Real Time 3D Observations of Portland Cement Carbonation at CO2 Storage Conditions.

Depleted oil reservoirs are considered a viable solution to the global challenge of CO2 storage. A key concern is whether the wells can be suitably sealed with cement to hinder the escape of CO2. Under reservoir conditions, CO2 is in its supercritical state, and the high pressures and temperatures involved make real-time microscopic observations of cement degradation experimentally challenging. Here, we present an in situ 3D dynamic X-ray micro computed tomography (µ-CT) study of well cement carbonation at realistic reservoir stress, pore-pressure, and temperature conditions. The high-resolution time-lapse 3D images allow monitoring the progress of reaction fronts in Portland cement, including density changes, sample deformation, and mineral precipitation and dissolution. By switching between flow and nonflow conditions of CO2-saturated water through cement, we were able to delineate regimes dominated by calcium carbonate precipitation and dissolution. For the first time, we demonstrate experimentally the impact of the flow history on CO2 leakage risk for cement plugging. In-situ µ-CT experiments combined with geochemical modeling provide unique insight into the interactions between CO2 and cement, potentially helping in assessing the risks of CO2 storage in geological reservoirs.

Nonionic Fluorinated Surfactant Removal from Mesoporous Film Using sc-CO2.

Surfactant templated silica thin films were self-assembled on solid substrates by dip-coating using a partially fluorinated surfactant R8F(EO)9 as the liquid crystal template. The aim was 2-fold: first we checked which composition in the phase diagram was corresponding to a 2D rectangular highly ordered crystalline phase and second we exposed the films to sc-CO2 to foster the removal of the surfactant. The films were characterized by in situ X-ray reflectivity (XRR) and grazing incidence small angle X-ray scattering (GISAXS) under CO2 pressure from 0 to 100 bar at 34 °C. GISAXS patterns reveal the formation of a 2-D rectangular structure at a molar ratio R8F(EO)9/Si equal to 0.1. R8F(EO)9 micelles have a cylindrical shape, which have a core/shell structure ordered in a hexagonal system. The core contains the R8F part and the shell is a mixture of (EO)9 embedded in the silica matrix. We further evidence that the extraction of the template using supercritical carbon dioxide can be successfully achieved. This can be attributed to both the low solubility parameter of the surfactants and the fluorine and ethylene oxide CO2-philic groups. The initial 2D rectangular structure was well preserved after depressurization of the cell and removal of the surfactant. We attribute the very high stability of the rinsed film to the large value of the wall thickness relatively to the small pore size.