Archive / Volume LXXVIII 2025

Volodymyr BABIZHETSKYY, Olha ZHAK, Stanislav STOYKO

Ivan Franko National University of Lviv, Kyryla i Mefodia Str., 6, 79005 Lviv, Ukraine
e-mail: volodymyr.babizhetskyy@lnu.edu.ua

DOI:

PHASE EQUILIBRIA AND CRYSTAL STRUCTURE OF THE COMPOUNDS IN Y–Ni–As SYSTEM AT 970 K

Phase equilibria and the crystal structure of the compounds of the ternary system Y–Ni–As were studied using X-ray phase and structural analyses, and the phase diagram was constructed at 970 K in the range of 0–0.67 mol. % As.
Samples for investigation were prepared by sintering of the pressed pellets of the mixtures of the pure components in evacuated silica tubes at 970 K for 240 h, and then were arc-melted under purified argon atmosphere. The as-cast samples were again sealed in a silica tubes, and then heat treated at 970 K during 1500 h. Annealed alloys were quenched in cold water without breaking the ampoules. The X-ray powder diffraction data were collected on a powder diffractometers DRON-3M (CuKα-radiation), and Image Plate Huber G 670 (CuK1- radiation). All calculations were performed using WinCSD and FullProf software.
The existence of six ternary compounds was confirmed: YNi4As2 (ZrFe4Si2 type), Y2Ni12As7 (Zr2Fe12P7 type), Y6Ni20.04As12.78 (Y6Ni20.04As12.78 type), Y6Ni15As10 (Tb6Ni15As10 type), Y20Ni42As31 (Sm20Ni42P31 type), and YNiAs (LiBaSi type). Moreover, the crystal structures of two ternary arsenides were refined for the first time using the X-ray powder diffraction data: Y2Ni12As7, Zr2Fe12P7 type structure, space group P-6, lattice parameters a = 9.3582(2) Å, c = 3.8149(1) Å, final residual values are RB = 0.078, RP = 0.084; and Y6Ni15As10, Tb6Ni15As10 type structure, space group P63/m, a = 17.0101(1) Å, c = 3.88759(4) Å, RB = 0.053, RP = 0.106. For the last arsenide, the splitting of the positions of arsenic atoms As1 and As2 on the 63-axis is observed, and, as a result, neighboring nickel atoms also occupy split positions. For split positions Ni2/Ni3/Ni4, the total occupancy is about 100%. As a consequence, it has been confirmed that the refined composition of this arsenide coincides with the previously known formula Y6Ni15As10.
The crystal structures of ternary arsenides Y2Ni12As7 and Y6Ni15As10 belong to a homologous series of flat bilayer hexagonal structures with a metal:metalloid ratio of 2:1, whose composition is described by the formula Lnn(n-1)M(n+1) (n+2)Xn(n+1)+1.

Keywords: rare earth metal arsenides, isothermal section, crystal structure, X-ray powder diffraction method.

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