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Title: Enhancement in magnetocaloric properties of holmium chromite by gadolinium substitution

Abstract

HoCrO{sub 3}, Ho{sub 0.67}Gd{sub 0.33}CrO{sub 3}, and GdCrO{sub 3} bulk powder samples were prepared by citrate route. The phase purity and the structural properties of the samples were examined by x-ray diffraction and Raman spectroscopic measurements. The dc magnetization data revealed that the Cr{sup 3+} ordering temperatures (Néel temperature) for the HoCrO{sub 3}, Ho{sub 0.67}Gd{sub 0.33}CrO{sub 3}, and GdCrO{sub 3} samples are 140 K, 148 K, and 167 K, respectively, while the ac magnetization data revealed that the rare-earth (Ho) ordering occurs at ∼8 K for HoCrO{sub 3} and Ho{sub 0.67}Gd{sub 0.33}CrO{sub 3} samples. Temperature-induced magnetization reversal and spin reorientation were observed in GdCrO{sub 3} bulk sample, which depends on applied magnetic field and disappears at ∼1500 Oe and 500 Oe, respectively. By fitting the dc magnetic data with Curie-Weiss law, the effective magnetic moments were calculated to be 11.66 μ{sub B}, 10.23 μ{sub B}, and 9.90 μ{sub B} for the HoCrO{sub 3}, Ho{sub 0.67}Gd{sub 0.33}CrO{sub 3}, and GdCrO{sub 3} samples, respectively. The isothermal magnetization data showed that the magnetic behavior changed from canted antiferromagnetic in low temperature region (below Néel temperature) to paramagnetic at high temperature. It was found that Gd substitution considerably improves the magnetocaloric effect of HoCrO{sub 3}. Pure GdCrO{sub 3} bulk sample showed giantmore » magnetocaloric entropy change (31.6 J/kg K at temperature ∼5 K and at ∼70 kOe), which is higher than that for polycrystalline RMnO{sub 3}, RCrO{sub 3}, and RFeO{sub 3} bulk powder samples. This renders GdCrO{sub 3} useful for potential applications in low-temperature magnetic refrigeration.« less

Authors:
 [1];  [1];  [2]
  1. Department of Physics, University of Connecticut, Storrs, Connecticut 06269 (United States)
  2. (United States)
Publication Date:
OSTI Identifier:
22597778
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Applied Physics; Journal Volume: 120; Journal Issue: 4; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ANTIFERROMAGNETISM; CHROMITES; CHROMIUM IONS; CITRATES; CURIE-WEISS LAW; ENTROPY; GADOLINIUM; HOLMIUM; MAGNETIC FIELDS; MAGNETIC MOMENTS; MAGNETIC PROPERTIES; MAGNETIZATION; MANGANATES; PARAMAGNETISM; POLYCRYSTALS; POWDERS; REFRIGERATION; TEMPERATURE RANGE 0065-0273 K; TEMPERATURE RANGE 0400-1000 K; X-RAY DIFFRACTION

Citation Formats

Yin, S., Jain, M., E-mail: menka.jain@uconn.edu, and Institute of Materials Science, University of Connecticut, Storrs, Connecticut 06269. Enhancement in magnetocaloric properties of holmium chromite by gadolinium substitution. United States: N. p., 2016. Web. doi:10.1063/1.4959253.
Yin, S., Jain, M., E-mail: menka.jain@uconn.edu, & Institute of Materials Science, University of Connecticut, Storrs, Connecticut 06269. Enhancement in magnetocaloric properties of holmium chromite by gadolinium substitution. United States. doi:10.1063/1.4959253.
Yin, S., Jain, M., E-mail: menka.jain@uconn.edu, and Institute of Materials Science, University of Connecticut, Storrs, Connecticut 06269. Thu . "Enhancement in magnetocaloric properties of holmium chromite by gadolinium substitution". United States. doi:10.1063/1.4959253.
@article{osti_22597778,
title = {Enhancement in magnetocaloric properties of holmium chromite by gadolinium substitution},
author = {Yin, S. and Jain, M., E-mail: menka.jain@uconn.edu and Institute of Materials Science, University of Connecticut, Storrs, Connecticut 06269},
abstractNote = {HoCrO{sub 3}, Ho{sub 0.67}Gd{sub 0.33}CrO{sub 3}, and GdCrO{sub 3} bulk powder samples were prepared by citrate route. The phase purity and the structural properties of the samples were examined by x-ray diffraction and Raman spectroscopic measurements. The dc magnetization data revealed that the Cr{sup 3+} ordering temperatures (Néel temperature) for the HoCrO{sub 3}, Ho{sub 0.67}Gd{sub 0.33}CrO{sub 3}, and GdCrO{sub 3} samples are 140 K, 148 K, and 167 K, respectively, while the ac magnetization data revealed that the rare-earth (Ho) ordering occurs at ∼8 K for HoCrO{sub 3} and Ho{sub 0.67}Gd{sub 0.33}CrO{sub 3} samples. Temperature-induced magnetization reversal and spin reorientation were observed in GdCrO{sub 3} bulk sample, which depends on applied magnetic field and disappears at ∼1500 Oe and 500 Oe, respectively. By fitting the dc magnetic data with Curie-Weiss law, the effective magnetic moments were calculated to be 11.66 μ{sub B}, 10.23 μ{sub B}, and 9.90 μ{sub B} for the HoCrO{sub 3}, Ho{sub 0.67}Gd{sub 0.33}CrO{sub 3}, and GdCrO{sub 3} samples, respectively. The isothermal magnetization data showed that the magnetic behavior changed from canted antiferromagnetic in low temperature region (below Néel temperature) to paramagnetic at high temperature. It was found that Gd substitution considerably improves the magnetocaloric effect of HoCrO{sub 3}. Pure GdCrO{sub 3} bulk sample showed giant magnetocaloric entropy change (31.6 J/kg K at temperature ∼5 K and at ∼70 kOe), which is higher than that for polycrystalline RMnO{sub 3}, RCrO{sub 3}, and RFeO{sub 3} bulk powder samples. This renders GdCrO{sub 3} useful for potential applications in low-temperature magnetic refrigeration.},
doi = {10.1063/1.4959253},
journal = {Journal of Applied Physics},
number = 4,
volume = 120,
place = {United States},
year = {Thu Jul 28 00:00:00 EDT 2016},
month = {Thu Jul 28 00:00:00 EDT 2016}
}
  • In this work, structural, magnetic, and magnetocaloric properties of HoCrO 3 and Fe substituted HoCrO 3 and DyCrO 3 (i.e. HoCr 0.7Fe 0.3O 3 and DyCr 0.7Fe 0.3O 3) powder samples were synthesized via a solution route. The structural properties of the samples were examined by Raman spectroscopy and x-ray diffraction techniques, which were further confirmed using first-principle calculations. The dc magnetic measurements indicate that the Cr 3+ ordering temperatures for the HoCrO 3, HoCr 0.7Fe 0.3O 3, and DyCr 0.7Fe 0.3O 3 samples are 140 K, 174 K, and 160 K, respectively. The ac magnetic measurements not only confirmedmore » the Cr 3+ ordering transitions in these samples (obtained using dc magnetic measurements), but also clearly showed the Ho 3+ ordering at ~10 K in the present HoCrO 3 and HoCr 0.7Fe 0.3O 3 samples, which to our knowledge, is the first ac magnetic evidence of Ho 3+ ordering in this system. The effective magnetic moments were determined to be 11.67μB, 11.30μB, and 11.27μB for the HoCrO 3, HoCr 0.7Fe 0.3O 3, and DyCr 0.7Fe 0.3O 3 samples, respectively. For the first time, the magnetocaloric properties of HoCrO 3 and HoCr 0.7Fe 0.3O 3 were studied here, showing their potential for applications in magnetic refrigeration. In an applied dc magnetic field of 7 T, the maximum magnetocaloric value were determined to be 7.2 (at 20 K), 6.83 (at 20 K), 13.08 J/kg K (at 5 K) and the relative cooling power were 408, 387, and 500 J/kg for the HoCrO 3, HoCr 0.7Fe 0.3O 3, and DyCr 0.7Fe 0.3O 3 samples, respectively.« less
  • In this work, a polycrystalline bulk DyCrO{sub 3} sample was prepared by a solution route and the structural and magnetic properties were investigated. The phase purity and ionic valence state of the DyCrO{sub 3} sample were determined by x-ray diffraction/Raman spectroscopy and x-ray photoelectron spectroscopy, respectively. The AC and DC magnetization measurements revealed the onset of antiferromagnetic order at 146 K with an effective moment of 8.88 μ{sub B}. Isothermal magnetization measurements of this material are presented for the first time, showing a peak in the coercive field at 80 K that is explained by the competition between the paramagneticmore » Dy{sup 3+} and Cr{sup 3+} sublattices. DyCrO{sub 3} was found to display a large magnetocaloric effect (8.4 J/kg K) and relative cooling power (217 J/kg) at 4 T applied field, which renders DyCrO{sub 3} useful for magnetic refrigeration between 5 K and 30 K.« less
  • No abstract prepared.
  • The effect of nickel substitution on defect chemistry, electrical properties, and dimensional stability of calcium-doped yttrium chromite was studied for use as an interconnect material in high temperature solid oxide fuel cells (SOFCs). The compositions of Y0.8Ca0.2Cr1-xNixO3±δ (x=0-0.15), prepared using the glycine nitrate process, showed single phase orthorhombic perovskite structures over a wide range of oxygen partial pressures (10^-17 atm ≤ pO2 ≤ 0.21 atm). X-ray diffraction (XRD) analysis indicated that most of the nickel ions replacing chromium ions are divalent and act as acceptor dopants, leading to a substantial increase in conductivity. In particular, the conductivity at 900 degreemore » C in air increased from 10 S/cm to 34 S/cm with 15% nickel substitution, and an increase in charge carrier density was confirmed by Seebeck measurements. A point defect model was derived, and the relationship between electrical conductivity and oxygen partial pressure was successfully fitted into the proposed model. The defect modeling results indicated that nickel substitution improves the stability of calcium-doped yttrium chromite toward reduction and suppresses the oxygen vacancy formation, which results in significantly increased electrical conductivity in reducing environment. The electrical conductivity of Y0.8Ca0.2Cr0.85Ni0.15O3±δ at 900 degree C in reducing atmosphere (pO2=10^-17 atm) was 5.8 S/cm, which was more than an order of magnitude higher than that of Y0.8Ca0.2CrO3±δ (0.2 S/cm). Improved stability in reducing atmosphere was further confirmed by dilatometry measurements showing reduced isothermal "chemical" expansion, and the isothermal expansion in reducing atmosphere (pO2=10^-17 atm) at 900 degree C decreased from 0.07% for Y0.8Ca0.2CrO3±δ to 0.03% for Y0.8Ca0.2Cr0.85Ni0.15O3±δ. Based on these results, enhanced electrical performance and mechanical integrity is expected with nickel substitution on calcium-doped yttrium chromite in SOFC operating conditions.« less
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