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Title: Gd3Ni2 and Gd3CoxNi2-x: magnetism and unexpected Co/Ni crystallographic ordering

Journal Article · · Journal of Materials Chemistry C
DOI:https://doi.org/10.1039/c6tc01035k· OSTI ID:1357796
 [1];  [2];  [3];  [4];  [4];  [4];  [1];  [5]
  1. Ames Lab., and Iowa State Univ., Ames, IA (United States). Division of Materials Sciences and Engineering; Univ. of Genova (Italy). Dept. of Chemistry; Inst. SPIN-CNR, Genoa (Italy)
  2. Ames Lab., and Iowa State Univ., Ames, IA (United States). Division of Materials Sciences and Engineering; Iowa State Univ., Ames, IA (United States). Dept. of Materials Science and Engineering
  3. Ames Lab., and Iowa State Univ., Ames, IA (United States). Division of Materials Sciences and Engineering
  4. Ames Lab., and Iowa State Univ., Ames, IA (United States). Division of Materials Sciences and Engineering; Iowa State Univ., Ames, IA (United States). Dept. of Materials Science and Engineering
  5. Inst. SPIN-CNR, Genoa (Italy); Univ. of Genova (Italy). Dept. of Physics
+ Show Author Affiliations

The crystal structure, composition and physical properties of Gd3Ni2, which was earlier reported to exist in the Gd–Ni system without any details of its structure and properties, have been determined. This rare earth binary compound is a high-temperature phase: it forms via a peritectic reaction at 988 K (715 °C) and decomposes below ≈923 K (650 °C). The compound can be retained at room temperature as a metastable phase by quenching after high temperature annealing. Gd3Ni2 crystallizes in the monoclinic Dy3Ni2 structure type [mS20, C2/m (No. 12), Z = 4; with lattice parameters a = 13.418(3) Å, b = 3.720(1) Å, c = 9.640(2) Å, β = 106.250(3)°]. Ni can be substituted by Co up to 50% (i.e. up to and including Gd3CoNi) with no change in the structural prototype; the substitution of Co for Ni stabilizes the R3CoxNi2-x phases down to room temperature. The crystal structure, magnetic properties and magnetocaloric effect (MCE) have been investigated for both Gd3Ni2 and the related Gd3CoxNi2-x solid solution alloys (0 ≤ x ≤ 1). The crystal structure of the Gd3CoNi is a ternary ordered derivative of the monoclinic Dy3Ni2-type, where Co fully occupies only one of the two 4i Wyckoff sites available for the transition metal. To the best of our knowledge, this is the first example of an intermetallic phase showing ordered site occupations by the chemically quite similar elements Co and Ni. All compounds show long range ferromagnetic ordering, with TC progressively increasing from 147 K (for Gd3Ni2) to 176 K (for Gd3CoNi) as a cubic function of the Co content. Evidence of Co contributing to the magnetic interactions in these compounds has been found. First-principles total energy calculations predicted the ordered occupation of Co and Ni at the crystallographic sites of Gd3CoNi, which was later confirmed by single crystal X-ray diffraction. The increased conduction electronic state (3d) exchange splitting at the Fermi level supports the experimentally observed enhanced Curie temperature in Gd3CoNi compared to Gd3Ni2.

Research Organization:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
Grant/Contract Number:
AC02-07CH11358
OSTI ID:
1357796
Report Number(s):
IS-J-9059
Journal Information:
Journal of Materials Chemistry C, Vol. 4, Issue 25; ISSN 2050-7526
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (2)

Tb 3 Pd 2 , Er 3 Pd 2 and Er 6 Co 5– x : structural variations and bonding in rare-earth-richer binary intermetallics journal August 2018
Simulation of the magnetocaloric effect by means of theoretical models in Gd3Ni2 and Gd3CoNi systems journal February 2020

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