalorganic vapour phase epitaxy and characterised. Growth is conducted using the precursors of trimethylgallium, trimethylindium, trimethylantimony and tertiarybutylarsine. Focus is then placed on the characterisation of the materials, carried out by the techniques of X-ray diffraction, photoluminescence spectroscopy, Hall measurements and photocurrent spectroscopy. It is observed that V/III ratio plays a vital role in the growth of the GaSb and InAsSb layers. Epilayers of GaSb showed best crystalline quality when a V/III ratio of 1.2 was used at a growth temperature of 600 °C and a cell pressure of 600 Torr. Resultant Hall measurements indicated p-type GaSb. The Hall carrier concentrations of the p-type GaSb samples were analyzed considering electrical neutrality conditions and found to be highly compensated with evidence of band impurity conduction at low measurement temperatures. Both the donor and acceptor concentrations were determined to be of the order of 1016 cm−3 for all samples. For low temperature (< 150 K) a monovalent acceptor concentration is calculated to have an activation energy at approximately 20 meV. At high temperature (> 150 K) a divalent acceptor is extracted with an activation energy varying between samples based on compensation in a range of 90 meV to 70 meV. Photoluminescence measurements show four peaks with recombination mechanisms linked to the native acceptor identified in literature as either the gallium antisite and/or vacant gallium site. A fifth peak observed is attributed to the longitudinal phonon of the native acceptor. InAs and InAsSb epilayer are all grown at a temperature of 600 °C and cell pressure of 600 Torr. InAs is grown at a V/III ratio of 9.5 on GaAs substrate. Photoluminescence of the InAs layer shows two distinct peaks, one of which is an extrinsic band to band recombination. The other is attributed to free electron to acceptor or a donor-acceptor pair transition. An additional weak peak is also observed which is assigned to the longitudinal phonon of the band to band. InAsSb growth was conducted under a range of V/III ratios of 4.8 to 5, with a vapour phase composition of 0.4 to 0.435. Structural analysis via X-ray diffraction showed a 6 % to 12 % solid antimony content. Photoluminescence exhibited a single broad peak for all samples, with extended band tails. Temperature and power dependant analysis of luminescence indicated a convolution of extrinsic band to tail and band to band recombinations. Hall measurements indicated the InAsSb was n-type material with an apparent measured maximum mobility at 120 K of 9.5 × 103 cm2/V.s. and a room temperature apparent mobility of 7.5 × 103 cm2/V.s. Analysis of hall results using a two-layer model calculated a true bulk mobility of the epilayer at room temperature with an increased value of 15.4 × 103 cm2/V.s. The two-layer model details the effects of the surface conduction. From photoconductivity measurements and further analysis a resultant effective lifetime, at room temperature, was found to be on same order of magnitude as that of InAs materials. Application of a single Einstein oscillator extrapolated 0 K energy gaps for two samples of solid Sb contents of 6 % and 12 %, of 354 meV and 332 meV, respectively. Finally consideration was given to the growth of aluminium containing compounds, particularly AlGaSb. Multiple phases were observed under scanning electron microscope showing growth of GaSb regions surrounded by amorphous solid aluminium and/or aluminium oxide phases. The failure of the aluminium to incorporate into the desired crystal structure is speculated to be due to impure precursor introducing oxygen into the films. Additionally, the effectiveness of the gallium precursor compared to the aluminium precursor in helping the removal of the methyl groups at the growth surface, could also promote a preference for GaSb growth.
- Full Text:
- Date Issued: 2020
Productivity and resilience of intertidal resources available to extant human foragers on South Africa’s cape south coast: behavioural implications for early Homo sapiens
- Authors: De Vynck, Jan Carlo
- Date: 2018
- Subjects: Marine invertebrates -- South Africa -- Prehistory , Shellfish -- South Africa -- Prehistory Fishes -- Behavior
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/30172 , vital:30854
- Description: Studies of pre-historic lifestyles can be limited by a lack of preserved material and sites and resource misinterpretation is augmented by the vagueness of pre-historic subsistence lifestyles. The present can inform the past and this study‟s ethnoarchaeological approach, through modern analogues, examines productivity, resilience and temporal and spatial size variation of intertidal invertebrates on the Cape‟s south coast. O‟Connell (1995) defined the mutualistic relationship between ethnography and archaeology thus: “Archaeology‟s ultimate aim is understanding past human behaviour by patterns in the form and distribution of objects made or modified by humans in the past and knowledge of human behaviour and its material consequences in the present. The first provides direct evidence of past behaviour; the second, a basis for interpreting that evidence”. Coastal archaeology, specifically the contribution of coastal resources to pre-historic subsistence, has gained increased global interest (Erlandson, 2001; Erlandson and Rick, 2008; Codding et al., 2014). Apart from the high representation of preserved shell in coastal archaeological sites, interest in intertidal resources has also been sparked by their economic value compared to terrestrial resource options. Intertidal resources offer low-risk protein acquisition whereas terrestrial protein can be dangerous to procure. However, in the past intertidal subsistence was thought to offer low caloric yields or unfavourable cost-to-benefit relationships until Meehan (1982) convincingly demonstrated the potential caloric „profit‟ possible from coastal foraging; the Anbarra women of northern Australia were contributing significantly to the overall caloric requirements of those people. In South Africa, two possible evolutionary behavioural hypotheses arose from the addition of intertidal resources to pre-historic diets. As background, it is important to note that the oldest global evidence for shellfish procurement [164 000 years ago (ka)] is found on the Cape‟s south coast (Jerardino and Marean, 2010) and the evidence is enriched by other sites from around 110 ka (Voight, 1973; Thackeray, 1988; Henshilwood et al., 2001; Langejans et al., 2012). Furthermore, this period coincides with the emergence of cognitively modern Homo sapiens as evidenced in xx the palaeoarchives from many sites in the region (d‟Errico et al., 2005; Marean et al., 2007; Wurz, 2008; Henshilwood et al., 2009; Watts, 2010; d‟Errico et al., 2012). These features have greatly enhanced the significance and importance of this area to understanding human evolution. The two hypotheses are centred around the effect that intertidal resources could have had on the emergence of our unique species. The addition of a nutritionally beneficial resource to cognitive development is seen by some (Broadhurst et al., 2002; Parkington, 2010) to have driven this cognitive evolution, where others suggest that resources which are both productive and dependable create pro-social proclivities that drive cognitive development (Whitaker and Byrd, 2014; Marean, 2014) and facilitate the migration of humans (Fa, 2008; Codding et al., 2014). Both hypotheses argue that resources on the Cape‟s coast must have been productive and had to be a frequent addition to diet to underpin brain development. The increased frequency of coastal resource procurement or coastal adaptation is therefore seen as an attribute of, or requisite for our species. This thesis attempts to shed light on the contribution of intertidal resources to prehistoric ‒ especially Middle Stone Age (MSA) – subsistence economy on the Cape‟s south coast and the possible effect thereof on human behavioural evolution. The first aim was to investigate the spatial productivity (once-off patch caloric profitability in numerous patches) of intertidal resources and the environmental and behavioural variables affecting it. The second aim was to investigate the resilience of caloric profitability (numerous harvests in the same patch) of these resources to sustained human predation. Productivity itself cannot affect human temporal social dynamics if the resource is swiftly depleted within a specific patch after one or a few harvests. Archaeological records that show the body size of shellfish decreasing over time are usually interpreted to indicate intensive exploitation and the depletion of these resources, but there may be other explanations for such patterns. Therefore, the third aim was to compare temporal and spatial variations in the body size of Turbo sarmaticus in the MSA, Later Stone Age (LSA) and the present day, in order to investigate whether such variations result from human exploitation or environmental changes.
- Full Text:
- Date Issued: 2018
- Authors: De Vynck, Jan Carlo
- Date: 2018
- Subjects: Marine invertebrates -- South Africa -- Prehistory , Shellfish -- South Africa -- Prehistory Fishes -- Behavior
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/30172 , vital:30854
- Description: Studies of pre-historic lifestyles can be limited by a lack of preserved material and sites and resource misinterpretation is augmented by the vagueness of pre-historic subsistence lifestyles. The present can inform the past and this study‟s ethnoarchaeological approach, through modern analogues, examines productivity, resilience and temporal and spatial size variation of intertidal invertebrates on the Cape‟s south coast. O‟Connell (1995) defined the mutualistic relationship between ethnography and archaeology thus: “Archaeology‟s ultimate aim is understanding past human behaviour by patterns in the form and distribution of objects made or modified by humans in the past and knowledge of human behaviour and its material consequences in the present. The first provides direct evidence of past behaviour; the second, a basis for interpreting that evidence”. Coastal archaeology, specifically the contribution of coastal resources to pre-historic subsistence, has gained increased global interest (Erlandson, 2001; Erlandson and Rick, 2008; Codding et al., 2014). Apart from the high representation of preserved shell in coastal archaeological sites, interest in intertidal resources has also been sparked by their economic value compared to terrestrial resource options. Intertidal resources offer low-risk protein acquisition whereas terrestrial protein can be dangerous to procure. However, in the past intertidal subsistence was thought to offer low caloric yields or unfavourable cost-to-benefit relationships until Meehan (1982) convincingly demonstrated the potential caloric „profit‟ possible from coastal foraging; the Anbarra women of northern Australia were contributing significantly to the overall caloric requirements of those people. In South Africa, two possible evolutionary behavioural hypotheses arose from the addition of intertidal resources to pre-historic diets. As background, it is important to note that the oldest global evidence for shellfish procurement [164 000 years ago (ka)] is found on the Cape‟s south coast (Jerardino and Marean, 2010) and the evidence is enriched by other sites from around 110 ka (Voight, 1973; Thackeray, 1988; Henshilwood et al., 2001; Langejans et al., 2012). Furthermore, this period coincides with the emergence of cognitively modern Homo sapiens as evidenced in xx the palaeoarchives from many sites in the region (d‟Errico et al., 2005; Marean et al., 2007; Wurz, 2008; Henshilwood et al., 2009; Watts, 2010; d‟Errico et al., 2012). These features have greatly enhanced the significance and importance of this area to understanding human evolution. The two hypotheses are centred around the effect that intertidal resources could have had on the emergence of our unique species. The addition of a nutritionally beneficial resource to cognitive development is seen by some (Broadhurst et al., 2002; Parkington, 2010) to have driven this cognitive evolution, where others suggest that resources which are both productive and dependable create pro-social proclivities that drive cognitive development (Whitaker and Byrd, 2014; Marean, 2014) and facilitate the migration of humans (Fa, 2008; Codding et al., 2014). Both hypotheses argue that resources on the Cape‟s coast must have been productive and had to be a frequent addition to diet to underpin brain development. The increased frequency of coastal resource procurement or coastal adaptation is therefore seen as an attribute of, or requisite for our species. This thesis attempts to shed light on the contribution of intertidal resources to prehistoric ‒ especially Middle Stone Age (MSA) – subsistence economy on the Cape‟s south coast and the possible effect thereof on human behavioural evolution. The first aim was to investigate the spatial productivity (once-off patch caloric profitability in numerous patches) of intertidal resources and the environmental and behavioural variables affecting it. The second aim was to investigate the resilience of caloric profitability (numerous harvests in the same patch) of these resources to sustained human predation. Productivity itself cannot affect human temporal social dynamics if the resource is swiftly depleted within a specific patch after one or a few harvests. Archaeological records that show the body size of shellfish decreasing over time are usually interpreted to indicate intensive exploitation and the depletion of these resources, but there may be other explanations for such patterns. Therefore, the third aim was to compare temporal and spatial variations in the body size of Turbo sarmaticus in the MSA, Later Stone Age (LSA) and the present day, in order to investigate whether such variations result from human exploitation or environmental changes.
- Full Text:
- Date Issued: 2018
On the development of ZnO nanorods on silicon substrate for light-emitting diode applications
- Djiokap, Stive Roussel Tankio
- Authors: Djiokap, Stive Roussel Tankio
- Date: 2018
- Subjects: Zinc oxide , Chemical reactions , Compound semiconductors
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/29973 , vital:30802
- Description: The interest in zinc oxide (ZnO), a promising material for blue/ultraviolet light emitting devices, arises from its large exciton binding energy (60 meV). The main challenge associated with this promising compound semiconductor, however, arises from the difficulty to achieve stable and/or reproducible p-type doping. Since silicon (Si) technology still dominates the semiconductor industry, the objective of this thesis is to probe into the possibility of using ZnO nanorods (NRs) on p-type silicon for opto-electronic devices. ZnO NRs have been grown on seeded Si, as well as on nickel oxide (NiO) and aluminum nitride (AlN) coated Si, using a two-step chemical bath deposition (CBD) process. Various techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy and transmission electron microscopy (TEM), have been used to characterize the samples. The electrical characteristics of the heterojunction between the substrate and the ZnO nanostructures were evaluated by current-voltage (I-V) and capacitance-voltage (C-V) measurements. SEM and XRD studies have confirmed that, irrespective of the orientation of the Si substrate (Si (100) and Si (111)), the two-step CBD process yielded NRs that crystallised in the wurtzite structure and exhibited a hexagonal shape. Most of the rods developed perpendicularly to the surface of the substrate, with the orientation and distribution of the rods dictated by the seed layer density. Similarly, irrespective of the substrate, the luminescence of the ZnO nanostructures is dominated by near band edge (NBE) emission in the UV region (~ 3.29 eV) and deep level emission (DLE) in the visible region (2 eV to 2.6 eV). Annealing at moderate temperatures (~ 300 °C) increased the NBE emission and decreased the DLE. The removal of surface adsorbed impurities and enhanced defect passivation by hydrogen are responsible for these changes. The diode characteristics of the ZnO/Si heterojunction was studied by I-V and C-V measurements. Rectification was observed when the Si substrate had a relatively low acceptor density of ~1016 cm-3, while diodes produced on substrate with p ~1018 cm-3 were ohmic. From the C-V analysis the donor density in the ZnO was deduced to be ~1018 cm-3. In the case of rectifying junctions, thermionic emission did not dominate the charge transport. The carrier transport mechanism was therefore probed by the temperature dependent I-V xiii measurements (100 K to 295 K). Defect-assisted multistep tunneling was deduced to dominate in the n-ZnO/p-Si diodes at low forward bias. The band alignment between n-ZnO and p-Si predicts a much smaller barrier for electrons than for holes at the interface, which results in recombination on the Si side of the junction for a forward-biased diode. NiO intermediate layers (formed on Si by the thermal oxidation of Ni) were used to reduce electron injection from ZnO into Si. Scanning probe microscopy (SPM) and XRD analysis showed that while the grain size of the poly-crystalline NiO increased with NiO film thickness, the orientation and distribution of the subsequently grown ZnO nanorods were unaffected by the underlying NiO layer. Also, the photoluminescence response of the ZnO rods remained unchanged. I-V measurements did illustrate rectifying behaviour, with both the forward and reverse currents strongly decreased due to the resistive nature of the NiO. In another attempt at confining electrons to the ZnO side of the junction, AlN-coated Si (111) was used as a substrate for ZnO nanorods. CBD parameters that normally yield nanorods resulted in a plate-like architecture of the ZnO. By modifying the ZnO seed density on the AlN/Si substrate, the rod-like morphology could be recovered. Both the forward and reverse current decreased in these diodes. From studies aimed at identifying the transport mechanism it was concluded that trap-assisted tunnelling, resulting from a high density of defects in the seed layer, dominates in these devices. In conclusion, while no ZnO electroluminescence could be achieved from any of the devices, this study provides insight into the transport mechanisms in n-ZnO/barrier/p-Si heterostructures and highlights the importance of the heterointerface quality for light emitting devices.
- Full Text:
- Date Issued: 2018
- Authors: Djiokap, Stive Roussel Tankio
- Date: 2018
- Subjects: Zinc oxide , Chemical reactions , Compound semiconductors
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/29973 , vital:30802
- Description: The interest in zinc oxide (ZnO), a promising material for blue/ultraviolet light emitting devices, arises from its large exciton binding energy (60 meV). The main challenge associated with this promising compound semiconductor, however, arises from the difficulty to achieve stable and/or reproducible p-type doping. Since silicon (Si) technology still dominates the semiconductor industry, the objective of this thesis is to probe into the possibility of using ZnO nanorods (NRs) on p-type silicon for opto-electronic devices. ZnO NRs have been grown on seeded Si, as well as on nickel oxide (NiO) and aluminum nitride (AlN) coated Si, using a two-step chemical bath deposition (CBD) process. Various techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy and transmission electron microscopy (TEM), have been used to characterize the samples. The electrical characteristics of the heterojunction between the substrate and the ZnO nanostructures were evaluated by current-voltage (I-V) and capacitance-voltage (C-V) measurements. SEM and XRD studies have confirmed that, irrespective of the orientation of the Si substrate (Si (100) and Si (111)), the two-step CBD process yielded NRs that crystallised in the wurtzite structure and exhibited a hexagonal shape. Most of the rods developed perpendicularly to the surface of the substrate, with the orientation and distribution of the rods dictated by the seed layer density. Similarly, irrespective of the substrate, the luminescence of the ZnO nanostructures is dominated by near band edge (NBE) emission in the UV region (~ 3.29 eV) and deep level emission (DLE) in the visible region (2 eV to 2.6 eV). Annealing at moderate temperatures (~ 300 °C) increased the NBE emission and decreased the DLE. The removal of surface adsorbed impurities and enhanced defect passivation by hydrogen are responsible for these changes. The diode characteristics of the ZnO/Si heterojunction was studied by I-V and C-V measurements. Rectification was observed when the Si substrate had a relatively low acceptor density of ~1016 cm-3, while diodes produced on substrate with p ~1018 cm-3 were ohmic. From the C-V analysis the donor density in the ZnO was deduced to be ~1018 cm-3. In the case of rectifying junctions, thermionic emission did not dominate the charge transport. The carrier transport mechanism was therefore probed by the temperature dependent I-V xiii measurements (100 K to 295 K). Defect-assisted multistep tunneling was deduced to dominate in the n-ZnO/p-Si diodes at low forward bias. The band alignment between n-ZnO and p-Si predicts a much smaller barrier for electrons than for holes at the interface, which results in recombination on the Si side of the junction for a forward-biased diode. NiO intermediate layers (formed on Si by the thermal oxidation of Ni) were used to reduce electron injection from ZnO into Si. Scanning probe microscopy (SPM) and XRD analysis showed that while the grain size of the poly-crystalline NiO increased with NiO film thickness, the orientation and distribution of the subsequently grown ZnO nanorods were unaffected by the underlying NiO layer. Also, the photoluminescence response of the ZnO rods remained unchanged. I-V measurements did illustrate rectifying behaviour, with both the forward and reverse currents strongly decreased due to the resistive nature of the NiO. In another attempt at confining electrons to the ZnO side of the junction, AlN-coated Si (111) was used as a substrate for ZnO nanorods. CBD parameters that normally yield nanorods resulted in a plate-like architecture of the ZnO. By modifying the ZnO seed density on the AlN/Si substrate, the rod-like morphology could be recovered. Both the forward and reverse current decreased in these diodes. From studies aimed at identifying the transport mechanism it was concluded that trap-assisted tunnelling, resulting from a high density of defects in the seed layer, dominates in these devices. In conclusion, while no ZnO electroluminescence could be achieved from any of the devices, this study provides insight into the transport mechanisms in n-ZnO/barrier/p-Si heterostructures and highlights the importance of the heterointerface quality for light emitting devices.
- Full Text:
- Date Issued: 2018
Data transport over optical fibre for ska using advanced modulation flexible spectrum technology
- Authors: Dlamini, Phumla Patience
- Date: 2020
- Subjects: Fiber optics
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/50666 , vital:42329
- Description: Flexible Spectrum Dense Wavelength Division Multiplexed (DWDM) optical fibre networks are next-generation technology for handling extremely high data rates of the kind produced by MeerKAT and SKA.We optimise the flexible spectrum for real-time dynamic channel wavelength assignment, to ensure optimum network performance. We needed to identify and develop novel hardware and dynamic algorithms for these networks to function optimally to perform critical tasks. Such tasks include wavelength assignment, signal routing, network restoration and network protection. The antennas of the Square Kilometre Array (SKA) network connect to the correlator and data processor in a simple point-to-point fixed configuration. The connection of the astronomer users to the data processor, however, requires a more complex network architecture. This is because the network has users scattered around South Africa, Africa and the whole world. This calls for upgrade of the classical fixed wavelength spectrum grids, to flexible spectrum grid that has improved capacity, reliable, simple and cost-effectiveness through sharing of network infrastructure. The exponential growth of data traffic in current optical communication networks requires higher capacity for the bandwidth demands at a reduced cost per bit. All-optical signal processing is a promising technique to improve network resource utilisation and resolve wavelength contention associated with the flexible spectrum. Flexible Spectrum Dense Wavelength Division Multiplexed (DWDM) optical fibre networks are next-generation technology for handling extremely high data rates of the kind produced by MeerKAT and SKA. Each DWDM channel is capable of 10 Gbps transmission rate, which is sliceable into finer flexible grid 12.5 GHz granularity to offer the network elastic spectrum and channel spacing capable of signal routing and wavelength switching for the scalability of aggregate bandwidth. The variable-sized portions of the flexible spectrum assignment to end users at different speeds depend on bandwidth demand, allowing efficient utilisation of the spectrum resources. The entire bandwidth of dynamic optical connections must be contiguously allocated. However, there is an introduction of spectrum fragmentation due to spectrum contiguity related to the optical channels having different width. Thus large traffic demands are likely to experience blocking regardless of available bandwidth. To minimise the congestion and cost-effectively obtain high performance, the optical network must be reconfigurable, achievable by adding wavelength as an extra degree of freedom for effectiveness. This can introduce colourless, directionless and contentionless reconfigurability to route individual wavelengths from fibre to fibre across multiple nodes to avoid wavelength blocking/collisions, increasing the flexibility and capacity of a network. For these networks to function optimally, novel hardware and dynamic algorithms identification and development is a critical task. Such tasks include wavelength assignment, signal routing, network restoration and network protection. In this work, we for the first time to our knowledge proposed a spectrum defragmentation technique through reallocation of the central frequency of the optical transmitter, to increase the probability of finding a sufficient continuous spectrum. This is to improve network resource utilisation, capacity and resolve wavelength contention associated with a flexible spectrum in optical communication networks. The following chapter provides details on a flexible spectrum in optical fibre networks utilising DWDM, optimising transmitter-receivers, advanced modulation formats, coherent detection, reconfigurable optical add and drop multiplexer (ROADM) technology to implement hardware and middleware platforms which address growing bandwidth demands for scalability, flexibility and cost-efficiency. A major attribute is tunable lasers, an essential component for future flexible spectrum with application to wavelength switching, routing, wavelength conversion and ROADM for the multi-node optical network through spectrum flexibility and cost-effective sharing of fibre links, transmitters and receivers. Spectrum slicing into fine granular sub-carriers and assigning several frequency slots to accommodate diverse traffic demands is a viable approach. This work experimentally presents a spectral efficient technique for bandwidth variability, wavelength allocation, routing, defragmentation and wavelength selective switches in the nodes of a network, capable of removing the fixed grid spacing using low cost, high bandwidth, power-efficient and wavelength-tunable vertical-cavity surface-emitting laser (VCSEL) transmitter directly modulated with 10 Gbps data. This to ensure that majority of the spectrum utilisation at finer channel spacing, wastage of the spectrum resource as caused by the wavelength continuity constraint reduction and it improves bandwidth utilisation. The technique is flexible in terms of modulation formats and accommodates various formats with spectrally continuous channels, fulfilling the future bandwidth demands with transmissions beyond 100 Gbps per channel while maintaining spectral efficiency.
- Full Text:
- Date Issued: 2020
- Authors: Dlamini, Phumla Patience
- Date: 2020
- Subjects: Fiber optics
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/50666 , vital:42329
- Description: Flexible Spectrum Dense Wavelength Division Multiplexed (DWDM) optical fibre networks are next-generation technology for handling extremely high data rates of the kind produced by MeerKAT and SKA.We optimise the flexible spectrum for real-time dynamic channel wavelength assignment, to ensure optimum network performance. We needed to identify and develop novel hardware and dynamic algorithms for these networks to function optimally to perform critical tasks. Such tasks include wavelength assignment, signal routing, network restoration and network protection. The antennas of the Square Kilometre Array (SKA) network connect to the correlator and data processor in a simple point-to-point fixed configuration. The connection of the astronomer users to the data processor, however, requires a more complex network architecture. This is because the network has users scattered around South Africa, Africa and the whole world. This calls for upgrade of the classical fixed wavelength spectrum grids, to flexible spectrum grid that has improved capacity, reliable, simple and cost-effectiveness through sharing of network infrastructure. The exponential growth of data traffic in current optical communication networks requires higher capacity for the bandwidth demands at a reduced cost per bit. All-optical signal processing is a promising technique to improve network resource utilisation and resolve wavelength contention associated with the flexible spectrum. Flexible Spectrum Dense Wavelength Division Multiplexed (DWDM) optical fibre networks are next-generation technology for handling extremely high data rates of the kind produced by MeerKAT and SKA. Each DWDM channel is capable of 10 Gbps transmission rate, which is sliceable into finer flexible grid 12.5 GHz granularity to offer the network elastic spectrum and channel spacing capable of signal routing and wavelength switching for the scalability of aggregate bandwidth. The variable-sized portions of the flexible spectrum assignment to end users at different speeds depend on bandwidth demand, allowing efficient utilisation of the spectrum resources. The entire bandwidth of dynamic optical connections must be contiguously allocated. However, there is an introduction of spectrum fragmentation due to spectrum contiguity related to the optical channels having different width. Thus large traffic demands are likely to experience blocking regardless of available bandwidth. To minimise the congestion and cost-effectively obtain high performance, the optical network must be reconfigurable, achievable by adding wavelength as an extra degree of freedom for effectiveness. This can introduce colourless, directionless and contentionless reconfigurability to route individual wavelengths from fibre to fibre across multiple nodes to avoid wavelength blocking/collisions, increasing the flexibility and capacity of a network. For these networks to function optimally, novel hardware and dynamic algorithms identification and development is a critical task. Such tasks include wavelength assignment, signal routing, network restoration and network protection. In this work, we for the first time to our knowledge proposed a spectrum defragmentation technique through reallocation of the central frequency of the optical transmitter, to increase the probability of finding a sufficient continuous spectrum. This is to improve network resource utilisation, capacity and resolve wavelength contention associated with a flexible spectrum in optical communication networks. The following chapter provides details on a flexible spectrum in optical fibre networks utilising DWDM, optimising transmitter-receivers, advanced modulation formats, coherent detection, reconfigurable optical add and drop multiplexer (ROADM) technology to implement hardware and middleware platforms which address growing bandwidth demands for scalability, flexibility and cost-efficiency. A major attribute is tunable lasers, an essential component for future flexible spectrum with application to wavelength switching, routing, wavelength conversion and ROADM for the multi-node optical network through spectrum flexibility and cost-effective sharing of fibre links, transmitters and receivers. Spectrum slicing into fine granular sub-carriers and assigning several frequency slots to accommodate diverse traffic demands is a viable approach. This work experimentally presents a spectral efficient technique for bandwidth variability, wavelength allocation, routing, defragmentation and wavelength selective switches in the nodes of a network, capable of removing the fixed grid spacing using low cost, high bandwidth, power-efficient and wavelength-tunable vertical-cavity surface-emitting laser (VCSEL) transmitter directly modulated with 10 Gbps data. This to ensure that majority of the spectrum utilisation at finer channel spacing, wastage of the spectrum resource as caused by the wavelength continuity constraint reduction and it improves bandwidth utilisation. The technique is flexible in terms of modulation formats and accommodates various formats with spectrally continuous channels, fulfilling the future bandwidth demands with transmissions beyond 100 Gbps per channel while maintaining spectral efficiency.
- Full Text:
- Date Issued: 2020
Development of InSb/GaSb quantum dots by MOVPE
- Authors: Ahia, Chinedu Christian
- Date: 2018
- Subjects: Semiconductors , Quantum electronics Organometallic compounds
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/23382 , vital:30537
- Description: There has been an increasing interest in the modification of semiconductor band structures through the reduction of their dimensions, which simultaneously increases the band gap energy of the material and gives rise to flexibility in device properties. Advances in III-V antimony (Sb) based semiconductor fabrication have triggered the quest for extension of the emission/absorption wavelength range of this family of compounds for optoelectronic devices operating in the mid-infrared region of the electromagnetic spectrum. An interesting material system for mid-infrared (MIR) applications is indium antimonide (InSb) quantum dots (QDs) within a gallium antimonide (GaSb) matrix. However, its band alignment and emission wavelength has been the subject of some interest and controversy over the years. This study focuses on the development of InSb/GaSb QDs by metal organic vapour phase epitaxy (MOVPE). The samples were grown on different substrates using various growth parameters in order to vary the size, density and aspect ratio of the dots. Interfacial growth interruptions while flowing various source precursors through the reactor were investigated in order to influence the chemical termination of the surface, and hence the resulting strain in the structures. The samples were characterized using photoluminescence spectroscopy, scanning probe microscopy, scanning electron microscopy, X-ray diffraction and transmission electron microscopy. Likewise, the band alignment, energy levels, and carrier wave functions of the samples in this work were modelled theoretically using the nextnanomat software (version 3.1.0.0). A comparison of growth on two different GaSb substrates [(100) 2° off towards <111>B ± 0.1ᵒ and (111) ± 0.1ᵒ] using similar growth conditions yielded a higher dot density on the (100) substrate compared to the (111) substrate. This was attributed to the presence of terraces/atomic steps induced by the misorientation on the (100) substrate, which invariably gives rise to increased adsorption and an enhanced sticking coefficient of adatoms. Studies on the influence of a buffer layer on the morphology of uncapped dots showed that the shape and size of the dots are sensitive to the thickness of the buffer layer. In some case a corrugated buffer surface resulted, which introduced order in the arrangement of the dots, which formed preferentially inside the troughs. An increase in the V/III ratio from 1.0 to 3.0 was found to reduce the areal density of the QDs, while an analysis of the diameter histograms showed a narrowing of the size distribution with an increase in V/III ratio. The larger size distribution at low V/III was ascribed to the increase in indium species and the increased indium adatom migration length. This leads to increased dot density and nucleation sites, and thus triggers an increase in the conversion of tiny QDs into thermodynamically more suitable larger dots via coalescence. However, as the V/III ratio increased, the number of indium adatoms available for growth on the surface reduced, which automatically led to a decrease in the migration length of indium species which is unfavourable for the production of nucleation sites and to a decrease in dot density. Low growth rates were found to be beneficial for the growth of a high density (~5×1010cm-2) of QDs. Photoluminescence (PL) analysis of the capped samples at low temperature (~10 K), using an excitation power of 2 mW, showed a PL peak at ∼732 meV. Upon an increase in laser power to 120 mW, a blue shift of ∼ 8 meV was noticed. This emission typically persisted up to 60–70 K. An increase in the number of InSb QD-layers, was observed to cause an increase in the luminescence spectral line width and a long-wavelength shift of the PL lines, together with an enhancement in the strength of the PL emission. However, high resolution transmission electron microscopy (HRTEM) of the capped dots revealed the formation of an InGaSb quantum well-like structure, ∼10 nm thick, which was responsible for the PL signal mentioned above. The absence of QDs in the capped sample was attributed to inter-diffusion of Ga and In during the deposition of the cap layer, giving rise to a quantum well (QW) instead of the intended QDs. The presence of threading dislocations and stacking faults were also observed in the TEM micrographs of the samples containing multilayers, which can account for the fast quenching of the PL emission with increasing temperature from these samples. Theoretical simulations of the band alignment, wave functions and energy levels were in good agreement with the data collected from the PL spectra of the samples.
- Full Text:
- Date Issued: 2018
- Authors: Ahia, Chinedu Christian
- Date: 2018
- Subjects: Semiconductors , Quantum electronics Organometallic compounds
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/23382 , vital:30537
- Description: There has been an increasing interest in the modification of semiconductor band structures through the reduction of their dimensions, which simultaneously increases the band gap energy of the material and gives rise to flexibility in device properties. Advances in III-V antimony (Sb) based semiconductor fabrication have triggered the quest for extension of the emission/absorption wavelength range of this family of compounds for optoelectronic devices operating in the mid-infrared region of the electromagnetic spectrum. An interesting material system for mid-infrared (MIR) applications is indium antimonide (InSb) quantum dots (QDs) within a gallium antimonide (GaSb) matrix. However, its band alignment and emission wavelength has been the subject of some interest and controversy over the years. This study focuses on the development of InSb/GaSb QDs by metal organic vapour phase epitaxy (MOVPE). The samples were grown on different substrates using various growth parameters in order to vary the size, density and aspect ratio of the dots. Interfacial growth interruptions while flowing various source precursors through the reactor were investigated in order to influence the chemical termination of the surface, and hence the resulting strain in the structures. The samples were characterized using photoluminescence spectroscopy, scanning probe microscopy, scanning electron microscopy, X-ray diffraction and transmission electron microscopy. Likewise, the band alignment, energy levels, and carrier wave functions of the samples in this work were modelled theoretically using the nextnanomat software (version 3.1.0.0). A comparison of growth on two different GaSb substrates [(100) 2° off towards <111>B ± 0.1ᵒ and (111) ± 0.1ᵒ] using similar growth conditions yielded a higher dot density on the (100) substrate compared to the (111) substrate. This was attributed to the presence of terraces/atomic steps induced by the misorientation on the (100) substrate, which invariably gives rise to increased adsorption and an enhanced sticking coefficient of adatoms. Studies on the influence of a buffer layer on the morphology of uncapped dots showed that the shape and size of the dots are sensitive to the thickness of the buffer layer. In some case a corrugated buffer surface resulted, which introduced order in the arrangement of the dots, which formed preferentially inside the troughs. An increase in the V/III ratio from 1.0 to 3.0 was found to reduce the areal density of the QDs, while an analysis of the diameter histograms showed a narrowing of the size distribution with an increase in V/III ratio. The larger size distribution at low V/III was ascribed to the increase in indium species and the increased indium adatom migration length. This leads to increased dot density and nucleation sites, and thus triggers an increase in the conversion of tiny QDs into thermodynamically more suitable larger dots via coalescence. However, as the V/III ratio increased, the number of indium adatoms available for growth on the surface reduced, which automatically led to a decrease in the migration length of indium species which is unfavourable for the production of nucleation sites and to a decrease in dot density. Low growth rates were found to be beneficial for the growth of a high density (~5×1010cm-2) of QDs. Photoluminescence (PL) analysis of the capped samples at low temperature (~10 K), using an excitation power of 2 mW, showed a PL peak at ∼732 meV. Upon an increase in laser power to 120 mW, a blue shift of ∼ 8 meV was noticed. This emission typically persisted up to 60–70 K. An increase in the number of InSb QD-layers, was observed to cause an increase in the luminescence spectral line width and a long-wavelength shift of the PL lines, together with an enhancement in the strength of the PL emission. However, high resolution transmission electron microscopy (HRTEM) of the capped dots revealed the formation of an InGaSb quantum well-like structure, ∼10 nm thick, which was responsible for the PL signal mentioned above. The absence of QDs in the capped sample was attributed to inter-diffusion of Ga and In during the deposition of the cap layer, giving rise to a quantum well (QW) instead of the intended QDs. The presence of threading dislocations and stacking faults were also observed in the TEM micrographs of the samples containing multilayers, which can account for the fast quenching of the PL emission with increasing temperature from these samples. Theoretical simulations of the band alignment, wave functions and energy levels were in good agreement with the data collected from the PL spectra of the samples.
- Full Text:
- Date Issued: 2018
The social sustainability of low-cost housing: the role of social capital and sense of place
- Authors: Williams-Bruinders, Leizel
- Date: 2019
- Subjects: Housing -- South Africa , City planning -- South Africa Cities and towns -- Research Urban geography
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/44390 , vital:37161
- Description: In the past twenty years we have seen the South African government deliver the largest number of houses in the world (NDHS, 2011). However, this great effort does not appeal to the principles that policies have set out in terms of equality. Along with the delivery of this high level of state funded housing, many of the RDP dwellers feel as though they have been marginalised and forced out of the area of opportunity, namely, the CBD and the northern suburbs (Huchzermeyer, 2003). Many researchers believe that the South African housing delivery pattern resembles that of apartheid segregationist planning, which exacerbated the social inequalities in the country (Huchzermeyer, 2003; Donaldson, 2001; Harrison et al., 2003). To gain an in-depth understanding of the lived experiences of residents of a low-cost housing settlement, an interpretative phenomenological analysis was undertaken. The emergent themes emanating from the research study revealed that social problems were pertinent factors to the lack of formulation of community social cohesion. Without this aspect, community building will be hampered, and thus cohesive neighbourhoods will be lacking. To this end, social innovation is proposed as a solution to the Zanemvula development. The issue of social development needs to placed back on the housing agenda, as is stated in the latest Housing Act.
- Full Text:
- Date Issued: 2019
- Authors: Williams-Bruinders, Leizel
- Date: 2019
- Subjects: Housing -- South Africa , City planning -- South Africa Cities and towns -- Research Urban geography
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/44390 , vital:37161
- Description: In the past twenty years we have seen the South African government deliver the largest number of houses in the world (NDHS, 2011). However, this great effort does not appeal to the principles that policies have set out in terms of equality. Along with the delivery of this high level of state funded housing, many of the RDP dwellers feel as though they have been marginalised and forced out of the area of opportunity, namely, the CBD and the northern suburbs (Huchzermeyer, 2003). Many researchers believe that the South African housing delivery pattern resembles that of apartheid segregationist planning, which exacerbated the social inequalities in the country (Huchzermeyer, 2003; Donaldson, 2001; Harrison et al., 2003). To gain an in-depth understanding of the lived experiences of residents of a low-cost housing settlement, an interpretative phenomenological analysis was undertaken. The emergent themes emanating from the research study revealed that social problems were pertinent factors to the lack of formulation of community social cohesion. Without this aspect, community building will be hampered, and thus cohesive neighbourhoods will be lacking. To this end, social innovation is proposed as a solution to the Zanemvula development. The issue of social development needs to placed back on the housing agenda, as is stated in the latest Housing Act.
- Full Text:
- Date Issued: 2019