The addition of rare earth (RE) alloying elements is a promising method for improving the strength, ductility and overall formability of magnesium (Mg) alloys. However, the underlying mechanism for this phenomenon remains unclear. An investigation on the effect of the rare earth element, scandium (Sc), on binary Mg-Sc alloys has been pursued. Tension and compression tests were performed on a series of dilute binary Mg-Sc alloys at temperatures of 298 K, 78 K and 4.2 K. As a reference, pure Mg was also investigated for comparative purposes. Differences in tension and compression stress-strain curves highlighted distinct activated mechanisms, where slip dominated in tension and twinning governed compression. The observed increase in ductility and prolonged necking was attributed to a weaker basal texture, enhanced twinning and non-basal slip. A decreased work hardening rate suggests an improvement in dislocation recovery with Sc addition. In compression, Mg-Sc alloys followed Fleischer’s theory of solution hardening, where stress scales with concentration, c, as c^1/2; however, there was a very weak fit with both Fleischer and Labusch models under tension. The strengthening rate displayed by Mg-Sc was relatively weak compared to previously studied Mg-RE systems. However, considering the estimated misfit parameters, the size and modulus misfit was not enough to account for the strengthening rate. The results suggest that hardening of the twinning mode may influence strength. Constitutive modelling, based on a self-consistent plasticity model, was used to characterize the deformation behaviour. The simulations predicted an increased relative activity of non-basal <c+a> slip with Sc addition, supporting experimental results and proposed mechanisms in literature. The results of Mg-Sc alloys have been connected to theories that identify a decrease in stacking fault energy (SFE) as the determining factor for increased strength and ductility of Mg-RE alloys. A comparison of the SFE of previously studied REEs with Sc, demonstrated strong evidence towards the theory’s validity. Sc has been shown to only moderately reduce the SFE of Mg and hence, the present experimental results have shown a moderate increase in strength and ductility. Additional modelling and detailed dislocation analysis are suggested as future steps to further support this theory. / Thesis / Master of Applied Science (MASc)

No description available.

No description available.

No description available.

Among Al alloys, 2219 Al alloy possesses highest strength at elevated temperatures. However, the application of this alloy is also restricted to a maximum temperature of 150°C, above which, the strengthening precipitates coarsen rapidly resulting in a steep loss in strength. In the present investigation, an attempt has been made to improve the elevated as well as the room temperature properties of commercial 2219 alloy by the addition of small amounts of Sc & Mg, Sc & Zr, and Nb & Zr, and these are designated as 2219ScMg, 2219ScZr and 2219NbZr alloys, respectively. All the three alloys were cast in the form of strips in a water cooled copper mould using suction casting technique with a cooling rate of 102 to 103 K/s. The as-cast strips of 2219ScMg alloys were naturally aged and cold rolled by following three different routes (a) cold rolling, (b) homogenization and cold rolling and (c) hot rolling and cold rolling. A significant improvement in strength has been achieved by all the three wrought processing routes with greater than 140 MPa increase in 0.2% proof stress at room temperature and greater than 110 MPa increase in 0.2% proof stress at 200°C as compared to 2219-T851 alloy having 0.2% proof stress of 345 MPa at room temperature and 205 MPa at 200°C. Hardness values, measured at room temperature after exposure at 200°C, remain stable up to 1000 h. Microstructural analysis of 2219ScMg alloy reveals that Al3Sc or Al3(Sc,Zr) dispersoids form during casting and GP zones form on {100} and {111} plane during natural ageing. Subsequently, rolling introduces higher dislocation densities in the matrix. All these microstructural features contribute to the improvement of the room temperature strength of the alloy. On exposure at 200°C, GP zones transform to mainly θ′ and a few Ω precipitates. A finer, homogeneous distribution of θ′ and Ωprecipitates yields higher strength. Sc and Mg atoms are segregated at the θ′/matrix interface, which gives rise to slower growth kinetics of θ′ precipitates. As a result, the alloy exhibits better thermal stability at 200°C. For 2219ScZr and 2219NbZr alloys, the processing of the cast strip involves a two stage ageing procedure. This includes first stage ageing at 375°C for 2219ScZr alloy and at 400°C for 2219NbZr alloy. This is followed by solution treatment at 535°C for 30 minutes and second stage ageing at 200°C for both the alloys. For 2219ScZr alloy, tensile tests performed at room temperature, 200°C and 250°C show 0.2% proof stress of 456 ± 22 MPa, 295 ± 20 MPa and 227 ± 2 MPa respectively. The alloy is found to be thermally stable at 200°C. It is found that the addition of Sc and Zr results in the formation of Al3(Sc,Zr) precipitates during ageing at 375°C. These precipitates are fully coherent with the matrix and have a significant precipitation hardening effect. They also stimulate the nucleation of θ′′ and θ′precipitates during ageing at 200°C making them finer, homogeneously distributed and thermally stable. Therefore, the strength of the alloy at ambient and elevated temperature is improved. For 2219NbZr alloy, the tensile tests show that 0.2% proof stress is 409 ± 10 MPa at room temperature and 252 ± 22 MPa at 200°C. Microstructural observations reveal that the increase in strength is mainly due to the high volume fraction of Al3Zr precipitates, which form during ageing at 400°C, and due to the formation of θ′′ and θ′precipitates during ageing at 200°C. It is observed that Al3Zr precipitates facilitate the nucleation of θ′′ and θ′ precipitates making them finer, homogeneously distributed and thermally stable, as in the case of 2219ScZr alloy.

O Escândio é um elemento terra rara, utilizado principalmente em ligas de alumínio, células combustíveis de óxido sólido e na produção de lâmpadas de haletos metálicos. Apesar de ser o 31° elemento mais abundante na crosta terrestre, raramente é encontrado concentrado na crosta terrestre, e sua produção é sempre associada ao processamento de outros minerais na forma de um subproduto, ou a recuperação de sucata. Minérios de Níquel podem conter teores de Sc variando de 50 a 350ppm e resíduos gerados durante seu processamento pode concentrar o Sc acima de 1000ppm. A recuperação do Escândio de um resíduo da cadeia de produção do Níquel foi estudada, de modo a obter um óxido com pureza acima de 99,0% para aplicações industriais. O resíduo utilizado é um precipitado, na forma de hidróxido, e contém principalmente Fe, Cu, Ni e Co, sendo o teor de Escândio em base seca aproximadamente 1000ppm. O processo de recuperação proposto consiste na lixiviação atmosférica do resíduo, precipitação seletiva para concentração do escândio e extração por solventes. A lixiviação atmosférica em meio sulfúrico 2,0mol.L-1 a 70°C permitiu a recuperação de 92,5% do Escândio contido no resíduo. Entretanto, não foi seletiva, lixiviando também parte dos demais metais presentes. Após a lixiviação para concentrar o Escândio, antes da extração por solventes, foi realizada uma precipitação com NaOH. O intuito foi precipitar o Fe, principal contaminante presente no lixiviado, entretanto ocorreu a co-precipitação de 95,5% do Sc junto a 65,6% Fe em pH 2,0. O precipitado representou uma concentração do Escândio do resíduo em 5,6 vezes. Esse concentrado de Escândio obtido foi dissolvido em solução de H2SO4 para recuperação do Escândio por extração por solventes. O extrante escolhido foi o Cyanex 923, uma mistura de óxidos alquil-fósfinicos. O mecanismo de extração do Sc pelo Cyanex 923 observado foi a solvatação e a estequiometria da reação 1:2. Foi observado um aumento na extração do Sc com o aumento da concentração de H+. O processo de extração do Sc com o Cyanex 923 é exotérmico, sendo favorecido a temperatura ambiente. O teor de Fe na solução aquosa antes da extração é 35 vezes maior que o Escândio, e apesar do Cyanex 923 ser mais seletivo para o Sc do que para o Fe, parte do Fe é co-extraído. O Fe co-extraído foi removido da fase orgânica por meio de uma lavagem com H2SO4 3mol.L-1 com uma perda de Sc de 1,3%. A reextração do Sc na fase orgânica não foi efetiva utilizando ácidos fortes devido a formação de um complexo estável. Foi utilizado ácido oxálico, técnica consolidada para reextração de terras raras, para recuperação do Sc da solução orgânica e a recuperação do Sc foi de 84,3% para uma solução com 4,0% de ácido oxálico. O oxalato de Sc precipitado foi recuperado por filtração e calcinado a 600°C. O óxido obtido apresentou pureza mínima de 99,0%. / Scandium is a rare earth element, used mainly in special aluminum alloys, SOFC\'s and metal halide lamps production. Despite of being the 31st element more abundant in Earth\'s Crust, it is rarely found concentrated in ores, and its production is always related to other minerals processing as a by-product or scrap recovering. Scandium content in Nickel ore may vary between 50 and 350ppm and residues produced during its processing can concentrate Sc above 1000ppm. Scandium recovery from a residue of Nickel processing was studied in order to obtain an oxide with purity higher than 99,0% for industrial applications. The residue used is a hydroxide precipitate, which contains mainly Fe, Cu, Ni and Co, Sc content is around 1000ppm (dry basis). The recovery process proposed consists in atmospheric leaching of the residue, selective precipitation to concentrate the Scandium and solvent extraction. The atmospheric leaching in sulfuric acid 2,0mol.L-1 at 70°C allowed the recovery of 92,5% of the Scandium present in the residue. However it was not selective and part of the other metals present in the residue were also leached. After leaching, in order to concentrate the Sc before solvent extraction, a precipitation with NaOH was performed. The initial aim was to precipitate the Iron - main contaminant present in the leach liquor - nevertheless it occurred the co-precipitation of 95,5% of the Sc besides 65,6% of Fe in pH 2,0. The precipitantion represented a concentration of the Sc in the residue of 5,6 times. The Scandium concentrate obtained was dissolved in a sulfuric acid solution to Sc recovery by solvent extraction. The extractant selected was Cyanex 923, a mixture of alkyl-phosphinic oxides. The mechanism of extraction of Scandium observed was solvation and reaction stechiometry was 1:2. It was observed an increase in Sc extraction rates by increasing the concentration of H+. The extraction of Scandium with Cyanex 923 is exothermic, and favorable at room temperature. The Iron content in aqueous solution before extraction is 35 times higher than that of Scandium, and even though Cyanex 923 being more selective for Sc than Fe, part of the Fe is co-extracted. The Fe co-extracted was removed of the organic phase by H2SO4 3mol.L-1 scrubbing with a Sc loss of 1,3%. The stripping of Scandium from organic phase was not accomplished by using strong acids due to formation of a stable complex. Afterwards, it was used oxalic acid - a technique consolidated for rare earths stripping - and the Sc recovery of organic phase was 84,3% with a solution of 4,0% oxalic acid. The Scandium oxalate precipitated was recovered by filtration and calcinated at 600°C. The Scandium oxide obtained presented 99,0% minimum purity.

L'imagerie 3γ est une technique innovante d'imagerie médicale nucléaire qui est étudiée au laboratoire SUBATECH. Elle repose sur la localisation tridimensionnelle d'un radioisotope émetteur (β+, γ), le 44Sc, à l'aide d'un télescope Compton au xénon liquide. Le lieu de désintégration de ce radioisotope est obtenu par l'intersection de la ligne de réponse, construite à partir de la détection des deux photons de 511 keV issus de l'annihilation d'un positron, et du cône déterminé à partir du troisième photon. Un prototype de petite dimension XEMIS1 (XEnon Medical Imaging System) a été développé afin de faire la preuve expérimentale de la faisabilité de l'imagerie à 3γ. Les résultats de ce prototype sont très promoteurs en terme de résolution en énergie, de pureté du xénon liquide et de faible bruit électronique. La simulation Monte Carlo est un outil indispensable pour accompagner la R&D et évaluer les performances de la nouvelle technique d'imagerie proposée. Les travaux rapportés dans cette thèse concernent le développement de la simulation du système d'imagerie 3γ avec GATE (Geant4 Application for Tomographic Emission). De nouvelles fonctionnalités ont été implémentées dans GATE afin de simuler un détecteur de type TPC (Time Projection Chamber). Nous avons effectué une simulation du prototype XEMIS1 et obtenu des résultats en bon accord avec nos données expérimentales. La prochaine étape du projet consiste à construire une caméra cylindrique au xénon liquide pour l'imagerie du petit animal. Les résultats des simulations de cette caméra présentés dans cette thèse montrent la possibilité de localiser chaque désintégration le long de la ligne de réponse avec une très bonne précision et une bonne sensibilité de détection. Des premières images de fantômes simples, réalisées évènements par événements, et après reconstruction tomographiques ont également présentées.

This Thesis reports the synthesis and reactivity of scandium and titanium borylimides. New, versatile synthetic routes to such complexes of these two metals were targeted, and their reactions with small, unsaturated compounds were explored, with a particular focus being the reactivity of alkynes with these systems. <b>Chapter One</b> provides a background on Group 4 imido and hydrazido complexes. Group 4 alkoxyimides are also reviewed, as well as the developing field of rare earth imides. The Chapter focuses on the synthesis, structure, and stoichiometric and catalytic reactions of these complexes with unsaturated substrates, and ends with a description of the handful of known transition metal borylimides. <b>Chapter Two</b> first describes the synthesis and structures of new titanium borylimido synthons prepared from Ti(NMe₂)₂Cl₂. From the borylimide Ti{NB(NAr'CH)₂}Cl₂(py)₃ are then formed five new compounds supported by a range of tridentate, nitrogen-based ligands. <b>Chapter Three</b> describes the synthesis of half-sandwich titanium borylimides through tertbutylimide/borylamine exchange. A sandwich compound is also described, and the electronic structures of these complexes are analysed by DFT, QTAIM and NBO studies. Reactivity with heteroallenes, and exchange reactions with amines are also explored. <b>Chapter Four</b> describes the reactivity of diamide-donor-supported titanium borylimides with terminal alkynes. The principal reaction outcomes are [2+2] cycloadditions and C–H bond activations, and an interesting C–F bond activation is also described. Kinetic studies of some reactions are presented, and will be supported by further DFT studies. <b>Chapter Five</b> explores attempts to prepare the first rare earth borylimide. Kinetic and computational evidence is presented for the existence of a transient scandium borylimide which rapidly undergoes interesting sp, sp² and sp³ C–H bond activations. <b>Chapter Six</b> presents full experimental procedures and characterising data for the new complexes reported.

O Escândio é um elemento terra rara, utilizado principalmente em ligas de alumínio, células combustíveis de óxido sólido e na produção de lâmpadas de haletos metálicos. Apesar de ser o 31° elemento mais abundante na crosta terrestre, raramente é encontrado concentrado na crosta terrestre, e sua produção é sempre associada ao processamento de outros minerais na forma de um subproduto, ou a recuperação de sucata. Minérios de Níquel podem conter teores de Sc variando de 50 a 350ppm e resíduos gerados durante seu processamento pode concentrar o Sc acima de 1000ppm. A recuperação do Escândio de um resíduo da cadeia de produção do Níquel foi estudada, de modo a obter um óxido com pureza acima de 99,0% para aplicações industriais. O resíduo utilizado é um precipitado, na forma de hidróxido, e contém principalmente Fe, Cu, Ni e Co, sendo o teor de Escândio em base seca aproximadamente 1000ppm. O processo de recuperação proposto consiste na lixiviação atmosférica do resíduo, precipitação seletiva para concentração do escândio e extração por solventes. A lixiviação atmosférica em meio sulfúrico 2,0mol.L-1 a 70°C permitiu a recuperação de 92,5% do Escândio contido no resíduo. Entretanto, não foi seletiva, lixiviando também parte dos demais metais presentes. Após a lixiviação para concentrar o Escândio, antes da extração por solventes, foi realizada uma precipitação com NaOH. O intuito foi precipitar o Fe, principal contaminante presente no lixiviado, entretanto ocorreu a co-precipitação de 95,5% do Sc junto a 65,6% Fe em pH 2,0. O precipitado representou uma concentração do Escândio do resíduo em 5,6 vezes. Esse concentrado de Escândio obtido foi dissolvido em solução de H2SO4 para recuperação do Escândio por extração por solventes. O extrante escolhido foi o Cyanex 923, uma mistura de óxidos alquil-fósfinicos. O mecanismo de extração do Sc pelo Cyanex 923 observado foi a solvatação e a estequiometria da reação 1:2. Foi observado um aumento na extração do Sc com o aumento da concentração de H+. O processo de extração do Sc com o Cyanex 923 é exotérmico, sendo favorecido a temperatura ambiente. O teor de Fe na solução aquosa antes da extração é 35 vezes maior que o Escândio, e apesar do Cyanex 923 ser mais seletivo para o Sc do que para o Fe, parte do Fe é co-extraído. O Fe co-extraído foi removido da fase orgânica por meio de uma lavagem com H2SO4 3mol.L-1 com uma perda de Sc de 1,3%. A reextração do Sc na fase orgânica não foi efetiva utilizando ácidos fortes devido a formação de um complexo estável. Foi utilizado ácido oxálico, técnica consolidada para reextração de terras raras, para recuperação do Sc da solução orgânica e a recuperação do Sc foi de 84,3% para uma solução com 4,0% de ácido oxálico. O oxalato de Sc precipitado foi recuperado por filtração e calcinado a 600°C. O óxido obtido apresentou pureza mínima de 99,0%. / Scandium is a rare earth element, used mainly in special aluminum alloys, SOFC\'s and metal halide lamps production. Despite of being the 31st element more abundant in Earth\'s Crust, it is rarely found concentrated in ores, and its production is always related to other minerals processing as a by-product or scrap recovering. Scandium content in Nickel ore may vary between 50 and 350ppm and residues produced during its processing can concentrate Sc above 1000ppm. Scandium recovery from a residue of Nickel processing was studied in order to obtain an oxide with purity higher than 99,0% for industrial applications. The residue used is a hydroxide precipitate, which contains mainly Fe, Cu, Ni and Co, Sc content is around 1000ppm (dry basis). The recovery process proposed consists in atmospheric leaching of the residue, selective precipitation to concentrate the Scandium and solvent extraction. The atmospheric leaching in sulfuric acid 2,0mol.L-1 at 70°C allowed the recovery of 92,5% of the Scandium present in the residue. However it was not selective and part of the other metals present in the residue were also leached. After leaching, in order to concentrate the Sc before solvent extraction, a precipitation with NaOH was performed. The initial aim was to precipitate the Iron - main contaminant present in the leach liquor - nevertheless it occurred the co-precipitation of 95,5% of the Sc besides 65,6% of Fe in pH 2,0. The precipitantion represented a concentration of the Sc in the residue of 5,6 times. The Scandium concentrate obtained was dissolved in a sulfuric acid solution to Sc recovery by solvent extraction. The extractant selected was Cyanex 923, a mixture of alkyl-phosphinic oxides. The mechanism of extraction of Scandium observed was solvation and reaction stechiometry was 1:2. It was observed an increase in Sc extraction rates by increasing the concentration of H+. The extraction of Scandium with Cyanex 923 is exothermic, and favorable at room temperature. The Iron content in aqueous solution before extraction is 35 times higher than that of Scandium, and even though Cyanex 923 being more selective for Sc than Fe, part of the Fe is co-extracted. The Fe co-extracted was removed of the organic phase by H2SO4 3mol.L-1 scrubbing with a Sc loss of 1,3%. The stripping of Scandium from organic phase was not accomplished by using strong acids due to formation of a stable complex. Afterwards, it was used oxalic acid - a technique consolidated for rare earths stripping - and the Sc recovery of organic phase was 84,3% with a solution of 4,0% oxalic acid. The Scandium oxalate precipitated was recovered by filtration and calcinated at 600°C. The Scandium oxide obtained presented 99,0% minimum purity.

Master's thesis deals with the experimental determination of process parameters reaching densities >99 % for scandium modified aluminium alloy (Scalmalloy®) processed by SLM. The alloy achieves higher mechanical properties than the AlSi10Mg aluminum alloy commonly used. The theoretical part deals mainly with the results of Scalmalloy® alloys. Experimental bodies, testing methodology and evaluation method were designed on the basis of the theoretical parts,. The practical part is divided into four main stages: experimental determination of process parameters, a description of the effect of the parameters used on the relative density achieved, examination of the influence of process parameters on surface quality and mechanical testing. The mechanical properties were determined for the best parameters.