This paper reports the evaluation results of the mechanical structures of MEMS (micro electro mechanical systems) sensor implemented in the integrated MEMS inertial sensor for a wide sensing range from below 0.1 G to 20 G (1 G = 9.8 m/s^2). To investigate the mechanical tolerance, a maximum target acceleration of 20G was applied to the sub-1G sensor which had the heaviest proof mass of all that sensors had. The structure stability of Ti/Au multi-layered structures was also examined by using Ti/Au micro cantilevers. The results showed that the stoppers effectively functioned to prevent the proof mass and the springs from self-destruction, and that the stability of Ti/Au structures increased with an increase in width. Those results suggest that the proposed stopper and spring structures could be promising to realize MEMS sensors.

The electroplating industries use soluble nickel salts in numerous applications. Over the past few years this has become problematic due to the reclassification of these salts from a harmful substance to now a toxic substance. The introduction of the legislation REACH (Registration, Evaluation, Authorisation & restriction of CHemicals) has meant the electroplating industry has had to use less harmful chemicals where possible, thus meaning companies are investing in research to find an alternative to the nickel deposit. In this study, alternative deposits under investigation as a potential replacement to the nickel deposit under the decorative chromium deposit has been characterised in terms of the appearance, surface topography and corrosion resistance by using spectrophotometry, scanning electron microscopy (SEM), atomic force microscopy (AFM), linear polarisation, electrochemical impedance spectroscopy (EIS) and accelerated corrosion salt spray methods. Spectrophotometry identified that a white Cu-Sn alloy gave a bluer appearance in comparison to the nickel deposit, when the chromium deposit was plated on top this modified the colour slightly giving the white Cu-Sn alloy with chromium a similar appearance to the nickel and chromium deposit. The yellow Cu-Sn alloy was yellow in colour with a visibly dull appearance, but when chromium was plated on top of the yellow Cu-Sn alloy the colour was improved but still remained dull. The SEM and AFM results identified that the white Cu-Sn alloy deposit had similar nodulated topography to the nickel deposit and when the chromium was plated on top the topography changed only slightly. While the yellow Cu-Sn alloy deposits showed a more crystalline structure and increased roughness in comparison to the nickel deposit, the chromium deposit plated on top did not change the structure of the underlying deposit but it did reduce the roughness slightly. Electrochemical corrosion tests showed the white Cu-Sn alloy to have a higher polarisation resistance compared to the nickel deposit, thus suggesting it would provide similar corrosion protection to the nickel deposit. The yellow Cu-Sn alloy proved to have a faster corrosion rate in comparison to the nickel deposit. Accelerated corrosion tests proved the white Cu-Sn alloy to be more corrosive than the nickel despite the electrochemical test results, it was concluded that the white Cu-Sn alloy deposit was porous and therefore provided less corrosion protection to the substrate in comparison to the nickel deposit. The yellow Cu-Sn alloy had a lower corrosion protection than the nickel deposit and when combined as a duplex Cu-Sn alloy with the white Cu-Sn alloy deposit there was no improvement in corrosion performance. The plated chromium deposit did improve the corrosion protection for most deposits but none of the alternatives could match the corrosion protection offered by the standard nickel with chromium deposit. This study concluded that the white Cu-Sn alloy with chromium deposit was found to be a potential alternative to the nickel with chromium deposit for applications where appearance is primary, no alternative could be found to match the corrosion protection provided by the standard nickel and chromium process.

Theoretical waste minimisation opportunities and options for electroplating were sought from the literature. Their suitability under the specific site conditions of a chromium electroplating plant were evaluated using the results of a waste minimisation audit (audit). The audit showed that many waste minimisation practices were already in place. These included counter current flowing rinse systems, multiple use of rinses and recycling of the drag-out solution back into the plating solution. Two types of information were collected during the audit, namely new chemical monitoring (concentration levels of sodium, iron, zinc, copper, lead, chromium and nickel and conductivity, total dissolved solids and pH) and flow rate data and existing data (composition of the process solutions, products and waste outputs, and raw materials, workpieces and utility inputs). The data were analysed using four established waste minimisation techniques. The Scoping Audit and the Water Economy Assessment results were determined using empirically derived models while the Mass Balancing and the True Cost of Waste results were obtained through more detailed calculations. The results of the audit showed that the three most important areas for waste minimisation were water usage, effluent from rinse water waste streams and nickel consumption. Water usage has the highest waste minimisation potential followed by nickel. Dragged-out process chemicals and rinse water consumption contribute to ranking the effluent stream the most important waste minimisation opportunity identified by the True Cost of Waste Analysis. Potential financial savings were roughly estimated to be in the order of R 19949 and R 126603 for water and nickel respectively. Intervention using only "low cost-no-cost" waste minimisation measures was recommended as a first step before contemplating further focus areas or technical or economical feasibility. / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2004.

A chromium plating line used by a local company was monitored to identify any potential waste minimisation opportunities. Plating of the workpiece surface is carried out by immersing the workpiece in seven process (treatment) solutions including nickel and chromium plating baths. Between each process step the workpieces are rinsed. The chromium plating process was evaluated using the results of a waste minimisation audit. This involved gathering data on the composition, flow rates and costs of the inputs of the process. Two types of data were collected namely new and existing data. The new data included chemical monitoring (concentration levels of Ni, Cr, Na, S, B, P, Si, Fe, Cu, Zn, Pb as well as conductivity, TDS, SS and pH measurements) and water usage data. The existing data included raw materials, utility inputs, composition of process solutions and product outputs. The data were analysed using three established waste minimisation techniques. The Water Economy Assessment (a form of Monitoring and Targeting) results were determined using an empirically derived model. The Water Balance and True Cost of Waste results were obtained through more detailed calculations using the results of the chemical analysis. The results from the audit showed that the water usage on the chromium plating line has the highest waste minimisation potential. The True Cost of Waste analysis showed there is no significant chemical wastage in the effluent stream. The potential savings of the effluent stream was negligible (approximately R10 for 238 days). Drag-out calculations were also performed and showed that the drag-out volumes were in good agreement with the typical volumes found in the metal finishing industry. Intervention using simple lowcost and no-cost waste minimisation opportunities were recommended as a first step before contemplating further focus areas for technical or feasibility studies. / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2009.

Growth mechanism of electroplated copper columns has been systematically studied by simulations and characterizations. A two-dimensional cross-sectional kinetic Monte Carlo (2DCS-KMC) model has been developed to simulate the electrodeposition of single crystal copper. The evolution of the microstructure has been visualized. The cluster density, average cluster size, variance of the cluster size and average aspect ratio were obtained from the simulations. The growth history of the deposition from the first atom to an equivalent of 100 monolayers was reconstructed. Following the single-lattice 2DCS-KMC model for a single crystal, a two-dimensional cross-sectional poly-lattice kinetic Monte Carlo (2DCSP-KMC) model has been developed for simulation of the electrodeposition of polycrystalline copper on both a copper and a gold substrate. With this model, the early-stage nucleation and the grain growth after impingement of nuclei can be simulated; as such the entire growth history is reconstructed in terms of the evolution of microstructure, grain statistics and grain boundary misorientation. The model is capable of capturing some key aspects of nucleation and growth mechanisms including the nucleation type (e.g. homogeneous or heterogeneous), texture development, the growth of grains and higher energetic state of grain boundaries. The model has also proven capable of capturing the effects of deposition parameters including applied electrode potential, concentration of cupric ions and temperature. Their effects are largely dependent on the substrates. The early-stage electrocrystallization of Cu on polycrystalline Au has been studied by ex-situ AFM observations. The evolution of surface morphology of the electrodeposited copper on a sputtered Au seed layer from 16ms to 1000s was observed and their formation mechanism discussed. The heterogeneous nucleation phenomenon, the competitive growth both longitudinally and laterally, and the dominant growth of some nuclei were experimentally observed, which are also visualized by the relevant KMC simulation results at a smaller size scale and a shorter time scale. A heuristic model is therefore proposed to describe the mechanism of the early-stage electrocrystallization of Cu on a polycrystalline Au seed layer. Electroplated copper columns plated for different times have been characterized in terms of the evolution of their external morphology, cross-sectional microstructure and crystal structure. The microstructure of electroplated copper columns is characteristic of bi-modal or tri-modal grain size distribution. The results indicate that recrystallization has occurred during or after the plating, top-down and laterally. Slight changes of the crystal structure were observed by in-situ XRD and it was found that the changes of the (111) and (200) planes occurred at different stages of self-annealing. Finally, the results indicate the presence of organic additives is not essential for self-annealing of a copper column to occur.

Ruthenium, proposed as a new candidate of diffusion barrier, has three different kinds of oxides, which are native oxide, electrochemical reversible oxide and electrochemical irreversible oxide. Native oxide was formed by naturally exposed to air. Electrochemical reversible oxide was formed at lower anodic potential region, and irreversible oxides were formed at higher anodic potential region. In this study, we were focusing on the effect of copper electrodeposition on each type of oxides. From decreased charge of anodic stripping peaks and underpotential deposition (UPD) waves in cyclic voltammetry (CV), efficiency of Cu deposition dropped off indicating that interfacial binding strength between Cu and Ru oxides was weakened when the Ru surface was covered with irreversible oxide and native oxide. Also, Cu UPD was hindered by both O2 and H2 plasma modified Ru surfaces because the binding strength between Cu and Ru was weakened by O2 and H2 plasma treatment. Cu/Ru and Cu/Ta bimetallic corrosion was studied for understanding the corrosion behavior between diffusion barrier (Ta and Ru) and Cu interconnects under the post chemical mechanical planarization (CMP) process in semiconductor fabrication. Gallic acid is used in post CMP slurry solution and is known well as antioxidant which is supposed to oxidize itself to prevent other species from oxidizing. However, in this study under the observation of Cu microdot corrosion test, copper was corroded only in gallic acid at specific pH region of alkaline condition which is close to the pH region for post CMP solution formula. With different pH alkaline condition, gallic acid formed different oxidized products which are characterized by cyclic voltammetry and UV-Vis spectroscopy. Therefore, the specific oxidized product from particular pH region condition caused the Cu corrosion. Also, the corrosion rate of Cu microdots was influenced by substrate effect (Cu/Ru and Cu/Ta) and ambient control, which was included in this study.

An extremely facile and novel method called spontaneous deposition, to deposit noble metal nanoparticles on a most stable form of carbon (C) i.e. diamond is presented. Nanometer sized particles of such metals as platinum (Pt), palladium (Pd), gold (Au), copper (Cu) and silver (Ag) could be deposited on boron-doped (B-doped) polycrystalline diamond films grown on silicon (Si) substrates, by simply immersing the diamond/Si sample in hydrofluoric acid (HF) solution containing ions of the corresponding metal. The electrons for the reduction of metal ions came from the Si back substrate. The diamond/Si interfacial ohmic contact was of paramount importance to the observation of the spontaneous deposition process. The metal/diamond (M/C) surfaces were investigated using Raman spectroscopy, scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS) and x-ray diffractometry (XRD). The morphology (i.e. size and distribution) of metal nanoparticles deposits could be controlled by adjusting the metal ion concentration, HF concentration and deposition time. XRD data indicate the presence of textured and strained crystal lattices of Pd for different Pd/C morphologies, which seem to influence the electrocatalytic oxidation of formaldehyde (HCHO). The sensitivity of electrocatalytic reactions to surface crystal structure implies that M/C could be fabricated for specific electrocatalytic applications. The research also presents electroplating of Cu on ruthenium (Ru), which a priori is a promising barrier material for Cu interconnects in the sub 0.13 μm generation integrated circuits (ICs). Cu plates on Ru with over 90% efficiency. The electrochemical nucleation and growth studies using the potentiostatic current transient method showed a predominantly progressive nucleation of Cu on Ru. This was also supported by SEM imaging, which showed that continuous thin films of Cu (ca. 400 Å) with excellent conformity could be plated over Ru without dendrite formation. Scotch tape peel tests and SEM on Cu/Ru samples both at room temperature (RT) and after annealing at 800 oC, showed no sign of delamination of the Cu film from Ru indicating strong adhesion. XRD patterns from Cu/Ru samples at RT through 800 oC indicated Cu in its characteristic face centered cubic (fcc) form with (111) phase dominating. Most importantly no new XRD peak emerged, even after annealing to 800 oC showing Cu and Ru did not interact much. The excellent adhesion and lack of metallurgical interactions between Cu and Ru underscored the potential application of Ru as a new Cu diffusion barrier in the next generation ICs.

Spontaneously active monolayer neuronal networks cultured on photoetched multimicroelectrode plates (MMEPs) offer great potential for use in studying neuronal networks. However, there are many problems associated with frequent, long-term use of MMEPs. The major problems include (1) polysiloxane insulation deterioration and breakdown, (2) and loss of gold at the gold electroplated indium-tin oxide (ITO) electrodes. The objective of this investigation was to correct these major problems. Quality control measures were employed to monitor MMEP fabrication variables. The phenotypes of polysiloxane degradation were identified and classified. Factors that were found to contribute most to insulation deterioration were (1) moisture contamination during MMEP insulation, (2) loss of the quartz barrier layer from excessive exposure to basic solutions, and (3) repetitive use in culture. As a result, the insulation equipment and methods were modified to control moisture-dependent insulation deterioration, and the KOH reprocessing solution was replaced with tetramethylguanidine to prevent damage to the quartz. The problems associated with gold electroplating were solved via the addition of a pulsed-DC application of gold in a new citrate buffered electroplating solution.

O lodo gerado em processos de galvanoplastia é classificado pela ABNT NBR 10.004/04 como perigoso (classe I). Na literatura encontram-se poucos estudos referentes à recuperação do cromo presente no lodo gerado em sistemas de tratamento de efluentes de indústrias de galvanoplastia. Neste sentido, o presente estudo avaliou a remoção do cromo presente no lodo de galvanoplastia por meio de dois processos, visando avaliar à eficiência técnica e a viabilidade econômica de ambos. O Processo 1 consistiu na remoção do cálcio utilizando o ácido cítrico, seguida de lixiviação ácida. Na etapa de oxidação, variou-se a temperatura em 40ºC, 60ºC e 80ºC e no tempo de 30, 60 e 90 minutos, tendo em vista que a eficiência do processo de oxidação depende da temperatura e tempo. Nesta etapa do processo as concentrações de peroxido de hidrogênio (H2O2) utilizadas foram de 1,50, 3,00 e 4,50 mol.L-1. O Processo 2 realizou a oxidação do cromo sem efetuar as etapas de extração do cálcio e a lixiviação ácida. A oxidação do cromo ocorreu pelo mesmo método apresentado no Processo 1. A caracterização elementar da amostra determinou que o principal elemento constituinte do lodo é o cálcio (20,05% em massa), e que dentre os metais pesados destacam-se o cromo e o níquel (6,52% e 4,33% em massa, respectivamente). A maior eficiência de remoção do cálcio foi obtida na razão mássica de 8,00 (ácido cítrico/hidróxido de cálcio), com 51,76% em massa, seguida pela razão mássica de 5,50 com 36,75% em massa e 2,50 com 24,83% em massa. O melhor resultado de oxidação do cromo no Processo 1 foi obtido com tempo de 30 minutos, temperatura de 60ºC e concentração de peroxido de hidrogênio de 3,00 mol.L-1, com eficiência de 41,09% em massa. No Processo 2, obteve-se a remoção de 37,96% em massa de cromo a temperatura de 80ºC, por uma hora e 3,00 mol.L-1 de peróxido de hidrogênio. Avaliando os custos para remoção do cromo dos dois processos, determinou-se que o Processo 1 foi mais oneroso que o 2, porém ambos não apresentaram viabilidade econômica para aplicação em escala industrial. Nos dois processos efetuou-se a oxidação do cromo presente no lodo de galvanoplastia, permitindo a sua remoção parcial neste resíduo. Com isso obtiveram-se ganhos ambientais, pela diminuição deste elemento no resíduo de galvanoplastia, que na maioria das vezes é disposto em aterros classe I, gerando um passivo ambiental. / The sludge generated in electroplating processes is classified by NBR 10.004/04 as a hazardous material (class I). In the literature, few studies report the recovery of chromium present in the electroplating sludge generated in the industries. In this sense, the present study conducted the removal of chromium in the electroplating sludge through two different processes, aiming to evaluate their efficiency and economic viability. The first process removed calcium through the use of citric acid being performed by varying the ratio of citric acid/calcium hydroxide (2.5, 5.5 and 8.0). Then, were performed the leaching of the samples. According to the literature, the efficiency of the oxidation process varies depending on the reaction temperature, time and concentration of hydrogen peroxide. For this reason, samples were heated to a temperature ranging from 40°C, 60°C and 80°C. Also, were conducted variations in the concentrations of hydrogen peroxide (1.5, 3.0 and 4.5 mol.L-1) and reaction time (30, 60 and 90 minutes). The second Process consisted in the chrome recovery by using the galvanic sludge without removal of the calcium and acid leaching. The chrome oxidation occurred by the same method shown in Process 1. Elemental characterization of the samples determined that the primary sludge constituent was calcium (20.05% by weight), and in terms of heavy metals, the chromium and the nickel (6.52% and 4.33% by mass, respectively). Most of calcium removal efficiency was obtained at a rate of 8 with 51.76% by mass, then the ratio of 5.50 to 36.75% by mass and 2.50 to 24.83% by mass. The best oxidation result of chromium in Process 1 was obtained using a time of 30 minutes, 60°C and hydrogen peroxide concentration of 3 mol.l-1, with 41.09 wt% efficiency. In Process 2 was obtained the removal of 37.96% by mass of chromium temperature of 80°C, for one hour and 3,00 mol.l-1 of hydrogen peroxide. Evaluating the costs for chrome removal of the two processes was determined that the Process 1 was more costly than 2, but both showed no economic feasibility for implementation on an industrial scale. However, in both cases occurred the oxidation of chromium present in the electroplating sludge, allowing its removal from the residue. Thus, environmental gains have been achieved by the reduction of this element in electroplating waste, which mostly is intended for landfill class I, generating an environmental liability.

As doenças bucais ocupacionais e os acidentes de trabalho requerem medidas de prevenção implantadas no sistema de gestão de segurança e saúde no trabalho, a fim de estabelecer um ambiente de trabalho mais seguro. No caso do ambiente de trabalho apresentado no presente estudo, equacionar prevenção de doenças bucais ocupacionais é uma tarefa árdua. A legislação vigente exige da empresa, elaborar e manter um Programa de Prevenção de Riscos Ambientais (PPRA), visando preservar e manter a segurança e saúde de seus trabalhadores, em consonância com as demais normas regulamentadoras e com os demais requisitos legais, adentrando nesta interface a Odontologia do Trabalho. Por meio do conhecimento técnico-científico da Odontologia do Trabalho, este trabalho propõe incluir nas diretrizes para elaboração e implementação de um PPRA em um processo específico de galvanoplastia os riscos químicos com potencial de inferir na saúde bucal do trabalhador. Obtendo a associação entre a identificação no PPRA dos riscos ambientais e dos possíveis agravos e comprometimento da saúde bucal do trabalhador. Concluindo ser viável a contribuição da odontologia do trabalho na elaboração do PPRA visando à prevenção da saúde bucal dos que neste ambiente laboram; sendo necessário o monitoramento do binômio ambiente laboral e saúde bucal do trabalhador, a análise dos critérios para o estabelecimento de limites de tolerância, a eficácia dos equipamentos de proteção e a descrição dos riscos à saúde bucal na ficha de informação de segurança de produto químico. / Oral diseases and occupational accidents require prevention measures to be implemented in the systems of health and safety management at the workplace for a safer work environment. In the case of the work environment presented in this study, the prevention of occupational oral diseases is a daunting task. The current Brazilian legislation requires companies to establish and enforce a program named Occupational Hazard Prevention Program (PPRA) to help keep good safety and health conditions of their workers in line with regulatory standards and other legal requirements. This paper aims to include potentially damaging chemical risks to oral health of workers in the guidelines of the PPRA program and use them in a specific electroplating process. Through technical and scientific research, this work seeks to associate PPRA identification of environmental risks and its hazards to the possible risk of compromising the oral health of workers. It concludes by proving the positive contribution of dentistry labour in PPRA especially in the prevention of oral health damage, the requirement of monitoring the binomial work environment to maintain a good oral health of workers, analysis of criteria to establish tolerance limits, studies to assess efficiency level of equipment, and description of chemical products risks to oral health to be included in the safety guideline forms.