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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci
SUBATECH, CNRS-IN2P3, Ecole des Mines de Nantes, Universit de Nantes, 4 rue Alfred Kastler, BP 20722, 44307 Nantes cedex 03, France
LUNAM Universit, Institut des Molcules et Matriaux du Mans, UMR CNRS 6283, Universit du Maine, Avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France
c
CEA, DEN, DANS/DPC/SEARS/LISL, F-91191 Gif-sur-Yvette, France
b
a r t i c l e
i n f o
Article history:
Received 22 April 2014
Accepted 10 July 2014
Available online 18 July 2014
Keywords:
A. Carbon steel
B. Raman spectroscopy
B. SEM
C. Microbiological corrosion
a b s t r a c t
We investigated the carbon steel corrosion in carbon dioxide clay-rich environment to understand its
behavior under geological conditions. The results show the formation of magnetite as the main corrosion
product in the rst step of the corrosion process, followed by the formation of different corrosion products with complex mixtures of iron-oxide, hydroxycarbonate, hydroxychloride and sulde phases. These
results strongly contrast with similar experiments conducted under H2 atmosphere where the major corrosion products consisted of iron suldes. It appears then important to consider all the geochemical
parameters including gas composition to better study corrosion of steel buried in geological formations.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
Deep geological disposal remains the preferred option for management of long-lived radioactive waste in several countries
including Belgium, Finland, Japan, Republic of Korea, Sweden, Switzerland, USA and France [18].
The French radioactive waste management agency (ANDRA) is
designing a deep geological repository in Callovo Oxfordian claystone (COx) formation in Eastern France. Current investigations
are conducted to optimize and nalize this repository concept with
the aim to ensure its long-term safety and its reversibility. The
high-level waste (HLW) shall be conned in a glass matrix and
then encapsulated into cylindrical carbon steel overpacks. These
containers shall be placed into micro-tunnels in the highly impermeable COx layer at a depth of 500 m [6,9,10]. Carbon steel containers must remain leakproof for a few thousand years as a
contribution to the multi-barrier containment system for the
waste [9,11,12]. The long-term safety assessment of the geological
repository has to take into account the degradation of the carbon
steel used for the waste overpacks, which is mainly caused by corrosion processes.
One of the most important features of any deep geological
repository is that the nature of the environment evolves over time.
Generally, the environment evolves in such a way that corrosion
becomes less severe and more predictable with time. However,
the presence of microorganisms can also affect the environment
[6,13]. In a recent study [6], we have shown the presence of
Corresponding author. Tel.: +33 2 51 85 86 35; fax: +33 2 51 85 84 52.
E-mail address: elmendil@subatech.in2p3.fr (Y. El Mendili).
http://dx.doi.org/10.1016/j.corsci.2014.07.020
0010-938X/ 2014 Elsevier Ltd. All rights reserved.
57
role of the corrosion product layer formed under sequential aerobicanaerobic conditions.
Although great care was taken to investigate the inuence of
major factors on carbon steel corrosion under geological conditions, the mechanism responsible is probably more complex.
Indeed, the corrosion of iron and steel surfaces in natural environments often lead to the formation of corrosion layers made of
extremely complex mixtures of iron-sulde, (hydro)oxide, carbonate, and chloride solids [16,17]. According to Anderko and Shuler
[18], magnetite and siderite are precursors to a less stable form
of iron sulde such as mackinawite. Mackinawite is a particular
form of iron sulde that is commonly observed in immersion corrosion studies and also easily produced from iron and iron oxides
by SRB activity [19]. Mackinawite can then transform into pyrrhotite which is considered to be more thermodynamically favored in
anoxic environments, hence pyrrhotite is expected to predominate
over long term conditions [18,2022].
In the present work, we investigate the carbon steel corrosion
under carbon dioxide-rich atmosphere in the presence of claystone. The morphology and the nature of corrosion products evolution were analyzed step by step using both scanning electron
microscopy (SEM) and confocal micro-Raman spectroscopy and
the role of SRB in the mechanism of steel corrosion was then
discussed.
2. Experimental section
2.1. Materials
The Callovo-Oxfordian (COx) claystone from the Bure site (east
of France) contains three main mineralogical phases: a dominant
argillaceous phases 4050% clay (5070% interstratied illite/
smectite), a carbonate phase (2230%, essentially calcite with a
few percent of dolomite) and a quartz phase (1832%) [23]. These
three main phases are accompanied by other minor phases including pyrite, feldspar, and organic matter, in mass quantities of less
than a few percent. The clay used for our experiments was sampled
under oxygen-free conditions, sealed in plastic/aluminium bags,
and transferred to the laboratory. Powder samples were prepared
for batch experiments in a glove box lled with nitrogen gas. A
simplied groundwater composition was calculated by BRGM
(French Geological Survey) and beaucaire et al. [24,25], from analyses of samples coming from the site of the Meuse/Haute-Marne
laboratory (France). The simulated groundwater was prepared in
the laboratory at 25 C with the following reagents: NaHCO3,
Na2SO4, Na2SiO39H2O, NaCl, KCl, CaCl22H2O, MgCl26H2O,
SrCl6H2O. All the reactants except metasilicate (Na2SiO39H2O)
were weighed out and grinded, then placed in a 2-liter ask containing 1.5 L of ultrapure water. The ask was closed and the solution is then brought into equilibrium (pH stabilization) under
magnetic stirring for 24 h until the reagents were completely dissolved. The solution was bubbled with a mixture of 89.5% Ar + 5%
H2 + 5.5% CO2 until the pH reached about 6.5. Metasilicate was
then added and the solution volume in the ask was adjusted to
2 L. After clarication, the solution was again degassed to pH 7.2.
The nal groundwater composition is detailed in Table 1. Lactate
(1 ppm) was added at the beginning of the experiments to simulate
the SRB activity as indicated by El Hajj et al. [11].
2.2. Steel preparation
The P235GH carbon steel was used because it has a number of
obvious benets as a canister material, including good combination of strength and ductility, good corrosion properties in the
expected repository environment, extensive experience with
Table 1
Synthetic water composition in equilibrium with the COx claystone (pH = 7.2).
Elements
Measured concentration
(mmol/L)
Theoretical concentration
(mmol/L) [25]
Na+
K+
Mg2+
Ca2+
Cl
SO2
4
44.9
1
6.4
7.3
42.1
15.5
45.6
1.03
6.67
7.36
41.0
15.6
58
Fig. 1. (a) SEM image of the steel surface after 1 month, (b) zoom of the SEM photograph with the corresponding chemical microanalysis spectrum and (d and c) Raman
spectrum of the corrosion products formed on the steel surface after 1 month of time exposure. The elemental composition is Fe: 41, S: 3, O: 53, C: 2 and Al: 1 (atomic %).
59
Fig. 2. (a) SEM photograph of the steel surface after 3 months, (b) zoom of the SEM photograph (a) with the corresponding chemical microanalysis SEM micrograph, 1, 2 and
3: spectra associated with carbonate, iron sulde and magnetite. The elemental composition is Fe: 38, Ca: 3, S: 7, O: 36 and C: 16 (atomic %).
60
Fig. 3. (a) SEM photograph of the steel surface after 6 months; (b) zoom of the SEM photograph; (c) the Raman spectra correspond to the corrosion products formed onto
surface: mackinawite, magnetite, carbonate (Ca, Mg)FeCO3, chukanovite and hydroxychloride b-Fe2(OH)3Cl.
61
CO2g ! CO2aq
2FeOHaq
CO2
3aq
Fe2 OH2 CO3s CO2
3aq ! 2FeCO3s 2OHaq
3
4
Thus, a slightly basic pH, resulting from e.g. water reduction at the
steel surface, would favor the chukanovite over siderite.
In addition to the described corrosion products, ferrous
hydroxychloride b-Fe2(OH)3Cl was also clearly identied by Raman
spectroscopy (Fig. 3). Our attribution is based on a similar Raman
spectrum reported by Rmazeilles et al., Neff et al. and Rguer
et al. on terrestrial ferrous archaeological objects [4244]. Their
spectra shows peaks around 127, 161, 322, 429, 615, 789 and
985 cm1, but no Raman band assignment was given by theses
authors. Accordingly, to reveal clearly the formation of ferrous
hydroxychloride phase, we have tested the transformation of ferrous hydroxychloride into Akaganeite (b-FeOOH containing chlorine) [42] in oxidizing conditions by exposing the steel coupons
to open air for 1 month. Indeed, Akaganeite the b phase of ferric
oxihydroxide b-FeO12x(OH)1+xClx, is often observed as a corrosion
product of iron in chloride containing environments, such as marine environments or in corroded archaeological iron artefacts
[45,46]. Akaganeite has a monoclinic crystal structure and always
contains some chloride ions. As shown by Keller [47], it can contain
up to 6% chloride. It is also preferentially formed compared to goethite and lepidocrocite in environments with high chloride and
Fe2+ concentration, by the oxidation of ferrous hydroxychloride
b-Fe2(OH)3Cl [48,49].
Fig. 4 shows the Raman spectrum obtained after oxidation of
ferrous hydroxychloride for 1 month. The Raman spectrum with
the bands around 308, 390, 535 and 720 cm1 is characteristic
for akaganeite [43,44,50] and our Raman spectrum is similar to
that reported by Neff et al. [43,44]. This corroborates the identication of the ferrous hydroxychloride as a corrosion product in our
experiments.
Finally, the Raman spectrum of black zone (Fig. 3) clearly identies the presence of mackinawite vibrational modes at 225 cm1
(B1g), 255 cm1 (Eg), 367 cm1 (A1g) and 398 cm1 (Eg) [51]. In
addition, the observation of band at 175 demonstrates the presence of elemental sulfur onto the corroded surface. Accordingly,
our Raman investigations reveal clearly the formation of poorly
crystallised FeS after 1 month of time exposure followed by the
crystallization of mackinawite after 6 months.
The corrosion of steel surface under CO2 pressure leads to the
formation of different corrosion products with extremely complex
mixtures of iron-oxide (magnetite), carbonates (siderite and chukanovite), sulde (mackinawite), and chloride (hydroxychloride).
Fig. 4. Raman spectrum of akaganeite formed on the steel surface after 1 month of
ferrous hydroxychloride oxidation.
the surface will give minimum iron transport and thus maintaining
low Fe concentration in solution.
The evolution of dissolved concentration of sulfate ([SO2
4 ]aq)
and sulde ([S2]aq) as a function of experiment time is presented
in Fig. 6. It is important to note that the concentration of sulfate at
the beginning of the runs (1325 mg/L) is higher than that expected
in COx water (1023 mg/l), which can be explained by the possible
slight oxidation of claystone (oxidation of pyrite) during transport
and storage before being used in the experiments.
Between 0 and 6 months, [SO2
4 ]aq decreased by about 45 mg/L
(0.47 mM) while sulde was produced. This indicates the SRB bioactivity in the rst step of the corrosion processes, which explains
the presence of sulde in the EDS spectrum (Fig. 1d). The high
2
decrease in [SO2
]aq, are
4 ]aq paralleled by the low increase of [S
the signature of the formation of iron sulde on the steel surface.
In fact, after 6 months the average measured mass loss for each
coupon is 75.5 mg and the expected total mass loss for the 4 coupons used in the experiment is 302 mg in 100 mL of solution.
Hence the maximum iron concentration provided by the steel corrosion is 3020 mg/L (54 mM). This indicates that only a minor fraction of oxidized Fe (less than 1%) is needed to co-precipitate the
entire amount of produced sulde. This is consistent with SEM
observations of the corroded steel showing that mackinawite is
only a minor corrosion product.
We did not measure oxygen concentrations in the systems but a
measurement of redox potential in the beginning of the experiments give values (+100 mV) indicating the presence of some
oxygen traces. However, at the end of the experiment, Eh measurements (200 mV) show reducing conditions, which is consistent
with the activity of sulfate-reducing bacteria. Hence at the
62
beginning of the experiment where oxygen traces persist, magnetite (Fe3O4) is expected to form as follow:
Hydrogen production leads then to establish reducing conditions propitious for SRB growth. In fact, SRB are anaerobic bacteria
that gain energy by oxidizing organic compounds such as lactate or
H2 formed by the steel corrosion. The SRB bacteria promote reduction of dissolved sulfate to H2S. SRB metabolize as follows:
4H2 SO2
4 2H ! 4H2 O H2 S
Bisulde dissociation:
3.3. pH variation
The variation results of solution pH as a function of time exposure is given in Fig. 8. The pH increases from 7 to 9 within
3 months. This increase of pH can due to the overall corrosion process in our system, according to the reaction:
4Fe SO2
4 3HCO3 5H ! FeS 3FeCO3 4H2 O
10
Fe2 H2 S ! FeS H2
11
12
13
63
Table 2
Concentrations of Cl, Ca2+, Na+ and Si4+ in the COx groundwater as function of time
experiment.
Elements (mg/l)
First day
30 days
60 days
90 days
180 days
[Cl]
[Ca2+]
[Na+]
[Si4+]
1353
318
887
2.1
1335
324
891
3.2
1310
321
894
5.0
1299
326
900
6.9
1270
364
922
12.0
CO2 H2 O ! H2 CO3
14
H2 CO3 ! H HCO3
15
HCO3 ! H CO2
3
16
17
Fe
CO2
3 ! FeCO3
18
or
19
20
21
Fig. 9. Evolution of the steel corrosion rate as a function of time exposure and
under different atmospheres. Under CO2: this study and under H2: El Mendili et al.
[14].
Schlegel et al. [68] studied the corrosion of steel under anaerobic conditions in the presence of COx claystone reacted at 90 C
and 50 bar (pH = 6.7 and PCO2 = 0.43 atm) for 8 months. Their
results show the presence of a corrosion layer and a clay transformation layer. The corrosion layer is made of a magnetite-containing internal sub-layer and a Fe-phyllosilicate external sub-layer
enriched in Na, with traces of goethite. The clay transformation
layer is made of predominantly Ca-rich siderite (FeCO3). Silica
released upon clay dissolution diffused into the corrosion layer
and co-precipitated with oxidized Fe to form Fe-phyllosilicate.
The absence of iron sulde is probably due to the high temperature
conditions which prevent bacterial activity. It is important to also
notice that in our study conducted at 30 C, Fe-phyllosilicates are
not detected within the corrosion products after 8 months of experience. The absence of silicates is related to a problem of dissolution kinetics of silicate, very low compared to that of the
carbonate at 30 C [69].
Under only H2 atmosphere, the main corrosion product is a
continuous iron sulde layer [14] which led to a drastic drop in
corrosion rate with time due to the formation of well crystallized
iron sulde phases (pyrrhotite). Under disposal conditions sulde
production may be promoted by SRB activity due to hydrogen
production at low temperature (3050 C) and perhaps by COx
claystone pyrite reduction by hydrogen at higher temperature
(90 C).
While this experiment was too short to determine what rates
are achievable after long-term experiment of corroded steel under
anaerobic conditions and CO2 atmosphere, it demonstrates the formation of corrosion layers made of extremely complex mixtures of
iron-sulde, oxide, carbonate, and chloride solids. Formation of
iron sulde is not expected to increase the corrosion but could play
a protective role via the formation of highly stable iron sulde minerals including pyrrhotite and pyrite as indicated by El Mendili
et al. [14].
64
4. Conclusion
Carbon steel corrosion in simulated geological conditions (clay
and groundwater) results in a variety of corrosion products of
varying proportions with exposure time. Hence, at short time
exposure magnetite was identied as the main corrosion product
while at longer times carbonate (siderite and chukanovite), mackinawite and ultimately iron hydroxychloride are formed. These
structural modications are due to changes of localized geochemical conditions with time exposure including hydrogen and sulde
production due to steel corrosion and SRB activity, respectively.
The present work shows that it is important to take into account
all the components of a disposal site including the atmosphere
composition to intent to explain the corrosion mechanism. A lack
of hydrogen would lead to a mineralogical paragenesis dominated
by iron carbonate while under sufcient hydrogen supply, sulde
production via SRB stimulation by hydrogen and possibly via pyrite
reduction by hydrogen would lead to iron sulde formation with
ultimately high passivation properties.
Acknowledgment
Special thanks to the Institut des Matriaux de Nantes (CNRS/
universit de Nantes) for the SEM-EDX measurements.
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