Comparison of the phase transitions of high-pressure phases of ammonium fluoride and ice at ambient pressure

Abstract

The phase diagrams of water and ammonium fluoride (NH4F) display some interesting parallels. Several crystalline NH4F phases have isostructural ice counterparts and one of the famous anomalies of water, the fact that the liquid is denser than ice Ih, is also found for NH4F. Here, we investigate the phase transitions of the pressure-quenched high-pressure phases of NH4F upon heating at ambient pressure with x-ray diffraction and calorimetry, and we compare the results with the corresponding ices. NH4F II transforms to NH4F Isd, which is a stacking-disordered variant of the stable hexagonal NH4F Ih polymorph. Heating NH4F III gives a complex mixture of NH4F II and NH4F Isd, while some NH4F III remains initially. Complete conversion to NH4F Isd is achieved above ∼220 K. The NH4F II obtained from NH4F III persists to much higher temperatures compared to the corresponding pressure-quenched NH4F II. Quantification of the stacking disorder in NH4F Isd reveals a more sluggish conversion to NH4F Ih for NH4F Isd from NH4F III. In general, the presence of stress and strain in the samples appears to have pronounced effects on the phase transition temperatures. NH4F shows a complete lack of amorphous forms at low temperatures either upon low-temperature compression of NH4F Ih or heating NH4F III at ambient pressure. The amorphous forms of ice are often used to explain the anomalies of water. It will, therefore, be interesting to explore if liquid NH4F displays more water-like anomalies despite the apparent lack of amorphous forms at low temperatures.