Nuclear Engineering and Technology 55 (2023) 2742e2746

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Nuclear Engineering and Technology

journal homepage: www.elsevier.com/locate/net

Technical Note

Electrochemical and surface investigations of copper corrosion in

dilute oxychloride solution
Gha-Young Kim a, *, Junhyuk Jang b, Jeong-Hyun Woo a, Seok Yoon a, Jin-Seop Kim c
a
Disposal Safety Evaluation R&D Division, Korea Atomic Energy Research Institute (KAERI), 111 Daedeok-daero 989 Beon-gil, Yuseong-gu, Daejeon, 34057,
Republic of Korea
b
Decommissioning Technology Division, Korea Atomic Energy Research Institute (KAERI), 111 Daedeok-daero 989 Beon-gil, Yuseong-gu, Daejeon, 34057,
Republic of Korea
c
Disposal Performance Demonstration R&D Division, Korea Atomic Energy Research Institute (KAERI), 111 Daedeok-daero 989 Beon-gil, Yuseong-gu,
Daejeon, 34057, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: The corrosion behavior of copper immersed in dilute oxychloride solution (100 mM) was studied through
Received 6 April 2023 surface investigation and in-situ monitoring of open-circuit potential. The copper corrosion was initiated
Received in revised form with copper dissolution into a form of CuCl
2 , resulting in mass decrease within the first 40 h of im-
16 May 2023
mersion. This was followed by a hydrolysis reaction initiated by the CuCl
2 at the copper surface, after
Accepted 17 May 2023
which oxide products were formed and deposited on the surface, resulting in a mass increase. The
Available online 17 May 2023
formation of nucleation sites for copper oxide and its lateral extension during the corrosion process were
examined using focused ion beam (FIB)-scanning electron microscopy (SEM). The presence of metastable
Keywords:
Copper
compounds such as atacamite (CuCl2$3Cu(OH)2) on the corroded copper surface was revealed by X-ray
Corrosion photoelectron spectra (XPS) and transmission electron microscopy (TEM)-energy dispersive spectrom-
Oxide etry (EDS) analysis.
Chloride © 2023 Korean Nuclear Society, Published by Elsevier Korea LLC. This is an open access article under the
Surface analysis CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction quite different by country. Recently, we presented an electro-

Deep geological disposal (DGD) is a promising method for nu-
clear fuel treatment. The aim of DGD is to isolate used nuclear fuel
and prevent its potential harm to human society and the ecosystem
using a multi-barrier system. In the DGD multibarrier system, the
used nuclear fuel is enclosed in a sealed disposal canister by
embedding it in a bentonite buffer. Then, the fuel-containing
canister is placed in bedrock 500 m below the ground surface
[1e3]. Because the disposal canister is the first barrier, the safety of
DGD depends primarily on its performance. As the disposal period
progresses, the bentonite buffer can be saturated with ground-
water, causing the disposal canister to be exposed to an aqueous
environment. Thus, canister corrosion is a major research topic for
DGD multibarrier systems.
The study of canister corrosion should be conducted in an
adequately realistic disposal repository environment because re-
pository conditions vary with geological characteristics and are
* Corresponding author.
E-mail address: gkim@kaeri.re.kr (G.-Y. Kim).
chemical investigation of the early corrosion behavior of canister
materials in oxic Korean domestic groundwater collected from the
KAERI underground research tunnel (KURT) [4e6]. KURT is located
in Daejeon, Republic of Korea, and was constructed to simulate the
Korean domestic disposal environment for DGD and multi-barrier
system research. KURT is located 84e110 m above sea level, sur-
rounded by steep uplands of 300e500 m, and its host rock is
Mesozoic granite-granodiorite [7]. Groundwater from the upper
weathered zones is of the CaeHCO3 type [8]. It is alkaline with a pH
of approximately 8 and contains several anions such as Cl
, SO2
4 ,
NO


3 , and HCO3 [4]. Specifically, the chloride concentration in the
KURT groundwater (3 mg/L) is much lower than that in other
countries, e.g., Sweden's Forsmark-North Uppland (95e6900 mg/L)
[9], Finland's Olkiluoto site (2500e16000 mg/L) [10], and Canada
(crystalline: 6099 mg/L; sedimentary: 168,500 mg/L) [11,12].
The aim of this study was to observe the corrosion behavior and
products of copper in the presence of chloride ions at similar con-
centrations in Korean domestic groundwater. Copper was selected
for the KAERI repository system (KRS) [13] and a long-term corro-
sion field test of copper has been carried out to estimate the
corrosion rate [14]. Considering the relative difficulties of sample

https://doi.org/10.1016/j.net.2023.05.021
1738-5733/© 2023 Korean Nuclear Society, Published by Elsevier Korea LLC. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/
licenses/by-nc-nd/4.0/).
G.-Y. Kim, J. Jang, J.-H. Woo et al. Nuclear Engineering and Technology 55 (2023) 2742e2746

retrieval and real-time investigation of corrosion products in long-

term on-site experiment, this study was conducted to gain insight
into the corrosion behavior such as microscopic examination of
corroded surface and identification of corrosion products. For the
purpose, we carried out an immersion test of Cu in NaCl solution,
which has the same chloride concentration as the KURT ground-
water, using electrochemical measurements. As mentioned above,
many anions present in KURT groundwater play various roles in
metal corrosion [15]. For example, HCO
3 is known to inhibit the
corrosive reaction, whereas Cl
, SO2


4 , and NO3 promote corrosion.

led to the surface formation of Cu2O. It was deposited in response to
Among the latter, NO3 activates the cathodic reaction owing to its
oxidizing nature, whereas Cl
and SO2
4 facilitate the copper disso-
lution kinetic, resulting in the retardation of the formation of surface
products, such as copper oxide [9,16]. Therefore, to clarify the effect
of chloride ions on copper corrosion and exclude the influence of
other anions, the test solution was prepared in a lab to match the
chloride concentration of the KURT groundwater (100 mM). During
the immersion test, in situ monitoring of the open-circuit potential
(OCP) and mass change measurements were performed simulta-
neously. The OCP is an indicator of the corrosion potential and can be
used to identify corrosion reactions at the electrode surface, which
are associated with a mass change related to the formation of
corrosion products on the Cu surface (dissolution/deposition).
Additionally, various surface analyses were performed to examine
the corroded Cu surfaces and corrosion products.
Cu þ 2Cl
/ CuCl

2 þe


(a)
This reaction (a) occurred from
0.2 to ~0 V vs. SCE depending
on the concentration of Cl
[18]. The OCP value for the initial 40 h
shown in Fig. 1 corresponds to this range. Thus, the initial decrease
in the mass of Cu in the test solution was induced by the dissolution
of Cu as CuCl
2 . The dissolved Cu(I) species were then hydrolyzed to
cuprous oxide (b) [12]. The formation of cuprous oxide in the
presence of chloride ions was attained through hydrolysis, which
the increase in the local concentration of cuprous chloride complex
(CuCl
2 ) [19]. This explains the OCP and mass change in the range of
50e150 h. Subsequently, it was further oxidized to Cu(OH)2 (c) [20]
and/or reacted with the Cl
adsorbed on the surface oxide film,
resulting in the formation of CuCl2$3Cu(OH)2 (atacamite,
Cu2(OH)3Cl) (d) [21,22].
2CuCl
þ
2 þ H2 O / Cu2 O þ 2H þ 4Cl


(b)

2. Experimental

For the corrosion test, a Cu electrode (diameter: 5 mm, surface

area: 0.196 cm2) comprising a copper layer (thickness: 300 nm)
sputtered onto Ti (10 nm) coated quartz plate was immersed in
naturally aerated 100-mM NaCl solution (99.5%, Junsei Chemical
CO., LTD.). The open-circuit potential (OCP) and mass change of the
Cu electrode were in situ monitored using an electrochemical
quartz crystal microbalance (EQCM) with a 9-MHz oscillator
(QCA922A, 9 MHz, SEIKO EG&G CO., LTD) connected to a poten-
tiostat (Bio-Logic, Claix, France SP-300). A saturated calomel
reference electrode (SCE) and Pt wire counter electrode were used
in the test. The morphology of the corroded Cu electrode was
observed using focused ion beam (FIB)/scanning electron micro-
scopy (SEM) (Helios Nanolab 450F1, FEI Company) and trans-
Fig. 1. In situ measurement of open-circuit potential (solid) and mass change (dash) of
mission electron microscopy (TEM)/energy dispersive
Cu immersed in dilute oxychloride solution (100 mM NaCl) for 400 h.
spectrometry (EDS) (Talos F200X, FEI Company). X-ray photoelec-
tron spectra (XPS) of the Cu samples were obtained using an X-ray
photoelectron spectroscope (Axis-Supra, Kratos) to measure Al Ka
radiation (1486.7 eV). The binding energies were calculated with
respect to the C 1s peak of the contaminated carbon at 284.8 eV. All
surface analyses were performed at the KAIST Analysis Center for
Research Advancement (KARA).

3. Results and discussion

The OCP and mass change of Cu immersed in 100 mM NaCl so-

lution were monitored on-line for 400 h. The OCP value (solid line)
dropped sharply within the first 40 h and then gradually decreased
to
0.17 V vs. SCE until 147 h of exposure to the solution. Subse-
quently, it increased rapidly to approximately 0.07 V vs. SCE and
finally reached close to 0.03 V with periodic fluctuations during the
last 200 h. The mass decreased slightly at the beginning of the test
and then continued to increase. More specifically, the initial mass
loss was caused by the dissolution of copper and the subsequent
mass increase was induced by the deposition of corrosion products
such as oxides and hydroxides. In an O2-containing Cl
solution, the
copper preferentially dissolves owing to the presence of Cl
on the Fig. 2. Pourbaix diagram for the Cu/Cl
/H2O system at 25  C for [Cu] dissolved ¼ 10
6
surface [17]. and [Cl
] ¼ 10
4 M.

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G.-Y. Kim, J. Jang, J.-H. Woo et al. Nuclear Engineering and Technology 55 (2023) 2742e2746

Fig. 3. FIB/SEM images of Cu immersed in dilute oxychloride solution (Note that the Ti layer coated on quartz is the substrate material for the Cu electrode used in this study).

proceeded as a result of the deposition of corrosion products. The

Cu2 O þ H2 O þ 2OH
/ 2CuðOHÞ2 þ 2e

2Cu2 O þ O2 þ 2Cl
þ 4H2 O / CuCl2  3CuðOHÞ2 þ 2OH

The OCP value as the oxide/hydroxide film grew on the Cu
surface was determined from the equilibrium potential for redox
reactions of Cu/Cu2O and Cu2O/Cu(OH)2. Although it is known that
the OCP in a Cl
solution at pH < 9 is determined via the Cu
dissolution reaction [23], the [Cl
] in the test solution was as low as
10
4 M and the thermodynamically stable species in the test so-
lution were Cu2O and Cu(OH)2, as shown in the Pourbaix diagram
(Fig. 2). Therefore, the OCP value increased as the reaction
(c) increase in mass during the last 150 h of the test, in which the OCP
value was maintained in the range of 0.025e0.05 V vs. SCE, can be
explained by the above reactions.
(d) The surfaces of the corroded Cu at the middle and end of the
immersion in the test solution were observed using FIB/SEM
analysis. As shown in Fig. 3 (a), the Cu surface was partially covered
with well-developed crystals (copper oxide) after 200 h of expo-
sure to the test solution. Subsequently, the surface was more
completely covered with crystals of various sizes, some of which
grew horizontally into one large mass after 400 h of immersion
[24]. The thickness of the surface film in Fig. 3b varied in the range
of 400 nme1.2 mm.

Fig. 4. TEM/EDS images of Cu after exposure to dilute oxychloride solution (Note that the presence of Ti and O at the bottom can be attributed to the Ti sputtered quartz plate used
for the Cu electrode substrate material).

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Fig. 4 shows the TEM/EDS analysis results for a part of the sur-
face layer after the termination of the test. The distribution of O and
Cl on the corroded Cu surface indicates the presence of O (41.3 at.%),
Cl (13.9 at.%), and Cu (44.8 at.%). This ratio and the green color
(observed optically; data not shown) suggest that atacamite may be
present in the copper corrosion products on the surface [25].
Notably, the potentially metastable phases would not appear in the
predominance diagrams because the Pourbaix diagram considers
thermodynamic equilibrium; however, it could be present in the
corrosion products. Atacamite is the case of metastable phases, and
it was identified in corrosion pits in saline solutions despite its
absence in the Pourbaix diagram [26]. Similar to a previous report,
here, atacamite was formed according to reaction (d). Thus, the
presence of metastable species such as atacamite was reliable, as
examined by TEM-EDS in this study.
The chemical composition of the copper corrosion products in
the oxychloride solution was observed using XPS analysis. The
narrow-scan XPS spectra (red line) revealed the characteristics of
the corroded surface of copper specimen in oxic 100 mM NaCl so-
lution. The bare Cu sample (black line) was also analyzed for
comparison (Fig. 5a and b). As shown in Fig. 5a, the Cu 2p3/2 and Cu
2p1/2 peaks of Cu corroded in dilute oxychloride solution are dou-
blets, whereas those of bare Cu show relatively broad Cu 2p peaks.
The Cu 2p3/2 and Cu 2p1/2 peaks at 932.6 and 952.2 eV, respectively,
can be attributed to the Cu0 and/or Cuþ species, which are observed
at the same positions as bare Cu [27e29]. The Cu 2p3/2 and Cu 2p1/2
peaks at approximately 935 and 955 eV, respectively, can be
attributed to the presence of Cu2þ species [30], as confirmed by
shake-up satellites in the range of 941e945 eV [31,32]. Specifically,
the peaks at 941.5 and 944 eV are attributable to CuO and the weak
peak at 942.2 eV corresponds to the presence of Cu(OH)2 [32] and/
or Cu2(OH)3Cl [33]. Fig. 5b shows that the peak Cl 2p of the
corroded Cu in the test solution is a doublet, with binding energies
of Cl 2p3/2 and Cl 2p1/2 observed at ca. 198.5 and 200.1 eV, respec-
tively. These results are consistent with those of a previous report,
suggesting that the difference in the binding energy of Cl 2p peak
separation is 1.6 eV [34]. XPS analysis revealed the formation of Cuþ
and Cu2þ species as corrosion products, specifically copper oxy-
chloride compounds such as atacamite. Atacamite is not thermo-
dynamically favored; however, it can be present in the corrosion
reaction. Thus, the XPS and TEM-EDS analyses show that meta-
stable species (atacamite) can exist in copper corrosion in a low-
chloride solution.

4. Conclusion
Fig. 5. XPS spectra of (a) Cu 2p, and (b) Cl 2p regions of the Cu sample before (black)
and after (red) corrosion of Cu in dilute oxychloride solution. (For interpretation of the
Electrochemical and surface investigations were carried out to
references to color in this figure legend, the reader is referred to the Web version of
study the copper corrosion in aerated dilute chloride solution this article.)
(100 mM NaCl). The initial dissolution of copper and the deposition
of oxide and hydroxide compounds as corrosion products were
observed via in situ measurements of the OCP and mass change. The Declaration of competing interest
formation of nucleation sites for copper oxide and lateral extension
were investigated using FIB-SEM analysis. As copper corrosion The authors declare that they have no known competing
products in aerated dilute chloride solution, the presence of Cuþ financial interests or personal relationships that could have
and Cu2þ compounds and metastable phases such as atacamite was appeared to influence the work reported in this paper.
confirmed via TEM-EDS and XPS analyses. These results show that
the concentration of chloride ions in Korean domestic groundwater
does not significantly affect the copper corrosion behavior. Notably, Acknowledgements
this research focused on the initial stages of copper corrosion
compared to the disposal period. Future work will involve the This work was supported by a National Research Foundation of
evaluation of long-term corrosion performance of copper canister Korea (NRF) grant and the Institute for Korea Spent Nuclear Fuel
under conditions that reflect the evolution of disposal (iKSNF) funded by the Korea government (Ministry of Science and
environment. ICT, MSIT) (2021M2E3A2041351, 2021M2E1A1085193).
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