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 degrees C) to fabricate dense pellets which preserve the original Li:Fe ratios. Li-content on both powders and pellets has been deter-mined 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 tech-niques, 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 approximate to 600 nm in the powders up to 3.8(6) mu m for dense LiFeO2 and 10(2) mu m 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. Vibrating sample magnetometry on the ceramic samples has confirmed the ex-pected soft ferrimagnetic behavior of LiFe5O8 (with Ms = 61.5(1) Am2/kg) and the paramagnetic character of LiFeO2 at room temperature. A density of 92.7(6)% is measured for the ceramics, ensuring the mechanical integrity required for both their direct utilization in bulk shape and their use as targets for thin-film deposition.
We have studied the influence of the annealing treatment on the crystalline growth of SrFe 12 O 19 previously deposited on Si (100) substrates using radio frequency (RF) magnetron sputtering. For this goal, two grown films, with and without ex situ heating step, have been analyzed and compared to determine the differences in their structural, compositional, and magnetic properties. The results obtained by the different analysis techniques, in particular Mössbauer spectroscopy together with EXAFS and XANES data, suggest that the as-grown film is composed of nanocrystalline maghemite nanoparticles and amorphous strontium oxide. Specifically, Mössbauer spectroscopy results pointed out the presence of Fe 3+ cations occupying octahedral and tetrahedral sites with hyperfine magnetic fields 49.3 T and 44.2 T, respectively, characteristic of a spinel-related structure. A strontium hexaferrite canonical structure with a c-axis orientation in the sample plane was found for the annealed film. Graphical abstract
CoFe2O4 thin films (5 nm and 20 nm thick) were grown by oxygen assisted molecular beam epitaxy on Pt(111) at 523~K and subsequently annealed at 773 K in vacuum or oxygen. They were characterized in-situ using Auger Electron Spectroscopy, Low-Energy Electron Diffraction, Scanning Tunneling Microscopy and Conversion Electron M\"ossbauer Spectroscopy. The as-grown films were composed of small, nanometric grains. Annealing of the films produced an increase in the grain size and gave rise to magnetic order at room temperature, although with a fraction of the films remaining in the paramagnetic state. Annealing also induced cobalt segregation to the surface of the thicker films. The measured M\"ossbauer spectra at low temperature were indicative of cobalt ferrite, the both films showing very similar hyperfine patterns. Annealing in oxygen or vacuum affected the cationic distribution, which was closer to that expected for an inverse spinel in the case of annealing in an oxygen atmosphere.
Strontium hexaferrite nanocrystalline powders were synthesized using a citrate combustion method and subsequently subjected to post-synthesis processing with the aim of tuning the micro-nanostructure to improve the magnetic properties. Firstly, the synthesis thermal treatments were optimized in order to minimize the formation of secondary phases, mainly hematite. Secondly, the as-synthesized powders were conditioned by a two-step process: ball milling in wet medium (ethanol) and high-speed mixing. The final processed powders exhibited a saturation magnetization of 74 emu g −1 and a coercivity of 6450 Oe. Following a low-temperature combustion synthesis, the coercivity is one of the largest values reported for strontium ferrites. The combination of the two-step conditioning procedure results in a useful methodology to obtain SrFe 12 O 19 nanocrystalline powders with competitive properties. The morphological, structural and magnetic properties of the processed material make it a promising candidate for hard-soft ferrite-based composite magnets, where large coercivity values are highly desirable.
Permanent magnets based on hard hexaferrite represent the largest family of magnets being used today by volume. They generate moderate remanence induction, but present crucial advantages in terms of availability, cost, resistance to demagnetization and corrosion and absence of eddy current losses. As a consequence, ferrites are the most logical candidate for substitution of rare-earths in selected applications that do not demand the best performing magnets. If the remanence of ferrite-based magnets was to be improved, even mildly, the door to a larger scale substitution could be opened. In this framework, we review here current strategies to improve the properties of hexaferrites for permanent magnet applications. We first discuss the potential of exploring the nanoscale. Second, progress related to controllably doping hexaferrites is revised. Third, results achieved by fabricating hard-soft magnetic composites using ferrites as the hard phase are presented. Finally, future prospects and new potential end applications for ferrite magnets are discussed.
In order to obtain competitive strontium ferrite sintered magnets, SiO2 and CaO are added to avoid exaggerated grain growth. Besides favoring proper densification, these additives prevent the collapse of coercivity associated to grain growth. However, these additives may lead to slight decreases in density and the formation of paramagnetic alpha-Fe2O3 that hampers magnetization. Here, with the motivation of simplifying the production process, we present a study to maximize the magnetic performance of strontium ferrite ceramics using silica as the sole additive. A microscopic study offers insights into the grain growth mechanism activated by Silica. As a result, a compromise between relative density, coercivity and saturation magnetization is attained. It is found that sintering for 4 h up to 1200 degrees C with a SiO2 content of 1 wt% leads to the best compromise between coercivity, magnetization and density values. Competitive densities are reported in the absence of CaO, the usual co-additive. In addition, Confocal Raman Microscopy is employed for the first time to characterize the decomposition of strontium ferrite onto alpha-Fe2O3. (C) 2020 Elsevier B.V. All rights reserved.
Carbon monoxide (CO) adsorption on ultrathin fcc Fe films is known to result in the rotation of magnetization from out-of-plane to in-plane.
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 SrFe$_{12}$O$_{19}$ ceramic magnets with properties comparable to state-of-the-art ferrite magnets are obtained. In particular, the SrFe$_{12}$O$_{19}$ magnet containing 0.2% PVA and 0.6% wt SiO$_2$ 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 7.109 kWh per year.
The growth of mixed cobalt-iron oxides on Ru(0001) by high-temperature oxygen-assisted molecular beam epitaxy has been monitored in real time and real space by x-ray absorption photoemission microscopy. The initial composition is a mixed Fe-Co(II) oxide wetting layer, reflecting the ratio of the deposited materials. However, as subsequent growth of three dimensional spinel islands nucleating on this wetting layer takes place, the composition of the oxide in the wetting layer changes as iron is transferred into the spinel islands. The composition of the islands themselves also changes during growth.
Due to the issues associated with rare-earth elements, there arises a strong need for magnets with properties between those of ferrites and rare-earth magnets that could substitute the latter in se...
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.
We have studied micrometer-thick cobalt ferrite films deposited on Si (1 0 0) single crystal substrates by nanosecond pulsed laser deposition at 1064 nm. The thickness of the deposited films (1.3 mu m) was monitored by AFM. The chemical and structural characterisation of the films was carried out by Raman spectroscopy and transmission Mossbauer spectroscopy at 300 and 26 K. For comparison purposes, transmission Mossbauer data at these two temperatures were also recorded from a commercial cobalt ferrite powder and the home-made target used to grow the films. The surface characterisation was performed by X-ray Photoelectron Spectroscopy (XPS) and Integral Low Energy Electron Spectroscopy (ILEEMS). XPS showed Co and Fe to be present as Co2+ and Fe3+, as expected for cobalt ferrite. The Raman spectra showed the lines characteristic of cobalt ferrite. The Mossbauer spectra, both in the transmission and backscattering modes, were fitted to two sextets whose hy-perfine parameters are in good agreement with those expected from Fe3+ cations occupying the tetrahedral and octahedral sites in the spinel-related structure. No significant differences were observed in the relative areas of the two sextets in the transmission and ILEEMS spectra, suggesting that the cation distribution at the surface and the bulk are not too different. However, the relative areas of the two components changed drastically with temperature both in the spectra of the films as in those recorded from the cobalt ferrite standards. We discuss the possible origin of the evolution with temperature of those relative areas.
Platelets of strontium hexaferrite (SrFe 12 O 19 , SFO), up to several micrometers in width, and tens of nanometers thick have been synthesized by a hydrothermal method. They have been studied by a combination of structural and magnetic techniques, with emphasis on Mössbauer spectroscopy and X-ray absorption based-measurements including spectroscopy and microscopy on the iron-L edges and the oxygen-K edge, allowing us to establish the differences and similarities between our synthesized nanostructures and commercial powders. The Mössbauer spectra reveal a greater contribution of iron tetrahedral sites in platelets in comparison to pure bulk material. For reference, high-resolution absorption and dichroic spectra have also been measured both from the platelets and from pure bulk material. The O-K edge has been reproduced by density functional theory calculations. Out-of-plane domains were observed with 180° domain walls less than 20 nm width, in good agreement with micromagnetic simulations.
9th IWSP: Nanostructured surfaces, Trzebnica, Poland, 24 – 28 June 2019. -- http://www.iwsp2019.ifd.uni.wroc.pl/
In pulsed laser deposition, the laser irradiation wavelength and the substrate nature and temperature crucially affect the composition, crystallinity, structure and magnetic properties of the grown deposits. In this work, cobalt ferrite (CoFe2O4) thin films were deposited on Si (1 0 0) and SrTiO3 (1 0 0) single crystal substrates at room temperature and 770 K using laser wavelengths of 213, 532 and 1064 nm. The deposited films were characterized by atomic force microscopy to determine the surface morphology, by X-ray diffraction to examine their crystallinity, and by micro-Raman, scanning electron microscopy/ energy-dispersive X-ray spectroscopy, X-ray photoelectron and Mossbauer spectroscopies to investigate their composition and stoichiometry. Magnetic characterization was carried out by superconducting quantum interference device magnetometry. At 770 K and 1064 nm, the films consisted of singlecrystal CoFe2O4 ((1 0 0) orientation) when grown on SrTiO3, and of polycrystalline CoFe2O4 when grown on Si. The composition of the films became more complex at shorter wavelengths as they contained magnetite and other minority phases in different concentrations. The crystalline quality of the films also decreased with decreasing wavelength even including superparamagnetic species. In general, for the same wavelength, the deposits obtained at room temperature were less crystalline than those produced with the substrate heated at 770 K. (C) 2018 Elsevier B.V. All rights reserved.
Nanocrystalline textured EuO thin films are prepared by an oxygen loss process from a pure Eu2O3 bulk ceramic target through pulsed laser deposition in vacuum at room temperature. X-ray diffraction spectra evidence a well-defined diffraction peak corresponding to the EuO phase textured along the (110) direction. Analysis of the XRD peak profile indicates that the films are nanocrystalline (average crystallite size of 11 nm) with a compressive residual strain. The formation of stoichiometric EuO is further confirmed by a strong signal from Eu2+ in the X-ray photoelectron spectra. The complex refractive index in the near infrared has been determined by spectroscopic ellipsometry and shows that the EuO films have a high transparency (k < 10-3) and a refractive index of 2.1. A band-gap shift of 0.25 eV is found with respect to the EuO bulk. These films, deposited by an accessible and efficient method, open a new route to produce EuO films with optical quality, suitable for NIR optoelectronic components.
Exchange-coupled hard-soft biphase magnets are technologically relevant systems in that they enable tailoring the magnetization reversal process. Here, exchange-spring behavior is observed in CoFe2O4/FeCo bilayers for soft thicknesses as thin as 2 nm, at least four times below the exchange length of the system. This result is in contrast with the accepted theory for spring magnets that states that the exchange length defines the critical thickness below which both magnetic phases should be rigidly coupled. In combination with micromagnetic calculations, this surprising observation is understood as a consequence of the dominance of domain-wall propagation in the soft phase during the reversal process, so far unaccounted for in theoretical descriptions. Our results emphasize the need to expand the existing spring theory from coherent rotation to domain-wall related processes in multidomain configurations in order to accurately design magnetic heterostructures with controllable reversal.