Orientador: Matthieu Tubino / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-12T12:56:08Z (GMT). No. of bitstreams: 1 Queiroz_CarlosAlbertodaRocha_M.pdf: 1138911 bytes, checksum: 67f676e059efece3b6d64b209273d054 (MD5) Previous issue date: 2008 / Resumo: Neste trabalho foram desenvolvidos dois procedimentos de análise quantitativa em fluxo, um para níquel e o outro para sulfato, usando a refletância difusa na região do visível. O primeiro sistema químico estudado faz uso da clássica reação de níquel (II) com dimetilglioxima em meio alcalino amoniacal, formando o precipitado de cor rosa forte, Ni(DMG)2. Este precipitado, como se sabe, é bastante volumoso e adere facilmente às paredes do recipiente onde se encontra. Também, coagula rapidamente formando aglomerados. Estas características já desqualificam, em princípio, este precipitado para uso em sistemas de fluxo, por anunciarem problemas de entupimento nas tubulações e problemas de aderência nas janelas da cela de medida colorimétrica, se esta for a técnica usada. No presente trabalho logrou-se contornar todos estes problemas utilizando-se um sistema de fluxo muito simples. A cela desenvolvida para medidas de refletância foi construída em PTFE branco, sendo nela inseridos o detector (LDR) e emissor de luz (LED verde). O LED foi alimentado com uma fonte com voltagem adequada e o LDR foi introduzido numa ponte de Wheatstone que forneceu as medidas analíticas. Dentro desta cela foi colocado um tudo de vidro, conectado à tubulação do sistema de fluxo, onde passava o precipitado suspenso no carregador. As medidas analíticas de refletância foram feitas na cela contendo esta suspensão. O segundo sistema químico estudado foi a reação de sulfato com íons bário, formando o precipitado branco de sulfato de bário. A aplicação desta reação de precipitação em sistemas de fluxo já foi estudada, por outros autores, em medidas turbidimétricas e nefelométricas. Nossa intenção, ao usar esta reação de precipitação, foi de verificar a coerência do sistema de fluxo desenvolvido neste trabalho com aqueles da literatura, particularmente com o procedimento turbidimétrico. A cela de refletância usada para o sistema com sulfato é semelhante àquela acima descrita para a determinação de níquel. A diferença é que no presente caso o PTFE usado para a confecção do corpo da cela é preto. Esta escolha teve por intenção diminuir a refletância da luz nas suas paredes internas. Nos dois sistemas estudados, os resultados foram muito satisfatórios inclusive quando aplicados em amostras reais. / Abstract: Two flow quantitative analytical systems were developed in this work, using the diffuse reflectance in the visible region of the spectrum: one for the analysis of nickel and the other for the analysis of sulfate. The first studied chemical system used the classical analytical reaction of nickel (II) with dimethylglyoxime in presence of ammonia, forming a pink precipitate, Ni(DMG)2. This precipitate, as currently known, is volumous and easily adheres to the walls of the recipient where it is placed. Also, it easily coagulates forming agglomerates. These characteristics are enough to disqualify this precipitate for application in flux analytical systems, as they announce problems with clogging of the tubes and problems with the adherence on the cell windows if this detecting technique was used. In this work, we succeeded avoid these problems using a very simple flux system. The developed reflectance cell was constructed in white PTFE. The light emitter (green LED) and the light detector (LDR) were placed in its body. The energy was furnished to the LED by a power supplier and the LDR was introduced in a Wheatstone bridge which gave the analytical signal. Into the PTFE cell was placed a glass tube, connected to the flow system, where flowed the carrier with the suspended precipitate. The analytical reflectance measurements were done in the cell containing this suspension. The second chemical system studied was the well known reaction of sulfate with barium ions, forming the precipitate of barium sulfate. The use of this reaction in flux systems was already studied by other authors, with turbidimetric and nephelometric measurements. Our intention, when we select this precipitation reaction, was to verify the coherence among the flux system developed in this work with those already related, particularly with the turbidimetric procedure. The reflectance cell used in the sulfate system is similar to that above described for the determination of nickel. The difference is that in this cell black PTFE was used in order to decrease the reflectance of the light in the internal walls. In the two studied systems the results were quite satisfactory, also when real samples were analyzed. / Mestrado / Quimica Analitica / Mestre em Química

Orientador: Luiz Valdrighi / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-04T03:57:00Z (GMT). No. of bitstreams: 1 Heck_AlexandreRoberto_D.pdf: 1868066 bytes, checksum: b350ae21133640d625c8404b77a05dd4 (MD5) Previous issue date: 2005 / Resumo: O presente estudo teve como objetivo avaliar, comparativamente, em 45 raízes mesiais de molares inferiores, totalizando 90 canais, divididos em 3 grupos, o tempo, a média da área desgastada e a espessura média da parede dentinária remanescente na distal da raiz mesial, antes e após o emprego da técnica escalonada, da técnica híbrida modificada pela FOP-Unicamp, e da técnica rotatória Easy Endo-Multitaper. Foram realizados cortes transversais a 3 e 8 mm do ápice denominados segmento apical e cervical. As imagens dos segmentos transversais foram obtidas, antes e após o preparo dos canais, com uma câmara digital acoplada a uma lupa estereoscópica. As medidas das áreas dos canais e as medidas das espessuras das paredes distais da raiz foram registradas por meio do ¿software¿ Imagelab/98. Estas medidas, bem como a variável tempo e a ampliação das áreas foram analisados estatisticamente. Os resultados mostraram diferenças significativas no segmento cervical entre a técnica manual e as técnicas híbrida e rotatória. A ampliação das áreas, no segmento apical, foi significativamente maior na técnica manual, e, no segmento cervical, maior para as técnicas híbrida e rotatória. A espessura da parede distal da raiz mesial mostrou-se significativamente menor após a realização da instrumentação sem diferença entre as técnicas. As técnicas híbrida e rotatória foram significativamente mais rápidas que a técnica manual / Abstract: The present study was aimed to evaluate comparatively, in mesial roots of lower molars, before and after the use of the ¿step-back¿ manual technique, the hybrid technique modified by FOP-Unicamp, and the Easy Endo-Multitaper rotary technique, the time, the mean of the trimmed area and the mean of the thickness of the remained dentine wall in the distal region of the mesial root. Transversal sections were made 3 to 8 mm of the apical terminus, named apical and coronal sections. The images of these sections were captured by stereoscopic magnification lens with a video camera and stored in a computer. Then, the measurements of the root canal area and a linear measurement were carried out using a ImageLab software. The before and after measurements, as well as the increments, were statistically analized. The results showed significant differences in the coronal segment when comparing manual to hybrid and rotary techniques. The increment was significantly larger in the apical segment using the manual technique. In the coronal segment, the increment was larger using the hybrid and rotary techniques. The distance between the distal wall and the mesial root was significantly less after instrumentation, not showing differences among the techniques. The hybrid and rotary techniques were significantly less time-consuming than the manual technique / Doutorado / Endodontia / Doutor em Clínica Odontológica

L’Inconel 738 est un superalliage base nickel utilisé dans les turbines de moteurs aéronautiques. Le soudage engendre souvent l’apparition de fissures, ce qui constitue un handicap pour ce matériau car on ne peut ni le réparer par rechargement, ni concevoir de pièces assemblées par soudage. L'objectif de la thèse est de définir les conditions de soudage de ce superalliage, de manière à exclure tout risque de fissuration à la suite d’opérations de rechargement, de réparation ou d'assemblage par soudage.Une étude expérimentale a tout d’abord permis de comprendre et de relier les mécanismes de fissuration aux paramètres opératoires du procédé (intensité, tension…). Puis un modèle de simulation numérique du soudage a été développé sur la base d’un couplage entre aspects thermiques, métallurgiques et mécaniques. La corrélation entre les résultats expérimentaux et numériques a permis de déterminer des critères de fissuration pour ce superalliage et d’optimiser les paramètres de soudage. / Abstract

Ce mémoire de thèse est consacré à une étude du fluage isotherme et anisotherme à diversniveaux de température et à l’analyse fine des évolutions microstructurales associées à diverschargements thermomécaniques imposés du superalliage monocristallin, CMSX-4®. Cetravail est complété par la validation d’un modèle de comportement mécanique permettantd’intégrer ces évolutions microstructurales (fraction volumique des phases en présence,largeur des couloirs de matrice gamma, ...) pour déterminer la durée de vie du matériau.Parallèlement, le rôle de la microstructure initiale du matériau associée aux traitementsthermiques imposés dans la phase d’élaboration a été étudié. Il a été montré un effet marquéde cette microstructure initiale lors des essais de fluage à basse température (< 900°C), ainsique lors des essais de fluage anisotherme. Une microstructure de précipitation en radeaux detype N a été montrée comme particulièrement néfaste pour la résistance en fluageanisotherme. Enfin, le comportement du CMSX-4® est systématiquement comparé à celuiprécédemment établi dans des conditions similaires sur d’autres superalliages monocristallinspour pales haute pression. / This thesis is dedicated to the study of the isothermal and non-isothermal creep behavior in awide temperature range, and to the analysis of the microstructural evolution during differentthermomechanical paths on the superalloy single crystal, CMSX-4®. Moreover, the validationof a mechanical behavior model validation completes this work. This model takes intoaccount the microstructural evolutions (e.g. phase volume fraction, gamma-matrix channelwidth…) to predict the creep life. Additionally, the effect of the initial microstructure fromthe heat treatment has been investigated. It has been shown a strong impact of the as-receivedmicrostructure on the low temperature isothermal creep properties, and during non-isothermalcreep. A N-type rafted microstructure has been shown to be particularly detrimental to thenon-isothermal creep properties. Finally, the behavior of the CMSX-4® has been comparedwith the previous studies realized in the same conditions on other single crystal superalloysfor blades applications.

Les superalliages à base nickel des turbines aéronautiques sont susceptibles de subir des phénomènes de corrosion et/ou d’oxydation à haute température par les environnements agressifs rencontrés en service. Aussi, des revêtements d’aluminure sont appliqués par dépôt chimique afin d’assurer la protection des pièces contre ces phénomènes. La dégradation progressive de ces revêtements mène à la nécessité de les enlever afin d’en appliquer des nouveaux. Les bains chimiques industriels pour enlever les revêtements et les oxydes sont très toxiques, polluants et plutôt empiriques. Ainsi, ce travail de thèse se proposait d’étudier une méthode alternative et originale, par voie électrochimique permettant de contrer les limitations des approches chimiques. La voie électrochimique par application d’un potentiel (mode potentiostatique) a été étudiée afin de procurer la sélectivité entre le substrat et le revêtement lors de la dissolution, ainsi que le contrôle in-situ du procédé à l’aide d’une cellule à 3 électrodes. La faisabilité de la méthode a d’abord été démontrée, puis différentes procédures (par cycles cathodique/anodique, en continu et, parfois, avec modification du potentiel imposé) ont été développées. Nous avons pu mettre en relation les états métallurgiques des systèmes revêtement/substrat avec leur comportement électrochimique et avons mis également en lumière que le taux de dissolution est principalement gouverné par la concentration d’aluminium dans le revêtement alors que lorsque le platine est incorporé à ce même revêtement, le taux de dissolution est homogène. De même, nous avons démontré par XPS et par MET que la teneur en chrome modifie de manière significative l’homogénéité du décapage lors des phases de polarisation cathodique par un mécanisme de passivation de la surface, qui bloque l’activité électrochimique. Cependant, la tenue en oxydation cyclique des revêtements décapés par voies chimique et électrochimique n’a pas pu véritablement être démontrée car les revêtements avaient une microstructure différente. Enfin, des essais sur pièces de turbine ont montré le haut degré de sélectivité de l’approche ici étudiée. / Nickel based superalloys of aeronautical turbines are subjected to high temperature oxidation and/or corrosion in service conditions. Thus, protective aluminide coatings are applied onto the parts by chemical vapor deposition. The degradation of the coatings with time requires them to be removed prior to recoating the parts. The chemical baths industrially employed are toxic, polluting and quite empirical. Therefore, this thesis aimed at studying an alternative and original electrochemical method to circumvent the drawbacks of the chemical approach. Fixed potentials (potentiostatic mode) were thus applied to provide selectivity between the coating and the substrate upon the dissolution process, as well as to ensure in-situ control through a 3-electrode cell. The feasibility of the method was first demonstrated, then different procedures (cathodic/anodic cycles; continuous anodic and sometimes with modification of the potential) were investigated. The correlations between the metallurgical phases of the coating/substrate systems were elucidated. It also appeared that dissolution is mainly governed by the concentration of aluminium in the coating whereas the incorporation of platinum to the coating brought about the homogeneous dissolution. In addition, XPS and MET confirmed the hypothesis by which the chromium content drastically change the stripping homogeneity upon the cathodic polarization step by passivation of the surface and the subsequent electrochemical blocking. However, the results on the cyclic oxidation behaviour of the coatings priorly stripped chemically or electrochemically were not conclusive enough as the microstructure of the original coatings was different. Finally, quite a few stripping trials were carried out onto real turbine parts that confirmed the high selectivity of the electrochemical approach studied.

Compte tenu de l’évolution des températures d’entrée de turbines, le principal enjeu pour les métallurgistes est d’élaborer des alliages capables de présenter d’excellentes propriétés mécaniques à des températures de plus en plus élevées. Dans ce contexte, connaitre les relations entre les différents paramètres microstructuraux et les propriétés mécaniques à haute température (700°C et plus) est capital.La durabilité en fluage et en fatigue-temps de maintien ainsi que les processus d’endommagement de l’alliage AD730™, un nouveau superalliage pour disques de turbines, ont été analysés. Plusieurs paramètres ont été étudiés, qu’ils soient microstructuraux (joints de grains, taille de grains, taille et distribution des précités γ′), ou expérimentaux (température, environnement, contrainte appliquée, temps de maintien). L’utilisation de monograins de composition chimique identique à l’alliage de l’étude a permis de mettre en évidence le fait qu’une microstructure monogranulaire ne présente pas nécessairement de meilleures propriétés en fluage qu’une microstructure polycristalline. Ceci est attribué au rôle durcissant des joints de grains. Il a de plus été montré qu’à 700°C, la taille et la distribution des précipités γ′ est le paramètre microstructural pilotant les propriétés viscoplastiques à l’ordre 1.En fatigue avec temps de maintien, un comportement original a été observé pour les longs temps de maintien en fonction de la contrainte appliquée. Ce phénomène est attribué à un effet « type Bauschinger » apparaissant lors des phases de décharges. / In view of the turbine entry temperature evolution, the main challenge for metallurgists is to elaborate new alloys able to withstand higher temperatures while keeping great mechanical properties. Therefore, knowing the relationships between microstructural parameters and mechanical properties at high temperatures (700°C and more) is mandatory.The creep and dwell-fatigue durability as well as the damage mechanisms of AD730™, a new nickel base superalloy developed for turbine disks, have been analyzed. Several microstructural parameters were studied (grain boundaries, grain size, size and distribution of γ′ precipitates) as well as experimental parameters (temperature, environment, applied stress or dwell period). By using single crystalline specimens having the same chemical composition of the studied alloy, it has been shown unambiguously that single crystalline microstructures do not necessarily present better creep properties compared to polycristalline ones. This result is supposed to be caused by a grain boundary strengthening mechanism. Moreover, in creep at 700°C, it has been shown that the main viscoplasticity controlling parameters are the size and distribution of γ′ precipitates.An unexpected dwell-fatigue behavior has been observed for long hold times and in a specific applied stress window. This phenomena is attributed to a “Bauschinger type” effect, occurring during unloading phases.

D.Tech. (Extraction Metallurgy) / Please refer to full text to view abstract

M.Tech. (Chemical Engineering) / Please refer to full text to view abstract

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The potential of non-viable Azalia filiculaides for the removal of Cu and Ni from aqueous solutions and the possibility of scaling up existing lab scale Azalia column systems was investigated. The effects of factors such as metal starting concentration, pH and two metals in solution on the removal of Ni and Cu from aqueous solution by dried and crushed Azalia biomass were studied in batch systems. Aqueous solutions of Ni with starting concentrations between 1000 and 2000J.lmolll gave the most efficient Ni removal by Azalla biomass. For Cu the optimum starting concentration for adsorption was 50J.lmol/l. The adsorption capacity of both eu and Ni increased as the starting pH of the sorption media increased. The optimum pH for Ni adsorption was found at pH 7 and for Cu, at pH 5. - Awlla biomass had a higher. maximum binding capacity (qrnax) for Cu than for Ni at pH 5. The removal of both Cu allct Ni showed little or no variation with the presence another metal in solution. Kinetic studies show that both Cu and Ni adsorbed rapidly onto the Azalia biomass. The removal of Cu and Ni from aqueous solutions using non-viable Azalia biomass was investigated in a lab scale fixed-bed column and an upscaled 4L column system. The nonviable Azalla filiculaides biomass when dried and used in a column for adsorption of Cu and Ni showed good physical stability under many different conditions. Preparation of the biomass before it could be used in the columns was very simple and did not involve any significant pretreatment steps. Prolonged exposure to UV light decreases Azalia biomass capacity for Ni and Cu adsorption. Column adsorption of Cu and Ni from aqueous solutions was successfully upscaled approximately 100 times. Relative to the lab scale column, the 4L column performed better for the uptake of Cu and Ni per gram of biomass. The larger column was also able to operate at relatively higher flow rates. The biomass showed good reusability with little change in the amount of Ni adsorbed in 10 consecutive cycles. Electron micrographs showecf little or no change in the physical structure and integrity of the Azolla biomass after exposure to mineral acids, Ni solution and high flow rates over 10 consecutive adsorption and desorption cycles. As much as 80% Ni and 70 % Cu was recovered when desorption profiles were generated using O.lMHCI as a desorption agent. The 4L column system was also tested using a highly concen~rat:~ Ni plating bath solution.(Nicrolyte 1). Only 18 % of the Ni could be removed from the expended Nicrolyte 1 pla~Jng solution after treating only 25L, indicating that Azolla biomass is more suited for removal of metals from more dilute industrial effluents.