Stress corrosion cracking of low-alloy, reactor-pressure-vessel steels in oxygenated, high-temperature water

The stress corrosion cracking (SCC) behaviour of low-alloy, reactor-pressure-vessel (RPV) steels in oxygenated, high-temperature water and its relevance to boiling water reactor (BWR) power operation, in particular its possible effect on both RPV structural integrity and safety, has been a subject of controversial discussions for many years. This paper presents the results of an experimental study on crack growth through SCC in three, nuclear-grade, steels (SA 533 B Cl.1, SA 508 Cl.2, 20 MnMoNi 5 5) under simulated, BWR water-chemistry conditions. Modern, high-temperature water loops, on-line crack-growth monitoring and fractographic analysis in the scanning electron microscope were used to quantify the cracking response of pre-cracked, fracture-mechanics specimens under a variety of mechanical and environmental conditions. Corrosion-assisted crack advance could be only initiated by active loading within the environment. If SCC crack advance at constant load was observed, initiation of crack growth had always occurred while increasing the load to the intended value for subsequent, static-load testing. During the constant load period the rate of SCC crack advance rapidly decayed and crack arrest occurred within a period of <100 h (for tests with K_I60 MPa m^1/2). Supplementary experiments with slowly increasing loading revealed that the initiation of crack growth, and the extent of further crack advance, are crucially dependent upon maintaining both a positive crack-tip strain rate and a high sulphur-anion activity in the crack-tip environment. It is concluded that there is no sustainable susceptibility to SCC crack growth under purely static loading, as long as small-scale-yielding conditions prevail at the crack-tip and the water chemistry is maintained within current BWR/NWC operational practice (EPRI water chemistry guidelines). However, sustained, fast SCC (with respect to operational time scales) cannot be excluded for faulted water-chemistry conditions (>EPRI action level 3) and/or for highly stressed specimens either loaded near to K_IJ or with a high degree of plasticity in the remaining ligament.     

高温水中氯离子对316L不锈钢应力腐蚀裂纹扩展速率的影响

本文采用直流电压降(DCPD)方法,使用恒K(K=27.5 MPa·m1/2)加载方式,在核电厂高温高压水环境中研究了氯离子对316L不锈钢的应力腐蚀裂纹扩展速率的影响。实验结果表明:在高温除氧水中,氯离子会加快316L不锈钢的应力腐蚀裂纹扩展速率,且当水中存在溶解氧时,氯离子对应力腐蚀裂纹扩展速率的影响更明显。     

The Efficiency of Noble Metals in Reducing the Corrosion Potential in the Primary Coolant Circuits of Boiling Water Reactors Operating under Hydrogen Water Chemistry Operation

In order to promote the effectiveness of hydrogen water chemistry (HWC) and to achieve a more effective reduction in electrochemical corrosion potential (ECP) in the primary coolant circuits of boiling water reactors (BWRs), the technology of noble metal chemical addition (NMCA) was brought into practice about 10 years ago. NMCA aims at enhancing the oxidation of hydrogen on metal surfaces and lowering the concentrations of the oxidants (oxygen and hydrogen peroxide) via recombination with hydrogen on the catalyzed surfaces, and therefore reducing the corrosion potentials of the structural alloys in a BWR primary heat transport circuit. Previous research indicates that the effectiveness of NMCA in combination with a low HWC might be evaluated via model predictions of the hydrogen-to-oxidant molar ratio (M_H/O) in the primary coolant circuit. If the M_H/O at a certain location is calculated to be greater than 2, it is justified that the NMCA would be effective in reducing the ECP to much below the critical potential for Intergranular Stress Corrosion Cracking (IGSCC), E_IGSCC, of --0.23 V_SHE. However, this statement is true only when the recombination efficiency of hydrogen with oxygen and/or hydrogen peroxide at the location of interest is 100%. Otherwise, significant amounts of oxidants may still be present, even with a stoichiometric M_H/O of greater than 2. With the aid of a computer model DEMACE, we explored the impact of incomplete recombination and found that the ECP might be reduced under given circumstances, but not to a great extent, and might remain well above E_IGSCC. Accordingly, considerable caution should be exercised upon using the M_H/O as a sole indicator for evaluating the effectiveness of NMCA with low HWC as a means of mitigating IGSCC in a BWR. An important finding of this study is that it is necessary to quantify the recombination efficiencies of hydrogen with oxygen and/or hydrogen peroxide on the noble metal treated stainless steel surfaces in order to qualify the use of M_H/O as an indicator for NMCA effectiveness in the primary coolant circuit of a BWR.     

Hydrazine and Hydrogen Co-injection to Mitigate Stress Corrosion Cracking of Structural Materials in Boiling Water Reactors (IV)

A calculation model has been developed in order to evaluate effectiveness of hydrazine and hydrogen co-injection (HHC) into reactor water for mitigation of intergranular stress corrosion cracking of structural materials used in boiling water reactors (BWRs). The HHC uses the strong reducing power of hydrazine radical, which is produced in the downcomer region under irradiation by γ-rays and neutrons. Some reactions and their reaction rate constants were determined based on experiments which were carried out in aerated water, hydrogenated water, and deaerated water. The calculated results were in good agreement with experimental data by a factor of two. The model was applied to a BWR and it was found that the HHC cut oxygen and hydrogen peroxide amounts dissolved in reactor water more effectively than hydrogen water chemistry alone. Thus, the required amount of hydrogen for hydrazine injection was much lower than that for hydrogen water chemistry. Consequently, electrochemical corrosion potential of structural materials could be lowered below–0:1V vs. SHE without any increase of MS line dose rate, which has been a limitation of the conventional hydrogen water chemistry. The HHC was predicted to decrease crack growth rate of structural materials by a factor of 10.     

Intergranular stress corrosion cracking initiation model of austenite stainless steels used in BWRs for optimized water chemistry control

A calculation model on intergranular stress corrosion cracking (IGSCC) initiation time of materials used in boiling water reactors (BWRs) has been developed to evaluate effectiveness of water chemistry control for mitigation of the IGSCC. The model was composed of four terms which determine passive film break time: (1) a chemical term based on electrochemical corrosion potential (ECP) and impurity concentration; (2) a mechanical term based on strain rate; (3) a material term based on sensitization; and (4) an irradiation term based on acceleration of corrosion by γ-rays and neutron irradiation. The contribution of the chemical term in the passive film break was calculated based on a deterministic local corrosion model. Then, the local corrosion model was modified by adding mechanical acceleration of the film rupture to treat the IGSCC phenomenon. The model could reproduce the behavioral tendency seen in the slow strain rate tensile test on high carbon contents with sensitization heat treatment (for example, 620°C × 24 h). Under BWR operating conditions, IGSCC initiation time could be extended by a factor of 5 by lowering the electric conductivity from 1.0 to 0.06 μS/cm. If the ECP was reduced below the critical potential by a mitigation method, the IGSCC initiation time was predicted to become sufficiently long for pipings and components.     

Hydrogen and Hydrazine Co-injection to Mitigate Stress Corrosion Cracking of Structural Materials in Boiling Water Reactors, (VI) The Effect of Ammonia on Intergranular Stress Corrosion Cracking

Hydrogen and hydrazine co-injection into a boiling water reactor was considered as a new mitigation method of stress corrosion cracking (SCC). In this method, some amount of ammonia will be formed by the decomposition of hydrazine. The effect of ammonia on SCC susceptibility was studied over a wide range of electrochemical corrosion potentials (ECPs) in 288_C water by conducting slow strain rate technique SCC experiments (SSRTs). ECP was changed from _0:6V versus the standard hydrogen electrode (V(SHE)) to 0.1 V(SHE) by controlling dissolved oxygen concentration. Ammonia concentration was controlled to have values of 100 and 530 ppb. Similarly, sulfuric acid was injected to confirm the difference in the effect of injected chemical compounds on SCC susceptibility. The intergranular stress corrosion cracking (IGSCC) fraction, which was used as the index of SCC susceptibility, decreased with decreasing ECP for the case of no chemical injection. Sulfuric acid enhanced the IGSCC fraction. These data were in good agreement with literature data. On the other hand, ammonia at less than 530 ppb did not affect IGSCC fraction. It is expected that 51–280 ppb hydrazine and 0–53 ppb hydrogen will be injected into reactor water to mitigate SCC in BWRs. In the bottom region of the reactor pressure vessel, ECP and ammonia concentration will be _0:1 V(SHE) and 15–60 ppb, respectively. Under these conditions, ammonia did not affect SCC susceptibility. So SCC susceptibility will be mitigated by decreasing the ECP using hydrazine and hydrogen co-injection.     

Characterization of the stress corrosion cracking behavior of thermally sensitized 20Cr-25Ni stainless steel in a simulated cooling pond environment

Niobium stabilized 20Cr-25Ni stainless steel is used for nuclear fuel cladding in the UK's fleet of advanced gas cooled reactors (AGRs). The cladding can have chromium-depleted grain boundaries as a consequence of irradiation in a reactor core, rendering a small proportion of cladding susceptible to intergranular stress corrosion cracking in cooling pond waters after removal from the reactor. In this work, thermal sensitization was used to simulate chromium depletion and the sensitized material was assessed for its susceptibility to pitting corrosion and stress corrosion cracking using slow strain rate testing (SSRT). Elevated chloride concentrations were used to accelerate corrosion initiation and propagation. In 10 ppm chloride and 80 °C, the pitting potential was at potentials between +375 mV and +400 mV (SCE). SSRT appeared to lower the pitting potential, with intergranular corrosion and intergranular stress corrosion cracks observed to nucleate at potentials of +200 mV (SCE).     

Environmentally-assisted cracking behaviour in the transition region of an Alloy182/SA 508 Cl.2 dissimilar metal weld joint in simulated boiling water reactor normal water chemistry environment

The stress corrosion cracking (SCC) and corrosion fatigue behaviour perpendicular and parallel to the fusion line in the transition region between the Alloy 182 Nickel-base weld metal and the adjacent SA 508 Cl.2 low-alloy reactor pressure vessel (RPV) steel of a simulated dissimilar metal weld joint was investigated under boiling water reactor normal water chemistry conditions. A special emphasis was placed to the question whether a fast growing interdendritic SCC crack in the highly susceptible Alloy 182 weld metal can easily cross the fusion line and significantly propagate into the adjacent low-alloy RPV steel. Cessation of interdendritic SCC crack growth was observed in high-purity or sulphate-containing oxygenated water under constant or periodical partial unloading conditions for those parts of the crack front, which reached the fusion line. In chloride containing water, on the other hand, the interdendritic SCC crack in the Alloy 182 weld metal very easily crossed the fusion line and further propagated with a very high rate as a transgranular crack into the heat-affected zone and base metal of the adjacent low-alloy steel. The observed SCC cracking behaviour at the interface correlates excellently with the field experience of such dissimilar metal weld joints, where SCC cracking was usually confined to the Alloy 182 weld metal.     

Effect of corrosion potential on the corrosion fatigue crack growth behaviour of low-alloy steels in high-temperature water

The low-frequency corrosion fatigue (CF) crack growth behaviour of different low-alloy reactor pressure vessel steels was characterized under simulated boiling water reactor conditions by cyclic fatigue tests with pre-cracked fracture mechanics specimens. The experiments were performed in the temperature range of 240-288 °C with different loading parameters at different electrochemical corrosion potentials (ECPs). Modern high-temperature water loops, on-line crack growth monitoring (DCPD) and fractographical analysis by SEM were used to quantify the cracking response. In this paper the effect of ECP on the CF crack growth behaviour is discussed and compared with the crack growth model of General Electric (GE). The ECP mainly affected the transition from fast (‘high-sulphur’) to slow (‘low-sulphur’) CF crack growth, which appeared as critical frequencies ν_crit = f(ΔK, R, ECP) and ΔK-thresholds ΔK_EAC = f(ν, R, ECP) in the cycle-based form and as a critical air fatigue crack growth rate da/dt_Air,crit in the time-domain form. The critical crack growth rates, frequencies, and ΔK_EAC-thresholds were shifted to lower values with increasing ECP. The CF crack growth rates of all materials were conservatively covered by the ‘high-sulphur’ CF line of the GE-model for all investigated temperatures and frequencies. Under most system conditions, the model seems to reasonably well predict the experimentally observed parameter trends. Only under highly oxidizing conditions (ECP ? 0 mV_SHE) and slow strain rates/low loading frequencies the GE-model does not conservatively cover the experimentally gathered crack growth rate data. Based on the GE-model and the observed cracking behaviour a simple time-domain superposition-model could be used to develop improved reference CF crack growth curves for codes.