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Title: Structural and magnetic characterization of BiFe{sub x}Mn{sub 2-x}O{sub 5} oxides (x=0.5, 1.0)

Abstract

The title compounds have been synthesized by a citrate technique followed by thermal treatments in air (BiFe{sub 0.5}Mn{sub 1.5}O{sub 5}) or under high oxygen pressure conditions (BiFeMnO{sub 5}), and characterized by X-ray diffraction (XRD), neutron powder diffraction (NPD) and magnetization measurements. The crystal structures have been refined from NPD data in the space group Pbam at 295 K. These phases are isostructural with RMn{sub 2}O{sub 5} oxides (R=rare earths) and contain infinite chains of Mn{sup 4+}O{sub 6} octahedra sharing edges, linked together by (Fe,Mn){sup 3+}O{sub 5} pyramids and BiO{sub 8} units. These units are strongly distorted with respect to those observed in other RFeMnO{sub 5} compounds, due to the presence of the electronic lone pair on Bi{sup 3+}. It is noteworthy the certain level of antisite disorder exhibited in both samples, where the octahedral positions are partially occupied by Fe cations, and vice versa. BiFe{sub x}Mn{sub 2-x}O{sub 5} (x=0.5, 1.0) are short-range magnetically ordered below 20 K for x=0.5 and at 40 K for x=1.0. The main magnetic interactions seem to be antiferromagnetic (AFM); however, the presence of a small hysteresis in the magnetization cycles indicates the presence of some weak ferromagnetic (FM) interactions. - Graphical Abstract: BiFe{sub x}Mn{sub 2-x}O{submore » 5} (x=0.5, 1.0) samples are isostructural with BiMn{sub 2}O{sub 5}, belonging to the Pbam space group. The crystal structure contains infinite chains of edge-sharing Mn{sup 4+}O{sub 6} octahedra, interconnected by dimer units of Fe{sup 3+}O{sub 5} square pyramids. These units are strongly distorted due to the presence of the electronic lone pair on Bi{sup 3+}. They are magnetically ordered at low temperatures. The main magnetic interactions seem to be antiferromagnetic with the presence of some weak ferromagnetic response. Highlights: > Two new compounds of formula BiFe{sub x}Mn{sub 2-x}O{sub 5} (x=0.5, 1.0) have been obtained. > Their crystallographic structure is isotypical with that of RMn{sub 2}O{sub 5} materials. > The presence of the electronic lone pair on Bi{sup 3+} severely distorts the crystal structure. > There is no establishment of a long-range ferrimagnetic structure.« less

Authors:
 [1];  [2];  [1];  [3];  [4];  [1]
  1. Instituto de Ciencia de Materiales de Madrid, C.S.I.C., Cantoblanco, E-28049 Madrid (Spain)
  2. (United States)
  3. Institute for Nuclear Research and Nuclear Energy, Bulgarian Academy of Sciences, 72 Tsarigradsko Chaussee Boulevard, Sofia 1784 (Bulgaria)
  4. Institut Laue-Langevin, BP156X, Grenoble F-38042 (France)
Publication Date:
OSTI Identifier:
21580267
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 184; Journal Issue: 9; Other Information: DOI: 10.1016/j.jssc.2011.07.009; PII: S0022-4596(11)00378-1; Copyright (c) 2011 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANTIFERROMAGNETISM; BISMUTH IONS; CRYSTAL STRUCTURE; CRYSTALLOGRAPHY; ELECTRICAL PROPERTIES; HEAT TREATMENTS; INTERACTIONS; IRON IONS; MAGNETIC PROPERTIES; MAGNETIZATION; MANGANESE IONS; NEUTRON DIFFRACTION; OXIDES; RARE EARTHS; SPACE GROUPS; TEMPERATURE RANGE 0065-0273 K; X-RAY DIFFRACTION; CHALCOGENIDES; CHARGED PARTICLES; COHERENT SCATTERING; DIFFRACTION; ELEMENTS; IONS; MAGNETISM; METALS; OXYGEN COMPOUNDS; PHYSICAL PROPERTIES; SCATTERING; SYMMETRY GROUPS; TEMPERATURE RANGE

Citation Formats

Retuerto, M., E-mail: retuerto@rci.rutgers.edu, Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, 610 Taylor Road Piscataway, NJ 08854-808, Martinez-Lope, M.J., Krezhov, K., Fernandez-Diaz, M.T., and Alonso, J.A.. Structural and magnetic characterization of BiFe{sub x}Mn{sub 2-x}O{sub 5} oxides (x=0.5, 1.0). United States: N. p., 2011. Web. doi:10.1016/j.jssc.2011.07.009.
Retuerto, M., E-mail: retuerto@rci.rutgers.edu, Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, 610 Taylor Road Piscataway, NJ 08854-808, Martinez-Lope, M.J., Krezhov, K., Fernandez-Diaz, M.T., & Alonso, J.A.. Structural and magnetic characterization of BiFe{sub x}Mn{sub 2-x}O{sub 5} oxides (x=0.5, 1.0). United States. doi:10.1016/j.jssc.2011.07.009.
Retuerto, M., E-mail: retuerto@rci.rutgers.edu, Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, 610 Taylor Road Piscataway, NJ 08854-808, Martinez-Lope, M.J., Krezhov, K., Fernandez-Diaz, M.T., and Alonso, J.A.. Thu . "Structural and magnetic characterization of BiFe{sub x}Mn{sub 2-x}O{sub 5} oxides (x=0.5, 1.0)". United States. doi:10.1016/j.jssc.2011.07.009.
@article{osti_21580267,
title = {Structural and magnetic characterization of BiFe{sub x}Mn{sub 2-x}O{sub 5} oxides (x=0.5, 1.0)},
author = {Retuerto, M., E-mail: retuerto@rci.rutgers.edu and Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, 610 Taylor Road Piscataway, NJ 08854-808 and Martinez-Lope, M.J. and Krezhov, K. and Fernandez-Diaz, M.T. and Alonso, J.A.},
abstractNote = {The title compounds have been synthesized by a citrate technique followed by thermal treatments in air (BiFe{sub 0.5}Mn{sub 1.5}O{sub 5}) or under high oxygen pressure conditions (BiFeMnO{sub 5}), and characterized by X-ray diffraction (XRD), neutron powder diffraction (NPD) and magnetization measurements. The crystal structures have been refined from NPD data in the space group Pbam at 295 K. These phases are isostructural with RMn{sub 2}O{sub 5} oxides (R=rare earths) and contain infinite chains of Mn{sup 4+}O{sub 6} octahedra sharing edges, linked together by (Fe,Mn){sup 3+}O{sub 5} pyramids and BiO{sub 8} units. These units are strongly distorted with respect to those observed in other RFeMnO{sub 5} compounds, due to the presence of the electronic lone pair on Bi{sup 3+}. It is noteworthy the certain level of antisite disorder exhibited in both samples, where the octahedral positions are partially occupied by Fe cations, and vice versa. BiFe{sub x}Mn{sub 2-x}O{sub 5} (x=0.5, 1.0) are short-range magnetically ordered below 20 K for x=0.5 and at 40 K for x=1.0. The main magnetic interactions seem to be antiferromagnetic (AFM); however, the presence of a small hysteresis in the magnetization cycles indicates the presence of some weak ferromagnetic (FM) interactions. - Graphical Abstract: BiFe{sub x}Mn{sub 2-x}O{sub 5} (x=0.5, 1.0) samples are isostructural with BiMn{sub 2}O{sub 5}, belonging to the Pbam space group. The crystal structure contains infinite chains of edge-sharing Mn{sup 4+}O{sub 6} octahedra, interconnected by dimer units of Fe{sup 3+}O{sub 5} square pyramids. These units are strongly distorted due to the presence of the electronic lone pair on Bi{sup 3+}. They are magnetically ordered at low temperatures. The main magnetic interactions seem to be antiferromagnetic with the presence of some weak ferromagnetic response. Highlights: > Two new compounds of formula BiFe{sub x}Mn{sub 2-x}O{sub 5} (x=0.5, 1.0) have been obtained. > Their crystallographic structure is isotypical with that of RMn{sub 2}O{sub 5} materials. > The presence of the electronic lone pair on Bi{sup 3+} severely distorts the crystal structure. > There is no establishment of a long-range ferrimagnetic structure.},
doi = {10.1016/j.jssc.2011.07.009},
journal = {Journal of Solid State Chemistry},
number = 9,
volume = 184,
place = {United States},
year = {Thu Sep 15 00:00:00 EDT 2011},
month = {Thu Sep 15 00:00:00 EDT 2011}
}
  • The spinel oxides Zn{sub x}Mg{sub 1.5-x}Mn{sub 0.5}FeO{sub 4} (x = 0.0 to 0.6) and MgAl{sub x}Cr{sub x}Fe{sub 2-2x}O{sub 4} (x = 0.0 to 0.6) abbreviated as ZMMFO and MACFO respectively, were synthesized by standard ceramic processing. The compositional purity of all the specimens was checked by EDAX technique. The X-ray diffractometry was employed to determine the lattice constants and distribution of cations in the interstitial voids. The initial decrease of cell edge parameter (a) for ZMMFO up to x = 0.2 and thereafter expected rise in the ‘a’ and the initial slower rate of reduction in the lattice constant formore » MACFO are explained as basic of cation occupancy. The magnetic ordering in both systems is explained by invoking statistical canting models. The compositional variation of magneton number (n{sub B}) for ZMMFO could be very well explained by Localized canting of spin (LCS) model while Random canting of spin (RCS) model was used for MACFO system.« less
  • In order to further elucidate the local structure of vanadate glasses, x-ray photoelectron spectroscopy (XPS) and magnetization studies are reported on a series of SrO-vanadate and SrO-borovanadate glasses: [(SrO){sub x}(V{sub 2}O{sub 5}){sub 1-x}], [(SrO){sub 0.5-y}(B{sub 2}O{sub 3}){sub y}(V{sub 2}O{sub 5}){sub 0.5}], and [(SrO){sub 0.2}(B{sub 2}O{sub 3}){sub z}(V{sub 2}O{sub 5}){sub 0.8-z}]. From the analysis of the XPS spectra for the Sr 3p, B 1s, V 2p, and O 1s core levels, several distinct concentration regimes are identified in terms of various structural units being present. Metavanadate chainlike structures of SrV{sub 2}O{sub 6} and individual VO{sub 4} units occur in vanadate glassesmore » with low SrO content x{<=}0.2 with VO{sub 5} polyhedra also appearing at higher SrO content. The SrV{sub 2}O{sub 6} and VO{sub n} polyhedra predominate in the low B{sub 2}O{sub 3} containing SrO-borovanadate glasses as the B substitutes into the V sites of the various VO{sub n} polyhedra and only when the B{sub 2}O{sub 3} concentration exceeds the SrO content do BO{sub n} structures appear. This qualitative picture of three distinct structural groupings for the Sr-vanadate and Sr-borovanadate glasses is consistent with the proposed glass structure based on previous IR and extended x-ray absorption fine structure (EXAFS) studies on these types of vanadate glasses.« less
  • A new material of nominal stoichiometry YGaMnO{sub 5} has been prepared in polycrystalline form from citrate precursors followed by thermal treatments under high-oxygen pressure. This compound has been characterized from neutron powder diffraction (NPD) data and magnetic measurements. For comparison, the parent compound YMn{sub 2}O{sub 5} has also been synthesized and its crystal structure refined by NPD data. The new oxide has an actual stoichiometry YGa{sub 1-x}Mn{sub 1+x}O{sub 5} (x = 0.23), determined by NPD, showing an important cationic disorder between both metal sites; it is orthorhombic, Pbam (SG), and its crystal structure contains chains of Mn{sup 4+}O{sub 6} edge-sharingmore » octahedra, linked together by Ga{sup 3+}O{sub 5} pyramids and YO{sub 8} units. With respect to YMn{sub 2}O{sub 5}, containing axially elongated MnO{sub 5} pyramids due to the Jahn-Teller effect of Mn{sup 3+} cations, the GaO{sub 5} pyramidal units in YGa{sub 0.77}Mn{sub 1.23}O{sub 5} are substantially flattened. This compound has a paramagnetic behaviour with two weak anomalies at about 50 K and 350 K. The magnetic structures, studied at 1.4 K and 100 K show a ferromagnetic coupling along the chains of MnO{sub 6} octahedra.« less
  • X-ray diffraction and X-ray absorption spectroscopy experiments were used to study chemical and electrochemical Li insertion and extraction reactions of LiNi{sub 0.5}Mn{sub 0.5}O{sub 2}. These results, along with galvanostatic cycling data, suggest that LiNi{sub 0.5}Mn{sub 0.5}O{sub 2} layered electrodes in lithium batteries operate predominantly off two-electron redox couples, Ni{sup 4+}/Ni{sup 2+}, between approximately 4.5 and 1.25 V and Mn{sup 4+}/Mn{sup 2+} between 1.25 and 1.0 V versus metallic Li, respectively. The retention of a stable layered framework structure and the apparent absence of Jahn-Teller ions Ni{sup 3+} and Mn{sup 3+} in the high- or low-voltage region is believed to bemore » responsible for the excellent structural and electrochemical stability of these electrodes. The LiNi{sub 0.5}Mn{sub 0.5}O{sub 2} layered oxide reversibly reacts chemically or electrochemically with Li to form an air-sensitive, dilithium compound, Li{sub 2}Ni{sub 0.5}Mn{sub 0.5}O{sub 2}, with a hexagonal structure analogous to Li{sub 2}MnO{sub 2}. The cycling behavior of Li/LiNi{sub 0.5}Mn{sub 0.5}O{sub 2} cells over a large voltage window (4.6-1.0 V) and with very slow rates shows that rechargeable capacities >500 mA{center_dot}h/g can be obtained.« less
  • Highlights: ► Al{sup 3+} ion substituted Mn–Zn ferrite nanoparticles. ► Single phase cubic spinel structure changes with Al{sup 3+} substitution. ► Magnetization and coercivity decreased with increasing Al{sup 3+}. ► Resistivity increased with Al{sup 3+} substitution. - Abstract: In this work the nano-structural, magnetic and resistivity properties of Al{sup 3+} substituted Mn–Zn ferrites powders were investigated. Mn{sub 0.5}Zn{sub 0.5}Al{sub x}Fe{sub 2−x}O{sub 4} powders, where x = 0.0, 0.1, 0.2, 0.3, 0.4 and 0.5 were obtained by the sol–gel auto-combustion method. X-ray diffraction data indicate that, after substitution, all the samples consisted of the main spinel phase in combination with amore » small amount of a foreign Al{sub 2}O{sub 3} phase. The addition of Al{sup 3+} resulted in a reduction of particle size and density of the prepared samples. Cation distribution in the present study was estimated by using X-ray diffraction data. The tetrahedral site radii initially increased with Al{sup 3+} content while the octahedral site radii decreased with the Al{sup 3+} substitution. FTIR spectra show two strong absorption bands at 529–548 cm{sup −1} and 445–452 cm{sup −1} which are the typical bands for the cubic spinel crystal structure. The magnetic properties were measured by employing a vibrating sample magnetometer. It was observed that the saturation magnetization, coercivity and anisotropy field decreased with the increase of Al{sup 3+} substitution. Introduction of Al{sup 3+} ions into the Mn–Zn ferrite increased the values of the resistivity, especially in the lower temperature range.« less