Dans le contexte actuel de recherche d’efficacité énergétique, c’est-à-dire de maîtrise de l’énergie incluant la valorisation de l’énergie perdue, ce projet de thèse propose de synthétiser et caractériser les propriétés thermoélectriques de la polyaniline dopée. Nous avons ainsi synthétisé plusieurs échantillons de polyaniline et étudié l’influence des conditions de synthèse, du taux de dopage, du type de dopant, du taux de cristallinité ou de la mise en forme du matériau fini sur leurs propriétés thermoélectriques. Tout d’abord, nous avons mesuré les dépendances en température des conductivités électriques et thermiques ainsi que du coefficient Seebeck de la polyaniline dopée à l’acide chlorhydrique (Pani/HCl). Nous avons montré que lors de la synthèse, une température de polymérisation basse (223K) permet d’obtenir de meilleures conductivités électriques et donc des propriétés thermoélectriques améliorées. D’autre part, la valeur de la pression utilisée pour compresser le matériau et le mettre en forme doit être assez élevée (1.109GPa) pour optimiser les performances thermoélectriques. Afin de mieux comprendre les propriétés de transport de la polyaniline dopée au chlorure, nous nous sommes ensuite intéressés à ses propriétés magnétiques et calorifiques. Les mesures de la susceptibilité magnétique et de la capacité calorifique du polymère dopé en fonction de la température ont ainsi permis de déterminer la nature de ses états électroniques et de déduire le type de transport au sein du polymère. Enfin, nous avons synthétisé et étudié la polyaniline dopée au camphresulfonate en faisant varier le taux de dopage entre 30% et 90%. Les mesures de conductivités électriques, thermiques et du coefficient Seebeck en fonction de la température montrent qu’un optimum peut être trouvé pour un taux de dopage de 50%. / In the actual frame of energy efficiency research, namely, the energy management including wasted energy, this PhD project deals with the synthesis and characterization of thermoelectric properties of doped polyaniline. Consequently, polyanilines have been synthesized and the effect of the synthesis conditions, the doping level, the type of dopant, the crystallinity or the sample preparation of the final material on the thermoelectric properties have been studied. Firstly, we measured the thermal dependencies of electrical and thermal conductivities as well as Seebeck coefficient hydrochloric acid doped polyaniline (Pani/HCl). We showed that a low polymerization temperature (223K) lead to better electric conductivity and so improved thermoelectric properties. On the other side, the pressure used to compress powders should as high as 1.109GPa to optimize the thermoelectric performance. Then, in order to have a better understanding of the transport properties of chloride doped polyaniline, we investigate the magnetic and thermal properties. Measurements of the specific heat and the magnetic susceptibility of chloride doped polyaniline as a function of the temperature allowed to determine the electronic states and the mechanism of transport in the polymer chains. Finally, we synthesized and studied camphorsulfonate doped polyaniline by varying the doping level between 30% and 90%. The electrical, thermal conductivities and Seebeck coefficient as a function of the temperature show clearly on optimum of doping level at 50% with camphorsulfonate doping agent.

<p>Coal provides for 77% of South Africa&rsquo / s primary energy needs and is therefore a major resource that supports the socio-economic needs of South African citizens. Power stations are the major consumers of coal in South Africa and produces electricity from burned coal. The burning of coal produces a large volume of ash that is disposed in the form of ash dump systems. The ash&nbsp / dump system is treated with high salinity process water from the power station for dust suppression. The process water contains salts due to evaporation processes from the recirculation&nbsp / &nbsp / of&nbsp / water in the cooling water system. Various studies to evaluate the sustainability of the ash dump system as a sustainable salt sink were therefore conducted. This study aimed to develop a conceptual model for the ash dump system by evaluating the movement of the process water trough the ash dump and the impacts it might have on the underlying weathered dolerite aquifer. This was achieved by evaluating the hydraulic and transport properties of the ash dump system. An initial site conceptual model was first established prior to the application of the hydraulic&nbsp / and transport methods. The initial conceptual model was based on the literature, previous reports and an initial site walk over. Known and tested hydraulic and transport methods were applied&nbsp / n bo.th field and laboratory scale for the saturated part of the ash dump system. The laboratory experiments comprised of column and core experiments. These methods assisted in&nbsp / parameter estimation of hydraulic and transport properties and also assisted in the planning of the field experiments. The field experiments were conducted in the form of slug tests, tracer&nbsp / dilution and natural gradient divergent tracer test experiments. The combined laboratory and field experiments provided statistically significant values that were then used as inputs into the&nbsp / conceptual model. Field experiments were also applied to a surrogate aquifer that represented the underlying shallow weathered dolerite aquifer of the ash dump system. The components of&nbsp / the updated conceptual model identified and investigated include the physical environment, the calculated hydraulic and transport properties.The ash dump can be conceptualized as a 20 to&nbsp / &nbsp / 30 meter high heap of consolidated clay size ash&nbsp / particles built on top of an underlying shallow weathered dolerite aquifer. The ash dup is directly connected to the underlying weathered&nbsp / dolerite aquifer. The saline water within the saturated zone has the ability to move through the ash dump system with hydraulic conductivities ranging between 10-1-10- 2 m/day, with flow&nbsp / velocities of 7-8m/day and effective porosities of 1%-2%. The hydraulic properties of the ash dump are, amongst others, controlled by the ash geology, contact time of the process water with the&nbsp / sh and show a significant reduction in hydraulic conductivity over time, before reaching a steady state. The transport properties are controlled by advection and spreading in available&nbsp / pathways. Results for the surrogate underlying fractured rock aquifer show flow velocities of 31m/day and an effective porosity of 1%.This suggests that the underlying weathered dolerite&nbsp / aquifer is vulnerable to process water contamination from the ash dump system. The study illustrates the importance of a site conceptual model before the application of investigative&nbsp / methods. Hence having a site conceptual model provides an excellent platform for hydraulic and transport estimation. The development of a site conceptual model enhanced the&nbsp / understanding of flow and transport movement of the processed&nbsp / water trough the ash dump, it also assisted as a beneficial tool to enhance ash dump management.</p>

<p>Coal provides for 77% of South Africa&rsquo / s primary energy needs and is therefore a major resource that supports the socio-economic needs of South African citizens. Power stations are the major consumers of coal in South Africa and produces electricity from burned coal. The burning of coal produces a large volume of ash that is disposed in the form of ash dump systems. The ash&nbsp / dump system is treated with high salinity process water from the power station for dust suppression. The process water contains salts due to evaporation processes from the recirculation&nbsp / &nbsp / of&nbsp / water in the cooling water system. Various studies to evaluate the sustainability of the ash dump system as a sustainable salt sink were therefore conducted. This study aimed to develop a conceptual model for the ash dump system by evaluating the movement of the process water trough the ash dump and the impacts it might have on the underlying weathered dolerite aquifer. This was achieved by evaluating the hydraulic and transport properties of the ash dump system. An initial site conceptual model was first established prior to the application of the hydraulic&nbsp / and transport methods. The initial conceptual model was based on the literature, previous reports and an initial site walk over. Known and tested hydraulic and transport methods were applied&nbsp / n bo.th field and laboratory scale for the saturated part of the ash dump system. The laboratory experiments comprised of column and core experiments. These methods assisted in&nbsp / parameter estimation of hydraulic and transport properties and also assisted in the planning of the field experiments. The field experiments were conducted in the form of slug tests, tracer&nbsp / dilution and natural gradient divergent tracer test experiments. The combined laboratory and field experiments provided statistically significant values that were then used as inputs into the&nbsp / conceptual model. Field experiments were also applied to a surrogate aquifer that represented the underlying shallow weathered dolerite aquifer of the ash dump system. The components of&nbsp / the updated conceptual model identified and investigated include the physical environment, the calculated hydraulic and transport properties.The ash dump can be conceptualized as a 20 to&nbsp / &nbsp / 30 meter high heap of consolidated clay size ash&nbsp / particles built on top of an underlying shallow weathered dolerite aquifer. The ash dup is directly connected to the underlying weathered&nbsp / dolerite aquifer. The saline water within the saturated zone has the ability to move through the ash dump system with hydraulic conductivities ranging between 10-1-10- 2 m/day, with flow&nbsp / velocities of 7-8m/day and effective porosities of 1%-2%. The hydraulic properties of the ash dump are, amongst others, controlled by the ash geology, contact time of the process water with the&nbsp / sh and show a significant reduction in hydraulic conductivity over time, before reaching a steady state. The transport properties are controlled by advection and spreading in available&nbsp / pathways. Results for the surrogate underlying fractured rock aquifer show flow velocities of 31m/day and an effective porosity of 1%.This suggests that the underlying weathered dolerite&nbsp / aquifer is vulnerable to process water contamination from the ash dump system. The study illustrates the importance of a site conceptual model before the application of investigative&nbsp / methods. Hence having a site conceptual model provides an excellent platform for hydraulic and transport estimation. The development of a site conceptual model enhanced the&nbsp / understanding of flow and transport movement of the processed&nbsp / water trough the ash dump, it also assisted as a beneficial tool to enhance ash dump management.</p>

Magister Scientiae - MSc / Coal provides for 77% of South Africa’s primary energy needs and is therefore a major resource that supports the socio-economic needs of South African citizens. Power stations are the major consumers of coal in South Africa and produces electricity from burned coal. The burning of coal produces a large volume of ash that is disposed in the form of ash dump systems. The ash dump system is treated with high salinity process water from the power station for dust suppression. The process water contains salts due to evaporation processes from the recirculation of water in the cooling water system. Various studies to evaluate the sustainability of the ash dump system as a sustainable salt sink were therefore conducted. This study aimed to develop a conceptual model for the ash dump system by evaluating the movement of the process water trough the ash dump and the impacts it might have on the underlying weathered dolerite aquifer. This was achieved by evaluating the hydraulic and transport properties of the ash dump system. An initial site conceptual model was first established prior to the application of the hydraulic and transport methods. The initial conceptual model was based on the literature, previous reports and an initial site walk over. Known and tested hydraulic and transport methods were applied n bo.th field and laboratory scale for the saturated part of the ash dump system. The laboratory experiments comprised of column and core experiments. These methods assisted in parameter estimation of hydraulic and transport properties and also assisted in the planning of the field experiments. The field experiments were conducted in the form of slug tests, tracer dilution and natural gradient divergent tracer test experiments. The combined laboratory and field experiments provided statistically significant values that were then used as inputs into the conceptual model. Field experiments were also applied to a surrogate aquifer that represented the underlying shallow weathered dolerite aquifer of the ash dump system. The components of the updated conceptual model identified and investigated include the physical environment, the calculated hydraulic and transport properties.The ash dump can be conceptualized as a 20 to 30 meter high heap of consolidated clay size ash particles built on top of an underlying shallow weathered dolerite aquifer. The ash dup is directly connected to the underlying weathered dolerite aquifer. The saline water within the saturated zone has the ability to move through the ash dump system with hydraulic conductivities ranging between 10-1-10- 2 m/day, with flow velocities of 7-8m/day and effective porosities of 1%-2%. The hydraulic properties of the ash dump are, amongst others, controlled by the ash geology, contact time of the process water with the sh and show a significant reduction in hydraulic conductivity over time, before reaching a steady state. The transport properties are controlled by advection and spreading in available pathways. Results for the surrogate underlying fractured rock aquifer show flow velocities of 31m/day and an effective porosity of 1%.This suggests that the underlying weathered dolerite aquifer is vulnerable to process water contamination from the ash dump system. The study illustrates the importance of a site conceptual model before the application of investigative methods. Hence having a site conceptual model provides an excellent platform for hydraulic and transport estimation. The development of a site conceptual model enhanced the understanding of flow and transport movement of the processed water trough the ash dump, it also assisted as a beneficial tool to enhance ash dump management. / South Africa