White Paper

R. Autengruber1 | J.Faderl1 | G. Luckeneder1

T. Kurz1 | K.H. Stellnberger1

Corrosion protection of galvanized

press-hardening steel: Main influencing
factors and mechanisms
1
voestalpine Stahl Linz, Austria | voestalpine Straße 3, 4020 Linz | Phone: 0043 50304 1577740 | Email: Gerald.Luckeneder@voestalpine.com

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Content
03 Abstract
04 01. Introduction
05 02. Experimental
02.01. Materials

02.02. Thermal Treatment

02.03. Test Specimens

02.04. Corrosion Test

06 02.05. Characterisation
07 03. Results and Discussion
03.01. Microstructure of Press Hardened Galvanized Steel Sheet before Exposure

08 03.02. Electrochemical Behaviour of Press Hardened Galvanized Steel

09 03.03. Cross Section Analyses of Corroded Press Hardened Galvanized Steel Sheet

10 03.04. Paint Creepage on Mechanical Defects

11 04. Conclusion
05. References

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abstract
Based on standard cyclic laboratory corrosion tests for automotive applications in Europe
(VDA 621-415 / EN ISO 11997/1 and VDA 233-102), the corrosion protection performance
of galvanized press-hardened steels was studied in unpainted and painted condition.
The results show, that the steel corrosion attack and paint creepage of galvanized press-
hardened steels (PHS-ZnFe) is significantly retarded in comparison to conventional galvanized
steels (GI) and galvannealed steels (GA). Mechanisms for this performance improvement
will be presented and discussed. Keywords: press-hardening; galvanized; galvannealed;
corrosion; VDA621-415; VDA 233-102; cathodic-protection

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01 Introduction

Nowadays automotive industry has to face up a multitude of challenges. Ecological aspects like the reduc-
tion of fuel consumption and environmental protection are major driving forces for lightweight construc-
tion, while higher demands on passive safety tend to increase weight. The application of advanced-high
strength steels (Rm > 800 MPa) was a first answer to ensure the required safety directives in a light weight
car body construction. Due to the lack of cold formability of these materials at ambient temperature, hot
forming processes have been implemented leading to components with 1500 MPa strength and above
in combination with high complexity of geometry. Hardenable boron steel (between 0,002% and 0,005%
boron) is austenitized at a temperature of >850 °C and quenched between cold tools with cooling rates
greater than 25 K/s to attain martensitic microstructure. The utilization of hardenable steel in combination
with press hardening applications began in the 1990´s and is mainly used for producing passive safety
components such as side impact beams, B-pillars, tunnel, rocker panels and different types of reinforce-
ment components.

Beside passive safety and weight reduction, corrosion protection is another major aspect for materials in
automotive industry. Systems of particular interest are those who are able to act as a sacrificial anode for
the base material like galvanized steel. The use of continuous galvanized steel sheet as feedstock material
for press hardening leads to components of very high strength levels, high complexity of geometry and
classical cathodic corrosion protection [1]. A hot dipped galvanized boron steel for press hardening is
produced by voestalpine Stahl GmbH under the trade name phs-ultraform.

Heat treatment of galvanized steel sheet causes a transformation of the original zinc coating. The chem-
ical interdiffusion of zinc with the steel substrate leads to a new zinc-iron coating, which contains much
more Iron than galvannealed coatings (GA). A good description of this coating as well as the zinc-iron
reactions during austenitization as a part of the press hardening process is found in [2]. The Zn-Fe system
itself was investigated since the beginning of 20th century and has been subject of a number of publi-
cations. One of the most widely accepted Zn-Fe equilibrium phase diagram is that of B. P. Burton and
P. Perrot. [3] Burton et. al. describe the system Zn-Fe consisting of liquid phase, several Zn-Fe-Phases
named Γ1-, Γ2-, δ-, ζ-Phase, as well as mixed crystals of α- and γ-Fe.

In this paper the focuses is on the anticorrosion behaviour of press hardened galvanized steel sheet in
unpainted and painted condition, based on standard cyclic corrosion tests for automotive applications in
Europe (VDA 621-415 and VDA 233-102).

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02 Experimental

02.01. Materials
The material used for this study was supplied by voestalpine Stahl GmbH. Steel base was a common
hardenable boron alloyed carbon manganese steel 22MnB5 with a blank thickness between 1 and 2 mm.
The main alloying components were 0,22 wt.% C, 0,25 wt.% Si, 1,2 wt.% Mn, 0,32 wt.% Cr and 30 ppm
B. The samples used for the study were hot-dipped galvanized steel sheet with a conventional zinc coa-
ting (Z) consisting of Zn with 0.5 wt% Al, produced on a industrial production plant. The average coating
weight per side was 70 gm-2.

02.02. Thermal Treatment

Heat treatment was done in a 12 kW Nabertherm L20/14-S1 radiation furnace. The furnace was prehe-
ated at 910°C and all experiments were performed at ambient atmosphere. All samples were oiled with
PL3802-39S from Quaker before austenitization.

02.03. Test Specimens

For corrosion in the painted condition the test specimens were treated by the following system:

- 5 Minutes degreasing with Ridoline 1565-1 from Henkel at 55°C

- 45 Seconds activating with Fixodine 50 CF (1g/l) from Henkel
- Zinc phosphating with Granodine 958 from Henkel
- Electro coating with EV2000 from PPG (220V; 135sec; 25min curing at 175°C)

The painted panels were manually scribed down to the zinc-iron coating with a Sikkens 1mm scratch-tool
and stone chipped following DIN EN ISO 20567.

The non-painted panels were sealed at edges and reverse side by an adhesive tape.

02.04. Corrosion Test

The samples were exposed to cyclic corrosion tests VDA 621-415 / EN ISO 11997/1 the newly de-
veloped corrosion test VDA 233-102 and to salt spray test with 5 wt.% NaCl. The solution of the salt
spry test was regulated to pH 6.5 – 7.2 by adding sodium hydroxide and sprayed via nozzles into an
Erichsen salt spray chamber at a constant temperature of 34.5 C ± 0.5 °C. The VDA 621-415 test was
performed automatically in a Weiss SC 1000 chamber. Details on weekly cycle of the VDA 621-415 test
are presented in Figure 1.

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The VDA 233-102 test is composed of three dif-  

ferent subcycles forming a weekly cycle by the
sequence of A – B – A – C – A – B – B, shown in
Salt spray (EN ISO 9227)  
Figure 2. The VDA 233-102 test includes a free- 24 hours  

1 Cycle = 7 Days
zing phase at -15°C (cycle C) which alternates
with wet and dry cycles at temperatures up to
50°C and salt spray phases at a lower sodium Condensing water climate
(EN ISO 6270-2)  
96 hours  
chloride concentration (1 wt.%) than the VDA
621-415 (5 wt.%). The VDA 233-102 test was
performed automatically in a Weiss WK 1000 Ambient climate (EN ISO 14698)  
chamber where the salt solution was sprayed as 48 hours  
a fog. [4]

The VDA 621-415 and VDA 233-102 tests differ

largely regarding the salt concentration, tempe- Figure 1: One week cycle of VDA 621-415 / / EN ISO 11997/1 cor-
rosion test
rature, humidity cycles and the test durations.
The painted specimens for cosmetic corrosion
were exposed for the nominal duration of 70
days in the VDA 621-415 test and 42 days in the
VDA 233-102 test.

02.05. Characterisation

The surface was conditioned by shot blast cleaning before all experiments. Cross-sections, were prepa-
red and examined by secondary electron microscopy (short SEM) and energy dispersive X-ray analysis
(short EDX). SEM investigations of the cross-section were carried out by using the back-scattered elec-
tron mode to emphasize the different metallic phases. The investigation of the corrosion characteristics
was done by galvanostatic dissolution.

For SEM and EDX investigations a Zeiss Supra 35 scanning electron microscope combined with an EDAX
LEO 1530 was used. Electrochemistry was done with a Princeton Potentiostat / Galvanostat - Model
263A. The electrolyte consists of 100gl-1 ZnSO4.7H2O and 200gl-1 NaCl. Temperature was 35°C and
the electrolyte was ventilated. The current density was 11,76 mAcm-2 and the reference electrode was an
Ag/AgCl electrode in 3 moll-1 KCl.

For characterisation of cosmetic corrosion the painted panels were rinsed with deionized water and dried
by air-blowing. Then they were scraped and taped to remove loose paint blistering around the scribes
and the stone chipped surfaces. Corrosion creep was evaluated through an electronic visual evaluation
program named SMART.

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Figure 2: Humidity and temperature cycles / subcycles of the

VDA 233-102 test [4]

03 Results & Discussion

03.01. Microstructure of Press Hardened Galvanized Steel Sheet before
Exposure:
A significant change in the coating occurs
during press hardening process. The formally
10μm thick zinc coating changes into an about Γ-FeZn
20μm thick coating consisting of zinc saturat-
ed α-iron and Γ-ZnFe Phase regions. Figure 3
shows the SEM image of a sample cross-sec- α-Fe(Zn)
tion from galvanized steel after press harden-
ing. The light areas represent Γ-ZnFe-Phase
and dark areas zinc ferrite. The martensitic steel
substrate can be identified as separated darker
Martensite 10μm
area under the coating.

There is no essential difference in the micro-

structure between press-hardened galvanized Figure 3: Cross-cut SEM image of galvanized steel sheet after press
hardening
steel sheet and galvannealed steel sheet by
corresponding thermal treatment. The corro-
sions behaviour in case of similar microstruc-
ture is the same. [6]

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03.02. electrochemical Behaviour of Press hardened galvanized steel:

Figure 4 shows a galvanostatic measurement of galvanized steel before and after press hardening. All
potentials were measured against Ag/AgCl (3M). At the beginning of the galvanostatic dissolution the
press hardened sample represented through the black line has a potential of -0,74V representing the
Γ-ZnFe Phase which dissolves first. After a measurement time of approx. 5 Minutes a potential of about
0,6V sets in. This means that the Γ-ZnFe Phase is consumed and zinc ferrite is now dissolved. After a
measurement time of approx. 75 Minutes the electrochemical potential reaches the steel potential of
-0,42V. The potentials for the Γ-ZnFe Phase and the zinc-ferrite are significantly lower than the steel
potential. This indicates that after press hardening the formally galvanized coating offers cathodic cor-
rosion protection for the substrate. In comparison to the unhardened sample with a zinc potential of
0,96V, the difference between the potential of the Zn-Fe Phases in the coating and the steel substrate
is much lower. This portends that the corrosion rate, on thermodynamic observation, for hardened
samples is lower than those for unhardened. Oppositional the cathodic protection in distance should
be lower.

The dissolution time of the coating for press hardened samples is more than twice, which can be ex-
plained by higher coating thickness

Figure 4: Galvanostatic measurement of galvanized steel before (red line) and after press hardening (black line) vs. SHE. Elektrolyte: 100gl-1
ZnSO4.7H2O + 200gl-1 NaCl; T=35°C; ventilated; I=11,76mAcm-2 [6]

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03.03. Cross Section Analyses of Corroded Press Hardened Galvanized

Steel Sheet:
Cross-sections of the corroded specimens after VDA 621-415 test and VDA 233-102 test were prepared
and analysed with SEM (Figure 5). Press hardened galvanized steel sheet shows red corrosion products
right from the start of exposure [5]. Therefore the determination of basic material attack is only possible by
the means of cross-cuts. A good description of the surface of corroded press-hardened galvanized steel
sheet as well as a corrosion product analysis can be found in [5].

Fig. 5: Cross cut SEM micrographs of press hardened galvani-

zed steel sheet after different exposure times in VDA 621-415
test (left) and VDA 233-102 test (right). Initial state at the top
descending ordered in steps of 1 week.

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The inspection of cross-sections in Figure 5 observes that there is no base material attack after 10 weeks
VDA 621-415 test respectively after 6 weeks VDA 233-102 test. This results confirm that the appear-
ance of red corrosion products on corroded press hardened galvanized steel sheet is no indication of
basic material attack.

Unhardened samples show basic material attack after 2 weeks VDA 621-415 test respectively 4 weeks
VDA 233-102 test. Galvanized steel sheet after press hardening on the other hand shows more than 5
times longer protection for base material attack in VDA 621-415 test and 1.5 times longer in VDA 233-102
test. An explanation for this is the higher coating thickness and the lower corrosion rate [6]. So all in all hot
dipped galvanized steel sheet has a much higher corrosion resistance after press hardening.

The comparison of the corroded samples to the initial state illustrates that the Γ-ZnFe Phase, represented
by the light areas in the coating, is the first compound to corrode. This behaviour is expected due to the
more negative potential compared to zinc-ferrite. When the Γ-ZnFe Phase is dissolved zinc ferrite cor-
rodes and gives sacrificial protection for the basic material, which is also expected due to electrochem-
ical behaviour. Overall galvanostatic measurements and cross-section analysis illustrate that the Γ-ZnFe
Phase shows cathodic protection for zinc-ferrite which in turn protects the steel substrate.

03.04. Paint Creepage on Mechanical Defects

Figure 6 and Figure 7 show the corrosion creepage of unhardened, press-hardened and galvannealed
small sized samples in terms of scribe and stone chipped corrosion creepage. Reported values indicate
that press hardened galvanized steel sheet shows significantly more resistance to cosmetic corrosion
than unhardened galvanized or galvannealed 7,00
steel sheet in VDA 621-415 test. In VDA 233- Z140 before press-hardening

6,00
102 the corrosion behaviour is nearly similar. Z140 after press-hardening (PHS)
scribe corrosion creep / mm

The corrosion creepage of press-hardened 5,00

ZF100

steel sheet in salt spray test for stone chipped

surfaces is quite similar to galvannealed coat- 4,00

ings and much better than galvanized coat- 3,00

ings. The corrosion creepage for scribe defects
is nearly zero for press-hardened steel sheet 2,00

which is significantly better than galvannealed

1,00
or galvanized coatings.
0,00
VDA N-VDA SST 240h SST 480h SST 720h SST 840h
The reason why press hardened galvanized
steel sheet develop less corrosion creepage
Figure 6: Cosmetic corrosion (scribe corrosion creep) after 10 weeks
compared to unhardened galvanized steel
VDA 621-415; 6 weeks VDA 233-102; 240h SST; 480h SST; 720h SST;
sheet can be explained by their higher coating 840h SST. Comparison of press hardened, unhardened and galvan-
thickness and reduced corrosion rate [6]. nealed samples.

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Figure 7: Cosmetic corrosion (stone chipped corrosion 100

Z140 before press-hardening
creep) after 10 weeks VDA 621-415; 6 weeks N-VDA; 240h 90
Z140 after press-hardening (PHS)
SST; 480h SST; 720h SST; 840h SST. Comparison of press 80
hardened, unhardened and galvannealed samples. ZF100

corrosion creep / %
70

60

50

40

30

20

10

0
VDA N-VDA SST 240h SST 480h SST 720h SST 840h

04 Conclusion
The heat treatment during hot forming of galvanized steel sheet causes a significant change in coating
formation. The formally 10μm thick zinc coatings change into more than 20μm thick coatings, consisting
of zinc saturated α-iron and Γ-ZnFe-Phase regions.

This generated coating shows corrosion protection for the steel substrate according to the cathodic pro-
tection effect. Γ ZnFe Phase shows sacrificial protection for zinc-ferrite which in turn protects the steel.
In comparison with un-annealed galvanized steel sheet the corrosion rate is lower, leading in combination
with at least doubled coating thickness to a significant better corrosion protection of steel substrate and
a lower corrosion creepage for scribe defects and stone chipped surfaces.

05 References
[1] D. CLOSE, R. LALLEMENT, P. FEUSER, J. BOLD (2014) Challenges in Corrosion Protection for Press-Hardened Steels;
Tagungsband zum 9. Erlanger Workshop Warmblechumformung 2014 in Erlangen, Germany
[2] R. AUTENGRUBER; G. LUCKENEDER; S. KOLNBERGER; J. FADERL; A.W. HASSEL (2010) Surface and coating analysis of
press-hardened hot-dipped galvanized steel sheet; Steel Res. Int. 83 (2012); No. 11, 1005
[3] B. P. BURTON and P. PERROT (1993). In H. Okamoto (Ed.); Phase Diagram of Binary Iron Alloys; ASM International; Materials
Park, OH, 459
[4] K.H. STELLENBERGER; G. LUCKENEDER; et.al. (2011) A new laboratory cyclic corrosion test for automotive implication;
Proceeding for Galvatech 2011 in Genoa, Italy
[5] R. AUTENGRUBER; G. LUCKENEDER; A.W. HASSEL (2012) Corrosion of press-hardened ganvanized steel; Corr.Sci. Volume
63, 12-19
[6] G. LUCKENEDER; R. AUTENGRUBER; K.H. STELLNBERGER; J. FADERL; T. KURZ; (2014) Einflussfaktoren auf die Korro-
sionsschutzleistung von pressgehärteten Stahlwerkstoffen; Proceeding for 3-Länder Korrosionstagung in Linz, Austria

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