Structure of grain boundaries in wet,synthetic polycrystalline,statically recrystallizing halite – evidence from cryo‐SEM observations

It is well known from nature and experiments that the presence of brine strongly affects the microstructural evolution and the mechanical and transport properties of halite. Existing interpretations of the grain boundary structure in deformed, wet, salt samples annealed statically at room temperature are based on indirect evidence from reflected light microscopy and conventional scanning electron microscopy. This paper presents direct observations of fluid‐filled grain boundaries using the cryogenic‐scanning electron microscope (cryo‐SEM) in which the grain boundary fluids were frozen before breaking the samples. The rapid cooling transforms the brine into two phases, i.e. ice and hydrohalite, which are easily recognized from characteristic segregation patterns. We studied samples of wet, synthetic, polycrystalline halite annealed under static conditions at room temperature. In coarse‐grained samples, fine‐scale segregation patterns were observed at the boundaries of the primary recrystallizing grains. These points indicate the existence of fluid films with a thickness in the range of 30 nm, but the finer scale structure of the fluid remains unknown. In fine‐grained samples, the distribution and reorganization of fluids with annealing time is recorded by the combination of contact healing and successive accumulation of fluids in triple junction tubes. The contact healing is attributed to the small initial grain size, such that the fluid film necks down by accumulating the fluids into previously existing triple junctions via neck growth. Electron backscatter diffraction measurements of both primary and secondary recrystallized grains indicate that they are euhedral, i.e. the grain growth morphology is controlled by the anisotropy of the grain boundary energy of the growing grain, which results in planar growth faces.     

Cryogenic vitrification and 3D serial sectioning using high resolution cryo‐FIB SEM technology for brine‐filled grain boundaries in halite: first results

The structure of brine films in grain boundaries of halite has been the subject of much controversy over the past 20 years; although a number of innovative methods have been developed to study these structures, much is still unknown and fundamental information is missing. In this study, we investigated different methods of plunge‐freezing to vitrify the brine fill of grain boundaries for natural salt polycrystal. This was followed by a preliminary study of the 3D morphology of a vitrified grain boundary in a natural rock salt sample with a focused ion beam (FIB) excavation system. We have shown that brine‐filled grain boundaries in rock salt can be efficiently well frozen when dimensions are less than about 1 mm. Coupled with an ion beam tool, cryo‐SEM allows 3D observation of the well‐frozen grain boundaries in large volumes and high resolution. Initial results of brine‐filled natural halite grain boundaries show non‐faceted crystal–brine interfaces and unexpectedly low dihedral angles at room temperature and pressure.