Many industries including the medical, aerospace, and automobile industries have increasingly adopted the use of shape memory alloys (SMAs) for a plethora of applications due to their unique thermomechanical properties. From the commercially available SMAs in the market, binary NiTi SMAs have shown the most desirable properties. However, SMA properties can be significantly affected by the fabrication process. One of the most familiar applications of NiTi SMAs is in the design of actuating devices where the shape memory effect properties are highly advantageous. Spring NiTi SMA actuators are among the most commonly used and are generally made by torsion loading a straight wire. Consequently, stress concentrations are formed causing a reduction in recovery force. Other methods for producing springs and other NiTi SMA components is the fast emerging manufacturing method of additive manufacturing (AM). AM often uses metal powders to produce the near-net shape components. A major challenge for SMAs, in particular, is their well-known composition sensitivity. Therefore, it is critical to control composition in NiTi SMAs. In this thesis, a novel method for processing NiTi SMAs for pre-alloyed NiTi SMA powders and springs is presented. A low pressure and low temperature hydriding-pulverization-dehydriding method is used for preparing the pre-alloyed NiTi SMA powders with well-controlled compositions, size, and size distributions from wires. By hydrogen charging as-drawn martensitic NiTi SMA wires in a heated H3PO4 solution, pulverizing, and dehydriding, pre-alloyed NiTi powders of various well-controlled sizes are produced. In addition, a low pressure and low temperature hydriding-dehydriding method is used for producing NiTi SMA helixes from wires. The helix pattern in the pre-alloyed NiTi SMA wires was obtained by hydrogen charging NiTi SMA 500 μm diameter wires at different time intervals, followed by dehydriding to remove the hydrogen. The wires, powders, and resulting helixes were characterized using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and x-ray diffraction (XRD). The relationship between the wire diameter, powder particle size, and helix geometry as a function of hydrogen charging time is investigated. Lastly, the recovery behavior due to the shape memory effect is also investigated after dehydriding.

As a part of the production of nitride nuclear fuel for use in fast nuclear reactors, zirconium is hydrided followed by nitriding and mixing with uranium nitride. This work concludes a study of unwanted metallic particles present in a powder that is supposed to be a zirconium hydride. Sponge zirconium was hydrided at different temperatures and different time intervals, and the resulting hydride was milled into a powder. The powders were analyzed using SEM and XRD after which the powders were pressed into pellets for light optical microscopic study. The primary goals were determination of the structure of the particles and thereafter elimination of them. It was seen that hydriding at 500 C results in less metal particles but more experiments need to be conducted to confirm this.

Pressure tubes pick up hydrogen while they are in service within CANDU reactors. Sufficiently high hydrogen concentration can lead to hydride precipitation during reactor shutdown/repair at flaws, resulting in the potential for eventual rupture of the pressure tubes by a process called Delayed Hydride Cracking (DHC). The threshold stress intensity factor (KIH) below which the cracks will not grow by delayed hydride cracking of Zr-2.5Nb micro pressure tubes (MPTs) has been determined using a load increasing mode (LIM) method at different temperatures. MPTs have been used to allow easy study of the impact of properties like texture and grain size on DHC. Previous studies on MPTs have focused on creep and effects of stress on hydride orientation; here the use of MPTs for DHC studies is confirmed for the first time. Micro pressure tube samples were hydrided to a target hydrogen content of 100 ppm using an electrolytic method. For DHC testing, 3 mm thick half ring samples were cut out from the tubes using Electrical Discharge Machining (EDM) with a notch at the center. A sharp notch with a root radius of 15 µm was introduced by broaching to facilitate crack initiation. The direct current potential drop method was used to monitor crack growth during the DHC tests. For the temperature range tested the threshold stress intensity factors for the micro pressure tube used were found to be 6.5-10.5 MPa.m1/2 with the value increasing with increasing temperature. The average DHC velocities obtained for the three different test temperatures 180, 230 and 250oC were 2.64, 10.87 and 8.45 x 10-8 m/s, respectively. The DHC data obtained from the MPTs are comparable to the data published in the literature for full sized CANDU pressure tubes. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2009-04-24 12:55:36.917

Lors d’un scénario hypothétique d’Accident par Perte de Réfrigérant Primaire (APRP), les gainages combustibles en alliage de zirconium subissent des sollicitations thermomécaniques sévères dans des environnements chimiques très oxydants. L’évolution des conditions de pression et de température ainsi que la présence du fluide réfrigérant peuvent entraîner dans un premier temps le ballonnement-éclatement puis l’oxydation sous vapeur et la prise d’hydrogène à haute température ainsi que des chargements mécaniques axiaux lors du renoyage final.L’objectif de la thèse est d’identifier les mécanismes et les paramètres clés qui gouvernent la rupture lors de la phase de renoyage sous traction. Des essais semi-intégraux, visant à reproduire un scénario APRP sur des tronçons de gaines de Zircaloy−4, ont été réalisés afin d’étudier le comportement de ce matériau dans de telles conditions.Un seuil fonction de la durée d’oxydation à haute température, à partir duquel la gaine rompt lors du renoyage, est mis en évidence. Deux lieux de rupture sont identifiés : la zone ballonnée où l’oxydation est maximale et la prise d’hydrogène nulle, ainsi que la zone dite « d’hydruration secondaire », sous la zone ballonnée, où la prise d’hydrogène est conséquente et l’oxydation moindre. Par ailleurs, un scénario de la rupture par rapport à la chronologie du renoyage a été établi.Cependant, le traitement macroscopique de ces essais ne permet pas de discriminer ces deux lieux de rupture, car la rupture intervient indépendamment dans le ballon et hors zone ballonnée en fonction du transitoire appliqué et de la morphologie du ballonnement-éclatement. Une approche locale a été mise en place, à partir de la caractérisation microstructurale et fractographique systématique des éprouvettes d’essai, afin d’établir un critère de rupture dépendant de l’état du matériau.La distribution complexe des éléments chimiques et des phases dans l’épaisseur de la gaine a été déterminée. Les changements de phase dans le ballon fortement oxydé, menant à une microstructure globalement fragile, ont été explicités. Une loi de seuil à rupture, en zone d’hydruration secondaire, a été identifiée à l’aide des mesures d’épaisseurs de phases et du profil de teneur en hydrogène. / During hypothetical Loss-Of-Coolant-Accident (LOCA) scenarios, zirconium alloy fuel cladding tubes are subjected to severe thermo- mechanical loading conditions in highly oxidising chemical environments. Pressure and temperature evolution together with cooling water can lead to ballooning and burst followed by steam oxidation and hydrogen uptake at high temperature, and then axial loading during the final reflooding stage.This study focuses on the identification of mechanisms and key parameters which drive cladding fracture during the reflooding stage under axial tensile load.Laboratory-scale semi-integral tests simulating LOCA transients on Zircaloy−4 test rods have been realised. A fracture/no-fracture threshold of oxidation duration at high temperature has been determined. Two fracture locations have been identified: i) the burst zone with maximal oxidation and no hydrogen uptake, and ii) the “secondary hydriding” zone below the burst zone, with substantial hydrogen absorption and lower oxidation levels. Moreover, a scenario of fracture as a function of the reflooding chronology has been identified. Nevertheless, the macroscopic treatment of these tests has not permitted to discriminate these two fracture locations because fracture independently occurs in and out of the burst zone, whatever the applied transient and the balloon and burst morphologies.From systematic microstructural and fractographic characterisation of test specimens, a local approach aiming at identifying a fracture threshold as a function of the microstructural state of the material has been applied. The complex distribution of chemical elements and phases across the cladding thickness has been determined. Phase transformations in the highly-oxidised balloon, leading to a globally brittle microstructure have been explicated. In the secondary hydriding zone, a fracture threshold criterion has been identified by means of layer thickness measurements and hydrogen uptake profile.

Reatores PWR empregam, como combustível nuclear, pastilhas de UO2 acondicionadas em tubos de ligas de zircônio, chamados de encamisamento. Na sua fabricação são gerados cavacos de usinagem que não podem ser descartados, pois a reciclagem deste material é estratégica quanto aos aspectos de tecnologia nuclear, econômicos e ambientais. As ligas nucleares têm altíssimo custo e não são produzidas no Brasil, sendo importadas para a fabricação do combustível nuclear. Neste trabalho são abordados dois métodos para reciclar os cavacos de Zircaloy. No primeiro, os cavacos foram fundidos utilizando um forno elétrico a arco para obter lingotes. O segundo usa a técnica da metalurgia do pó, onde os cavacos foram submetidos à hidretação e o pó resultante foi moído e isostaticamente prensado e, a seguir, sinterizado a vácuo. A composição química, as fases presentes e a dureza no material foram determinadas. Os lingotes foram tratados termicamente e laminados, sendo que as microestruturas foram caracterizadas por microscopia óptica e eletrônica de varredura. Os resultados para ambos os métodos mostraram que a composição do Zircaloy reciclado cumpre as especificações químicas e apresentaram microestrutura adequada para uso nuclear. Os bons resultados do método de metalurgia do pó sugerem a possibilidade de produzir pequenas peças, como as tampas do encamisamento - end-caps, usando a sinterização no formato quase final (near net shape). / PWR reactors employ, as nuclear fuel, UO2 pellets with Zircaloy clad. In the fabrication of fuel element parts, machining chips from the alloys are generated. As the Zircaloy chips cannot be discarded as ordinary metallic waste, the recycling of this material is important for the Brazilian Nuclear Policy, which targets the reprocess of Zircaloy residues for economic and environmental aspects. This work presents two methods developed in order to recycle Zircaloy chips. In one of the methods, Zircaloy machining chips were refused using an electric-arc furnace to obtain small laboratory ingots. The second one uses powder metallurgy techniques, where the chips were submitted to hydriding process and the resulting material was milled, isostatically pressed and vacuum sintered. The ingots were heat-treated by vacuum annealing. The microstructures resulting from both processing methods were characterized using optical and scanning electron microscopies. Chemical composition, crystal phases and hardness were also determined. The results showed that the composition of recycled Zircaloy comply with the chemical specifications and presented adequate microstructure for nuclear use. The good results of the powder metallurgy method suggest the possibility of producing small parts, like cladding end-caps, using near net shape sintering.

This thesis is focused on the mechanisms for corrosion andhydriding of Zircaloy. Special attention is paid tomicrostructural characterisation by cross sectionaltransmission electron microscopy of the oxide layer formed.Three main topics have been treated in this work: (i)Pre-transition oxides were investigated with the purpose ofevaluating if it is possible to predict post-transitionbehaviour of different alloys. (ii) The reason for the commonlyobserved accelerated corrosion of Zircaloy in the presence oflithium hydroxide was investigated by studying the phasetransformation of differently stabilised zirconium oxides andby corrosion studies. (iii) Pre-hydrided Zircaloy-2 was studiedto investigate the influence of hydrogen on the oxidationbehaviour. Characterisation of pre-transition oxides formed onzirconium alloys, has been accomplished with the aim ofdetermining if there are any differences in the properties(morphology, pores, cracks and phases) of the oxide layersformed which might explain the differences in corrosionbehaviour later in life. Four Zircaloy-2 versions and oneZircaloy-4 version were tested in an autoclave at 288° Cfor 20h and 168h and at 360˚C for 96h. Based on thecharacterisation of pre-transition oxide layers only small orno differences were found between the different alloycompositions, thus it is not possible to predict long-timecorrosion behaviour by studying pre-transition oxides. However,large differences were found between the two test temperatures.The higher oxidation temperature results in increased oxidationrates and larger oxide grains, the columnar grains are a factorof 3-4 longer, and the equiaxed grains have an almost doubledmaximum diameter. The fraction of columnar grains andtetragonal phase also increases with temperature. The reasonfor the difference in morphology between the two temperaturesis not fully understood, but the results show that acceleratedtesting at elevated temperatures may be a questionableapproach. One of the Zircaloy-2 samples was also anodicallyoxidised. The oxide layer formed only contains equiaxed grainsand phase analysis shows both monoclinic and tetragonal phasesare present. Oxidation tests of Zircaloy-2 and Zircaloy-4 in water andlithiated water at 360 ° C show that the pre-transitionoxidation rate is not affected by the presence of LiOH, but thetransition occurs earlier and the post-transition oxidationrate is increased. The oxidation rate correlates with thedensity of cracks in the oxide layer and the morphology of theoxide grains. The oxides formed have a layered structure andfor samples oxidised in LiOH solution the inner protectivelayer is thin. The effect of LiOH is suggested to be the resultof partial dissolution of the oxide and subsequentincorporation of lithium ions during adissolution-precipitation process. Newly formed oxide isprobably more hydrous, and the grain boundaries areparticularly liable to dissolution. The increased concentrationof LiOH within cracks and pores could reach the detrimentallevels necessary for dissolution. This is supported by theinsensitivity in the pre-transition region to both thecompositions of the alloy and to the environment. The alloycomposition influences the microstructure of the oxide layer,and thereby the resistance to accelerated corrosion rate inlithiated water. The hydrogen pickup ratio follows the weightgain, not the oxidation rate, up to the second transition. Whenthe protective oxide layer is degraded the hydrogen pickupratio increases markedly. To evaluate if hydrogen is a cause for or a consequence ofaccelerated corrosion, pre-transition oxidation tests ofZircaloy-2 have been performed with hydrogen present in threedifferent states: i) Hydrogen in solid solution in thezirconium alloy, corresponding to the initial oxidation priorto precipitation of hydrides. ii) Uniformly distributedhydrides simulating a situation in whish hydrides starts toprecipitate and iii) Massive surface hydride claimed to be themain cause of accelerated oxidation. Based on the resultsobtained, it is concluded that the oxidation of massivezirconium hydride resembles the oxidation of zirconium metal.This fact clearly shows that accelerated oxidation of zirconiumalloys cannot be due solely to the presence of a massivehydride layer, but also requires a combined effect offorexample interfacial roughness and hydride precipitation. <b>Keywords:</b>Zircaloy, Zirconium alloys, Oxidation, Oxidelayer, Pre-Transition, Hydriding, Pre-Hydrided, Hydrides,Lithium Hydroxide (LiOH), Lithiated Water, Dissolution, CrossSectional TEM

<p>This thesis is focused on the mechanisms for corrosion andhydriding of Zircaloy. Special attention is paid tomicrostructural characterisation by cross sectionaltransmission electron microscopy of the oxide layer formed.Three main topics have been treated in this work: (i)Pre-transition oxides were investigated with the purpose ofevaluating if it is possible to predict post-transitionbehaviour of different alloys. (ii) The reason for the commonlyobserved accelerated corrosion of Zircaloy in the presence oflithium hydroxide was investigated by studying the phasetransformation of differently stabilised zirconium oxides andby corrosion studies. (iii) Pre-hydrided Zircaloy-2 was studiedto investigate the influence of hydrogen on the oxidationbehaviour.</p><p>Characterisation of pre-transition oxides formed onzirconium alloys, has been accomplished with the aim ofdetermining if there are any differences in the properties(morphology, pores, cracks and phases) of the oxide layersformed which might explain the differences in corrosionbehaviour later in life. Four Zircaloy-2 versions and oneZircaloy-4 version were tested in an autoclave at 288° Cfor 20h and 168h and at 360˚C for 96h. Based on thecharacterisation of pre-transition oxide layers only small orno differences were found between the different alloycompositions, thus it is not possible to predict long-timecorrosion behaviour by studying pre-transition oxides. However,large differences were found between the two test temperatures.The higher oxidation temperature results in increased oxidationrates and larger oxide grains, the columnar grains are a factorof 3-4 longer, and the equiaxed grains have an almost doubledmaximum diameter. The fraction of columnar grains andtetragonal phase also increases with temperature. The reasonfor the difference in morphology between the two temperaturesis not fully understood, but the results show that acceleratedtesting at elevated temperatures may be a questionableapproach. One of the Zircaloy-2 samples was also anodicallyoxidised. The oxide layer formed only contains equiaxed grainsand phase analysis shows both monoclinic and tetragonal phasesare present.</p><p>Oxidation tests of Zircaloy-2 and Zircaloy-4 in water andlithiated water at 360 ° C show that the pre-transitionoxidation rate is not affected by the presence of LiOH, but thetransition occurs earlier and the post-transition oxidationrate is increased. The oxidation rate correlates with thedensity of cracks in the oxide layer and the morphology of theoxide grains. The oxides formed have a layered structure andfor samples oxidised in LiOH solution the inner protectivelayer is thin. The effect of LiOH is suggested to be the resultof partial dissolution of the oxide and subsequentincorporation of lithium ions during adissolution-precipitation process. Newly formed oxide isprobably more hydrous, and the grain boundaries areparticularly liable to dissolution. The increased concentrationof LiOH within cracks and pores could reach the detrimentallevels necessary for dissolution. This is supported by theinsensitivity in the pre-transition region to both thecompositions of the alloy and to the environment. The alloycomposition influences the microstructure of the oxide layer,and thereby the resistance to accelerated corrosion rate inlithiated water. The hydrogen pickup ratio follows the weightgain, not the oxidation rate, up to the second transition. Whenthe protective oxide layer is degraded the hydrogen pickupratio increases markedly.</p><p>To evaluate if hydrogen is a cause for or a consequence ofaccelerated corrosion, pre-transition oxidation tests ofZircaloy-2 have been performed with hydrogen present in threedifferent states: i) Hydrogen in solid solution in thezirconium alloy, corresponding to the initial oxidation priorto precipitation of hydrides. ii) Uniformly distributedhydrides simulating a situation in whish hydrides starts toprecipitate and iii) Massive surface hydride claimed to be themain cause of accelerated oxidation. Based on the resultsobtained, it is concluded that the oxidation of massivezirconium hydride resembles the oxidation of zirconium metal.This fact clearly shows that accelerated oxidation of zirconiumalloys cannot be due solely to the presence of a massivehydride layer, but also requires a combined effect offorexample interfacial roughness and hydride precipitation.</p><p><b>Keywords:</b>Zircaloy, Zirconium alloys, Oxidation, Oxidelayer, Pre-Transition, Hydriding, Pre-Hydrided, Hydrides,Lithium Hydroxide (LiOH), Lithiated Water, Dissolution, CrossSectional TEM</p>

Reatores PWR empregam, como combustível nuclear, pastilhas de UO2 acondicionadas em tubos de ligas de zircônio, chamados de encamisamento. Na sua fabricação são gerados cavacos de usinagem que não podem ser descartados, pois a reciclagem deste material é estratégica quanto aos aspectos de tecnologia nuclear, econômicos e ambientais. As ligas nucleares têm altíssimo custo e não são produzidas no Brasil, sendo importadas para a fabricação do combustível nuclear. Neste trabalho são abordados dois métodos para reciclar os cavacos de Zircaloy. No primeiro, os cavacos foram fundidos utilizando um forno elétrico a arco para obter lingotes. O segundo usa a técnica da metalurgia do pó, onde os cavacos foram submetidos à hidretação e o pó resultante foi moído e isostaticamente prensado e, a seguir, sinterizado a vácuo. A composição química, as fases presentes e a dureza no material foram determinadas. Os lingotes foram tratados termicamente e laminados, sendo que as microestruturas foram caracterizadas por microscopia óptica e eletrônica de varredura. Os resultados para ambos os métodos mostraram que a composição do Zircaloy reciclado cumpre as especificações químicas e apresentaram microestrutura adequada para uso nuclear. Os bons resultados do método de metalurgia do pó sugerem a possibilidade de produzir pequenas peças, como as tampas do encamisamento - end-caps, usando a sinterização no formato quase final (near net shape). / PWR reactors employ, as nuclear fuel, UO2 pellets with Zircaloy clad. In the fabrication of fuel element parts, machining chips from the alloys are generated. As the Zircaloy chips cannot be discarded as ordinary metallic waste, the recycling of this material is important for the Brazilian Nuclear Policy, which targets the reprocess of Zircaloy residues for economic and environmental aspects. This work presents two methods developed in order to recycle Zircaloy chips. In one of the methods, Zircaloy machining chips were refused using an electric-arc furnace to obtain small laboratory ingots. The second one uses powder metallurgy techniques, where the chips were submitted to hydriding process and the resulting material was milled, isostatically pressed and vacuum sintered. The ingots were heat-treated by vacuum annealing. The microstructures resulting from both processing methods were characterized using optical and scanning electron microscopies. Chemical composition, crystal phases and hardness were also determined. The results showed that the composition of recycled Zircaloy comply with the chemical specifications and presented adequate microstructure for nuclear use. The good results of the powder metallurgy method suggest the possibility of producing small parts, like cladding end-caps, using near net shape sintering.

Les problèmes environnementaux et économiques, engendrés par l’usage des produits pétroliers, et la pénurie de ces énergies fossiles ont conduit à rechercher d’autres sources d’énergies, renouvelables et respectueuses de l’environnement. Nombre de ces sources sont intermittentes et nécessitent de prévoir des solutions de stockage. Le gaz de dihydrogène apparait comme un bon candidat pour remplir cette fonction. L’élément hydrogène, abondant dans la nature, présente sous sa forme gazeuse un pouvoir calorifique de 140 MJ/kg, soit 2,5 fois celui de l’essence. La filière ’hydrogène’ s’appuie sur 3 piliers : la production, le stockage-la distribution et l’utilisation. Le stockage d’hydrogène est traditionnellement réalisé par compression, sous des pressions allant de quelques bars à plusieurs centaines, et par liquéfaction à 20 K. La faible densité volumique de ces deux types de stockage (42 et 70 kgH2/m3) associée à de sérieux problèmes de sécurité et de conception mécanique, rend le stockage solide dans les alliages métalliques particulièrement pertinent pour certaines applications. Cette solution favorise le développement de réservoirs de conception sûre, compacts et ayant une grande densité volumique de 120 kgH2/m3 pour les alliages TiFe par exemple. Ce type d’hydrure a été retenu dans le cadre de ce travail parce qu’il présente des températures et pressions d’utilisation relativement proches des conditions ambiantes, mais aussi parce qu’il ne contient pas de terre rare d’utilisation relativement proches des conditions ambiantes, mais aussi parce qu’il ne contient pas de terre rare. La présente étude vise à caractériser et modéliser le comportement d’hydruration/déshydruration de l’alliage TiFe0.9Mn0.1, en vue d’améliorer ses performances lorsqu’il est intégré à un système de stockage. Dans un premier temps, nous nous sommes attachés à caractériser expérimentalement l’alliage TiFe0.9Mn0.1 sous forme de poudre en le décrivant sur les plans morphologique, chimique et thermodynamique. Ensuite, deux stratégies d’amélioration ont été testées, la première repose sur un traitement mécanique par broyage planétaire à billes, la deuxième considère un traitement thermochimique à température et durée de maintien données. Ces deux stratégies ont permis d’accélérer le processus d’activation de la poudre, mais le broyage planétaire à billes a détérioré de façon notable la cinétique apparente de désorption. Le traitement thermochimique n’a quant à lui pas dégradé les domaines d’équilibre et n’a donc pas eu d’effet néfaste sur les cinétiques de réaction. Les deux paramètres les plus importants de ce traitement, température et temps de maintien, ont été optimisés. D’autres paramètres restent à affiner.[...]La conception d’un système de stockage solide d’hydrogène exige la bonne compréhension des aspects macroscopiques, mais aussi microscopiques, de la réaction d’hydruration, et requiert donc des recherches complémentaires pour trouver de nouveaux axes d’amélioration de ses performances. / He environmental and economic problems caused by the use of petroleum products and the scarcity of these fossil fuels have led to the search for alternative sources of energy, which are renewable and respectful of the environment. Many of these sources are intermittent and require storage solutions. Hydrogen gas appears as a good candidate for this function. The hydrogen element, abundant in nature, has in its gaseous form a calorific value of 140 MJ / kg, i.e. 2.5 times that of gasoline. The 'hydrogen' sector is based on 3 pillars: production, storage, distribution and use. The storage of hydrogen is traditionally carried out by compression, under pressures ranging from a few bars to several hundreds, and by liquefaction at 20 K. The low density of these two types of storage (42 and 70 kgH2 / m3) associated with serious problems of safety and mechanical design, make solid storage in metal alloys particularly relevant for some applications. This solution favors the development of safe, compact design tanks with a high density of 120 kgH2/m3for TiFe alloys, for example. This type of hydride has been retained in this work because it has operating conditions of temperatures and pressures that are relatively close to ambient conditions, and also because it does not contain rare earth elements. The aim of this study is to characterize and model the hydriding/dehydriding behavior of the TiFe0.9Mn0.1 alloy, in order to improve its performance when it is integrated into a storage system. We first tried to characterize the alloy TiFe0.9Mn0.1 in powder form by describing it morphologically, chemically and thermodynamically. Then, two strategies of improvement were tested, the first one based on a mechanical treatment by planetary ball milling, the second considers a thermochemical treatment at given temperature and duration. Both strategies accelerated the process of powder activation, but the planetary ball milling significantly impaired the apparent desorption kinetics. The thermo-chemical treatment did not degrade the equilibrium domains and thus did not have an adverse effect on the reaction kinetics. The two most important parameters of this treatment, temperature and holding time, have been optimized. Other parameters remain to be refined.In addition to this experimental characterization, we have undertaken to describe the hydriding / dehydriding reaction macroscopically. The model allows to account for the thermodynamic response of the hydride within a reservoir. This work presents the results obtained on a tank containing 4 kg of TiFe0.9Mn0.1 powder when different hydrogen loading / unloading scenarios are considered: (i) loading / unloading under constant pressure, (ii) loading / unloading under an initial dose ( Method of Sievert), iii) loading / unloading under inlet or outlet flux of hydrogen. For each scenario, the effect of the coupling with a heat exchange system on the filling / emptying times is analyzed and optimal operating conditions are proposed. Finally, a sensitivity study using the Morris method is presented, and the most influential parameters of the model on the reaction rates are identified. The design of a solid hydrogen storage system requires a good understanding of the macroscopic as well as the microscopic aspects of the hydriding reaction and therefore requires further research to find new directions for improving its performance.

In this work a manufacturing method for UN, ZrN and (U,Zr)N pellets was established at the nuclear fuel laboratory at KTH Stockholm/Sweden, which consists of the production of nitride powders and their sintering into pellets by spark plasma sintering. The nitride powders were produced by the hydriding-nitriding route using pure metal as starting material. This synthesis was performed in a stream of the particular reaction gas. A synthesis control and monitoring system was developed, which can follow the reactions in real time by measuring the gas flow difference before and after the reaction chamber. With the help of this system the hydriding and nitriding reactions of uranium and zirconium were studied in detail. Fine nitride powders were obtained; however, the production of zirconium nitride involved one milling step of the brittle zirconium hydride. Additionally uranium and zirconium alloys with different zirconium contents were produced and synthesized to nitride powders. It was found that also the alloys could be reduced to fine powder, but only by cyclic hydriding-dehydriding. Pellets were sintered out of uranium nitrides, zirconium nitrides, mixed nitrides and alloy nitrides. These experiments showed that relative densities of more than 90% can easily be achieved for all those powders. Pellets sintered from mechanically mixed nitride powders were found to still consist of two separate nitride phases, while nitride produced from alloy was demonstrated to be a monophasic solid solution both as powder and as sintered pellets.