Desalination 311 (2013) 234–240

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Desalination
journal homepage: www.elsevier.com/locate/desal

Electrochemical scaling of stainless steel in artificial seawater: Role of experimental

conditions on CaCO3 and Mg(OH)2 formation
Héla Karoui a, b, Benoit Riffault a, Marc Jeannin c, Abdelkarim Kahoul d, Otavio Gil a,
Mohamed Ben Amor b, Mohamed M. Tlili b,⁎
a
Equipe de Recherche en Physico-Chimie et Biotechnologies E.R.P.C.B. (EA3914) Campus II- Sciences 2- IUT de Caen—Université de Caen Basse-Normandie,
Bd du Maréchal Juin 14032 CAEN, France
b
Laboratoire de Traitement des Eaux Naturelles, Centre des Recherches et Technologies des Eaux, Technopole Borj Cédria, BP 273 Soliman 8020, Tunisie
c
Laboratoire d'Etude des Matériaux en Milieux Agressifs (LEMMA) EA 3167, Université de la Rochelle, Av Michel Crépeau, 17042 La Rochelle, France
d
Laboratoire d'Energétique et d'Electrochimie du solide, Université F. Abbas de Sétif, 19000-Sétif, Algérie

H I G H L I G H T S

► Unlike other substrates, stainless steel promotes Mg(OH)2 electrochemical scale.

► The temperature favours the brucite formation on stainless steel.
► Scaling process starts by brucite formation; then, the aragonite occurs on it.

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

Article history: In seawater, during the application of cathodic protection, a scale layer forms on the metal surface. As func-
Received 7 March 2012 tion of its chemical composition and compactness, it can improve the metal protection against corrosion by
Received in revised form 5 July 2012 reducing the oxygen diffusion. The present investigation focuses on the electrochemical scaling of stainless
Accepted 7 July 2012
steel in artificial seawater. Formed scales were characterized by X-ray diffraction, Raman spectroscopy and
Available online 15 August 2012
scanning electron microscopy. It was found that the formed scales are mainly CaCO3 aragonite. The brucite
Keywords:
(Mg(OH)2) was identified, as a component of the scale layer, only for a high temperature and a more cathodic
Stainless Steel potential. It was also shown that, unlike other substrates, stainless steel promotes the precipitation of brucite.
Scaling If the experimental conditions favoured its formation, the scaling process starts with brucite deposition. The
Brucite growth of CaCO3 nucleuses, developed on interstice, recovers after brucite layer.
Seawater © 2012 Elsevier B.V. All rights reserved.
Calcium carbonate

1. Introduction
Stainless steels (SS) are one of the most tonnage alloy materials used
for industrial and domestic purposes. Its corrosion resistance in a wide
variety of aqueous environments determines its use in many applications.
However, SS like other materials is a scaling prone. Mineral deposition can
have a beneficial effect in terms of corrosion protection especially in the
field of the cathodic protection, whereas, in industries where saline fluids
are transported such as in water desalination systems, oil recovery and
power generation it can generate major problems [1,2]. As function of
the water use and chemical composition, different precipitates were iden-
tified in heat exchange surfaces [3,4], cooling water systems [5] and
oilfield production wells [5,6]: BaSO4, CaSO4 and CaCO3; each having dif-
ferent thermodynamic tendencies and kinetics of formation, but scale is
far dominated by calcium carbonate.
⁎ Corresponding author. Tel.: +216 79 32 50 44; fax: +216 79 32 58 02.
E-mail address: mohamed.tlili@certe.rnrt.tn (M.M. Tlili).
In sea water, the high concentration of the magnesium ions plays an
important role on scale formation for physico-chemical properties of
the deposit and kinetics' point of view. For instance, some studies
were devoted to investigate the magnesium ions' contribution on the
nucleation-growth process of calcareous deposition [7–13]. It has been
shown that Mg2+ delays the CaCO3 deposition and promotes the arago-
nite shape instead of calcite and vaterite [12–20]. In addition, it was
shown that magnesium ions favour the heterognenous precipitation
of calcium carbonate [12].
Under cathodic protection conditions, when chemical and thermo-
dynamical conditions are gathered, magnesium can lead in seawater to
the precipitation of brucite Mg(OH)2 [7]. Below we recall briefly the pos-
sible chemical and electrochemical reactions which can evolve on the
cathode for a potential range of −0.8 to −1.2 V/SCE (Saturated Calomel
Electrode): it can create the reduction of oxygen which can be split into
two elementary steps:
− −
O2 þ 2e þ 2H2 O→2OH þ H2 O2 ð1Þ

0011-9164/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2012.07.011
 H. Karoui et al. / Desalination 311 (2013) 234–240
− −
H2 O2 þ 2e →2OH ð2Þ
and, the reduction of water leading to hydrogen evolution.
− −
2H2 O þ 2e →2OH þ H2 ð3Þ
The production of OH− ions on the electrode surface increases the
local pH and changes the inorganic carbonic equilibrium in the adjacent
electrolyte.
− − 2−
HCO3 þ OH →CO3 þ H2 O ð4Þ
As a result, CaCO3 precipitates.
2þ 2−
Ca þ CO3 →CaCO3 ↓ ð5Þ
The pH increase may also allow magnesium hydroxide precipitation.
2þ −
Mg þ 2OH →MgðOHÞ2 ↓ ð6Þ
Laboratory studies on the electrochemical scaling of metallic surfaces
in artificial seawater show that brucite formation is material-dependent.
For gold substrate, it was obtained only for a potential of −1.2 V/SCE
and in absence of calcium ions [21]. On steel and titanium, brucite
co-precipitates with calcium carbonate for an applied potential of
−1.2 V/SCE [7] and −1.4 V/SCE [22], respectively. In spite of its abun-
dant use in marine environment, developed studies were not focused
on the co-precipitation of CaCO3-Mg(OH)2 scale on stainless steel in sa-
line waters. Nevertheless, some works were developed but in experi-
mental conditions which cannot favour Mg(OH)2 formation. Thus,
Morizot et al. [23] used supersaturated solutions exempt of magnesium
prepared from CaCl2 and Na2CO3. Euvrard et al. [24] and Ghizellaoui
and Euvrard [25] have tested a commercial mineral water and an
underground water poor in magnesium ([Mg 2+] =0.6 and 1.25 mM
with a molar rations Mg/Ca =0.2 and 0.4, respectively) with respect to
seawater (e.g. for standard sea water [Mg2+] =55 mM with a molar
ration Mg/Ca =5.2). Martinod et al. [26], were tested brine solutions
(salinity= 83 g/L; [Mg2+] =29 mM and Mg/Ca =0.2) with and with-
out 9 mM carbonate ions. For these last investigations, the applied po-
tential was about −1 V/SCE and calcium carbonate was the only
found precipitate. Otherwise, numerous works studying the SS scaling
by spontaneous precipitation were presented [8,12,27–32]. Scales
were identified in all cases to be CaCO3 even in presence of magnesium
ions.
The aim of the present work was then to study the SS scaling in stan-
dard seawater under catodic protection conditions. The influence of
temperature, applied potential and the hydrodynamic conditions on
the scaling kinetics and on the nature of the scale deposits were there-
fore investigated. For this, accelerated electrochemical scaling tech-
nique was used. Chronoamperometry method was applied to assess
the precipitation rate and X-ray diffraction (XRD), scanning electron
microscopy (SEM) and Raman techniques were exploited to character-
ize the formed scales.
2. Experimental
Experiments were performed in a standard sea water (SSW) solu-
tion containing the main species present in natural seawater, as de-
scribed by the ASTM norm D1141 (American Society for Testing
Materials) (Table 1). The pH of seawater, fixed by the buffering reac-
tion of carbonates, was adjusted in all cases at 8.2 with a 0.1 M NaOH
solution. An electrochemical thermostated glass cell was used. Its
large volume (500 mL) allowed to avoid a significant variation of spe-
cies concentration during the formation of deposits. The working
electrode was a 304 L austenitic stainless steel (SS) rotating disk elec-
trode with 0.785 cm 2 area. The electrode surfaces were polished with
235
Table 1
Electrolytes composition (mol L−1).
Composition
NaCl 0.42
MgCl2 5.46 × 10−2
Na2SO4 2.8 × 10−2
CaCl2 1.05 × 10−2
KCl 9.3 × 10−3
NaHCO3 2.8 × 10−3
silicon carbide paper (P # 1200), rinsed thoroughly with Milli-Q water
and carefully dried. Potentials were measured versus the Ag-AgCl refer-
ence electrode. A large Pt grid was used as counter electrode.
Electrochemical experiments were carried out under potentiostatic
condition using GAMRY potentiostat controlled by microcomputer.
Ex-situ characterization of the deposits was performed by SEM, X-ray dif-
fraction (XRD) and μ-Raman spectrometer. SEM pictures were obtained
on a QUANTA 2000 without a specific calibration. XRD was carried out
at room temperature with a Philips X'PERT PRO diffractometer in step
scanning mode using Co_Kα radiation. Micro Raman spectrometry inves-
tigation was obtained using a Jobin Yvon High Resolution Raman Spec-
trometer (LabRAM HR).
3. Results and discussion
To show the electrochemical behaviour of SS compared to already
tested materials, in terms of oxygen and water reduction, current–
potential curves have been performed on gold, steel and stainless
steel substrates. The steel electrode was a carbon steel polished
with silicon carbide (grad 220: 68 μm); its composition in weight
percentage is: Fe: 98.9, Mn: 0.504, Si: 0.176, C: 0.131, Cu: 0.129, Ni:
0.078, and Cr: 0.058. Experiments have been carried out in SSW solution
free of Ca 2+ and Mg2+ to avoid CaCO3 and Mg(OH)2 precipitation.
Fig. 1 shows that the oxygen reduction starts on less cathodic po-
tential with the highest diffusion plateau in the case of gold electrode
where the two steps of the oxygen reduction were observed. The first
diffusional plateau (− 0.3 to − 0.4 V) corresponds to the reaction (1),
and the second one to both reactions (1) and (2). Nevertheless, for
steel and stainless steel electrodes, the first step of the oxygen reduc-
tion is merged in the second one because the reaction (2) is the
fastest on steel and SS then on gold [7]. For more cathodic potentials,
hydrogen evolution (Eq. (3)) is also observed. The latter begins ap-
proximately at − 1, −1.1 and − 1.2 V/Ag-AgCl on steel, SS and gold,
respectively. This difference in the hydrogen evolution overvoltage
should lead to a difference in the interfacial pH values.
Fig. 1. Current–potential curves obtained on different substrates at a scan rate 2 mV/s,
625 rpm in SSW without Mg2+ and Ca2+, (a) stainless steel, (b) steel and (c) gold
electrodes.
236 H. Karoui et al. / Desalination 311 (2013) 234–240
As established previously using a gold electrode [21], the measured
pH was almost constant at about 9 between − 0.6 ≥ E ≥ − 1 V/SCE and
increases only when hydrogen evolution proceeds; the interfacial
pH value was about 9.3 for a potential of − 1.1 V/SCE. Therefore, for
− 1.1 V/Ag-AgCl, this pH at SS-SSW interface will at least equal or ex-
ceed 9.3 which may promote the formation of brucite Mg(OH)2
requiring a minimum value of 9.3. Thus, for this study a potential of
− 1.1 V/Ag-AgCl has been taken as an optimum between suitable
basic pH and a softly H2 evolution that does not perturb the precipitat-
ed layer.
3.1. Effect of temperature
The influence of temperature on the kinetics and the nature of the
scale deposit on the SS electrode were studied at a rotating speed of
625 rpm. Fig. 2 shows the current–potential curves for temperatures
ranging between 20 and 50 °C. It can be concluded that the measured
currents increase with temperature which can be explained by an ac-
celeration of water and oxygen reduction reactions.
The current increase at the diffusion plateau was a consequence of
the complex effect of the temperature on the electrochemical reduction
rate of O2 and on its diffusion coefficient. Thus, although the decrease of
the dissolved O2 solubility, Fig. 2 shows that the current rises with tem-
perature increasing. This result agrees those of Barchiche [33] and
Kunjapur et al. [34]. It seems that the effect of temperature on the diffu-
sion coefficient prevails over the one of the solubility. Indeed, the in-
crease of thermal agitation and the decrease of the solution viscosity
increase the diffusion coefficient. In reality, the diffusion coefficient of
hydroxide ions also increases and leads to the acceleration of their ejec-
tion from the electrode. It comes to counterbalance the increase in OH−
production via the oxygen reduction reaction. However, the O2 reduc-
tion reaction rate increase does have not a significant impact on pH
value which remains stable [21]. Moreover, water reduction begins for
a less cathodic potential when temperature increases. The corresponding
current increase is, therefore, due partially to the activation of this reac-
tion leading to an increase of OH− ions (pH increases) which could fa-
vour the brucite precipitation.
As expected, the chronoamperometric curves plotted in Fig. 3 with
SSW show that the higher the temperature is the shorter is the deposi-
tion time. This result agrees with literature for different substrates as
steel [34–37] and gold [38]. Indeed, the solubility of CaCO3 decreases
with temperature (Ksp= 3.52× 10−9 at 20 °C and 2.17× 10−9 at
50 °C [39]).
XRD analyses of the deposited layers (Fig. 4) performed at different
temperatures show diffraction peaks of aragonite and brucite with a
minority of vaterite accompanied by those of the SS substrate. The
-I (mA)
E (V)
Fig. 2. Current–potential curves for oxygen and water reduction on SS electrode in SSW
at 2 mV/s, 625 rpm and different temperatures.
Time (h)
Fig. 3. Chronoamperometric curves of deposits on SS electrode in SSW at 625 rpm,
−1.1 V and different temperatures.
temperature does not affect the allotropic form of CaCO3 since the pre-
dominant phase remains aragonite. When magnesium is present in
sufficient concentration (SSW case), it leads to the aragonite precipi-
tation rather than thermodynamically favoured calcite phase which
is in agreement with earlier studies [13,40]. Using Raman Spectroscopy
(spectra not shown here), only aragonite peaks are observed. However,
XRD diffraction reveals both aragonite and brucite. Since the Raman
spectrometer is a confocal type and only a local deep of a few microme-
ters depth was analysed, the precipitation takes part, therefore, in the
first step while that of CaCO3 occurs after and above the brucite layer.
This result is consistent with that of Gil et al. [41] who showed the pres-
ence of a magnesian layer under CaCO3. Moreover, XRD patterns show
that the diffraction lines of Mg(OH)2 become more pronounced with
temperature increasing (Fig. 4). These results are in agreement with pre-
vious studies [33,42] in which it is reported that Mg(OH)2 is missing at
ambient temperature. Nevertheless, Philipponneau [35] showed that
Mg(OH)2 remains invariant to the increase of temperature and Kunjapur
[34] showed that Mg(OH)2 is thermodynamically more stable at lower
temperature.
These confusing and contradictory results may be explained by the
fact that the majority of authors did not consider the pH value change
which is the real driving force for precipitation. So, two main parame-
ters that are potential and temperature should be considered.
On one hand, if the applied potential was on the oxygen diffusion
plateau, the pH would not change and only thermodynamic state
could be kept so brucite is not favoured. On the other hand, when the
potential is in the domain of hydrogen evolution, the increase of the
temperature causes an activation of both oxygen and water reduction.
Fig. 4. XRD patterns of the deposit formed on SS electrode in SSW at 625 rpm and
−1.1 V at different temperatures (A and B refer to aragonite and brucite, respectively).
 H. Karoui et al. / Desalination 311 (2013) 234–240 237

20°C 30°C

40°C 50°C
Fig. 5. SEM photographs of the deposit formed in SSW on SS substrate at different temperatures.

So, pH is high and permits the brucite precipitation. Knowing that at the current I/Imax remaining constant between 2 and 28 h of polarisation in-
working temperature range the solubility of brucite is slightly dicates that there is no deposition. For curves obtained in the potential
influenced (Ksp(20 °C) = 6.30× 10−12 and Ksp(50 °C) = 5.25 × 10−12 range of −0.9 to −1.1 V, the decrease of current becomes faster with
[43]), it is clear that the main effect of temperature in the present exper- decreasing potential and a I/Imax value close to zero is reached after
imental conditions was to increase the interfacial pH. about 40 h for E =−1 and −1.1 V. Reddy et al. [40] have reported
SEM photos (Fig. 5) show that the precipitates consisting of aragonite that the scaling of steel in seawater increases when the potential be-
are more compact with smaller crystals at low temperature. These crys- comes more cathodic. For −1.2 V, the precipitation is still faster but
tals become fewer and larger at 40 and 50 °C. Indeed, the size of arago- the curve shows again an increase of current indicating a detachment
nite crystal evolves from 8.70 μm at 30 °C to 26.5 μm for 40 °C and of the scale layer previously formed on the electrode due to an intensive
36.28 μm at 50 °C. However, Garcia [44], using a gold electrode at
−1 V/SCE in soft water containing low Mg2+ concentration, reported
that CaCO3 precipitation leads to a high crystal number with a low size
at 50 °C regarding those formed at ambient temperature. Obtained mor-
phology (Fig. 5) could be interpreted by the fact that, in addition to the
more applied cathodic potential of −1.1 V leading to pH increase, the
higher Mg2+ concentration in SSW is sufficient to allow a fast precipita-
tion of Mg(OH)2 having a screening effect on crystallisation of CaCO3.
The active surface reduction leads to the formation few CaCO3 nuclei
and then big size crystals.
The magnesium deposits, according to XRD patterns, obtained at
higher temperatures (see Fig. 5) appear like homogeneous dark
layers covering the SS surface. Using the SEM and EDS (Energy disper-
sive spectrometry) techniques, Krauss [22] has observed similar layer
containing magnesium on a polarized electrode in SSW.

3.2. Influence of potential Time (h)

Fig. 6 shows chronoamperometric curves plotted for potential Fig. 6. Chronoamperometric curves obtained in SSW on SS electrode at 625 rpm, 30 °C
values between −0.8 and −1.2 V/Ag-AgCl. At −0.8 V, the normalized and different potentials, (a) −0.8; (b) −0.9; (c) −1.0; (d) −1.1; (e) −1.2 V.
238 H. Karoui et al. / Desalination 311 (2013) 234–240
Fig. 7. XRD patterns of the deposit formed at different potentials.
H2 evolution. Fast precipitation rate leads to maintain a potential of
−1.1 V as the best compromise for scale deposits on the SS electrode.
It is important to mention that for E ≥ − 1.1 V, the curves begin
with a plateau followed by a current decrease (Fig. 6). This plateau
whose duration decreases with potential is attributed according to
Jaouhari [45] to the passive layer that obstructs the active sites of
the deposit at the SS surface.
XRD analyses (Fig. 7) show that, for potentials E≤ −1.1 V/Ag-AgCl,
the deposits are composed of aragonite and brucite. For potentials
E ≥−1 V only aragonite is detected. In agreement with [33], μ-Raman
analyses of the deposited layers (Fig. 8a) show characteristic peaks of
aragonite (wavenumbers: 155, 209, 703, 708 and 1087 cm−1). At
E = −1.2 V, Mg(OH)2 is easily identified (Fig. 8b) according to peaks
at 280 and 460 cm−1 attributed to symmetric Eg and Alg stretching
modes and a strong vibrational peak at 3650 cm−1 associated to OH
vibration [43].
The SEM photos (Fig. 9) show that the deposits obtained at −0.9
and −1.1 V are made of crystals assembled in cauliflower morphology,
as often observed for aragonite [7,46,47]. The brucite deposit obtained
at −1.2 V, appearing like a homogeneous and porous layer is made of
small assembled crystals. The small white and dispersed particles may
be a few crystals of NaCl.
When a more cathodic potential is applied, competition between
brucite and aragonite precipitation resulting from the negatively
charged surface and Ca 2+ and Mg 2+ cations occurs. Indeed, while
OH − ions are produced on the SS surface the CO32− transportation is
disfavoured. Thus, formation of brucite is rather favoured [48]. On
gold electrode, the deposits formed in artificial seawater is composed
of aragonite in the potential range − 0.8 to − 1.2 V/SCE [45]. Layer
containing Mg was only observed at − 1.2 V/SCE in SSW solution
free of Ca 2+ [21]. In the case of steel electrode, CaCO3 was obtained
for − 0.9 ≥ E ≥ − 1.1 V/SCE whereas Mg(OH)2 was the phase forming
only at E ≤ − 1.3 V/SCE. A deposit containing both phases could only
be obtained at − 1.2 V/SCE [7]. Krauss obtained Mg(OH)2 on titanium
electrode for E = −1.4 V/Ag-AgCl [22]. The brucite which appears
earlier on SS electrode could be due to the evolution and heterogene-
ity of the SS passive layer and therefore to the potential and pH distri-
bution. Indeed, some zones of the surface would be more cathodic
with a high pH value favouring the local rate precipitation of brucite.
In the less cathodic zones where the pH value is lower, Mg(OH)2 pre-
cipitation rate decelerates while that of CaCO3 precipitation increases.
3.3. Influence of hydrodynamic conditions
The chronoamperometric curves plotted in Fig. 10 show that the
scale layer growth rate decreases with the electrode rotation speed.
This behaviour is different from that observed on gold [47] and steel
[7] electrodes where the effect of rotation disappears at a value higher
than about 360 rpm. According to XRD patterns (Fig. 11), the stirring
(cm-1)
b
(cm-1)
Fig. 8. Raman spectra of the deposit formed at different potentials (a) −0.9, −1,
−1.1 V; (b) −1.2 V.
does not affect the CaCO3 allotropic form. This is in agreement with
previous works [7,46,47] where only CaCO3 crystal sizes were affect-
ed by stirring.
At 100 rpm, the aragonite peaks are difficult to be detected. Only a
few aragonite crystals were observed by μ-Raman, whereas, almost
overall surface is covered by Mg(OH)2 (Fig. 12 spectrum a). At 225 rpm,
the number of aragonite crystals observed is more numerous than that
obtained at 100 rpm and the surface is covered by the Mg(OH)2 as
shown in Fig. 12 b. At 1225 rpm, only a minor fraction of brucite is
detected.
It is known [33,41,47] that highly rotation speed reduces the
boundary diffusion layer and therefore the thickness of the layer in
which Mg(OH)2 stable precipitate can be formed. So, the stirring fa-
vours the CaCO3 precipitation for three complementary causes. In a
first time, one could attempt to say that the pH increases with the ag-
itation. However, as it was demonstrated by Deslouis et al. [47] that,
for sufficiently cathodic potentials (corresponding to water reduction
reaction), the increase of rotation speed reduces the pH because of
the increase of hydroxides ions ejection from the electrode surface
neighbourhood. Secondly, because of the reduction of the viscous
magnesium layer observed by Maillot [38] and Barchiche [7,33], the
precipitation and growth of calcium carbonate through this layer be-
come easy. Finally, the hydrogen carbonate transportation to the in-
terfacial region is accelerated with increasing the rotation speed.
4. Conclusion
In this study electrochemical scaling of SS in standard seawater
was investigated. Scales are mainly CaCO3 (aragonite) and Mg(OH)2
(brucite). It was shown that, unlike other substrates, the stainless
 H. Karoui et al. / Desalination 311 (2013) 234–240 239

-0.9 V -1.1 V

-1.2 V
Fig. 9. SEM photographs of the deposit formed at different potentials.

steel promotes the precipitation of brucite at different experimental
conditions, such as temperature, applied potential and stirring. Brucite
precipitation is more pronounced for high temperatures (T≥30 °C),
more cathodic potentials (E≤ −1.1 V/Ag-AgCl) and low rotation
speeds. These three parameters provoke the increase of the interfacial
pH, which is the real driving force of the brucite precipitation. The
brucite layer acts as an inhibitor on the aragonite deposition by blocking
partially the surface of the electrode. However, in the beginning of the
scaling process, CaCO3 precipitates between brucite crystals and in a
second time it finishes by recovering the initial layer.

(h)

Fig. 10. Influence of stirring on deposition at 30 °C, −1.1 V in SSW, (a) 1225 ; (b) 625 ; Fig. 11. XRD patterns of the deposit formed in SSW at different speed rotation, 30 °C
(c) 225 and (d) 100 rpm. and −1.1 V.
240 H. Karoui et al. / Desalination 311 (2013) 234–240
a from sea water, Geochim. Cosmochim. Acta 39 (1975) 489–504.
(cm -1)
b [24] M. Euvrard, F. Membrey, C. Filiatre, C. Pignolet, A. Foissy, Kinetic study of the
(cm -1)
Fig. 12. Raman spectrum of deposit formed at 30 °C in SSW for (a) −1.1 V at 100 rpm
(b) −1.1 V in SSW (a), (b) refers to 225 and (c) to 1225 rpm.
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