Ce travail de thèse a pour objet le développement d'une nouvelle voie de synthèse de nanomatériaux métalliques à base d'éléments légers : bore et phosphore. L'intérêt porté à ces composés s'explique par les propriétés variées qu'ils présentent, tels que la supraconductivité, la thermoélectricité ou le stockage d'énergie. Dans le cadre de ce travail, les domaines de la catalyse et de l'électrocatalyse sont explorés. Les borures de différents métaux de transition, en particulier le nickel, le palladium et un composite nickel-cobalt, ont tout d'abord été étudiés. Pour cela une synthèse a été mise au point, reposant sur la réactivité de nanoparticules métalliques avec un précurseur de bore en milieu sels fondus inorganiques. Elle a notamment permis d'obtenir des nanoparticules de borures de nickel avec un bon contrôle de composition, structure, morphologie et taille. Les propriétés de ces nanomatériaux ont par la suite été étudiées en catalyse dans la réaction d'hydrodésoxygénation, et en électrocatalyse dans les réactions de génération d'hydrogène ou d'oxygène à partir de l'eau. Enfin la réactivité du phosphore rouge en milieu sels fondus a été abordée, ouvrant ainsi une nouvelle voie vers l'élaboration de phosphures de métaux de transition. / This PhD work deals with a novel synthesis of metal boride and metal phosphide nanomaterials. Nanostructures of these solids are subject to an increasing interest due to their exciting properties for various applications fields such as superconductivity, high temperature thermoelectricity, energy conversion and storage. In this work, the catalytic and electrocatalytic properties of these nanomaterials are explored. First of all, borides of various transition metals, such as nickel, palladium or a nickel-cobalt composite are studied. To do so, a new liquid-phase synthesis was developed, based on the reactivity of already formed metal nanoparticles with a boron precursor in inorganic molten salts. This new synthesis allowed a precise control over the nanoparticle morphology, size, composition and crystalline structure. By accessing such nanoscale objects, we were able to investigate their properties and performances, especially in the fields of catalysis with the hydrodeoxygenation reaction and electrocatalysis for the hydrogen evolution reaction and oxygen evolution reaction. Finally, the reactivity of red phosphorus in molten salts was addressed, thus paving the way to the extension of this synthetic pathway to metal phosphides.

Borides and carbides of tantalum and hafnium are of great interest due to their ultrahigh temperature applications. Properties of these ceramics including oxidation resistance and mechanical properties might be further improved through solid solution/composite formation. Synthesis of single-phase TaxHf1-xC and TaxHf1-xB2 solid solution powders including nanopowders via carbothermal reduction (CTR) is complicated due to noticeable difference in reactivity of parent oxides with carbon, and also the low solubility of those oxides in each other. Moreover, for TaC-HfC system the solid solution may go through phase separation due to the presence of a miscibility gap at temperatures below 887°C.In this study, a method of low-cost aqueous solution processing followed by CTR was used to synthesize TaxHf1-xC and TaxHf1-xB2 solid solution powders. In fact, method was first used to synthesize boron carbide (B4C) powders as it paves the way for a detailed study on the synthesis of TaxHf1-xC and TaxHf1-xB2 solid solutions powders considering the fact that B4C contains both carbon and boron in its structure. Particular emphasis was given to investigate the influences of starting compositions and processing conditions on phase separation during the formation of both carbide and boride phase(s). It was found that individual TaC-HfC and TaB2-HfB2 phases always form quickly but separately during the CTR process (e.g., at 1600 °C within a few minutes). Those carbides and borides remain phase-separated unless heated to much higher temperatures for long time due to the slow inter-diffusion between them. It was also found that for TaxHf1-xC applying a DC electric field through the use of spark plasma sintering (SPS) system significantly accelerates the inter-diffusion of Ta and Hf leading to formation of a single-phase TaxHf1-xC solid solution at 1600 °C for 15 minutes. On the other hand, for borides alkali metal reduction reaction (AMR) method appears to be an excellent alternative to CTR-based method for formation of a single-phase TaxHf1-xB2 solid solution. In this method, chlorides of tantalum and hafnium are directly reduced using sodium borohydride (NaBH4) giving rise to formation of a single-phase Ta0.5Hf0.5B2 solid solution nanopowders in one step at much lower temperatures (e.g., 700 °C) by avoiding the oxides formation and the associated phase separation of individual borides as observed in the CTR-based process.

Intermetallic borides are characterized by a great variety of crystal structures and bonding interactions, however, a comprehensive rationalisation of the electronic structure is missing. A more general interpretation will be targeted towards comparing several boride phases of one particular transition metal on one hand side, but also isostructural borides of various metals at the other side. Finally, a concise model should result from a detailed analysis of excellent data both from experimental charge density analysis and quantum chemical methods. Ultimate target is a transferability model based on typical building blocks. Experimental investigations of the electron density derived from diffraction data are very rare for intermetallic compounds. One of the main reasons is that the suitability of such compounds for charge density analysis is estimated to be relatively low as compared to organic compounds. In the present work, X-ray single crystal diffraction measurements up to high resolution were carried out for TiB2, VB2, V3B4, and VB crystals. The respective experimental electron densities were reconstructed using the multipole model introduced by Hansen and Coppens [1]. The topological aspects of the experimental electron density were analysed on the basis of the multipole parameters using Bader’s Quantum Theory, Atoms in Molecules [2] and compared with theoretical calculations. References [1] Hansen, N.K.; Coppens, P. Acta Crystallogr. 1978, A34, 909 [2] Bader, R.F.W. Atoms in Molecules─A Quantum Theory; Oxford University Press: Oxford, 1990

The aim of this study was to investigate synthesis of lithium borides by mechanochemical synthesis from oxides. Lithium borides have promising properties in the area of high energy additives and hydrogen storage. Lithium oxide (Li2O), boron oxide (B2O3) and Mg were used to synthesize lithium borides. Experiments were conducted in a planetary ball mill under argon atmosphere. Analyses of the products were done by X-ray diffraction and scanning electron microscopy. Trilithium tetradecaboride (Li3B14) peaks were observed in the product powder. Removal of other phases that were formed during experiments was done by leaching in HCl/water solution. Leaching in 0.5 M HCl/water solution for 10 minutes was found to be sufficient to remove / iron (Fe) and magnesium oxide (MgO). Effects of ball milling parameters such as milling speed, ball to powder ratio, milling duration were investigated and milling for 20 hours with 300 rpm and 30:1 ball to powder ratio was found to be the optimum conditions. Syntheses of other lithium borides (LiB4, Li2B6, LiB13) were also experimented with the same milling parameters. Formation of LiB4, Li2B6 and LiB13 was not observed in the product powders. However, the results of LiB4 and LiB13 production experiments showed also Li3B14 peaks in the product. Li2B6 synthesis experiments resulted in Li2B9 peaks in the product powders.

Zirconium diboride (ZrB₂) is a ceramic material possessing ultra-high melting temperatures. As such, this compound could be useful in the construction of thermal protection systems for aerospace applications. This work addresses a primary shortcoming of this material, namely its propensity to destructively oxidize at high temperatures, as well as secondary issues concerning its heat transport properties.To characterize and improve oxidation properties, thermogravimetric studies were per- formed using a specially constructed experimental setup. ZrB₂-SiC two-phase ceramic composites were isothermally oxidized for ∼90 min in flowing air in the range 1500-1900°C. Specimens with 30 mol% SiC formed distinctive reaction product layers which were highly protective; 28 mol% SiC - 6 mol% TaB₂ performed similarly. At higher temperatures, specimens containing lower amounts of SiC were shown to be non-protective, whereas specimens containing greater amounts of SiC produced unstable oxide layers due to gas evolution. Oxide coating thicknesses calculated from weight loss data were consistent with those measured from SEM micrographs. In order to characterize one aspect of the materials' heat transport properties, the thermal diffusivities of ZrB₂-SiC composites were measured using the laser flash technique. These were converted to thermal conductivities using temperature dependent specific heat and density data; thermal conductivity decreased with increasing temperature over the range 25-2000°C. The composition with the highest SiC content showed the highest thermal conductivity at room temperature, but the lowest at temperatures in excess of ∼400°C, because of the greater temperature sensitivity of the thermal conductivity of the SiC phase, as compared to more electrically-conductive ZrB₂. Subsequent finite difference calculations were good predictors of multi-phase thermal conductvities for the compositions examined. The thermal conductivities of pure ZrB₂ as a function of temperature were back-calculated from the experimental results for the multi-phase materials, and literature thermal conductivities of the other two phases. This established a relatively constant thermal conductivity of 88-104 W/m·K over the evaluated temperature range. Further heat transport characterization was performed using pre-oxidized, directly resistively heated ZrB₂-30 mol% SiC ribbon specimens under the observation of a spectral radiometer. The ribbons were heated and held at specific temperatures over the range 1100- 1330°C in flowing Ar, and normal spectral emittance values were recorded over the 1-6 μm range with a resolution of 10 nm. The normal spectral emittance was shown to decrease with loss of the borosilicate layer over the course of the data collection time periods. This change was measured and compensated for to produce traces showing the emittance of the oxidized composition rising from ∼0.7 to ∼0.9 over the range of wavelengths measured.

Haynes alloy 282 is a new gamma prime (γ’) precipitation strengthened nickel-base superalloy developed for high temperature applications in land-based and aero turbine engines. Joining is a crucial process both during the manufacturing of new components and repair of service-damaged turbine parts. Unfortunately, the new superalloy cracks during laser beam welding (LBW), which is an attractive technique for joining superalloys components due to its low heat input characteristic that preclude the geometrical distortion of welded components. This research is therefore initiated with the goal of studying and developing an effective approach for preventing or minimizing cracking during LBW of the new superalloy Haynes 282. Careful and detailed electron microscopy and spectroscopy study reveal, for the first time, the formation of sub-micron grain boundary M5B3 particles, in the material. Microstructural study of welded specimens coupled with Gleeble thermo-mechanical physical simulations shows that the primary cause of weld heat affected zone (HAZ) cracking in the alloy is the sub-solidus liquation reaction of intergranular M5B3 borides in the material. Further weldability study showed that the HAZ liquation cracking problem worsens with reduction in welding heat input, which is normally necessary to produce the desired weld geometry with minimum distortion. In order to minimize the HAZ cracking during low heat input laser welding, microstructural modification of the alloy by heat treatment at 1080 - 1100oC has been developed. The pre-weld heat treatment minimizes cracking in the alloy by reducing the volume fraction of the newly identified M5B3 borides, while also minimizing non-equilibrium grain boundary segregation of boron liberated during dissociation of the boride particles. Further improvement in resistance to cracking was produced by subjecting the material to thermo-mechanically induced grain refinement coupled with a pre-weld heat treatment at 1080oC. This approach produces, for the first time, crack-free welds in this superalloy, and the benefit of this procedure in preventing weld cracking in the new material is preserved after post-weld heat treatment (PWHT), as additional cracking was not observed in welded specimens subjected to PWHT.

Haynes alloy 282 is a new gamma prime (γ’) precipitation strengthened nickel-base superalloy developed for high temperature applications in land-based and aero turbine engines. Joining is a crucial process both during the manufacturing of new components and repair of service-damaged turbine parts. Unfortunately, the new superalloy cracks during laser beam welding (LBW), which is an attractive technique for joining superalloys components due to its low heat input characteristic that preclude the geometrical distortion of welded components. This research is therefore initiated with the goal of studying and developing an effective approach for preventing or minimizing cracking during LBW of the new superalloy Haynes 282. Careful and detailed electron microscopy and spectroscopy study reveal, for the first time, the formation of sub-micron grain boundary M5B3 particles, in the material. Microstructural study of welded specimens coupled with Gleeble thermo-mechanical physical simulations shows that the primary cause of weld heat affected zone (HAZ) cracking in the alloy is the sub-solidus liquation reaction of intergranular M5B3 borides in the material. Further weldability study showed that the HAZ liquation cracking problem worsens with reduction in welding heat input, which is normally necessary to produce the desired weld geometry with minimum distortion. In order to minimize the HAZ cracking during low heat input laser welding, microstructural modification of the alloy by heat treatment at 1080 - 1100oC has been developed. The pre-weld heat treatment minimizes cracking in the alloy by reducing the volume fraction of the newly identified M5B3 borides, while also minimizing non-equilibrium grain boundary segregation of boron liberated during dissociation of the boride particles. Further improvement in resistance to cracking was produced by subjecting the material to thermo-mechanically induced grain refinement coupled with a pre-weld heat treatment at 1080oC. This approach produces, for the first time, crack-free welds in this superalloy, and the benefit of this procedure in preventing weld cracking in the new material is preserved after post-weld heat treatment (PWHT), as additional cracking was not observed in welded specimens subjected to PWHT.

Specimens of ZrB2 containing various concentrations of B4C, SiC, TaB2, and TaSi2 were pressureless-sintered and post-hot isostatic pressed to their theoretical densities. Oxidation resistances were studied by scanning thermogravimetry over the range 1150 - 1550 degree C. SiC additions improved oxidation resistance over a broadening range of temperatures with increasing SiC content. Tantalum additions to ZrB2-B4C-SiC in the form of TaB2 and/or TaSi2 increased oxidation resistance over the entire evaluated spectrum of temperatures. TaSi2 proved to be a more effective additive than TaB2. Silicon-containing compositions formed a glassy surface layer, covering an interior oxide layer. This interior layer was less porous in tantalum-containing compositions. The oxidation resistances of ZrB2 containing SiC, TaB2, and TaSi2 additions of various concentrations was studied using isothermal thermogravimetry at 1200, 1400, and 1500 degree C, and specimens were further characterized using x-ray diffraction and electron microscopy. Increasing SiC concentration resulted in thinner glassy surface layers as well as thinner ZrO2 underlayers deficient in silica. This silica deficiency was argued to occur by a wicking process of interior-formed borosilicate liquid to the initially-formed borosilicate liquid at the surface. Small (3.32 mol%) concentrations of TaB2 additions were more effective at increasing oxidation resistance than equal additions of TaSi2. The benefit of these additives was related to the formation of zirconium-tantalum boride solid solution during sintering, which during oxidation, fragmented into fine particles of ZrO2 and TaC. These particles resisted wicking of their liquid/glassy borosilicate encapsulation, which increased overall oxidation resistance. With increasing TaB2 or TaSi2 concentration, oxidation resistance degraded, most egregiously with TaB2 additions. In these cases, zirconia dendrites appeared to grow through the glassy layers, providing conduits for oxygen migration.

Thesis (Ph. D.)--University of Nevada, Reno, 2008. / "December 2008." Includes bibliographical references (leaves 161-173). Online version available on the World Wide Web.

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