Leonardo Soriano

This work presents a comprehensive reaction and kinetic model of the pyrite thin films formation by sulfuration of Fe monosulfides when a molecular sulfur (S₂) atmosphere is used. This investigation completes the results already published on the explanation and interpretation of the sulfuration process that transforms metallic iron into pyrite. It was previously shown that the monosulfide species (i.e., orthorhombic and hexagonal pyrrhotite phases) are intermediate phases in the sulfuration reaction. Based on experimental data we now show that the sulfuration of pyrrhotite to pyrite takes place in two distinct stages: (i) conversion of orthorhombic pyrrhotite to pyrite (Fe_1-x S^O → FeS₂) while the hexagonal pyrrhotite (Fe_1-x S^H) phase remains unaltered, and (ii) final transformation of hexagonal pyrrhotite to pyrite (Fe_1-x S^H → FeS₂). Both processes occur via interstitial sulfur diffusion through the previously formed pyrrhotite layer. Consequently, the monosulfide is sulfurated at the internal Fe_1-x S/FeS₂ interface. The reaction mechanism at each stage has been validated using the corresponding kinetic model to fit the experimental data on time evolution of Fe_1-x S and FeS₂ layers thicknesses and some of the film transport properties. The concluding global reaction mechanism proposed in some of our former papers and completed here (Fe → Fe_1-x S → FeS₂) can explain the resulting microstructure of the pyrite films (i.e., Kirkendall effect and formation of a porous layer in the film). Simultaneously, it also justifies the presence of intrinsic defects, such as iron and sulfur vacancies, and the accumulation of interstitial sulfur at the film grain boundaries. The conductivity of pyrite films is tentatively explained using a two-band model where the changes in the Seebeck coefficient and the S/Fe ratio during the pyrite recrystallization stage can be successfully explained.

Understanding the interactions in hybrid systems based on graphene and functional oxides is crucial to the applicability of graphene in real devices. Here, we present a study of the structural defects occurring on graphene during the early stages of the growth of CoO, tailored by the electronic coupling between graphene and the substrate in which it is supported: as received pristine graphene on polycrystalline copper (coupled), cleaned in ultra-high vacuum conditions to remove oxygen contamination, and graphene transferred to SiO₂/Si substrates (decoupled). The CoO growth was performed at room temperature by thermal evaporation of metallic Co under a molecular oxygen atmosphere, and the early stages of the growth were investigated. On the decoupled G/SiO₂/Si samples, with an initial low crystalline quality of graphene, the formation of a CoO wetting layer is observed, identifying the Stranski-Krastanov growth mode. In contrast, on coupled G/Cu samples, the Volmer-Weber growth mechanism is observed. In both sets of samples, the oxidation of graphene is low during the early stages of growth, increasing for the larger coverages. Furthermore, structural defects are developed in the graphene lattice on both substrates during the growth of CoO, which is significantly higher on decoupled G/SiO₂/Si samples mainly for higher CoO coverages. When approaching the full coverage on both substrates, the CoO islands coalesce to form a continuous CoO layer with strip-like structures with diameters ranging between 70 and 150 nm.

Lithium manganese oxides (LMOs) are key materials due to their role in Li-ion batteries and lithium recovery from aqueous lithium resources. In the present work, we investigated the effect of the crystallization temperature on the formation by hydrothermal synthesis of LMO nanocomposites with high Li/Mn ratios. It is demonstrated that LMOs with a high Li/Mn ratio can be formed by systematically favoring the lithium-rich layered monoclinic phase (Li₂MnO₃) in a mixture of monoclinic and spinel crystalline phases. LMO nanocomposites have been characterized in terms of morphology, size, crystallinity, chemical composition and surface properties. Moreover, lithium adsorption experiments were conducted using acid-treated LMOs (HMOs) to evaluate the functionality of the nanocomposites as lithium adsorbent materials in a LiCl buffer solution. This study spotlights the structural, compositional, and functional properties of different LMO nanocomposites obtained by the hydrothermal method using the same Li and Mn precursor compounds at slightly different crystallization temperatures. According to our knowledge, this is the first report of the successful application of the lithium-rich Li₂MnO₃ phase in lithium manganese oxide nanocomposites as lithium adsorbent materials. Therefore, specific LMO nanocomposites with controlled amounts of the layered phase can be engineered to optimize lithium recovery from aqueous lithium resources.

The interaction of graphene with metal oxides is essential for understanding and controlling new devices’ fabrication based on these materials. The growth of metal oxides on graphene/substrate systems constitutes a challenging task due to the graphene surface’s hydrophobic nature. In general, different pre-treatments should be performed before deposition to ensure a homogenous growth depending on the deposition technique, the metal oxide, and the surface’s specific nature. Among these factors, the initial state and interaction of graphene with its substrate is the most important. Therefore, it is imperative to study the initial local state of graphene and relate it to the early stages of metal oxides’ growth characteristics. Taking as initial samples graphene grown by chemical vapor deposition on polycrystalline Cu sheets and then exposed to ambient conditions, this article presents a local study of the inhomogeneities of this air-exposed graphene and how they influence on the subsequent ZnO growth. Firstly, by spatially correlating Raman and x-ray photoemission spectroscopies at the micro and nanoscales, it is shown how chemical species present in air intercalate inhomogeneously between Graphene and Cu. The reason for this is precisely the polycrystalline nature of the Cu support. Moreover, these local inhomogeneities also affect the oxidation level of the uppermost layer of Cu and, consequently, the electronic coupling between graphene and the metallic substrate. In second place, through the same characterization techniques, it is shown how the initial state of graphene/Cu sheets influences the local inhomogeneities of the ZnO deposit during the early stages of growth in terms of both, stoichiometry and morphology. Finally, as a proof of concept, it is shown how altering the initial chemical state and interaction of Graphene with Cu can be used to control the properties of the ZnO deposits.

Magnetic pulse welding (MPW) has potential applications where fusion welding is problematic, such as in dissimilar joints or where the very part integrity, as in electronic components, is likely to be threatened by hot environments. The paper describes some critical applications such as: joining of similar joints between Al wire to Al plate for electric and hybrid applications, dissimilar joints of Al to Cu for electrical conductors, Al to Steel for vehicles, Manganin to Copper for cryogenic applications and joining flexible printed circuit boards. The inductor design and the part set up for the aforementioned applications are critical for successful implementation of MPW. Generally, an air gap between the driver part and the opposite stationary part is required. This prerequisite becomes penalizing in mass production. To circumvent this, the authors have developed innovative solutions via localized humps in case of sheets. The paper proposes to discuss process highlights and characterization of the joints.