Pressure-induced migration of zeolitic water in laumontite

Abstract

A polycrystalline sample of natural laumontite (Pleasant Valley, Connecticut) was studied up to 6.8 (1) GPa at room temperature using monochromatic synchrotron X-ray powder diffraction and a diamond-anvil cell. A methanol: ethanol: water mixture was used as a penetrating pressure-transmitting fluid. A dry sample measured before adding the pressure fluid inside the diamond-anvil cell contained ~12 H₂O per formula unit, consistent with the water content of partially dehydrated laumontite. Upon increasing the pressure to 0.2 (1) GPa, fully hydrated laumontite with 18 H₂O per unit cell formed and the unit-cell volume expanded by 2.6%. Further pressure increase up to 2.4 (1) GPa resulted in a gradual contraction of the unit-cell volume and individual cell lengths. During this process, a successive order–disorder transition of hydrogen-bonded water molecules from their symmetry sites was observed, concomittent with an inflectional behavior of the monoclinic beta angle and the channel ellipticity. Above 3 GPa, a tripling of the b axis was detected. Thereafter, up to 6.8 (1) GPa, the compression behavior was reversed for the c axis length and the monoclinic beta angle which showed a gradual increase and decrease, respectively, without any apparent volume discontinuity. We suspect that different ordering of the water molecules or Ca cations inside the channels along the b axis may be responsible for the observed supercell transition above 3 GPa.