Corrosion Science 55 (2012) 246–253

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Electrochemical study of the corrosion rate of carbon steel in soil: Evolution

with time and determination of residual corrosion rates under cathodic protection
M. Barbalat a,b, L. Lanarde b, D. Caron b, M. Meyer b, J. Vittonato c, F. Castillon d, S. Fontaine e, Ph. Refait a,⇑
a
Laboratoire d’étude des matériaux en milieux agressifs (LEMMA), EA 3167, Université de La Rochelle, Bât. Marie Curie, Av. Michel Crépeau, 17042 La Rochelle Cedex 01, France
b
GDF SUEZ, CRIGEN, 361 Av. du Président Wilson, BP 33, 93211 Saint Denis La Plaine, France
c
TOTAL, EP/TDO/TEC/COR Tour Coupole 22D67, 92078 Paris-La Défense Cedex, France
d
TIGF, 49 Av. Dufau, BP 5222, 64022 Pau, France
e
GRTgaz/CTE/PNE, 5 rue Ferdinand de Lesseps, 60200 Compiègne, France

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

Article history: Steel coupons were buried in soil boxes for 2.5 months, with or without cathodic protection. A soil from
Received 4 July 2011 the field was used and moistened by demineralized water or 5 g L1 Na2SO4 solution. Instantaneous
Accepted 20 October 2011 corrosion rates were deduced from voltammetry experiments while average values were obtained by
Available online 3 November 2011
weight loss measurements. A detailed analysis of the polarization curves led to an estimation of residual
corrosion rates (src) of coupons under cathodic protection. This residual phenomenon could be followed
Keywords: with time and it was observed that src decreased down to 10 lm yr1. Cathodic protection could be
A. Steel
optimised with this methodology.
C. Cathodic protection
B. Cyclic voltammetry
Ó 2011 Elsevier Ltd. All rights reserved.
B. Weight loss
B. Polarization

1. Introduction damage of underground corrosion of iron and steel [26–32].

Buried carbon steel pipelines are protected against external
corrosion by the combination of organic coating and cathodic pro-
tection (CP). The EN 12954: 2001 standard [1] specifies reference
values of the protection potentials to be applied according to soil
conditions. The cathodic protection is assumed to be efficient when
the residual corrosion rate is lower or equal to 10 lm yr1.
However, the feedback highlights that the reference values of pro-
tection potential can be insufficient or excessive, or not even appli-
cable, depending on the local soil specificities. The relationship
between the polarization level and the true residual corrosion is
still questionable.
The behaviour of carbon steel in soils has already been exten-
sively studied, various methods to evaluate soil corrosiveness were
proposed, and the influence of various parameters such as degree
of aeration, pH, moisture, ionic species, electrical resistivity or
microbiological activity was already described (e.g. [2–24]). From
the overall results of such studies, the DIN 50929: 1985 standard
[25] proposes a qualitative evaluation of soil corrosiveness based
on 12 criteria. Statistical corrosion prediction models were also
developed to evaluate quantitatively from soil parameters the
⇑ Corresponding author. Tel.: +33 5 46 45 82 27; fax: +33 5 46 45 72 11.
E-mail address: prefait@univ-lr.fr (Ph. Refait).
However, such an evaluation requires an elaborate highly-special-
ized analysis of soil chemistry. Due to the large variability of soil
parameters along a same pipeline, a quite large number of analyses
is necessary and therefore this approach is very expensive. To
comply with these field requirements, various studies focused on
a restricted number of criteria, related to soil: electrical resistivity,
redox potential, pH or moisture, that may have a predominant rela-
tionship with soil corrosiveness [5,6,15,18]. In particular, attempts
were made to correlate free corrosion rate with soil resistivity [33]
using data obtained with steel samples buried 2 years in various
soils [34]. The free corrosion rate of carbon steel in soil was ob-
served to decrease regularly with increasing soil resistivity and a
linear variation was proposed. The correlation coefficient was how-
ever small, between 0.3 and 0.5, due to an important dispersion of
the measured corrosion rates. This dispersion is mostly due to the
physical and chemical heterogeneity of the soils. Note also that
most soil parameters are linked to each other and consequently
the observed link between one given parameter and corrosiveness
may be only apparent. For these reasons, it would be particularly
interesting to be able to estimate directly the dissolution rates of
steel structures in soil environment, not only under free corrosion,
but also when subjected to cathodic polarization.
The present laboratory study is part of a project initiated by GDF
SUEZ and TOTAL, with the general aim to improve guidance on
cathodic protection criteria by (i) developing tools and methods

0010-938X/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2011.10.031
 M. Barbalat et al. / Corrosion Science 55 (2012) 246–253
directly applicable on the field, to estimate soil corrosiveness from
a limited but absolutely necessary number of electrochemical and/
or physico-chemical parameters and (ii) identifying the ‘‘necessary
and sufficient’’ conditions to guarantee a negligible corrosion rate
on a case by case basis. The present study was then focused on
the behaviour of carbon steel in free corrosion or under CP, in
one given type of soil, with controlled moisture. A specific electro-
chemical cell was designed for that purpose. Two resistivity values
were obtained by moistening the soil, at the same water content
relative to the water saturation level, either with demineralized
water or a Na2SO4 solution. This allowed us to evaluate the influ-
ence of the soil electrical resistivity parameter ‘‘in itself’’ without
being ‘‘constrained’’ by the influence of other connected parame-
ters (moisture for instance) as these were maintained constant.
The main aim of this work was however to estimate the residual
corrosion rate of steel under CP from voltammetry experiments,
using a first type of soil as an example. The idea is based on the
possibility to deduce the anodic current from the overall current
by subtracting the cathodic part estimated via a cathodic Tafel
straight line. This concept is not new [35], but it seemed interest-
ing to develop it with some refinements. In particular, the effects of
CP were followed with time using this methodology and the
obtained results were compared with those given by weight loss
measurements.
2. Materials and methods
2.1. Materials
All experiments were performed in a natural clay sand soil ex-
tracted from the field in Brittany (North-West of France). This soil
was characterised as received and the results are summarised in
Table 1. The analysis was performed according to various relevant
standards, namely NF X31-1017: 2003 for the determination of the
proportions of minerals [36], ISO 10390: 2005 for the determina-
tion of pH [37], ISO 14235: 1998 for the determination of the
organic carbon content [38], ISO 11048: 1995 for the chloride
and sulphate contents in aqueous extract [39], NF T 90-019:
1984 for Na+ and K+ contents in aqueous extract [40]. A specific
methodology was used for the determination of Ca2+ and Mg2+ con-
tents in aqueous extract. It can be noted that the main mineral
component was sand, the pH was slightly acidic and the chloride
content was low.
The soil samples used for experiments were prepared at a con-
trolled water content corresponding to 40% of the saturation
level. This preparation was achieved by incorporating and mixing
adequate amounts of an aqueous solution to pre-weighted and
pre-dried samples of the soil. Two different aqueous solutions were
used in order to vary the resistivity of the soil. Demineralized
water was used first and the corresponding soil was named
Table 1
Main features of the Brittany soil as received from the field and properties of the soils prepared for experiments.
Main features of the Brittany soil as received
Type of minerals (% weight)
Clay Silt Sand
9.7 17.4 72.9
Concentration (mg L1) of various ions in aqueous extract (accuracy: ±6%)
Cl SO2 Na+
4
11.7 10.4 16.6
Properties of the soils prepared for experiments
Soil naming Added electrolyte
Br-100 Demineralized water
Br-20 5 g L1 Na2SO4 in demineralized water
247
Br-100 as its average resistivity was about 100 X m. Secondly, a
solution of 5 g L1 Na2SO4 dissolved in demineralized water was
used. This procedure led to a smaller resistivity of 20 X m and this
second soil was consequently named Br-20. Each soil sample was
manually compacted inside the electrochemical cell using a Proc-
tor Compactor, an apparatus that consisted in a weight of 2.5 kg
dropped from a height of 305 mm. The atmosphere inside the cell
was constantly renewed via a flow of reconstituted air (80% N2, 20%
O2) which circulated above the soil surface in the upper part of the
cell. The experiments were performed at room temperature.
An electrochemical cell was specifically designed for the pres-
ent study (Fig. 1). It consisted of a 30 L hermetically sealed cylindri-
cal Plexiglas vessel. Eight holes were managed in the cell top cap
for four working electrodes, one reference electrode, one auxiliary
electrode and a gas entry. The gas exit was set at the bottom of the
cell. An opening was set in the side of the cell in order to sample a
small part of the soil from time to time. This sampling allowed us
to monitor pH and moisture during the experiments. Both param-
eters fluctuated only slightly and similar values were found in each
soil. For instance, the pH was measured between 4.8 and 5.6 and
the moisture between 38% and 44% of the water saturation level.
The temperature, also measured regularly, fluctuated between 19
and 23 °C.
The counter electrode was a Mixed Metal Oxide Dimensional
Stable Anode (MMO DSA) that is a titanium grid coated with tan-
talum and iridium oxides (Ta2O5 and IrO2). Reference electrodes
were copper–copper sulphate electrodes Cu/CuSO4 (+0.316 V/SHE
at 25 °C) commonly used in the field. In the following sections of
the article, electrochemical potentials are expressed with respect
to this reference electrode.
The X70 carbon steel commonly used for pipelines was consid-
ered for this study. Its average chemical composition was (in
weight%): 98.06% Fe, 0.09% C, 1.53% Mn, 0.29% Si, 0.013% P,
0.002% S and 0.02% V. Cylindrical coupons (diameter: 30 mm,
thickness: 2 mm) were cut in the purchased sheets. Each coupon
was grit blasted and degreased prior to its mounting in a TeflonÒ
sample-holder so that only one plane circular side of the coupons,
with an active area of 5 cm2, was exposed to the soil.
2.2. Electrochemistry
All electrochemical measurements were performed in the cell
described above (Fig. 1).
First, Electrochemical Impedance Spectroscopy (EIS) was used
to determine the electrical resistance of the soil (Rs) between the
reference electrode and each of the four steel coupons set in the
cell. The experiments were performed with a GAMRY femtostat
PC4 monitored by the Framework V4.35 software. The frequency
was varied between 10,000 and 0.01 Hz and the AC voltage pertur-
bation amplitude (peak to peak) was 10 mV around the open
pH Organic carbon content (mg per g of dry matter)
5.7 ± 0.1 0.8
K+ Ca2+ Mg2+
4.7 3.9 2.5
Water content (% saturation) Resistivity (X m)
40 100 ± 15
40 22 ± 2
248 M. Barbalat et al. / Corrosion Science 55 (2012) 246–253
Fig. 1. Schematic representation of the electrochemical system designed for the study of the behaviour of steel coupons in soils.
Fig. 2. Typical EIS Nyquist diagram obtained with a carbon steel coupon set in the
Br-20 soil.
circuit potential of the sample. Results were analysed with the
GAMRY Echem Analyst software. A typical Nyquist plot obtained
from the EIS experiments performed in Br-20 soil is presented as
an example in Fig. 2. The diagram shows only one flattened capac-
itive loop. In principle, the resistance of the electrolyte corresponds
to Re(Z) when the frequency tends towards infinite. In the case of
the diagram of Fig. 2, it can be seen that at high frequency, the real
part of the impedance varies from 420 to 380 X while its imaginary
part remains almost constant. An extrapolation of this curve to
obtain Re(Z) was not possible and the estimated value Rs = 400 X
was retained. Rs was determined similarly in each case since all
the EIS diagrams obtained in Br-20 and -100 soils showed similar
features. Note that a complete analysis of the EIS spectra was at-
tempted, in particular to determine the charge transfer resistance
Rtc. However, the obtained results were not consistent with those
given by weight loss measurements. Actually, it proved difficult
in most cases to model accurately the spectra. For this reason they
are not presented here.
Secondly, voltammetry experiments were performed in order to
study the behaviour of the carbon steel coupons in soil without CP.
The electrolyte resistance Rs was determined before each experi-
ment so as to correct the potential of the electrode from ohmic
drop. The corrected potential Eoff was obtained from the applied
potential Eon via the equation Eoff = Eon  Rs  I, where I is the
current flowing through the electrode. All voltammograms were
then drawn as Eoff vs. log |j|, where j is the current density equal
to I/A with the active area A of the steel electrode equal to 5 cm2.
The experiments were started at OCP and the potential was first
decreased down to Eon(1) = 1.2 V vs. Cu/CuSO4 and then increased
up to Eon(2) = OCP + 0.25 V. A GAMRY femtostat PC4 monitored by
the Framework V4.35 software was used for all experiments. Scan
rates from 0.2 up to 20 mV s1 were considered. The results ob-
tained with scan rates between 0.2 and 5 mV s1, and in particular
the corrosion rate deduced from the curves, proved independent of
the scan rate. Once this preliminary study was performed it was
decided to use a scan rate of 1 mV s1 for all experiments and
the results presented here were then obtained with this potential
scan rate.
Finally, coupons were left under CP for 34–60 days, the cathodic
polarisation being applied using an AMEL potentiostat. In any case,
the coupons were left at OCP (7 or 15 days) before that CP was
applied. The OCP after 15 days was measured between 0.55 and
0:8 VCu=CuSO4 and around 0:7=  0:75 VCu=CuSO4 in most cases (see
Section 3 for details). The applied protection potential value, Eprot,
was then set at 0:950 VCu=CuSO4 (corrected from ohmic drop) for
both Br-20 and -100 soils. This value is recommended by the EN
12954: 2001 standard [1] when the OCP is low, that is when it is
comprised between 0:8 and  0:65 VCu=CuSO4 . Such OCP values
are considered to correspond to anaerobic conditions [1].
Voltammetry was also used to study the behaviour of the
coupons under CP. In this case, experiments were started at the ap-
plied protection potential Eprot ð¼ 0:950 VCu=CuSO4 Þ. The ohmic
drop was estimated from the corresponding I value and the poten-
tial was decreased down to an estimated Eoff(1) value of 1.2 V. It
was then increased up to an estimated Eoff(2) value of Eprot + 0.2 V.
The cathodic polarisation was applied again immediately after the
end of each voltammetry experiment. The corrosion process
induced by the voltammetry experiments was assumed to be neg-
ligible as the steel was anodically polarised for less than 3 min and
at potential values smaller than Eprot + 0.2 V.
2.3. Weight loss measurements
The studied steel coupons were left 2.5 months in soil at OCP
and their weight losses were estimated at that time. However,
 M. Barbalat et al. / Corrosion Science 55 (2012) 246–253
corrosion rates are usually greater at the beginning of the corrosion
process. They tend to decrease with time as the steel surface is
progressively covered by corrosion products, and stabilise at a
somehow constant value once the corrosion system, finally consti-
tuted of the metal, its layer of corrosion products and the environ-
ment, has reached a quasi steady state. In order to evaluate the
corrosion rate during the initial stages of the process, three steel
samples were buried during 15 days in Br-20 and -100 soils, left
at OCP, and their weight losses measured. The resulting average
15-day thickness loss obtained was 7.3 ± 0.5 lm in Br-100 and
10.1 ± 0.6 lm in Br-20. This corresponds to an average corrosion
rate for the first 15 days, s0cor;wtl , of 178 and 246 lm yr1,
respectively.
Weight loss measurements were performed according to the NF
ISO 8407: 2010 standard [41]. So, as described by this standard, the
corrosion products covering the steel coupons at the end of the
experiments were eliminated by successive cleanings in inhibited
hydrochloric acid aqueous solution, until no significant weight
change was observed after deducting weight loss of the metallic
substrate.
For the coupons under CP that were left 15 days at OCP, the
average of the first 15-day weight loss for coupons under OCP, esti-
mated as explained above, was subtracted from the overall weight
loss. All the weight losses given for such coupons were obtained
this way and correspond consequently to the residual corrosion
process that occurred under CP between the 15th day and the
end of the experiment.
3. Results and discussion
3.1. Determination of free corrosion rates in Br-20 and -100 soils
Two typical polarization curves obtained with steel electrodes
in the Br-20 soil are presented in Fig. 3. They were drawn after
1 day (curve a) and 12 days (curve b) in the soil. First, a hysteresis
phenomenon can be seen in the cathodic region. This point illus-
trates the effects of the cathodic polarization on the steel/soil inter-
face. During the decrease of the potential from OCP down to
Eoff = 1.0 VCu=CuSO4 , the cathodic reaction was activated. Whatever
the nature of this reaction, i.e. reduction of water or reduction of
dissolved O2, it produced OH species:
Fig. 3. Voltammograms (E vs. log |j|) obtained with a carbon steel coupon after (a)
1 day and (b) 12 days in the Br-20 soil. Scan rate dE/dt = 1 mV s1.
249
O2 þ 2H2 O þ 4e ! 4OH ð1Þ
2H2 O þ 2e ! H2 þ 2OH ð2Þ
So the interfacial pH increased and, if dissolved O2 was
involved, the O2 concentration at the interface decreased as O2
was consumed. The importance of such concentration gradients
depends on mass transport limitation effects and is expected to
increase if the rate of this transport is low. This may be the case
in soils and consequently the steel/soil interface composition
may have been continuously modified by polarization while the
cathodic polarization level was increased. When the potential scan
was reversed, at Eoff = 1.0 VCu=CuSO4 , the overall current took new
values that reflected these changes and the curve drawn during
the positive-going scan differed from that drawn during the nega-
tive-going scan. As a consequence, the overall current reached zero
for a potential value Ecor different from OCP. Actually, Ecor was
found smaller than OCP which is consistent with an increase of
pH and/or a decrease of dissolved O2 concentration at the interface.
It must be noted that the OCP of the carbon steel coupons left
1–15 days in Br-20 and -100 soils was measured between 0.55
and 0.8 VCu=CuSO4 , and in most cases around 0.70/0.75 VCu=
CuSO4 . Such values are low and according for instance to the EN
12954: 2001 standard [1] would correspond to anaerobic condi-
tions. Actually, the pH of the soils was measured between 4.8
and 5.6 during the experiments. At the average pH value of 5.2,
the H+/H2 equilibrium potential is equal to 0.62 VCu=CuSO4 . This
confirms that the main contribution to the cathodic process was
water reduction in most cases.
The anodic part of the curves did not show any linear behaviour
between Eoff and log j and so only the cathodic regions could be
envisioned to estimate the corrosion current density. In this case,
the corrosion current density jcor has to be estimated via the
extrapolation of a cathodic Tafel line. It is well known that this
method requires (i) that the kinetic of the cathodic reaction is con-
trolled by charge transfer and (ii) that the steel/soil interface is not
modified by the polarization. This may not be strictly verified and
the estimated values of jcor must be considered with caution. For
example, the second cathodic part of the curves drawn during
the positive-going scan had to be discarded. It could not represent
the behaviour of steel at OCP since the steel/soil interface was
clearly modified by polarization. So, only the first cathodic part
of the curves was used. Actually, it is characterised by a large
region (approx. between 0.75 and 0.95 V) where Eoff varies lin-
early with log |j|. Therefore, it can be assumed reasonably that the
kinetic of the cathodic reaction was controlled by charge transfer,
which confirms that (almost) anoxic conditions were established
at the steel surface. A cathodic Tafel line was deduced and extrap-
olated up to OCP as illustrated in Fig. 3 with voltammogram b
(12 days in soil). This gave an estimated value of the corrosion cur-
rent density jcor. The values deduced from the voltammograms of
Fig. 3 were for instance jcor = 180 mA m2 after 1 day in soil, and
jcor = 90 mA m2 after 12 days in soil.
Finally, it can be seen that the voltammograms changed with
the duration of the immersion in soil. The OCP increased with time
while jcor decreased. This phenomenon may be attributed to the
formation of a layer of corrosion products on the steel surface. This
layer hindered both anodic and cathodic reactions, as it can be seen
in Fig. 3, and consequently jcor decreased. The variation of the OCP
indicates that one of these reactions was more hindered than the
other. In our case the OCP increased which implies that the anodic
reaction was more strongly hindered by the growth of corrosion
products than the cathodic reaction.
The instantaneous corrosion rates scor (t) deduced from the
polarization curves as explained above and the average corrosion
rates scor,wtl determined from weight loss measurements are given
in Table 2. The average and extreme values given in this table were
250 M. Barbalat et al. / Corrosion Science 55 (2012) 246–253
Table 2
Average corrosion rates s0cor;wtl and scor,wtl determined by weight loss measurements after 15 days and 2.5 months at OCP, respectively, and
instantaneous corrosion rates scor (t) deduced from polarization curves at 24 h and 12 days. The values are given in lm yr1.
scor (t = 24 h)
Br-20 Average 223
Min. value 207
Max. value 252
Br-100 Average 19
Min. value 13
Max. value 42
obtained from 2 to 5 experiments. One can see that the main fea-
ture of these results is the variability of the corrosion rate, mainly
due to the heterogeneous nature of soil. It is illustrated by both
methods. The largest dispersion is observed in Br-100 soil, where
scor,wtl is comprised between 33 and 201 lm yr1 and scor
(t = 12 days) between 40 and 304 lm yr1. As expected, weight
loss measurements after 2.5 months led to corrosion rates scor,wtl
(100 lm yr1) smaller than s0cor;wtl (200 lm yr1) measured
after 15 days. This progressive decrease of the corrosion rate is also
clearly observed via voltammetry in Br-20 soil, as it decreased from
an average of 223 lm yr1 at 24 h to reach 163 lm yr1 at 12 days.
In contrast, scor (t = 24 h) proved to be very small in the Br-100 soil,
with an average value of 19 lm yr1 while scor (t = 12 days) was
high, with an average value of 172 lm yr1 similar to that found
in Br-20 soil. The low corrosion rate after 24 h might be attributed
to an air-formed pre-existing oxide film (formed after the prepara-
tion steps of the steel samples prior to their introduction in the test
cell and their exposure to the soil) covering the steel surface when
the samples were exposed to the soil medium. This film subse-
quently dissolved owing to the fact that conditions prevailing un-
der the corrosion test in the soil were less oxidative than the ones
prevailing in air, when the oxide film was formed. In Br-100 soil,
this film might have dissolved slowly and protected the steel
surface for a few days. When this protective film was finally fully
dissolved, the corrosion rate could reach the high values typical
of a totally active surface, as observed after 12 days. Note that this
initial pseudo-passivation state may also have induced the greater
dispersion of corrosion rates observed in this soil. The stability of
the air-formed pre-existing oxide film is rather highly sensitive
to the chemical conditions at the steel/soil interface and this film
might persist for a long time in some cases. As a matter of fact,
the minimum value scor,wtl = 33 lm yr1 observed for one coupon
after 75 days may be due to the persistence of this protective initial
oxide film.
Finally, the corrosion rate in Br-100 decreased as expected
since, despite the differences observed at the initial stages, the
average corrosion rate deduced from weight loss measurements
after 75 days was similar to that found in Br-20 soil, i.e.
scor,wtl  100 lm yr1. Moreover, the corrosion rates reached after
12 days, scor (t = 12 days), were similar in both soils, at about
170 lm yr1. These results demonstrate that the change of soil
electrical resistivity from 100 to 20 X m had almost no significant
influence, in the experimental conditions considered here, on the
corrosion rate.
3.2. Monitoring of cathodic protection in Br-20 soil via voltammetry
In the first experiment described here, a steel coupon was left
7 days without cathodic protection and 34 days with cathodic pro-
tection in Br-20 soil. Voltammetry experiments were performed
the 7th day, just before CP was applied and after 2, 6, 9 and 34 days
of CP. Four of the five obtained voltammograms are presented in
Fig. 4, the one obtained after 6 days being omitted for clarity. It
scor (t = 12 days) s0cor;wtl (0–15 days) scor,wtl (0–75 days)
163 246 105
81 236 71
294 263 181
172 178 107
40 165 33
304 190 201
Fig. 4. Voltammograms (E vs. log |j|) obtained with a carbon steel coupon in the Br-
20 soil after 7 days without cathodic protection (a) followed by 2 days (b), 9 days (c)
and 34 days (d) with cathodic protection. Scan rate dE/dt = 1 mV s1.
can be noted first that the hysteresis effect was small when the
coupon was under CP (curves b–d). This could be expected since
the coupon was already cathodically polarised. The decrease of
the potential towards more cathodic values produced only minor
changes at the steel/soil interface. The hysteresis phenomenon
was important only when the steel coupon was initially at OCP
(curve a) and it is noticeable that the Ecor value, about
0.95 VCu=CuSO4 , is similar to those obtained when the coupon was
under CP, measured between 0.925 and 0.98 VCu=CuSO4 . Note also
that the OCP was particularly low, about 0.8 VCu=CuSO4 , which is
typical of (almost) anoxic conditions.
Secondly, it can be seen that the voltammograms of the coupon
under CP changed with time. Schematically, the curves were
shifted towards smaller current density values as the duration of
CP increased and this is observed in both anodic and cathodic
regions. This could indicate that the residual dissolution of steel
under CP decreased with time. To verify this assumption and to
estimate this residual corrosion rate, the following procedure
was applied to each voltammogram obtained with the coupon un-
der CP.
The methodology is based on the assumption that the cathodic
part of the voltammograms obey the Tafel law, i.e. that the poten-
tial varies linearly with the logarithm of the current density far
from Ecor. In other words, it is assumed that the cathodic reaction
is controlled by charge transfer. The small hysteresis effect ob-
served for the steel coupons under CP is consistent with this
assumption. In this case, the cathodic current density jK, consid-
ered as a negative current (jK < 0), is given at each potential by
the equation of the cathodic Tafel line, Eoff = ac  bc log |jK|. Assum-
ing uniform distribution of both anodic and cathodic processes
throughout the whole sample surface, the anodic current density
 M. Barbalat et al. / Corrosion Science 55 (2012) 246–253 251

Fig. 5. Voltammogram (E vs. log |j|) obtained with a carbon steel coupon in the Br- Fig. 7. Voltammogram (E vs. log |j|) obtained with a carbon steel coupon in the Br-
20 soil after 2 days (curve b of Fig. 4) under cathodic protection, cathodic Tafel 20 soil after 9 days (curve c of Fig. 4) under cathodic protection, cathodic Tafel
straight line (E vs. log |jK|) and resulting anodic curve (E vs. log jA where jA = j  jK). straight line (E vs. log |jK|) and resulting anodic curve (E vs. log jA where jA = j  jK).
Scan rate dE/dt = 1 mV s1. Scan rate dE/dt = 1 mV s1.

Fig. 6. Voltammogram (E vs. log |j|) obtained with a carbon steel coupon in the Br-
Fig. 8. Voltammogram (E vs. log |j|) obtained with a carbon steel coupon in the Br-
20 soil after 6 days under cathodic protection, cathodic Tafel straight line (E vs.
20 soil after 34 days (curve d of Fig. 4) under cathodic protection, cathodic Tafel
log |jK|) and resulting anodic curve (E vs. log jA where jA = j  jK). Scan rate dE/
straight line (E vs. log |jK|) and resulting anodic curve (E vs. log jA where jA = j  jK).
dt = 1 mV s1.
Scan rate dE/dt = 1 mV s1.

can then be obtained by subtracting jK from the overall current Table 3

density j, that is: jA = j  jK. Tafel slope bc of the cathodic Tafel straight line used for computation, residual anodic
current under CP jA,resid and corresponding residual corrosion rate src obtained from
The results obtained are presented in Figs. 5–8. The procedure
the polarization curves of Figs. 5–8.
was only applied to the positive-going scan. For the voltammo-
grams obtained after 2, 6 and 9 days of CP (Figs. 5–7) the resulting Duration of CP bc/V per decade jA,resid/mA m2 src/lm yr1
curve Eoff vs. log jA proved to be close to a straight line. This means 2 days 0.17 ± 0.01 27 ± 3 30 ± 4
that the subtraction of a theoretical cathodic component jK mod- 6 days 0.21 ± 0.01 19 ± 4 22 ± 5
9 days 0.21 ± 0.01 16 ± 3 19 ± 4
elled by a Tafel line from the experimental overall current density
34 days 0.29 ± 0.015 9±2 10 ± 3
j gave (approximately) an anodic Tafel straight line. This shows
that both cathodic and anodic currents did obey the Tafel law, in
other words, that both cathodic and anodic reactions were con-
trolled by charge transfer. This case is of course the best situation potentials. This shift from linearity is due to the modifications
to illustrate the relevance of the proposed methodology since the occurring at the steel/soil interface when the dissolution of steel
basic assumption, i.e. the cathodic process obeys the Tafel law, was accelerated by the anodic polarization.
can be validated by the computation. For the last voltammogram The corresponding data are given in Table 3. The residual anodic
(Fig. 8), obtained after 34 days of CP, Eoff varied linearly with log jA current density jA,resid is the value of jA corresponding to the poten-
in a large range of potential, that is in the cathodic region and tial Eprot applied during CP. Eprot is clearly seen on the voltammo-
around Ecor, but this linear behaviour was lost at more anodic grams since it corresponds to the departure of the potential scan.
252 M. Barbalat et al. / Corrosion Science 55 (2012) 246–253
Fig. 9. Evolution with time of the residual corrosion rate src (estimated from
polarization curves, see Figs. 5–8) of a steel coupon under cathodic protection in Br-
20 soil. The coupon was left 7 days in soil before cathodic protection was applied
and its corrosion rate at that time is indicated by a circle. The experimental curve
was fitted as an exponential decay (dash line).
The slope bc of the cathodic Tafel line used for computations
increased from 0.17 to 0.29 V per decade while the residual anodic
current decreased from 27 to 9 mA m2. Note that we did not try to
extract anodic Tafel slopes ba from the computed anodic compo-
nent (jA = j  jK) even though it seemed to obey the Tafel law.
Part of the error made through the procedure comes from the
location of the cathodic Tafel straight line. For this reason, two
extreme lines were used to obtain the error made on the determi-
nation of the Tafel slope bc and then the error made on the deter-
mination of the residual anodic current density. However, there
may remain a slight error due to the method itself. This error is
the difference between a straight line and the real E vs. log |j|K
curve and it cannot be easily quantified. As explained earlier this
error is connected to the hysteresis phenomenon visible on the
voltammograms, i.e. the difference between the negative and posi-
tive-going scans.
The evolution with time of the residual corrosion rate, src, was
plotted and compared to the corrosion rate measured from the
polarization curve just before CP was applied (Fig. 9). It can be seen
that CP led immediately to a decrease of the dissolution of steel,
from 85 lm yr1 down to 30 lm yr1. The residual corrosion rate
went on decreasing and stabilised at 10 lm yr1. This phenomenon
is certainly due to the evolution with time of the steel/soil inter-
face. In particular, the corrosion process is slowed down by CP
but the corrosion rate is not nil and corrosion products are still
forming. This was for instance observed in the case of carbon steel
under CP in seawater [42]. Moreover, the increase of pH at the
interface (Eqs. 1 and 2) may induce the precipitation of a calcare-
ous deposit. This phenomenon is however more likely marginal
in our case since the solutions used to moisten the soil did not con-
tain carbonate species neither calcium nor magnesium ions.
The src vs. time curve could be fitted as an exponential decay,
which led to the equation given in Fig. 9, that is src = 9.7 + 65
exp(d/8) where d is the time in soil given in days. From the area
under the curve, a theoretical weight loss was computed. It corre-
sponded to an average corrosion rate of 14 ± 4 lm yr1 that is a
thickness loss of 1.3 lm during the 34 days of CP. This value can
be compared to the result of the weight loss measurement per-
formed on the same coupon at the end of the experiment. The
overall weight loss corresponded to a thickness loss of 5.1 lm. If
1.3 lm were lost during the 34 days of CP, then 3.8 lm were lost
during the initial 7 days when the coupon was left at OCP. This
initial thickness loss corresponds to an initial corrosion rate of
200 lm yr1, a value fully consistent with those determined from
both electrochemical and weight loss measurements (see Table 2).
In addition, three coupons were buried for 75 days, 15 days un-
der OCP and next 60 days under CP. Weight loss measurements
were performed with subtracting the weight loss due to the corro-
sion of the first 15th days. The average src determined from weight
loss measurements was 25 ± 17 lm yr1. The complete electro-
chemical treatment based on polarization curves was achieved
on one of the three coupons. The main trends illustrated by Fig. 9
were observed again, i.e. src decreased rapidly and the src vs. time
curve could be fitted again as an exponential decay. In this case, the
current density reached a final value of 19 ± 6 lm yr1 and the
average residual corrosion rate was estimated from the area under
the src vs. time curve to be 24 ± 6 lm yr1 for the 60 days of CP. The
average residual corrosion rate seemed to stabilise again after
40 days in this second experiment. Of course, this stabilisation
time may be different in other soils.
It is now necessary to check the relevance of this methodology
in soils with other chemistries and in conditions where dissolved
oxygen plays the main role in the cathodic process.
4. Conclusions
In this work, free corrosion rates and residual corrosion rates of
carbon steel under CP, exposed to a clay sand type soil, with a
water content of 40% relative to the saturation level and with resis-
tivity between 20 and 100 X m, were determined from weight loss
measurements and voltammetry experiments. In the case of
unprotected steel coupons, a large scattering of corrosion rate
values was observed by both methods. This is inherent to the het-
erogeneous nature of soil and only general trends can be deduced.
Actually, the corrosion rate reached a maximum of 200 lm yr1
during the first stages of the process and decreased to an average
value of 100 lm yr1 after 2 months, independently of the elec-
trical resistivity that was 100 X m in one soil and 20 X m in the
other. Note however that the influence of electrical resistivity
may be more significant in other soils.
With a steel coupon under CP, it proved possible to obtain a reli-
able estimate of the residual corrosion rate from voltammetry
experiments, as it gave an average value consistent with weight
loss measurements. The variation with time of this residual corro-
sion rate could be monitored and it was shown that it decreased
rapidly during the first 20 days to stabilise after 1 month at around
10 lm yr1. This method was based on the approximation of the
cathodic part of the curve by a cathodic Tafel line Eoff = ac  bc
log |jK|. This assumption proved to be verified in the experimental
conditions considered here (almost anoxic), and the anodic current
density derived from the method (jA = j  jK) also verified Tafel law.
Actually, the steel coupon was already polarised cathodically
before the voltammetry experiment and the steel/soil interface
was only slightly modified (if any) by the variations of potential
in the cathodic region.
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