Microelectronics integration continuously follows the trend of miniaturisation for which the technologies enabling fine pitch interconnection are in high demand. The recent advancement in the assembly of Hybrid Pixel Detectors, a high resolution detecting and imaging device, is an example of where novel materials and processes can be applied for ultra-fine pitch interconnections. For this application, indium is often used for the fine pitch bump bonding process due to its unique properties that make it especially suitable, in particular in a cryogenic environment where some types of detector have to serve. Indium bumps are typically fabricated through vacuum evaporation at the wafer level; however, this thesis investigates an alternative low cost manufacturing process at the wafer scale for the deposition of indium micro-bumps through electroplating. The work has placed its emphasis on the requirements of future technologies which will enable a low temperature (<150oC), high density interconnection (> 40,000 IOs/cm2) with a high throughput and high production yield. This research is a systematic investigation of the wafer-scale indium bumping process through electrodeposition using indium sulphamate solution. An intensive experimental study of micro-bump formation has been carried out to elaborate the effects of two of the main electroplating factors that can significantly influence the quality of bumps in the course of electrodeposition, namely the current distribution and mass transport. To adjust the current density distribution, various waveforms of current input, including direct current (DC), unipolar pulse current and bipolar pulse reverse current, were employed in the experiments. To assist mass transportation prior to or during electroplating, acoustic agitation including ultrasonic agitation at 30 kHz frequency as well as megasonic agitation at 1 MHz, were utilised. The electrochemical properties of the indium sulphamate solution were first investigated using non-patterned plain substrates prior to indium bumping trials. This provided understanding of the microstructural characteristics of indium deposits produced by electroplating and, through cathodic polarisation measurements, the highest current density suitable for electrodeposition was achieved as approximately 30 mA/cm2 when electroplating was carried out at room temperature and with no agitation applied. The typical surface morphology of DC electroplated indium contained a granular structure with a surface feature size as large as 10 µm. Pulse and pulse reverse electroplating significantly altered the surface morphology of the deposits and the surface became much smoother. By introducing acoustic agitation, the current density range suitable for electrodeposition could be significantly expanded due to the greater mass transfer, which led to a higher speed of deposition with high current efficiency. Wafer-scale indium bumping (15 µm to 25 µm diameter) at a minimum pitch size of 25 µm was successfully developed through electroplating trials with 3 inch test wafers and subsequently applied onto the standard 4 inch wafers. The results demonstrate the capability of electroplating to generate high quality indium bumps with ultrafine pitch at a high consistency and yield. To maximise the yield, pre-wetting of the ultrafine pitch photoresist patterns by both ultrasonic or megasonic agitation is essential leading to a bumping yield up to 99.9% on the wafer scale. The bump profiles and their uniformity at both the wafer and pattern scale were measured and the effects of electrodeposition regimes on the bump formation evaluated. The bump uniformity and microstructure at the feature scale were also investigated by cross-sectioning the electroplated bumps from different locations on the wafers. The growth mechanism of indium bumps were proposed on the basis of experimental observation. It was found that the use of a conductive current thief ring can homogenise the directional bump uniformity when the electrical contact is made asymmetrically, and improve the overall uniformity when the electrical contact is made symmetrically around the periphery of the wafer. Both unipolar pulse electroplating and bipolar pulse reverse electroplating improved the uniformity of the bump height at the wafer scale and pattern scale, and the feature scale uniformity could be significantly improved by pulse reverse electroplating. The best uniformity of 13.6% for a 4 inch wafer was achieved by using pulse reverse electroplating. The effect of ultrasonic agitation on the process was examined, but found to cause damage to the photoresist patterns if used for extended periods and therefore not suitable for use throughout indium bumping. Megasonic agitation enabled high speed bumping without sacrifice of current efficiency and with little damage to the photoresist patterns. However, megasonic agitation tended to degrade some aspects of wafer scale uniformity and should therefore be properly coupled with other electroplating parameters to assist the electroplating process.

Hybrid pixel detectors are widely used in many fields, including military, environment, industry and medical treatment. When integrating such a detector, a vertical connection technique called flip-chip bonding is almost the only way to realize the high-density interconnection between each pixel detector to the read-out chip. Such bonding can offer high-density I/O and a short interconnect distance, which can make the resulting device show excellent performance. Electro deposition is a promising approach to enable a low cost and high yield bump bonding process, compared with conventional sputtering or evaporation which is currently utilized for small-scale production. Due to that, Indium bumping process using electroplating is selected, as a result of which indium bump arrays with a pitch of 220 μm and a diameter of 30 μm have been fabricated using a standard silicon wafer processing. UBM (under bump metallization) for indium bumping was Ti/Ni (300 Å/ 2000 Å). It helps to increase adhesion between the wafer and the bumps and also serves as an excellent diffusion barrier both at room temperature and at 200°C. The indium is electroplated, using an indium sulfamate plating bath, and then formed into bumps through a reflow process. The reflow is made on a 200°C hot plate with a continuous flow of nitrogen over the wafer. During the reflow the indium is melted and forms into bumps due to surface tension. All the corresponding procedural processing steps and results are incorporated in this paper.

Em processos de eletrodeposição, substâncias à base de cianeto são empregadas como complexantes e portadores do metal a ser depositado. Entretanto, a toxicidade associada ao cianeto e a evolução das legislações ambiental e trabalhista impulsionaram a exploração de matérias-primas alternativas aos sais cianídricos. Um estudo desenvolvido no Instituto de Pesquisas Tecnológicas avaliou a modificação de um banho comercial isento de cianeto para processos de deposição de cobre em substratos de Zamac. Neste estudo, foi utilizado um banho à base do ácido 1,hidroxietano-1,1- difosfônico, ou HEDP, um composto orgânico capaz de formar complexos estáveis com íons metálicos. Para viabilizar a substituição do cianeto pelo HEDP, deve-se consolidar uma metodologia para o tratamento do efluente gerado nas operações que o envolvam. A técnica de eletrodiálise surge como uma alternativa considerada limpa, que dispensa mudanças de fase e adição de produtos químicos ao processo. O método consiste na utilização de membranas íon-seletivas para promover a separação de espécies iônicas entre soluções utilizando a diferença de potencial elétrico entre dois pólos como força motriz. Neste trabalho, avaliou-se a aplicação da eletrodiálise no tratamento de um efluente galvânico à base de HEDP. Foram utilizadas soluções sintéticas simulando as águas de lavagem de um banho toque composto por complexos de cobre e HEDP. A construção das curvas de polarização permitiu a determinação da densidade de corrente limite a ser empregada na eletrodiálise. Nos ensaios de eletrodiálise, foi avaliada a extração percentual dos íons de cobre e de HEDP das soluções sintéticas. As membranas utilizadas também foram analisadas para investigação de possíveis alterações estruturais. Os resultados mostraram extração de até 99,7% de cobre e 94,4% de HEDP, possibilitando o reaproveitamento das soluções tratadas nos tanques de lavagem e, simultaneamente, a reutilização dos íons extraídos, compensando perdas por arraste. As análises químicas comprovaram a presença de complexos aniônicos formados entre o cobre e o HEDP. A alteração na acidez do meio permite a separação deste complexo e a recuperação de cobre e de HEDP em compartimentos separados. As análises realizadas por MEV/EDS mostraram a presença de picos de cobre e fósforo nas superfícies das membranas. A avaliação feita por um processo de lixiviação indicou a ocorrência de depósitos nas superfícies das membranas. Os incrementos na acidez das soluções finais indicam recuperação do HEDP e as análises de foto-oxidação do ácido orgânico apontaram degradação inferior a 7% nos ensaios avaliados. / In electroplating processes, cyanide-based substances are used as complexing agents and as raw materials in form of metal salts. However, the toxicity associated with cyanide and the evolution of environmental and employment laws have been promoting research for the development of new raw materials in electroplating processes. A study conducted at the Institute for Technological Research evaluated the modification of commercial cyanide free bath for processes of copper coating on zinc alloys. In the performed study, a news alkaline copper bath was formulated using 1 hydroxyethane-1, 1 diphosphonic, or HEDP, an organic compound known for forming stable complexes with metal ions. To support the replacement of cyanide, it becomes necessary to consolidate a methodology for treatment of the wastewaters generated by operations involving HEDP. Electrodialysis is considered a clean technology which dispenses phase changes and the addition of chemicals to the treatment process. The method consists in the use of ion-selective membranes to promote the separation of ionic species from solutions, using as driving force the difference of electrical potential between two electrodes. In this study the application of electrodialysis in the treatment of electroplating wastewaters containing HEDP was evaluated. Synthetic solutions were prepared, simulating the rinsing water from a bath composed of copper and HEDP complexes. The construction of the current-voltage-curves allowed the determination of the limiting current density applied in the electrodialysis stack. During electrodialysis, the percentage of extraction of copper and HEDP from synthetic solutions were evaluated. The membranes used were analyzed to investigate possible structural changes. The results showed extracting rates up to 99,7% copper and 94,4% HEDP, allowing the reuse of solutions in rinse steps and simultaneously reuse of copper and HEDP ions to compensate drag-out losses. Chemical analysis confirmed the presence of anionic complexes formed between copper and HEDP. The decrease of pH allows the separation of these complexes and the recovery of copper and HEDP in separate compartments. The results of SEM/EDS analysis of membranes showed the presence of peaks of copper and phosphorus. The analysis made by a leaching process showed the occurrence of deposits on the membranes surface. The increases in acidity of the final solutions indicate recovery of HEDP and the photooxidation analysis indicated degradation of the organic acid under 7% in evaluated samples.

Neste trabalho, buscou-se verificar a possibilidade de, com a utilização do processo eletrolítico, se obter dióxido de manganês a partir da reciclagem de pilhas e baterias exauridas, visto a grande demanda por produtos que utilizam esse mineral. Utilizou-se, para tanto, uma solução eletrolítica que continha os íons metálicos: Ca (270mg/L), Ni (3000 mg/L), Co (630 mg/L), Mn(115300 mg/L), Ti (400 mg/L) e Pb (20 mg/L) em meio de ácido sulfúrico, sintetizada, seguindo-se dados de pesquisa anterior. A produção do dióxido de manganês eletrolítico (DME) foi realizada galvanostaticamente, com a utilização de uma fonte estabilizada que monitorava o potencial do eletrodo de trabalho. Utilizaram-se, preliminarmente, um eletrodo de trabalho de chumbo e dois contra-eletrodos de grafite, à temperatura de 98 ºC (±2ºC) e densidade de corrente de 1,69 A.dm-2. Após a verificação preliminar da possibilidade de obtenção do DME, repetiu-se sistematicamente o processo, aplicando-se variações de densidade de corrente (0,61 A.dm-2 a 1,93 A.dm-2) e de pH (0,00 a 1,20). O material obtido com essas variações foi analisado através dos processos de espectrometria de fluorescência de raios-X, difração de raios-X, área superficial específica pelo método BET e microscopia eletrônica de varredura (MEV). Os melhores resultados quanto a eficiência de corrente, pureza e área superficial se obtiveram com densidade de corrente entre 1,02 A.dm-2 e 1,39 A.dm-2 e com pH 0,50. Em todos os experimentos, como comprova a análise de difração de raios-X, foi constatada a obtenção da variedade alotrópica -MnO2, uma das formas viáveis para utilização na fabricação de pilhas. Os resultados apontam para a viabilidade desse processo de reciclagem como alternativa diante da escassez de fontes naturais de MnO2 com características compatíveis com a aplicação em questão e como forma de diminuição da poluição ambiental causada pelo descarte de pilhas e baterias. / Considering the growing demand for products containing manganese in its composition, this work seeks to verify the possibility of using depleted batteries as a source of manganese applying the electrolytic process. It was used an electrolyte solution containing the metal ions: Ca (270mg / L), Ni (3000 mg / L), Co (630 mg / L), Mn (115300 mg / L), Ti (400 mg / L) and Pb (20 mg / L) in concentrated sulfuric acid, following data from previous research. The production of electrolytic manganese dioxide (EMD) was performed through galvanization using a stabilized source that monitored the potential of the working electrode. It was preliminary used an electrode of lead and two counter electrodes of graphite at a temperature of 98ºC (± 2ºC) and current density of 1.69A.dm-2. After preliminary verifying the possibility of obtaining electrolytic manganese dioxide (EMD), the process was systematically repeated, applying different current density (0.61A.dm-2 to 2.51A.dm-2) and pH (0.00 to 1.20). The material obtained at these variations was analyzed through the process of X-ray fluorescence spectrometry, X-ray diffraction, specific surface area (BET) and scanning electron microscopy (SEM). The best values referring to current efficiency, level of purity and specific surface area were obtained with the current density ranging between 1.02 A.dm-2 and 1.39 A.dm-2, and pH 0.50. In any of the tested electrolysis conditions the -MnO2 structure was obtained as evidenced by the diffraction of X-rays analysis. The results indicate the feasibility of this recycling process as an alternative before shortage of natural sources of MnO2 and as a means of reducing environmental pollution caused by the disposal of batteries.

by Fung King-yuen Debera. / On t.p., "2+" is superscript. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1994. / Includes bibliographical references (leaves 102-112). / Acknowledgement --- p.i / Abstract --- p.ii / Table of Content --- p.iv / Chapter 1. --- Introduction --- p.1 / Chapter 1.1 --- Literature review --- p.1 / Chapter 1.1.1 --- Problems of heavy metals in the environment --- p.1 / Chapter 1.1.2 --- Methods of removal of heavy metal from industrial effluent --- p.5 / Chapter 1.1.3 --- The properties of magnetites --- p.10 / Chapter 1.1.4 --- Role of magnetites in water treatment --- p.12 / Chapter 1.1.5 --- The advantages of using magnetites and further application of magnetites --- p.16 / Chapter 1.2 --- Objectives of the study --- p.21 / Chapter 2. --- Materials and methods --- p.23 / Chapter 2.1 --- Selection of the organisms --- p.23 / Chapter 2.2 --- Culture media and chemicals --- p.23 / Chapter 2.3 --- Growth of the bacterial cells --- p.25 / Chapter 2.4 --- Immobilization of the bacterial cells on magnetites --- p.27 / Chapter 2.4.1 --- Effects of chemical and physical factors on the immobilization of the bacterial cells on magnetites --- p.27 / Chapter 2.4.2 --- Effect of pH on the desorption of cells from magnetites --- p.28 / Chapter 2.5 --- Nickel ion uptake experiments --- p.28 / Chapter 2.6 --- Effects of operational conditions on the nickel removal capacity of the magnetite-immobilized bacterial cells --- p.29 / Chapter 2 .6.1 --- Effect of physical factors --- p.29 / Chapter 2.6.2 --- Effect of chemical factors --- p.30 / Chapter 2.7 --- Optimization of the nickel removal efficiency --- p.30 / Chapter 2.8 --- Nickel adsorption isotherm of the magnetite- immobilized cells of Enterobacter sp4-2 --- p.30 / Chapter 2.9 --- Recovery of adsorbed Ni2+ from the magnetite- immobilized cells of Enterobacter sp4-2 --- p.31 / Chapter 2.9.1 --- Multiple adsorption-desorption cycles of Ni2+ by using citrate buffer --- p.32 / Chapter 2.9.2 --- Multiple adsorption-desorption cycles of Ni2+ by using ethylenediaminetetraacetic acid (EDTA) --- p.33 / Chapter 2.10 --- Effect of acidic treatment --- p.33 / Chapter 2.10.1 --- Effect of acidic treatment on the nickel removal capacity of the magnetites and the magnetite- immobilized cells of Enterobacter sp4-2 --- p.33 / Chapter 2.10.2 --- Effect of acidic treatment on the recovery of the adsorbed Ni2+ from magnetites and the magnetite- immobilized cells Enterobacter sp4-2 --- p.34 / Chapter 2.11 --- Removal and recovery of Ni2+ from the electroplating effluent --- p.34 / Chapter 3. --- Results --- p.36 / Chapter 3.1 --- Effects of chemical and physical factors on the immobilization of the bacterial cells on magnetites --- p.36 / Chapter 3.1.1 --- Effect of pH --- p.36 / Chapter 3.1.2 --- Effect of cells to magnetites ratio --- p.36 / Chapter 3.1.3 --- Effect of temperature --- p.39 / Chapter 3.2 --- Effect of pH on the desorption of cells from magnetites --- p.39 / Chapter 3.3 --- Nickel ion uptake experiments --- p.44 / Chapter 3.4 --- Effects of operational conditions on the nickel removal capacity of the magnetite-immobilized bacterial cells --- p.44 / Chapter 3.4.1 --- Effect of reaction temperature --- p.44 / Chapter 3.4.2 --- Effect of retention time --- p.44 / Chapter 3.4.3 --- Effect of pH --- p.47 / Chapter 3.4.4 --- Effect of the presence of cations --- p.50 / Chapter 3.4.5 --- Effect of the presence of anions --- p.50 / Chapter 3.5 --- Optimization of the nickel removal efficiency --- p.55 / Chapter 3.6 --- Nickel adsorption isotherm of the magnetite- immobilized cells of Enterobacter sp4-2 --- p.55 / Chapter 3.7 --- Recovery of adsorbed Ni2+ from the magnetite- immobilized cells of Enterobacter sp4-2 --- p.59 / Chapter 3.7.1 --- Multiple adsorption-desorption cycles of Ni2+ by using citrate buffer --- p.59 / Chapter 3.7.2 --- Multiple adsorption-desorption cycles of Ni2+ by using ethylenediaminetetraacetic acid (EDTA) --- p.63 / Chapter 3.8 --- Effect of acidic treatment --- p.63 / Chapter 3.8.1 --- Effect of acidic treatment on the nickel removal capacity of the magnetites and the magnetite-immobilized cells of Enterobacter sp4-2 --- p.63 / Chapter 3.8.2 --- Effect of acidic treatment on the recovery of the adsorbed Ni2+ from the magnetites and the magnetite-immobilized cells of Enterobacter sp4-2 --- p.66 / Chapter 3.9 --- Removal and recovery of Ni2+ from the electroplating effluent --- p.69 / Chapter 4. --- Discussion --- p.72 / Chapter 4.1 --- Selection of the organisms --- p.72 / Chapter 4.2 --- Effects of chemical and physical factors on the immobilization of the bacterial cells on magnetites --- p.72 / Chapter 4.2.1 --- Effect of pH --- p.72 / Chapter 4.2.2 --- Effect of cells to magnetites ratio --- p.74 / Chapter 4.2.3 --- Effect of temperature --- p.75 / Chapter 4.2.4 --- Effect of pH on the desorption of cells from magnetites --- p.76 / Chapter 4.3 --- Nickel ion uptake experiments --- p.78 / Chapter 4.4 --- Effects of operational conditions on the nickel removal capacity of the magnetite-immobilized bacterial cells --- p.80 / Chapter 4.4.1 --- Effect of reaction temperature --- p.80 / Chapter 4.4.2 --- Effect of retention time --- p.81 / Chapter 4.4.3 --- Effect of pH --- p.82 / Chapter 4.4.4 --- Effect of the presence of cations --- p.83 / Chapter 4.4.5 --- Effect of the presence of anions --- p.84 / Chapter 4.5 --- Optimization of the nickel removal efficiency --- p.85 / Chapter 4.6 --- Nickel adsorption isotherm of the magnetite- immobilized cells of Enterobacter sp4-2 --- p.86 / Chapter 4.7 --- Recovery of adsorbed Ni2+ from the magnetite- immobilized cells of Enterobacter sp4-2 --- p.87 / Chapter 4.7.1 --- Multiple adsorption-desorption of Ni2+ --- p.89 / Chapter 4.7.2 --- Effect of acidic treatment on the nickel removal capacity and recovery --- p.91 / Chapter 4.8 --- Removal and recovery of Ni2+ from the electroplating effluent --- p.93 / Chapter 5. --- Conclusion --- p.96 / Chapter 6. --- Summary --- p.99 / Chapter 7. --- References --- p.102

Sin Wai-Chu. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references. / Abstracts in English and Chinese. / ABSTRACT --- p.i / 論文摘要 --- p.ii / ACKNOWLEDGEMENT --- p.iii / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Electroplating history --- p.1 / Chapter 1.2 --- Electroplating bath --- p.7 / Chapter 1.3 --- Electroplating analytical methods --- p.8 / Chapter 1.3.1 --- Metal content and elemental impurities analysis --- p.10 / Chapter 1.3.2 --- "Metal complex, inorganic anion and cation analysis" --- p.11 / Chapter 1.3.3 --- Organic brighteners and levelers analysis --- p.12 / Chapter 1.4 --- HPLC literature review --- p.15 / Chapter 1.5 --- My research work --- p.16 / Chapter 1.6 --- References for Chapter 1 --- p.19 / Chapter Chapter 2 --- General Experimental --- p.23 / Chapter 2.1 --- The HPLC System --- p.23 / Chapter 2.2 --- The factors that affect the separation --- p.26 / Chapter 2.2.1 --- The composition of the solvent system --- p.27 / Chapter 2.2.2 --- The selection of column --- p.30 / Chapter 2.2.3 --- The most suitable analytical wavelength for UV detection --- p.34 / Chapter 2.3 --- Challenges in analyzing electroplating baths solution --- p.35 / Chapter 2.3.1 --- High metal content --- p.36 / Chapter 2.3.2 --- Strong ligand or complexing agent --- p.36 / Chapter 2.3.3 --- Interference --- p.37 / Chapter 2.3.4 --- Extreme pH --- p.37 / Chapter 2.3.5 --- Other difficulties --- p.38 / Chapter 2.3.6 --- Maintenance of HPLC instrument --- p.38 / Chapter 2.4 --- References for Chapter 2 --- p.38 / Chapter Chapter 3 --- Palladure 200 bath HPLC analysis --- p.41 / Chapter 3.1 --- Introduction --- p.41 / Chapter 3.2 --- Experimental --- p.43 / Chapter 3.3 --- Problems in the existing UV analysis for monitoring Palladure200 process --- p.45 / Chapter 3.4 --- HPLC method development for monitoring Palladure 200 process --- p.49 / Chapter 3.5 --- Analysis of aged Palladure 200 plating bath from production line --- p.55 / Chapter 3.6 --- Conclusion --- p.57 / Chapter 3.7 --- References for Chapter 3 --- p.58 / Chapter Chapter 4 --- Nickel PC3 bath HPLC analysis --- p.59 / Chapter 4.1 --- Introduction --- p.59 / Chapter 4.2 --- Experimental --- p.60 / Chapter 4.3 --- Problems in the existing Titration method for monitoring Nickel PC3 process --- p.62 / Chapter 4.4 --- HPLC method development for monitoring Nickel PC3 process --- p.63 / Chapter 4.4.1 --- Identify individual component of Nickel PC3 process --- p.63 / Chapter 4.4.2 --- Set up a calibration curve for the Nickel PC3 Additive --- p.67 / Chapter 4.4.3 --- Analysis of aged Nickel PC3 plating bath from production line --- p.68 / Chapter 4.5 --- Conclusion --- p.71 / Chapter 4.6 --- References for Chapter 4 --- p.72 / Chapter Chapter 5 --- Solderon SC bath HPLC analysis --- p.73 / Chapter 5.1 --- Introduction --- p.73 / Chapter 5.2 --- Experimental --- p.74 / Chapter 5.3 --- Instability in the existing Cyclic Voltammetric Stripping (CVS) method for monitoring Solderon SC process --- p.76 / Chapter 5.4 --- HPLC method development for monitoring Solderon SC process --- p.77 / Chapter 5.4.1 --- Identify the individual components --- p.77 / Chapter 5.4.2 --- Set up a calibration curve for the Solderon SC Primary --- p.82 / Chapter 5.4.3 --- Analysis of aged Solderon SC plating bath from production line --- p.84 / Chapter 5.5 --- Conclusion --- p.86 / Chapter 5.6 --- References for Chapter 5 --- p.86 / Chapter Chapter 6 --- Copper Gleam PPR bath HPLC analysis --- p.87 / Chapter 6.1 --- Introduction --- p.87 / Chapter 6.2 --- Experimental --- p.89 / Chapter 6.3 --- Problems in the existing Cyclic Voltammetric Stripping (CVS) method for monitoring Copper Gleam PPR process --- p.91 / Chapter 6.4 --- HPLC method development for monitoring Copper Gleam PPR process --- p.92 / Chapter 6.4.1 --- Identify Individual components and copper PPR additivein standard bath --- p.92 / Chapter 6.4.2 --- Set up a calibration curve for the Copper Gleam PPR Additive --- p.95 / Chapter 6.4.3 --- Analysis of aged Copper Gleam PPR plating bath from production line --- p.96 / Chapter 6.4.5 --- Study of H202 effect --- p.101 / Chapter 6.4.6 --- Study of air agitation effect --- p.104 / Chapter 6.4.7 --- Study of Copper anode effect --- p.105 / Chapter 6.5 --- Conclusion --- p.107 / Chapter 6.6 --- References for Chapter 6 --- p.107 / Chapter Chapter 7 --- Silverjet220 bath HPLC analysis --- p.109 / Chapter 7.1 --- Introduction --- p.109 / Chapter 7.2 --- Experimental --- p.110 / Chapter 7.3 --- HPLC method development for monitoring Silverjet 220 process --- p.112 / Chapter 7.3.1 --- Identify individual components and Silverjet 220 Additive in the plating bath --- p.112 / Chapter 7.3.2 --- Optimize the condition for HPLC analysis --- p.117 / Chapter 7.3.3 --- Analysis of aged Silverjet 220 plating bath from production line --- p.119 / Chapter 7.4 --- Conclusion --- p.122 / Chapter 7.5 --- References for Chapter 7 --- p.123 / Chapter Chapter 8 --- Conclusions and Further Studies --- p.124 / Chapter 8.1 --- Conclusions --- p.124 / Chapter 8.2 --- Further Studies --- p.126 / APPENDIX --- p.128 / The User guide for HPLC --- p.128 / HPLC System Calibration Maintenance --- p.135 / HPLC System Preventive Maintenance --- p.145

Na Região Metropolitana de São Paulo, em uma área impactada por resíduos de galvanoplastia estudaram-se fenômenos de fixação e mobilidade dos íons Ni, Cu e Cr associados ao solo e águas subterrâneas e superficiais. No solo, próximo à área de descarte do resíduo, detectou-se preocupante enriquecimento em íons metálicos na forma precipitada/adsorvida, disponíveis ao meio ambiente em função das condições ambientais. Baixos valores de CTC e matéria orgânica do solo constituído essencialmente por caulinita, bem como a declividade do terreno, favoreceram a mobilização iônica com fixação no terreno próximo ao Rio Aricanduva. Experimentalmente, através de lixiviações em extrator do tipo sohxlet e em colunas de percolação sob diferentes condições, demonstrou-se que o Ni é intensamente mobilizado, que o cromo praticamente mantem-se fixo e o cobre teve comportamento intermediário. Em trabalhos de campo verificou-se que o comportamento dos íons foi o mesmo, isto é, o cromo, na forma de óxi-hidróxido, se manteve precipitado junto às partículas do solo; o cobre, pouco ou quase nada se alterou, encontrado praticamente fixo (Cu(OH)2, CuO.nH2O) e o níquel apresentou comportamento dividido entre a solução intersticial e como íon adsorvido. Os resíduos galvânicos, embora sejam diferenciados quanto a composição química, em geral, mesmo em condições ambientais e características diversas dos solos, liberam elevadas concentrações de íons de metais pesados para o meio ambiente excedendo os limites estabelecidos pela CETESB. / In a contaminated site by electroplating wastes located in the Metropolitan region of São Paulo, São Paulo State, were studied phenomena of Ni, Cu and Cr ions fixation and mobility, associated with soils and superficial and groundwater water. The soil situated nearby an irregular area of waste disposal, presented high concentrations of heavy metals as adsorbed/precipitated ions, in available state depending on climate conditions. Low values of cationic exchange capacity (CEC), low organic matter content in soils and kaolinite dominant mineralogy, in addition to land slope favored ionic mobilization followed by its fixation in soils near Aricanduva River. Extractions with sohxlet extractor and with percolation columns in different conditions, show that the nickel is intensely mobilized and chromium remained precipitated; copper behavior was mediator. In works in study area the ions behavior was same, Cr as oxi-hydroxide, remained precipitated in soil; Cu is fixed (Cu(OH)2, CuO.nH2O) and Ni was distributed between soil and water. Solid waste produced by electroplating industry activities present high concentrations of heavy metals, regardless the different conditions and characteristics of soils, when inadequately dumped or disposed, heavy metals ions are released to environment, normally exceeding CETESB (environmental protection agency of São Paulo State) limits.

abstract: Lithium metal is a promising anode for the next generation lithium batteries owing to its high capacity (3860 mAh g-1) and the lowest negative reduction potential (-3.04 V). Commercial produced lithium anodes have a native rough surface which deteriorates the cycling performance of the battery. Here, an attempt has been made to deposit lithium on copper from an electrolytic cell consisting of simple electrolyte of pyridine and lithium chloride at room temperature. Water is known to react aggressively with the lithium metal, however in the electrochemical plating process, it has a significant beneficial effect in catalyzing the electrochemical reactions. The effect of trace amounts of water was investigated in air as well as in controlled atmosphere of argon, nitrogen, breathing grade dry air and ultra-zero dry air. The electrochemical products examined by Fourier transform infrared spectroscopy revealed the deposition might require the reduction of pyridine to facilitate the reduction of the lithium salt. Purity of the lithium film was determined by inductively coupled plasma mass spectrometry. / Dissertation/Thesis / Masters Thesis Materials Science and Engineering 2019

Present state-of-the-art hydrogen sensors are limited by a number of defects such as poisoning effects, slow response, and/or the range of concentrations that can be detected. Thus, hydrogen sensors are currently under investigation. In the search for the ultimate sensor, a variety of materials have been employed as the sensing layer. One of these materials is palladium. Palladium is widely used for hydrogen sensing due to its high selectivity and property of spontaneously absorbing hydrogen. Thin and thick film palladium hydrogen sensors have been reported, as well as palladium nanostructures. Specifically, palladium nanowires for hydrogen sensing have had improved results relative to other types of sensors; these have been reported with a response time down to 75ms and do not suffer from poisoning effects. Additionally, the fabrication of these nanostructures via electrodeposition is simple and cost efficient. For this reason, palladium nanostructures were chosen as the front-end for a novel hydrogen sensor. The nanostructures were to be employed as the sensing front-end of a Surface Acoustic Wave (SAW) sensor. It was theorized that the response time would be vastly improved if these were used as opposed to a thin or thick palladium film due to the decreased hydrogen diffusion distance, which is a result of the structures being one-dimensional. Because it was theorized that the dimensions of the nanostructures play an integral role in the response time to hydrogen, control of the morphology was required. This control was achieved by varying the plating variables in the electrodeposition experiments. The plating variables investigated were deposition potential, time, and counter-electrode area. The dimensions of the resulting nanostructures were measured via Scanning Electron Microscopy (SEM) and correlated to the conditions of the electrodeposition experiments. Nanowires under 40nm were successfully fabricated.

Mercury amalgam microelectrodes, typically fabricated by electrodeposition of mercury onto metal (platinum, gold, silver) inlaid disks, possess certain advantageous properties for scanning electrochemical microscopy (SECM) and electroanalysis. But as applications require more and more precision, fundamental questions concerning the exact shape and constitution of the amalgam can become important for interpreting SECM experimental data. The purpose of this study is to analyze in depth the formation of the amalgam, in order to provide a better understanding of the key physical processes, and so be able to judge of the accuracy of the currently used models and refine them when necessary. The amalgam formation is the result of several processes that occur roughly at two different scales: the global scale, which is microscopic, and the local scale, of the order of few nanometers. On the global scale, the dominant physical process is the mass transport, driven almost entirely by diffusion, which determines the rate of mercury deposition. Other phenomena occur at the smaller local scale. Their understanding is essential to predict precisely the volume and shape of the amalgam at shorter times. Among these local phenomena, nucleation and droplet interactions appear critical. The former sets the formation rate and the size of the isolated mercury droplets that are initially formed at the surface of the electrode. An understanding of the latter is necessary to determine the droplet coalescence process. Among the specific accomplishments of this Master thesis work, a time scale analysis of the global phenomena has been performed leading to the conclusion that quasi-steady state diffusion of mercury ions in the bulk mainly defines the electrodeposition rate. Then, a series of analytical formulations for diffusion-limited electrodeposition current available in the literature has been quickly analyzed, leading to development of analytical/numerical models. These latter have been implemented, and results were critically compared with experimental data, leading to the conclusion that the early electrodeposition was not enough finely modeled. Mercury droplets nucleation and surface interaction have been identified as relevant processes of this period. They have next been investigated in detail, leading to the characterization of the nucleation process, and the derivation of two complimentary approaches on charged droplet stability. Regime maps have been developed, providing first explanations and quantitative information on charged droplet stability dependence on potential applied, electrolyte and droplet size. Finally, through analysis of theoretical predictions, a series of electroanalytical experiments have been proposed for the future validation of the suggested theoretical models.