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Niobium (Nb) has the highest superconducting transition temperature (9.2 K) of the pure metals, which makes it the most used material for the construction of superconducting radio frequency (SRF) accelerators. The performance of the accelerator is critically dependent upon the quality of Nb surface. Electropolishing (EP) in hydrofluoric acid (HF)-containing electrolytes is the currently accepted treatment process. The presence of HF is necessary for the removal of the passive oxide surface film formed in aqueous electrolytes. But HF is hazardous and must be contained without human exposure and eliminated in an environmentally appropriate manner. In the present dissertation project, HF-Free EP of Nb was performed in sulfuric acid-methanol electrolytes. Sulfuric concentrations of 0.1 M, 0.5 M, 1 M, 2 M, and 3 M were used. Cyclic voltammetry and potential hold experiments were performed in cells of both two-electrode and three-electrode setups to evaluate the electrochemical process. The influence of electrolyte concentration, temperature, and EP duration was investigated. At room temperature, both the corrosion rate and the surface quality obtained were comparable to those currently obtained with HF-based processing. With decreasing temperature, the mean current level decreased and the surface quality improved substantially. For a desired average material removal of 100 μM, nanometer scale surface roughness was obtained under multiple conditions. Mechanism of EP was also investigated by electrochemical impedance spectroscopy (EIS). The EIS diagram indicates the presence of a compact film during EP at mass transport controlled limiting current and a film-free surface during EP at ohmic controlled current. Transfer from a film-free surface to an anodic film precipitation with decreasing temperature was also observed. Microsmoothing is only achieved under mass transport control. Nb⁵⁺ ions are determined to be the mass transport limiting species. / Ph. D.

This work presents the development of a laser-induced fluorescence technique to measure atmospheric formaldehyde. In conjunction with the technique, the design of a compact, narrow linewidth, etalon-tuned titanium:sapphire laser cavity which is pumped by the second harmonic of a kilohertz Nd:YAG laser is also presented. The fundamental tunable range is from 690-1100 nm depending on mirror reflectivities and optics kit used. The conversion efficiency is at least 25% for the fundamental, and 2-3% for intracavity frequency doubling from 3.5-4W 532 nm pump power. The linewidth is < 0.1 cm-1, and the pulsewidth is 18 nsec. Also presented are observations of gas-phase sulfuric acid from the NEAQS-ITCT 2K4 (New England Air Quality Study Intercontinental Transport and Chemical Transformation) field campaign in July and August 2004. Sulfuric acid values are reported for a polluted environment and possible nucleation events as well as particle growth within the boundary layer are explored. Sulfate production rates via gas phase oxidation of sulfur dioxide are also reported. This analysis allows an important test of our ability to predict sulfuric acid concentration and probe its use as a fast time response photochemical tracer for the hydroxyl radical, OH. In comparison, the NASA time-dependent photochemical box model is used to calculate OH concentration. Nighttime H2SO4 values are examined to test our understanding of nocturnal OH levels and oxidation processes. In comparison, sulfuric acid from a large ground based mission in Tecámac, México (near the northern boundary of Mexico City) during MIRAGE-Mex field campaign (March 2006) is presented. The observations in conjunction with the NASA LARc Photochemical box model are used to explore ozone production, nitrate and sulfate formation, and radical levels and radical production rates during the day. The one minute observations of sulfuric acid, sulfur dioxide, and aerosol surface area were again used to calculate OH levels assuming steady state, and are in good agreement with observations of OH (R2 = 0.7). Photochemical activity is found to be a maximum during the morning hours, as seen in ozone and nitrate formation.

Thesis ((DMed)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: We have developed an innovative multimedia e-learning resource, the Electrolyte Workshop, to provide students and clinicians with instruction and the opportunity for simulated practice in managing electrolyte and acid-base disorders. Our teaching approach is built around relevant physiology and makes use of real cases and storytelling to engage the learner. We have documented the challenges encountered during the development process and have made recommendations for the managing of similar projects. While there are many factors that must be in place to ensure successful e-learning, this dissertation focuses on an important but under-appreciated factor, namely the usability of the computer interface. Usability describes how easy technology interfaces are to use and is routinely evaluated and optimized in the software development industry. This is not yet the case with e-learning, especially in the area of medical education. Poor usability limits the potential benefit of educational resources, as this means that learners will struggle with the interface as well as with the challenges of the content presented. A comprehensive usability evaluation of our Electrolyte Workshop was completed. This included testing with typical end-users, where data were collected via standardized questionnaires and by observing and analysing their interactions with our application. We employed heuristic evaluation as an additional approach and assembled a panel of experts to evaluate our application against a set of heuristics, or principles of good interface design. Many serious usability problems were identified, thus severely limiting the potential educational impact of our Electrolyte Workshop. There was a striking disconnect between the objective measures of usability and self-reported questionnaire data. Our user-testing data make a useful contribution to the debate on how many users are required to find most of the usability problems in an interface. Heuristic evaluation proved to be a very efficient approach. However, both user testing and heuristic evaluation detected serious problems which were missed with the other method. These evaluations informed a comprehensive revision of our application and we could then compare the original with an optimized version in a randomized trial. We found large improvements in objective usability measures, which are likely to increase the satisfaction and motivation of learners. There were similar scores on measures of learning. This was not surprising as our participants were all relatively high-knowledge learners and not novices as regards the subject matter. Our study clearly indicates that the usability evaluation of e-learning resources is critical, and provides an example of how clinician-teachers can improve the usability of the resources they develop. Usability should be evaluated as a routine part of the development and implementation of e-learning materials, modules and programmes. This should start with the earliest versions of the resource, when making changes is easier and less costly. We have demonstrated that a combination of methods should be employed and have highlighted the utility of heuristic evaluation. An iterative approach should be followed, with several cycles of testing and re-design. User testing should always include the study of objective usability measures and not rely only on self-reported measures of user satisfaction. / AFRIKAANSE OPSOMMING: Ons het ’n innoverende multimediahulpbron vir e-leer, die Electrolyte Workshop, ontwikkel om studente en klinici van ’n onderrighulpmiddel sowel as die geleentheid vir gesimuleerde oefening in die hantering van elektroliet en suur-basis stoornisse te voorsien. Ons onderrigbenadering is gegrond op relevante fisiologie en maak gebruik van werklike gevalle en vertelkuns om die leerder te betrek en te boei. Ons het die uitdagings gedurende die ontwikkelingsproses opgeteken en aanbevelings oor die bestuur van soortgelyke projekte gedoen. Hoewel suksesvolle e-leer van etlike faktore afhang, konsentreer hierdie verhandeling op ’n belangrike dog onderskatte faktor, naamlik die bruikbaarheid van die rekenaarkoppelvlak. Bruikbaarheid verwys na die gemak waarmee tegnologiekoppelvlakke gebruik kan word, en word gereeld in die sagtewareontwikkelingsbedryf beoordeel en verbeter. Tog is dit nog nie die geval met e-leer nie, veral op die gebied van mediese onderrig. Swak bruikbaarheid beperk die moontlike voordeel van opvoedkundige hulpbronne, aangesien leerders voor die dubbele uitdaging van ’n ingewikkelde koppelvlak én die voorgeskrewe inhoud te staan kom. ’n Omvattende bruikbaarheidsbeoordeling is van die Electrolyte Workshop onderneem. Dit het toetsing met tipiese eindgebruikers ingesluit, waarvoor data met behulp van gestandaardiseerde vraelyste ingesamel en gebruikers se interaksie met die toepassing waargeneem en ontleed is. Ons het heuristiese evaluering as bykomende benadering gebruik en ’n kennerspaneel saamgestel om ons toepassing aan die hand van ’n stel heuristiek, oftewel beginsels van goeie koppelvlakontwerp, te beoordeel. ’n Hele aantal ernstige bruikbaarheidsprobleme is uitgewys, wat die moontlike opvoedkundige impak van die Electrolyte Workshop erg beperk. Daar was merkbare teenstrydigheid tussen die objektiewe bruikbaarheidsmaatstawwe en die selfaangemelde vraelysdata. Ons gebruikerstoetsdata lewer ’n waardevolle bydrae tot die debat oor hoeveel gebruikers nodig is om die meeste van die bruikbaarheidsprobleme met ’n koppelvlak te ontdek. Heuristiese evaluering was ʼn baie doeltreffende benadering. Tog het gebruikerstoetsing op sekere ernstige probleme afgekom wat heuristiese evaluering misgekyk het, en andersom. Hierdie beoordelings het as grondslag gedien vir ’n omvattende hersiening van die toepassing, waarna ons die oorspronklike weergawe in ’n verewekansigde proef met ’n verbeterde weergawe kon vergelyk. Die objektiewe bruikbaarheidsmaatstawwe het groot verbeterings getoon, wat waarskynlik leerders se tevredenheid en motivering sal verhoog. Leermaatstawwe het soortgelyke tellings opgelewer. Dít was egter te wagte gewees, aangesien die deelnemers almal betreklik ingelig was oor die vakmateriaal, eerder as nuwelinge. Ons studie het bevestig dat die bruikbaarheidsbeoordeling van e-leerhulpbronne noodsaaklik is, en bied ’n voorbeeld van hoe klinici-opvoeders bruikbaarder hulpbronne kan ontwikkel. Bruikbaarheid behoort as ’n roetinedeel van die ontwikkeling en inwerkingstelling van e-leermateriaal, -modules en -programme beoordeel te word. Dit behoort reeds by die vroegste weergawes van die hulpbron te begin, wanneer dit makliker en goedkoper is om veranderinge aan te bring. Ons het ook getoon dat ’n kombinasie van metodes gebruik behoort te word, en het die nut van heuristiese evaluering beklemtoon. ’n Herhalende benadering moet gevolg word, met etlike siklusse van toetsing en herontwerp. Gebruikerstoetsing behoort altyd die beoordeling van objektiewe bruikbaarheidsmaatstawwe in te sluit, en moenie slegs op selfaangemelde maatstawwe van gebruikerstevredenheid staatmaak nie.

Le dopage non covalent de nanostructures carbonées par transfert de charge depuis/vers des molécules donneuses ou acceptrices (EDA) ou bien par des molécules d’acide sulfurique H2SO4, est considéré comme potentiellement intéressant pour de nombreuses applications. Parmi celles-ci on peut citer: capteur chimique, transistor à effet de champ, et d’autre l'électronique. Cependant, d'un point de vue théorique, on en sait peu au sujet de ces processus de transfert de charge par électrons ou par trous.Dans un premier temps, nous nous sommes intéressés à l’interaction entre des molécules d’acide sulfurique et des nanostructures modèles, car elles sont capables de doper des nanotubes, de s’intercaler dans le graphite et même d’aligner les tubes dans une phase nématique, ce qui pourrait mener à la création de matériaux composites à forte valeur ajoutée.Bien que certaines études théoriques DFT ont été menées récemment, leurs résultats restent source de confusion. Par exemple, même s’il est rapporté un transfert de charge entre une molécule de H2SO4 et un plan de graphène, tous nos efforts pour reproduire ces calculs ont été infructueux. Nous proposons dans ce travail de thèse, un mécanisme de réaction qui expliquent la "protonation" des parois du tube, tel que proposé dans la littérature. Enfin nous proposons un scénario possible pour une meilleure compréhension de la structuration à grande échelle des molécules d'acide autour de points d'ancrage, telles que des défauts, de la structure carbonée / Non-covalent doping of carbon nanostructures by charge transfer from/to donor/acceptor molecules (EDA) or by H2SO4 molecules, be it with holes or electrons, is usually thought as potentially interesting for many applications of carbon based nano-devices. However, from a theoretical point of view, little is known about such “charge transfer” processes.Employing first-principles method based on Density Functional Theory (DFT), we have studied in details, and proposed a model to rationalize, the interaction between a prototypical donor molecule the tetrathiafulvalene (TTF), a standard acceptor organic molecule, tetracyanoethylene (TCNE) and carbon nanostructures: graphene layer and SWNTs with various chiral indices. Main results concern structural and thermodynamic aspects including dispersion forces effects, and evidently electronic structure modifications of the nanostructures. Various adsorption modes and concentration effects have been investigated. At very low coverage values, we have reported a charge transfer between graphene and TCNE or TTF. Moreover, we have shown that the charge transfer can be enhanced by increasing the concentration of those two EDA molecules, as it has been demonstrated experimentally. Those results are beneficial for comprehending the nonchemical doping mechanism in graphene structure by means of charge transfers. Considering the interaction between these prototypical molecules and carbon nanotubes, we have found that charge transfers tend to decrease while the curvature of nanotube is increasing. Besides, a strong influence of the metallic/semi-conductor character of the SWNTs can be observed and be explained by the change of polarisability of the curved carboneous substrates. Additionally, we have studied the adsorption properties of sulfuric acid molecules, in its non-hydrated form, on carboneous nanostructures. Against the common believe, no charge transfer is observed in the H2SO4@graphene or H2SO4@CNTs cases, even at very high concentrations. Instead, in order to elucidate the origin of p-doping observed experimentally, we have proposed that molecule is responsible of the reversible doping. Besides we have shown that a proton transfer could cause the experimental phenomenon of crystallization of H2SO4 molecules on SWNT’s surface. Finally in such process, defects like vacancy are of first importance, since they could provide anchorage points for hydrogen atoms. The results of the present work will certainly help to understand the charge transfer and doping mechanism of carbon nanostructures by means of non-covalent functionalization, which is a promising method for their future applications

Ligas de níquel têm atualmente uma vasta gama de aplicações, sendo a agressividade do meio e as elevadas temperaturas que estas ligas suportam, um diferencial excepcional. A liga UNS N07090, objeto deste trabalho, encontra aplicações muito diversas, entre elas turbocompressores, sistemas de exaustão e de pós-tratamento de motores a diesel. Nestas aplicações a liga está exposta a gases, que ao condensarem formam ácido sulfúrico (H2SO4). Torna-se, assim, importante, o conhecimento da resistência à corrosão da liga nesse meio. O presente trabalho tem como objetivo caracterizar o comportamento eletroquímico da liga através de curvas de polarização potenciodinâmica em diferentes concentrações de ácido sulfúrico. Observou-se que quanto maior a concentração de ácido, maior é a corrosão da liga. Este fato pode ser discutido pela adsorção do íon sulfato (SO42-), que prejudica tanto a formação quanto a cinética de crescimento da película passiva do níquel. Em contrapartida, a presença de Cr na liga UNS N07090 apresentou um benefício sobre a resistência à corrosão desta muito acima do esperado, influenciando de forma direta as curvas de polarização da liga e mantendo-a em condição de elevada resistência à corrosão em detrimento do pior desempenho observado em outros elementos pertecentes à liga, como Co, Al e Ti. Tempos de imersão de 24h em ácido sulfúrico elevam discretamente os parâmetros de corrosão da liga, mantendo-os, no entanto em patamares bastante baixos, permitindo finalmente concluir que a liga UNS N07090, quando exposta a concentrações que variam de 1M a 4M H2SO4, a 25°C, apresenta boa resistência à corrosão e que esta não se altera com o tempo de exposição. A análise dos resultados mostrou que o processo corrosivo é controlado por reações catódicas de sulfato e hidrogênio, as quais podem ter diferentes contribuições dependendo da concentração do ácido e do tempo de imersão da liga UNS N07090 no meio corrosivo. / Nickel alloys have a wide range of application nowadays due to their excellent resistance to aggressive media and high temperatures. UNS N07090, the nickel alloy studied herein, is used for turbochargers, exhaust and after treatment systems of diesel engines. These applications expose the alloy to hot gases, which condensate forming sulfuric acid (H2SO4). It is thus important to know the corrosion resistance of the alloy in this media. The goal of this work is the characterization of the electrochemical behaviour of UNS N07090 alloy through potentiodynamic polarization curves in different sulfuric acid concentrations. On the one hand, higher acid concentrations were noticed to lead to higher corrosion of the alloy. This phenomenon can be discussed by sulfate (SO42-) adsorption, which negatively influences not only the formation but also the growth of the passive film on nickel. On the other hand, the presence of Cr in UNS N07090 composition, improves the corrosion resistance of the alloy far more than expected, directly affecting the shape of the polarization curves of the alloy, placing it in a condition of high corrosion resistance despite the worst performance shown by the other elements present in the chemical composition of the alloy, such as Co, Al and Ti. 24h immersion periods in sulfuric acid slightly raise corrosion parameters of UNS N07090 alloy, but still ranking the alloy in very good corrosion resistance. Finally, it can be concluded that UNS N07090 alloy exposed to 1M to 4M H2SO4 at 25°C presents good corrosion resistance and that this is not affected by longer immersion periods. The results showed that the corrosion process of alloy UNS N07090 is controlled by sulfate and hidrogen cathodic reactions, which have stronger or weaker contribution depending on acid concentration and immersion time on the corrosive media.

O presente trabalho tem como objetivo caracterizar o aco inoxidavel ferritico UNS S44400 quanto a sua resistencia a corrosao em comparacao a dois acos inoxidaveis austeniticos UNS S30403 e S31603, utilizando ensaios de perda de massa e eletroquimicos, tanto em meio acido quanto em meio contendo cloreto. A utilizacao dos inoxidaveis ferriticos vem crescendo em detrimento da utilizacao dos austeniticos tanto no Brasil, quanto no mundo, principalmente devido ao cenario instavel do preco do Ni. Sendo assim, cada vez mais se torna necessaria a obtencao de argumentos tecnicos e cientificos que permitam comparar diferencas entre as duas familias, mostrando suas vantagens e desvantagens. Os metodos utilizados para a avaliacao da resistencia a corrosao generalizada foram perda de massa (apos imersao) e polarizacao potenciodinamica em 0,5M H2SO4. A resistencia a corrosao por pite foi estudada atraves de polarizacao potenciodinamica ciclica em 3,5%NaCl. No caso especifico dos meios contendo cloreto, alem de se estudar os materiais com acabamento de lixa #600, obtido em laboratorio, optou-se por um estudo mais detalhado em funcao do acabamento superficial obtido em usina. Os acabamentos examinados foram: (i) material recozido, decapado em Usina e lixado em laboratório (até lixa #600) - (LL); (ii) material recozido e decapado em Usina - (RD); e (iii) material recozido, decapado em Usina, tratado termicamente em laboratório e lixado (até lixa #600) - (SL). Em meio acido, os acos austeniticos nao apresentaram corrosao, enquanto o ferritico apresentou uma taxa de corrosao constante de 0,0146 mg.cm-2.min-1 (8,4x10-4 A.cm-2) para imersoes ate 24h. Pela aplicacao do metodo de extrapolacao do trecho linear de Tafel foi obtido valor similar de densidade de corrente, de 4,57x10-4 A.cm-2, ou seja possuem a mesma ordem de grandeza. Diferentemente dos resultados obtidos em meio acido, nos ensaios de resistencia a corrosao em meio contendo cloreto, o aco UNS S44400 apresentou potencial de pite superior (em 3,5%NaCl) ao UNS S30403 e valores muito proximos ao do aco UNS S31603, para todas as condicoes de acabamento superficial examinadas. Alem disso, foi observado um relevante efeito das condicoes de tratamento termico de solubilizacao dos materiais: o tratamento de solubilizacao realizado em laboratorio aumentou o potencial de pite. Os resultados de potencial de pite medio - Ep - obtidos antes do tratamento termico foram: 77mVAg/AgCl para o UNS S44400, 43mVAg/AgCl para o UNS S30403 e 345mVAg/AgCl para o UNS S31603, sendo que apos solubilizacao o Ep medio foi de: 336mVAg/AgCl; 294mVAg/AgCl e 374mVAg/AgCl, respectivamente. Por sua vez, ha diferenca de desempenho quando aplicados os diferentes acabamentos superficiais. Com relacao ao acabamento proveniente de Usina, ou seja, recozido e decapado (RD), foi o que resultou em melhor desempenho. Apesar da media resultante alta para o acabamento RD, a dispersao dos resultados tambem foi alta. Comparando-se os acos UNS S44400 e UNS S31603, recozidos e decapados o 444 teve um potencial de pite de (500 + 173)mVAg/AgCl, e o aco 316 apresentou (568 + 167)mVAg/AgCl. Nota-se, portanto, que quando a aplicacao exige resistencia a corrosao em meio contendo ion cloreto, o aco 444 pode substituir o 316L. / The main reason of this work is the characterization of the ferritic stainless steel UNS44400 regarding its corrosion resistance when compared to two austenitic steels, UNS 30403 and UNS31603, using loss of weight and electrochemical tests, in acid and chloride environments. The application of ferritic stainless steel is increasing, both in the Brazilian an international market, especially because of the nickel cost instability. So, more information is necessary regarding each kind of material, allowing the comparison of these two families showing their advantages and disadvantages in different applications. For that reason, the main purpose of this work is the characterization of the corrosion resistance of a ferritic stainless steel, UNS S44400, comparing it with two austenitic stainless steels, UNS S30403 and S31603. Weight loss and electrochemical tests were conducted in acid or chloride environments. The general corrosion resistance was analyzed through weight loss measurements and electrochemical polarization in 0,5M H2SO4. The pitting corrosion resistance was studied through polarization in 3,5%NaCl. For the tests in chloride environment, it was done a study comparing laboratory and mill finishing proceducts: annealed and pickled and wet sand in laboratory - (LL); annealed and pickled - (RD); annealed and pickled, heat treated in laboratory and wet sand in laboratory - (SL). In acid environment, the austenitic stainless steel did not show weight loss, while the ferritic had a constant corrosion rate of 0,0146 mg.cm-2.min-1 (8,4x10-4. A.cm-2) until 24 hours of immersion. This result was confirmed by the extrapolation of linear portion of the polarization curves (Tafel method), whose current density was 4,57x10-4 A.cm-2. In chloride environment, the UNS S44400 steel showed higher pitting potential in 3,5%NaCl compared to UNS S30403 and similar results for all finishes when compared with UNS S31603. Besides, it was observed that the heat treatment that was done in laboratory raised pitting potential. The pitting potential results were: before heat treatment, 77mVAg/AgCl for UNS S44400, 43mVECS, for UNS S30403 and 345mVAg/AgCl for UNS S31603; and after heat treatment they were: 336mVAg/AgCl; 294mVAg/AgC; and 374mVAg/AgCl, respectively. The annealed and pickled material that was tested directly from the Mill (RD) presented the highest pitting potential showing the importance of pickling process. Comparing the annealed and pickled UNS S44400 steel with UNS S31603, the mean pitting potential was (500 + 173)mVAg/AgCl and (568 + 167)mVAg/AgCl respectively, and considering the deviation of the tests, it was proved that it is possible to apply both UNS S44400 or UNS S31603 when a high pit corrosion resistance is required.