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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
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
1
2
The production of OH ions on the electrode surface increases the local pH and changes the inorganic carbonic equilibrium in the adjacent
electrolyte:
2
OH HCO
3 $ H2 O CO3 :
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C. Deslouis et al.
Fig. 1. CaCO3 deposit formed at 1200 rpm, 1.2 V vs SCE and I = 0.5 I(0).
CO2
3
! CaCO3 # :
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, CaCl22H2O:
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.
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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, CaCl22H2O 1.05 102 mol L1.
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.
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Fig. 4. I0, I1 and k1 vs I/I(0) during CaCO3 formation at 1.2 V vs SCE and 600 rpm.
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Fig. 5. ac impedance diagrams during CaCO3 formation at 1.2 V vs SCE and 120 rpm.
1
I1
1
;
k1 O1=2
where
I1 Ib or Ip
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.
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Fig. 8. EHD diagrams during CaCO3 formation at 1.2 V vs SCE and 360 rpm.
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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).
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
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Fig. 10. Average dimension of the active sites for dierent polarization and rotation speed applied.
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C. Deslouis et al.
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.
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