Search for: All records

Balcite (Ba x Ca 1− x CO 3 ) is a synthetic analog of rhombohedral carbonate minerals like calcite and dolomite that is disordered on both the cation and anion sublattices. Here, we show that multiple exotic superlattice structures, including a dolomite analog that we call balcomite, can form from balcite at elevated temperatures. The second-order balcite-to-balcomite conversion at temperatures between 150–600 °C is driven by the preference of barium and calcium for different oxygen coordination numbers and facilitated by local carbonate reorientation. At elevated pressure, further superlattice order arises from cation segregation in all three dimensions, producing a supercell with the same R 3̄ m symmetry as balcite but 6× larger. This highly ordered structure relaxes back to the balcomite structure upon returning to ambient conditions. None of the three naturally occurring polymorphs of Ba 0.5 Ca 0.5 CO 3 (alstonite, paralstonite, barytocalcite) formed from balcite despite being putatively energetically favored. Instead, alstonite transformed to a balcomite-like structure via a first-order process after transiently converting to a paralstonite-like structure via a second-order process. Together, these results show that high temperature transformation pathways between structures in the barium calcium carbonate system can be driven by coarsening and are facilitated by similarity in short-range order, conceptually analogous to previously described low-temperature transformations. Many of the exotic high temperature carbonate structures are unstable, but may participate in transformation pathways between naturally observed metastable mineral phases, suggesting important roles for ephemeral phases in shaping past and current mineral distributions. 

Abstract The direct observation of amorphous barium carbonate (ABC), which transforms into a previously unknown barium carbonate hydrate (herewith named gortatowskite) within a few hundred milliseconds of formation, is described. In situ X‐ray scattering, cryo‐, and low‐dose electron microscopy were used to capture the transformation of nanoparticulate ABC into gortatowskite crystals, highly anisotropic sheets that are up to 1 μm in width, yet only about 10 nm in thickness. Recrystallization of gortatowskite to witherite starts within 30 seconds. We describe a bulk synthesis and report a first assessment of the composition, vibrational spectra, and structure of gortatowskite. Our findings indicate that transient amorphous and crystalline precursors can play a role in aqueous precipitation pathways that may often be overlooked owing to their extremely short lifetimes and small dimensions. However, such transient precursors may be integral to the formation of more stable phases.