Los dos baños de cobre más utilizados comercialmente son el baño ácido a base de sulfato y el baño alcalino a base de cianuro. Los baños alcalinos son utilizados principalmente para producir recubrimientos en piezas con geometría compleja y para evitar la deposición galvánica cuando se deposita un metal en un sustrato menos noble. Debido a la toxicidad de los compuestos de cianuro, se han desarrollado baños alternativos usando diferentes agentes complejantes. El punto de partida de la presente investigación es un baño primario sin cianuros para deposición de cobre en sustratos de Zamak desarrollado en el Instituto de Investigaciones Tecnológicas del Estado de Sao Paulo / Brasil. La sustitución de materias primas como el cianuro debe ser económicamente ventajosa y técnicamente viable. De esta manera, la investigación presentada pretendió proponer una alternativa para el tratamiento de residuos líquidos del baño ya mencionado con la finalidad de recuperar de manera simultánea el agua y las materias primas en un sistema cerrado. Se ha estudiado el proceso de separación por membranas de intercambio iónico, la electrodiálisis, usando un sistema en escala de laboratorio y una disolución sintética que simulaba las aguas residuales del baño a base de HEDP. Se ha evaluado la viabilidad del sistema por medio del análisis de los parámetros de operación, como la extracción de iones, la tasa de desmineralización, el porcentaje de concentración, la eficiencia de la intensidad calculada para cada especie y el consumo medio de energía. Debido a que el ácido HEDP es un agente quelante, se ha evaluado el transporte de los quelatos Cu(II) HEDP a través de membranas de intercambio de aniones por medio de métodos electroquímicos. Se han construido curvas cronopotenciométricas y curvas intensidad-potencial para diferentes disoluciones sintéticas que contenían los mismos compuestos que el baño original. Se ha establecido la relación entre la presencia de los quelatos en las disoluciones y los grupos fijos de intercambio de aniones. Por fin, se han realizado las pruebas de deposición usando electrólitos conteniendo los compuestos reciclados y se han evaluado las características de los depósitos obtenidos. Los resultados indicaron que el sistema de electrodiálisis usando membranas de intercambio de aniones con grupos de intercambio de base fuerte ha podido producir disoluciones tratadas y un concentrado conteniendo los iones del baño. Se ha podido añadir el concentrado al baño original para compensar eventuales perdidas del arrastre sin afectar la calidad de los depósitos. Por lo tanto, la aplicación de la electrodiálisis demostró ser una alternativa viable para la recuperación del agua y de las materias primas de la disolución evaluada, reduciendo la generación de residuos líquidos y ahorrando los recursos naturales. / The two most common commercial copper baths are the acid sulfate copper bath and the alkaline cyanide copper bath. Alkaline copper baths are mostly used to coat parts with complex geometry and to avoid galvanic deposition when depositing a metal on a less noble substrate. Because of the toxicity of cyanide compounds, alternative baths have been developed using different complexing agents. The starting point of the present study is a cyanide free strike bath developed for copper plating on Zamak substrates developed by the Institute for Technological Research of the State of São Paulo/ Brazil. The replacement of a raw material such as cyanide must be economically advantageous and technically feasible. Therefore, this study intended to propose an alternative to the treatment of liquid wastes from the mentioned bath, aiming at simultaneous water reclamation and chemicals recovery in a closed system. The electrodialysis membrane separation process was studied, using a laboratory-scale system operating with a synthetic solution simulating the rinsing waters from the HEDP-based bath. The feasibility of the technique was evaluated by analyzing operational parameters such as ion extraction, demineralization rate, concentration rate, current efficiency for each anionic specie and average energy consumption. Because HEDP is a chelating agent, the transport of Cu(II) HEDP chelates through anion exchange membranes was also evaluated by means of electrochemical methods. Chronopotentiometric and current-voltage curves were constructed for different model solutions containing the same compounds as the original bath. A relation between the presence of chelates in the solutions and the fixed ion exchange group could be established. Lastly, deposition tests were performed using electrolytes containing the recycled inputs and the characteristics of the coatings were analyzed. The results showed that an electrodialysis stack using strongly basic anion exchange membranes was suitable to produce treated solutions and a concentrate containing the ions from the bath. The concentrate could be added to the copper bath to compensate eventual drag-out losses without affecting the quality of the coatings. Thus, the application of electrodialysis was shown to be a feasible alternative for recovering water and inputs from the evaluated solution, reducing the wastewater generation and saving natural resources. / Els dos banys de coure més utilitzats comercialment són el bany àcid a base de sulfat i el bany alcalí a base de cianur. Els banys alcalins són utilitzats principalment per a produir recobriments en peces amb geometria complexa i per a evitar la deposició galvànica quan es deposita un metall en un substrat menys noble. A causa de la toxicitat dels compostos de cianur, s'han desenrotllat banys alternatius usant diferents agents complexants. El punt de partida de la present investigació és un bany primari sense cianurs per a deposició de coure en substrats de Zamak desenrotllat en l'Institut d'Investigacions Tecnològiques de l'Estat de Sao Paulo / Brasil. La substitució de matèries primeres com el cianur ha de ser econòmicament avantatjosa i tècnicament viable. D'aquesta manera, la investigació presentada va pretendre proposar una alternativa per al tractament de residus líquids del bany ja mencionat amb la finalitat de recuperar de manera simultània l'aigua i les matèries primeres en un sistema tancat. S'ha estudiat el procés de separació per membranes d'intercanvi iònic, electrodiàlisi, usant un sistema en escala de laboratori i una dissolució sintètica que simulava les aigües residuals del bany a base d'HEDP. S'ha avaluat la viabilitat del sistema per mitjà de l'anàlisi dels paràmetres d'operació, com l'extracció d'ions, la taxa de desmineralització, el percentatge de concentració, l'eficiència de la intensitat calculada per a cada espècie i el consum mitjà d'energia. Pel fet que l'àcid HEDP és un agent quelant, s'ha avaluat el transport dels quelats Cu (II)-HEDP a través de membranes d'intercanvi d'anions per mitjà de mètodes electroquímics. S'han construït corbes cronopotenciomètriques i corbes intensitat-potencial per a diferents dissolucions sintètiques que contenien els mateixos compostos que el bany original. S'ha establit la relació entre la presència dels quelats en les dissolucions i els grups fixos d'intercanvi d'anions. Finalment, s'han realitzat les proves de deposició usant electròlits contenint els compostos reciclats i s'han avaluat les característiques dels depòsits obtinguts. Els resultats van indicar que el sistema d'electrodiàlisi usant membranes d'intercanvi d'anions amb grups d'intercanvi de base forta ha pogut produir dissolucions tractades i un concentrat que conté els ions del bany. S'ha pogut afegir el concentrat al bany original per a compensar eventuals perdudes de l'arrossegament sense afectar la qualitat dels depòsits. Per tant, l'aplicació de l'electrodiàlisi va demostrar ser una alternativa viable per a la recuperació de l'aigua i de les matèries primeres de la dissolució avaluada, reduint la generació de residus líquids i estalviant els recursos naturals. / Scarazzato, T. (2017). Treatment of a cyanide-free copper electroplating solution by electrodialysis: study of ion transport and evaluation of water and inputs recovery [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/98502

Magnesium and its alloys are extensively used for various industries such as aerospace, automobile and electronics due to their excellent properties such as low density, high strength and stiffness and electromagnetic shielding. However, the wide spread applications of these alloys are limited due to the undesirable properties such as poor corrosion, wear and creep resistance and high chemical reactivity. These alloys are highly susceptible to galvanic corrosion in sea water environment due to their high negative potential (-2.37 V vs SHE). The effective way of preventing corrosion is through the formation of a protective coating, which acts as a barrier between the corrosive medium and the substrate. Many surface modification methods such as electro/ electroless plating, conversion coating, physical and chemical vapour depositions, thermal spray coating etc., are available currently to improve the corrosion resistance of Mg alloys. Of these methods, the electroless nickel plating has gained considerable importance because of its excellent properties such as high hardness, good wear and corrosion resistance. The properties of binary electroless nickel coating have been further improved by the addition of a third element such as cobalt, tungsten, tin and copper etc. It has been reported that the addition of tungsten as the third element in the Ni-P improves the properties such as hardness, wear and corrosion resistance, thermal stability and electrical resistance. Magnesium alloys are categorized as a “difficult to plate metal”, because of their high reactivity in the aqueous solution. They react vigorously with atmospheric oxygen and water, resulting in the formation of the porous oxide/ hydroxide film which does not provide any protection in the corrosive environment. Further, the presence of this oxide film prevents the formation of a good adhesive bond between the coating and the substrate. The surface treatment process for removal of the oxide layer is very much essential before plating the Mg alloy. Currently two processes such as zinc immersion and direct electroless nickel plating are adopted to plate Mg alloys. Etching in a solution of chromate and nitric acid followed by immersion in HF solution to form a conversion film is necessary for direct electroless nickel (EN) plating of Mg alloy. However, strict environmental regulations restrict their usage because of hazardous nature. Expensive palladous activation treatment is a well-known process as a replacement for chromate-HF pretreatments for Mg alloys. It has been reported that EN plating has been carried out over Mg alloys by using conversion coating followed by HF treatment. Formation of an intermediate oxide layer by electrolytic methods is also one of the ways these toxic pretreatments can be avoided. Microarc oxidation (MAO) is an environment friendly surface treatment technique which provides high hardness, better corrosion and wear resistance properties for the Mg alloys. EN coating has been prepared on MAO layer for improving the corrosion resistance. These MAO/EN composite coatings have been prepared using chromic acid and HF pretreatment process. As the replacement for the chromate-HF pretreatment, SnCl2 and PdCl2 sensitization and activation procedures respectively were adopted over MAO layer for the deposition of Ni-P coating. From the above reported literature, it can be inferred that for the activation of inert MAO layer to deposit electroless nickel coating, the hazardous chromate/HF and highly expensive PdCl2 activation processes were followed. Therefore, there is a need for identifying an alternative simple and cost effective pretreatment process for the deposition of electroless nickel. It is well known that borohydride is a strong reducing agent that has been used for the deposition of Ni-B coatings. In the present study, an attempt has been made to utilize borohydride in the pretreatment process for the reduction of Ni2+ ions over the MAO interlayer, which provides the nucleation sites for the deposition of Ni-P coating. Ni-P and Ni-P/Ni-W-P duplex coatings were deposited from stabilizer free carbonate bath on AZ31B Mg alloy to improve the corrosion resistance of the base substrate. The conventional chromate and HF pretreatment processes were followed for the deposition of electroless nickel coating. In order to improve the corrosion resistance of the duplex coating, post treatments such as heat treatment (4 h at 150°C) and chromate passivation were adopted. EDX analysis of AZ31B Mg alloy showed the presence of 2.8 wt.% of Al and 1.2 wt. % Zn with the balance of Mg for AZ31B Mg alloy. After the chromic acid and HF treatment, the magnesium content was reduced from 90.0 wt % to 54.9 wt%, which could be due to the incorporation of chromium on the surface layer. The surface showed about 17.8 wt. % of F. The alloy exhibited the roughness of about 0.29± 0.01µm after mechanical polishing. The roughness value was significantly changed after the chromic acid treatment processes. The maximum roughness of about 1.28±0.06 µm was obtained after the HF activation. XPS analysis confirmed the existence of chromium in +3 oxidation state after the chromic acid treatment. The Ni-P coating thickness of about 25 microns was obtained in 1 h and 15 min. In the case of duplex coatings, Ni-P plating was done for 45 min. to obtain approx. 17 microns thickness and Ni-W-P plating was done for 1.15 h to obtain a thickness of approx. 10 microns, resulting in a total thickness of 25 ± 5 microns. Ni–P coating exhibited nodular morphology with porosity. The size of these cluster nodules were of about 10 µm in diameter. On the other hand, the duplex coating exhibited a less nodular, dense and smooth appearance. From the compositional analysis it was found that Ni–P coating contained about 6 wt. % P. In the case of duplex coating, the P content was reduced to 3 wt % due to the incorporation of about 2 wt% of tungsten. In corrosion studies, the potentiodynamic polarization data obtained for bare Ni-P coating in 0.15 M NaCl solution exhibited a higher current of about 218 μA/cm2 as compared to the substrate due to the porosity of the coating. However, the Ni-P/Ni-W-P duplex showed 55 times improvement in corrosion resistance, vis-a-vis Ni-P due to the dense nature of the coating. The corrosion resistance of the coatings increased in the following order: Ni-P < bare alloy < duplex < duplex-passivated < duplex-heat treated passivated. In EIS study, the Nyquist plot obtained for the bare substrate and Ni–P coating showed the presence of inductance behavior at the lower frequency region due to the adsorption of electroactive species over the substrate through the porous oxide layer. However, the passivated and duplex passivated coatings exhibited only capacitive behavior due to their compact nature. From the above, it can be concluded that, direct deposition of Ni-P coating over the chosen Mg alloy using chromic acid and HF pretreatment process resulted in porous morphology, which affected the corrosion resistance of the coating. As an alternative strategy, the microarc oxidation conversion coating was developed on Mg alloy and characterized. The MAO coating was developed using silicate electrolyte at three different current densities (0.026, 0.046 and 0.067 A/cm2) for about 15 min. With respect to the MAO coating, an increase in the current density increased the pore diameter and decreased the pore density. The surface of the coating became coarser and rough. The cross-sectional morphology of the coating showed two district layers namely the dense and thin inner layer and a porous thick outer layer. The thickness of the coating increased with increase in current density. MAO coating prepared at an intermediate current density of 0.046 A/cm2 exhibited a higher thickness of about 12 µm and a further increase in current density showed a decrease in thickness, due to the greater rate of dissolution of Mg, relative to the rate of deposition. The surface roughness of the MAO coatings also increased with increase in current density. The Ra value increased from 1.39±0.06 to 3.52±0.17 µm with increase in current density. XRD peaks obtained for the Mg substrates corresponded predominately to magnesium. However, the coated specimens showed the presence of peaks corresponding to Mg2SiO4 along with Mg and MgO. The corrosion measurements for the bare substrate and MAO coatings were carried out in 3.5% NaCl medium (0.6 M). Based on potentiodynamic polarization studies, the MAO coating prepared at 0.046 A/cm2 exhibited a lower corrosion current density with a higher Rp value, which was about five orders of magnitude higher than the bare substrate, due to the dense nature of the coating. In EIS study, MAO coatings were fitted with the two time constants equivalent circuit containing outer porous layer and inner barrier layer. The barrier layer resistance values were higher than that of porous layer resistance, which indicated that the resistance offered by barrier layer was higher than the porous layer. The total resistance value obtained for the coating prepared at 0.046 A/cm2 were higher compared to the other coatings, which attested to its better corrosion resistance. The electrochemical noise measurement was carried out for longer immersion durations upto 336 h in 3.5% NaCl solution. The noise resistance value obtained for the base Mg alloy was about 100 Ω at 1h immersion, whereas for the MAO coating prepared at 0.04 A/cm2 a maximum value of about 34.8 MΩ was achieved and it was retained even after 96 h of immersion. Mott–Schottky analysis showed that the oxide layer on magnesium substrate acted as a n-type semiconductor, whereas the MAO coatings exhibited p-type semiconductor behavior. The MAO coating obtained at an intermediate current density showed a higher acceptor density and the flat band potential, which resulted in the better performance of the coating in corrosive environment. In another set of investigations, the Ni-P and Ni-P/Ni-W-P coatings were deposited on AZ31B Mg alloy with MAO coating as an interlayer. The MAO layer was activated by a simple borohydride pretreatment process. During the pretreatment process, the MAO coating was subjected to mild alkali treatment, immersion in the Ni-P plating solution and finally immersion in borohydride solution. During each pretreatment step, the sample was characterized for their surface morphology and composition. The surface morphology showed the distribution of spherical particles over the surface of MAO coating after immersion in the Ni-P plating solution. EDX analysis showed the presence of 2.4 wt. % of Ni, which confirmed that Ni ions were adsorbed over the surface of the MAO coating during the pretreatment process. XPS analysis carried out after immersion in the Ni-P plating solution indicated that Ni existed in +2 oxidation state. The surface became smooth and uniform with flake- like morphology after the borohydride treatment, which indicated that the surface was etched by the borohydride solution. EDX analysis showed the presence of 1.8 wt.% of Ni after borohydride reduction. XPS analysis confirmed the reduction of nickel to the zero oxidation state. Additionally, MAO/Ni-P and MAO/Ni-P/Ni-W-P duplex coatings were developed on MAO coating after a simple borohydride pretreatment. Ni-P and duplex coatings showed uniform and dense nodular morphology without any defects, which clearly indicated that the borohydride treatment provided a uniform and homogeneous active surface for the deposition of electroless nickel based coatings. Borohydride pretreatment process resulted in excellent bonding between MAO/Ni-P layers in the cross section. Based on potentiodynamic polarization studies, the corrosion current values obtained for MAO/ Ni-P and MAO/Ni-P/Ni-W-P duplex coatings were about 1.44 and 1.42 µA/cm2, respectively. The coating showed about 97 times improvement in corrosion resistance compared to the bare substrate, attesting to the dense nature of the coating. In EIS study, the single time constant equivalent circuit was used for fitting the spectra, which pertained to the coating /electrolyte interface. The single time constant could be attributed to the pore-free dense, uniform coatings developed over the MAO interlayer. For the MAO/Ni-P and MAO/Ni-P-Ni-W-P duplex coatings, the charge transfer resistance of about 15 and 11 kΩcm2 were obtained for duplex and Ni-P coatings, which reinforce the better corrosion protective ability of the coating. The above investigation confirms that MAO coatings have good corrosion resistance in the aggressive chloride medium. Consequently, they can serve as an ideal interlayer for the deposition of the electroless nickel coating. Even if the electroless nickel coating is found to fail in harsh environments, the MAO interlayer can protect the base substrate due to its higher corrosion resistance. It is also noteworthy that the borohydride treatment provides better adhesion between the MAO/Ni-P interlayer.

Cette thèse s’est focalisée sur le développement et l’optimisation de techniques de métallisation électrochimique permettant le dépôt de métaux conducteurs, l’argent et le cuivre, par voie électrolytique ou par la technique dite LIP (Light-Induced Plating). Deux approches ont été abordées pour l’élaboration des contacts en face avant : l’épaississement de contacts sérigraphiés d’une part, et la réalisation de contacts entièrement par voie électrochimique sans recours à la sérigraphie. Pour cette dernière solution, le dépôt d’une couche d’accroche avant l’étape d’épaississement est nécessaire afin d’assurer une résistivité de contact faible, une bonne adhérence et une bonne sélectivité au travers de la couche anti-reflet. Ces objectifs ont été atteints grâce à la mise en œuvre et l’optimisation de dépôts electroless de nickel-phosphore (NiP), y compris sur émetteur peu dopé. Les investigations menées ont également permis une meilleure compréhension des mécanismes de formation du contact NiP/Si. La faisabilité des techniques de dépôt électrochimique a été démontrée pour diverses applications: cellules avec contacts électrochimiques NiP/Ag en face avant, cellules de type n, épaississement de contacts fins sérigraphiés… Des résultats très prometteurs d’amélioration de facteur de forme FF et de rendement η ont été obtenus et permettent d’envisager une ouverture potentielle vers de nouvelles structures de cellules photovoltaïques à haut rendement : cellules à émetteur peu dopé, cellules à émetteur sélectif avec ouverture laser de la couche anti-reflet, cellules à contacts arrières…. / This thesis is focused on the development and the optimization of electrochemical metallization techniques allowing the deposition of conductive metals, silver and the copper, by electrolytic deposition or by lip (light-induced plating). Two approaches were studied to realize the front side contacts of silicon solar cells: the thickening of screen-printed contacts and the fabrication of contacts completely by electrochemical deposition without screen-printing. For this solution, the deposition of a seed layer before thickening is necessary to insure a low contact resistivity, a satisfying adhesion and selectivity through the anti-reflection coating. These objectives were reached thanks to the optimization of electroless nickel-phosphorous (nip) deposits, including on low doped emitter. The investigations also allowed a better understanding of the NiP/Si contact formation mechanisms. The feasibility of electrochemical deposition techniques was demonstrated for various applications : cells with electrochemical front side contacts NiP/Ag, type n cells, thickening of fine line screen-printed contacts… very promising results of fill factor ff and efficiency improvement were obtained and allow to realize new structures of high efficiency photovoltaic cells : cells with low doped emitter, cells with selective emitter and with laser ablated anti-reflection coating, rear contact cells…

The anode-free battery concept is proposed to pursue the aspiration of energy-dense, rechargeable metal batteries, but this has not been achieved with dual-ion batteries. Herein, the first anode-free Zn–graphite battery enabled by efficient Zn plating–stripping onto a silver-coated Cu substrate is demonstrated. The silver coating guides uniform Zn deposition without dendrite formation or side reaction over a wide range of electrolyte concentrations, enabling the construction of anode-free Zn cells. In addition, the graphite cathode operates efficiently under reversible bis(trifluoromethanesulfonyl)imide anion (TFSI−) intercalation without anodic corrosion. An extra high-potential TFSI− intercalation plateau is recognized at 2.75 V, contributing to the high capacity of graphite cathode. Thanks to efficient Zn plating–stripping and TFSI− intercalation–deintercalation, an anode-free Zn–graphite dual-ion battery that exhibits impressive cycling stability with 82% capacity retention after 1000 cycles is constructed. At the same time, a specific energy of 79 Wh kg−1 based on the mass of cathode and electrolyte is achieved, which is over two times higher than conventional Zn–graphite batteries (<30 Wh kg−1).

This study is an investigation of the chemical vapor deposition (CVD) of aluminum and copper on fluoropolymer surfaces and the subsequent interfacial interactions.

The two most common commercial copper baths are the acid sulfate copper bath and the alkaline cyanide copper bath. Alkaline copper baths are mostly used to coat parts with complex geometry and to avoid galvanic deposition when depositing a metal on a less noble substrate. Because of the toxicity of cyanide compounds, alternative baths have been developed using different complexing agents. The starting point of the present study is a cyanide-free strike bath developed for copper plating on Zamak substrates developed by the Institute for Technological Research of the State of São Paulo/ Brazil. The replacement of a raw material such as cyanide must be economically advantageous and technically feasible. Therefore, this study intended to propose an alternative to the treatment of liquid wastes from the mentioned bath, aiming at simultaneous water reclamation and chemicals recovery in a closed system. The electrodialysis membrane separation process was studied, using a laboratoryscale system operating with a synthetic solution simulating the rinsing waters from the HEDP-based bath. The feasibility of the technique was evaluated by analyzing operational parameters such as ion extraction, demineralization rate, concentration rate, current efficiency for each anionic specie and average energy consumption. Because HEDP is a chelating agent, the transport of Cu(II)-HEDP chelates through anion-exchange membranes was also evaluated by means of electrochemical methods. Chronopotentiometric and current-voltage curves were constructed for different model solutions containing the same compounds as the original bath. A relation between the presence of chelates in the solutions and the fixed ion exchange group could be established. Lastly, deposition tests were performed using electrolytes containing the recycled inputs and the characteristics of the coatings were analyzed. The results showed that an electrodialysis stack using strongly basic anion-exchange membranes was suitable to produce treated solutions and a concentrate containing the ions from the bath. The concentrate could be added to the copper bath to compensate eventual drag-out losses without affecting the quality of the coatings. Thus, the application of electrodialysis was shown to be a feasible alternative for recovering water and inputs from the evaluated solution, reducing the wastewater generation and saving natural resources. / Os dois banhos de cobre comerciais mais comuns são o banho ácido à base de sulfato e o banho alcalino à base de cianeto. Os banhos alcalinos são usados principalmente para recobrir peças com geometria complexa e para evitar a deposição por deslocamento galvânico quando se deposita um metal em um substrato menos nobre. Por causa da toxicidade dos compostos cianídricos, banhos alternativos vêm sendo desenvolvidos usando diferentes agentes complexantes. O ponto de partida do presente estudo é um banho toque isento de cianeto para deposição de cobre em substratos de Zamak, desenvolvido pelo Instituto de Pesquisas Tecnológicas / Brasil. A substituição de matérias-primas como o cianeto deve ser economicamente vantajosa e tecnicamente viável. Desta forma, este estudo pretendeu propor uma alternativa para o tratamento de resíduos líquidos do banho mencionado, visando à recuperação simultânea da água e das matérias-primas em um sistema fechado. Foi estudado o processo de separação por membranas de eletrodiálise, usando um sistema em escala laboratorial operando com uma solução sintética que simulava as águas de lavagem do banho à base de HEDP. A viabilidade da técnica foi avaliada por meio da análise de parâmetros operacionais, como a extração dos íons, a taxa de dessalinização, o percentual de concentração, a eficiência de corrente calculada para cada espécie iônica e o consumo médio de energia. Devido ao HEDP ser um agente quelante, o transporte de quelatos Cu(II)-HEDP através de membranas aniônicas foi avaliado por meio de métodos eletroquímicos. Curvas cronopotenciométricas e curvas corrente-potencial foram construídas para diferentes soluções sintéticas que continham os mesmos compostos que o banho original. A relação entre a presença de quelatos nas soluções e os grupos fixos de troca iônica pôde ser estabelecida. Por fim, testes de deposição foram realizados usando eletrólitos contendo os compostos reciclados e as características dos depósitos foram analisadas. Os resultados mostraram que o sistema de eletrodiálise usando membranas aniônicas contendo grupos de troca fortemente básicos pôde produzir soluções tratadas e um concentrado contendo os íons do banho. O concentrado pôde ser adicionado ao banho original para compensar eventuais perdas por arraste sem afetar a qualidade dos depósitos. Assim, a aplicação da eletrodiálise se mostrou uma alternativa viável para a recuperação de água e de insumos da solução avaliada, reduzindo a geração de efluentes e economizando recursos naturais.

This research presents a novel microfabrication approach and testing methodology for cylindrical ion trap (CIT) microarray tunable for mass- spectrometers. The growing interest in cylindrical ion trap (CIT) mass-spectrometers is primarily due to ease with which cylindrical geometry can be realized as compared to hyperbolic surfaces found in conventional quadrupole ion traps. Also due to the fact that the potential at the center of hyperbolic electrode in quadrupole ion trap and cylindrical electrode in cylindrical ion trap (CIT) does not differ significantly[2]. Since the RF voltage required to eject a given mass-to-charge ion scales as the square of the ion trap radius, a decrease in ion trap dimensions provides a significant reduction in electronics requirements, thereby providing a pathway for overall system miniaturization. The reduction in sensitivity due to reduced ion storage capacity as a result of miniaturization can be improved by employing an array of identically sized ion traps. Microfabrication approach promises excellent uniformity in the fabrication of identically sized holes which in turn leads to low-cost high performance CIT microarray for mass spectrometers[1,2]. The criterion used for the determination of trap diameter was to ensure that the hole to be 1.09 times the wafer thickness to provide optimal potential to trap ions[1]. The end- plates were designed to optimize the electron and ion transmission into and out of the ion trap and provide a high quality electric field definition within each cylindrical ion trap (CIT)[3]. Two different approaches, namely deep reactive ion etching (DRIE) and mechanical drilling using ultrasonic disc cutter were proposed and used for the fabrication of ring-electrode which forms the main body of the ion trap. Excellent uniformity in hole diameter was observed in both the approaches. The end-plates were fabricated using deep reactive ion etching (DRIE) which provided high transmission rigid grid structure for ions and electrons. Standard Bosch process was used for deep reactive ion etching (DRIE). The two electrodes were metallized using electroless plating which provides excellent uniformity of coating even on end-plate structures with 5micro m through holes. CYTOP[trademark], a cyclized perfluoro polymer, was used as an insulation layer and intermediate bonding layer between the ring electrode and end-plates. The breakdown voltage for a released 16 micro m thick CYTOP[trademark] layer was found to be 1.47KV. An assembly for testing miniature cylindrical ion trap (CIT) was designed and built. An electron impact ionization source was used for generation of ions. Mass selective instability scan was used to selectively eject ions with different mass-to-charge ratio. A cylindrical ion trap (CIT) with 4mm diameter was fabricated and tested for analyte gases such as krypton and xenon.

The objective of this project is to establish a new technology to grow high quality GaN based material by nano selective area growth (NSAG). The motivation is to overcome the limit of the conventional growth method, which yield a high density of dislocation in the epitaxial layer. A low dislocation density in the epitaxial layer is crucial for high performance and high efficiency devices. This project focuses on growth and material characterization of GaN based nanostructures (nanodots and nanostripes) grown using the NSAG method that we developed. NSAG, with a precise control of diameter and position of nanostructures opens the door to new applications such as: 1) single photon source, 2) photonic crystal, 3) coalescence of high quality GaN template, and 4) novel nanodevices.

Electroless plating is a metal deposition technique widely used in the coating industry. It is the method of choice to plate substrates with complex geometries and nonconductive surfaces, such as polymers and ceramics, since it is based on a chemical reduction in solution rather than on an external electrical energy source like the electroplating method. Among others, examples of well-established applications are the electroless deposition of decorative metal coatings such as gold and silver, wear and corrosion resistant nickel coatings, particularly to coat drive shafts, rotors, and bathroom fixtures, as well as the electroless deposition of copper in electronic devices as diffusion barriers and conductive circuit elements. In the academic research, electroless plating is extensively used thanks to its low cost, simple equipment and versatility that allow rapid prototyping. Two common applications are the coating of small particles and the selective plating of flat surfaces. Metal coated ceramic particles are of enormous interest in many scientific fields, e.g. fluorescent diagnostics in biochemistry, catalysis, and fabrication of photonic crystals. Metal coated ceramic nanoparticles and microparticles are also gaining attention as potential candidates in the fabrication of higher quality metal matrix Composites, which is one of the applications addressed by this work. Metal coated ceramic particles are easier to integrate in metal matrix composites, avoiding aggregation caused by the low wettability of the particles by the matrix metal, and are potentially shielded from oxidation and undesired chemical reactions that take place at the interface between the particles and the metal Matrix. Electroless plating is an autocatalytic process, meaning that the deposited metal atoms catalyze the deposition of further metal. In order to achieve the first stable metal seeds on a surface, the latter has to be functionalized. Without this functionalization the metal ions in the electroless plating bath are not reduced or are simply reduced to metal nanoparticles in solution. The traditional activation step for nonconductive surfaces is performed by immersion of the substrate in palladium based solutions, which is very time-consuming and extremely expensive. In particular for nanoparticles, previous work showed that at least 1015 Pd atoms/cm2 are required for a uniform activation of a surface, meaning that in the case of nanoparticles with a surface area of about 100 m2/g are necessary 6.4 g of palladium for each gram of substrate. Assuming a price of about 150 €/g (laboratory scale) for palladium nanoparticles and palladium precursors used for surface activation, it results that the activation of 1 g of nanoparticles costs around 1000 €. Such costs are suboptimal considering the typical production scale, and therefore alternative functionalization methods are desired. In this work, new organic-based functionalization methods based on (3-mercaptopropyl)triethoxysilane to functionalize oxide particles, 3-aminopropylphosphonic acid to activate carbide particles and a substrate-independent method based on the bioinspired polydopamine are developed and investigated in detail, together with the respective electroless plating baths, which often have to be specifically tailored regarding the different reactivity of the different molecules and substrates. Furthermore, in the fabrication of metallic patterns on substrates by electroless plating, new, simple, and cost-effective activation and metal deposition processes are desired. In this work, two new methods are presented, one based on the printing of (3-mercaptopropyl)triethoxysilane by microcontact printing, the other based on the capillary force lithography of polymethylmethacrylate.

Thesis (M.S.)--University of Alabama at Birmingham, 2008. / Description based on contents viewed May 30, 2008; title from title screen. Includes bibliographical references (p. 50-51).