Reaction-Induced Fracturing of Porous Carbonate Rocks during Volume-Increasing Replacement by Witherite
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.
Authors
- Carolyn Grace Cooke
- Juliane Weber (ORCID: https://orcid.org/0000-0001-7961-0220)
- Andrew G. Stack (ORCID: https://orcid.org/0000-0003-4355-3679)
- Lawrence M. Anovitz (ORCID: https://orcid.org/0000-0002-2609-8750)
- Vitalii Starchenko (ORCID: https://orcid.org/0000-0003-2313-7379)
- Mark L. Rivers (ORCID: https://orcid.org/0000-0003-4728-4189)
- Elliot P. Gilbert (ORCID: https://orcid.org/0000-0001-6413-7813)
- Ján Ilavský (ORCID: https://orcid.org/0000-0003-1982-8900)
- Michael J. Zachman (ORCID: https://orcid.org/0000-0003-1910-1357)
- Jitendra Mata (ORCID: https://orcid.org/0000-0001-9225-7900)
- Rui Zhang (ORCID: https://orcid.org/0000-0003-0840-5056)
Institutions
- Argonne National Laboratory (US)
- Oak Ridge National Laboratory (US)
- Australian Nuclear Science and Technology Organisation (AU)
- The University of Queensland (AU)
- UNSW Sydney (AU)
- Nanophase Technologies (United States) (US)
- Physical Sciences (United States) (US)
- NOAA Chemical Sciences Laboratory (US)
- Agriculture and Food (AU)
- Material Sciences (United States) (US)
- Advanced Center for Orthopedics (US)
- Tennessee Technological University (US)
Publication Details
- Journal
- Crystal Growth & Design
- Published
- 2025-08-11
- DOI
- https://doi.org/10.1021/acs.cgd.5c00522
- Primary Topic
- Hydraulic Fracturing and Reservoir Analysis
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Basic Energy Sciences