PII:

Electrochimica Acta, Vol. 43, Nos 1213, pp. 18911901, 1998

# 1998 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
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Characterization of calcareous deposits in

articial sea water by impedance techniquesI.
Deposit of CaCO3 without Mg(OH)2
C. Deslouis,a* D. Festy,b O. Gil,c G. Rius,c S. Touzainc and B. Tribolleta
a

UPR 15 du CNRS, ``Physique des Liquides et Electrochilmie, 4 Place Jussieu, 75252 Paris Cedex 05,
France
b

IFREMER, Centre de Brest, Laboratoire Materiaux Marins, BP 70, 29280 Plouzane, France

Laboratoire des Materiaux en Milieux Agressifs, Universite de la Rochelle, La Rochelle, France

(Received 21 March 1997; in revised form 2 July 1997)

AbstractCalcium carbonate deposits grown under cathodic polarization in the conditions of cathodic protection were characterized by ac and EHD impedances. The transition between a regime dominated by the
germination of calcium carbonate crystals and the progressive development of a 3-D (three dimensional)
porous layer occurs when the actual current has decreased to half its value measured at time zero where
the interface is bare. In particular from the EHD impedance data, it was possible to estimate the average
value of the crystals size in the rst phase to about 3050 mm and the covered fraction from the high frequency capacitance, in perfect agreement with direct SEM examination. # 1998 Elsevier Science Ltd. All
rights reserved.
Key words: scale deposition, impedances, articial sea-water, mass transport, interfacial pH.

INTRODUCTION
A mathematical modeling of the calcareous deposits
formation on cathodically protected steel in sea
water has been recently proposed [1, 2]. In this
theoretical paper, the anodic dissolution of iron is
neglected as long as steel is under cathodic protection. Therefore, and at least during the growth
stage, the surface has no specic inuence and the
experimental work presented here was carried out
with a gold electrode. In previous investigations
with fresh water, it had been shown that calcium
carbonate plays the major role in the properties of
the calcareous deposits and in particular provides
the better screening against further deposition.
Hence, in view of the very complex situation where
both components are present [CaCO3 and
Mg(OH)2], a preliminary study described here,
focuses on CaCO3 deposition only, the composition

of other components involved (except for Mg2+

ions of course) followed the ASTM standards for
articial sea-water.
The potential applied for cathodic protection is
in the range 0.8 V, 1.2 V vs SCE, and the electrochemical reactions that occur, depending on the potential, are the elementary steps of the reduction of
oxygen:
O2 2H2 O 2e !H2 O2 2OH
H2 O2 2e !2OH

1
2

and the reduction of water with hydrogen evolution:

2H2 O 2e ! H2 2OH

The production of OH ions on the electrode surface increases the local pH and changes the inorganic carbonic equilibrium in the adjacent
electrolyte:

*Author to whom correspondence should be addressed.

E-mail: ple@ccr.jussieu.fr
1891

2
OH HCO
3 $ H2 O CO3 :

1892

C. Deslouis et al.

Fig. 1. CaCO3 deposit formed at 1200 rpm, 1.2 V vs SCE and I = 0.5 I(0).

As a result, CaCO3 precipitates:

Ca

CO2
3

! CaCO3 # :

The amount of OH produced by reactions (1)(3)

and, therefore, the interfacial pH are functions of
the applied potential. In a recent paper, the dependence of the interfacial pH on the applied potential
was theoretically calculated and directly measured [3].
In particular, for a potential of 0.5 V vs SCE, the
interfacial pH is close to 9.3 and to 9.6 for 1.0 V vs
SCE. The dierence of 0.3 pH unit was explained by
the fact that two electrons are exchanged at 0.5 V vs
SCE [reaction (1) only] and four electrons at 1.0 V
vs SCE [reactions (1) and (2)] and so the dierence is
log2 [3].
In the experimental conditions of theis study, calcium carbonate precipitates under the form of calcite easily recognisable by its cubic shape and under
the form of aragonite recognizable by the ower
shape of the deposited crystals which have been
observed by scanning electron microscopy (Fig. 1).
The basic technique used to investigate scaling
processes has been chronoamperometry [4, 5]. The
current of oxygen reduction, passing through the
electrode, is recorded vs time during the calcareous
deposit while the electrode is polarized at dierent
potentials corresponding to dierent interfacial pH.

However, the chronoamperometry gives only a partial information on the screening eect of the insulating scale deposit on the electrode surface. In the
present work, the dependence of the dc current on
the rotation speed of the electrode is also used in
conjunction with ac electrical impedance and EHD
impedance technique to complement the information about the morphology of the calcareous
deposit [6, 7].
EXPERIMENTAL
The experiments were peformed with articial
sea-water that complies with the ASTM D1141
characteristics but without MgCl2 salt. The composition as follows: NaCl: 0.5 M, NaHCO3:
2  103 M, Na2CO3: 2  104 M, CaCl2
2H2O:
1.05  102 M. The buering reaction of the carbonates [equation (4)] xed the bulk pH at 8.2.
A cylindrical electrochemical cell (volume of
about 0.5 l) was used in the work. The working
electrode was a gold rod (diameter = 5 mm), the
counter electrode was a platinum grid of large area
and the reference celectrode was a saturated calomel
electrode (SCE). The experiments were carried out
in potentiostatic conditions and the rotation speed
of the disk electrode was monitored between 120
and 1200 rpm.

Characterization of calcareous deposits in articial sea water

1893

Fig. 2. (a) Currentpotential curves for oxygen reduction at 120 and 1200 rpm in the solution: NaCl 0.5, NaHCO3
2  103, Na2CO3 2  104 mol L1. (b) Interfacial pHpotential curves for oxygen reduction at dierent Reynolds number in the solution: NaCl 0.5, NaHCO3 2  103, Na2CO3 2  104, CaCl2
2H2O 1.05  102 mol L1.

A potentiostat (Solartron 1286) was used with a

1250 Solartron frequency analyzer controlled by a
microcomputer to measure the ac and EHD impedances.
STEADY-STATE MEASUREMENTS
Figure 2(a) shows currentvoltage curves plotted
for various rotation speeds of the rotating disk electrode. The two steps of the oxygen reduction can be
detected. The pHpotential curves are reported in
Fig. 2(b). The interfacial pH was measured with the
technique proposed by Romankiw et al. [8], but by
using an impinging jet cell according to the pro-

cedure developed in [3]. In agreement with the calculations of [3], these curves slightly depend on the
Reynolds number Re dened from the ow characteristics at the nozzle outlet of the impinging jet.
The ow was laminar for the three curves. On the
pHpotential curves, the two plateaus are well
dened, the rst one in potential range 0.3; 0.4 V
vs SCE corrresponds to the exchange of two electrons following the reaction (1) and on the second
plateau four electrons are exchanged following reactions (1) and (2). The measurements performed in
this work, are obtained in the potential range 0.8
to 1.2 V vs SCE.

1894

C. Deslouis et al.

Fig. 3. Inuence of stirring for CaCO3 deposition at 1.2 V vs SCE.

The chronoamperometric curves are plotted in

Fig. 3 for dierent rotation speeds. The current is
normalized by I(0), the current value at t = 0. Two
behaviours are clearly detected: for OR 360 rpm
the curves I/I(0) = f(t) are well separated and for
O>360 rpm the curves almost collapse. The curves

given in Fig. 3, as an example, are obtained

at 1.2 V vs SCE and the behavior is very similar
for the other potentials.
The fact that the deposition time does not depend
substantially on O beyond 360 rpm indicates that
CaCO3 deposition is partly controlled by mass

Fig. 4. I0, I1 and k1 vs I/I(0) during CaCO3 formation at 1.2 V vs SCE and 600 rpm.

Characterization of calcareous deposits in articial sea water

1895

Fig. 5. ac impedance diagrams during CaCO3 formation at 1.2 V vs SCE and 120 rpm.

transport at low rotation speeds. At high rotation

speeds, the growth rate is only controlled by the
crystallization kinetics of CaCO3.
At dierent deposition times, so for dierent
I/I(0) values, the dc current is recorded vs the rotation speed of the disk electrode. This measure is
performed during a time short enough to not aect
the chronoamperometric curve. It is well known
that the non diusional part of the current
measured on the diusion plateau is due to the
hydrogen reaction (3). In general, the current is
equal to I0+Idif, where I0 is the hydrogen current
and Idif the diusional current due to the oxygen reduction, which is identical at t = 0 to the Levich
current IL=kO1/2. k is the Levich coecient.
When an electrode is covered by dendrites, its
behavior is similar to a partially blocked
electrode [6] and the variation of the diusional
component of the current vs the rotation speed fol1
1
lows a law [9]: I 1
dif=I b +I L , where Ib is a current
function of the blockage characteristics (coverage
ration y and dimension d of the active sites) and
independent of the rotation speed.
When an electrode is coated by a porous layer,
the variation of the current vs the rotation speed
1
1
follows a law [10]: I 1
where
dif=I p +I L ,
Ip=nFDfc1/l (c1 is the bulk concentration of the
reactive species, Df its diusion coecient in the
porous layer, l is the porous layer thickness, F the
Faraday number and n the number of exchanged
electrons in the electrochemical reaction).
A priori, even after studying the SEM photography (Fig. 1), it is impossible to know whether the
calcareous deposit follows a model corresponding
to a partial blockage or to a coated layer.
Nevertheless, whatever the nature of the coverage,
the variation of the current vs the rotation speed

must follow a single law:

I I0

1
I1

1
;
k1 O1=2

where
I1 Ib or Ip

The recorded current I = f(O) can be analyzed on

the basis of equation (6) with an excellent accuracy.

Fig. 6. Scheme of partly covered interface with calcium

carbonate crystals and related electrical equivalent circuit.

Fig. 7. (a) CHF vs time during CaCO3 formation at 1.2 V vs SCE and dierent rotation speeds. (c) Comparison of
the blocked fraction of the interface from capacitance measurements and from direct SEM examination (t%). (b) CHF vs
I/I0 during CaCO3 formation at 1.2 V vs SCE at dierent rotation speeds.

Characterization of calcareous deposits in articial sea water

1897

Fig. 8. EHD diagrams during CaCO3 formation at 1.2 V vs SCE and 360 rpm.

The parameters involved in expression (6) are

obtained with a tting procedure and the corresponding results are presented in Fig. 4.
The hydrogen current I0 is maximum at t = 0 [I/
I(0) = 1] and monotonically decreases with time.
This slight decrease can be due to the decrease of
the active area by the calcareous deposit. The value
of k1 is almost constant until I/I(0) = 0.5, then the
dierent models corresponding to (6) are valid only
for 1 R I/I(0)R 0.5. The increase of k1 corresponding to a longer time can be due to a dramatic reduction of the electroactive area. The value of I1
1

increases slowly to I/I(0) = 0.5 and more rapidly

for a stronger deposit.
AC IMPEDANCE
The ac impedance diagrams plotted in Fig. 5
were measured at dierent deposition times for an
electrode polarized at 1.2 V vs SCE and for a rotation speed of 120 rpm. For short or mid times
(tR 9000 s) these diagrams show a attened capacitive loop which may, due to the electrochemical
involved process, contain two poorly resolved

1898

C. Deslouis et al.

Fig. 9. EHD diagrams at dierent rotation speeds for a CaCO3 deposit formed at 120 rpm, 1.2 V vs SCE and 0.7 I(0).

loops, one in high frequency due activation and one

in low frequency due to convection diusion. At
the highest deposition time (t = 9900 s) there
appears a supplementary high frequency loop. This
last feature can reect the behavior of a dielectric
lm containing defects, which corresponds to the
development of the calcium carbonate lm.
According to a recent work devoted to a similar
system [4, 5]. the ac impedance in the last stages (ie
when a continuous lm covers the metal after a
long deposition time) is charactized by a faradaic
inpedance Zf at the pores' bottom in parallel to the
double layer capacitance Cdf relative to the same

area. These two elements are in series to a resistance Rf due to the nite conductivity of the electrolyte solution in the thin pores and the whole
arrangement is placed in parallel to a capacitance
Cf reecting the dielectric nature of the CaCO3
layer.
Therefore, at intermediate deposition times, one
may assume that the metal is shared between calcium carbonate islands with inner porous defects
and macroscopic uncovered areas.
For such a geometry, an electrical equivalent circuit can thus be built, that is based on the parallel
combination of the characteristic impedance of the

Characterization of calcareous deposits in articial sea water

1899

Fig. 10. Average dimension of the active sites for dierent polarization and rotation speed applied.

CaCO3 sites (see above) and the parallel association

Z/Cd over the uncovered areas displayed in Fig. 6.
Z and Zf, Cd and Cdf respectively, have the same
physico-chemical meanings but for very dierent
area values.
The lm capacitance Cf, when considering the
dielectric constant of CaCO3 (e 1 6) and the thickness range (110 mm) of the lm, is smaller by several orders of magnitude than Cd. This means that
for moderate blockage ratios of the interface,
Cd>>Cf, the resulting parallel combination of those
two capacitances being therefore equivalent to Cd,
which is proportional to the active area. When the
CaCO3 sites coalesce, the Z/Cd impedance branch
gradually disappears and the equivalent circuit in
Fig. 6 takes the aspect of the equivalent circuit
already proposed for organic coatings in [11]. The
latter situation is likely to be considered for very
high deposition times which are not considered
here.
The variations of the high frequency capacitance
CHF (virtually equal to the double-layer capacitance
over the uncovered area), which thus closely follow
the variations of the free area of the metal, have
been recorded vs time for dierent potentials and
dierent rotation speeds. As an example, in
Fig. 7(a), the results obtained at 1.2 V vs SCE are
given. At t = 0, the usual value for a double-layer
capacitance is obtained. The CHF variation vs time
[Fig. 7(a)] is very similar to the chronoamperometric curve I/I(0) vs time (Fig. 3), in particular for
its variation vs the rotation speed. This fact is conrmed by plotting CHF vs I/I(0) [Fig. 7(b)]. The
curves obtained at dierent rotation speeds collapse
in this representation, then the evolution laws for
the normalized current I/I(0) and for CHF are identical. However, it is clear that CHF which directly
reects the value of the active area is not proportional to the current especially at short times
[0.5 < I/I(0) < 1] as evidenced in Fig. 7(b).

From these capacitance values, it is also possible

to calculate the fraction of covered electrode area
(1 CHF/CHF0). This value is compared to the coverage ratio t obtained from the examination of microscopy photographies [Fig. 7(c)]. To this end, an
image processing software coupled to the SEM providing both the total area occupied by the crystals
and the distribution in sizes was used.
EHD IMPEDANCE
This impedance was introduced by Bruckenstein
et al. [12] and a quantitative expression was rst
proposed for a uniform accessible electrode [13]. A
review of this method was recently published [7].
The two particular cases presented above: partially blocked surface and electrode coated by a
porous layer, give, in steady state, the same form of
expression (6). Each case had been studied with
EHD impedance and for each, the two corresponding EHD diagrams have particular shapes and
properties. For a partially blocked electrode, the
diagrams show two characteristic frequencies and
fall onto a single curve when plotted vs a dimensionless frequency p (=o/O). The high frequency
domain is characteristic of the response of the sum
of the individual active sites [7, 9]. The average site
dimension, d, was deduced from the two characteristic frequencies corresponding respectively to the
high frequency behavior and to the low frequency
behavior, namely pHF and pLF , ie


pHF 3=2
;
7
d 2:13=2 R
pLF
where R is the electrode radius, and pHF and pLF
are obtained for a p/2 phase shift of the EHD impedance.
The EHD impedances DI/DO were recorded
during the calcareous deposition every 10 min for

1900

C. Deslouis et al.

dierent potentials and dierent mean velocity

values. As an example, in Fig. 8 the diagrams corresponding to 1.2 V vs SCE and 360 rpm are plotted
in the Bode plane (log of normalized modulus and
phase vs log of dimensionless frequency).
On the bare surface (t = 0), the EHD diagrams
showed only one time constant corresponding to
the diusion time in the electrolyte and the data fall
on a single diagram when plotted for various mean
rotation speeds as expected for a uniform accessible
electrode [12]. The diusion time in the electrolyte
is equal to d2N/D, where dN is the Nernst diusion
layer thickness and D the diusion coecient of the
electroactive species. d2N/D is proportional to Sc1/3/
O, where the Schmidt number Sc is the ratio of the
dynamic viscosity n to the diusion coecient D.
Those diagrams are function of only one parameter
Sc [12].
The dierent diagrams recorded after dierent
polarization times (Fig. 8) were qualitatively identical. The same constant as for a bare surface was
found in the low frequency range with a slight shift
of diagrams to lower reduced frequencies when the
deposition time increases. At high frequency (above
p = o/O = 1), a second time constant appeared.
Both these features characterized the presence of a
partially blocked surface with a moderate value of
the active fraction of the electrode.
Although the theory predicts that the diagrams at
dierent mean velocities would merge in both low
and high frequency domains the dierent diagrams
appear separate especially in the high frequency
range. For the same deposition time, corresponding
to I/I(0) = 0.7, the EHD diagrams are recorded for
three rotation speeds (Fig. 9). In the low frequency
range, the three diagrams are identical and in the
high frequency range only a common asymptotic
behavior is obtained for the modulus. For the
phase shift, the dierence is due to the fact that the
asymptotic value is not reached.
The slight separation of the EHD diagrams
observed in the low frequency region, when the deposition time is increasing, accounted for the existence of a diusion through a porous layer, that
corresponding to the area covered by scale. This
result is in agreement with the (Rf, Cf) HF loop
which appears on the ac impedance diagrams.
Following expression (7), the average dimension
of the active sites can be deduced from the EHD
diagrams. The results are plotted in Fig. 10 for
dierent polarizations. Clearly, the dimension of the
active site is not a function of the potential and the
active site is almost constant for 0.5 < I/I(0) < 1
and equal to 30m, this value is smaller than that
found with another salt concentration [5]. This
result must be compared with the results of Fig. 4.
1
I 1
1 is also constant for 0.5 < I/I(0) < 1 and I 1 is
characteristic of the blockage; these two results are
in agreement. For I/I(0) smaller than 0.5, the
dimension of the active site increases dramatically

with the deposition time. The theory developed

in [9] and which corresponds to equation (7) is
valid for k constant in equation (6). When k1
increases, the hypotheses corresponding to
equation (7) are not veried. Another explanation
would imply the inactive site instead of the active
site. The theory has been so far developed for an
inactive surface having some active spots. Now,
when the calcium carbonate deposition starts one
just deals with the opposite situation where the surface is active with some inactive spots. Intuitively,
one can assume that the charateristic frequency
which is involved in the EHD response contains a
dimension relevant to the perturbed spatial domain,
in the present case to inactive site. This would
explain in fact why we observe a small increase of
the charateristic dimension until I/I(0) = 0.5; it corresponds to the slow growth of the calcite crystals.
At larger times, the fast increase of the charateristic
dimension reects the development of a porous
layer and the use of equation (7) is incorrect.

CONCLUSION
This work was aimed at developing an electrochemical technique to characterizing the calcareous
layers which grow under cathodic polarization in
the very conditions of cathodic protection. This information is needed for optimizing the current to
be imposed according to the degree of protection
provided by the calcareous deposits. In this paper,
the ac and EHD techniques have been rst applied
to the simplest case of a calcium carbonate layer,
this component giving the major protection eect in
the calcareous deposit.
The chronoamperometry curves show a monotonic decrease of the current. At short times for
which 1r I/I(0)r 0.5, it has been shown that the
current corresponding to the oxygen reduction is
mostly controlled by diusion convection. From the
ac and EHD impedance measurements, it has been
proved that the calcium carbonate deposition proceeds by growth of isolated crystals, the size of
which slightly increases between 30 and 50 mm. The
situation is then that of a 2-D type or a partial
blocking one. This result was conrmed by the
SEM observations. In particular, the blocked area
values deduced from the high frequency capacitance
or directly estimated from the interface images were
very similar.
For larger deposition times, and therefore larger
blocked areas, the crystals start to coalesce and a 3D porous layer builds-up.
In conclusion, an on-line analysis of the impedance can provide information on the characteristics of the growing calcium carbonate layers,
which can then be used to monitor the cathodic
protection conditions.

Characterization of calcareous deposits in articial sea water

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