Hydrogen water chemistry for BWRs: a status report on the EPRI development program

Many boiling water reactors (BWRs) have experienced extensive intergranular stress corrosion cracking (IGSCC) in their austenitic stainless steel reactor coolant system piping, resulting in serious adverse impacts on plant capacity factors, O&M costs, and personnel radiation exposures. A major research program to provide remedies for BWR pipe cracking was co-funded by EPRI, GE, and the BWR Owners Group for IGSCC Research between 1979 and 1988. Results from this program show that the likelihood of IGSCC depends on reactor water chemistry (particularly on the concentrations of ionic impurities and oxidizing radiolysis products) as well as on material condition and the level of tensile stress. Tests have demonstrated that the concentration of oxidizing radiolysis products in the recirculating reactor water of a BWR can be reduced substantially by injecting hydrogen into the feedwater. Recent plant data show that the use of hydrogen injection can reduce the rate of IGSCC to insignificant levels if the concentration of ionic impurities in the reactor water is kept sufficiently low. This approach to the control of BWR pipe cracking is called hydrogen water chemistry (HWC). This paper presents a review of the results of EPRI's HWC development program from 1980 to the present. In addition, plans for additional work to investigate the feasibility of adapting HWC to protect the BWR vessel and major internal components from potential stress corrosion cracking problems are summarized.     

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.     

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.     

Tensile and stress corrosion cracking properties of type 304 stainless steel irradiated to a very high dose

Certain safety-related core internal structural components of light water reactors, usually fabricated from Type 304 or 316 austenitic stainless steels (SSs), accumulate very high levels of irradiation damage (20–100 displacement per atom or dpa) by the end of life. Our databases and mechanistic understanding of the degradation of such highly irradiated components, however, are not well established. A key question is the nature of irradiation-assisted intergranular cracking at very high doses, i.e. is it purely mechanical failure or is it stress-corrosion cracking? In this work, hot-cell tests and microstructural characterization were performed on Type 304 SS from the hexagonal fuel can of the decommissioned EBR-II reactor after irradiation to ≈50 dpa at ≈370 °C. Slow-strain-rate tensile tests were conducted at 289 °C in air and in water at several levels of electrochemical potential (ECP), and microstructural characteristics were analyzed by scanning and transmission electron microscopies. The material deformed significantly by twinning and exhibited surprisingly high ductility in air, but was susceptible to severe intergranular stress corrosion cracking (IGSCC) at high ECP. Low levels of dissolved O and ECP were effective in suppressing the susceptibility of the heavily irradiated material to IGSCC, indicating that the stress corrosion process associated with irradiation-induced grain-boundary Cr depletion, rather than purely mechanical separation of grain boundaries, plays the dominant role. However, although IGSCC was suppressed, the material was susceptible to dislocation channeling at a low ECP, and this susceptibility led to a poor work-hardening capability and low ductility.     

Cracking in stabilized austenitic stainless steel piping of German boiling water reactors—characteristic features and root cause

Cracks have been found in the welds of piping systems made from stabilized austenitic stainless steels in German boiling water reactors (BWR). In the course of the intensive failure analysis metallographic examinations, microstructural investigations by electron microscopy, corrosion experiments and welding tests have been performed. The results show that cracking under the given medium conditions is due to intergranular stress corrosion cracking (IGSCC) in those parts of the heat affected zone (HAZ) which are overheated during welding and where solution of titanium carbides and subsequent precipitation of chromium carbides and depletion of chromium along the affected grain boundaries could occur.     

Age-related degradation of boiling water reactor vessel internals

Researchers at the Idaho National Engineering Laboratory performed an assessment of the aging of the reactor internals in boiling water reactors (BWRs), and identified the unresolved technical issues related to the degradation of these components. The overall life-limiting mechanism is intergranular stress corrosion cracking (IGSCC). Irradiation-assisted stress corrosion cracking, fatigue, and thermal aging embrittlement are other potential degradation mechanisms. Several failures in BWR internals have been caused by a combination of factors such as environment, high residual or preload stresses, and flow-induced vibration. The ASME Code Section XI in-service inspection requirements are insufficient for detecting aging-related degradation at many locations in reactor internals. Many of the potential locations for IGSCC or fatigue are not accessible for inspection.     

Experience and assessment of stress corrosion cracking in L-grade stainless steel BWR internals

The stress corrosion cracking (SCC) rate of reactor internals of boiling water reactors (BWR) continues to increase with on-line operating years. The recent occurrences of cracking in the weld heat affected zones of high carbon stainless steel core shrouds correlate with the years of operation and the water chemistry history. Recently, cracking has also been found in shrouds that were constructed of low carbon or stabilized stainless steels. While these steels are more resistant to intergranular stress corrosion cracking (IGSCC) in the as-fabricated condition, this field experience establishes that the conditions under which the materials will crack in core structures are attributable to the combined effects of high residual stresses, associated with the shroud construction, the presence of a more aggressive, oxidizing environment in the core and to microstructural changes in the material. These changes result from the manufacturing process as well as thermal exposure during operation. Studies of materials that have cracked in the field, as well as high temperature material studies in the laboratory, are being performed to understand the mechanisms. The use of highly oxidizing, high purity water environments is integral to reproducing the conditions for cracking. The status of the laboratory efforts to gain understanding and to verify the mechanisms are presented. Modeling of IGSCC is also a key tool used to understand the cracking behavior of the low carbon stainless steels. The PLEDGE (Plant Life Extension Diagnosis by GE) model is used to support the hypotheses that tie together the role of the different contributing elements: residual stress, core water chemistry and microstructural features. The crack growth modeling is also used to evaluate the benefits of different strategies to manage and mitigate cracking of reactor internals such as hydrogen water chemistry.     

Current understanding of radiation-induced degradation in light water reactor structural materials

Current phenomenological knowledge and understanding of mechanisms are reviewed for radiation embrittlement of reactor pressure vessel low alloy steels and irradiation assisted stress corrosion cracking of core internals of stainless steels. Accumulated test data of irradiated materials in light water reactors and microscopic analyses by using state-of-the-art techniques such as a three-dimensional atom probe and electron backscatter diffraction have significantly increased knowledge about microstructural features. Characteristics of solute clusters and deformation microstructures and their contributions to macroscopic material property changes have been clarified to a large extent, which provide keys to understand in the degradation mechanisms. However, there are still fundamental research issues that merit study for long-term operation of reactors that requires reliable quantitative prediction of radiation-induced degradation of component materials in low-dose rate high-dose conditions.     

SCC testing of pipe materials in BWR environment

A test loop has been installed in Ringhals 1 BWR, including facilities for Constant Elongation Rate Testing (CERT) and Electrochemical Potential (ECP) measurements in primary reactor water at reactor operation temperature. The loop is designed as to minimize transport time for reactor water from the reactor pressure vessel to the specimens being tested. Thus the testing environment is representative of the primary piping systems of BWRs, also with regard to short-lived constituents like hydrogen peroxide.The test program, which is in progress, has covered seven tests during start-up conditions or during power operation with presently current reactor water chemistry. In this presentation only CERT testing results on heavily sensitized austenitic chromium—nickel stainless steel are presented, although many other materials have been tested.Results show sensitized austenitic stainless steel is more prone to intergranular stress corrosion cracking (IGSCC) in actual than in simulated BWR environment and that start-up environment is chemically more aggressive than power operation environment. Reproducibility of the CERT technique as used is excellent.     

Corrosion of ZrO2 treated type 304 stainless steels in high temperature pure water with various amounts of hydrogen peroxide

As boiling water reactors (BWRs) age, intergranular stress corrosion cracking (IGSCC) of the structural materials in the reactor piping systems and vessel internals has become a major degradation problem. Several approaches to mitigating IGSCC in the structural components have been developed and investigated. Among them, the technique of inhibitive protective coatings is deemed the most promising one since it is expected to work even in the absence of the well-known hydrogen water chemistry technology.Following our earlier work on exploring the electrochemical characteristics of important oxidizing species on zirconium oxide (ZrO₂) treated Type 304 stainless steels (SSs), we targeted on the characteristics of hydrogen peroxide, which is another strongly oxidizing species in the reactor coolant other than oxygen, in this study. Tests were conducted to determine electrochemical parameters such as electrochemical corrosion potential (ECP), corrosion current density, exchange current density and Tafel constant of the reduction reaction of hydrogen peroxide on 304 SS specimens before and after the ZrO₂ treatment. The surface morphologies of the treated and untreated specimens were examined by scanning electron microscopy, energy dispersive X-ray spectroscopy, and laser Raman spectra. Furthermore, the corrosion mitigation efficiency of ZrO₂ treatment was evaluated by electrochemical polarization tests in simulated BWR environments. Test results showed that there were no significant differences in ECP between the untreated and ZrO₂ treated specimens in the test environments of various hydrogen peroxide concentrations. However, it was found via polarization analysis that the exchange current density of the reduction reaction on and the corrosion current density of the treated specimens were markedly lower than those on and of the untreated ones in the same environments. The ZrO₂ treatment was able to deter the reduction rate of hydrogen peroxide on the Type 304 SS surface.     

A review of irradiation effects on LWR core internal materials - IASCC susceptibility and crack growth rates of austenitic stainless steels

Austenitic stainless steels (SSs) are used extensively as structural alloys in the internal components of light water reactor (LWR) pressure vessels because of their relatively high strength, ductility, and fracture toughness. However, exposure to neutron irradiation for extended periods changes the microstructure (radiation hardening) and microchemistry (radiation-induced segregation) of these steels, and degrades their fracture properties. Irradiation-assisted stress corrosion cracking (IASCC) is another degradation process that affects LWR internal components exposed to neutron radiation. The existing data on irradiated austenitic SSs were reviewed to evaluate the effects of key parameters such as material composition, irradiation dose, and water chemistry on IASCC susceptibility and crack growth rates of these materials in LWR environments. The significance of microstructural and microchemistry changes in the material on IASCC susceptibility is also discussed. The results are used to determine (a) the threshold fluence for IASCC and (b) the disposition curves for cyclic and IASCC growth rates for irradiated SSs in LWR environments.     

Analysis of water radiolysis in relation to stress corrosion cracking of stainless steel at high temperatures - Effect of water radiolysis on limiting current densities of anodic and cathodic reactions under irradiation

Electrochemical corrosion potential (ECP) is an important measure for environmental factor in relation to stress corrosion cracking (SCC) of metal materials. In the case of SCC for in-core materials in nuclear reactors, radiolysis of coolant water decisively controls ECP of metal materials under irradiation. In the previous models for ECP evaluation of stainless steel, radiolysis of reactor water in bulk was considered to calculate the bulk concentrations of the radiolysis products. In this work, the radiolysis not only in bulk but also in the diffusion layer at the interface between stainless steel and bulk water was taken into account in the evaluation of ECP. The calculation results shows that the radiolysis in the diffusion layer give significant effects on the limiting current densities of the redox reactions of the radiolysis products, H₂O₂ and H₂, depending on dose rate, flow rate and water chemistry, and leads to the significant increase in the ECP values in some cases, especially in hydrogen water chemistry conditions.     

Electrochemical noise measurements of stainless steel in high temperature water

Corrosion in a high purity aqueous environment simulating a boiling water reactor (BWR) is addressed in this work. This condition necessitates autoclave experiments under high pressure and temperature.Long-term electrochemical noise measurements were explored as a mean to detect and monitor stress corrosion cracking phenomenon. An experimental set up, designed to insulate the working electrode from external interference, made possible to detect and monitor stress corrosion cracking in slow strain rate tests for sensitized and solution annealed 304 stainless steel at 288 °C. Time-series analysis showed variations in the signature of the current density series due to transgranular stress corrosion cracking (TGSCC) and intergranular stress corrosion cracking (IGSCC).     

Electrochemical Corrosion Potential Modeling in the Primary Heat Transport Circuit of the Chinshan Boiling Water Reactor under the Condition of Hydrogen Water Chemistry with Noble Metal Coating

The technique of noble metal treatment, such as noble metal coating (NMC) or noble metal chemical addition, accompanied by a low level hydrogen water chemistry, is being employed by a number of nuclear power plants around the world for mitigating intergranular stress corrosion cracking in the vessel internals of their boiling water reactors (BWRs). A computer model DEM ACE was expanded and employed to assess the effectiveness of NMC throughout the primary heat transport circuit (PHTC) of a BWR. The effectiveness of NMC was justified by the electrochemical corrosion potential (ECP) and crack growth rate (CGR) predictions. In calculating the ECP, enhancing factors for the exchange current densities of redox reactions available from recently published data, were employed. The Chinshan BWR was selected as a model reactor. According to the modeling results, it was found that the effectiveness of NMC in the PHTC of a BWR could vary from region to region at different feedwater hydrogen concentrations. For the selected BWR, NMC was predicted to be of little benefit when the feedwater hydrogen concentration reached 0.9 ppm or over. In particular, the NMC technique proved to be beneficial in reducing ECP and CGR along the PHTC even if the BWR was operated under normal water chemistry.     

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).     

Stress corrosion cracking susceptibility of steam generator tube materials in AVT (all volatile treatment) chemistry contaminated with lead

Alloy 600 steam generator tubing has shown a high susceptibility to stress corrosion degradation at the operation conditions of pressurized water reactors. Several contaminants, such as lead, have been postulated as being responsible for producing the secondary side stress corrosion cracking that has occurred mainly at the location where these contaminants can concentrate. An extensive experimental work has been carried out in order to better understand the effects of lead on the stress corrosion cracking susceptibility of steam generator tube materials, namely Alloys 600, 690 and 800. This paper presents the experimental work conducted with a view to determining the influence of lead oxide concentration in AVT (all volatile treatment) conditions on the stress corrosion resistance of nickel alloys used in the fabrication of steam generator tubing.     

In-Core SCC Growth Behavior of Type 304 Stainless Steel in BWR Simulated High-Temperature Water at JMTR

Irradiation-assisted stress corrosion cracking (IASCC) is one of the critical concerns when stainless steel components have been in service in light water reactors for a long period. In-core IASCC growth tests have been carried out using the compact tension-type specimens of type 304 stainless steel that had been pre-irradiated up to a neutron fluence level around 1 × 10²⁵ n/m² under a pure water simulated boiling water reactor (BWR) coolant condition at the Japan Materials Testing Reactor (JMTR). In order to investigate the effect of synergy of neutron/gamma radiation and stress/water environment on SCC growth rate, we performed ex-core IASCC tests on irradiated specimens at several dissolved oxygen contents under the same electrochemical potential condition. In this paper, results of the in-core SCC growth tests are discussed and compared with the results obtained by ex-core tests from a viewpoint of the synergistic effects on IASCC. From results of in-core and ex-core tests using pre-irradiated specimens, the effect of synergy of neutron/gamma radiation and stress/water environment on SCC growth rate was considered to be small, because the in-core data under the same ECP condition were similar to the ex-core data under the DO = 32 ppm condition.     

Stress corrosion cracking of low-alloy reactor pressure vessel steels under boiling water reactor conditions

The stress corrosion cracking (SCC) behaviour of different reactor pressure vessel (RPV) steels and weld filler/heat-affected zone materials was characterized under simulated boiling water reactor (BWR) normal water (NWC) and hydrogen water chemistry (HWC) conditions by periodical partial unloading, constant and ripple load tests with pre-cracked fracture mechanics specimens. The experiments were performed in oxygenated or hydrogenated high-purity or sulphate/chloride containing water at temperatures from 150 to 288 °C. In good agreement with field experience, these investigations revealed a very low susceptibility to SCC crack growth and small crack growth rates (<0.6 mm/year) under most BWR/NWC and material conditions. Critical water chemistry, loading and material conditions, which can result in sustained and fast SCC well above the ‘BWRVIP-60 SCC disposition lines’ were identified, but many of them generally appeared atypical for current optimized BWR power operation practice or modern RPVs. Application of HWC always resulted in a significant reduction of SCC crack growth rates by more than one order of magnitude under these critical system conditions and growth rates dropped well below the ‘BWRVIP-60 SCC disposition lines’.     

Modeling the effects of nuclear environments on crevice corrosion of pure nickel by coupling of phase and polarization behavior

As from long-term operating experience the high purity primary water cycle of light water nuclear reactors may exhibit excursions from the recommended water chemistry leading to potentially favorite conditions for stress corrosion cracking (SCC) which may be initiated and its propagation controlled by local pitting and crevice corrosion. Deterministic modeling of local corrosion including incubation times for crevice corrosion should therefore provide a basis for lifetime predictions of components, which have been subjected to sporadic intermediate water chemistry fluctuations. Based on previous work for room temperature (RT), the chloride-induced crevice corrosion at 288 °C of pure nickel as an important base element in respective high alloyed nuclear materials is modeled by coupling anodic polarization with the precipitation of nickel oxide and nickel chloride calculated from the water–hydrogen–nickel chloride heterogeneous phase equilibrium diagram. The surface corrosion potentials are fixed by bulk levels of hydrogen and oxygen contents as well as pH simulating hydrogen treatment of irradiation subjected cooling water for the reduction of corrosion potentials and mitigation of SCC at operating temperature 288 °C in Boiling Water Reactors (BWRs). Assuming chemical equilibrium conditions during the selected time steps in a relevant component crevice the calculated change of the crevice solution composition is quantitatively shown to initiate crevice corrosion by the breakdown of the passive nickel oxide layer followed by the formation of non-passive nickel chloride and the subsequent acidification of the crevice solution. The effects of corrosion potentials, bulk levels of pH and chlorides, are investigated. As a result, the reduction of corrosion potentials and increase in bulk pH provide significant increases in the passive layer breakdown times and acidification times inside the crevice. Depending on bulk pH and corrosion potentials the reduction of bulk chlorides down to recommended levels in BWRs retards crevice corrosion significantly. For a standard 100,000 h time for crevice acidification to locally less than pH = 0 the respective chloride–pH domain is evaluated. Such diagrams may be related to respective effects on stress corrosion cracking and its mitigation by hydrogen water chemistry (HWC).     

Characterization of crud deposited on fuel rods under HWC environment in Kuosheng Nuclear Power Plant

Under normal water chemistry conditions, the oxygen and hydrogen peroxide produced by water radiolysis in the coolant of boiling water reactors(BWRs) can lead to intergranular stress corrosion cracking in the constituent materials of plant components. This fact has led to the wide-scale adoption of hydrogen water chemistry(HWC) in the nuclear industry to counteract these effects.This study seeks to characterize the metallic composition and the surface properties of the constituent materials of plant components in order to determine their effects on the accumulation of chalk river unidentified deposits(crud) on fuel rods in the BWR Unit-1 of the Kuosheng Nuclear Power Plant in Taiwan. Inductively coupled plasma-atomic emission spectroscopy was used to calculate the concentrations of surface crud and gamma spectrometry was used to determine the radioactivity of the corrosion products, as well as their axial distribution across the surface of the fuel rods. X-ray diffraction analysis and scanning electron microscopy/energy-dispersive X-ray spectroscopy were used to identify the crystalline phase and morphology of the crud as irregular shapes and flakes. The amount of crud deposited during the fourth fuel cycle exceeded that of the third fuel cycle due to extended burn-up time. Our analytical results indicate that the implementation of HWC had no significant effect on the characteristics of subsequent crud.