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Corrosion Science 108 (2016) 4759

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Corrosion Science
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Effect of the electrolyte pH on the corrosion mechanisms of Zn-Mg

coated steel
J. Rodriguez a, , L. Chenoy b , A. Roobroeck c , S. Godet d , M.-G. Olivier a,c
University of Mons-UMONS, Faculty of Engineering, Materials Science Department, Place du Parc 20, 7000 Mons, Belgium
University of Mons-UMONS, Faculty of Engineering, Chemical and Biochemical Process Engineering Department, Place du Parc 20,7000 Mons, Belgium
Materia Nova ASBL, Avenue Copernic 1, 7000 Mons, Belgium
4MAT, Universit Libre de Bruxelles, 194/03 Avenue F. Roosevelt 50, 1050 Brussels, Belgium

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

Article history: The initial pH effect on the dissolution of zinc-magnesium coated steel is investigated with or with-
Received 22 October 2015 out chlorides for long immersion periods. The coating is characterized by TEM, SEM and GDOES. With
Received in revised form 26 February 2016 immersion time, the alloy electrochemical behaviour is investigated by EIS and the corrosion products are
Accepted 26 February 2016
analysed using ICP-OES and XPS. In alkaline medium, the formation of zincite is inhibited and chlorides
Available online 3 March 2016
do not hinder a passive layer formation. In chloride electrolyte at natural pH, chlorides are not detected
on the metal surface. Chemical composition of corrosion products and their protective effect depend on
the initial pH and its evolution.
A. Metal coatings
A. Magnesium 2016 Elsevier Ltd. All rights reserved.
C. Anodic dissolution

1. Introduction contradictory. Nevertheless, the strong dependence of the protec-

tive action of magnesium on the corrosion conditions can explain
The corrosion protection of steel is commonly obtained by these disagreements. The corrosion of magnesium is always char-
cathodic protection. In automotive, building and house hold appli- acterized by a release of hydrogen due to a phenomenon called
ance industries, zinc coatings are widely used as a sacricial layer. negative difference effect (NDE). This unexpected phenomenon
In addition to the galvanic protection, the insoluble zinc corrosion can be explained by the two-step magnesium oxidation reaction
products formed on the surface in atmospheric conditions assure involving the existence of an adsorbed species Mg+ ads [2632].
a barrier effect [1]. Nevertheless, the composition of those corro- This singular mechanism promotes the formation of a large quan-
sion products is depending on the exposure conditions and this tity of hydroxide ions and therefore a straight increase in pH. In
protection is not observed in all environments [26]. neutral environment without hydrolysis, the selective dissolution
In the last twenty years, a large effort has been made in order to of magnesium occurs due to the formation of galvanic couplings
improve the corrosion resistance of zinc coatings without increas- between magnesium and another metal [4,30,33]. In atmospheric
ing their thickness or resorting to additional corrosion protection conditions, the cathodic and anodic areas are well separated giving
such as protective layers. New metallic coatings coupling zinc with at the rst stage for this substrate a high galvanic current and a
aluminium, magnesium or a combination of both elements have high corrosion rate [33]. The dissolution mechanism of magnesium
been the subject of numerous studies [225]. Many of them demon- induces a buffering of the pH into alkaline value and avoids the
strate a corrosion resistance improvement of coatings based on strong acidication on the anodic areas. At this pH, the formation
zinc alloyed with magnesium by comparison to zinc coatings in of semi-conducting ZnO is inhibited [34]. This corrosion product
atmospheric conditions. A lot of hypotheses have been reported to leads to the activation of cathodic reaction and causes corrosion
explain the effect of Mg on the corrosion mechanism of the Zn-Mg [16,35]. In addition, the selective dissolution of magnesium allows
alloys and the interpretations are often different and sometimes the formation of magnesium hydroxides and carbonates. These cor-
rosion products are known to be deposited into cathodic areas and
therefore to decrease the rate of the oxygen reduction reaction. This
phenomenon promotes the passivation of the alloy [24]. It was
Corresponding author. also proved that magnesium can inhibit galvanic corrosion on the
E-mail address: (J. Rodriguez).
0010-938X/ 2016 Elsevier Ltd. All rights reserved.
48 J. Rodriguez et al. / Corrosion Science 108 (2016) 4759

anodic and cathodic areas by forming a dielectric MgO layer cover- Table 1
Chemical composition and pH values of different immersion media of the zinc-
ing the entire alloy surface [3]. This lm decreases the efciency of
magnesium coated steel substrate.
the cathodic reaction and the corrosion rate.
The presence of chlorides, carbonates and the exposure condi- Media Initial pH Composition
tions, namely cyclic salt spray tests [24,21] and humid chamber Chloride at natural pH 5.6 0.1 M NaCl
exposure with or without chloride contamination [17,18], are key Alkaline 12 0.01 M NaOH
parameters which inuence the corrosion mechanism and the for- Alkaline chloride 12 0.01 M NaOH0.1 M NaCl
Neutral buffer 7.2 0.001 M NH4 OH0.05 M (NH4 )2 SO4
mation of corrosion products. In atmospheric conditions in the
presence of chlorides, Hosking et al. [4] attributed to Mg the abil-
ity to facilitate the formation of the protective simonkolleite layer
buffered medium without chloride. The electrochemical activity
(Zn5 (OH)8 Cl2 H2 O). For their part, Volovitch et al. [2] proved that
of the metallic coating in these electrolytes was studied versus
magnesium is also able to avoid the transformation of the protec-
immersion time using electrochemical impedance spectroscopy
tive simonkolleite layer into a mixed layer of smithsonite (ZnCO3 ),
(EIS). The chemical composition of electrolytes during immersion
hydrozincite (Zn5 (CO3 )2 (OH)6 ) and zincite (ZnO). Based on these
was determined by inductively coupled plasma optical emission
papers, in atmospheric conditions and in presence of chlorides
spectrometry (ICP-OES) while the pH was monitored. All these
the corrosion reactions of Zn-Mg alloys involve the formation of
measurements were carried out by keeping the sample surface
simonkolleite which preserves the surface [36] by opposition with
and the electrolyte volume constant in order to obtain comparable
other corrosion products of zinc. By contrast, simonkolleite was not
information about the kinetics of phenomena. Corrosion products
detected in corrosion products when the alloy is exposed to climatic
formed in the bath were analyzed using ICP-OES and X-ray pho-
conditions after contamination by chloride ions [3,17], to climatic
toelectron spectroscopy (XPS) was used to analyze the extreme
chamber without chloride contamination [18] or during the early
surface, because of the low thickness of the layer of corrosion prod-
stages of atmospheric corrosion [19,20].
ucts [18].
Salgueiro et al. [6,22] studied the corrosion mechanisms of Zn-
Mg-Al coatings immersed in different electrolytes at initial pH 9.
Actually, they demonstrated that according to the thermodynam- 2. Experimental
ics, ZnO is more stable than basic zinc salts and focused on the
inuence of Mg on the kinetics of reactions. They proved that Mg 2.1. Materials
acts principally on the kinetics of the corrosion mechanism by sup-
pressing or delaying the transformation of initially formed basic The Zn-Mg coated steel (ZM) was prepared and supplied
zinc salts (as hydrozincite) into zincite, which presents poorer bar- by Arcelor Mittal (Belgium). The substrate is composed of a
rier properties. Thanks to the buffering effect of Mg, Mg(OH)2 is conventional mild steel. Metallic surface was rstly electrogal-
quickly precipitated on surface and physically blocks the access of vanized, leading to the formation of a 7 m pure zinc coating.
hydroxide ions to the initially formed basic zinc salts. Physical vapour deposition (PVD) process was then used to
The corrosion resistance of Zn-Mg alloys was also investigated deposit a magnesium layer with a thickness between 2.25 and
by means of microelectrochemical techniques in order to under- 2.6 m. The magnesium deposition was made by continuous pro-
stand the dissolution mechanism occurring close to the surface in cess of evaporation from a metallic source under low pressure
borate buffered solution at pH 7.4 [23] or to study the cut-edges (105 109 mbar). Afterwards, a thermal treatment was done in
corrosion of Zn-Mg coated steel for different magnesium contents order to promote the Mg diffusion into the Zn coating. The coating
[24]. was present in both faces of the steel plate.
Although the corrosion mechanisms of Zn-Mg and Zn-Mg-Al Different immersion media were selected with varying chem-
coatings were investigated in numerous papers in different atmo- ical composition and pH. The sodium chloride salt was chosen in
spheric conditions or in contact with a very small quantity of order to simulate aggressive marine environment and evaluate its
electrolyte for a short time, there is a lack of information on the participation to the formation of simonkolleite. The pH ranges were
behaviour of Zn-Mg coatings immersed for a long duration in an chosen to reproduce pH variations undergone by the corrosive envi-
aqueous electrolyte at controlled pH. Even if atmospheric expo- ronment and correlated with the zinc and magnesium pH/potential
sure conditions are closer to real environments, this study presents diagrams [39]. The neutral pH 7 was used to be close to the rain
a great interest in the case of rain water retention during storage. pH in normal atmosphere. Neutral buffer solution was made from
In these conditions, the content in carbonate is low and the pH may the ammoniac/ammonium couple to obtain a pH value of 7.2. pH
evolve with immersion time. Furthermore, the presence of galvanic 12 was also selected to shift magnesium in its passive range or to
couplings involves the preferential dissolution of one of the species induce the passivation of magnesium. The electrolytes were not
and inuences the electrolyte pH and composition [37,38]. These stirred and were maintained in contact with the air in order to be
changes of pH according to the Pourbaix diagrams will change the in conditions as close as possible to atmospheric immersion.
stability of the oxide species of zinc and magnesium [39]. The electrolytes were prepared from (NH4 )2 SO4 (Merck), NaCl,
This work aims at improving the understanding of the behaviour NaOH and NH4 OH (VWR-BDH Prolabo) by diluting salts or concen-
of the metallic coating for a long immersion period in an aqueous trated solutions in demineralized water. Table 1 is a summary of
electrolyte in absence of drying period. The study focuses more the different compositions and pH of the immersion electrolytes.
specically on the inuence of the initial electrolyte pH on the dis- The solutions are not too concentrated in salts in order to be able to
solution of Zn-Mg coated steel and on the modication of this pH differentiate the behaviour as function of the initial pH in the case
due to the corrosion phenomena. This coating is prepared using a of a metallic coating susceptible to corrosion and not protected by
two-step method which allows the incorporation of a high rate of inhibitive species.
Mg (around 20 wt.%) by comparison with hot-dip galvanized steel
with baths containing alloying elements (around 3 wt.%) [15,40]. 2.2. Characterization techniques
The alloy composition and the deposit morphology were largely
investigated. Several electrolytes at different pH containing or not Before being used, the samples were stored at room temperature
chlorides were used: an alkaline medium with or without chlo- in a desiccator and the metallic surface was cleaned using acetone
rides, an electrolyte containing chlorides at natural pH and a neutral before characterization.
J. Rodriguez et al. / Corrosion Science 108 (2016) 4759 49

Fig. 1. GDOES quantitative depth prole of zinc-magnesium coated steel.

Fig. 2. SEM micrograph of the cross section of zinc-magnesium coated steel: (1)
mild steel substrate, (2) electrodeposited zinc layer, (3) zinc-magnesium coating
The depth composition was analysed by glow discharge optical obtained by PVD and thermal treatment.

emission spectroscopy (GDOES) on a HoribaJobinYvon GD proler

equipped with a standard 4 mm diameter anode, a polychroma-
tor with 28 acquiring channels, an Rf-generator (13.6 MHz) and
a Quantum XP software. An Ar pressure of 650 Pa and an applied
power of 25 W were employed as source conditions for the anal-
ysis. The instrument was equipped with a 0.5 m Paschen Runge
polychromator with nitrogen purged optical path. The working
method was calibrated using 30CRM (Certied Reference Mate-
rials) and SUS (Setting Up Samples) samples in order to obtain
quantitative results. The diameter of the analysed area is 4 mm. In
order to analyse the coating microstructure, thin sections were pre-
pared with a FEIs Quanta 200 3D Dual-Beam focus ion beam (FIB).
The electron accelerating voltage was 30 kV. The thin sections were
characterized by transmission electron microscopy (TEM) using a
CM20 Ultratwin model from Philips with an accelerating voltage
equal to 200 kV.
The surface morphology of the metallic coating was observed
by scanning electron microscopy (SEM) using a JEOL-JSM-59000
LV equipment. Before analysis, samples were etched with a Nital Fig. 3. TEM micrograph of the thin section of the zinc-magnesium layer prepared
solution containing 0.5 wt.% HNO3 in ethanol from VWR-BDH Pro- by FIB: (1) MgZn2, (2) Mg-rich phase, (3) Zn-rich phase, (4) phase containing Zn and
labo. For the cross-section analyses, the samples were embedded Mg in equal proportions.
in an epoxy-resin (Struers) and polished using Diapro Nap B 1 m
(Struers) and rinsed with a mix of ethanol and acetone (VWR-BDH 2.4. Chemical analyses
Prolabo) in an ultrasonic bath.
The dissolution rates of zinc and magnesium inside the elec-
2.3. Electrochemical measurements trolytes were measured by inductively coupled plasma optical
emission spectrometry (ICP-OES). The used equipment is an Iris
The electrochemical behaviour of ZM was studied by elec- Intrepid II model supplied by Thermo Fisher Scientic. After immer-
trochemical impedance spectroscopy in order to evaluate the sion of ZM samples (exposed area = 7.07 cm2 and volume = 40 ml),
corrosion resistance of the coating as a function of immersion time the electrolytes had to be conditioned before analysis. The differ-
in the different electrolytes (Table 1). The stability of the open cir- ent solutions were ltered using lter paper circles MN 640 dd from
cuit potential (OCP) was previously checked for 20 h of immersion. Machenerey-Nagel in order to remove solid corrosion products. The
EIS measurements were performed using a Parstat Model 2273 con- limit of quantication (LOQ) was calculated as being three times
trolled by Powersuite software in a frequency range from 100 kHz higher than the standard deviation signal (3) of the lowest cali-
to 30 mHz. At lower frequency, the signal is disturbed for this sub- bration standard. The LOQ values for the magnesium and the zinc
strate and cannot be exploited. The electrochemical impedance were 3 ppb and 2.1 ppb respectively.
data were analysed using ZsimpWin software. All the spectra were The pH of the electrolytes during immersion was measured by
recorded at OCP, applying 5 mV sinusoidal perturbation. A conven- using a CG 840 pH-meter from Schottwith a H62 glass electrode
tional three-electrode electrochemical cell was used, composed of from SI Analytics. Calibration was made using pH 4 and pH 7 buffer
an Ag/AgCl/KCl saturated reference electrode, a platinum counter- solutions supplied by VWR BDH-Prolabo.
electrode and a working electrode, namely the studied sample. The
sample area in contact with the electrolyte was 7.07 cm2 and the 2.5. Corrosion product analyses
electrolyte volume was 20 ml. The cell was placed in a Faraday cage
in order to avoid external interferences. All the measurements were After 7 days of immersion in electrolytes, ZM samples were
reproduced three times in order to check the reproducibility. rinsed with demineralized water and dried with a dehydrated
50 J. Rodriguez et al. / Corrosion Science 108 (2016) 4759

Fig. 4. Variation of the open circuit potential of Zn-Mg coated steel immersed in NaCl 0.1 M at natural pH (initial pH 5.6), NaCl 0.1 M at alkaline pH (initial pH 12), NaOH
0.01 M (initial pH 12) and NH4 OH 0.001 M(NH4 )2 SO4 0.05 M (initial pH 7.2) for 20 h.

compressed air system. The metallic surface covered by corrosion the composition heterogeneity of the coating especially in terms of
products was characterized by X-ray photoelectron spectroscopy magnesium content.
(XPS). These analyses were carried out with a PHI VERSAPROBE
5000 spectrometer. The X-ray power was 35 W and the diameter 3.2. Electrochemical measurements in the different electrolytes
was 200 m. All the spectra were shown after energy calibration.
The reference peak was the aliphatic C1s at 285.0 eV. The corrosion mechanism of Zn-Mg coated steel immersed in
Corrosion products formed in 0.1 M NaCl solution after 14 days aqueous solutions at different pH with or without chlorides was
of immersion were ltered. They were then dissolved in a concen- deeply studied by electrochemical impedance spectroscopy versus
trated HNO3 solution (analytical grade from VWR-BDH Labo) and immersion time. First of all, the stability of the OCP was checked
analysed using ICP-OES equipment. for 20 h in the different electrolytes (Fig. 4). In the chloride medium
at natural pH (0.1 M NaCl at pH 5.6) and in the buffered neutral
medium (0.001 M NH4 OH0.05 M (NH4 )2 SO4 ), the OCP values are
stabilized at 1.25 and 1.13 V versus Ag/AgCl after 6 h of immer-
3. Results sion, respectively. The OCP values at alkaline pH are less stable.
In the chloride medium at alkaline pH (0.1 M NaCl0.01 M NaOH),
3.1. Morphology of the Zn-Mg coated steel the OCP is stabilized around 0.9 V versus Ag/AgCl after 6 h of
immersion and a sharp increase is observed after 9 h of immersion.
A quantitative depth prole of the layer was carried out by Nevertheless, the value returns to the baseline after 11 h of immer-
GDOES (Fig. 1). A metallic coating composed of 75 wt.% zinc25 wt.% sion. The higher values of the OCP compared with those obtained
magnesium is present on the surface with an approximatively 4 m in neutral (buffered and non-buffered) environments indicate that
thick layer. Between 4 and 6 m in depth the amount of zinc the substrate is more protected in this medium. The abrupt increase
increases while the quantity of magnesium decreases to reach zero. in OCP can be explained by a pitting initiation of the formed passive
The zinc/iron interface is observed between 6 and 8 m in depth. A layer by chloride ions.
slight amount of oxygen is detected on the rst 2 m of the coating In the alkaline environment without chloride (0.01 M NaOH), the
and is related to the presence of oxides on the surface. OCP value increases signicantly until 6 h of immersion and reaches
Fig. 2 is the SEM micrograph of the cross-section after etching. a value of 0.6 V versus Ag/AgCl. This value slightly increases with
The two layers of the coating are well distinguished. The rst layer immersion time up to 0.5 V versus Ag/AgCl. This high value is
close to the steel surface is homogeneous and composed of zinc representative of a passivation of the surface at alkaline pH.
while the external layer is more heterogeneous and composed of In order to obtain a stable value of the OCP before EIS measure-
zinc and magnesium. The picture points out that the diffusion of ments, the rst experiment was performed after 6 h of immersion
magnesium into the zinc coating is not regular and that interface in each electrolyte.
boundaries are not well dened in depth. As a rst step, EIS measurements were carried out on ZM sam-
In order to characterize the Zn-Mg layer, a thin section is pre- ples immersed in two different non-buffered electrolytes chosen
pared by FIB and observed by TEM (Fig. 3). The layer represents the according to the pH and the conductivity. Firstly, in order to be able
rst micrometres of the top surface, richer in magnesium. Many to compare impedance results, the medium conductivity should
areas with different compositions were localized: the intermetallic be in the same order of magnitude. Secondly, according to poten-
MgZn2 which is the main compound of the layer (area 1), a mag- tial/pH diagrams, both zinc and magnesium should be in their
nesium phase with slight zinc impurities (area 2), a zinc phase passive range in alkaline pH. Thus, these measurements were car-
with magnesium impurities (area 3) and a phase containing zinc ried out in the 0.1 M NaCl solution at natural pH (pH 5.6) and in
and magnesium in equal proportion (area 4). This analysis reveals the 0.1 M NaCl solution with pH adjusted to 12 using 0.01 M NaOH.
J. Rodriguez et al. / Corrosion Science 108 (2016) 4759 51

Fig. 5. Bode plots of Zn-Mg coated steel immersed in NaCl 0.1 M at natural pH (initial pH 5.6) and in NaCl 0.1 M at alkaline pH (initial pH 12) obtained after 6 h, 1 day and 3
days of immersion.

Fig. 6. Optical observations of the surface of Zn-Mg coated steel after 24 h of immersion in a) NaCl 0.1 M at alkaline pH (initial pH 12), b) NaCl 0.1 M at natural pH (initial pH
5.6), c) NaOH 0.01 M (initial pH 12) and d) NH4 OH 0.001 M(NH4 )2 SO4 0.05 M (initial pH 7.2).

Fig. 7. Bode diagrams of Zn-Mg coated steel immersed in NaOH 0.01 M (initial pH 12) recorded after 6 h, 1 day, 3 days and 7 days of immersion.
52 J. Rodriguez et al. / Corrosion Science 108 (2016) 4759

Fig. 8. Nyquist spectra of EIS measurements recorded after 6 h of immersion of Zn-Mg coated steel in NaCl 0.1 M at natural pH (initial pH 5.6), NaCl 0.1 M at alkaline pH
(initial pH 12) and in NaOH 0.01 M (initial pH 12).

Fig. 9. Bode spectra of Zn-Mg coated steel immersed in the buffered neutral medium (NH4 OH 0.001 M(NH4 )2 SO4 0.05 M, initial pH 7.2) obtained after 6 h, 1 day, 3 days
and 7 days of immersion.

Fig. 5 shows the Bode diagrams of ZM immersed for different times Fig. 7 presents the Bode diagrams in this medium. The low
in both electrolytes. frequency modulus at 30 mHz is high considering a naked metal-
At natural pH, the low frequency modulus at 30 mHz sharply lic surface with an approximated value of 105 ohm cm2 . It is also
decreases from 104 to 103 ohm cm2 according to the immersion possible to notice that the high frequency modulus related to the
time. The phase also decreases and a second time constant appears resistance of electrolyte changes with immersion time.
after 3 days of immersion. This means that the corrosion resistance So, this alkaline medium without aggressive ions will be con-
of the metallic coating decreases according to the immersion time. sidered for the rest of the work as an alkaline model electrolyte in
The surface is probably modied by the formation of a complex which the substrate is protected keeping in mind that for this sys-
oxide layer having no protective effect. At alkaline pH, the low tem the ohmic drop cannot be neglected as shown by the high value
frequency modulus values are higher in comparison with values of the electrolyte resistance at high frequency (9 102 ohm cm2
obtained in the natural pH medium whatever the immersion time. after 7 days of immersion).
The low frequency modulus values stay constant with immersion Fig. 8 presents the experimental Nyquist spectra of the ZM sam-
time and are about 2 104 ohm cm2 . The phase slightly decreases ples and the electrical equivalent circuit used for tting the EIS
but the time constant remains in the same frequency range. These data obtained after 6 h of immersion in 0.01 M NaOH solution,
results conrm that the corrosion resistance in alkaline media is 0.1 M NaCl solution at pH 12 and 0.1 M NaCl solution at natural
higher than in natural pH media. pH. In this circuit, Re corresponds to the electrolyte resistance, Q is
The metallic surface after 24 h of immersion in 0.1 M NaCl solu- the constant phase element relative to the interface phenomenon
tion at pH 12 and in 0.1 M NaCl solution at natural pH is represented (electrochemical double layer and/or oxide layer) and Rpol is an
in Fig. 6 (a) and (b) respectively. The surface is generally covered by image of the corrosion resistance of the metallic surface. The tting
corrosion products in the case of natural pH electrolyte, while in the results are given in Table 2. In 0.01 M NaOH solution, the resistance
case of alkaline medium white corrosion products locally appear. of the electrolyte varies signicantly versus immersion time. This
These results seem to indicate that the metallic surface is covered by can be explained by the low conductivity of the solution and the
a passivating oxide layer in alkaline medium by comparison with variation of composition in hydroxide ions in the electrolyte. The
the natural one. Nevertheless, the oxide layer is not completely values of polarisation resistances are in agreement with the values
homogeneous in the presence of chlorides and in contact with a of the modulus at low frequencies. Actually the Rpol values increase
conductive electrolyte. Metallic samples were immersed in an alka- with immersion time conrming the improvement of the protec-
line electrolyte (NaOH at pH 12) without other corrosive species tive behaviour of the oxide layer in this environment. In 0.1 M NaCl
in order to conrm this hypothesis. The metallic surface observed solution at alkaline pH, the electrolyte resistance stays stable over
after 24 h of immersion is preserved (Fig. 6(c)) and moreover this time even if a slight increase is observed due to the hydroxide ions
protection is maintained even after several days of immersion. consumption associated to the slight dissolution of the metal. The
J. Rodriguez et al. / Corrosion Science 108 (2016) 4759 53

Table 2
Results of tting of EIS spectra recorded for ZM immersed in NaCl 0.1 M at natural
pH (initial pH 5.6), NaCl 0.1 M at alkaline pH (initial pH 12) and in the alkaline model
medium NaOH 0.01 M (initial pH 12).

Re ( cm2 ) Q (1 sn cm2 ) n Rpol ( cm2 )

NaCl 0.1 M pH12

6h 117.5 2.5 105 0.8 2.3 104
24 h 121.3 2.6 105 0.8 2.8 104
72 h 125.3 2.5 105 0.8 2.7 104

NaOH 0.01 M
6h 522.5 2.1 105 0.8 1.0 105
24 h 238.2 2.2 105 0.8 1.4 105
72 h 288 2.2 105 0.7 1.9 105
168 h 714.4 2.2 105 0.7 2.8 105

NaCl 0.1 M
6h 100.3 3.8 105 0.7 1.2 104

values of the polarisation resistance are about one order of magni-

tude lower than without chloride ions but increase between 6 h and
24 h of immersion and remain stable after 72 h. These results con- Fig. 10. Evolution of the pH of NaOH 0.01 M (initial pH 12), NaCl 0.1 M (initial pH
rm the presence of an oxide layer which passivates the surface 5.6) and NH4 OH 0.001 M(NH4 )2 SO4 0.05 M (initial pH 7.2) as a function of the
immersion time of Zn-Mg coated steel.
in presence of chlorides. The tting parameters obtained for ZM
immersed in 0.1 M NaCl solution at natural pH are difcult to obtain
for an immersion time higher than 6 h due to the high reactivity magnesium and zinc to form carbonate species. An equilibrium
of the ZnMg coating in this electrolyte. The electrical equivalent between hydroxide and carbonate ions occurs. This mechanism is
circuit was only used for obtaining tting parameters until 6 h of in good agreement with the variation of the electrolyte resistance
immersion. For longer immersion times, the metallic surface is too which is observed during EIS measurements. In the aggressive and
degraded and the oxide layer is too complex and heterogeneous. non-buffered electrolyte, the chemical composition of the solution
Finally, EIS measurements were performed in the buffer solu- evolves and the pH is progressively shifted to a pH value close to
tion at neutral pH (pH 7.2). The ZM substrate was immersed in this 11 probably due to the production of hydroxide ions. Moreover,
solution for 7 days. EIS measurements were carried out in order the dispersion of pH values is very low in the case of the model
to evaluate the corrosion resistance in this electrolyte. Bode dia- electrolyte, whereas in the aggressive electrolyte the standard devi-
grams are represented in Fig. 9. The shape of the curve is typical ation is higher and reaches one pH unity after 7 days of immersion.
of a galvanic coupling behaviour between the different phases of This is due to the heterogeneity of the coating which differently
the surface alloy [41]. This kind of curve cannot be suitably tted. behaves in an aggressive solution. In the buffered neutral medium,
The corrosion rate is so high that the resistance of the solution at the pH increases slightly and reaches 8. The standard deviation is
high frequency is difcult to distinguish from the charge transfer also very low below 0.2 pH unity.
resistance at low frequency. The low frequency modulus is very ICP-OES measurements were performed in the three elec-
low with an approximated value of 100 ohm cm2 and still decreases trolytes in order to correlate the increase in pH and the composition
with immersion time. in zinc and magnesium ions. Fig. 11 shows the evolution of the
Fig. 6(d) represents the metallic surface after 24 h of immer- cation concentrations in the aggressive electrolyte at natural pH
sion in this electrolyte. The surface attack is uniform and corrosion (0.1 M NaCl), in the alkaline model electrolyte (0.01 M NaOH) and in
products are not detected. the neutral buffered medium (0.001 M NH4 OH0.05 M (NH4 )2 SO4 )
The EIS measurements and the optical observations are in good versus immersion time. In the aggressive medium, the dissolution
agreement with the OCP measurements performed for 20 h. of magnesium occurs preferentially. The amount of magnesium
increases as a function of time to reach approximatively 9 ppm. This
3.3. Chemical analyses of immersion baths concentration remains quite stable after 3 days of immersion. As
shown in Figs. 10 and 11(a), the magnesium dissolution stops when
In order to study the evolution of the ZM coating corrosion, the the pH reaches a value close to 11. The zinc concentration remains
compositions of electrolytes were analysed after different immer- constant after 24 h of immersion and does not exceed 2 ppm. In the
sion times. Fig. 10 shows the evolution of pH in the alkaline alkaline medium, the magnesium concentration is very low and
model electrolyte (0.01 M NaOH), the aggressive electrolyte (0.1 M does not exceed 0.35 ppm whatever the immersion time. The stan-
NaCl) at natural pH and the buffered neutral electrolyte (0.001 M dard deviation is also very low (around 0.1 ppm). The magnesium
NH4 OH0.05 M (NH4 )2 SO4 ) as a function of the immersion time of dissolution is negligible in comparison with the results obtained in
ZM. non-buffered chloride environment and the concentration in zinc
In the case of the alkaline model solution, pH slowly decreases to is in the same order of magnitude as in the aggressive medium. The
reach a value of approximatively 11, while in the chloride medium, magnesium is responsible of the sharp pH variation in the elec-
pH value strongly increases during the rst 24 h of immersion to trolytes, whereas the composition in zinc in solution does not vary
reach a value of approximatively 1011 and stays constant during according to the type of electrolyte (alkaline or natural pH).
the following days of immersion. In the alkaline medium, the low Comparing with results obtained in the non-buffered solution,
decrease in pH (from 12 to 11) can be explained by two phenomena. the zinc dissolution in the buffered neutral medium is not inhibited
Firstly, at this pH, hydroxides can precipitate, inducing a consump- (Fig. 11(c). As this pH does not allow the precipitation of corrosion
tion of the hydroxide ions. Secondly, as the electrolytes are open products, the zinc dissolution in the electrolyte is continuous and
to air, a slight amount of carbon dioxide can be dissolved in the the concentration in zinc reaches approximatively 120 ppm after 7
electrolyte during the immersion period. Due to the alkaline pH of days of immersion. The magnesium dissolution is also signicant
the solution the formed carbonate ions can be consumed by both and higher than the zinc dissolution for short immersion times. The
54 J. Rodriguez et al. / Corrosion Science 108 (2016) 4759

Fig. 11. Evolution of the Mg2+ and Zn2+ concentrations inside a) NaCl 0.1 M (initial pH 5.6), b) NaOH 0.01 M (initial pH 12) and c) NH4 OH 0.001 M(NH4 )2 SO4 0.05 M versus
Zn-Mg coated steel immersion time.

concentration in magnesium is stable after three days of immersion 3.4. Corrosion product analysis
with an approximated concentration of 40 ppm.
The results are an indication that galvanic couplings are formed In the case of the chloride medium at natural pH, the insoluble
on the sample surface, which is composed of a lot of phases with corrosion products which were not attached to the metallic sur-
gradients of corrosion potential with a preferential dissolution of face were analysed using ICP. They were removed after 14 days of
the areas rich in magnesium. immersion in 0.1 M NaCl solution. This solution was ltered and
corrosion products were solubilized in 20 ml of HNO3 65%. The
J. Rodriguez et al. / Corrosion Science 108 (2016) 4759 55

Table 3
Quantication of the coating elements obtained by XPS after exposure to air and
after 24 h of immersion in the alkaline model solution (NaOH 0.01 M) and in chloride
solution at natural pH (NaCl 0.1 M).

Element Peak Concentration (at.%)

Exposed to air 0.01 M NaOH 0.1 M NaCl

Carbon C1s 58.1 20.2 4.3

Oxygen O1s 33.1 55.7 70.3
Magnesium Mg2p 7.2 13.8 7.5
Zinc Zn2p3/2 1.7 10.3 11.9

amount of zinc is 31.9 0.6 wt.%. This value is almost 20 times

higher than the quantity of magnesium, which is about 1.60 wt.%
with a very high standard deviation (1.40 wt.%). Hence, zinc and
magnesium oxidation occurs. Complex corrosion products from
zinc precipitate inside the electrolyte whereas magnesium ions
remain in solution until equilibrium is reached. The dissolution of
Mg2+ in solution can be correlated with the increase in pH.
XPS survey was carried out in order to characterize the sur- Fig. 12. C1s spectra of the surface after exposure to air and after 7 days of immersion
in NaOH 0.01 M (initial pH 12) and in NaCl 0.1 M (initial pH 5.6).
face composition of the zinc-magnesium coated steel exposed to
air, after 7 days of immersion in the aggressive natural electrolyte
(0.1 M NaCl) and after 7 days of immersion in the alkaline model
electrolyte (0.01 M NaOH).
Table 3 lists the composition of the surface exposed to the three
environments and indicates the presence of zinc, magnesium, car-
bon and oxygen for each electrolyte.
For the substrate only exposed to air, the magnesium is present
in higher amount than the zinc. This is in good agreement with the
layer morphology studied by TEM.
The carbon content is very high by comparison with the other
elements detected on surface. This important rate can be partially
explained by the surface contamination due to the degreasing with
acetone before analysis. Moreover, the detection of carbon can also
be justied by the dissolution of the atmospheric carbon dioxide in
the electrolytes which are open to air or by exposure of the surface
to air during the storage. After immersion in the alkaline medium,
the proportion of oxygen, zinc and magnesium increases compared
to the carbon content. The passive oxide layer is composed of cor-
rosion products of both zinc and magnesium. This is in correlation
with the ICP measurements which show that the dissolution of both
elements in this electrolyte is prevented. After immersion in the Fig. 13. O1s spectra of the surface after exposure to air and after 7 days of immersion
in NaOH 0.01 M (initial pH 12) and in NaCl 0.1 M (initial pH 5.6).
chloride electrolyte, the main detected element is oxygen, reveal-
ing the formation of a lot of corrosion products. The content in Mg
at the extreme surface remains almost constant, with an atomic contribution is present for all the exposure modes, it is more dif-
concentration which evolves from 7.2 to 7.5 at.%. On the contrary, cult to distinguish it after exposition to air and immersion inside
the atomic concentration in zinc is equal to 1.7 at.% after exposure the sodium chloride electrolyte in comparison with immersion in
to air and increases to reach 11.9 at.% after 7 days of immersion in the alkaline solution.
the chloride medium. This is in good agreement with ICP analy- Fig. 13 represents the O1s spectrum for the three immersion
ses which indicate that the zinc dissolution is very limited while exposure modes. The peak at 532.2 eV is attributed to hydroxide or
the magnesium dissolution occurs. The ratio zinc/magnesium is carbonate species. The distinction between both species is difcult
inversed. due to the symmetry of the peak. Nevertheless, the carbon chemical
Chloride is not detected by XPS after 7 days of immersion in the state in the oxide layer indicates the existence of carbonate species.
sodium chloride medium. So, corrosion products containing chlo- Thus, the oxygen could be in both forms. After immersion in the
ride such as simonkolleite (Zn5 (OH)8 Cl2 H2 O) are not present on chloride medium a second peak clearly appears at 529.8 eV which
the substrate surface even when the immersion medium contains corresponds to oxide forms. In the case of the substrate immersed
chloride ions. in alkaline solution, this peak is not detected. For the substrate
The chemical state of the four elements was studied. Fig. 12 exposed to air, this peak is present but difcult to detect because
shows the C1s spectrum. The C1s peak attributed to the surface of the surface contamination.
contamination [25] is detected for binding energies of 284287 eV Mg2p XPS spectrum is shown in Fig. 14. In the case of the
whatever the exposure conditions. However, as expected, the car- substrate exposed to air, the peak at high binding energy can be
bon contamination originating from degreasing is more important attributed to MgO or MgCO3 , while the slight peak at low binding
for the substrate exposed to air. A second peak between 288 eV and energy can be associated to the Mg or Mg(OH)2 [19]. The distinc-
291 eV is related to the presence of carbonates [17,18,25] which tion between Mg and Mg(OH)2 contributions is difcult because
can be correlated to the atmospheric carbon dioxide absorption on the Mg2p peak positions corresponding to both species are close,
the surface and its incorporation in the electrolytes. Although this practically equal. In order to distinguish these species, the MgKLL
56 J. Rodriguez et al. / Corrosion Science 108 (2016) 4759

Fig. 14. Mg2p and Mg KLL spectra of the surface after exposure to air and after 7
days of immersion in NaOH 0.01 M (initial pH 12) and in NaCl 0.1 M (initial pH 5.6). Fig. 15. Zn2p3/2 and ZnLMM Auger spectra of the surface after exposure to air and
after 7 days of immersion in NaOH 0.01 M (initial pH 12) and in NaCl 0.1 M (initial
pH 5.6).
Auger spectrum is investigated. The peak at 300.2 eV is attributed
to pure Mg whereas the peak at 306 eV corresponds to corrosion
products of the Mg. In literature [17], Diler et al. attribute this peak presence of peaks in the same range of binding energies. Neverthe-
to oxide and hydroxide forms of magnesium. After immersion in less, in the case of the alkaline medium, the O1s spectrum does not
solution, alkaline or natural, the peak corresponding to the metal- show the presence of oxides. So, the peak at low energy could be due
lic magnesium disappears. The Mg2p peak at high binding energy to the presence of metallic zinc or ZnCO3 . The ZnLMM Auger spec-
is maintained but is slightly shifted towards higher values. These trum was performed for both media. For ZM in immersion in 0.01 M
results indicate that the magnesium is linked with carbon to form NaOH solution, only the peak at 499.8 eV which corresponds to
carbonate species [17,18]. Zn5 (CO3 )2 (OH)6 is detected. For the substrate which was immersed
The last element which was detected on the surface is the zinc in 0.1 M NaCl solution, a second contribution is present around
(Fig. 15). The Zn2p3/2 spectrum was investigated. The surface after 498 eV but the exact tting is difcult to perform. Therefore, as a
air exposure reveals the presence of a peak which is composed function of the position of the peak and by comparing with the O1s
of two components. A rst contribution at 1021.6 eV is related to spectrum result, this contribution is assumed to be due to ZnO. As a
corrosion species [17,18]. Duchoslav et al. attribute this signal to consequence, the immersion in the alkaline model medium inhibits
carbonates (hydrozincite Zn5 (CO3 )2 (OH)6 or zincite ZnO) [28]. A the formation of zincite ZnO by comparison with the immersion in
second component is present at 1020.5 eV and according to the the aggressive chloride medium. The simonkolleite is not detected
literature [17,18,25] can be associated to metallic Zn, oxides or car- even when the immersion medium contains chloride ions.
bonates. In order to distinguish these species, the ZnLMM auger
spectrum was also analysed. Both peaks are present, one with 4. Discussion
low binding energy (494 eV) which is relative to metallic zinc and
one with high binding energy. The peak with characteristic shoul- Zinc and magnesium are present in the coating under different
der at the highest binding energy is attributed to Zn5 (CO3 )2 (OH)6 compositions and morphologies leading to a high heterogeneity.
[19]. After immersion in the alkaline model medium and in the The rst four micrometres of the coating mainly consisted of MgZn2
aggressive chloride environment, the Zn2p3/2 spectrum reveals the intermetallics. A second layer mainly composed of metallic zinc is
J. Rodriguez et al. / Corrosion Science 108 (2016) 4759 57

present, due to the electrolytic zinc deposit. The extreme surface A large quantity of hydroxide ions is formed and explains the
contains magnesium and zinc in their metallic form. During the increase in pH. The pH reaches a value of 1011 associated to the
storage at room temperature in dry air, a natural oxide layer is equilibrium between magnesium ions and corrosion products of
formed within the rst few nanometres from the interface with magnesium. Moreover, at this pH, carbonate ions are present in
air and is mainly composed of magnesium hydroxide and hydroz- solution, due to the dissolution of carbon dioxide present in the
incite Zn5 (CO3 )2 (OH)6 . The quantity of magnesium is higher than air. Hence, corrosion products of magnesium precipitate on the
the quantity of zinc. The heterogeneity of this coating is one of the metallic surface and as a consequence, the pH is maintained around
explanations of the substrate reactivity. The difference between the 1011.
corrosion potentials of the different components involves the for- The proposed precipitation reactions are the following:
mation of galvanic couplings [4,30,33]. The reactivity of the galvanic
Mg2+ + 2OH Mg(OH)2 (5)
couplings is more or less important depending on the immersion
conditions and especially on the pH of the electrolyte. As shown by MgO + H2 O Mg + 2OH Mg(OH)2 (6)
electrochemical measurements and surface analyses, the galvanic 2+ 2
couplings are exacerbated at buffered neutral pH. Mg + CO3 MgCO3 (7)
In alkaline solution (pH 12) with or without chlorides, EIS mea- 2+ 2
5 Mg + 4CO3 + 2OH Mg5 (CO3 )4 (OH)2 (8)
surements highlighted the formation of a protective layer. The
modulus at low frequency is stable with immersion time and the Corrosion products of magnesium are detected on the extreme
passive oxide layer is formed on the substrate. The presence of surface but not in the corrosion products detached from the sur-
chloride ions does not prevent the formation of a passive layer face. When the pH reaches the alkaline range, magnesium corrosion
even if the protection performance of this layer is reduced in this products are maintained on the surface as proved by XPS and ICP-
conductive medium. In alkaline solution without chloride, the pH OES analyses.
slightly decreases to reach a value close to 11 because of the neu- The zinc composition of the media shows that the presence of
tralization of hydroxide and carbonate ions present in the solution zinc in the cationic form is limited in chloride solution and in alka-
open to air by both magnesium and zinc. In the alkaline electrolyte line solution. Surface analyses highlight that zinc in the metallic
in absence of chlorides, small amounts of magnesium ions are form is mainly present below corrosion products.
detected in solution (below 0.4 ppm). Indeed, extreme surface anal- Zn Zn2+ + 2 e Zinc oxidation at neutral pH (9)
yses proved that the surface is covered by MgCO3 , Mg5 (CO3 )4 (OH)2
and Zn5 (CO3 )2 (OH)6 . At this pH, the formation of zincite ZnO is
inhibited [17,18,22]. The oxide layer is stable at this pH. These Zn + 4OH ZnO2 2 + 2 e
results are in accordance with the corrosion mechanism of mag-
nesium and the effect of an alkaline pH on the corrosion products + 2H2 O Zinc oxidation at alkaline pH (10)
of zinc reported in literature [2,4,16,22,30,35].
In chloride solution at natural pH (pH 5.6), EIS measurements
show a sharp decrease of the modulus at low frequencies after 6 h
of immersion. This phenomenon can be related to the dissolution 5 Zn2+ + 2CO3 2 + 6OH
of the oxide layer formed during the sample storage. The pH and
the magnesium ion content of the solution strongly rise during the Zn5 (CO3 )2 (OH)6 Formation of hydrozincite (11)
rst days of immersion. When the pH value reaches 1011, the
magnesium dissolution stops and corrosion products of magne-
sium appear on the metallic surface as demonstrated by EIS and Zn2+ + 2OH ZnO + H2 O Formation of zincite (12)
ICP measurements. Even if after this immersion time, the pH is
in the same range as the one of the alkaline solution, the corro- Considering corrosion reactions at neutral or alkaline pH, the
sion products formed are not protective as shown by the low value oxidation reactions of magnesium and zinc must also be associated
of the modulus at low frequencies determined after three days of to the reduction reaction of dissolved oxygen which contributes to
immersion (Fig. 5). the formation of hydroxide ions and to the increase in pH:
The zinc ion content is of the same order of magnitude in natural
O2 + 4e + 2H2 O 4OH (13)
chloride and in alkaline solutions. The dissolution of zinc is not
impacted by the initial pH value of the solution. Corrosion products are composed of a complex mix of car-
After 7 days of immersion in a solution containing chloride bonates, hydroxides and oxides but do not contain chlorides as
ions at natural pH, the extreme surface is covered by an oxide shown in literature in the case of atmospheric conditions [2,4].
layer composed of corrosion products from zinc and magnesium. The formation of corrosion products is depending on the exposure
Nevertheless, the zinc content is higher than magnesium content conditions. These results are in good agreement with the recent
comparing with the metallic surface before immersion due to the work of Diler et al. [17,18]. When the substrate is immersed in a
preferential dissolution of the magnesium following the corrosion chloride-containing electrolyte, its behaviour seems to be closer
reactions proposed in literature [27,28,3032]. to the one observed in climatic chamber with or without chloride
contamination conditions than the one reported when the sam-
2 H+ + 2 e H2 Cathodic partial reaction (1)
ples were exposed to salt spray test [2,4,21]. This can be explained
+ by the non-renewable chloride contamination and the horizontal
2 Mg 2 Mg ads + 2 e Anodic partial reaction (2)
arrangements of the substrates. The pH and composition changes
+ 2+
2 Mg ads + 2 H2 O 2 Mg + H2 + 2 OH Chemical reaction (3) which occur during immersion are related to the formed corrosion
products. The alkalinisation of the solution involves the formation
of hydroxide and carbonate species containing both magnesium
2 Mg + 2H2 O + 2 H+ 2 Mg2+ + 2 H2 + 2 OH Overall reaction and zinc. These corrosion products passivate the surface when the
substrate is initially immersed in an alkaline medium. Nevertheless,
the oxide layer formed during immersion in chloride media at ini-
tial pH 5.6 contains zincite ZnO. The presence of zincite inside the
58 J. Rodriguez et al. / Corrosion Science 108 (2016) 4759

layer critically decreases the protection performance of the layer formation of zincite is inhibited. The presence of chloride ions
even if the nal pH reaches alkaline values [16,35]. Besides, the does not hinder the formation of a protective layer. Neverthe-
dissolution-rate of magnesium during the rst hours of immersion less, according to the Pourbaix diagram of zinc [34], the pH must
is very high and therefore magnesium oxide cannot contribute to not exceed 13 because of the depassivation of zinc to form sol-
the layer of corrosion products. These results are in accordance with uble zincate ZnO2 2 .
the recent study of Salgueiro et al. [6,22]. In the case of immersion If the initial value of the pH is close to the neutrality and
in a chloride solution at natural pH, the dissolution of magnesium non-buffered, magnesium dissolution occurs and involves the
allows a quick increase in pH and the formation of a lot of hydrox- buffering of the pH around 1011 after several hours of immer-
ide ions. As the formation of magnesium hydroxides is delayed at sion. When the pH threshold value is reached, insoluble oxides
initial neutral pH, the transformation of hydrozincite into zincite are formed and were detected using XPS analyses. However,
cannot be inhibited. The presence of semi-conducting ZnO radically these products are not able to protect the surface as demon-
decreases the barrier properties of the oxide layer. strated by EIS technique. The corrosion products do not contain
In immersion in a buffered media with a neutral pH, the dis- zinc combined with chloride based oxide products. The layer is
solution of both Mg and Zn is continuous as demonstrated using essentially composed of zinc based oxides products as zincite
ICP-OES and EIS measurements. The pH cannot reach an alkaline ZnO and hydrozincite Zn5 (CO3 )2 (OH)6 and does not contain
value and so the precipitation of corrosion products protecting the chloride.
surface does not occur. The high reactivity of the numerous gal- 3) The concentration in zinc ions in solution is not depending on the
vanic couplings due to the different phases on the sample surface initial pH of non-buffered solutions. This value remains low and
induces a high corrosion rate as discussed in literature [4,30,33]. constant with the immersion time whatever the initial pH value.
The low corrosion potential of magnesium by comparison with In immersion in a neutral and non-buffered solution as sodium
zinc induces the formation of galvanic couplings, especially for this chloride, magnesium dissolves preferentially compared with
coating which contains a lots of different phases on its surface as zinc as shown by ICP measurements. The magnesium inhibits
shown in Figs. 2 and 3. The formation of galvanic couplings was also the dissolution of zinc and promotes the increase in pH into
highlighted by EIS measurements, which show that the impedance alkaline value. In these conditions, the formation of zinc based
diagrams are typical of a galvanic coupling behaviour between dif- oxides occurs.
ferent phases on the metallic surface (Fig. 9). As shown in Fig. 11(c), 4) In buffered solutions, combined EIS measurements and ICP anal-
after one day of immersion, the magnesium ion content in solution yses show that the magnesium consumption is complete after
is signicant and higher than the zinc ion content due to the prefer- three days of immersion due to the number of galvanic couplings
ential dissolution of magnesium in the different phases. This value and is followed by a strong dissolution of the zinc.
tends to a constant value after three days of immersion and then
the strong zinc dissolution starts due to the depletion of magnesium
content. The dissolution of magnesium leads to the production of a
large amount of hydroxide ions due both to the negative difference
effect and to the dissolved oxygen reduction [3032]. The buffer-
The authors would like to thank ArcelorMittal for providing the
ing capacity of the solution is not sufcient to completely avoid this
metallic substrate. They also acknowledge Alex Lanzutti, Francesco
slight increase in pH. The dissolution of magnesium before buffer-
Andreatta and Lorenzo Fedrizzi from the Department of Chemistry,
ing the pH of the solution is the limiting reaction. So, if the pH
Physics and Environment of the University of Udine, Italy, for the
is buffered in neutral range, the magnesium dissolution does not
GDOES measurements. This study was done in the framework of
allow the increase in pH to alkaline value and the stability of the
Clearzinc project nanced by the Walloon Region (Belgium) and
insoluble corrosion products. The surface is submitted to a contin-
the European community and the Opti2mat, Flycoat Programmes
uous light etching.
dExcellence nanced by the Walloon Region (Belgium).

5. Conclusions References

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