Surface & Coatings Technology 245 (2014) 55–65

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Surface & Coatings Technology

journal homepage: www.elsevier.com/locate/surfcoat

Effects of manganese addition on microstructures and corrosion behavior

of hot-dip zinc coatings of hot-rolled steels
Youbin Wang, Jianmin Zeng ⁎
State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi'an 710072, PR China

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

Article history: In the present work, the Zn coatings of hot-rolled steel sheets with different Mn additions were prepared by hot
Received 23 October 2013 dipping process. The effects of Mn addition on the microstructures and corrosion resistances of the hot-dip Zn
Accepted in revised form 19 February 2014 coatings were investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS),
Available online 26 February 2014
and X-ray diffractometry (XRD). The Mn distribution in δ-layer is lower than that of ζ-layer. Mn addition could
promote the growth of δ-layer of the coating and inhibit the growth of the columnar ζ phase which morphology
Keywords:
Hot dip
was changed to discontinuous phase. It is also found that the surface color of Zn–Mn coating varies with the
Zn coating dipping temperatures. Such phenomenon is supposed to be attributed to the optical interference effect of the
Mn addition Mn oxide film formed on the coating surface. For the corrosion behavior, the as-dipped and ζ layer-exposed Zn
Microstructure coatings were subjected to both Tafel polarization measurements and electrochemical impedance spectroscopy
Corrosion (EIS) tests in 3.5% NaCl solution. The results indicate that Mn addition enhances the corrosion resistance of
the as-dipped coatings. The dense corrosion products formed on the top η layer of the Zn–Mn coatings after Tafel
polarization corrosion are assumed to inhibit the further corrosion of the coating. However, minor effects of Mn
addition to the anti-corrosion performance of ζ layer were noticed.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction [15,17–19]. However, due to prolonged processing time, high operating

Hot-dip Zn coatings have been widely used for protection of steel
work pieces against atmospheric corrosion owing to their excellent
corrosion performance and low cost [1]. The coating typically consists
of multiple sub-layers including η-Zn layer, ζ-FeZn13 layer, δ-FeZn10
layer and Γ-Fe3Zn10 layer [1]. The enhancement of the corrosion resis-
tance of steel work pieces with Zn coatings is realized in two ways in
general, i.e., barrier protection to simply insulate the steel work pieces
from corrosive environment, as well as galvanic protection to prevent
the substrate steel from corrosion serving as sacrificial anode [1,2].
The overall performance of hot-dip Zn coating depends on many aspects
such as chemical compositions of steel work pieces [3], alloying element
contents in Zn bath [4], as well as dipping time and temperature [5].
Numerous works have been carried out in order to improve the corro-
sion resistance of the coating by alloying Zn with small amounts of
other elements, such as Al [6,7], Si [8,9], Ni [10], Ti [11], Mg [12], Co
[13], and Sb [14], through better controlling the growth of the Zn–Fe
phase, coating thickness, adhesion strength, Sandelin effect, and so on.
Among the investigated Zn coatings, the Zn–Mn coating were of
great interest due to the better anti-corrosion performance than
pure Zn coating [15,16]. Electrochemical deposition is one of effective
means to produce the Zn–Mn coating with better corrosion resistance
⁎ Corresponding author. Tel.: +86 771 3231238.
E-mail address: zjmg2008@gmail.com (J. Zeng).
cost, and limited work piece size and shape, the electrochemical deposi-
tion process is not accepted widely in the industry. On the other hand,
the hot dipping process would still be the primary choice for Zn–Mn
coating preparation because of its low cost and easy operation in the
industry [1]. Many works have been carried out to investigate the
anti-corrosion performance of hot-dip Zn–Mn coating. For example,
E. Pavlidou [20] reported that 1.0% Mn addition improved the anti-
corrosion performance of the hot-dip Zn coating, where Mn acts as a
sacrificial anode to protect Zn. L.D. Ballote [21] discovered that the addi-
tion of Mn introduced Mn-rich oxides on the coating surface which
therefore increased the corrosion resistance of hot-dip Zn coatings.
However, most of the previous researches were focused on the effect
of Mn addition on the corrosion resistance of the coating surface only.
To the authors' best knowledge, the effect of Mn addition on the micro-
structure and corrosion behavior of the Zn–Fe sub-layers of the hot-dip
Zn coating are still not yet well studied. In practice, the Zn–Fe sub-layers
would probably be exposed to the corrosion environments especially
when the coating has been subjected to some physical and/or chemical
damages, such as accident peeling off of the top η-Zn layer during mov-
ing, acid attack, etc. The Zn–Fe sub-layers would then be serving the
important role in the protection of the substrates from corrosion. It is
therefore worthwhile to investigate the corrosion resistance of such
sub-layers to further understand the anti-corrosion mechanisms of the
Zn–Mn coatings. For this, the present work is trying to give more in-
sightful investigation on the microstructure and corrosion resistance

http://dx.doi.org/10.1016/j.surfcoat.2014.02.040
0257-8972/© 2014 Elsevier B.V. All rights reserved.
56 Y. Wang, J. Zeng / Surface & Coatings Technology 245 (2014) 55–65
of both the surface and the ζ-FeZn13 layer of the hot-dip Zn coating with
Mn addition. The effects of Mn addition on the corrosion behavior of
other Zn–Fe layers (Delta & Gamma) of the coating will be studied in fu-
ture work.
2. Experimental
The Zn–Mn alloys with different Mn contents (0.2, 0.5 and 0.7 wt.%)
used for steel hot dip coating were prepared by adding certain amounts
of as-purchased Zn–Mn intermediate alloy (5.0 wt.% Mn) into the mol-
ten pure Zn (99.99 wt.%) which was previously melted at 650 °C in a
resistance furnace with a graphite crucible (25 cm in diameter and
30 cm in depth). For the sake of simplicity, Zn–xMn is denoted for the
prepared Zn coating with x wt.% Mn addition throughout the whole ar-
ticle. After sufficient mixing, the molten Zn–Mn alloy was hold at certain
temperatures, such as 430, 450, and 470 °C for steel dipping in the next
step. The chemical compositions of the prepared Zn alloys with different
Mn additions were determined by XRF (Olympus Innov-X) and listed in
Table 1.
Hot-rolled steel sheet (Grade Q235, containing 0.11 wt.% C, 0.55 wt.%
Mn, 0.012 wt.% Si, 0.016 wt.% P and balance Fe, 3 mm in thickness) was
cut into specimens with the size of 90 mm (L) × 30 mm (W). Alkali–acid
wash was used to clean the surface of steel work pieces. The specimens
were first degreased in 10 wt.% NaOH solution for 20 min, followed by
rinsing in distilled water several times to completely remove the alkali
solution. The specimens were then pickled in an acid solution with
16 vol.% HCl for 20 min, followed by rinsing in distilled water multiple
times to remove the residual acid. The cleaned specimens were fluxed
in an aqueous solution containing 15 wt.% ZnCl2 and 15 wt.% NH4Cl
for 10 min, and then dried in a furnace at 120 °C. The flux coated on
the specimens helps prevent the steel surface from oxidation during
the dipping process. Finally the specimens were dipped in the molten
Zn bath hold in the resistance furnace. The dipping temperatures of
the specimens were controlled at 430, 450, and 470 °C, respectively.
After 180 s of dipping, the specimens were removed from the molten
Zn bath and cooled in air naturally.
The coating morphology was observed using a Hitachi S-3400N
scanning electron microscope (SEM), and the chemical compositions
of the crystal phases in the coating was investigated using an energy-
dispersive X-ray spectrometer (EDS). The phase of the coating surface
was analyzed by X-ray diffraction (XRD) using a Rigaku D/Max-2500V
diffractometer with Cu Kα radiation and the monochromator operated
at 40 kV and 200 mA. The scanning rate was set at 10°/min. The Mate-
rials Data Inc. software Jade 5.0 and Powder Diffraction File were used
for phase identification. X-ray photoelectron spectroscopy (XPS) analy-
ses were also carried out using ESCALAB 250 (Thermo VG) with a Al Kα
source at 1486.6 eV in order to identify the film composition on the
coating surface.
The corrosion behavior of the surface and the ζ layers of the Zn coat-
ings with different Mn contents prepared at 450 °C/180 s were charac-
terized using an electrochemical workstation (Gamry Reference 600).
The hot dipped specimens were divided into two groups: as-dipped
specimens with no further treatment for the study of the coating's sur-
face corrosion resistance, and ζ layer-exposed specimens which were
obtained by fully removing the η layer from the as-dipped specimens
with #2000 silicon carbide grinding papers down to the ζ layer for the
Table 1
Chemical compositions of the prepared Zn alloys for hot dipping analyzed by XRF.
Alloy Zn Mn
Nominal Experimental Nominal Experimental
Zn 100 100 0 0
Zn–0.2Mn 99.8 99.785 0.2 0.215
Zn–0.5Mn 99.5 99.506 0.5 0.494
Zn–0.7Mn 99.3 99.272 0.7 0.728
investigation of the ζ layer's corrosion resistance. As we can see from
Fig. 3, a 30–35 μm removal would be sufficient enough to expose the ζ
layer. In order to reach the desired ζ layer, a micrometer (FMS 283,
1 μm resolution) was initially used to estimate the thickness of the coat-
ing being removed. After roughly 30 μm of coating being removed, SEM
and XRD were used to confirm the arrival of ζ layer, and the polishing
process was repeated until the ζ layer is completely exposed. All the
samples were sealed by epoxy resin but leaving the testing surface
(1 cm2) uncovered for the corrosion tests. The electrochemical experi-
ments were performed in 3.5% NaCl solution at 20 °C with a classic
three-electrode cell configuration in which a Pt plate served as
the counter electrode and a saturated calomel electrode (SCE) was
used as the reference electrode. The polarization tests were carried
out at the scan rate of 0.2 mV/s and the scan range from − 200 mV
(SCE) to +200 mV (SCE) relative to the open-circuit potential. The elec-
trochemical impedance spectroscopy (EIS) measurements were con-
ducted at the potential amplitude of 10 mV relative to the open-circuit
potential and the frequency from 10 mHz to 100 kHz.
3. Results and discussion
3.1. Microstructure
For comparison, the steel samples with hot-dip pure Zn and Zn–
0.5Mn coatings prepared under different hot-dipping temperatures
are presented in Fig. 1. Fig. 1(a) shows the hot-dip pure Zn coating
prepared at 450 °C in which the coating color appears gray white. No
color variation was observed for the pure Zn coatings prepared at any
other hot-dipping temperatures. However, the colors were different
for those Zn–0.5Mn coatings prepared at different hot dipping temper-
atures. The surface color changes in a sequence of pale yellow, purple
and cyan, as shown in Fig. 1(b–d), with the increase of the dipping
temperature (430, 450 and 470 °C, respectively). It, to some extent, in-
dicates that the surface color of Zn–0.5Mn coating could be controlled
by the dipping temperature. For other specimens with 0.2 wt.% and
0.7 wt.% Mn additions, same color variations were also observed.
The color variation of the Zn–0.5Mn coating with dipping tempera-
ture could be attributed to the Mn oxide film formed on the coating sur-
face during the hot dipping process. The presence of Mn oxides is
evidenced by XPS/EDS/XRD characterization and more details will be
discussed in the following section. The formation of Mn oxide film
would introduce a visible light interference effect with which a specific
surface color will appear at certain film thickness and refractive index of
the oxides. M. Tomita also reported that the color variations were due to
Fig. 1. The coating colors of the steel work pieces hot dipped into (a) Zn at 450 °C/180 s,
(b) Zn–0.5Mn at 430 °C/180 s, (c) Zn–0.5Mn at 450 °C/180 s and (d) Zn–0.5Mn at
470 °C for 180 s, respectively.
 Y. Wang, J. Zeng / Surface & Coatings Technology 245 (2014) 55–65 57

Fig. 2. (a) XPS survey spectra and high resolution spectra of (b) O 1s, (c) Zn 2p, and (d) Mn 2p for the pure Zn and Zn–0.5Mn coatings at different dipping conditions.

the different thicknesses of the Mn oxides film on the coating surface if dipping at different temperatures. As a result, the Mn oxide film
[24]. This is quite true in our case, since different times are needed for formed on the coating surface would have various thicknesses, and pos-
the specimens to be cooled till no further significant oxidation occurs sibly different oxidation levels, compositions of Mn oxides as well. These

(a) (b)

steel δ ζ η steel

25 µm 25 µm

(c) (d)

Fig. 3. SEM micrographs of the cross-section of hot-dip (a) Zn coating and (b) Zn–0.5Mn coating; (c) EDS line scan along the red line as shown in (b); (d) the magnified EDS line profile
corresponding to the dot-line highlighted area in (c).
58 Y. Wang, J. Zeng / Surface & Coatings Technology 245 (2014) 55–65

Table 2
EDS elemental compositions (wt.%) of the hot-dip Zn–0.5Mn coating at the positions indi-
cated in Fig. 3.
Spot Zn Mn
A 89.27 0 10.73
B 91.84 0.42
C 93.46 2.24
D 93.96 2.03
E 93.63 1.45
factors combined together would eventually lead to the distinct coating
surface colors of the specimens dipped at different temperatures.
XPS surface analyses of the Zn and Zn–0.5Mn coatings were carried
out trying to identify the compounds of the oxides on the coating.
Fig. 2(a) shows the XPS survey spectra for the pure Zn and Zn–0.5Mn
coatings at different dipping conditions. It was found that the main
peaks of Zn–0.5Mn coating in the XPS spectrum correspond to Zn, Mn,
O and C, respectively. Mn peak was not able to be detected in the pure
Zn coating, and the other peaks of the Zn coating were similar in all Zn
coatings with and without Mn addition. The intensities of Mn peaks
are far less than those of Zn, which is consistent with the fact of small
addition of Mn to the Zn coatings. High resolution XPS spectra of some
characteristic peaks would be necessary to differentiate the differences
in these Zn coatings.
The high resolution XPS spectra of O 1s, Zn 2p, and Mn 2p are shown
in Fig. 2(b–d). The C 1s peak at 284.6 eV corresponds to binding energy
of the contaminated C. The O 1s peak at 531.3 eV suggests that the pres-
ence of metal oxides (Zn\O or Mn\O bonds). The Zn 2p3/2 peak at
1022.1 eV is coincident with the literature value of the ZnO [22]. The
Mn 2p3/2 peak at around 641.5 eV is ascribed to Mn oxides [23]. Howev-
er, it was too difficult to deconvolve the Mn 2p peaks to identify the in-
dividual compositions of the Mn oxides due to very close binding
energies of Mn for all the possible Mn oxides, such as MnO, Mn2O3,
and MnO2. However, careful inspection of the Mn 2p peaks of the spec-
imens prepared from different dipping temperatures would still give
subtle peak variations, as shown in Fig. 2(d), which may indicate the
compositional difference of the Mn oxides in all these samples. The re-
fractive index of the Mn oxide film would then be slightly different. At
Fe this moment, we are not able to distinguish the oxide film thicknesses
of the specimens which may have only a few hundred nanometer vari-
7.74 ation according to the wavelengths of the light spectrum. But as de-
4.30 scribed previously, the different allowable oxidation times would
4.01
most likely lead to various oxide film thicknesses. According to the vis-
4.92
ible light interference effect theory, only the light having characteristic
wavelength determined by both the oxide film thickness and refractive
index could be observed. Therefore, the surface color of the specimen
varies with dipping temperature.
The cross-section SEM micrographs of Zn and Zn–0.5Mn coatings
prepared at the hot-dipping conditions of 450 °C/180 s are shown
in Fig. 3(a) and (b). Layers with different Zn–Fe phases (δ-FeZn10,
ζ-FeZn13 and η-Zn) can be clearly distinguished on the hot-dip pure
Zn coating, which is consistent with the previous report [1]. However,
the Γ phase mentioned in the report [1] is hardly to be observed in
Fig. 3(a). It is most likely that the dipping time was too short for the
Γ phase to be formed by diffusion [25]. Mn addition seems to have sig-
nificant effects on both microstructure and Fe–Zn phase distribution
in each layer of the coating. For example, the ζ layer of Zn–0.5Mn coat-
ing mainly consists of discontinuous small-sized ζ phases, as shown in
Fig. 3(b), while the ζ layer of the pure Zn coating is in continuous
bulky columnar form (Fig. 3(a)). The morphological change of the
ζ layer is strongly associated with the Mn addition in the coatings. To
better explain this, one might need to take a close look at the elemental
analysis of the coating. Table 2 lists the elemental compositions of
five positions A, B, C, D and E indicated in Fig. 3(b). The results clearly
show the presence of Mn at positions C, D and E in the ζ layer, and the
Mn contents (above 1.4 wt.%) are higher than 0.5 wt.% in the Zn–
0.5Mn alloy bath for dipping. On the other hand, the Fe contents
(in the range of 4–5 wt.%) at these positions are lower than the theoret-
ical value of 6.2 wt.% in the pure FeZn13 phase, while the corresponding
mass percent of Mn and Fe in the phase is about 6.3% in total and the

(a) (b)

200 µm 200 µm

(c) (d)

200 µm 200 µm

Fig. 4. SEM micrographs of the surface of as-dipped (a) pure Zn coating and (b) Zn–0.5Mn coating; (c) Mn and (d) O mapping of the Zn–0.5Mn coating shown in (b).
 Y. Wang, J. Zeng / Surface & Coatings Technology 245 (2014) 55–65
Fig. 5. XRD patterns of the surface of as-dipped (a) pure Zn coating and (b) Zn–0.5Mn coating.
Zn contents of the position compositions are close to the theoretical
value of 93.8 wt.% in the FeZn13 phase. Due to the fact of spot based
EDS elemental analysis, multiple points other than the presented posi-
tions in the ζ layer have been analyzed and the results were quite
repeatable. All of these indicate partial replacement of Fe with Mn in
the FeZn13 phase of the Zn–0.5Mn coating. According to the Zn–Fe–
Mn ternary phase diagram at 450 °C studied by Reumont et al. [26]
and Raghavan et al. [27], ζ-FeZn13 extends widely from the Fe–Zn binary
system to the Mn–Zn side because Mn could replace up to 75% of the
Fe in ζ-FeZn13 phase. Such replacement of Fe with Mn in the ζ phase
could be accounted for the phase change from the continuous columnar
FeZn13 to discontinuous phase.
To illustrate the Mn distribution at different layers of the Zn–0.5Mn
coating, EDS line scanning analysis along the red line shown in Fig. 3(b)
was performed and the corresponding data is presented in Fig. 3(c).
It could be confirmed that the Zn–0.5Mn coating layer consists of
three sub-layers from the surface to matrix steel, i.e., η, ζ and δ in
terms of Fe content. As we can see, Mn dominantly distributes in the ζ
layer and top surface of the coating. The dot-line highlighted block
area in Fig. 3(c) with a spiking Mn content peak at the top surface is
magnified in Fig. 3(d). This significantly increased Mn content suggests
that Mn is segregated and enriched on the top surface of the η-layer and
forms a Mn-rich sub-layer during hot dipping process. The thickness of
the Mn-rich sub-layer is estimated at about 3 μm as shown by the line
scan in Fig. 3(d).
Interestingly, the Mn distribution line in Fig. 3(c) shows that the
Mn in δ-layer is lower than that in ζ-layer while the δ layer thickness
(25 μm) of Zn–0.5Mn coating is larger than that (10 μm) of pure Zn coat-
ing. Together considering the fact of increased thickness of δ layer with
Mn addition to the Zn coating, it indicates that Mn addition can promote
the growth of δ-FeZn10 phase. Similar phenomenon had been observed
in a previous work by N. Gao et al. [28]. They explained that the Mn ad-
dition in the zinc bath can stabilize the δ-FeZn10 phase and promote the
(a)
η-Zn
ζ-FeZn13
10 µm
Fig. 6. SEM micrographs of the ζ layer-exposed (a) pure Zn coating and (b) Zn–0.5Mn coating.
59
formation of δ-FeZn10 phase in the liquid Zn phase. As a result, the thick-
ness of the δ layer was then increased in the Mn added Zn coatings.
The SEM micrographs of the as-dipped Zn and Zn–0.5Mn coating
surfaces are shown in Fig. 4. As we can see from the figures, Mn addition
has a significant effect on the microstructure of the coating surface. The
grain boundary can be obviously observed on the Zn coating surface, but
not clearly for the Zn–0.5Mn coating. Fig. 4(c) and (d) shows the EDS
mapping of the Mn and O elements on the Zn–0.5Mn coating, which
indicates the uniform distribution of the Mn element throughout the
surface. The content of Mn in the Zn–0.5Mn coating surface is around
8.4 wt.% measured by the EDS mapping, much higher than the Mn con-
tent of the as-prepared Zn–0.5Mn alloy. The result is consistent with the
previous test by EDS line scanning (see Fig. 3).
The XRD patterns for the as-dipped pure Zn and Zn–0.5Mn coating
surfaces are shown in Fig. 5. Indexing of the XRD pattern indicates
that the Zn coating contains Zn, ZnO and Zn–Fe phases, and the Zn–
0.5Mn coating contains Mn, Zn, and Zn–Fe phases and Mn oxides
(for example, MnO). The Mn oxides formed on the Zn–0.5Mn coating
surface is responsible for tuning the surface color of the coating (see
Fig. 1), as discussed previously. Zn–Fe phases are present in both pure
Zn and Zn–0.5Mn coatings, which can be explained that the iron diffuses
from the steel matrix to the molten Zn bath and forms Fe–Zn phases,
particularly FeZn13 phase, in the molten Zn, and the FeZn13 phase ad-
heres to the coating surface.
The formation of Mn oxides at the surface of Zn–0.5Mn coatings
could be related to the unevenly distributed Mn in the Zn melt. Mn is
a surface active element in the molten Zn, which tends to migrate to
the surface from the bulk to form a Mn-rich layer at the surface of the
molten Zn. The Mn content at the surface of molten Zn could be more
than 10 times higher than that inside the melt and will be oxidized pref-
erentially due to the direct air exposure [29,30]. Hence, a Mn oxide film
could be easily formed on the surface of the coating when withdrawing
the steel from the molten Zn–0.5Mn alloy at the high temperature.
(b)
η-Zn
ζ-FeZn13
10 µm
60 Y. Wang, J. Zeng / Surface & Coatings Technology 245 (2014) 55–65
Fig. 7. (a) XPS survey spectra and (b) the high resolution Mn 2p spectra for the ζ-layer of the Zn coatings.
In order to observe the microstructure of the ζ layer of the coating,
the coating was polished down to the ζ layer by means as described
in the Experimental section. Fig. 6 shows the corresponding ζ-layer
microstructures of Zn and Zn–0.5Mn coatings. It appears that the ζ-
layer of the Mn-free Zn coating still contains discrete Zn phase which
is surrounded by bulky FeZn13 phases. The ζ-layer of the Zn–0.5Mn
coating also contains FeZn13 phase and Zn phase, but the sizes of the
FeZn13 phase are much smaller than the FeZn13 phase in pure Zn coat-
ing. This is consistent with the cross-section observation of the coating
in Fig. 3. The EDS analysis determined that the Fe content is around
6.8 wt.% in the FeZn13 phase of the pure Zn coating which is very close
to the theoretical content of 6.2 wt.%. The Fe and Mn contents were
estimated by the EDS analysis at around 4.4 wt.% and 2.1 wt.% in the
FeZn13 phase of the Zn–0.5Mn coating. This is in line with the previous
elemental analysis of the FeZn13 phase in the cross-sectional microanal-
ysis (see Table 2). Same as previous discussion, partial Fe sites in FeZn13
phase were substituted by Mn to form ζ-(Fe,Mn)Zn13 phase.
Fig. 7(a) shows the XPS survey spectra for the ζ layers of the pure Zn
and Zn–0.5Mn coatings. Similar to the surface of the as-dipped Zn coat-
ings, the Mn peaks can only be observed in ζ layer of Zn–Mn coating,
and all other peaks are like for both Zn and Zn–Mn coatings, including
Fe peaks which are not present in the surface of all as-dipped Zn coat-
ings. The high resolution XPS spectra of Mn 2p are shown in Fig. 7(b).
The Mn 2p3/2 peak has the binding energy at around 640.7 eV, slightly
shifted from higher binding energy of Mn oxides, which may be as-
cribed to Mn metal [23]. The XRD patterns of the ζ layers of Zn and
Zn–0.5Mn coatings are shown in Fig. 8. Indexing of the XRD pattern in-
dicates that the ζ layer of Zn and Zn–0.5Mn coatings mainly contain
FeZn13 and Zn phases. However, no Mn-containing phases could be
distinguished in the XRD patterns, while the EDS analysis in Fig. 3
shows the existence of Mn. This is most likely due to the formation of
Fig. 8. XRD patterns of the ζ layer-exposed (a) pure Zn coating and (b) Zn–0.5Mn coating.
(Fe,Mn)Zn13 phase which has the non-distiguishable XRD pattern as
the FeZn13 crystal, and the low contents of Mn oxides and Mn contained
alloys which are below the XRD detection limit, if they do exist in the
ζ layer of Zn–0.5Mn coating.
3.2. The corrosion properties
The Tafel polarization curves of the as-dipped and the ζ layer-
exposed Zn coatings with different Mn additions in 3.5% NaCl solution
are shown in Fig. 9. The corresponding polarization parameters such
as corrosion potential (Ecorr), corrosion current (Icorr), anodic polariza-
tion slope (βa) and cathodic polarization slope (βc) for the as-dipped
and the ζ layer-exposed Zn coatings are shown in Tables 3 and 4,
respectively.
The data in Table 3 reveal that the corrosion potentials (from
− 0.996 to − 0.981 mV) of the as-dipped Zn coatings with different
Mn contents are significantly higher than that (− 1.039 mV) of the
pure Zn coating. This seems to be opposite to the typical findings in elec-
trodeposition obtained Zn–Mn coatings where the corrosion potential
became more negative with Mn addition since Mn is electrically a
more negative element than Zn [15,31]. However, in our case, all the
as-dipped samples were not further polished to remove the oxide film
on the coating surface which actually provided an additional protection
layer to the as-dipped specimen. Mn oxides may provide higher passiv-
ating potential which therefore lifts the apparent corrosion potential
for those Zn–Mn coatings. This could also contribute to the slightly
increased corrosion potential for the Zn coating with higher Mn addi-
tion, as shown in Table 3, due to higher content of Mn oxides and film
thickness. As for the corrosion current of the as-dipped Zn coating, it
decreases with the increasing of Mn addition. The corrosion current of
the as-dipped pure Zn coating is 2.32 × 10−5 A·cm−2 which is much
 Y. Wang, J. Zeng / Surface & Coatings Technology 245 (2014) 55–65 61

Fig. 9. Tafel polarization curves of (a) the as-dipped and (b) ζ layer-exposed Zn coatings with different Mn additions in 3.5% NaCl solution.

higher than that of Zn–Mn coating (around 3.0 × 10−6 A·cm−2 despite modify its properties [21,32–34]. As a result, the Zn–Mn coatings had
the Mn levels). This to some extent proves that the Mn addition can sig- lower cathodic polarization slope than that of pure Zn coating.
nificantly inhibit the anodic dissolution of Zn. Comparing the Tafel On the other hand, the polarization data of the ζ layer of the coatings
slopes of the as-dipped Zn–Mn coatings shown in Table 3, one can easily with different Mn additions listed in Table 4 indicate no significant
conclude that Mn addition decreases the cathodic polarization slope of change of the corrosion current for the ζ layers and the corresponding
the as-dipped coating, while it has no significant effect on the anodic po- magnitudes for the Mn-added Zn coatings were increased significantly
larization slope. To explain the slope tendencies with Mn addition upon partially due to loss of the passivating layer protection of oxides. As
cathodic and anodic polarizations, one must understand the involved for the corrosion potential of the ζ layer, it also shows the increase
corrosion reactions first. with the Mn addition, but with minor difference. This may indicate
In dilute solutions of salts such as NaCl, the following anodic and ca- slight enhancement of the corrosion resistance for the Zn–Mn coating.
thodic reactions would take place during the polarization process, and In fact, such increase may be resulted from the oxides on the surface
ZnO, Zn(OH)2, MnO and Mn(OH)2 are the common corrosion products of ζ layer which was formed during the η layer removal process. How-
within which the oxides have been observed to be the primary ones ever the quantity of the oxides would be much lower so that slight effect
[22]. has been introduced. The possible existence of oxides also leads to the
relatively lower anodic current density in Zn–Mn coatings. Similar as
2þ −
Anode : Zn→Zn þ 2e ð1  aÞ the observation for the as-dipped coatings, the anodic polarization
slopes for the ζ layer exposed specimens are almost identical. From
2þ − these results, it could be concluded with caution that the Mn addi-
Mn→Mn þ 2e ð1  bÞ
tion would possibly provide further positive anodic protection to the
Cathode : O2 þ 2H2 O þ 4e →4OH
− −
ð2Þ ζ layer from corrosion.
Although the data in Table 4 shows that the cathodic polarization
2þ −
slope also decreases with Mn addition to the Zn coating, the variation
Zn þ 2OH →ZnðOHÞ2 ð3  aÞ is smaller and the value is larger compared to those for the as-dipped
coatings. In fact, the cathodic polarization curves for all four specimens
2þ − are quite overlapped with almost the same cathodic polarization behav-
Mn þ 2OH →MnðOHÞ2 ð3  bÞ
ior. From this point, no significant effect of Mn addition on the cathodic
performance could be concluded, partially because of the much lower
ZnðOHÞ2 →ZnO þ H2 O ð4  aÞ
Mn content in the ζ layer and direct exposure of Zn phase in the
ζ layer to the corrosion environment.
MnðOHÞ2 →MnO þ H2 O: ð4  bÞ The EIS spectra for the surfaces of Zn coatings with different contents
of Mn are shown in Fig. 10(a1–a3). In Fig. 10(a3), the maximum phase
The oxides and hydroxides formed on the coating surface actually angles of the Zn, Zn–0.2Mn, Zn–0.5Mn, and Zn–0.7Mn coatings are esti-
serve as a barrier protection for the coatings from further corrosion. Re- mated at −55°, −60°, −60°, and −65°, respectively; and in Fig. 10(a2),
gardless of the thickness, the oxide film layer will provide very close the high impedance values at low frequencies increase from 600, 1900,
protection against moderate range of anodic polarization. Therefore, 2600, to 3000 Ω·cm2 with the addition of more Mn content. The EIS
change of the corrosion rate will not be significantly different during spectra for the ζ layers are shown in Fig. 10(b1–b3). Different from
the anodic polarization whether or not the Zn coating contains Mn. In that evaluated for the surface layer, the high impedance value at low
contrast, the decrease of cathodic polarization slope could be due the frequencies for the ζ layer of the Zn coating seems not to change with
fact that ZnO is a semiconductor and doping, and Mn addition can Mn content and maintains around 500 Ω·cm2, which is aligned with

Table 3
The polarization data of the as-dipped Zn coatings with different Mn additions in 3.5% NaCl solution.

Coating Ecorr (V) Icorr (A·cm−2) Tafel slope βa (V/decade) Tafel slope βc (V/decade)

Zn −1.039 2.32 × 10−5 2.24 × 10−2 1.568

Zn–0.2Mn −0.996 3.79 × 10−6 2.14 × 10−2 0.401
Zn–0.5Mn −0.992 2.92 × 10−6 2.50 × 10−2 0.369
Zn–0.7Mn −0.981 2.85 × 10−6 2.61 × 10−2 0.466
62 Y. Wang, J. Zeng / Surface & Coatings Technology 245 (2014) 55–65

Table 4
The polarization data of the ζ layer-exposed Zn coatings with different Mn additions in 3.5% NaCl solution.

Coating Ecorr (V) Icorr (A·cm−2) Tafel slope βa (V/decade) Tafel slope βc (V/decade)

Zn −1.050 1.46 × 10−5 2.53 × 10−2 1.16

Zn–0.2Mn −1.021 1.21 × 10−5 2.42 × 10−2 1.12
Zn–0.5Mn −1.013 1.10 × 10−5 2.65 × 10−2 0.92
Zn–0.7Mn −1.006 1.12 × 10−5 2.21 × 10−2 0.75

the conclusion of almost constant corrosion current for the ζ layer in the
above polarization tests.
The EIS spectra of the surface and ζ layer can be interpreted in terms
of the equivalent circuit as shown in Fig. 11. In this model, Rs corre-
sponds to the resistance of the solution, Cdl to the double-layer ca-
pacitance, and Rct to the charge-transfer resistance. The parameters of
Rpr and Cpr element are related to the resistance and capacity of the
corrosion products. The impedance of a phase element is defined as
ZCPE = [C(jw)n]−1, where 0 ≤ n ≤ 1. ZCPE represents an ideal capacity
of an interface when n = 1, and an ideal resistance of an interface
when n = 0. For the corrosion impedance, the value of n is associated
with the coating and affected by many factors, such as surface heteroge-
neity, Mn oxide film, and so on.
Table 5 summarizes the resistance, capacitance and n values of
the coating surface by fitting the model described in Fig. 11 to the
corresponding EIS spectra. The value that is normally correlated with
the corrosion rate is the polarization resistance (Rp = Rct + Rpr). The
polarization resistances of the as-dipped coatings for Zn, Zn–0.2Mn,
Zn–0.5Mn, Zn–0.7Mn are 697, 2129, 3013, and 4040 Ω·cm2, respective-
ly, which indicates that the polarization resistance of the as-dipped
coating increases with Mn addition. Similarly, the corresponding
model fitted data for the ζ layer are listed in Table 6. As we can see
from the data, there is no significant variation in Rct and Rpr with the
increasing of Mn addition, where the polarization resistances (Rp) of
ζ layers are about 550 Ω·cm2. The EIS results indicate that Mn addition
can significantly improve the corrosion resistance of the surface of the
as-dipped Zn coating, but has a little effect on the corrosion resistance
of the ζ layer in the coating.
High resolution XPS spectra of Zn 2p and Mn 2p for pure Zn and Zn–
0.5Mn coatings after Tafel polarization corrosion are shown in Fig. 12. As

Fig. 10. EIS spectra of (a1–a3) the as-dipped and (b1–b3) ζ layer-exposed Zn coatings with different Mn additions in 3.5% NaCl solution.
 Y. Wang, J. Zeng / Surface & Coatings Technology 245 (2014) 55–65 63

Fig. 11. Equivalent circuit model used to fit EIS spectra.

we can see from Fig. 12(a), all the Zn 2p peak shifted from 1022.1 eV
(which is associated with ZnO) to roughly 1022.8 eV after the polariza-
tion tests. The binding energy of 1022.8 eV is belonging to Zn(OH)2 — a
corrosion product on the coating surface [22]. Similarly, the binding
energy of Mn 2p3/2 peak for the Zn–0.5Mn coating after corrosion test
increases from 641.4 eV (ascribed to MnO) to 642.5 eV, as shown in
Fig. 12(b), which indicates the formation of Mn(OH)2 on the coating
after corrosion [23].
SEM micrographs of the surfaces of as-dipped Zn and Zn–0.5Mn
coatings after Tafel polarization tests were used to inspect the morpho-
logical changes, which are presented in Fig. 13. Significant differences
could be identified between the presented surface corrosion micro-
graphs of the as-dipped Zn and Zn–0.5Mn coatings. Pitting corrosion
can be observed anywhere in the pure Zn coating, while dense corrosion
products can be found on the Zn–0.5Mn coating with few pitting corro-
sion. The ZnO tends to form a porous film on the coating surface and
allows the anions and cations to transport through the pores. The corro-
sion of Zn in deep site of the pores would have higher chance to contin-
ue and therefore results in the so-called pitting corrosion in the pure Zn
coating. But for the coatings with Mn addition, the MnO formed on the
surface tends to be more compact and dense, and leaves very few local
pores. Therefore much less pitting corrosion could be observed on the
as-dipped Zn–0.5Mn coating surface after polarization tests. It seems
that the dense corrosion products formed on the Zn–0.5Mn coating
could inhibit further pitting corrosion and therefore improve the corro-
sion resistance of the coating.
Similarly, slight enhancement of corrosion resistance of ζ layer by
Mn addition can also be visually observed by the SEM corrosion micro-
graphs of ζ layers for the Zn and Zn–0.5Mn coatings after the Tafel polar-
ization tests, as shown in Fig. 14. Possibly because of the relatively
higher corrosive resistance of the ζ-FeZn13 phase, corrosion tends to
be focusing on the Zn phase area so that deep cracks can be observed
on the ζ layer of the pure Zn coating, as shown in Fig. 14(a) and (b).
But still corrosion cracks could also be found in the ζ-FeZn13 phase. On
the other hand, in Fig. 14(c) and (d), for the ζ layer of the Zn–0.5Mn
coating, pitting corrosion in the Zn phase can be observed, but no cracks
are visible in the FeZn13 phase. Interestingly, dense corrosion products
can also be found anywhere in the ζ phase of the Zn–0.5Mn coating.
As indicated by previous discussion, the formation of MnO would be
accounting for prevention of the FeZn13 phase from more serious corro-
sion. Due to the fact of more electrochemically active for Mn over
Zn [22], reaction (1-b) occurs prior to reaction (1-a). The preferential
dissolution of Mn can provide an active protection layer of MnO to
avoid further anodic dissolution of Zn. Besides, because of the much
higher solubility product constants (Ksp) for Mn(OH)2 [35], hydrolysis
of Mn2+ can be more difficult compared with Zn2+, which can reduce
the local acidification inside the pores and therefore further reduce
the anodic corrosion to prevent the pitting corrosion in the ζ-FeZn13

Table 5
The model fitted equivalent circuit components from the EIS spectra of the as-dipped Zn coatings with different Mn additions in 3.5% NaCl solution.

Coating Rs (Ω·cm2) Rpr (Ω·cm2) Cpr (Ω−1·cm−2·s−n) Rct (Ω·cm2) Cdl (Ω−1·cm−2·s−n)

CPE n1 CPE n2

Zn 7.4 471 2.5 × 10−5 0.83 226 2.8 × 10−3 0.95

Zn–0.2Mn 6.5 1414 2.1 × 10−6 0.76 715 0.9 × 10−3 0.87
Zn–0.5Mn 4.0 2283 3.9 × 10−6 0.70 730 1.2 × 10−3 0.94
Zn–0.7Mn 4.4 2260 3.1 × 10−6 0.75 1780 0.6 × 10−3 0.96

Table 6
The model fitted equivalent circuit components from the EIS spectra of the ζ layer-exposed Zn coatings with different Mn additions in 3.5% NaCl solution.

Coating Rs (Ω·cm2) Rpr (Ω·cm2) Cpr (Ω−1·cm−2·s−n) Rct (Ω·cm2) Cdl (Ω−1·m−2·s−n)

CPE n1 CPE n2

Zn 8.4 361 3.0 × 10−5 0.85 170 3.0 × 10−3 0.93

Zn–0.2Mn 11.5 351 4.0 × 10−5 0.73 205 1.2 × 10−3 0.94
Zn–0.5Mn 12.0 367 3.1 × 10−5 0.83 180 1.9 × 10−3 0.95
Zn–0.7Mn 11.4 344 3.9 × 10−5 0.72 240 1.1 × 10−3 0.92
64 Y. Wang, J. Zeng / Surface & Coatings Technology 245 (2014) 55–65

phase [22]. But the overall corrosion resistance would not be significant-
ly improved for the ζ-FeZn13 layer of Zn–0.5Mn coating due to the
presence of Zn phase, as evidenced by the Tafel polarization and EIS
data. For this reason, the Mn addition may have slight effects on improv-
ing the corrosion resistance of the ζ layer of Zn coatings.

4. Conclusions

The effects of Mn addition on the microstructures and corrosion per-

Fig. 12. The high resolution XPS spectra of (a) Zn 2p and (b) Mn 2p for the coatings after
Tafel polarization tests.
formance of both surface and ζ layer of the hot-dip Zn coatings have
been carefully investigated. The Mn oxide film can be easily formed on
the Zn–Mn coating surface during the hot dipping process. The surface
color of the coating is found varying with the dipping temperatures
and being attributed to the optical interference of the Mn oxide film.
The Mn distribution in δ layer is lower than that in the δ layer of the
hot-dip Zn–0.5Mn coating. Mn addition could lead to the increasing of
the δ layer thickness of the Zn coating. It is also found that Mn would re-
place partial Fe in the FeZn13 phase and change the FeZn13 phase from
the continuous columnar to discontinuous phase.
Both Tafel polarization and EIS tests indicate that Mn addition in the
coating can enhance the corrosion resistance of the as-dipped coatings.
The corrosion micrographs of the coating surfaces after the Tafel polar-
ization tests reveal the dense corrosion products formed on the surface
of the Zn–Mn coatings. It is assumed that the dense corrosion products
could inhibit the further pitting corrosion of the coating.
On the other hand, the corrosion potential of the ζ layer of the Zn
coating slightly increases with Mn addition, but the Mn addition has a
very limited effect on the corrosion current and impedance. As for the
ζ layers of both Zn and Zn–Mn coatings, the corrosion of Zn phase
seems to occur prior to the ζ phase. Dense corrosion products could
also be observed in the ζ phase of the coatings with Mn addition from
the SEM micrographs of the samples after polarization tests. To some
extent, Mn addition may help a little in the corrosion resistance of
ζ layer of the coating, but more investigation is needed.

(a) (b)

200 µm 10 µm

(c) (d)

200 µm 10 µm

Fig. 13. SEM micrographs of the surface of as-dipped (a, b) pure Zn coatings and (c, d) Zn–0.5Mn coatings after Tafel polarization tests; (b) and (d) are the magnified micrographs of se-
lected areas indicated by the red boxes in (a) and (c).
 Y. Wang, J. Zeng / Surface & Coatings Technology 245 (2014) 55–65 65

(a) (b)

ζ-FeZn13

20 µm 5 µm

(c) (d)

ζ-FeZn13

20 µm 5 µm

Fig. 14. SEM micrographs of the ζ layer of hot-dip (a, b) pure Zn coating and (c, d) Zn–0.5Mn coating after Tafel polarization tests; (b) and (d) are the magnified micrographs of selected
areas indicated by the red boxes in (a) and (c).

Acknowledgment [16] N. Boshkov, K. Petrov, S. Vitkova, G. Raichevsky, Surf. Coat. Technol. 194 (2005)
276–282.
[17] P. Díaz-Arista, Z.I. Ortiz, H. Ruiz, R. Ortega, Y. Meas, G. Trejo, Surf. Coat. Technol. 203
This work is financially supported by the Guangxi Natural Science (2009) 1167–1175.
Foundation with the granted number of 2011GXNSFF018001. Prof. [18] C. Müller, M. Sarret, T. Andreu, Electrochim. Acta 48 (2003) 2397–2404.
[19] D. Sylla, C. Savall, M. Gadouleau, C. Rebere, J. Creus, P. Refait, Surf. Coat. Technol. 200
Hongwei Liu and Xiyong Chen at the Guangxi University are very (2005) 2137–2145.
much appreciated for constructive discussion and advices to this work. [20] N. Pistofidis, G. Vourlias, S. Konidaris, E. Pavlidou, A. Stergiou, G. Stergioudis, Mater.
Lett. 60 (2006) 786–789.
[21] L.D. Ballote, R. Ramanauskas, P. Bartolo-Perez, Corros. Rev. 18 (2000) 41–52.
References [22] B. Zhang, H.B. Zhou, E.H. Han, W. Ke, Electrochim. Acta 54 (2009) 6598–6608.
[23] M.C. Biesinger, B.P. Payne, A.P. Grosvenor, L.W.M. Lau, A.R. Gerson, Appl. Surf. Sci.
[1] A.R. Marder, Prog. Mater. Sci. 45 (2000) 191–271. 257 (2011) 2717–2730.
[2] X.G. Zhang, Corrosion and Electrochemistry of Zinc, Plenum Press, New York, 1996. [24] M. Tomita, S. Yamamoto, C. Tominaga, US Patent 5, 160, 552, (1992).
[3] C.E. Jordan, R. Zuhr, A.R. Marder, Metall. Mater. Trans. A 28 (1997) 2695–2703. [25] M. Onishi, Y. Wakamatsu, H. Miura, Trans. Jpn. Inst. Met. 15 (1974) 331–337.
[4] Y. Adachi, M. Arai, Mater. Sci. Eng. A 254 (1998) 305–310. [26] G. Reumont, G. Dupont, P. Perrot, Z. Metallkd. 86 (1995) 608–613.
[5] C.E. Jordan, A.R. Marder, J. Mater. Sci. 32 (1997) 5593–5602. [27] V. Raghavan, J. Phase Equilib. 24 (2003) 556–557.
[6] T. Kato, K. Nunome, K. Kaneko, H. Saka, Acta Mater. 48 (2000) 2257–2262. [28] N. Gao, Y.H. Liu, N.Y. Tang, J. Phase Equilib. Diffus. 31 (2010) 523–531.
[7] J.H. Selverian, A.R. Marder, M.R. Notis, Metall. Trans. A 19 (1988) 1193–1203. [29] C. Wagner, J. Electrochem. Soc. 99 (1952) 369–380.
[8] D. Phelan, B.J. Xu, R. Dippenaar, Mater. Sci. Eng. A 420 (2006) 144–149. [30] C. Wagner, J. Electrochem. Soc. 103 (1956) 627–633.
[9] J.H. Selverian, A.R. Marder, M.R. Notis, Metall. Trans. A 20 (1989) 543–555. [31] M. Bučko, J. Rogan, S.I. Stevanović, S. Stanković, J.B. Bajat, Surf. Coat. Technol. 228
[10] N. Pistofidis, G. Vourlias, S. Konidaris, E. Pavlidou, G. Stergioudis, Mater. Lett. 61 (2013) 221–228.
(2007) 2007–2010. [32] H. Leidheiser, I. Suzuki, J. Electrochem. Soc. 128 (1981) 242–249.
[11] J.D. Culcasi, P.R. Sere, C.I. Elsner, A.R. Di Sarli, Surf. Coat. Technol. 122 (1999) 21–23. [33] J. Vilche, K. Jüttner, W. Lorenz, W. Kautek, W. Paatsch, M. Dean, U. Stimming,
[12] N.C. Hosking, M.A. Ström, P.H. Shipway, C.D. Rudd, Corros. Sci. 49 (2007) 3669–3695. J. Electrochem. Soc. 136 (1989) 3773–3779.
[13] N. Boshkov, K. Petrov, S. Vitkova, S. Nemska, G. Raichevsky, Surf. Coat. Technol. 157 [34] P. Sharma, A. Gupta, K. Rao, F.J. Owens, R. Sharma, R. Ahuja, J.O. Guillen, B. Johansson,
(2002) 171–178. G. Gehring, Nat. Mater. 2 (2003) 673–677.
[14] S. Chang, J.C. Shin, Corros. Sci. 36 (1994) 1425–1436. [35] D.R. Lide, CRC Handbook of Chemistry and Physics, 84th ed. CRC Press, Boca Raton,
[15] N. Boshkov, Surf. Coat. Technol. 172 (2003) 217–226. 2003.