ARTICLES

Surface darkening phenomenon of Zn–Mg alloy coated steel exposed

to aqueous environment at high temperature
Sung Jin Kima)
Graduate Institute of Ferrous Technology (GIFT), Pohang University of Science and Technology (POSTECH),
Pohang 790-784, Republic of Korea
Young Jin Kwak, Tae Yeob Kim, and Woo Sung Jung
Surface Treatment Research Group, POSCO Technical Research Center Kumho-dong, Gwangyang, Jeonnam
545-090, Republic of Korea
Kyoo Young Kim
Pohang University of Science and Technology (POSTECH), Pohang 790-784, Republic of Korea

(Received 11 July 2015; accepted 30 October 2015)

Steel coils coated with Zn–Mg alloy containing high Mg content develop dark rust when exposed to
an extremely limited amount of aqueous environment. To understand the nature of the dark rust and
its formation mechanism, the steel is evaluated by the immersion test and high temperature–humidity
test followed by critical evaluation with transmission electron microscopy for cross-sectional
observation, field-emission scanning electron microscopy for surface morphology observation, Auger
electron spectroscopy and glow discharge spectroscopy for identification of chemical composition as
a function of depth. The results indicate that the dark rust is formed by precipitation of Mg-based
corrosion product on the outermost surface when the steel is exposed to aqueous environment at
high temperature. This is due mainly to preferential dissolution of Mg phases by the galvanic action
with MgZn2 and Mg2Zn11 composed of the coating layer, and easy precipitation of Mg21 ion in
a form of Mg(OH)2 in a limited volume of the condensed water film on the surface.

I. INTRODUCTION corrosion resistance. The effect of Mg in Zn–Mg alloy

Galvanizing has been one of the most practical coatings on the corrosion resistance of galvanized steel
commercial methods for prevention of steel corrosion has been proposed by numerous researchers.7–12 Never-
by providing a galvanic protection to the steel substrate theless, the exact mechanism has not been fully clarified.
and a barrier protection as well. To improve further the The Zn–Mg alloy coated steels are commercially pro-
performance of galvanized steel (or galvanized iron: GI), duced by the traditional hot dip coating process. Although
a small amount of alloying elements such as aluminum this process is one of the most reliable methods, it has
(Al) and magnesium (Mg) is added to the zinc coating.1 major disadvantages such as the formation of dross in the
The commercial grades of galvanized steel alloyed with molten Zn bath, formation of intermetallic compound layers
Al are Galfan (Zn 1 5 wt% Al) and Galvalume (Zn 1 between the coating layer and steel substrate, and genera-
55 wt% Al 1 1.6 wt% Si).2 They exhibit higher corrosion tion of polluted wastes. Moreover, due to the burning
resistance than the conventional GI steel because of the phenomenon of Mg in the molten bath, no more than 3 wt
formation of aluminum-based thin oxide film (Al2O3) % Mg can be added successfully in the commercial
known as the protective passive film on the coating operation. To overcome such industrial and environmental
surface.3–6 Addition of Mg to Zn coating also improves problems, the dry coating method has been considered as
greatly the corrosion resistance of galvanized steel.7–12 an alternative commercial option.13 Out of many dry
Successful examples of the coating development are coating methods, the physical vapor deposition (PVD)
Super Zinc, Super Dyma, and Dymazinc by Nippon Steel technique by evaporation is considered as a promising
Corporation (Tokyo, Japan) and ZAM (Zn-Al-Mg alloy one for commercial application of high volume production.
coated steel product) by Nisshin Steel Corporation The Zn–Mg alloy coated steel produced by PVD
(Tokyo, Japan). Since 1960s, many attempts have been method has a superior corrosion resistance in chloride-
made to develop Zn–Mg alloy coating with superior containing environment.11,14 Particularly, Volovitch
et al.11 have reported that the high corrosion resistance
of the coated steel is closely associated with the stability
Contributing Editor: Eric A. Stach
a)
Address all correspondence to this author. of the simonkolleite [Zn5(OH)8Cl2] known as a protective
e-mail: pogksj@naver.com corrosion product. In spite of the superior corrosion
DOI: 10.1557/jmr.2015.356 resistance in chloride-containing environment, its major

J. Mater. Res., Vol. 30, No. 23, Dec 14, 2015 Ó Materials Research Society 2015 3605
 S.J. Kim et al.: Surface darkening phenomenon of Zn–Mg alloy coated steel exposed to aqueous environment at high temperature

drawback is the surface darkening of the Zn–Mg alloy used. In addition, the TEM was used for the cross-sectional
coating layer when exposed to high humidity environment observation.
of over 60% relative humidity at a temperature over
50 °C.15,16 The surface of the Zn–Mg alloy coated steel B. Corrosion test
produced by PVD process easily turns to dark within a short Two different kinds of corrosion tests were used to
time when its surface is exposed to an extremely thin layer understand the nature of the dark rust, and they were the
of water film in high humid and temperature environment. immersion test and exposure test to a high humidity and
The present authors have suspected that Mg contained in temperature environment. The immersion test was per-
the Zn–Mg alloy coated layer plays an important role for formed by immersing the specimens in boiling deionized
the surface darkening phenomena, and a Mg-based corro- (DI) water at 100 °C for 5 min. Before immersion, the
sion product could be formed on the coating surface by specimens were ultrasonically rinsed in ethanol and dried
precipitation. Although a great deal of attention has been in air. Instead of DI water, tap water, 0.2 M NaHCO3
focused on the electrochemical corrosion behaviors of the solution and 0.2 M K2CO3 solution containing 0.1 M
Zn–Mg alloy coated steel in wet–dry environment contain- ZnCl2 were also used as the other immersion test solution
ing chloride, no attention has been paid to the surface color to evaluate the effect of bicarbonate ion on the prevention
degradation phenomenon appeared mostly in the humid of surface darkening. The reason why the tap water was
environment at high temperature. In fact, during shipment used is that the tap water contains bi-carbonate ion
and storage of the Zn–Mg alloy coated steel sheets, its (HCO3 ). According to the ion chromatography analysis,
surface can be easily turned to dark if it is exposed to the the amount of HCO3 in the tap water is around 81.3 mg/L.
high humid environment at high temperature. Since the By the addition of 0.1 M ZnCl2 to the 0.2 M K2CO3
surface darkening phenomenon may lead to degrading of solution, Zn21 ion used for the precipitation of Zn-based
the coating quality regardless of its superior corrosion protective film on the coating surface can be supplemented.
resistance, it is very critical industrial problem for the Zn– After the test, the surface was analyzed by FE-SEM,
Mg alloy coating. To develop a proper mitigation method EDS, GDS, XPS, and scanning vibrating electrode
for this surface darkening problem, it is necessary to clearly technique (SVET).
understand the nature and formation mechanism of the A high temperature–humidity exposure test was per-
surface darkening phenomenon. formed to simulate the corrosion by water films condens-
This study is mainly focused on understanding the ing on the surfaces of narrow gaps of the galvanized steel
nature and formation mechanism of the dark rust formed roll. The two specimens were ultrasonically rinsed in
on the Zn–Mg alloy coated steel produced by a PVD ethanol and dried in air. After two drops of DI water were
method. Various analytical techniques including trans- dropped on the surface of one steel specimen, the other
mission electron microscopy (TEM), field-emission scan- specimen was folded on this specimen to make them in
ning electron microscopy (FE-SEM), Auger electron face-to-face contact. Then, a constant load (compressive
spectroscopy (AES), glow discharge spectroscopy stress) was applied to press these two specimens together
(GDS), x-ray photoelectron spectroscopy (XPS), and in such a way that the small amount of water in the gap
Fourier transformation infrared (FT-IR) spectroscopy between these two specimens cannot be evaporated
are utilized for the analysis on the surface film. easily. Figure 1 illustrates the exact description of the
experimental procedure. The temperature and humidity
levels were kept at 50 °C and at 95%, respectively, for
II. EXPERIMENTAL PROCEDURES 3 days. After the test, the surface was analyzed by digital
A. Specimen preparation and microstructure camera and AES.
examination
The Zn–Mg alloy coated steel was obtained by a high III. RESULTS AND DISCUSSION
speed PVD using evaporation method. The nominal com-
position of the alloy coating was 90 wt% Zn-10 wt% Mg. A. Microstructure analysis
Firstly, the cold rolled steel was cleaned by sputter etching Figure 2 presents X-ray diffraction (XRD) patterns of
method before deposition. The coating thickness on the the Zn–Mg alloy coated surface of as-received specimen.
specimens was in the range of 1–2 lm. The microstructure Detected phases are two intermetallic compounds of
and morphology of specimens were analyzed by the FE- MgZn2 and Mg2Zn11. Figure 3(c) exhibits the cross
SEM and energy dispersive spectroscopy (EDS). The sectional image of the coating layer analyzed by TEM,
specimen was ultrasonically cleaned in ethanol, dried in and Table I lists the result of the EDS quantitative
air, and coated with platinum before observation of the analysis at each point marked on Fig. 3. From these
surface morphology by FE-SEM. To determine the com- analyses, it is found that the light and dark images in
position of coating layer as a function of depth, GDS was Fig. 3(c) are identified as MgZn2 phase and Mg2Zn11

3606 J. Mater. Res., Vol. 30, No. 23, Dec 14, 2015
 S.J. Kim et al.: Surface darkening phenomenon of Zn–Mg alloy coated steel exposed to aqueous environment at high temperature

MgO film on the outermost surface plays a positive role

in the corrosion resistance of Zn–Mg alloys since the film
is stable enough to ensure good barrier properties to ion
and electron transfer comparing to other oxide films such
as Zn-based oxide (ZnO). Considering the resistance of
MgO (1012–1013 X m at 573 K) is almost 1010–1011 order
higher than that of ZnO (94 X m at 433 K),17 it is
expected that the cathodic reaction of oxygen reduction
can be effectively suppressed on the MgO so that the
corrosion resistance can be improved under the condition
that the oxides have the same physical size such as the
thickness.

B. Surface morphology after corrosion test

1. Surface analysis after immersion test
Figure 5 presents the surface morphology after various
immersion tests examined by digital camera. Contrary to
the steel with electro-galvanized steel (EG; pure Zn
coating), Zn–Mg alloy coated steel specimens exposed to
boiling DI water turned to dark in 5 min. In the case of the
steel with pure Mg coating, the surface was also changed
to dark brown within 10 min. However, in this case, the
extent of surface color change is not as severe as that of
Zn–Mg alloy coated steel and the time required to change
the surface color was longer. The two different Zn–Mg
alloy coated steel specimens shown at the second row of
Fig. 5 show the result of the immersion test using solutions
containing the carbonate ion (CO32 ). The left one is the
coating surface after immersion test in 0.2 M NaHCO3
solution and the right one is the surface after immersion
test in 0.2 M K2CO3 solution. Contrary to the results of
FIG. 1. High temperature–humidity exposure test procedure. immersion test in DI water, no discernible change in the
surface color was observed. The reason for this phenom-
enon will be discussed in detail later in this section.
phase, respectively. Besides these two main intermetallic To determine the nature of the dark surface shown in
phases, however, presence of metallic Mg phase was also Zn–Mg alloy coated steel, the cross-sectional observation
identified by the backscattered electron images (BEI) of was carried out by TEM and the results are shown in
the Zn–Mg coating surface and EDS quantitative analysis Fig. 6(d). The coating layer was covered with a thin corrosion
examined by FE-SEM. Figures 3(a) and 3(b) and Table I product with thickness of around 100 nm. It is estimated
show BEI of the coating surface and the result of that the thin layer formed on the coating surface is closely
quantitative EDS analysis, respectively. Considering that associated with the surface darkening phenomenon.
the black-colored region in BEI indicates the presence of Figures 6(a) and 6(b) exhibit the surface morphology of
the low atomic weight element and that the atomic percent the coating before and after the immersion test in DI
of Mg is much higher than that of Zn at the point marked water by utilizing FE-SEM. For the specimen after the
“A” on the Fig. 3(a), it is estimated that metallic Mg immersion test, it is evident that the needle-like corrosion
phases are also present along with MgZn2 and Mg2Zn11 products are formed on the outermost surface. In addi-
intermetallic compounds. This may be due to the fact that tion, as clearly seen in Fig. 6(c), the corrosion products
the Zn–Mg alloy coating was developed by a nonequilib- are presented in the dark region examined by digital
rium process in the PVD method and the metallic Mg camera. Therefore, it can be strongly suspected that the
phases could be formed abnormally on the coating layer. nature of dark rust is closely associated with the corrosion
From Fig. 3(c), the outermost coating layer is covered product on the outermost surface. Some researches have
with a thin film of Mg-based oxide (MgO) and it can also indicated that the black staining phenomenon of zinc
be identified by the GDS analysis as shown in Fig. 4(a). coated steel is due mainly to the oxygen deficient
Larché et al.14 have reported that the presence of the phenomenon (ZnO1 x) occurring in zinc oxide.18 It can

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 S.J. Kim et al.: Surface darkening phenomenon of Zn–Mg alloy coated steel exposed to aqueous environment at high temperature

FIG. 2. XRD spectra of Zn–Mg alloy coated surface.

FIG. 3. (a) Surface morphology of Zn–Mg alloy coated steel examined by FE-SEM in the BEI mode; (b) magnified view of (a); (c) cross sectional
view of Zn–Mg alloy coating layer examined by TEM.

TABLE I. EDS quantitative analysis at each point marked on Fig. 3. deficient phenomenon in ZnO can degrade the surface to
O (wt%) Mg (wt%) Zn (wt%) Total (wt%)
a certain extent, it seems that it is not directly associated
with the dark rust formation discussed here, and the dark
Point A 25.47 40.57 33.96 100 rust formation cannot be fully explained by the mecha-
Point B 0.51 87.82 11.67 100
Point A9 35.53 41.28 23.19 100
nism of oxygen deficiency in ZnO. To understand the
Point B9 1.81 10.31 87.88 100 nature of the corrosion product formed on the coating
Point C9 1.03 5.05 93.89 100 surface, GDS analysis was additionally carried out.
According to the analysis shown in Figs. 4(b) and 4(c),
there is a clear increase in Mg peak on the outermost
lead to the change of band gap energy related to the surface in case of the specimen immersed in DI water for
optical property. This kind of phenomenon has also been 5 min contrary to the case of the specimen immersed in
identified after the immersion test in this research. In the 0.2 M NaHCO3 solution. The effect of solution contain-
case of the EG, surface has some local staining like dot. ing carbonate ion on the suppression of surface darkening
However, as it is seen clearly in Fig. 5, dominant dark is mainly discussed in Sec. III. B. 2. The results of
color was not observed. Therefore, although the oxygen various analyses on the surface of the steel with pure Mg

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 S.J. Kim et al.: Surface darkening phenomenon of Zn–Mg alloy coated steel exposed to aqueous environment at high temperature

FIG. 4. GDS analysis on (a) as-received Zn–Mg alloy coated specimen, and (b) and (c) coating surface after immersion test in 0.2 M NaHCO3
solution and DI water, respectively.

FIG. 5. Surface morphology of Zn–Mg alloy coated, pure Mg coated and EG steels after various immersion and high-temperature humidity
tests.

coating and Zn–Mg alloy coated steel after immersion that of MgZn2 and Mg2Zn11 phases acting as cathode, the
test suggest that Mg plays a crucial role in the formation dissolution of Mg can be accelerated drastically. Figure 7
of dark rust formed on the coating surface. It is known shows the surface morphology examined by FE-SEM in
that when two dissimilar metals are coupled electrochem- the BEI mode before and after the immersion test for 40 s.
ically or galvanically, the active metal is preferentially Although large Mg phases appearing as black-colored
corroded while the noble one is protected from corro- region in Fig. 7 still remain, the amount of fine size of
sion.19 Since Mg is more electroactive than Zn and also Mg phases is clearly reduced, suggesting that the metallic
more electroactive than MgZn2 and Mg2Zn11, Mg has Mg phases are dissolved at a short period of immersion.
a tendency to dissolve preferentially when Mg is elec- Furthermore, the remaining large Mg phases after the
trochemically coupled with MgZn2 and Mg2Zn11 in the immersion test in 40 s are precisely observed and the
Zn–Mg coating. In the Zn–Mg alloy coating, since the results are shown in magnified view of Fig. 7(b). It
area of Mg phase acting as an anode is much smaller than appears that the needle-like corrosion products were

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FIG. 6. FE-SEM images showing the surface morphology of Zn–Mg alloy coated steel (a) before, and (b) and (c) after immersion test in DI water for
5 min and 25 s, respectively; (d) TEM image showing the cross section of the coated steel after immersion test in DI water for 5 min.

scarcely precipitated only on the remaining Mg phases. It are very sensitive to variations in metal particle size and/
implies that the Mg phases act as anode and the high or shape,20 it could be also possible that accelerated
anodic dissolution could occur preferentially at those sites. dissolution of Mg from the coating surface makes the
To confirm this phenomenon, ion-chromatography (ICP) surface rougher, leading to the scattering of visible ray
analysis was performed on the dissolved Zn and Mg ion and therefore it could contribute additionally to the
after immersion test in DI water. The amount of dissolved surface color change to dark.
Mg ion was 0.05 ppm, whereas that of dissolved Zn ion Lindstrom et al.21 have also reported that Mg surface is
was less than 0.01 ppm. This ICP analysis result is covered with dark Mg(OH)2 when Mg is exposed to
consistent with the discussion above. It is believed that corrosive wet environment, especially in the absence of
this is the reason why the extent of surface staining of Zn– CO2. In addition, it is known that the solubility of Mg
Mg alloy coated steel is more severe than that of pure Mg (OH)2 in aqueous water at 100 °C is around 4 mg/L
coated steel. Although an electrochemical potential map which is only one third of that in the water at room
analyzed by SVET, which is found in Fig. 8, cannot give temperature (25 °C).22 This suggests that as the temper-
the potential level at each phase in the microstructure, it ature of the aqueous water increases, the solubility of
can be surely indicated that there are a lot of local anodes Mg(OH)2 in the water is decreased and therefore easy
and cathodes in the coating surface. precipitation of Mg(OH)2 on the coating surface can be
In summary, the dark rust is closely associated with the facilitated. Considering these facts, the dark rust forma-
precipitation of the Mg-based corrosion product in a form tion of Zn–Mg alloy coated steel in aqueous solution at
of Mg(OH)2. Although it is known that the color of pure high temperature could be well explained by the prefer-
Mg(OH)2 is white, its color can be changed to gray or ential dissolution of Mg from the coating layer and easy
other dark colors depending on the kind and level of precipitation of Mg(OH)2 on the coating surface. The
impurity. Considering the fact that the optical properties preferential dissolution of Mg and subsequent precipitation

3610 J. Mater. Res., Vol. 30, No. 23, Dec 14, 2015
 S.J. Kim et al.: Surface darkening phenomenon of Zn–Mg alloy coated steel exposed to aqueous environment at high temperature

FIG. 7. Surface morphology of the coating surface examined by FE-SEM in the BEI mode (a) before and (b) after the immersion test for 40 s;
(c) magnified view of (b).

FIG. 8. Potential map of Zn–Mg alloy coated steel after immersion test in DI water, analyzed by SVET.

of Mg(OH)2 are basically attributed to the pre-existing process, the conditions of the coating process should be
metallic Mg on the coating layer. To avoid the formation of optimized or efficient surface treatment should be devel-
abnormal Mg phase on the coating layer during the PVD oped. However, detailed discussion on the prevention

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 S.J. Kim et al.: Surface darkening phenomenon of Zn–Mg alloy coated steel exposed to aqueous environment at high temperature

methods are beyond the scope of this paper and the present Zn-based corrosion product is assumed to be hydrozincite
study is focused sorely on the mechanistic study of the dark [Zn5(OH)6(CO3)2] since the hydrozincite becomes stable
rust formation. between pH 7 and 8.5 of the bicarbonate buffer solution.23
Contrary to the result of immersion test in DI water, dark The surface analysis by FT-IR, which is found in Fig. 10,
rust is not observed from Zn–Mg alloy coated steel clearly supports this assumption. The peaks at 1499,
specimens when tested by immersion in a solution con- 1387.15, and 845 cm 1 are attributed to hydrozincite.10
taining bi-carbonate ion (HCO3 ) and Zn21 ion. The According to Chung et al.,24 the presence of hydrozincite
extent of surface color change to dark was less severe as a passive film is widely accepted as being advantageous
when immersed in tap water containing a small amount of for the longevity and protectively, which is primarily
carbonate ion than when immersed in DI water. Secondly, attributed to a superior insolubility comparing to oxidation
little change of surface color was observed after the test products such as simple oxides and chloride species. Figure
using solutions containing the carbonate ion such as 9(b) showing FE-SEM image obtained from the carbonate
NaHCO3 and K2CO3. After immersion test in the solutions treated specimen after immersion test by using DI water for
containing NaHCO3 and K2CO3, the specimen surface did 30 min indicates that the hydrozincite particles which can
not show any discernible change in the color and pattern by act as a protection barrier against the formation of dark rust
observation with naked eye. As shown in Fig. 4(b), Mg gradually disappear by dissolution in boiling DI water, and
peak was not detected on the outermost surface in case of therefore the coating layer containing Mg is exposed to the
the specimen immersed in 0.2 M NaHCO3 solution, which DI water. As a result, the dark rust is gradually formed on
is attributed to the precipitation of Zn-based thin film on the coating surface. A number of test results obtained by
the surface. The morphology Zn-based film is presented in a variety of analysis equipment such as FE-SEM, EDX,
Fig. 9. Consequently, the surface darkening phenomenon GDS, and FT-IR supports the fact that the outermost layer
can be avoided. Considering the fact that pH of the solution of carbonate treated specimen is composed of hydrozincite
containing 0.2 M NaHCO3 is around 8.3, the thin film of and there is no evidence that Mg rich layer such as MgCO3

FIG. 9. Surface morphology of the coating surface (a) before and (b) after immersion test in 0.2 M NaHCO3 solution, (c) EDS analysis on the
coating surface.

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is present on the coating surface. This could be due mainly 2. Surface analysis after high temperature–humidity
to the fact that the Gibbs free energy of formation for test
hydrozincite ( 3160 kJ/mol at room temperature to At the third and fourth row of Fig. 5, the surface
100 °C) is much lower than that for MgCO3 ( 1100 kJ/ morphology examined by digital camera after high
mol at room temperature to 100 °C), suggesting that the temperature–humidity exposure test are presented. Since
hydrozincite could be preferentially formed on the coating the condition of high temperature–humidity exposure test
surface. Nevertheless, it would not be possible to entirely is different from that of immersion test, the mechanism of
exclude the fact that some Mg rich layers are also present dark rust formation is not the exactly same as that of
on the coating surface. immersion test. Contrary to immersion test, an extremely
small amount of water exists on the coating surface
during this test. This suggests that the precipitation rate of
metallic ions, specifically Mg ions, increases since their
solubility limit exceeds rapidly because of a small
volume of solution in the thin water film condensed on
the surface. Therefore, MgO/hydroxide can be formed
rapidly by precipitation from the water.25 As seen clearly,
the extent of surface change was the most severe in the
case of Zn–Mg alloy coated steel due to the combined
effects of galvanic action between Mg and two interme-
tallic phases of MgZn2 and Mg2Zn11, and fast precipita-
tion of Mg ions. Although a similar pattern was observed
in the case of the pure Mg, the extent of surface change
was not as severe as that of Zn–Mg alloy coated steel. In
the case of the EG, there was no discernable change on
the coating surface. This result shows that it is pretty
much the same as the result of immersion test. Consid-
FIG. 10. FT-IR spectra of the coating surface after immersion test in ering these results of Zn–Mg alloy coated steel and pure
0.2 M NaHCO3 solution. Mg shown in Fig. 5, it seems that the dark surface is

FIG. 11. Surface morphology of Zn–Mg alloy coated steel after high temperature–humidity exposure test and AES analysis at (a) dark region and
at (b) light region.

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(1) The coating layer of the Zn–Mg alloy coated steel

is composed of metallic Mg phase and two intermetallic
compounds of MgZn2 and Mg2Zn11.
(2) The formation of dark rust is observed from both
Zn–Mg alloy coated steel and pure Mg coated steel after
the immersion test in DI water at high temperature.
Preferential anodic dissolution occurs at the Mg phase
in the coating surface of the Zn–Mg alloy coated steel,
and it is estimated that the formation of Mg(OH)2 on the
outermost surface of the coating layer is main responsible
for the dark rust. In addition, it could be also possible that
the preferential anodic dissolution of Mg from the coating
surface leads to the rougher surface. The scattering of
visible ray due to the rougher surface can contribute
additionally to the surface color change to dark.
FIG. 12. XPS analysis on the coating surface after immersion test in
(3) The darkening effect is more serious when the
DI water for 5 min. Zn–Mg alloy coated steel is exposed to an extremely
small amount of condensed water on the steel surface. It
caused by precipitation of Mg(OH)2. Figure 11 can surely is due to the preferential dissolution of metallic Mg
support this assumption by AES analysis. As seen in phases by the galvanic action with intermetallic phases of
Fig. 11, there are locally darker part and lighter part from MgZn2 and Mg2Zn11 mainly present in the Zn–Mg
the same test specimen. The AES analysis from the dark coating layer, and easy precipitation of Mg21 ion in
region indicates that the region is composed of Mg oxide/ a form of Mg(OH)2 in a limited volume of the condensed
hydroxide. Very small amount of Zn is present on the water film on the steel surface.
outermost surface. On the other hand, in the case of the
comparatively light region, Mg oxide/hydroxide is not REFERENCES
sufficiently present to make the surface completely dark; 1. M. Dutta, A.K. Halder, and S.B. Singh: Morphology and proper-
Zn peak continuously increases as a function of depth. ties of hot dip Zn–Mg and Zn–Mg–Al alloy coatings on steel
Little change in the surface color is observed due to the sheet. Surf. Coat. Technol. 205, 2578 (2010).
2. S. Schuerz, M. Fleischanderl, G.H. Luckeneder, K. Preis,
lack of Mg oxide/hydroxide. To clarify the nature of dark
T. Haunschmied, G. Mori, and A.C. Kneissl: Corrosion behaviour
rust formed on the surface, XPS analysis is additionally of Zn–Al–Mg coated steel sheet in sodium chloride-containing
conducted and Fig. 12 also supports that outermost layer environment. Corros. Sci. 51, 2355 (2009).
is composed of Mg(OH)2. In addition, to determine the 3. H.C. Shih, J.W. Hsu, C.N. Sun, and S.C. Chung: The lifetime
effect of temperature on the surface color degradation assessment of hot-dip 5% Al–Zn coatings in chloride environ-
ments. Surf. Coat. Technol. 150, 70 (2002).
phenomena, an exposure test was carried out at room
4. K.G. Watkins, R.D. Jones, and P.G. Beahan: Electrochemical
temperature (25 °C). As it is clearly seen at the bottom of investigation of the corrosion rate of 55 aluminium-zinc alloy
Fig. 5, little change can be observed. It seems that coated steel. Mater. Lett. 8, 26 (1989).
relatively high temperature is required to form the dark 5. G.A. El-Mahdy, A. Nishikata, and T. Tsuru: AC impedance study
rust on the coating surface, suggesting that the anodic on corrosion of 55%Al–Zn alloy-coated steel under thin electrolyte
layers. Corros. Sci. 42, 1509 (2000).
dissolution of Mg is getting faster at high temperature. As
6. E. Palma, J.M. Puente, and M. Morcillo: The atmospheric
a result, the precipitation rate of Mg in the form of corrosion mechanism of 55%Al-Zn coating on steel. Corros. Sci.
Mg(OH)2 becomes faster, too. Furthermore, considering 40, 61 (1998).
the fact that the solubility of Mg(OH)2 in aqueous water 7. N.C. Hosking, M.A. Ström, P.H. Shipway, and C.D. Rudd:
decreases as the temperature of the water increases, the Corrosion resistance of zinc–magnesium coated steel. Corros.
Sci. 49, 3669 (2007).
dark rust formation due to the precipitation of Mg(OH)2
8. T. Koll, K. Ullrich, J. Faderl, J. Hagler, and A. Spalek: Properties
on the coating surface will be inevitable when the Zn–Mg and potential applications of novel ZnMg alloy coatings on steel
alloy coated steel is exposed to a limited amount of sheet. In Galvatech’04. Proc. AIST, Chicago, IL, United States,
aqueous environment at elevated temperature. 2004; p. 803.
9. C. Schwerdt, M. Riemer, S. Koehler, B. Schuhmacher,
M. Steinhorst, and A. Zwick: A study of the application related
IV. CONCLUSIONS properties of novel Zn-Mg coated steel sheet produced in
This research is focused on the understanding of the nature a continuous pilot line. In Galvatech’04. Proc. AIST, Chicago,
IL, United States, 2004; p. 783.
of dark rust, and its formation mechanism on the surface of 10. T. Prosek, A. Nazarov, U. Bexell, D. Thierry, and J. Serak:
Zn–Mg alloy coated steel for which a PVD method is used. Corrosion mechanism of model zinc–magnesium alloys in atmo-
The results are briefly summarized as follows: spheric conditions. Corros. Sci. 50, 2216 (2008).

3614 J. Mater. Res., Vol. 30, No. 23, Dec 14, 2015
 S.J. Kim et al.: Surface darkening phenomenon of Zn–Mg alloy coated steel exposed to aqueous environment at high temperature

11. P. Volovitch, C. Allely, and K. Ogle: Understanding corrosion via 18. L. Yanping, Q. Zuyu, and J. Yanming: Investigation of black
corrosion product characterization: I. Case study of the role of Mg tarnished film on zinc plated surface. Corros. Sci. Prot. Technol.
alloying in Zn–Mg coating on steel. Corros. Sci. 51, 1251 (2009). 12, 273 (2000).
12. M. Vlot, R. Bleeker, T. Maalman, and E. van Perlstein: A new 19. D.A. Jones: Principles and Prevention of Corrosion, 2nd ed.
generation of hotdip galvanised products. In Galvanized Steel (Prentice Hall, New Jersey, 1996).
Sheet Forum. Proc. ILZRO and IZA, Dusseldorf, Germany, 2006. 20. I.O. Wallinder, W.H.P. Augustsson, and C. Leygraf: Character-
13. S. Kazutoshi, S. Hiroshi, T. Masao, N. Hidetoshi, I. Koki, K. Junji, ization of black rust staining of unpassivated 55% Al-Zn alloy
M. Shoji, N. Shingo, and S. Hirohiko: Zn-Mg alloy vapor coatings, effect of temperature, pH and wet storage. Corros. Sci.
deposition plated metals of high corrosion resistance, as well as 41, 2229 (1999).
method of producing them. Patent 5135817, (1992). 21. R. Lindstrom, L.G. Johansson, G.E. Thompson, P. Skeldom, and
14. N. Larché, T. Prosek, A. Nazarov, and D. Thierry: Zn-Mg J.E. Svensson: Corrosion of magnesium in humid air. Corros. Sci.
Automotives Steel Coatings. (Institut de la Corrosion technical 46, 1141 (2004).
report, 2008). 22. S. Ambrose, F.D. Gnanam, and P. Ramasamy: Influence of
15. Y.J. Kwak, D.Y. Kim, W.S. Jung, K.H. Nam, D.Y. Lee, S.J. Hong, additives on periodic crystallisation in Gel(I). Theory. Int. J.
T.Y. Kim, Y.H. Jung, M.J. Eom, M.H. Choi, G.Y. Kim, S.H. Park, Chem. Sci. 92, 239 (1983).
S.C. Lee, and Y.W. Nam: A composition for forming the film for 23. H. Sontheimer and F. Kuch: Internal Corrosion of Water
preventing the black stain of steel sheet, the steel sheet containing Distribution Systems, 2nd ed. (American Water Works Associa-
the film formed from the composition and method for forming the tion Research Foundation, Colorado, 1996).
film. Korea Patent 10-2011-0027814, (2011). 24. S.C. Chung, A.S. Lin, J.R. Chang, and H.C. Shih: EXAFS study
16. F. Yasushi, M. Masanori, T. Hiroshi, M. Tadaaki, S. Kazushi, and of atmospheric corrosion products on zinc at the initial stage.
A. Yasumi: Steel sheet with Zn-Mg binary coating layer excellent Corros. Sci. 42, 1599 (2000).
in corrosion resistance and manufacturing method thereof. Euro- 25. M. Liu, S. Zanna, H. Ardelean, I. Frateur, P. Schmutz, G. Song,
pean Patent 00730045, (2000). A. Atrens, and P. Marcus: A first quantitative XPS study of the
17. G.V. Samsonov: The Oxide Handbook, 2nd ed. (Plenum, New surface films formed, by exposure to water, on Mg and on the Mg–Al
York, 1982). intermetallics: Al3Mg2 and Mg17Al12. Corros. Sci. 51, 1115 (2009).

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