C2012-0001493
Timothy Alexander Keppert
Christian Doppler Laboratory of Localized
Corrosion
Franz-Josef-Straße 18
8700 Leoben
Austria
Gerald H. Luckeneder
voestalpine Stahl GmbH
voestalpine-Str. 3
4021 Linz
Austria
Karl-Heinz Stellnberger
voestalpine Stahl GmbH
voestalpine-Str. 3
4021 Linz
Austria
Gregor Mori
Christian Doppler Laboratory of Localized
Corrosion
Franz-Josef-Straße 18
8700 Leoben
Austria
ABSTRACT
Previous studies of our group showed that Zn-Al-Mg hot-dip galvanized steel sheets have a superior
corrosion resistance compared to conventional hot-dip galvanized steel sheets.
This work especially focuses on the stability of this material at different pH values and the formation of
corrosion products. Therefore experiments based on the normal salt spray test according to DIN EN
ISO 9227 were conducted. During those tests the solution was adjusted to different pH values from
acidic to alkaline. All other parameters were left untouched. The samples were compared to
conventional hot-dip galvanized steel sheets of the same coating thickness.
The results showed that the corrosion resistance is severely influenced by the pH value of the testing
medium. Also the amount and the type of corrosion products formed in the course of the tests varies
greatly. While in severely acidic conditions mainly Simonkolleite is formed. In mildly acidic to neutral
conditions Simonkolleite and Hydrozincite is formed, while in strongly basic conditions Simonkolleite
and ZnO is formed.
Corrosion products were analyzed by SEM, EDX, XRD, IR and RAMAN spectroscopy. A cross section
analysis in SEM showed that the severity of the attack of the coating is very much dependent on the pH
value of the testing solution. The corrosion products could be identified as Simonkolleite and
Hydrozincite. In alkaline conditions the formation of Zincoxide and Zn-Al-Hydrotalcite was also
observed.
©2012 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to NACE International,
Publications Division, 1440 South Creek Drive, Houston, Texas 77084. The material presented and the views expressed in this paper are solely those of the
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Influence of the pH value on the corrosion of Zn-Al-Mg hot-dip galvanized steel sheets in
chloride containing environments
Key words: hot-dip galvanizing, alloy coating, Zn-Al-Mg coating, salt spray test, pH value, corrosion
products
INTRODUCTION
In the last 30 years there has been a large increase in the research on new zinc alloys for hot-dip
galvanizing led by the increasing demands in the automotive and buildings industry. In this regard ZnAl-Mg alloys displayed the best properties for corrosion protection. Several alloys were developed in
the 1990s by Japanese steelmakers. 2,3,4,5 The aluminum and magnesium content in these zinc based
coatings varies from 0.2 to 11.0 wt.%. While all researches agreed on the enhanced corrosion
protection of Zn-Al-Mg hot-dip galvanized steel sheets several corrosion mechanisms were proposed.
Tanaka et al.3 attributes the higher corrosion resistance of their alloy to the formation of a basic zinc
chloride containing Mg and Si. Nishimura et al.4 found that the corrosion products formed on their alloy
inhibited the cathodic reaction. Tsujimura et al.5 showed that their alloy formed a protective layer
composed of zinc aluminum carbonate hydroxide.
In recent years European steelmakers developed their own compositions.6,7,8,9 These alloys have a
maximum magnesium and aluminum content of 3.5 wt.%. The corrosion mechanism of the European
Zn-Al-Mg systems is of greatest interest in the moment. Schuerz et al. 10 observed the formation of an
aluminum rich protection layer identified as zinc aluminum carbonate hydroxide. This compound is
formed after a relatively short time in chloride containing environments.
Understanding the corrosion mechanism of Zn-Al-Mg alloys becomes more and more important as
customers aim to reduce coating weights as much as possible without reducing the life of their
products. This demand can only be accomplished if the corrosion mechanism is fully understood.
The aim of this work is to investigate the corrosion products formed at different pH values. For this
reason salt spray tests based on DIN EN ISO 922711,(1) were performed. The only variable that was
varied was the pH value of the sprayed solutions. After the corrosion tests the samples were analyzed
by SEM, EDX, XRD, IR and RAMAN spectroscopy. The corrosion products that form at different
conditions were determined and the degree of corrosive attack was observed by analyzing cross
section cuts in SEM.
EXPERIMENTAL PROCEDURE
Materials
In this study two different hot-dip galvanized materials were used. The Zn-Al-Mg alloy (ZM) investigated
had a composition of 2 wt.% Al, 2 wt.% Mg and 96 wt.% Zn. The average coating weight on one side
was 45 g/m², which results in an average coating thickness of 7 µm per side. The substrate of those
samples was a DX54D low carbon steel. As a reference material a conventionally hot-dip galvanized
material (Z) was used. The composition was 0.2 wt.% Al and 99.8 wt.% Zn. The average coating weight
of this material was 50 g/m² on one side. This also corresponds to an average coating thickness of
(1)
DIN Deutsches Institut für Normung e. V., Am DIN-Platz Burggrafenstraße 6, 10787 Berlin, Germany.
©2012 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to NACE International,
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author(s) and are not necessarily endorsed by the Association.
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Hot-dip galvanizing is the most important process for protecting steel sheets from corrosion. Zinc
coatings provide barrier and galvanic protection. In barrier protection the coating protects the steel by
separating it from the corrosive environment. The steel can only corrode if it is reached by electrolyte.
In galvanic protection the zinc coating is less noble than the steel and will sacrificially corrode before
the steel corrodes.1
7µm. The substrate of the conventionally hot-dip galvanized material was a DX56D low carbon steel.
Table 1 illustrates the used materials for the corrosion tests. The samples were cut to 150 x 100mm. All
samples were de-oiled in an alkaline cleaning solution at 40°C. The cut edges were covered with an
adhesive tape prior to corrosion testing.
Conventional
zinc (HDG)
Zn-Al-Mg alloy
(ZM)
DX56D
0.81
50
99.8
0.2
-
DX54D
0.82
45
96
2
2
Corrosion Testing
Five different salt spray tests based on DIN EN ISO 922711,(2) were performed. To that effect samples of
HDG and ZM were prepared as stated above. Then the samples were placed in an ascott CC1000t (3)
cyclic corrosion test cabinet 20 degrees out of the vertical axis. The temperature during all tests was 35
± 1 °C. The NaCl concentration was 5 ± 0.5 wt.% and the amount of sprayed solution was 36 ± 12 ml
per day collected in the chamber in an area of 80 cm². The pH value was set with HCl or NaOH
respectively. Both the NaCl concentration and the pH value was controlled daily in the collected
solution after spraying. The five tested pH values were 1,3,7,10 and 12. Samples were collected after
24, 48, 72 and 100h. After that samples were collected every 100h until the sample surface was
covered at least 5 % with red rust or 1000h were reached. After the corrosion test the samples were
washed with deionized water and air dried. Then the samples were photographed.
Analyses
For the analysis of the cross section cuts a Zeiss Supra 35 (4) SEM with an EDAX Nova 600(5) EDX was
used. All samples were sputtered with gold before the analysis. The corrosion products were analyzed
with XRD, RAMAN and IR. The XRD diffractograms were obtained from a PANanalytical X’Pert PRO
MPD(6) diffractometer with a cobalt anode. The RAMAN analysis was carried out on a Horiba Jobin
Yvon LabRAM 300(7) while for the IR spectroscopy a Bruker Tensor 27(8) was used.
(2)
DIN Deutsches Institut für Normung e. V., Am DIN-Platz Burggrafenstraße 6, 10787 Berlin, Germany.
Ascott Analytical Equipment Limited, Unit 6 Gerard, Lichfield Road Industrial Estate, Tamworth Staffordshire,
B79 7UW, Great Britain.
(4)
Carl Zeiss NTS GmbH, Carl-Zeiss-Straße 56, 73447 Oberkochen, Germany.
(5)
EDAX Inc., 91 McKee Drive, Mahwah, NJ 07430.
(6)
PANalytical B.V., Lelyweg 1, 7602 EA ALMELO, The Netherlands.
(7)
HORIBA Jobin Yvon Inc, 3880 Park Avenue, Edison New Jersey NJ 08820-3097.
(8)
Bruker Optik GmbH, Rudolf-Plank-Str. 27, 76275 Ettlingen, GERMANY.
(3)
©2012 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to NACE International,
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author(s) and are not necessarily endorsed by the Association.
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Coating
Table 1
Overview of the materials used for corrosion testing
Coating composition
Steel
Substrate
Average coating weight
(wt.%)
substrate thickness (mm) per side (g/m²)
Zn
Al
Mg
RESULTS
Corrosion Test
Figure 2 illustrates the results of the salt spray test at pH 3. Everything that has been said for the
neutral test can be said for this test as well. The conventional material fails after 100h while the new ZM
material shows no visible red rust after 1000h at which time the test was aborted. If anything the
appearance of the samples is slightly better. Again the ZM samples show significantly fewer white rust
particles.
Figure 3 gives an overview of the samples tested at pH1. The conventionally hot-dip galvanized
material again fails after 100h and shows no significant differences to the samples test at pH7 or pH3.
But the ZM samples have a very different appearance compared to the other test at acidic to neutral
conditions. They form fewer corrosion products. The formation of white corrosion products seems to be
even more retarded than at the former samples. After 600h in the test one can see the first appearance
of red rust. The red rust seems to only occur at places near the sticker that was used to mark the
samples. This could be the case because at that position the sprayed solution can collect and remains
longer on the sample before running down. After 900h the samples fail. This experiment showed that
ZM is nine times more resistant than HDG at this condition.
HDG 0h
HDG 24h
HDG 48h
HDG 72h
HDG 100h
HDG 200h
ZM 0h
ZM 24h
ZM 48h
ZM 72h
ZM 100h
ZM 200h
ZM 300h
ZM 500h
ZM 600h
ZM 700h
ZM 800h
ZM 900h
Figure 1: Overview of tested samples at pH7
ZM 1000h
ZM 400h
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Figure 1 shows the samples that were tested at pH7. In this conditions the conventional HDG material
shows the first appearance of red rust after 72h, while the material fails after 100h. In contrast the ZM
samples show no red rust after 1000h at which point the test was aborted. In this test ZM performs at
least ten times better than the conventional hot-dip galvanized material. After visible inspection of the
samples one can see that the HDG samples form significantly more white rust than the ZM samples.
HDG 24h
HDG 48h
HDG 72h
HDG 100h
HDG 200h
ZM 0h
ZM 24h
ZM 48h
ZM 72h
ZM 100h
ZM 200h
ZM 300h
ZM 400h
ZM 500h
ZM 600h
ZM 700h
ZM 800h
ZM 900h
Figure 2: Overview of tested samples at pH3
ZM 1000h
HDG 0h
HDG 24h
HDG 48h
HDG 72h
HDG 100h
HDG 200h
ZM 0h
ZM 24h
ZM 48h
ZM 72h
ZM 100h
ZM 200h
ZM 400h
ZM 500h
HDG 0h
HDG 24h
ZM 300h
ZM 600h
ZM 700h
ZM 800h
ZM 900h
Figure 3: Overview of tested samples at pH1
HDG 48h
HDG 72h
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HDG 0h
ZM 24h
HDG 0h
HDG 24h
ZM 0h
ZM 24h
ZM 48h
ZM 72h
ZM 100h
ZM 200h
Figure 4: Overview of tested samples at pH10
HDG 48h
ZM 300h
HDG 72h
ZM 48h
ZM 72h
ZM 100h
Figure 5: Overview of tested samples at pH12
The samples tested at pH10 are illustrated in figure 4. In this conditions the HDG samples fail after 48h.
The ZM samples fail after 200h in this environment. In contrast to the acidic and neutral test in this test
the ZM samples form much more white rust from the beginning of the test. At pH10 the ZM material
performs four times better than the conventional HDG material.
Figure 5 shows the samples tested at pH12. In this conditions the HDG samples fail after 72h. But first
appearance of red rust starts after 24h. It appears that the red rust forms under the white rust and the
samples look relatively well, though they actually fail after 24h. This fact is not readily apparent from
figure 5 due to the small magnification of the samples. The time of failure would probably be after 72h,
where at least five percent of the sample surface is covered by red rust. But since after visible
inspection the substrate is visibly attacked after 24h, we are inclined to give a time of failure of 24h for
HDG at pH12. The ZM samples fail after 100h in this environment. They again form significantly more
white rust than in acidic or neutral conditions. But in contrast to pH10 the formation of the white rust
seems to take more time. In this conditions ZM seems to last about two times as long as HDG.
Figure 6 shows the time to red rust as a function of the pH value.
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ZM 0h
Analysis of the cross section cuts
Figures 7 to 11 show SEM pictures of the cross section cuts at different pH values. The samples tested
in acidic to neutral conditions are all very similar. They show two kinds of areas. On the one hand there
are areas where the samples are almost not attacked, while on the other hand there are areas where
the ZM coating completely reacted to corrosion products. Both areas have in common that the
substrate is still protected from corrosion. The completely attacked areas cover approximately five
percent of the sample area. EDX spectra of the heavily corroded sections show a very inhomogeneous
aluminum distribution. This indicates that the samples did not form a zinc aluminum carbonate
hydroxide layer.
The samples that were tested at alkaline conditions show no unattacked areas. Both figure 9 and 10
show samples where the ZM coating has reacted to corrosion products. However the substrate still is
not attacked. EDX spectra indicate that the coatings mainly reacted to ZnO.
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Figure 6: pH value vs time to red rust failure
Zn
Zn
Substrate
Cl
Corrosion products
Al
Al
Cl
Figure 7: Cross section cut after 300h at pH7 ZM
Zn
Al
O
Cl
Figure 8: Cross section cut after 300h at pH1 ZM
Zn
Al
Zn
O
Cl
Al
Cl
Figure 9: Cross section cut after 300h at pH3 ZM
Zn
Zn
Zn
Zn
Zn
O
O
O
O
Al
Cl
O
Al
Cl
Al
Cl
Al
Cl
Al
Cl
Figure 10: Cross section cut after 100h at pH10 ZM
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O
ZM layer
Zn
O
Figure 11: Cross section cut after 72h at pH12 ZM
Corrosion product analysis
For the analysis of the corrosion products samples with enough corrosion products were selected.
Ideally samples collected after the same exposure time should have been used. However the acidic
and neutral samples show almost no corrosion products at times where the basic samples already fail.
Table 2 gives an overview of the samples used for corrosion product analyses.
Table 2
Overview of the samples used for corrosion product analyses
pH
XRD
RAMAN
IR
1
3
7
10
12
300h
300h
300h
100h
72h
300h
300h
300h
100h
72h
600h
300h
300h
100h
72h
Figure 12 and 13 show the XRD diffractograms of the selected samples. One can clearly see the
differences between acidic and neutral conditions on the one side and alkaline conditions on the other
hand. On all samples the main corrosion product seems to be Simonkolleite Zn 5(OH)8Cl2.H2O, while
only at pH10 and pH12 ZnO is formed. Also Hydrozincite Zn4CO3(OH)6.H2O seems to be only stable at
neutral to moderately acidic conditions. Contrary to that the Hydrotalcite phase
Zn0.7Al0.3(OH)2(CO3)0.15.H2O is only formed at strongly basic conditions. Since the samples at pH3 and
pH7 display the best corrosion protection it is likely that Hydrozincite is mostly responsible for the good
corrosion performance of ZM coatings. However Simonkolleite also seems to have some positive
effect. Table 3 sums up the corrosion products that form at different conditions.
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Cl
Al
Figure 13: XRD diffractograms of selected samples in alkaline to neutral conditions
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Figure 12: XRD diffractograms of selected samples in acidic to neutral conditions
Table 3
Main corrosion products at different conditions
Corrosion Products
1
3
7
10
12
Simonkolleite
Simonkolleite, Hydrozincite
Simonkolleite, Hydrozincite
Simonkolleite, Zincoxide
Simonkolleite, Zincoxide
The RAMAN spectra illustrated in figure 14 and 15 were made in two distinct sample areas. All samples
formed grey and white areas. While the sample at pH1 formed almost no white areas the samples at
basic conditions formed almost no grey areas. The spectra of the grey areas show the formation of
Simonkolleite12. This is in accordance to the XRD data. The spectra of the white areas show the
formation of Hydrozincite and ZnO 13,14. The sample tested at pH3 shows the clearest formation of
Hydrozincite. One can also clearly see from the peaks at 391.3 cm -1 and 437.9 cm-1 that all samples
form ZnO. But only the samples exposed to basic conditions show the formation of crystalline ZnO.
Figure 14: RAMAN spectrum of grey areas of selected samples
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pH Value
Figure 16 displays the IR spectra of the selected samples. The double peak at 3489 and 3449 cm -1
seems to be caused by Simonkolleite 15. The double peak at 2920 and 2848 cm -1 results from ZnO16.
There also seems to be a ZnO peak from 3216 to 3644 cm-1 superimposed by the Simonkolleite peaks.
The other peaks ranging from 1510 cm-1 to 700 cm-1 originate from Hydrozincite13. Altogether the
samples don’t differ all that much. Only the sample exposed to pH1 shows significantly less formation
of Hydrozincite and ZnO.
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Figure 15: RAMAN spectrum of white areas of selected samples
CONCLUSIONS
The ZM material shows a more then ten times better corrosion protection than conventional materials.
Even under severe acidic or alkaline conditions ZM performs significantly better than HDG. SEM
pictures of cross section cuts show that ZM samples exposed to acidic to neutral conditions exhibit a
significantly better corrosion performance than samples exposed to alkaline conditions. ZM samples
tested at mildly acidic to neutral conditions showed no steel substrate attack, while the ZM coating
tested in strongly acidic or severe alkaline conditions showed a significantly stronger attack. Corrosion
product analyses by XRD, RAMAN and IR revealed that different corrosion products are formed at
different conditions. In severely acidic conditions mainly Simonkolleite is formed. In mildly acidic to
neutral conditions Simonkolleite and Hydrozincite is formed, while in strongly basic conditions
Simonkolleite and ZnO is formed. Together with the different times to failure in the corrosion test this
indicates that the main protective species is Hydrozincite, while Simonkolleite also seems to have some
protective capacities. Also the formation of an Al-rich protective layer comprised of zinc aluminum
carbonate hydroxide could not be observed.
ACKNOWLEDGEMENTS
We thank voestalpine Stahl GmbH for supplying testing materials and corrosion testing facilities.
Analyses were carried out with the support of voestalpine Stahl Linz - Microstructure and Surface
Analysis department, voestalpine Stahl Linz - Environmental and Operating Analysis.
This work was carried out under the financial support of the Christian Doppler Research Association
(CDG).
©2012 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to NACE International,
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Figure 16: IR spectrum of selected samples
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Publications Division, 1440 South Creek Drive, Houston, Texas 77084. The material presented and the views expressed in this paper are solely those of the
author(s) and are not necessarily endorsed by the Association.
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©2012 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole, must be in writing to NACE International,
Publications Division, 1440 South Creek Drive, Houston, Texas 77084. The material presented and the views expressed in this paper are solely those of the
author(s) and are not necessarily endorsed by the Association.