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Artículo escrito por un elevado número de autores, solo se referencian el que aparece en primer lugar, el nombre del grupo de colaboración, si le hubiere, y los autores pertenecientes a la UAM, Hydrides based on magnesium and intermetallic compounds provide a viable solution to the challenge of energy storage from renewable sources, thanks to their ability to absorb and desorb hydrogen in a reversible way with a proper tuning of pressure and temperature conditions. Therefore, they are expected to play an important role in the clean energy transition and in the deployment of hydrogen as an efficient energy vector. This review, by experts of Task 40 'Energy Storage and Conversion based on Hydrogen' of the Hydrogen Technology Collaboration Programme of the International Energy Agency, reports on the latest activities of the working group 'Magnesium- and Intermetallic alloys-based Hydrides for Energy Storage'. The following topics are covered by the review: multiscale modelling of hydrides and hydrogen sorption mechanisms; synthesis and processing techniques; catalysts for hydrogen sorption in Mg; Mg-based nanostructures and new compounds; hydrides based on intermetallic TiFe alloys, high entropy alloys, Laves phases, and Pd-containing alloys. Finally, an outlook is presented on current worldwide investments and future research directions for hydrogen-based energy storage

Magnesium alloys and more especially the Mg2Ni compound remain of high interest for reversible hydrogen storage, in spite of high temperature and poor sorption kinetics. Conventionally the Mg-based hydrides are prepared as activated powders by using the High Energy Ball-Milling technique, as well involving some amounts of activating additives. We have developed the technique of Fast Forging (FF) of mixed Mg and Ni samples. Early results show that when processing at low or medium temperatures the FF process acts better as other Severe Plastic Deformation (SPD) techniques. When processing at a temperature high enough, the formation of a mixture of Mg and binary Mg2Ni was promptly achieved by FF. XRD and first hydrogenation kinetics illustrate well the two different sides of the FF-technique that can be compared to Ball-Milling and Mechanical Alloying procedures, respectively.

The crystal structure and overall magnetic properties of RE(Fe0.25Co0.75)2Hywith RE = Ho and Er, were analyzed versus y, the hydrogen content. The single phase C15 type compounds, synthesized using cold crucible HF melting, were hydrogenated and controlled using a PCI apparatus. The impact of hydrogen insertion on the cell parameter, the Curie temperature TCand the magnetization saturation were determined. All compounds and hydrides were found to be ferrimagnets, the magnetic moment of RE and 3d elements being opposite since Ho and Er belong to the 2ndrow of rare earth elements. Depending on the formula, a typical compensation point was in evidence. The 2ndorder character of the ferri ↔ paramagnetic transition was established using the Arrott plot method. Magnetization isotherms vs. magnetic field gives quantified results for the magnetic entropy variation by application of the Maxwell relation. Control of y, the hydrogen content, shows it is interesting for improvement of the MCE of the starting compounds. However increasing y leads to decreased TCat the lowest temperatures, suggesting potential cryogenic uses.

Magnetic and magnetocaloric effect (MCE) of the Er(Fe0.8&minus, xMn0.2&minus, yCox+y)2 Laves phase-type compounds have been investigated. X-ray diffraction (XRD) analysis has revealed that these compounds crystallize with the C15 type Laves phase structure (Space Group Fd-3m). The magnetization curves indicate a ferri-magnetic-ordering resulting of the antiparallel coupling between the moments of the heavy rare earth Er and the transition metal (TM). The partial substitution of Fe/Mn by Co increases the Curie temperature from 355 K for Er(Fe0.8Mn0.2)2 to 475, 550, and 555 K for Er(Fe0.7Mn0.2Co0.1)2, Er(Fe0.8Mn0.1Co0.1)2, and Er(Fe0.7Mn0.1Co0.2)2, respectively. According to the nature of the TM elements, arguments were presented forwards either Molecular Field or Spin Fluctuation Theory, even Stoner type pictures should be considered for. MCE was calculated according to the Maxwell relation based on isotherm magnetization measurements. The magnetic entropy change (&minus, ∆SM) observed on a 300&ndash, 400 K temperature range can be understood in terms of a Spin Fluctuation Theory picture supported by both the different magnetic polarization levels that were shared by the TM elements and the related interatomic exchange forces.

An alternative route for metal hydrogenation has been investigated: cold plasma hydrogen implantation on polyol-made transition metal nanoparticles. This treatment applied to a challenging system, Ni-H, induces a re-ordering of the metal lattice, and superstructure lines have been observed by both Bragg-Brentano and grazing incidence X-ray diffraction. The resulting intermetallic structure is similar to those obtained by very high-pressure hydrogenation of nickel and prompt us to suggest that plasma-based hydrogen implantation in nanometals is likely to generate unusual metal hydride, opening new opportunities in chemisorption hydrogen storage. Typically, almost isotropic in shape and about 30 nm sized hexagonal-packed Ni

Fast-Forging was used as a Severe Plastic Deformation technique to process Mg/Ni fine powder mixtures at a ratio corresponding to the eutectic composition. The samples were processed at different temperature, increased successively from room temperature up to above 500 °C. The one shock forging operation led to a reduction rate comprised between 80 to more than 90% depending of the applied temperature. Interestingly, a threshold temperature was pointed out for which amounts of the binary Mg2Ni alloy were directly synthesized in increasing proportions when increasing temperature. A maximum amount of Mg2Ni was synthesized according the nominal proportions at the highest applied temperature. Besides, numerical simulations were developed to consider and integrate to the forging process, the heat arising from the mechanical energy at deformation. Interestingly the total temperature at shock – heat applied to and heat developed in – indicates that the threshold temperature correspond well with the eutectic temperature as reported in the phase diagram. Early hydrogenation cycles suggest that both mechanical defects in brittle Mg and presence of amounts of Mg2Ni as catalyst should be combined to optimize the hydrogenation characteristics.

International audience; An alternative route for metal hydrogenation has been investigated: cold plasma hydrogen implantation on polyol-made transition metal nanoparticles. This treatment applied to a challenging system, Ni-H, induces a reordering of the metal lattice, and superstructure lines have been observed by both Bragg-Brentano and grazing incidence X-ray diffraction. The resulting intermetallic structure is similar to those obtained by very high-pressure hydrogenation of nickel and prompt us to suggest that plasma-based hydrogen implantation in nanometals is likely to generate unusual metal hydride, opening new opportunities in chemisorption hydrogen storage. Typically, almost isotropic in shape and about 30 nm sized hexagonal-packed Ni 2 H single crystals were produced starting from similarly sized cubic face-centred Ni polycrystals.

The volume expansion, which occurs during the storage of hydrogen by metal hydrides, is a phenomenon linked to the lattice swelling or structural transition some samples. An experimental study realized out in order to characterize the progressive swelling and shrinking observed during the hydrogen absorption and desorption cycles by the compacted LaNi5 powder. The sample LaNi5 compacted has been submitted to 30 hydrogen absorption/desorption cycles, at the same cooling temperature equal 40 °C, under pressure 0.2 bar for the description state and 6 bars for absorption. As expected, the experimental results clearly indicate that the cyclic hydrogenation causes pellet volume changes, i.e. an almost reversible swelling/shrinking in the radial direction. However, this phenomenon can generate major mechanical stresses on the cell containing the pellet. The deformations react on the tank wall tantamount to the initial pressure of hydrogen. The values of the amplitude of the displacement increase progressively up to the 30th cycle, then, the phenomenon is stabilized up to 35 cycles, and this is explained that the relaxation of the metal limited the radial expansion.

This review deals with the destabilization methods for improvement of storage properties of metal hydrides. Both theoretical and experimental approaches were used to point out the influence of various types of defects on structure and stability of hydrides. As a case study, Mg, and Ni based hydrides has been investigated. Theoretical studies, mainly carried out within various implementations of DFT, are a powerful tool to study mostly MgH 2 based materials. By providing an insight on metal-hydrogen bonding that governs both thermodynamics and hydrogen kinetics, they allow us to describe phenomena to which experimental methods have a limited access or do not have it at all: to follow the hydrogen sorption reaction on a specific metal surface and hydrogen induced phase transformations, to describe structure of phase boundaries or to explain the impact of defects or various additives on MgH 2 stability and hydrogen sorption kinetics. In several cases theoretical calculations reveal themselves as being able to predict new properties of materials, including the ways to modify Mg or MgH 2 that would lead to better characteristics in terms of hydrogen storage. The influence of ion irradiation and mechanical milling with and without additives has been discussed. Ion irradiation is the way to introduce a well-defined concentration of defects (Frankel pairs) at the surface and sub-surface layers of a material. Defects at the surface play the main role in sorption reaction since they enhance the dissociation of hydrogen. On the other hand, ball-milling introduce defects through the entire sample volume, refine the structure and thus decrease the path for hydrogen diffusion. Two Severe Plastic Deformation techniques were used to better understand the hydrogenation/dehydrogenation kinetics of Mg- and Mg 2 Ni-based alloys: Equal-Angular-Channel-Pressing and Fast-Forging. Successive ECAP passes leads to refinement of the microstructure of AZ31 ingots and to instalment therein of high densities of defects. Depending on mode, number and temperature of ECAP passes, the H-sorption kinetics have been improved satisfactorily without any additive for mass H-storage applications considering the relative speed of the shaping procedure. A qualitative understanding of the kinetic advanced principles has been built. Fast-Forging was used for a “quasi-instantaneous” synthesis of Mg/Mg 2 Ni-based composites. Hydrogenation of the as-received almost bi-phased materials remains rather slow as generally observed elsewhere, whatever are multiple and different techniques used to deliver the composite alloys. However, our preliminary results suggest that a synergic hydrogenation / dehydrogenation process should assist hydrogen transfers from Mg/Mg 2 Ni on one side to MgH 2 /Mg 2 NiH 4 on the other side via the rather stable a-Mg 2 NiH 0.3 , acting as in-situ catalyser. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim This is the peer reviewed version of the following article: Grbović Novaković, J., Novaković, N., Kurko, S., Milošević Govedarović, S., Pantić, T., Paskaš Mamula, B., ... & Skryabina, N. (2019). Influence of Defects on the Stability and Hydrogen‐Sorption Behavior of Mg‐Based Hydrides. ChemPhysChem., which has been published in final form at [http://dx.doi.org/10.1002/cphc.201801125]. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.

International audience; Different fast forging processes are used for microstructure optimization in an attempt to improvehydrogen storage in Mg-based composites obtained from a mixture of Mg-22 wt.% Ni powders.First, fast forging is employed at room temperature to change the amount of structural defects,produce fine grains and modify crystallographic textures. The effects of such microstructuremodifications (including the exact nature of phases) on the H-storage behavior are investigated.A Mg {0001} basal fiber texture develops upon fast cold forging, which facilitates the initialactivation of hydrogenation while, owing to the high stability of the MgH2 hydride, the kineticsof desorption remains rather slow. Second, to promote hydrogen desorption, forging is conductedat elevated temperature to form Mg2Ni phase. Interestingly, for this sample, faster desorption isrecorded while slower absorption kinetics is obtained due to the occurrence of dynamicrecrystallization inducing weaker texture and lower amount of structural defects. Third, annealingfollowed by cold forging is used to produce a microstructure consisting of fragmented Mg2Nilamellae embedded in a textured Mg-matrix. Using this third approach, both hydrogen absorptionand desorption kinetics are found to be markedly improved.

TiVCr alloys known for their potentially large hydrogen uptake were formulated as (TiCr1.8)100-xVx in order to quantify the impact of vanadium concentration. Parallel to this series of pure ternary, a 2nd ones was synthesized with 4 at.% of Zr7Ni10 addition. Electrochemical charging with hydrogen reveals a fair dependence of hydrogen uptake and hydrides stability versus the x (V) content, moreover conversely different due to the presence of the Zr-Ni additive.

Fast forging of compacts made up of Mg and Ni powders is shown to be an effective method to induce severe plastic deformation with improved H2 sorption properties. Here, using such processed samples, a comprehensive analysis of the sorption properties reveals that the first hydrogenation sequence significantly depends on the forging temperature, through different microstructures. More in detail, no phase transformation occurs upon cold forging, while solid-state reaction leads to the formation of the Mg2Ni intermetallic compound upon forging above 400 °C. Forging below the brittle-to-ductile transition (225–250 °C) leads to faster H2 uptake upon first absorption owing to a more textured fiber along the c-axis and internal strains which promote hydrogen diffusion through the bulk material. Desorption kinetics remain slower with low-temperature forging, despite Ni recombining to form Mg2Ni during the first desorption. After several cycles, a two-step behavior is observed with a fast absorption step occurring up to about 3 wt.%. Despite this limited uptake performance, the forging process can be considered as a straightforward, safe, and cost-efficient process to produce large amounts of Mg-based alloys for hydrogen storage. In particular, such severe plastic deformation processes can be considered as reliable substitutes for ball-milling, which is highly efficient but energy- and time-consuming.

Both numerical simulation and hardness measurements were used to determine the mechanical and microstructural behavior of AZ31 bulk samples when submitted to the Equal Channel Angular Pressing (ECAP) technique. Billets of this representative of Mg-rich alloys were submitted to different numbers of passes for various ECAP modes (anisotropic A, isotropic BC). The strain distribution, the grain size refinement, and the micro-hardness were used as indicators to quantify the effectiveness of the different processing routes. Structural characterizations at different scales were achieved using Scanning Electron Microscopy (SEM), micro-analysis, metallography, Small Angle Neutron Scattering SANS, X-Ray Diffraction (XRD), and texture determination. The grain and crystallite size distribution and orientation as well as defect impacts were determined. Anelastic Spectroscopy (AS) on mechanically deformed samples have shown that the temperature of ECAP differentiate the fragile to ductile regime. MgH2 consolidated powders were checked for using AS to detect potential hydrogen motions and interaction with host metal atoms. After further optimization, the different mechanically-treated samples were submitted to hydrogenation/dehydrogenation (H/D) cycles, which shows that, for a few passes, the BC mode is better than the A one, as supported by theoretical and experimental microstructure analyses. Accordingly, the hydrogen uptake and (H/D) reactions were correlated with the optimized microstructure peculiarities and interpreted in terms of Johnson-Avrami-Mehl-Kolmogorov (JAMK) and Jander models, successively, This research received no external funding.

The hydrogen storage properties of LaNi3.6Mn0.3Al0.4Co0.7 alloy were improved by the addition of Co, Mn and Al. The phase compositions and crystal structures of this alloy were characterized via X-ray diffraction and Scanning Electron Microscopy. The gravimetric study showed that the average size of the particles was about 10 μm. The isotherms of reactions and the hydrogen absorption capacity were measured in the temperature range of 20–40 °C. Hence, the enthalpy (ΔH) and entropy (ΔS) were also calculated. The obtained experimental results showed that this compound can absorb and desorb hydrogen in a reversible way in normal operating conditions (temperature T = 20 °C and pressure P = 6 bar). The hydrogen sorption measurements revealed the effect of the partial substitution of Ni by Al, Mn and Co on the crystal structure of our compound. This substitution led to a significant reduction of hysteresis between hydriding and dehydriding. Thus, the substitution of Ni by these elements led to a larger size of interstitial voids and, therefore, the possibility of a higher number of hydrogen atoms in the cell.

International audience; In situ dilatometry measurements were performed in order to characterize the progressive swelling which is observed upon cycling on compacted disks made of ball-milled MgH2. Each sample was submitted to 200 hydrogen cycles at 310 C, under 0.1 MPa for desorption and 1 MPa for absorption. These measurements clearly show a dilatation on absorption and a contraction on desorption especially in the radial direction. However, at the end of the desorption, the initial position is not recovered and a ''cumulate displacement'' is observed which increases progressively up to about 30 cycles where a stabilisation of the phenomenon is achieved. The introduction of Natural Expanded Graphite (NEG) appears very efficient to limit the radial expansion, with a maximal amplitude three times lower than without NEG and a radial stress equivalent to an applied pressure of 3.4 MPa.

Both series of MnFe0.35−xCo0.65NixP and MnFe0.35Co0.65−xNixP orthorhombic compounds were analyzed for their structural characteristics versus x and versus temperature, as well for the changes induced to the magnetic behaviors (ordering temperature, saturation magnetization, magnetic entropy change). The operated Ni substitutions lead to decrease the Curie point closer to room temperature, especially when Ni substitutes to Co. However, in both systems, the saturation magnetization evolves unexpectedly. Even if remaining rather weak, the corresponding changes of magneto-caloric entropy at the transition are significantly increased, being more than twice and three times the initial value for Ni substituted to Fe and to Co respectively. Chemical and topological arguments are then proposed to discuss the noticeable difference of behaviors observed between the hexagonal (e.g. MnFeP1−xAsx) and the orthorhombic (e.g. MnFe1−xCoxP) series of polytype pnictides.

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Perturbed Angular Correlation (PAC) measurements were performed at room temperature on samples of Hf7Ni10 and of Hf7Ni10 combined with TiV0.8Cr1.2, and at temperatures in the range from 17 K to 350 K in a concentrated hydride of the combined alloy. The PAC results show that the Hf7Ni10 intergranular phase becomes amorphous in the combination process. The results for the hydride composite show in the Hf7Ni10 phase the formation of a stable interstitial hydrogen state below 100 K and a smooth rearrangement of the hydrogen atoms position above 100 K,corresponding to a slow diffusion movemnet of a short-range nature. A second phase transition is observed at around 300 K, presumably to aphase precursor of the hydrogen desorption of the hydride.

International audience; Rods of highly magnetostrictive polycrystalline TbxDy1-xFey materials are elaborated by casting in a cylindrical mould with cooling imposed from the bottom which leads to a fast vertical unidirectional growth. A [1 1 0] orientation is obtained along the axis of the rods parallel to the growth direction. The magnetostrictive properties are remarkable along the rods axis comparable to those of [1 1 1] rods. The saturated magnetostriction measured in a parallel magnetic field is lambda(parallel to) = 1124 x 10(-6) under 0 MPa and increases to 1760 x 10(-6) under a compressive stress of 25 MPa. The pseudolinear variation of the magnetostriction with the internal magnetic field Delta lambda(parallel to)/mu(0)Delta H-int reaches 640 x 10(-6)/0.04 T under 9.9 Mfa. The texture and the good magnetostrictive properties are reproducible.

Le stockage solide de l'hydrogene sous forme d'hydrure de magnesium (MgH2) permet la conversion a grande echelle de l'energie electrique, notamment d'origine renouvelable. Des poudres nanostructurees tres reactives sont obtenues par cobroyage de MgH2 et de metaux de transition. Apres compaction avec du graphite expanse, ces poudres conduisent a des materiaux composites performants en termes de capacite de stockage et de cinetique de sorption de l'hydrogene. Les reactions d'hydruration (deshydruration) etant fortement exothermiques (endothermiques), le developpement de reservoirs performants impose une gestion thermique pointue. Des outils numeriques et analytiques ont ete developpes afin d'aider a la conception de ces systemes de stockage.

A solid oxide fuel cell (SOFC) based combined heat and power (CHP) system in the power range of 1 kWe fed by pure hydrogen stored in a MgH2 tank thermally integrated with the SOFC is presented. Different system configurations were first simulated to compare the system performances in each case. An experimental setup specially designed to test the thermal integration of a magnesium hydride tank with a 1 kWe SOFC stack is fully described. The difficulties encountered during the coupling tests are useful to understand how to solve these technical issues.

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International audience; The experimental study of a large scale magnesium hydride tank (10 kg) is presented. In order to enhance thermal exchanges and improve storage time, the MgH2 powder has been compacted with 10 wt.% of Expanded Natural Graphite. An efficient heat exchanger has been designed to transfer the heat from the endo/exothermic sorption reactions to an external heat source/sink through a high temperature heat transfer fluid. An improvement of the loading and discharging time along the first hydrogenation cycles is observed owing to material thermal conductivity modifications. The properties of the cycled material have been studied in order to understand this evolution of the tank behavior.

International audience; Hydrogen storage in metal hydride tanks (MHT) is a very promising solution. Several experimental tanks, studied by different teams, have already proved the feasibility and the interesting performances of this solution. However, in much cases, an optimization of tank geometry is still needed in order to perform fast hydrogen loading. The development of efficient numerical tools is a key issue for MHT design and optimization. We propose a simple model representing a metal hydride tank exchanging its heat of reaction with a thermal fluid flow. In this model, the radial and axial discretisations have been decoupled by using Matlab (R) one-dimensional tools. Calculations are compared to experimental results obtained in a previous study. A good agreement is found for the loading case. The discharging case shows some discrepancies, which are discussed in this paper.

International audience; Occurrence of phase transitions in Ti(x)V(y)Cr(z)-H systems was analyzed versus temperature. Hydrogen evacuates from the hydrogenated compounds via two main steps. The 1(st) step corresponds to the destabilization of the fcc hydrogenated lattice leading to a fcc -> bcc martensitic type transformation. The 2(nd) step occurs according to the decomposition of the resulting hydride via evacuation of hydrogen from the bcc lattice. Both the kinetics and temperature of 1(st) and 2(nd) step transformations depend on the composition of the starting Ti(x)V(y)Cr(z) alloys.

Colloque avec actes et comité de lecture. Internationale.; International audience; Afin de démontrer la faisabilité du stockage de l'hydrogène grâce à l'hydrure de magnésium activé, un réservoir de 250 cm3 contenant 120 g d'hydrure a été réalisé. Le magnésium réagit avec l'hydrogène de façon réversible et absorbe jusqu'à 7,6% massique. Le fonctionnement de ce réservoir fait l'objet de cette étude. Le logiciel Fluent a été utilisé pour le modéliser numériquement. Le code s'appui sur des conditions aux limites et certaines données thermiques déduites de l'expérience. La pression est considérée comme homogène dans le réservoir. Les simulations sont en accord avec l'expérience dans les domaines de température et de pression favorables à une charge ou une déchage du réservoir rapide.

International audience; Iron provides a larger magnetization than cobalt, besides rather expensive rare-earth (R) cobalt-rich materials are increasingly replaced by R-Fe based alloys. The R element is chosen to develop high anisotropy parameters and a small amount of a light element X (e.g. B, C, N) is present to stabilize the axial crystal structure and (or) to reinforce the two previous intrinsic characteristics (magnetization and anisotropy). Three main families of hard magnet materials, effective and potential, are derived from Nd(2)Fe(14)B, Sm(2)Fe(17)N(3) and Nd(Fe,M)(12)N structure types. The extrinsic properties of a magnet, that are remanence and coercivity, are sufficiently high when optimizing the micro- and nano-structure of the polycrystalline materials as done for sintered or bonded magnet. It is worth to note that, for optimization of all the magnetic parameters, the grain size and the granular texture must be comprised within well defined ranges, and as homogeneous as possible. Several types of mechano-chemical processes have been successfully developed in order to achieve hard magnet extrinsic performances. They can be classified in two categories, those where the main process is of metallurgy type, and those where interstitial insertion of a light element is used to improve the intrinsic or (and) extrinsic properties.

International audience; Structural alignment in Fe-0.4C alloy transformed in high magnetic field has been evaluated by quantitative microscopy analysis, An aligned two-phase structure is formed in high magnetic field by austenite to ferrite transformation during slow cooling. Ferrite grains are elongated and connected with each other along the direction of magnetic field. The degree of alignment can be evaluated by measuring the number of intersections between test lines and ferrite/austenite phase boundaries. Results of measurement show that the degree of alignment increases continuously with increasing magnetic field strength up to 10 Tesla.

Gd 3+ is shown to be a sensitive probe to characterize slight changes of structural environment in powdered samples of the La 2 CuO 4 high- T c oxide superconductor family. In particular, the approach of the orthorhombic-tetragonal phase transition yields significant line shifts in the low-temperature phase and the change of structure that takes place around 500 K manifests itself by the vanishing of spectral lines.

International audience; A high speed hot forging process was applied to Nd-Fe-B and Nd-Fe-V as cast alloys in order to develop both the microstructure and the crystallographic texture appropriate for permanent anisotropic magnet properties. Neutron diffraction texture analyses are used to demonstrate the effect of the hot forging process on both kind of alloys. Microstructural changes are an important feature on forging in both cases. Coercivity is developed in the Nd-Fe-B alloy mainly from grain size reduction and disappearance of free iron. Stabilisation of the Nd(Fe,V)(12) hard magnetic phase is achieved from the iron and Nd-rich microstructure of the starting Nd-Fe-V material. A comparison of the crystallographic textures of Nd2Fe14B and Nd(Fe,V)(12) phases is done to account for the development of extrinsic magnetic anisotropy. In both cases, a nearly fibre texture is obtained in correlation with the symmetry of the deformation. However, the orientations are quite different in both alloys and the consequences on the magnetic properties are evidenced.

Most of ternary pnictides with general formula MM’X (where M and M’ are transition metals and X being a p-element such as P and As) crystallize with a Fe2P type structure exhibiting high magnetocaloric effect (MCE) with d-electron concentration close to that of Fe. Surprisingly, polytype systems MM’X of Co2P-type lead to low performances, even when involving the same metal elements, i.e., MnFeP1-xAsx (hexagonal) and MnFe1-xCoxP (orthorhombic), which exhibit very similar magnetic phase diagrams. So the aim of the work was first to better understand the main crystalline and magnetic fundamental trends of the orthorhombic series when controlling substitutions of selected elements to specific sites e.g. Cr to Mn, Ni to Fe or Co, Si tor Ge to P. Then, the goal was to optimize formula and process aiming being able to design hexagonal type compounds where As is fully replaced by safer Si, for high MCE characteristics, in view of pilot production.At first, synthesis efforts followed by XRD analyzes, magnetization vs field and temperature, neutron scattering investigations of magnetic structures, calorimetry and comparative MCE measurements, were carried out on numerous samples forming a representative panel. Unexpectedly, the less magnetic 3d metal Ni caused cell volume anomalies vs substitution rate to Fe or Co leading the saturation magnetization to evolve non-linearly. From the several attempts, and combining mixed substitutions on metallic and non metallic sites (e.g. Ni to Co / Ge to P), the initial variation of the magnetic entropy at transition (ΔSm) was improved by about 3 times, to reach the reference level Gd. Besides non-collinear and non-commensurate magnetic structures were established, agreeing well with 57Fe Mössbauer analysis and electronic structure calculations.The second action of this work consists in 3 parts. First, analysis involving XRD, SEM, magnetization, calorimetry… was deployed to characterize well the peculiarities of MCE promising Mn1-xFexP1-xSix powders of Fe2P-type produced at a large scale by gas atomization. Of the most critical parameters was the post annealing treatment, which is expected delivering high MCE performances. Several attempts have progressively revealed the best range of temperature, annealing time and cooling down rate. Thus the ΔSm characteristic upgraded from 0.2 to 4 J/kg.K for a variation of 0-2 T. To confirm the above results, works focused to a simple formula MnFeP0.5Si0.5 prepared from precursors and using HF melting. The goal was to better control the phase equilibrium in the quaternary system. From this step, ΔSm up to 16 J/kg.K (0-2 T) was achieved. At the end, the method of dedicated precursor and HF melting was applied to produce different formula (various Mn/Fe and P/Si ratios), comprising the use of the atomized powders. With the gained experience 18 and then close to 24 J/kg.K (0-2 T) was reached.In a final conclusion, chemical and topology parameters driving the critical differences in between related to the Fe2P and Co2P types of MM’X pnictides were discussed., La plupart des pnictures ternaires de formule générale MM'X (où M et M' sont des métaux de transition et X un élément p tel que P et As) cristallisent avec une structure dérivée de type Fe2P présentant un effet magnétocalorique (MCE) élevé avec une concentration en électrons d proche de celle de Fe. Au contraire, les systèmes polytypes MM'X de type Co2P conduisent à des performances modestes, même lorsque les éléments métalliques sont identiques, à savoir les phases MnFeP1-xAsx (hexagonale) et MnFe1-xCoxP (orthorhombique) présentes dans des diagrammes de phases magnétiques très similaires. Ainsi, le but de ce travail était tout d'abord de mieux comprendre l'évolution fondamentale des comportements structuraux et magnétiques de la série orthorhombique lorsqu'on effectue des substitutions partielles d'éléments choisis sur des sites spécifiques, tels que Mn par Cr, Ni par Fe ou Co, et P par Si ou Ge. D'autre part, il s'agissait d'optimiser la formulation et le procédé d'élaboration visant à concevoir des composés de type hexagonal dans lesquels As est entièrement remplacé par Si plus sûr, et présentant des performances MCE élevées, en vue d'une production pilote.Dans un premier temps, des efforts de synthèse suivis d'analyses DRX, de mesures d'aimantation en fonction du champ et de la température, d'analyses par diffraction de neutrons des structures magnétiques, de caractérisations calorimétriques et de mesures comparatives de MCE, ont été réalisées sur de nombreux échantillons formant un panel représentatif. De manière inattendue, Ni, le métal 3d qui porte le moment magnétique le plus faible, a conduit à des anomalies de volume de la maille en fonction du taux de substitution de Fe ou de Co, induisant une évolution non linéaire de l'aimantation à saturation. Après plusieurs tentatives, et en combinant des substitutions mixtes sur les sites métalliques et non métalliques (par exemple Ni à Co / Ge à P), la variation initiale de l'entropie magnétique à la transition (ΔSm) a été améliorée par environ un facteur 3, pour atteindre le niveau de référence du Gadolinium. En outre, des structures magnétiques non colinéaires et non commensurables aient été établies, en bon accord avec l'analyse Mössbauer 57Fe et les calculs de structure électronique.Le deuxième volet de ce travail comporte 3 parties. D'une part, des analyses de type XRD, MEB, aimantation, calorimétrie... ont été réalisées afin de caractériser les particularités des poudres magnétocaloriques Mn1-xFexP1-xSix de type Fe2P produites à grande échelle par atomisation sous jet de gaz. Le traitement de recuit après atomisation est apparu comme étant l'un des paramètres les plus importants pour accéder à des performances MCE élevées. Plusieurs essais ont permis de définir la meilleure gamme de température, le temps de recuit et la vitesse de refroidissement. Ainsi, la caractéristique ΔSm a été améliorée de 0,2 à 4 J/kg.K pour une variation de 0-2 T. Pour conforter les résultats ci-dessus, des travaux ont été focalisés sur une formule simple - MnFeP0.5Si0.5 - préparée à partir de précurseurs et en utilisant la fusion HF. L'objectif était de mieux contrôler l'équilibre de phases dans le système quaternaire. A partir de cette étape, des performances très intéressantes ont été atteintes, avec un ΔSm de 15 J/kg.K (0-2 T). Enfin, l'emploi de précurseurs spécifiques et de la fusion HF ont été appliqués pour produire des formules différentes (différents rapports Mn / Fe et P / Si), comprenant l'utilisation de poudres atomisées. Avec l'expérience acquise, des valeurs de 18 et de près de 24 J/kg.K (0-2 T) ont été atteintes.En conclusion, les paramètres chimiques et topologiques gouvernant les différences majeurs entre les pnictures MM'X de type Fe2P et de type Co2P ont été discutées.

The last decade the magnesium hydride stood out as the most attractive candidatefor solid storage of hydrogen at large scale. The main subject of this study is thephenomenon of irreversible swelling of the composites based on magnesium hydride, duringthe hydriding/dehydriding cycles as well as the evolution of their mechanical properties.In-situ dilatometry measurements and the microstructural characterizations (SEM,granulometry) were performed on magnesium hydride samples co-milled with vanadium orTi-V-Cr additive. The results reveal that the coalescence of nanometric particles tends tocreate large agglomerates, which induce an increase in porosity, and explain the progressiveswelling of composites.The nanoindentation tests performed on compacted pellets show an enhancement ofabout 30 % of the Young modulus after 10 cycles. From the Vickers hardness measured oncompacted powders, the hardness of a highly densified magnesium hydride wasextrapolated to 0.58 GPa, which shows that the magnesium hydride is harder thanmagnesium., Lors de la dernière décennie, l’hydrure de magnésium est apparu comme le candidat le plus intéressant pour le stockage solide de l’hydrogène à grande échelle. La présente étude s’est intéressée au gonflement irréversible de composites à base d’hydrure de magnésium durant les cycles d’hydruration/déshydruration ainsi qu’à l’évolution de leurs propriétés mécaniques.Les expériences de dilatométrie in-situ et les caractérisations microstructurales (MEB,granulométrie), menées sur des échantillons de MgH₂co-broyés avec des additifs devanadium ou Ti-V-Cr ont montré que la coalescence des particules nanométriques favorise la formation de larges agglomérats qui induisent une augmentation de la porosité et qui expliquent le gonflement irréversible des composites.Les tests de nano-indentation ont montré une augmentation du module de Young de plus de 30 % après 10 cycles d’hydruration/déshydruration. Les mesures de la dureté Vickers sur des pastilles de MgH2 sans additif ont permis d’estimer sa dureté en fonction de la densité relative. Ainsi la dureté d’une pastille qui aurait une densité proche de la densitéthéorique (95 %) a été extrapolée à 0.58 GPa.

The main target of the thesis was to study the thermal integration of a magnesium hydride (MgH2) tank with an external heat source. At first, the evolution of material properties upon cycling were investigated. A large microstructural evolution was observed during the first cycles which impacts on kinetics of reaction and thermal conductivity. An expansion of the composites is also observed. Quantity and/or nature of the additives used during material preparation was identified as an important parameter controlling this phenomenon. Our measures show that mechanical strains on the tank wall due to this expension are stable after 40 hydrogenation cycles. A large number of cycles was applied to these composites which exhibits a very high stability upon cycling. A large scale magnesium hydride tank (10 kg MgH2) storing 6500 Nl of hydrogen in 35 minutes was developed and tested. The energy of reaction is exchanged with an external heat source by a heat transfer fluid. This installation allows to simulate the integration of a magnesium hydride tank into a co-generation system. A numerical model was developed in order to better understand and predict the behavior of this tank. A thermal integration test of the MgH2 with a high temperature fuel cell (SOFC) was performed at Politecnico di Torino., L'objectif de la thèse était d'étudier la faisabilité d'un couplage thermique entre un réservoir d'hydrure métallique et une source externe de chaleur. L'évolution des propriétés de composites à base d'hydrure de magnésium (MgH2) a été étudiée en fonction du nombre de cycles d'hydruration. On observe une très bonne stabilité de la capacité massique d'absorption sur le long terme (600 cycles réalisés). Les premiers cycles sont néanmoins marqués par une évolution importante de la microstructure qui dépend de la proportion et/ou de la nature de l'additif utilisé lors de la mécano-synthèse des poudre d'hydrure. Cette évolution est associée à une augmentation de la conductivité thermique, mais également à une légère dégradation des cinétiques intrinsèques de réaction ainsi qu'à une expansion volumique des composites. Nos mesures montrent que l'amplitude des contraintes mécaniques engendrées sur les parois d'un réservoir se stabilisent après une cinquantaine de cycles. Un réservoir contenant 10 kg de MgH2, et capable de stocker 6500 Nl d'hydrogène en 35 minutes a ensuite été développé au laboratoire. L'énergie des réactions d'absorption et de désorption est échangée avec une source externe de chaleur via un fluide caloporteur. Ce système permet de représenter l'intégration thermique d'un réservoir d'hydrure dans un système de cogénération. Un modèle numérique a été développé afin de mieux appréhender le comportement de ce réservoir. Des essais de couplage entre un réservoir de taille plus modeste et une pile à combustible haute température (SOFC) développant une puissance électrique de 1 kW ont également été réalisés au Politecnico di Torino.

The thesis's subject is about creation and modeling of a solid state hydrogen tank using magnesium hydride (MgH2). The main characteristic of this tank is the ability to store the heat of absorption due to the use of a Phase Change Material (PCM). In order to prove the sustainability of this system, a study, on the magnesium hydride's behavior, has been carried out. On one hand, kinetic properties and the amount of the stored hydrogen do not decrease after 100 cycles. On the other hand, a significant change on material morphology has been noticed. Indeed, a swelling and an increasing of thermal conductivity have been measured. Investigations about the MCP showed the importance of the thermal conductivity and the heat of fusion. That's why a metallic eutectic alloy has been selected. His atomic composition is Mg69Zn28Al3, he is a good thermal conductor, having a high heat of fusion, and presenting a good chemical stability during cycling. The designed tank contains 10 kg of magnesium hydride ball-milled added with Expanded Natural Graphite. It can absorb 7000 NL (625 g) of hydrogen in 3 hours and a half. On one total cycle, the energetic efficiency can be estimated to more than 70 %. At the same time, two numerical modeling have been achieved with Fluent and Matlab softwares, in order to make the design of next generation of tanks easier., La thèse porte sur la conception et la simulation d'un réservoir de stockage solide de l'hydrogène sous forme d'hydrure de magnésium (MgH2). La particularité du réservoir conçu réside dans sa capacité à stocker l'énergie d'absorption grâce à un matériau de changement de phase (MCP). Afin de pouvoir prouver la viabilité du système, une étude portant sur le comportement de l'hydrure de magnésium compacté lors du cyclage à été effectuée. Celle-ci montre qu'après 100 cycles, les cinétiques de réaction et les taux massiques de stockage d'hydrogène ne sont pas affectés. En revanche, un changement de morphologie important a été observé puisqu'une dilatation ainsi qu'une augmentation importante de la conductivité des matériaux composites ont été relevées. L'étude du MCP révéla l'importance de certains paramètres, en particulier la conductivité thermique et l'enthalpie de fusion. Le MCP sélectionné est un alliage métallique en composition eutectique. Celui ci est bon conducteur de chaleur, présente une enthalpie de fusion élevée et une stabilité de comportement thermique au cyclage. Le réservoir construit contient 10 kg d'hydrure de magnésium co-broyé + 5 % de Graphite Naturel Expansé. Il est capable de stocker 7000 NL d'hydrogène (625 g) en 3h. L'avantage principal du réservoir est son efficacité énergétique, puisque la chaleur stockée par le MCP à l'absorption est refournie lors de la désorption. Afin de pouvoir prédire les comportements thermiques et cinétiques des prochains réservoirs basés sur cette technologie, 2 modèles numériques utilisant Matlab et Fluent ont été développés et validés.

The thesis's subject is about creation and modeling of a solid state hydrogen tank using magnesium hydride (MgH2). The main characteristic of this tank is the ability to store the heat of absorption due to the use of a Phase Change Material (PCM). In order to prove the sustainability of this system, a study, on the magnesium hydride's behavior, has been carried out. On one hand, kinetic properties and the amount of the stored hydrogen do not decrease after 100 cycles. On the other hand, a significant change on material morphology has been noticed. Indeed, a swelling and an increasing of thermal conductivity have been measured. Investigations about the MCP showed the importance of the thermal conductivity and the heat of fusion. That's why a metallic eutectic alloy has been selected. His atomic composition is Mg69Zn28Al3, he is a good thermal conductor, having a high heat of fusion, and presenting a good chemical stability during cycling. The designed tank contains 10 kg of magnesium hydride ball-milled added with Expanded Natural Graphite. It can absorb 7000 NL (625 g) of hydrogen in 3 hours and a half. On one total cycle, the energetic efficiency can be estimated to more than 70 %. At the same time, two numerical modeling have been achieved with Fluent and Matlab softwares, in order to make the design of next generation of tanks easier.; La thèse porte sur la conception et la simulation d'un réservoir de stockage solide de l'hydrogène sous forme d'hydrure de magnésium (MgH2). La particularité du réservoir conçu réside dans sa capacité à stocker l'énergie d'absorption grâce à un matériau de changement de phase (MCP). Afin de pouvoir prouver la viabilité du système, une étude portant sur le comportement de l'hydrure de magnésium compacté lors du cyclage à été effectuée. Celle-ci montre qu'après 100 cycles, les cinétiques de réaction et les taux massiques de stockage d'hydrogène ne sont pas affectés. En revanche, un changement de morphologie important a été observé puisqu'une dilatation ainsi qu'une augmentation importante de la conductivité des matériaux composites ont été relevées. L'étude du MCP révéla l'importance de certains paramètres, en particulier la conductivité thermique et l'enthalpie de fusion. Le MCP sélectionné est un alliage métallique en composition eutectique. Celui ci est bon conducteur de chaleur, présente une enthalpie de fusion élevée et une stabilité de comportement thermique au cyclage. Le réservoir construit contient 10 kg d'hydrure de magnésium co-broyé + 5 % de Graphite Naturel Expansé. Il est capable de stocker 7000 NL d'hydrogène (625 g) en 3h. L'avantage principal du réservoir est son efficacité énergétique, puisque la chaleur stockée par le MCP à l'absorption est refournie lors de la désorption. Afin de pouvoir prédire les comportements thermiques et cinétiques des prochains réservoirs basés sur cette technologie, 2 modèles numériques utilisant Matlab et Fluent ont été développés et validés.

The purpose of this thesis was to study the Hydrogen Decrepitation (HD) process as a way to recycle waste scraps of Nd-Fe-B sintered magnets into highly coercitive and anisotropic powders, for the industry of bonded magnets. The process consists in a first hydrogenation, the bulk material being reduced into powder, as a result of the large volume expansion of the lattice. Then Hydrogen Desorption and annealing treatments are requested to restore the initial characteristics of the precursor (coercivity and anisotropy). Starting with sintered (NdDy)2-(FeCoNbCu)14-B magnets as a precursor, the different steps of the HD process have been studied. Differential Scanning Calorimetry (DSC) and Hydrogenation Kinetics measurements were used to investigate the hydrogen absorption and desorption characteristics. Thermal-magnetization measurement was used to investigate the effect of the residual hydrogen content on magnetic properties of the anisotropic (NdDy)-(FeCoNbCu)-B powders. The thesis focuses on the effect of the applied experimental conditions such as hydrogen decrepitation temperature, twice hydrogen decrepitation cycle, hydrogen desorption temperature, magnetic field during hydrogen desorption, annealing temperature etc... on magnetic properties of (NdDy)-(FeCoNbCu)-B powders. Among these factors, hydrogen absorption temperature, hydrogen desorption temperature and annealing temperature play important roles on the magnetic properties. Twice hydrogen decrepitation improves the size distribution of the powders. Hydrogen desorption under magnetic field reduces the residual hydrogen content of the anisotropic powders, resulting in raising their remanence (Br). After optimization of the successive steps of the process, anisotropic powders with good properties have been achieved : Br = 10.29 kGs (1.029 T), Hcj = 14.3 kOe (1138 kA/m), (BH)max = 21.67 MGOe (172.5 kJ/m3). It corresponds respectively to 93%, 46% and 74% of the magnetic properties of the precursor sintered (NdDy)-(FeCoNbCu)-B permanent magnets., L'objectif de la thèse était d'étudier le procédé de Décrepitation à l'Hydrogène (HD) en tant que moyen de recycler les rebus d'aimants frittés Nd-Fe-B en poudres fortement coercitives et anisotropes, pour l'industrie d'aimants liés. Le procédé consiste à appliquer une première hydruration, afin de réduire le matériau massif en poudre, grâce à l'expansion du volume de la maille. Des traitements de désorption de l'hydrogène et de recuit sont ensuite nécessaires pour rétablir les caractéristiques initiales du précurseur (coercivité et anisotropie). Les différentes étapes du procédé HD ont été étudiées à partir d'aimants frittés (NdDy)2(FeCoNbCu)14B utilisés comme précurseurs. Les caractéristiques d'absorption et de désorption de l'hydrogène ont été étudiées par Calorimétrie Différentielles (DSC) et par des mesures de cinétique d'hydruration. Des mesures magnétothermiques ont permis d'analyser l'effet de la présence d'hydrogène résiduel sur les propriétés magnétiques des poudres (NdDy)-(FeCoNbCu)-B. La thèse se focalise sur l'impact des conditions expérimentales appliquées, telles que la température de décrepitation, l'application d'un double cycle de décrépitation, la température de désorption, l'application d'un champ magnétique pendant la désorption de l'hydrogène, la température de recuit, etc... sur les propriétés magnétiques des poudres (NdDy)-(FeCoNbCu)-B. Parmi ces facteurs, les températures d'absorption et de désorption, et la température de recuit jouent un rôle prépondérant sur les propriétés magnétiques. La double décrépitation améliore la distribution de taille des poudres. La désorption de l'hydrogène sous le champ magnétique réduit le contenu d'hydrogène résiduel des poudres anisotropes, et conduit ainsi à une augmentation de la rémanence (Br). Après l'optimisation des étapes successives du procédé, des poudres anisotropes présentant des propriétés satisfaisantes ont été obtenues : Br = 10.29 kGs (1.029 T), Hcj = 14.3 kOe (1138 kA/m), (BH)Max = 21.67 MGOe (172.5 kJ/m3). Les propriétés magnétiques initiales des aimants frittés (NdDy)-(FeCoNbCu)-B ont été restaurées respectivement à 93 %, 46 % et 74 %.