Objectif : il a été rapporté que l’utilisation d’agents prophylactiques fluorés pouvait favoriser la corrosion galvanique au sein des alliages de titane. L’objectif de la présente étude était d’évaluer l’effet d’un rince-bouche fluoré sur les propriétés mécaniques de fils en nickel-titane (NiTi) et de fils en cuivre-nickel-titane (CuNiTi) lorsque ces derniers sont couplés à des boîtiers de compositions différentes (boîtiers de marques Smartclip, Clarity, et Sprint). Matériels et Méthodes : 90 segments de fils en NiTi et 90 segments de fils en CuNiTi ont été chacun couplés à 2 boîtiers de chaque marque. Chaque assemblage fil-boîtiers a été par la suite incubé pendant 3 heures à 37°C, soit dans une solution de fluore neutre (Fluorinse™ 0,05% NaF), soit dans une solution de salive artificielle (solution contrôle). Suite à l’incubation, les échantillons étaient nettoyés avec de l’eau déshydrogénée, les fils séparés des boîtiers et montés sur un support pour subir un test de pliage en trois points en milieu humide (salive artificielle) à 37°C. Les modules d’élasticité ainsi que les limites conventionnelles d’élasticité en activation et en désactivation ont été mesurés et comparés. Des analyses de Variance (ANOVA) et des comparaisons post-hoc avec la correction de Bonferronni ont été utilisées pour comparer les groupes entre eux (α = 0,05). Résultats : L’utilisation d’un rince-bouche fluoré a produit une réduction du module d’élasticité et de la limite conventionnelle d’élasticité en activation et en désactivation pour les fils en NiTi ; cependant, cet effet a été modulé par le type de boîtier auquel le fil a été couplé. Les propriétés mécaniques de fils en CuNiTi n’ont pas été affectées par le fluor, ou par le type de boîtier utilisé. Conclusions : L’utilisation d’un rince-bouche fluoré modifie les propriétés mécaniques des fils en NiTi seulement. Cet effet est modulé par le boîtier auquel le fil en NiTi est couplé. A la différence des autres études publiées dans la littérature, nos résultats ne nous permettent pas de conclure que la modification des propriétés mécaniques des fils en NiTi entrainerait obligatoirement un allongement de la durée du traitement orthodontique. Mots clés : Fluor, fils nickel-titane, boîtiers orthodontiques, corrosion galvanique, propriétés mécaniques. / Aim: it has been reported that the use of fluoride prophylactic agents can cause galvanic corrosion of the titanium based alloys used in orthodontics. The purpose of the present study was to investigate the effects of a fluoride mouthrinse on the mechanical properties of nickel-titanium (NiTi) and copper–nickel-titanium (CuNiTi) orthodontic archwires that have been coupled with different types of orthodontic brackets (Smartclip, Clarity, and Sprint brackets). Materials and Methods: 90 segments of NiTi and 90 segments of CuNiTi archwires were tested. Every segment was coupled with 2 brackets of each brand. The wire–bracket assembly obtained was incubated, at 37°C for three hours either in a solution of a commercially available mouthwash (Fluorinse™ 0,05% NaF), or in a solution of artificial saliva (control). Following the incubation, the wires were separated from the brackets, rinsed, mounted on a stainless steel support and placed in a waterbath of artificial saliva at 37°C. A 3-point bending test was made to calculate the loading and unloading elastic modulus and yield strength of the wires. Analysis of variance (ANOVA) and post hoc comparisons were made using Bonferronni’s correction to identify the statistically significant differences (α = 0,05). Results: The use of a fluoridated mouthrinse reduced the loading and unloading elastic modulus and yield strength of the NiTi wires. This reduction, however, varies with the type of bracket that was coupled with the wire. The mechanical properties of the CuNiTi wires were not modified by the use of the fluoride rinse or by the type of bracket to which they were coupled. Conclusions : The use of a fluoride mouthrinse alters the mechanical properties of NiTi wires only. This effect varies with the type of bracket that was in contact with the wire. However our results do not allow us to conclude that the alteration of the mechanical properties of the wires would necessarily imply a prolongation of the orthodontic treatment time. Key words: Fluoride, nickel-titanium archwires, galvanic corrosion, mechanical properties,orthodontic brackets.

Implantable sensors have been extensively investigated to facilitate diagnosis or to provide a means to generated closed loop control of therapy by yielding in vivo measurements of physical and chemical signals. Biodegradable sensors which degrade gradually after they are no longer functionally needed exhibit great potential in acute or shorter-term medical diagnostic and sensing applications due to the advantages of (a) exclusion of the need to a secondary surgery for sensor removal, and (b) reduction of the risk of long-term infection. The objective of this research is to design and characterize microfabricated RF wireless pressure sensors that are made of completely biodegradable materials and degrade at time-controlled manner (in the order of years and months). This was achieved by means of investigation of appropriate biodegradable materials and development of appropriate fabrication processes for these non-standard (Microelectromechanical systems) MEMS materials. Four subareas of research are performed: (1) Design of sensors that operate wirelessly and are made of biodegradable materials. The structure of the wireless sensor consists a very compact and relatively simple design of passive LC resonant circuits embedded in a polymer dielectric package. To design the sensor with a particular resonant frequency range, an electromagnetic model of the sensor and a mechanical model for circular plate are developed. The geometry of the sensor is established based on the analytical and finite element simulations results. (2) Investigation of the biodegradable materials in the application of implantable biodegradable wireless sensors to achieve controllable degradation lifetimes. Commercially available and FDA approved biodegradable polymers poly(L-lactic acid) (PLLA) and a "shell-core" structure of poly(lactic-co-glycolic acid) (PLGA) and polyvinyl alcohol (PVA) are utilized as the dielectric package for slow and rapid degradation sensors, respectively. Biodegradable metallic zinc and zinc/iron couples are chosen as conductor materials. The degradation behavior of Zn and Zn/Fe-couple are investigated in vitro. (3) Development of novel fabrication processes. The process exploit the advantages of MEMS technology in fabricating miniaturized devices, while protecting vulnerable biodegradable materials from the strong and/or hazardous chemicals that are commonly used in conventional MEMS fabrication process. These new processes enable the fabrication of biocompatible and biodegradable 3-D devices with embedded, near-hermetic cavities. (4) Testing the pressure response functionality and studying the degradation behavior of the wireless biodegradable pressure sensors. Both PLLA-based and PLGA/PVA-based sensors are characterized in vitro by being immersed in 0.9% saline for prolonged time. All the sensors exhibit three stages of behavior in vitro: equilibration, functional lifetime, and performance degradation. During the functional lifetime, most sensors exhibit fully stable functionality. The PLLA-based sensors show no significant weight loss within 8 month and are expected to fully degrade after 2 years, while the PLGA/PVA-based sensors can degrade completely within 26 days.

Diss. (sammanfattning) Linköping : Univ., 2004. / Härtill 5 uppsatser.

Des méthodes électrochimiques classiques, et des caractérisations photoélectrochimiques (PEC), utiliséesex-situ et in-situ, ont permis d’étudier le phénomène de Shadow Corrosion, considéré ici comme une corrosion galvanique entre des alliages de zirconium et de nickel, corrosion influencée par l’environnement chimique et l’irradiation de ces alliages. Une cellule électrochimique simulant les conditions d’un réacteur à eau bouillante (REB), permettant l’illumination UV--Visible des échantillons et le contrôle de la chimie de l’eau, a été conçue, développée et validée. Cette cellule a permis de mesurer pour la première fois des spectres en énergie de photocourant d’un alliage de zirconium, in-situ en milieu REB simulé. Par ailleurs, les résultats expérimentaux obtenus tendent à montrer que les impuretés de type cations métalliques jouent un rôle important dans le mécanisme d’activation du couplage galvanique, donc potentiellement dans le mécanisme d’activation du phénomène de Shadow Corrosion, alors que la présence d’oxygène et/ou de peroxyde d’hydrogène n’induit pas de différences significatives du comportement électrochimique des échantillons. Il est montré également que l’illumination UV--Visible des échantillons, qui amplifie notablement les courants de couplage, est un paramètre important du phénomène de Shadow Corrosion. / Conventional electrochemical methods as well as photoelectrochemical characterisations (PEC), performedex-situ et in-situ, were used to study the Shadow corrosion phenomenon, considered as a galvanic corrosion between Zr-based and Ni-based alloys. The Shadow corrosion is influenced by the chemical environment and the irradiation of these alloys. An electrochemical cell , simulating the conditions of a boiling water reactor (BWR), allowing the illumination of the samples with UV--Visible as well as monitoring the water chemistry was designed, developed and validated. The cell allowed, for the first time, recording of emph{in-situ} photocurrent energy spectra on a Zr-based alloy in simulated BWR environment. Furthermore, the obtained experimental results pointed out that the metallic cation impurities played an important role in the activation mechanism of the galvanic coupling, thus potentially in the activation mechanism of the Shadow corrosion phenomenon, whereas the presence oxygen and/or hydrogen peroxide did not induce significant differences in terms of electrochemical behavior of the samples. It was also shown that the illumination of the sample with UV--visible light, which significantly amplified the galvanic current, is an important parameter of the Shadow corrosion phenomenon.

Le soudage par friction (Friction Stir Welding - FSW) est un processus efficace de se joindre des alliages d'aluminium à haute résistance en évitant les défauts que l'on trouve habituellement lorsque les techniques de soudage classiques sont utilisés. L'industrie de l'aviation a montré un grand intérêt pour cette méthode de soudage, tant pour l'union des alliages semblables comme pour dissemblables. Cependant, ce processus entraîne des changements de microstructure dépendantes des conditions de traitement thermique ou thermomécanique. Le contact électrique entre les différentes zones de microstructures, à son tour, peut conduire à un couplage galvanique entre les différentes zones. Dans la présente étude, le soudage FSW a été utilisé pour joindre deux alliages d'aluminium dissemblables,AA2024-T3 et AA7475-T651. La résistance à la corrosion des joints soudés a été évaluée par des tests électrochimiques, en particulier, les mesures de potentiel en circuit ouvert(OCP), les courbes de polarisation, et des mesures de spectroscopie d'impédance électrochimique, soit globale (EIS) ou local (LEIS) en solution de 0,1 M Na2SO4 ou 0,1MNa2SO4 + 1 mM NaCl. Les tests électrochimiques ont montré l'effet de couplage galvanique dans les joints soudés. La résistance à la corrosion intergranulaires et la résistance à corrosion par exfoliation des joints soudés ont également été évaluées et comparées à celles du AA2024-T3 et les alliages AA7475-T651 non soudées. Les résultats ont montré une réactivité accrue des joints soudés en comparaison avec les alliages non soudés en notant l'attaque plus intense sur l'alliage AA7475-T651. L'identification des zones cathodiques et anodiques dans les joints soudées ont été évaluée par un test consistant à déposer un gel(agar) avec l'indicateur universel et il a été observé que l'alliage AA2024-T3 a agi en tant que cathode, tandis que la AA7475- T651 comme anode. Par ailleurs, le dégagement d'hydrogène a été observée dans la région d'interface entre la zone affectée thermomécaniquement et l'alliage AA7475-T651 affectée par la chaleur. Les résultats des essais de LEIS effectuées dans différentes zones des deux alliages soudés par FSW ont montré l'engagement galvanique à l'interface entre eux pour de courtes durées d'analyse etde déplacement de la région la plus active dans le temps de test pour l'alliage AA7475-T651,plus précisément à l'interface entre la zone affectée thermomécaniquement et la thérmique affectée de cette alliage. / Friction Stir Welding (FSW) is an efficient process of joining high strength aluminum alloys avoiding defects that are usually created when conventional welding techniques are used. The aircraft industry has shown great interest in this welding method, both for welding of similar or dissimilar alloys. However, this process causes microstructural changes that are dependent on the thermal or thermomechanical conditions applied. Electrical contact between zones of different microstructures, in turn, can result in galvanic coupling. In the present study, FSW was used to join two dissimilar aluminum alloys, AA2024-T3 and AA7475-T651 and the effect of this processon the corrosion resistance of the welded joints and on the microstructure of the alloys was evaluated. For corrosion resistance evaluation, electrochemical tests were used, specifically,open circuit potential measurements (OCP) as a function of time of exposure time to the corrosive environment, polarization tests, and electrochemical impedance spectroscopy, global (EIS) orlocal (LEIS), in two solutions, either 0.1 M Na2SO4 or 0.1M Na2SO4 + 1 mM NaCl. The electrochemical tests showed galvanic coupling effects in the welded joints. Microstructural characterization was carried out by optical microscopy, scanning electron microscopy,transmission electron microscopy and differencial scanning calorimetry. The welded affected zones showed significant microstructural changes indicated by precipitation and dissolution of precipitates that affect the localized corrosion resistance. Intergranular and exfoliation corrosion resistance of the welded joints were also evaluated and compared to those of unwelded AA2024-T3 and AA7475-T651 alloys. The results showed increased susceptibility of welded joints to these forms of corrosion in comparison with the unwelded alloys with more severe attack associated tothe AA7475-T651 alloy. Identification of anodic and cathodic areas due to galvanic coupling in the welded joints was evaluated by a test consisting in depositing a gel layer (ágar-ágar) with universal indicator on the surface of the welded alloys. The AA2024-T3 alloy worked as cathode,while the AA7475-T651 as anode in the galvanic coupling. Furthermore, hydrogen evolution was observed at the interface region between the thermomechanically affected zone and the heat affected alloy AA7475-T651 showing that cathodic reactions also occurred on this last alloy. LEIS results obtained in different zones of the two FSW welded alloys showed galvanic coupling at the interface between them for short test times and displacement of the most active region to theAA7475-T651 alloy, at longer periods of test, specifically to the interface between the thermomechanically affected and the heat affected zones of this last alloy. / A soldagem por fricção (Friction Stir Welding - FSW) é um processo eficiente de unir ligas dealumínio de alta resistência evitando defeitos que são usualmente criados quando técnicasconvencionais de soldagem são utilizadas. A indústria aeronáutica tem mostrado grande interesseneste método de soldagem, tanto para a união de ligas similares como dissimilares. Entretanto,este processo causa modificações microestruturais dependentes das condições de tratamentotérmico ou termomecânico. Contato elétrico entre zonas de microestruturas diferentes, por sua vez,pode resultar em acoplamento galvânico. No presente estudo, a soldagem por FSW foi usada paraunir duas ligas de alumínio dissimilares, AA2024-T3 e AA7475-T651 e o efeito desta soldagem naresistência à corrosão das juntas soldadas e na microestrutura das ligas foi avaliada. Nainvestigação da resistência à corrosão foram utilizados ensaios eletroquímicos, especificamente,medidas de potencial de circuito aberto (OCP) em função do tempo de exposição ao meio corrosivo,ensaios de polarização e de espectroscopia de impedância eletroquímica, global (EIS) ou local(LEIS), em duas soluções, seja 0,1 M Na2SO4 ou 0,1 M Na2SO4 + 1 mM NaCl. Os ensaioseletroquímicos evidenciaram efeito de acoplamento galvânico nas juntas soldadas. Acaracterização microestrutural foi realizada por microscopia ótica, microscopia eletrônica devarredura, microscopia eletrônica de transmissão e por calorimetria diferencial. As zonas afetadaspela solda tiveram importantes modificações na microestrutura indicadas pela precipitação edissolução de precipitados que afetam a resistência à corrosão localizada. A resistência à corrosãointergranular e a resistência à esfoliação das juntas soldadas também foram avaliadas ecomparadas com as das ligas AA2024-T3 e AA7475-T651 não soldadas. Os resultados mostraramaumento da suscetibilidade das juntas soldadas a estas formas de corrosão em comparação comas ligas não soldadas sendo observado ataque mais severo na liga AA7475-T651. A identificaçãodas áreas anódicas e catódicas resultantes do acoplamento galvânico nas juntas soldadas foirealizada por teste que consistiu na deposição de camada de gel (ágar-ágar) com indicadoruniversal na superfície das ligas soldadas. A liga AA2024-T3 atuou como cátodo, enquanto aAA7475-T651, como ânodo no par galvânico. Além disso, evolução de hidrogênio foi observada naregião de interface entre a zona termomecanicamente afetada e a termicamente afetada da ligaAA7475-T651 mostrando que reações catódicas também ocorreram localmente nesta última liga.Resultados de LEIS obtidos nas diferentes zonas das duas ligas soldadas por FSW mostraramacoplamento galvânico na interface entre elas para tempos curtos de ensaio e deslocamento daregião mais ativa com o tempo de ensaio para a liga AA7475-T651, mais precisamente para ainterface entre a zona termomecanicamente afetada e a térmicamente afetada desta liga.

Made available in DSpace on 2014-12-17T15:01:30Z (GMT). No. of bitstreams: 1 AlfredoJFS_DISSERT.pdf: 1130528 bytes, checksum: d7a64b847a80a2de8b89250f09f06bd0 (MD5) Previous issue date: 2012-11-05 / Copper is one of the most used metals in platingprocesses of galvanic industries. The presence of copper, a heavy metal, in galvanic effluents is harmful to the environment.The main objective of this researchwas the removal ofcopperfromgalvanic effluents, using for this purpose anionic surfactants. The removal process is based on the interaction between the polar head group of the anionic surfactant and the divalent copper in solution. The surfactants used in this study were derived from soybean oil (OSS), coconut oil (OCS), and sunflower oil (OGS). It was used a copper synthetic solution (280 ppm Cu+2) simulating the rinse water from a copper acid bath of a galvanic industry. It were developed 23and 32 factorial designs to evaluate the parameters that have influence in theremoval process. For each surfactant (OSS, OCS, and OGS), the independent variables evaluated were: surfactant concentration (1.25 to 3.75 g/L), pH (5 to 9) and the presence of an anionic polymer (0 to 0.0125 g/L).From the results obtained in the 23 factorial design and in the calculus for estimatingthe stoichiometric relationship between surfactants and copper in solution, it were developed new experimental tests, varying surfactant concentration in the range of 1.25 to 6.8 g/L (32 factorial design).The results obtained in the experimental designs were subjected to statistical evaluations to obtain Pareto charts and mathematical modelsfor Copper removal efficiency (%). The statistical evaluation of the 23 and 32factorial designs, using saponifiedcoconut oil (OCS), presented the mathematical model that best described the copper removal process.It can be concluded that OCS was the most efficient anionic surfactant, removing 100% of the copper present in the synthetic galvanic solution / O cobre ? um dos metais mais utilizados nos processos decorativos das ind?strias galv?nicas. A presen?a do cobre nos efluentes galv?nicos, por ser um metal pesado, compromete a vida das pessoas e dos animais. O principal objetivo deste trabalho ? remover o cobre destes efluentes, utilizando para este prop?sito tensoativos ani?nicos. O processo de remo??o consiste em utilizar a partepolar do tensoativo ani?nico para interagir com o cobre bivalente em solu??o. Os tensoativos utilizados neste estudo foram derivados dos ?leos de soja, coco e girassol. Utilizou-se a ?gua de lavagem do processo de cobre ?cido de uma ind?stria galv?nica como base para a obten??o do efluente sint?tico (280 ppm Cu+2). Para avaliar os par?metros que influenciam no processo foram desenvolvidos planejamentos experimentais fatoriais 23 e 32.Para cada tensoativo derivado dos ?leos vegetais avaliados (OSS, OCS e OGS) as vari?veis independentes utilizadas no planejamento foram: a concentra??o de tensoativo (1,25 a 3,75 g/L), pH (5 a 9) e presen?a de um pol?mero ani?nico (0 a 0,0125 g/L).A partir dos resultados colhidos neste primeiro planejamento experimental e dos c?lculos obtidos atrav?s da rela??o estequiom?trica entre os tensoativos e o cobre em solu??o foram realizados novos ensaios experimentais, variando a concentra??o do tensoativo na faixa de 1,25 a 6,8 g/L. Os resultados obtidos atrav?s do planejamento experimental foram submetidos a avalia??o estat?stica para obten??o de gr?ficos de pareto e do modelo matem?tico que descreve a efici?ncia do processo na remo??o do cobre. A avalia??o estat?stica dos planejamentos experimentais fatoriais 23 e 32,onde se utilizou ?leo de coco saponificado, apresentou o modelo matem?tico que melhor descreveu o processo de remo??o do cobre. Conclui-se que, atrav?s da utiliza??o de metodologias de planejamento experimental e da varia??o da concentra??o dos 3tensoativos(1,25 a 6,8g/L), o OCS foi o tensoativo mais eficiente, chegando a remover 100% do cobre presente na solu??o

Este trabalho objetiva avaliar o uso de resíduos galvânicos de douração/prateação como fonte de micronutrientes (principalmente cobre e níquel) para as plantas, estudando as reações químicas que determinam os processos de solubilidade e adsorção na interface solo-solução-planta. Para isso, resíduos galvânicos foram caracterizados por ICP OES e FAAS, determinando os teores de Al, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, Pb, S e Zn após digestão ácida, detectando Cu entre 2 e 35% e Ni entre 0,007 e 9,7% (m/m), e baixas quantidades de Cd, Cr e Pb em relação aos anteriores. Aspectos físico-químicos caracterizam os resíduos como aglomerados quebradiços, com possível ordenação estrutural na forma de sulfatos, óxidos, hidróxidos ou carbonatos, sendo pouco higroscópicos e facilitando, assim, aplicação agronômica na forma pulverizada. Ensaios de solubilidade em meio aquoso por sistema em fluxo indicaram a dependência da solubilidade de cobre e níquel ao pH. Cobre já apresentaria melhor solubilidade em pHs inferiores a 5, o que não ocorreu, mas simulações em software de equilíbrio químico indicaram solubilidade de cobre no formato de brochantita [Cu4SO4(OH)6] em pHs abaixo de 3, e análises por DRX confirmaram sua presença. Dois dos resíduos utilizados apresentaram solubilidade de níquel em água, provavelmente como NiCl2 ou NiSO4, e todos apresentaram boa solubilização quando complexados com DTPA. Estudos de adsorção e difusão de Cu e Ni em solos por percolação de água em colunas de PVC, após adição de pastilhas de resíduos galvânicos ao meio, mostraram baixa mobilidade dos metais e influência da presença destes pela dissolução das pastilhas, intensificando as reações de adsorção e dessorção. Quando combinados com as isotermas de adsorção e extração sequencial, conclui-se que os solos apresentam elevada capacidade máxima de adsorção e que estes metais estão ligados na maior parte às frações menos disponíveis, mas apresentando aumento da disponibilidade após inserção dos resíduos. Ensaios de solubilidade na presença de plantas em sistema similar ao experimento de adsorção, porém, com os resíduos na forma pulverizada, mostraram a presença de Cu e Ni nas raízes por influência da inserção dos resíduos e na parte aérea somente para níquel, talvez por suficiência nutricional de cobre. As principais reações que ocorrem na interface solo-solução-planta, como de adsorção/dessorção, precipitação/dissolução, complexação e oxirredução, explicam os mecanismos da maior ou menor disponibilidade destes micronutrientes, favorecendo determinadas condições pelos conceitos de equilíbrio químico. Ácidos orgânicos exsudados na rizosfera podem acidificar o meio ou complexar os metais, aumentando sua solubilidade e favorecendo seu transporte para as plantas. Por isso, é recomendado que os resíduos sejam aplicados bem próximo às raízes. Ensaios microbiológicos mostraram que os resíduos apresentam baixa toxicidade, e, associado aos fatos da baixa mobilidade de Cu e Ni e da baixa influência dos contaminantes Cd, Cr e Pb no solo, estima-se que oferecem baixo risco ambiental. O conjunto de resultados confere aos resíduos galvânicos de douração/prateação viabilidade para serem utilizados como fertilizantes agrícolas para suprir deficiências de cobre e níquel, concordando com os objetivos da Política Nacional de Resíduos Sólidos, que estimulam a reciclagem de materiais perigosos, para que voltem à cadeia produtiva, evitando, assim, o desperdício de seu potencial por meio do descarte / This work aims evaluate the use of galvanic wastes of gold/silver-plating as micronutrients source (mainly copper and nickel) for plants, by studying the chemical reactions which determine the solubility and adsorption processes on the soil-solution-plant interface. For this purpose, galvanic wastes were characterized by ICP OES and FAAS, determining the levels of Al, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, Pb, S and Zn after acid digestion, detecting Cu in the range of 2 and 35% and Ni in the range of 0.007 and 9.7% (m/m), and low quantities of Cd, Cr and Pb compared to the previous ones. Physicochemical aspects characterize the wastes as brittle conglomerate, with possible structural ordination in the form of sulfates, oxides, hydroxides or carbonates, low hygroscopicity and facilitating, thus, agronomic application in the pulverized form. Solubility essays in aqueous media by flow system indicating the dependency of copper and nickel solubility with pH. Cupper would present better solubility in pH below 5, what did not happen, but simulations in chemical equilibrium software indicated copper solubility in the form of brochantite [Cu4SO4(OH)6] in pH below 3, and DRX analysis confirmed the their presence. Two of the wastes used presented nickel solubility in water, probably as NiCl2 or NiSO4, and all presented good solubilization when complexed with DTPA. Adsorption and diffusion studies of Cu and Ni in soils by water percolation in PVC column, after addiction of galvanic wastes tablets to the center, demonstrated low metals mobility and influence of their presence by the tablet dissolution, intensifying the adsorption and desorption reactions. When combined with the adsorption isotherms and sequential extraction, it concludes that the soils presented high maximum adsorption capacity and these metals are mostly bonded to less available fractions, but presenting an increasing availability after wastes addition. Solubility essays in the present of plants in a similar system to the adsorption experiment, however, with the wastes in the pulverized form, demonstrated the presence of Cu and Ni in the roots by the influence of the residues insertion and only nickel in the aerial parts, maybe by nutritional sufficiency of copper. The main reactions that occurred in the soil-solution-plant interface, as adsorption/desorption, precipitation/dissolution, complexation and redox, explain the mechanism of the higher or lower availability of these micronutrients, favoring determinate conditions by the chemical equilibrium concepts. Organic acids exuded in the rhizosphere can acidify the medium or complex the metals, increasing their solubility and favoring their transport to the plants. Therefore, it is recommended that the residues must be applied very close to the roots. Microbiological tests have shown that the wastes present low toxicity, and, associated with the low mobility of Cu and Ni and with the low influence of the Cd, Cr and Pb in the soil, it estimated to offer low environmental risk. The results set gives galvanic wastes of gold/silver-plating viability to be used as agricultural fertilizers to supply copper and nickel deficiencies, in line with the objectives of the National Solid Waste Policy, which encourages the recycling of hazardous materials, to get back to productive chain, thus avoiding the waste of its potential by means of the discard

Extensive research has shown that electrochemistry is one of the factors that govern the flotation of sulfide minerals. Flotation is often adversely affected by uncontrolled oxidation, which is also an electrochemical process. The interest in pyrrhotite recovery arose after observing that there is a substantial loss of PGM due to the depression of pyrrhotite and the subsequent loss of any PGMs associated with it. The first part of this study focuses on the influence of chemical composition and crystal structure on the electrochemical behaviour of pyrrhotite in a 0.05 M Na2B4O7 solution. Rest potential and polarisation resistance measurements, as well as anodic polarisation diagrams, showed that the magnetic 4C type pyrrhotite is anodically more reactive than the non-magnetic 6C type pyrrhotite. It was also shown in cathodic polarisation diagrams that the non-magnetic 6C type pyrrhotite is a better substrate for oxygen reduction and is less susceptible to oxidation. ToF-SIMS showed the formation of an oxide layer on the pyrrhotite surface after oxidation. In the second part of this work, the influence of galvanic interactions on the electrochemical behaviour of pyrrhotite in contact with pentlandite was investigated. It was observed that, under oxygen-saturated conditions, as the amount of pentlandite increases, the reactivity towards oxidation of the mixed mineral system is reduced. Impedance measurements showed a decrease in capacitance values, indicating the formation of a continuous oxide layer on the surface and an increase in oxide layer thickness with decreasing pentlandite content. Anodic polarisation diagrams showed that under oxygen-deficient conditions and in the low potential region, pentlandite behaves as an inert material and does not have an influence on the oxidation behaviour of pyrrhotite. Hence, the anodic activities of the different magnetic 4C type pyrrhotites from Sudbury Gertrude, Phoenix and Russia were compared. It was shown that the oxidation reactivity decreased in the following order: Sudbury Gertrude magnetic 4C pyrrhotite > Phoenix magnetic 4C pyrrhotite > Russian magnetic 4C pyrrhotite; it also varied according to location. In the transpassive region, higher anodic currents were observed on the mixed samples because both pentlandite and pyrrhotite reacts. The reactivity increased in the order: pure pyrrhotite (Russia) < medium-pentlandite (Sudbury Gertrude) < high-pentlandite (Phoenix). In the presence of potassium ethyl xanthate, there was no change in the initial anodic reactivities of the different pyrrhotites. The anodic polarisation diagrams of the pure and mixed samples showed a reduction in the maximum anodic peak current, suggesting the presence of xanthate on the surface, which hinders oxidation of the mineral surface. In addition, the influence of cleaning of oxidised pyrrhotite with gaseous carbon dioxide was studied, using electrochemical and microflotation measurements. Electrochemical measurements indicated that CO2 treatment resulted in depassivation of the oxidised surfaces; this was supported by ToF-SIMS measurements that demonstrated a reduction in the oxide layer thickness after CO2 treatment. Anodic polarisation diagrams showed a higher anodic peak current, indicating that the surface is more reactive. Gaseous carbon dioxide conditioning of oxidised pyrrhotite resulted in improved flotation response of pyrrhotite with the aid of copper activation and higher air flow rate. Copyright / Dissertation (MEng)--University of Pretoria, 2010. / Materials Science and Metallurgical Engineering / unrestricted

Master‘s thesis deals with analysis solutions and construction of the devices for data collection. At the beginning, they describe the basic types of devices for data collection. In other parts of the work is compared few commercial devices for data collection, under which the requirements will be selected on the proposed device for data collection. In other chapters of the work devoted to the design of schemes and selecting components for their manufacture. The last chapters are devoted to describing the design of device for data collection.

Cílem této diplomové práce jse najít nejnižší možnou tloušťku nikl-fosforového povlaku, který může být galvanicky pokoven mědí bez defektů na horčíkové slitině, nikl-fosforového nebo měděného povlaku. V teoretické části jsou shrnuty poznatky o hořčíkových slitinách a jejich korozi. Navíc se teoreticá část zaměřuje na popis procesu bezproudého niklování a elektrochemického pokovování mědí a jejich porovnání. Na konci teoretické části je shrnut současný výzkum o elektrochemickém pokovování hořčíkových slitin. V experimentální části byl popsán proces přípravy povlaků Ni-P a Cu na horčíkové slitině AZ91. Na jedné vrstvě a dvojité vrstvě Ni-P povlaku byla provedena elektrodepozice mědi. Navíc byl diskutován vliv předůpravy před samotnou elektrodepozicí mědi. Za účelem zjištění korozních vlastností vzorků byl vykonán potenciodynamický test. Následně byly připraveny metalografické výbrusy jednotlivých vzorků a pomocí světelného a rastrovacího elektronového mikroskopu byla provedena charakterizace. Na konec bylo zjištěno prvkové složení jednotlivých povlaků pomocí EDX analýzy.