Enhancement of the Characteristics of Cement Matrix by the Accelerated Carbonation Reaction of Portlandite with Supercritical Carbon Dioxide

This research investigated the feasibility of the accelerated carbonation of cement waste forms with carbon dioxide in a supercritical state. Hydraulic cement has been used as a main solidification matrix for the immobilization of radioactive and/or hazardous wastes. As a result of the hydration reaction for major compounds of portland cement, portlandite (Ca(OH)$_2$) is present in the hydrated cement waste form. The chemical durability of a cement form is expected to increase by converting portlandite to the less soluble calcite (CaCO$_3$). For a faster reaction of portlandite with carbon dioxide, SCCD (supercritical carbon dioxide) rather than gaseous $CO_2$, in ambient pressure is used. The cement forms fabricated with an addition of slated lime or Na-bentonite were cured under ambient conditions for 28days and then treated with SCCD in an autoclave maintained at 34$^{\circ}C$ and 80atm. After SCCD treatment, the physicochemical properties of cement matrices were analyzed to evaluate the effectiveness of accelerated carbonation reaction. Conversion of parts of portlandite to calcite by the carbonation reaction with SCCD was verified by XRD (X-ray diffraction) analysis and the composition of portlandite and calcite was estimated using thermogravimetric (TG) data. After SCCD treatment, tile cement density slightly increased by about 1.5% regardless of the SCCD treatment time. The leaching behavior of cement, tested in accordance with an ISO leach test method at 7$0^{\circ}C$ for over 300 days, showed a proportional relationship to the square root of the leaching time, so the major leaching mechanism of cement matrix was diffusion controlled. The cumulative fraction leached (CFL) of calcium decreased by more than 50% after SCCD treatment. It might be concluded that the enhancement of the characteristics of a cement matrix by an accelerated carbonation reaction with SCCD is possible to some extent.