In this study, the impact of galvanic coupling of magnesium to steel on the corrosion rate, surface morphology, and surface film formation was investigated. In particular, the role of self-corrosion was quantified as previous studies showed discrepancies between model predictions and experimental results that were likely due to significant self-corrosion. This experimental study examined the corrosion of Mg coupled to steel in 5 wt% NaCl at cathode-to-anode area ratios that ranged from 5 to 27. Results showed that self-corrosion was significant and accounted for, on average, one-third of total corrosion. Moreover, self-corrosion varied with time and cathode size, and was accelerated by the high dissolution rate. Film formation was observed on the magnesium surface that inhibited the corrosion rates. This film contained approximately 30% of the Mg lost to corrosion. The morphology of the coupled Mg showed the rapid formation of pits with considerable depth, and was quite distinct from previously studied filiform and disk corrosion for uncoupled Mg. This study demonstrates the important role of self-corrosion during galvanic corrosion of Mg and the need to account for such corrosion when predicting corrosion rates. This study also provides important insight into the processes that control Mg corrosion under several conditions.

Regional differences in sweat gland output, skin temperature and thermoreceptor distribution can account for variations in regional perceptions of temperature, thermal comfort and wetness sensation. Large cohorts of studies have assessed these perceptual responses during sedentary activity but the findings are typically applied to a multitude of conditions, including exercise. Increases in sweat gland output, redistribution of blood flow and changes in skin and core temperature are basic responses to exercise in most conditions and these ultimately influence our perceptual responses. The primary aim of this thesis is to determine factors that influence regional differences in thermal sensation, thermal comfort and wetness sensation during exercise in moderate to hot conditions. The secondary aim is to develop and understand an additional variable, galvanic skin conductance (GSC) that can be used to predict thermal comfort and wetness sensation. The aim of the first study (Chapter 4) was to determine the influence of exercise on thermal sensitivity and magnitude sensation of warmth to a hot-dry stimulus (thermal probe at 40°C) and assess if any gender-linked differences and/or regional differences exist. From the data, body maps indicating sensitivity were produced for both genders during rest and exercise. Females had more regional differences than males. Overall sensitivity was greatest at the head, then the torso and declined towards the extremities. The data showed that exercise did not cause a significant reduction in thermal sensitivity but magnitude estimation was significantly lower after exercise for males and selected locations in females. The cause of a reduced magnitude sensation is thought to be associated with exercise induced analgesia; a reduction in sensitivity due to exercise related increases in circulating hormones. As the literature suggests that thermal comfort in the heat is influenced by the presence of sweat, the next study and all proceeding studies were concerned with this concept. In Chapter 5, building on earlier studies performed in our laboratories, the influence of local skin wettedness (wlocal) on local thermal comfort and wetness sensation was investigated in a neutral dry condition (20.2 ± 0.5°C and 43.5 ± 4.5% RH) whilst walking (4.5 km∙hr-1). Regional differences in wlocal were manipulated using specialised clothing comprising permeable and impermeable material areas. Strong correlations existed between local thermal comfort and local wetness sensation with the various measured wlocal (r2>0.88, p<0.05 and r2>0.83, p<0.05, respectively). The thermal comfort limit was defined as the wlocal value at which the participants no longer felt comfortable. Regional comfort limits for wlocal were identified (in order of high-low sensitivity); lower back (0.40), upper legs (0.44), lower legs (0.45), abdomen (0.45), chest (0.55), upper back (0.56), upper arms (0.57) and lower arms (0.65). The maximum degree of discomfort and wetness sensation experienced during the investigation was kept deliberately low in an attempt to determine the threshold values. Therefore comfort scores and wetness scores rarely reached a state of uncomfortable or wet so the next step was to assess these relationships when sweat production is high and the sensations worsened. However, pilot testing indicated that a ceiling effect would occur for wlocal at high levels of sweat production whilst thermal discomfort increased indicating wlocal was not the determining parameter in that case. Thus an additional parameter was required. The chosen parameter was galvanic skin conductance (GSC) due to its alleged ability to monitor pre-secretory sweat gland activity, skin hydration and surface sweat. In Chapter 6, the reliability, reproducibility and validity of GSC were confirmed in a series of pilot tests. Moderate to strong correlations were found between GSC and regional sweat rate (RSR) (r2>0.60, p<0.05) and wlocal (r2>0.55, p<0.05). The literature suggests standardising GSC relative to a minimum and maximum GSC value; however uncertainties arise when attempting to achieve maximum GSC. Therefore a change from baseline (∆GSC) was chosen as the proposed method of standardisation for further use. Additional results (from Chapter 9) revealed that ∆GSC also reflects pre-secretory sweat gland activity as it increased prior to sweat being present on the skin surface and prior to an increase in RSR. In Chapter 9, also hydration of the stratum corneum was measured using a moisture meter and the results revealed that it has an upper limit; indicating maximal hydration. From this point of full skin saturation ∆GSC and RSR markedly increase though sensations did not. It was also found that ∆GSC is only influenced by surface sweat that is in direct contact with the electrode and is not influenced by sweat elsewhere on the skin surface between electrodes. Higher levels of thermal discomfort have rarely been explored and neither has its relationship with wlocal. The ability of ∆GSC and wlocal to predict local thermal comfort and wetness sensation were compared in two different conditions to elicit low and high sweat production. Unlike Chapter 5, the body sites were not manipulated to control wlocal but allowed to vary naturally over time. The test was carried out on males (Chapter 7) and females (Chapter 8) to compare any gender linked differences and the results suggest that females are more sensitive than males to the initial presence of sweat. For both genders, wlocal and ∆GSC are strong predictors of thermal comfort and wetness sensation. More importantly, wlocal can only be used to predict local thermal comfort in conditions of low sweat production or low levels of thermal discomfort. However, once sweat production increases and thermal discomfort worsens ΔGSC (and not wlocal) can predict thermal comfort. Due to low sweat production observed in females indicates that this is only relevant for females. It appears that epidermal hydration has an important role on influencing thermal comfort. Receptors influencing our perceptual responses are located in the epidermis and when sweat is produced and released onto the skin surface, this epidermis swells and the sensitivity of receptors are said to increase. wlocal indicates the amount of moisture present on the skin surface, yet ∆GSC indicates presecretory sweat gland activity and epidermal hydration where the receptors are located. This may explain why on numerous occasions thermal comfort had a stronger relationship with ∆GSC than wlocal. Where Chapter 5 indicated the true local comfort limits for each respective zone, Chapter 7 and 8 provided a global picture of how local regions interact and influence local thermal comfort across the body. When wlocal varies naturally, the torso areas naturally produce more sweat than the extremities and it seemed that these areas produce so much more sweat than the extremities that they dominate local thermal comfort across the whole body. This is referred to in this thesis as a model of segmental interaction. As with thermal comfort, wetness sensation had strong relationships with wlocal and ∆GSC. The results also revealed a strong relationship between wetness sensation and thermal comfort. In contrast to the widely supported claim, a drop in skin temperature is not required to stimulate a wetness sensation. The point at which we detect sweat and when it becomes uncomfortable occurs at different wlocal values across the body. Thermal comfort is shown to be influenced by sweat during exercise in moderate-to-hot conditions. As w has an upper limit the findings suggest that it cannot predict thermal comfort during high sweat rates. Galvanic skin conductance monitors the process of sweat production more closely and thus is a better predictor of thermal comfort during all conditions and particularly during high sweat production. The strong relationship between thermal comfort and wetness sensation confirm the role of sweat production on thermal comfort. Gender differences to perceptual responses were observed, with females generally being more sensitive to sweat and a warm thermal stimulus than males. Regional differences to sweat and a warm stimulus generally suggest that the torso area is more sensitive than the extremities. This is important not only for sports clothing design but also protective clothing at the work place.

Chemical systems containing oxidants are widely used at various stages in semiconductor processing, particularly for wet cleaning and polishing applications. This dissertation presents a series of studies related to oxidative removal of materials in the Front-End-Of-Line (FEOL) and Chemical Mechanical Planarization (CMP) processes during IC fabrication. In the first part of this study, stripping of photoresists exposed to high dose of ions (1E16 As/cm²) was investigated in activated hydrogen peroxide systems. Stripping of photoresists (PR) exposed to high dose (>1E15/cm²) ion beams is one of the most challenging steps in FEOL processing. This is due to unreactive crust layer that forms on the resist surface during ion implantation. The use of hydrogen peroxide systems activated by metal ion or UV light, for disrupting crust formed on deep UV resist to enable complete removal of crust as well as underlying photoresist was investigated. A systematic evaluation of variables such as hydrogen peroxide and metal ion concentration, UV intensity, temperature and time was conducted and an optimal formulation capable of attacking the crust was developed. A two step process involving pretreatment with activated hydrogen peroxide solution, followed by treatment with sulfuric acid-hydrogen peroxide mixture (SPM) was developed for complete removal of crusted resist films. In the second part of this study, electrochemically enhanced abrasive removal of Ta/TaN films was investigated in solutions containing 2,5 dihydroxy benzene sulfonic acid (DBSA) and potassium iodate (KIO₃). This method known as Electrically-assisted Chemical Mechanical Planarization (ECMP) is generating a lot of interest in IC manufacturing. Ta/TaN films were abraded at low pressures (<0.5 psi) on a polyurethane pad under galvanostatic conditions. The effect of variables including pH, KIO3 concentration, and current density has been explored. In the optimized formulation, tantalum and tantalum nitride removal rates of ~170 A⁰/min and ~200 A⁰/min, respectively have been obtained at a current density of 1 mA/cm². The use of benzotriazole as a copper inhibitor was required to obtain Ta to Cu selectivity of 0.8:1. Additionally, the nature of the oxide film formed on tantalum during the electrochemical abrasion process was characterized.

Premise plumbing can contain copper and lead bearing fixtures, and although copper is considered primarily an aesthetic issue, the neurotoxic effects of lead present a significant public health concern. Utilities approach corrosion control in low alkalinity water by increasing the pH (>9) or adding a phosphate inhibitor at neutral pH. Phosphate inhibitors, pH and chlorine are known to affect lead and copper release through their direct action as corrosion inhibitors or oxidizing agents or through an indirect action via microbial growth. Biofilms are often an implied cause of premise plumbing corrosion, although little is known about their community structure or ability to store metals. The central hypothesis of this thesis is that biofilm contributes to lead and copper release in premise plumbing. This thesis addresses a unique gap in corrosion literature by integrating traditional corrosion chemistry methods with microbiological and molecular biology techniques. The experiments used three distinct approaches: (i). electrochemical cell experiments to determine the key factors in decreasing lead and copper corrosion in galvanically coupled systems while maintaining microbial control (ii). galvanic macrocells using premise plumbing components to examine the unintended consequences of adding a phosphate based corrosion inhibitor and (iii). an annular reactor study to examine the impacts of two commonly applied corrosion control strategies. In the electrochemical cell experiments, the pH 9.2 with zinc orthophosphate and chlorine treatment achieved both goals: decreased lead and copper release and limited microbial growth. In galvanic macrocells experiments with premise plumbing components, zinc orthophosphate addition was shown to be positively correlated with increased bulk water bacteria, biofilm growth and biofilm community structure as measured by DGGE. Biofilm was also observed to sorb 3-29% of lead and 3-16% of copper from the bulk water. The comparison of the two corrosion control strategies showed that the majority of lead released was in the particulate form, and the results further alluded to the potentially significant role lead particles play in biofilm formation.

Electrodermal responding (EDR) and heart rate (HR) were assessed for seven subjects participating in a reaction time task consequated with monetary bonuses (250, 100, and 10), monetary penalties (250,100, and 10), and a monetary neutral value (00). Unlike previous research employing group designs and a tonic measure (i.e., mean over long periods of time), this study utilized a single-subject design and a phasic measure (i.e., mean over 2-s intervals). Heart rate data was too variable for meaningful analysis. EDR data showed that the peak levels of EDR were higher for penalties than for the corresponding values of bonuses (e.g., -250 vs. +250) for most subjects. Similarly, peak levels of EDR were generally higher during sessions in which consequences were presented than in sessions during which consequences were absent.

As propriedades protetoras à corrosão dos polímeros condutores, especialmente da poli(anilina) (PANI), têm sido amplamente explorada. Entretanto, o mecanismo pelo qual esta proteção é efetuada ainda não foi completamente elucidado. Evidências mostram que a habilidade protetora à corrosão da PANI está ligada à formação de um par galvânico entre o polímero e o metal. Neste trabalho, foi feito um estudo sobre a formação de um par galvânico entre a PANI e diferentes substratos metálicos (zinco, ferro, níquel e cobre) em meios ácidos e neutros. Medidas de potencial de circuito aberto mostram que há a possibilidade de formação de um acoplamento galvânico e medidas de corrente galvânica mostram que há uma corrente galvânica fluindo entre todos os pares PANI-metal. Durante este trabalho, foi sintetizada uma suspensão à base de epóxi e PANI, a qual foi eletroforeticamente depositada sobre um eletrodo de ferro. Medidas de potencial de circuito aberto e impedância em uma solução aquosa de ácido sulfúrico mostraram que o revestimento à base de PANI protegeu o substrato metálico em questão através da formação de um par galvânico entre o metal e o polímero. / The corrosion protection properties of conducting polymers, especially poly(aniline) (PANI) ones, have been widely exploited. However, the mechanism by which this protection is made has not been completely cleared yet. Evidences show the ability of PANI\'s corrosion protection is connected to the building of a galvanic couple between the polymer and the metal. In this work, a study about the building of a galvanic couple between PANI and distinct metallic substrates (zinc, iron, nickel and copper) in acid and neutral environment was done. Measurements of open circuit potential showed the possibility of the building of a galvanic coupling and measurements of galvanic current showed the flux of a galvanic current between all the couples PANI-metal. In the course of this work, a suspension based on epoxy and PANI was synthesized and electrophoretically depositated on a iron electrode. Measurements of open circuit potential and impedance in a aqueous sulfuric acid solution showed that the revestiment based on PANI protected the metallic substrate by the building of a galvanic couple between the metal and the polymer.

La présente étude porte sur les problématiques d’entreposage de colis de déchets nucléaires. En France, via le projet Cigéo, il est envisagé d’entreposer les déchets radioactifs de moyenne et haute activité à vie longue à 500 mètres de profondeur dans un conteneur en acier API 5L X65 (chemisage) déposé dans des galeries creusées au sein d’une formation argileuse (argilites). Une température maximum de 90°C est attendue à la surface de l’acier en raison de l’intense radioactivité. Finalement, un coulis cimentaire (matériau de remplissage) sera injecté entre le chemisage et les argilites. La synthèse de couches de produits de corrosion susceptibles d’être rencontrées à la surface de l’acier dans les conditions de stockage a constitué le premier objectif de ce travail. Les conditions pour l’obtention de sidérite (FeCO3), de mackinawite (FeS) et de magnétite (Fe3O4) ont été déterminées. Par la suite, des essais de couplage impliquant deux électrodes recouvertes de produits différents ont été réalisés dans le but de simuler le comportement d’une surface d’acier recouverte d’une couche hétérogène de produits de corrosion. Il est apparu que l’acier recouvert d’une couche de mackinawite se comportait dans chaque cas comme une cathode. Ce phénomène est associé au caractère plutôt protecteur de la couche de mackinawite. Parallèlement, les essais de formation de la mackinawite par polarisation anodique ont montré que la formation d’une couche de produits de corrosion composée de magnétite/mackinawite était associée à un phénomène de corrosion localisée. Le comportement de l’acier au contact du matériau de remplissage envisagé pour combler l’espace entre le chemisage et les argilites a ensuite été étudié. Ce deuxième volet de l’étude a montré que la couche de produits de corrosion se formant à la surface de l’acier était principalement composée de magnétite, associée à des sulfures de fer tels que la mackinawite. L’hétérogénéité du matériau de remplissage, la présence de sulfures en son sein et la présence d’oxygène dissous dans les solutions de test sont les principales causes de l’apparition d’un phénomène de corrosion localisée. Ce résultat traduit également le caractère imparfaitement protecteur des couches d’oxyde se formant sur l’acier au contact du matériau cimentaire. Enfin, la dernière partie de ce travail de recherche a porté sur l’étude d’éventuels effets galvaniques entre une zone recouverte d’argilites et une zone recouverte de matériau de remplissage impliquant la présence de magnétite et de mackinawite et pouvant faire office de cathode. De tels effets n’ont pas été mis en évidence, ce qui est attribué à l’absence d’un véritable état passif de l’acier en contact avec le matériau cimentaire. / The present study relates to the problem of long-term disposal of nuclear waste. In France, with the Cigéo project, it is envisaged to store high and intermediate level long lived radioactive waste at a depth of 500m inside a carbon steel (API 5L X65) casing in a deep geological disposal, drilled in a very stiff clay formation. A maximum temperature of 90°C is expected at the carbon steel surface, because of the intense radioactivity. Finally, a specific cement grout will be injected between the carbon steel casing and the argilites. The synthesis of corrosion product layers likely to form on the steel surface was the first objective of this work. The different parameters to obtain siderite (FeCO3), mackinawite (FeS) and magnetite (Fe3O4) have been determined. Subsequently, coupling tests were carried out with two steel electrodes covered with different corrosion products in order to simulate the behaviour of a steel surface covered with a heterogeneous corrosion product layer. It appeared that the steel electrode covered with mackinawite was in each case the cathode. This phenomenon is associated with the somewhat protective properties of the mackinawite layer. Besides, anodic polarization experiments conducted to prepare mackinawite layers showed that the formation of a corrosion product layer composed of magnetite/mackinawite was associated with localized corrosion. The behaviour of carbon steel in contact with cement grout envisaged to fill the gap between casing and argillites was studied next. This second part of the study showed that the corrosion product layer forming on the steel surface was mainly composed of magnetite, associated with iron sulphides such as mackinawite. Heterogeneity of the cement grout, presence of sulphide within it, and presence of dissolved oxygen in the test solutions are the main causes of the appearance of localized corrosion processes. This result also shows that the oxide layers forming on the steel surface in the specific cement grout only provides an imperfect protection. Finally, the last part of this research work focused on the study of possible galvanic effects between a zone covered with argilites, and a zone covered with cement grout implying the presence of magnetite and mackinawite and thus able to act as cathode. Such effects could not be evidenced which is attributed to the absence of a real passive state of the steel in contact with the cement grout.

Made available in DSpace on 2015-04-22T22:02:04Z (GMT). No. of bitstreams: 1 Dissertacao-Radames Goncalves de Lemos.pdf: 2300476 bytes, checksum: b260dba8302641c2121be562b02901a8 (MD5) Previous issue date: 2009-09-01 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / We conducted a study on the feasibility of using waste galvanic industry from an Industrial Pole of Manaus (PIM). In the first phase of work aimed to identify leaching tests for those potentially toxic metals dangerousness which gave the residue, were subsequently made specimens with different ratios of sand, pebble, cement and water. Next we sought a way to reduce the amount of cement residue, making replacement cement by waste in the following proportion 2.5 5.0 10.0 and 20.0%. From 7 and 28 days tests were made rupture. In second phase the residue was mixed with organic material (sugar) and inorganic (kaolinite), followed by calcination at temperatures ranging from 500 to 900 ⁰ C. The results indicated that among the specimens analyzed those containing from 5.0 and 10.0% showed no changes in behavior. Mixing waste / kaolinite when calcined at 500 ⁰ C suffered a process crystallization was more pronounced from 600 to 900 ⁰ C. With relation to the mix waste / sugar was observed that between 500 and 600 ⁰ C for crystallization process, but at 700 ⁰ C disappears occurring again between 800 and 900 ⁰ C. / Foi realizado um estudo sobre a viabilidade de uso do resíduo galvânico, proveniente de uma indústria do Pólo Industrial de Manaus (PIM). Na primeira fase do trabalho buscou-se identificar por ensaios de lixiviação aqueles metais potencialmente tóxicos que conferiam periculosidade ao resíduo, posteriormente foram confeccionados corpos de prova com diferentes relações de areia, seixo, cimento e água. Em seguida buscou-se uma forma de reduzir a quantidade cimento por resíduo, fazendo substituição de cimento por resíduo na seguinte proporção 2,5 5,0 10,0 e 20,0%. A partir de 7 e 28 dias foram realizados testes de ruptura. Na segunda fase o resíduo foi misturado a material orgânico (açúcar) e inorgânico (caulinita), seguida de calcinação em temperaturas variando de 500 a 900 ⁰C. Os resultados indicaram que entre os corpos de prova analisados aqueles contendo de 5,0 e 10,0% não apresentavam alterações de comportamento. A mistura resíduo/caulinita quando calcinada a 500 ⁰C sofria um processo de cristalização, sendo mais acentuada de 600 a 900 ⁰C. Com relação à mistura resíduo/açúcar observou-se que entre 500 e 600 ⁰C há processo de cristalização, mas que em 700 ⁰C desaparece, ocorrendo novamente entre 800 e 900 ⁰C.

Although tic disorders are diagnosed as neurological disorders, neurobehavioral models suggest that tics are controlled by premonitory urges that may be conditioned to become aversive through childhood, and that tics are exhibited to alleviate such phenomena. However, only indirect measures have been used to assess the presence of the premonitory urge. This study utilized self-report and GSR measurements to examine whether a punishing contingency conditioned stimuli to be aversive during conditions of tic suppression and whether punishing contingencies exacerbate aversive private phenomena in two adults. Results indicated that conditions of response cost (RC) and differential reinforcement (DRO) were effective at reducing the number of tics compared to baseline. Moreover, GSR was unrelated to urge and suppression conditions despite higher self-reported urge ratings in DRO and RC conditions. Implications of findings are discussed.

Aluminized steel Type 2 (AST2), often used for culvert pipes, is subject to corrosion which is the most important durability limitation factor. It was desired to determine if the outer aluminized layer will retain passivity and if protective galvanic action will develop. Thus, corrosion of unblemished and blemished AST2 surfaces was investigated in simulated natural waters. Experiments with unblemished specimens showed passive corrosion rates (~0.06 µm/yr) in scale-forming, 0.01 M Cl- solutions but sustained corrosion in other less protective media (with rates 3~10 µm/yr). Corrosion was manifested macroscopically by discoloration and few macro pits, but it likely proceeded also microscopically at the Fe-rich inclusion space scale. For blemished specimens, the aluminized coating galvanically protected to some extent the steel in all solutions. However, in 0.01 M Cl- solutions, protection was delayed until after some steel corrosion had occurred. In some solutions, complete consumption of the outer aluminized coating around exposed steel was noted. Elsewhere, coating appearance was similar to that of the unblemished condition. Nominal durability projections made for 16-gage AST2 ranged from >100 yr for unblemished AST2 to ~10 yr for the blemished condition. The present findings were used as a first step in proposing refinements of presently used durability guidelines of AST2 culvert pipe. Cyclic cathodic polarization tests to examine O2 and H2 reduction at the Fe-rich inclusions showed significant hysteresis, more pronounced with decreasing scan rate. The effect was tentatively associated to the amount of Fe+2 being deposited during the downward scan, a hypothesis supported by results from a physical model. A static polarization model was formulated for the blemished configuration. Results matched experimental trends and permitted evaluating the effect of solution conductivity s beyond the experimental range. Exposed steel corrosion rates at the steel were increasingly large for decreasing s. For the lowest s, corrosion rates at the exposed steel center were distinctly larger than at the edge, consistent with experiments. An impedance behavior model was also formulated. Results showed frequency dependent current distribution and predicted relatively small artifacts that were and not evident experimentally, but should be considered when exploring other system conditions.