The phase diagram of NiSi under the conditions of small planetary interiors

The phase diagram of NiSi has been determined using in situ synchrotron X-ray powder diffraction multi-anvil experiments to 19 GPa, with further preliminary results in the laser-heated diamond cell reported to 60 GPa. The low-pressure MnP-structured phase transforms to two different high-pressure phases depending on the temperature: the ε-FeSi structure is stable at temperatures above ∼1100 K and a previously reported distorted-CuTi structure (with Pmmn symmetry) is stable at lower temperature. The invariant point is located at 12.8 ± 0.2 GPa and 1100 ± 20 K. At higher pressures, ε-FeSi-structured NiSi transforms to the CsCl structure with CsCl-NiSi as the liquidus phase above 30 GPa. The Clapeyron slope of this transition is −67 MPa/K. The phase boundary between the ε-FeSi and Pmmn structured phases is nearly pressure independent implying there will be a second sub-solidus invariant point between CsCl, ε-FeSi and Pmmn structures at higher pressure than attained in this study. In addition to these stable phases, the MnP structure was observed to spontaneously transform at room temperature to a new orthorhombic structure (also with Pnma symmetry) which had been detailed in previous ab initio simulations. This new phase of NiSi is shown here to be metastable.