Unveiling a New High-Temperature Ordered Magnetic Phase in ϵ-Fe2O3

Iron oxides are among the most abundant materials on Earth, and yet there are some of their basic properties which are still not well-established. Here, we present temperature-dependent magnetic, X-ray, and neutron diffraction measurements refuting the current belief that the magnetic ordering temperature of ϵ-FeO is ∼500 K, i.e., well below that of other iron oxides such as hematite, magnetite, or maghemite. Upon heating from room temperature, the ϵ-FeO nanoparticles' saturation magnetization undergoes a monotonic decrease while the coercivity and remanence sharply drop, virtually vanishing around ∼500 K. However, above that temperature the hysteresis loops present a nonlinear response with finite coercivity, making evident signs of ferrimagnetic order up to temperatures as high as 850 K (T). The neutron diffraction study confirms the presence of ferrimagnetic order well above 500 K with Pna'2' magnetic symmetry, but only involving two of the four Fe sublattices which are ordered below T ≈ 480 K, and with a reduced net ferromagnetic component, that vanishes at above 850 K. The results unambiguously show the presence of a high-temperature magnetic phase in ϵ-FeO with a critical temperature of T ∼ 850 K. Importantly, this temperature is similar to the Curie point in other iron oxides, indicating comparable magnetic coupling strengths. The presence of diverse magnetic phases is further supported by the nonmonotonic evolution of the thermal expansion. The existence of a high-temperature ferrimagnetic phase in ϵ-FeO may open the door to further expand the working range of this multifunctional iron oxide

Nanopartícules magnètiques en matrius de sílice

Descripció del recurs: el 21 setembre 2011En aquest treball s'han estudiat diferents aproximacions a la síntesi de compòsits de nanopartícules magnètiques en matrius de sílice de tipus aerogel o xerogel. Així, s'han obtingut materials amb propietats molt diferents tant pel que fa al seu magnetisme (materials durs o tous), a les seves propietats òptiques (transparents, opacs, anisotròpics) o la seva densitat, i se n'han estudiat algunes de les seves possibles aplicacions magnetoòptiques. Les matrius de sílice en forma de xerogel també s'han fet servir per a estabilitzar, gràcies al confinament, l'ε-Fe2O3, un polimorf metastable d'óxid de Fe (III) molt poc conegut. S'ha fet una caracterització de les propietats magnètiques del material i s'ha vist que la seva temperatura de Curie és de 510 K i que a temperatura ambient és un ferrimagnet colineal amb una imantació moderada (20 emu/g a saturació) i una anisotropia magnètica elevada que fan que la seva coercitivitat sigui molt elevada per a un òxid de Fe (20 kOe). Entre 150 i 80 K l'ε-Fe2O3 presenta una transició de fase magnètica i estructural de segon ordre que té com a resultat l'aparició d'una estructura magnètica incommensurada de tipus "ona quadrada". S'ha posat de manifest que coincidint amb aquesta transició de fase, el material presenta un acoblament magnetoelèctric.In this Thesis, different approximations to the synthesis of composites of magnetic nanoparticles in silica aerogel or xerogel matrices have been studied. In particular, we have obtained materials with a range of different properties regarding its magnetism (hard or soft magnetic materials), optical properties (transparent, opaque, anisotropic) or density and we have studied its potential magneto-optical applications. The xerogel matrices have also been used to stabilize by confinement a rare iron (III) oxide polymorph, the ε-Fe2O3, which has not been much studied so far. The magnetic properties of the polymorph have been studied in detail and it has been established that it has a Curie temperature of 510 K. At room temperature, it presents a collinear ferromagnetic order with a moderate magnetization (20 emu/g at saturation) and a large magnetic anisotropy which result in a huge coercivity of about 20 kOe. Between 150 and 80 K, ε-Fe2O3 presents a second order magnetic and structural transition to a "square-wave" incommensurate magnetic order. Concomitantly with this transition it has been shown that the material presents a magnetoelectric coupling.En este trabajo se han estudiado diferentes aproximaciones a la síntesis de composites de nanopartículas magnéticas en matrices de sílice de tipo aerogel o xerogel. Así, se han obtenido materiales con propiedades muy distintas tanto en relación a su magnetismo (materiales duros o blandos), a les sus propiedades ópticas (transparentes, opacos, anisotrópicos) o a su densidad, y se han estudiado algunas de sus posibles aplicaciones magnetoópticas. Las matrices de sílice en forma de xerogel también se han utilizado para estabilizar, gracias al confinamiento, el ε-Fe2O3, un polimorfo metaestable de óxido de Fe (III) muy poco conocido. Se ha hecho una caracterización de sus propiedades magnéticas y se ha establecido que su temperatura de Curie es de 510 K y que a temperatura ambiente es un ferrimagneto co-lineal con una imantación moderada (20 emu/g a saturación) y una anisotropía magnética elevada que hacen que su coercitividad sea muy elevada para un óxido de Fe (20 kOe). Entre 150 i 80 K el ε-Fe2O3 presenta una transición de fase magnética y estructural de segundo orden que da lugar a una estructura magnética inconmensurable de tipo "onda cuadrada". Se ha puesto de manifiesto que coincidiendo con esta transición de fase, el material presenta un acoplamiento magnetoeléctrico

High-coercivity ultralight transparent magnets

This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.Magnetic silica-aerogel composites have been synthesized by dispersing hard magnetic Nd2Fe14B particles in a sol during a fast sol-gel process and subsequently supercritically drying the resulting gels. The composites are found to retain most of the outstanding properties of their constituents: the large coercivity and moderate remanence of the magnetic powders and the transparency and low density of silica aerogels. Moreover, aerogels synthesized in the presence of a magnetic field exhibit the alignment of the particles, forming needle-like structures along the direction of the applied magnetic field, which results in optical and magnetic anisotropies. Due to their unique combination of properties, these types of materials may be appealing for magneto-optics and magnetic actuator applications

Epitaxial stabilization of ε-Fe2O3 (00l) thin films on SrTiO3 (111)

This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.Thin films of the metastable and elusive ε-Fe2O3 have been epitaxially stabilized on SrTiO3 (111) substrates. The ε-Fe2O3 films present a (001) orientation perpendicular to the substrate and three in-plane domains measuring a few nanometers and showing atomically sharp interfaces. We argue that this domain structure, rather than the epitaxial-strain, plays an essential role in stabilizing the ε-Fe2O3 by minimizing the energy of (100) surfaces. The ε-Fe2O3 films show a large in-plane coercivity ∼ 8 kOe which combined with the magnetoelectric character claimed for this oxide may lead to novel applications in spintronics

Unveiling a New High-Temperature Ordered Magnetic Phase in ϵ-Fe2O3

Iron oxides are among the most abundant materials on Earth, and yet there are some of their basic properties which are still not well-established. Here, we present temperature-dependent magnetic, X-ray, and neutron diffraction measurements refuting the current belief that the magnetic ordering temperature of ϵ-FeO is ∼500 K, i.e., well below that of other iron oxides such as hematite, magnetite, or maghemite. Upon heating from room temperature, the ϵ-FeO nanoparticles' saturation magnetization undergoes a monotonic decrease while the coercivity and remanence sharply drop, virtually vanishing around ∼500 K. However, above that temperature the hysteresis loops present a nonlinear response with finite coercivity, making evident signs of ferrimagnetic order up to temperatures as high as 850 K (T). The neutron diffraction study confirms the presence of ferrimagnetic order well above 500 K with Pna'2' magnetic symmetry, but only involving two of the four Fe sublattices which are ordered below T ≈ 480 K, and with a reduced net ferromagnetic component, that vanishes at above 850 K. The results unambiguously show the presence of a high-temperature magnetic phase in ϵ-FeO with a critical temperature of T ∼ 850 K. Importantly, this temperature is similar to the Curie point in other iron oxides, indicating comparable magnetic coupling strengths. The presence of diverse magnetic phases is further supported by the nonmonotonic evolution of the thermal expansion. The existence of a high-temperature ferrimagnetic phase in ϵ-FeO may open the door to further expand the working range of this multifunctional iron oxide