Rozprawy doktorskie na temat „Electrochemical technique”

This thesis aims to investigate structural, optical and photoelectrochemical behavior of CdS nanowires and their heterojunctions with CdTe and polypyrrole nanowires. In the first part, CdS nanowires have been synthesized via electrochemical template-based route. It has been observed that synthesis conditions, such as bias voltage and deposition time, affect the morphology, optical and photoelectrochemical characteristics of CdS nanowires. Depending on the deposition time, length of the CdS nanowires changed from 100-200 nm to 3-4 m. Also the diameter of the nanowires increased with increasing the deposition time. Structure of the CdS nanowires has been confirmed by X-ray diffraction spectrometry and EDX analysis. Phototelectrochemical performances of the CdS nanowires have been changed dramatically with bias voltage and deposition time.In the second part of this thesis, CdTe nanostructures have been deposited on CdS nanowires. Change in optical and photoelectrochemical behavior of CdS nanowires after CdTe deposition has been investigated. Organic semiconductors and their composites with inorganic materials have been gaining attention due to tunable optical, electrical and magnetic properties. Also, ease of fabrication techniques, and therefore, low cost made these materials attractive for lots of applications including photovoltaic devices and flexible electronics. In the last part of this thesis, heterojunctions of CdS and Polypyrrole (Ppy) nanowires have been synthesized. Like CdS/CdTe heteronanostructures, first the CdS nanowires have been electrochemically deposited in anodized alumina template and then Ppy has been successfully deposited on CdS nanowires. In order to investigate the effects of polypyrrole synthesis conditions on CdS/Ppy heteronanostructures, CdS nanowire synthesis conditions have been kept constant. It has been observed that morphology and photoelectrochemical behavior of the Ppy nanowires has been affected from Ppy synthesis conditions. The photoelectrochemical performance changes of CdS/Ppy heteronanostructures have been also investigated in this part.

Aniline was chosen as an atmospheric pollutant which might be monitored using an electrochemical sensor. The effect of pH and of different organic solvents on electrode poisoning was investigated for the analysis of aniline by voltammetry and it was concluded that it was not possible to prevent poisoning of the electrode by the reaction products. The analysis of aniline by flow injection analysis (fia) with DC (constant potential) and pulsed (double pulse) amperometric detection also suffered from electrode poisoning and the latter had a relatively high detection limit. Secondary and tertiary substituted anilines with similar volatilities to aniline at room temperature were examined as suitable alternatives to aniline using voltammetry. Dimethyl-p-toluidine poisoned the electrode to a small extent when analysed by voltammetry. Detection of this compound by fia with pulsed amperometric detection showed improved electrode stability but was not judged suitable for long term monitoring of atmospheric samples of the amine. A satisfactory method for monitoring aniline on line was developed using fia with triple pulse amperometric detection (PAD). The PAD waveform was optimised with respect to a low detection limit and a degree of selectivity towards possible atmospheric interferents for the detection of aniline in dilute aqueous acid at a platinum electrode. A wall jet cell was designed for the analysis of aniline vapour in air which was continuously trapped in dilute acid and periodically injected into a fia system. The cell was not affected by small gas bubbles and was reasonably portable.

Mineral scaling poses a far greater problem to any industry that uses or produces water. The quality of water used by industry varies widely and gives rise to numerous scaling problems. Mineral scale formation and deposition on equipment surface causes major flow assurance concerns particularly apparent in the offshore oil and gas industry. An improper of scale management programmes could lead to a rapid mineral scale build up and subsequently significant reductions in productivity and compromises the operational safety of process equipment (i.e. safety valves) as a result of blockage. The result is costly workovers increasing project operating costs (OPEX) due to the need for scale dissolver treatments and significant production losses. As part of scale management programme, it is desirable to be able to quantify the extent of the mineral scale that has deposited on component surface and also to be able to monitor the changes of likelihood that a production fluid will precipitate out mineral scale. The nature of this research is focus on exploring a simple approach or a methodology to detect the mineral scale formed specifically for calcium carbonate on the electrode surface. The application of a submerged impinging jet (SIJ) in conjunction with an electrochemical technique was developed. The development of this technique has been taken into the consideration of advantages and disadvantages of the current available scale detection techniques. Not only has the complexity of equipment and facilities been considered during the development stage, but the data interpretation of the existing technologies has been considered. In general, efforts have concentrated upon strategies to develop and to validate this methodology for the scale coverage on the electrode surface as well as monitoring the scaling tendency through the electrochemical technique measurement. Various verifications and experiments were undertaken to ensure the reliability of the use of electrochemical measurement and SIJ geometry configurations. The influence of surface condition on the sensitivity of this technique were also assessed This technique clearly demonstrated that various levels of mineral deposition on the surface could be quantified. This included the calcium carbonate deposition in the presence and absence of magnesium ions. In this study, a similar SIJ set up configuration was used for scaling tendency measurement to quantify and predict whether scaling will occur in water or brine solution. The scaling tendency results illustrated that there was a good correlation between the saturation ratio and the scaling tendency slope measurement by an electrochemical analysis. The contribution main of this research contributes to a better understanding of the used of SIJ for scale detection, monitoring and quantification of calcium carbonate scale formation.

[EN] The increase in energy needs, particularly in terms of environmental protection, has greatly stimulated research in the field of photovoltaic conversion in recent years. Solar radiation provides an excellent resource for producing clean and sustainable electricity without toxic pollution or global warming, but in terms of high demand for energy for electricity production as well as the toxicity or scarcity of components constitute the solar cells, this solar transformation technology is still somewhat limited. Because these parameters constitute the main environmental concerns surrounding the photovoltaic industry. The compound Cu2ZnSnS4 (CZTS) can be considered as one of the most promising absorbent layer materials for low cost thin film solar cells. The abundance and non-toxicity of the constituent elements this promising material is the subject of this work. Obviously, this leads us to think about optimizing the other parameters influencing the formation of thin layers by the electrodeposition method. An electrochemical deposition technique which offers an advantageous alternative from an economic point of view and especially from the possibility of using large surface substrates. The initial focus was on determining the optimal parameters for the CZTS quaternary thin film development process. The electrodeposition is implemented by the technique of polarization of a potentiostatic electrode. Because this technique is based on the deposition potential of each substance constituting the electrolytic bath, a study has been conducted on the effect of the factors of complexity in order to assimilate these reduction potentials. Then, the annealing process which is a necessary step in the formation of absorbent layers in CZTS was mastered, under the influence of the complexity factor so as to reduce the annealing temperature while preserving the properties of the material. High quality kesterite films with a compact morphology and a well-defined crystal structure at low temperatures were synthesized using Na2SO4 as the complexing agent. Subsequently, the CZTS kesterite films were prepared on different conductive substrates (ITO, FTO and Mo / glass) due to specifying the effect of back contact. The best behavior is a specific combination of the parameters studied. This work made it possible in particular to master the composition of the films deposited, the annealing process as well as the necessary characterization techniques. Finally, our strategy implements a digital simulation of the CZTS solar cell using the SCAPS-1D software. After the experimental visualization of the thin layers of CZTS on different conductive substrates, modeling by the SCAPS-1D software of the CZTS solar cell device showed that the back-contact Mo mounts the best performances.
[ES] El aumento de las necesidades energéticas, particularmente en términos de protección del medio ambiente, ha estimulado en gran medida la investigación en el campo de la conversión fotovoltaica en los últimos años. La radiación solar proporciona un recurso excelente para producir electricidad limpia y sostenible sin contaminación tóxica o calentamiento global, pero en términos de alta demanda de energía eléctrica, así como la toxicidad o escasez de componentes que constituyen las células solares, esta tecnología de transformación solar todavía es algo limitada. En consecuencia estos parámetros constituyen las principales preocupaciones ambientales que rodean a la industria fotovoltaica. El compuesto Cu2ZnSnS4 (CZTS) puede considerarse como uno de los materiales absorbentes más prometedores para las células solares de película delgada de bajo costo. La abundancia y la no toxicidad de los elementos constitutivos de este prometedor material es el tema de este trabajo. Este objetivo nos ha llevado a pensar en optimizar los parámetros que influyen en la formación de capas delgadas por métodos electroquímicos. La técnica de deposición electroquímica o electrodeposición catódica ofrece una alternativa ventajosa desde un punto de vista económico y especialmente ofrece la posibilidad de utilizar sustratos de gran superficie. El enfoque inicial fue determinar los parámetros óptimos para el proceso de desarrollo de película delgada cuaternaria de CZTS. La electrodeposición se implementó mediante la técnica de polarización de un electrodo por el método potenciostático, o sea a potencial constante. Debido a que esta técnica se basa en el potencial de deposición de cada sustancia que constituye el baño electrolítico, se ha llevado a cabo un estudio sobre el efecto de los factores de complejidad para acercar estos potenciales de reducción. Una vez fueron depositadas las capas, se continuó con el estudio del proceso de recocido, que es un paso necesario en la formación de capas absorbentes de CZTS bajo la influencia del factor de complejidad, debido a que conviene reducir la temperatura de recocido mientras se intenta conservan las propiedades del material. Se sintetizaron películas de kesterita de alta calidad con una morfología compacta y una estructura cristalina bien definida a bajas temperaturas usando Na2SO4 como agente acomplejante. Posteriormente, las películas de kesterita CZTS se prepararon en diferentes sustratos conductores (ITO, FTO y Mo / vidrio) para estudiar el efecto del contacto posterior. Comprobamos que el mejor comportamiento se produce para una combinación específica de los parámetros estudiados. En particular este trabajo nos ha permitido controlar la composición de las películas depositadas, dominar el proceso de recocido y usar las técnicas de caracterización necesarias para evaluar la composicion, calidad y propiedades optoelectrónicas de las capas de CZTS sintetizadas. Finalmente, nuestra estrategia implementa una simulación digital de la célula solar CZTS utilizando el software SCAPS-1D. Después de la visualización experimental de las capas delgadas de CZTS en diferentes sustratos conductores, el modelado por el software SCAPS1D del dispositivo de células solares CZTS demostró que el contacto trasero Mo ofrece los mejores rendimientos.
[FR] L'augmentation des besoins énergétiques, notamment en matière de protection de l'environnement, a fortement stimulé la recherche dans le domaine de la conversion photovoltaïque ces dernières années. Le rayonnement solaire fournit une excellente ressource pour produire de l'électricité propre et durable sans pollution toxique ni réchauffement climatique, mais en termes de forte demande d'énergie pour la production de l’électricité ainsi que la toxicité ou la rareté des composants constituent les cellules solaires, cette technologie de transformation solaire est encore un peu limitée. En raison que ces paramètres constituent les principales préoccupations environnementales entourant l'industrie photovoltaïque. Le composé C2ZnSnS4 (CZTS) peut être considéré comme l'un des matériaux de couche absorbante les plus prometteurs pour les cellules solaires en couches minces à faible coût. L’abondance et la non-toxicité des éléments constitutifs ce matériau prometteur fait l'objet de ce travail. De toute évidence, cela nous amène à réfléchir pour optimiser les autres paramètres influençant la formation de couches minces par la méthode d'électrodéposition. Une technique de dépôt par voie électrochimique qui offre une alternative avantageuse du point de vue économique et surtout de la possibilité d’utiliser des substrats de grande surface. Initialement, l'accent était mis sur la détermination des paramètres optimaux pour le processus d’élaboration de couches minces du quaternaire CZTS. L'électrodéposition est mise en œuvre par la technique de polarisation d'une électrode potentiostatique. En raison, que cette technique reposant sur le potentiel de dépôt de chaque substance constituant le bain électrolytique, une étude a été menée sur l'effet des facteurs de complexité afin de rapprocher ces potentiels de réduction. Ensuite, Le processus de recuit qui est une étape nécessaire dans la formation de couches absorbantes en CZTS a été maîtriser, sous l'influence du facteur de complexité en raison de réduire la température de recuit tout en conservant les propriétés du matériau. Des films de kësterite de haute qualité avec une morphologie compacte et une structure cristalline bien définie à basse température ont été synthétisés en utilisant Na2SO4 comme agent complexant. Par la suite, les films de kestérite CZTS ont été préparés sur différents substrats conducteurs (ITO, FTO et Mo / verre) en raison de spécifier l'effet du contact arrière. Le meilleur comportement est une combinaison spécifique des paramètres étudiés. Ces travaux ont permis notamment de maîtriser la composition des films déposés, le processus de recuit ainsi que les techniques de caractérisation nécessaire. Finalement, notre stratégie met en œuvre une simulation numérique de la cellule solaire CZTS à l'aide du logiciel SCAPS − 1D. Après la visualisation expérimentale des couches minces de Czts sur différent substrats conducteur, une modélisation par le logiciel SCAPS-1D du dispositif CZTS cellules solaires a montré que le Mo contact arrière monte les meilleures performances.
[CA] L'augment de les necessitats energètiques, particularment en termes de protecció de l'entorn, ha estimulat en gran mesura la investigació en el camp de la conversió fotovoltaica en els últims anys. La radiació solar proporciona un recurs excel·lent per produir electricitat neta i sostenible sense contaminació tòxica ni escalfament global, però en termes de l'alta demanda d'energia elèctrica, així com la toxicitat o escassetat de components que constitueixen les cèl·lules solars, aquesta tecnologia de transformació solar encara trova barreres limitadores. En conseqüència aquests paràmetres constitueixen les principals preocupacions ambientals que envolten a la indústria fotovoltaica. El compost Cu2ZnSnS4 (CZTS) pot considerar-se com un dels materials absorbents més prometedors per a les cèl·lules solars de pel·lícula prima i de baix cost. L'abundància i la no toxicitat dels elements constitutius d'aquest prometedor material és el tema d'aquest treball. Aquest objectiu ens ha portat a treballar en l’optimització dels paràmetres que influeixen en la formació de capes primes de CZTS per mètodes electroquímics. La tècnica de deposició electroquímica o electrodeposició catòdica ofereix una alternativa avantatjosa des d'un punt de vista econòmic i especialment ofereix la possibilitat d'utilitzar substrats de gran superfície. L'enfocament inicial va ser determinar els paràmetres òptims per al procés de desenvolupament d’una pel·lícula prima quaternària de CZTS. La electrodeposició es va implementar mitjançant la tècnica de polarització d'un elèctrode pel mètode potenciostàtic, o siga a potencial constant. Aquesta tècnica es basa en el potencial de deposició de cada substància que constitueix el bany electrolític es diferent i per tant s'ha dut a terme un estudi sobre l'efecte dels factors de complexitat per tal apropar aquests potencials de reducció de tots els components involucrats. Un cop van ser dipositades les capes, es va continuar amb l’estudi del procés de recuit, que és un pas necessari en la formació de capes absorbents de CZTS sota la influència del factor de complexitat, a causa de la reducció de la temperatura de recuit mentre es conserven les propietats de l'material. Es van sintetitzar pel·lícules de kesterita d'alta qualitat amb una morfologia compacta i una estructura cristal·lina ben definida a baixes temperatures usant Na2SO4 com a agent acomplexant. Posteriorment, les pel·lícules de kesterita CZTS es van preparar en diferents substrats conductors (ITO, FTO i Mo / vidre) per estudiar l'efecte del contacte posterior sobre les capes fines. Obtinguerem que el millor comportament és una combinació específica dels paràmetres estudiats. En particular aquest treball ens ha permès controlar la composició de les pel·lícules dipositades, controlar el procés de recuit i usar les tècniques de caracterització necessàries per avaluar la composició, qualitat i propietats optoelectròniques de les capes de CZTS depositades. Finalment, en la nostra estratègia es va implementar una simulació numérica d’una cèl·lula solar de CZTS utilitzant el programari SCAPS-1D. Després de la visualització experimental de les capes primes de CZTS en diferents substrats conductors, el modelatge pel programari SCAPS-1D del dispositiu fotovoltaic de CZTS va demostrar que el contacte posterior de Mo és el que ofereix el millor rendiment.
I would like to thank the Moroccan Center for Scientific and Technical Research and the Doctoral school of the Polytechnic University of Valencia for the financial assistance they have allocated. I also extend my sincere thanks to the UPV Electron Microscopy Service and to Mr Ángel Sans Tresserras for their help to learn how to work with characterization techniques.
Toura, H. (2020). Elaboration and characterization by electrochemical technique CZTS thin layers for photovoltaic application [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/154334
TESIS

Electrochemical methods were researched for the analysis of metals, proteins and the identification of metal binding proteins. Adsorptive cathodic stripping voltamrnetry for metal analysis combines the inherent sensitivity of electrochemical techniques with the specificity of ligands for the nonfaradaic preconcentration of analytes at the electrode. The utility of catechol, resorcinol, 4-methylcatechol and 4-t-butylcatechol as ligands was explored for the sensitive analysis of copper, bismuth, cadmium and lead on a mercury film glassy carbon electrode. Metal complexes of lead, copper and bismuth with resorcinol showed the largest increase in current with increase in metal concentration, whereas complexes of these metals with 4-t-butylcatechol showed the lowest current response. Cadmium showed the highest current responses with 4-methylcatechol. The four metals could be determined simultaneously in the presence of resorcinol, although considerable interference was observed between bismuth and copper. The electroanalysis of cysteine and cysteine containing proteins at carbon electrodes are impaired by slow electron transfer rates at carbon electrodes, exhibiting high overpotentials, greater than 1 V vs Ag! Agel. Metallophthalocyanines have been shown to promote the electrocatalysis of cysteine at lowered potentials. Chemical modification of electrodes with appropriate modifiers is a means of incorporating specificity into electroanalysis, with applications in electrocatalysis. A glassy carbon electrode was modified by electrodeposition of cobalt (II) tetrasulphophthalocyanine [Co(II)TSPct to produce a chemically modified glassy carbon electrode (CMGCE). The CoTSPc-CMGCE catalysed the oxidation of cysteine in the pH range 1 to 10. The significance of this electrode is an application for analysis of proteins at biological pH's. A biscyanoruthenium(II) phthalocyanine CMGCE catalysed the oxidation of cysteine at 0.43 V vs Ag/AgCl a significant lowering in the overpotential for the oxidation of cysteine. Metallothionein, a metal binding protein, is believed to be involved in metal homeostasis and detoxification in the peripheral organs of living systems. A method for the quantitative determination of this protein utilising its high cysteine content was presented. At pH 8.4 Tris-HCl buffer, and using a CoTSPc-CMGCE modified by electrodeposition of the modifier, the anodic peaks for the oxidation of metallothionein was observed at 0. 90 V vs Ag/ AgCI. Ferredoxin is a simple iron-sulphur protein. One tenth of its residues are cysteine. Ferredoxin is involved in simple electron transfer processes during photosynthesis and respiration. Electrochemical studies of spinach ferredoxin were conducted at a CoTSPc-CMGCE. Anodic currents for the oxidation of the cysteine fragment of ferredoxin was observed at 0.85 V vs Ag/AgCl in HEPES buffer at pH 7.4, representing a new method for analysis of this protein. Voltammetric studies of its ferric/ferrous transition have shown quasi-reversible waves atE~ -0.62 V vs Ag/AgCl only in the presence of promoters. At a CoTSPc-CMGCE, a cathodic wave attributed to the reduction of Fe(III)/Fe(II) was observed at Epc -0.34 V vs Ag/AgCl. This represents an alternative method for voltammetric studies of the ferric/ferrous transition at significantly lowered potentials. Melatonin, a pineal gland hormone functions m setting and entraining circadian rhythms and in neuroprotection as a free radical scavenger and general antioxidant. Using adsorptive cathodic stripping voltammetry, the binding affinities of melatonin, serotonin and tryptophan for metals, were measured. The results showed that the following metal complexes were formed: aluminium with melatonin, serotonin and tryptophan; cadmium with melatonin and tryptophan; copper with melatonin and serotonin; iron (III) with melatonin and serotonin; lead with melatonin, tryptophan and serotonin, zinc with melatonin and tryptophan and iron (II) with tryptophan. The studies suggest a further role for melatonin in the reduction of free radical generation and in metal detoxification and may explain the accumulation of aluminium in Alzheimer's disease.

This thesis presents the development of electrochemical etch-stop techniques (ECES) to achieve high precision 3-dimensional integrated MEMS sensors with wet anisotropic etching by applying proper voltages to various regions in silicon. The anisotropic etchant is selected as tetra methyl ammonium hydroxide, TMAH, considering its high silicon etch rate, selectivity towards SiO2, and CMOS compatibility, especially during front-side etching of the chip/wafer. A number of parameters affecting the etching are investigated, including the effect of temperature, illumination, and concentration of the etchant over the etch rate of silicon, surface roughness, and biasing voltages. The biasing voltages for passivating the n-well and enhancing the etching reactions on p-substrate are determined as -0.5V and -1.6V, respectively, after a series of current-voltage characteristic experiments. The surface roughness due to TMAH etching is prevented with the addition of ammonium peroxodisulfate, AP. A proper etching process is achieved using a 10wt.% TMAH at 85°
C with 10gr/lt. AP. Different silicon etch samples are produced in METU-MET facilities to understand and optimize ECES parameters that can be used for CMOS microbolometers. The etch samples are fabricated using various processes, including thermal oxidation, boron and phosphorus diffusions, aluminum and silicon nitride layer deposition processes. Etching with the prepared samples shows the dependency of the depletion layer between p-substrate and n&
#8209
well, explaining the reason of the previous failures during post-CMOS etching of CMOS microbolometers from the front side. Succesfully etched CMOS microbolometers are achieved with back side etching in 6M KOH at 90 °
C, where &
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3.5V and 1.5V are applied to the p-substrate and n-well. In summary, this study provides an extensive understanding of the ECES process for successful implementations of integrated MEMS sensors.

Doutoramento em Ciência e Engenharia de Materiais
A síntese eletroquímica de filmes finos de óxido usando a técnica de oxidação de alta tensão e a investigação da estrutura, propriedades físicas e químicas dos filmes obtidos são os principais objetivos desta tese. A anodização de metais sob a ação de vários kilovolts produz filmes com espessura pequena (até 180 nm) e com propriedades diferentes dos filmes formados usando técnicas eletroquímicas convencionais. As camadas de óxido depositadas desta forma conferem, frequentemente, melhores propriedades de proteção, semicondutoras e fotoeletroquímicas. No âmbito deste trabalho filmes finos sobre titânio e alumínio foram preparados em diferentes eletrólitos, incluindo soluções de ácidos e sais, bem como em água desionizada e peróxido de hidrogénio. Mostra-se que os filmes preparados por oxidação com descarga pulsada de alta tensão têm estrutura superficial e propriedades elétricas mais uniformes em comparação com os obtidos por anodização convencional. Outro objetivo do trabalho é a dopagem dos filmes anódicos com diferentes dopantes, por incorporação de espécies do eletrólito durante a formação do filme. Os filmes preparados por oxidação de descarga pulsada de alta tensão no titânio mostram uma melhor resposta de fotocorrente a comprimentos de onda pequenos e uma concentração mais baixa de dadores ionizados, relativamente aos filmes obtidos por anodização convencional. Os filmes preparados por descarga no alumínio e titânio são formados por uma camada compacta. Estudos sobre o processo de descarga revelaram que o principal fator que influencia a cinética de crescimento do filme de óxido é a concentração de defeitos pontuais, que por sua vez é determinada pela composição do eletrólito. Também se mostrou que as técnicas usando alta tensão permitem preparar filmes anódicos não só em soluções convencionais, mas igualmente em outros meios, tal como água desionizada, água destilada e peroxido de hidrogénio, onde a anodização por métodos convencionais (potenciostático ou galvanostático) é impossível. Além disso é revelado que a técnica da descarga pulsada de alta tensão é um método eficiente para encapsulação de nanocilindros de metal, preliminarmente depositados em nanoporos de titânia e alumina alinhados verticalmente.
Electrochemical synthesis of thin oxide films by using the high-voltage oxidation technique and investigation of structure, physical and chemical properties of the obtained films are the main objectives of this thesis. Anodisation of metals under action of several kilovolts allow to produce films with rather low thickness (up to 180 nm) and with properties different from the films created by using conventional electrochemical approaches. The oxide layers deposited in this way often confer advanced protective, semiconductor and photoelectrochemical properties. In the frame of this thesis thin films on titanium and aluminium were prepared in several electrolytes, including solutions of acids and salts as well as in deionised water and hydrogen peroxide. It is shown that the films prepared by powerful pulsed discharge oxidation are characterized by more uniform surface structure and electrical properties in comparison to those obtained by conventional anodization. Another aim of the work is doping of the anodic films with different dopants by incorporation of species from the electrolyte during the film formation. Films prepared by powerful pulsed discharge oxidation technique on titanium demonstrate a significantly improved photocurrent response at short wavelengths and an essentially lower concentration of ionized donors as compared with the films obtained by conventional anodization. The discharge-prepared films on both aluminium and titanium are composed by one compact layer. Studies of the discharge processes revealed that the main factor influencing the kinetics of the oxide film growth is the concentration of point defects which, in turn, is determined by the composition of electrolyte. Also, it was shown that the high voltage techniques allow to prepare anodic films not only in conventional solutions, but also in other media such as deionised water, distilled water and hydrogen peroxide, where anodisation by conventional (potentiostatic or galvanostatic) methods is impossible. Furthermore, the powerful pulsed discharge technique is shown as efficient method for encapsulation of metal nanorods preliminarily deposited into the vertically aligned titania and alumina nanopores.

In the present work the effect of isothermal ageing treatment on the microstructure and on the localized corrosion resistance of a duplex stainless steel (DSS) was investigated. Specimens taken from a hot rolled cylindrical duplex stainless bar with 22% Cr grade were solution annealed at 1050°
C and then sensitization heat treatments were conducted at 650, 725 and 800°
C with duration ranging from 100 to 31622 min. The microstructural changes were examined by the light optical microscopy (LOM) and scanning electron microscopy (SEM). XRD technique and EDS analysis were used for microstructural evolution. Double Loop Electrochemical Potentiodynamic Reactivation (DLEPR) and standard weight loss immersion acid tests were performed in order to determine the degree of sensitization (DOS) to intergranular corrosion. The surfaces remained after the DLEPR test and the weight loss immersion test were also examined to observe the attack locations and their relationship with the chromium depleted zones. The degree of sensitization is measured by determining the ratio of the maximum current generated by the reactivation (reverse) scan to that of the anodic (forward) scan, (Ir/Ia) x 100. Ir is very small (less than 10-5 A/cm2) for solution annealed samples at 1050°
C for 1 hr and those aged at 650°
C for 100 and 316 min after the solution heat treatment, with the Ir/Ia ratios of 0.027634%, 0.033428% and 0.058928% respectively. Hence these samples were considered as unsensitized and their microstructure was composed of primary ferrite and austenite. However, Ir increased to values as high as 10-2 A/cm2 and even approached Ia for all samples aged for other temperatures and times, associated with high Ir/Ia ratios. The increased degree of sensitization can be attributed to stronger effect of chromium and molybdenum depleted areas. The microstructure was composed of primary ferrite and austenite including also sigma phase and the secondary austenite that would be responsible for the localized chromium impoverishment. The time required for sensitization was shorter in samples aged at higher temperatures. Accordingly ageing times of 1000 min at 725°
C and of 316 min at 800°
C were sufficient, whereas times longer than 10000 min was needed to achieve a sensitized structure at 650°
C.

Philosophiae Doctor - PhD
The depletion of fossil fuel resources such as coal and the concern of climatic change arising from the emission of greenhouse gases (GHG) and global warming [1] lead to the identification of the 'hydrogen economy' as one of the renewable energy sources and possible futuristic energy conversion solution. Sources of hydrogen as fuel such as water through electrolysis and liquid organic fuel (Hydrogen carriers) have been found as potential game-changers and received increased attention, due to its low-carbon emission.

Electro-oxidation of ethanol on smooth platinum surfaces was studied in thetemperature range 21C to 140C for 0.2 M ethanol in 0.5 M sulphuric acid.This was done by use of cyclic voltammetry and electrochemical impedancespectroscopy. In addition cyclic voltammetry with different ethanol concentrationsfrom 0.1 M to 1 M, in 0.5 M sulphuric acid was done at room temperature.Cyclic voltammetry with different ethanol concentrations showed a shift to morepositive potentials for the first oxidation peak in positive going scan as the ethanolconcentration increased. A shift to more positive potentials was also observed forthe oxidation peak in the negative scan as the concentration increased from 0.1M to 1 M. This indicates that the optimum surface condition is reached at higherpotentials for higher ethanol concentrations. This can be because ethanol andadsorbed ethanol derivatives take up more active sites at the surface, thus leavingless active sites available for adsorbed water derivatives which is necessary for theoxidation of ethanol to acetic acid and CO2.Cyclic voltammetry was done for increasing temperatures from 21C up to 140Cfor 0.2 M ethanol in 0.5 M sulphuric acid. These results showed an increasein oxidation current for all oxidation peaks as the temperature increased. Adecrease in peak potential for the first oxidation peak was observed for increasingtemperatures. This indicates that the optimum surface condition for ethanoloxidation is reached at lower potentials at higher temperatures. There was alsoseen an decrease in the apparent onset potential of the first oxidation peak as thetemperature increases. These effects can come from increased thermal activity forwater adsorption at higher temperatures. The peak potential for the oxidationpeak in negative going scan increased with increasing temperatures. This cancome from an easier reduction of platinum oxide at higher temperatures.Dynamic electrochemical impedance spectroscopy measurements was done atdifferent temperatures from 21C up to 140C for 0.2 M ethanol in 0.5 Msulphuric acid solution. The results from the measurements at 60C was fittedto electrochemical equivalent circuits. This gave indications of one kineticallysignificant surface adsorbed species in most potential regions with a notableoxidation current. This in combination with literature suggesting that acetic acidand acetaldehyde is the major products from ethanol electro-oxidation suggestthat the adsorbed intermediate is something other than CO(ads). Results fromthis work together with existing literature on ethanol oxidation was used to givea suggested simplified reaction mechanism for ethanol electro-oxidation.

Die vorliegende Arbeit beschäftigt sich mit der Entwicklung von Sol-Gel-Beschichtungen durch Optimierung der Ausgangszusammensetzung und der Applikations-Parameter für den Korrosionsschutz der Aluminium-Legierung AA7075. Verschiedene Arten von Silanen, z. B. Tetraethoxysilan (TEOS), Phenyltriethoxysilan (PTES) und Phenyltrim­ethoxysilan (PTMS) sind verglichen worden: Der Sol-Gel-Film aus PTMS präpariert, weist dabei die höchste Hydrophobizität auf, was sich insbesondere in den Barriere-Eigenschaften dieser Verbindung zeigte. Die Wirkung von Essigsäure als Katalysator in Sol-Gel-Prozessen wurden untersucht, um die optimale Katalysatorkonzentration für den Korrosionsschutz der beschichteten Proben zu ermitteln. Die Korrosionsbeständigkeit der beschichteten Proben sinkt bei höheren Konzentrationen des sauren Katalysators durch die Auflösung des Aluminiumoxids an der Substratoberfläche. Allerdings führten zu niedrige Konzentrationen des Katalysators zur Verlangsamung der Hydrolysereaktionen der Silane und es bildete sich poröse Sol-Gel-Schichten. Die Wärmebehandlung der beschichteten Aluminium-Proben ist für die Vernetzung des Films erforderlich. Eine Wärmebehandlung bei 300 ˚C für 2,5 Stunden ergab dabei den besten Korrosionsschutz. Höhere Temperaturen führten zu einer Verschlechterung der Eigenschaften der Filme, was mit der Zerstörung des organischen Teil des Films erklärt werden kann. Darüber hinaus verursachen zu niedrige Temperaturen einen geringeren Korrosionsschutz der beschichteten Aluminium-Proben. Vermutlich ist die geringe Vernetzung des Sol-Gel-Films bei Temperaturen was für als 300 ˚C verantwortlich. Die beschichteten Aluminium-Proben wuden mittels Raster-Elektronenmikroskopie (SEM), Energiedispersive Röntgenspektroskopie (EDX), Röntgen-Photoelektronenspektroskopie (XPS) und elektrochemischen Techniken charakterisiert
The present work pertains to the development of sol-gel coatings by optimizing the composition and the application parameters for corrosion protection of aluminum alloy AA7075. Different kinds of silanes e.g. tetraethoxysilane (TEOS), phenyltriethoxysilane (PTES) and phenyltrimethoxysilane (PTMS) have been compared: the sol-gel film prepared from PTMS shows highest hydrophobicity manifested by the best barrier property of this compound. The effect of acetic acid as a catalyst on the chemistry of the sol is investigated in order to estimate the best catalyst concentration for better corrosion protection of the coated samples. The corrosion resistance of the coated samples is found to be decreasing at higher concentrations of the catalyst due to the dissolution of the aluminum oxide at the substrate surface in the acid sol. However, lower concentrations of the catalyst lead to low hydrolysis reactions of the silanes and non-dense sol-gel films have been formed. The heat treatment of the coated aluminum samples is required for cross-linking of the film. The heat treatment at 300 ˚C for 2.5 hours exhibits the best corrosion protection. Higher treatment-temperatures lead to degradation of the properties of the film which can be described in terms of destroying the organic part of the film. Moreover, low treatment-temperatures cause low corrosion protection of the coated aluminum samples which is presumably attributed to the low cross-linking of the sol-gel film at temperatures less than 300 ˚C. The coated aluminum samples are characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS) and electrochemical techniques

La pile à combustible apparaît comme une technologie prometteuse pour la conversion énergétique à faible impact environnemental mais sa commercialisation à grande échelle nécessite de relever certains défis économiques et technologiques. Tout d'abord, pour fonctionner, la pile a besoin de systèmes (compresseurs, convertisseurs,...) parfois volumineux et coûteux en énergie. Ensuite, le prix de certains éléments constituants la pile reste élevé car ce sont des produits à haute valeur technologique utilisant des matériaux parfois très onéreux (membrane polymère, couche catalytique,...). L'optimisation du système pile à combustible et des éléments environnants n'est pas le seul défi à relever. En effet, la durabilité des assemblages membrane-électrodes (AME) constitue une barrière majeure à la commercialisation de ces systèmes pour des applications stationnaires ou dans les transports. Afin d'améliorer la durabilité de ces assemblages, il est nécessaire de bien caractériser les différents éléments les constituant et de déterminer et de quantifier les mécanismes de dégradation. Le premier chapitre de cette thèse présente une étude bibliographique sur les PEMFC et l'électrochimie fondamentale régissant le fonctionnement de ces systèmes. Le second chapitre présente les matériaux composant les différents éléments du système ainsi que les méthodes expérimentales utilisées pour caractériser les AME. Le chapitre suivant évoque l'étude et la mise en oeuvre d'une technique électrochimique de caractérisation d'un empilement, notamment la mesure de surface active des différentes cellules. Enfin, le quatrième et dernier chapitre concerne une étude du vieillissement hétérogène d'empilements de trois cellules
Proton exchange membrane (PEM) fuel cells are seen as a promising technology for environmentally friendly energy conversion but its wide spread commercialization need taking up several technological and economic challenges. First, to operate PEM fuel cells require sizeable and energy consuming surrounding systems (compressors, converters,...). Then, elements constituting the cell remain costly because with high technological value and using expensive materials (polymer membrane, catalyst layer,...). The optimization of the system and the surrounding elements is not the only challenge to take up. Indeed, durability of the membrane electrode assembly (MEA) constitutes the major barrier to commercialization of these systems for stationary or transport applications. In order to increase durability of the assemblies, a better understanding of the aging mechanisms is necessary. The first chapter of the thesis introduces a bibliographical study on PEMFC and the fundamental electrochemistry governing the system operation. The second chapter introduces materials composing the different system elements and experimental methods used for PEMFC characterization. The next chapter deals with a study on stack characterization, particularly the development of an electrochemical technique allowing active surface area measurement of the cells composing the stack. Finally, the last chapter deals with heterogeneous aging within PEMFC stacks

Environmentally-assisted cracking (EAC) phenomena affect the in-service behaviour of austenitic stainless steels in nuclear power plants. EAC includes such degradation phenomena as Stress Corrosion Cracking (SCC) and Corrosion Fatigue (CF). Factors affecting EAC include the material type, microstructure, environment, and stress. This is an important degradation issue for both current and Gen III+ light water reactors, particularly as nuclear power plant lifetimes are extended ( > 60 years). Thus, it is important to understand the behaviour of the alloys used in light water reactors, and phenomena such as SCC to avoid failures. Although there is no agreement on the mechanism(s) of SCC, the importance of localized electrochemical reactions at the material surface is widely recognised. Considerable research has been performed on SCC and CF crack growth, but the initiation phenomena are not fully understood. In this project, novel in situ analytical TEM techniques have been developed and applied to explore localised reactions in Type 304 austenitic stainless steel. In situ transmission electron microscopy has become an increasingly important and dynamic research area in materials science with the advent of unique microscope platforms and a range of specialized in situ specimen holders. In metals research, the ability to image and perform X-ray energy dispersive spectroscopy (XED) analyses of metals in liquids are particularly important for detailed study of the metal-environment interactions with specific microstructural features. To further facilitate such studies a special hybrid specimen preparation technique involving electropolishing and FIB extraction has been developed in this thesis to enable metal specimens to be examined in the liquid cell TEM specimen holder using both distilled H2O and H2SO4 solutions. Furthermore, a novel electrode configuration has been designed to permit the localized electrochemical measurement of electron-transparent specimens in the TEM. These novel approaches have been benchmarked by extensive ex situ experiments, including both conventional electrochemical measurements and microcell measurements. The results are discussed in terms of validation of in situ test data as well as the role of the electron beam in the experiments. In situ liquid cell TEM experiments have also explored the localized dissolution of MnS inclusions in H2O, and correlated the behaviour with ex situ experiments. Based on the research performed in this thesis, in situ liquid cell and in situ electrochemical cell experiments can be used to study nanoscale reactions pertaining to corrosion and localized dissolution leading to "precursor" events for subsequent EAC phenomena.

[Truncated abstract] Corrosion of steel structures caused by sulphide is a common engineering problem encountered by many industries, such as the petroleum, chemical processing, mining and mineral processing industries. The control of sulphide corrosion is still a controversial topic among corrosion engineers. There is an absence of guideline for a reliable acceptable limit of sulphide level in service and each processing industry has its own empirical values. Selection of inhibitors in the sulphide environment depends on laboratory testing before its actual application in pipelines and reaction vessels. Many investigators have postulated the corrosion mechanisms due to sulphide based on operating envelopes such as pH, chloride, manganese, hydrogen sulphide, sulphate reducing bacteria levels and inhibitor concentration. It is recommended in the literature that the batch dosing of inhibitor and biocide needs to be evaluated in regards to sulphide reducing bacteria (SRB) level, which may produce sulphide concentrations up to 2000 ppm. Although sulphide scale formation may protect the base metal by providing a physical barrier, the detrimental effects of sulphide are often inevitable, such as stress corrosion cracking, hydrogen embrittlement, etc. Currently, there are many chemicals that are used as inhibitors to prevent corrosion by scavenging the sulphide from the environment. Cerium, a rare-earth element, is not used as inhibitor in the sulphide environment. Also, there are no previous research findings on the effects of compounds of rare-earth metals, such as cerium chloride (CeCl3), in sulphide environment. This research examines the corrosion behaviour of 0.4Mo-0.8Cr steel, a High Strength Low Alloy (HSLA) steel, in sulphide-polluted artificial seawater with the addition of CeCl3 and glutaraldehyde. ... It is postulated that the moderate inhibiting effect of CeCl3 is due to the scavenging effect thereby forming Ce2S3 complex. Further reaction of sulphide with steel resulted in ferrous sulphide, leading to an increased corrosion rate. It is also concluded that the CeCl3 interferes with both anodic and cathodic reactions in deaerated conditions. Addition of glutaraldehyde in the sulphide-polluted seawater was found to decrease the corrosion rate. According to the electrochemical measurements conducted, the concurrent addition of glutaraldehyde and CeCl3 appeared to have an added effect on reducing the corrosion of the steel, as evidenced by the increase of the open circuit potential during the short-term testing. From the weight loss measurements after 60 days, sulphide pollution in deaerated seawater was found to increase corrosion rate. This is attributed to the increase of sulphide activity whereby continual dissolution of steel was encountered. From the weight loss tests, it was found that the addition of CeCl3 and glutaraldehyde reduced the corrosion rate of the steel in the solutions containing 0-10 ppm sulphide. There is no noticeable corrosion rate decrease for the solution containing 100 ppm sulphide. The added effect of CeCl3 and glutaraldehyde to the SRB medium has resulted in lower corrosion rates. Further detailed experimentation is required to elucidate the corrosion reduction mechanism in glutaraldehyde-containing environments.

Electrochemical Jet Processing (EJP) techniques have been traditionally limited in application by the inherent geometric inflexibility and limited process precision in comparison to alternative processes. It has been stated that process resultant geometries are defined by the Gaussian in-jet energy distribution and the hydrodynamic stagnation region formed under a jet on an impinging surface. This thesis reports upon investigations and innovations designed to challenge these assumptions. EJP is an emergent manufacturing process with a unique capability of subtraction and deposition of metals within a common machine tool. EJP demonstrates advantages beyond traditional electrochemical machining and electrochemical deposition including a high degree of flexibility, simplistic and therefore low-cost plant, requiring no complex, high-cost tooling and no masking requirement to achieve high fidelity geometries. These process traits are attractive to industry but EJP has yet to find significant commercial use. Electromechanical and electrochemical innovations are presented here demonstrated by electrochemical jet machining (EJM) the subtractive mode of EJP, which allow modulation of the properties of the inter-electrode gap leading to a paradigm shift in the functionality, precision and application of EJP. Electromechanical innovations demonstrate that the Gaussian energy distribution can be modified through the articulation of the jet angle of address and modified jet nozzles to manipulate the in-jet resistance. The outcome being the capability to produce bespoke removal profiles with increased precision and flexibility of form alongside refined surface finishes. Electrochemical innovations demonstrate an increase in precision through reducing overcut and reducing the feature shoulder radius when using a modified electrolyte. When these electromechanical and electrochemical innovations are coupled together, the overcut traditionally seen to be twice the nozzle diameter is reduced by 99%. Therefore, features can be created at kerfs approaching the nozzle diameter. Alongside this, a bespoke research platform has been built and developed to exploit these findings and incorporate features such as the rotational head for constant profiling and multiplexing of electrolytes to enhance the flexibility of the process. Process enhancements developed through this thesis have allowed the manipulation of the in-jet energy density profile and dissociation of the dissolution region from hydrodynamic phenomena thus allowing surface structuring by EJP to be developed well beyond the state-of-the-art.

L'applicabilite de la technique de l'effet mirage comme outil d'analyse quantitative des echanges de matiere entre un systeme electroactif depose sur une electrode et la solution a ete demontree dans cet ouvrage. L'effet mirage est base sur la propriete d'un faisceau lumineux de devier de sa trajectoire initiale lorsqu'il traverse un milieu dont l'indice de refraction n'est pas homogene. Or, l'indice de refraction depend de la temperature de ce milieu (effet mirage thermique) et de la concentration d'une espece dissoute (effet mirage de concentration). Il est montre que la technique de l'effet mirage de concentration s'applique a l'etude de la dynamique ionique de systemes electrochimiques aussi varies que l'oxydation catalytique de l'hypophosphite sur une electrode de nickel, le comportement d'une electrode sacrificielle carbone-soufre, et le processus d'oxydoreduction des polycarbazoles. La correction du delai de propagation des especes entre l'electrode et le faisceau lumineux a ete realisee grace a l'outil mathematique de convolution temporelle. Il est ainsi possible de comparer quantitativement le courant mesure a l'electrode et le signal mirage mesure a une centaine de micrometres de cette derniere. L'utilisation de cet outil pour l'etude du processus d'oxydoreduction d'un polymere conducteur electronique modele, tel que le polypyrrole, a permis de discriminer les flux anionique et cationique. Enfin, le couplage in situ des techniques de voltamperometrie cyclique, d'effet mirage et de microbalance a quartz a ete realise pour la premiere fois. Il a permis de mesurer simultanement l'evolution des flux d'anions, de cations et de solvant au cours du processus d'oxydoreduction du polypyrrole

This thesis presents work on the development of a number of scanned electrochemical probe microscopies. Such techniques have widespread applications, from materials science to the life sciences. Advances in flexible instrumentation, coupled with the theoretical description of electrochemical systems, are central themes which allowed for the fruitful investigation of a variety of experimental systems. Theoretical descriptions of scanning ion conductance microscopy (SICM) were developed, particularly to investigate the effect of tip-geometry on imaging resolution. This technique has already found a number of applications in the life sciences, but image resolution has not previously been addressed adequately. Images were recorded showing tip-convolution that were in agreement with theoretical predictions. The scanning microcapillary contact method (SMCM) was developed, as a method of assessing spatial heterogeneities in electrode activity on the submicron length-scale. An electrolyte filled microcapillary containing a reference/auxiliary electrode was approached to a substrate (working) electrode surface, via piezoelectric positioners. Contact of the electrolyte meniscus with the substrate electrode was sensed by a current flowing. Electrochemical measurements were performed before the microcapillary was retracted and another point on the sample was characterised. Spatial heterogeneities in electrode activity were imaged on a sub-micron length-scale and the activity of basal plane highly oriented pyrolytic graphite (HOPG) was demonstrated. Tip position modulation scanning electrochemical microscopy (SECM-TPM), where an ultramicroelectrode (UME) is oscillated perpendicularly to a surface and an amperometric current is recorded, was investigated experimentally and theoretically. A model including convective mass-transport was developed that gave an accurate description of the experimental situation. It was demonstrated that SECM-TPM is a potentially powerful approach for the measurement of the permeability of a sample. SECM experiments were performed investigating the growth of Ag particles at a liquid/liquid interface, which was caused through the electrodissolution of a Ag UME in an aqueous phase, and the reduction of the Ag+ ion by an electron donor in the organic phase. A model was created that allowed for the interpretation of data. Cyclic voltammetry investigations of HOPG covered with a Nafion film containing a redox mediator confirmed the activity of basal plane HOPG, as demonstrated by SMCM measurements. Nafion slowed diffusion sufficiently to allow the spatial-decoupling of surface sites with different activity.

The conventional method for synthesis of supported metal catalysts is a multi step reaction that produces large amounts of waste. The focus of this work has been to look at alternative methods of catalyst production which eliminate or lower the number of steps and therefore waste produced. The aim of the project was to synthesise supported metal catalysts by alternative (greener) techniques and then to test these catalysts alongside conventional catalysts for improved and novel activity. It was proposed that catalysts could be synthesized by a novel electrochemical route where the pure metal is electrochemically oxidized into solution to form a transient soluble complex. This complex is then reduced electrochemically/electrolessly and the metal is deposited onto a support with the ligand of the complex being recovered in solution for subsequent cycles. The development of such a system was studied for gold using ionic liquids, the stripping and depositing of gold was demonstrated using dicyanamide ligand ([DCAn but attempts to prove the recyclability of the ligand were not successful. However during these studies a set of active gold catalysts where prepared by the electroless deposition of gold from H[AuCI4].3H20 in [C4mim][NTf2] onto silica and titania. The activity of these catalysts was compared to standard wet impregnated catalysts, interestingly the preparation method was found to control the selectivity of the reaction. The standard catalysts showed activity for the oxidation of benzyl alcohol in toluene whereas the catalysts prepared by electroless deposition from ionic liquids showed Friedel-Crafts alkylation of benzyl alcohol with toluene. This is the first time that heterogeneously supported gold catalysts have been found to be active in Friedel--Crafts alkylations. Ag/AI203 and PtlAI203 catalysts have been prepared by means of solvent-free mechanochemistry using a ball mill. Remarkable catalytic activity was observed using a Ag/AI203 catalyst by ball milling (Ag20) for octane-SCR, compared with a conventionally prepared Ag/AI203 catalyst (wet impregnation) the ball milled catalyst shows an increase in activity with a reduction in the light off temperature of -150°C and NOx conversion below 200°C which is the first time this has been achieved in the absence of hydrogen.

Heterogenous interfacial electron transfer processes are of fundamental and applied importance to electrochemists and are extensively studied by a wide range of electrochemical techniques. This thesis focuses on the development of analysis strategies and electrochemical methodologies for more detailed quantitative investigations of electron transfer kinetics at a plethora of electrode materials, with an emphasis on carbon-based materials. Of interest are the techniques of Fourier-transformed large amplitude alternating current voltammetry (FTACV) and scanning electrochemical microscopy (SECM). The complementary electrochemical techniques of FTACV and SECM are used for measurements of fast electron transfer to reveal the impact of the complex heterogeneous surface of degenerately-doped polycrystalline boron-doped diamond electrode surfaces compared to conventional electrode materials such as platinum and gold. This part of the work highlights the importance of understanding the influence of measurement technique and further demonstrates how electron transfer at semi-metallic electrodes differ from conventional metallic electrodes. The oxidation of a ferrocene-derivative at highly oriented pyrolytic graphite is used to demonstrate the effects of reversible reactant adsorption on the SECM response. The high surface area-to-solution volume ratio of nanogap SECM measurements depicts the importance of understanding the impact of such surface effects. Precise quantitative kinetic analysis requires understanding of the mass transport between the SECM probe and electrode surface. Finite element method modelling was used to extensively investigate the effects of electrode reactant processes and the results of the models shed light on important factors that need to be accounted for in quantitative analysis of nanogap voltammetric measurements. FTACV is further developed as a tool for kinetic selectivity at heterogeneous electrode surfaces. This is achieved by taking advantage of the harmonic-dependent measurement timescale of FTACV to deconvolute a dual-heterogeneity electrochemical response into its individual components. Protocols are developed for this application and demonstrated experimentally using the ruthenium hexamine and ferrocene methanol redox couples.

A new system for the generation of hydrodynamic modulation voltammetry (HMV) is presented. This system consists of an oscillating jet produced through the mechanical vibration of a large membrane/piston. The structure of the cell is such that a relatively small vibration is transferred to a large (~ 1 m s-1) fluid flow at the jet outlet. High-speed imaging of the system shows vortex behaviour of the flow at the exit of the jet. Positioning of an electrode over the exit of this jet enables the detection of the modulated flow of liquid. The periodic character of the signal recorded at the electrode allows a “lock-in” approach to be employed. This enables discrimination of the background processes signal from the mass transport component. This is demonstrated for Fe(CN)6 3-/4- 3-/4-. Here “lock-in” to the modulated hydrodynamic signal is achieved through the deployment of bespoke software. The apparatus and procedure is shown to produce a simple and efficient way to obtain the desired signal. In addition the spatial variation of the HMV signal, phase correction and time averaged current with respect to the jet orifice is presented. The detection limit for the analysing system is shown to be 45 × 10-9 mol dm-3. The HMV method is employed to study the reduction of molecular oxygen at high surface area (HI-Pt) modified electrodes. The successful elimination of background signals is achieved for the 0.5 mm diameter nanostructured Pt electrode with roughness factor (RF) of 42.4. Employment of higher roughness factors (>50) HIPt electrodes revealed an anomalous “drop off” effect characterising these electrodes. It is demonstrated that the “drop off” is not caused by the hydrogen peroxide production at the electrode or pH change near the electrode surface. However, a clear dependence of the current deflection on the roughness factor of the electrodes is observed. The shape of the “drop off” followed the shape of the hydrogen adsorption region. It is suggested that the surface characteristics of the electrodes are important in these investigations. It is proposed here, that the capacitance of the electrode influences the HMV signal. Another type of hydrodynamic modulation method, specifically a vibrating 50 μm diameter Pt or Au wire or “tight-rope” electrode was studied. High frequency modulation (80 Hz) is employed. FFT data processing was employed to extract the desired signal from the total current. This technique was applied to study reduction of molecular oxygen at the modulated electrodes. A current “drop off” in hydride region was again observed. This is shown to be related to the uncompensated resistance of the cell. In particular, the resistance of the reference electrode is demonstrated to contribute to this effect

Des revêtements anticorrosion de zinc et d'aluminium ont été développés respectivement par des techniques de pulvérisation à froid à haute pression et à basse pression. Pour les revêtements de zinc, la dépendance de la température de pulvérisation sur l'épaisseur a été analysée et la température critique de dépôt a été trouvée à 230°C. Des variations de pression de 2 MPa, 2,5 MPa et 3 MPa à température constante 290 °C ont montré la valeur d'épaisseur de couche plus élevée à 2 MPa. Il a été également confirmé que l'épaisseur du revêtement à tendance à diminuer avec la pression. Le taux d'alimentation en poudre ainsi que la distance de pulvérisation ont également été considérés comme des paramètres influençant l'épaisseur. Les conditions optimales de projection ont été trouvées pour 3 rps et 30 mm, respectivement. Enfin, la température et la pression du gaz ont été optimisées par le plan d’experience dit de Doehlert. Leurs influences sur la qualité du revêtement de zinc ont été discutées en termes de microstructure, de porosité, d'épaisseur et de résistance à la corrosion. Une porosité maximale de 4,2% a été atteinte avec la pression la plus élevée et avec une température modérée (260 ° C < T < 300 ° C). Ces conditions favorisait l'érosion du substrat et la faible déformation des particules lors de l'impact. Deux conditions optimales ont ainsi été trouvées: 320 ° C – 2,5 MPa et 260 ° C – 2,5 MPa. Des expériences électrochimiques macroscopiques et locales ont été ensuite réalisées. Une résistance à la corrosion plus élevée a été détectée pour la condition 320 ° C – 2,5 MPa. Les revêtements étaient alors suffisamment épais pour protéger le substrat et le mécanisme de corrosion était liée au comportement des couches d'hydroxyde et d'oxyde de Zn. Il est a noter que la rugosité du revêtement devra être pour réduire l'amorçage de la corrosion. Pour les revêtements d'aluminium, les paramètres de déposition optimaux ont été trouvés à 400 ° C / 0,65 MPa. Des particules de céramique ont été ajoutées pour densifier le revêtement permettant une réduction de porosité de 8% à 6,4%. Un traitement de surface par laser a été ensuite effectué. Dans ce travail, la puissance du laser s’est révelée insuffisante pour atteindre le point de fusion de l’aluminium, cependant, la dureté des revêtement a pu être modifée. Les résultats ont montré une augmentation de la microdureté des revêtements de 5% avec l'ajout de particules céramiques tandis qu’une réduction de dureté de 39% et 35% a été mesurée sur le revêtement en aluminium pur et composite respecitvement. La diminution de dureté lors le traitement au laser a été attribuée au recuit de surface, à la libération de contraintes internes et à une possible recristallisation locale. Enfin, les caractérisations électrochimiques ont montré une résistance à la corrosion plus élevée pour les revêtements composites céramiques que l'aluminium pur et les revêtements traités au laser
Anticorrosion coatings of Zinc and Aluminium were developed by high pressure and low-pressure Cold Spray techniques, respectively. For Zinc coatings, the dependence of spraying temperature on thickness has been analyzed and the critical temperature of deposition was found at 230 oC. For lower temperatures, the coating was considerably thinner. Dependence of thickness on pressure variation 2 MPa, 2,5 MPa and 3 MPa at constant temperature 290 oC has shown the highest thickness value at 2 MPa. It was confirmed that the coating thickness tends to decrease with the pressure rise. The powder feeding rate as well as the spraying distance were also considered to influence the thickness. The optimal conditions were found for 3ps and 30 mm, respectively. Finally, the gas temperature and pressure were optimized by a Doehlert uniform shell design. Their influences on the zinc coating quality were discussed in terms of microstructure, porosity, thickness, and corrosion resistance. A maximum porosity of 4.2% was reached with the highest pressure and with a moderate temperature (260 °C < T < 300 °C). These conditions promoted erosion of the substrate and a lower accommodation of particles at the impact. Thicker coatings were obtained at higher temperatures because of better particle straining. Two optimal conditions were then identified: 320 °C–2.5 MPa and 260 °C–2.5 MPa. Macroscopic and local electrochemical experiments were performed. Higher corrosion resistance was detected for the condition 320 °C–2.5 MPa. Coatings were enough thick to protect the substrate and the corrosion mechanism was driven by the classical Zn hydroxide and oxide layers. Note that the coating roughness may be optimized later to reduce the corrosion initiation. For aluminum coatings deposited by a low-pressure cold spray method, the optimal spraying parameters according to deposition efficiency were found at 400 °C /0.65 MPa. Ceramic particles were added to densify the coating and allowed to reduce porosity from 8% to 6.4%. Instead of ceramic particle addition, laser surface treatment was performed after coating design. Laser power was not enough high to reach the surface melting, however, the coating microhardness was modified. Results showed a microhardness increase of coatings of 5% with the addition of hard particles whereas the microhardness decreased after the post-heat treatment (pure aluminum coating reduction of 39% and for composite coating 35%). The hardness reduction during the laser treatment was attributed to surface annealing and the release of internal stresses and possible recrystallization with the subsequent grain growth. Finally, the results of the electrochemical investigations showed higher corrosion resistance of ceramic composite coatings than both pure aluminum and laser-treated coatings

The synthesis of the gramicidin A (gA) analogue gram-2-(nicotinamido)ethyl carbamate (gAN) has been performed. Like gA itself, monomers of the nicotinamide analogue undergo self-assembly in lipid membranes to form K+ selective transmembrane ion channels. Scanning electrochemical microscopy (SECM) has been used to monitor the movement of permeable ions across these channels under a range of physiological conditions. Feedback curve results suggest that K+ ions only pass across the channels when a certain external potential, referred to as the switching potential, is applied to the membrane. This implies that ion transport in the system is controlled by the redox properties of the nicotinamide sub-unit, which acts as a pendant able to occlude the channel opening in the 'ball and chain' model of inactivation. Chronoamperometric measurements demonstrate that the gAN channel can be repetitively cycled between the opened and closed states. This controllable, predictable switching behaviour has possible applications in membrane transport and drug delivery systems. The permeability of gAN channels to Tl+ and Eu 3+ ions has also been tested by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) with gold electrode supported lipid bilayers. Results indicate that the channel is permeable to the Tl+ ion although not to the multicharged Eu3+ ion, which is believed to bind occluding the channel entrance. It was also possible to directly monitor the passage of Tl+ ions across the gAN channel by using Prussian Blue as a dual-purpose electrolyte and electrochromic indicator.

This thesis describes the development of an electrochemical scanned probe microscope, SECCM, outlining the need for such a development, by highlighting previous techniques and their limitations. SECCM consists of a double barrel capillary pulled to small dimensions, filled with electrolyte solution and a redox mediator of choice, with a QRCE is inserted into each channel. A potential is applied between the QRCEs, whilst modulating the pipet normal to the surface. The probe is translated towards the surface and once contact is established, a modulation in the ion current arises due to the physical oscillation of the probe, which is then used as a feedback parameter for imaging. The potential at the working electrode substrate is also controlled. SECCM is introduced using a model test substrate, gold bands on glass, showing that the probe is able to track topographical features, making simultaneous electrochemical measurements. Ion conductance measurements between the two QRCEs, are shown to be sensitive to the nature of the substrate investigated. The fundamental electrochemical behaviour of CVD graphene and SWNT is investigated. A multimicroscopy approach is used for CVD graphene studies, correlating surface structure and activity, deducing heterogeneous electron transfer kinetics through simulation. The SWNT samples are studied in two different morphologies: as 3D forests; and, as a 2D network. In the forests, the probe is positioned at the ends and sidewalls, making spot measurements. The voltammetric behaviour shows very similar responses, whilst in the network, a nanosized probe is scanned across the surface, showing relatively uniform activity across an entire tube. These new insights indicate that SWNTs are highly active electrode materials. The fabrication and characterisation of SECM-SICM probes, in a straightforward manner is also presented. These types of probes were found to be ideal for the investigation of biological samples, being extremely easy and quick to fabricate.

Electrochemical techniques have potential for use in conservation, both to evaluate the protectiveness of existing coatings on metal artefacts and to evaluate potential new conservation coatings. Three electrochemical methods have been examined in this study for their applicability to conservation problems. Corrosion Potential Measurement is simple but provides only minimal information on the corrosion processes occurring in an electrochemical system. Electrochemical Impedance Spectroscopy provides both mechanistic and predictive information on coating performance, but the data are complex to interpret and measurements require equipment that is at present too bulky for effective on-site use and beyond the budget of most conservation laboratories. Electrochemical Noise Measurement can be performed using cheap, portable instrumentation and theoretically requires relatively simple statistical processing and interpretation, making it attractive for conservation applications. This project looks at the development of a simple, low cost electrochemical noise measurement system for conservation needs, and uses it to compare Electrochemical Noise Measurement with the other two techniques.

Scanning Kelvin Nanoprobe (SKN) microscopy is a new technique, based on Lord Kelvin's theory of contact electrification, which is able to measure changes in the work function of a surface with nanometre- scale precision. This technique has great potential in the analysis of surface chemistry, especially that of self-assembled monolayers and biochemical interactions. This thesis examines the potential of SKN microscopy in analytical chemical applications. SKN microscopy is used and contrasted against a range of other analytical techniques, including atomic force microscopy (AFM), confocal Raman spectroscopy and common electrochemical techniques such as cyclic voltammetry and electrochemical impedance spectroscopy. A short background is given on SKN microscopy, as well as the other analytical techniques used. This is followed by a chapter discussing the theory behind basic electrochemistry and the electroanalytical techniques used in the thesis. Work is then presented on the hydrogen bonding environment in mixtures of dimethylsulfoxide (DMSO) in water. Confocal Raman spectroscopy showed that the hydrogen bonding environment in DMSO:water mixtures had a profound effect on the S-H (thiol) group of the amino acid cysteine, as well as on the thiol groups of the small-molecule protein analogue BMC. As molecular biologists use DMSO:water mixtures extensively in studies, this work brings up important issues concerning these experiments. SKN microscopy was used with a range of other analytical techniques including AFM, Raman spectroscopy and cyclic voltammetry to probe the formation and characteristics of a new derivative of phthalocyanine synthesised to avoid crystalline formation and to naturally form an amorphous thin-film. Films were deposited on a variety of substrates, including gold, high-order pyrolytic graphite and glassy carbon, and were compared with a range of other phthalocyanine compounds. Simple computer modelling was also carried out on the compound. The derivative was found to form nanoporous films which allowed the passage of positively-charged molecules less then 7Å in diameter. Self-assembling monolayers of organothiols on gold were then probed using the SKN and electrochemical impedance spectroscopy. Selections of linear, branched, cyclic, aromatic and biological organothiols were tested. The SKN was capable of directly measuring the length of a linear alkanethiol from the change in work function of the monolayer. The SKN also proved capable of measuring the degree of organisation of the monolayer - branched and cyclic alaknethiols, which are expected to form looser-packed layers, recorded more significant changes in work function. These results were confirmed by the use of electrochemical impedance spectroscopy to measure the effects of a monolayer on an electrode surface.

This thesis documents studies directed towards the development of electrochemical measurement procedures capable of quantifying corrosion resistance and/or the corrosion rate in Tin Mill products, and in particular steel food/beverage cans. Chapters 3 and 4 describe electrochemical studies carried out using commercially produced cans. Conventional corrosion evaluation techniques were compared with Electrochemical Impedance Spectroscopy (EIS) data. EIS was found to provide useful information regarding container corrosion performance, however statistical variation from can to can required the use of large sample populations unless cans could be conserved between measurements. This was achieved by the development of "sealed-in-electrodes", which were used to identify trends in can coating performance. Sealed-in-electrodes form the basis of a predictive corrosion test method, whereby short-term electrochemical measurements may be extrapolated to predict long-term corrosion performance. Conventional electrochemical techniques provide a surface averaged measurement of the corrosion performance of coated metals, giving no information regarding the spatial distribution of penetrative defect sites in the organic coating. For this reason, a novel method for defect detection was developed, exploiting the phenomenon of electrogenerated chemiluminescence (ECL) in conjunction with digital (CCD) photography. The development, optimisation and evaluation of techniques for the spatially resolved characterisation of penetrative coating defect populations using luminol ECL is described in chapters 5 - 7. A proposed mechanism and kinetic model for the ECL process is described in chapter 5. Chapter 6 describes the application of luminol ECL to the detection of induced defects in a polymer laminate material, and an estimation of the limits of the technique. Chapter 7 describes the application of luminol ECL to the detection of defect populations in commercially produced polymer laminate cans. ECL images were suitable for computerised image analysis, providing information on the frequency, size distribution and location of penetrative defects.

Um eletrodo de carbono vítreo foi modificado pela deposição de uma camada de nanotubos de carbono de paredes múltiplas, funcionalizados e decorados com nanopartículas de ouro. Este eletrodo foi caracterizado por microscopia ótica, mostrando uma superfície homogeneamente recoberta. Além disto, a sua morfologia foi investigada por microscopia eletrônica de transmissão, onde observou-se a distribuição e o tamanho médio aproximado de 20 nm das nanopartículas de ouro. Estas nanopartículas metálicas também foram caracterizadas por espectroscopia de absorção na região do UV-vis, mostrando um máximo de absorção em aproximadamente 525nm, o que confirma o seu tamanho médio de 20 nm. Os eletrodos modificados foram caracterizados eletroquimicamente pelo seu comportamento voltamétrico em uma solução de H2SO4 0,1 mol L-1, com uma velocidade de varredura de 0,100 V s-1. Nestes experimentos, ficou evidente os picos de formação e redução do óxido de ouro em potenciais acima de 0,8 V vs Ag/AgCl. Ainda foi observado o bom funcionamento dos eletrodos pela resposta voltamétrica do par redox [Ru(NH3)6]Cl2 / [Ru(NH3)6]Cl3 em meio de KCl. O desempenho deste eletrodo modificado para a oxidação dos pesticidas carbaril, etil-paration, malation e carbendazim foi investigado por voltametria de onda quadrada em tampão fosfato pH 7, porém apenas o inseticida e fungicida carbendazim mostrou eletroatividade. Desta forma, os estudos posteriores se focaram neste pesticida. O voltamograma cíclico do carbendazim mostrou um pico de oxidação e, na varredura reversa, um pico bem menor de redução. Isto sugeriu um mecanismo EC e um esquema da reação de oxidação foi proposto. Com o perfil voltamétrico estabelecido, a voltametria de onda quadrada foi utilizada para a determinação da curva analítica para o pesticida. Com todos os parâmetros da voltametria de onda quadrada otimizados, uma dependência linear da corrente de pico de oxidação com a concentração de carbendazim foi obtida, com a equação: Ip = 0,1 + 4,30 [carbendazim], com r2 = 0,9911 (n = 5). Esta curva analítica mostrou que a metodologia apresenta um limite de detecção de 17 x 10-8 mol L-1. Esta metodologia foi empregada na determinação de carbendazim em amostras de suco de laranja contaminadas artificialmente. A utilização de um teste t, de Student, mostrou que os valores recuperados pela voltametria não apresentaram qualquer diferença significante em relação àqueles adicionados às amostras. Assim, esta metodologia foi validada para a utilização na análise de suco de laranja contaminado com carbendazim
A glassy carbon electrode was modified by depositing a layer of multi-walled carbon nanotubes, functionalized and decorated with gold nanoparticles. This electrode was characterized by optical microscopy, showing a evenly coated surface. In addition, the morphology was investigated by transmission electron microscopy, where the distribution and the average size of 20 nm of the gold nanoparticles were observed. These metal nanoparticles were also characterized by absorption spectroscopy in the UV-vis region showing an absorption maximum at approximately 525 nm, which confirms their average size of 20 nm. The modified electrodes were electrochemically characterized by its voltammetric behavior in a 0.1 mol L-1H2SO4 solution, with a scanning rate of 0.100 V s-1. In these experiments, it became clear the formation and reduction of gold oxide peaks at potentials above 0.8 V vs. Ag/AgCl. It was also observed the proper functioning of the electrodes for the voltammetric response of the redox couple [Ru(NH3)6]Cl2/[Ru(NH3)6]Cl3 in a KCl electrolyte. The performance of the modified electrode for the oxidation of the pesticides: carbaryl, ethyl-parathion, malathion and carbendazim was investigated by square wave voltammetry in phosphate buffer, pH 7, but only the insecticide and fungicide carbendazim showed electroactivity. Thus, future studies focused on this pesticide. The cyclic voltammogram of carbendazim in phosphate buffer showed an oxidation peak and in the reverse scan, a much smaller reduction one. It suggested an EC mechanism and an oxidation reaction scheme was proposed. With the voltammetric profile established, square wave voltammetry was used to determine the calibration curve for the pesticide. With all square wave voltammetric parameters optimized, a linear dependence of the oxidation peak current with the concentration of carbendazim was obtained, with equation: Ip = 0.1 ± 4.30 [carbendazim] with r2 = 0, 9911 (n = 5). This calibration curve showed that the method has a detection limit of 17 x 10-8mol L-1. This methodology was used in the determination of carbendazim in orange juice samples artificially contaminated. A t-test of Student showed that the amounts recovered by voltammetry showed no significant difference in relation to those added to the samples. Thus, this methodology has been validated for use in analysis of orange juice contaminated with carbendazim