On the anomalous high-pressure phase transition of inderite, MgB3O3(OH)5·5H2O

Abstract

The high-pressure behaviour of inderite [ideally MgB3O3(OH)5·5H2O, Sp. Gr. P21/c with a = 6.8105 (2), b = 13.0955 (5), c = 12.0144 (6) Å, β = 104.556 (4)° at room conditions], has been studied by in-situ single-crystal synchrotron X-ray diffraction up to 17 GPa, in order to explore its stability field at high-pressure, the anisotropy of its compressional behaviour and the deformation mechanisms at the atomic scale. Between 6.45 (5) and 6.94 (5) GPa, inderite experiences a first-order phase transition (from P21/c to P21/n, with a = 13.4308 (7), b = 11.9970 (5), c = 10.4466 (8) Å, and β = 100.030 (6)° at 6.45 (5) GPa, ΔV⁓ 7%), reconstructive in character, to the inderite-II polymorph, whose structure was successfully solved and refined. The isothermal bulk modulus (KV0 = β−1P0,T0, where βP0,T0 is the volume compressibility coefficient) of inderite was found to be KV0 = 26.5 (7) GPa, whereas in inderite-II the KV0 value increases to 41(5) GPa. The compressional anisotropy of the two polymorphs is drastically different, being the ratio between the principal components of the unit-strain ellipsoid: ε1:ε2:ε3 ⁓ 4.3:2.7:1 for the low-P polymorph and ε1:ε2:ε3 ⁓3.0:2.7:1 for the high-pressure one. The deformation mechanisms at the atomic scale, in inderite and inderite-II, are here described. The pressure at which the phase transition of inderite occurs represents an anomalous and (so far) unique case among the hydrated polyionic borates.