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2nd International Conference on New Material and Chemical Industry (NMCI2017) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 292 (2018) 012101 doi:10.1088/1757-899X/292/1/012101
1234567890‘’“”

Galvanealed coating evolution for hot forming steel

F Fang1, X F Du and Y M Chen

Research and Development Center, Wuhan Iron and Steel Co., Wuhan, 430080, China
1
E-mail: [email protected]

Abstract. The aim of the galvanealing experiments with three parameters of dew point,
protective atmosphere and galvanealing time was to monitor the changes in coating quality and
the evolution of coating after hot forming. The results show that, the three parameters have
little effect on coating weight (thickness), and the average iron amount was within 9.51 to
14.9 %. The ζ, δ and Γ phase for the as-received galvanealed samples transformed to Γ-
Fe4Zn9and α-Fe (Zn) after reheating. The existence of a thin film of Γ-Fe4Zn9 increases the
electrochemical potential to the base steel by a good amount and will not generate LME.

1. Introduction
Corrosion resistance and the avoidance of scale formation during the heating of the material are the
main drivers for the development of new coatings for hot stamping [1].Currently there are three
industrial relevant coating systems available in producing hot forming steel: Zinc, Aluminum/Silicon
and x-tec. The friction coefficient of Al-Si coated steel was generally higher and unstable due to
galling of the Al-Si coating on the tool [2]. Moreover, it is not sufficient in corrosive protection for Al-
Si coated steel sheets to be applied to wet under body areas, compared with galvanized or
galvannealed steel sheets [3, 4].X-tec is a paint system based on nanotechnology which avoids scale
formation during heating but offers only a limited corrosion resistance for the formed component. The
coating can be used for both process variants of hot stamping [5].
Zinc coated hot forming steels offer the chance to have cathodic corrosion protection as an
advantage compared to today’s standard applications with uncoated and AlSi coated materials. To
utilize all the potential of the coating it is favourable to have at least a little amount of Γ-Fe4Zn9 in the
coating. This increases the electrochemical potential to the base steel by a good amount [6]. In which,
galvanealing (Zn-Fe coating) is a well knownalloying process whereby zinc from the galvanizecoating
and iron from the steel substrate combine in various zinc-iron intermetallic phases.Previous research
work [7-9] have mentioned the primary factors appear to be alloyingtime, alloying temperature, steel
chemistry and pot aluminum. But the effect of dew point and protective atmosphere on the coating
thickness and structure change also needs more attention. It is essential to permitthe alloying process
to achieve desired coating thickness with proper alloying phases in avoiding "powdering" or flaking
when the finished product is subjected to forming operations.
Despite of the industrial application of hot stamping for almost 20 years, there isstill only one base
material that is used for this application, the boron alloyed steel 22MnB5. Therefore, by changing dew
point, protective atmosphere and alloying time, the steel of 22MnB5 was used in the paper to study
their effect on the thickness and structure of Zn-Fe coating.

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Published under licence by IOP Publishing Ltd 1
2nd International Conference on New Material and Chemical Industry (NMCI2017) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 292 (2018) 012101 doi:10.1088/1757-899X/292/1/012101
1234567890‘’“”

2. Experimental procedure
The hot forming steel used in the paper was industrially produced with a regular cold-rolled mill finish
to thickness of 1.5mm. The material chemistry was 22MnB5 (0.22C-0.25Si-1.35Mn-0.003B, wt%)
with a small amount of Cr and Ti to achieve the desirable mechanical properties.
The galvannealed samples were conducted on Iwatani-Surtec HDPS simulator. The coupons
comprised 110mm  220mm with the long axis parallel to both the rolling and dipping directions,
cleaned and dried per standard practice [10]. The samples were assembled to perform the following
processes: heating by rate of 5 ℃/s to 800 ℃, with slow cooling rate of 4 ℃/s and fast cooling rate of
30 ℃/s to 475 ℃, dipping in the zinc bath with temperature stabilized at 460 ℃, after cooling by
wiping knife, the hot dipped samples were reheated to 500 ℃ and cooling by rate of 10 ℃/s to room
temperature. Changing the dew points from -50 to 30 ℃, protective atmosphere contents from 5 to
30 %H2-N2 and galvanealing time from 5 to 15 s to study their effects on coating quality. The
galvanealed samples will be reheated on 910 ℃ for 5 min, and hot formed after that to analyze the
coating evolution.
Surface state (zinc coating weight and thickness), average iron content of samples galvanealed by
the simulator were analyzed by Glow Discharge Optical Emissivity Spectroscopy (GDOES) using a
Horiba Jobin- Yvon Profiler. Coating quality and reactive wetting were assessed by the counting of
bare spots and bare spot area in the uniform 90mm 90mm coating area of the coated panel [11].
Samples were also taken from this area for SEM (HITACHI-S-4300) examination of the
coating/substrate interfacial layer.

3. Results and Discussions

3.1. Effect of galvanealing parameters on coating weight (thickness)

It is widely accepted that dew point affect greatly the selective oxidation formed on the steel surface
during annealing, the increase of dew point will transfer the external oxidation to inner oxidation
which will contribute to galvanizing [12]. However, the results obtained in the experiment displayed
that the change of dew point has no significant effect on coating weight, as shown in figure 1a. When
dew point changed from dry to moist (-60 to 30 ℃), the coating weight was among 46.2 and 59.2 g/m2,
and coating thickness was among 6.66 and 8.25 μm. Although there is a minute difference of coating
weight and thickness, the trend is not regular.
However, when controlling the H2 content from 5 to 30%, as shown in figure 1b, the coating
weight and thickness decreased from 84.15 to 53 g/m2 and from 12 to 7.63 μm, respectively.
Especially, the trend become obvious when H2 content was above 20%, which enlarge the Hydrogen
reduction ability on steel surface to suppress the diffusion of Fe and alloying elements from steel to
coat.
70 9 90 13 55 8.5

(a) (b) 12
(c)
80 54
Coating weight, g/m2

8
Coating thickness, m

Coating thickness, m
Coating thickness, m

Coating weight, g/m2

Coating weight, g/m2

60 11 8.0
70 53
7 10
60 52
50 9 7.5
6 coating weight
50 coating thickness 51 coating weight
coating weight 8
coating thickness coating thickness
40 5 40 7
-60 -40 -20 0 20 40 50 7.0
5 10 15 20 25 30 5 10 15
Dew point,℃
Atmosphere, H2% Galvanealing time, s

Figure 1. Coating weight and thickness controlled by:

(a) dew point, (b) H2 content, (c) galvanealing time detected by GDOES.
Generally, the coating weight increase with longer dipping and reheating (galvanealing) time, as
shown in figure 1c, the trend is obvious. The specific data showed that, the coating weight and
thickness decreased from 50.6 to 54 g/m2 and from 7.37 to 8 μm, respectively. Although the trend is

2
2nd International Conference on New Material and Chemical Industry (NMCI2017) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 292 (2018) 012101 doi:10.1088/1757-899X/292/1/012101
1234567890‘’“”

obvious, the differences were not large enough to specify if there is a relationship of galvanealing time
with coating weight, but the phase structure may differentiate with the time, which will be discussed
next.

3.2. Effect of galvanealing parameters on iron content

The iron amount has a close relationship with phase structure for galvanealed coating. The average
content of iron amount was measured under different galvanealing parameters, as shown in figure 2.
When dew point changed from -60 to 30 ℃, the iron amount was within 9.67 and 10.9%; when H2
content changed from 5 to 30 %, the iron amount was within 9.51 and 10.3%; when galvanealing time
changed from 5 to 15 s, the iron amount was within 10.2 and 14.9%. All of the iron contents
correspond to the existence of ζ and δ phases in the coat, and the existence of Γ phase need further
analysis which will be shown later. The iron contents were stable by changing of dew point and H2
content, but increase with galvanealing time. So that, if the time increase further, the iron content will
reach another range and Γ phase will appear.
12 12 16
(a) (b) 15 (c)
Iron amount in coating, %
Iron amount in coating, %

Iron amount in coating, %

11 11 14
13
10 10 12
11
9 9 10
9
8 8
-60 -30 0 30 8
5 10 15 20 25 30 5 10 15
Dew point, ℃ Atmosphere, H2% Galvanealing time, s

Figure 2. Iron amount controlled by:

(a) dew point, (b) H2 content, (c) galvanealing time detected by GDOES.

3.3. Structure changes before and after hot forming process

The morphology of zinc coating before and after hot forming was analyzed by SEM shown in figure 3.
As the average iron content of coating was shown in figure 2, the detailed energy spectrum were
measured to make sure if there exists Γ phase. As shown in figure 3a, Spectrum 1 to 3 displayed iron
content as 5.87, 8.48 and 25.89 wt %, which correspond to ζ, δ and Γ phase. Combined figure 2 and
figure 3a, the amount of Γ phase was very little, which will not damage the whole coating affiliation
with steel matrix.
(a) (b) (c)

α-Fe (Zn) Γ-Fe4Zn9

ζ

Γ ZnO

Figure3.SEM Morphology of zinc coating before and after hot forming:

(a) beforeand (b) after hot forming, (c) elements distribution after hot forming.
The coating morphology and elements distribution after hot forming were shown in figure 3b and
3c. The coating generally contained two distinctive phases, i.e. the Zn-rich gamma phase (Γ-Fe4Zn9)
and Fe-rich alpha phase (α-Fe (Zn)). Surface oxidation occurred during annealing, leading to a surface
covered with ZnO (figure 3b). Coatings contained greater than 30 % Zn in α-Fe (Zn) which verified

3
2nd International Conference on New Material and Chemical Industry (NMCI2017) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 292 (2018) 012101 doi:10.1088/1757-899X/292/1/012101
1234567890‘’“”

cathodic protection potential through corrosion testing and electrochemical work. The coating become
thicker significantlyafter hot forming, caused by the elements in the matrix diffuse into the coating.
There is a thin film of Γ-Fe4Zn9distributed above α-Fe (Zn) phase, the little amount of Zn in the Γ
phase can not generate liquid metal brittlement (LME) in the later welding process. Also, as it was
mantioned in the beginning of the paper, the Γ phase increases the electrochemical potential to the
base steel by a good amount. However, the Zn coating can easily be oxidized in the reheating
procedure, the oxides need to be removed by shot blasting.

4. Conclusions
(1) The coating weight (thickness) measured by GDOES displayed that: the change of dew point has
no significant effect; the more H2 content, the thinner of coating thickness, especially when H2 was
above 20%; when galvanealing time was limited within 5 to 15 s, the differences were not large
enough to specify if there is a relationship of galvanealing time with coating weight;
(2) The average contents of iron amount were almost the same when changing dew point from -60
to 30 ℃ and H2 content from 5 to 30%, but increase obviously with the rising galvanealing time. The
iron amount was within 9.51 to 14.9 % for all the parameters, correspond to the existence of ζ and δ
phases;
(3) The result of energy spectrum for the different area of coat make sure that Γ phase exited on the
interface of coat and matrix. The three phases transformed to Γ-Fe4Zn9and α-Fe (Zn).

References
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[2] Sergej M 2015 5th International Conference Proceeding on Hot Sheet Metal Forming of High-
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Canada p 167-175
[3] Berto F 2016 International Journal of Fatigue 93(41) pp168-172
[4] Berto F 2015 Strength of Materials 47(5) pp 719-727
[5] Lenze F-J 2008 Proceedings of the 1st International Conference in Hot Sheet Metal Formingof
High-performance Steel (CHS2) Kassel Germany pp 15-21
[6] Thomas K 2015 5th International Conference Proceeding on Hot Sheet Metal Forming of High-
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