Foram estudados os efeitos da presença de surfatantes aniônicos (dodecilsulfato de sódio - SDS e dodecilbenzenosssulfonato de sódio - SDBS) e catiônico (cloreto de dodecilamônio - DAC) em diferentes interfases metal/cloreto de sódio, em valores de pH iguais a 5,8 e 3,0 . Platina, cobre e níquel foram utilizados como substratos. Técnicas eletroquímicas (polarizações potenciostáticas catódicas e anódicas; voltametria cíclica; cronoamperometria; impedância eletroquímica, com eletrodo parado e com eletrodo de disco rotativo - EDR) foram empregadas, bem como técnicas não eletroquímicas (espectroscopia Raman \"in situ\" SERS; microscopia eletrônica de varredura (MEV) / espectroscopia de dispersão de energia - EDS) a fim de caracterizar a ação destes surfatantes em processos anódicos e catódicos que ocorrem nas interfases citadas. DAC apresentou ação inibidora acentuada para as reações de oxidação e redução da água, na interfase Pt/NaCl 0,1 mol.L1 , não sendo eletroativo na faixa de potenciais compreendida entre estes dois processos. Utilizando-se eletrodo parado, o surfatante mostrou ação inibidora mais acentuada para os processos anódicos do que para os catódicos. Com convecção forçada empregando EDR, o surfatante apresentou graus de inibição da ordem de 90 % para ambos os processos, sugerindo que o transporte de massa favorece a adsorção do DAC sobre a platina. Tal comportamento pôde também ser comprovado quando se utilizou cobre e níquel como substratos, -1 em meio de pH igual a 5,8. Para a interfase Cu / NaCl 0,1 mol.L-1 pH = 3, com EDR, os três surfatantes tiveram seus efeitos estudados na região catódica, a fim de se verificar a sua atuação na reação de desprendimento de hidrogênio. Os surfatantes aniônicos não apresentaram efeito inibidor sobre a referida reação, aumentando a sua velocidade para potenciais mais negativos + do que -1,0 V / ECS. DAC, ao contrário, inibiu a reação H+ / H2 , com valores de grau de cobertura 2 da ordem de 50 %. A adsorção dos surfatantes sobre cobre foi caracterizada por espectroscopia Raman (SERS), cujos estudos mostraram que os três surfatantes são adsorvidos através da cadeia carbônica (hidrofóbica), no potencial de corrosão (Ecorr ) e a valores de potencial mais positivos e Ecorr . Os resultados espectroscópicos sugerem a presença da parte polar do SDS na interfase, enquanto que, no no caso do DAC, não foi possível caracterizar, por esta técnica, a adsorção do grupamento amônio Foram realizados também estudos sobre o efeito destes surfatantes em processo de eletrodeposição de níquel sobre cobre. SDS apresentou aumento de rendimento de 28% para 43% a um potencial de -1,10 V / ECS, em relação ao processo efetuado em ausência de surfatante. Os depósitos obtidos em presença de SDS e SDBS apresentaram-se mais brilhantes e visualmente mais homogêneos do que aquele obtido em ausência de surfatante, confirmando a ação abrilhantadora destes aditivos utilizados em banhos comerciais de deposição. A presença de DAC inibiu a reação Ni2+ /Ni, obtendo-se depósito de níquel apenas nas bordas do eletrodo de cobre. As superfícies de cobre niqueladas foram caracterizadas por medidas de potencial de circuito aberto, polarização anódica, cronoamperometria, impedância eletroquímica e por MEV / EDS. Os resultados obtidos, empregando as diferentes técnicas, indicaram que a deposição de níquel sobre cobre em meio de NaC1 0,1 mol.L-1, pH = 3, contendo 1,0X10-3 mol.L-1 de SDS foi a apresentou melhores características tanto em relação ao rendimento quanto à qualidade do depósito formado. / The effect of anionic (sodium dodecylsulphate - SDS and sodium dodecylbenzenesulphonate - SDBS) and cationic (dodecylammonium chloride - DAC) surfactants has been studied in different metal / sodium chloride interfaces, at pH = 5.8 and pH = 3.0 . Platinum, copper and nickel have been used as substracts. Electrochemical (anodic and cathodic potentiostatic polarisation, cyclic voltammetry, chronoamperometry, and electrochemical impedance, using stationary and rotating disk electrodes - RDE) and non-electrochemical techniques (\"in situ\" Raman spectroscopy / SERS ; scanning electronic microscopy - SEM / energy dispersion spectroscopy - EDS) have been used to study the action of these surfactants on anodic and cathodic reactions that occur in the interfaces. DAC has shown strong -1 inhibitory action on reduction and oxidation water reactions, on Pt / 0.1 mol.L-1 NaCl interfhace, without electroactivity in all the potential range studied. Stationary electrode, has shown that DAC is more effective as inhibitor for the anodic processes than for the cathodic one. Using rotating disc electrode (RDE), surfactant presents about 90 % of inhibitory efficiency in both processes, suggesting that mass transport favours DAC adsorption on Pt. Furthermore the inhibitory action is the same when using copper and nickel as substract , at pH = 5.8. The three surfactants (SDS, SDBS and DAC) were studied on cathodic potential range, in order to verify their action on hydrogen evolution reaction, in Cu / NaCl 0.1 mol.L-1 , pH = 3.0, using RDE. Anionic surfactants have not shown inhibitory action on the mentioned reaction, increasing its rate at more negative potentials than -1.0 V / ECS. On the other hand, DAC inhibits the same reaction, showing 50 % inhibitory efficiency. Surfactants adsorption on copper have been studied by Raman Spectroscopy (SERS) \"in situ\". These studies have shown the adsorption of DAC, SDS and SDBS through carbonic chain (hydrophobic) at corrosion potential (Ecorr) and at more negative and more positive potentials. The presence of the polar head at the interface have been confirmed for SDS and SDBS. For DAC, however, it was not possible to characterize the ammonium group adsorption from Raman spectra. The effect of these surfactants have also been studied for nickel electrodeposition process on copper. SDS increased the process yield (28 % to 43 %, at E = -1.1 V / ECS), when compared to the results obtained without surfactant. Deposits were brighter and more homogeneous than those obtained in the absence of SDS and SDBS surfactants, confirming the brightening action of these additives in commercial deposition baths. DAC also inhibits Ni /Ni2+ reduction, producing nickel deposit just on the edge of copper electrode. The results, obtained from different techniques, have shown that nickel deposition on copper, in 0.1 mol.L-1 NaC1, pH = 3, containing 1.0X10-3 mol.L-1 SDS, presented the best performance, if it is considered the yield values and the quality of the deposit.

Foram desenvolvidos sensores magnéticos tipo \\ita miniaturizados, paralelos planos e ortogonais, com os núcleos compostos por ligas ferromagnéticas eletrodepositadas. O foco no desenvolvimento dos sensores paralelos planos foi a redução da complexidade do processo de microfabricação, utilizando apenas uma camada de bobinas. Para isto foram propostos dois leiautes em que as bobinas de excitação e as coletoras foram posicionadas no mesmo plano. Foram então construídos sensores miniaturizados utilizando um processo de microfabricação simplificado com apenas quatro máscaras fotolitográficas e núcleos de NiFe eletrodepositando. Os dispositivos resultantes apresentaram boa linearidade para campos de até 200 ?T, com responsividades máximas de 16 V/T e 8 V/T quando operados com a excitação senoidal e frequência de 100 kHz. O ruído\\ita contidos na faixa de 0,1 a 10 Hz foi estimado em 40 nT e 59 nT. Também foram desenvolvidos sensores tipo \\ita ortogonais. Foi proposto e validado um modelo matemático para o sinal de saída quando este tipo de sensor é operado em constante saturação. Desta maneira a permeabilidade magnética é modulada pela rotação da magnetização, reduzindo os saltos de Barkhausen. Os sensores foram construídos a partir de fios de cobre com diâmetros de 45 e 120 ?m eletrodepositados com ligas de NiFe e NiFeP, e envoltos por um solenoide. Os melhores dispositivos, com núcleo de NiFe, operados no modo de rotação da magnetização apresentaram considerável redução do ruído em relação ao modo convencional. A amostra menos ruidosa foi de 8 nT para 0,55 nT \\ita contidos na faixa de 0,1 Hz a 10 Hz. O preço pago foi uma diminuição na responsividade, de 796 para 211 V/T e o aumento no efeito \\ita, de 2 para 4,5 ?T. / Two kinds of miniaturized fluxgate magnetic sensor have been developed, a planar parallel and an orthogonal one, with electroplated ferromagnetic alloy cores. The development of the parallel one had focus on the overall manufacture complexity reduction. Two planar layouts making use of only one layer of coils were proposed and constructed with a simplified micromachinig process that used only four photolithographic masks. The cores were obtained by electroplating NiFe thought molds. The sensors presented a maximum sensitivity of 16 V/T and 8 V/T, depending on the layout, for a 100 kHz sine excitation. Also the rms noise levels contained in the 0.1-10 Hz range were measured, resulting in 40 nT and 59 nT. It has been also developed some orthogonal fluxgate sensors. The output signal generated by this kind of sensor operated in constant saturation mode was mathematical modeled and experimentally validated. In this case, the core magnetic permeability is no longer modulated by the domain walls movement but rather by the magnetization rotation. The advantage being the suppression of Barkhausen jumps, one of the main sources of noise. The sensors were build using cooper wires with two diameter, 45 and 120 ?m, electroplated with NiFe and NiFeP alloys. The best devices, with NiFe cores, operated in the magnetization rotation mode had their noise levels reduced by a factor of about 10 when compared to the conventional mode. The less noisy sample went from 8 nT to 0.55 nT \\ita contained in the 0,1-10 Hz range. The drawback was a decrease in the sensitivity, from 796 to 211 V/T and an increase in the perming error, from 2 to 4,5 ?T.

Adherent Cu films were electrodeposited onto polycrystalline W foils from purged solutions of 0.05 M CuSO4 in H2SO4 supporting electrolyte and 0.025 M CuCO3∙Cu(OH)2 in 0.32 M H3BO3 and corresponding HBF4 supporting electrolyte, both at pH = 1. Films were deposited under constant potential conditions at voltages between -0.6 V and -0.2 V versus Ag/AgCl. All films produced by pulses of 10 s duration were visible to the eye, copper colored, and survived a crude test called "the Scotch tape test", which involves sticking the scotch tape on the sample, then peeling off the tape and observing if the copper film peels off or not. Characterization by scanning electron microscopy (SEM)/energy dispersive X-ray (EDX) and X-ray photon spectroscopy (XPS) confirmed the presence of metallic Cu, with apparent dendritic growth. No sulfur impurity was observable by XPS or EDX. Kinetics measurements indicated that the Cu nucleation process in the sulfuric bath is slower than in the borate bath. In both baths, nucleation kinetics does not correspond to either instantaneous or progressive nucleation. Films deposited from 0.05 M CuSO4/H2SO4 solution at pH > 1 at -0.2 V exhibited poor adhesion and decreased Cu reduction current. In both borate and sulfate baths, small Cu nuclei are observable by SEM upon deposition at higher negative overpotentials, while only large nuclei (~ 1 micron or larger) are observed upon deposition at less negative potentials. Osmium metal has been successfully electrodeposited directly onto p-Si (100) from both Os3+ and Os4+ in both sulfuric and perchloric baths. This electrochemical deposition of osmium metal can provide sufficient amount of osmium which overcome ion beam implantation limitations. The deposited metal can undergo further processing to form osmium silicides, such as Os2Si3, which can be used as optical active materials. The higher osmium concentration results in large deposition currents and more negative peak potential due to larger transfer coefficient. No matter which supporting electrolyte is used, no stripping peak exists in this study. The oxidation ability of anion plays an important role in osmium electrodeposition because it will change the silicon substrate conductivity. In our case, perchloric acid oxidized silicon surface severely. Os4+ seems more favorable for reduction but has a stronger oxidization ability to lower the conductivity. The microscopic images verified osmium is deposited on silicon and forms cluster sizes of < 1 µm to > 10 µm. The Rutherford backscattering spectroscopy (RBS) data indicate osmium can diffuse into the silicon as far as 500 nm and the Si crystal structure is unchanged by the process. This means that the Si does not disassociate and migrate into deposited Os. Osmium is distributed randomly throughout the lattice interstitially. It appears field assisted diffusion can significantly drive the Os into Si (100). This finding is very valuable but needs further study.

Thesis advisor: Michael J. Naughton / In this dissertation, I first discuss many different kinds of transparent conductors in Chapter one. In Chapter two, I focus on transparent conductors based on crackle temples. I and my colleagues developed three (one sputter-free and two fully all-solution) methods to fabricate metallic networks as transparent conductors. The first kind of all-solution process is based on crackle photolithography and the resulting silver networks outperform all reported experimental values, including having sheet resistance more than an order of magnitude lower than ITO, yet with comparable transmittance. The second kind of all-solution proceed transparent conductor is obtained by integrating crackle photolithography-based microwires with nanowires and electroplate welding. This combination results in scalable film structures that are flexible, indium-free, vacuum-free, lithographic-facility-free, metallic-mask-free, with small domain size, high optical transmittance, and low sheet resistance (one order of magnitude smaller than conventional nanowire-based transparent conductors). / Thesis (PhD) — Boston College, 2019. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

The electroplating industry has not evolved substantially over the years. Typically, the industry relies on experience as well as the common sense of its personnel to produce parts and to deal with any waste products that the plating process produces. With the heightened environmental awareness of the 1990s, past practices which produced acceptable treatment levels are no longer good enough. There are numerous methods for meeting the environmental laws of the 1990's. Technology can range from the simple to the complex. Several established methods for the electroplating industry are ion exchange, reverse osmosis, electrodialysis, ion flotation, sulfide precipitation and activated carbon. Internal waste reduction programs, discharging to publicly owned treatment works and zero discharge are as well viable options for the industry. With the combination of regulations and compliance scenarios facing today's etectroplating operations, it is necessary to define a protocol or methodology which will enable them to make economically feasible decisions as to what compliance option best fits with their corporate strategy. By doing so, the decision will allow them to continue to operate into the 21st century. The selection process must be flexible enough so that state of the art technologies are not the only solution. It must allow for multiperson evaluation of systems with multiattributes. This report represents the development and application of a methodology for evaluating different environmental compliance scenarios for the electroplating industry. The methodology was developed using the analytical hierarchy process, AHP. The strength of AHP lies in its ability to incorporate complex, multiattribute systems into a single decision making process which is robust enough to allow for multiperson evaluation. / Master of Science

B.S.

A hard chromium electroplating process is normally used for preventing mechanical and electrical parts such as roller, piston and mold from the harmful environments and giving the good physical properties on the surface such as increased wear resistance, increased hardness, low frictional coefficient as well as good aesthetic look on the surface of workpieces. The problem that often found in this process is the deflected workpieces after plating process due to the low plating performance during a plating period. These deflected workpieces are needed to replating it again. However, the replating method causes a large amount of resource consumptions and increases the production time. To handle this problem, the plating solution temperature is needed to maintain the plating solution temperature at a set point about 50 °C in order to improve the plating performance during the plating period and decrease the occurrence of the deflected workpieces. In this work, the mathematical models are developed to explain the dynamic behavior of the plating solution temperature during the plating time and validated with the real data from a plant. The conventional (PID) controller is applied to this process for the purpose of keeping the plating solution temperature at the set point throughout the plating time. The result demonstrates that the developed mathematical models can be used to explain the dynamic behavior of the plating solution temperature because it gives the good simulation of the plating solution temperature with a slightly different from the real data. Furthermore, the PID controller shows the high control performance for maintaining the plating solution temperature at the set point throughout the plating period with small overshoot at the beginning of every batch.

B.S.

Submitted in fulfilment of the requirements of the egree of Master of Technology: Chemical Engineering, Durban University of Technology, 2011. / The South African electroplating industry generates large volumes of hazardous waste water that has to be treated prior to disposal. The main source of this waste water has been the rinse system. Conventional end-ofpipe waste water treatment technologies do not meet municipality standards. The use of technologies such as membranes, reverse osmosis and ion exchange are impractical, mainly due to their cost and technical requirements. This study identified source point reduction technologies, close circuiting of the electroplating process, specific to the rinse system as a key development. Specifically the application of a low flow counter current rinse system for the recovery of the rinse water in the plating bath was selected. However, the recovery of the rinse tank water was impeded by the low rates of evaporation from the plating bath, which was especially prevalent in the low temperature operating plating baths. This master’s study proposes the use of an induced draft evaporative cooling tower for facilitation of evaporation in the plating bath. For total recovery of the rinse tank water, the rate of evaporation from the plating bath has to be equivalent to the rinse tanks make up water requirements. A closed circuit plating system mathematical model was developed for the determination of the mass evaporated from the plating bath and the cooling tower for a specified time and the equilibrium temperature of the plating bath and the cooling tower. The key criteria in the development of the closed circuit plating system model was the requirement of minimum solution specific data as this information is not readily available. The closed circuit plating system model was categorised into the unsteady state and steady state temperature regions and was developed for the condition of water evaporation only. The closed circuit plating system model was programmed into Matlab and verified. The key factors affecting the performance of the closed circuit plating system were identified as the plating solution composition and operational temperature, ambient air temperature, air flow rate and cooling tower iv packing surface area. Each of these factors was individually and simultaneously varied to determine their sensitivity on the rate of water evaporation and the equilibrium temperature of the plating bath and cooling tower. The results indicated that the upper limit plating solution operational temperature, high air flow rates, low ambient air temperature and large packing surface area provided the greatest water evaporation rates and the largest temperature drop across the height of the cooling tower in the unsteady state temperature region. The final equilibrium temperature of the plating bath and the cooling tower is dependent on the ambient air temperature. The only exception is that at low ambient air temperatures the rate of water evaporation from the steady state temperature region is lower than that at higher ambient air temperatures. Thus the model will enable the electroplater to identify the optimum operating conditions for close circuiting of the electroplating process. It is recommended that the model be validated against practical data either by the construction of a laboratory scale induced draft evaporative cooling tower or by the application of the induced draft evaporative cooling tower in an electroplating facility.

For years, the alloy of choice for electroplating electronic components has been tin-lead (Sn-Pb) alloy. However, the legislation established in Europe on July 1, 2006, required significant lead (Pb) content reductions from electronic hardware due to its toxic nature. A popular alternative for coating electronic components is pure tin (Sn). However, pure tin has the tendency to spontaneously grow electrically conductive Sn whisker during storage. Sn whisker is usually a pure single crystal tin with filament or hair-like structures grown directly from the electroplated surfaces. Sn whisker is highly conductive, and can cause short circuits in electronic components, which is a very significant reliability problem. The damages caused by Sn whisker growth are reported in very critical applications such as aircraft, spacecraft, satellites, and military weapons systems. They are also naturally very strong and are believed to grow from compressive stresses developed in the Sn coating during deposition or over time. The new directive, even though environmentally friendly, has placed all lead-free electronic devices at risk because of whisker growth in pure tin. Additionally, interest has occurred about studying the nature of other metal whiskers such as zinc (Zn) whiskers and comparing their behavior to that of Sn whiskers. Zn whiskers can be found in flooring of data centers which can get inside electronic systems during equipment reorganization and movement and can also cause systems failure.Even though the topic of metal whiskers as reliability failure has been around for several decades to date, there is no successful method that can eliminate their growth. This thesis will give further insights towards the nature and behavior of Sn and Zn whiskers growth, and recommend a novel manufacturing technique that has potential to mitigate metal whiskers growth and extend life of many electronic devices.