Asuka Namai

First Observation of Phase Transformation of All Four Fe2O3 Phases (γ → ε → β → α-Phase)

Iron oxide (Fe(2)O(3)) has four crystal structures: gamma-, epsilon-, beta-, and alpha-Fe(2)O(3). Until now, routes of the phase transformations among the four Fe(2)O(3) phases have not been clarified because a systematic synthesis that yields all four Fe(2)O(3) phases has yet to be reported. Herein we report the synthesis of a series of Fe(2)O(3) nanoparticles using mesoporous SiO(2). The crystal structures of the Fe(2)O(3) nanoparticles change in the order of gamma-Fe(2)O(3) --> epsilon-Fe(2)O(3) --> beta-Fe(2)O(3) --> alpha-Fe(2)O(3) as the particle size increases. Threshold sizes were estimated as gamma --> epsilon at 8 nm, epsilon --> beta at 30 nm, and beta --> alpha at 50 nm in the synthesis using FeSO(4) as a precursor. The phase transformations among the four Fe(2)O(3) phases have been observed for the first time.

Synthesis of a metal oxide with a room-temperature photoreversible phase transition

Photoinduced phase-transition materials, such as chalcogenides, spin-crossover complexes, photochromic organic compounds and charge-transfer materials, are of interest because of their application to optical data storage. Here we report a photoreversible metal-semiconductor phase transition at room temperature with a unique phase of Ti(3)O(5), lambda-Ti(3)O(5). lambda-Ti(3)O(5) nanocrystals are made by the combination of reverse-micelle and sol-gel techniques. Thermodynamic analysis suggests that the photoinduced phase transition originates from a particular state of lambda-Ti(3)O(5) trapped at a thermodynamic local energy minimum. Light irradiation causes reversible switching between this trapped state (lambda-Ti(3)O(5)) and the other energy-minimum state (beta-Ti(3)O(5)), both of which are persistent phases. This is the first demonstration of a photorewritable phenomenon at room temperature in a metal oxide. lambda-Ti(3)O(5) satisfies the operation conditions required for a practical optical storage system (operational temperature, writing data by short wavelength light and the appropriate threshold laser power).

Synthesis of an Electromagnetic Wave Absorber for High-Speed Wireless Communication

Millimeter waves (30-300 GHz) are starting to be used in next generation high-speed wireless communications. To avoid electromagnetic interference in this wireless communication, finding a suitable electromagnetic wave absorber in the millimeter wave range is an urgent matter. In this work, we prepared a high-performance millimeter wave absorber composed of a series of aluminum-substituted epsilon-iron oxide, epsilon-Al(x)Fe(2-x)O(3), nanomagnets (0 < or = x < or = 0.40) with a particle size between 25 and 50 nm. The materials in this series have an orthorhombic crystal structure in the Pna2(1) space group, which has four nonequivalent Fe sites and Al ion that predominantly occupies the tetrahedral [FeO(4)] site. The field-cooled magnetization curves showed that the T(C) values were 448, 480, and 500 K for x = 0.40, 0.21, and 0, respectively. The magnetization versus external magnetic field showed that the coercive field H(c) values at 300 K were 10.2, 14.9, and 22.5 kOe for x = 0.40, 0.21, and 0, respectively. The millimeter wave absorption properties were measured at room temperature by terahertz time domain spectroscopy. The frequencies of the absorption peaks for x = 0.40, 0.30, 0.21, 0.09, 0.06, and 0 were observed at 112, 125, 145, 162, 172, and 182 GHz, respectively. These absorptions are due to the natural resonance achieved by the large magnetic anisotropies in this series. Such frequencies are the highest ones for magnetic materials. Because aluminum is the third most abundant atom, aluminum-substituted epsilon-iron oxide is very economical, and thus these materials are advantageous for industrial applications.

Hard magnetic ferrite with a gigantic coercivity and high frequency millimetre wave rotation

Magnetic ferrites such as Fe3O4 and Fe2O3 are extensively used in a range of applications because they are inexpensive and chemically stable. Here we show that rhodium-substituted ε-Fe2O3, ε-RhxFe2−xO3 nanomagnets prepared by a nanoscale chemical synthesis using mesoporous silica as a template, exhibit a huge coercive field (Hc) of 27 kOe at room temperature. Furthermore, a crystallographically oriented sample recorded an Hc value of 31 kOe, which is the largest value among metal-oxide-based magnets and is comparable to those of rare-earth magnets. In addition, ε-RhxFe2−xO3 shows high frequency millimetre wave absorption up to 209 GHz. ε-Rh0.14Fe1.86O3 exhibits a rotation of the polarization plane of the propagated millimetre wave at 220 GHz, which is one of the promising carrier frequencies (the window of air) for millimetre wave wireless communications.

Ultrafast time domain demonstration of bulk magnetization precession at zero magnetic field ferromagnetic resonance induced by terahertz magnetic field

We report the first observation of sub-terahertz bulk-magnetization precession, using terahertz time-domain spectroscopy. The magnetization precession in gallium-substituted epsilon-iron oxide nano-ferromagnets under zero magnetic field is induced by the impulsive magnetic field of the THz wave through the gyromagnetic effect. Just at the resonance frequency, the linear to circular polarized wave conversion is realized. This is understood as the free induction decay signal radiated from a rotating magnetic dipole corresponding to the natural resonance. Furthermore, this demonstration reveals that the series of gallium-substituted epsilon-iron oxide nano-ferromagnets is very prospective for magneto-optic devices, which work at room temperature without external magnetic field, in next-generation wireless communication.

Nanometer-size hard magnetic ferrite exhibiting high optical-transparency and nonlinear optical-magnetoelectric effect

Development of nanometer-sized magnetic particles exhibiting a large coercive field (Hc) is in high demand for densification of magnetic recording. Herein, we report a single-nanosize (i.e., less than ten nanometers across) hard magnetic ferrite. This magnetic ferrite is composed of ε-Fe2O3, with a sufficiently high Hc value for magnetic recording systems and a remarkably high magnetic anisotropy constant of 7.7 × 106 erg cm−3. For example, 8.2-nm nanoparticles have an Hc value of 5.2 kOe at room temperature. A colloidal solution of these nanoparticles possesses a light orange color due to a wide band gap of 2.9 eV (430 nm), indicating a possibility of transparent magnetic pigments. Additionally, we have observed magnetization-induced second harmonic generation (MSHG). The nonlinear optical-magnetoelectric effect of the present polar magnetic nanocrystal was quite strong. These findings have been demonstrated in a simple iron oxide, which is highly significant from the viewpoints of economic cost and mass production.

Zeta-Fe2O3 – A new stable polymorph in iron(III) oxide family

Iron(III) oxide shows a polymorphism, characteristic of existence of phases with the same chemical composition but distinct crystal structures and, hence, physical properties. Four crystalline phases of iron(III) oxide have previously been identified: α-Fe2O3 (hematite), β-Fe2O3, γ-Fe2O3 (maghemite), and ε-Fe2O3. All four iron(III) oxide phases easily undergo various phase transformations in response to heating or pressure treatment, usually forming hexagonal α-Fe2O3, which is the most thermodynamically stable Fe2O3 polymorph under ambient conditions. Here, from synchrotron X-ray diffraction experiments, we report the formation of a new iron(III) oxide polymorph that we have termed ζ-Fe2O3 and which evolved during pressure treatment of cubic β-Fe2O3 ( space group) at pressures above 30 GPa. Importantly, ζ-Fe2O3 is maintained after pressure release and represents the first monoclinic Fe2O3 polymorph (I2/a space group) that is stable at atmospheric pressure and room temperature. ζ-Fe2O3 behaves as an antiferromagnet with a Néel transition temperature of ~69 K. The complex mechanism of pressure-induced transformation of β-Fe2O3, involving also the formation of Rh2O3-II-type Fe2O3 and post-perovskite-Fe2O3 structure, is suggested and discussed with respect to a bimodal size distribution of precursor nanoparticles.

External stimulation-controllable heat-storage ceramics

Commonly available heat-storage materials cannot usually store the energy for a prolonged period. If a solid material could conserve the accumulated thermal energy, then its heat-storage application potential is considerably widened. Here we report a phase transition material that can conserve the latent heat energy in a wide temperature range, T<530 K and release the heat energy on the application of pressure. This material is stripe-type lambda-trititanium pentoxide, λ-Ti3O5, which exhibits a solid–solid phase transition to beta-trititanium pentoxide, β-Ti3O5. The pressure for conversion is extremely small, only 600 bar (60 MPa) at ambient temperature, and the accumulated heat energy is surprisingly large (230 kJ L−1). Conversely, the pressure-produced beta-trititanium pentoxide transforms to lambda-trititanium pentoxide by heat, light or electric current. That is, the present system exhibits pressure-and-heat, pressure-and-light and pressure-and-current reversible phase transitions. The material may be useful for heat storage, as well as in sensor and switching memory device applications.

High-frequency millimeter wave absorption of indium-substituted ε-Fe2O3 spherical nanoparticles (invited)

In this work, we prepared indium-substituted e-iron oxide (e-InxFe2−xO3) spherical nanoparticles by a combination method of reverse-micelle and sol-gel techniques. The powder X-ray diffraction pattern with Rietveld analysis shows that e-InxFe2−xO3 has an orthorhombic crystal structure (space group: Pna21), and the In3+ ions mainly replace the Fe3+ ions at B site among the four nonequivalent Fe3+ sites (A–D sites). The magnetic measurements show that the coercive field (Hc) at 300 K decreases with increasing x, i.e., Hc = 21.9 kOe (x = 0), 12.2 kOe (x = 0.04), 11.6 kOe (x = 0.09), 7.8 kOe (x = 0.13), and 5.9 kOe (x = 0.18). Millimeter wave absorption was measured by terahertz time-domain spectroscopy, and the decrease of resonance frequency (fr) is observed, i.e., fr = 182 GHz (x = 0), 160 GHz (x = 0.04), 143 GHz (x = 0.09), 123 GHz (x = 0.13), and 110 GHz (x = 0.18). This decrease in the fr value is understood by the decrease of magnetic anisotropy, which is caused by the replacement of Fe3+ (S = 5/2) wit...

Mesoscopic bar magnet based on ε-Fe2O3 hard ferrite.

Ferrite magnets have a long history. They are used in motors, magnetic fluids, drug delivery systems, etc. Herein we report a mesoscopic ferrite bar magnet based on rod-shaped ε-Fe2O3 with a large coercive field (>25 kOe). The ε-Fe2O3–based bar magnet is a single crystal with a single magnetic domain along the longitudinal direction. A wide frequency range spectroscopic study shows that the crystallographic a-axis of ε-Fe2O3, which corresponds to the longitudinal direction of the bar magnet, plays an important role in linear and non-linear magneto-optical transitions, phonon modes, and the magnon (Kittel mode). Due to its multiferroic property, a magnetic-responsive non-linear optical sheet is manufactured as an application using an ε-Fe2O3–based bar magnet, resin, and polyethylene terephthalate. Furthermore, from the viewpoint of the large coercive field property, we demonstrate that a mesoscopic ε-Fe2O3 bar magnet can be used as a magnetic force microscopy probe.