Phase behaviour and thermoelastic properties of ammonia hydrate and ice polymorphs from 0 - 2 GPa

Mathematics – Logic

Scientific paper

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3672 Planetary Mineralogy And Petrology (5410), 3919 Equations Of State, 3924 High-Pressure Behavior, 3954 X-Ray, Neutron, And Electron Spectroscopy And Diffraction, 5460 Physical Properties Of Materials

Scientific paper

Ammonia remains amongst the most plausible planetary "antifreeze" agents, and its physical properties in hydrate compounds under the appropriate conditions (roughly 0 - 5 GPa, 100 - 300 K) must be known in order for it to be accommodated in planetary models. The pressure melting curve, and the expected polymorphism of the stoichiometric ammonia hydrates have implications for the internal structure of large icy moons like Titan, leading to phase layering and the possible persistence of deep subsurface oceans, the latter being sites of high astrobiological potential. Aqueous ammonia is also a candidate substance involved in cryomagmatism on Titan, and again the melting behaviour, and densities of liquids and solids, in the ammonia-water system must be known to model properly the partial melting and propagation of magma. We describe the results of a series of powder neutron diffraction experiments over the range 0 - 2.0 GPa, 150 - 280 K which were carried out with the objective of determining the phase behaviour and thermoelastic properties of ammonia dihydrate. In addition to the low-pressure cubic crystalline phase, ADH I, we have identified two closely related monoclinic polymorphs of ammonia dihydrate (ADH IIa and IIb) in the range 0.45 - 0.60 GPa (at 175 K), and have determined that this phase dissociates to a mixture of ammonia monohydrate phase II and ice II when warmed to ~190 K, which in turn melts at a binary eutectic at ~196 K; AMH II has a large (Z = 16) orthorhombic unit cell. Above 0.60 GPa, an orthorhombic polymorph of ammonia dihydrate, which we have referred to previously as ADH IV, persists to pressures > 3 GPa, and appears to be the liquidus phase over this whole pressure range. We have observed this phase co- existing with both ice II and ice VI. Here we describe the most plausible synthesis of the high-pressure phase diagram which explains our observations, and provide measurements of the densities, thermal expansion, bulk moduli, and crystal growth kinetics of the high-pressure ammonia dihydrate, ammonia monohydrate and ice polymorphs obtained from our data.

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