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Title: Structural chemistry and magnetic properties of the compounds EuOs/sub 4/B/sub 4/ and EuIr/sub 4/B/sub 4/ and of the solid solutions (RE)Os/sub 4/B/sub 4/-(RE)Ir/sub 4/B/sub 4/(RE = Ce, Pr, Sm)

Abstract

New ternary metal borides, EuOs/sub 4/B/sub 4/ and EuIr/sub 4/B/sub 4/, have been synthesized from the elements. The compounds were found to crystallize with the structure type of NdCo/sub 4/B/sub 4/. Effective paramagnetic moments derived from chi/sup -1/vs. T plots over the range 1.8-800 K are in good agreement with theoretical values according to a Hund's rule ground-state /sup 8/S/sub 1/2/ for a free Eu/sup 2 +/ ion. Complete solid solution was found for mixed crystals of CeOs/sub 4/B/sub 4/-CeIr/sub 4/B/sub 4/ (arc melted, quenched, NdCo/sub 4/B/sub 4/-type structure) revealing a positive deviation from Vegard's law. Magnetic susceptibilities were determined for the temperature range 1.8-1000 K. At high temperature the magnetic properties are characterized by Van Vleck paramagnetism of closely spaced multiplets due to admixture of the excited term J = /sup 7///sub 2/ of the Ce/sup 3 +/F/sub 5///sub 2/ ground state. At lower temperatures the paramagnetic behavior of cerium changes from that of a practically pure Ce/sup 4 +/ state in CeOs/sub 4/B/sub 4/ (..mu../sub eff/ = 0.49 ..mu beta..) to that of a pronounced Ce/sup 3 +/ state in CeIr/sub 4/B/sub 4/ (..mu../sub eff/ = 2.21 ..mu beta..) presumably due to the larger iridium metal framework and/ormore » the higher electron-to-atom ratio. At very low temperatures, less than or equal to 3.5 K, ferromagnetic ordering was observed for CeIr/sub 4/B/sub 4/ and CeIr/sub 3/Os/sub 1/B/sub 4/. For comparison, the magnetic behavior was studied over the range 1.5-300 K of the pseudobinary sections PrOs/sub 4-x/Ir/sub x/B/sub 4/ and SmOs/sub 4-x/Ir/sub x/B/sub 4/. Although a slight negative deviation from Vegard's law was observed, there was practically no change from a valence state of Sm/sup 3 +/ for samarium. On the basis of Miedema's model, a thermodynamic calculation for the valence change (Ce/sup III/ ..-->.. Ce/sup IV/, Eu/sup II/ ..-->.. Eu/sup III/) has been found to be in good accord with the magnetic behavior observed. 7 figures, 4 tables.« less

Authors:
 [1]; ;
  1. Cornell Univ., Ithaca, NY
Publication Date:
OSTI Identifier:
5455832
Resource Type:
Journal Article
Journal Name:
Inorg. Chem.; (United States)
Additional Journal Information:
Journal Volume: 21:3
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CERIUM BORIDES; LATTICE PARAMETERS; SOLID SOLUTIONS; EUROPIUM BORIDES; CRYSTAL STRUCTURE; MAGNETIC SUSCEPTIBILITY; IRIDIUM BORIDES; OSMIUM BORIDES; PRASEODYMIUM BORIDES; SAMARIUM BORIDES; ARGON; DIFFRACTION METHODS; EXPERIMENTAL DATA; HIGH TEMPERATURE; INERT ATMOSPHERE; INTERMETALLIC COMPOUNDS; LOW TEMPERATURE; MEDIUM TEMPERATURE; MELTING; METALLOGRAPHY; MIXTURES; NITROGEN; TEMPERATURE DEPENDENCE; ULTRALOW TEMPERATURE; VERY HIGH TEMPERATURE; VERY LOW TEMPERATURE; X-RAY DIFFRACTION; ALLOYS; BORIDES; BORON COMPOUNDS; CERIUM COMPOUNDS; COHERENT SCATTERING; DATA; DIFFRACTION; DISPERSIONS; ELEMENTS; EUROPIUM COMPOUNDS; FLUIDS; GASES; INFORMATION; MAGNETIC PROPERTIES; NONMETALS; NUMERICAL DATA; OSMIUM COMPOUNDS; PHASE TRANSFORMATIONS; PHYSICAL PROPERTIES; PRASEODYMIUM COMPOUNDS; RARE EARTH COMPOUNDS; RARE GASES; SAMARIUM COMPOUNDS; SCATTERING; SOLUTIONS; TRANSITION ELEMENT COMPOUNDS; 400201* - Chemical & Physicochemical Properties

Citation Formats

Hiebl, K, Rogl, P, and Sienko, M J. Structural chemistry and magnetic properties of the compounds EuOs/sub 4/B/sub 4/ and EuIr/sub 4/B/sub 4/ and of the solid solutions (RE)Os/sub 4/B/sub 4/-(RE)Ir/sub 4/B/sub 4/(RE = Ce, Pr, Sm). United States: N. p., 1982. Web. doi:10.1021/ic00133a049.
Hiebl, K, Rogl, P, & Sienko, M J. Structural chemistry and magnetic properties of the compounds EuOs/sub 4/B/sub 4/ and EuIr/sub 4/B/sub 4/ and of the solid solutions (RE)Os/sub 4/B/sub 4/-(RE)Ir/sub 4/B/sub 4/(RE = Ce, Pr, Sm). United States. https://doi.org/10.1021/ic00133a049
Hiebl, K, Rogl, P, and Sienko, M J. 1982. "Structural chemistry and magnetic properties of the compounds EuOs/sub 4/B/sub 4/ and EuIr/sub 4/B/sub 4/ and of the solid solutions (RE)Os/sub 4/B/sub 4/-(RE)Ir/sub 4/B/sub 4/(RE = Ce, Pr, Sm)". United States. https://doi.org/10.1021/ic00133a049.
@article{osti_5455832,
title = {Structural chemistry and magnetic properties of the compounds EuOs/sub 4/B/sub 4/ and EuIr/sub 4/B/sub 4/ and of the solid solutions (RE)Os/sub 4/B/sub 4/-(RE)Ir/sub 4/B/sub 4/(RE = Ce, Pr, Sm)},
author = {Hiebl, K and Rogl, P and Sienko, M J},
abstractNote = {New ternary metal borides, EuOs/sub 4/B/sub 4/ and EuIr/sub 4/B/sub 4/, have been synthesized from the elements. The compounds were found to crystallize with the structure type of NdCo/sub 4/B/sub 4/. Effective paramagnetic moments derived from chi/sup -1/vs. T plots over the range 1.8-800 K are in good agreement with theoretical values according to a Hund's rule ground-state /sup 8/S/sub 1/2/ for a free Eu/sup 2 +/ ion. Complete solid solution was found for mixed crystals of CeOs/sub 4/B/sub 4/-CeIr/sub 4/B/sub 4/ (arc melted, quenched, NdCo/sub 4/B/sub 4/-type structure) revealing a positive deviation from Vegard's law. Magnetic susceptibilities were determined for the temperature range 1.8-1000 K. At high temperature the magnetic properties are characterized by Van Vleck paramagnetism of closely spaced multiplets due to admixture of the excited term J = /sup 7///sub 2/ of the Ce/sup 3 +/F/sub 5///sub 2/ ground state. At lower temperatures the paramagnetic behavior of cerium changes from that of a practically pure Ce/sup 4 +/ state in CeOs/sub 4/B/sub 4/ (..mu../sub eff/ = 0.49 ..mu beta..) to that of a pronounced Ce/sup 3 +/ state in CeIr/sub 4/B/sub 4/ (..mu../sub eff/ = 2.21 ..mu beta..) presumably due to the larger iridium metal framework and/or the higher electron-to-atom ratio. At very low temperatures, less than or equal to 3.5 K, ferromagnetic ordering was observed for CeIr/sub 4/B/sub 4/ and CeIr/sub 3/Os/sub 1/B/sub 4/. For comparison, the magnetic behavior was studied over the range 1.5-300 K of the pseudobinary sections PrOs/sub 4-x/Ir/sub x/B/sub 4/ and SmOs/sub 4-x/Ir/sub x/B/sub 4/. Although a slight negative deviation from Vegard's law was observed, there was practically no change from a valence state of Sm/sup 3 +/ for samarium. On the basis of Miedema's model, a thermodynamic calculation for the valence change (Ce/sup III/ ..-->.. Ce/sup IV/, Eu/sup II/ ..-->.. Eu/sup III/) has been found to be in good accord with the magnetic behavior observed. 7 figures, 4 tables.},
doi = {10.1021/ic00133a049},
url = {https://www.osti.gov/biblio/5455832}, journal = {Inorg. Chem.; (United States)},
number = ,
volume = 21:3,
place = {United States},
year = {Mon Mar 01 00:00:00 EST 1982},
month = {Mon Mar 01 00:00:00 EST 1982}
}