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We have grown high-quality magnetite micrometric islands on ruthenium stripes on sapphire through a combination of magnetron sputtering (Ru film), high-temperature molecular beam epitaxy (oxide islands), and optical lithography. The samples have been characterized by atomic force microscopy, Raman spectroscopy, X-ray absorption and magnetic circular dichroism in a photoemission microscope. The magnetic domains on the magnetite islands can be modified by the application of current pulses through the Ru stripes in combination with magnetic fields. The modification of the magnetic domains is explained by the Oersted field generated by the electrical current flowing through the stripes underneath the magnetite nanostructures. The fabrication method is applicable to a wide variety of rock salt and spinel oxides.

We have monitored the Verwey transition in micrometer-wide, nanometer-thick magnetite islands on epitaxial Ru films on Al2O3(0001) using Raman spectroscopy. The islands have been grown by high-temperature oxygen-assisted molecular beam epitaxy. Below 100 K and for thicknesses above 20 nm, the Raman spectra correspond to those observed in bulk crystals and high-quality thin films for the sub-Verwey magnetite structure. At room temperature, the width of the cubic phase modes is similar to the best reported for bulk crystals, indicating a similar strength of electron-phonon interaction. The evolution of the Raman spectra upon cooling suggests that for islands thicker than 20 nm, structural changes appear first at temperatures starting at 150 K while the Verwey transition itself takes place at around 115 K. However, islands thinner than 20 nm show very different Raman spectra, indicating that while a transition takes place, the charge order of the ultrathin islands differs markedly from their thicker counterparts.

In the search for improved permanent magnets, fueled by the geostrategic and environmental issues associated with rare-earth-based magnets, magnetically hard (high anisotropy)-soft (high magnetization) composite magnets hold promise as alternative magnets that could replace modern permanent magnets, such as rare-earth-based and ceramic magnets, in certain applications. However, so far, the magnetic properties reported for hard-soft composites have been underwhelming. Here, an attempt to further understand the correlation between magnetic and microstructural properties in strontium ferrite-based composites, hard SrFe12O19 (SFO) ceramics with different contents of Fe particles as soft phase, both in powder and in dense injection molded magnets, is presented. In addition, the influence of soft phase particle dimension, in the nano- and micron-sized regimes, on these properties is studied. While Fe and SFO are not exchange-coupled in our magnets, a remanence that is higher than expected is measured. In fact, in composite injection molded anisotropic (magnetically oriented) magnets, remanence is improved by 2.4% with respect to a pure ferrite identical magnet. The analysis of the experimental results in combination with micromagnetic simulations allows us to establish that the type of interaction between hard and soft phases is of a dipolar nature, and is responsible for the alignment of a fraction of the soft spins with the magnetization of the hard. The mechanism unraveled in this work has implications for the development of novel hard-soft permanent magnets.

[EN] We show here for the first time the use of a cold sintering process (CSP) to sinter CoSb-based thermoelectric materials. CSP at 150 °C for 90 min under a uniaxial pressure of 750 MPa yields pieces with a relative density of 86 %, which is increased to around 92 % after a post-annealing at temperatures ≥ 500 °C in Ar atmosphere. The reported CSP produces Te doped-CoSb nanocomposites with similar morphological and structural characteristics to the starting nanopowders obtained by ball milling in air atmosphere. The post-thermal treatment induces grain coalescence and grain growth, crystallite size growth as well as compositional changes in the nanocomposite, decreasing the amount of the main phase, CoSb, and increasing the weight of secondary phase, CoSb, up to a 30 wt% at 600 °C. Remarkably, the average valence for the Co, Sb and Te absorbing atoms is neither transformed by the sintering process nor by the subsequent heat treatment. The functional response of the sintered thermoelectric nanocomposites exhibits a maximum figure of merit of 0.12(3) at room temperature for the nanocomposites sintered by CSP with a subsequent post-annealing at 500 °C. This is mainly due to its low thermal conductivity in comparison with similar powders sintered by other approaches, and it is explained by the morphological and structural properties. These findings represent an attractive alternative for obtaining efficient thermoelectric skutterudites by a scalable and cost-effective route.

We present a spatially resolved X-ray magnetic linear dichroism study of high quality micron-sized mixed nickel-cobalt oxide (NCO) crystals. NixCo1-xO was prepared in-situ by high-temperature oxygen-assisted molecular beam epitaxy on a Ru(0001) single crystal substrate. To check the effect of incorporating Ni into the cobalt oxide films, three different compositions were prepared. The element-specific XMLD measurements reveal strong antiferromagnetic contrast at room temperature and magnetic domains up to one micron in size, reflecting the high structural quality of the NCO islands. By means of vectorial magnetometry, the antiferromagnetic spin axis orientation of the domains was determined with nanometer spatial resolution, and found to depend on the stoichiometry of the prepared crystals.

Owing to their multiple applications, lithium ferrites are relevant materials for several emerging technologies. For instance, LiFeO2 has been spotted as an alternative cathode material in Li-ion batteries, while LiFe5O8 is the lowest damping ferrite, holding promise in the field of spintronics. The Li-content in lithium ferrites has been shown to greatly affect the physical properties, and in turn, the performance of functional devices based on these materials. Despite this, lithium content is rarely accurately quantified, as a result of the low number of electrons in Li hindering its identification by means of routine materials characterization methods. In the present work, magnetic lithium ferrite powders with Li:Fe ratios of 1:1, 1:3 and 1:5 have been synthesized, successfully obtaining phase-pure materials (LiFeO2 and LiFe5O8), as well as a controlled mixture of both phases. The powders have been compacted and subsequently sintered by thermal treatment (Tmax = 1100 °C) to fabricate dense pellets which preserve the original Li:Fe ratios. Li-content on both powders and pellets has been determined by two independent methods: (i) Rutherford backscattering spectroscopy combined with nuclear reaction analysis and (ii) Rietveld analysis of powder X-ray diffraction data. With good agreement between both techniques, it has been confirmed that the Li:Fe ratios employed in the synthesis are maintained in the sintered ceramics. The same conclusion is drawn from spatially-resolved confocal Raman microscopy experiments on regions of a few microns. Field emission scanning electron microscopy has evidenced the substantial grain growth taking place during the sintering process – mean particle sizes rise from ≈ 600 nm in the powders up to 3.8(6) µm for dense LiFeO2 and 10(2) µm for LiFe5O8 ceramics. Additionally, microstructural analysis has revealed trapped pores inside the grains of the sintered ceramics, suggesting that grain boundary mobility is governed by surface diffusion

SrFe12O19 (SFO) films grown on Si (100) substrates by radio-frequency magnetron sputtering have been characterized in terms of composition, structural and magnetic properties by a combination of microscopy, diffraction and spectroscopy techniques. Mössbauer spectroscopy was used to determine the orientation of the films magnetization, which was found to be controlled by both the sputtering power and the thickness of the films. Additionally, the coupling between the SFO films and a deposited cobalt overlayer was studied by means of synchrotron-based spectromicroscopy techniques. A structural coupling at the SFO/Co interface is suggested to account for the expetimental observations. Micromagnetic simulations were performed in order to reproduce the experimental behaviour of the system.

[EN] CoFe2O4/Co–Fe magnetic composites are usually prepared through partial reduction of CoFe2O4, which often yields monoxides (i.e., FeO, CoO) as secondary phases. Since these compounds are paramagnetic at ambient conditions, the presence of a small amount of monoxide is generally downplayed in the literature, and the possible effects on the magnetic properties are simply ignored. However, the present study shows that even a low concentration of monoxide results in decoupling of the soft and hard magnetic phases, which inevitably leads to a deterioration of the magnetic properties. Additionally, it is confirmed that a partial reduction of CoFe2O4 is a suitable method to produce CoFe2O4/Co–Fe nanocomposites, provided that the treatment is well controlled with respect to duration, temperature and flow of reductant. A monoxide-free nanocomposite was produced and its magnetic properties evaluated both at room and low temperature. Our model system exemplifies the potential of exchange-coupling (and decoupling) as a tool to tune the magnetic properties of a material within a relatively wide range of values, thus widening its spectrum of potential applications.

©2022 The Author(s). Published by Elsevier B.V. CC_BY_NC_ND_4.0 This work has been supported by the Ministerio Español de Ciencia e Innovación (MICINN), Spain, through the projects MAT2017-86540-C4-1-R and RTI2018-095303-A-C52, and by the European Commission through Project H2020 No. 720853 (Amphibian). C.G.-M. and A.Q. acknowledge financial support from MICINN through the “Juan de la Cierva” program (FJC2018-035532-I) and the “Ramón y Cajal” contract (RYC-2017-23320). S. R.-G. gratefully acknowledges the financial support of the Alexander von Humboldt foundation, Germany. A.S. acknowledges the financial support from the Comunidad de Madrid, Spain, for an “Atracción de Talento Investigador” contract (No. 2017-t2/IND5395)., The use of rare-earth-based permanent magnets is one of the critical points for the development of the current technology. On the one hand, industry of the rare-earths is highly polluting due to the negative environmental impact of their extraction and, on the other hand, the sector is potentially dependent on China. Therefore, investigation is required both in the development of rare-earth-free permanent magnets and in sintering processes that enable their greener fabrication with attractive magnetic properties at a more competitive price. This work presents the use of a cold sintering process (CSP) followed by a post annealing at 1100 degrees C as a new way to sinter composite permanent magnets based on strontium ferrite (SFO). Composites that incorporate a percentage <= 10% of an additional magnetic phase have been prepared and the morphological, structural and magnetic properties have been evaluated after each stage of the process. CSP induces a phase transformation of SFO in the composites, which is partially recovered by the post thermal treatment improving the relative density to 92% and the magnetic response of the final magnets with a coercivity of up to 3.0 kOe. Control of the magnetic properties is possible through the composition and the grain size in the sintered magnets. These attractive results show the potential of the sintering approach as an alternative to develop modern rare-earth-free composite permanent magnets., Unión Europea. Horizonte 2020, Ministerio de Ciencia e Innovación (MICINN) /FEDER, Ministerio de Ciencia e Innovación (MICINN), Comunidad de Madrid, Programa Ramón y Cajal, Depto. de Física de Materiales, Fac. de Ciencias Físicas, TRUE, pub

CRUE-CSIC (Acuerdos Transformativos 2022) ©2022 The Authors. Published by Elsevier B.V. This work has been supported by the Ministerio de Ciencia e Innovacion (MCINN), Spain, through the projects: MAT2015-65445-C2-1-R, MAT2017-86450-C4-1-R, MAT2015-67557-C2-1-P, RTI2018-095856-B-C21, RTI2018-095303-A-C52, PIE: 2021-60-E-030, PIE: 2010-6-OE-013; and Comunidad de Madrid, Spain, by S2013/MIT-2850 NANOFRONTMAG and S2018/NMT-4321 NANOMAGCOST. The authors are also grateful for the electron mi-croscopy characterization performed in the Centro Nacional de Microscopia Electronica at the Universidad Complutense de Madrid (ICTS ELECMI, UCM) , support from MCINN grant #RTI2018-097895-B-43. C.G.-M. acknowledges the financial support from MICINN through the "Juan de la Cierva" Program (FJC2018-035532-I)., Fe_3C/few-layered graphene core/shell nanoparticles embedded in a carbon matrix are synthesized by a novel two-step surfactant sol-gel strategy, where the processes of hydrolysis, polycondensation and drying take place in a one-pot. The present approach is based on the combined action of oleic acid and oleylamine, which act sterically on the precursor micelles when a densification temperature is performed in a reducing atmosphere. The structural and magnetic evolution of the formed compounds is investigated, ranging from iron oxides such as Fe_3O_4 and FeO, to the formation of pure Fe_3C/C samples from 700 degrees C onwards. Interestingly, Fe_3C nanoparticles with a size of similar to 20 nm crystallize immersed in the carbon matrix and the surrounding environment forms an oriented encapsulation built by few-layered graphene. The nanostructures show a saturation magnetization of similar to 43 emu/g and a moderate coercivity of similar to 500 Oe. Thereby, an innovative chemical route to produce single phase Fe_3C nanoparticles is described, and an effective method of few-layered graphene passivation is proposed, yielding a product with a high magnetic response and high chemical stability against environmental corrosion., Ministerio de Ciencia e Innovación (MICINN), Ministerio de Economía y Competitividad (MINECO), Comunidad de Madrid, Depto. de Física de Materiales, Fac. de Ciencias Físicas, TRUE, pub

The nature of the magnetic coupling between a SrFe12O19 particle (hard phase) and a Co layer grown on top (soft phase) has been studied by means of photoemission electron microscopy (PEEM) and spatially-resolved x-ray absorption (XAS) and magnetic circular dichroism (XMCD) at CIRCE, ALBA synchrotron (Spain). Our study reveals the soft metallic overlayer presents an in-plane magnetization despite the strong out-of-plane magnetocrystalline anisotropy of the hard platelet. Thus, the two phases show completely uncorrelated magnetic domain patterns. Micromagnetic simulations seem to indicate the degree of exchange-coupling is low or null, although the conditions for rigid coupling are a priori well met.

[EN] Powder X-ray diffraction (PXRD) and neutron powder diffraction (NPD) have been used to investigate the crystal structure of CoFe2O4 nanoparticles prepared via different hydro­thermal synthesis routes, with particular attention given to accurately determining the spinel inversion degrees. The study is divided into four parts. In the first part, the investigations focus on the influence of using different diffraction pattern combinations (NPD, Cu-source PXRD and Co-source PXRD) for the structural modelling. It is found that combining PXRD data from a Co source with NPD data offers a robust structural model. The second part of the study evaluates the reproducibility of the employed multipattern Rietveld refinement procedure using different data sets collected on the same sample, as well as on equivalently prepared samples. The refinement procedure gives reproducible results and reveals that the synthesis method is likewise reproducible since only minor differences are noted between the samples. The third part focuses on the structural consequences of (i) the employed heating rate (achieved using three different hydro­thermal reactor types) and (ii) changing the cobalt salt in the precursors [aqueous salt solutions of Co(CH3COOH)2, Co(NO3)2 and CoCl2] in the synthesis. It is found that increasing the heating rate causes a change in the crystal structure (unit cell and crystallite sizes) while the Co/Fe occupancy and magnetic parameters remain similar in all cases. Also, changing the type of cobalt salt does not alter the final crystal/magnetic structure of the CoFe2O4 nanoparticles. The last part of this study is a consideration of the chemicals and parameters used in the synthesis of the different samples. All the presented samples exhibit a similar crystal and magnetic structure, with only minor deviations. It is also evident that the refinement method used played a key role in the description of the sample.

[EN] Fe3C/few-layered graphene core/shell nanoparticles embedded in a carbon matrix are synthesized by a novel two-step surfactant sol-gel strategy, where the processes of hydrolysis, polycondensation and drying take place in a one-pot. The present approach is based on the combined action of oleic acid and oleylamine, which act sterically on the precursor micelles when a densification temperature is performed in a reducing atmosphere. The structural and magnetic evolution of the formed compounds is investigated, ranging from iron oxides such as Fe3O4 and FeO, to the formation of pure Fe3C/C samples from 700 ºC onwards. Interestingly, Fe3C nanoparticles with a size of ~20 nm crystallize immersed in the carbon matrix and the surrounding environment forms an oriented encapsulation built by few-layered graphene. The nanostructures show a saturation magnetization of ~43 emu/g and a moderate coercivity of ~500 Oe. Thereby, an innovative chemical route to produce single phase Fe3C nanoparticles is described, and an effective method of few-layered graphene passivation is proposed, yielding a product with a high magnetic response and high chemical stability against environmental corrosion.

[EN] The use of rare-earth-based permanent magnets is one of the critical points for the development of the current technology. On the one hand, industry of the rare-earths is highly polluting due to the negative environmental impact of their extraction and, on the other hand, the sector is potentially dependent on China. Therefore, investigation is required both in the development of rare-earth-free permanent magnets and in sintering processes that enable their greener fabrication with attractive magnetic properties at a more competitive price. This work presents the use of a cold sintering process (CSP) followed by a post-annealing at 1100 °C as a new way to sinter composite permanent magnets based on strontium ferrite (SFO). Composites that incorporate a percentage ≤ 10% of an additional magnetic phase have been prepared and the morphological, structural and magnetic properties have been evaluated after each stage of the process. CSP induces a phase transformation of SFO in the composites, which is partially recovered by the post-thermal treatment improving the relative density to 92% and the magnetic response of the final magnets with a coercivity of up to 3.0 kOe. Control of the magnetic properties is possible through the composition and the grain size in the sintered magnets. These attractive results show the potential of the sintering approach as an alternative to develop modern rare-earth-free composite permanent magnets.

We show that it is possible to tune the Néel temperature of nickel(II)-cobalt(II) oxide films by changing the Ni to Co ratio. We grow single crystalline micrometric triangular islands with tens of nanometers thickness on a Ru(0001) substrate using high temperature oxygen-assisted molecular beam epitaxy. Composition is controlled by adjusting the deposition rates of Co and Ni. The morphology, shape, crystal structure and composition are determined by low-energy electron microscopy and diffraction, and synchrotron-based x-ray absorption spectromicroscopy. The antiferromagnetic order is observed by x-ray magnetic linear dichroism. Antiferromagnetic domains up to micrometer width are observed.

During the past decade, CoFe2O4 (hard)/Co–Fe alloy (soft) magnetic nanocomposites have been routinely prepared by partial reduction of CoFe2O4 nanoparticles. Monoxide (i.e., FeO or CoO) has often been detected as a byproduct of the reduction, although it remains unclear whether the formation of this phase occurs during the reduction itself or at a later stage. Here, a novel reaction cell was designed to monitor the reduction in situ using synchrotron powder X-ray diffraction (PXRD). Sequential Rietveld refinements of the in situ data yielded time-resolved information on the sample composition and confirmed that the monoxide is generated as an intermediate phase. The macroscopic magnetic properties of samples at different reduction stages were measured by means of vibrating sample magnetometry (VSM), revealing a magnetic softening with increasing soft phase content, which was too pronounced to be exclusively explained by the introduction of soft material in the system. The elemental compositions of the constituent phases were obtained from joint Rietveld refinements of ex situ high-resolution PXRD and neutron powder diffraction (NPD) data. It was found that the alloy has a tendency to emerge in a Co-rich form, inducing a Co deficiency on the remaining spinel phase, which can explain the early softening of the magnetic material.

With an annual production amounting to 800 kilotons, ferrite magnets constitute the largest family of permanent magnets in volume, a demand that will only increase as a consequence of the rare-earth crisis. With the global goal of building a climate-resilient future, strategies towards a greener manufacturing of ferrite magnets are of great interest. A new ceramic processing route for obtaining dense Sr-ferrite sintered magnets is presented here. Instead of the usual sintering process employed nowadays in ferrite magnet manufacturing that demands long dwell times, a shorter two-step sintering is designed to densify the ferrite ceramics. As a result of these processes, dense SrFeO ceramic magnets with properties comparable to state-of-the-art ferrite magnets are obtained. In particular, the SrFeO magnet containing 0.2% PVA and 0.6% wt SiO reaches a coercivity of 164 kA/m along with a 93% relative density. A reduction of 31% in energy consumption is achieved in the thermal treatment with respect to conventional sintering, which could lead to energy savings for the industry of the order of 7.10 kWh per year.