A series of tetravalent zirconium and hafnium complexes were supported by diarylamido-phosphino [PNP]- (bis(o-diisopropylphosphinophenyl)amide) ligand. The reaction of MCl4(THF)2 (M = Zr, Hf) with [PNP]Li in toluene at room temperature generates [PNP]MCl3 as solid in 60 % yield. Polyalkyl complexes which are lack of £]-hydrogen have been achieved in synthesis of [PNP]MR3 (R = Me, CH2SiMe3) or [PNP]M(CH2SiMe3)2(E) (E = Cl, Me) since we could control the desired product from steric effect. An X-ray diffraction study of [PNP]ZrCl3 showed it to be a chloride-bridged binuclear species {[PNP]MCl2(£g-Cl)}2 in which both metal atoms are 7-coordinate whereas that of [PNP]MCl3(THF) revealed a mononuclear, 7-coordinate core structure. The phosphine fluxional exchange were found in those complexes, monitoring variable temperature 31P NMR, their fluxionality were calculated by line shape analysis. By heating [PNP]M(CH2SiMe3)2(Cl) in solution, we can afford new alkylidene complexes [PNP]M(Cl)(=CHSiMe3) via intramolecular £\-abstraction. Through Eyring plot analysis, the activation energy of [PNP]Zr(CH2SiMe3)2(Cl) £\-abstraction is ∆H‡ = 16.49(19) kcal/mol and ∆S‡ = −25.64(19) cal/mol•K; [PNP]Hf(CH2SiMe3)2(Cl) £\-abstraction is ∆H‡ = 18.70(36) kcal/mol and ∆S‡ = −23.12(36) cal/mol•K. The mixture [PNP]Hf(=CHSiMe3)(Cl) could not isolate with any purification, but [PNP]Hf(=CHSiMe3)(CH2SiMe3) obtained through directly alkylation. Here we also identified multiple alkylidene derivatives of [PNP]M(=CHSiMe3)(X) (X = Cl, CH2SiMe3). The X-ray structured and solution NMR data of those alkylidene complexes can be ascribed to evidence of £\-agostic interaction with metal center. A novel zwitterionic complex [PNP]Zr(£g2-CHSiMe3)2(AlMe2) was characterized by X-ray and been received a bisalkylidene complex which was synthesized through addition Lewies acid (AlMe3) into [PNP]Zr(=CHSiMe3)(CH2SiMe3). Group 4 alkylidene was acting as catalyst to metathesize ethylene or norbornene. The complexes [PNP]M(=CHSiMe3)(Cl) have highly streotic selectivity catalyst for ring-opening metathesis polymerization (ROMP) of norbornene. It is important to emphasize the great significance of the catalyst discoveries and improvements for both academic research and industry.

Stainless steel – zirconium alloys were developed by the US Department of Energy Laboratories as metallic waste forms for noble metal fission products. This thesis evaluates iron–zirconium–rhenium alloys to establish a technical basis for using metal waste form alloys for technetium-99 immobilization. Rhenium is used as a surrogate for Tc-99 since Tc is not naturally available and Re is metallurgically similar to Tc. The iron-zirconium system has two eutectic compositions, Fe-15 wt % Zr and Zr- 16 wt% Fe. Ten test samples were successfully cast in yttrium oxide crucibles at 1600°C, half near each eutectic composition, with Re amounts varying from 2.5 to 12.5 weight percent. A scanning electron microscope (SEM) with energy dispersive X-ray spectroscopy (EDS) capability was employed to determine the phase structure and phase composition of each sample. Iron rich samples were found to form up to three phases, with the rhenium content favoring the intermetallic phases: 1) an Fe solid solution phase, 2) an FeZr2-type intermetallic with 11 wt % or less Re, and 3) a second intermetallic with about 18 wt % Re. Zirconium rich samples formed as many as five distinct phases: 1) a Zr solid solution phase, 2) a Zr3Fe-type intermetallic with as much as 13 wt% Re, 3) a rhenium-zirconium intermetallic, 4) another Fe-Zr intermetallic with very little Re, and 5) a Fe-Re intermetallic. Potentiostatic and potentiodynamic electrochemical tests were performed using sulfuric acid to evaluate the corrosion resistance of each sample. These tests found that the zirconium rich samples were very corrosion resistant but became increasingly susceptible at higher rhenium concentrations. The iron rich samples were not very resistant to corrosion under the test conditions; there was no notable trend in corrosion behavior related to the introduction of rhenium.

A process for recycling spent nuclear fuel cladding, a zirconium alloy (Zircaloy), into a metal powder that may be used for advanced nuclear fuel applications, was investigated to determine if it is a viable strategy. The process begins with hydriding the Zircaloy cladding hulls after the spent nuclear fuel has been dissolved from the cladding. The addition of hydrogen atoms to the zirconium matrix stresses the lattice and forms brittle zirconium hydride, which is easily pulverized into a powder. The dehydriding process removes hydrogen by heating the powder in a vacuum, resulting in a zirconium metal powder. The two main objectives of this research are to investigate the dehydriding process and to design, build and demonstrate a specialized piece of equipment to process the zirconium from cladding hulls to metal powder without intermediate handling. The hydriding process (known from literature) took place in a 95 percent argon - 5 percent hydrogen atmosphere at 500 degrees C while the dehydriding process conditions were researched with a Thermogavimetric Analyzer (TGA). Data from the TGA showed the dehydriding process requires vacuum conditions (~0.001 bar) and 800 degrees C environment to decompose the zirconium hydride. Zirconium metal powder was created in two separate experiments with different milling times, 45 minutes (coarse powder) and 12 hours (fine powder). Both powders were analyzed by three separate analytical methods, X-Ray Diffraction (XRD), size characterization and digital micrographs. XRD analysis proved that the process produced a zirconium metal. Additionally, visual observations of the samples silvery color confirmed the presence of zirconium metal. The presence on zirconium metal in the two samples confirmed the operation of the hydriding / milling / hydriding machine. Further refining of the hydride / milling / dehydride machine could make this process commercially favorable when compared to the high cost of storing nuclear waste and its components. An additional important point is that this process can easily be used on other metals that are subject to hydrogen embrittlement, knowing the relevant temperatures and pressures associated with the hydriding / dehydriding of that particular metal.

The sintering behavior of uranium and uranium-zirconium alloys in the alpha phase were characterized in this research. Metal uranium powder was produced from pieces of depleted uranium metal acquired from the Y-12 plant via hydriding/dehydriding process. The size distribution and morphology of the uranium powder produced by this method were determined by digital optical microscopy. Once the characteristics of the source uranium powder were known, uranium and uranium-zirconium pellets were pressed using a dual-action punch and die. The majority of these pellets were sintered isothermally, first in the alpha phase near 650°C, then in the gamma phase near 800°C. In addition, a few pellets were sintered using more exotic temperature profiles. Pellet shrinkage was continuously measured in situ during sintering. The isothermal shrinkage rates and sintering temperatures for each pellet were fit to a simple model for the initial phase of sintering of spherical powders. The material specific constants required by this model, including the activation energy of the process, were determined for both uranium and uranium-zirconium. Following sintering, pellets were sectioned, mounted, and polished for imaging by electron microscopy. Based on these results, the porosity and microstructure of the sintered pellets were analyzed. The porosity of the uranium-zirconium pellets was consistently lower than that of the pure uranium pellets. In addition, some formation of an alloyed phase of uranium and zirconium was observed. The research presented within this thesis is a continuation of a previous project; however, this research has produced many new results not previously seen. In addition, a number of issues left unresolved by the previous project have been addressed and solved. Most notably, the low original output of the hydride/dehydride powder production system has been increased by an order of magnitude, the actual characteristics of the powder have been measured and determined, shrinkage data was successfully converted into a sintering model, an alloyed phase of uranium and zirconium was produced, and pellet cracking due to delamination has been eliminated.

Stainless steel - zirconium alloys were developed by the US Department of Energy Laboratories as metallic waste forms for noble metal fission products. This thesis evaluates iron-zirconium-rhenium alloys to establish a technical basis for using metal waste form alloys for technetium-99 immobilization. Rhenium is used as a surrogate for Tc-99 since Tc is not naturally available and Re is metallurgically similar to Tc. The iron-zirconium system has two eutectic compositions, Fe-15 wt % Zr and Zr- 16 wt% Fe. Ten test samples were successfully cast in yttrium oxide crucibles at 1600°C, half near each eutectic composition, with Re amounts varying from 2.5 to 12.5 weight percent. A scanning electron microscope (SEM) with energy dispersive X-ray spectroscopy (EDS) capability was employed to determine the phase structure and phase composition of each sample. Iron rich samples were found to form up to three phases, with the rhenium content favoring the intermetallic phases: 1) an Fe solid solution phase, 2) an FeZr2-type intermetallic with 11 wt % or less Re, and 3) a second intermetallic with about 18 wt % Re. Zirconium rich samples formed as many as five distinct phases: 1) a Zr solid solution phase, 2) a Zr3Fe-type intermetallic with as much as 13 wt% Re, 3) a rhenium-zirconium intermetallic, 4) another Fe-Zr intermetallic with very little Re, and 5) a Fe-Re intermetallic. Potentiostatic and potentiodynamic electrochemical tests were performed using sulfuric acid to evaluate the corrosion resistance of each sample. These tests found that the zirconium rich samples were very corrosion resistant but became increasingly susceptible at higher rhenium concentrations. The iron rich samples were not very resistant to corrosion under the test conditions; there was no notable trend in corrosion behavior related to the introduction of rhenium.

Cette thèse présente la mise en place d'une méthodologie pour un dialogue multi-échelle entre la caractérisation microstructurale, consistant en une étude de la morphologie et de la texture cristallographique du matériau, et celle des champs mécaniques associés, notamment de déformation. Cette méthode est basée sur un couplage entre la caractérisation expérimentale de la microstructure, des essais mécaniques macroscopiques, des mesures de champs de déformation déterminées à l'échelle intragranulaire, et des simulations numériques par éléments finis. Enfin une définition d'une fonction coût est proposée dans le but d'optimiser les paramètres de la loi de comportement cristallographique retenue. <br /><br />Cette méthode a été appliquée à l'étude des alliages de zirconium dans le but d'améliorer la compréhension de leur comportement mécanique en relation avec leur microstructure. Compréhension qui est un point clef de leur utilisation dans le domaine de l'industrie nucléaire. Cette thèse a été réalisée dans le cadre du CPR SMIRN, regroupant des laboratoires du CNRS, du CEA et d'EDF.

Reproduction de : Thèse de doctorat : Chimie Théorique : Reims : 2004. / Titre provenant de l'écran titre. Bibliogr. p. 239-249.

Thesis (Ph. D.)--School of Materials Science and Engineering, Georgia Institute of Technology, 2004. Directed by Meilin Liu. / Includes bibliographical references (leaves 180-190).

The amide unit constitutes the backbone of proteins, and it is present in a large number of pharmaceutically active molecules, polymeric materials such as nylon and Kevlar, as well as in food additives like aspartame. Amides are produced in enormous amounts every year, thus, environmentally friendly and selective methods for their formation are of great importance. This thesis deals with the direct formation of amides from non-activated carboxylic acids and amines with the aid of group (IV) metal complexes. Water is the only by-product of this environmentally benign process. This fact stands in contrast to the most common methods for amide formation to date, which involve the use of waste-intensive, expensive and often toxic coupling reagents. The catalytic protocols presented herein use titanium, zirconium and hafnium complexes under mild reaction conditions to produce amides in good to excellent yields. Furthermore, carbamates are demonstrated to be suitable sources of gaseous amines for the formation of primary and tertiary amides under catalytic conditions. In addition, preliminary results from on-going mechanistic investigations of the zirconium- and hafnium-catalyzed processes are presented. / Amidbindningen är en kemisk enhet som utgör ryggraden i proteiner, och som även återfinns i en stor mängd läkemedelsmolekyler, polymera material som nylon och Kevlar, samt i tillsatser i livsmedelsindustrin, exempelvis aspartam. Amider produceras i enorma mängder varje år, och det är av stor vikt att utveckla miljövänliga och selektiva metoder för deras framställning. Denna avhandling behandlar direkt amidering av icke-aktiverade karboxylsyror och aminer med hjälp av katalytiska mängder metallkomplex, baserade på titan, zirkonium och hafnium. Den enda biprodukten från denna amideringsreaktion är vatten. Jämfört med de metoder som generellt används idag för amidsyntes, så är de presenterade metoderna avsevärt mer miljövänliga med avseende på toxicitet hos reagensen såväl som på mängden avfall som genereras. Dessutom redovisas här en katalytisk metod för syntes av primära och tertiära amider genom att använda olika karbamat som källa till gasformiga aminer, vilka annars kan vara praktiskt svåra att arbeta med. Preliminära resultat från en pågående mekanistisk studie av de zirkonium- och hafnium-katalyserade processerna är också inkluderade. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 2: Accepted.</p>

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