Ammonium Fluoride as a Hydrogen-disordering Agent for Ice

TL;DR

This study demonstrates that ammonium fluoride (NH4F) acts as a hydrogen-disordering agent for ice VIII, significantly affecting hydrogen ordering kinetics and residual disorder, with implications for other ice-rule systems.

Contribution

We show that NH4F doping induces long-range hydrogen-disordering effects and slows hydrogen-ordering kinetics in ice VIII, revealing a new method to control hydrogen ordering in ice structures.

Findings

NH4F causes ~31% residual hydrogen disorder in ice VIII.

Doping with ND4F delays hydrogen-ordering, extending the supercooling range.

Local ferroelectric domains likely exist between ionic defects.

Abstract

The removal of residual hydrogen disorder from various phases of ice with acid or base dopants at low temperatures has been a focus of intense research for many decades. As an antipode to these efforts, we now show using neutron diffraction that ammonium fluoride (NH4F) is a hydrogen-disordering agent for the hydrogen-ordered ice VIII. Cooling its hydrogen-disordered counterpart ice VII doped with 2.5 mol% ND4F under pressure leads to a hydrogen-disordered ice VIII with ~31% residual hydrogen disorder illustrating the long-range hydrogen-disordering effect of ND4F. The doped ice VII could be supercooled by ~20 K with respect to the hydrogen-ordering temperature of pure ice VII after which the hydrogen-ordering took place slowly over a ~60 K temperature window. These findings demonstrate that ND4F-doping slows down the hydrogen-ordering kinetics quite substantially. The partial hydrogen order of the doped sample is consistent with the antiferroelectric ordering of pure ice VIII. Yet, we argue that local ferroelectric domains must exist between ionic point defects of opposite charge. In addition to the long-range effect of NH4F-doping on hydrogen-ordered water structures, the design principle of using topological charges should be applicable to a wide range of other 'ice-rule' systems including spin ices and related polar materials.