XPS investigations of ruthenium deposited onto representative inner surfaces of nuclear reactor containment buildings

In the case of a hypothetical severe accident in a nuclear power plant, interactions of gaseous RuO₄ with reactor containment building surfaces (stainless steel and epoxy paint) could possibly lead to a black Ru-containing deposit on these surfaces. Some scenarios include the possibility of formation of highly radiotoxic RuO₄(g) by the interactions of these deposits with the oxidizing medium induced by air radiolysis, in the reactor containment building, and consequently dispersion of this species. Therefore, the accurate determination of the chemical nature of ruthenium in the deposits is of the high importance for safety studies. An experiment was designed to model the interactions of RuO₄(g) with samples of stainless steel and of steel covered with epoxy paint. Then, these deposits have been carefully characterised by scanning electron microscopy (SEM/EDS), electron probe microanalysis (EPMA) and X-ray photoelectron spectroscopy (XPS). The analysis by XPS of Ru deposits formed by interaction of RuO₄(g), revealed that the ruthenium is likely to be in the IV oxidation state, as the shapes of the Ru 3d core levels are very similar with those observed on the RuO₂·xH₂O reference powder sample. The analysis of O 1s peaks indicates a large component attributed to the hydroxyl functional groups. From these results, it was concluded that Ru was present on the surface of the deposits as an oxyhydroxide of Ru(IV). It has also to be pointed out that the presence of “pure” RuO₂, or of a thin layer of RuO₃ or Ru₂O₅, coming from the decomposition of RuO₄ on the surface of samples of stainless steel and epoxy paint, could be ruled out. These findings will be used for further investigations of the possible revolatilisation phenomena induced by ozone.