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Molecular studies of initial atmospheric corrosion of copper: Exploration of ultra-sensitive techniques for the inhibiting effect of self assembled monolayers, and the effect of gamma radiation
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Atmospheric corrosion indoors is of great practical importance for the degradation of metals, for example in electronics, military equipment, and cultural heritage items. It involves a wide range of chemical, electrochemical, and physical processes occurring in gas, liquid, and solid phases, and at the interfaces between them. Hence, a molecular understanding of the fundamental interactions during atmospheric corrosion is of utmost importance.

Copper is one of the most used metals in electrical contacts, power generators, heat exchangers, etc. and is prone to indoor atmospheric corrosion. Although corrosion and oxidation of copper in the presence of corrosion stimulators is thermodynamically inevitable, there are ways to reduce the kinetics of corrosion and oxidation reactions.

Self assembled monolayers (SAMs) of organic molecules, when adsorbed on copper surfaces, have proven to be efficient barriers against copper corrosion. However, understanding at the molecular level of the initial stages of corrosion of SAM covered copper in atmospheric corrosion conditions is lacking. The main reason is the inability of the conventional analytical methods to detect and characterize very thin corrosion products formed during the initial stages (from seconds to days) of atmospheric corrosion of SAM covered copper. To overcome this situation a highly surface sensitive technique, vibrational sum frequency spectroscopy (VSFS), has been utilized in situ and ex situ in this thesis to detect and follow the oxidation of alkanethiol SAM covered copper in dry air as well as to assess the conformational changes of SAM molecules during oxidation.  A very sensitive gravimetric method, quartz crystal microbalance with dissipation monitoring (QCM-D), and a highly sensitive and versatile optical technique, nanoplasmonic sensing (NPS), were combined in situ with VSFS to quantify this very slow oxidation process. This combination allowed the heterogeneity of the oxidation process as well as the mass and the rigidity of the corrosion products to be detected simultaneously.

To address indoor atmospheric corrosion conditions where carboxylic acids play an important role we next studied the interaction between SAM covered copper and humidified air, to which formic acid was added. The in situ identification of the corrosion products and their formation kinetics was done using near surface sensitive infrared reflection/absorption spectroscopy (IRAS), and the effect of hydrocarbon chain length in alkanethiol SAMs on their corrosion protection efficiency was investigated. The effect of the anchoring group in the SAMs on their corrosion protection efficiency was studied for hexaneselenol using -SeH as the anchoring group, and the results were compared with its thiol counterpart, hexanethiol, with -SH as the anchoring group. Complementary in situ and ex situ VSFS measurements were performed to assess the quality of the SAMs before, during, and after exposure.

It was shown that the SAMs of alkanethiols greatly inhibited the formation of copper (I) oxide and slowed down the formation of other corrosion products, i.e. copper formate and copper hydroxid. This was due to a selective hindrance of the corrosion stimulators, oxygen, water, and formic acid molecules reaching the copper-SAM interface. The corrosion inhibiting effect increased with the hydrocarbon chain length. The SAMs of hexaneselenols, on the other hand, exhibited an accelerated formation of copper (I) oxide, copper formate and copper hydroxide compared to an unprotected surface as a result of the partial removal of hexaneselenol molecules from the copper surface during prolonged exposure.

The experience gained in characterizing and quantifying thin copper oxides was further used to explore the influence of gamma (γ) radiation on copper corrosion in anoxic water. This multi-analytical approach included IRAS, cathodic reduction, confocal Raman microscope, atomic force microscopy, scanning electron microscopy, x-ray photoelectron spectroscopy, and inductively coupled plasma - atomic emission spectroscopy. The results clearly showed that copper dissolution as well as the oxide layer thickness increase with gamma radiation under the exposure conditions.

Abstract [sv]

Atmosfärisk korrosion under inomhusförhållanden är av stor praktisk betydelse på grund av dess inverkan på exempelvis vårt kulturarv i museimiljöer, tillförlitligheten hos elektronik i olika industriella sammanhang, eller militär utrustning förvarad i olika förråd. Den atmosfäriska korrosionen styrs av ett brett spektrum av kemiska, elektrokemiska och fysikaliska processer som äger rum i tre faser: atmosfären, den tunna fuktfilmen på objektytan och den fasta fasen, samt i de bägge fasgränserna mellan de tre faserna. För att kunna hitta motmedel mot korrosionen är det av yttersta vikt att öka den molekylära förståelsen för dessa processer.

Koppar är en mycket använd metall i elektriska eller elektroniska komponenter, i värmeväxlare eller VVS-sammanhang, som beslag och i en rad olika dekorer. Metallen korroderar eller oxiderar spontant i många korrosiva miljöer, men det finns ett brett spektrum av metoder för att minska korrosions- eller oxidationshastigheten. Monoskikt av tätpackade självassocierande organiska molekyler (engelska: self assembled monolayers, förkortat SAM) adsorberade på kopparytan har visat sig vara effektiva barriärer för kopparkorrosion. Den molekylära insikten i dessa monoskikts funktionssätt för att minska den atmosfäriska korrosionen är dock ännu rätt så begränsad. Den främsta orsaken är oförmågan hos mer etablerade analytiska metoder att kunna karakterisera de ytterst små mängder av korrosionsprodukter som bildas under den atmosfäriska korrosionens inledande skeenden upp till några dagars exponering.

Den extremt ytkänsliga och i korrosionssammanhang fortfarande relativt oprövade analysmetoden summafrekvensspektroskopi (engelska: vibrational sum frequency spectroscopy, förkortat VSFS) har därför använts för att under pågående exponering följa det mycket långsamma oxidationsförlopp som uppstår när koppar, skyddat av något organiskt monoskikt, exponeras för torr luft. VSFS har även kunnat användas för att under pågående oxidation följa strukturella förändringar hos monoskiktet. För att kvantifiera en så långsam oxidationsprocess har även en annan extremt masskänslig metod kunnat kombineras med VSFS, en kvartskristallmikrovåg med s.k. dissipationsövervakning, förkortat QCM-D. Ytterligare en i korrosionssammanhang oprövad men lika masskänslig teknik har kunnat kombineras med VSFS. Den metoden besitter än så länge bara ett engelskt namn, nanoplasmonic sensing (NPS). Kombinationen VSFS–QCM-D–NPS har utnyttjats i en serie unika försök, där inte bara de ytterst långsamma oxidationshastigheterna kunnat mätas upp, utan även andra viktiga faktorer såsom graden av heterogenitet i den bakomliggande oxidationsprocessen.

För att närma sig en miljö som kan efterlikna korrosiva inomhusförhållanden har atmosfären i nästa steg befuktats och dessutom har låga halter av myrsyra tillsats. Just tillsatsen av karboxylsyror har visat sig generera korrosionsprodukter med en sammansättning som på koppar och vissa andra metaller efterliknar de som bildas under atmosfärisk korrosion inomhus. Identifiering av korrosionsprodukter och deras tillväxthastighet på koppar, skyddat av olika långa tätpackade kolkedjor med en tiolgrupp i ena ändan som binder till kopparsubstratet, har kunnat ske med infraröd reflektions-absorptionsspektroskopi (IRAS) under in situ-förhållanden. Ju längre kolvätekedjor desto större korrosionsinhibieringsförmåga kunde påvisas. När den på koppar förankrade tiolgruppen ersattes med en selenolgrupp blev korrosionsinhibieringsförmågan sämre. Kompletterande mätningar in situ och ex situ  utfördes med hjälp av VSFS för att undersöka kvaliteten på de tätpackade kolvätekedjorna, varvid kunde påvisas att graden av tätpackning hos kolkedjorna försämrades med ökad exponeringstid.

Förutom den allmänna nedbromsningen av korrosionshastigheten på koppar blev sammansättningen av bildade korrosionsprodukter på oskyddat koppar en annan än på  koppar skyddat av tioler. I det förra fallet detekterades korrosionsprodukterna koppar(I)oxid, koppar(II)format och koppar(II)hydroxid, under det att ingen koppar(I)oxid påvisades på skyddat koppar, endast små mängder koppar(II)format och koppar(II)hydroxid kunde detekteras. De adsorberade kolkedjorna tycks hindra de korrosionsstimulerande molekylerna vatten, myrsyra och syrgas från att nå kopparytan lika effektivt. När de tiolförankrade kolvätekedjorna ersattes med selenolförankrade kolvätekedjor desorberades en del kolvätekedjor från kopparsubstratet vid längre exponeringstider. Resultatet blev att mängden korrosionsprodukter nu blev signifikant större än på oskyddat koppar, sannolikt på grund av galvanisk korrosion.

Erfarenheterna från detta doktorsarbete vad gäller kvantifiering av små mängder kopparoxider har även utnyttjats för att undersöka inverkan av g-strålning på kopparkorrosion i rent vatten. Härvid användes ett multianalytiskt angreppssätt bestående av IRAS, katodisk reduktion, konfokal Ramanmikroskopi, atomkraftsmikroskopi, svepelektronmikroskopi, fotoelektronspektroskopi, samt analys av utlöst mängd koppar i vattenlösningen med induktivt kopplad plasmaatomemissionsspektroskopi. Resultaten visar tydligt att utlösningen av koppar, liksom det bildade oxidskiktets tjocklek, ökar med g-strålningen under rådande exponeringsförhållanden.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2013. , xvii, 85 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2013:50
Keyword [en]
Corrosion, copper, self assembled monolayer, sum frequency spectroscopy, qcm, gamma radiation
National Category
Corrosion Engineering
Identifiers
URN: urn:nbn:se:kth:diva-136267ISBN: 978-91-7501-950-5 (print)OAI: oai:DiVA.org:kth-136267DiVA: diva2:675792
Public defence
2013-12-20, Kollegiesallen, Brinellvägen 8, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20131206

Available from: 2013-12-06 Created: 2013-12-04 Last updated: 2013-12-06Bibliographically approved
List of papers
1. Initial Oxidation of Alkanethiol-Covered Copper Studied by Vibrational Sum Frequency Spectroscopy
Open this publication in new window or tab >>Initial Oxidation of Alkanethiol-Covered Copper Studied by Vibrational Sum Frequency Spectroscopy
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2011 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 115, no 48, 23871-23879 p.Article in journal (Refereed) Published
Abstract [en]

The oxidation of octadecanethiol (ODT, CH3-(CH2)17SH)-covered copper in dry air has been studied by in situ vibrational sum frequency spectroscopy (VSFS), infrared reflection absorption spectroscopy (IRAS), and cathodic reduction (CR). During the first 10 h of exposure, the VSF spectral line shape in the CH stretching region changed

significantly, with resonances observed as dips being transformed into peaks. This was attributed to a phase change in the nonresonant sum frequency signal due to the formation of a thin layer of copper(I) oxide beneath the ODT. Complementary cathodic reduction and infrared reflection/absorption spectroscopy studies yielded a thickness of the oxide layer of <2 nm after 19 h exposure. An orientation analysis on the adsorbed molecules by VSFS indicated a decreased tilt angle of the terminating methyl groups with respect to the surface normal during the formation of the oxide layer.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2011
National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:kth:diva-67442 (URN)10.1021/jp207028e (DOI)000297446300028 ()2-s2.0-82555167517 (Scopus ID)
Funder
Swedish Research Council
Note
QC 20120207Available from: 2012-02-07 Created: 2012-01-27 Last updated: 2017-12-08Bibliographically approved
2. Integration of Quartz Crystal Microbalance with Vibrational Sum Frequency Spectroscopy-Quantification of the Initial Oxidation of Alkanethiol-Covered Copper
Open this publication in new window or tab >>Integration of Quartz Crystal Microbalance with Vibrational Sum Frequency Spectroscopy-Quantification of the Initial Oxidation of Alkanethiol-Covered Copper
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2012 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 116, no 46, 24549-24557 p.Article in journal (Refereed) Published
Abstract [en]

We report the first integration of the interface sensitive technique vibrational sum frequency spectroscopy (VSFS) and the mass sensitive technique quartz crystal microbalance (QCM). VSFS-QCM has been applied in-situ to follow the formation of a thin Cu2O-like oxide on octadecanethiol-covered copper in dry air at ambient pressure conditions. We observed significant changes and an evolution of the VSF spectra caused by alterations in the electronic properties of the metal surface, and simultaneous shifts in the QCM resonance frequency due to a mass change during the formation of the oxide. QCM and VSFS exhibit a resolution corresponding to the formation of around 2% and 5% of an ideal monolayer of Cu2O, respectively. The successful integration of QCM increases the versatility of VSFS in numerous applications, where simultaneous in situ mass and spectroscopic information is desirable.

Keyword
Optical 2nd-Harmonic Generation, Self-Assembled Monolayers, In-Situ, Atmospheric Corrosion, N-Alkanethiols, Metal-Surfaces, Adsorption, Ir, Interfaces, Acid
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-109184 (URN)10.1021/jp3066426 (DOI)000311461100019 ()2-s2.0-84870260183 (Scopus ID)
Funder
Swedish Foundation for Strategic Research Swedish Research Council
Note

QC 20130107

Available from: 2013-01-07 Created: 2012-12-21 Last updated: 2017-12-06Bibliographically approved
3. Combined in Situ Quartz Crystal Microbalance with Dissipation Monitoring, Indirect Nanoplasmonic Sensing, and Vibrational Sum Frequency Spectroscopic Monitoring of Alkanethiol-Protected Copper Corrosion
Open this publication in new window or tab >>Combined in Situ Quartz Crystal Microbalance with Dissipation Monitoring, Indirect Nanoplasmonic Sensing, and Vibrational Sum Frequency Spectroscopic Monitoring of Alkanethiol-Protected Copper Corrosion
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2013 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 29, no 23, 7151-7161 p.Article in journal (Refereed) Published
Abstract [en]

In this study, we have applied three techniques to simultaneously and in situ study the initial stage of corrosion of copper protected by a self-assembled monolayer of octadecanethiol (ODT). We combined quartz crystal microbalance with dissipation monitoring (QCM-D), indirect nanoplasmonic sensing (INPS), and vibrational sum frequency spectroscopy (VSFS) and obtained complementary information about mass uptake and optical and spectroscopic changes taking place during the initial corrosion phase. All three techniques are very sensitive to the formation of a corrosion film (thickness in the range 0-0.41 nm) under mildly corrosive conditions (dry air, <0.5% relative humidity). The three techniques yield information about the viscoelasticity of the corrosion film (QCM-D), the homogeneity of the corrosion reaction on the surface (INPS), and the stability of the ODT. protection layer (VSFS). Furthermore, by also studying the corrosion process in humid air (ca. 70% relative humidity), we illustrate how the combination of these techniques can be used to differentiate between simultaneously occurring processes, such as water adsorption and corrosion product formation.

Keyword
Corrosion products, Corrosion reaction, Corrosive conditions, Quartz crystal microbalance with dissipation monitoring, Situ quartz crystal microbalance, Spectroscopic changes, Spectroscopic monitoring, Vibrational sum-frequency spectroscopies
National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:kth:diva-124729 (URN)10.1021/la4009224 (DOI)000320485400046 ()2-s2.0-84878983446 (Scopus ID)
Funder
Swedish Foundation for Strategic Research Swedish Research Council, 2010-4041
Note

QC 20130730

Available from: 2013-07-30 Created: 2013-07-29 Last updated: 2017-12-06Bibliographically approved
4. Nanoplasmonic Sensing for Monitoring the Initial Stages of Atmospheric Corrosion of Cu Nanodisks and Thin Films
Open this publication in new window or tab >>Nanoplasmonic Sensing for Monitoring the Initial Stages of Atmospheric Corrosion of Cu Nanodisks and Thin Films
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2013 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 160, no 10, C487-C492 p.Article in journal (Refereed) Published
Abstract [en]

Nanoplasmonic sensing as a powerful experimental technique for corrosion kinetics monitoring is demonstrated. Its versatility is illustrated by studies of initial corrosion carried out on model systems consisting of copper nanodisks and extended copper films in both dry (<0.5% relative humidity, RH) and humid (65 +/- 5% RH) air. Samples with and without a protective self-assembled monolayer of octadecanethiol (ODT) were studied. Thus, we studied four different corrosion situations. Two versions of the technique were employed, direct and indirect nanoplasmonic sensing (INPS). The former used disk-shaped nanoparticles as both sample structures and sensing particles, the latter used extended films as the sample, with the nanoplasmonic sensing particles embedded under the sample. Corrosion kinetics were recorded with high sensitivity and high temporal resolution (submonolayer detection limit; temporal resolution 1-2 seconds). In dry air, six times lower oxidation rates were observed for ODT-covered Cu compared to bare Cu, demonstrating the protection efficiency of the ODT as a corrosion inhibitor. In humid air, a higher oxidation rate was measured for both bare (2.4 times higher) and ODT-covered (1.7 times higher) samples, compared to the same samples exposed to the dry air environment. Oxidation occurred first after a short induction period during which water was adsorbed. For the Cu nanodisks (direct sensing) and Cu films (indirect sensing) studied here, very similar oxidation kinetics were observed.

Keyword
Self-Assembled Monolayers, Quartz-Crystal Microbalance, Alkanethiol-Covered Copper, Sum-Frequency Spectroscopy, Chain-Length, In-Situ, Protection, Oxidation, Inhibitors, Surfaces
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-134769 (URN)10.1149/2.051310jes (DOI)000326207400052 ()
Funder
Swedish Research Council, 2010-4041
Note

QC 20131128

Available from: 2013-11-28 Created: 2013-11-28 Last updated: 2017-12-06Bibliographically approved
5. Alkanethiols as inhibitors for the atmospheric corrosion of copper induced by formic acid: Effect of chain length
Open this publication in new window or tab >>Alkanethiols as inhibitors for the atmospheric corrosion of copper induced by formic acid: Effect of chain length
2013 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 160, no 6, C270-C276 p.Article in journal (Refereed) Published
Abstract [en]

Self assembled monolayers (SAMs) of n-alkanethiols of different chain length (4, 6, 8, 12, and 18 carbons in the chain) have been explored as corrosion inhibitors for copper exposed to humidified air containing formic acid, an environment used to mimic accelerated indoor atmospheric corrosion. Near-surface sensitive in-situ infrared reflection/absorption spectroscopy combined with interface sensitive vibrational sum frequency spectroscopy revealed unique molecular information on the role of each SAM during ongoing corrosion. All SAMs protect copper against corrosion, and this ability increases continuously with chain length. Their structural order is high prior to exposure, but an increased disorder is observed as a result of the corrosion process. The protection ability of the SAMs is attributed to a selective hindrance of the corrosion stimulators water, oxygen gas, and formic acid to reach the copper-SAM interface through each SAM, which results in different corrosion mechanisms on SAM protected copper and unprotected copper. This significantly retards the formation of the corrosion products copper hydroxide and copper formate, and results in essentially no formation of cuprite.

Keyword
Corrosion mechanisms, Corrosion products, Indoor atmospheric corrosions, Infrared reflections, Interface-sensitive, Molecular information, Structural ordering, Vibrational sum-frequency spectroscopies
National Category
Other Chemistry Topics
Identifiers
urn:nbn:se:kth:diva-133255 (URN)10.1149/2.104306jes (DOI)000320074700051 ()2-s2.0-84884332776 (Scopus ID)
Funder
Swedish Foundation for Strategic Research Swedish Research Council
Note

QC 20131030

Available from: 2013-10-30 Created: 2013-10-29 Last updated: 2017-12-06Bibliographically approved
6. Self-Assembled Monolayers as Inhibitors for the Atmospheric Corrosion of Copper Induced by Formic Acid: A Comparison between Hexanethiol and Hexaneselenol
Open this publication in new window or tab >>Self-Assembled Monolayers as Inhibitors for the Atmospheric Corrosion of Copper Induced by Formic Acid: A Comparison between Hexanethiol and Hexaneselenol
2014 (English)In: Journal of the Electrochemical Society, ISSN 0013-4651, E-ISSN 1945-7111, Vol. 161, no 1, C50-C56 p.Article in journal (Refereed) Published
Abstract [en]

The corrosion protection by self-assembled monolayers (SAMs) of hexanethiol and hexaneselenol has been explored on copper exposed to humid air containing formic acid, a corrosive environment relevant for indoor atmospheric corrosion. The kinetics of the formation of corrosion products on SAM covered copper was followed using in-situ infrared reflection/absorption spectroscopy (IRAS) and compared with that of bare copper. Both SAMs initially showed a corrosion protection ability. The prolonged exposure of hexanethiol copper resulted in a reduced formation rate of copper formate and copper hydroxide compared to bare copper, while on bare and hexaneselenol covered samples copper (I) oxide, copper formate, and copper hydroxide were observed. To assess the quality of the SAMs during the sample exposure, vibrational sum frequency spectroscopy (VSFS) was used. It was found that hexaneselenol molecules are locally removed from the surface during corrosion in contrast to their thiol counterparts. This created localized galvanic effects which resulted in an accelerated corrosion of selenol covered copper. X-ray photoelectron spectroscopy at elevated pressure demonstrated that the hexanethiol removed thin oxide layers upon adsorption. A contributing parameter to the enhanced corrosion inhibiting ability of hexanethiol could be its greater ability than hexaneselenol to bind to the copper surface during its deposition and sample exposure.

Place, publisher, year, edition, pages
Electrochemical Society, 2014
Keyword
Sum-Frequency Spectroscopy, Generation Vibrational Spectroscopy, N-Dodecaneselenol Monolayers, Quartz-Crystal Microbalance, Alkanethiol-Covered Copper, X-Ray, Initial Oxidation, Organic-Surfaces, Force Microscopy, Chain-Length
National Category
Corrosion Engineering
Identifiers
urn:nbn:se:kth:diva-136323 (URN)10.1149/2.056401jes (DOI)000330680900041 ()
Funder
Swedish Research Council
Note

QC 20131206

Available from: 2013-12-04 Created: 2013-12-04 Last updated: 2017-12-06Bibliographically approved
7. 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
8. 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
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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

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