UC Santa Barbara

Formation of a high density of Mn-Ni-Si nanoscale precipitates in irradiated reactor pressure vessel steels could lead to severe, unexpected embrittlement, which may limit the lifetimes of our nation’s light water reactors. While the existence of these precipitates was hypothesized over 20 years ago, they are currently not included in embrittlement prediction models used by the Nuclear Regulatory Commission. This work aims to investigate the mechanisms and variables that control Mn-Ni-Si precipitate (MNSP) formation as well as correlate their formation with hardening and embrittlement.

A series of RPV model steels with systematic variations in Cu and Ni contents, two variables that have been shown to have a dominant effect on hardening, were irradiated in a series of test reactor and power reactor surveillance irradiations. Atom probe tomography (APT) measurements show that large volume fractions (fv) of MNSPs form in all the steels irradiated at high fluence, even those containing no added Cu, which were previously believed to have low sensitivity to embrittlement. It is demonstrated that while Cu enhances the rate of MNSP formation, it does not appear to significantly alter their saturation fv or composition. The high fluence MNSPs have compositions consistent with known intermetallic phases in the Mn-Ni-Si system and have fv very near those predicted by equilibrium thermodynamic models. In addition, X-ray diffraction experiments by collaborators shows that these precipitates also have the expected crystal structure of the predicted Mn-Ni-Si phases.

Post irradiation annealing experiments are used to measure the hardness recovery at various temperatures as well as to determine if the large fv of MNSPs that form under high fluence neutron irradiation are thermodynamically stable phases or non-equilibrium solute clusters, enhanced or induced by irradiation, respectively. Notably, while post irradiation annealing of a Cu-free, high Ni steel at 425°C results in dissolution of most precipitates, a few larger MNSPs appear to remain stable and may begin to coarsen after long times. A cluster dynamics model rationalizes the dissolution and reduction in precipitate number density, since most are less than the critical radius at the annealing temperature and decomposed matrix composition. The stability of larger precipitates suggests that they are an equilibrium phase, consistent with thermodynamic models.

Charged particle irradiations using Fe3+ ions are also used to investigate the precipitates which form under irradiation. Two steels irradiated to a dose of 0.2 dpa using both neutrons and ions show precipitates with very similar compositions. The ion irradiation shows a smaller fv, likely due to the much higher dose rate, which has been previously shown to delay precipitation to higher fluences. While the precipitates in the ion irradiated condition are slightly deficient in Mn and enriched in Ni and Si compared to neutron irradiated condition, the overall similarities between the two conditions suggest that ion irradiations can be a very useful tool to study the susceptibility of a given steel to irradiation embrittlement.

Finally, the large fv of MNSPs that are shown to form in all steels, including those low in Cu, at high fluence, even those without added Cu, result in large amounts of hardening and embrittlement. A preliminary embrittlement prediction model, which incorporates MNSPs at high fluence, is presented, along with results from a recent test reactor irradiation to fluences representative of extended lifetimes. This model shows very good agreement with the data.