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No description available.

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.

Nickel-boron coatings are used to improve friction and wear properties (and, in some cases, corrosion resistance). The nickel-boron coating investigated here is 5-6 wt% boron, and is deposited by electroless plating on a 1018 steel substrate. It is amorphous as-plated, and heat treatment is used to crystallize the coating to improve its hardness. To better understand and predict the effects of heat treatment, samples that had been isothermally annealed at various temperatures from 500ºC to 800ºC for either 2h or 5h were examined by several methods to determine the diffusion effects taking place during annealing. Samples were examined by XRD, both at the coating surface and at multiple depths within the coating. Optical microscopy and SEM were used to view the structure of the coating in cross-section. Cross sections were etched and examined by optical microscopy and SEM, as well as EDS, which was used to develop a Ni-Fe composition profile at the coating-substrate interface. Microhardness measurements were taken and used to develop microhardness profiles. Additional samples were annealed to investigate boron oxidation at the coating surface. Based on the data, there is a reduced amount of Ni3B near the outer surface of the heat-treated coatings, with the thickness of the resultant γ-Ni layer increasing with annealing time and temperature, from 2.4 to just over 13 µm. This low-boron region indicates that boron is diffusing out through the surface of the coating and oxidizing, which the literature indicates should result in the formation of B2O3. Because B2O3 is water-soluble, it is likely that it dissolved during the water quench that concluded most anneals. Diffraction and EDS data also indicate interdiffusion of the nickel in the coating and the iron in the steel substrate. This leads to the formation of a soft interdiffusion layer between the Ni3B coating bulk and steel substrate that appears to be a mix of ferrite and Ni3Fe.

Au cours de la dernière décennie, le procédé de fabrication additive par fusion sélective d'un lit de poudre SLM a attiré une grande attention dans le domaine de l'industrie, car il permet de produire rapidement des pièces de formes complexes. Le but de ce travail est d'étendre les performances des procédés SLM en étudiant la possibilité d'élaborer des pièces en atmosphère raréfiée. Pour atteindre cet objectif, une approche théorique et expérimentale a été développée, avec la mise en place d'une machine de fusion sélective par laser capable de travailler dans le domaine de pression de 1 à 10-2 mbar.Le travail sous vide permet d'éviter la formation du "bouclier" de plasma généré à partir de l'atmosphère de gaz ionisé par l'énergie du laser. Ceci permet d'une part d'éviter la contamination chimique du matériau (oxydation, nitruration,...) au cours des processus de fusion et d'autre part de réduire le taux de porosité. L'effet des paramètres du laser et des variables d'environnement sur la qualité de pièces a été étudié en considérant le cas du fer pur, de l'acier Inox 316L et du titane.Par ailleurs nous avons étudié la possibilité d'obtenir des alliages in-situ au cours de la fabrication par la technique SLM à partir de mélanges de poudres.Des essais ont été conduits à partir de mélanges Mg/Al, Fe/Ni et Ti/Ni. Dans tous les cas nous avons pu obtenir des alliages in-situ pour les domaines de composition visés qui correspondent à des applications pratiques (structures légères, alliage magnétique à faible coercivité, alliage à mémoire de forme). Les propriétés des matériaux obtenus, d'après les premières caractérisations effectuées, se comparent de façon favorable par rapport aux techniques classiques d'élaboration et de mise en œuvre. / During the last decade, selective laser melting attracted attention in industry because it could allow producing parts with complex shapes rapidly and accurately. The aim of this work is to obtain parts with desired properties by SLM technology. To achieve this point, a theoretical and experimental approach was developed concerning a new process which carries out the selective laser melting process at pressures in the range 1 to 1×10-2 mbar.Vacuum operating under allows avoiding the plasma shield generated from the gas atmosphere ionized by the high laser energy, which on the one hand avoids the chemical contamination (oxidizing, nitriding…) during the melting process and on the other hand reduces the porosity rate. The effect of laser parameters and environment variables on the quality of parts was studied by considering the case of pure iron, stainless steel 316L and titanium.Moreover, we studied the possibility of obtaining in-situ alloys during the SLM manufacturing technique from mixtures of powders.Tests were conducted from mixtures Mg/Al, Fe/Ni and Ti/Ni. In all cases we were able to obtain in-situ alloys for areas covered composition corresponding to practical applications (lightweight structures, low coercivity magnetic alloy, shape memory alloy). The properties of material obtained from the characterizations performed, which are comparable with the conventional development and implementation.

Les accumulateurs Ni-MH (Nickel-Métal-Hydrure) sont un sujet prometteur et largement étudié dans les recherches d’une énergie propre et durable. Trouver le matériau idéal pour l'électrode négative à haute densité volumétrique et gravimétrique est la clé pour l’application de cette technologie. Les hydrures métalliques à base de Ti-Ni ont des propriétés équilibrées entre la capacité d’hydrogène et les performances électrochimiques.L’objectif de cette thèse est d’étudier les effets de substitutions/additions d’éléments et de la mécanosynthèse sur la structure et les propriétés d’hydrogène des alliages Ti-Ni. Dans cette étude, une série d’alliages à base de Ti-Ni avec des substitutions/additions de Mg ou de Zr ont été systématiquement étudiés.Les alliages (TiNi)1-xMgx, (TiH2)1.5Mg0.5Ni, and Ti2-xZrxNi ont été synthétisés par mécanosynthèse à partir de poudres élémentaires. Dans un premier temps, l’influence du temps de broyage et les effets de substitutions/additions sur les microstructures ont été caractérisés par des techniques telles que la DRX, le MEB et le MET. Dans un second temps, les propriétés d’hydrogénation des différents alliages ont été mesurées par des réactions solid-gaz et par cyclage électrochimique.La théorie de la fonctionnelle de la densité (DFT) en utilisant le programme CASTEP a permis de calculer les enthalpies de formation afin de comparer la stabilité thermodynamique des alliages obtenus. Dans ces travaux de recherche, nous avons identifié les priorités d’alliage des ternaires Ni-Ti-Mg et Ti-Ni-Zr dans des conditions de broyage. La transformation structurale du Ti en phase CFC, induite par l’introduction d’éléments étrangers, a été mise en évidence.Les courbes PCI (Pression-Composition-Isothermes) et les capacités de décharge en fonction du nombre de cycles indiquent les propriétés d’hydrogène des alliages obtenus, y compris TiNi, Ti2Ni (amorphe), Ti-Mg et Ti-Zr. / Ni-MH (Nickel-Metal-Hydride) batteries have been a promising and extensively studied topic among clean and sustainable energy researches. Finding the ideal material for the negative electrode with high volumetric and gravimetric densities is the key to apply this technology on broader applications. Metal hydrides based on Ti-Ni have balanced properties between hydrogen capacity and electrochemical performances in cycling.The objective of this thesis is to study the effects of element substitution/doping and mechanical alloying on the structural and hydrogen properties of Ti-Ni alloys. In this study, a series of Ti-Ni based systems with Mg or Zr doping/substitution have been systematically investigated.The metallic compounds (TiNi)1-xMgx, (TiH2)1.5Mg0.5Ni, and Ti2-xZrxNi were synthesized by mechanically alloying from elemental powders.The milling time and effects of Mg, Zr substitution/doping were studied firstly in respect of their microstructures, using characterization techniques including XRD, SEM, TEM (EDX support), followed by the hydrogen properties measurements of the samples by hydrogen solid-gas reaction and electrochemical cycling.A first principle calculation tool based on DFT (Density Functional Theory) was carried out to further investigate the enthalpy of formation in order to compare the thermodynamical stability of the obtained compounds. In the study, we have found the alloying priorities in the ternary alloys Ti-Ni-Mg and Ti-Ni-Zr under milling conditions.A structure transformation of Ti to FCC induced by foreign elements is reported and investigated. Enthalpy of formation per atom of the compounds were obtained by DFT calculations, which helped interpreting the experimental results. PCI (Pressure Composition Isotherms) curves and discharge capacities as the function of cycling numbers revealed the hydrogen properties of the obtained compounds, including TiNi, Ti2Ni (amorphous), Ti-Mg and Ti-Zr.

Le stockage de l'hydrogène est l'un des plus grands problèmes techniques qui restreignent l'application pratique de l'hydrogène. Les hydrures métalliques sont considérés comme la solution principale à ce problème puisqu'ils peuvent absorber et désorber de façon réversible une grande quantité d'hydrogène sous une température et une pression modérées. Par ailleurs, les hydrures métalliques utilisés comme électrodes négatives dans les accumulateurs Nickel-Métal Hydrure (Ni-MH) sont également les composants clés des performances de ces derniers.Dans cette thèse, les alliages métalliques TiMgNix, MgTi1-xNix et TiMg1-xNix ont été synthétisés par broyage mécanique à partir de poudres élémentaires. La microstructure et les transformations de phase des échantillons préparés ont été caractérisées par DRX, MEB et MET (avec microanalyse EDS).Les propriétés d'hydrogénation ont été mesurées par réaction d'hydrogène solide-gaz et par des essais électrochimiques. Un diagramme de composition-capacité 3D a été établi sur la base du diagramme de phase ternaire Ti-Mg-Ni. Un procédé de broyage en deux étapes a été mis en œuvre pour améliorer les performances électrochimiques des alliages Ti-Mg-Ni.De plus, les alliages TiNi1-xCux ont été synthétisés par broyage mécanique et ensuite recuits. L 'influence de la substitution du nickel par le cuivre sur la structure et les propriétés électrochimiques est étudiée en utilisant une double approche: expérimentale et par simulation.Les résultats obtenus par la théorie de la fonctionnelle de la densité (DFT) en utilisant le programme CASTEP montrent que l'enthalpie de formation et l'énergie d'adsorption de l¿hydrogène de la phase pseudo-binaire Ti(Ni, Cu) sont en bon accord avec les résultats expérimentaux. / The storage of hydrogen is one of the biggest technical problem that restrict the practical application of hydrogen. Metal hydrides are mainly regarded as the solution facing to this issue since it can reversibly absorb and desorb big amount of hydrogen under moderate temperature and pressure. Meanwhile, metal hydrides used as the negative electrodes of Ni-MH batteries are also the key components to the battery performance.In this thesis, the metallic composite TiMgNix, MgTi1-xNix and TiMg1-xNix were synthesized by mechanical alloying from elemental powder. The microstructure and phase transformation of prepared samples were characterized by XRD, SEM, TEM (EDS support). The hydrogenation properties were measured by hydrogen solid-gas reaction and electrochemical tests. Based on the Ti-Mg-Ni ternary phase diagram, a 3D composition-capacity diagram have been established. Two-step mill process was proposed for meliorating the electrochemical performance of Ti-Mg-Ni alloys.Additionally, TiNi1-xCux alloys had been synthesized by mechanical alloying and subsequent annealing and studied using experimental and computational approaches. The influence of Cu substitution for Ni on the phase structure and electrochemical properties are investigated. The first principle calculation was carried out to study the formation enthalpy and hydrogen adsorption energy of pseudo-binary Ti(Ni, Cu) phase. The computational results are in good agreement with experimental results.

Neste trabalho, um sensor eletroquímico avançado baseado em eletrodo de grafite de lápis modificado via eletropolimerização do monômero de N,N\'-bis(salicilideno)etilenodiaminoníquel(II) na presença de nanopartículas de Ni(OH)2 suportadas em carbono (chamado aqui de poli[Ni(salen)] e Ni(OH)2C) foi desenvolvido e investigado para quantificação de furosemida (FUR) em meio alcalino. O sensor eletroquímico e seus componentes foram extensivamente caracterizados por técnicas físico-químicas, enquanto que o processo de oxidação da furosemida foi investigado por espectroscopia no infravermelho com transformada de Fourier in situ (FTIV in situ). Estes resultados indicam que a oxidação da furosemida nestas condições leva à formação de 2-amino-4-cloro-5-sulfamoilbenzoato e 5-hidroxi-furano-2-carboxilato. A resposta eletroquímica do eletrodo de grafite modificado (EGM) para a determinação de furosemida foi medida por voltametria cíclica (VC). A curva de calibração (mudança de corrente de pico voltamétrico versus concentração de FUR) apresentou uma faixa linear de 2,5 × 10-10 mol L-1 a 2,7 × 10-9 mol L-1 com um limite de detecção calculado tão baixo quanto 1,45 × 10-10 mol L-1 nas condições otimizadas, que é menor do que os valores relatados na literatura. A sensibilidade ultrabaixa obtida com sensor desenvolvido foi atribuída a um efeito sinérgico entre o filme de poli[Ni(salen)] e as nanopartículas de Ni(OH)2/C. / In this work, an advanced electrochemical sensor based on pencil graphite electrode modified via electropolymerization of the N,N\'-bis(salicylidene)ethylenediaminonickel(II) monomer in the presence of carbon supported Ni(OH)2 nanoparticles (here called as poly[Ni(salen)] and Ni(OH)2/C) was developed and investigated for furosemide (FUR) quantification in alkaline medium. The electrochemical sensor and its components were extensively characterized by physico-chemical techniques, while the furosemide oxidation process was investigated by in situ Fourier transform infrared spectroscopy (in situ FTIR). These results indicate that the oxidation of furosemide in these conditions leads to the formation of 2-amino-4-chloro-5-sulfamoylbenzoate and 5-hydroxy-furan-2-carboxylate. The electrochemical response of the modified graphite electrode (MGE) for the determination of furosemide was measured by cyclic voltammetry (CV). The calibration curve (change of voltammetric peak current vs. FUR concentration) presented a linear range from 2.5 × 10-10 mol L-1 to 2.7 × 10-9 mol L-1 with a calculated limit of detection as low as 1.45 × 10-10 mol L-1 under the optimized conditions, which is lower than values reported in the literature. The ultra-low sensitivity obtained with the MGE sensor was attributed to a synergistic effect between the poly[Ni(salen)] film and Ni(OH)2/C nanoparticles.

The Garson Ni-Cu-PGE deposit is located on the South Range of the 1850 Ma Sudbury structure along the contact between the Sudbury Igneous Complex (SIC) and the underlying metasedimentary and metavolcanic rocks of the Paleoproterozoic Huronian Supergroup. It comprises four ore bodies that are hosted by E-W-trending shear zones that dip steeply to the south. The shear zones formed as south-directed D1 thrusts in response to flexural-slip during regional buckling of the SIC. They imbricated the ore zones, the SIC norite, the underlying Huronian rocks and they emplaced slivers of Huronian rocks and anatectic breccia into the overlying Main Mass norite. Coexisting garnet-amphibole pairs yielded syn-D1 amphibolite facies metamorphic temperatures ranging from ~550°C to 590°C. The shear zones were coeval with the moderately southdipping South Range and Thayer Lindsley shear zones, which formed to accommodate the strain in the hinge zone as the SIC tightened with progressive D1 shortening. The SE limb of the SIC was overturned together with the D1 thrusts, which were then reactivated as steeply south-dipping reverse shear zones during syn-D2 greenschist metamorphism. Syn-D2 metamorphic titanite yield a U-Pb age of ca. 1849 ± 6 Ma, suggesting that D1 and D2 are part of a single progressive deformation event that occurred immediately after crystallization of the SIC during the Penokean Orogeny. The ore bodies plunge steeply to the south parallel to the colinear L1 and L2 stretching mineral lineations. Ore types consist mainly of pyrrhotite-pentlandite-chalcopyrite breccia ores, but also include pyrrhotite-pentlandite-chalcopyrite disseminated sulfide mineralization in norite, and syn-D2 quartz-calcite-chalcopyrite-pyrrhotite-pentlandite iv veins. In the breccia ores, matrix sulfides surround silicate rock fragments that have a strong shape-preferred orientation defining a pervasive foliation. The fragments are highly stretched parallel to the mineral lineations in wall rocks, suggesting that the ore bodies are zones of high strain. Pyrrhotite and chalcopyrite occur in piercement structures, in boudin necks between fragments, in fractures in wall rocks and in fold hinges, suggesting that the sulfides were mobilized by ductile plastic flow. Despite evidence of high strain in the ore zones, the sulfide matrix in D1 and D2 breccia ores show little evidence of strain as they consist predominantly of polygonal pyrrhotite aggregates, suggesting that they recrystallized during, or immediately after D1 and D2. However, rare elongate pyrrhotite grains aligned parallel to S2 are locally preserved only in D2 breccia ores. Exsolution of pentlandite loops along grain boundaries of elongate pyrrhotite formed S2-parallel pentlandite-rich layers in D2 breccia ores, whereas the pentlandite loops are multi-oriented in D1 contact breccia as they were exsolved along grain boundaries polygonal pyrrhotite. Because exsolution of pentlandite post-date D1 and D2, and that individual pentlandite grains neither have a shape-preferred orientation nor show evidence for cataclastic flow, the sulfides reverted to, and were mobilized as a homogeneous metamorphic monosulfide solid solution (mss) during D1 and possibly D2. This is in agreement with predictions from phase equilibria as the average Garson composition plots within the mss field in Fe-Ni-S ternary diagram at temperatures above ~400°C. Disseminated and breccia ores at Garson have similar mantle-normalized multi-element chalcophile patterns as undeformed contact-type disseminated and massive ore, v respectively, at the well known Creighton mine in the South Range. This suggests that the Garson ores are magmatic in origin and that their compositions were not significantly altered by hydrothermal fluids and deformation. The lack of variations in Ni tenors between the disseminated and breccias ores suggest that the R-factor was not the process controlling metal tenors because the disseminated sulfides do not consistently have higher metal tenors than the breccia ore. The breccia ores are enriched in Rh-Ru-Ir and are depleted in Cu-Pd-Pt-Au, in contrast to footwall-type ore at the nearby Garson Ramp mine which is enriched in the same metals. When Ni100, Rh100, Ir100, Pt100 and Pd100 are plotted against Cu100, the breccia and footwall-type ore analyses plot along model mss fractionation and sulfide melt model curves, suggesting that these two ore types are related by mss fractionation. In summary, the Garson breccia ores are mss cumulates that settled quickly at the base of the SIC via a gravity filtration process, and were mobilized as a metamorphic mss by ductile plastic flow during D1 and D2. Despite minor local hydrothermal mobilization of some metals, the study confirms findings from other studies that highly deformed Ni-Cu- PGE deposits, such as the Garson deposit, can provide important information on the genesis of the deposits.