Dissertationen zum Thema „Thermo precipitation“

Effective methods for isolation and purification of glycoproteins are of increasing significance to the rapidly growing biopharmaceutical and diagnostic industry. Glycoproteins represent the majority of therapeutic proteins on the market and are effectively used to treat immune disorders, infections, cancers, and other diseases. Targeting these glycoproteins is also critical to an emerging field of glycoproteomics aimed to understand structure-function relationships of glycans. Architecturally, these glycoproteins are proteins with covalently linked oligosaccharide chains of varying monosaccharide composition. Affinity chromatography has proven to be an excellent method of glycoprotein purification at the bench scale. However, chromatography in large scale production has its drawbacks. Column fowling, flowrate limitations, and diffusional constraints collectively hinder the effectiveness of the method. An alternative proposed in this dissertation is the use of affinity precipitation as a purification technique. The three main objectives are 1) develop and produce dual-functional, thermo-responsive affinity ligands from a biological host, 2) characterize and optimize the accompanying affinity precipitation method, and 3) apply the ligand and process to relevant, unmodified glycoproteins. The design of the thermo-responsive affinity construct was comprised of two main functional domains. The binding capability was achieved by selection of small ligands with affinity to a specific monosaccharide moiety. Two different lectins, or sugar binding proteins, were used in the fusion design: a fucose binding lectin from Ralstonia solanacearum, and a sialic acid binding lectin from Vibrio cholera. The thermo-responsive functionality was obtained by use of an elastin-like peptide (ELP), which confers inverse solubility relationship properties to the fusion construct. A small library of varying ELP chain lengths were designed to find the optimal size fusion for both production and function. These dual functional ligands were cloned and expressed in the microbial host, E. coli. Furthermore, secretion of these constructs was achieved by employing the Tat secretion pathway in combination with an outer membrane lipoprotein deletion mutant with a leaky periplasm phenotype. This secretory mechanism allows for easy isolation, avoidance of inclusion bodies, and no additional protease inhibitors. After successful production, the ligands were tested to confirm that dual functionality was preserved in fusion form. Once binding conditions and precipitation properties were ascertained, the purification ability was tested on model glycoproteins. Experimentation was carried out monitoring the purification yield, purity, and retained activity of the target enzymes. High contaminant solutions, such as cell lysates, were spiked with the model glycoproteins to mimic crude protein solutions. The purification ability of the constructs in these models was observed. The method was then implemented on two relevant glycoprotein applications: 1) purification of soybean peroxidase from a crude protein extract and 2) targeting the therapeutic protein erythropoietin from albumin rich, used CHO cell media. By implementation of the fucose targeting fusion construct, the unmodified soybean peroxidase is isolated from a natural crude extract from the soybean hull, a by-product of the soybean industry. The affinity precipitation method parameters were optimized with respect to ratios, temperatures, recycle, and elution buffers to achieve successful isolation of the low abundance enzyme. Under the optimized conditions, >95% recovery yield and a purification of 22.7 fold of an active, pure product was attainable. The purification of erythropoietin led to additional experimentation with high-abundant glycoprotein solutions, as well as expansion of the affinity ligand platform. The concept of multi-lectin affinity precipitation, using the fucose and sialic acid binding lection sequentially, was introduced and tested for purification capability. An industrially relevant scheme involving isolation of the erythropoietin from used CHO cell media allowed for an achievable yield of about 60%, with a resulting albumin depletion of about 85%. In addition to development of a pair of novel thermo-responsive affinity ligands for glycoprotein purification, this dissertation provides insight on possible improvements and future directions with respect to the thermo-responsive affinity ligand platform. This unique concept employs novel lectin fusions to target valuable glycoproteins using a method avoiding the major drawbacks associated with chromatography.

Isolated from marine sponges, many bromopyrrole alkaloids have become natural products of intense scientific interest. The oroidin-derived class of dimeric bromopyrrole alkaloids that include ageliferin, bromoageliferin, and dibromoageliferin exhibit interesting biological properties, including actomycin ATPase, antiviral and antibacterial activities. As a prelude to the total synthesis of ageliferin, an intramolecular Diels-Alder (IMDA) reaction was explored as a means to introduce the three contiguous stereocenters. Toward this end, various IMDA precursors were synthesized, and several strategies for the synthesis of IMDA substrates were devised and explored. Affinity chromatography is a powerful technique that enables the purification of a specific protein from a complex mixture. However, traditional affinity chromatography techniques are somewhat limited due to the solid state of the matrix. To overcome these limitations, the utility of a soluble polymer as an alternative affinity matrix was explored for the isolation of natural product receptors. This polymer displays physical properties that make it an ideal matrix for protein isolation and purification. The parent polymer is soluble in aqueous solution at 4 °C and precipitates once the mixture reaches 32 °C. Furthermore, employing this polymer for affinity chromatography may limit the nonspecific binding of proteins. It is also possible to determine the ligand loading using standard analytical techniques such as 1H and 13C NMR. For proof of concept, a dexamethasone-containing macroligand was synthesized to isolate the known glucocorticoid receptor. In addition, a cyclosporin A-containing macroligand was synthesized and employed to isolate the well known and more robust cyclophilins. In this work, it was demonstrated that indeed the ligand loading can be determined by 1H NMR technique. In addition, it was established, as expected, that the water solubility of the macroligands varies based on the hydrophilicity and hydrophobicity of the ligand and degree of ligand loading.

Les travaux de cette thèse concernent le développement d’un modèle par éléments discrets du comportement thermo-mécanique d’un alliage d’aluminium et de son évolution microstructurale lorsqu’il est soumis à des conditions de grandes déformations et/ou de grandes vitesses de déformation (soudage par friction-malaxageou FSW). Le procédé de « soudage par friction malaxage » (Friction Stir Welding,FSW) est un procédé de soudage récent, inventé en 1991 par « The Welding Institute (TWI) ». Ce procédé se distingue des autres par sa capacité à souder la matière à l’état visqueux, sans atteindre le point de fusion. Le principe est relativement simple et comparable à une opération de fraisage, si ce n’est que l’outil coupant est remplacé par un outil malaxant composé d’un pion et d’un épaulement. Ce procédé revêt un fort intérêt pour l’industrie aéronautique, car il offre la possibilité de souder des alliages d’aluminium des séries 2XXX et 7XXX, réputés difficiles à souder par d’autres procédés.Le soudage par friction-malaxage étant un procédé récent, il demeure encore un sujet de recherche actif, pour mieux appréhender certains points comme l’écoulement de la matière, l’influence des paramètres du procédé (vitesse de rotation, forme de l’outil, ...)et la modification de la microstructure. Ce dernier point est particulièrement important pour les alliages à durcissement structural comme ceux des séries 2XXX et 7XXX. Pour ces alliages d’aluminium, les propriétés mécaniques dépendent étroitement de leur état de précipitation, lui-même influencé par l’apport de chaleur généré lors du soudage.L’optimisation des paramètres de soudage par rapport aux propriétés mécaniques passe obligatoirement par la prédiction de l’état de la précipitation le long du joint soudé. Le travail de la thèse vise à mettre en place des modèles à l’échelle de la microstructure permettant de prévoir la modification des propriétés de la matière liées aux paramètres du procédé
The work of this thesis concerns the development of a model using the discrete element method, for the thermo-mechanical behavior of an aluminum alloy and its microstructural evolution when exposed to conditions of large deformations and/or high deformation rates (Friction StirWelding or FSW). Friction stir welding is a recent welding process invented in 1991 by "The welding Institute" (TWI). This process is different from the others by its ability to weld material in the viscous state, without reaching the melting point. The principle is relatively simple and similar to a milling process except that the cutting tool is replaced by a rotary tool composed of a pin and a shoulder. This process is of great interest in the aircraft industry because it offers the possibility to weld aluminum alloys 2XXX and 7XXX series, known to be difficult to weld by other processes. Since friction stir welding is a recent process, it still remains a subject of active research, to better understand certain issues such as material flow, influence of process parameters (rotation speed, tool shape, ...) and the modification of the microstructure. This last point is particularly important for structural hardening alloys such as those of the 2XXX and 7XXX series. For these aluminum alloys, the mechanical properties are highly dependent on their state of precipitation, which is itself influenced by the heat generated during thewelding. The optimization ofwelding parameters in order to obtain good mechanical properties requires the prediction of precipitation state along thewelded joint. Thework of this thesis is to develop required models at the scale of microstructure allowing to predict the modification of material properties related to the process parameters

This diploma thesis deals with the issue of adhesion of pollution to the final surface treatments of the ETICS system. The theoretical part deals with important factors and processes that affect the degree of adhesion of pollution. The practical part of the diploma thesis follows the diploma thesis of Ing. Jakub Krejčík. Optimization of test methods for simulation of artificial pollution on tested samples was proposed. These samples were then evaluated in the laboratory and also compared with plasters that were exposed to real pollution from the natural environment.

CAPES
No presente trabalho foi estudado a influência do pH final de precipitação, tempo e modo de agitação, onde foi avaliado o modo de agitação mecânico e por ultrassom na obtenção do dióxido de cério. Para a otimização do processo, fez-se o uso de uma ferramenta chamada Planejamento Fatorial, na qual, a partir dos dados experimentais fornece uma estimativa para melhores condições levando em consideração uma variável resposta. As variáveis resposta adotadas no trabalho foram Temperatura Final de Decomposição e Tamanho médio de Partícula. O dióxido de cério foi obtido a partir da decomposição térmica do complexo tris(8-hidroxiquinolinato)cério(III), que foi sintetizado por meio da técnica de precipitação química, empregando o quelante 8-hidroxiquinolina e caracterizado por meio de espectroscopia na região do infravermelho (FTIR) e microscopia eletrônica de varredura (MEV), foi também realizado o estudo do comportamento térmico do complexo, com auxílio da térmogravimetria (TG), térmogravimetria derivada (DTG) e análise térmica diferencial (DTA); o dióxido de cério foi caracterizado por meio de FTIR e difratometria de raios X (DRX), a partir dos dados de DRX foi calculado o tamanho médio de partículas com o auxílio da fórmula de Scherrer. O Planejamento Fatorial indicou para variável resposta Temperatura Final de Decomposição, que para ambos modos de agitação as melhores condições de síntese são para maiores valores de pH´s finais de precipitação, o tempo de agitação não teve influência significativa a 95% de significância, dentro da faixa estudada. Para variável resposta Tamanho Médio de Partícula, o teste mostrou para os dois modos de agitação, que nenhuma das variáveis teve influência significativa a 95% de significância, dentro da faixa estudada, atribuindo então o tamanho médio de partículas somente ao método de síntese. Não houve diferença significativa entre os modos de agitação também.
In the present work, it was investigated the influence of the final pH of precipitation, agitation time and mode of agitation, which assessed the mechanical agitation mode and ultrasound to obtain the cerium dioxide. For process optimization, it was used a tool called Planning Factor, which provides an estimative of better conditions, considering a response variable from the experimental data. The responsible variable adopted in this work was Decomposition Final Temperature and Particle Average Size. The cerium dioxide was obtained from the thermal decomposition of the complex tris (8-hydroxyquinolinate) cerium (III), synthesized by chemical precipitation using 8-hydroxyquinolinechelator and characterized by infrared spectroscopy (FTIR) and scanning electronic microscopy (SEM). In addition, it was performed the study of the complex thermal behavior with assistance of thermogravimetry (TG), derivative thermogravimetry (DTG) and differential thermal analysis (DTA); The cerium dioxide was characterized by FTIR and X-ray diffraction (XRD), in which it was based to the determination of the particle average size using Scherrer's formula. The Factorial design pointed out to response variable Decomposition Final temperature that, for both modes of agitation, the best synthesis conditions are for higher values of final pH's precipitation. Also, the stirring time had no significant influence when used the 95% significance studied range. For response variable Average Size, the test pointed out to both ways of stirring, when none of the variables had significant influence at 95% significance within the studied range, assigning the average particle size only to the method of synthesis. Thereby, there was no significant difference between the stirring modes.

Multifunctional superparamagnetic iron oxide nanoparticles (SPIONs) coated with silica are a promising research field for lots of biomedical applications. The scope of this work is a preparation of SPIONs and coating them with silica to form core-shell structured nanoparticles for nanomedicine applications. SPIONs were synthesized by two chemical methods – co-precipitation and thermal decomposition of organic iron precursor. Prepared nanoparticles were carefully characterized –average size, size distribution, morphology, crystallinity, colloidal stability and magnetic properties were studied. After comparing SPIONs synthetized by two routes the most suitable method for biomedical applicable nanoparticles preparation is determined. The nanomedicine requires nanoparticles of the highest quality. The next step was coating SPIONs with silica shell. For this purpose inverse microemulsion method was chosen. TEOS was used as a silica precursor. Mean size, size distribution, magnetic properties, structure of silica shell were studied.

Les exigences des clients du secteur aéronautique imposent aux entreprises de prendre en compte pour le dimensionnement les effets de la température sur toute la durée de vie du produit. Cependant, aucune loi ne permet actuellement de prévoir l’impact du vieillissement thermique sur le comportement des matériaux. Ce travail a pour objectif de comprendre le mécanisme de vieillissement thermique des alliages d’aluminium et son impact sur les propriétés mécaniques, mais surtout d’acquérir un outil performant capable d’obtenir rapidement des données matériaux après vieillissement.Au cours de cette étude, de nombreuses analyses microstructurales et mécaniques ont été réalisées sur trois alliages d’aluminium à durcissement structural. Différentes combinaisons temps-température de vieillissement ont été testées afin de disposer d’une large base de données sur ces matériaux (caractéristiques mécaniques statiques Rm, Rp0,2 et dureté et tailles des précipités durcissants). Ces données ont ensuite été compilées dans un modèle de vieillissement basé sur les théories classiques de durcissement structural, de croissance et de coalescence des précipités.Le modèle de vieillissement créé répond au besoin initial et prédit de façon conservative le comportement mécanique des alliages ayant subi un vieillissement thermique isotherme. Des axes d’amélioration sont envisagés pour ce modèle évolutif, comme l’intégration de la prévision du comportement en fatigue ainsi que le traitement de cas anisothermes pour une représentation plus réelle des conditions de service des pièces aéronautiques
In aeronautics, customers ask companies to consider the effects of temperature over the entire life of the product in structural requirements. Indeed, aircraft parts are demanded to last longer (up to 90 000 hours) and operate at higher temperatures (up to 250°C). No laws enable to predict the impact of thermal ageing on materials behavior. Current practices are to perform mechanical testing after ageing in ovens at various temperatures, but they are expensive and incompatible with the development schedules. This work aims to understand the thermal aging mechanism of aluminum alloys and its impact on mechanical properties, but especially to acquire a powerful tool able to quickly obtain material data after aging.During this study, many microstructural and mechanical analyses were conducted on three precipitation hardened aluminum alloys. Different combinations of aging time and temperature were tested to get a large database of these materials (static mechanical characteristics Rm, Rp0,2 and hardness and sizes of hardening precipitates). These data were then compiled into a computing aging model based on the classical theories of precipitation hardening, growth and coarsening of precipitates.The created aging model responds to the initial need and can conservatively predict the mechanical behavior of aluminum alloys under isothermal aging. Improvement areas are considered for this evolutionary model, such as the integration of fatigue behavior prediction and the inclusion of thermal cycles for a more realistic representation of service conditions of aircraft parts

Thermal mismatch between different components of a system could be sources of problems like residual stress induced cracking, thermal fatigue or even optical misalignment in certain high technology applications. Use of materials with tailored thermal expansion coefficient is a counter-measure to overcome such problems. With its negative thermal expansion coefficient zirconium tungstate (ZrW2O8) is a candidate component to be used in synthesis of composites with controlled thermal expansion coefficient (CTE). ZrW2O8 is typically produced by solid-state reaction between zirconium oxide and tungsten oxide at 1200oC. However, it has been demonstrated that ZrW2O8 can also be synthesized using wet chemical techniques, which provide a superior chemical homogeneity that often extents down to the atomic scale, and the convenient means of controlling nucleation and growth of the primary crystallites. With the commonly adopted wet chemical approaches, it is possible to crystallize particles with sizes in the submicrometer range at temperatures as low as 600 oC or even lower. In these studies, precursors are aged either below 100 oC (7 days &ndash
3 weeks), or at 160-180 oC under hydrothermal conditions (1&ndash
2 days). Besides the obvious disadvantage in the ageing steps, use of tungsten sources with high cost in all approaches, constitutes the other disadvantage. Production of composites with tunable controlled thermal expansion (CTE) has been achieved by blending negatively and positively expanding materials in different proportions. In majority of these studies composites have been produced by conventional sintering methods. Spark Plasma Sintering (SPS) is a recent technique
in which sintering can be achieved at relatively low temperatures in short durations. There is only one study made by Kanamori and coworkers on the use of SPS in sintering of a composite, in which ZrW2O8 is one of the constituents [1]. This study aims the synthesis of ZrW2O8 particles and composites that possess tunable or zero CTE. A novel precursor recipe for ZrW2O8 synthesis was developed. In preparation of the precursor a total of 2 days of ageing and a temperature less than 100 oC was used. It was developed using a cost-effective tungsten source, namely tungstic acid and its final pH was lower than 1. The particles obtained from &lsquo
unwashed&rsquo
procedure had sizes in micrometer range, while those obtained from &lsquo
washed&rsquo
case had sizes in the range of 400-600 nm. These precursors could readily be crystallized at 600 oC, which in turn provided the desired particle sizes for composite applications. Experimental details on the precursor development are hereby presented with a discussion on the effects of solution parameters (i.e. solubility of tungstic acid, adjustment of the stoichiometry, ageing time) on the phase purity of the fired product. Zirconium oxide (ZrO2) has positive vi thermal expansion, therefore ZrW2O8/ZrO2 was selected as the composite system, and for their synthesis both conventional and spark plasma sintering methods were experimented. Composition ranges that provide composites with almost zero CTE&rsquo
s were determined. The composite having a composition of containing 35% ZrW2O8, 65% ZrO2, and 35 w/o Al2O3 and sintered at 1200 oC for 24 hours had an expansion coefficient of 0.20 x 10-6/K for conventional method, while the one having a composition of 55% ZrW2O8, 45% ZrO2 and sintered at 1000 oC for 5 minutes had an expansion coefficient of 0.94 x 10-6/K for spark plasma sintering method. For characterization of the products X-ray diffraction (XRD), scanning electron microscopy (SEM), photon correlation spectroscopy (PCS), and thermal and dilatometer analyses (DTA/TGA/DMA) were used.

Elevated temperatures accompanying climate warming are expected to have adverse effects on sensitive lichen species. This premise was examined by measuring the sensitivity of different lichen species to elevated temperatures in the laboratory and in the field. Laboratory studies involved the exposure of nine hydrated lichen species (Xanthoparmelia austro-africana, X. hyporhytida, Xanthoparmelia sp., Xanthomaculina hottentotta, Teloschistes capensis, Ramalina sp., Flavopuntelia caperata, Lasallia papulosa, Parmotrema austrosinensis) collected from sites of different aridity and mean annual temperature for 2 hourly intervals to temperatures ranging from 24º
C to 48º
C in a forced daft oven and measuring their respiration rates and maximum quantum yield of PSII. Field studies involved simultaneous hourly measurements of ground surface air temperatures and Lichen effective quantum yield of PSII of hydrated lichen species populations under ambient and artificially modified environmental conditions.

La sécurité des installations nucléaires est constamment un souci majeur lors de leur exploitation, mais aussi lors de la conception de nouveaux réacteurs. Leurs durées de vie est limitée à cause des changements de comportement mécanique de leurs composants métalliques (principalement la cuve du réacteur mais aussi ses composants internes), qui sont accélérés ou induits par l’irradiation de neutrons. Une prédiction quantitative précise de ces changements, en fonction de la composition des matériaux et des conditions d'irradiation, est par conséquent un objectif de première importance pour la science des matériaux nucléaires. La modélisation est, de nos jours, considérée comme un complément vital aux approches expérimentales, avec l'objectif d’apporter une meilleure compréhension des processus physiques et chimiques qui se produisent dans les matériaux métalliques sous irradiation de neutrons.

La modélisation des effets de l'irradiation de neutrons dans les aciers est par nature un problème multi-échelle. Le point de départ est la simulation des cascades de collisions atomiques initiées par les neutrons à hautes énergies qui pénètrent dans le matériau, créant ainsi des défauts ponctuels mobiles. Différents modèles physiques, considérant des échelles de temps et de longueur croissantes, doivent être développés afin de convenablement tenir en compte de tous les différents processus qui provoquent des changements de comportement macroscopique, à cause de la présence de ces défauts ponctuels mobiles. En outre, des liens entre les différents modèles doivent être créés, parce que les prédictions de chacun d'entre eux doivent servir de paramètres d'entrée pour les modèles qui travaillent aux échelles supérieures. Dans cette thèse, un tel lien est créé entre le niveau atomique et les modèles à gros-grains, en développant un nouvel algorithme Monte-Carlo cinétique atomistique (MCCA), où le matériau est décrit comme une collection d'atomes occupant des sites cristallographiques réguliers. Le processus simulé est dès lors naturellement décomposé en séries d'évènements élémentaires activés thermiquement, correspondant à la migration des défauts ponctuels (lacunes ou interstitiels) vers des positions de proches voisins, qui sont en permanence en compétition en fonction de leurs fréquences d'occurrences respectives. Ces dernières sont calculées en fonction des énergies de migrations, qui sont elles-mêmes calculées avec peu d'approximations par une méthode qui prend en compte tous les effets de la relaxation statique et des interactions chimiques à longue portée. Le nouvel algorithme MCCA est par conséquent un modèle physique, entièrement basé sur un potentiel inter-atomique approprié qui est utilisé de la manière la plus complète possible, sans définir de paramètres empiriques qui devraient être, par exemple, fittés depuis des données expérimentales. Finalement, l'algorithme est accéléré de plusieurs ordres de grandeur en utilisant des réseaux de neurones artificiels (RNA), entraînés à prédire les énergies de migrations des défauts ponctuels en fonction de leur environnement atomique local.

Le nouvel algorithme MCCA est utilisé avec succès pour simuler des expériences de recuits (pour lesquels une seule lacune doit être introduite dans la boîte), afin de valider le modèle grâce à une comparaison directe de ses prédictions avec des résultats expérimentaux trouvés dans la littérature. Une comparaison très satisfaisante est accomplie pour deux alliages modèles importants pour la science des matériaux nucléaires. Dans les deux cas, l'évolution avec le temps de recuit du rayon moyen des précipités formés, ainsi que de leur densité, est en très bonne adéquation avec les mesures expérimentales trouvées dans la littérature, contrairement à ce que d'autres auteurs avaient jusqu’à présent réussi. Ensuite, l'algorithme est généralisé avec succès afin de permettre l'introduction d'un grand nombre de lacunes, ce qui est un des deux ingrédients nécessaires pour la simulation des effets de l'irradiation de neutrons dans les métaux. Cet accomplissement permet la simulation de processus longs et complexes, par exemple le calcul de coefficients de diffusions et temps de vies d'amats de cuivre-lacunes, qui sont des paramètres d'entrée nécessaires pour des modèles de simulation à gros-grains. Finalement, des preuves convaincantes sont apportées que l'algorithme MCCA peut être, dans un futur proche, généralisé d'avantage et permettre la prise en compte des interstitiels, ouvrant ainsi la voie vers la simulation de cycles complets d'irradiation.

Doctorat en Sciences
info:eu-repo/semantics/nonPublished

Thesis (MScEng (Mechanical and Mechatronic Engineering))--University of Stellenbosch, 2009.
ENGLISH ABSTRACT: In the primary circuit components of high temperature reactors, various unwanted particles have been found. These particles include, for example, graphite and silver- 110 (110mAg). The silver-110 (110mAg) particles are radioactive, with a half-life of 253 days. The presence of radioactive particles in the primary circuit components constitutes an unwanted maintenance problem from a radiation hazard point of view. The development of a method to remove these particles from the helium stream is therefore needed. This thesis consideres two possible methods of removing silver from the helium stream, namely laser ablation of microparticles and electrostatic precipitation. These methods require the generation of silver ions or charged particles, the deflection of these particles in a helium gas stream passing through an electric field and the subsequent plate-out of these particles onto deflection electrodes. To find a suitable method of generating ions, various methods to generate the silver ions were investigated and evaluated. These methods include existing ion sources, thermionic, field and photoelectric emission and laser ablation of microparticles. No existing ion sources could be found which could be utilised in helium at high pressure. From calculations it was concluded that thermionic, field and photoelectric emission could also not be used to raise the energy of the emitted electrons sufficiently to ionize silver in a helium flight path. These methods were found not to be feasible ion sources in helium at high pressures. However, laser ablation of microparticles was found to constitute a feasible technology. Laser ablation was successfully utilised by Nichols et al. (2000) to deflect silver nanoparticles in an electric field across a two bar helium stream. An apparatus, similar to the one developed by Nichols et al. (2000), was designed and built. The apparatus included a silver insertion mechanism and tests with this apparatus were called the microparticle tests. To determine the efficacy of the silver insertion mechanism, the microparticle tests were done without the use of a laser. It was found that a laser was not necessary as microparticles collected on both the deflection electrodes. Dielectrophoresis was proposed as a possible explanation for the deflection and the plate-out of the mcroparticles. To theoretically model the deflection of the silver particles, two models were proposed, namely the deterministic and the stochastic deflection models. The latter describes the deflection of atoms, ions and polarized particles by using probability theory. From this model it was found that the Brownian motion force is far larger that the force created by the polarizibility of the atom due to an electric field. The deterministic deflection model describes the deflection of larger particles in a continuum. From this model it was found that a silver microparticle with a radius of 3 mm in a helium stream with bulk velocity of 0.0198 m/s would deflect 4.6 mm per helium flight path length of 140 mm. From these calculation it was found that the apparatus which had been built was not long enough to deflect and plate-out all the silver microparticles. The dielectrophoresis force on nanoparticles cannot be calculated, as the theory of dielectrophoresis is only valid for particles with diameter larger than 1 mm. Changes were therefore made to the apparatus to generate nanoparticles as their mobility is larger than that of microparticles. The nanoparticles were created by means of an arc discharge in helium; therefore tests with this modified apparatus were called the arc discharge test. The nanoparticles so created, deflected and deposited on both deflection electrodes. With the use of an atomic force microscope some of the particles could be classified as microparticles. According to the deterministic deflection model they should not have deflected. Combined with the fact that oxygen was in the plasma, due to the oxidation of the electrodes, a hypothesis of bipolar charging was thus proposed. The deterministic deflection model was used and supplemented with field and diffusion charging calculations, to support this hypothesis. A reasonable correlation between the theoretical model and this experimental results was obtained. Based on the arc discharge test, electrostatic precipitation was proposed as the indicated means of scrubbing silver and other particles such as graphite from a helium stream. It is recommended that a new apparatus be built and that the deterministic deflection model be used to predict the deflection of the particles. With this apparatus the uncertainties of breakdown voltage, the effect of thermionic emission and the size of the particles, all of which have been identified as being important, can then also be determined.
AFRIKAANSE OPSOMMING: In die primêre komponente van die kringloop van hoë temperatuurreaktors, was verskillende ongewenste partikels soos grafiet en silwer-110 (110mAg) teenwoordg. Silwer- 110 (110mAg) is radioaktief met ’n halfleeftyd van 253 dae. Vanuit ’n radiasie-risiko oogpunt word daar onderhoudsimplikasies geskep deur die teenwoordigheid van radioaktiewe partikels in die primêre komponente. Die ontwikkeling van ’n metode om hierdie partikels uit die heliumstroom the verwyder was dus nodig. Hierdie tesis ondersoek twee moontlike metodes van verwydering van silwer uit die heliumstroom, naamlik laser-ablasie van mikropartikels en elektrostatiese presipitasie. Hierdie metodes benodig die generasie van silwer ione of gelaaide partikels, die defleksie daarvan in ’n heliumstroom wat deur ’n elektriese veld vloei en die platering van die partikels op defleksie elektrodes. Om ’n geskikte metode the vind wat ione genereer was, verskillende metodes om die silwer ione te verkry, ondersoek en geëvalueer. Hierdie metodes sluit in bestaande ioonbronne, termioniese, veld en fotoëlektriese emissie en laser-ablasie van mikropartikels. Geen ioonbronne was gevind wat gebruik kan word in helium by hoë druk nie. Die gevolgtrekking is gemaak vanaf berekeninge dat termioniese, veld en fotoëlektriese emissie ook nie gebruik kan word om die energie van die voortgebronge elektrone genoeg te verhoog om silwer in ’n heliumstroom te ioniseer nie. Daar was gevind dat hierdie metodes nie geskik is as ioonbronne in helium by hoë druk nie. Daarenteen was laser-ablasie van mikropartikels gevind om ’n geskikte tegnologie voor te stel. Laser-ablasie van mikropartikels was suksesvol deur Nichols et al. (2000) gebruik om silwer nanopartikels te deflekteer in ’n elektriese veld oor helium van twee bar. ’n Apparaat soortgelyk aan Nichols et al. (2000) se eksperiment, was dus ontwerp en gebou. Die apparaat het ’n silwer insitmeganisme bevat en toetse met hierdie apparaat was die mikropartikel toetse genoem. Om die effektiwiteit van die insitmeganisme te bepaal, was toetse gedoen sonder opstelling van die laser. Daar was eksperimenteel gevind dat die laser nie nodig was nie, omdat mikropartikels op beide defleksie elektrodes geplateer het. Dielektroforese was voorgestel as ’n moontlike verduideliking vir deflektering en platering vir die silwer mikropartikels. Om die defleksie van silwer partikels teoreties te moduleer was twee modelle voorgestel, naamlik deterministiese en stogastiese defleksiemodelle. Laasgenoemde beskryf die defleksie van atome, ione en gepolariseerde partikels deur gebruik te maak van waarskynlikheidsteorie. Die stogastiese defleksiemodel dui aan dat die Brownian bewegingskrag veel groter is as die krag wat geskep word deur die polarisasie van ’n atoom as gevolg van ’n elektriese veld. Die deterministiese defleksiemodel beskryf die defleksie van groter partikels in ’n kontiuum. Met hierdie model was gevind dat silwer mikropartikels met ’n radius van 3 mmin ’n heliumstroom van snelheid van 0.0198 m/s, 4.6 mm sal deflekteer per 140 mm van heliumstroom lengte. Dit bewys dat die apparaat wat gebou was, se lengte onvoldoende was om al die silwer mikropartikels te deflekteer en te laat neerslaan. Die dielektroforese krag van nanopartikels kan nie uitgewerk word nie, omdat die dielektroforese model slegs geldig is vir partikels groter as 1 mm. Veranderings was dus aan die apparaat gemaak om nanopartikels te genereer omdat hul mobiliteit hoër is as die van mikropartikels. Die nanopartikels was geskep deur gebruik van ’n boogontlading in helium; daarom was toetse met hierdie gemodifiseerde apparaat die boogontladingstoets genoem. Die nanopartikels wat so geskep was, het gedeflekteer en het op beide elektrodes neergeslaan. Met die gebruik van ’n atomiese krag mikroskoop was dit gevind dat sommige van hierdie partikels mikropartikels was. Volgens die deterministiese defleksiemodel moes hul nie gedeflekteer het nie. Gekombineerd met die feit dat daar, weens oksidasie van die elektrodes, suurstof in die plasma was, was ’n hipotese van bipolêre lading voorgestel. Die deterministiese defleksiemodel is saam met die veld- en diffusielading gebruik om hierdie hipotese te staaf. ’n Redelike korrelasie tussen die teoretiese en eksperimentele data was gevind. Gebaseer op die boogontladingstoets, was elektrostatiese presipitasie voorgestel as ’n metode om silwer en ander partikels soos grafiet uit ’n heliumstroom te verwyder. Daar word voorgestel dat ’n nuwe apparaat gebou word en dat die deterministiese defleksiemodel gebruik word vir die bepaling van defleksie van die partikels. Deur die nuwe apparaat te gebruik kan die onsekerhede van deurslagspanning, effek van termioniese emissie en grootte van die partikels wat geidentifiseer is as belangrik, ook bepaal word.

Este trabalho propõe o método de precipitação química para a produção de óxido de zinco (ZnO), por decomposição térmica de um precursor organometálico, obtido pela reação do nitrato de zinco com 8-hidroxiquinolina. Dessa forma, foram sintetizados 8-hidroxiquinolinatos de zinco sob quatro condições, em pH 5,0 e 9,0, em ácido acético ou acetona, obtendo-se quatro amostras, cujo rendimento médio da síntese foi de 92,98% em massa. Os complexos foram caracterizados pelas técnicas de difratometria de raios X (DRX), espectroscopia na região do infravermelho com transformada de Fourier (FTIR), espectroscopia na região do ultravioleta- visível (UV-Vis), análise elementar (CHN), microscopia eletrônica de varredura (MEV), Análise elementar e espectroscopia de absorção atômica (AAS). O estudo do comportamento térmico desses complexos foi realizado pelas técnicas de análise termogravimétrica (TGA) e análise térmica diferencial (DTA) em atmosfera dinâmica de ar sintético, que revelou a perda de massa em três etapas para amostras obtidas em ácido acético e quatro etapas para amostras sintetizadas em acetona devido a coprecipitação da 8-hidroxiquinolina. Em atmosfera dinâmica de nitrogênio (N2), a decomposição ocorre em duas etapas, mas sem estabilização de massa até a temperatura de 800 °C. As amostras foram submetidas à decomposição térmica em três diferentes razões de aquecimento e a partir das curvas de DTA foram determinadas as energias de ativação dos processos de desidratação e de recristalização dos compostos. Os dados instrumentais apontam que as sínteses geraram complexos na forma di-hidratada e o resíduo final de decomposição térmica o ZnO. As condições apresentadas no estudo do comportamento térmico foram utilizadas para a produção do ZnO nas temperaturas de 700 e 900 °C, com tempos de permanência de 2 e 4 h. A caracterização por DRX indicou que a estrutura do óxido obtido é hexagonal e em geral, com aumento da temperatura de calcinação e tempo de permanência, houve aumento no tamanho do cristalito, cujos valores ficaram entre 27,87 e 58,49 nm nas estimativas feitas pelo método de Williamson-Hall e pela equação de Scherrer. Os espectros de FTIR do ZnO apresentaram uma única banda em aproximadamente 400 cm-1 referente a ligação metal-oxigênio. Os espectros de UV-Vis foram utilizados para a estimativa do band-gap, obtendo-se valores que variaram entre 3,22 e 3,46 eV. Portanto, o método de precipitação química proposto, demonstrou-se tecnicamente viável para a produção do ZnO.
This work proposes chemical precipitation method for the zinc oxide (ZnO) production, by decomposition of an organometallic precursor, obtained with zinc nitrate and 8-hydroxyquinoline reaction. Therefore, zinc 8-hydroxyquinolinates were synthesized in four conditions, at pH 5.0 and 9.0, in acetic acid or acetone conditions, obtaining four samples, with an average yield of 92.98% dry matter. The compounds were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible (UV-Vis) spectroscopy, scanning electron microscopy (SEM), elemental analysis and atomic absorption spectroscopy (AAS). The thermal behavior of the complexes was performed by thermogravimetric analysis (TGA) and differential thermal analysis (DTA) in a dynamic synthetic air atmosphere, which revealed the mass loss in three stages for samples obtained in acetic acid and four stages for samples synthesized in acetone due to the co-precipitation of 8-hydroxyquinoline. In dynamic nitrogen atmosphere (N2), the decomposition occurs in two steps, but without mass stabilization up to 800 °C. From the samples submitted to thermal decomposition in three different heating ratios and from the obtained curves, the activation energies of the dehydration and recrystallization processes of the complexes had been determined. The data indicate that the synthesis generated complexes in the dihydrate form and the final residue of thermal decomposition zinc oxide. The conditions in the study of the behavior thermal were used to produce the ZnO at temperatures of 700 and 900 ° C, with calcination times of 2 and 4 h. XRD characterization showed that the structure of the zinc oxide was hexagonal structure and increasing temperature calcination and residence time, there was an increase in the crystallite size, whose range were 27.87 to 58.49 nm in estimates by Williamson-Hall method and Scherrer's equation. FTIR spectra of ZnO showed a single band at approximately 400 cm-1 for metal-oxygen bonding. UV-Vis spectra were used to estimate the band-gap values, that varied between 3.22 and 3.46 eV. Therefore, chemical precipitation method proposed, was demonstrated technically practicable for ZnO production.

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No presente estudo, os compósitos MgO-CeO2 e ZnO-CeO2 foram obtidos via decomposição térmica de quelatos dos metais Ce, Mg e Zn com o quelante 8-hidroxiquinolina, caracterizados e testados como catalisadores na degradação do corante Vermelho Reativo BF-4B por processo de fotocatálise heterogênea. Os complexos dos metais com o quelante 8-hidroxiquinolina foram obtidos por uma rota sintética de coprecipitação em meio aquoso por elevação do pH. Análises de FTIR das misturas de complexos sintetizados comprovaram a obtenção dos complexos pela observação das bandas características que evidenciaram a ligação do quelante com os metais. Análise térmica simultânea TGA-DTG-DTA dos complexos possibilitaram traçar e caracterizar o perfil do comportamento térmico dos complexos nas condições a que foram submetidos, assim como identificar os eventos de decomposição térmica dos complexos e temperaturas de obtenção dos compósitos desejados. Resultados de DRX mostraram características de semi-cristalinidade dos complexos, e possibilitaram a identificação das fases dos compósitos obtidos, assim como a comprovação da obtenção dos mesmos. As imagens obtidas por MEV dos compósitos mostraram que as partículas dos compósitos obtidos possuíam características de aglomeração, policristalinidade e variação de tamanho de partículas para todas as amostras, onde também foi possível observar que as partículas do compósito MgO-CeO2 apresentavam a forma de bastões ocos e de base quadrada, que melhor definiram sua forma com o aumento da temperatura final de tratamento térmico utilizada, e para o compósito ZnO-CeO2, morfologia de partículas disformes juntamente com partículas no formato de placas lisas e irregulares de diversos tamanhos. Os resultados de DRS possibilitaram a obtenção dos valores de band-gap dos compósitos, que apresentaram aumento de seu valor conforme se aumentou a temperatura de tratamento térmico para obtenção dos mesmos. Os resultados dos testes aplicando os materiais como catalisadores no processo de degradação do corante têxtil Vermelho Reativo BF-4B por fotocatálise heterogênea indicaram que os materiais não são adequados, visto que a sua presença no processo tem efeito retardante na degradação do corante testado. Estes efeitos nos testes catalíticos podem ser associados à baixa afinidade entre os compósitos e o corante Vermelho Reativo BF-4B, mostrados pelos testes de adsorção do corante pelos compósitos, nas condições utilizadas para os testes.
In the present study, MgO-CeO2 and ZnO-CeO2 composites were obtained by thermal decomposition of the chelates of the Ce, Mg and Zn metals with the 8-hydroxyquinoline chelator, characterized and tested as catalysts in the degradation of BF-4B Red Reactive dye by heterogeneous photocatalysis process. The metal complexes with the 8-hydroxyquinoline chelator were obtained by a synthetic coprecipitation route in aqueous medium by raising the pH. FTIR analysis of the synthesized mixed complexes proved to obtain the complexes by observing the characteristic bands that showed the binding of the chelant to the metals. Simultaneous thermal analysis (TGA-DTG-DTA) of the complexes made it possible to trace and characterize the thermal behavior profile of the complexes under the conditions to which they were subjected, as well as to identify the thermal decomposition events of the complexes and the temperatures of obtaining the desired composites. XRD results showed semi-crystallinity characteristics of the complexes, and enabled the identification of the phases of the composites obtained, as well as the proof of obtaining them. SEM images of the composites showed that the obtained composites particles presented characteristics of agglomeration, polycrystallinity and variation of particle size for all the samples, where it was also possible to observe that the particles of the MgO-CeO2 composite were in the form of hollow rods and square basis, which best defined their shape with the increase of the final heat treatment temperature used, and for the ZnO-CeO2 composite, morphology of deformed particles together with particles in the shape of smooth and irregular plates of various sizes. DRS results allowed to obtain the band gap values of the composites, whose values increased with the increasing in the thermal treatment temperature. Results of the tests applying the materials as catalysts in the degradation process of the BF-4B Reactive Red dye by heterogeneous photocatalysis indicated that the materials are not suitable, since their presence in the process has a retarding effect on the degradation of the dye tested. These effects on the catalytic tests may be associated with the low affinity between the composites and the BF-4B Red Reactive dye, shown by the dye adsorption tests by the composites, under the conditions used for the tests.

Atualmente estudos com óxidos de metal de terras raras com estrutura perovskitas vem sendo realizados devido as suas propriedades interessantes, como a alta condutividade eletrônica e iônica, e suas potenciais aplicações em baterias, células combustíveis, catalisadores, sensores de gás, sensores químicos, entre outros. Neste trabalho apresentam-se os resultados obtidos para obtenção da LaCoO3 a partir da decomposição térmica de 8-hidroxiquinolinatos de cobalto e lantânio, obtidos pelo método de coprecipitação, em pH final de 5 e 9, e em meio de acetona ou ácido acético. Os complexos foram caracterizados por Difratometria de Raios X (DRX), por Espectroscopia de Absorção na Região do Infravermelho (FTIR), Absorção Atômica (AAS), Análise Elementar (AE) e Microscopia Eletrônica de Varredura (MEV). O estudo do comportamento térmico foi realizado por Análise Termogravimétrica (TGA), Termogravimetria Derivada (DTG) e Análise Térmica Diferencial (DTA) em diferentes razões de aquecimento e atmosfera, até 800 ºC. Os óxidos obtidos por decomposição térmica foram caracterizados por DRX, FTIR e AAS. Com o estudo do comportamento térmico observou-se que as amostras apresentaram três etapas de decomposição térmica sob atmosfera de ar sintético e cinco etapas em atmosfera de N2, foi ainda possível observar que o percentual de resíduo final para os pH 9 foi superior ao resíduo final nos pH 5, porém as temperaturas finais de decomposição foram menores em pH 5. Os resultados indicaram maior eficiência do processo de obtenção da LaCoO3 para os pH 9 em ambos os meios reacionais, caracterizado por DRX, com rendimento médio de 93%.
Currently, studies with rare earth metal oxides with perovskite structure have been carried out due to their interesting properties, such as high electronic and ionic conductivity, and their potential applications in batteries, fuel cells, catalysts, gas sensors, chemical sensors, among others. This work presents the results obtained to obtain LaCoO3 from the thermal decomposition of cobalt and lanthanum 8-hydroxyquinolinates obtained by the coprecipitation method, at final pH of 5 and 9, and in acetone or acetic acid medium. The complexes were characterized by X-ray diffraction (XRD), Infrared Region Absorption Spectroscopy (FTIR), Atomic Absorption (AAS), Elemental Analysis (AE) and Scanning Electron Microscopy (SEM). The thermogravimetric analysis (TGA), Derived Thermogravimetry (DTG) and Differential Thermal Analysis (DTA) in different heating and atmosphere ratios up to 800 ºC were performed. The oxides obtained by thermal decomposition were characterized by XRD, FTIR and ASA. By studying the thermal behavior, it was observed that the samples presented three stages of thermal decomposition under a synthetic air atmosphere and five steps under N2 atmosphere, it was still possible to observe that the percentage of final residue for pH 9 was higher than the final residue at pH 5, but the final decomposition temperatures were lower in pH 5. Results showed higher efficiency of the process of obtaining LaCoO3 for pH 9 in both reaction media, characterized by XRD, with an average yield of 93%.

De nombreux alliages de structure doivent leurs propriétés mécaniques à la présence de précipités inter ou intragranulaires. Ainsi les superalliages à base nickel, de matrice austénique γ, sont souvent renforcés par des précipités de phases intermétalliques ordonnées. Au sein de l’alliage Inconel 718, outre la phase γ’ de structure L12 (cubique simple), on trouve des précipités de Ni3Nb sous la forme métastable γ" (D022 - tétragonal centré) ou sous la forme stable δ (D0a - orthorhombique). Le rôle des précipités γ’, γ" et δ sur les propriétés macroscopiques de l'alliage est connu et largement utilisé en contexte industriel. Cependant les mécanismes de précipitation et de transformation de ces précipités ne sont toujours pas complètement élucidés, ce qui a motivé ce travail. La microstructure de l’alliage a été caractérisée par microscopie optique (MO) et électronique (à balayage et en transmission ; MEB et MET) dans l’état de livraison et après des traitements thermiques isothermes et anisothermes. Les essais d’analyse thermique différentielle (ATD) nous ont permis de préciser les domaines de température de précipitation et de dissolution des différentes phases présentes (γ’, γ" et δ). Différents états de précipitation ont été obtenus à l’aide de traitements thermiques isothermes basés sur les diagrammes temps-températuretransformation (T.T.T.) disponibles dans la littérature. Les observations en MET « à haute résolution » des précipités des phases δ et γ’’ ont permis de caractériser certains des défauts structuraux présents dans ces précipités. Nous montrons ainsi que les défauts d’empilement au sein de la phase γ’’ peuvent servir de germes pour la précipitation de . Alors que la structure des interfaces δ/γ ainsi que les défauts d’orientation au sein des lamelles de δ suggèrent que la croissance de la phase δ a lieu directement à partir de la matrice
Many structural alloys are strengthened by the presence of precipitates in the grains or at grain boundaries. Nickel based superalloys often present an austenitic γ matrix in which ordered intermetallic phases precipitate. In the alloy Inconel 718, one can find γ’ L12 cubic ordered precipitates together with the compound Ni3Nb in its metastable form γ" (D022 - tetragonal) or the stable phase δ (D0a - orthorhombic). The incidence of those precipitates on macroscopic properties of the alloy 718 is well known and widely used in industrial applications. However the mechanisms responsible for the precipitation and transformation of these phases are not fully understood, which motivated the present study. The alloy microstructure has been observed by optical microscopy (OM) and electron microscopy (scanning and transmission, SEM and TEM) in the as received state as well as after heat treatment (isothermal and anisothermal). Differential thermal analysis (DTA) was used to determine the precipitation and dissolution temperatures of the phases γ', γ" and δ. Various precipitation microstructures were obtained by heat treatments based on available TTT diagrams. Some of the structural defects present in γ" and δ precipitates have been characterised by lattice imaging TEM observations. It is shown that stacking faults in γ’’ phase can act as a seed for the germination of . The structure of the δ/γ interface and the orientation defects in δ lamellae suggest that the growth of δ phase occurs directly from the matrix (and not by transformation of the γ’’ phase)

Ce travail présente les résultats d'un modèle théorique de précipitation de particules Al$_2$Cu dans un alliage d'aluminium de fonderie de type 319 traité thermiquement T7, prenant en compte les équations de la théorie de la coalescence. L'utilisation d'une distribution de taille de particules expérimentale discrétisée comme point de départ du modèle rend possible l'utilisation d'une équation de flux afin de modéliser l'évolution du rayon moyen des particules dans un élément de volume représentatif de l'alliage. L'utilisation d'un schéma numérique implicite permet de ramener la résolution du problème physique à l'inversion d'une matrice tridiagonale. Ainsi, l'évolution du rayon critique de coalescence, du nombre total et de la fraction volumique de précipités sont obtenus pour plusieurs vieillissements. Les résultats du modèle a été confrontés aux résultats des mesures expérimentales qui ont été réalisées à l'aide d'observations en microscopie électronique à transmission et qui ont permis une mesure de la taille des précipités. Ces derniers ont été assimilés à des sphères de volume équivalent aux plaquettes réelles et ont été analysés numériquement. Les résultats fournis par le modèle théorique sont en bon accord avec les mesures expérimentales et ont permis le couplage du modèle de coalescence avec un modèle micromécanique fondé sur la théorie des dislocations et calibré à l'aide d'essais de traction en température. Il permet de déterminer la limite d'élasticité de l'alliage pour un vieillissement jusqu'à 1000h compris entre 23°C et 300°C. La limite d'élasticité est alors assimilée à une somme de trois contraintes~: une contrainte liée à la friction de réseau (contrainte de Peierls), une contrainte liée au contournement des précipités par les dislocations (contrainte d'Orowan) et une contrainte liée à la présence de solution solide. Enfin, des essais de fatigue oligocyclique à différentes températures ont permis de déterminer les variables internes de la loi de comportement macroscopique. Il s'agit d'une loi élasto-viscoplastique de type Lemaitre et Chaboche, à laquelle la limite d'élasticité calculée par le modèle micromécanique est couplée. Ainsi, le comportement physique macroscopique de l'alliage est fonction de la coalescence des précipités. Des calculs 1D ou 3D, par éléments finis, permettent alors de déterminer le comportement général d'une culasse soumise à de la fatigue thermomécanique
This work highlights the results of a theoretical Al$_2$Cu particles coarsening model in a T7 thermal treated 319 aluminum alloy. As an input of the model, the experimental and discretised size distribution of the precipitates, in a 1$mu$m$^3$ representative volume element of the alloy, is used and coupled to a flux equation. The use of a numerical implicit scheme allows us to solve the problem by the inversion of a tridiagonal matrix. Thus, the evolution of the critical radius of coarsening, of the total number and of the volumical fraction of particles are modeled in a range of temperature going from 23°C to 300°C up to 1000h ageing time. Results were then compared to transmission electron microscope observations and are in good agreement with experimental measurements. Hence, the model was then coupled to a micro-mechanical model which is based on the theory of dislocations. It determines the real yield stress of the alloy generated by the interaction of the dislocations with the lattice (Peierls stress), with the precipitates (Orowan stress) and with the atoms in solid solution. Both models were then combined into a mechanical macro-scale model in order to represent the LCF behavior of the material. An elasto-viscoplastic law has been used and all the internal variables were experimentally determined using LCF stress/strain loops for the mechanical steady state. The simulation results are in good agreement with the experiments. Finally, 1D and 3D finite element computations could be run, taking into account the evolution of the microstructure during ageing and its impact on the evolution of the mechanical properties, to determine the head cylinder behavior under thermomechanical fatigue

L’ingestion de sables et de cendres volcaniques par les moteurs d’avion conduit à la formation de dépôts silicatés (CMAS) qui s’infiltrent dans la porosité du revêtement barrière thermique (BT) en zircone yttriée des aubes de turbine. De nouvelles compositions de BT issues du système ZrO2-RE2O3 (RE = La-Lu) sont donc envisagées. En effet, leur réactivité chimique au contact des CMAS peut conduire à la formation de phases cristallisées, notamment la phase apatite Ca2RE8(SiO4)6O2, qui bloquent l’infiltration du CMAS. Cependant, divers silicates du système CaO-RE2O3-SiO2 sont susceptibles d’entrer en compétition avec sa formation et de plus, la composition du CMAS varie selon les régions survolées. L’objectif de ces travaux de thèse est de déterminer l’influence de la composition du CMAS et de la terre rare sur les mécanismes réactionnels de dissolution et de précipitation. Divers oxydes RE2O3 à basicité croissante (RE = Yb, Dy, Gd, Sm et Nd) et un CMAS de composition simplifiée du système CaO-Al2O3-SiO2 (CAS) ont été choisis. Des teneurs fixes en MgO et Fe2O3 ont été ensuite ajoutées au CAS en faisant varier le rapport CaO/SiO2 entre 0,4 et 1,6. Les phases apatite et cyclosilicate Ca3RE2(Si3O9)2 ont également été synthétisées afin d’étudier leur dissolution. Il est montré que le mécanisme de dissolution des RE2O3 est indirect, les équilibres locaux établis avec cet oxyde imposant systématiquement la formation de la phase apatite. Sa cristallisation est favorisée par un rayon cationique RE3+ proche de celui de Ca2+. Lorsque l’écart est important, la nucléation de la phase cyclosilicate est rapidement observée dans le CAS avec une répartition préférentielle de ces cations RE3+ dans les sites de coordinence 6. La solubilité en RE dans le liquide silicaté augmente avec la basicité de l’oxyde RE2O3 et en présence de MgO et Fe2O3. La variation de composition du CMAS modifie la nature des phases à l’équilibre. Leurs limites de solubilité en RE sont inférieures à celles de la phase apatite, ce qui réduit d’autant leur vitesse de redissolution dans le liquide silicaté
Fine particles of sand, dust or volcanic ashes ingested by aircraft engines are well-known to damage Thermal Barrier Coatings (TBC) when they infiltrate their porous microstructure as molten silicate (CMAS). They are mainly constituted of CaO-MgO-Al2O3-SiO2 in variable proportions and also contain metallic oxides. RE2Zr2O7 compositions are TBC candidate materials as they have shown efficiency to mitigate CMAS infiltration due to their reactivity with synthetic CMAS. Indeed, the dissolution reaction leads to rapid sealing of the topcoat porosity mainly due to the formation of crystalline Ca2Gd8(SiO4)6O2 apatite. However, many rare-earth silicates are likely to compete with apatite crystallization and little is known on reaction kinetics and thermodynamics involving RE2O3 and multi-component CMAS system. This work aims to determine the influence of CMAS and rare earth composition on dissolution and precipitation mechanisms. A simplified CAS was first selected with eutectic (1170°C), 65SiO2-26CaO-9Al2O3 (mol. %) composition. Dissolution of various RE2O3 with increasing basicity (RE = Yb, Dy, Gd, Sm and Nd) as well as synthetic apatite and cyclosilicate Ca3RE2(Si3O9)2 phases was then performed at 1200°C in CAS-melt. Finally, fixed MgO and Fe2O3 contents were added to CAS melt with an increasing CaO/SiO2 ratio. The results showed that RE2O3 dissolution mechanism is indirect. Apatite formation results from local equilibrium at the interface with solid RE2O3 whatever the rare earth and CMAS composition. Its crystallization is favored when Ca2+ and RE3+ ionic radii are close as they are both distributed within 9-fold coordination sites. Conversely, Ca and RE mismatch leads to rapid nucleation of cyclosilicate phase in CAS as they are preferentially distributed within a 6-fold coordination site. MgO and Fe2O3 addition in CAS as well as RE2O3 basicity tend to increase RE solubility in silicate melt. Phases in thermodynamic equilibrium strongly depend on CMAS composition but generally exhibits lower RE solubility and dissolution rate in melt than apatite

CAPES
Os materiais cerâmicos são amplamente estudados devido às suas diversas aplicações. Com isso, o objetivo deste trabalho consistiu na obtenção de Óxido de Cério (IV) via decomposição térmica do 8-Hidroxiquinolinato de Cério, sintetizado pelo método de precipitação, em pH’s finais 5 e 9, e caracterizado pelas técnicas de Espectroscopia Vibracional de Absorção no Infravermelho com Transformada de Fourier (FTIV), Difratometria de raios X (DRX) e Microscopia Eletrônica de Varredura (MEV). Realizou-se o estudo do comportamento térmico dos complexos sintetizados, utilizando-se, para este fim, as técnicas de Termogravimetria (TGA) e Análise Térmica Diferencial (DTA). Com base no estudo térmico, definiu-se que as amostras de complexo seriam calcinadas em três razões de aquecimento, sendo elas 5, 10 e 20 °C min-1 com temperatura final de 800 °C. Os óxidos obtidos, a partir da calcinação em mufla, foram caracterizados por DRX e MEV. A caracterização dos complexos e os estudos térmicos realizados, mostraram que houve coprecipitação de 8-Hidroxiquinolina nas amostras e que a diferença de pH interferiu na quantidade de coprecipitado. Apesar disso, foi possível identificar a formação do Óxido de Cério (IV), tanto para as amostras obtidas em pH final 5 quanto para as obtidas em pH final 9. Os resultados de DRX para os óxidos mostram que as amostras possuem elevada cristalinidade e, a partir da equação de Scherrer, encontrou-se cristalitos com tamanhos aproximados entre 12,1 e 25,3 nm. Por fim, a MEV, indicou que as partículas possivelmente sofreram processo de sinterização. Desta forma, a obtenção de Óxido de Cério (IV) a partir da decomposição térmica do 8-Hidroxiquinolinato de Cério provou ser eficiente.
Ceramic materials are widely studied due to their many applications. The objective of this work was to obtain Cerium (IV) Oxide by thermal decomposition of 8-Hydroxyquinolinato of Cerium, synthesized by the precipitation method, at final pH 5 and 9, and characterized by the techniques of Fourier Transform Infrared Spectroscopy (FTIR), X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). To study the thermal behavior of the synthesized complexes Thermogravimetric Analysis (TGA) and Differential Thermal Analysis (DTA) techniques were used. Based on the thermal study, it was defined that the complex samples would be calcined in three heating ratios, being 5, 10 and 20 ° C min-1 with final temperature of 800 ° C. The oxides obtained by calcination were characterized by XRD and SEM. The characterization of the complexes and the thermal studies showed that there was co-precipitation of 8-Hydroxyquinoline in the samples and that the pH difference interfered with the coprecipitate amount. Besides, it was possible to notice the obtaining of Cerium (IV) Oxide for both samples, with final pH 5 and those obtained in final pH 9. The oxides XRD results presented high crystallinity and, from the Scherrer equation, crystallites with sizes between 12.1 and 25.3 nm were found. Finally, the SEM indicated that the particles probably underwent a sintering process. Then, the Cerium (IV) Oxide obtaining by the precipitation method proved to be efficient.

Les nano-composés de type Sn1-xTaxO2 (0 ≤ x ≤ 0,03) ont été étudiés en vue de leurs propriétés thermoélectriques. Une méthode de co-précipitation a été utilisée pour synthétiser des nano-poudres ayant une taille des grains moyenne d’environ 3 nm. L’étude structurale et microstructurale a suggéré une limite de solubilité pour le Ta de 0,008 ≤ x < 0,010. Ces nano-poudres ont été ensuite densifiées par Spark Plasma Sintering, avec des compacités atteignant ~ 95%. Le dopage en Ta a permis une amélioration des propriétés thermoélectriques du SnO2 et, en accord avec la limite de solubilité, une valeur maximale du facteur de mérite de 4,7x10-5 K-1 a été observée pour l’échantillon x = 0,008. De plus, nous avons démontré qu’une diminution de la taille des grains permettait d’améliorer le coefficient Seebeck, de diminuer la conductivité thermique, mais conduisait à une diminution de la conductivité électrique. La stabilité des oxydes, notamment à l'échelle nanométrique, est remise en question par des caractérisations physico-chimiques. Partant de ces matériaux à base de SnO2, un nano-composite (ZnO-SnO2) a été étudié. Le composé Zn1-xGdxO (0 ≤ x ≤ 0,03) a été préparé par la méthode de Péchini et caractérisé en comparant avec d’autres matériaux à base de ZnO. Un premier test de nano-composite M30 (30% en masse Sn0.996Ta0.004O2 et 70% en masse Zn0.997Gd0.003O) a été mené. Le résultat obtenu a montré qu’une concentration de nano-inclusion Sn0.996Ta0.004O2 de 30 % ne permettait pas d’améliorer les propriétés thermoélectriques du nano-composite M30, par rapport aux matériaux de départ
The nano-compound Sn1-xTaxO2 (0 ≤ x ≤ 0.03) was studied with a view to their thermoelectric properties. A method of co-precipitation was used to synthesize nano-powders having an average grain size of about 3 nm. The structural and microstructural study suggested a solid solubility limit of 0.008 ≤ x < 0.010. These nano-powders were then densified by Spark Plasma Sintering, with density reaching ~ 95%. The doping of Ta improved the thermoelectric properties, and in good agreement with the solubility limit, a maximum value of the factor of merit of 4.7x10-5 K-1 was observed for the sample x = 0.008. The stability of oxides, particularly at the nanoscale, is questioned by physicochemical characterizations. From these SnO2-based materials, a nano-composite (ZnO-SnO2) was studied. The compound Zn1-xGdxO (0 ≤ x ≤ 0.03) was prepared by the method of Pechini and characterized by comparing with other ZnO-based materials. A first test of nano-composite M30 (30 wt% Sn0.996Ta0.004O2 and 70 wt% Zn0.997Gd0.003O) was conducted. The result showed that a concentration of 30% nano-inclusion Sn0.996Ta0.004O2 did not allow to improve the thermoelectric properties of nano-composite M30, compared to the starting materials

Il existe actuellement une dynamique de développement d’aciers à très haute résistance, destinés à l’industrie automobile, et présentant des propriétés de formabilité améliorées. Ces travaux font partie d'un projet de recherche qui vise à produire des aciers à phase complexe (CP) par laminage à chaud, en recherchant une combinaison améliorée de résistance et d’aptitude à l’étirement des bordures. Ainsi, ces travaux ont porté sur la description et la compréhension des évolutions de la microstructure au cours des différentes étapes du laminage à chaud d’aciers microalliés à faible teneur en carbone. Dans un premier temps, l’évolution de l’état de précipitation et de la taille des grains austénitiques au cours du réchauffage des brames ont été étudiés. Un modèle de précipitation a été développé et couplé à un modèle de croissance de grain simple basé sur l'épinglage Zener pour décrire les évolutions de la microstructure qui se produisent pendant le réchauffage. Ensuite, les évolutions microstructurales prenant places après la déformation à chaud lors du laminage ont été analysées. Les cinétiques de recristallisation de l'austénite et de la précipitation induite par déformation ont été étudiées par des essais de relaxation de contraintes couplées à observations directes de la microstructure. Des modèles ont également été développés pour décrire ces évolutions microstructurales. Un dernier chapitre a été consacré à l'établissement des relations entre les paramètres de laminage à chaud, les microstructures et les propriétés mécaniques obtenues. Les transformations de phase au cours de refroidissements continus ont été établis, en prenant en compte l’effet de la déformation de l’austénite. Ensuite, six procédés différents de laminage à chaud différents ont été appliqués et les microstructures et propriétés mécaniques résultantes ont été caractérisées de manière détaillée. Ce travail de thèse a permis de mieux comprendre les évolutions de la microstructure se produisant lors du laminage à chaud, ainsi que les microstructures et les propriétés mécaniques qui en résultent. Les travaux de modélisation présentés pourraient s’étendre à l’étude d’autres alliages. Plusieurs stratégies visant à améliorer la combinaison de résistance et d’aptitude à l’étirement des bordures ont été proposées
There are nowadays major driving forces for the development of Advanced High Strength steels presenting enhanced formability properties for automotive applications. This PhD-work is part of a research project that aims at producing complex phase (CP) steels by hot rolling, seeking for an enhanced combination of strength and stretch flangeability. Thus, this PhD-work focused on the description and the understanding of the microstructural evolutions during the various steps of the hot rolling process of low carbon microalloyed steels. First, the evolution of the precipitation state and austenite grain sizes during the reheating stage of hot rolling were studied. A precipitation model was developed and coupled to a simple grain growth model based on Zener pinning to describe microstructural evolutions that occurs during reheating. Then, the microstructural evolutions occurring after the hot rolling deformation passes were analyzed. The kinetics of austenite recrystallization and strain-induced precipitation were determined by stress relaxation and direct microstructural observations. Models were also developed for describing these microstructural evolutions. A final chapter focused on establishing the relationships between the hot rolling parameters, the microstructures, and the mechanical properties obtained. The phase transformation during continuous cooling was established, including the effect of austenite deformation. Then, six different hot rolling processes were applied, and the resulting microstructures and mechanical properties were extensively characterized. This PhD-work provided a better understanding of the microstructural evolutions taking place during hot rolling and of the resulting microstructures and mechanical properties. The modeling work presented could extended to the study of other alloys. Several strategies for improving the combination of strength and stretch flangeability were proposed

Les aciers appelés ODS (pour Oxide Dispersion Strengthened), renforcés par une dispersion homogène de nano-oxydes, sont des matériaux de structure avancés pour les futurs réacteurs nucléaires de fusion et de fission. En effet ces nano-oxydes, à base d’Y et Ti, servent comme centres de recombinaison de défauts ponctuels et d'obstacles aux mouvements des dislocations, améliorant de ce fait leur résistance aux radiations et aux températures élevées. La fabrication conventionnelle des aciers ODS est réalisée par broyage mécanique suivi de traitements thermo-mécaniques, et ne permet pas facilement de comprendre les mécanismes physiques conduisant à la précipitation des nano-oxydes, ce qui serait potentiellement utile pour optimiser leur production. La cinétique de formation de ces nano-oxydes peut être étudiée en utilisant une technique alternative, à savoir la synthèse par faisceaux d’ions, qui présente de nombreux avantages, notamment le contrôle précis des paramètres expérimentaux et la possibilité de décorréler divers facteurs contribuant à la cinétique de précipitation. Au cours de cette thèse, cette technique a été utilisée pour étudier la coprécipitation d'ions métalliques (Y et/ou Ti) et d'oxygène implantés dans un alliage modèle Fe-Cr de composition proche de celle typique des aciers ODS commerciaux. Des ions de Y, Ti et O à basse énergie ont été implantés dans des échantillons d'alliage Fe10wt%Cr de haute pureté à température ambiante. Les échantillons implantés ont ensuite été recuits à diverses températures entre 600 à 1100°C pour favoriser la précipitation de nano-oxydes, conformément au principe de cette technique. La microscopie électronique à transmission a été utilisée pour caractériser la structure cristallographique et la composition chimique des nano-oxydes formés lors de trois séries d'expériences. Tout d'abord, l'implantation séquentielle d'ions Ti et O a été mise en œuvre. Un recuit ultérieur a révélé qu’il n’y avait pas de précipitation d'oxyde de titane jusqu’à des températures inférieures à 1000°C, mais la présence de nano-oxydes riches en chrome avec une structure hexagonale de type corundum, qui contiennent une certaine quantité de Ti à des températures suffisamment élevées. Ce n’est qu’après le recuit à 1100°C que des nano-oxydes d’un autre type à cœur enrichi en Ti et coquille enrichie en Cr ont également été observés. Deuxièmement, l'implantation séquentielle d’ions Y et O a entraîné la formation à 800°C de nano-oxydes probablement riches en yttrium. Le recuit à 1100°C a favorisé la croissance des particules identifiées comme étant des nano-oxydes d’yttrium avec une coquille enrichie en Cr. Enfin, une implantation ionique séquentielle de deux ions métalliques (Y et Ti) a été réalisée, suivie d'une implantation d’O. L'ordre d'implantation des ions métalliques s'est révélé crucial pour la précipitation de nano-oxydes lors du recuit ultérieur. Lors de la séquence avec une implantation de Ti en premier, une précipitation d'oxyde riche en chrome de structure corundum hexagonale a été observée, très similaire au cas de l'implantation d’ions Ti et O. En revanche, la séquence avec une implantation d’ions Y en premier a produit des nano-oxydes d'yttrium-titane qui possèdent une structure non identifiable. En résumé, l’étude a démontré la faisabilité de la formation de nano-oxydes de Y, Ti et (Y, Ti) par implantation ionique. La thèse présente la caractérisation détaillée de ces nano-oxydes, ainsi que certaines de leurs caractéristiques spécifiques, telles que la présence de relations d'orientation entre les nano-oxydes et la matrice FeCr, qui ont été observées même dans le cas de nano-oxydes de type corundum riches en Cr. Enfin, les résultats obtenus, combinées avec les données de la littérature, sont discutées pour une meilleure compréhension des mécanismes impliqués dans la formation des nano-oxydes dans les aciers ODS
Oxide Dispersion Strengthened (ODS) steels, that is steels reinforced with a homogeneous distribution of (Y,Ti) oxide nano-particles, are advanced structural materials for nuclear applications. The oxide particles serve as point defect recombination centres and obstacles to dislocation motion thereby improving radiation resistance and high-temperature strength of these steels making them perfect candidate materials for future fusion and fission nuclear reactors. The conventional fabrication of ODS steels is achieved by mechanical alloying followed by thermomechanical heat treatments. This way of ODS steel production seems complicated to understand the physical mechanisms leading to the precipitation of nano-oxide particles. The kinetics of nanoparticle formation can be much better studied using an alternative technique of nanoparticle growth, namely Ion Beam Synthesis (IBS). This approach has many advantages including the precise control of experimental parameters and the ability to de-correlate various factors contributing to precipitation kinetics. A better knowledge gained in this way would be potentially helpful for optimization of ODS steel production routines. In the course of this PhD study, the IBS approach was applied to investigate the co-precipitation of metal (Y and/or Ti) and oxygen ions implanted into a model Fe-Cr alloy with the composition close to those typical for commercial ODS steels. Following the standard IBS schedule, consisting of ion implantation followed by high-temperature heat treatment, ions of Y, Ti and O at low energies were implanted into high-purity Fe10wt%Cr alloy samples at room temperature. The implanted samples were then annealed at various temperatures ranging from 600 to 1100°C to promote the precipitation of nano-oxide particles. A range of Transmission Electron Microscopy techniques were used to characterize the crystallographic structure and chemical composition of the nanoparticles. The study has been performed following three sets of experiments. First of all, the sequential implantation of Ti and O ions was implemented. Subsequent annealing at temperatures below 1000°C revealed that precipitation of titanium oxide was suppressed. Instead, chromium-rich nano-oxide particles with corundum hexagonal structure were found to precipitate. At sufficiently high temperatures these corundum particles were found to contain certain amount of Ti. Only after annealing at the highest temperature of 1100°C, particles of another type with Ti enriched core and Cr enriched shell were additionally fixed. Secondly, sequential Y and O ion implantation resulted in the formation of probable yttrium-rich oxides at 800°C. Annealing at 1100°C promoted their growth to larger sized yttria (Y₂O₃) particles with a Cr enriched shell. Finally, sequential ion implantation of both metal ions (Y and Ti) was performed, followed by O implantation. The order of metal ion implantation has been found to be crucial for subsequent oxide precipitation at the annealing stage. With the Ti implantation first in the sequence, the precipitation of corundum hexagonal chromium-rich oxide was observed, very similar to the case of Ti and O implantation. In contrast, implantation starting with Y produced yttrium-titanium oxide particles with unidentifiable structure. Summing up, the study has demonstrated the feasibility of the formation of Y, Ti and (Y,Ti) oxides by ion implantation. The thesis presents the detailed characterization of the nanoparticles, as well as the discovered specific features of precipitated particles, such as the presence of orientation relationships between the particles and the FeCr matrix, which was observed even for the case of Cr-rich corundum particles. Finally, the implications of the obtained results, in conjunction with the already known data from the existing literature, for the better understanding of the mechanisms involved in the formation of nano-oxide particles in ODS steels are discussed

碩士
國立臺灣大學
材料科學與工程學研究所
96
Nickel-based superalloy Inconel 718 is largely used due to its good mechanical properties and good corrosion resistance. For gas turbine engine disks and shafts, fatigue resistance, particularly low cycle fatigue resistance, may in fact be the limiting factor in the establishment of the useful operating lives of such components. Ultra fine grain 718 has been developed for this application. Overaged δ phase which are stable above recrystallization temperature used as pinning phase during recrystallization. Studying on δ phase and choosing good parameter for thermal mechanical process are important for grain refining Inconel 718. The research work used optical microscopy and transmission electron microscopy to observe the precipitation and crystallography of δ phase precipitated during high temperature aging in Inconel 718. The orientation relationship between matrix (γ) and δ phase was determined by several diffraction patterns. TEM images shows that the growth of needle-shaped or plate δ phase was connected by periods of small part δ phase. δ. Some TEM observation shows that γ” crystal structure existed inside the needle-shape precipitation. The precipitation and growth of overaged δ phase associated with metastable γ” phase. Thermal process results shows Inconel 718 aged at 900˚C precipitate larger amount of δ phase than other aging temperature. Select two thermal process precipitating δ phase for thermal mechanical process. The results was that after 60% compression the δ phase broken as globular shape and has uniform distribution. The compression at 1100˚C has apparent recrystallization and all δ phase been solid solute; compression at 1025˚C shows some recrystallization and almost all δ phase been solid solute. At 900˚C no recrystallization occurs and δ phase conserve during compression. The work results providing the good thermal mechanical process temperature for ultra fine grain 718 was 980~990˚C. 60% compression for uniform distribution and globular δphase.

碩士
國立臺灣海洋大學
機械與機電工程學系
107
After cold-rolled (CR) deformation, super duplex stainless steel (DSS) was annealed at 1100 °C for a two-phase solid–solution region. Preferred orientations in δ and γ phases changed to (111)δ, (100)δ, and (101)γ from the rough random orientation of as-received super DSS. The kernel average misorientation (KAM) angle was less than 5° implying the grain boundary strain shifted to a higher value after cold rolling, which was consistent with the X-ray diffraction (XRD) microstrain results. After annealing, the misoriented angle was restored to a low angle of approximately 0.5°, which implied the elimination of grain boundary strain when the annealing time increased from 15 to 30 min. The calculated microstrain based on XRD peaks demonstrated that the γ phase deformed before the δ phase at 50% CR. The recrystallized δ grains with slow growth and high staking fault energy (SFE) mainly showed recovery and a wide distribution of high angle grain boundary (HAGB) in the range between 15°–58°, whereas the recrystallized γ grains with low SFE exhibited rapid recrystallization; the majority of HAGB angles were greater than 50°, because of depletion of the stored strain energy. This recrystallized austenite adhered to the Kurdjumov–Sachs relationship with ferrite. The effect of thermal cycling on duplex stainless steel was studied to understand its phase transformation comprehensively. Cyclic thermal processing is a nonisothermal heat treatment method known to accelerate the kinetics of phase transformation. In this study, when the number of thermal cycles increased, the ferrite grains gradually contracted from the grain boundaries and finally disappeared due to the eutectoid reaction. However, the austenite phase demonstrated a parabolic increase and the intermetallic sigma (σ) phase, formed at the grain boundaries, exhibited a similar trend. The calculated thermal stress of 422 MPa assisted the σ formation by reducing the activation energy and accelerating the alloying element diffusion. The σ phase formation caused by thermal cycling increased the yield strength and ultimate strength but degraded ductility. The formation of tensile cracks was related to the σ phase at the interface or the σ matrix.

abstract: Increasing demand for high strength powder metallurgy (PM) steels has resulted in the development of dual phase PM steels. In this work, the effects of thermal aging on the microstructure and mechanical behavior of dual phase precipitation hardened powder metallurgy (PM) stainless steels of varying ferrite-martensite content were examined. Quantitative analyses of the inherent porosity and phase fractions were conducted on the steels and no significant differences were noted with respect to aging temperature. Tensile strength, yield strength, and elongation to fracture all increased with increasing aging temperature reaching maxima at 538oC in most cases. Increased strength and decreased ductility were observed in steels of higher martensite content. Nanoindentation of the individual microconstituents was employed to obtain a fundamental understanding of the strengthening contributions. Both the ferrite and martensite hardness values increased with aging temperature and exhibited similar maxima to the bulk tensile properties. Due to the complex non-uniform stresses and strains associated with conventional nanoindentation, micropillar compression has become an attractive method to probe local mechanical behavior while limiting strain gradients and contributions from surrounding features. In this study, micropillars of ferrite and martensite were fabricated by focused ion beam (FIB) milling of dual phase precipitation hardened powder metallurgy (PM) stainless steels. Compression testing was conducted using a nanoindenter equipped with a flat punch indenter. The stress-strain curves of the individual microconstituents were calculated from the load-displacement curves less the extraneous displacements of the system. Using a rule of mixtures approach in conjunction with porosity corrections, the mechanical properties of ferrite and martensite were combined for comparison to tensile tests of the bulk material, and reasonable agreement was found for the ultimate tensile strength. Micropillar compression experiments of both as sintered and thermally aged material allowed for investigation of the effect of thermal aging.
Dissertation/Thesis
M.S. Materials Science and Engineering 2011

Indiana University-Purdue University Indianapolis (IUPUI)
Heat is one of the most important factors in our atmosphere for precipitation (thunderstorm) formation. Thermal energy from local urban land-cover is also a common source of heat in the lower atmosphere. This phenomenon is known as the urban heat island effect (UHI) and is identified as a substantial cause to a changing climate in surface weather modification. The proceeding study investigates this connection between the UHI and surface weather using remote sensing platforms A ten-year analysis of the Indianapolis UHI and thunderstorms were studied from the summer months of May, June, July, August and September (MJJAS) from 2002 until 2011. LANDSAT space borne satellite technology and land-surface based weather radar technology was used in this analysis for thunderstorm investigation. Precipitation areas identified from land-based NEXRAD WSR-88D technology were used to identify convection from non-synoptic forcing and non-normal surface diurnal heating scenarios. Only convection appearing from the UHI were studied and analyzed. Results showed twenty-one events over eighteen days with the year 2005 and 2011 having the largest frequency of events. The month of August had the largest concentration with seven events during the late afternoon hours. UHI results showed July had the largest heat island magnitude with April and September having the lowest magnitude in UHI temperatures. Three events of the twenty-one storm paths did not had a significant mean temperature difference in the heat island below the storm reflectivity. The nineteen storm paths that were significant had a warmer area underneath storm path development by an average 6.2°C than surrounding areas. UHI initiation points showed twelve of the twenty-one events having statistically significant differences between 2 km initiation areas and the rest of the study areas. Land-cover results showed low intensity developed areas had the most land-cover type (48%) in the 2km initiation buffer regions.