Stabilization of LnB12 (Ln = Gd, Sm, Nd, and Pr) in Zr1–x Ln x B12 under Ambient Pressure

• Published in: Inorganic chemistry 2016-12, Vol.55 (23), p.12419-12426
• Main Authors: Akopov, Georgiy, Sobell, Zachary C, Yeung, Michael T, Kaner, Richard B
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.6b02311

We report ambient pressure stabilization of a previously synthesized high-pressure (6.5 GPa) phase, GdB12, in a Zr1–x Gd x B12 solid solution (with ∼54 at. % Gd solubility, as determined by both powder X-ray diffraction and energy-dispersive spectroscopy). Limited solubilities of Sm (∼15 at. % Sm), Nd (∼7 at. % Nd), and Pr (∼4 at. % Pr), in ZrB12 were also achieved. Previous attempts at preparing these rare-earth borides were unsuccessful even under high pressure. On the basis of insights provided from the unit cell sizes observed via solid solutions, at least 6.5 GPa of pressure would be needed to synthesize these rare-earth borides since Sm, Nd, and Pr atomic radii are larger than that of Gd. The solid-solution formation for Zr1–x Gd x B12 and Zr1–x Sm x B12 can be seen in the change of the unit cell of each of the solid solutions relative to their pure parent compounds as well as in the change of color of the respective alloys. For Zr0.45Gd0.55B12 and Zr0.70Sm0.30B12, the cubic unit cell parameter (a) reached a value of 7.453 and 7.428 Å, respectively, compared to 7.412 Å for pure ZrB12.