High-pressure behavior and P-induced phase transition of CaB3O4(OH)3·H2O (colemanite)

Colemanite (ideally CaB3O4(OH)3·H2O, space group P21/a, unit-cell parameters: a ~ 8.74, b ~ 11.26, c ~ 6.10 Å, β ~ 110.1°) is one of the principal mineralogical components of borate deposits and the most important mineral commodity of boron. Its high-pressure behavior is here described, for the first time, by means of in situ single-crystal synchrotron X-ray diffraction with a diamond anvil cell up to 24 GPa (and 293 K). Colemanite is stable, in its ambient-conditions polymorph, up to 13.95 GPa. Between 13.95 and 14.91 GPa, an iso-symmetric first-order single-crystal to single-crystal phase transition (reconstructive in character) toward a denser polymorph (colemanite-II) occurs, with: aCOL-II=3·aCOL, bCOL-II=bCOL, and cCOL-II=2·cCOL. Up to 13.95 GPa, the bulk compression of colemanite is accommodated by the Ca-polyhedron compression and the tilting of the rigid three-membered rings of boron polyhedra. The phase transition leads to an increase in the average coordination number of both the B and Ca sites. A detailed description of the crystal structure of the high-P polymorph, compared to the ambient-conditions colemanite, is given. The elastic behaviors of colemanite and of its high-P polymorph are described by means of III- and II-order Birch-Murnaghan equations of state, respectively, yielding the following refined parameters: KV0=67(4) GPa and KV′=5.5(7) [βV0=0.0149(9) GPa-1] for colemanite; KV0=50(8) GPa [βV0=0.020(3) GPa-1] for its high-P polymorph.