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Title: Evidence for a short-range chemical order of Ge atoms and its critical role in inducing a giant magnetocaloric effect in Gd5Si1.5Ge2.5

Abstract

Crystal structure and magnetic properties of Gd5Si1.5Ge2.5 and Gd4.9Zr0·1Si1.5Ge2.5 were investigated using high-energy X-ray diffraction and magnetic measurements. Results showed that a Zr substitution for 2% Gd reduces unit cell volumes of a room-temperature monoclinic and a low-temperature orthorhombic lattice and a difference between them at a magnetostructural transition. At a microscopic level, the Zr substitution increases length of disconnected interlayer T–T bonds of the monoclinic lattice at the expense of length of connected interlayer T–T bonds (T = Si, Ge). These opposing changes of the interlayer T–T bonds provided evidence for existence of a short-range chemical order of Ge atoms in lattices of Gd5Si1.5Ge2.5 and its weakening by the Zr substitution. Magnetic measurements revealed that the Zr substitution brings about a change of the magnetic structure and a reduction of a giant magnetocaloric effect of Gd5Si1.5Ge2.5. Based on such structural and magnetic changes due to the Zr substitution, we propose a relation between the short-range chemical order and the total entropy change at the magnetostructural transition. Finally, using this relation, a giant magnetocaloric effect and an annealing effect observed over a wide range of Gd5(Si,Ge)4 composition can be explained quantitatively.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [2];  [3];  [4];  [5]
  1. Northeastern Univ., Shenyang (China)
  2. Beijing Inst. of Technology (China)
  3. Univ. of Science and Technology, Beijing (China)
  4. Northern Illinois Univ., De Kalb, IL (United States)
  5. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Natural Science Foundation of China (NSFC); Ministry of Science and Technology of the People's Republic of China
OSTI Identifier:
1618451
Alternate Identifier(s):
OSTI ID: 1701869
Grant/Contract Number:  
AC02-06CH11357; 51831003; 2012CB619405; DE–AC02–06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Alloys and Compounds
Additional Journal Information:
Journal Volume: 808; Journal Issue: C; Journal ID: ISSN 0925-8388
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Synchrotron radiation; crystal structure; magnetocaloric effect; rare earth compound; x-ray diffraction

Citation Formats

Kou, Ronghui, Gao, Jianrong, Nie, Zhihua, Wang, Yandong, Brown, Dennis E., and Ren, Yang. Evidence for a short-range chemical order of Ge atoms and its critical role in inducing a giant magnetocaloric effect in Gd5Si1.5Ge2.5. United States: N. p., 2019. Web. https://doi.org/10.1016/j.jallcom.2019.151751.
Kou, Ronghui, Gao, Jianrong, Nie, Zhihua, Wang, Yandong, Brown, Dennis E., & Ren, Yang. Evidence for a short-range chemical order of Ge atoms and its critical role in inducing a giant magnetocaloric effect in Gd5Si1.5Ge2.5. United States. https://doi.org/10.1016/j.jallcom.2019.151751
Kou, Ronghui, Gao, Jianrong, Nie, Zhihua, Wang, Yandong, Brown, Dennis E., and Ren, Yang. Wed . "Evidence for a short-range chemical order of Ge atoms and its critical role in inducing a giant magnetocaloric effect in Gd5Si1.5Ge2.5". United States. https://doi.org/10.1016/j.jallcom.2019.151751. https://www.osti.gov/servlets/purl/1618451.
@article{osti_1618451,
title = {Evidence for a short-range chemical order of Ge atoms and its critical role in inducing a giant magnetocaloric effect in Gd5Si1.5Ge2.5},
author = {Kou, Ronghui and Gao, Jianrong and Nie, Zhihua and Wang, Yandong and Brown, Dennis E. and Ren, Yang},
abstractNote = {Crystal structure and magnetic properties of Gd5Si1.5Ge2.5 and Gd4.9Zr0·1Si1.5Ge2.5 were investigated using high-energy X-ray diffraction and magnetic measurements. Results showed that a Zr substitution for 2% Gd reduces unit cell volumes of a room-temperature monoclinic and a low-temperature orthorhombic lattice and a difference between them at a magnetostructural transition. At a microscopic level, the Zr substitution increases length of disconnected interlayer T–T bonds of the monoclinic lattice at the expense of length of connected interlayer T–T bonds (T = Si, Ge). These opposing changes of the interlayer T–T bonds provided evidence for existence of a short-range chemical order of Ge atoms in lattices of Gd5Si1.5Ge2.5 and its weakening by the Zr substitution. Magnetic measurements revealed that the Zr substitution brings about a change of the magnetic structure and a reduction of a giant magnetocaloric effect of Gd5Si1.5Ge2.5. Based on such structural and magnetic changes due to the Zr substitution, we propose a relation between the short-range chemical order and the total entropy change at the magnetostructural transition. Finally, using this relation, a giant magnetocaloric effect and an annealing effect observed over a wide range of Gd5(Si,Ge)4 composition can be explained quantitatively.},
doi = {10.1016/j.jallcom.2019.151751},
journal = {Journal of Alloys and Compounds},
number = C,
volume = 808,
place = {United States},
year = {2019},
month = {8}
}

Journal Article:

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Cited by: 2 works
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Figures / Tables:

Table 1 Table 1: Comparison of previously measured and predicted total entropy changes of Gd5(Si,Ge)4 composition at a magnetic field change from 0 to 5 T. Measured data are taken from Refs. [9,14].

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Works referenced in this record:

Materials Challenges for High Performance Magnetocaloric Refrigeration Devices
journal, September 2012

  • Smith, Anders; Bahl, Christian R. H.; Bjørk, Rasmus
  • Advanced Energy Materials, Vol. 2, Issue 11
  • DOI: 10.1002/aenm.201200167

Mixed Magnetism for Refrigeration and Energy Conversion
journal, September 2011

  • Dung, Nguyen H.; Ou, Zhi Qiang; Caron, Luana
  • Advanced Energy Materials, Vol. 1, Issue 6
  • DOI: 10.1002/aenm.201100252

Giant Magnetocaloric Effect in Gd5(Si2Ge2)
journal, June 1997


Gd5(SixGe1-x)4: An Extremum Material
journal, May 2001


Phase relationships and crystallography in the pseudobinary system Gd5Si4Gd5Ge4
journal, September 1997


Making and Breaking Covalent Bonds across the Magnetic Transition in the Giant Magnetocaloric Material Gd 5 ( Si 2 Ge 2 )
journal, May 2000


Tunable magnetic regenerator alloys with a giant magnetocaloric effect for magnetic refrigeration from ∼20 to ∼290 K
journal, June 1997

  • Pecharsky, V. K.; Gschneidner, K. A.
  • Applied Physics Letters, Vol. 70, Issue 24
  • DOI: 10.1063/1.119206

Recent developments in magnetocaloric materials
journal, May 2005

  • Gschneidner, K. A.; Pecharsky, V. K.; Tsokol, A. O.
  • Reports on Progress in Physics, Vol. 68, Issue 6, p. 1479-1539
  • DOI: 10.1088/0034-4885/68/6/R04

Electron correlation effects on the magnetostructural transition and magnetocaloric effect in Gd 5 Si 2 Ge 2
journal, April 2006

  • Paudyal, Durga; Pecharsky, Vitalij K.; Gschneidner, Karl A.
  • Physical Review B, Vol. 73, Issue 14
  • DOI: 10.1103/PhysRevB.73.144406

Role of Ge in Bridging Ferromagnetism in the Giant Magnetocaloric Gd 5 ( Ge 1 x Si x ) 4 Alloys
journal, June 2007


Electronic structure of Gd5(Si, Ge)4
journal, July 2002


The giant magnetocaloric effect of optimally prepared Gd5Si2Ge2
journal, April 2003

  • Pecharsky, A. O.; Gschneidner, K. A.; Pecharsky, V. K.
  • Journal of Applied Physics, Vol. 93, Issue 8
  • DOI: 10.1063/1.1558210

The effect of varying the crystal structure on the magnetism, electronic structure and thermodynamics in the Gd 5 (Si x Ge 1−x ) 4 system near x =0.5
journal, February 2003


Phase Transformation Driven by Valence Electron Concentration:  Tuning Interslab Bond Distances in Gd 5 Ga x Ge 4 - x
journal, December 2003

  • Mozharivskyj, Yurij; Choe, Wonyoung; Pecharsky, Alexandra O.
  • Journal of the American Chemical Society, Vol. 125, Issue 49
  • DOI: 10.1021/ja037649z

Gd 5 Si 4− x P x : Targeted Structural Changes through Increase in Valence Electron Count
journal, February 2009

  • Svitlyk, Volodymyr; Miller, Gordon J.; Mozharivskyj, Yurij
  • Journal of the American Chemical Society, Vol. 131, Issue 6
  • DOI: 10.1021/ja8085033

Reduction of hysteresis losses in the magnetic refrigerant Gd5Ge2Si2 by the addition of iron
journal, June 2004

  • Provenzano, Virgil; Shapiro, Alexander J.; Shull, Robert D.
  • Nature, Vol. 429, Issue 6994
  • DOI: 10.1038/nature02657

The nonpareil R5(SixGe1−x)4 phases
journal, May 2000


Crystal structures, phase relationships, and magnetic phase transitions of R 5 M 4 compounds ( R = rare earths, M = Si, Ge)
journal, September 2013


The magnetocaloric effect, magnetic refrigeration and ductile intermetallic compounds
journal, January 2009


Charge transfer-tuned magnetism in Nd-substituted Gd 5 Si 4
journal, December 2018


“Nanoscale Zippers” in the Crystalline Solid. Structural Variations in the Giant Magnetocaloric Material Gd 5 Si 1.5 Ge 2.5
journal, April 2003

  • Choe, Wonyoung; Miller, Gordon J.; Meyers, John
  • Chemistry of Materials, Vol. 15, Issue 7
  • DOI: 10.1021/cm020928l

Effect of a magnetic field on the magnetostructural phase transition in Gd 5 ( Si x Ge 1 x ) 4
journal, March 2004


Magnetic phase transitions and ferromagnetic short-range correlations in single-crystal Tb 5 Si 2.2 Ge 1.8
journal, July 2008


Griffiths-like behavior in Ge-rich magnetocaloric compounds Gd5(SixGe1−x)4
journal, August 2010


Some common misconceptions concerning magnetic refrigerant materials
journal, November 2001

  • Pecharsky, V. K.; Gschneidner, K. A.
  • Journal of Applied Physics, Vol. 90, Issue 9
  • DOI: 10.1063/1.1405836

Pressure-Induced Three-Dimensional Ferromagnetic Correlations in the Giant Magnetocaloric Compound G d 5 G e 4
journal, November 2003


The Curie temperature of the ferromagnetic transition metals and their compounds
journal, December 1987


Elastic properties of Gd 5 Si 2 Ge 2 studied with an ultrasonic pulse-echo technique
journal, November 2006


Magnetocaloric effect in strong magnetic fields
journal, February 1990


On the nature of the magnetocaloric effect of the first-order magnetostructural transition
journal, September 2012


Preparation, crystal structure, magnetic and magnetothermal properties of (Gd[sub x]R[sub 5−x])Si[sub 4], where R=Pr and Tb, alloys
journal, January 2001

  • Spichkin, Y. I.; Pecharsky, V. K.; Gschneidner, K. A.
  • Journal of Applied Physics, Vol. 89, Issue 3
  • DOI: 10.1063/1.1335821

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.