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.     

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 aspects of neutron embrittlement of reactor pressure vessel steels - A view from positron annihilation spectroscopy

A comprehensive review of positron annihilation studies of Cr---Mo---V reactor pressure vessel (RPV) steels (Soviet type 15Kh2MFA) in unirradiated and neutron irradiated states is presented. The influences of lattice defects, impurity atom distribution, irradiation temperature, flux and fluence of fast neutrons on positron annihilation parameters, especially during isochronal annealing, are discussed in terms of the positron trapping model. In contrast to the literature, where irradiation-enhanced Cu precipitates and solute coated microvoids are thought to be major defect types responsible for strengthening and hence embrittling of RPV steels, we suggest irradiation-induced precipitates, i.e. probably carbides, to play this role. Possibilities to probe this model are suggested.     

Combined effects of neutron irradiation and hydrogen absorption on mechanical properties of pure iron

To obtain a fundamental knowledge of the combined effect of neutron-irradiation and hydrogen, mechanical properties and the fracture mode were studied for pure neutron irradiated iron, followed by hydrogen charging. The effect of interaction between neutron irradiation and hydrogen absorption for a pure iron could be clarified. Under the hydrogen charged condition, the ductility is higher in the neutron irradiated specimen than in the unirradiated. The cause could be sought in hydrogen trap sites of the iron and the fracture mode. As a result of interaction between many irradiation defects and hydrogen atoms, the fracture mode of a hydrogen charged specimen after irradiation, is a mixed mode of quasi-cleavage crack and dimple pattern. That of a hydrogen charged unirradiated specimen is predominantly intergranular cracking.     

Monitoring of a radiation recovery in neutron-irradiated RPV steel by using the magnetic methods

The effects of a neutron irradiation on the magnetic parameters of a reactor pressure vessel (RPV) steel with different microstructures, partially due to a difference in the steel refining processes were investigated. The samples were irradiated in a research reactor with a fluence of 4.5 × 10¹⁹ n/cm² at 288 °C. The measurement of the Barkhausen noise (BN) was conducted to explore the relationship between the microstructural state and the domain wall motion. The BN profiles of the unirradiated samples showed a consistent change with the microstructure (grain size, carbide morphology, lath width), but the neutron-irradiated sample did not show a consistent change with microstructural state. The radiation hardening and recovery characteristics have been investigated by using the Vickers hardness method, and the relationship between the BN and the microhardness is obtained for four different steels. The linear relationship between mechanical and magnetic properties can be used as a nondestructive evaluation for radiation damage.     

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.     

Embrittlement of irradiated ferritic/martensitic steels in the absence of irradiation hardening

Irradiation damage caused by neutron irradiation below 425-450 °C of 9-12% Cr ferritic/martensitic steels produces microstructural defects that cause an increase in yield stress. This irradiation hardening causes embrittlement observed in a Charpy impact test as an increase in the ductile-brittle transition temperature. Little or no change in strength is observed in steels irradiated above 425-450 °C. Therefore, the general conclusion has been that no embrittlement occurs above these temperatures. In a recent study, significant embrittlement was observed in F82H steel irradiated at 500 °C to 5 and 20 dpa without any change in strength. Earlier studies on several conventional steels also showed embrittlement effects above the irradiation-hardening temperature regime. Indications are that this embrittlement is caused by irradiation-accelerated or irradiation-induced precipitation. Observations of embrittlement in the absence of irradiation hardening that were previously reported in the literature have been examined and analyzed with computational thermodynamics calculations to illuminate and understand the effect.     

Synthesis of atom probe experiments on irradiation-induced solute segregation in French ferritic pressure vessel steels

Microstructural changes due to neutron irradiation cause an evolution of the mechanical properties of reactor pressure vessels (RPV) steels. This paper aims at identifying and characterising the microstructural changes which have been found to be responsible in part for the observed embrittlement. This intensive work relies principally on an atom probe (AP) study of a low Cu-level French RPV steel (Chooz A). This material has been irradiated in in-service conditions for 0–16 years in the frame of the surveillance program. Under this aging condition, solute clustering occurs (Cu, Ni, Mn, Si, P, …). In order to identify the role of copper, experiments were also carried out on Fe–Cu model alloys submitted to different types of irradiations (neutron, electron, ion). Cu-cluster nucleation appears to be directly related to the presence of displacement cascades during neutron (ion) irradiation. The operating basic physical process is not clearly identified yet. A recovery of the mechanical properties of the irradiated material can be achieved by annealing treatments (20 h at 450°C in the case of the RPV steel under study, following microhardness measurements). It has been shown that the corresponding microstructural evolution was a rapid dissolution of the high number density of irradiation-induced solute clusters and the precipitation of a very low number density of Cu-rich particles.     

Atom probe characterization of nano-scaled features in irradiated ODS Eurofer steel

Our previous investigations of unirradiated ODS Eurofer by tomographic atom probe (TAP) revealed numerous nano-scaled features (nanoclusters) enriched in vanadium, yttrium and oxygen. In this work the effect of neutron irradiation on nanostructure behaviour of ODS Eurofer (9%-CrWVTa) was investigated. The irradiation was performed in the research reactor BOR-60 (Dimitrovgrad, Russia) where materials were irradiated at 330 °С to 32 dpa. TAP studies were performed on the needles prepared from parts of broken Charpy specimens. For all specimens except one, which was tested at 500 °C, the Charpy tests were performed at temperatures not exceeding the irradiation temperature. A high number density 2-4 × 10²⁴ m⁻³ of ultra fine 1-3 nm diameter nanoclusters enriched in yttrium, oxygen, manganese and chromium was observed in the irradiated state. The composition of detected clusters differs from that for unirradiated ODS Eurofer. It was observed in this work that after neutron irradiation vanadium atoms had left the clusters, moving from the core into solid solution. The concentrations of yttrium and oxygen in the matrix, as it was detected, increase several times under irradiation. In the samples tested at 500 °C both the number density of clusters and the yttrium concentration in the matrix decrease by a factor of two.     

Characterization of neutron-irradiated ferritic model alloys and a RPV steel from combined APT, SANS, TEM and PAS analyses

Understanding the behavior of reactor pressure vessel (RPV) steels under irradiation is a mandatory task that has to be elucidated in order to be able to operate safely a nuclear power plant or to extend its lifetime. To build up predictive tools, a substantial experimental data base is needed at the nanometre scale to extract quantitative information on neutron-irradiated materials and to validate the theoretical models. To reach this experimental goal, ferritic model alloys and French RPV steel were neutron irradiated in a test reactor at an irradiation flux of 9 × 10¹⁷ nm⁻² s, doses from 0.18 to 1.3 × 10²⁴ nm⁻² and 300 °C. The main goal of this paper is to report the characterization of the radiation-induced microstructural change in the materials by using the state-of-the-art of characterization techniques available in Europe at the nanometre scale. Possibilities, limitations and complementarities of the techniques to each other are highlighted.     

Copper precipitate hardening of irradiated RPV materials and implications on the superposition law and re-irradiation kinetics

Copper is known to play an important role in irradiation hardening and embrittlement of RPV materials. This is particularly true for old vessels. Indeed, while the Cu-content is low (<0.1%) in modern RPV materials, it often exceeded 0.15% in older vessels. Within the RADAMO irradiation program aiming to provide a reliable and extensive (chemistry, heat treatments, fluence, irradiation temperature) databank to investigate irradiation-induced hardening of RPV materials, we irradiated steels and welds with copper contents ranging from 0.06 to 0.31% at 300 and 265 °C. Experiments on re-irradiation after annealing were also performed to investigate the re-irradiation kinetics. It is found that copper plays a role in the very early stage of irradiation but saturates quite rapidly. The peak hardening is in agreement with the ageing data. Considering a two-component model, the linear superposition law provides the most appropriate one to rationalize the experimental data including re-irradiation path.     

The effect of prior cold-work on the deformation behaviour of neutron irradiated AISI 304 austenitic stainless steel

Cold-work is intentionally employed to increase the yield strength of austenitic stainless steels and also occurs during fabrication processes, but it has also been associated with greater incidence of stress corrosion cracking. This study examined the effect of up to 3.85 dpa neutron irradiation on the deformation behaviour and microstructures of 30% cold-worked AISI 304 material tensile tested at 300 °C. While the deformation behaviour of 0.07 dpa material was similar to non-irradiated material tested at the same temperature, its stress-strain curve was shifted upwards by about 200 MPa. Materials irradiated to over 2 dpa hardened some 400-500 MPa, but showed limited strain hardening capacity, exhibiting precipitous softening with further straining beyond the yield point. The observed behaviour is most likely a consequence of planar deformation products serving as strengtheners to the unirradiated bulk on the one hand, while promoting strain localization on the other, behaviour exacerbated by the subsequent neutron irradiation.     

The terminal solid solubility of hydrogen in irradiated Zircaloy-2 and microscopic modeling of hydride behavior

Differential scanning calorimetry (DSC) has been applied to elucidate the terminal solid solubility (TSS) of hydrogen in Zircaloy-2 cladding tubes and spacer bands irradiated in commercial BWRs. While recovery of irradiation defects during the first heating stage of as-irradiated specimens made the DSC peak of hydride dissolution dull or broader, no significant difference was detected in the TSS between unirradiated and irradiated Zircaloy-2, irrespective of fast neutron fluence. The effect of post-irradiation annealing on TSS was also examined. The results suggest almost no interaction between irradiation defects and dissolved hydrogen or hydrides at temperatures around 300 °C. Using the present TSS data and reported hydrogen- and hydride-related properties, a microscopic analysis code HYMAC for analyzing hydride behavior in cladding tube with textured grains was constructed. Stress-induced preferential precipitation and dissolution of hydrides were reproduced by adopting a TSS sub-model in which the solubilities decrease in proportion to stress normal to the habit plane in grains and to grain faces. Analyzed results by the code were consistent with typical experimental results of hydride behavior.     

Recent applications of small-angle neutron scattering in the characterization of irradiated steels for nuclear technologies

Small-angle neutron scattering (SANS) is a powerful experimental tool to investigate the microstructural evolution under irradiation in steels for fission and future fusion reactor systems. We present recent SANS results concerning the modelling of helium bubble growth in F82H-mod. steel implanted with α-particles and the dose dependence of microstructural radiation damage in Eurofer-97 steel for fusion reactors irradiated at 250 °C. The discussion of these results is focussed on the quality of the metallurgical information obtained by such SANS measurements and consequently on their usefulness also for engineering and design purposes.     

Neutron irradiation studies on low density pan fiber based carbon/carbon composites

Carbon has been extensively used in nuclear reactors and there has been growing interest to develop carbon-based materials for high-temperature nuclear and fusion reactors. Carbon-carbon composite materials as against conventional graphite material are now being looked into as the promising materials for the high temperature reactor due their ability to have high thermal conductivity and high thermal resistance. Research on the development of such materials and their irradiation stability studies are scant. In the present investigations carbon-carbon composite has been developed using polyacrylonitrile (PAN) fiber. Two samples denoted as Sample-1 and Sample-2 have been prepared by impregnation using phenolic resin at pressure of 30 bar for time duration 10 h and 20 h respectively, and they have been irradiated by neutrons. The samples were irradiated in a flux of 10¹² n/cm²/s at temperature of 40 °C. The fluence was 2.52 × 10¹⁶ n/cm². These samples have been characterized by XRD and Raman spectroscopy before and after neutron irradiation. DSC studies have also been carried out to quantify the stored energy release behavior due to irradiation. The XRD analysis of the irradiated and unirradiated samples indicates that the irradiated samples show the tendency to get ordered structure, which was inferred from the Raman spectroscopy. The stored energy with respect to the fluence level was obtained from the DSC. The stored energy from these carbon composites is very less compared to irradiated graphite under ambient conditions.     

Tensile properties of the ferritic martensitic steel F82H after irradiation in a spallation target

Ferritic/Martensitic (FM) steel, F82H, was irradiated up to a displacement dose of 20 dpa (displacement per atom) at temperatures ranging from 510 to 1075 K in the third experiment of the SINQ Target Irradiation Program (STIP-III). Tensile testing was performed at 295 and 723 K. The tensile test results demonstrate that not only the specimen irradiated in the low temperature regime (<∼675 K) but also those irradiated at elevated temperatures ?710 K show significant hardening effect. After annealing at 873 K for 2 h the irradiated specimens still persist great hardening, which is usually not observed in FM steels after neutron irradiation at low temperatures and annealing at 873 K. The hardening observed in the specimens is believed to be due to the high-density He-bubbles formed in the specimens.     

Irradiation embrittlement characterization of the EUROFER 97 material

The paper summarizes original results of irradiation embrittlement study of EUROFER 97 material that has been proposed as one candidate of structural materials for future fusion energy systems and GEN IV.Test specimens were manufactured from base metal as well as from weld metal and tested in initial unirradiated condition and also after neutron irradiation.Irradiation embrittlement was characterized by testing of toughness properties at transition temperature region - static fracture toughness and dynamic fracture toughness properties, all in sub-size three-point bend specimens (27 × 4 × 3 mm³). Testing and evaluation was performed in accordance with ASTM and ESIS standards, fracture toughness K_JC and K_Jd data were also evaluated with the “Master curve” approach. Moreover, J-R dependencies were determined and analyzed.The paper compares unirradiated and irradiated properties as well as changes in transition temperature shifts of these material parameters. Discussion about the correlation between static and dynamic properties is also given.Results from irradiation of EUROFER 97 show that this steel - base metal as well as weld metal - is suitable as a structural material for reactor pressure vessels of innovative nuclear systems - fusion energy systems and GEN IV. Transition temperature shifts after neutron irradiation by 2.5 dpa dose show a good agreement in the case of EUROFER 97 base material for both static and dynamic fracture toughness tests. From the results it can be concluded that there is a low sensitivity of weld metal to neutron irradiation embrittlement in comparison with EUROFER 97 base metal.     

Monitoring the embrittlement of reactor pressure vessel steels by using the Seebeck coefficient

The degree of embrittlement of the reactor pressure vessel (RPV) limits the lifetime of nuclear power plants. Therefore, neutron irradiation-induced embrittlement of RPV steels demands accurate monitoring. Current federal legislation requires a surveillance program in which specimens are placed inside the RPV for several years before their fracture toughness is determined by destructive Charpy impact testing. Measuring the changes in the thermoelectric properties of the material due to irradiation, is an alternative and non-destructive method for the diagnostics of material embrittlement. In this paper, the measurement of the Seebeck coefficient () of several Charpy specimens, made from two different grades of 22 NiMoCr 37 low-alloy steels, irradiated by neutrons with energies greater than 1 MeV, and fluencies ranging from 0 up to 4.5 × 10¹⁹ neutrons per cm², are presented. Within this range, it was observed that increased by ≈500 nV/°C and a linear dependency was noted between and the temperature shift ΔT_41 J of the Charpy energy vs. temperature curve, which is a measure for the embrittlement. We conclude that the change of the Seebeck coefficient has the potential for non-destructive monitoring of the neutron embrittlement of RPV steels if very precise measurements of the Seebeck coefficient are possible.     

Microstructural characteristics and embrittlement phenomena in neutron irradiated 309L stainless steel RPV clad

The effects of neutron irradiation on the microstructural features and mechanical properties of 309L stainless steel RPV clad were investigated using TEM, SEM, small tensile, microhardness and small punch (SP) tests. The neutron irradiations were performed at 290 °C up to the fluences of 5.1 × 10¹⁸ and 1.02 × 10¹⁹ n/cm² (>1 MeV) in Japan Materials Testing Reactor (JMTR). The microstructure of the clad before and after irradiation was composed of main part of fcc austenite, a few percent of bcc δ-ferrite and small amount of brittle σ phase. After irradiation, not only the yield stress and microhardness, but SP ductile to brittle transition temperature (SP-DBTT) were increased. However, the increase in SP-DBTT is almost saturated, independent of the neutron fluence. Based on the TEM observation, the origin of irradiation hardening was accounted for by the irradiation-produced defect clusters of invisible fine size (<1-2 nm), and the shift of SP-DBTT was primary due to the higher hardening and the preferential failure of δ-ferrite. The embrittlement of the clad was strongly affected by the initial microstructural factors, such as the amount of brittle σ phase, which caused a cracking even in an early stage of deformation.