The stability of Haynes 230 and Hastelloy C-276 nickel alloys exposed to high temperature molten salt with trace contaminants (i.e., water and oxygen) is found to be acceptable for using these metals to house anaerobic MgCl2-KCl and NaCl-KCl-ZnCl2 molten salts at 800oC. The corrosion rate determined by gravimetric tests range from -98 µm/year to 20. 13 µm/year at 800˚C. The corrosion rate is estimated to be 16.14 µm/year for Haynes 230 and 10.03 µm/year for Hastelloy C-276 based on the weight loss and surface area of the coupons when the coupons of Haynes 230 and Hastelloy C-276 alloys are immersed in molten MgCl2-KCl salt in sealed quartz containers and left in an oven at a temperature of 800˚C up to 16 days. The corrosion rate is estimated to be -20.46 µm/year for Haynes 230 and -7.36 µm/year for Hastelloy C-276 based on the weight loss and surface area of the coupons when the alloys are immersed in molten NaCl-KCl-ZnCl2 salt in sealed quartz containers and left in an oven at 800˚C up to 56 days. The corrosion rate of the alloys are well below the DOE requirement of 50 µm/year for the alloys in molten chloride salts to be considered acceptably stable. Ultimate tensile strength (UTS) after immersion of Haynes 230 and Hastelloy C-276 in molten salt ranged from 634 MPa to 860 MPa. The UTS of Haynes 230 is estimated to be 642 MPa after exposure to NaCl-KCl-ZnCl2 for 4 weeks at 800˚c and 841 MPa after exposure to MgCl2-KCl for 4 weeks at 800˚c compared to an untreated sample which achieved a UTS of 851 MPa. Likewise, the UTS of Hastelloy C-276 is estimated to be 692 MPa after exposure to NaCl-KCl-ZnCl2 for 4 weeks at 800˚c and 842 MPa after exposure to MgCl2-KCl for 4 weeks at 800˚c compared to an untreated sample which achieved a UTS of 830 MPa. Molten chloride salts, such as NaCl-KCl-ZnCl2 and KCl-MgCl2, are pretreated by heating and bubbling dry Argon gas in the salt in order to remove oxygen and water and thereby reduce the corrosion of metal containers of molten salt. Monitoring the relative humidity and percent oxygen of the exhaust gas during the sparging of dry Argon at 240 sccm into 150 g of molten chloride salt at 500˚C for NaCl-KCl-ZnCl2 and 700˚C for KCl-MgCl2 allows an estimation time to reach a low level of oxygen and water in the salt and to estimate the amount of oxygen and water removed. Results show water is more difficult to remove than oxygen from the salt. Ten minutes of sparging with dry argon brings oxygen content of exhuast gas to<0.1% O2. Approximately fifty minutes of sparging leaves the exhaust gas only containing<0.7% RH. The total moles of oxygen removed from the salts are estimated to be 0.0043 moles for molten NaCl-KCl-ZnCl2 and 0.0076 moles for KCl-MgCl2. The total moles of water removed from the NaCl-KCl-ZnCl2 salt is estimated to be 0.016108379 moles and 0.002321214 moles from molten KCl-MgCl2.

Mainly two different morphologies of martensite can be obtained in steels depending on the amount of alloying elements. The first morphology, referred to as lath martensite, forms in low alloy, low carbon steels. It is, by far, the most extensively studied form of martensite due to its industrial applications. The second morphology of martensite, referred to as plate martensite, forms in highly alloyed and in high carbon steels and in particular in Fe-High Ni alloys. In this case, the transformation product is disc shaped and internally twinned. This morphology is the only form of martensite that has the potential to exhibit shape memory properties. It is therefore of great interest to understand the mechanisms of its formation. This is investigated in the present dissertation through the study of the martensitic transformation occurring in a Fe-30.5%Ni-0.155%C alloy. More precisely, the influence of stress and grain size on the crystallography of plate martensite is discussed in the general framework of the phenomenological theory of martensite crystallography. This theory allows associating a unique shape deformation to each orientational variant. In this way, the experimental observations carried out at different length scales by means of optical microscopy, EBSD and TEM can be used to infer the transformation path followed under different conditions. Firstly, the burst configurations of variants observed in coarse-grained austenite under stress free conditions are rationalized by considering the mechanical couplings between the variants. It is shown that self-accommodating and autocatalytic couplings are responsible for the formation of hierarchical configurations of variants. More precisely, the transformation is shown to occur through the alternate formation of perpendicular plate groups of variants. Self-accommodation is the dominant coupling between variants of the same plate group while autocatalytic couplings are responsible for the transfer of the transformation from one generation to the next. It is suggested that the plastic accommodation of the shape deformation plays a dominant role in propagating the transformation to a lower length scales. Secondly, the influence of a uniaxial stress state on the transformation is studied. It is seen experimentally that only the most favoured variants are systematically formed in coarse Cube grains while coarse non-Cube grains generally transform into plate groups of variants that are only moderately favoured by the stress. These observations are well explained by considering the interaction energy between the applied stress and the shape deformation associated with the transformation. Thirdly, the influence of the austenitic grain size on the transformation is also studied. A decrease in grain size is seen to decrease the martensite start temperature. For a grain size below about 10µm, the thermal transformation in liquid nitrogen is indeed suppressed in the present alloy. This observation is related to the increasing yield strength of austenite as the grain size is reduced. A noticeable change in the morphology of martensite also accompanies the decrease in grain size. Indeed, martensite forming in coarse-grained austenite is mostly lens shaped and partially twinned while it appears plate shaped and fully twinned in smaller grains. Furthermore, martensite forming in fine-grained austenite develops self-accommodating configurations suggesting that most of the transformation deformations are elastically accommodated in this case. This is believed to be related to the observance of a shape memory effect in the present alloy in its fine-grained condition. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

Submitted by Kilvya Braga (kilvyabraga@hotmail.com) on 2018-04-23T13:59:14Z No. of bitstreams: 1 SUELENE SILVA ARAÚJO - DISSERTAÇÃO (PPGEM) 2015.pdf: 3709690 bytes, checksum: 1d6f1a6f3675dd7c45fb2cd75c6c92bf (MD5) / Made available in DSpace on 2018-04-23T13:59:14Z (GMT). No. of bitstreams: 1 SUELENE SILVA ARAÚJO - DISSERTAÇÃO (PPGEM) 2015.pdf: 3709690 bytes, checksum: 1d6f1a6f3675dd7c45fb2cd75c6c92bf (MD5) Previous issue date: 2015-08-07 / CNPq / Neste trabalho foi avaliado o comportamento dinâmico e a fadiga termomecânica de fios de uma liga com memória de forma (LMF) CuAlNi submetidos a ensaios cíclicos utilizando um analisador dinâmico mecânico (DMA). Assim, foram realizadas análises para determinar a capacidade de amortecimento e o módulo de elasticidade dos fios e adicionalmente a fadiga estrutural sob controle de deformação em modo de flexão simples alternada, a partir da variação da amplitude de deslocamento, para três temperaturas distintas. O comportamento dinâmico revelou uma considerável capacidade de amortecimento dos fios, principalmente durante a transformação de fase martensitica, apresentando um expressivo pico de absorção de energia. Além disso, o módulo de elasticidade (rigidez) apresentado pelos fios revelou a existência de um importante aumento durante a transformação, diferenciando as duas distintas fases. Notou-se também a partir dos resultados dos ensaios de fadiga que as características funcionais dos fios dependem de forma direta da amplitude de deformação imposta, influenciando nos valores de tensão e no tempo de vida dos fios, revelando que a fadiga pode ser considerada de baixo ciclo. / This study evaluated the dynamic behavior and the thermomechanical fatigue of CuAlNi SMA wires subjected to cyclic tests using a DMA device. Therefore, analyzes were performed to determine the damping capacity and stiffness of SMA wires, in addition to structural fatigue under strain control from the amplitude variation at three different temperatures. The evolution of the wire’s behavior has shown a considerable damping capacity, mainly during the martensitic phase transformation, presenting a significant peak of energy absorption. Moreover, the storage modulus (stiffness), revealed a significant increase during transformation, differentiating the distinct phases. It has been also noted, from the results of fatigue tests, that the functional behavior of the SMA wires depend directly on the amplitude of the imposed strain, influencing on the stress values as well as on the wire’s lifetime, revealing that fatigue can be considered of low cycle type.

Replacement of cobalt in cemented carbides has gained in attention recently because threats of regulations due to health issues (cancerogenic effect), increased demand from the electric vehicle industry and the questionable extraction from countries like Democratic Republic of Congo. In this report the use of Ni-based binder as an alternative binder for cemented carbides has been explored. The design is based on producing a Ni-based superalloy binder which contains dispersed Ni3Al Gamma Prime (γ’) -phase precipitates in the binder matrix. The investigation focuses on the design of cemented carbide compositions and processes that ensures the formation of γ’- precipitates, the control of their morphology and distribution as well as the effect of heat treatment. To do this a Ni-Al master alloy has been designed that enables the formation of γ’-precipitates in WC-Ni-Al-X systems, produced by conventional powder metallurgy process including standard free sintering. Furthermore, the addition of usual elements in the cemented carbide industry (such as Ti, Cr, Ta, Nb) and their effect on the stability of γ’-precipitates has been investigated. A method to reveal the precipitates including ion-polishing and electro-etching has been developed. Basic mechanical properties such as hardness and toughness have been investigated, revealing particular crack propagation in Ni-based binder reinforced with γ’-precipitates. It was found that the common variables in cemented carbide manufacturing influence all aspects regarding the stability of γ’-phase. By varying the powder type, binder composition and content, the carbon balance, the WC grain size and the heating/cooling steps; the formation of γ’-precipitates (size, morphology, distribution, etc.) can be controlled to tailor the properties of the cemented carbide. / Att hitta en ersättning av kobolt i hårdmetall har nyligen uppmärksammats bl.a. eftersom regleringar hotar användning av ämnet pga. dess cancerogenitet, en ökande efterfrågan från elfordonsindustrin samt den moraliskt tvivelaktiga utvinningen som sker i länder som Demokratiska Republiken Kongo. I denna rapport har användningen av ett nickel-baserat bindemedel som ett alternativt bindemedel för hårdmetaller undersökts. Designen är baserad på att producera en nickel-baserad superlegering som bindemedel som innehåller dispergerad Ni3Al Gamma Prim (γ’) – fas utfälld i bindemedlet. Utredningen fokuserar på designen av hårdmetallskompositioner och processer som försäkrar formationen av γ’-utfällningar, kontroller av dess morfologi, distributionen samt hur värmebehandlingar påverkar. För att kunna göra detta har en Ni-Al masterlegering skapats som möjliggör γ’-utfällningar i ett WC-Ni-Al-X system, producerat med konventionell pulvermetallurgiprocess inkluderat standard fri sintring. Dessutom har tillsatsen av vanliga ämnen i hårdmetallindustrin (such as TI, Cr, Ta, Nb) samt deras effekt på stabiliteten hos γ’-utfällningarna undersökts. En metod för att upptäcka utfällningarna, som inkluderar jonpolering och elektroetsning har utvecklats. Grundläggande mekaniska egenskaper som hårdhet och seghet har undersökts, vilket har avslöjat en speciell sprickutbredning i den nickelbaserade bindaren förstärkt med γ’-utfällningar. Det visade sig att de vanliga variablerna förenade med tillverkning av hårdmetall påverkar samtliga aspekter gällande stabiliteten hos γ’-utfällningar. Genom att variera pulvertyp, bindemedelkomposition och innehåll, kolbalansen, WC-kornstorlek och uppvärmning samt kylningssteg så påverkas bildningen av γ’-utfällningar (storlek, morfologi, distribution, etc..) som kan kontrolleras för att skräddarsy egenskaperna för hårdmetallen.