Abstract

Phase stability and elasticity of ammonia hydrate have been studied using Raman spectroscopy and Brillion scattering in diamond-anvil cells up to 53 GPa at 300 K. Here we have established the high-pressure phase diagram of ammonia hydrate in three different compositions, including ammonia monohydrate (AMH, NH3·H2O), dihydrate (ADH, NH3·2H2O), and trihydrate (ATH, NH3·3H2O). In contrast to previous experimental results, our Raman and Brillouin measurements at 300 K have shown that all three ammonia hydrates start to dehydrate at 2.1–2.2 GPa. Dehydration of the ammonia hydrate leads to the formation of single-crystal ice-VII and an increase in the concentration of NH3 in the residual liquid. The residual liquid finally turns into solid ammonia hemihydrate phase II (AHH-II) at 4–4.6 GPa, leading to a 28% jump in the compressional-wave velocity (VP). Considering a 10–15 vol% NH3 in the mantle of ice giants, AHH should thus be the dominant form of NH3 coexisting with H2O-ice in the ice giants. Further Brillouin measurements provide crucial constraints on the VP of AHH and the single-crystal elasticity of ice-VII at high pressures and 300 K. VP of AHH increases smoothly with pressure. No anomalous change in VP of AHH was identified up to 39 GPa, although a solid to solid phase transition was noted to occur at ~18 GPa by Raman measurements. In addition, the elasticity of single-crystal ice-VII, which was the dehydration product of ammonia hydrate, has been determined up to 53 GPa at 300 K. The deviation of C12 from C44 observed at 11.4 and 14.6 GPa could be caused by the hydrogen bond symmetrizations or the ordering of dipole of single-crystal ice-VII. An abnormal softening in the elastic moduli C11, C12, and the adiabatic moduli KS together with stiffening in C44 was observed between 42 and 53 GPa, which should be caused by the transition from ice-VII to its pre-transitional state. Of particular interest is the dramatic increase in the anisotropy of ice-VII with increasing pressure. Combining the sound velocity of AHH and ice-VII, we have modeled the VP of ice giants with a volume ratio of 20% AHH and 80% ice-VII in the mantle. The obtained high-pressure phase diagram and elastic properties of ammonia hydrate could contribute to understanding the structure of the mantle in the ice giants and satellites.

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