Made available in DSpace on 2016-04-18T21:36:01Z (GMT). No. of bitstreams: 2 Douglas Marquezin Felippe1.pdf: 1519362 bytes, checksum: 40709b1c88a4aa5d83632f3034ffa9cf (MD5) Douglas Marquezin Felippe2.pdf: 3740401 bytes, checksum: c124e8cef0b0b36e025714367db7c937 (MD5) Previous issue date: 2010-02-23 / Fundo Mackenzie de Pesquisa / Heat treatment processes are related to control heating and quenching with the aim of improving physical properties, such as: hardness, abrasion resistance, toughness, among others. During the heat treatment process, the quenching media are of great importance steps, because it extracts heat from the part with the achieve of obtaining specification properties. However, the hardening process causes undesired distortion that can be related to the permanent residual stress in the parts, generated during quenching. Some conventional hardening heat treatments do not have the control of the position during quenching, this control is usually applied in induction heat treatment, improving the homogeneity of heat exchange in the quenching process, suggesting lower distortion. The induction process can be a sustainable one, because the heating is applied just in the part. This survey compared both metallurgical and mechanical properties between two heat treatment processes of DIN 100Cr6 steel bearings: conventional and induction. With the result of this survey, it is intended, to change the conventional heat treatment process for the induction process in bearing manufacturing, with the objective of reducing the typical out-of-roundness from the conventional heat treatment process, and a reduction the bearing manufactured costs. / A têmpera compreende operações de aquecimento e resfriamento controlado, que objetivam melhorias nas propriedades físicas como dureza, resistência à abrasão, tenacidade entre outras. Durante o processo de têmpera, o meio de resfriamento é uma das etapas mais críticas, pois extrai calor da peça com o objetivo de obter as propriedades desejadas. Porém, o processo de têmpera gera deformações não desejadas, que podem estar relacionadas às tensões residuais que ficam permanentes na peça, introduzidas durante o resfriamento. Alguns tratamentos térmicos de têmpera convencional não têm controle da posição da peça durante o resfriamento. Este controle é normalmente utilizado em processos de têmpera por indução, melhorando a homogeneidade da extração de calor durante o resfriamento, sugerindo menores índices de deformação. O processo por indução pode ser considerado sustentável, pois o aquecimento é localizado apenas no componente. Este trabalho comparou as propriedades metalúrgicas e mecânicas entre dois processos de têmpera de rolamentos do aço DIN 100Cr6: convencional e por indução. Como resultado deste trabalho, pode-se substituir o tratamento térmico com aquecimento convencional pelo tratamento térmico com aquecimento por indução para a manufatura de rolamento, com objetivo de redução da deformação de ovalização característica do processo de tratamento térmico convencional.

Línguas eletrônicas constituídas de filmes nanoestruturados depositados sobre eletrodos metálicos, e empregando a técnica de espectroscopia de impedância como princípio de detecção, vêm apresentando excelentes resultados para a diferenciação de substâncias que constituem os paladares básicos e na detecção de impurezas em amostras líquidas. A principal limitação para o uso comercial é a necessidade da substituição das unidades sensoriais do arranjo, que necessita de recalibração. Nesta tese introduzimos um novo arranjo de unidades sensoriais, constituídos de eletrodos de cromo eletrodepositados, que não necessitam de filmes finos. Usando arranjos de cinco ou dez unidades sensoriais nominalmente idênticas, obtivemos uma língua eletrônica capaz de detectar paladares básicos e íons de cobre em água em concentrações abaixo de 1μM. As diferenças nas respostas elétricas dos eletrodos são oriundas das diferenças na sua morfologia. A alta sensibilidade apresentada foi explorada na análise de vinhos e amostras de águas coletadas de vários rios e lagos. Similarmente às línguas eletrônicas com filmes nanoestruturados, o arranjo sensorial de eletrodos de cromo foi capaz de distinguir vinhos de uma mesma varietal e produtor, mas de diferentes safras, e de um mesmo produtor e safra, mas de diferentes varietais. Tentamos também melhorar o desempenho das línguas eletrônicas combinando unidades constituídas de filmes finos de quitosana e poli(o-etoxianilina). Apesar do interesse nas propriedades advindas da interação entre esses materiais, especialmente quando a quitosana foi utilizada na forma de nanopartículas, o desempenho foi similar ao da língua eletrônica contendo eletrodos de cromo sem filmes. / Electronic tongues based on nanostructured films and employing impedance spectroscopy as the principle of detection have proven excellent to distinguish between basic tastes and detect trace amounts of impurities in liquid samples. The main limitation for a commercial use, though, is the need to replace the sensing units of the sensor array, which requires recalibration, owing to the relatively poor stability of the nanostructured films. In this thesis we introduce a new arrangement for the sensing units, which are produced from electrodeposited chrome electrodes, with no need to adsorb an organic film. Using an array with 5 or 10 nominally identical chrome electrodes, we obtained an electronic tongue capable of detecting basic tastes and copper ions in water down to the 1μM level. The differences in electrical properties for the electrodes arose from differences in morphology. Furthermore, this high sensitivity could be exploited in the analysis of wines, and water samples collected from various rivers and lakes. Similarly to electronic tongues made with nanostructured films, the sensor array with electrodeposited chrome electrodes was capable of distinguishing wines from the same grape and producer, but different vintages, or from the same producer and vintage but different grapes. We also attempted to optimize the performance of electronic tongues by combining sensing units made of chitosan and poly(o-ethoxyaniline). In spite of the interesting properties deriving from the interaction between these components, especially when chitosan nanoparticles were used, the performance of the sensor array was similar to that of the electronic tongue obtained with bare chrome electrodes.

The first browser war took place during the second half the 1990s, and Internet Explorer cameout as the winner over Netscape Navigator. Today a new browser war is being fought withmany competitors and the future is uncertain. The purpose of the thesis is to find out how theweb browser market has developed since the start of the previous conflict, and we ask ourselveshow it will continue to develop in the future. This is accomplished with, among otherthings, interviews, tests and already existing statistics. The thesis' conclusions shows that theweb browser market has developed in a positive way from several perspectives, both for theusers as well as for the web developers. The conclusions also show that the web browser market'sfuture looks stable and indicate a probability that the browser war will transition into anormal, healthy market situation with several competitors.The first browser war took place during the second half the 1990s, and Internet Explorer cameout as the winner over Netscape Navigator. Today a new browser war is being fought withmany competitors and the future is uncertain. The purpose of the thesis is to find out how theweb browser market has developed since the start of the previous conflict, and we ask ourselveshow it will continue to develop in the future. This is accomplished with, among otherthings, interviews, tests and already existing statistics. The thesis' conclusions shows that theweb browser market has developed in a positive way from several perspectives, both for theusers as well as for the web developers. The conclusions also show that the web browser market'sfuture looks stable and indicate a probability that the browser war will transition into anormal, healthy market situation with several competitors.

Actuellement, 80 à 85% des cuirs sont tannés au chrome. Ce procédé permet d'obtenir d'excellentes propriétés physico-mécaniques dans des conditions économiques optimales. Les sels de chrome sous forme trivalente utilisés lors de la fabrication du cuir ne sont pas nocifs; cependant sous certaines conditions et associés à d'autres substances, le chrome trivalent peut se transformer en chrome hexavalent, très allergisant et pouvant s'avérer dangereux pour la santé du consommateur. Depuis le 1er mai 2015, la présence de chrome hexavalent dans le cuir est soumise à la législation européenne; la teneur en chrome hexavalent ne doit pas excéder plus de 3 mg/kg de poids sec total du cuir (REACh ANNEXE 17, §47). A ce jour, de nombreux travaux de recherche ont été réalisés et des premières hypothèses ont été avancées pour expliquer la formation du chrome hexavalent dans le cuir. L'objectif de ce projet de recherche a été de rationaliser et d'approfondir ces différentes études pour essayer de mieux appréhender cette problématique. Ce projet de thèse a permis d'améliorer la spécificité et la fiabilité la méthode d'analyse pour la détermination de la teneur en chrome hexavalent en introduisant la chromatographie ionique. Ensuite, l'influence de la composition du cuir (matière grasse, indice d'iode, pH, chrome total et chrome extractible) sur la formation de chrome hexavalent dans le cuir a été étudiée afin d'expliquer l'origine et d'éventuels mécanismes d'oxydation du chrome trivalent (en chrome hexavalent). Enfin, cette étude s'est intéressée aux facteurs environnementaux (température, humidité relative, lumière et durée d'exposition), aux conditions de fabrication du cuir ou encore au cycle de vie du cuir (transport, transformation en produit fini, utilisation par le consommateur) afin de déterminer l'impact de ces paramètres sur la formation du chrome hexavalent. A l'issue de ce travail, une méthode de vieillissement "artificiel" représentative de l'évolution réelle d'un cuir a été proposée, et ce quelles que soient les caractéristiques et la nature du cuir / Currently, 80 to 85% of leather is tanned with chrome. This process allows to obtain excellent physico-mechanical properties with optimum economic conditions. The chromium salts in trivalent form used in the manufacturing of leather are not harmful; however under some conditions and associated with other substances, trivalent chromium can be transformed into hexavalent chromium, highly allergenic and potentially harmful to the health of the consumer. Since 1st May 2015, the presence of hexavalent chromium in leather is subject to European legislation; the hexavalent chromium content must not exceed 3 mg/kg of the total dry weight of leather (REACh ANNEX 17, § 47). To date, a great amount of research has been done and initial hypothesis have been able to explain the formation of hexavalent chromium in leather. The objective of this research project was to rationalize and to deal with these various studies in order to understand this problem in more detail. In this thesis project, the introduction of ion chromatography has improved the specificity and reliability of the analysis method for the determination of hexavalent chromium. Secondly, the influence of leather composition (fat liquor, iodine value, pH, total chromium and extractible chromium) on the formation of hexavalent chromium in leather was studied. The objective was to explain the potential oxidation mechanisms of trivalent chromium (in hexavalent chromium). The third part of this study deals with environmental factors (temperature, relative humidity, light and duration of exposure), leather manufacturing conditions or the life cycle of leather (transport, transformation into finished product, consumer use). The aim was to determine the impact of these parameters on the formation of hexavalent chromium. To conclude, an "artificial" ageing method representing the natural evolution of leather, and which corresponds to the characteristics and the nature of the leather, has been proposed

La protection des gaines de combustible de réacteur nucléaire contre l’oxydation à haute température en conditions accidentelles est essentielle pour garantir leur intégrité, c’est-à-dire celle de la première barrière de confinement. Celle-ci peut s’effectuer par le dépôt d’un revêtement sur leur paroi interne et ce sont les procédés CVD qui sont les plus à même de le faire. Il s’agit plus précisément du procédé DLI-MOCVD qui a été utilisé ici pour déposer des revêtements à base de chrome (chrome métallique Cr(S) cristallisé) et de carbures de chrome (carbures de chrome CrxCy amorphes non recyclés, recyclés et CrxSizCy dopés au Si), réputés pour leur bonne résistance à l’oxydation. Afin d’améliorer la qualité des revêtements, le procédé de dépôt a été optimisé à l’aide de simulations numériques. Après une réflexion sur le mécanisme chimique, un modèle cinétique réactionnel du dépôt d’un revêtement CrxCy amorphe a pu être ajusté et validé. Il a aussi été montré que la solution utilisée de précurseur organométallique bis(arène)chrome et de solvant toluène pouvait être directement recyclée, augmentant ainsi le potentiel d’industrialisation du procédé. Les propriétés physico-chimiques et structurales des revêtements déposés avec ce procédé ont été caractérisées. Une étude des propriétés mécaniques de ces revêtements a par ailleurs été entreprise. Il en ressort que, comparés à des revêtements apparentés déposés par d’autres procédés, ceux déposés par DLIMOCVD possèdent notamment une dureté élevée (jusqu’à une trentaine de GPa), des contraintes résiduelles en compression, une bonne adhérence avec leur substrat et enfin une résistance à l’usure abrasive différente suivant la température. L’évaluation de leur résistance à l’oxydation à 1200 °C a révélé les excellentes performances des revêtements en carbures de chrome amorphes, qui permettent de retarder l’oxydation catastrophique de plus de deux heures pour une épaisseur de 10 µm. Tous les autres revêtements augmentent la tenue en température des substrats en zircaloy mais ne retardent pas autant l’oxydation catastrophique. / Nuclear fuel cladding tubes resistance against high temperature oxidation during accident conditions is crucial because it means protecting the first containment barrier. This can be done by coating the inner wall of the cladding tube with CVD processes, which are most likely to do so. More specifically, we used DLI-MOCVD to grow chromium based (Cr(S), metallic crystalline chromium) and chromium carbides based (amorphous chromium carbides CrxCy, recycled CrxCy, silicon doped CrxSizCy) coatings, known for their good oxidation resistance. The coating process was optimized using numerical modelling to improve coatings performance. A reaction kinetics model of the deposition process of amorphous CrxCy coatings was adjusted and validated after the identification of the chemical mechanism. It was also shown that the liquid solution containing organometallic precursor (bis(arene)chromium) and solvent (toluene) could be directly recycled, thereby increasing the industrialization potential of such process. Physical, chemical and structural properties of coatings deposited with this process were characterized. A study of the coatings mechanical properties has also been undertaken. It shows that compared to related coatings grown with other processes, those deposited by DLI-MOCVD exhibit a particularly high hardness (up to 30 GPa), compressive residual stresses, good adhesion with the substrate and finally a different abrasive wear resistance depending on the temperature. The assessment of their oxidation resistance at 1200 °C revealed excellent performances of amorphous chromium carbides coatings, which can delay catastrophic oxidation up to two hours with only a 10 µm thickness. All the other coatings only increase the thermal resistance of zircaloy substrates.

This master thesis deals with the topic of browser extensions, their environment and analysis. The goal is to describe the extensions environment, online Webstores, that offers extensions and to show best practices for analysis and optimization of its extensions and their assets. Within the thesis you can find very precise analysis of online Webstores for Google Chrome extensions and Mozilla Firefox add-ons. Conclusions are made based on this analysis that include special characteristics of the previously mentioned browsers. The master thesis consists of two parts, theoretical and practical. The theoretical parts deals with the description of the browser extensions environment and it presents specific characteristics about online Webstores and browser extensions to the reader. In the practical part the thesis is focused on objectives set by the thesis and it presents the results of the Webstore analysis and description of the universal Google Analytics solution that helps developers to analyze their extensions The thesis contributes to the topic mainly with the precise description of the browser Webstores and extensions environment, best practices and recommendations and by creating the universal Google Analytics solutions for the developers.

Content: Synchrotron small-angle X-ray scattering (SAXS) technique was applied to leather research to understand the changes in molecular-level collagen structure during tanning and denaturation (shrinkage), which can help reduce the environmental impact from the extensive chrome usage. Based on SAXS results from realtime denaturation experiments on leather samples, we established a mechanistic model of chrome tanning indicated by the structural changes of collagen. It suggests that only a low level of chromium species is effectively involved in the cross-linking with collagen, which highlights the overuse of chrome during conventional tanning processes. Any extra amount of chrome added, however, can support the stabilisation of collagen possibly via a non-covalent mechanism. Such mechanism points towards a more environment-friendly tanning method by using suitable supplementary reagents to benefit tanning effect non-covalently instead of chrome. By pre-treating with complexing agents such as sodium formate and disodium phthalate, as well as nanoclay (sodium montmorillonite), the uniformity through bovine hide collagen matrix were improved significantly. These pre-treatments effectively reduce the reactivity of chromium during its cross-linking reaction with collagen while retaining its bound water. However, collagen pre-treated with a covalent cross-linker (glutaraldehyde) results in a decrease in both chromium-collagen cross-linking and bound water while improving uniformity. These molecular-level insights can be developed into metrics to guide us towards a more sustainable future for the leather industry. The coating on collagen fibrils can provide a pseudo-stabilisation effect of increasing the heat resistance of collagen. A group of tanning experiments were also conducted in situ on the SAXS beamline to observe the different mechanisms of free-of-chrome alternative tannages as potential replacements. Overall, synchrotron SAXS provides valuable information about collagen structure changes that could lead to more efficient use of chrome (or other tanning agents) in the global leather tanning industry. Take-Away: 1. Kinetics of hydrothermal denaturation and collagen crosslinking mechanism proceed through different pathways 2. Alternative chemistries to enhance chrome uptake at low offers. 3. The role of collagen structure studies in understanding tanning mechanims

Content: Tannery effluent with high salinity and chromium have a serious environmental impact. The traditional chrome tannage that involved the use of sodium chloride, acid and chromium is one of the main origins of salt and chromium pollution. In this study, a non-pickling, low-chrome tanning technology was developed. The novel Chrome-free agent SL can be directly employed to tan bated cattle pelts and the wet white was obtained. Then the shaved wet white was pre-treated by Poly-carboxylate auxiliary agent and tanned by chrome powder. It was tested that the shrinkage temperature of the wet white, the initial pH of chrome tanning, the consumption of chrome powder, the shrinkage temperature of the chrome-tanned leather, the content of Cr2O3 in effluent, the absorption of chromium and the other properties of the chrome-tanned leather. It was found that the shrinkage temperature of the wet white tanned by SL reached over 80oC, the optimal consumption of Poly-carboxylate auxiliary agent was 2wt% based on the weight of the shaved wet white, the better low-chrome tanning conditions were that the wet white was tanned by 4wt% chromium powder for 150～180min at room temperature when the initial pH value was 3.5. The next processes were same as traditional chrome tannage. Meanwhile, the shrinkage temperature of the leather tanned by the low-chrome tannage reached more than 95oC, the absorption of chromium was 96%, the content of Cr2O3 in the effluent was under 200mg/L. For the low-chrome tanned leather, the absorption of dyestuff, fat-liquor reached 99.5%, 82.5% respectively. Compared with the traditional chrome tanned process, not only the conventional pickling process was eliminated, the process was been shorten and reduce the pollution of sodium chloride, but it can reduce 50% of the consumption of Chrome powder, improve the absorption of chromium and can reduce content of Cr2O3 in effluent. Take-Away: 1. LUO JIAN-XUN, LI JING, LIAO XUE-PIN,etc.Cleaner Chrome Tanning – A Non-Pickling Process Using an Aliphatic Aldehyde as Pre-tanning Agent. J. Soc. Leather. Technol.Chem. 2012,96 (1):21-26. 2.LUO JIAN-XUN,FENG YANJUAN.Cleaner Processing of Bovine Wet-white: Synthesis and Application of a Novel Chrome-free Tanning Agent Based on an Amphoteric Organic Compound. J. Soc. Leather. Technol.Chem. 2015,99 (4):190-195. 3.XU JIA-LI, LUO JIAN-XUN.Synthesis and application of a polycarboxylate auxiliary agent. China Leather.2017,46(3):35-41.

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A neutron activation analysis procedure for the simultaneous determination of Au, Pd and Ir, and separate determination of Os is described and applied to the determination of these metals in the Mount Albert ultramafic pluton, Quebec. The Mount Albert is an alpine-type ultramafic body whose petrography, geology and geochemistry has been discussed in some detail by MacGregor (1962, 1964). It consists mainly of serpentinized dunite and peridotite. However, it is distinguished by the presence of an eastern lobe which is essentially unserpentinized. In addition to ferromagnesians, two varieties of spinel including disseminated accessory chrome spinel and massive, discordant chromite veins or schlieren are important mineralogical constituents. Twenty samples were analyzed including 5 fresh dunites and peridotites, 8 serpentinized equivalents, 4 disseminated chrome spinels, 1 clinopyroxenite, and 2 massive chromite. The concentrations (in p. p. b.) of average fresh ultramafics and their serpentinized equivalents are:-------------------------------------- ---------------------Pd----Os----Ir----Au------------------------------------------- Fresh rocks------------7.7----7.2--2.5--0.99------------------------------------------- Serpentinized rocks---10----6.6--2.2---2.4-------------------------------------------- The piuton was intruded as a nearly solid mass of olivine and some orthopyroxene with about 15 weight per cent melt. A small concentration of the precious metals, a factor of 2 to 3, in the melt relative to crystalline phases appears to have occurred. The disseminated chrome spinel and massive chromite appear to concentrate the precious metals. In particular, Os and Ir content of the massive chromite is approximately 10 times that of fresh or serpentinized whole rocks. There is little change in average precious metal content with serpentinization. Pd shows a slight increase, and Ir and Os slight decreases in concentration with degree of serpentinization. Only Au appears significant to be enriched in serpentinized rocks where a twofold increase occurs. The variation in precious metal content of all four metals increase when the rocks are serpentinized: When normalized to chondrite meteorites, the precious metal data give fractionation trends similar to that of average chondrite. These trends are compatible with a model in which alpine ultramafics are regarded as residua from the partial melting of parental material of approximately chondritic composition. / Thesis / Master of Science (MSc)