Dissertations / Theses on the topic 'Secondary precipitation'

Hot-work tool steels make up an important group of steels that are able to perform with good strength and toughness properties at elevated temperatures and stresses. They are able to gain this behavior through their alloy composition and heat treatment, which relies on the precipitation of alloy carbides to counter the loss in strength as the tempered material becomes more ductile. As demand grows for materials that are suitable for even harsher applications and that show improved mechanical qualities, the steel industry must continuously investigate the development of new steel grades. Within this context, the present work focuses on examining the mechanical properties and microstructure of two hot-work tool steels, of which one is a representative steel grade (Steel A) and the second a higher-alloyed variant (Steel B), at different tempering conditions. To complement the experimental work, precipitation simulations are used to monitor the progression of secondary carbide precipitation and to examine the predicted microstructural changes through varying the alloy composition. The study finds that Steel B does not actually have improved properties with respect to Steel A and suggests that the precipitation behavior of both steels is virtually identical. Despite this, the simulation work reveals that this behavior can change dramatically to favor more positive hardness contributions by increasing the alloy content of V. In short, with the project being part of an ongoing investigation, there remain several areas of analysis that need to be completed before offering a complete picture that can ultimately play a part in the development of a new hot-work tool steel grade.

CARDOSO, J. L. Evaluation of the precipitation of secondary phases on CO2 environment corrosion resistance of austenitic and super austenitic stainless steels. 2016. 133 f. Tese (Doutorado em Ciência de Materiais) – Centro de Tecnologia, Universidade Federal do Ceará, Fortaleza, 2016.
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Austenitic stainless steels are widely used in several applications including the manufacture of pipelines for the oil and gas industry. This work discusses the corrosion behavior of austenitic and super austenitic stainless steels in CO2-containing environments. The steels used in this work were the AL-6XN PLUS™ (UNS Designation N08367) and 904L (UNS Designation N08904) super austenitic stainless steels. Two conventional austenitic stainless steels, 316L (UNS S31600/ S31603) and 317L (UNS S31703) were also used for comparison purposes. Potentiodynamic polarization measurements were taken in CO2-saturated synthetic oil field formation water, deaerated with nitrogen to simulate some conditions in the pre-salt region. Potentiostatic measurements were also carried out to evaluate the corrosive level of the solution without the presence of CO2. Pressurized experiments using autoclave in CO2-containing environment and in synthetic air environment were also conducted to evaluate the corrosion resistance of the alloys when pressure and temperature act together. Heat treatments at high temperatures between 600 °C and 760°C in different ranges of time were also conducted to evaluate the possible sigma phase precipitation and its effect on the corrosion resistance. The AL-6XN PLUS™ and 904L super austenitic stainless steels showed a good performance in CO2-containing environment. The AL-6XN PLUS™ steel also exhibited the best performance in the pressurized experiments. The conventional 316L and 317L steels showed susceptibility to pitting and crevice corrosion. The results showed that the conventional alloys are not suitable for the use in CO2-containing environment under severe conditions. Pitting potential of the 316L alloy was affected by the pH of the solution in CO2-saturated solution. No sigma phase precipitated in the heat treatments for the range of time used indicating that its precipitation kinetics in austenitic stainless steels is very slow. This result is an advantage when working with austenitic stainless steels for long periods of exposure at high temperatures.
Os aços inoxidáveis austeníticos e super austenític os são amplamente utilizados na fabricação de tubulações na industria de petróleo e gás. Esse trabalho discute o comportamento da corrosão de aços inoxidáveis austeníticos e super a usteníticos em meio contendo CO 2 . Os aços usados nesse trabalho foram os aços super aust eníticos AL-6XN PLUS™ (Designação UNS N08367) e 904L (Designação UNS N08904). Dois aç os austeníticos convencionais, 316L (UNS S31600/ S31603) e 317L (UNS S31703), tamb ém foram usados para comparação. Foram realizadas medidas de polarização potenciodinâmica em água artificial de formação de poço de petróleo saturada com CO 2 e desaerada com nitrogênio para simular algumas condições do pré-sal. Foram também realizad as medidas potenciostáticas para avaliar o nível corrosivo da solução sem a presença de CO 2 . Experimentos pressurizados usando autoclaves em meio contendo CO 2 e ar sintético também foram realizados para avalia r a resistência à corrosão das ligas quando pressão e t emperatura agem juntas. Foram realizados tratamentos térmicos em altas temperaturas entre 60 0 °C e 760 °C em diferentes faixas de tempo para avaliar a formação de fase sigma e seu e feito na resistência à corrosão. Os aços super austeníticos AL-6XN PLUS™ e 904L mostraram um a boa performance em meio contendo CO 2 . O aço AL-6XN PLUS™ também exibiu uma boa performa nce nos experimentos pressurizados. Os aços convencionais 3 16L e 317L apresentaram susceptibilidade à corrosão por pites e frestas. Os resultados mostraram que os aços convencionais não são apropriados para uso em meio contendo CO 2 sob condições severas. O potencial de pite do aço 316L foi afetado pelo pH d a solução em meio saturado com CO 2 . Não houve precipitação de fase sigma nos tratamento s térmicos para as faixas de tempo usadas indicando que sua cinética de precipitação e m aços inoxidáveis austeníticos é muito lenta. Esse resultado é uma vantagem ao se trabalha r com aço inoxidáveis austeníticos em logos períodos de exposição em altas temperaturas.

L'altération chimique des roches primaires et des minéraux dans les systèmes naturels a un impact majeur sur la formation des sols et leur composition. L'altération chimique est largement pilotée par la dissolution des minéraux. Les éléments chimiques libérés dans les eaux souterraines par la dissolution des minéraux réagissent facilement pour former des minéraux secondaires comme les argiles, zéolites et carbonates. Les carbonates se forment par réaction des cations divalents (Ca, Fe et Mg) avec CO2 dissous tandis que la formation des kaolins et de la gibbsite est attribuée à l'altération des minéraux riches en aluminium, le plus souvent les feldspaths. Le projet Carbfix à Hellisheiði (sud-ouest de l'Islande) a pour but d'utiliser les processus d'altération naturelle pour former des minéraux carbonatés par réinjection dans les roches basaltiques environnantes de CO2 provenant d'une centrale géothermique. Ce processus trouve son origine dans la dissolution des roches basaltiques riches en cations divalents (Ca, Fe et Mg) qui se combinent au CO2 injecté pour former des minéraux carbonatés. Cette thèse est centrée sur la dissolution du basalte cristallin de Stapafell qui est composé essentiellement de trois phases minérales (plagioclase, pyroxène et olivine) et qui est riche en cations divalents. La vitesse de libération des éléments du basalte à l'état stationnaire et loin de l'équilibre a été mesurée dans des réacteurs à circulation à des pH de 2 à 12 et des températures de 5 à 75°C. Les vitesses de libération de Si et Ca à l'état stationnaire présentent une variation en fonction du pH en forme de U avec une diminution des vitesses lorsque le pH augmente en conditions acides et une augmentation avec le pH en conditions alcalines. Les vitesses de libération du silicium par le basalte cristallin sont comparables à celles par le verre basaltique de même composition chimique aux faibles pH et aux températures = 25°C mais elles sont plus lentes aux pH alcalins et aux températures = 50°C. Par contre, les vitesses de libération de Mg et Fe diminuent de manière monotone avec l'accroissement du pH à toutes les températures. Ce comportement a pour cause les variations contrastées, en fonction du pH, des vitesses de dissolution des trois minéraux constitutifs du basalte: plagioclase, olivine et pyroxène. Les vitesses de libération des éléments déduites de la somme des vitesses de dissolution du plagioclase, pyroxène et olivine normalisées à la fraction volumique de ces minéraux sont, à un ordre de grandeur près, les mêmes que celles mesurées dans cette étude. En outre, les résultats expérimentaux montrent que, durant l'injection d'eaux chargées en CO2 de pH proche de 3. 6, le basalte cristallin libère préférentiellement Mg et Fe en solution par rapport à Ca. L'injection de fluides acides chargés en CO2 dans des roches cristallines basaltiques peut donc favoriser la formation de carbonates de Mg et Fe aux dépends de la calcite aux conditions de pH acides à neutres. Le plagioclase, qui est la phase la plus abondante du basalte, influence fortement la réactivité de ce dernier. La vitesse de dissolution du plagioclase, basée sur la libération de la silice, présente une variation en forme de U en fonction du pH, diminuant lorsque le pH augmente aux conditions acides mais augmentant avec le pH aux conditions alcalines. En accord avec les données de la littérature, la vitesse de dissolution du plagioclase à pH constant, en conditions acides, augmente avec sa teneur en anorthite. L'interprétation et le fit des données obtenues suggèrent que la vitesse de dissolution du plagioclase est contrôlée par la décomposition d'un complexe activé riche en silice, formé par le départ de Al de la structure du minéral. Le plus remarquable, par comparaison aux hypothèses antérieures, est que la vitesse de dissolution du plagioclase en conditions alcalines est indépendante de sa teneur en anorthite - e. G. Les vitesses de dissolution des plagioclases riches en anorthite augmentent avec le pH aux conditions alcalines. A ces conditions, il est probable que la vitesse de dissolution rapide du plagioclase domine, en raison de sa forte teneur en Ca, la libération vers la phase fluide des cations divalents du basalte cristallin. La gibbsite est généralement le premier minéral qui précipite lors de la dissolution du plagioclase. C'est un hydroxyde d'aluminium que l'on trouve dans divers sols et qui est aussi la phase principale des minerais de bauxite. Les vitesses de précipitation de la gibbsite ont été mesurées dans des réacteurs fermés, en conditions alcalines à 25 et 80°C, en fonction de l'état de saturation du fluide. Les analyses des solides après réaction ont démontré que la précipitation de gibbsite s'est produite dans toutes les expériences. L'interprétation de l'évolution dans le temps de la chimie du fluide réactif fournit des vitesses de précipitation de la gibbsite qui sont près des vitesses de dissolution du plagioclase. En plus, des vitesses de précipitation de la gibbsite diminuent plus rapidement que des vitesses de dissolution du plagioclase quand le pH descende. Ceci suggère que l'étape limitant de l'altération du plagioclase sur la surface de la terre est plutôt la consommation d'Al par formation de la gibbsite que la dissolution même du plagioclase. La kaolinite est en général le second minéral formé après la gibbsite lors de la dissolution du plagioclase à basse température. Les vitesses de précipitation de la kaolinite ont été mesurées dans des réacteurs à circulation à pH = 4 et t = 25°C, en fonction de l'état de saturation du fluide. Au total, 8 expériences de précipitation de longues durées ont été réalisées dans des fluides légèrement supersaturés par rapport à la kaolinite, en utilisant comme germes pour la précipitation une quantité connue de de kaolinite de Géorgie (KGa-1b) contenant peu de défauts et préalablement nettoyée. Les vitesses de précipitation de kaolinite mesurées sont relativement lentes comparées aux vitesses de dissolution du plagioclase. Cette observation suggère que la formation de kaolinite lors de l'altération est limitée par sa vitesse de précipitation plutôt que par que la disponibilité en Al et Si issus de la dissolution du plagioclase. L'ensemble des résultats de cette étude fournit un certain nombre de principes scientifiques de base nécessaires à la prédiction des vitesses et des conséquences de la dissolution du basalte cristallin et du plagioclase à la surface de la Terre et lors de l'injection du CO2 à proximité de la surface dans le cadre des efforts de stockage du carbone. Les résultats obtenus indiquent, bien que les vitesses de précipitation de la gibbsite soient relativement rapides, que la vitesse de précipitation relativement lente de la kaolinite peut être le processus contrôlant la formation de ce minéral à la surface de la Terre. Cette observation souligne la nécessité de poursuivre la quantification de la précipitation de ce minéral secondaire aux conditions typiques de la surface de la Terre. En outre, comme les proportions des différents métaux divalents libérés par les basaltes cristallins varient sensiblement avec le pH, la carbonatation des basaltes doit produire un changement systématique de l'identité des minéraux carbonatés et des zéolites précipités en fonction de la distance au puits d'injection. Cette dernière conclusion pourra être directement testée dans le cadre du projet CarbFix actuellement conduit à Hellisheiði en Islande
The chemical weathering of primary rocks and minerals in natural systems has a major impact on soil development and its composition. Chemical weathering is driven to a large extent by mineral dissolution. Through mineral dissolution, elements are released into groundwater and can readily react to precipitate secondary minerals such as clays, zeolites, and carbonates. Carbonates form from divalent cations (e. G. Ca, Fe and Mg) and CO2, and kaolin clay and gibbsite formation is attributed to the weathering of aluminium- rich minerals, most notably the feldspars. The CarbFix Project in Hellisheiði SW-Iceland aims to use natural weathering processes to form carbonate minerals by the re-injection of CO2 from a geothermal power plant back into surrounding basaltic rocks. This process is driven by the dissolution of basaltic rocks, rich in divalent cations, which can combine with injected CO2 to form and precipitate carbonates. This thesis focuses on the dissolution behaviour of Stapafell crystalline basalt, which consists of three major phases (plagioclase, pyroxene, and olivine) and is rich in divalent cations. Steady-state element release rates from crystalline basalt at far-from-equilibrium conditions were measured at pH from 2 to 11 and temperatures from 5° to 75° C in mixed-flow reactors. Steady-state Si and Ca release rates exhibit a U-shaped variation with pH, where rates decrease with increasing pH at acid condition but increase with increasing pH at alkaline conditions. Silicon release rates from crystalline basalt are comparable to Si release rates from basaltic glass of the same chemical composition at low pH and temperatures =25°C but slower at alkaline pH and temperatures =50°C. In contrast, Mg and Fe release rates decrease continuously with increasing pH at all temperatures. This behaviour is interpreted to stem from the contrasting dissolution behaviours of the three major minerals comprising the basalt: plagioclase, pyroxene, and olivine. Element release rates estimated from the sum of the volume fraction normalized dissolution rates of plagioclase, pyroxene, and olivine are within one order of magnitude of those measured in this study. In addition, these experimental results show that during injection of CO2-charged waters with pH close to 3. 6, crystalline basalt preferentially releases Mg and Fe relative to Ca to the fluid phase. The injection of acidic CO2-charged fluids into crystalline basaltic rocks may therefore favour the formation of Mg and Fe carbonates rather than calcite at acidic to neutral conditions. Plagioclase is the most abundant phase in crystalline basalts and thus influences strongly its reactivity. Plagioclase dissolution rates based on Si release show a common U-shaped behaviour as a function of pH where rates decrease with increasing pH at acid condition but increase with increasing pH at alkaline conditions. Constant pH plagioclase dissolution rates increase with increasing anorthite content at acid conditions, in agreement with literature findings. Interpretation and data fitting suggests that plagioclase dissolution rates are consistent with their control by the detachment of Si-rich activated complexes formed by the removal of Al from the mineral framework. Most notably, compared with previous assumptions, plagioclase dissolution rates are independent of plagioclase composition at alkaline conditions, e. G. Anorthite-rich plagioclase dissolution rates increase with increasing pH at alkaline conditions. At such conditions rapid plagioclase dissolution rates likely dominate divalent metal release from crystalline basalts to the fluids phase due to its high Ca content. Gibbsite is commonly the first mineral formed during low temperature dissolution of plagioclase. Gibbsite is an aluminium-hydroxide that is found in various soils as well as the dominant phase in many bauxite ores. Gibbsite precipitation rates were measured in closed system reactors at alkaline condition, both at 25 °C and 80 °C as a function of fluid saturation state. Analyses of the solids demonstrate that gibbsite precipitation occurred in all experiments. The comparison of gibbsite precipitation to the dissolution rates of plagioclase at pH 11 shows that the rates are close to equal. The precipitation rates of gibbsite, however, decrease faster with decreasing pH than plagioclase dissolution rates. As such it seem likely that plagioclase dissolution is faster than gibbsite precipitation at near to neutral pH, and the relatively slow rate of gibbsite precipitation influences plagioclase weathering in many Earth surface systems. Kaolinite is commonly the second secondary mineral formed during low temperature dissolution of plagioclase. Kaolinite precipitation rates were measured in mixed flow reactors as a function of fluid saturation state at pH=4 and 25 °C. In total eight long-term precipitation experiments were performed in fluids mildly supersaturated with respect to kaolinite, together with a known quantity of cleaned low defect Georgia Kaolinite as seeds. Measured kaolinite precipitation rates are relatively slow compared with plagioclase dissolution rates. This observation suggests that kaolinite formation during weathering is limited by its precipitation rates rather than by the availability of aqueous species sourced from plagioclase dissolution. Taken together the results of this study provide some of the fundamental scientific basic for predicting the rates and consequences of crystalline basalt and plagioclase dissolution at both the Earth's surface and during the near surface injection of CO2 as part of carbon storage efforts. Results indicate that although gibbsite precipitation rates are relatively rapid, the relatively slow precipitation rates of kaolinite may be the process controlling the formation of this mineral at the Earth's surface. This observation highlights the need to further quantify this secondary mineral precipitation rates at conditions typical at the Earth's surface. Moreover, as the composition of divalent metals released from crystalline basalts varies significantly with pH, CO2 carbonation in basalt should yield a systematic variation in the identity of carbonate and zeolite minerals precipitated with distance from the injection site. This latter conclusion can be tested directly as part of the currently on-going CarbFix project in Hellisheiði, Iceland

A detailed understanding of cloud microphysical processes is crucial for a large range of scientific disciplines that require knowledge of cloud particles for accurate climate and weather prediction. This thesis focuses on 3 measurement campaigns, encompassing both airborne and ground based measurements of the microphysical structures observed in cold, warm and occluded frontal systems around the United Kingdom, stratocumulus clouds in the Arctic and many different clouds observed over a 6 week period at a high-alpine site in the Swiss Alps. Particular attention was paid to the origin and distribution of both primary and secondary ice and the dominant features associated with ice phase processes. During investigation of cold, warm and occluded frontal systems associated with mid-latitude cyclones around the U.K., secondary ice was often found to dominate the number and mass concentrations of ice particles in all systems. The presence of large liquid droplets was sometimes observed in close proximity to regions of secondary ice production. The existence of these provides a possible mechanism by which rime-splintering is greatly enhanced through the creation of instant rimers as the large drops freeze. In-situ measurements during the cold frontal case were used to calculate rates of diabatic heating during a comparison between bin-resolved and bulk microphysics schemes. Observations in arctic stratocumulus clouds during spring and summer seasons revealed higher ice concentrations in the summer cases when compared to the spring season. This is attributed to secondary ice production actively enhancing ice concentrations in the summer, due to the higher temperature range the clouds spanned. At Jungfraujoch in the Swiss Alps, ground based measurements allowed us to obtain high spatial scale resolution measurements of cloud microphysics and we found transitions between high and low ice mass fractions that took place on differing temporal scales spanning seconds to hours. During the campaign measurements of aerosol properties at an out of cloud site, Schilthorn, were made. When analysing a Saharan Dust Event that took place a possible link between the number of U.V. fluorescent particles and the number of ice particles was found in the temperature range around -10 ºC.

The development of tool steels for making and shaping other materials requires a better understanding of the material's properties during manufacture. These high-quality steels include many alloying elements, which give increased hardness during tempering. For producing hardened microstructures, austenite generation is essential. The martensite formed by rapid quenching of austenite followed by tempering helps develop high strength steels. Studying carbide precipitation is a challenge as they are very small in size, present only in small volume fractions and high number densities. The carbide reactions are complicated due to so-called metastable carbides, which are only present as part of the precipitation process. This work focuses on model alloys with two main elements in addition to iron and carbon, molybdenum, and vanadium, to clarify and simplify the carbide characterization. This is done to determine the effect of molybdenum and vanadium carbides on the overall hardness. In this work, two model alloys, A and B, are tempered at 550°C and 600°C with the same vanadium content but different molybdenum contents. The hardness of the materials is evaluated and compared at these temperatures. A more detailed characterization work is done for material A with Scanning Transmission Electron Microscopy-Energy Dispersive Spectroscopy (STEM-EDS) to understand the microstructure and analyze the precipitates. Simulations are performed with Thermo-Calc Prisma (TC-Prisma) to support the experimental work, which includes the simulation of the secondary carbide precipitation, mainly molybdenum carbides in material A tempered for 24h at 600°C, and predicts the carbide precipitation behavior in this steel. The results from STEM-EDS and TC-Prisma for material A, show that the small secondary carbides in the martensite contribute to the increased strength of material A. Due to the overaging of the carbides at 600°C, the hardness at 550°C is higher than at 600°C for material A. The given thesis work is an attempt to interpret the development of secondary carbides of Mo and V in the martensitic matrix and their role in the overall hardness.
Den ständiga utvecklingen av högpresterande stål för transport, konstruktion och energisektorn kräver bättre förståelse för materialets egenskaper vid tillverkning. Dessa martensitiska stål inkluderar många legeringselement vilket ger ökad hårdhet vid härdning och anlöpning. Att studera utskiljning av karbider är en utmaning eftersom de är närvarande endast i liten volymsfraktion. Karbidreaktionerna är komplexa till följd av så kallade metastabila karbider vilka endast är närvarande vid en del av utskiljningsförloppet. För att tydliggöra och förenkla karbidkarakteriseringen fokuserar detta arbete på modellegeringar med två huvudelement utöver järn och kol, molybden och vanadin. Detta görs för att fastställa effekten av molybden och vanadinkarbider på den totala hårdheten. I detta arbete studeras två modellegeringar, A och B, härdade och anlöpta vid 550 °C och 600 °C med samma vanadininnehåll men olika molybdeninnehåll. Materialens hårdhet utvärderas och jämförs vid dessa temperaturer. Ett mer detaljerat karaktäriseringsarbete görs för material A med hjälp av STEM-EDS för att förstå mikrostrukturen och analysera utskiljningarna. Simuleringar görs med TC-PRISMA för att stödja det experimentella arbetet, vilket inkluderar simulering av den sekundära karbidutskiljningen och predikterar karbidstrukturen i dessa stål. Resultaten visar att de små sekundärkarbiderna i martensiten bidrar till den ökade styrkan hos material A. Hårdheten vid 550 °C är högre än vid 600 °C för material A eftersom både utskiljningen av karbider är sker långsammare och även dislokationsåterhämtning.

This thesis systematically investigates the effects of a recently developed modified ageing procedure of aluminium alloys, termed the T6I6 temper, on the microstructural development and mechanical properties of the Al ??? Mg ??? Si - Cu alloy 6061. For the T6I6 temper, a conventional single stage T6 temper is interrupted by an ageing period at a reduced temperature (65??C) to facilitate secondary precipitation, before resuming the final ageing at the temperature of the initial T6 treatment. The T6I6 temper was found to cause simultaneous increases in tensile properties, hardness, and toughness as compared with 6061 T6. Al ??? Mg ??? Si ??? Cu alloys are medium strength alloys widely used in the automotive industry and their further improvement is underpinned by stringent demands for weight reduction placed on the transportation industry in recent years. The potential for further improvement of the mechanical properties was found in the control of secondary precipitation that may take place even in some fully aged alloys when exposed to reduced temperatures. The overall improvement in the mechanical properties of 6061 T6I6 was attributed to the formation of finer and more densely dispersed precipitates in the final microstructure. The refinement of precipitates was facilitated by control of the precipitation processes and gradual evolution of the microstructure throughout each stage of the T6I6 treatment. The results indicated that the concentration and the chemical environment of the vacancies controlled the precipitation processes in this alloy. Findings also show that the proportion of the different precipitate phases present in the final microstructure, as well as the amount of the solute in these precipitates, can be controlled and modified utilizing secondary precipitation. A number of analytical techniques were used in this study. The evolution of the microstructure was studied using Transmission Electron Microscopy (TEM), High Resolution TEM (HRTEM) and Three Dimensional Atom Probe (3DAP). Vacancy-solute interactions were studied using Positron Annihilation Lifetime Spectroscopy (PALS) and 3DAP. The distribution of the solute was studied using 3DAP and Nuclear Magnetic Resonance (NMR). Differential Scanning Calorimetry (DSC) was used to identify precipitation reactions and to determine the stability of vacancy-associated aggregates.

L’objectif de ce travail est d’améliorer la durée de vie en fluage d’un alliage résistant à haute température. L’alliage étudié, nommé « C », appartient à la classe des aciers austénitiques de type HP utilisés pour la fabrication des tubes de reformage. L’évolution microstructurale de l’alliage « C » a été étudiée dans une vaste gamme de températures, s’étendant de 700 à 1040°C pour des temps de vieillissement allant jusqu’à 1000 h. La caractérisation de ces états vieillis a été réalisée au moyen de la microscopie électronique (MEB-FEG, MET) et de la diffraction des rayons X. L’accent a été mis sur une caractérisation fine de la précipitation secondaire présente Ces résultats ont ensuite été utilisés afin d’identifier les conditions thermiques optimales pour l’affinement de la précipitation en vue d’amélioration du comportement macroscopique de l’alliage. La cinétique de précipitation a été modélisée à l’aide du logiciel PRISMA ThermoCalc. Un bon accord entre la simulation et les mesures expérimentales a pu être obtenu.Dans la gamme de températures étudiée, la précipitation secondaire est majoritairement constituée de deux carbures : M23C6 (M=Cr, Fe) et NbC. En condition de service (980°C), la croissance du M23C6 est rapide. La coalescence des précipités survient dès 200 h de vieillissement. Nous avons prouvé qu’un vieillissement à des températures plus basses (700-750°C) permet d’affiner cette précipitation. De plus, notre étude a montré l’efficacité d’un prétraitement à des températures basses, effectué avant la mise en service du matériau à 980°C. Une nette amélioration de la résistance en fluage dans des essais accélérés a été obtenue pour l’alliage « C » ayant subi le prétraitement cité ci-dessus. Outre l’affinement et le retardement de la coalescence du M23C6, la présence d’une précipitation nanométrique du NbC sur des lignes de dislocations est probablement à l’origine de cet effet
The purpose of this work is to optimise the microstructure of a creep-resistant alloy of the type HP, called “C” (industrial denomination). These austenitic steels are used for the manufacture of reformer tubes. The microstructural evolution of the alloy "C" has been studied in a wide range of temperatures, ranging from 700 to 1040 °C for aging times up to 1000 h. The characterization of these aged states was performed using electron microscopy (FEG-SEM, TEM) and X-ray diffraction, with emphasis on a detailed characterization of this secondary precipitation. This knowledge was then used to identify the optimal thermal conditions for the refinement of precipitation to improve the macroscopic behaviour of the alloy. The precipitation kinetics was modelled using the PRISMA ThermoCalc. A good agreement between simulation and experimental measurements has been obtained.In the studied range of temperature, the secondary precipitation consists mainly of two carbides M23C6 (M = Cr, Fe) and NbC. In the service conditions (980°C), the growth of M23C6 is fast. The coalescence of the precipitates starts after only 200h of aging. Aging at lower temperatures (700-750°C) refines this precipitation. Our study showed the efficacy of pre-treatment of the alloy at low temperatures, before the service of the material at 980°C. In the alloy "C", treated in such conditions, a significant increase in creep resistance was obtained in accelerated testing. In addition to refinement of the secondary precipitation and delaying the effects of coalescence of M23C6, the presence of a nanoscale precipitation of NbC on dislocation lines is probably the origin of this effect

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The AA7050 class from the 7XXX series alloys based on Al-Zn-Mg-Cu are widely used in aerospace structures and fuselage components, when the same are subjected to high stress loading due to its high ratio mechanical strength to density, in addition, to its corrosion resistance. The increased resistance of these alloys is obtained by heat treatment that involves solution treatment and ageing followed precipitation of a fine and homogeneous phase from the own chemical composition. In this, the present study aimed to perform the of AA7050 aluminum alloy microstructural characterization with different ageing heat treatment from the T7451, T6 and T6I4-65 conditions. Thus, different characterization techniques from the Optical Microscopy (OM), Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), Extraction of second phase particles, X-ray Diffraction (XRD) and Transmission Electron Microscopy (TEM) were used. It was evaluated which condition results is higher precipitation hardening phases that are responsible for the increased resistance of the alloy. The most significant results were obtained by TEM where it was possible to determine the morphology of the GPII zones in needles form with approximate size of 30nm and 10nm for both T6 and T6I4-65 conditions, respectively. Moreover, the metastable η' phase was identified in platelets form in the T7451, T6 and T6I4-65 conditions with approximate size of 50nm, 20nm and 10nm, respectively. The surface roughness analyses obtained by AFM have revealed that the T6I4-65 condition has higher surface roughness (Ra=14,87nm) when compared to the T7451 (Ra=7,65nm) and T6 (Ra=8,35nm) conditions. Indicating in this case, a higher density of small particles homogeneously distributed in the T6I4-65 aluminum alloy matrix.
As ligas da série 7XXX, da classe AA7050, à base de Al-Zn-Mg-Cu, são muito utilizadas na indústria aeroespacial, em estruturas de fuselagem e componentes sob alta tensão de carregamento, devido à sua alta relação entre resistência mecânica e densidade, além de sua resistência à corrosão. O aumento da resistência destas ligas é obtido por tratamento térmico de solubilização e envelhecimento, através da precipitação de uma fase fina e homogênea, proveniente da própria composição química. Neste contexto, o presente trabalho teve como objetivo principal realizar a caracterização microestrutural de uma liga de alumínio AA7050, submetida a diferentes tratamentos térmicos de envelhecimento nas condições T7451, T6 e T6I4-65. Desse modo, fez-se o uso de diferentes técnicas de caracterização entre elas Microscopia Ótica (MO), Microscopia Eletrônica de Varredura (MEV), Microscopia de Força Atômica (AFM), Extração de Partículas de segunda fase, Difração de Raios X (DRX) e Microscopia Eletrônica de Transmissão. Consequentemente, avaliou-se qual condição apresenta maior precipitação de fases endurecedoras que são responsáveis pelo aumento de resistência da liga. Os resultados mais significativos foram obtidos por MET onde foi possível determinar a morfologia das zonas GPII presentes na forma acicular (needles) com tamanho aproximado de 30nm na condição T6 e 10nm na condição T6I4-65. A fase metaestável η’ foi identificada na forma de plaquetas finas (platelets) nas condições T7451, T6 e T6I4-65 com tamanho aproximado de 50nm, 20nm e 10nm respectivamente. A rugosidade superficial obtida por AFM revelou que a condição T6I4-65 apresenta maior rugosidade superficial (Ra=14,87nm) quando comparado às condições T7451(Ra=7,65nm) e T6 (Ra=8,35nm), indicando maior densidade de partículas de pequena dimensão distribuída homogeneamente na matriz da liga de alumínio.

L'altération chimique des roches primaires et des minéraux dans les systèmes naturels a un impact majeur sur la formation des sols et leur composition. L'altération chimique est largement pilotée par la dissolution des minéraux. Les éléments chimiques libérés dans les eaux souterraines par la dissolution des minéraux réagissent facilement pour former des minéraux secondaires comme les argiles, zéolites et carbonates. Les carbonates se forment par réaction des cations divalents (Ca, Fe et Mg) avec CO2 dissous tandis que la formation des kaolins et de la gibbsite est attribuée à l'altération des minéraux riches en aluminium, le plus souvent les feldspaths. Le projet Carbfix à Hellisheiði (sud-ouest de l'Islande) a pour but d'utiliser les processus d'altération naturelle pour former des minéraux carbonatés par réinjection dans les roches basaltiques environnantes de CO2 provenant d'une centrale géothermique. Ce processus trouve son origine dans la dissolution des roches basaltiques riches en cations divalents (Ca, Fe et Mg) qui se combinent au CO2 injecté pour former des minéraux carbonatés. Cette thèse est centrée sur la dissolution du basalte cristallin de Stapafell qui est composé essentiellement de trois phases minérales (plagioclase, pyroxène et olivine) et qui est riche en cations divalents. La vitesse de libération des éléments du basalte à l'état stationnaire et loin de l'équilibre a été mesurée dans des réacteurs à circulation à des pH de 2 à 12 et des températures de 5 à 75°C. Les vitesses de libération de Si et Ca à l'état stationnaire présentent une variation en fonction du pH en forme de U avec une diminution des vitesses lorsque le pH augmente en conditions acides et une augmentation avec le pH en conditions alcalines. Les vitesses de libération du silicium par le basalte cristallin sont comparables à celles par le verre basaltique de même composition chimique aux faibles pH et aux températures ≥ 25°C mais elles sont plus lentes aux pH alcalins et aux températures ≥ 50°C. Par contre, les vitesses de libération de Mg et Fe diminuent de manière monotone avec l'accroissement du pH à toutes les températures. Ce comportement a pour cause les variations contrastées, en fonction du pH, des vitesses de dissolution des trois minéraux constitutifs du basalte: plagioclase, olivine et pyroxène. Les vitesses de libération des éléments déduites de la somme des vitesses de dissolution du plagioclase, pyroxène et olivine normalisées à la fraction volumique de ces minéraux sont, à un ordre de grandeur près, les mêmes que celles mesurées dans cette étude. En outre, les résultats expérimentaux montrent que, durant l'injection d'eaux chargées en CO2 de pH proche de 3.6, le basalte cristallin libère préférentiellement Mg et Fe en solution par rapport à Ca. L'injection de fluides acides chargés en CO2 dans des roches cristallines basaltiques peut donc favoriser la formation de carbonates de Mg et Fe aux dépends de la calcite aux conditions de pH acides à neutres. Le plagioclase, qui est la phase la plus abondante du basalte, influence fortement la réactivité de ce dernier. La vitesse de dissolution du plagioclase, basée sur la libération de la silice, présente une variation en forme de U en fonction du pH, diminuant lorsque le pH augmente aux conditions acides mais augmentant avec le pH aux conditions alcalines. En accord avec les données de la littérature, la vitesse de dissolution du plagioclase à pH constant, en conditions acides, augmente avec sa teneur en anorthite. L'interprétation et le fit des données obtenues suggèrent que la vitesse de dissolution du plagioclase est contrôlée par la décomposition d'un complexe activé riche en silice, formé par le départ de Al de la structure du minéral. Le plus remarquable, par comparaison aux hypothèses antérieures, est que la vitesse de dissolution du plagioclase en conditions alcalines est indépendante de sa teneur en anorthite - e.g. les vitesses de dissolution des plagioclases riches en anorthite augmentent avec le pH aux conditions alcalines. A ces conditions, il est probable que la vitesse de dissolution rapide du plagioclase domine, en raison de sa forte teneur en Ca, la libération vers la phase fluide des cations divalents du basalte cristallin. La gibbsite est généralement le premier minéral qui précipite lors de la dissolution du plagioclase. C'est un hydroxyde d'aluminium que l'on trouve dans divers sols et qui est aussi la phase principale des minerais de bauxite. Les vitesses de précipitation de la gibbsite ont été mesurées dans des réacteurs fermés, en conditions alcalines à 25 et 80°C, en fonction de l'état de saturation du fluide. Les analyses des solides après réaction ont démontré que la précipitation de gibbsite s'est produite dans toutes les expériences. L'interprétation de l'évolution dans le temps de la chimie du fluide réactif fournit des vitesses de précipitation de la gibbsite qui sont près des vitesses de dissolution du plagioclase. En plus, des vitesses de précipitation de la gibbsite diminuent plus rapidement que des vitesses de dissolution du plagioclase quand le pH descende. Ceci suggère que l'étape limitant de l'altération du plagioclase sur la surface de la terre est plutôt la consommation d'Al par formation de la gibbsite que la dissolution même du plagioclase. La kaolinite est en général le second minéral formé après la gibbsite lors de la dissolution du plagioclase à basse température. Les vitesses de précipitation de la kaolinite ont été mesurées dans des réacteurs à circulation à pH = 4 et t = 25°C, en fonction de l'état de saturation du fluide. Au total, 8 expériences de précipitation de longues durées ont été réalisées dans des fluides légèrement supersaturés par rapport à la kaolinite, en utilisant comme germes pour la précipitation une quantité connue de de kaolinite de Géorgie (KGa-1b) contenant peu de défauts et préalablement nettoyée. Les vitesses de précipitation de kaolinite mesurées sont relativement lentes comparées aux vitesses de dissolution du plagioclase. Cette observation suggère que la formation de kaolinite lors de l'altération est limitée par sa vitesse de précipitation plutôt que par que la disponibilité en Al et Si issus de la dissolution du plagioclase. L'ensemble des résultats de cette étude fournit un certain nombre de principes scientifiques de base nécessaires à la prédiction des vitesses et des conséquences de la dissolution du basalte cristallin et du plagioclase à la surface de la Terre et lors de l'injection du CO2 à proximité de la surface dans le cadre des efforts de stockage du carbone. Les résultats obtenus indiquent, bien que les vitesses de précipitation de la gibbsite soient relativement rapides, que la vitesse de précipitation relativement lente de la kaolinite peut être le processus contrôlant la formation de ce minéral à la surface de la Terre. Cette observation souligne la nécessité de poursuivre la quantification de la précipitation de ce minéral secondaire aux conditions typiques de la surface de la Terre. En outre, comme les proportions des différents métaux divalents libérés par les basaltes cristallins varient sensiblement avec le pH, la carbonatation des basaltes doit produire un changement systématique de l'identité des minéraux carbonatés et des zéolites précipités en fonction de la distance au puits d'injection. Cette dernière conclusion pourra être directement testée dans le cadre du projet CarbFix actuellement conduit à Hellisheiði en Islande.

In South Africa, being the second largest global coal exporter, coal mining plays a pivotal role in the growth of our economy, as well as supplying our nation’s ever increasing electricity needs; while also accounting for more than 10% of the 20 x 109 m3 water used annually in the country. Coal mining may thus be classified as a large-scale water user; known to inevitably generate wastewater [acid mine drainage (AMD)] and other waste material, including fly ash (FA). Current and conventional AMD treatment technologies include precipitation–aggregation (coagulation/flocculation) – settling as hydroxides or insoluble salts. The process stream resulting from these precipitation processes is still highly saline, therefore has to undergo secondary treatment. The best available desalination techniques include reverse osmosis (RO), electro dialysis (ED), ion exchange and evaporation. All available treatment methods associated with raw AMD and its derived process stream fall prey to numerous drawbacks. The result is that treatment is just as costly as the actual coal extraction. In addition, remediation only slows the problem down, while also having a short lifespan. Research conducted into converting fly ash, an otherwise waste material, into a marketable commodity has shown that direct mixing of known ratios of FA with AMD to a pre-determined pH, erves a dual purpose: the two wastes (AMD and FA) could be neutralized and produced a much cleaner water (secondary co-disposal [FA/AMD]-process water), broadly comparable to the process water derived from precipitation-aggregation treated AMD. The collected post process solid residues on the other hand, could be used for production of high capacity ion exchange material (e.g. zeolite A, faujasite, zeolite P, etc.). The produced ion exchange material can subsequently be utilized for the attenuation of metal species in neutralized FA/AMDprocess waters.
Magister Scientiae - MSc

Les aciers nano-bainitiques représentent une nouvelle classe d’alliages, avec une microstructure bainitique nano-structurée obtenue à basse température avec une fraction importante d’austénite résiduelle conduisant à une limite d’élasticité et à une ductilité élevées. Récemment, il a été observé que l’addition d’éléments carburigènes comme le V et le Mo dans ces microstructures augmente la résistance à l’adoucissement ainsi que les propriétés mécaniques à moyennes températures. Ainsi l’étude de la précipitation des carbures secondaires dans les microstructures nano-bainitiques est nécessaire pour optimiser la microstructure et les traitements thermiques de revenu pour cette nouvelle classe d’aciers. Trois microstructures initiales ont été étudiées : martensite, martensite + austénite résiduelle et nano-bainite. L’étude de microstructures martensitiques plus conventionnelles a servi de base pour une meilleure compréhension des évolutions microstructurales dans la microstructure nano-bainitique. La précipitation pendant le revenu a été étudiée avec des techniques expérimentales : la dilatométrie, la diffraction des rayons X de haute énergie sur synchrotron et la microscopie électronique en transmission haute résolution. Il a été montré que les séquences de précipitation et de dissolution des carbures sont similaires pour les trois microstructures initiales. Les cinétiques sont similaires ainsi que la composition chimique de la cémentite et les distributions de taille de la cémentite et des carbures alliés. Nous avons aussi mis en évidence une importante stabilité de l’austénite résiduelle des trois microstructures. L’analyse des évolutions des paramètres de maille associé à des bilans de teneur en carbone ont permis de mieux comprendre sa distribution entre les carbures et les phases des matrices. Un modèle décrivant la germination et la croissance des précipités a été développé prenant en compte la précipitation des carbures secondaires, une cinétique de restauration basée sur les résultats expérimentaux et de nouvelles hypothèses comme le para-équilibre. Ce modèle prédit les cinétiques de précipitation mais aussi la densité de particules, les distributions de taille et la composition moyenne de la matrice et des carbures pour différentes conditions de revenu. Hormis la comparaison avec les résultats expérimentaux qui est discutée, le modèle a permis d’interpréter le comportement similaire des microstructures initiales au cours du revenu
Nano-bainitic steels represent a new class of alloys, whose microstructure consists of nanostructured bainitic ferrite formed at low temperature with a high amount of retained austenite leading to a high ductility and high tensile strength of the steel. Formation of nano-bainite has been studied thoroughly in literature as well as tempering of nano-bainitic steels. More recently it has been shown that adding carbide forming elements such as V and Mo increases the resistance to softening and hence the mechanical properties of nano-bainite at moderate temperature. Investigating the secondary carbide precipitation inside a nano-bainitic microstructure is thus necessary to optimize the thermal treatments for this promising new class of steels. Three initial microstructures of the same steel composition are investigated: martensite, martensite + retained austenite and nano-bainite. Studying the more conventional case of martensite has served as a basis to better understand the microstructure evolutions inside the nano-bainitic steel. The microstructural evolutions during the tempering were followed by complementary experimental techniques including dilatometry, in situ high energy synchrotron X-ray diffraction (HEXRD), conventional and high resolution TEM. The sequence of carbides precipitation and dissolution (transition-iron-carbides, cementite, and alloyed carbides) both during heating and holding is shown similar for the three initial microstructures. The kinetics are similar as well as cementite chemical composition and size distributions of cementite and alloyed carbides. It has been shown too that the three microstructures present a high retained austenite stability. Moreover, the analyses of the lattice parameters evolutions all along the tempering treatment associated with carbon mass balances have allowed to better understand the carbon distributions between carbides and matrix phases. The nucleation and growth model from a previous work was upgraded to take into account secondary precipitation and different new features (e.g. para-equilibrium interface condition for first stage of cementite growth, etc.). This model predicts the kinetics of precipitation, the particle densities and size distributions as well as matrix and carbides mean composition for different tempering conditions. Apart from the comparison with the experimental results that is discussed, it allowed to interpret the similar tempering behaviour for the three initial microstructures

Adolescent school violence is a serious health problem that adversely affects the learning process. Prevention of juvenile delinquency and antisocial behavior has become a major field of research and policy making worldwide. The present study has been undertaken in an attempt to study the phenomenon of female juvenile delinquency in the schools in Cyprus since there is a lack of research on this challenging issue and its diverse parameters. The aim of this study has been to examine the extent of the phenomenon of female juvenile delinquency in secondary schools in Cyprus and the role of gender in delinquency. Further, emotional factors precipitating delinquent behavior, specifically the role of depression and traumatic experiences have been examined. The role of ethnicity in a rapidly changing, multicultural society has also been taken into consideration.

Mise en evidence par microscopie electronique en transmission, spectrometrie sims et photoelectron d'une amorphisation superficielle et de la formation de fins precipites cristallins tin::(x) dans le cas d'une implantation, d'azote. Influence de la temperature et de la dose d'ion sur l'epaisseur de la couche. Correlation entre la microstructure d'implantation et les proprietes tribologiques. Le coefficient de frottement se trouve reduit et la resistance a l'usure se trouve amelioree de facon durable. L'initiation et la propagation des processus de degradation sont ainsi ralenties

The aim of this work was to study the separate effect of fission fragment damage on the structural integrity and matrix dissolution of uranium dioxide in water. Radiation damage similar to fission damage was created by irradiating bulk undoped and doped ‘SIMFUEL’ disks of UO2, undoped bulk CeO2 and thin films of UO2 and CeO2 with high energy Xe and U ions. The UO2 thin films, with thicknesses in the range of 90 – 150 nm, were deposited onto (001), (110) and (111) orientations of single crystal LSAT (Al10La3O51Sr14Ta7) and YSZ (Yttria-Stabilised Zirconia) substrates. The CeO2 thin films were deposited onto single crystal silicon (001) substrates. Part of the bulk UO2 and CeO2 samples, the thin films of UO2 on the LSAT substrates and the thin films of CeO2 were irradiated with 92 MeV 129Xe23+ ions to a fluence of 4.8 × 1015 ions/cm2 to simulate the damage produced by fission fragments in uranium dioxide nuclear fuel. Part of the bulk UO2 and CeO2 samples and the thin films of UO2 on the YSZ substrates were irradiated with 110 MeV 238U31+ ions to a fluence of 5 × 1010, 5 × 1011 and 5 × 1012 ions/cm2 to study the accumulation of the damage induced. The irradiated and unirradiated samples were studied using scanning electron microscopy (SEM), focused ion beam (FIB), atomic force microscopy (AFM), energy dispersive X-ray (EDX) spectroscopy, electron probe microanalysis (EPMA), X-ray diffraction (XRD), electron backscatter diffraction (EBSD), secondary ion mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS) techniques to characterise the as-produced samples and assess the effects of the ion irradiations. Dissolution experiments were conducted to assess the effect of the Xe ion irradiation on the dissolution of the thin film UO2 samples on the LSAT substrates and the bulk and thin film CeO2 samples. The solutions obtained from the leaching of the irradiated and unirradiated samples were analysed using inductively coupled plasma mass spectrometry (ICP-MS). XRD studies of the bulk UO2 samples showed that the ion irradiations resulted in an increased lattice parameter, microstrain and decreased crystallite size, as expected. The irradiated UO2 thin films on the LSAT substrates underwent significant microstructural and crystallographic rearrangements. It was shown that by irradiating thin films of UO2 with high energy, high fluence ions, it is possible to produce a structure that is similar to a thin slice through the high burn-up structure. It is expected that the ion irradiation induced chemical mixing of the UO2 films with the substrate elements (La, Sr, Al, Ta). As a result, a material similar to a doped SIMFUEL with induced radiation damage was produced.

碩士
國立交通大學
理學院應用科技學程
100
Olanzapine, quetiapine and aripiprazole were new generation atypical antipsychotics. Several methods have been developed to determinate these drugs in human blood, plasma, or serum with different analyzing methods. For LC/MS, liquid-liquid extraction or solid-phase extraction pretreatments were usually used before analysis. These pretreatment methods were complex, expensive, and time consuming. In this study, a rapid and effective protein precipitating procedure was used for extraction of antipsychotics in human plasma for LC/MS analysis. First, the parameters of MS including flow rate of dry gas, pressure of nebulize gas, capillary voltage and temperature were optimized for each analytes for best sensitivity. Mirtazapine was added as internal standard which has similar structure construction with analyte olanzapine, quetiapine, and aripiprazole. A three analytes and internal standard were observed under positive mode with m/z 313, 384, 448 and 266 corresponding to related [M + H]+ adducts. By using acetonitrile and H2O containing 20 mM ammonium acetate and 0.15% triethylamine as mobile phase, 3 analytes and spiked internal standard were separated within 9 minutes. Organic solvents with different polarity were compared for both extracting and interferences removing (most iv were serum albumins) efficiency. Methanol was chosen as extraction organic solvent for best recovery and better resolution of HPLC separation. Then, different extraction organic solvent volume was optimized for lowest sample dilution, which affects the signal and sensitivity in MS. Under optimized conditions, all analytes have good linear range from 2.5 to 100 ng/ml, 100 to 800 ng/ml, 50 to 350 ng/ml for olanzapine, quetiapine and aripiprazole separately, which were suitable for actual clinical dosed concentrations. The coefficients of determination (r2) were between 0.9926 to 0.9965 and the estimated detection limits were 0.94, 0.95 and 1.35 ng/ml for olanzapine, quetiapine and aripiprazole. The analytes performing good recoveries in proposed method in real human serum sample. The method presented in this study was related simple but existed good extraction efficiency for all three analytes and removed most of interferences contained in human serum samples, which providing a better way of sample pretreatment for LC/MS analysis.