Effect of sulphide exposure on mechanical

properties of CuOFP
K. Sipila*, E. Arilahti, T. Lehtikuusi and T. Saario
In Finland and Sweden nuclear waste disposal is planned to be executed according to the KBS-3concept. In the concept copper canisters containing the used nuclear fuel are buried in 400
500 m deep in the bedrock. Eventually the surface of the copper canister will come in contact with
bentonite pore water which contains corrosive species such as sulphide. In this paper the effect
of exposure to sulphide containing bentonite pore water at room temperature on the mechanical
properties of oxygen free phosphorous doped copper (CuOFP) was studied with standard ex situ
tensile and creep tests. Stress corrosion cracking (SCC) susceptibility of CuOFP was studied with
in situ slow strain rate testing (SSRT). Tensile tests performed at room temperature showed a
slight trend of degradation in mechanical properties with increasing sulphide concentration.
Creep tests were accelerated by performing them at an elevated temperature of T5215uC, but
still within the power law creep regime. In creep tests the same kind of trend as in the tensile tests
could be observed but when the results were compared to the publicly available CuOFP creep
data the variations between the exposed and reference samples lay within the data scatter.
Keywords: Nuclear waste canister, Repository, Sulphide, Oxygen free phosphorous doped copper, Mechanical properties

This paper is part of a special issue on Long-Term Prediction of Corrosion Damage in Nuclear Waste Systems

Introduction
Disposal of spent nuclear fuel in Sweden and Finland is
planned to be executed according to the Swedish KBS-3concept. The concept includes a canister which outer
shell is manufactured from CuOFP. The outer CuOFP
shell acts as a corrosion barrier while inner cast iron
insert provides the required mechanical strength to the
canister. The spent nuclear fuel is inserted to such
canisters and buried in 400500 m deep bedrock.
Bentonite clay is used to isolate the canister from the
surrounding bedrock and hinder groundwater flows in
the near field of the canister.1,2 The canister is expected
to last over 100?000 years if proper environmental
conditions are present throughout the disposal process.
After the closure of the repository air will remain
trapped within it. The oxygen contained in the air will be
consumed by various reactions such as microbial
activity, reactions with rock minerals and copper
corrosion. When evaluating copper corrosion the initial
oxic period is considered to be most harmful to the
copper canister. Various calculations with different
circumstances at the repository site estimate that the
oxic period would last from 1 month to 5000 years.3,4
Some starting values used in the calculations represent
extreme situation at the repository so a more realistic
estimation of the duration of the oxic period would be in
the range of 10 to 300 years.5 During this period oxygen
VTT Technical Research Centre of Finland, PO Box 1000, FI-02044 VTT,
Finland
*Corresponding author, email konsta.sipila@vtt.fi

410

2014 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 14 February 2014; accepted 1 May 2014
DOI 10.1179/1743278214Y.0000000180

and chloride are the main constituents which stimulate

the corrosion processes.6 When all entrapped oxygen
is consumed by various reactions corrosion will be
sustained by sulphide. Copper is generally known to be
thermodynamically unstable in sulphide containing
environments and some studies have been conducted
concerning the sulphide induced copper corrosion in
anoxic environments.79 Sulphide is present at the deep
groundwater and corrosion rates will depend on the
amount of dissolved sulphide reaching the surface of the
copper canister.5 According to the simulations of
hydrogeochemical conditions at repository depth maximum sulphide concentration during the temperate
phase is 42 mg L21 (Ref. 10) and local concentrations
due to microbial activity may reach a maximum of 400
500 mg L21.11 Such high concentrations of HS2 are
considered to be unlikely at the canister surface when
bentonite is compact but as a result of piping and/or
erosion a channel can be formed within the bentonite
which in extreme cases enables continuous HS2 flow to
the canister surface. In this kind of situation HS2
concentrations at the canister surface can exceed the
ones normally present at the bentonite pore water.12
The temperature of the repository will be elevated for
thousands of years due to the decay heat of the spent
nuclear fuel. After about 10 000 years the temperature
will approach the natural temperature value. The
maximum temperature of the canister at the near field
will be reached about 20 years after the closure of the
repository site. Various simulations of the canister near
field has resulted that the maximum temperature rise at
the near field of canister for dry bentonite would be 81uC

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and for wet bentonite 66uC. This would mean that the
actual temperature of the canister near field would not
exceed 100uC.13 The resulted temperature along with the
mechanical stresses applied to the canister enable creep
phenomenon in the copper canister until the designed
gap between the insert and outer shell is closed by
deformation of copper shell.
Copper and copper based alloys have been shown to
be susceptible to sulphur induced intergranular attack at
temperatures beyond 100150uC.14 In 2008 a Japanese
research group reported that sulphide (HS2) can cause
intergranular stress corrosion cracking (IGSCC) in pure
copper under anoxic seawater conditions at T580uC.15
As a result of slow strain rate testing (SSRT) clear stress
corrosion cracks formed at sulphide concentration of
320 mg L21, whereas at lower concentrations of 160 and
32 mg L21 slits and crevasses were found, indicative of
intergranular attack. The weight loss samples indicated
also an increasing corrosion rate as a function of
sulphide concentration.
Later in a VTT study16 CT-specimens with a precrack were used instead of SSRT specimens, because of
the stress-strain state of a CT-specimen more closely
simulates that of the thick walled canister. Constant
load was used in contrast with the Japanese study. No
clear indication of crack growth caused by exposure to
sulphide (up to 200 mg L21 HS2) containing bentonite
pore water was found in the experiments. However,
post-test fractography with energy dispersive X-ray
spectroscopy (EDS) indicated high concentrations of
sulphur on the crack surfaces and transmission electron
microscope (TEM) studies indicated sulphur and chloride containing precipitates along grain boundaries some
0?3 mm below the fracture surface.17 This was taken as
an indication of sulphide/sulphur being able to diffuse
from Olkiluoto-type bentonite pore water into the
CuOFP grain boundaries which could cause embrittlement, e.g. stress corrosion cracking (SCC) and/or brittle
creep failure.
In this study the effect of sulphide exposure on the
mechanical properties of CuOFP and the diffusion of
sulphide from bentonite pore water into the copper
matrix are examined. Mechanical properties were
examined by conducting tensile, SSRT, constant load
and creep tests for reference materials and materials
exposed to sulphide containing artificial bentonite pore
water (ABW). The diffusion of sulphide to the copper
matrix was evaluated by using scanning electron
microscope (SEM)/EDS analysis.

Effect of sulphide exposure on mechanical properties of CuOFP

in the first batch a range of tensile samples were exposed

to ABW which constitution simulated the one present at
the Olkiluoto site (presented in Table 1) with sulphate
additions of 1, 10 and 200 mg L21. The exposure time
during this batch was 5 weeks. In the second batch
tensile specimens underwent first a plastic deformation
treatment (ca. 3540%) to simulate the effect where
bentonite clay swells and causes stresses and strains to
the copper canister. The amount of plastic deformation
is considered to be conservative since investigations of
insert lid under shearing have resulted in maximum
strain of 30%.18 After the deformation treatment the
specimens (both tensile and SEM/EDS coupons) were
exposed to ABW with sulphide addition of 200 mg L21
for 7 and 14 weeks. The tensile test results of each
environment and exposure time combinations are
calculated as average of three tensile specimens.
The constant load tests and SSRT test were conducted
simultaneously with the exposure to sulphide containing
ABW. The constant load tests were conducted with a
load of 20 N mm22 at ABW environment with sulphide
additions of 1 and 200 mg L21 and with notched
specimens. SSRT tests were conducted with a strain
rate of 2?461027 1 s21 at ABW environment with
sulphide addition of 200 mg L21. After the test samples
were etched with HCl to remove the sulphide layer and
the sides of the sample just above the point of fracture
were examined with SEM in order to define whether any
stress corrosion cracks had formed during the exposure
and loading.
Prior to the creep testing, rod formed samples with
50 mm gauge length were exposed to ABW containing
200 mg L21 sulphide for a five week period. The
temperature (215uC) and stress levels (125 and
115 MPa) used in creep tests were chosen to stay within
the power law creep regime. The creep tests were
performed according to the standard SFS-EN ISO
204. The surface films on exposed specimens were not
removed before starting the creep experiments. The test
arrangements and results have been described in detail
in.19
In examination of surface films SEM/EDS analyses
and optical microscopy (OM) were used. SEM was used
to examine the structure of the sulphide layer of the
coupons. The composition of the sulphide layer was
determined by performing EDS analyses on the cross
sectional area of the sample and at the surface of the
sample. The sample used in cross sectional study was
Table 1 Composition of articial groundwater

Experiments
The examined test material was the same as is planned to
be used in copper canister and was delivered by Posiva
Ltd. The composition of the used CuOFP was 99?993%
of Cu, 55 ppm P, 11?2 ppm Ag, 3?7 ppm S and 1?5 ppm
O. The addition of P in the canister material improves
the creep properties. The sample exposures were done in
a gas tight autoclave which had a servo-hydraulic
loading machine combined to it. This machine enables
simultaneous SSRT and constant load tests with the
sulphide exposure.
Tensile tests were conducted according to standard
SFS-EN ISO 6892-1. Flat tensile test specimens with 40
and 8 mm gauge length were used. Tensile testing of the
material was conducted in two different batches where

Concentration
Element

mg L21

mmol L21

Naz
Kz
Ca2z
Mg2z
Sr2z
B3z
SO422
Cl2
F2
Br2
I2
pH

4800
21
4000
54.6
35
0.92
4.2
14500
1.2
104.7
0.9
8.2

208.8
0.54
100
2.3
0.4
0.08
0.044
412.7
0.063
1.31
0.007

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Effect of sulphide exposure on mechanical properties of CuOFP

1 Surface structure of CuOFP coupon exposed to ABW

z 200 mg L21 HS2 for ve weeks

made from one of the coupons by cutting it in half after

which the cross sectional area was polished with micro
grit diamond paste. The sulphide film thickness formed
on the surfaces of the coupons was then examined with
OM.
Fracture surfaces of the exposed creep specimen were
analysed with EDS to determine whether sulphide can
diffuse into the bulk material. Three areas at about
0?5 mm inwards from the outer edge of the fracture
surface, three areas about 0?5 mm further inwards and
one area in the centre of the fracture surface were
analysed.

Results and discussion

The SEM picture presented in Fig. 1 shows the surface
appearance of a CuOFP coupon exposed to ABW z
200 mg L21 HS2 for five weeks. Optical examination
revealed that the samples were evenly covered with black
corrosion product layers. According to the SEM
analysis the surface film consists mainly of small crystals
in the few micron size scale. The analysis of the
corrosion layer thickness based on the cross sectional
sample gave an average thickness of 9?2 mm for the
formed corrosion product layer. The surface film
compositional analyses revealed that the sulphur concentration (about 8 at-%) was rather low in comparison

2 Effect of sulphide concentration to fracture strain (FS),

yield stress (YS) and ultimate tensile stress (UTS) of
CuOFP during ve week exposure

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3 Effect of sulphide exposure in 200 mg L21 HS2 containing ABW to fracture strain (FS), yield stress (YS)
and ultimate tensile stress (UTS) as function of time at
room temperature on prestrained samples

to the presumed stoichiometric composition of Cu2S (i.e.

33 at-%). However, in the compositional analyses of a
cross-section of a similar sample a much higher sulphur
concentration within the surface film, i.e. 23 at-% was
found just a 2 mm distance from the very surface. The
low sulphur concentration and high oxygen concentration (30 at-%) on the sample surface may be result of
surface reacting with air during the sample storing
before EDS analysis. Small amounts of elements
apparently originating from the bentonite pore water
(Na, Mg, Cl and Ca) could be detected in the bulk
CuOFP metal when cross sectional sample was examined. However, these could be carry-over from the
surface film due to the polishing operation.
The tensile test results are presented in Fig. 2. There
seems to be a trend towards a higher yield stress and
ultimate tensile stress while fracture strain is decreased
as a function of increasing sulphide concentration in the
bentonite pore water. Based on the tensile test results
reported by Posiva Ltd for the same material lot (with
specimens extracted from the same piece of material but
at a distance of roughly 100 mm) there is a rather high
inherent scatter in tensile properties of the studied
material lot. However, it seems reasonable to conclude
even taking into account the scatter that there is some

4 Comparison of displacement (right axis) and displacement rate (left axis) during exposure to ABW z
1 mg L21 HS2 (green line) and ABW z 200 mg L21
HS2 (blue line)

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Effect of sulphide exposure on mechanical properties of CuOFP

6 Strain as function of time for two reference and

exposed samples (in 200 mg L21 HS2 containing ABW)
at 215uC
5 Grain boundaries opening near to point of fracture
after exposure to 200 mg L21 HS2 containing ABW for
seven week period

detrimental effect of exposure to bentonite pore water

with 200 mg L21 sulphide for five weeks on the tensile
properties of CuOFP.
When the effect of exposure time to the mechanical
properties was studied with prestrained samples it was
noticed that sulphide exposure had no effect on fracture
strain, but a slight decreasing effect on ultimate tensile
strength and yield strength as time increases (illustrated
in Fig. 3). Whether the decrease seen in ultimate tensile
strength and yield strength is real, experiments with
longer exposure times is required since the possible
diffusion of sulphide to the CuOFP matrix depends on
time.
During each 5 week exposure where the sulphide
additions were 1 and 200 mg L21 one circumferentially
notched specimen was kept under constant load.
Figure 4 shows the comparison of displacement for a
specimen exposed to bentonite pore water z
200 mg L21 HS2 and a specimen exposed to bentonite
pore water z1 mg L21 HS2 as a function of time. The
specimen exposed to the lower sulphide concentration
shows a smaller increase in displacement. To ensure the
degrading effect of sulphide more replicate measurements are required. The step-wise increase in displacement close to the end of exposure of specimen P1 was
caused by a small peak in loading (malfunction of the
servo-hydraulic loading machine). In SEM/EDS studies
of specimens P1 and P3 only traces of or no sulphur was
found on the fracture surface. This is in contradiction
with the earlier findings of high sulphur concentrations
on CT-specimen fracture surfaces.16
After the SSRT test the samples were examined with
SEM. No actual stress corrosion cracks were found but
slight opening of grain boundaries was detected on side
of the sample, near to the point of fracture, as shown in
Fig. 5. The current finding differs from the earlier results
presented by Taniguchi and Kawasaki where cracks
found at high sulphide concentrations were interpreted
to be stress corrosion cracks. This difference may result
from the different temperature used in the experiments.
The slightly opened grain boundaries were interpreted to
be the possible source of the observed minor degradation in mechanical properties during the tensile tests.
Figure 6 shows the creep curves, i.e. strain log(time)
curves. For the two stress levels at which the tests have

been completed (115 and 125 MPa), the reduction of

area, time to fracture and fracture strain all are
consistently smaller for the specimens that have been
pre-exposed to the sulphide containing bentonite pore
water. The creep test results at elevated temperature
seem to indicate a degradation of the mechanical
properties due to the pre-exposure. In order to
determine whether the variations in the obtained rupture
times between exposed and reference data are remarkable, the results were compared to publicly available
creep data presented by SKB.20 Owing to different
testing parameters used in creep tests the creep data
must be normalized. One way to normalise creep data is
to use the so-called Wilshire model.21 The creep results
seem to indicate a degrading effect of sulphide exposure
on the creep properties, but when normalised by using
Wilshire model and shown with data from various heats
and laboratories, the scatter between the different sets of
data is of the same magnitude as the difference between
the reference and exposed specimens in the present
study. Therefore, it cannot be distinguished whether the
sulphide exposure has a degrading effect on creep
properties of CuOFP or not at chosen stress levels and
temperature.
The fracture surfaces of pre-exposed samples were
examined with SEM. The morphology showed a typical
dimple structure, where voids have opened at sites of
internal particles. Also a compositional analysis was
performed with EDS on the fracture surfaces. As a result
S, Na, Cl and Ca (0?67, 2?96, 1?52 and 0?36 at-%
respectively) supposedly originating from the bentonite
pore water were found at the edges of the fracture
surfaces, but not at the areas more inwards. This would
indicate that no significant sulphur ingress into the
CuOFP matrix exists.

Conclusions
In this study only small concentrations or no sulphur at
all was found on fracture surfaces, in contradiction with
earlier studies with precracked CT-specimens under
constant load. It is suggested that the high concentrations found earlier may have been caused by the method
of opening up the fracture surfaces (i.e. post-exposure
fatigue in air) and that the in-diffusion of sulphide does
not take place with such a large scale as previously was
reported, if at all. Equipment with higher resolution is
required to confirm whether the sulphide concentrates
on the grain boundaries.

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Effect of sulphide exposure on mechanical properties of CuOFP

The tensile tests performed after the exposure to sulphide

containing bentonite pore water indicate a slight degrading
influence of the exposure on mechanical properties of
CuOFP. The effect of exposure time on the mechanical
properties of prestrained samples is not so evident at least at
relatively short (up to 14 weeks) exposure times. Whether
the decrease seen in ultimate tensile strength and yield
strength is genuine, experiments with longer exposure times
are required since the possible diffusion of sulphide to the
CuOFP matrix depends on time.
The SSRT tests indicated that CuOFP is not
susceptible to SCC when exposed to Olkiluoto site type
of bentonite pore water with 200 mg L21 sulphide
addition at room temperature. Only slight opening of
grain boundaries were found on the specimen surfaces
and no sulphide was found on the fracture surface of the
specimens. The slight opening of the grain boundaries
was interpreted to possibly cause the minor decrease in
mechanical properties of CuOFP. However it must be
stated that the obtained results do not exclude the fact
SCC would become possible at higher temperatures as it
was observed by Taniguchi and Kawasaki.
The creep test results presented within this paper seem
to indicate a degrading influence of the exposure to
sulphide containing bentonite pore water. However,
when compared with the publicly available creep data
on CuOFP from different heats and laboratories the
current finding is still within the scatter band.

Acknowledgements

7.

8.

9.

10.

11.

12.

13.

14.

16.

17.

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