TEM and PAS study of neutron irradiated VVER-type RPV steels

Conventional transmission electron microscopy and positron lifetime and Doppler broadening positron annihilation spectroscopy techniques have been used to investigate the radiation-induced microstructural changes in surveillance specimens of VVER-type reactor pressure vessel (RPV) steels, and RPV steels irradiated in the research reactor. Defects visible in transmission electron microscopy consist of black dots, dislocation loops and precipitates concentrated along the dislocation substructure. Their size and density depend on the neutron flux and fluence. The parallel set of thermally aged specimens, specimens recovery annealed after irradiation and specimens irradiated in a lower neutron flux was investigated too. No defects discernible in transmission electron microscopy were found after accelerated irradiation in the research reactor. In addition to visible defects, the small-volume vacancy clusters were identified by positron annihilation spectroscopy.     

Microstructural examination of reactor pressure vessel steels by positron annihilation point of view

This paper presents a comparison of commercially used German and Russian reactor pressure vessel steels from the positron annihilation spectroscopy (PAS) point of view, having in mind knowledge obtained also from other techniques from the last decades.The second generations of Russian RPV steels seems to be fully comparable with German steels and their quality enables prolongation of NPP operating lifetime over projected 40 years. The embrittlement of CrMoV steel is very low due to the dynamic recovery of radiation-induced defects at reactor operating temperatures.     

Positron annihilation study and computational modeling of defect production in neutron-irradiated reactor pressure vessel steels

Positron annihilation spectroscopy (PAS) and a computer simulation were used to investigate a defect production in reactor pressure vessel (RPV) steels irradiated by neutrons. The RPV steels were irradiated at 250 °C in a high-flux advanced neutron application reactor. The PAS results showed that mainly single vacancies were created to a great extent as a result of a neutron irradiation. Formation of vacancies in the irradiated materials was also confirmed by a coincidence Doppler broadening measurement. For estimating the concentration of the point defects in the RPV steels, we applied computer simulation methods, including molecular dynamics (MD) simulation and point defect kinetics model calculation. MD simulations of displacement cascades in pure Fe were performed with a 4.7 keV primary knock-on atom to obtain the parameters related to displacement cascades. Then, we employed the point defect kinetics model to calculate the concentration of the point defects. By combining the positron trapping rate from the PAS measurement and the calculated vacancy concentrations, the trapping coefficient for the vacancies in the RPV steels was determined, which was about 0.97 × 10¹⁵ s⁻¹. The application of two techniques, PAS and computer simulation, provided complementary information on radiation-induced defect production.     

Study of PRIMAVERA steel samples by a positron annihilation spectroscopy technique

In the present article, a positron annihilation spectroscopy investigation of VVER-440/230 weld materials is discussed. Important characteristics of metals such as Fermi energy, concentration of electrons in the conduction band, size and concentration of defects were experimentally determined for three model materials with higher level of copper (0.16 wt.%) and phosphorus (0.027-0.038 wt.%). The impact of neutron irradiation and subsequent annealing on crystal lattice parameters was investigated. The experiments with the angular correlation of positron annihilation radiation (ACAR) complement the published positron annihilation spectroscopy (PAS) studies of the radiation treated VVER materials as well as previous experiments on PRIMAVERA materials. The availability of the experimental reactor to prepare strong ⁶⁴Cu positron sources provided for unique experimental conditions, such as good resolution of spectra (0.4 mrad) and reasonable short time of measurement (36 h). The present paper aims to contribute to further understanding of RPV (reactor pressure vessel) steels behaviour under irradiation conditions as well as annealing recovery procedures, which have already been applied at several VVER NPP units in Europe.     

The micro structural study of 15Kh2MFA and 15Kh2NMFA reactor pressure vessel steels using positron-annihilation spectroscopy, mössbauer spectroscopy and transmission electron microscopy

The micro structure of the non-irradiated low-alloyed steels (15Kh2MFA and 15Kh2NMFA) was studied using different spectroscopic methods as the positron annihilation lifetime and Doppler broadening techniques, the Mössbauer spectroscopy, and the Integral low-energy electron Mössbauer spectroscopy as well as the Transmission electron microscopy. Differences in the microstructural parameters of these types of RPV steels are well detectable using all methods. It was confirmed that the heat-affected zone of these steels is the most sensitive place for thermal embrittlement in the reactor. Positron-annihilation lifetime measurements on the successive annealed specimens (XTA, YTA), which simulated the heat-affected zone, showed the rapid increase in the vacancy-type defects formation in the temperature region 525–600°C. Therefore these specimens were studied using Transmission electron microscopy in more detail.     

Positron annihilation study of neutron irradiated model alloys and of a reactor pressure vessel steel

The hardening and embrittlement of reactor pressure vessel steels are of great concern in the actual nuclear power plant life assessment. This embrittlement is caused by irradiation-induced damage, and positron annihilation spectroscopy has been shown to be a suitable method for analysing most of these defects. In this paper, this technique (both positron annihilation lifetime spectroscopy and coincidence Doppler broadening) has been used to investigate neutron irradiated model alloys, with increasing chemical complexity and a reactor pressure vessel steel. It is found that the clustering of copper takes place at the very early stages of irradiation using coincidence Doppler broadening, when this element is present in the alloy. On the other hand, considerations based on positron annihilation spectroscopy analyses suggest that the main objects causing hardening are most probably self-interstitial clusters decorated with manganese in Cu-free alloys. In low-Cu reactor pressure vessel steels and in (Fe, Mn, Ni, Cu) alloys, the main effect is still due to Cu-rich precipitates at low doses, but the role of manganese-related features becomes pre-dominant at high doses.     

Considerations about irradiation-induced precipitates in Soviet type reactor pressure vessel steels

Small angle neutron scattering (SANS) results on neutron irradiated Fe-Cu are presented and discussed and compared to positron annihilation results. An extended discussion is presented regarding a comparison of earlier positron annihilation and SANS measurements and their interpretation for different Soviet type reactor pressure vessel steels. It is suggested that the irradiation-induced precipitates contain vacancies and might be metal carbides.     

Positron annihilation and nano-indentation analysis of irradiation effects on the microstructure and hardening of A508-3 steels used in Chinese HTGR

The irradiation and annealing behavior of Chinese A508-3 reactor pressure vessel (RPV) steel (0.04 wt% Cu) after 3 MeV Fe-ion irradiation ranging from 0.1 to 20 dpa at room temperature (called RTRPV) and high temperature (250?°C, called HTRPV) was studied by positron annihilation Doppler broadening (PADB) spectroscopy and nano-indentation hardness. PADB showed that the density of vacancy-type defects was higher for low-temperature irradiations. The higher hardness was found after high-temperature irradiation because of the formation of solute clusters during irradiation. Positron annihilation measurements revealed the interaction and clustering of vacancies with solute clusters which were introduced by Fe-ion irradiation. For both RTRPVs and HTRPVs, the positron defect parameter and positron diffusion length showed the recovery of the irradiation-induced defects. Total recovery was observed after annealing at 450 °C.     

Positron affinity for precipitates in reactor pressure vessel steels

The sensitivity of positron annihilation spectroscopy to irradiation-induced precipitates in reactor pressure vessel steels is discussed in the light of recent positron affinity and lifetime calculations. Carbide and nitride precipitates are found to trap positrons only if they contain metal vacancies. Copper precipitates are also attractive to positrons but they are probably detected through annihilation at the precipitate-matrix interface. These findings are related to available experimental data.     

Study of radiation-induced degradation of RPV steels and model alloys by positron annihilation and Mössbauer spectroscopy

The influence of different microstructural processes on the degradation due to radiation embrittlement has studied by positron annihilation and Mössbauer spectroscopy. The materials studied consisted of WWER-440 base (15Kh2MFA) and weld (10KhMFT) RPV steels which were neutron-irradiated at fluence levels of 0.78 × 10²⁴ m⁻², 1.47 × 10²⁴ m⁻² and 2.54 × 10²⁴ m⁻²; WWER-1000 base (15Kh2NMFAA) and weld (12Kh2N2MAA) irradiated at a fluence level 1.12 × 10²⁴ m⁻²; three different model alloys implanted with protons at two dose levels (up to 0.026 dpa), finally the base metal of WWER-1000 (15Kh2NMFAA) was thermally treated with the intention to simulate the P-segregation process. It has been shown possible to correlate the values of parameters obtained by such techniques and data of mechanical testing (ductile-to-brittle transition temperature and upper shelf energy).     

低铜合金反应堆压力容器钢辐照脆化预测评估模型

反应堆压力容器（RPV）材料辐照脆化预测评估对保证核反应堆安全运行、预防重大灾难性事故的发生具有重要意义。通过深入了解RPV材料辐照损伤机理和分析国外较为成熟的RPV辐照脆化预测模型,揭示了国外有关压力容器辐照脆化预测模型对低铜RPV辐照脆化预测的不足及其原因。在此基础上,发展和建立了适用于低铜RPV辐照脆化趋势的预测模型CIAE-2009。利用辐照性能数据对CIAE-2009模型进行了验证。结果表明,CIAE-2009对低铜含量RPV材料辐照脆化趋势预测具有较高的准确性和可靠性。     

The properties of WWER-1000 type materials obtained on the basis of a surveillance program

The surveillance test results of the reactor pressure vessels (RPV) of three Russian WWER-1000 units designated unit-1, -2 and -3 are given and the embrittlement rates compared to those predicted by the Russian Regulatory Guide. Dependence of the radiation behavior of WWER-1000 type RPV steels on metallurgical variables and the damage dose is considered. The trend curves for the steels under investigation are proposed.     

Neutron induced damage in reactor pressure vessel steel: An X-ray absorption fine structure study

The radiation damage produced in reactor pressure vessel (RPV) steels during neutron irradiation is a long-standing problem of considerable practical interest. In this study, an extended X-ray absorption fine structure (EXAFS) spectroscopy has been applied at Cu, Ni and Mn K-edges to systematically investigate neutron induced radiation damage to the metal-site bcc structure of RPV steels, irradiated with neutrons in the fluence range from 0.85 to 5.0 × 10¹⁹ cm⁻². An overall similarity of Cu, Ni and Mn atomic environment in the iron matrix is observed. The radial distribution functions (RDFs), derived from EXAFS data have been found to evolve continuously as a function of neutron fluence describing the atomic-scale structural modifications in RPVs by neutron irradiations. From the pristine data, long range order beyond the first- and second-shell is apparent in the RDF spectra. In the irradiated specimens, all near-neighbour peaks are greatly reduced in magnitude, typical of damaged material. Prolonged annealing leads annihilation of point defects to give rise to an increase in the coordination numbers of near-neighbour atomic shells approaching values close to that of non-irradiated material, but does not suppress the formation of nano-sized Cu and/or Ni-rich-precipitates. Total amount of radiation damage under a given irradiation condition has been determined. The average structural parameters estimated from the EXAFS data are presented and discussed.     

Precipitation in long term thermally aged high copper,high nickel model RPV steel welds

Copper precipitation in irradiated RPV steels is well known to have a deleterious effect on mechanical properties. In order to understand the contribution of thermal ageing to RPV embrittlement a high copper (0.44 at.%), high nickel (1.6 at.%) model RPV weld was thermally aged at 365 °C for times up to 90,000 h. Atom Probe Tomography (APT) was employed to study the precipitation of solutes, primarily copper, nickel, manganese and silicon within the matrix and at grain boundaries. As expected, a high number density of 1–4 nm radius copper rich precipitates was observed. Nickel, manganese and silicon were found at the precipitate matrix interface, and the evolution of the composition of this interface was investigated with ageing time. Segregation of solutes to grain boundaries particularly P, Mo and C was observed, along with enrichments of Ni, Mn and Si, which have not previously been reported in long term thermally aged RPV steels. Preliminary results on several large (>10 nm) Ni–Mn–Si rich features observed at a grain boundary are also presented. These features are rich in Ni (∼30%), Mn (∼15%) and Si (∼12%) and are virtually copper-free.     

Effect of the Cu-rich precipitates on thermal conductivity of RPV model steel

Cu-rich precipitates are the important influence factors for the irradiation embrittlement of the reactor pressure vessel model steels. The microstructure of the Cu-rich precipitates could be revealed by mechanical and magnetic properties. In this article, the effect of the Cu-rich precipitates on thermal conductivity was studied. The reactor pressure vessel (RPV) model steels were aged for different time at 500°C. The results show that the thermal conductivity of RPV model steel is first decreased and then increased during the experiment, with a minimum value at 48.33 ± 0.21 W·m^?1·K^?1 after being aged for 200 h. The changing thermal conductivity is decided by the synergistic effect of the following three factors: (1) the crystal structure transformation of Cu-rich precipitates, (2) the orientation relationship between the matrix and Cu-rich precipitates, (3) the content of Cu atoms in the matrix.     

Comparison of microstructural features of radiation embrittlement of VVER-440 and VVER-1000 reactor pressure vessel steels

Comparative microstructural studies of both surveillance specimens and reactor pressure vessel (RPV) materials of VVER-440 and VVER-1000 light water reactor systems have been carried out, following irradiation to different fast neutron fluences and of the heat treatment for extended periods at the operating temperatures. It is shown that there are several microstructural features in the radiation embrittlement of VVER-1000 steels compared to VVER-440 RPV steels that can cause changes in the contributions of different radiation embrittlement mechanisms for VVER-1000 steel.     

Influence of different chemical elements on irradiation-induced hardening embrittlement of RPV steels

Fe–Cu binary alloys are often used to mimic the behaviour of reactor pressure vessel steels. Their study allows identifying some of the defects responsible for irradiation-induced hardening. But recently the influence of manganese and nickel in low-Cu steels has been found to be important as well. In contrast with existing models found in the literature, which predict that hardening saturates after a certain dose, Fe alloys containing nickel and manganese irradiated in a material test reactor (BR2) show a continuous increase of hardening, up to doses equivalent to about 40 years of operation. Considerations based on positron annihilation spectroscopy analyses suggest that the main objects causing hardening in Cu-free alloys are most probably self-interstitial clusters decorated with manganese. In low-Cu reactor pressure vessel steels and in Fe–CuMnNi alloys, the main effect is still due to Cu-rich precipitates at low doses, but the role of manganese-related features becomes predominant at higher doses.     

Effects of hydrazine addition and N2 atmosphere on the corrosion of reactor vessel steels in diluted seawater under gamma-rays irradiation

Seawater was injected into the reactor cores in the Fukushima Daiichi Nuclear Power Station. Corrosion of primary containment vessel (PCV) steel and reactor pressure vessel (RPV) steel is considered to progress until the molten fuel debris is removed. To evaluate durability of the PCV and RPV steels, corrosion tests were conducted in diluted seawater at 50 °C under gamma-rays irradiation of dose rates of 4.4 and 0.2 kGy/h. To evaluate the effect of hydrazine (N₂H₄) as an oxygen scavenger under gamma-rays irradiation, 10 and 100 mg/L N₂H₄ were added to the diluted seawater. Without addition of N₂H₄, weight loss in the PCV and RPV steels irradiated with the 0.2 kGy/h dose rate was comparable with those without irradiation and weight loss in the vessel steels irradiated with the 4.4 kGy/h dose rate was higher than those without irradiation. Under irradiation, weight loss in the PCV and RPV steels in diluted seawater containing N₂H₄ was comparable with that in diluted seawater without N₂H₄. When gas phase in the flask was replaced with N₂, weight loss in the PCV and RPV steels, and O₂ and H₂O₂ concentrations in the diluted seawater decreased.     

Doppler-broadening measurements of positron annihilation with high-momentum electrons in pure elements

Doppler-broadening measurements of the electron–positron annihilation line in twenty-seven single-element samples are presented. A coincidence technique has been used to suppress the background and to evidence the contribution of positron annihilation with core electrons. Systematic dependences on the atomic number of the target material are found in ratio curves obtained dividing the measured spectra by the spectrum of a reference material. The positron lifetime technique has been used to detect the presence of positron traps in all the samples. The change in the high-momentum part of the annihilation line due to positron trapping is illustrated. The measured data are in a good qualitative agreement with recent theoretical calculation and constitute the most complete measurement series, up to now, to establish a future data-base for positron annihilation spectroscopy.