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).     

Evaluation of stainless steel pipe cracking: Causes and fixes

This paper discusses (1) studies of impurity effects on susceptibility to intergranular stress corrosion cracking (IGSCC), (2) intergranular crack growth rate measurements, (3) finite-element studies of the residual stresses produced by induction heating stress improvement (IHSI) and the addition of weld overlays to flawed piping, (4) leak-before-break analyses of piping with 360° part-through cracks, and (5) parametric studies on the effect of through-wall residual stresses on intergranular crack growth behavior in large diameter piping weldments. The studies on the effect of impurities on IGSCC of Type 304 stainless steel show a strong synergistic interaction between dissolved oxygen and impurity concentration of the water. Low carbon stainless steel (Type 316NG) appear resistant to IGSCC even in impurity environments. However, they can become susceptible to transgranular SCC with low levels of sulfate or chloride present in the environment. The finite-element calculations show that IHSI and the weld overlay produce compressive residual stresses on the inner surface, and that the stresses at the crack tip remain compressive under design loads at least for shallow cracks.     

Materials aspects of BWR plant life extension

Considerable experience with plant equipment performance in nuclear power stations has indicated that the principal factors limiting the life of BWRs and PWRs are materials related. Specifically, for LWRs it is known that these materials issues generally include parameters related to stress corrosion cracking, corrosion fatigue, wear and radiation embrittlement. Not only do these parameters affect and limit the actual useful design life of plant components but also affect the plant's operating availability. In all these cases, the elimination or control of one or more of these critical parameters should improve the plants availability and significantly extend the useful service life.In the present paper, research performed to address the intergranular stress corrosion cracking (IGSCC) area is described. Specific emphasis is placed on Type 304 stainless steel which has suffered IGSCC in piping in the heat-affected-zone (HAZs) adjacent to the welds in the BWR primary system. Research has developed and qualified a number of techniques which address the three necessary conditions for IGSCC in BWRs: (1) sensitized microstructure, i.e., chromium depletion at the grain boundaries during welding; (2) over yield tensile stress; and (3) oxygenated (200 ppb) high temperature (288Another potential life-limiting IGSCC phenomenon for certain components, irradiation assisted stress corrosion cracking (IASCC) of stainless steel exposed to a high neutron flux, is also discussed. Unlike the IGSCC, IASCC results in intergranular cracking of annealed material at low stress. Fortunately, preliminary research has indicated that some of the techniques utilized for IGSCC control in piping as well as new controlled impurity level stainless steel alloys may reduce the future potential IASCC concern to an insignificant level.     

Probability of crack-induced failure in BWR recirculation piping

The Lawrence Livermore National Laboratory (LLNL) has estimated the probability of double-ended guillotine break (DEGB) in the reactor coolant piping of Mark I boiling water reactor (BWR) plants. Two causes of pipe break are considered: crack growth at welded joints and the seismically-induced failure of component supports. For the former a probabilistic fracture mechanics model is used, for the latter a probabilistic support reliability model. This paper describes a probabilistic model developed to account for effects of intergranular stress corrosion cracking (IGSCC). The IGSCC model, based on experimental and field data compiled from several sources, correlates times to crack initiation and crack growth rates for Types 304 and 316NG stainless steel against material-specific ‘damage parameters’ which consilidate the separate effects of coolant environment (temperature, dissolved oxygen content, level of impurities), stress (including residual stress), and degree of sensitization. Application of this model to actual BWR recirculation piping shows that IGSCC clearly dominates the probability of failure in 304SS piping, mainly due to cracks that initiate within a few years after plant operation has begun. Replacing Type 304 piping with 316NG reduces failure probabilities by several orders of magnitude.     

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.     

Surface melting technique of small diameter stainless steel pipe by means of yttrium aluminium garnet laser

A new method of surface melting by using a high power yttrium aluminium garnet laser was developed. This method is applicable to a long distance and narrow space, because of the good accessibility of the laser beam through optical fibre.A desensitization of sensitized type 304 stainless steel pipe was demonstrated by using this technique. A melted layer of thickness approximately 200 μm had a very finite solidification structure, which contained approximately 1.5% δ-ferrite. The average chemical composition of this layer was almost the same as that of type 304 stainless steel, and a band of 300 μm thickness under the melted layer underwent solution heat treatment (SHT).As a result of such surface melting, the melted layer exhibited superior resistance to intergranular stress corrosion cracking (IGSCC). Since the SHT layer is highly resistant to IGSCC generally, it may be possible to improve the IGSCC resistance of base metal to a comparatively deep extent (500 μm from the surface) by this technique.     

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.     

Tensile behaviour of 9Cr-1Mo tempered martensitic steels irradiated up to 20 dpa in a spallation environment

Tensile specimens of 9Cr-1Mo (EM10) and mod 9Cr-1Mo (T91) martensitic steels in the normalized and tempered metallurgical conditions were irradiated with high energy protons and neutrons up to 20 dpa at average temperatures up to about 360 °C. Tensile tests were carried out at room temperature and 250 °C and a few samples were tested at 350 °C. The fracture surfaces of selected specimens were characterized by Scanning Electron Microscopy (SEM). While all irradiated specimens displayed at room temperature considerable hardening and loss of ductility, those irradiated to doses above approximately 16 dpa exhibited a fully brittle behaviour and the SEM observations revealed significant amounts of intergranular fracture. Helium accumulation, up to about 0.18 at.% in the specimens irradiated to 20 dpa, is believed to be one of the main factors which triggered the brittle behaviour and intergranular fracture mode. One EM10 and one T91 specimen irradiated to 20 dpa were annealed at 700 °C for 1 h following irradiation and subsequently tensile tested. In both cases, a remarkable recovery of ductility and strain-hardening capacity was observed after annealing, while the strength remained significantly above that of the unirradiated material.     

The Influence of Dissolved Hydrogen on the Corrosion of Type 304 Stainless Steels Treated with Inhibitive Chemicals in High Temperature Pure Water

In order to assess the influence of dissolved hydrogen on the intergranular stress corrosion cracking (IGSCC) characteristics of Type 304 stainless steels treated with inhibitive chemicals, electrochemical corrosion potential (ECP) measurements and slow strain rate tensile (SSRT) tests were conducted in high temperature pure water. A number of thermally sensitized specimens were prepared and then pre-oxidized in a 288°C pure water environment with the presence of 300ppb dissolved oxygen for 360h. Most of the specimens were then separately treated with various inhibitive chemicals including powdered zirconium oxide (ZrO₂), powdered titanium oxide (TiO₂), and zirconyl nitrate [ZrO(NO₃)₂] via hydrothermal deposition at 150°C. Test environments with a dissolved oxygen concentration of 300ppb and various dissolved hydrogen concentrations at 288°C were created. Test results showed that the ECPs of the treated specimens were lower than that of the untreated one no matter what the dissolved hydrogen concentration was. In addition, IGSCC was observed on all specimens (treated or untreated) in all tested environments. However, the untreated specimen exhibited lower elongation, shorter failure time, and more secondary cracks on the lateral surfaces. It was therefore suggested that inhibitive chemicals such as ZrO₂, TiO₂, and ZrO(NO₂)₂ did provide a certain degree of enhancement in improving the mechanical behavior of the treated specimens and in prolonging IGSCC initiation times.     

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.     

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.     

Intergranular stress corrosion cracking susceptibility of sensitized type 304 steel in 561 K pure water under γ-ray irradiation

Intergranular stress corrosion cracking (IGSCC) of sensitized type 304 stainless steel has been investigated in 561 K water under γ-ray irradiation at a flux of 2.6 × 10³ C kg⁻¹ h⁻¹ by slow-strain-rate tensile tests. The IGSCC susceptibility was enhanced by γ-ray irradiation in water containing 8 ppm dissolved oxygen (DO). The DO dependence of the IGSCC susceptibility was observed in the water under γ-irradiation. Although slight IGSCC susceptibility was observed even in deaerated water (less than 1 ppb DO) under γ-ray irradiation, the susceptibility was completely suppressed by injection of hydrogen into the water. The enhancement of IGSCC susceptibility seems to be related to the formation of H₂O₂ in high temperature water by radiolysis under γ-ray irradiation and the H₂O₂ formation rate is markedly decreased by hydrogen injection.     

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.     

压水堆压力壳堆焊不锈钢的动电位再活化行为与晶间应力腐蚀破裂敏感性

用动电位再活化方法研究了压水堆压力壳堆焊不锈钢衬里材料的活化与再活化行为以及晶界形貌,用高温水恒变形和慢应变速率应力腐蚀破裂试验比较了晶间应力腐蚀破裂的敏感程应。结果表明再活化行为与晶间应力腐蚀破裂敏感性之间有一致关系。动电位再活化有可能作为核动力装置中不锈钢焊接件晶间应力腐蚀破裂敏感程度的无损检验方法。     

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.     

Segregation effects on the corrosion behaviour of a phosphorus-doped AISI type 304L stainless steel

The effect of grain boundary (GB) segregation on intergranular stress corrosion cracking (IGSCC) in hot water environments at 150°C and 250°C was studied in a P-doped AISI type 304L stainless steel. The extent of segregation was measured by an exposure test in boiling 5 N HNO₃ + 8g/L K₂Cr₂O₇ solution as well as by a potentiostatic etch test at +1325 mV (SHE) in 5 N H₂SO₄ solution. Although GB segregation was detected in all the aged specimens, IGSCC was shown by only the specimens aged for 550°C/1000 h. The results suggest that it is the GB chromium depletion, rather than the segregation of phosphorus at the GBs, that controls IGSCC of stainless steels in the hot water environments studied.     

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.     

Proton irradiation study of GFR candidate ceramics

This work investigated the microstructural response of SiC, ZrC and ZrN irradiated with 2.6 MeV protons at 800 °C to a fluence of 2.75 × 10¹⁹ protons/cm², corresponding to 0.71-1.8 displacement per atom (dpa), depending on the material. The change of lattice constant evaluated using HOLZ patterns is not observed. In comparison to Kr ion irradiation at 800 °C to 10 dpa from the previous studies, the proton irradiated ZrC and ZrN at 1.8 dpa show less irradiation damage to the lattice structure. The proton irradiated ZrC exhibits faulted loops which are not observed in the Kr ion irradiated sample. ZrN shows the least microstructural change from proton irradiation. The microstructure of 6H-SiC irradiated to 0.71 dpa consists of black dot defects at high density.     

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.     

Influence of post irradiation annealing on the mechanical properties and defect structure of AISI 304 steel

The effect of post irradiation annealing on the mechanical properties and the radiation induced defect structure was investigated on stainless steel, of type AISI 304, that was irradiated up to 24 dpa in the decommissioned Chooz A reactor. The material was investigated both in the as-irradiated state as well as after post irradiation annealing. In the as-irradiated specimen the typical radiation induced defects were found as well as γ′-precipitates (Ni₃Si). Annealing at 400 °C had almost no effect on the radiation induced defects, but annealing at 500 °C resulted in the immediate unfaulting of the Frank loops. As to the mechanical properties, annealing at 400 °C did not strongly affect the yield strength and the ductility of the material, although the fraction of intergranular fracture during slow strain rate tensile tests under pressurised water reactor conditions, was significantly reduced. Annealing at 500 °C did reduce the yield strength and restored substantially the ductility and the strain hardening capability of the material. The microstructure investigated by transmission electron microscopy correlates to the mechanical test results. It was found that the observed defect changes after post irradiation annealing provide a reasonable explanation for the observed changes of the mechanical properties.