coatings

Article
Effect of Hot-Dip Galvanizing Process on Selective
Oxidation and Galvanizability of Medium
Manganese Steel for Automotive Application
Zhang Chen 1,2 , Yanlin He 1,2, *, Weisen Zheng 1,2, *, Hua Wang 1 , Yu Zhang 3 and Lin Li 1,2
1 School of Materials Science and Engineering, Shanghai University, Shanghai 200044, China;
chenzhangvv@shu.edu.cn (Z.C.); wh225@shu.edu.cn (H.W.); liling@shu.edu.cn (L.L.)
2 State Key Laboratory of Advanced Special Steel, Shanghai University, Shanghai 200044, China
3 Ansteel Group Beijing Research Institute, Beijing 102211, China; zhangyu@ansteel.com.cn
* Correspondence: ylhe@t.shu.edu.cn (Y.H.); wszheng@shu.edu.cn (W.Z.)




Received: 2 December 2020; Accepted: 16 December 2020; Published: 21 December 2020


Abstract: A medium manganese steel with 7.5 wt.% Mn for automobile application was galvanized
in a continuous Hot Dip Galvanizing (HDG) simulator under different galvanizing conditions. It was
shown that the effects of dew point, annealing temperature and annealing atmosphere on the surface
oxidation of steel could be comprehensively evaluated by the consideration of oxygen partial pressure
P(O2 ). Although Mn2 SiO4 was a thermodynamic stable phase when P(O2 ) varied from 10−28 to
10−21 atm, it was difficult to form Mn–Si–O composite oxide because there was no enrichment of
silicon on the steel surface. So, this oxide was generally formed in the Fe substrate and had little effect
on the galvanizability. With the increase in P(O2 ) above 10−25 atm, MnO particles in the form of the
thermodynamic stable phase became coarser and tended to aggregate, which hindered the formation
of a continuous inhibition layer, resulting in the defects of bare spots on the galvanized surface of the
steel. When the oxygen partial pressure greater than 10−22 atm, film-like MnO layer was formed on
the surface of steel sample, which obviously deteriorated the galvanizability. The galvanizability of
the steel can be improved by the regulation of oxygen partial pressure; based on this, the reasonable
zinc plating process parameters can be developed.

Keywords: hot-dip galvanizing process; medium-manganese steel; oxygen partial

pressure; galvanizability

1. Introduction
In recent years, the realization of automotive lightweight and high safety is a trend in the
development of global automobile industry. As one of the third generation of advanced high
strength steel (AHSS), medium manganese steel has received great interest from researchers due
to its combination of high strength and plasticity, which is the result of the partition of carbon and
manganese composites and the regulation of metastable phases [1–3]. In order to enhance the stability
of austenite in medium-manganese steel, alloying elements such as Mn or Si are often added to the
steel. However, these alloying elements are easy to be oxidized in the hot-dip galvanizing annealing
process. The presence of film-like or granulated SiO2 and MnO surface oxides lead to deterioration of
the reactive wettability of liquid zinc and hindrance of the formation of Fe–Al–Zn inhibition layer,
thus worsening the quality of zinc coatings [4–8].
In the previous work, the effects of annealing process and composition on the selective oxidation
and galvanizability of advanced high-strength steel were investigated during a continuous hot-dip
galvanizing process. Maderthaner et al. [9] showed that for 1.5 Si–2.5 Mn high strength steel at the

Coatings 2020, 10, 1265; doi:10.3390/coatings10121265 www.mdpi.com/journal/coatings

Coatings 2020, 10, 1265 2 of 15

dew point of −30 and −58 ◦ C, the segregation of Mn and Si was significantly reduced at the lower
dew point. Moreover, the decrease in the dew point could convert the film-like oxides into particles
which was helpful in forming a continuous inhibition layer, say, the galvanizability of steel at lower
dew point would be better. On the contrary, Mousavi et al. [10] indicated that when the high strength
steel with a composition of 0.1 C–2 Mn–1.3 Si was annealed at the dew point of −50, −30, and +5 ◦ C,
the types of oxides formed on the surface were basically the same, but thick film-like oxides were
formed on the surface of steel annealed at the dew point of −50 ◦ C, and a large area of bare spots
appeared on the galvanized surface of this specimen. The surface quality of other specimen annealed
at higher dew point was better. So, it is obviously not enough to consider only the influence of dew
point on galvanizability for high strength steels. Recently, Pourmajidian et al. [11–13] studied the
effects of annealing temperatures, dew points and composition on the oxidation behavior and reactive
wetting of 0.1 C–6 Mn–2 Si steel. However, it was still difficult to find out the key factor that determines
the galvanizability of medium manganese steel and develop the reasonable galvanizing process
accordingly. Obviously, it could hinder the development and application of medium manganese steel.
Yang et al. [14] combined the experimental analysis and thermodynamic calculation to analyze
the effect of oxygen partial pressure on the formation of surface oxides in medium manganese
lightweight steel. It seems feasible to evaluate the galvanizability of experimental steel by calculating
the variation of oxide under different oxygen partial pressures. Based on this, the selective oxidation
and galvanizability of the medium manganese steel, which contains manganese and silicon, with a
more complex oxidization behavior were investigated in this work. Moreover, the relationship between
the oxygen partial pressure and galvanizability was attempted first to be established, which can
obtain the regulation method of the galvanizing process and provide a theoretical reference for
industrial production.

2. Materials and Experiments

The hot-dip galvanizing simulation experiment in this work is carried out on the Iwatani Surtec
hot-dip galvanizing simulator (Aichi, Japan). In addition, the process conditions for 0.2 C–7.5 Mn–0.2
Si (wt.%) steel used in the galvanizing simulation experiment are listed in Table 1.

Table 1. The annealing process of medium manganese steels.

No. Annealing Temperature/K Dew Point/◦ C H2 Content

1# 873 −10 20%
2# 5%
923 −10
3# 20%
4# −50
5# 1093 −10 20%
6# +10

The steel sheets used in this hot-dip galvanization are cut from the 1.2 mm thick as-received
cold-rolled sheets parallel to the rolling direction, with a size of 100 mm × 220 mm. The surfaces of
the sheets were washed with acetone and deionized water after the acid picking treatment, and then
polished with 4000 grit SiC paper to reduce the negative effect of surface roughness on the subsequent
galvanizing process. In this work, steel sheets were heated from room temperature to three different
annealing temperatures of 873 K (600 ◦ C), 923 K (650 ◦ C) and 1093 K (820 ◦ C) at a heating rate of 30 K/s,
held for 4 min, and subsequently cooled down to the dipping temperature of 733 K (460 ◦ C) at a cooling
rate of 20 K/s, respectively. A 1093 K annealing temperature, −10 ◦ C dew point and 20% H2 are the
frequently used parameters on the hot-dip galvanizing production line. Other parameters were set for
comparison in experiments, where −50 ◦ C is the lowest dew point that the galvanizing simulator can
reach. In addition, the steels annealed at 873 and 923 K have good mechanical properties, with the
tensile strength exceeding 1500 MPa and elongation exceeding 15% (the detailed study will be reported
Coatings 2020, 10, 1265 3 of 15
Coatings 2020, 10, x FOR PEER REVIEW 3 of 14

separately).
study will beAllreported
sheets were immersedAll
separately). in the liquid
sheets wereZnimmersed
bath containing
in the0.2 wt.%Zn
liquid Al bath
for 3 scontaining
before a final
0.2
rapid cooling to room temperature.
wt.% Al for 3 s before a final rapid cooling to room temperature.
Anti-rust
Anti-rust oil
oil is
is applied
applied toto the
the surface
surface ofof galvanized
galvanized steel
steel sheet
sheet to
to prevent
prevent surface
surface oxidation
oxidation inin
the
the subsequent experimental analysis. The dimension of all specimens for microscopic observation is
subsequent experimental analysis. The dimension of all specimens for microscopic observation is
10 mm × 10 mm. The specimens used to observe the oxidation were cut from the
10 mm × 10 mm. The specimens used to observe the oxidation were cut from the clamping ends whichclamping ends which
had
had not
not been
been immersed
immersed in in the
the zinc
zinc bath,
bath, while
while the
the specimens
specimens used
used toto observe
observe thethe interfacial
interfacial layer
layer
between the zinc coating and matrix were cut from the location covered with
between the zinc coating and matrix were cut from the location covered with zinc coating,zinc coating, which should
which
be removed
should before the
be removed observation.
before The sampling
the observation. positionposition
The sampling is shownisin Figurein1.Figure 1.
shown

Figure 1. Sampling diagram of galvanizing steel.

Figure 1. Sampling diagram of galvanizing steel.

In this
In this work,
work, aa Hitachi
Hitachi S-570S-570 field
field emission
emission scanning
scanning electron
electron microscope
microscope (FE-SEM,
(FE-SEM, Tokyo,Tokyo,
Japan) was used to observe the morphology of the oxide and
Japan) was used to observe the morphology of the oxide and inhibition layer on the inhibition layer on the surface
surface of
of
specimens, and
specimens, and equipped
equipped energyenergy dispersive
dispersive spectroscopy
spectroscopy (EDS) (EDS) was was used
used to
to analyze
analyze the the surface
surface
elements. Bellhouse et al. [15] pointed out that the zinc layer could be
elements. Bellhouse et al. [15] pointed out that the zinc layer could be removed by using fuming removed by using fuming
HNO33,, however
HNO however it it had
had been
been shown
shown thatthat the
the corrosion
corrosion time
time was
was difficult
difficult to
to control
control due
due to
to its
its excessive
excessive
corrosivenessin
corrosiveness inactual
actualoperation.
operation.Therefore,
Therefore,ininthis
thiswork,
work,thethe surfaces
surfaces of of
thethe specimens
specimens were were wiped
wiped by
by absorbent cotton dipped in 38% HCl solution for about 3 to 4 s until the
absorbent cotton dipped in 38% HCl solution for about 3 to 4 s until the Fe–Al–Zn layer appears. Fe–Al–Zn layer appears.
The Helios
The Helios 600i
600i focused
focused ion ion beam
beam (FIB,
(FIB, FEI,
FEI, Waltham,
Waltham, MA, MA, USA)
USA) is is used
used to
to prepare
prepare specimens
specimens
for the
for the transmission
transmission electron
electron microscope
microscope (TEM)
(TEM) to to observe
observe thethe microstructure
microstructure of of the
the interfacial
interfacial layer
layer
between the zinc coating and the substrate. The zinc coating was stripped
between the zinc coating and the substrate. The zinc coating was stripped to let its thickness be to let its thickness be
controlled within
controlled within 1nm
1nm to to facilitate
facilitate ion
ion beam
beam cutting,
cutting, andand all
all specimens
specimens are protected by
are protected Pt plating.
by Pt plating.
The JEOL-2100 field emission transmission electron microscope (Tokyo, Japan) was used in this work,
The JEOL-2100 field emission transmission electron microscope (Tokyo, Japan) was used in this work,
the accelerating
the accelerating voltage
voltage was was 200200 kV,
kV,and
andthe
theEDS
EDSenergy
energyspectrum
spectrumbeam beamspot spotsize
sizewas
was11nm. nm.

3. Experimental Results
3.

3.1.
3.1. Surface Structure of Samples
Samples Annealed
Annealed at
at Different
Different Annealing
Annealing Temperatures
Temperatures
Figure
Figure2 2shows
showsmacroscopic-profiles
macroscopic-profilesof theofgalvanized surfaces of
the galvanized steel samples.
surfaces of steelThesamples.
experimental The
dew point anddew
experimental H2 content
point andof the three samples
H2 content of the three −10 ◦ C and
were samples were20%,
−10respectively,
°C and 20%,while the annealing
respectively, while
temperatures
the annealing were separately
temperatures setseparately
were as 873, 923 setand 1093923
as 873, K and
for sample 1#, sample
1093 K for 3# and 1#,
5#.3#Itand
can5#.
be Itseen
can
that the quality
be seen that theofquality
the galvanized coating on
of the galvanized the surface
coating on the ofsurface
sampleof 5#sample
is far worse
5# is than the other
far worse thantwo the
samples.
other twoThe zinc coating
samples. on the
The zinc surface
coating on of
thesample
surface 1#ofis sample
complete 1#and smooth without
is complete and smoothobvious bare
without
spot, as shown
obvious in Figure
bare spot, 2a. Ainsmall
as shown number
Figure of aggregated
2a. A small number of bare spots could
aggregated be spots
bare observed
couldonbethe surface
observed
of
onsample 3#, ofofwhich
the surface samplethe3#,
maximum
of whichdiameter
the maximumis about 3 mm, as
diameter shown3in
is about Figure
mm, 2b. It can
as shown be found
in Figure 2b.
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that the steel sheet will exhibit better galvanizability under the annealing process with lower annealing
Coatings 2020, 10, x FOR PEER REVIEW 4 of 14
It can be found that the steel sheet will exhibit better galvanizability under the annealing process with
temperature by comparing three samples above.
lower annealing temperature by comparing three samples above.
It can be found that the steel sheet will exhibit better galvanizability under the annealing process with
lower annealing temperature by comparing three samples above.

Figure
Figure 2. Surfaces
Surfaces ofof hot-dip
hot-dip galvanized
galvanized samples
samples annealed
annealed at
at different
different temperatures.
temperatures. (a)
(a)1#
1#(873
(873K),
K),
(b)Figure
3# (923
(b) 3# (9232. Surfaces
K), (c) 5# of hot-dip
(1093
5# (1093 K). galvanized samples annealed at different temperatures. (a) 1# (873 K),
(b) 3# (923 K), (c) 5# (1093 K).
Figure 33 shows
Figure showsthe theSEMSEMmicrographs
micrographsofofsurface
surfaceoxides
oxidesofof samples
samples 1#,1#,
3# 3#
andand5#,5#, respectively.
respectively. It
It can
can bebeFigure
seen
seen 3
that shows
that
thethe the SEM
surface
surface micrographs of surface
compositionofofspecimens
composition oxides
specimensannealed of samples
annealedatat873 1#, 3# and
873KKisisclose 5#, respectively.
closetotothat
thatofofthe
thematrix,It
matrix,
and
andcan be seen
there
there that theno
is almost surface
oxidecomposition
formed on theof specimens annealed
surface. While
While shown
shownat 873 inKFigure
in is close3b,
Figure to that
3b, fineof the matrix,
oxide particles
particles
canand
be there is
observed almost
can be observed on the on no
the oxide
surface formed
of on
sample the
3#. surface.
When While
the shown
annealing in Figure
temperature 3b,
When the annealing temperature rises to 1093 K, fine
rises oxide
to particles
1093 K, itit can
can
can be
be observed observed
observed that that theon the
the size surface
size ofof the of sample
the oxide 3#.
oxideparticles When
particleson onthe the annealing
thesurface
surfaceof ofthe temperature
thesample
sample5# rises to
5#increases 1093 K, it can
increasessignificantly,
significantly,
be
andbeaobserved
layer of that the size
obvious of theoxide
film-like oxideisparticles
formed, onwhich
the surface
covers ofthe
thesubstrate
sample 5# increases
surface. Thesignificantly,
EDS analyses
and a layer of obvious film-like oxide is formed, which covers the substrate The EDS analyses
and a layer of obvious film-like oxide is formed, which covers the substrate surface. The EDS analyses
in Figure 3 show
in show thatthatsurface
surfaceoxides
oxidesofofthree
threesamples
samplesare areallall
MnO,MnO, and andthethe
content
contentof manganese
of manganese in thein
in Figure 3 show that surface oxides of three samples are all MnO, and the content of manganese in
oxide
the layer
oxide increases
layer from
increases 5.5 to
from 5.530.6 wt.%
to 30.6 withwith
wt.% the increase
the increase in annealing
in annealing temperature.
temperature.
the oxide layer increases from 5.5 to 30.6 wt.% with the increase in annealing temperature.

Figure 3.SEM
Figure SEMmicrographs
micrographs and and EDS
EDS analyses
analyses of of surface
surfaceoxides
oxidesofof
ofsamples
samplesannealed at at
annealed different
different
Figure 3. SEM micrographs and EDS analyses of surface oxides samples annealed at different
temperatures. (a) 1# (873 K), (b) 3# (923 K), (c) 5# (1093 K).
temperatures. (a)
temperatures. (a) 1#
1# (873
(873 K),
K), (b)
(b) 3#
3# (923
(923 K),
K), (c)
(c) 5#
5# (1093
(1093 K).
K).

3.2.
3.2. SurfaceStructure
Surface StructureofofSamples
SamplesAnnealed
Annealed at Different Dew Dew Points
Points
3.2. Surface Structure of Samples Annealed at Different Dew Points
Figure
Figure 4 showsmacroscopic
4 shows macroscopicprofiles
profilesofofthe
thegalvanized
galvanizedsurfaces
surfaces of
of steel
steel samples
samples after
after annealing
annealing at
at Figure
1093 K 4 shows
in the samemacroscopic
reductive profiles of the
atmosphere of galvanized
20% H surfaces of steel samples after annealing
2−80% N2, but under different dew points (DP)
1093 K in the same reductive atmosphere of 20% H2 −80% N2 , but under different dew points (DP)
at 1093 K −10
in the same reductive atmosphere of 20% H2−80% N2, but under different dew points (DP)
as as −50,
−50, −10 andand +10 ◦°C,
+10 respectively.
C, respectively. The
The zinc
zinccoating
coatingisisrelatively
relativelyuniform
uniform without
withoutlarge bare
large barearea
area
as formed
−50, −10onand +10 °C,
thesurface respectively.
surfaceofofsample
sample 4#, The zinc
4#, there
there are coating
are aa small is relatively uniform without large bare area
formed on the small number
numberofofconcentrated
concentratedacicular
acicularbare spots
bare spots
formed onasthe
instead, surface
shown of sample
in Figure 4a. In4#, there are
addition, for asample
small 5#
number
annealedof concentrated
with −10 °C DP,acicular bare
there are spots
a few
instead, as shown in Figure 4a. In addition, for sample 5# annealed with −10 ◦ C DP, there are a few
instead, as shown in Figure 4a. In addition, for sample 5# annealed with −10 °C DP, there
zinc coatings on the surface, as shown in Figure 4b. When the dew point increases to +10 °C, it can be are a few
zinc coatings on the surface, as shown in Figure 4b. When the dew point increases to +10 ◦ C, it can be
zinc coatings
seen on the4csurface,
from Figure that theas shownquality
coating in Figure 4b.sample
of the When6# theisdew pointdeteriorated
seriously increases tofor
+10 °C, it bare
a large can be
seen from Figure 4c that the coating quality of the sample 6# is seriously deteriorated for a large bare
seen from
area Figure
exists in the4csample
that the coating quality of the sample 6# is seriously deteriorated for a large bare
surface.
area exists in the sample surface.
area exists in the sample surface.
Coatings 2020, 10, 1265
x FOR PEER REVIEW 5 of 14
15
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.
Figure 4. The surface of hot-dip galvanized samples annealed at different dew points.
.
. (a) 4# (−50 °C),
Figure
(b) 5# 4. The
(−10 °C),surface
(c) 6# of hot-dip
(+10 °C). galvanized samples annealed at different dew points. (a) 4# (−50 ◦ C),
Figure 4. The surface of hot-dip galvanized samples annealed at different dew points. (a) 4# (−50 °C),
(b) 5#Figure ◦ C),
(−10 4. The(c)
surface
6# (+10 ◦ C).
of hot-dip galvanized samples annealed at different dew points. (a) 4# (−50 °C),
(b) 5# (−10 °C), (c) 6# (+10 °C).
(b) 5# (−10 °C), (c) 6# (+10 °C).
Figure 5 shows the SEM micrographs of surface oxides of sample 4#, 5# and 6#. It is shown that
Figure 5 shows the SEM micrographs of surface oxides of sample 4#, 5# and 6#. It is shown that as
as theFigure
dew point increases
5 shows
Figure 5 shows the SEM
the from
SEM −50 to +10of°C,
micrographs
micrographs the size
surface of of
oxides the
of oxide
sample particles
4#, 5# andonIt6#.
the Itsurface
is shown of that
the
the dew point increases from −50 to +10 ◦ C, of
thesurface
size ofoxides
the oxide sample 4#,
particles 5#
onand
the6#. is shown
surface of thethat
samples
samples
as the increases
dewdew
as the point
pointsignificantly,
increases
increasesfrom and
from−50 densely
−50 to
to +10 distributed
°C,the
+10 °C, thesize film-like
sizeofofthethe oxides
oxide
oxide are
particles
particles gradually
on surface
on the formed.
the surface The
of theof the
increases significantly, and densely distributed film-like oxides are gradually formed. The oxide in
oxide in Figure
samples 5a issignificantly,
increases
samples increases scattered on and
significantly, the
andsurface
denselyof
densely the substrate,
distributed
distributed while
film-like
film-like the oxide
oxides
oxides are are film in formed.
Figure
gradually
gradually 5c covers
formed.
The The
Figure 5a is scattered on the surface of the substrate, while the oxide film in Figure 5c covers the entire
the entire
oxide
oxide substrate
in Figure
in Figure issurface.
5a 5a is scatteredon
scattered onthe
the surface
surface of
ofthe
thesubstrate,
substrate, while thethe
while oxide filmfilm
oxide in Figure 5c covers
in Figure 5c covers
substrate surface.
the entire substrate surface.
the entire substrate surface.

Figure 5. SEM micrographs and EDS analyses of surface oxides on the steel surface of samples
Figure 5. SEM micrographs and EDS analyses of surface oxides on the steel surface of samples annealed
Figure 5. SEM
annealed micrographs
at different and EDS
dew points. (a) 4#analyses of 5#
(−50 °C), (b) surface oxides
(−10 °C), on the
(c) 6# (+10 °C). steel surface of samples
at different dew points. (a) 4# (−50 ◦ C), (b) 5# (−10 ◦ C), (c) 6# (+10 ◦ C).
annealed
Figure 5.atSEM
different dew points.
micrographs and(a)EDS4# (−50 °C), (b)
analyses of 5# (−10 °C),
surface (c) 6#on
oxides (+10
the°C).
steel surface of samples
3.3. Surface
3.3. Surface
annealed atMicrostructure
Microstructure
different dewinin Different
Different
points. (a)HH 2 Content Atmospheres
4#Content
(−50 °C),Atmospheres
(b) 5# (−10 °C), (c) 6# (+10 °C).
2
3.3. Surface Microstructure
Figure in Different
6 shows macroscopic H2 Content
profiles Atmospheres
of the galvanized surfaces of two medium Mn steel samples
Figure 6 shows macroscopic profiles of the galvanized surfaces of two medium Mn steel samples
3.3. Surface
after Microstructure
having been annealed in Different
at 923 K H 2 Content
under the Atmospheres
same −10 °C DP but different reductive Mn atmospheres
after Figure
having6beenshows macroscopic
annealed at 923 profiles
K underofthe thesame
galvanized
−10 ◦ C surfaces of two medium
DP but different steel samples
reductive atmospheres of
of 5% H2 and 20% H2, respectively. Concentrated pinhole-like bare spots distribute linearly in local
after having
Figure
5% Harea 6been
showsannealed
macroscopicat 923 K under
profiles ofthe
thesame −10
galvanized °C DP but
surfaces different
of two reductive
medium Mn atmospheres
steel samples
2 and 20% H 2 , respectively. Concentrated pinhole-like bare spots distribute
of both two samples. Morphologies of surface oxides on samples 2# and 3# are observed by SEM linearly in local area
of 5% having
after
of both H2 and 20% annealed
been H2, respectively.
at 923 KConcentrated
under pinhole-like
theoxides
same −10 °C DP bare
but spots3#distribute
different reductivelinearly in local
atmospheres
andtwo
EDS,samples.
as shownMorphologies
in Figure 7, the of surface
average diameter ofon samples
surface 2#inand
oxide sample are
2# observed by SEM
is bigger than that and
area
of of
5% both
H two samples. Morphologies of surface oxides on samples 2# and
shown3#.in Figure 7, the average diameter of surface oxide in sample 2# is bigger than in
EDS,inassample
2 and 20% H 2 , respectively. Concentrated pinhole-like bare spots 3# are
distribute observed
linearly by SEM
local
that in
and EDS,
area of 3#.
sample as shown in Figure 7, the average diameter of surface oxide in sample
both two samples. Morphologies of surface oxides on samples 2# and 3# are observed by SEM 2# is bigger than that
in sample
and EDS, 3#. as shown in Figure 7, the average diameter of surface oxide in sample 2# is bigger than that
in sample 3#.

Figure 6. Surfaces of hot-dip galvanized samples annealed in different H2 content atmospheres. (a) 2#
(5% H2), (b) 3# (20% H2).

Figure 6. 6. Surfaces
Surfaces ofof
hot-dip galvanized
hot-dip samples
galvanized annealed
samples in different
annealed H2 content
in different atmospheres.
H2 content (a) 2#
atmospheres.
(5%
(a) H
2# ),
(5% (b)
H 3#),
Figure 6. Surfaces
2 2 (20%
(b) 3#H ).
(20%
2 H ).
of hot-dip2galvanized samples annealed in different H2 content atmospheres. (a) 2#
(5% H2), (b) 3# (20% H2).
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Figure7.7.SEM
Figure SEMmicrographs
micrographs and
and EDS
EDS analyses
analyses of
ofsurface
surfaceoxides
oxidesofofsamples
samplesannealed in in
annealed different H2 H
different 2
content atmospheres. (a) 2# (5% H2), (b) 3# (20% H2).
content atmospheres. (a) 2# (5% H2 ), (b) 3# (20% H2 ).

Accordingtotothe
According theabove
aboveexperimental
experimental analyses,
analyses,the themain
maintype typeofofoxide
oxide formed
formed ononthethe
surfaces of of
surfaces
experimental steel is MnO. With the increase in annealing temperature
experimental steel is MnO. With the increase in annealing temperature and dew point, the amount and dew point, the amount
of oxides becomes more, while the contrary occurs when the H2 content increases from 5% to 20%. It
of oxides becomes more, while the contrary occurs when the H2 content increases from 5% to 20%.
is difficult to find oxide particles on the surface of sample 1#. On the surfaces of samples 3#, 4# and
It is difficult to find oxide particles on the surface of sample 1#. On the surfaces of samples 3#, 4# and
2#, oxide particles are relatively larger and more densely distributed, which leads to the tendency of
2#, oxide particles are relatively larger and more densely distributed, which leads to the tendency
aggregation into film-like oxides. On the surfaces of samples 5# and 6#, there are much larger film-
of aggregation into film-like oxides. On the surfaces of samples 5# and 6#, there are much larger
like oxides.
film-like oxides.
Correspondingly, with the change of oxide morphology and distribution, the zinc coating
Correspondingly,
quality of the experimental with the change
steel samples of oxide morphology
is different. Sampleand distribution,
1# with a few oxidesthe zinc
has nocoating
defectsquality
of
ofbare
the experimental
spots. Relatively steel samples
larger oxide is particles
different.lead Sample 1# with a few
to pinhole-like bareoxides
spots onhasthe
nosurface
defectsof ofsamples
bare spots.
Relatively
3#, 4# andlarger oxidea particles
2#. When dense layer lead of to pinhole-like
oxide bare spots
film is formed on theon the surface
surface of samples
of 5# and 3#, 4#
6# samples, and 2#.
a large
When a dense layer of oxide film is formed on the surface
area of bare area appears which means a serious deterioration of coating quality. of 5# and 6# samples, a large area of bare
area appears which means a serious deterioration of coating quality.
4. Discussion
4. Discussion
4.1. Thermodynamic Analysis on the Oxide Formation of Experimental Steel during Annealing
4.1. Thermodynamic Analysis on the Oxide Formation of Experimental Steel during Annealing
The formation of oxides on experimental steel was thermodynamically analyzed based on the
workTheofformation
Suzuki et of al.oxides on experimental
[16]. According to Suzuki steel
et was
al., itthermodynamically
was assumed that local analyzed based on the
thermodynamic
work of Suzuki et al. [16]. According to Suzuki et al., it was assumed
equilibrium was established between the oxide layer and metal ion diffusion layer of experimental that local thermodynamic
equilibrium
steel duringwas established
the annealing between
process. the oxide layer
In calculation, and metal iondata
the thermodynamic diffusion layer
of ferrite, of experimental
austenite as well
steel during
as oxide the annealing
phases are provided process. In calculation,
by the databases TCFE9 the andthermodynamic
SSUB6 in the commercial data of software
ferrite, austenite
Thermo- as
Calc
well as(Version: 2018b),
oxide phases arerespectively.
provided by Allthethedatabases
oxide reactions
TCFE9inand theSSUB6
calculation
in theare consideredsoftware
commercial to be
taking place (Version:
Thermo-Calc during high temperature
2018b), annealing
respectively. Allbecause
the oxide thereactions
dipping time
in thein the Zn bath isare
calculation very short.
considered
Based place
to be taking the onduring
previous high study [14], for annealing
temperature aluminum-containing
because thelight steel,time
dipping the oxygen
in the Zn partial
bath is
pressure
very short. is the major factor that determines the type and morphology of oxides on the surface of the
steel samples. In present work, according to Formulas (1) and (2) [17],
Based the on previous study [14], for aluminum-containing light steel, the oxygen partial pressure the oxygen potential
corresponding
is the major factor to annealing process the
that determines can betypeobtained as shown in of
and morphology Table 2. on the surface of the steel
oxides
samples. In present work, according to Formulas 26176 (1) and (2) [17], the oxygen potential corresponding
log P O 6.00 2 log 𝑃 H O ⁄P H (1)
to annealing process can be obtained as shown𝑇 in Table 2.
where T is the annealing temperature (K); P(H2) is the partial pressure of hydrogen; Psat(H2O) is the
26176
saturated vapor pressurelogofPH
(O2O.
2 )= 6.00 − + 2 log[ Psat (H 2 O)/P(H 2 )] (1)
T
The well-known equation for Psat(H2O) (saturated water vapor pressure) and DP follows:
where T is the annealing temperature (K); P(H2 ) is the partial pressure of hydrogen; Psat (H2 O) is the
9.8𝐷𝑃 13088
saturated vapor1pressure of H2 O. log𝑃 H 0.78 𝐷𝑃 0 ℃
273.15 𝐷𝑃
H O for Psat (H2 O) (saturated
log𝑃 equation 𝑇
The well-known
2 7.58𝐷𝑃 13088 water vapor pressure) and DP follows: (2)
log𝑃 H 0.78 𝐷𝑃 0 ℃
240
( 𝐷𝑃
9.8DP 𝑇13088
1 273.15+DP − T − log P ( H 2 ) + 0.78 DP ≤ 0 °C
log Psat (H2 O) = (2)
2 7.58DP
240+DP − 13088
T − log P ( H 2 ) + 0.78 DP > 0 °C
Coatings 2020, 10, x FOR PEER REVIEW 7 of 14
Coatings 2020, 10, 1265 7 of 15
Table 2. Oxygen partial pressures at different annealing conditions.
Coatings 2020, 10, x FOR PEER REVIEW 7 of 14
No. pressuresP(O
Table 2. Oxygen partial 2)/atm annealing conditions.
at different
1# pressures1.72
Table 2. Oxygen partial × 10 annealing conditions.
at different
−28
No. P(O )/atm
2
3# 7.24 × 10−27
No.
1#P(O2)/atm −28
4#4.28×× 10
1.72 10−27
−26
3#1#
1.72××10
7.24 10−25
−28
2#1.16 × 10−26
4#3#
7.24××10
4.28 10−27
5#1.86
2#4# × 10
4.28××10
1.16
−22
10−25
−26

6#4.16
5#2# × 10
1.16××10
1.86 −22
−21
10−25
6#5# 4.16 × 10 −21
1.86 × 10−22
Combining the calculation results of6#oxygen partial
4.16 × 10pressure
−21 and experimental results of oxide
formation on steelthe
Combining samples, it is results
calculation not difficult to find
of oxygen that as
partial P(O2) increases,
pressure the surface
and experimental oxidation
results of
of oxide
the Combining
experimental the calculation results of oxygen partial pressure and experimental results of oxide
formation on steelsteel becomes
samples, obvious.
it is not In to
difficult order
findto further
that as P(Oanalyze the oxidation behavior of steel
2 ) increases, the surface oxidation of the
formation
samples duringonthe
steel samples, it
annealing is not difficult
process, the to find
type and that as P(Oof
content 2) increases, the surface oxidation of
oxides corresponding to different
experimental steel becomes obvious. In order to further analyze the oxidation behavior of steel samples
the experimental steel becomes obvious. In order to further analyze the oxidation behavior of steel
oxygen partial pressures are thermodynamically calculated, as shown in Figure 8.
during the annealing process, the type and content of oxides corresponding to different oxygen partial
samples during the annealing process, the type and content of oxides corresponding to different
pressures arepartial
oxygen thermodynamically calculated, as shown
pressures are thermodynamically in Figure
calculated, 8. in Figure 8.
as shown

Figure
Figure 8. Variation
8. Variation
Figure ofofthe
8. Variation ofthe
theformation
formationofof
formation oxide
ofoxide with oxygen
oxide with
with oxygenpotential
oxygen potential
potential pressure
pressure obtained
obtained
pressure by
by by
obtained
thermodynamic
thermodynamic calculation.
calculation.
thermodynamic calculation.
As shown
As shownin Figure 8, the
in Figure mass
8, the mass fraction
fractionofof oxide formedon
oxide formed onthethesurface
surface of each
of each sample
sample can be
can be
As shownand
obtained,
in Figure
then the
8,content
the mass
of
fraction
oxide can
ofcompared
be
oxide formed in
on9.the
Figure It
surface
is shown
of each
that with
sample
the
can be
oxygen
obtained, and then the content of oxide can be compared in Figure 9. It is shown that with the oxygen
obtained, and
partial then the
pressure content
rising, of oxide canformed
be compared in Figure 9. It is shown that with the oxygen
partial pressure rising, thethe oxide
oxide firstly
firstly formed isisMn Mn22SiO
SiO44(TEPHROITE)
(TEPHROITE) andand
subsequently
subsequentlyMnO. MnO.
partialMoreover,
pressurethe rising,
mass the oxide
fraction of firstly
the two formed
oxides is Mn
will 2SiO
also 4 (TEPHROITE)
increase with the and subsequently
increase in oxygen MnO.
partial
Moreover, the mass fraction of the two oxides will also increase with the increase in oxygen partial
Moreover, the and
pressure, mass thefraction
content of MnOthe two oxides
is much will than
greater also that
increase
of Mnwith
2SiO4. the increase in oxygen partial
pressure, and the content of MnO is much greater than that of Mn2 SiO4 .
pressure, and the content of MnO is much greater than that of Mn2SiO4.

Figure 9. Comparison of the content of oxide on the samples according to thermodynamic calculation.

Figure
Figure9.9.Comparison
Comparisonof
ofthe
thecontent
contentofofoxide
oxideon
onthe
thesamples
samplesaccording
accordingtotothermodynamic
thermodynamiccalculation.
calculation.
Coatings 2020, 10, 1265 8 of 15

It is clear in Figure 9, there would be no oxide formation on the surface of sample 1#, while the
amount of manganese oxides formed on the surface of samples 3#, 4# and 2# increases as oxygen
partial pressure changes from 7.24 × 10−27 to 1.16 × 10−25 atm. Under the oxygen partial pressure
of 1.86 × 10−22 and 4.16 × 10−21 atm for samples 5# and 6#, it can be seen that the amount of oxides
on the surface of these two samples reaches the maximum. The presence of a large number of stable
oxides would form oxide layers. Moreover, as pointed by many authors [11,18,19], film-like MnO is
more likely to cause surface defects with a deterioration of the quality of zinc coating than that of
granulated oxide.
In addition, according to the EDS analysis of the surfaces of steel samples shown in
Figures 3, 5 and 7, the manganese contents under different oxygen partial pressures can be obtained,
as shown in Table 3.

Table 3. EDS analyses results of manganese contents on the surfaces of 1#–6# samples.

Sample No. P(O2 )/atm Mangnese Content/wt.%

1# 1.72 × 10−28 5.5
3# 7.24 × 10−27 11.7
4# 4.28 × 10−26 12.7
2# 1.16 × 10−25 23.3
5# 1.86 × 10−22 30.6
6# 4.16 × 10−21 35.3

It is shown that with the increase in oxygen partial pressures, the content of manganese becomes
higher correspondingly. It is not difficult to find out that under the condition of higher oxygen partial
pressure, the enrichment of manganese on the surface is more obvious, resulting in the higher content
of MnO formed. It should be noted that there is no silicon enrichment on the surface which probably
caused by the low content of 0.2 wt.% Si in the steel matrix. Therefore, although the Mn2 SiO4 is also
thermodynamic stable, the Mn–Si–O complex oxide is difficult to form on the surface of steel sample.

4.2. Analysis of Interfacial Microstructure of Experimental Steel

The result of the thermodynamic calculation shows that the oxides of experimental steel are
composed of MnO and Mn2 SiO4 . Moreover, the amount of oxide increases with the increase in
oxygen partial pressure. In addition, the amount of MnO is much larger than that of Mn2 SiO4 ,
and the Mn–Si–O complex oxide is difficult to form on the surface of steel sample. As is well known,
when the steel is dipped in the zinc bath, MnO and Mn2 SiO4 can react with aluminum in liquid zinc
(aluminothermic reduction). Obviously, in order to reduce a large number of oxides, more aluminum
would be consumed which hinders the formation of an Fe–Al–Zn intermetallic compound and leads
to the formation of Fe–Zn brittle phases. A good zinc coating would be obtained while there is a
continuous distributed inhibition layer formed on the surface of steels. If a large amount of oxides are
formed on the surface of the steel sheet, it will prevent the zinc liquid from contacting the steel sheet,
which is not conducive to the formation of the inhibition layer. Therefore, the inhibition layers of the
six samples were analyzed in order to further clarify the formation of surface oxides of experimental
steel under different oxygen partial pressures.
Figure 10 shows the microstructures of the inhibition layer of all six samples. For sample 1# under
the lowest oxygen partial pressure, the inhibition layer at the steel substrate/Zn coating interface is
composed of regular cubic crystals of an Fe–Al–Zn intermetallic compound with a thickness of only
tens to hundreds of nanometers, which can effectively hinder the formation of Fe–Zn brittle phases
and improve the adhesion of the coating for sample 1#. There are coarsened inhibition layer particles
which appear on the surfaces of samples 3#, 4# and 2#, which are still finely and tightly distributed,
and thus there is no large area of bare spot defect, as shown in Figure 10b–d. The distribution of the
inhibition layer of samples 5# and 6# under higher oxygen partial pressure is discontinuous, so that
 Coatings 2020, 10, x FOR PEER REVIEW 9 of 14

four samples stated above, especially for sample 6# under the highest oxygen partial pressure, where
a large area of the bare matrix can be seen on the surface.
Coatings 2020, According
10, 1265 to the analysis above, it is not difficult to find that with the increase in the oxygen 9 of 15
partial pressure, the amount of oxides increases, and the particle size of the inhibition layer on the
surface of the steel continues to coarsen, which leads to a decrease in the coverage of the inhibition
the coverage
layer. Toof further
the inhibition layer
investigate the is significantly
effect of surface lower
oxide on than
the that
zinc of the other
coating layer,four samples stated
the interface
above, microstructure
especially forbetween
samplethe 6# Zn coating/Fe
under substrates
the highest of samples
oxygen 1#,pressure,
partial 4#, 5# andwhere
6# under different
a large area of the
oxygen partial pressures were analyzed by transmission electron microscopy. The results are shown
bare matrix can be seen on the surface.
in Figures 11–14.

Figure Figure
10. SEM 10. micrographs
SEM micrographs andand EDSEDS analysesof
analyses of the
the inhibition
inhibition layer onon
layer thethe
steel/coating interfaces
steel/coating interfaces of
of all samples. (a) 1#, (b) 3#, (c) 4#, (d) 2#, (e) 5#, (f) 6#.
all samples. (a) 1#, (b) 3#, (c) 4#, (d) 2#, (e) 5#, (f) 6#.
Figure 11 shows TEM analysis of the coating/substrate interface of sample 1# under the 1.72 ×
According to the analysis above, it is not difficult to find that with the increase in the oxygen
10−28 oxygen partial pressure. It can be seen from the element distribution in Figure 11a,b that the
partial entire
pressure, the amount
cross-section of oxides
is composed increases,
of a zinc and thelayer
layer, inhibition particle size ofThe
and matrix. thefine
inhibition
particles oflayer
the on the
surfaceFeof2Al
the steel
5Zn continues
0.5 inhibition to coarsen,
layer whichand
are uniformly leads to adistributed
tightly decrease inonthe thecoverage
surface toofform
the inhibition
a good layer.
inhibition
To further layer with
investigate a thickness
the effect of about
of surface 116 nm.
oxide A very
on the zincsmall
coatingamount of fine
layer, MnO particles
the interface are
microstructure
between distributed above the inhibition
the Zn coating/Fe layer,ofwith
substrates a diameter
samples of about
1#, 4#, 5# and 78 nm. When combined
6# under different with
oxygenthe partial
thermodynamic calculation results in Figure 8, MnO is not a thermodynamic stable phase, so it
pressures were analyzed by transmission electron microscopy. The results are shown in Figures 11–14.
contains a negligible amount.
FigureFigure
11 shows12 showsTEMTEManalysis
analysis ofof thethe coating/substrate
coating/substrate interfaceinterface
of sample of sample
4# under 4.281#
× 10under
−26 the
1.72 × 10 −28
oxygenoxygen partial pressure.
partial pressure. It can
The thickness be inhibition
of the seen from theofelement
layer sample 4# distribution
is about 113 in
nm,Figure
which 11a,b
is that
the entire cross-section
almost the same asis composed
that of sample of1#.aHowever,
zinc layer, as inhibition
shown in Figure layer12c,
andMnO matrix. Theformed
particles fine particles
in of
sample 4# are coarser than those in sample 1#, and its diameter is about 120
the Fe2 Al5 Zn0.5 inhibition layer are uniformly and tightly distributed on the surface to form a good nm. MnO particles with
bigger
inhibition sizewith
layer are aformed in the
thickness of Fe 2Al5Zn0.4 inhibition layer, thereby hindering the continuous
about 116 nm. A very small amount of fine MnO particles are
distribution of the inhibition layer and causing the bare area on the surface. In addition, consistent
distributed above the inhibition layer, with a diameter of about 78 nm. When combined with the
with the prediction of thermodynamic calculation, a small amount of Mn2SiO4 oxide can be found
thermodynamic calculation
beside the steel substrate,results in Figure
as shown in Figure8, MnO is nothas
12e, which a thermodynamic stable phase, so it contains
little effect on galvanizability.
a negligible amount.
Figure 12 shows TEM analysis of the coating/substrate interface of sample 4# under
4.28 × 10−26 oxygen partial pressure. The thickness of the inhibition layer of sample 4# is about
113 nm, which is almost the same as that of sample 1#. However, as shown in Figure 12c, MnO particles
formed in sample 4# are coarser than those in sample 1#, and its diameter is about 120 nm. MnO particles
with bigger size are formed in the Fe2 Al5 Zn0.4 inhibition layer, thereby hindering the continuous
distribution of the inhibition layer and causing the bare area on the surface. In addition, consistent with
the prediction of thermodynamic calculation, a small amount of Mn2 SiO4 oxide can be found beside
the steel substrate, as shown in Figure 12e, which has little effect on galvanizability.
Coatings 2020, 10, 1265 10 of 15

Coatings 2020, 10, x FOR PEER REVIEW 10 of 14

Figure
Figure 11.11.(a)
(a) TEM
TEM analysis
analysis of
ofthe
theZn Zncoating/Fe
coating/Fe substrate interface
substrate of the
interface of galvanized sample1#.
the galvanized (b)
sample1#.
(b)cross-sectional
cross-sectionalelemental
elementalmaps
mapsofofthe thearea.
area.(c)(c)
Dark
Darkfiled image
filed imageand diffraction
and pattern
diffraction of of
pattern thethe
oxide
oxide
particle
particle correspondingtotozone
corresponding zoneAAin in(a).
(a). (d)
(d) Dark
Dark filed
filed image
imageand
anddiffraction
diffractionpattern ofof
pattern the inhibition
the inhibition
layer corresponding to zone B
layer corresponding to zone B in (a).in (a).

Figure 13 shows TEM analysis of the coating/substrate interface of sample 5# under

1.86 × 10−22 oxygen partial pressure. It can be seen from Figure 13a that MnO oxide particles on the
surface are coarsened and aggregated, so there is a tendency to form film-like oxides in local areas.
The size of manganese oxide particles is further increased, with a diameter of about 182 nm, as shown
in Figure 13c. Under the manganese oxide layer, there are abnormally grown grains with a size of
about 500 nm in the inhibition layer. Large particles of Mn2 SiO4 oxide with a size of about 190 nm are
formed in the Fe substrate. In addition, it can be observed that an Fe–Al–Zn intermetallic compound
is formed at the grain boundaries and extended into the Fe substrate, and the Fe–Zn intermetallic
compound is adjacent to Fe2 Al5 Zn0.4 layer. These results indicate that the zinc liquid could penetrate
into the iron substrate, and part of the Fe–Al–Zn phase transform into an Fe–Zn phase due to the
depletion of Al participating in aluminothermic reduction [20], the reaction equation is as follows:

3MnO + 2[Al] → [Mn] + Al2 O3 (3)

Figure 14 shows TEM analysis of the coating/substrate interface of sample 6# under

4.16 × 10−21 oxygen partial pressure. The surface manganese oxide particles are further coarsened,
with a size of about 420 nm, forming a dense MnO oxide layer on the surface with a thickness of
about 450 nm, which cannot be reduced by the aluminothermic reduction. The surface film-like oxides
completely block the contact between the zinc liquid and the substrate, so there is almost no formation
of inhibition layer. Meanwhile, Mn2 SiO4 is also found in the steel substrate due to the enrichment of
silicon on the steel surface.
Figure 11. (a) TEM analysis of the Zn coating/Fe substrate interface of the galvanized sample1#. (b)
cross-sectional elemental maps of the area. (c) Dark filed image and diffraction pattern of the oxide
Coatings
particle2020, 10, 1265
corresponding 11 of 15
to zone A in (a). (d) Dark filed image and diffraction pattern of the inhibition
layer corresponding to zone B in (a).

Figure 12. (a) TEM analysis of the Zn coating/Fe substrate interface of the galvanized sample 4#.
(b) cross-sectional elemental maps of the area shown in (a). (c) Dark filed image and diffraction pattern
of the oxide particle corresponding to zone A in (a). (d) Dark filed image and diffraction pattern of the
inhibition layer corresponding to zone B in (a). (e) Dark filed image and diffraction pattern of the oxide
particle corresponding to zone C in (a).

According to the above analysis results, it is not difficult to find that the galvanizability of
experimental steel with the lowest dew point (sample 4#) or the highest dew point (sample 6#) is not
the best, while the galvanizability of the steel (sample 2#) with the lowest H2 content is not the worst,
and the annealing temperature also cannot determine the galvanizability. The effect of annealing
process parameters on the galvanizability of experimental steel can be comprehensively evaluated using
oxygen partial pressure. For the experimental steel, it is shown that under a low oxygen partial pressure
of about 10−28 atm, manganese oxide particles in the form of the metastable phase are formed on the
surface in a small amount and the inhibition layer is uniformly and tightly distributed on the surface,
and then the ideal galvanizability of steel can be acquired. As the oxygen partial pressure increases to
higher than 10−25 atm, the manganese oxide particles are thermodynamic stable. So, its precipitation
constantly enlarges and aggregates on the surface, distributing continuously and tending to form an
oxide film. When the oxygen partial pressure is greater than 10−22 atm, the equilibrium phase content
of MnO is obviously higher than other samples. It is difficult for the aluminothermic reduction to
manganese oxide particles is further increased, with a diameter of about 182 nm, as shown in Figure
13c. Under the manganese oxide layer, there are abnormally grown grains with a size of about 500
nm in the inhibition layer. Large particles of Mn2SiO4 oxide with a size of about 190 nm are formed
in the Fe substrate. In addition, it can be observed that an Fe–Al–Zn intermetallic compound
Coatings 2020, 10, 1265 12 of 15
is
formed at the grain boundaries and extended into the Fe substrate, and the Fe–Zn intermetallic
compound is adjacent to Fe2Al5Zn0.4 layer. These results indicate that the zinc liquid could penetrate
into reduce
the irona large number of manganese oxides, these film-like MnO hinder the formation of the inhibition
substrate, and part of the Fe–Al–Zn phase transform into an Fe–Zn phase due to the
layer and deteriorate the galvanizability. Based on the above discussion, it is shown that the dew point,
depletion of Al participating in aluminothermic reduction [20], the reaction equation is −28as follows:
the annealing temperature and H2 content can be regulated to reach a condition below 10 oxygen
partial pressure, the solution of ideal3MnO + 2[Al] →of[Mn]
galvanizability medium
+ Almanganese
O
2 3 steel can be obtained. (3)

Figure
Figure (a) TEM
13. TEM
13. (a) analysis
analysis of the
of the ZnZn coating/Fesubstrate
coating/Fe substrateinterface
interface of
of the
the galvanized
galvanized sample
sample5#.5#. (b)
(b) cross-sectional
cross-sectional elemental
elemental mapsmaps of the
of the area
area showninin(a).
shown (a). (c)
(c) Dark
Darkfiled
filedimage
image and
anddiffraction pattern
diffraction pattern
of the
of the oxide
oxide particle
particle correspondingto
corresponding tozone
zone A A in
in (a).
(a).(d)
(d)Dark
Darkfiled image
filed image andand
diffraction pattern
diffraction of of
pattern
the inhibition layer corresponding to zone B in (a). (e) Dark filed image and diffraction pattern of the
the inhibition layer corresponding to zone B in (a). (e) Dark filed image and diffraction pattern of the
oxide particle corresponding to zone C in (a). (f) Dark filed image and diffraction pattern of the Fe-Zn
intermetallic corresponding to zone D in (a).
oxygen partial pressure. The surface manganese oxide particles are further coarsened, with a size of
about 420 nm, forming a dense MnO oxide layer on the surface with a thickness of about 450 nm,
which cannot be reduced by the aluminothermic reduction. The surface film-like oxides completely
block the contact between the zinc liquid and the substrate, so there is almost no formation of
Coatings 2020, 10, 1265 13 of 15
inhibition layer. Meanwhile, Mn2SiO4 is also found in the steel substrate due to the enrichment of
silicon on the steel surface.

Figure 14.
Figure (a)TEM
14. (a) TEManalysis
analysisofof the
the ZnZn coating/Fe
coating/Fe substrate
substrate interface
interface of the
of the galvanized
galvanized sample
sample 6#.
6#. (b)
(b) cross-sectional elemental maps of the area shown in (a). (c) Bright filed image and diffraction
cross-sectional elemental maps of the area shown in (a). (c) Bright filed image and diffraction pattern pattern
of the oxide particle
of particlecorresponding
correspondingtotozonezoneAAinin(a).
(a).(d)
(d)Bright
Brightfiled image
filed imageand diffraction
and pattern
diffraction of the
pattern of
oxide
the particle
oxide corresponding
particle to zone
corresponding B in B
to zone (a).
in(e)
(a).Bright filed filed
(e) Bright image and diffraction
image pattern
and diffraction of theof
pattern oxide
the
particle
oxide corresponding
particle to zone
corresponding toCzone
in (a).
C in (a).

5. Conclusions
According to the above analysis results, it is not difficult to find that the galvanizability of
experimental
Based onsteel with the lowest
thermodynamic dewof
analysis point
oxide(sample 4#) or
formation in the highest
annealingdew point the
process, (sample 6#)partial
oxygen is not
the best, while the galvanizability of the steel (sample 2#) with the lowest H content
pressure P(O2 ) can be used to comprehensively evaluate the effects of dew point, annealing temperature
2 is not the worst,
and
and the annealing
annealing temperature
atmosphere alsosurface
on the cannotoxidation
determineofthe galvanizability.
steel samples. Under The different
effect of annealing
process parameters
conditions, on the galvanizability
the thermodynamic stable oxides of formed
experimental
on the steel can be comprehensively
experimental evaluated
steel are consistently MnO
using
and Mn oxygen
2 SiO4 ,partial
and thepressure.
content For the experimental
of MnO is much higher.steel,
Asitoxygen
is shown that under
partial a low
pressure oxygenthere
increases, partial
is
pressure of aboutof
an enhancement 10equilibrium
−28 atm, manganese oxide particles in the form of the metastable phase are formed
precipitation of MnO accordingly.
on the surface
With the in a smallinamount
increase oxygenand the inhibition
partial pressure,layer is uniformly
the content and tightlyindistributed
of manganese on the
the steel surface
surface,
increasesand then the ideal During
correspondingly. galvanizability of steelthe
the annealing, can be acquired.
formation As the
of MnO oxygen
is caused bypartial pressure
the enrichment
increases
of manganese to higher thansurface.
towards 10−25 atm, the manganese
However, oxide
since there is noparticles
enrichmentare thermodynamic
of silicon on thestable. So, its
steel surface,
it is difficult to form a Mn–Si–O composite oxide. Composite oxides are generally formed in the Fe
substrate and have little effect on the galvanizability.
When the value of oxygen partial pressure is about 10−28 atm, there is no thermodynamic
stable oxide, the ideal galvanizability of steel can be obtained because its continuous inhibition layer
distributes on the surface. As P(O2 ) increases over 10−25 atm, MnO is a thermodynamic stable phase.
The oxide particles become coarser with a rise in their number and tend to aggregate, which has an
adverse effect on the formation of a continuous inhibition layer, resulting in the defects of bare spots
on the surface of the steel. When the oxygen partial pressure is greater than 10−22 atm, a film-like
Coatings 2020, 10, 1265 14 of 15

MnO layer is formed on the surface of steel sample, which obviously deteriorates the galvanizability.
The galvanizability of the steel can be improved by the regulation of oxygen partial pressure, therefore,
the reasonable zinc plating process parameters can be developed.

Author Contributions: Conceptualization, Y.H. and Z.C.; methodology, Y.H.; software, Z.C.; validation, Z.C.;
formal analysis, H.W.; investigation, Z.C.; resources, Y.H.; data curation, W.Z.; writing—original draft preparation,
Z.C.; writing—review and editing, Z.C.; visualization, Y.Z.; supervision, L.L.; project administration, Y.H.;
funding acquisition, Y.H. All authors have read and agreed to the published version of the manuscript.
Funding: This work is financially supported by the National Key R&D Program of China (2017YFB0304402) and
the National Natural Science Foundation of China (51971127).
Conflicts of Interest: The authors declare no conflict of interest.

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