Nuclear magnetic resonance (NMR) spectroscopy has proven to be an invaluable tool for the modern chemist, despite being a relatively insensitive spectroscopic technique. However, it is precisely this insensitivity that limits characterization of low-receptivity nuclides, which make up the bulk of transition metal nuclides, in particular. In this work, high-fields were used to collect the first 61Ni solid-state NMR (SSNMR) spectra of diamagnetic nickel compounds, specifically, bis(1,5-cyclooctadiene)nickel(0) (Ni(cod)2), tetrakis(triphenylphosphite)nickel(0) (Ni[P(OPh)3]4), and tetrakis(triphenylphosphine)nickel(0) (Ni(PPh3)4). This was complemented by NMR study of the co-ordinated ligands and 61Ni density functional theory (DFT) computations. 61Ni SSNMR spectra of Ni(cod)2 were used to determine its isotropic chemical shift (δiso = 965 ± 10 ppm), span (Ω = 1700 ± 50 ppm), skew (κ = -0.15 ± 0.05), quadrupolar coupling constant (CQ = 2.0 ± 0.3 MHz), quadrupolar asymmetry parameter (η = 0.5 ± 0.2), and the relative orientation of the chemical shift and EFG tensors. Solution study of Ni(cod)2 saturated in C6D6 yielded a narrow 61Ni signal, and the temperature dependence of δiso(61Ni) was assessed (δiso being 936.5 ppm at 295 K). The solution is proposed as a secondary chemical shift reference for 61Ni NMR in lieu of the extremely toxic Ni(CO)4 primary reference. For Ni[P(OPh)3]4, 61Ni SSNMR was used to infer the presence of two distinct crystallographic sites and establish ranges for δ¬iso in the solid state, as well as an upper bound for CQ (3.5 MHz for both sites). For Ni(PPh3)4, fitting provided a δiso value of 515 ± 10 ppm, Ω of 50 ± 50 ppm, κ of 0.5 ± 0.5, CQ of 0.05 ± 0.01 MHz, and η of 0.0 ± 0.2. Ni(cod)2 was chosen for study as it is a ubiquitous source of nickel(0), used for both further synthesis of nickel(0) compounds and directly as a catalyst. The study of Ni[P(OPh)3]4 and Ni(PPh3)4 demonstrated the utility of 61Ni SSNMR given the lack of a previously reported crystal structure for both and the transient nature of Ni(PPh3)4 in solution. The work begins in Chapter 1 by introducing the interactions fundamental to NMR spectroscopy, before moving on to briefly review the field of transition metal nuclide NMR, the chemistry of nickel (with an emphasis on homogeneous catalysis with nickel(0)), and the literature with respect to nickel NMR up to this point. In Chapter 2, the theory and practice of NMR are explained, including solid-state NMR, as well as the basic principles of density functional theory NMR computations. The specific experimental and computational methods of this work are also introduced. Lastly, in Chapter 3 the results are discussed in the context of the concepts presented and literature reviewed, and highlight the use of 61Ni NMR as a means to gain novel information about the chemistry of the compounds studied.

A study has been carried out to investigate the effects of heat treatment on microindentation hardness, abrasion and corrosion resistance of Electroless Nickel coatings. In particular, a proprietary coating system, NIKLAD 794 has been investigated. Samples of 4130 steel have been plated according to manufacturer's specifications. The plated samples have then been subjected to an array of heat treatment temperatures and times. Post heat treatment tests have been conducted including Taber Abrasion testing, salt fog chamber testing, and Knoop microindentation hardness testing. Results of the individual tests have been compared to determine the effects of heat treatment on, and the interactions between, the parameters examined.

School of Chemical and Metallurgical Engineering, Faculty of Engineering and Built in Environment, University of Witwatersrand, Johannesburg, South AfricaMay, 2016 / Trojan Nickel Mine in Bindura, Zimbabwe, produces nickel concentrates which, until 2008, were then processed at their smelter operations (Bindura Smelter and Refinery) and the subsequent product sent to the hydrometallurgical plant to produce nickel cathodes. However, due to economic challenges the smelter and hydrometallurgical plant operations were closed down in 2008. Currently, Trojan Mine produces nickel concentrates through flotation which are then sold to Glencore International, in China, for further processing. Since 2002, the MgO (also known as talc) content in the Trojan Nickel Mine final concentrates has increased from around 12% to a peak of 22%. The average MgO content in the concentrates for the year ending in March 2015 was 16.14%. An offtake agreement of sale was made with Glencore International, in China, whereby a penalty is charged for all concentrates with MgO levels greater than 5%. In the year 2015 alone, monthly revenue due to smelter penalties amounted to an estimated total of US$141 000. Higher MgO levels in the concentrates are prevalent when processing low grade ores, with nickel content ranging from 0.65-1.2%. This research focused on reducing the MgO content of the Trojan’s final concentrate to 12%; which was the smelter’s set target while it was still operational. In order to investigate the effect of pH and chemical depressants on the MgO levels in the concentrate, batch flotation tests were carried out at pH 8.95 and 10.2, using several guargum depressants namely: Betamin DZT 245 (standard), Cytec S9349, DLM PDE, DLM RS, and CMC (carboxy methyl cellulose) depressants namely: Depramin 177, 267 and 347, and ND 521, 522 and 523. The concentrates were collected at 1, 5, 15 and 25 minute intervals in order to understand the stage-wise recovery of nickel and MgO minerals. A flotation test, without a depressant, was also carried out in order to understand the kinetics of the gangue minerals. Stage addition of depressants was investigated, by adding another 50g/t dose of the DZT 245 depressant after 1 minute into the flotation test. Collector combination tests using SIPX, SIPX:NC228, SIPX:NC236 and SIPX:PNBX, were also carried out to determine the best reagent suite. To understand the recovery of nickel and MgO in the flotation circuit, a plant survey was carried out, and the particle size distribution (PSD) and assays of collected samples were determined. Flotation tests results indicated that DLM RS and DLM PDE guargum depressants had better selectivity towards MgO and higher nickel recoveries as compared to the Betamin DZT 245 depressant that is currently used in the plant. It is recommended that a plant trial be carried out using the DLM RS depressant, which further reduced the MgO and mass of concentrate recovered by 3.79% and 32% respectively. The stage recovery of MgO for a test carried out without a depressant showed that 57.7% of the MgO was recovered during the first five minutes of the test. Thus, there is need to effectively depress the fast floating MgO during the early stages of the flotation process. Nickel recovery and grade were increased by 2.7% and 2.1% respectively, after adding the second dose of the depressant after 1 minute into the flotation test. The results indicated that the fast floating MgO can depress the valuable mineral if the depressing effect of the depressant is short-lived, which in turn leads to reduced nickel recoveries. Hence, reducing the time between the two stage additions of the depressant in the plant will help further supress the fast floating MgO silicates. It was also noted that at least 60% of the nickel was recovered during the first five minutes of the tests. Hence, reducing the residence time of the rougher flotation bank would reduce MgO recovery into the concentrates without adversely affecting the nickel recoveries. Plant survey results showed that the scavenger bank feed that was deslimed, had less finer MgO particles and MgO content as compared to the rougher bank feed. This indicates that desliming before the coarse flotation process could reduce MgO slimes in the feed, reduce the recovery of MgO due to slime coatings in the final concentrates and the reagent consumption in the bank. Introducing the desliming unit could be beneficial since the desliming cyclones have low installation and operational costs. / MT2016

La région Centre Ouest du Brésil possède des massifs ultrabasiques (UB) avec des manteaux latéritiques représentants des réserves et ainsi des ressources économiques importantes de Ni. Ces massifs nickélifères permettent d’étudier le cycle du Ni sous contraintes anthropiques par une approche pluridisciplinaire, associant caractérisations chimiques, mesures physiques de sa spéciation solide, et traçage isotopique des sources et des processus affectant le nickel. Cette thèse focalisée sur l’utilisation des isotopes du Ni comme traceur a eu pour but d’identifier la signature isotopique au sein de plusieurs compartiments en interactions les uns avec les autres (roche mère, saprolite, latérite, sol et plantes) et d’associer les fractionnements observés aux processus biogéochimiques. De plus, du fait de leurs ressources économiques, les massifs étudiés, Barro Alto et Niquelândia, subissent une pression anthropique importante, minière et métallurgique. Ainsi, ils offrent une opportunité unique d’étudier le fractionnement isotopique du nickel associé à son cycle anthropique, et voir s’il est possible d’identifier la contribution anthropique dans le cycle naturel du Ni par sa signature isotopique. Les résultats ont montré que l’altération de roches UB conduit à un fractionnement isotopique du Ni, se traduisant par une perte en isotopes lourds de la phase solide, soit un Δ⁶⁰Ni de - 0,47 ‰ entre la roche mère et le top-sol. Ce fractionnement semble associé au moins en partie à l’incorporation et à la sorption des isotopes légers du Ni sur les oxydes de Fe lors de la remobilisation du Ni au cours de l’altération. Cet enrichissement en isotopes légers du Ni dans la partie solide conduit à une composition isotopique en Ni plus lourde dans la phase dissoute (eaux du massifs : 0.50 ‰ < δ⁶⁰Ni < 0,70 ‰). La zone saprolitique présente une variation importante de signature isotopique allant pour δ⁶⁰Ni de -0,04 ‰ à 1,41 ‰. Pour les échantillons présentant une signature isotopique lourde, le Ni se trouve principalement au sein de la serpentine fortement substitué, quand les signatures plus légères sont en lien avec une proportion de Ni plus importante au sein de la goethite. Dans un système comme celui-ci avec un nombre important de phases porteuses de Ni, il est cependant très difficile d’établir un lien entre la spéciation solide et l’isotopie du Ni. Le rôle des plantes dans le cycle du Ni a été abordé en étudiant le fractionnement isotopique du Ni dans trois espèces de plantes hyperaccumulatrices de Ni et deux espèces de plantes tolérantes. Il existe un fractionnement isotopique lors du transfert de Ni de la tige vers la feuille, qui est systématiquement enrichie en isotopes lourds du Ni. Les feuilles sont les compartiments des plantes où les teneurs en Ni sont les plus importantes. L’enrichissement en isotopes lourds du Ni des feuilles par rapport aux sols (- 1,05 ± 0,03 ‰ < Δ⁶⁰Ni_sol-feuilles < - 0,06 ± 0,12 ‰) semble indiquer que la restitution et la décomposition de cette matière organique au niveau du sol s’accompagnera d’un apport en isotopes lourds du Ni dans le sol. L’activité pyrométallurgique entraîne un fractionnement isotopique lors du processus de fusion en conditions réductrices qui conduit à la formation des scories de réduction. Ces résidus présentent un enrichissement en isotopes lourds (δ⁶⁰Ni = 0,18 ± 0,05 ‰) par rapport au matériel entrant (δ⁶⁰Ni = 0,08 ± 0,08 ‰) et au produit final, le FeNi (δ⁶⁰Ni = 0,06 ± 0,02 ‰). Enfin, cette étude montre que l’utilisation des isotopes du Ni pour tracer le Ni « anthropique » et le distinguer du Ni naturel possède certaines limites en raison du faible fractionnement induit par les processus pyrométallurgiques aux regards de la grande variabilité des échantillons naturels au sein de la littérature (-1.03 ‰ < δ⁶⁰Ni < 2.50 ‰). / The Centre region the West of Brazil possesses ultramafic massifs (UM) with coats lateritic representatives of the reserves and so the important economic resources of Ni. These nickelifere massifs allow to study the cycle of Ni under anthropological constraints by a multidisciplinary approach, associating chemical characterizations, physical measures, solid speciation, and the isotopic drawing of sources and the processes affecting the nickel. This work focused on the use of the isotopes of Ni as tracer aimed at identifying the isotopic signature within several compartments in interactions some with the others (source rock, saprolite, laterite, soil and plants) and to associate the fractionation observed in the biogeochemical processes. Furthermore, because of their economic resources, the studied massifs, Barro Alto and Niquelândia, undergo an important, mining and metallurgical anthropological pressure. So, they offer an opportunity to study the isotopic fractionation of the nickel associated with its anthropological cycle, and to see if it is possible to identify the anthropological contribution in the natural cycle of Ni by its isotopic signature. The results showed that the weathering of rocks UB leads to an isotopic fractionation of Ni, being translated by a loss in heavy isotopes of the solid phase with a Δ⁶⁰Ni of - 0,47 ‰ between the bedrock and the top-soil. This division seems associated at least partially with the incorporation and with the sorption of the light isotopes in iron oxides during the remobilization of Ni. This enrichment in light isotopes in the solid part leads to a heavier isotopic composition in the dissolved phase (waters of massifs: 0.50 ‰ < δ⁶⁰Ni < 0,70 ‰). The saprolitic zone presents an important variation of isotopic signature (δ⁶⁰Ni) from -0,04 ‰ to 1,41 ‰. For samples presenting a heavy isotopic signature, Ni is mainly within the serpentine strongly substituted, when the lighter signatures are in connection with a proportion of Ni more important within the goethite. In a system as this one with a significant number of Ni-bearing phases, it is however very difficult to establish a link between the solid speciation and the isotopic composition. The role of plants in the cycle of Ni was approached by studying the isotopic fractionation of Ni in three species of hyperaccumulating plants of Ni and two species of tolerant plants. There is an isotopic fractionation during the transfer of Ni between the stem and the leaf, which is systematically enriched in heavy isotopes of Ni. The leaves are the compartments of the plants where the Ni contents are the most important. The enrichment in heavy isotopes of Ni in leaves with regard to soils (- 1,05 ± 0,03 ‰ < Δ⁶⁰Ni_sol-feuilles < - 0,06 ± 0,12 ‰) seems to indicate that the return and the decomposition of this organic matter at soil level will come along with a contribution in heavy isotopes of Ni in the soil. The pyrometallurgical activity lead to an isotopic fractionation during the smelting process in reducing conditions which leads to the formaton of the reduction slag. These slags present an enrichment in heavy isotopes (δ⁶⁰Ni = 0,18 ± 0,05 ‰) compared with the feeding material (δ⁶⁰Ni = 0,08 ± 0,08 ‰) and the end product, the FeNi (δ⁶⁰Ni = 0,06 ± 0,02 ‰). Finally, this study shows that the use of the isotopes of Ni to decipher the Ni anthropogenic and natural is limited because of the low fractionation induced by the pyrometallurgical processes in the looks of the big variability of the natural samples within the literature (-1.03 ‰ < δ⁶⁰Ni < 2.50 ‰).

La phytoremediation consiste à utiliser les plantes pour nettoyer des sols contaminés. Jusqu’ici, des plantes naturellement capables de tolérer et d’accumuler les polluants ont été utilisées pour cette approche. Cependant, l’utilisation de plantes transgéniques doit être considérée pour optimiser l’efficacité de la phytoremédiation. Le peuplier est une espèce adaptée pour la phytoremédiation et peut être utilisé pour des approches transgéniques. Néanmoins, son efficacité de phytoextraction est limitée par une forte accumulation de métaux dans les feuilles qui retournent au sol lors de leur chute. L’ingénierie génétique pourrait être utilisée pour résoudre ce problème, en modifiant l’expression de transporteurs de métaux soit pour limiter l’accumulation de métaux dans les feuilles, soit pour stimuler leur accumulation dans le bois.Dans le cadre de cette thèse, trois transporteurs potentiellement impliqués dans la tolérance et l’accumulation de métaux ont été caractérisés : PtIREG1, PtNRAMP3.1 et PtNRAMP3.2. L’expression de PtIREG1 chez la levure et chez Arabidopsis thaliana a montré que ce transporteur contribue à la tolérance au nickel. Des peupliers transgéniques chez lesquels l’expression de PtIREG1 est globalement augmentée ou ciblée dans le bois ont été générés. Des peupliers transgéniques chez lesquels l’expression de PtNRAMP3.1 ou PtNRAMP3.2 est modifiée ont également été générés au cours de cette thèse. Cela a permis de montrer que ces protéines fortement homologues ont des localisations subcellulaires distinctes : la membrane vacuolaire pour PtNRAMP3.2 et un compartiment connecté à l’appareil de Golgi pour PtNRAMP3.1. Des mesures de concentrations en métaux dans les feuilles des peupliers transgéniques ptNRAMP3.1 et PtNRAMP3.2 ont montré des différences avec le type sauvage non transformé, pour le cuivre, le manganèse, le cadmium et le zinc. Les résultats obtenus contribueront à l’élaboration de stratégies biotechnologiques pour réhabiliter les sols pollués / Phytoremediation is the use of plants to clean up polluted soils. Previous approaches have mostly used native plants able to tolerate, degrade and accumulate environmental pollutants such as toxic metals, but transgenic plants may also be considered for phytoremediation in the future. Poplar is well adapted for phytoremediation and suitable for molecular genetic studies. However, high metal accumulation in poplar leaves limits phytoextraction due to toxic metal return to the soil after leaf abscission. In order to circumvent this problem, genetic engineering can be used to limit metal accumulation in leaves or direct metal accumulation in poplar trunks using relevant metal transporter genes under the control of tissue-specific promoters. This thesis focuses on the characterization of 3 candidate metal transporters potentially involved in metal tolerance and accumulation in poplar: PtIREG1, PtNRAMP3.1 and PtNRAMP3.2. Expression of PtIREG1 in yeast and in Arabidopsis thaliana indicated that it contributes to nickel tolerance. Transgenic poplars were generated in which PtIREG1is either ectopically overexpressed or expressed specifically in wood tissues. PtNRAMP3.1 and PtNRAMP3.2 transgenic plants were also generated during this thesis. Despite their high similarity, PtNRAMP3.1 and PtNRAMP3.2 displayed distinct localizations in poplar: PtNRAMP3.2 is targeted to the vacuolar membrane whereas PtNRAMP3.1 localizes in a compartment connected with the Golgi apparatus. Metal concentrations were modified in leaves of transgenic plants grown on metal-contaminated or non-contaminated soil. The results obtained will contribute to develop a biotechnological approach using transgenic plants for the rehabilitation in metal polluted soils.

Thèse de doctorat : Sciences physiques pour l'ingénieur. Mécanique et ingénierie : Bordeaux 1 : 2008. / Titre provenant de l'écran-titre.

No description available.

The damage clusters produced by low dose, 80 keV Ni⁺ and W⁺ heavy-ion bombardment of pure nickel; of two nichrome alloys (with 8% and 17%Cr); and of a ternary alloy and 321 stainless steel which have the same base composition (Fe/Ni10%/Cr17%) have been studied by means of transmission electron microscopy. In all cases where the defects could be identified with confidence they were found to be vacancy in nature. Most of the defects were identified as Frank loops, some of which had partially dissociated. The number of loops that were identified as dissociated and the average degree of dissociation were dependent on the stacking fault energy γ, being greater in the low-γ ternary alloy and the stainless steel than in the high-γ nickel and nichrome alloys. In the high-y materials a small proportion (< 5%) of perfect loops was also observed. Defect yield values were between a factor of 2 and 5 higher for W⁺ ion bombardment than for the corresponding Ni⁺ ion irradiations, but the effect on the mean defect size and cascade efficiency was much less pronounced. In the case of the Ni⁺ ion bombardment, the defect yields in the two nichrome alloys were lower than in pure Ni. No such effect was observed for the W⁺ ion irradiations, when defect yield and cascade efficiency values very similar to those of pure nickel were obtained. The defect yield in the W⁺ ion irradiated ternary alloy was considerbly smaller than in the nichrome alloys and there was a further major decrease in the stainless steel. These reductions in defect yields were not accompanied by a change in the mean defect size nor in the distribution of the defect sizes which were very similar in all the materials for irradiation by a given ion species. The defect yield in W⁺ ion irradiated Ni remained constant with increasing irradiation temperature up to ~450°C and then decreased sharply at higher irradiation temperatures. The defect yield in W⁺ ion irradiated Ni/Cr17% remained constant up to at least 500°C. Possible physical explanations for these results are discussed.

No description available.

No description available.