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Life extension of light water reactors requires robust models to predict the embrittlement of reactor pressure vessel (RPV) steels under long-term neutron irradiation. Embrittlement is due to nanoscale precipitation hardening by phases containing Cu, Mn, Ni, and Si, resulting in increases of the ductile to brittle transition temperature. Embrittlement data for low flux, high fluence extended life conditions, up to 80 years or more, are largely not available. Thus, higher flux, accelerated test reactor irradiations have been used to help develop models to predict low flux embrittlement at high fluence. Here flux, or dose rate, is expressed in units of displacements per atom per second (dpa/s). The dose rate can significantly influence precipitate evolution in a way that depends on fluence (dpa), temperature, and alloy composition, as well as flux itself. Here, we explore precipitation in surveillance steels with varying compositions at high fluxes (10−5–10−6 dpa/s) produced using 70 MeV Fe2+ ion irradiations. Atom probe tomography was used to characterize the dose dependence of precipitation at very high ion irradiation dose rates, and to evaluate corresponding similarities or differences compared to neutron irradiated steels at a much lower dose rate of ≈ 5 × 10−9 dpa/s. The data show that, on average, the ion irradiation precipitate volume fractions increase by factors of ∼ 1.5 to 2 between 0.3 dpa and 1.2 dpa. Limited data show that the major effect of neutron versus ion irradiation is the former has lower precipitate number densities and larger sizes. Otherwise, the precipitates are remarkably similar in composition and volume fraction. [ABSTRACT FROM AUTHOR]

The behavior of solute atoms in an undersaturated Fe-3.3 at.%Ni model alloy upon heavy and light particle irradiations was investigated by Atom Probe Tomography. Whereas first irradiations, performed using 27 MeV Fe ions at 400 °C, highlight significant Ni enrichment on point defect clusters, solute-rich features detected after 2.8 MeV H + ion (400 °C) and 1 MeV electron (320 °C) irradiations are only associated with pre-existent microstructural defects. Nanoindentation tests show no hardening in light particle irradiated samples, strongly suggesting that no dislocation loop formed. These observations put forward the importance of point defect clusters resulting from displacement cascades in Ni clusters' formation. Image, graphical abstract [ABSTRACT FROM AUTHOR]

Post irradiation annealing (PIA) clarified the induced versus enhanced controversy regarding nanoscale Mn-Ni-Si precipitate (MNSP) formation in pressure vessel steels. Radiation induced MNSPs would dissolve under high temperature PIA, while radiation enhanced precipitates would be stable above a critical radius (r c). A Cu-free, high Ni steel was irradiated with 2.8MeV Fe2+ ions at two temperatures to generate MNSPs with average radii (r ¯) above and below an estimated r c for PIA at 425°C up to 52 weeks. Atom probe tomography and energy dispersive x-ray spectroscopy showed MNSPs with r < r c dissolved, while those with r > r c slightly coarsened, consistent with thermodynamic predictions. Image, graphical abstract [ABSTRACT FROM AUTHOR]

Mn-Ni-Si intermetallic precipitates (MNSPs) that are observed in some Fe-based alloys following thermal aging and irradiation are of considerable scientific and technical interest. For example, large volume fractions (f) of MNSPs form in reactor pressure vessel low alloy steels irradiated to high fluence, resulting in severe hardening induced embrittlement. Nine compositionally-tailored small heats of low Cu RPV-type steels, with an unusually wide range of dissolved Mn (0.06–1.34 at.%) and Ni (0.19–3.50 at.%) contents, were irradiated at ≈ 290 °C to ≈ 1.4 × 1020 n/cm2 at an accelerated test reactor flux of ≈3.6 × 1012 n/cm2-s (E > 1 MeV). Atom probe tomography shows Mn-Ni interactions play the dominant role in determining the MNSP f, which correlates well with irradiation hardening. The wide range of alloy compositions results in corresponding variations in precipitates chemistries that are reasonably similar to various phases in the Mn-Ni-Si projection of the Fe based quaternary. Notably, f scales with ≈ Ni1.6Mn0.8. Thus f is modest even in advanced high 3.5 at.% Ni steels at very low Mn (Mn starvation); in this case Ni-silicide phase type compositions are observed. Image 1 [ABSTRACT FROM AUTHOR]

Neutron irradiation following thermal ageing experiments were performed using Fe-Cu, Fe-Cu-Ni, Fe-Cu-Ni-Mn, and Fe-Cu-Si alloys to investigate the effects of Ni, Mn, and Si on the formation of Cu-rich clusters and their chemical composition. Atom probe tomography showed that Ni and Mn increased the number density of Cu-rich clusters. This can be caused by that Ni and Mn reduce the formation energy of Cu nuclei, thus enhancing the Cu nucleation rate. Mn may also enhance the heterogeneous nucleation of Cu because of its strong interaction with self-interstitial atoms. In addition, Mn can accelerate solute diffusion during thermal ageing. A high Ni alloying content enhanced the Mn concentration in the clusters as well as the Ni concentration, which is believed to be caused by the thermodynamic relationship between Ni and Mn. In Fe-Cu-Si alloys, the Si concentration in the clusters was very low and was comparable to the Si alloying content. This indicates that Si atoms hardly cluster with Cu. [ABSTRACT FROM AUTHOR]

Formation of a high density of Mn–Ni–Si nanoscale precipitates in irradiated Cu-free and Cu-bearing reactor pressure vessel steels could lead to severe unexpected embrittlement. Models long ago predicted that these precipitates, which are not treated in current embrittlement prediction models, would emerge only at high fluence. However, the mechanisms and variables that control Mn–Ni–Si precipitate formation, and their detailed characteristics, have not been well understood. High flux irradiations of six steels with systematic variations in Cu and Ni contents were carried out at ∼295 °C to high and very high neutron fluences of ∼1.3 × 10 20 and ∼1.1 × 10 21 n cm −2 . Atom probe tomography shows that significant mole fractions of Mn–Ni–Si-dominated precipitates form in the Cu-bearing steels at ∼1.3 × 10 20 n cm −2 , while they are only beginning to develop in Cu-free steels. However, large mole fractions of these precipitates, far in excess of those found in previous studies, are observed at 1.1 × 10 21 n cm −2 at all Cu contents. At the highest fluence, the precipitate mole fractions primarily depend on the alloy Ni, rather than Cu, content. The Mn–Ni–Si precipitates lead to very large increases in measured hardness, corresponding to yield strength elevations of up to almost 700 MPa. [ABSTRACT FROM AUTHOR]

In this study, APT and TEM analyses were used to characterise two Zr-based alloys neutron-irradiated to 13.7 dpa. The high spatial and chemical resolution of these techniques has enabled the irradiation-induced nanoscale distribution of solute elements to be characterised. The results on both Zircaloy-2 and low-Sn ZIRLO support previous observations of Fe segregation to planar dislocation arrays with enhanced Sn between. In Zircaloy-2, the APT data in this study have also revealed short-range (∼2 nm) clustering of Fe and Sn atoms both within the Fe-enriched planes and in the regions between dislocation arrays. The resultant microstructure is reminiscent of spinodal decomposition. In low-Sn ZIRLO Nb-rich precipitates formed in the Sn-rich planes. The data in this article enhance our understanding of microstructural evolution in Zr alloys under neutron irradiation and are relevant for predicting changes in the properties of Zr alloys in-service in fission reactors. [Display omitted] [ABSTRACT FROM AUTHOR]

• The role of Si content on irradiation embrittlement was clarified. • Solute atom clusters of highly neutron-irradiated Japanese pressurized water reactor surveillance test specimens were analyzed by atom probe tomography. • The cluster radius and number density decreased and increased, respectively, with increasing Si content, resulting in a constant volume fraction of SCs. • Increase in Si reduces the degree of irradiation embrittlement. This is consistent with the results of our previous study based on Bayesian statistical analysis. Solute clusters (SCs) formed in pressurized water reactor surveillance test specimens neutron-irradiated to a fluence of 1 × 1020 n/cm2 were analyzed via atom probe tomography to understand the effect of silicon on solute clustering and irradiation embrittlement of reactor pressure vessel steels. In high-Cu bearing materials, Cu atoms were aggregated at the center of cluster surrounded by the Mn, Ni, and Si atoms like a core-shell structure. In low-Cu bearing materials, Mn, Ni, and Si atoms formed cluster and these solutes were not comprised core-shell structure in SCs. While the number of Cu atoms in clusters was decreased with decreasing nominal Cu content, the number of Si atoms had clearly increased. The cluster radius (r) and number density (N d) decreased and increased with increasing nominal Si content, respectively. The shift in the reference temperature for nil-ductility transition (ΔRT NDT) showed a good correlation with the square root of volume fraction (V f) multiplied by ( V f × r). The negative relation between the nominal Si content and ΔRT NDT indicated that increasing of nominal Si content reduces the degree of embrittlement. [ABSTRACT FROM AUTHOR]

• Chemical compositions of solute atom clusters in surveillance materials from four nuclear power plants were compared. • The balance of Mn-Ni-Si in solute clusters in a BWR material is similar to that of the Γ 2 phase. • Relative Si concentrations in solute clusters in PWR materials are higher than the Si concentration in the G phase. This suggests the contribution of radiation-induced segregation of Si. • The "catalyst effect" of Cu precipitates on the gathering of Mn and Ni may assist in Mn-Ni-Si cluster formation. In a highly irradiated reactor pressure vessel (RPV), solute Mn, Ni, and Si (MNS) atoms gather to form nanometer-sized microstructures, generally called MNS clusters. MNS often gather with Cu-rich precipitates, which can form in RPVs following lower dose irradiation. In this study, surveillance specimens provided from four nuclear power plants in Japan were analyzed using three-dimensional atom probe tomography (APT), and the nature of the solute enrichment was carefully compared. When analyzing the chemical composition of each cluster, a clear negative correlation was found between Si and Cu in all materials, but conversely, Mn was likely present in clusters with a high Cu concentration. Moreover, in a boiling water reactor material with high Cu, the ratio of MNS was shown to be similar to that of the Γ 2 phase [Mn (Ni, Si) 2 ]. In pressurized water reactor materials with medium and low Cu, however, Ni and Si enrichment was demonstrated to be higher than the ratio of the expected intermetallic compounds; such as a Γ 2 phase and a G phase [Mn 6 Ni 16 Si 7 ]. Ni and Mn atoms, once enriched in a copper-rich region, may elute out, and form an intermetallic compound with Si atoms within the vicinity. Particularly in highly irradiated RPV materials, such a structure may tend to be decorated by irradiation-induced lattice defects with Si segregation. Image, graphical abstract [ABSTRACT FROM AUTHOR]

Nuclear reactor lifetimes may be limited by nano-scale Cu-Mn-Ni-Si precipitates (CRPs and MNSPs) that form under neutron irradiation (NI) of pressure vessel (RPV) steels, resulting in hardening and ductile to brittle transition temperature increases (embrittlement). Physical models of embrittlement must be based on characterization of precipitation as a function of the combination of metallurgical and irradiation variables. Here we focus on rapid and convenient charged particle irradiations (CPI) to both: a) compare to precipitates formed in NI; and, b) use CPI to efficiently explore precipitation in steels with a very wide range of compositions. Atom probe tomography (APT) comparisons show NI and CPI for similar bulk steel solute contents yield nearly the same precipitate compositions, albeit with some differences in their number density, size and volume fraction (f) dose (dpa) dependence. However, the overall precipitate evolutions are very similar. Advanced high Ni (>3 wt%) RPV steels, with superior unirradiated properties, were also investigated at high CPI dpa. For typical Mn contents, MNSPs have Ni 16 Mn 6 Si 7 or Ni 3 Mn 2 Si phase type compositions, with f values that are close to the equilibrium phase separated values. However, in steels with very low Mn and high Ni, Ni 2-3 Si silicide phase type precipitate compositions are observed; and when Ni is low, the precipitate compositions are close to the MnSi phase field. Low Mn significantly reduces, but does not eliminate, precipitation in high Ni steels. A comparison of dispersed barrier model predictions with measured hardening data suggests that the Ni-Si dominated precipitates are weaker dislocation obstacles than the G phase type MNSPs. • Nuclear reactor life times are limited by nano precipitates formed under irradiation. • Ion irradiations provide a rapid & affordable way to gain insight into precipitation. • Atom Probe data estimates hardening and embrittlement at lower service dose. • Advanced high Ni steels, with superior unirradiated properties, were investigated. • Simple thermodynamic models are able to predict volume fraction for alloys. [ABSTRACT FROM AUTHOR]