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RMN 59Co en champ interne pour l'étude de nanostructures de cobalt, analyse des interactions et anisotropies magnétiques

Abstract : In contrast to classical NMR techniques, internal field (IF) NMR, also called ferromagnetic NMR (FNR) requires no applied constant external magnetic field as the internal field present in ferromagnetic compounds suffices to polarize the nuclear spins. It allows to simultaneously study the crystalline structure, the local Co environment and the magnetic structure of cobalt containing materials. As a result, it can be applied to characterize all different kinds of Co containing materials, which are important materials in many applications of the modern society. In this work, the initial goal was to assess the potential of IF NMR to study cobalt in battery materials but, as a preliminary, a large variety of structures has been studied to assess clearly the potential of the method.The first system of interest was Co-C composites produced by ball milling under a hydrogen for carbon hydrogasification (CHG) was studied. Amongst others, 59Co IF NMR allowed to analyze the evolution of the different Co-C intermediates (Co/C solid solution & Co3C) present inside the sample throughout the CHG reaction. A direct relationship between the total amount of Co-C intermediates and the CHG reaction rate was found, meaning that the formation of the Co-C bond is the rate determining step.The second system was a structure made of parallel Co nanowires. Besides the determination of the crystalline structure, a novelty of this work is the determination of the magnetic domain-wall structure inside the wire by variation of the orientation between the NMR excitation field and the wire axis. The 59Co IF NMR analysis proved that it is not only the wire geometry and its crystalline phase that are responsible for the magnetic structure of the wire, but also the crystallite size and quality.Finally, model assemblies of Co nanoparticles were studied. IF NMR provided a sample-wide overview of the particle crystalline structures inside the sample. In addition, the superparamagnetic – ferromagnetic transition at the so-called blocking-temperature allows to determine the particle size. During the analysis of cobalt nanoparticles inside conversion reaction battery materials, it has been observed in some cases that small sized nanoparticles exhibit a ferromagnetic signal above their theoretical blocking temperature, which might be explained by particle interactions. During the study of close-packed model assemblies of Co nanoparticles no increase of Tb was observed, highlighting the difference between the effect of weak and strong particle interactions.
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Submitted on : Thursday, March 10, 2022 - 2:13:09 PM
Last modification on : Friday, March 11, 2022 - 3:32:19 AM


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  • HAL Id : tel-03604413, version 1


Pascal Scholzen. RMN 59Co en champ interne pour l'étude de nanostructures de cobalt, analyse des interactions et anisotropies magnétiques. Physique [physics]. Université Paris sciences et lettres, 2022. Français. ⟨NNT : 2022UPSLS087⟩. ⟨tel-03604413⟩



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