Effects of nickel and manganese on the embrittlement of low-copper pressure vessel steels

Solute clustering is known to play a significant role in the embrittlement of reactor pressure vessel (RPV) steels. When precipitates form they impede the movement of dislocations, causing an increase in hardness and a shift in the ductile-brittle transition temperature. Over time this can cause the steel to become brittle and more susceptible to fracture. Thus, understanding precipitate formation is of great importance to the nuclear industry.
The first part of this thesis aims to isolate and better understand the thermal aging component of embrittlement in low copper, model RPV steels. Currently, relatively little is known about the effects of Ni and Mn in a low copper environment. Therefore, it is of interest to determine if Ni and Mn form precipitates under these conditions.
To this end, hardness measurements and atom probe tomography were utilized to link the mechanical properties to the microstructure. After 11,690 hours of thermal aging a statistically significant decrease in hardening was observed. Consistent with hardness measurements, no precipitates were present within the matrix of the thermally aged RPV steels. The local chemistry method was then applied to investigate the very early stages of solute clustering. Association was found to be statistically significant in both the thermally aged and as-received model RPV steels. Therefore, no apparent trends regarding the changes in solute association between the as-received and thermally aged RPV steels were identified.
Small, non-random clusters were observed at heterogeneous nucleation sites, such as carbide/matrix interfaces and grain boundaries, within the thermally aged material. The clusters found at the carbide/matrix interfaces were all rich in Mn and approximately 90-150 atoms in size. The clusters located along the observed low-angle grain boundary, however, were significantly larger (on the order of hundreds of atoms) and rich in Ni.
Lastly, copper-rich precipitates (CRPs) and Mn- and Ni-rich precipitates (MNPs) were observed within the cementite phase of a high copper and low copper RPV steel, respectively, following long term thermal aging. APT was used to characterize these precipitates and obtain more detailed chemical information. The presence of such precipitates indicates that a range of precipitation can take place within the cementite phase of thermally aged RPV steels.
The second part of this thesis aims to investigate the effects of ion irradiation on the microstructure of low copper RPV steels via APT. These steels were ion irradiated with 6.4 MeV Fe3+ ions with a dose rate of 1.5 × 10−4 dpa/s at 290◦C. MNPs were observed in all five of the RPV steels analyzed. These precipitates were found to have nucleated within the matrix as well as at dislocations and grain boundaries. Using the maximum separation method these MNPs were extracted and characterized. Precipitate composition, size, volume fraction, and number density were determined for each of the five samples. Lastly, several grain boundaries were characterized.
Several emerging trends were observed within the samples: Ni content within the precipitates did not vary significantly once a threshold between 30-50% was reached; bulk Mn content appeared to dictate Si and Mn content within the precipitates; and samples low in bulk Ni content were characterized by a higher number density of smaller precipitates. Additionally, by regressing precipitate volume fraction against the interaction of Ni and Mn, a linear relationship was found to be statistically significant.

Keywords: RPV steels
Gaussian mixture model
Clustering
Atom probe tomography
Thermal ageing
Advisor: Moody, M
Smith, G
Hyde, J