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Corrosion and Materials Degradation under Irradiation: From Understanding to Mitigation…
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Corrosion and Materials Degradation under Irradiation: From Understanding to Mitigation…

A special issue of Corrosion and Materials Degradation (ISSN 2624-5558).

Deadline for manuscript submissions: closed (31 July 2022) | Viewed by 22645

Special Issue Editor

Prof. Dr. Bernard Normand

E-Mail Website
Guest Editor
INSA Lyon, University of Lyon, MATEIS Laboratory, 7 av. Jean Capelle, F-69 621 Villeurbanne Cedex, Lyon, France
Interests: corrosion science; coatings; electrochemistry; tribocorrosion

Special Issue Information

Dear Colleagues,

You are invited to submit papers presenting your scientific and technological contributions concerning one of the biggest materials’ issue for nuclear plant structural integrity assessment and life extension.

Due to its complexity, corrosion is a fascinating scientific discipline. The economic stakes involved are enormous. Each Awareness Corrosion Day on 24 April, proposed by the World Corrosion Organization (WCO), is there to remind us of this. It concerns all areas of human activities. Considering the field of nuclear energy, we must also bear in mind the safety of people and infrastructure. This shows how crucial the involvement of corrosionists in the nuclear industry is. In fact, it has never been more crucial at a time when the energy transition makes it necessary to extend the operating life of power plants until the level of renewable energy necessary for humanity’s better living has been brought into service.

Today, the most operational decarbonized energy on the planet remains nuclear energy, whatever one may say.

Thus, it is natural that a journal such as Corrosion and Degradation of Materials should devote a Special Issue dedicated to highlighting the complexity of understanding, mastering and developing new knowledge in the field of corrosion under irradiation and the means to control it. The specificity of this mode of degradation does not consist in considering a specific corrosion mode only, but in considering a systemic approach which consists in identifying the synergy effects between the different damage factors. It is therefore not a question of characterizing the maintenance of the structural properties of a material or understanding the type of corrosion involved, but of quantifying the aggravating factor that contributes to the outburst of the degradation phenomenon exacerbated by irradiation.

In this Special Issue, the most committed specialists in the field have agreed to share their experience with us by illustrating with their work all the advances on the various points of the subject. Thus, this Special Issue will start with a paper detailing the effect of simultaneous irradiation and corrosion across several material/coolant systems proposed by Gary Was et al. (University of Michigan-USA). Damien Féron et al. (CEA-France) will develop the effects of irradiation on changes in solution chemistry, linked to the effects of radiolysis (to be confirmed). Digby D. Macdonald et al. (University of California-USA) will prolong the presentation of the effect of radiolysis on the passivity. Tetsuo Shoji et al. (Tohoku University-Japan) will consider the role of hydrogen on the oxidation of metal. Passive materials are widely used in the nuclear field; however, the behaviour of steels under gamma-ray irradiation in the nuclear field should not be underestimated. This topic will be discussed by Yutaka Watanabe et al. (Tohoku University-Japan). Beyond the work to understand the mechanisms of damage under irradiation, Tom Devine et al. (University of California-USA) will present their original work on how to inhibit the incorporation of irradiation product into passive film by adding aqueous zinc ions to PWR water. Because considering irradiation corrosion studies without addressing the issue of waste management would make this Special Issue an unfinished job, Fraser King et al. (Integrity Corrosion Consulting Ltd.-Canada) will develop the issue of radiation effects on nuclear waste canister materials.

You are invited to complete the list of these subjects. Many topics also have to be developed in term of methodology, ballistic effect of irradiations, IASCC, strategy of prevention or monitoring, etc. Thank you for letting us discover your recent work.

Prof. Dr. Bernard Normand
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Corrosion and Materials Degradation is an international peer-reviewed open access quarterly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1000 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

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Published Papers (6 papers)

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Research

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36 pages, 10268 KiB  
Article
Investigation via Electron Microscopy and Electrochemical Impedance Spectroscopy of the Effect of Aqueous Zinc Ions on Passivity and the Surface Films of Alloy 600 in PWR PW at 320 °C
by Yifan Jiang, Karen C. Bustillo and Thomas M. Devine
Corros. Mater. Degrad. 2023, 4(1), 54-89; https://doi.org/10.3390/cmd4010005 - 19 Jan 2023
Viewed by 2329
Abstract
Aqueous zinc ions lower the corrosion rate of Alloy 600, which helps lower the radiation dose rate in pressurized water reactors (PWRs). The influence of zinc on the electrochemical behavior of Alloy 600 in PWR primary water (PW) at 320 °C was investigated [...] Read more.
Aqueous zinc ions lower the corrosion rate of Alloy 600, which helps lower the radiation dose rate in pressurized water reactors (PWRs). The influence of zinc on the electrochemical behavior of Alloy 600 in PWR primary water (PW) at 320 °C was investigated using a combination of electron microscopy and electrochemical impedance spectroscopy (EIS). Secondary electron microscopy (SEM) and scanning transmission electron microscopy (STEM)/energy-dispersive X-ray spectroscopy (EDS) indicated duplex surface films were formed on the Alloy 600 in PWR PW with and without 100 ppb of zinc. There was no effect of zinc on the chromium-rich inner layer (IL) (of Cr2O3 and/or CrOOH). Zinc had a significant effect on the outer layer (OL). In the absence of zinc, a highly porous OL formed that was mostly composed of nickel oxide whiskers. In the presence of zinc, a zinc-containing, denser OL of oxide was formed. The EIS data were acquired in laboratory simulated PWR PW at 320 °C with and without 100 ppb zinc. The spectra were measured at nine different values of potential that spanned a 500 mV-wide range. The EIS indicated there was no effect of zinc on the oxidation rate of metals at the alloy/IL interface nor on the transport of ions through the IL. Zinc lowered the corrosion rate because the dense OL inhibited the release of nickel ions from the IL into the solution. Full article
(This article belongs to the Special Issue Corrosion and Materials Degradation under Irradiation: From Understanding to Mitigation…)
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22 pages, 18482 KiB  
Article
Role of Hydrogen in Metal Oxidation—Implication to Irradiation Enhanced Corrosion of Ni-Based Alloys and Stainless Steels in High Temperature Water
by Zihao Wang and Tetsuo Shoji
Corros. Mater. Degrad. 2022, 3(2), 281-302; https://doi.org/10.3390/cmd3020017 - 19 Jun 2022
Cited by 5 | Viewed by 2768
Abstract
Hydrogen plays various roles in metals or at metal–environment interfaces. Well known effects on metals are hydrogen embrittlement, hydrogen enhanced local plasticity, hydrogen enhanced strain-induced vacancy, hydrogen accelerated oxidation, hydrogen-induced creep, and their synergy. In this study, the potential roles of hydrogen in [...] Read more.
Hydrogen plays various roles in metals or at metal–environment interfaces. Well known effects on metals are hydrogen embrittlement, hydrogen enhanced local plasticity, hydrogen enhanced strain-induced vacancy, hydrogen accelerated oxidation, hydrogen-induced creep, and their synergy. In this study, the potential roles of hydrogen in materials degradation are demonstrated and studied by two different tests. One is the high temperature oxidation of Ni-based alloy in various environments with hydrogen penetration, and the other is the effects of neutron flux/fluence on the oxidation kinetics and SCC of 316L and 316LN stainless steels, regarding a possible role of transmuted H from N. The results emphasize that the hydrogen either permeated into metals from surrounding environments, such as high temperature water or gaseous hydrogen, or generated in metals by nuclei transmutation, such as hydrogen transmuted from N atoms in metals, which can promote metal oxidation through multiple mechanisms. Apparently, the oxidation/corrosion phenomenon is a synergy of sub-mechanisms. For instance, dissolved hydrogen (DH) is usually believed to slow down the corrosion process for lowering the open circuit potential (OCP). However, H also facilitates the transport of the cations in oxide, thereby accelerating the corrosion process. In this bi-mechanism system, two different, contradictory mechanisms work and exist simultaneously. Therefore, whether the metallic materials are benefited or degraded by the H during its oxidation process depends on which sub-mechanism is dominant. Namely, hydrogen can play the role an oxidant in the metal and metal/oxide interface to pre-oxidize metal elements, such as Cr, Ni, and Fe, and possibly promote inward oxygen diffusion and the oxidation rate at the interface. Moreover, hydrogen may play a role as a reductant in oxides where existing oxides can be reduced. Then, the protective capability of oxides will be decreased to result in corrosion acceleration at the metal–oxide interface. These phenomena were observed in Ni-based alloy and possibly austenitic stainless steel containing N such as 316LN SS. This work demonstrates a part of the role of hydrogen on oxidation, and more extensive and systematic work is needed to delineate the role of hydrogen on oxidation with and without irradiation. Full article
(This article belongs to the Special Issue Corrosion and Materials Degradation under Irradiation: From Understanding to Mitigation…)
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26 pages, 15985 KiB  
Article
Baseline Examinations and Autoclave Tests of 65 and 100 dpa Flux Thimble Tube O-Ring Specimens
by Wade Karlsen, Aki Toivonen and Pål Efsing
Corros. Mater. Degrad. 2021, 2(2), 248-273; https://doi.org/10.3390/cmd2020014 - 25 May 2021
Cited by 3 | Viewed by 3511
Abstract
This paper describes the methods and results of analytical TEM examinations and autoclave testing of two highly-irradiated flux thimble tube materials harvested from a commercial pressurized water reactor. The materials are cold-worked 316L, and accumulated 65 dpa and 100 dpa of radiation dose. [...] Read more.
This paper describes the methods and results of analytical TEM examinations and autoclave testing of two highly-irradiated flux thimble tube materials harvested from a commercial pressurized water reactor. The materials are cold-worked 316L, and accumulated 65 dpa and 100 dpa of radiation dose. To set the baseline for a broader study, the materials were examined in the as-irradiated condition and tested as O-ring specimens at relatively high constant loads in simulated PWR water conditions. Tests were also conducted with elevated hydrogen. For a given load, more rapid cracking was associated with higher radiation dose, and with the elevated hydrogen. Full article
(This article belongs to the Special Issue Corrosion and Materials Degradation under Irradiation: From Understanding to Mitigation…)
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Review

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65 pages, 15719 KiB  
Review
A Critical Review of Radiolysis Issues in Water-Cooled Fission and Fusion Reactors: Part II, Prediction of Corrosion Damage in Operating Reactors
by Digby D. Macdonald and George R. Engelhardt
Corros. Mater. Degrad. 2022, 3(4), 694-758; https://doi.org/10.3390/cmd3040038 - 30 Nov 2022
Cited by 7 | Viewed by 3084
Abstract
The radiolysis of water is a significant cause of corrosion damage in the primary heat transport systems (PHTSs) of water-cooled, fission nuclear power reactors (BWRs, PWRs, and CANDUs) and is projected to be a significant factor in the evolution of corrosion damage in [...] Read more.
The radiolysis of water is a significant cause of corrosion damage in the primary heat transport systems (PHTSs) of water-cooled, fission nuclear power reactors (BWRs, PWRs, and CANDUs) and is projected to be a significant factor in the evolution of corrosion damage in future fusion reactors (e.g., the ITER that is currently under development). In Part I of this two-part series, we reviewed the proposed mechanisms for the radiolysis of water and demonstrate that radiolysis leads to the formation of a myriad of oxidizing and reducing species. In this Part II, we review the role that the radiolysis species play in establishing the electrochemical corrosion potential (ECP) and the development of corrosion damage due to intergranular stress corrosion cracking (IGSCC) in reactor PHTSs. We demonstrate, that the radiolytic oxidizing radiolysis products, such as O2, H2O2, HO2−, and OH, when in molar excess over reducing species (H2, H, and O22−), some of which (H2) are preferentially stripped from the coolant upon boiling in a BWR PHTS, for example, renders the coolant in many BWRs oxidizing, thereby shifting the ECP in the positive direction to a value that is more positive than the critical potential (Ecrit = −0.23 Vshe at 288 °C) for IGSCC in sensitized austenitic stainless steel (e.g., Type 304 SS). This has led to many IGSCC incidents in operating BWRs over the past five decades that has exacted a great cost on the plant operators and electricity consumers, alike. In the case of PWRs, the primary circuits are pressurized with hydrogen to give a hydrogen concentration of 10 to 50 cm3/kgH2O (0.89 to 4.46 ppm), such that no sustained boiling occurs, and the hydrogen suppresses the radiolysis of water, thereby inhibiting the formation of oxidizing radiolysis products from water. Thus, the ECP is dominated by the hydrogen electrode reaction (HER), although important deviations from the HER equilibrium potential may occur, particularly at low [H2]. In any event, the ECP is displaced to approximately −0.85 Vshe, which is below the critical potential for IGSCC in sensitized stainless steels but is also more negative than the critical potential for the hydrogen-induced cracking (HIC) of mill-annealed Alloy 600. This has led to extensive cracking of steam generator tubing and other components (e.g., control rod drive tubes, pressurizer components) in PWRs that has also exacted a high cost on operators and power consumers. Although the ITER has yet to operate, the proposed chemistry protocol for the coolant places it close to a BWR operating on Normal Water Chemistry (NWC) without boiling or, if hydrogen is added to the IBED-PHTS, close to a BWR on Hydrogen Water Chemistry (HWC). In the current ITER technology, the concentration of H2 in the IBED-PHTS is specified to be 80 ppb, which is the concentration that will be experienced in both the Plasma Flux Area (PFA) and in the Out of Plasma Flux Area (OPFA). That corresponds to 0.90 cc(STP) H2/KgH2O, compared with 20–50 cc(STP) H2/KgH2O employed in a PWR primary coolant circuit and 5.5 to 22 cc(STP) H2/KgH2O in a BWR on hydrogen water chemistry (HWC). We predict that a hydrogen concentration of 80 ppb is sufficient to reduce the ECP in the OPFA to a level (−0.324 Vshe) that is sufficient to suppress the crack growth rate (CGR) below the practical, maximum level of 10−9 cm/s (0.315 mm/a) at which SCC is considered not to be a problem in a coolant circuit but, in the PFA, the ECP is predicted to be 0.380 Vshe, which gives a calculated standard CGR of 2.7 × 10−6 cm/s. This is more than three orders in magnitude greater that the desired maximum value of 10−9 cm/s. We recommend that the HWC issue in ITER be revisited to develop a protocol that is effective in suppressing both the ECP and the CGR in the PFA to levels that permit the operation of the IBED-PHTS in accordance with the experience gained in fission reactor technology. Full article
(This article belongs to the Special Issue Corrosion and Materials Degradation under Irradiation: From Understanding to Mitigation…)
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66 pages, 14990 KiB  
Review
A Critical Review of Radiolysis Issues in Water-Cooled Fission and Fusion Reactors: Part I, Assessment of Radiolysis Models
by Digby D. Macdonald, George R. Engelhardt and Andrei Petrov
Corros. Mater. Degrad. 2022, 3(3), 470-535; https://doi.org/10.3390/cmd3030028 - 31 Aug 2022
Cited by 12 | Viewed by 4346
Abstract
A critical review is presented on modeling of the radiolysis of the coolant water in nuclear power reactors with emphasis on ITER. The review is presented in two parts: In Part I, we assess previous work in terms of compliance with important chemical [...] Read more.
A critical review is presented on modeling of the radiolysis of the coolant water in nuclear power reactors with emphasis on ITER. The review is presented in two parts: In Part I, we assess previous work in terms of compliance with important chemical principles and conclude that no model proposed to date is completely satisfactory, in this regard. Thus, some reactions that have been proposed in various radiolysis models are not elementary in nature and can be decomposed into two or more elementary reactions, some of which are already included in the models. These reactions must be removed in formulating a viable model. Furthermore, elementary reactions between species of like charge are also commonly included, but they can be discounted upon the basis of Coulombic repulsion under the prevailing conditions (T < 350 °C) and must also be removed. Likewise, it is concluded that the current state of knowledge with respect to radiolytic yields (i.e., G-values) is also unsatisfactory. More work is required to ensure that the yields used in radiolysis models are truly “primary” yields corresponding to a time scale of nanoseconds or less. This is necessary to ensure that the impact of the reactions that occur outside of the spurs (ionizing particle tracks in the medium) are not counted twice. In Part II, the authors review the use of the radiolysis models coupled with electrochemical models to predict the water chemistry, corrosion potential, crack growth rate in Type 304 SS, and accumulated damage in the coolant circuits of boiling water reactors, pressurized water reactors, and the test fusion reactor, ITER. Based on experience with fission reactors, the emphasis should be placed on the control of the electrochemical corrosion potential because it is the parameter that best describes the state of corrosion in coolant circuits. Full article
(This article belongs to the Special Issue Corrosion and Materials Degradation under Irradiation: From Understanding to Mitigation…)
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30 pages, 5438 KiB  
Review
A Review of the Effect of Irradiation on the Corrosion of Copper-Coated Used Fuel Containers
by Fraser King and Mehran Behazin
Corros. Mater. Degrad. 2021, 2(4), 678-707; https://doi.org/10.3390/cmd2040037 - 17 Nov 2021
Cited by 11 | Viewed by 4635
Abstract
Radiation induced corrosion is one of the possible modes of materials degradation in the concept of long-term management of used nuclear fuel. Depending on the environmental conditions surrounding the used fuel container, a range of radiolysis products are expected to form that could [...] Read more.
Radiation induced corrosion is one of the possible modes of materials degradation in the concept of long-term management of used nuclear fuel. Depending on the environmental conditions surrounding the used fuel container, a range of radiolysis products are expected to form that could impact the corrosion of the copper coating. For instance, γ-radiolysis of pure water produces molecular oxidants such as H2O2 and the radiolysis of humid air produces compounds such as NOx and HNO3. This review is confined to a discussion of the effect of γ-radiation on the corrosion of copper-coated containers. A simplified mixed-potential model is also presented to calculate the extent of copper corrosion by using the steady-state concentration of H2O2 generated during the first 300 years of emplacement, when the radiation field is significant. Full article
(This article belongs to the Special Issue Corrosion and Materials Degradation under Irradiation: From Understanding to Mitigation…)
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