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Radiation induced corrosion of copper
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry. (Kärnkemi, Nuclear Chemistry)ORCID iD: 0000-0002-8341-094X
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The process of radiation induced corrosion of copper is not well understood. The most obvious situation where the knowledge of this process is crucial is in a deep repository for high level spent nuclear fuel where the fuel will be sealed inside copper canisters. The radiation will penetrate the canisters and be absorbed by the surrounding environment. In this study gamma irradiations of polished and pre-oxidized copper cubes in anoxic pure water, air of 60-100 % RH and in humid argon were performed. The copper surfaces were examined using IRAS, XPS, cathodic reduction, SEM, AFM, and Raman spectroscopy. The concentration of copper in the reaction solutions was measured using ICP-OES.  Also the formation of oxidative species caused by radiation absorption of water was studied by numerical simulations using MAKSIMA software. The corrosion of copper during gamma irradiation vastly exceeds what is expected. The production of oxidative species caused by radiation absorption of water is hundreds of times too low to explain the amount of oxidized copper. A possible explanation for this mismatch is an enhanced radiation chemical yield of HO· on the copper surface. Another one is an increased surface area due to oxidation of copper. One speculation is that HO· interacting with the copper oxide can cause oxidation of the metal. If the thermodynamic driving force is large enough then electrons can be conducted from the metal through the oxide to the oxidant. A dramatic increase in surface area together with an increased interfacial yield of HO· might explain the radiation enhanced corrosion process.   

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2015. , vii, 77 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2015:57
Keyword [en]
Corrosion, oxidation, copper, copper oxide, gamma radiation, radiolysis, hydrogen peroxide, hydroxyl radical
National Category
Physical Chemistry
Research subject
Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-175739ISBN: 978-91-7595-710-4 (print)OAI: oai:DiVA.org:kth-175739DiVA: diva2:862125
Public defence
2015-11-18, Kollegiesalen, Brinellvägen 8, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20151022

Available from: 2015-10-22 Created: 2015-10-20 Last updated: 2015-10-22Bibliographically approved
List of papers
1. Radiation Induced Corrosion of Copper in Anoxic Aqueous Solution
Open this publication in new window or tab >>Radiation Induced Corrosion of Copper in Anoxic Aqueous Solution
2012 (English)In: Electrochemical and solid-state letters, ISSN 1099-0062, E-ISSN 1944-8775, Vol. 15, no 5, C5-C7 p.Article in journal (Refereed) Published
Abstract [en]

The effect of gamma radiation on corrosion of copper under anoxic conditions in pure water has been studied experimentally. Copper samples submerged in water were exposed to dose rates of 0.37 or 0.77 kGy/h. Reference samples were used throughout. The copper surfaces have been examined using the techniques of SEM-EDS, IRAS, CR spectroscopy and AFM. Dissolution of copper was measured using ICP-OES. The results show that irradiated samples are more corroded than corresponding reference samples. This is also reflected by the increased concentration of copper in water after irradiation. Surface examination also reveals local corrosion features.

National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-93861 (URN)10.1149/2.022205esl (DOI)000301656700010 ()2-s2.0-84860178815 (Scopus ID)
Note

QC 20120502. Correction in: Electrochemical  And  Solid State Letters, vol. 15, issue. 6, pages. S5, doi: 10.1149/2.016206esl. ISI: 000306716000024

Available from: 2012-05-02 Created: 2012-05-02 Last updated: 2017-12-07Bibliographically approved
2. Radiation induced corrosion of copper for spent nuclear fuel storage
Open this publication in new window or tab >>Radiation induced corrosion of copper for spent nuclear fuel storage
Show others...
2013 (English)In: Radiation Physics and Chemistry, ISSN 0969-806X, E-ISSN 1879-0895, Vol. 92, 80-86 p.Article in journal (Refereed) Published
Abstract [en]

The long term safety of repositories for radioactive waste is one of the main concerns for countries utilizing nuclear power. The integrity of engineered and natural barriers in such repositories must be carefully evaluated in order to minimize the release of radionuclides to the biosphere. One of the most developed concepts of long term storage of spent nuclear fuel is the Swedish KBS-3 method. According to this method, the spent fuel will be sealed inside copper canisters surrounded by bentonite clay and placed 500 m down in stable bedrock. Despite the importance of the process of radiation induced corrosion of copper, relatively few studies have been reported. In this work the effect of the total gamma dose on radiation induced corrosion of copper in anoxic pure water has been studied experimentally. Copper samples submerged in water were exposed to a series of total doses using three different dose rates. Unirradiated samples were used as reference samples throughout. The copper surfaces were examined qualitatively using IRAS and XPS and quantitatively using cathodic reduction. The concentration of copper in solution after irradiation was measured using ICP-AES. The influence of aqueous radiation chemistry on the corrosion process was evaluated based on numerical simulations. The experiments show that the dissolution as well as the oxide layer thickness increase upon radiation. Interestingly, the evaluation using numerical simulations indicates that aqueous radiation chemistry is not the only process driving the corrosion of copper in these systems.

Keyword
Corrosion, Copper, Gamma irradiation, Dose, Oxidation
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-131704 (URN)10.1016/j.radphyschem.2013.06.033 (DOI)000324609900015 ()2-s2.0-84883052341 (Scopus ID)
Note

QC 20131018

Available from: 2013-10-18 Created: 2013-10-17 Last updated: 2017-12-06Bibliographically approved
3. Kinetics and mechanisms of reactions between H2O2 and copper and copper oxides
Open this publication in new window or tab >>Kinetics and mechanisms of reactions between H2O2 and copper and copper oxides
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2015 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 44, no 36, 16045-16051 p.Article in journal (Refereed) Published
Abstract [en]

One of the main challenges for the nuclear power industry today is the disposal of spent nuclear fuel. One of the most developed methods for its long term storage is the Swedish KBS-3 concept where the spent fuel is sealed inside copper canisters and placed 500 meters down in the bedrock. Gamma radiation will penetrate the canisters and be absorbed by groundwater thereby creating oxidative radiolysis products such as hydrogen peroxide (H2O2) and hydroxyl radicals (HO[radical dot]). Both H2O2 and HO[radical dot] are able to initiate corrosion of the copper canisters. In this work the kinetics and mechanism of reactions between the stable radiolysis product, H2O2, and copper and copper oxides were studied. Also the dissolution of copper into solution after reaction with H2O2 was monitored by ICP-OES. The experiments show that both H2O2 and HO[radical dot] are present in the systems with copper and copper oxides. Nevertheless, these species do not appear to influence the dissolution of copper to the same extent as observed in recent studies in irradiated systems. This strongly suggests that aqueous radiolysis can only account for a very minor part of the observed radiation induced corrosion of copper.

National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:kth:diva-172417 (URN)10.1039/C5DT02024G (DOI)000360471000033 ()2-s2.0-84940774487 (Scopus ID)
Note

QC 20150929. Updated from e-pub ahead of print to published.

Available from: 2015-08-21 Created: 2015-08-21 Last updated: 2017-12-04Bibliographically approved
4. The role of the oxide layerin radiation induced corrosion of copper in anoxic water
Open this publication in new window or tab >>The role of the oxide layerin radiation induced corrosion of copper in anoxic water
(English)Manuscript (preprint) (Other academic)
Identifiers
urn:nbn:se:kth:diva-175813 (URN)
Note

QS 2015

Available from: 2015-10-22 Created: 2015-10-22 Last updated: 2015-10-22Bibliographically approved
5. Radiation induced corrosion of copper in humid air and argon
Open this publication in new window or tab >>Radiation induced corrosion of copper in humid air and argon
(English)Manuscript (preprint) (Other academic)
Identifiers
urn:nbn:se:kth:diva-175816 (URN)
Note

QS 2015

Available from: 2015-10-22 Created: 2015-10-22 Last updated: 2015-10-22Bibliographically approved

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