- By:
- Weber, Juliane ; Cooke, Gace C.; Starchenko, Vitalii ; Rivers, M.; Ilavsky, Ian; Zhang, Rui ; Zachman, Michael J; Gilbert, Elliot; Mata, Jitendra; Stack, Andrew G; Anovitz, Lawrence M
- Journal Name:
- Crystal Growth & Design
- Page Number:
- 6604-6619
- Volume:
- 25
- Issue Number:
- 16
- Publication Date:
- August 18, 2025
- View DOI Listing:
- https://doi.org/10.1021/acs.cgd.5c00522
Abstract
Volume-increasing replacement reactions can lead either to fracturing of the parent phase or to the formation of cohesive layers that passivate further reaction, but the factors that drive one outcome or the other are not understood. In this experimental study, we investigated the volume-increasing replacement of carbonate rocks (consisting of CaCO3 and CaMg(CO3)2) of different porosity by witherite (BaCO3). Samples were characterized using scanning electron microscopy, Raman spectroscopy, small-angle neutron/X-ray scattering, X-ray tomography, and scanning transmission electron microscopy. We observed the formation of a witherite reaction layer and witherite formation within pores and along grain boundaries. Despite this being a volume-increasing replacement reaction, newly formed witherite was porous, potentially allowing further replacement. Filled fractures were observed in the low-porosity carbonates, whereas witherite formed within pores in high-porosity carbonates. We conclude that fracturing of the parent phase versus passivation is contingent on the initial microstructure of the parent with an optimal degree of porosity required for fracturing.
