DFT-based prediction of fission product sorption on carbon structures under O2 ingress conditions

An isotherm based model for the prediction of Cs sorption on the carbon components of a High Temperature Reactor (HTR) under O2 ingress conditions is presented. Isotherms are derived from a thermodynamic model based on binding energies calculated using Density Functional Theory (DFT). The DFT derived isotherms are compared with isotherms obtained from experimental calculations and sources of discrepancies are discussed. A DFT only model and a second model combining DFT and experimental calculations are used to predict fission product inventories in a HTR vessel during O2 ingress conditions. Results suggest that the carbon type (i.e. graphitic vs. amorphous) plays a central role on fission product sorption and release. During normal reactor conditions (T around 1400 K, low PO2) graphitic carbon will absorb a small percentage of a monolayer of Cs, while amorphous carbon will be approximately saturated at an entire monolayer of Cs. Results also indicate that, for the case of O2 ingress to the reactor's vessel, the Cs will form Cs2O. In the case of graphitic carbon, the Cs2O will bind more weakly than Cs, leading to Cs release in the form of Cs2O during O ingress. However, the weak binding of Cs to graphite means that only small release is expected. In the case of amorphous carbon, Cs2O binds almost as strongly Cs, and so no significant change in Cs absorbed to the amorphous carbon is predicted, although the form of the absorbed Cs is predicted to be Cs2O. For the case of low release conditions, consistent with modern TRISO fuels, the core will adsorb the entire Cs inventory at normal operating temperatures. However, for high Cs release conditions, consistent with older TRISO fuels, the surface sites on the core will be saturated and most of the Cs will remain in gas form or plate out on other surfaces.