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In situ evaluation of model copper-cast iron

canisters for spent nuclear fuel: a case of

microbiologically influenced corrosion (MIC)
N. R. Smart*1, A. P. Rance1, B. Reddy1, L. Hallbeck2, K. Pedersen2 and
A. J. Johansson3
The Swedish method for disposal of spent nuclear fuel in a deep geological repository (KBS-3)
relies on the stability of the granitic bed-rock and two engineered barriers: a copper-cast iron
canister and highly compacted bentonite clay. In order to develop a better understanding of the
internal corrosion processes that could take place if a leak were to occur in the outer copper
canister, five miniaturised copper cast iron canisters were installed at a depth of 450 m at the
A spo Hard Rock Laboratory, in Sweden. The experiments differed in the density of the
surrounding bentonite buffer, as well as in the number and position of leak points that were
introduced in the copper shell. Several electrochemical techniques (e.g. AC impedance, linear
polarisation resistance and electrochemical noise) were used to monitor the corrosion of different
components of the experiment. Copper specimens were installed for post-test evaluation of the
rate of general corrosion, localised corrosion and stress corrosion cracking (SCC). In addition,
mechanical and environmental parameters, such as surface strain, hydrostatic pressure, redox
potential, pH, water chemistry, dissolved gases, and microbial numbers, diversity, and activity
were measured regularly. After five years of in situ exposure one of the canisters was retrieved
and analysed to characterise and evaluate the corrosion processes that had occurred during the
experiment. Extensive sulphide production by sulphate reducing bacteria led to rapid corrosion of
iron, and the formation of iron sulphide deposits on the copper and iron electrodes disturbed the
electrochemical measurements. This paper describes the various analyses that were carried out
on the model canister and summarises the conclusions that can be drawn.
Keywords: Spent nuclear fuel, Radioactive waste disposal, Copper, Iron, Corrosion, In situ testing, Microbiologically influenced corrosion, Sulphate
reducing bacteria

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

Introduction to occur in the outer copper canister, five miniaturised,

model, copper-cast iron canisters were installed at the
To ensure the safe encapsulation of spent nuclear fuel beginning of 2007 at a depth of 450m at the A spo Hard
for geological disposal, the Swedish Nuclear Fuel and Rock Laboratory, which is located in the Baltic sea
Waste Management Company (SKB) has proposed a archipelago in Sweden. The ambient temperature at this
technology that consists of an outer copper canister with location is y15uC throughout the year. The experiment
a cast iron insert, commonly referred to as the KBS-3 is named MiniCan and its detailed design is shown in
concept. This design relies on the stability of granitic Fig. 1.
rock and two engineered barriers: a copper cast iron
The experiments differed in the density of the
canister and highly compacted bentonite clay. In order
surrounding bentonite buffer, as well as in the number
to develop a better understanding of the internal
and position of 1 mm pinholes that were deliberately
corrosion processes that could take place if a leak were
machined into the copper shell. Several electrochemical
techniques (e.g. AC impedance, linear polarisation
AMEC, B150 Harwell, Harwell Oxford, Didcot, Oxfordshire, OX11 0QB, resistance and electrochemical noise) were used to
continuously monitor the corrosion of different compo-
Microbial Analytics Sweden AB, Molnlycke Fabriker 9, SE-435 35
Molnlycke, Sweden
nents of the experiment.14 In addition, mechanical and
SKB, Swedish Nuclear Fuel and Waste Management Co., Box 250 SE- environmental parameters, such as surface strain,
101 24, Stockholm, Sweden hydrostatic pressure, redox potential, pH, water chem-
*Corresponding author, email istry, dissolved gases, and microbial numbers, diversity,

2014 AMEC Nuclear UK Limited

Published by Maney on behalf of the Institute
Received 18 February 2014; accepted 19 June 2014
548 DOI 10.1179/1743278214Y.0000000213 Corrosion Engineering, Science and Technology 2014 VOL 49 NO 6
Smart et al. Corrosion of copper-cast iron nuclear containers

(Experiment 3; bentonite y1?3 kg dm23 dry density,

1 mm defect at top and bottom weld) was retrieved and
analysed to characterise and evaluate the corrosion
processes that had occurred. Full details of the
procedure for removing the canister and analysing it
are presented in references;68 this paper presents and
discusses the key results from the post-test examination
of the retrieved container.

During removal of the canister from the A spo labora-
tory the experiment was extracted from its borehole,
whilst minimising exposure to oxygen. It was placed into
a tightly sealed, water-filled and nitrogen-purged transfer
flask and transported to the UK for analysis in an inert-
gas purged glovebox. Once in the glovebox the experi-
ment was dismantled and sectioned and various samples
were prepared for analysis without exposure to the
atmosphere. Samples from the dismantled experiment
were analysed using a range of analytical techniques to
characterise the extent of any corrosion and to identify
the corrosion products formed, as follows:
(i) visual observation and photography: to assess
the extent of any corrosion
(ii) raman spectroscopy; to identify mineral phases
(iii) X-ray diffraction (XRD): to identify crystalline
mineral phases.
(iv) scanning electron microscopy (SEM) and energy
dispersive X-ray analysis (EDX): to examine the
morphology of deposits and to determine the
elemental composition of materials
(v) SEM/EDX: to evaluate if stress corrosion
cracking (SCC) had occurred on U-bend speci-
(vi) X-ray photoelectron spectroscopy (XPS): to
determine the composition of very thin films
on the surface of specimens, with a surface
sensitivity of a few atomic layers
(vii) Fourier transform infra-red spectroscopy
(FTIR): to identify chemical bonds and func-
tional groups in the materials.
In addition, the following measurements were carried
(i) profilometry: to determine the extent of any
a stainless steel support cage showing bentonite pellets localised corrosion of the copper canister
in annulus between inner and outer stainless steel filters surfaces
and inner void holding copper cast iron model canister; (ii) analysis of dissolved hydrogen in copper: to
b copper canister being lowered into support cage; c determine whether any hydrogen produced by
inner cast iron components; d sensors and corrosion corrosion had entered the material
samples (including copper cast iron sandwich speci- (iii) gravimetric analysis: to determine the integrated
men to investigate corrosion induced expansion) corrosion rate of the metal coupons
mounted above model canister assembly, inside support (iv) diversity analysis and determination of the
numbers of microorganisms attached in bio-
1 MiniCan experiment
films on the steel and copper surfaces.
Prior to removal of Experiment 3 from the borehole a
and activity were measured regularly.5 The copper set of water samples was collected from the headspace
canister was made from oxygen-free phosphorous doped above the miniature canister and analysed for chemical
(OFP) copper and the insert was made from cast iron. composition, microorganisms and dissolved gases.7
Bentonite MX-80 clay was used. The support cage was
made from 316L stainless steel and the plastic support
table holding the electrodes and corrosion coupons was Results
made of nylon. The detailed design of the experiment is When the support cage was extracted from the transfer
described in reference1 and the set up and results flask it was seen to have a shiny appearance, meaning
obtained to date are summarised in references.24 After that the external surface of the stainless steel support
nearly five years of in situ exposure, one of the canisters cage had not suffered from significant corrosion. The

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Smart et al. Corrosion of copper-cast iron nuclear containers

,5 mm) predominantly composed of copper and sul-

phur, with small quantities of iron, silicon, oxygen,
carbon, calcium, and chlorine. The gravimetric analysis
gave an integrated corrosion rate for copper of
0?150?02 mm year21.

Iron electrodes and coupons

Elongated black whiskers of material were observed
hanging vertically down from the cast iron weight loss
coupon and the cast iron electrodes. The whiskers, and
the corrosion products adhering to the cast iron
electrodes and coupons themselves, were found to be
mainly amorphous and EDX analysis showed a high
content of iron and sulphur. Raman analysis showed the
presence of graphitic carbon and possibly weak sulphide
peaks, and XRD analysis showed that the material was
amorphous. EDX analysis showed that the main
elements were iron, silicon, sulphur and oxygen.
2 MiniCan experiment 3 after removal from borehole at Iron weight loss specimen
spo: (left) copper model canister; (right) sensors and
A Although the specimen was crumbly and cracked its
corrosion coupons dimensions remained approximately the same as the
initial coupon. Raman analysis showed that the material
was amorphous, as shown by the broad peaks, with no
striking feature about the appearance of all the evidence for the common iron oxides. The broad Raman
components inside the support cage when the lid was peaks overlapped with the position expected for pyrite,
removed was that they were all covered with a layer of FeS2, but it was not possible to identify the species
black deposit, as shown in Fig. 2. present conclusively from the Raman spectra. In the
The bentonite in the annulus of the support cage, XRD analysis the only crystalline phase detected was
which was originally present in pellet form, had swelled graphite, meaning that all metallic iron had been
to a homogeneous mass, without any indications of the corroded. The final weight of the coupon was 22% of
original boundaries between the bentonite pellets or its starting weight, giving a cast iron corrosion rate of at
channeling in the bentonite. No further analysis of the least 500 mm year21.
bentonite was carried out, but samples were removed for
microbial analysis.7 The bentonite had the consistency Black flaky material from support table
of butter, with some reddish staining in the bentonite. Raman and XRD analysis showed indications of Fe2O3,
Even though all surfaces were covered with a layer of carbonate, graphitic carbon and iron sulphide. The
black material, the iron surfaces appeared to have a material was amorphous. SEM/EDX analysis showed a
thicker layer of black material on them than the copper mass of closely compacted small crystallites (,5 mm), a
surfaces. There was significant, non-uniform blackening high concentration of iron, sulphur, silicon and oxygen,
of the surface of the canister and the blackening was and the flakes were approximately 0?1 mm thick. They
concentrated on areas facing the holes in the inner were probably formed by dissolution of iron from
cylinder of the support cage. In addition, there was a electrodes and weight loss specimens and precipitation
black flaky material on the plastic support table holding as iron sulphide.
the electrodes and coupons. A short summary of the
main results from analysis of the surfaces of various Copper canister with iron insert
components in the experiment is given below. No dimensional changes were measured compared with
the original design (to an accuracy of 0?05 mm) and
Copper electrodes and coupons there were no signs of crevice corrosion around the O-
SEM/EDX analysis showed mainly copper with small ring seal between the lid and body of the iron insert. The
quantities of iron, carbon, oxygen, silicon, sulphur, simulated fuel channels inside the cast iron insert were
chlorine, and calcium. Raman spectroscopy showed dry and showed no sign of corrosion. Flakes on the
predominantly non-crystalline material with possible outer surface were predominantly amorphous with a
indications of graphitic carbon and mixed oxide/ trace of FeS (troilite) or CuFeS2 (chalcopyrite). The
sulphide species (possibly a mixed CuFeS2 phase). results of the hydrogen analyses on two samples cut
These results are consistent with a thin film of copper from the canister were 0?594 ppm for a section cut from
sulphur/oxygen superimposed in some areas with a layer the inner surface of the copper canister and 0?536 ppm
rich in iron, sulphur and silicon. The corrosion product for the outer surface. Although the hydrogen content of
developed on copper specimens mounted outside the this specific copper material was not determined before
steel cage, thus exposed directly to the borehole water, installation of the experiment, earlier batches of OFP
was predominantly copper oxide, with only a trace of copper from the same manufacturer contained on
sulphide present. average 0?37 ppm (s50?14), and some batches had up
to 0?60 ppm hydrogen.9 This suggests that the hydrogen
Copper weight loss specimen content was largely unaffected by the corrosive exposure
SEM/EDX analysis of the weight loss specimen showed during the experiment. The machined defects in the
a uniform coating of very small particles (typically copper canister had become blocked with corrosion

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Smart et al. Corrosion of copper-cast iron nuclear containers

product, but locally high rates of corrosion of the cast (i.e. an ironsulphursilicon rich graphitic carbon
iron insert were observed opposite the machined defects phase), but the underlying copper surfaces were covered
in the copper canister, indicating high levels of microbial with a thin film of an unidentified mixed copper oxide
activity in these areas. sulphide. The copper weight loss sample appeared to be
coated with a layer of small (i.e. ,5 mm) crystals of
Microorganisms and biofilms copper sulphide, or a mixed ironcopper sulphide. The
The concentration of dissolved ferrous iron measured formation of a layer of copper sulphide on the surface of
inside the support cage had increased over the five year copper in the presence of SRB is well documented in the
test period, leading to a concentration of several 10 s of literature.10
mg L21. The concentration of sulphate had decreased, The weight loss measurement on the copper sample
with an accompanying increase in the numbers of SRB. gave an integrated corrosion rate of 0?150?02
Cultivation of samples from water and biofilms on mm year21. This is considerably lower than the corro-
various surfaces in the experiment revealed the presence sion rates measured by electrochemical methods,3 which
of sulphate reducing bacteria (SRB). On the canister are considered to be erroneous due to the deposition of a
surface, the population exclusively consisted of SRB. surface layer of conductive iron corrosion product
DNA analysis identified several species of SRB, includ- derived from the iron electrodes and coupons, and the
ing Desulfovibrio ferrophilus, which is able to metabolise neighbouring cast iron insert. This phenomenon has
metallic iron directly (using iron as an electron source). been observed by other workers.11 Corrosion rates
Cultivable heterotrophic aerobic bacteria (CHAB) and measured using the electrical resistance technique in
acetogenic autotrophes (AA) were present at the canisters not yet retrieved from the MiniCan experiment
beginning of the experiment, but they seem to have are closer to the gravimetrically measured rate (0?25
disappeared during the subsequent years.5 The diversity 0?39 mm year21).2,3 It should be noted that both the
of the microbial populations fluctuated over time but copper and iron weight loss specimens were electrically
the total number of microbes present was relatively isolated from other metallic parts of the experiment, and
constant. that the environment was aggressive due to the high
numbers of SRB inside the support cage, as well as in
Discussion biofilms on the canister. To that extent the experiment
In order to analyse the results obtained by post-test represents a severe test of microbiologically influenced
examination, it is helpful to briefly discuss the chemical corrosion (MIC) for the copper material, which may not
and biological environment inside the experiment. The be representative of conditions for a copper canister
results from the microbial analysis7 show that there was surrounded by highly compacted bentonite in the
a significant difference between the microbial popula- repository.12
tions on the outer surface of the support cage, which was Corrosion experiments performed under anaerobic
exposed to the borehole water, compared to the laboratory conditions, using simulated groundwater
population on the surface of the copper canister, which compositions, have shown that the abiotic anaerobic
was exposed to the water inside the support cage. The corrosion rate of iron is of the order of ,1 mm
outer surface of the support cage had higher numbers of year21.13,14 However, the corrosion rate measured
CHAB than the surface of the copper canister, whereas gravimetrically in the MiniCan experiment was approxi-
the surface of the copper canister had a very high mately three orders of magnitude higher and the
number of SRB but just a few CHAB. Both types of inevitable conclusion is that this increase in corrosion
bacteria were detected in the groundwater sampled from rate was due to the large numbers and vigorous activity
within the Experiment 3 support cage, although the of sulphate reducing bacteria (SRB) in the water filled
number of SRB was higher. During the course of the void inside the support cage of the experiment. SRB are
experiment the pH varied between 7?6 and 6?6, and well known to cause accelerated corrosion rates10 of iron
the concentration of Fe2z increased by more than one based alloys, with the end product being iron sulphide
order of magnitude. The concentration of SO422 films. Even though the exact mechanism utilised by SRB
remained nearly constant above 400 mg L21 during in the present case is unknown, there is a limited number
20072010, but fell to 271 mg L21 in 2011, and the of possibilities. The possibility of iron as the electron
sulphide concentration fluctuated below 0?1 mg L21. source for sulphate reduction according to reaction (1)
Some oxygen was present in the near-field initially, since has some experimental support, however, the composi-
the bentonite pore volume and other voids in the tion and stoichiometry of the iron sulphide depends on
experimental configuration contained air at installation the redox potential and pH (Ref. 10)
of the experiment (which might explain the presence of
some Fe2O3 in the Raman/XRD analysis of black flakes 4FezSO4 2{ z4H2 O?3Fe(OH)2 zFeSz2OH{ (1)
on the support table). The redox potential in the
borehole fell from an initial value of y0 mV(SHE), The stoichiometry of reaction (1) suggests that solid
which indicates the presence of residual oxygen, to iron sulphide and iron oxide should form in similar
2300 mV(SHE) within a few months, while the poten- quantities*. This could be the case in the experiment at
tial inside the support cage stabilised at around hand, since even if iron sulphide seems to be the major
2400 mV(SHE).3
*According to reaction 1, the ratio of solid iron hydroxide and sulphide
Corrosion of copper and iron coupons should be 3 : 1. However, the stoichiometry of iron sulphide can undergo
The copper electrodes were covered with a black alterations by long-term exposure to SRB.9 Also, the kinetic and/or
thermodynamic stability of solid iron hydroxide in reducing sulphidic water
material, which appears to have originated from is unclear to the authors, but is likely to affect the composition of the
corrosion of the iron components in the experiment corrosion products of iron.

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Smart et al. Corrosion of copper-cast iron nuclear containers

3 a optical micrograph of outside cross-section of copper U-bend specimen and b selected part of outer surface of cop-
per canister near top hole

solid corrosion product formed, solid iron oxides/ areas without this deposit it is still possible to see
hydroxides are observed and the concentration of machining marks, which is probably a reflection of the
ferrous iron in the water inside the steel cage has low rate of general corrosion discussed above (0?15
increased dramatically (from 0?82 mg L21 in 2007 to 0?02 mm year21).
49?6 mg L21 in 20117). SRB are able to metabolise
hydrogen to reduce sulphate to sulphide.15 Hydrogen Miniature canister
may be generated by the anaerobic corrosion of The analysis of components cut from the copper canister
iron;13,14 however, a recent study16 suggests that some showed the presence of a range of materials, including
strains of lithotrophic SRB can use iron as a direct crystals with a high concentration of copper and
electron source, without the need for intermediate sulphur. It was not possible to discern from the analysis
hydrogen formation. These strains were detected in the exact stoichiometry of the crystals because the
the MiniCan experiment.7 Another possibility is that analytical technique used, EDX, is semi-quantitative,
SRB oxidised dissolved organic material (or methane) but there is a range of stoichiometric and non-
in order to reduce sulphate. The exact mechanism of stoichiometric6,10 copper sulphides that could be present
the bacterial sulphate reduction is still a matter of on the surface of the canister and it is not possible to
investigation. determine the exact mineral composition from the
The form of attack of cast iron observed in the current dataset. The majority of the iron sulphide
MiniCan experiment is an example of graphitisation,17 deposited in the void inside the MiniCan experiment
which is common in the water industry where cast iron appears to have originated from dissolution and
pipes are used to transport water supplies. This results in precipitation of iron from the iron corrosion coupons.
the conversion of the metallic structure to a weak porous In summary, the experiment analysed shows that in a
mass of corrosion product and graphite residue. deep granitic repository, the establishment of sulphate
The conditions inside the MiniCan support cage are
reducing bacteria (SRB) can locally lead to rapid
conducive to SRB growth, because of the presence of
corrosion of cast iron (500 mm year21). Despite the
plenty of water, an abundant supply of sulphate and
presence and activity of SRB, the corrosion of copper
hydrogen, the absence of oxygen and traces of organic
was slight. The establishment of SRB would be
material in the bentonite. The conditions within
supported by the presence of low density bentonite,
compacted bentonite, as would be used in the KBS-3
but may be restricted by the use of compacted bentonite.
concept, would be less conducive to SRB activity
Increased compaction will reduce the availability of
because of the lower water activity and lower supply
water, which is an essential requirement for the
rate of sulphate.12,18
proliferation of bacteria. Furthermore, increased com-
Corrosion morphology paction will expose the bacteria to high mechanical
None of the U-bend specimens installed showed any stress that will eventually puncture and kill them. The
signs of stress corrosion cracking (SCC) when examined MiniCan in situ experiment is ongoing and two more
metallographically, i.e. no initiation of trans- or inter- canisters are planned to be retrieved; one with highly
granular cracks could be observed with SEM (Fig. 3a).8 compacted bentonite and one without bentonite. The
Optical microscopy and SEM revealed a partly rough post-test analysis of these canisters will give valuable
surface in agreement with earlier experiments with OFP information about the role of the bentonite buffer and
copper embedded in bentonite, in saline ground- its impact on microbiologically influenced corrosion.
water.16,19 A striking feature of the copper shell is that
some areas of the surface were relatively unaffected by
corrosion, despite the long term exposure to saline
ground water. Figure 3b shows an area of the outer A detailed analysis of MiniCan Experiment 3 has been
copper surface that is partly covered with a crystalline conducted under carefully controlled conditions and the
deposit (that was rich in iron and sulphur). Note that on main conclusions from the investigation are as follows.

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Smart et al. Corrosion of copper-cast iron nuclear containers

1. The corrosion observed in the MiniCan experiment References

was heavily influenced by the extensive activity of
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support and the technical assistance provided by staff at under expected conditions in a deep geologic repository, SKB
spo URL, and the University of Oxford Materials report TR-1067, 2010.
the A 19. F. King, C. Lilja and M. Vahanen: Progress in the understanding
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