We present a study of the high-pressure behaviour Bi14WO24, a high oxide ion conductor member of the Bi2O3-WO3 binary system. The tetragonal polymorph of Bi14WO24 was studied under high-pressure conditions using synchrotron powder X-ray diffraction. It was found that in contrast to isostructural Bi14CrO24 and Bi14MoO24 which experience a phase transition around 5 GPa, in our study Bi14WO24 undergoes an irreversible chemical decomposition into Bi2O3 and WO3 at 2.85(5) GPa. The pressure dependence of the unit-cell parameters of Bi14WO24 was also determined, and hence the linear compressibility along different axes and room-temperature pressure-volume equation of state were derived. Bulk modulus of tetragonal Bi14WO24 was found to be 49.8(2.6) GPa, and the linear compressibility of the two crystallographic axes, \k{appa}a and \k{appa}c were 6.94(2) 10-3 GPa-1 and = 3.73(1) 10-3 GPa-1, respectively. The pressure induced decomposition can be attributed to the favourable increasing density of the system to accommodate the pressure induced stress.
@article{arxiv.2508.05617,
title = {Pressure-induced decomposition of Bi14WO24},
author = {E. Karaca and D. Santamaria-Perez and A. Otero-de-la-Roza and R. Oliva and K. S. Rao and S. N. Achary and C. Popescu and D. Errandonea},
journal= {arXiv preprint arXiv:2508.05617},
year = {2025}
}