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Title: Experimental heat capacities, excess entropies, and magnetic properties of bulk and nano Fe 3 O 4 -Co 3 O 4 and Fe 3 O 4 -Mn 3 O 4 spinel solid solutions

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
DOE - BASIC ENERGY SCIENCES
OSTI Identifier:
1419873
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 259; Journal Issue: C
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Schliesser, Jacob M., Huang, Baiyu, Sahu, Sulata K., Asplund, Megan, Navrotsky, Alexandra, and Woodfield, Brian F. Experimental heat capacities, excess entropies, and magnetic properties of bulk and nano Fe 3 O 4 -Co 3 O 4 and Fe 3 O 4 -Mn 3 O 4 spinel solid solutions. United States: N. p., 2018. Web. doi:10.1016/j.jssc.2018.01.007.
Schliesser, Jacob M., Huang, Baiyu, Sahu, Sulata K., Asplund, Megan, Navrotsky, Alexandra, & Woodfield, Brian F. Experimental heat capacities, excess entropies, and magnetic properties of bulk and nano Fe 3 O 4 -Co 3 O 4 and Fe 3 O 4 -Mn 3 O 4 spinel solid solutions. United States. doi:10.1016/j.jssc.2018.01.007.
Schliesser, Jacob M., Huang, Baiyu, Sahu, Sulata K., Asplund, Megan, Navrotsky, Alexandra, and Woodfield, Brian F. Thu . "Experimental heat capacities, excess entropies, and magnetic properties of bulk and nano Fe 3 O 4 -Co 3 O 4 and Fe 3 O 4 -Mn 3 O 4 spinel solid solutions". United States. doi:10.1016/j.jssc.2018.01.007.
@article{osti_1419873,
title = {Experimental heat capacities, excess entropies, and magnetic properties of bulk and nano Fe 3 O 4 -Co 3 O 4 and Fe 3 O 4 -Mn 3 O 4 spinel solid solutions},
author = {Schliesser, Jacob M. and Huang, Baiyu and Sahu, Sulata K. and Asplund, Megan and Navrotsky, Alexandra and Woodfield, Brian F.},
abstractNote = {},
doi = {10.1016/j.jssc.2018.01.007},
journal = {Journal of Solid State Chemistry},
number = C,
volume = 259,
place = {United States},
year = {Thu Mar 01 00:00:00 EST 2018},
month = {Thu Mar 01 00:00:00 EST 2018}
}
  • The effect of Mn concentration on the formation of nano-domain structures in the spinel oxide (Co,Fe,Mn){sub 3}O{sub 4} was investigated by electron diffraction, bright-, and dark-field imaging technique with transmission electron microscopy. Large scale phase separation with nano-twin domains was observed in Co{sub 0.6}Fe{sub 1.0}Mn{sub 1.4}O{sub 4}, in contrast to the highly aligned checkerboard nano-domains in Co{sub 0.6}Fe{sub 0.9}Mn{sub 1.5}O{sub 4}. Diffusion of the Mn{sup 3+} ions with the Jahn-Teller distortions is suggested to play an important role in the formation of checkerboard nano-domain structure.
  • Magnetite and hercynite are candidate materials for electrodes in coal-fired MHD electric power generators. The cation distribution between tetrahedral and octahedral sites in the spinel crystal can be calculated from site-preference energies and used as an alternate method of determining some thermodynamic properties, including the Gibbs energy of mixing. 28 refs.
  • Graphical abstract: In Bi{sub 0.9}Ba{sub 0.1}Fe{sub 0.9}Ti{sub 0.1}O{sub 3} solid solution, both magnetic ions (Co{sup 3+}, Mn{sup 3+}) and nonmagnetic ions (Sc{sup 3+}, Al{sup 3+}) were chosen to partially replace Fe{sup 3+}. Their magnetic properties were carefully investigated. Figures show M-H loops at RT of Co{sup 3+} doped sample (left) and Sc{sup 3+} substituted solid solution (right). Highlights: {yields} The electrical resistivity of BiFeO{sub 3} is enhanced by forming solid solution with BaTiO{sub 3}. {yields} We replace Fe{sup 3+} by both magnetic ions Co{sup 3+}, Mn{sup 4+} and nonmagnetic ions Sc{sup 3+}, Al{sup 3+} to investigate the magnetic properties. {yields}more » Structure-magnetic property relationship has been established by Rietveld refinement. -- Abstract: Solid solutions with general formula Bi{sub 0.9}Ba{sub 0.1}Fe{sub 0.81}M{sub 0.09}Ti{sub 0.1}O{sub 3} (M = Co, Mn, Sc, Al) together with parental Bi{sub 0.9}Ba{sub 0.1}Fe{sub 0.9}Ti{sub 0.1}O{sub 3} were prepared by the traditional solid state reaction method. Their structural, room temperature magnetic, and dielectric properties were investigated. X-ray diffraction analysis indicated that all samples maintained original R3c space group. M-H hysteresis loop of Co{sup 3+} doped sample saturated at an applied field of 1 T with spontaneous magnetization of 1.735 emu/g, while Mn{sup 4+} substitution enhanced the magnetization of Bi{sub 0.9}Ba{sub 0.1}Fe{sub 0.9}Ti{sub 0.1}O{sub 3} less strongly; addition of Sc{sup 3+} helped decrease magnetic coercive field while Al{sup 3+} modified sample exhibited paramagnetic M-H hysteresis loop. Differential scanning calorimetry was applied to determine the Neel temperature (T{sub N}) and the T{sub N} for undoped, Co{sup 3+}, Mn{sup 4+}, Sc{sup 3+}, Al{sup 3+} doped solid solutions were 318.1, 324.3, 335.7, 293.9 and 295.8 respectively. Sc{sup 3+} substitution had little influence on the dielectric properties of Bi{sub 0.9}Ba{sub 0.1}Fe{sub 0.9}Ti{sub 0.1}O{sub 3} while Al{sup 3+} doping improved its dielectric constant. In contrast, Co{sup 3+}, Mn{sup 4+} doped samples showed decreased permittivity but inhibited tan {delta} at frequencies larger than 30 kHz.« less
  • Bond critical point, bcp, and local energy density properties for the electron density, ED, distributions, calculated with first principle quantum mechanical methods for divalent transition metal Mn-, Co- and Fe-containing silicates and oxides are compared with experimental model ED properties for tephroite, Mn 2SiO 4, fayalite, Fe 2SiO 4 and Co 2SiO 4 olivine, each determined with high energy synchrotron single crystal X-ray diffraction data. Trends observed between the experimental bond lengths, R(M-O), (M = Mn, Fe, Co), and the calculated bcp properties are comparable with those observed for non-transition M-O bonded interactions. The bcp, local total energy density, H(rmore » c), and bond length trends determined for the Mn-O, Co-O and Fe-O interactions are virtually identical. A comparison is also made with model experimental bcp properties determined for several Mn-O, Fe-O and Co-O bonded interactions for organometallic complexes and several oxides. Despite the complexities of the structures of the organometallic complexes, the agreement between the calculated and the model experimental bcp properties is good in several cases. The G(r c)/p(r c) vs. R(M-O) trends established for non-transition metal M-O bonded interactions hold for the given transition metal M O bonded interactions with the G(r c)/p(r c) ratio increasing in value as H(r c) becomes progressively more negative in value and the shared character of the interaction increases. As observed for the non-transition metal M-O bonded interactions, the Laplacian, (nabla) 2p(r c), increases in value as p(r c) increases and as H(r c) decreases. The Mn-O, Fe-O, and Co-O bonded interactions are indicated to be of intermediate character with a substantial component of closed-shell character compared with Fe-S and Ni-S bonded interactions which show greater shared character based on the |V(r c)|/G(r c) bond character indicator. The atomic charges conferred on the transition metal atoms for the three olivines decrease with increasing atomic number from Mn to Fe to Co.« less