Uranium (U) is a crucial contaminant in the Hanford Site. Remediation techniques to prevent contaminant migration of U located in the soils to other important water resources such as the Columbia River are of paramount importance. Given the location of the contaminant in the deep vadose zone, sequestration of U caused by ammonia (NH3) gas injections appears to be a feasible method to decrease U mobility in the contaminated subsurface via pH manipulation, ultimately converting aqueous U mobile phases to lower solubility precipitates that are stable in the natural environment. This study evaluated the stability of those U-bearing precipitates via preparation of artificial precipitates mimicking those that would be created after NH3 gas injections and sequential extractions experiment. Results showed that most of the U was recovered with the extracting solutions targeted to remove uranyl silicates and hard-to-extract U phases, suggesting that U present in the solid particles has strong bonds to the vadose zone sediments, causing the precipitates to be stable and therefore the remediation technology to be effective under the simulated conditions.

Nowdays biofuels are becoming a good alternative for petroleum fuels due to environmental issues like high carbon dioxide emission and increasing vehicles population, together with the high price and fast depletion of petroleum oils. This project aims to investigate the corrosive effects of wood Pyrolysis oil on a special grade of nitrogen alloyed tooling steels to be used for injector nozzles in Diesel engines, where high stress and strain encounter high acidity and corrosivity of the Pyrolysis oil and cause breakdown over short periods. Vanax 35 and Vanax 75 manufactured in Uddeholm are two types of powder metallurgy high nitrogen alloyed martensitic stainless steel with a high combination of hardness (over 56HRC), low friction properties, wear resistance, anti-galling and corrosion properties. In this work, the newly developed Vanax material together with the tool steels Elmax and AISI O1 were tempered at various temperatures from 200°Cto 500°C. The tempered steels were then exposed in pyrolysis oil at 4 different temperatures, 20°C, 70°C, 95°Cand 130°C. The materials were investigated by means of corrosion rate measurements, microscopy (LOM, SEM, confocal) and Thermo-Calc calculations. The corrosion rate measurement proved that Vanax tempered at lower ranges (200°C, 400°Cand 450°C) showed the best corrosion resistance while higher tempering temperatures such as 500°C, Elmax and AISI O1 tempered at 200°Csuffered a great deal of general corrosion attack. Thermo-Calc calculations showed the formation of a hard phase, VN as primary nitrides instead of primary chromium carbides at austenizing temperature for the Vanax group. Higher amount of chromium is dissolved in solid solution in Vanax at austenizing temperature hence the martensite matrix has, after quenching, a higher chromium content that helps passivation. The loss in corrosion properties at higher tempering temperatures was due to the formation of CrN secondary phase at around 400˚C which reduces the chromium content of the martensite matrix. The results of light optical and confocal microscopy showed the presence of pits when tempering at 400˚C and 450˚C. No pits were observed at 200˚C. Elmax was not passivated at all which resulted in general corrosion attacks, due to a high chromium loss from the austenite solid solution at the austenizing procedure temperature and also the tempering temperatures. The chromium depletion from the austenite can be explained by a high carbon and a low nitrogen content in the composition which resulted in formation of a high amount of Cr7C3.

Understanding the precipitation reaction is very important since precipitation hardening is one of the most effective strengthening mechanisms in metallic alloys. In martensitic steels, a tempering heat treatment is often performed. During tempering various new phases are precipitated and the spatial and temporal evolution of these precipitates strongly influences the properties of the steel, such as strength/ductility, creep, fatigue and hot corrosion resistance. Therefore, the possibility of quantitative modelling of the precipitation process will provide many opportunities for advanced materials and process design and optimization as well as service life assessments. The Fe-C-Cr system forms the basis for tool steels and is consequently used in many applications such as e.g. metal forming operations. They are characterized by a high hardness and good toughness, even at elevated temperatures.In the present work, the as-quenched martensitic microstructures of four Fe-C-Cr alloys with varying Cr and C contents were characterized by Light Optical Microscopy (LOM) and Electron Microscopy. The effects of Cr and C on the morphology of martensite were investigated. It was found that Cr addition had a similar effect as C on the martensitic morphology and on the ratio of high-angle grain boundary (HAGB) to low-angle grain boundary (LAGB). However, the micro-hardness was unaffected by the Cr addition whilst it was strongly influenced by the C addition.In addition, a quantitative experimental characterization of the precipitates formed during tempering of the martensite was performed. The Langer-Schwartz theory combined with the Kampmann-Wagner-Numerical (KWN) method, as implemented in the software TC-PRISMA, was used to predict the precipitation of carbides after tempering in one of the model alloys: Fe-0.15C-4.0Cr (mass%). The microstructure characterization of the as-quenched material provided vital input parameters for the modelling work and a comparison was made between the modelling predictions and the experimental results. The effect of parameters such as dislocation density, grain size and interfacial energy on the precipitation of carbides was discussed. / <p>QC 20151105</p>

A novel process for low-temperature (LT) epitaxial growth of silicon carbide (SiC) by replacing the growth precursor propane with chloro-methane was recently developed at Mississippi State University. However, only limited information was available about the defects and impurity incorporation in the various types of epitaxial layers produced by this new method like blanket epitaxial layers, selectively grown epitaxial mesas, and highly doped epitaxial layers, prior to their comprehensive characterization in this work. Molten potassium hydroxide (KOH) etching, mechanical polishing and a variety of other characterizing techniques were used to delineate and identify the defects both in the epilayer and substrates. Under optimum growth conditions, the concentration of defects in the epitaxial layers was found to be less than that in the substrate, which established the good quality of the LT growth process. Defect concentrations, on selectively grown epitaxial layers, strongly depended on the crystallographic orientation of the mesa sidewall. The addition of HCl to the growth process, aimed at increasing the growth rate, caused a significant concentration of triangular defects (TDs) to be formed in the epitaxial layers. The TDs were traced down to the substrate by a combination of repeated polishing and molten KOH etching steps. The TDs were found not to originate from any substrate defects. Their origin was traced to polycrystalline silicon islands which form on the surface during growth and subsequently get evaporated away, which had made it impossible to detect them and suspect their influence on the TD generation prior to this work. The TDs were found to include single or multiple stacking faults bound by partial dislocations and, in some cases, inclusions of other SiC polytypes. Gradual degradation of the epitaxial morphology was found in heavily aluminum doped p+ layers, with an increase in the level of doping, followed by much steeper degradation when approaching the solubility limit of Al in 4H-SiC. Precipitates were the dominating defect at the highest levels of doping and were observed beyond a doping of 3.5x1020 cm-3. A dislocation generation model for heavily doped epitaxial layers was developed accounting for the stress in the lattice caused by Al doping.

No description available.

Landfill leachate is generated as a result of reactions between water percolating through the landfill and wastes. Under normal conditions leachate is found at the bottom of landfills and from there, its movement can be controlled with collection systems to be treated, discharged, or recirculated. Landfill leachate collection systems are positioned above the liner and are designed to collect liquid under gravitational flow for the entire active, closure, and post-closure periods. Clogging of any portion of the system can lead to higher hydraulic heads and increase the potential for leakage through the liner. To reduce the quantity of municipal solid wastes (MSW) requiring landfilling, many municipalities have adopted waste-to-energy (WTE) facilities that yield energy in the form of combustible gases and noncombustible residues. Disposal practices for WTE residuals include landfilling in monofills or co-disposal with MSW and other materials such as residues from water and wastewater treatment facilities. There has been concern about co-disposal practices, because the impacts on leachate quality and waste interactions are not well known yet. This research was conducted to evaluate clogging of leachate collection systems due to co-disposal of MSW and combustion residues from WTE facilities. The use of laboratory lysimeters in conjunction with batch tests to predict short-term and long-term leaching characteristics of noncombustible residues from WTE facilities was also evaluated. Laboratory lysimeters were used to simulate monofills (WTE residues and MSW) and co-disposal practices. Relationships between waste composition and leachate quality were evaluated over a seven month period.

Squeeze casting is the practise of solidifying metals under mechanically applied pressure via a slow displacement of a die volume. It has been shown that squeeze casting enhances the mechanical properties of cast metals. Research into other high integrity casting processes has shown that using techniques that enhance melt quality can further increase the mechanical properties. Therefore a bottom-tapped, bottom-fed squeeze casting machine was designed and built around a pre-existing squeeze casting die designed for uniaxial pressure application. This was used to obtain quantitative metallurgical and microstructural information on the squeeze castings produced, including the effects of common micro-alloying additions of strontium modifier and titanium modifier on the microstructure and hardness of a commercial aluminium silicon eutectic alloy. These were examined using a Taguchi design of experiments approach. It was found that squeeze casting reduced porosity and secondary dendrite arm spacing and increased hardness, and reduced or eliminated increases in porosity and secondary dendrite arm spacing associated with micro-alloying addition. The size of possibly deleterious iron-rich precipitates was reduced, and the morphology of such precipitates changed to a possibly less deleterious form without further alloy additions of manganese. It was also found that melt control and handling is essential for consistent quality of castings in the production of small volume squeeze castings, such as the ones produced in this experimental work.

Ce travail est une contribution à une étude de recherche et développent, proposée par Hydro Aluminium, dans le domaine des mécanismes d'endommagement de filières d'extrusion et. L'originalité du travail de thèse est basée sur le développement d'un alliage Inconel 718 optimisé pour l'application spécifique de filière d’extrusion, ce qui représente un saut technologique dans l'emploi de ce superalliage dans le domaine des outils. L'impact des paramètres du procédé d'extrusion, appelés paramètres extrinsèques, - tels que la vitesse d'extrusion, la longueur de billette, le chargement thermo-mécanique - sur le comportement mécanique du matériau a été analysé. Les cycles traction-compression sont simulés à l'aide d’essais isothermes de fatigue oligocyclique (LCF) qui donnent des informations sur les différents mécanismes d'endommagement survenant dans la filière. Du point de vue scientifique, la sollicitation de fatigue oligocyclique isotherme (LCF) est considérée comme la plus représentative des conditions thermomécaniques agissant sur l'outil. Les résultats montrent que la vitesse de déformation et de temps de maintien ont un impact significatif sur la durés de vie en fatigue. Le développent du matériau, enfin, a été atteint en modifiant les paramètres intrinsèques au matériau - tels que la taille des grains et la morphologie des précipités intermétalliques. Des traitements thermiques alternatifs, permettant d'adapter le matériau aux conditions spécifiques imposées par le procédé d'extrusion, ont été formulés. Des essais de fatigue LCF supplémentaires, ont permit de comparer la réponse cyclique de ces nouvelles nuances à celle du traitement original. Un de ces traitement, élaboré au travers d’une approche pluridisciplinaire incluant les aspects métallurgie, chimie et mécanique, a été retenu comme la nouvelle procédure standard pour le traitement des matrices d'extrusion en Inconel 718. / This present work is a contribution to an extensive development study, promoted by Hydro Aluminium, in the field of the damage mechanisms of extrusion dies. The originality of the present work is based on the development of an optimized Inconel 718 alloy as bulk material for extrusion die., which corresponds to a new application of this alloy in the field of tools: The investigation of the impact of the so called “Material Extrinsic Parameters”, such as extrusion speed, billet length and thermo-mechanical loading on the mechanical behaviour of the material is proposed. The cyclic tensile and compressive stresses, acting on the die, are simulated by isothermal Low Cycle Fatigue (LCF) tests. Results show that strain rate and holding time have a significant impact on fatigue life. These considerations represent the “Input Data” for the design of an optimized Inconel 718 in order to adapt the material to the specific conditions imposed by the extrusion process. This objective is achieved by modifying the “Material Intrinsic Parameters” such as grain size or precipitates morphology through the formulation of alternative thermal treatments. Additional LCF tests, are carried out to compare the cyclic response of the alternative Inconel 718 grades. One of this treatment, elaborated by a multidisciplinary approach including metallurgical, chemical and mechanical experiments that has been implemented in the industrial production practice as the new standard procedure for the thermal treatment of the Inconel 718 extrusion dies.

Orientadores: Paulo Roberto Mei, Marcelo Martins / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-10T20:59:53Z (GMT). No. of bitstreams: 1 Ritoni_Marcio_M.pdf: 22898482 bytes, checksum: cebeda09f860c091710fa40d369a641d (MD5) Previous issue date: 2007 / Resumo: O aço inoxidável superaustenítico ASTM A 744 Gr. CN3MN é aplicado na fabricação de equipamentos que trabalham em ambientes sob corrosão severa com solicitação mecânica. Neste trabalho investigou-se a influência dos tratamentos térmicos na microestrutura e propriedades desse tipo de material. Foram realizados tratamentos térmicos de solubilização na faixa de temperaturas entre 1100 e 1250 °C, alívio de tensões entre 500 e 800 °C e tratamentos de envelhecimento a 900 °C, variando-se o tempo em 1,5, 12, 24 e 48 horas. Realizaram-se também ensaios mecânicos (dureza e impacto). As análises microestruturais foram feitas por meio de microscopia ótica, eletrônica de varredura, eletrônica de transmissão e difração de raios-X. Concluiu-se que, para maximizar a resistência ao impacto, a solubilização deve ser feita a 1200 °C, que produz a menor fração volumétrica de precipitados. À medida que a temperatura de alívio de tensões aumenta de 500 para 800 °C, a energia absorvida no impacto reduz-se. Além do aumento na fração volumétrica de precipitados, nas temperaturas acima de 550 °C, observa-se precipitados nos contornos de grãos. Quanto maior a exposição do material à temperatura de 900 °C, menor é a energia absorvida no impacto. Com 1,5 horas a 900 °C o material apresentou redução na resistência ao impacto de 127,7 para 25,0 Joules. A dureza do material apresentou resultado inversamente proporcional à energia absorvida no impacto para todas as temperaturas de tratamento térmico. A amostra bruta de fundição apresentou fase sigma (s) na matriz austenítica. As amostras solubilizadas a 1200 e 1240 °C apresentaram fase sigma (s) e carboneto M6C. O tratamento térmico a 900 °C por 48 horas causou a precipitação de algumas fases na matriz austenítica sendo as mais prováveis: sigma (s), chi (c) e carboneto M23C6 / Abstract: ASTM A 744 Grade CN3MN super-austenitic stainless steel is employed in the manufacture of equipment working in severely corrosive environments under mechanical loads. In this work, an investigation was made of the influence of heat treatments on the microstructure and properties of this type of material. Solution heat treatments were carried out at temperatures ranging from 1100 to 1250 ºC, stress relief between 500 and 800 ºC and aging treatments at 900 ºC, for periods of time varying from 1,5, 12, 24 and 48 hours. Mechanical tests (hardness and impact) were also conducted. The microstructural analyses were carried out by X-ray diffraction, optical microscopy, and by scanning and transmission electron microscopy. It was concluded that, to maximize the material¿s impact strength, the solution heat treatment should be done at 1200 ºC, at which temperature the volumetric fraction of precipitates is lower than at other solution heat treatment temperatures. As the stress relief temperature rose from 500 to 800 ºC, the energy absorbed during impact diminishes. In addition to the increase in the volumetric fraction of precipitates at temperatures above 550 ºC, precipitates were visible at the grain boundaries. The longer the material was exposed to a temperature of 900 ºC the lower the energy absorbed during impact. After 1,5 hours at 900 ºC the material¿s impact strength dropped from 127,7 to 25,0 Joules. The steel¿s hardness was also inversely proportional to the energy absorbed during impact at all the heat treatment temperatures. The as-cast sample presented sigma (s) phase in the austenitic matrix. The samples solution heat treated at 1200 and 1240 ºC presented sigma (s) and M6C carbide phases. The heat treatment at 900 ºC for 48 hours caused precipitation of some phases in the austenitic matrix, the most probable of which were sigma (s), chi (c) and M23C6 carbide / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

Le tantale est un métal très dense (d = 16,6) et fond à très haute température (2996°C), ce qui en fait un matériau potentiellement utilisable pour des creusets utilisés en pyrochimie. La littérature montre qu'il est possible de renforcer encore ces propriétés anti-corrosion par un traitement de cémentation. En effet, la corrosion intergranulaire du tantale est stoppée par la présence de précipités de Ta2C aux joints de grains. L'obtention du Ta saturé carbone avec Ta2C aux joints de grains en surface (Ta(C) + Ta2C), très pauvre en carbone, demande une bonne compréhension et une maitrise de la cémentation du tantale.La réalisation d'un cycle de cémentation sur des échantillons de tantale provoque l'apparition à la surface du tantale d'une couche de TaC (en surface) et d'une couche de Ta2C sous jacente. Un travail sur la réduction du flux de carbone à la surface du tantale a permis d'étudier les premiers stades de formation des couches de carbures de tantale. Ces conditions particulières de cémentation favorisent la croissance en épitaxie des couches de carbures sur le substrat Ta. Les analyses EBSD ont permis de mettre en évidence les relations cristallographiques entre chaque phase.Lors d'un cycle de cémentation, la croissance des couches de carbures doit être contrôlée du fait que celles-ci soient très riches en carbone. Plusieurs types de paramètres peuvent influer sur la croissance des couches : les paramètres de cycles (temps et température de cémentation) et des paramètres extérieurs aux cycles de cémentation, tels que la surface des échantillons. L'influence de ces paramètres sur la cinétique de croissance des couches a été étudiée. En complément des essais, la simulation numérique avec le logiciel CASTEM© a été utilisée afin d'étudier la diffusion du carbone dans le tantale. Les données expérimentales permettent d’ajuster les variables du modèle comme le coefficient de diffusion du carbone dans le tantale.La réalisation d'un recuit sous vide après cémentation permet d'obtenir en surface des microstructures autres que le TaC. Le recuit fait diffuser le carbone contenu en surface vers le coeur du tantale. Une étude a permis de déterminer les paramètres du traitement de recuit, pour obtenir en surface, au choix : du TaC, ou du Ta2C, ou du Ta(C) + Ta2C. / Tantalum is a very dense metal (d = 16.6) and has a very high melting temperature of 2996°C. This material is particularly required for crucibles used for pyrochemical applications. Early studies show that a carburizing treatment enhances corrosion resistance from liquid metals. Indeed, the intergranular attack of tantalum is stopped by Ta2C precipitates, which occupy the grain boundary regions. The production of the carbon saturated tantalum with Ta2C precipitates requires a good understanding of tantalum carburizing.A carburizing treatment on tantalum sample causes the emergence of a TaC layer on surface and Ta2C layer just below. A reduction of carbon flow has enabled the study of the first steps of tantalum carbides formation. This specific condition of carburizing leads to an epitaxic growth of carbide layers on tantalum substrate. EBSD analysis highlights the crystallographic relations between each phase.Tantalum carbide layers are highly carbon concentrated. So the growth of carbide layers has to be controlled during the carburizing treatment. Several parameters may affect carbide layers growth : process parameters (time and temperature of carburizing treatment) and external parameters such as the reactive surface of the samples. The influence of these parameters on tantalum carbide growth kinetics has been studied. In addition, the diffusion of carbon in tantalum has been modeled with CASTEM© software. Experimental data are used to compute parameters of the model, such as carbon diffusion coefficient in tantalum.Other microstructures than TaC can be obtained on surface by applying an annealing treatment after carburizing. With this treatment, the carbon contained on surface diffuses to the bulk of the metal. Annealing treatment parameters have been determined to get on surface TaC, or Ta2C, or carbon saturated tantalum with Ta2C precipitates.