Crystal chemistry of the G-phases in the {Ti, Zr, Hf}-Ni-Si systems

Author(s)
Andrij Grytsiv, Xingqiu Chen, Peter Franz Rogl, Raimund Podloucky, Harald Schmidt, Gerald Giester, Vladimir Pomjakushin
Abstract

Ternary compounds M 6Ni16Si7 (M =Ti, Zr, Hf) have been investigated by X-ray powder/single crystal and neutron powder diffraction. Compounds with Zr and Hf crystallize in the ordered Th6Mn23 type (Mg6Cu16Si7-type, space group Fm3¯m), whereas Ti6Ni16.7Si7 contains an additional Ni atom partially occupying the 24e site (M2 site, x=0.4637,0,0; occ.=0.119) inside a Ti octahedron; Ti atoms occupy a split position. Ti6Ni16.7Si7 represents a new variant of the filled Th6Mn23 type structure. Ab initio calculations confirm the structural difference: additional Ni atoms favour the 24e site for Ti6Ni16.7Si7, however, for the Zr and Hf-based compounds the unoccupied site renders an energetically lower ground state. Enthalpies of formation of Ti6Ni17Si7, Zr6Ni16Si7, and Hf6Ni16Si7 were calculated to be −68.65, −74.78, and −78.59 kJ/(mol of atoms), respectively.. © 2006 Elsevier Inc. All rights reserved.

Organisation(s)
Department of Physical Chemistry, Department of Mineralogy and Crystallography
External organisation(s)
Eidgenössische Technische Hochschule Zürich
Journal
Journal of Solid State Chemistry
Volume
180
Pages
733-741
No. of pages
9
ISSN
0022-4596
DOI
https://doi.org/10.1016/j.jssc.2006.11.031
Publication date
2007
Peer reviewed
Yes
Austrian Fields of Science 2012
105113 Crystallography
Portal url
https://ucrisportal.univie.ac.at/en/publications/ae6445c6-4717-4e43-82fe-73dd0c2437c0