skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Structure and magnetic properties of Ce₃(Ni/Al/Ga)₁₁—A new phase with the La₃Al₁₁ structure type

Abstract

Single crystals of Ce₃(Ni/Al/Ga)₁₁ were obtained from an Al flux reaction. Single crystals of the title compound crystallizing in the orthorhombic space group Immm (No. 71, Z = 2) with a = 436.38(14), b = 1004.5(3) and c = 1293.4(4) pm. This is a standardized unit cell of the previously published La₃Al₁₁ structure type. Wavelength dispersive microprobe provides the composition of Ce₃.₁₁₍₁₎Ni₀.₀₃₍₁₎Al₈.₉₅₍₁₎Ga₁.₉₀₍₁₎. Single crystal refinement provides the composition Ce₃Ni₀.₀₈Al₉.₁₃Ga₁.₇₈ with substitution of the Ni and Ga on the Al1 and Al4 sites with the Al2 and Al3 solely occupied by Al. Magnetic susceptibility measurements reveal antiferromagnetic ordering with T N = 4.8 K and there is no evidence for a ferromagnetic ordering that has been reported for Ce₃Al₁₁. The effective magnetic moment was found to be μ eff = 1.9μB/Ce, which is lower than the expected value for trivalent Ce (2.54μB/Ce).

Authors:
 [1];  [2];  [3];  [4];  [4];  [5]
  1. Univ. of California, Davis, CA (United States); Westfalische Wilhelms-Universitat, Munster (Germany)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Zhejiang Univ., Zhejiang (China)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Florida State Univ., Tallahassee, FL (United States)
  4. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  5. Univ. of California, Davis, CA (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1190777
Grant/Contract Number:
DMR-1100313
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Crystals
Additional Journal Information:
Journal Volume: 5; Journal Issue: 1; Journal ID: ISSN 2073-4352
Publisher:
MDPI
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cerium; single crystal; magnetism; aluminum

Citation Formats

Janka, Oliver, Shang, Tian, Baumbach, Ryan E., Bauer, Eric D., Thompson, Joe D., and Kauzlarich, Susan M. Structure and magnetic properties of Ce₃(Ni/Al/Ga)₁₁—A new phase with the La₃Al₁₁ structure type. United States: N. p., 2015. Web. doi:10.3390/cryst5010001.
Janka, Oliver, Shang, Tian, Baumbach, Ryan E., Bauer, Eric D., Thompson, Joe D., & Kauzlarich, Susan M. Structure and magnetic properties of Ce₃(Ni/Al/Ga)₁₁—A new phase with the La₃Al₁₁ structure type. United States. doi:10.3390/cryst5010001.
Janka, Oliver, Shang, Tian, Baumbach, Ryan E., Bauer, Eric D., Thompson, Joe D., and Kauzlarich, Susan M. 2015. "Structure and magnetic properties of Ce₃(Ni/Al/Ga)₁₁—A new phase with the La₃Al₁₁ structure type". United States. doi:10.3390/cryst5010001. https://www.osti.gov/servlets/purl/1190777.
@article{osti_1190777,
title = {Structure and magnetic properties of Ce₃(Ni/Al/Ga)₁₁—A new phase with the La₃Al₁₁ structure type},
author = {Janka, Oliver and Shang, Tian and Baumbach, Ryan E. and Bauer, Eric D. and Thompson, Joe D. and Kauzlarich, Susan M.},
abstractNote = {Single crystals of Ce₃(Ni/Al/Ga)₁₁ were obtained from an Al flux reaction. Single crystals of the title compound crystallizing in the orthorhombic space group Immm (No. 71, Z = 2) with a = 436.38(14), b = 1004.5(3) and c = 1293.4(4) pm. This is a standardized unit cell of the previously published La₃Al₁₁ structure type. Wavelength dispersive microprobe provides the composition of Ce₃.₁₁₍₁₎Ni₀.₀₃₍₁₎Al₈.₉₅₍₁₎Ga₁.₉₀₍₁₎. Single crystal refinement provides the composition Ce₃Ni₀.₀₈Al₉.₁₃Ga₁.₇₈ with substitution of the Ni and Ga on the Al1 and Al4 sites with the Al2 and Al3 solely occupied by Al. Magnetic susceptibility measurements reveal antiferromagnetic ordering with TN = 4.8 K and there is no evidence for a ferromagnetic ordering that has been reported for Ce₃Al₁₁. The effective magnetic moment was found to be μeff = 1.9μB/Ce, which is lower than the expected value for trivalent Ce (2.54μB/Ce).},
doi = {10.3390/cryst5010001},
journal = {Crystals},
number = 1,
volume = 5,
place = {United States},
year = 2015,
month = 3
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Save / Share:
  • The results of investigations of new ternary coherent GdTiGe compounds and corresponding hydrides by X-ray powder diffraction and magnetic measurements are reported. Coherent phases GdTiGe with CeScSi-type structure and GdTiGe with CeFeSi-type structure were found to coexist in the GdTiGe alloy when the sample mass was 5 g (melting in electric arc furnace in argon atmosphere). Annealing at 1,070 K for 200 h in argon atmosphere led to an increase in GdTiGe (CeScSi-type structure) phase in the GdTiGe alloy. The GdTiGe with CeScSi-type structure was characterized by Curie point T{sub c} = 376 K, while GdTiGe with CeFeSi-type structure demonstratedmore » Neel point T{sub N} = 412 K. The mechanical hydrogenization of the GdTiGe alloy led to formation of the GdTiGeH{sub {approximately}4} hydride with CdScSi-type structure and to a sharp decrease in magnetization; GdTiGe with CeFeSi-type structure remained passive.« less
  • The crystal structure of new Mo{sub 2}NiB{sub 2}-type (Gd, Tb, Dy){sub 2}Ni{sub 2.35}Si{sub 0.65} (Immm, No. 71, oI10) and La{sub 2}Ni{sub 3}-type (Dy, Ho){sub 2}Ni{sub 2.5}Si{sub 0.5} (Cmce No. 64, oC20) compounds has been established using powder X-ray diffraction studies. Magnetization measurements show that the Mo{sub 2}NiB{sub 2}-type Gd{sub 2}Ni{sub 2.35}Si{sub 0.65} undergoes a ferromagnetic transition at ~66 K, whereas isostructural Tb{sub 2}Ni{sub 2.35}Si{sub 0.65} shows an antiferromagnetic transition at ~52 K and a field-induced metamagnetic transition at low temperatures. Neutron diffraction study shows that, in zero applied field, Tb{sub 2}Ni{sub 2.35}Si{sub 0.65} exhibits c-axis antiferromagnetic order with propagation vectormore » K=[1/2, 0, 1/2] below its magnetic ordering temperature and Tb magnetic moment reaches a value of 8.32(5) μ{sub B} at 2 K. The La{sub 2}Ni{sub 3}-type Dy{sub 2}Ni{sub 2.5}Si{sub 0.5} exhibits ferromagnetic like transition at ~42 K with coexisting antiferromagnetic interactions and field induced metamagnetic transition below ~17 K. The magnetocaloric effect of Gd{sub 2}Ni{sub 2.35}Si{sub 0.65}, Tb{sub 2}Ni{sub 2.35}Si{sub 0.65} and Dy{sub 2}Ni{sub 2.5}Si{sub 0.5} is calculated in terms of isothermal magnetic entropy change and it reaches a maximum value of −14.3 J/kg K, −5.3 J/kg K and −10.3 J/kg K for a field change of 50 kOe near 66 K, 52 K and 42 K, respectively. Low temperature magnetic ordering with enhanced anisotropic effects in Tb{sub 2}Ni{sub 2.35}Si{sub 0.65} and Dy{sub 2}Ni{sub 2.35}Si{sub 0.65} is accompanied by a positive magnetocaloric effect with isothermal magnetic entropy changes of +12.8 J/kg K and ~+9.9 J/kg K, respectively at 7 K for a field change of 50 kOe. - Graphical abstract: The (Gd, Tb, Dy){sub 2}Ni{sub 2.35}Si{sub 0.65} supplement the series of Mo{sub 2}NiB{sub 2}-type rare earth compounds, whereas the (Dy, Ho){sub 2}Ni{sub 2.5}Si{sub 0.5} supplement the series of La{sub 2}Ni{sub 3}-type rare earth compounds. The variation of alloy’s composition by ~3 at% i.e. from Dy{sub 2}Ni{sub 2.35}Si{sub 0.65} to Dy{sub 2}Ni{sub 2.5}Si{sub 0.5} leads to significant transformation of crystal structure of compound with different variant of distortion of Po-type rare earth sublattice, as in Gd–Co–Ga and Er–Ni–In systems: the Mo{sub 2}NiB{sub 2}-type Gd{sub 2}Co{sub 2}Ga and La{sub 2}Ni{sub 3}-type Gd{sub 2}Co{sub 2.9}Ga{sub 0.1}, and Mo{sub 2}FeB{sub 2}-type Er{sub 2}Ni{sub 1.78}In and Mn{sub 2}AlB{sub 2}-type Er{sub 2}Ni{sub 2}In. Magnetization measurements indicate collinear ferromagnetic ordering of Mo{sub 2}NiB{sub 2}-type Gd{sub 2}Ni{sub 2.35}Si{sub 0.65} and a complex antiferromagnetic ordering with low-temperature metamagnetic nature for Mo{sub 2}NiB{sub 2}-type Tb{sub 2}Ni{sub 2.35}Si{sub 0.65} compounds. However, neutron diffraction study in zero applied field of Tb{sub 2}Ni{sub 2.35}Si{sub 0.65} reveals c-axis pure antiferromagnetic ordering of terbium sublattice with K=[1/2, 0, 1/2] propagation vector. Magnetization measurements indicate ferromagnetic order with coexisting antiferromagnetic interactions and low-temperature metamagnetic state for La{sub 2}Ni{sub 3}-type Dy{sub 2}Ni{sub 2.5}Si{sub 0.5}. We suggest possible polymorphism in other Mo{sub 2}FeB{sub 2}-type, Mo{sub 2}NiB{sub 2}-type, La{sub 2}Ni{sub 3}-type and Mn{sub 2}AlB{sub 2}-type rare earth compounds with corresponding change in their magnetic properties. - Highlights: • (Gd, Tb, Dy){sub 2}Ni{sub 2.35}Si{sub 0.65} compounds crystallize in the Mo{sub 2}NiB{sub 2}-type structure. • (Dy, Ho){sub 2}Ni{sub 2.5}Si{sub 0.5} compounds crystallize in the La{sub 2}Ni{sub 3}-type structure. • Gd{sub 2}Ni{sub 2.35}Si{sub 0.65} shows pure ferromagnetic type ordering. • Tb{sub 2}Ni{sub 2.35}Si{sub 0.65} and Dy{sub 2}Ni{sub 2.5}Si{sub 0.5} show mixed ferro-antiferromagnetic ordering. • Tb{sub 2}Ni{sub 2.35}Si{sub 0.65} and Dy{sub 2}Ni{sub 2.5}Si{sub 0.5} exhibit low-temperature metamagnetic behaviour.« less
  • The nonstoichiometric ternary compound In{sub 0.69} V{sub 6}S{sub 8} was prepared via a low temperature diffusion reaction between hexagonal V{sub 3}S{sub 4} and In metal. The crystal structure solution reveals that In is strongly disordered within the hexagonal channels of the structure. The analysis of the structural data in connection with the data of other ternary A{sub x} V{sub 6}S{sub 8} phases gives evidences that the V-V bond length within the metal atom zig-zag chains parallel to the crystallographic c-axis is nearly not affected by the valence electron concentration (VEC) per V atom. On the other hand the distance betweenmore » the chains increases with raising VEC, independent of the nature of the electropositive element A. The electrical resistivity of In{sub 0.69} V{sub 6}S{sub 8} was measured between 2 and 300 K. For the first time the authors have observed superconductivity in this compound. The title compound shows a transition into the superconducting state with a transition temperature {Tc} of 3.7 K.« less
  • Two related non-centrosymmetric, cubic, quaternary chalcogenides, containing europium have been synthesized employing the molten flux method and by the reaction of europium halides with the ternary seleno-germanate, Na{sub 6}Ge{sub 2}Se{sub 6}. The reactions of Eu, Ge and Se were accomplished in a molten Na{sub 2}Se{sub 2} flux at 800 deg. C for 150 h in an evacuated fused silica ampoule and yielded Na{sub 2}EuGeSe{sub 4} (I). Similarly, Na{sub 0.75}Eu{sub 1.625}GeSe{sub 4} (II), could be synthesized at slightly lower temperature (750 deg. C) with a different starting ratio of Eu, Ge, Se and Na{sub 2}Se{sub 2}. A reaction between EuCl{sub 3}more » and Na{sub 6}Ge{sub 2}Se{sub 6} in 1:2 ratio at 650 deg. C for 96 h in an evacuated fused silica ampoule yielded Na{sub 2}EuGeSe{sub 4} (I), while the reaction between EuI{sub 2} and Na{sub 6}Ge{sub 2}Se{sub 6} in 1:1 ratio under similar conditions yielded Na{sub 0.75}Eu{sub 1.625}GeSe{sub 4} (II). Crystal data for these compounds are as follows: I, cubic, space group I4-bar3m (no. 217), a=7.3466(3), Z=2; II, cubic, space group I4-bar3d (no. 220), a=14.7065(8), Z=16. The crystal structures of I and II are closely related and can be compared to a CsCl-type and its ordered superstructure, respectively. These compounds are semiconductors with optical band gaps around 2 eV. The temperature dependence of the magnetic susceptibility indicated that both compounds are paramagnetic with {mu} {sub eff.}=7.6 and 7.73 {mu} {sub B}, for I and II, respectively, close to the theoretical value of 7.94 {mu} {sub B} for Eu{sup 2+}. Raman spectroscopic characterization of the compounds is also reported. - Graphical abstract: Related quaternary chalcogenides, Na{sub 2}EuGeSe{sub 4} (I) and its ordered superstructure Na{sub 0.75}Eu{sub 1.625}GeSe{sub 4} (II), have been synthesized employing solid-state reactions. The structures of these compounds contain isolated GeSe{sub 4} trerahedra and are related to the CsCl-type structure. These compounds are semiconducting with optical band gaps around 2 eV.« less