The chlorate process is very energy intensive and a major part of the production costs are for electrical energy. Since the electricity prices are constantly increasing and may also vary periodically, the chlorate plants may be forced to adjust their production rate to the price at each moment in order to minimise their costs. Variation of current load requires increased knowledge regarding the electrode behaviour in a wide current range. In this thesis, the aim was to study the impact of the electrolyte on the electrode reactions in order to reduce the energy consumption. The work has mainly been experimental and additionally mathematical modelling has been carried out. A wide current range has been investigated in order to increase the understanding of the phenomena and to obtain results useful for low-load operation during the periods of high electricity cost. To operate the anode as energy efficiently as possible, the anode potential should not exceed the critical potential (Ecr), where the slope of the anodic polarisation curve increases, most likely due to ruthenium(VIII)-formation, and where the side reaction of oxygen evolution increases. In this work, the influence of different electrolyte parameters on Ecr has been studied. It was shown that a higher chloride concentration and an increased temperature lowered Ecr, which was expected to increase the risk of exceeding Ecr. However, this was not observed due to a simultaneous favouring of the chloride oxidation. Hence it was concluded that the electrolyte parameters should be optimised so that the lowest possible anode potential is obtained, which would enable higher current densities without exceeding Ecr. A further conclusion is that the increased slope of the polarisation curve at Ecr was possibly related to the lower activity for chloride oxidation on ruthenium oxidised to ruthenium(VIII). At full-load operation, the cathode potential was shown to be rather independent of the electrolyte composition despite a large variation of electrolyte parameters. The cathode composition appears to be more critical than the electrolyte composition when aiming at reducing the energy consumption. A strategy to increase the cathode activity could be to in situ apply a catalytic film onto the electrode surface. Therefore, Y(III) was added to a chloride electrolyte in order to form a yttrium hydroxide film on the alkaline cathode surface during hydrogen evolution. The yttrium-hydroxide film activated reduction of water (hydrogen evolution) and hindered hypochlorite reduction, proton reduction and nitrate reduction. The inhibiting properties are important for the prevention of side reactions, which currently are avoided by reducing Cr(VI) of the electrolyte on the cathode, producing an inhibiting chromium-hydroxide film. The studies on Y(III) increase the expectations for finding alternatives to the toxic Cr(VI). The addition of chromate to the chlorate electrolyte gives a high cathodic current efficiency and chromate has buffering properties in the electrolyte. The role of the buffer has been investigated for the oxygen evolution from water (one possible anodic side reaction), as well as cathodic hydrogen evolution. Models have been developed for these systems to increase the understanding of the interaction between buffer, electrode reactions and mass transport; the results have been verified experimentally. The chromate buffer increased the limiting current significantly for the cathodic H+ reduction and the cathodic overpotential was reduced drastically at currents lower than the limited current. A too low overpotential could result in the cathodic protection being lost. The presence of chromate buffer increased the limiting current for the oxygen evolution from OH-. The modelling of these systems revealed that the homogeneous reactions connected to the electrode reactions were not in equilibrium at the electrode surface. Further, a good resolution of the interface at the electrode surface was crucial since the, for the electrode reactions, important buffering takes place in an nm-thick reaction layer. / Framställning av klorat är mycket energiintensiv och kräver stora mängder elenergi. Stigande elpriser, som dessutom ofta varierar under dygnet eller säsongsvis, gör att man vill reducera onödiga förluster samt ibland försöka anpassa produktionen så att man när elpriset är högt minskar den, för att sedan öka produktionen igen då elpriset sjunker. Denna flexibla drift kräver ny kunskap om hur elektroderna beter sig i ett större strömintervall än vad som tidigare varit av intresse. Målet med detta arbete var att, med fokus på elektrolytens betydelse, identifiera möjliga förbättringar för kloratprocessen och därmed minska energiförbrukningen. Studierna har i huvudsak varit experimentella men även matematisk modellering har använts. Ett brett strömintervall har undersökts för att bättre förstå fenomenen och för att även kunna använda resultaten då höga elpriser gör att man vill köra processen vid lägre laster än normalt. För att driften av anoden ska vara så energieffektiv som möjligt bör anodpotentialen inte överskrida den kritiska potentialen (Ecr), där den anodiska polarisationskurvan får en högre lutning (troligtvis pga Ru(VIII)-bildning) och bireaktionen syrgasutveckling ökar. I detta arbete har påverkan av olika elektrolytparametrar på Ecr undersökts. Det visade sig att en ökad kloridkoncentration och ökad temperatur sänkte Ecr. Trots att detta borde göra att Ecr lättare överskrids, blev inte detta fallet eftersom kloridoxidationen samtidigt gynnades. Slutsatsen blir därför att elektrolytparametrarna bör optimeras så att lägsta möjliga anodpotential uppnås, vilket då även gör att strömtätheten kan ökas utan att Ecr överskrids. Slutsatsen är vidare att polarisationskurvans högre lutning vid Ecr kan ha att göra med att rutenium oxiderat till rutenium(VIII) har lägre aktivitet för kloridoxidation. Vid full last visade sig katodens potential vara relativt oberoende av elektrolytsammansättningen trots att denna varierades kraftigt. Katodens sammansättning verkar vara viktigare att ta hänsyn till än elektrolytens för kunna åstadkomma en större energibesparing. Ett alternativ till att öka katodens aktivitet skulle vara att in-situ belägga elektrodytan med en katalytisk film. Försök gjordes att sätta till Y(III) till kloridelektrolyt för att under vätgasutveckling fälla ut en yttriumhydroxidfilm på den alkaliska katodytan. Yttriumhydroxidfilmen aktiverade vattenreduktion (vätgasutveckling) och inhiberade hypokloritreduktion, protonreduktion och nitratreduktion. De inhiberande egenskaperna är viktiga för att förhindra bireaktioner, vilka idag hindras av att Cr(VI) i elektrolyten reduceras på katoden och bildar en hindrande kromhydroxidfilm. Försöken med Y(III) visar att det finns goda möjligheter att hitta alternativ till det miljöfarliga Cr(VI). Kromattillsatsen i kloratelektrolyt ger förutom ett högt katodiskt strömutbyte även en buffrande effekt till elektrolyten. Effekten av buffert har undersökts för en av de anodiska bireaktionerna, syrgasutveckling ur vatten, samt för vätgasutvecklingen på katoden. Dessa system har modellerats för att bättre förstå samspelet mellan buffert, elektrodreaktioner och materietransport och resultaten har verifierats experimentellt. Kromatbufferten ökade gränsströmmen för katodisk H+-reduktion betydligt och katodöverpotentialen sjönk kraftigt vid lägre strömmar än gränsströmmen. Detta kan vara ett problem om överpotentialen sjunker så lågt att elektroden inte är katodiskt skyddad. För syrgasutvecklingen ökade närvaron av kromatbuffert gränsströmmen för syrgasutveckling ur OH-. Modellering av dessa system visar att de homogena reaktioner som var kopplade till elektrodreaktionerna inte var i jämvikt vid elektrodytan. Vidare visade det sig vara mycket viktigt med en bra upplösning av gränsskiktet vid elektrodytan, då den buffring som är viktig för elektrodreaktionerna sker i ett mycket tunt reaktionsskikt (nanometertjockt). / <p>QC 20100901</p>

Preconditioners based upon sweeps and diffusion-synthetic acceleration (DSA) have been constructed and applied to the zeroth and first spatial moments of the 1-D transport equation using SN angular discretization and a strictly positive nonlinear spatial closure (the CSZ method). The sweep preconditioner was applied using the linear discontinuous Galerkin (LD) sweep operator and the nonlinear CSZ sweep operator. DSA preconditioning was applied using the linear LD S2 equations and the nonlinear CSZ S2 equations. These preconditioners were applied in conjunction with a Jacobian-free Newton Krylov (JFNK) method utilizing Flexible GMRES. The action of the Jacobian on the Krylov vector was difficult to evaluate numerically with a finite difference approximation because the angular flux spanned many orders of magnitude. The evaluation of the perturbed residual required constructing the nonlinear CSZ operators based upon the angular flux plus some perturbation. For cases in which the magnitude of the perturbation was comparable to the local angular flux, these nonlinear operators were very sensitive to the perturbation and were significantly different than the unperturbed operators. To resolve this shortcoming in the finite difference approximation, in these cases the residual evaluation was performed using nonlinear operators "frozen" at the unperturbed local psi. This was a Newton method with a perturbation fixup. Alternatively, an entirely frozen method always performed the Jacobian evaluation using the unperturbed nonlinear operators. This frozen JFNK method was actually a Picard iteration scheme. The perturbed Newton's method proved to be slightly less expensive than the Picard iteration scheme. The CSZ sweep preconditioner was significantly more effective than preconditioning with the LD sweep. Furthermore, the LD sweep is always more expensive to apply than the CSZ sweep. The CSZ sweep is superior to the LD sweep as a preconditioner. The DSA preconditioners were applied in conjunction with the CSZ sweep. The nonlinear CSZ DSA preconditioner did not form a more effective preconditioner than the linear DSA preconditioner in this 1-D analysis. As it is very difficult to construct a CSZ diffusion equation in more than one dimension, it will be very beneficial if the results regarding the effectiveness of the LD DSA preconditioner are applicable to multi-dimensional problems.

The sharing of the terrestrial TV frequency spectrum with Secondary Users (SUs) is presently the focus point of numerous research efforts worldwide. In many regulatory domains, contiguous blocks of VHF and UHF spectrum are available for exclusive use by the terrestrial TV broadcasting incumbents. However, this notion is currently challenged by the spectrum management paradigm of Dynamic Spectrum Access (DSA), advocating that this spectrum may be shared on a dynamic basis with SUs. The migration of analogue terrestrial TV to Digital Terrestrial Television (DTT) has also catalysed the notion that the terrestrial TV frequency spectrum will no longer be exclusively used for terrestrial broadcasting. Some administrations have already embraced this technology, reforming spectrum policy to allow unlicensed secondary access to the Spectral Opportunities (SOs) present in the terrestrial TV frequency bands. The Independent Communications Authority of South Africa (ICASA) has expressed early interest in the possibilities of TV white space technology and its possible utility in exploiting the SOs that exist in the terrestrial TV frequency bands. Core to the issues mentioned above is the quantification of the Spectral Opportunity (SO) available. To this end, the work presented in this thesis gives a quantified estimate of the SO available in South Africa. This work is the first of its kind for the South African environment and uncovers new knowledge regarding SO in South Africa. SO is analysed and quantified on provincial and national level for three discrete points in time: before the start of dual-illumination, during dual illumination and after analogue switch-off. A system model that is able to produce the required geo-referenced field strength coverage and SO maps is conceptualised and implemented. A complete standards compliant model is implemented from scratch, verified and validated, with design decisions specific to the South African context. The analysis methodology is developed with rigour. The construction of the TV transmitter database, definition of incumbent protection criteria and development of the required analysis metrics to quantify SO are presented. SO in the VHF and UHF terrestrial TV frequency bands is quantified by expressing SO in terms of the number of available channels, weighted respectively by land area and population density. The analysis results indicate that significant SO is available for exploitation by TV white space devices in the terrestrial TV spectrum in South Africa. The effects of radio astronomy advantage areas on the SO available are also investigated. The probability of finding contiguous channels in the Very High Frequency (VHF) and Ultra High Frequency (UHF) bands is also quantified. A comparative study, comparing the SO for South Africa with related work in Europe and the United States of America (USA), is also performed. Finally, maps that visualise the SO available are constructed for the three discrete time periods evaluated. / Thesis (PhD (Computer Engineering))--North-West University, Potchefstroom Campus, 2013

The sharing of the terrestrial TV frequency spectrum with Secondary Users (SUs) is presently the focus point of numerous research efforts worldwide. In many regulatory domains, contiguous blocks of VHF and UHF spectrum are available for exclusive use by the terrestrial TV broadcasting incumbents. However, this notion is currently challenged by the spectrum management paradigm of Dynamic Spectrum Access (DSA), advocating that this spectrum may be shared on a dynamic basis with SUs. The migration of analogue terrestrial TV to Digital Terrestrial Television (DTT) has also catalysed the notion that the terrestrial TV frequency spectrum will no longer be exclusively used for terrestrial broadcasting. Some administrations have already embraced this technology, reforming spectrum policy to allow unlicensed secondary access to the Spectral Opportunities (SOs) present in the terrestrial TV frequency bands. The Independent Communications Authority of South Africa (ICASA) has expressed early interest in the possibilities of TV white space technology and its possible utility in exploiting the SOs that exist in the terrestrial TV frequency bands. Core to the issues mentioned above is the quantification of the Spectral Opportunity (SO) available. To this end, the work presented in this thesis gives a quantified estimate of the SO available in South Africa. This work is the first of its kind for the South African environment and uncovers new knowledge regarding SO in South Africa. SO is analysed and quantified on provincial and national level for three discrete points in time: before the start of dual-illumination, during dual illumination and after analogue switch-off. A system model that is able to produce the required geo-referenced field strength coverage and SO maps is conceptualised and implemented. A complete standards compliant model is implemented from scratch, verified and validated, with design decisions specific to the South African context. The analysis methodology is developed with rigour. The construction of the TV transmitter database, definition of incumbent protection criteria and development of the required analysis metrics to quantify SO are presented. SO in the VHF and UHF terrestrial TV frequency bands is quantified by expressing SO in terms of the number of available channels, weighted respectively by land area and population density. The analysis results indicate that significant SO is available for exploitation by TV white space devices in the terrestrial TV spectrum in South Africa. The effects of radio astronomy advantage areas on the SO available are also investigated. The probability of finding contiguous channels in the Very High Frequency (VHF) and Ultra High Frequency (UHF) bands is also quantified. A comparative study, comparing the SO for South Africa with related work in Europe and the United States of America (USA), is also performed. Finally, maps that visualise the SO available are constructed for the three discrete time periods evaluated. / Thesis (PhD (Computer Engineering))--North-West University, Potchefstroom Campus, 2013

Este trabalho investigou a oxidação eletroquímica do ácido tânico em eletrodos do tipo Ânodo Dimensionalmente Estáveis (ADE) a base de SnO2 e IrO2 e eletrodos de Diamante Dopado com Boro (BDD). As eletrólises foram feitas em modo galvanostático em função de parâmetros como densidade de corrente e concentração de cloreto. A oxidação eletroquímica do ácido tânico foi capaz de promover a diminuição da concentração de fenóis totais, Carbono Orgânico Total (COT) e Demanda Química de oxigênio (DQO). Para os ADE os melhores resultados de remoção de Carbono Orgânico Total (COT) foram nas condições em que se utilizou 300 mg L-1 de cloreto e densidade de corrente de 25 mA cm-2. No entanto houve a formação de compostos organoclorados que não foram degradados com maiores tempo de reação. Para os eletrodos de BDD, obteve-se a remoção de aproximadamente 98% de COT após 10 horas de reação à 75 mA cm-2, na ausência de cloreto. Maiores remoções de COT são obtidas com o aumento da densidade de corrente. Eletrólises na presença de cloreto removeram quase 100% do COT em tempos menores de reação. Análises de compostos organohalogenados (AOX) mostraram que não houve a formação de compostos organoclorados. Menores densidades de corrente apresentaram maiores Eficiência de Corrente (EC) e menor Consumo de Energia (CE). As eletrólises na presença de cloro apresentaram melhores resultados de EC que na ausência do mesmo. A oxidação fotoeletroquímia do ácido tânico em eletrodos do tipo ADE de composição nominal Ti/ Sn0,7 Ir0,3 O2 também foi investigada nesse trabalho. O tratamento fotoeletroquímico foi realizado utilizando uma lâmpada de vapor de mercúrio de alta pressão de 125 W como fonte de irradiação. A variação da corrente não mostrou diferença significativa na oxidação do ácido tânico. A variação da concentração de cloreto no eletrólito suporte influenciou de forma acentuada a oxidação do ácido tânico. O tratamento fotoeletroquímico se mostrou mais eficiente na remoção de COT que os tratamentos eletroquímico e fotoquímico. No tratamento fotoeletroquímico ocorreu a formação de AOX no início da reação, no entanto com o passar do tempo esses compostos foram degradados. / This study investigated the electrochemical oxidation of tannic acid on electrodes of the Dimensionally Stable Anode (DSA) type based on SnO2 and IrO2 as well as on boron doped diamond (BDD) electrodes. The electrolyses were performed in the galvanostatic mode, as a function of such parameters as current density and chloride concentration. The electrochemical oxidation of tannic acid was able to promote the reduction of the concentration of total phenolics, total organic carbon (TOC), and chemical oxygen demand (COD). For the DSA the best results of Total Organic Carbon (TOC) removal were achieved at 300 ppm chloride and current density of 25 mA cm-2. However, organochlorine compounds were formed and were not degraded with increased reaction times. For the BDD electrodes, the removal of approximately 98% TOC was obtained after 10 hours of reaction at 75 mA cm-2, in the absence of chloride. Major TOC removals were obtained with increasing current density. Electrolyses in the presence of chloride removed almost 100% TOC in shorter reaction times. Analysis of organohalogen compounds (AOX) showed no formation of organochlorine compounds. Lower current densities led to higher current efficiency (CE) and lower Energy Consumption (EC). The electrolyses in the presence of chlorine produced better CE results than those performed in the absence of chlorine. The photoelectrochemical oxidation of tannic acid in ADE-type electrodes of nominal composition Ti / Sn0.9 Ir0.3 O2 was also investigated in this work. The photoelectrochemical treatment was performed using a high pressure mercury vapor lamp 125 W as the source of irradiation. The variation in current revealed no significant difference in the oxidation of tannic acid. The variation in chloride concentration in the electrolyte markedly influenced the oxidation of tannic acid. The photoelectrochemical treatment was more efficient for TOC removal than the electrochemical and photochemical treatments. Formation of AOX occurred at the beginning of the photoelectrochemical treatment, but over time these compounds were degraded.

Una parte importante del trabajo desarrollado en la presente tesis está basado en la puesta a punto y aplicación de la técnica de la microscopía electroquímica de barrido (SECM). Con esta técnica se han caracterizado electroquímicamente superficies sobre las que se han sintetizado una serie de materiales electroactivos desarrollados por nuestro grupo de investigación. Dichos materiales se sintetizan sobre diferentes substratos con el fin de disponer de electrodos de trabajo con aplicación en el contexto del tratamiento electroquímico de aguas residuales contaminadas con colorantes azoicos, provenientes de procesos de tintura en industrias textiles. Entre las superficies desarrolladas se incluyen: ¿ Ánodos dimensionalmente estables (DSAs) fabricados a partir de una superficie de Ti recubierta de SnO2 (Ti/SnO2), dopada con Sb (Ti/SnO2-Sb) y estabilizada con Pt (Ti/SnO2-Sb-Pt). ¿ Un tejido de poliéster (PES) recubierto de polipirrol (PPy) dopado con antraquinona sulfonato (PES/PPy-AQSA) o fosfotungstato (PES/PPy- PW12O403-). ¿ Un tejido de PES recubierto de polianilina (PANI) sintetizada en medios sulfúrico (PES/PANI-HSO4-) y clorhídrico (PES/PANI-Cl-). ¿ Un hilo de Pt recubierto de PANI con Pt electrodispersado (Pt/PANI-Pt). ¿ Un tejido de fibra de carbono recubierto de PANI (C/PANI) con o sin Pt electrodispersado (C/PANI-Pt). ¿ Un tejido de PES recubierto con óxido de grafeno (GO) o con su forma reducida (RGO). Los análisis locales efectuados a las superficies anteriormente descritas permitieron determinar su electroactividad frente a los pares redox Fe(CN)63-/4- y Ru(NH3)63+/2+ seleccionados como mediadores. Las curvas experimentales de aproximación obtenidas con el sistema en modo feedback, se compararon con las curvas teóricas establecidas por la teoría SECM para un substrato conductor (feedback +) y un substrato aislante (feedback -). Las imágenes SECM en 2D y 3D permitieron observar la distribución de la actividad electroquímica superficial para las diferentes muestras. Los resultados obtenidos con la microscopía SECM se utilizaron para validar los procedimientos de síntesis del material electroactivo en lo concerniente a su electroactividad y a la homogeneidad de su distribución. Las superficies textiles presentan una topografía muy irregular en comparación con la superficie metálica de un DSA. Aspecto especialmente reseñable en las muestras textiles es la influencia que ejerce la topografía del substrato textil en la imagen SECM de la electroactividad con el microelectrodo moviéndose a altura constante con respecto al substrato. En este sentido, las imágenes SECM obtenidas sobre las muestras textiles muestran como la electroactividad superficial reproduce el patrón geométrico del tejido. La influencia en la actividad electroquímica de aspectos tales como: tiempo de vida útil/corrosión en el caso de los DSAs, tipo de dopante/pH en el caso de la superficie PES/PPy, influencia del pH en las muestras de PES/PANI, el estado de oxidación de la especie electroactiva y la influencia del mediador (par redox) en el caso del grafeno, ha quedado puesta de manifiesto claramente en los estudios efectuados con la microscopía SECM. Una segunda parte importante del trabajo realizado en la presente tesis, se desarrolla como continuación a los trabajos que el grupo de investigación viene realizando dentro del contexto del tratamiento electroquímico de colorantes azoicos en disolución acuosa. Así, en el capítulo 2 de la presente tesis, se estudia el desarrollo, caracterización y aplicación de una serie de electrodos fabricados a partir de un tejido activo de fibra de carbono. El objetivo que persigue el desarrollo de estos electrodos está en su aplicación a procesos industriales tales como: la electrooxidación de moléculas relativamente sencillas como por ejemplo metanol o, de acuerdo con nuestra línea de investigación, para el tratamiento electroquímico de aguas contaminadas con colorantes azoicos provenientes de los procesos de tintura en industrias textiles. Entre los electrodos textiles de fibra de carbono desarrollados en el capítulo 2 de la presente tesis se incluyen: ¿ Electrodos textiles de carbono sin modificar. ¿ Electrodos textiles de carbono modificados con Pt disperso. ¿ Electrodos textiles de carbono recubiertos de PPy o PANI. ¿ Electrodos textiles de carbono recubiertos de PPy o PANI con Pt disperso. Dos tipos de geometrías se eligieron a la hora de fabricar los electrodos de fibra de carbono anteriormente citados. Los electrodos monodimensionales (WE1D) fueron preparados a partir de una hebra tomada del propio tejido. Los electrodos bidimensionales (WE2D) se prepararon a partir de una banda de (1 cm x 3 cm) cortada del tejido de carbono. Por medio de la voltametría cíclica (CV) y utilizando los WE1D se establecieron las condiciones de síntesis para la fabricación de los WE2D modificados. Además, por medio de la CV se estudió la respuesta electroquímica de los WE1Ds en diferentes sistemas electroquímicos tales como: una disolución de H2SO4, una disolución de CH3OH/H2SO4 y una disolución de amarante/H2SO4. Para este último sistema, además, se utilizó un electrodo de carbono vítreo (GCE) ya que proporcionaba una respuesta voltamétrica más precisa que la obtenida con los WE1Ds. En la caracterización electroquímica que se realizó a los electrodos WE2D, la microscopía SECM jugó un papel relevante. Con la configuración 2D no era posible obtener voltagramas precisos que nos permitieran observar el comportamiento electroquímico de los diferentes WE2D modificados. Con la microscopía SECM, sí se pudo medir la actividad electrocatalítica de las diferentes superficies validándose, entonces, las condiciones de síntesis utilizadas. Algunas de estas condiciones, como los rangos de potencial, se habían establecido previamente para los WE1D. Así, la microscopía SECM se muestra como alternativa a la CV para la medida de la electroactividad superficial y de la distribución del material electrocatalítico para este tipo de muestras. Además de la caracterización electroquímica, se realizó también una caracterización morfológica de las superficies electródicas mediante la toma de imágenes por medio de la microscopía electrónica de barrido (SEM) y del microscopio estereoscópico. El estudio voltamétrico efectuado para el sistema amarante/H2SO4 con los electrodos textiles WE1D y el electrodo GCE permitió el establecimiento de los potenciales de trabajo a los que realizar la electrólisis de oxidación y de reducción a potencial controlado con los electrodos WE2D, WE2D/Pt y WE2D/PANI-Pt. Con los electrodos de trabajo anteriores, se llevan a cabo diferentes electrólisis de electroreducción y electrooxidación a una disolución de amarante en medio sulfúrico utilizando una célula en forma de ¿H¿ con separación de compartimentos. El seguimiento del proceso de degradación de la molécula de amarante y por ende de la decoloración de la disolución, se efectuó por medio de la cromatografía líquida de alta resolución (HPLC) y las espectroscopías UV-visible, fluorescencia de emisión e infrarroja por transformada de Fourier con reflexión total atenuada (FTIR-ATR). Los resultados de eficiencia obtenidos en las electrólisis confirman la elección de los potenciales de trabajo seleccionados. El porcentaje de decoloración tanto con las electroreducciones como con las electrooxidaciones se sitúa por encima del 90 %. También se comprobó que la presencia de platino trae consigo una significativa reducción del tiempo de electrólisis para la electrooxidación a 900 mV. Los análisis de los espectros UV, de fluorescencia de emisión y FTIR-ATR permitieron establecer diferencias significativas en relación con el tipo de proceso electroquímico (electroreducción/electrooxidación), tipo de electrodo (modificado/no modificado) y la presencia/ausencia de cloruros en el medio de reacción. Con este trabajo se establece una metodología de cara a futuros estudios con otros colorantes azoicos utilizando electrodos basados en el tejido de fibra de carbono. / Fernández Sáez, J. (2014). Análisis por microscopía electroquímica de barrido de superficies electroactivas y desarrollo-caracterización de electrodos basados en un tejido de fibra de carbono [Tesis doctoral]. Editorial Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/38239 / Alfresco

Made available in DSpace on 2014-06-12T15:56:27Z (GMT). No. of bitstreams: 2 arquivo2929_1.pdf: 906828 bytes, checksum: b1fc906ed4fd92af1b2dac3b10567a00 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2009 / Leilões na internet são hoje uma indústria muito popular e rentável. Muitas empresas, como eBay e Arremate, têm investido em leilões não presenciais. O fato dos participantes não serem obrigados a estarem num mesmo local trouxe muitos benefí- cios, porém também trouxe muitas formas de se trapacear. Existem vários mecanismos de fraude e muitos protocolos seguros foram criados para solucioná-los. Esses protocolos são baseados em muitos conceitos criptográficos como: Assinatura de Grupo, Criptografia de Limiar, Assinatura de Schnorr e Assinatura baseada em prova de conhecimento. Cada solução utilizada para atender características de cada tipo de leilão. Nessa dissertação apresentaremos um protocolo seguro para leilões eletrônicos re- versos. O protocolo apresentado é baseado naqueles propostos por Byoungcheon Lee, Kwangjo Kim e Joongsoo [Lee et al., 2001] e por Chung [Chung et al., 2008] que fun- cionam muito bem para leilões ingleses e reversos (holandeses). Nosso protocolo vem a resolver problemas encontrados com o uso de certificação digital e apresenta um módulo para evitar técnicas de fraude conhecidas como Collusive Shill Biddings e Sniping

To solve the spectrum scarcity problem caused by the high number of wireless applications and users, the concept of cognitive radio (CR) was proposed in the past few years. Cognitive radio networks (CRNs) provide dynamic spectrum access (DSA), where the unlicensed users can access the spectrum without causing unacceptable level of interference to the primary user (PU). DSA was based on conventional spectrum sensing information or geolocation databases. Later, radio environment map (REM) as an improved geolocation database was introduced to enhance the DSA process. It is a comprehensive map consists of different integrated databases, and the interference field information is one of its databases. In this thesis, a description of the REM concept and its construction methods will be presented. The focus will be for the indirect methods for constructing interference map, which represents a layer of the REM. Indirect method refers to the methods that utilize known model information, to first estimate the primary transmitter parameters and then generate REM. Two indirect methods under lognormal shadowing were presented and compared. The better of these two methods is further investigated in different scenarios. These scenarios include different number of sensors, varied size of measurements, several shadowing spread values, different percentages of error in path-loss exponent, and the effect of the number of moving sensors and their speeds to the REM quality. The performance is evaluated using these metrics: “localization error, signal power error and correct detection zone ratio (CDZR). The results show that performance is enhanced as the number of sensors and the size of measurements increase, whereas clear degradation in REM quality is shown when shadowing spread increases or the model parameters are not well calibrated. Also, as the number of moving sensors or their speeds increase, the REM performance becomes less effective

ELECTROCHEMICAL TREATMENT OF DYE DISSOLUTIONS OBTAINED FROM THE MIXTURE OF HYDROLYZED BIFUNCTIONAL REACTIVE DYES In this Doctoral Thesis the degradation of the three reactive dyestuffs that make up the Tricromia Procion HEXL is studied by applying the oxidation-reduction electrochemical treatment to 125mA/cm2 in a filter-press cell using a stainless steel cathode, and as anode, an Ti / SnO2-Sb-Pt type DSA electrode are used. The degree of decolorization / mineralization is evaluated by Total Organic Carbon (TOC), Total Nitrogen (TN) and Chemical Oxygen Demand (COD), data that also allow us to know Average Oxidation State (AOS) at the end of each as well as information on the efficiency in each case through the Carbon Oxidation State (COS), State of Average Oxidation (EOP), Instantaneous Currente Efficiency (ICE) and Average Current Efficiency (ACE). The kinetics of discoloration and the evolution of the generated intermediates have been studied through measurements of High Resolution Liquid Chromatography (HPLC). The spectra obtained through UV-Visible Spectroscopy and FTIR allows us to follow the discoloration from the initial and final state of the solutions after the electrolysis. The main objective is to obtain discolored water with organic matter contents significantly lower than the initial values and to study the possibility of reuse of these purified waste water in subsequent dyeing processes. In this first part of the work we studied the electrochemical treatment for the degradation of these dyes using solutions with the hydrolyzed dyes. Na2SO4 is used as electrolyte. Next, we study the degradation and electrochemical behavior of baths containing the dyes: Procion Yellow HEXL, Procion Crimson HEXL and Procion Navy HEXL after the dyeing of cotton fabrics. Dyes are made at the laboratory level, subsequently the waters resulting from these dye baths are subjected to an electrochemical oxidation-reduction treatment at 125mA / cm2 in a filter-press cell. Proceed to study and to verify that these treated waters can be reused in later dyes obtaining acceptable values of equalization in the dyed tissues. We perform a color equalization study of the cotton fabrics tinted with the dyes of the Tricromia Procion HEXL, using solutions with different proportions of distilled water and recovery water and verify the equalization of the same, the data that we obtain from this study indicate us that good results are obtained from mixtures of 70% recovery water and 30% water. The color differences obtained in the fabrics dyed in the reuses are below the maximum limit of acceptance of color differences in the textile industry, which is one unit (DECMC(2:1) ¿ 1). Subsequently we study the degradation and mineralization of the bath resulting from the dyeing of cotton fabrics at the laboratory level with a mixture of the colorants the Tricromia Procion HEXL using NaCl as electrolyte by subjecting these baths to a treatment Oxide-reduction electrochemical at 125mA/cm2 in a filter-press cell. In all cases a decrease of COD, TOC and TN is obtained, AOS and COS data indicate that the oxidation state of Carbon in all solutions increases, the ACE and COS results show that the process takes place in a way efficient. The discoloration kinetics of all processes correspond to pseudo-first order, UV-Visible spectroscopy reveals that the bands corresponding to the chromophore group of the dyes are eliminated. This treatment of successive dyes and discolorations could be a viable alternative in the purification of actual textile effluents containing this type of dyes. / TRATAMIENTO ELECTROQUÍMICO DE DISOLUCIONES DE TINTURAS OBTENIDAS A PARTIR DE LA MEZCLA DE COLORANTES REACTIVOS BIFUNCIONALES HIDROLIZADOS Se estudia la degradación de los tres colorantes reactivos bifuncionales que componen la Tricromía Procion HEXL mediante la aplicación del tratamiento electroquímico de óxido-reducción a 125mA/cm2 en una célula filtro-prensa empleando un cátodo de acero inoxidable, y como ánodo se utiliza un electrodo tipo DSA de Ti/SnO2-Sb-Pt. Se evalúa el grado de decoloración/mineralización mediante medidas de Carbono Orgánico Total (COT), Nitrógeno Total (TN) y Demanda Química de Oxigeno (DQO), datos que además nos permiten conocer el Estado de Oxidación Promedio (EOP) al final de cada electrolisis, así como información de la eficiencia en cada caso a través del Estado de Oxidación del Carbono (EOC), Eficiencia en Corriente Instantanea (ECI) y Eficiencia en Corriente Promedio (ECP). La cinética de decoloración y la evolución de los intermedios generados se han estudiado a través medidas de Cromatografía Liquida de Alta Resolución (HPLC). Los espectros obtenidos a través de Espectroscopia UV-Visible y FTIR nos permiten hacer un seguimiento de la decoloración desde el estado inicial y final de las disoluciones tras la electrolisis. El objetivo principal es obtener aguas decoloradas con contenidos en materia orgánica sensiblemente inferiores a los valores iniciales y estudiar la posibilidad de reutilización de esas aguas residuales depuradas en posteriores procesos de tintura. En la primera parte del trabajo se estudió el tratamiento electroquímico para la degradación de estos colorantes empleando disoluciones con los colorantes hidrolizados. Se utiliza Na2SO4 como electrolito. Seguidamente se estudia la degradación y comportamiento electroquímico de baños que contienen los colorantes: Procion Yellow HEXL, Procion Crimson HEXL y Procion Navy HEXL tras la tintura de tejidos de algodón. Se realizan tinturas a nivel de laboratorio, posteriormente las aguas resultantes de estos baños de tintura se someten a un tratamiento electroquímico de óxido-reducción a 125mA/ cm2 en una célula filtro-prensa. Se procede a estudiar y verificar que estas aguas tratadas pueden ser reutilizadas en posteriores tinturas obteniendo valores aceptables de igualación en los tejidos teñidos. Se realiza un estudio de igualación del color de los tejidos de algodón tintados con los colorantes de la Tricromía Procion HEXL, utilizando disoluciones con distintas proporciones de agua destilada y agua de recuperación y comprobando la igualación de las mismas, los datos obtenidos en este estudio nos indican que se consiguen buenos resultados a partir de mezclas de 70% agua de recuperación y 30% agua. Las diferencias de color obtenidas en los tejidos tintados en cuatro reutilizaciones son inferiores al límite máximo de aceptación de diferencias de color en la industria textil, que es de una unidad (DECMC(2:1) ¿ 1). Posteriormente hemos estudiado la degradación y mineralización del baño resultante de la tintura de tejidos de algodón a nivel de laboratorio con una mezcla de los colorantes de la Tricromía Procion HEXL utilizando NaCl como electrolito al someterlos a un tratamiento electroquímico de óxido-reducción a 125mA/ cm2 en una célula filtro-prensa. En todos los casos se obtiene una disminución de DQO, COT y TN, los datos de EOP y EOC nos indican que aumenta el Estado de Oxidación del Carbono en todas las disoluciones, los resultados de ECP y EOC demuestran que el proceso tiene lugar de forma eficiente. La cinética de decoloración de todos los procesos corresponde a pseudo-primer orden, la espectroscopia UV-Visible revela que las bandas correspondientes al grupo cromóforo de los colorantes son eliminadas. Este tratamiento de sucesivas tinturas y decoloraciones podría ser una alternativa viable en la depuración de efluentes textiles reales que contienen es / TRACTAMENT ELECTROQUÍMIC DE DISSOLUCIONS DE TINTURES OBTINGUDES A PARTIR DE LA MESCLA DE COLORANTS REACTIUS BIFUNCIONALES HIDROLITZATS En la present Tesi Doctoral s'estudia la degradació dels tres colorants reactius bifuncionals que componen la Tricromia Procion HEXL mitjançant l'aplicació del tractament electroquímic d'òxid-reducció a 125mA/cm2 en una cèl¿lula filtre-premsa emprant un càtode d'acer inoxidable, i com a ànode s'utilitza un elèctrode tipus DSA de Ti/SnO2-Sb-Pt. S'avalua el grau de decoloració/mineralització mitjantçant mesures de Carboni Orgànic Total (COT), Nitrogen Total (TN) i Demanda Química d'Oxigen (DQO), dades que a més ens permeten conéixer l'Estat d'Oxidació Mitjana (EOM) al final de cada electròlisi, així com informació de l'eficiència en cada cas a través de l'Estat d'Oxidació del Carboni (EOC) , Eficiència en Corrent Instantània (ECI) i Eficiència en Corrent Mitjana (ECM). La cinètica de decoloració i l'evolució dels intermedis generats s'han estudiat a través de mesures de Cromatografia Liquida d'Alta Resolució (HPLC). Els espectres obtinguts a través d'Espectroscòpia UV-Visible i FTIR ens permet fer un seguiment de la decoloració des de l'estat inicial i final de les dissolucions després de l'electròlisi. L'objectiu principal és obtindre aigües decolorades amb continguts en matèria orgànica sensiblement inferiors als valors inicials i estudiar la possibilitat de reutilització d'eixes aigües residuals depurades en posteriors processos de tintura. A la primera part del treball es va estudiar el tractament electroquímic per a la degradació d'estos colorants emprant dissolucions amb els colorants hidrolitzats. S¿utilitza Na2SO4 com electròlit. A continuació s'estudia la degradació i comportament electroquímic de banys que contenen els colorants: Procion Yellow HEXL, Procion Crimson HEXL i Procion Navy HEXL després de la tintura de teixits de cotó. Es realitzen tintures a nivell de laboratori, posteriorment les aigües resultants d'estos banys de tintura se sotmeten a un tractament electroquímic d'òxid-reducció a 125mA/cm2 en una cèl¿lula filtre-premsa. Procedim a estudiar i verificar que estes aigües tractades poden ser reutilitzades en posteriors tintures aconseguint valors acceptables d'igualació en els teixits tenyits. Es realitza un estudi d'igualació del color dels teixits de cotó tintats amb els colorants de la Tricromia Procion HEXL, utilitzant dissolucions amb distintes proporcions d'aigua destil¿lada i aigua de recuperació i comprovant la igualació de les mateixes, les dades obtingudes en este estudi ens indiquen que s¿aconsegueixen bons resultats a partir de mescles de 70% aigua de recuperació i 30% aigua. Les diferències de color obtingudes en els teixits tintats en les quatre reutilitzacions són inferiors al límit màxim d'acceptació de diferències de color en la indústria tèxtil que és d'una unitat (DECMC(2:1) ¿ 1). Posteriorment hem estudiat la degradació i mineralització del bany resultant de la tintura de teixits de cotó a nivell de laboratori amb una mescla dels colorants de la Tricromia Procion HEXL, utilitzant NaCl com a electròlit al sotmetre'ls a un tractament electroquímic d'òxid-reducció a 125mA/cm2 en una cèl¿lula filtre-premsa. En tots els casos s'obté una disminució de DQO, COT i TN, les dades d'EOP i EOC ens indiquen que augmenta l'estat d'Oxidació del Carboni en totes les dissolucions, els resultats d'ECP i EOC demostren que el procés té lloc de forma eficient. La cinètica de decoloració de tots els processos correspon a pseudo-primer ordre, l'espectroscòpia UV-Visible revela que les bandes corresponents al grup cromóforo dels colorants són eliminades. Este tractament de successives tintures i decoloracions podria ser una alternativa viable en la depuració d'efluents tèxtils reals que contenen este tipus de colorants. / Orts Maiques, FJ. (2017). TRATAMIENTO ELECTROQUÍMICO DE DISOLUCIONES DE TINTURAS OBTENIDAS A PARTIR DE LA MEZCLA DE COLORANTES REACTIVOS BIFUNCIONALES HIDROLIZADOS [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/86153 / TESIS

Current needs of human communication came to status, when most of transferred messages are considered as private and transition over non-secured communication lines in open form is not possible. That originated a lot of different methods for securing of messages and transfers in ciphered form. Two mainstreams were established, symmetric cryptography and asymmetric cryptography. Second of mentioned groups is based on usage of two information – keys, when one of then is broadly known and is public and second, well protected and private. Using a public key it is possible to establish a cryptogram of message, but for deciphering it is necessary to know private key. Asymmetric methods are based on mathematical problems, for which there is not an effective computing algorithm. This thesis are focused for asymmetric cryptosystems based on discrete logarithm problem, where ciphering of message using public key is very easy and quick, but deciphering without knowledge of private key is extremely time consuming process. Work describes a mathematical base of discrete logarithm problem, its’ properties and methods developed for solving of this problem. Descriptions of particular cryptosystems are given, i.e. ElGamal cryptosystem, Diffie-Hellman protocol and DSA. Second part of thesis is focused for web application developed as study support of discrete logarithm problem and of cryptosystems using this problem. It describes functional and graphical interface, work with it and options given to user working with application. Mentions also lessons for user which should help with understanding of described problems and practicing.