Corrosion Science 51 (2009) 24292442

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Corrosion resistance of painted zinc alloy coated steels

Rajiv P. Edavan *, Richard Kopinski
Coil R&D, Akzo Nobel Pty Ltd., Sunshine, Vic. 3020, Australia

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

Article history: Organic coating in combination with sacricial metal coating is the most popular method of protecting
Received 25 February 2009 steel strips against atmospheric corrosion. Experiences over the years have proven that such duplex coat-
Accepted 18 June 2009 ing systems are best suited for the coil industry for the long term corrosion protection of steel. The excel-
Available online 23 June 2009
lent corrosion resistance of such systems has been attributed to the synergy between the cathodic
protection provided by the sacricial coating of zinc alloys and the combined barrier resistance of the
Keywords: metal and organic coatings. Traditionally continuously hot dip zinc-coated steels are used for such appli-
A. Galfan
cations. However, off late the quest for further extending the longevity of the coil coatings has led to the
A. Galvalume
A. Galvanized
replacement of the zinc coating with a host of other hot dip zincaluminium alloy coatings such as Gal-
A. Pre-coated sheets valume, Galfan, ZAM, SuperDyma, etc. Each of these metal coatings has its own unique metallurgical
A. Zn-alloy coatings features in terms of exibility, bonding, microstructure and electrochemical characteristics which may
signicantly inuence the performance of the organic coatings applied over it. This paper looks into
the various aspects of these features of the hot dip coatings on the corrosion performance of the pre-
painted steel strips. For simplicity only polyester paint system, the work horse of the coil industry, is
considered.
2009 Elsevier Ltd. All rights reserved.

1. Introduction developments of more versatile metal coatings which are chiey

Pre-painted steel sheets have acquired signicant growth in the
21st century due to its myriad applications [1]. From construction,
transportation to appliances industry they are used everywhere. As
the name suggests, the pre-painted steel sheets are steel sheets
continuously coated with organic based coatings before any form-
ing process. Continuous painting process or coil coating as it is
known more widely, is considered to be very environment friendly
and efcient process with a very good pre-treatment and process
control [2]. From the trends in the industry, pre-painted steel
sheets have a very high successful rate in terms of their perfor-
mance and longevity with a failure rate of less than 0.5% [3]. This
kind of success rate could be achieved only by engineering various
combination of properties such as strength, exibility and corro-
sion resistance into the coating system so as to provide excellent
all round performance.
The corrosion resistance of the pre-painted steels made of bare
steel is not very good for demanding applications such in housing,
construction, etc. Galvanized steels, especially produced by hot dip
process are preferred for such applications [4] because of their high
coating thickness, superior corrosion resistance and excellent sac-
ricial protection capability. However, the rising cost of zinc and
demand for better and more durable coatings have led to the
* Corresponding author. Tel.: +61 3 93134598; fax: +61 3 93101035.
E-mail address: rajiv.edavan@akzonobel.com (R.P. Edavan).
based on ZnAl alloys. Some of the notable ZnAl commercial al-
loys [5] are Galvalume (1972) [6], Galfan (1980) [7] and Lavegal
(1985) [8] containing predominantly 55%, 5% and 30% of Al, respec-
tively, in addition to other alloying additions to form the coatings.
All these coatings show excellent corrosion resistance e.g. Galfan
has a corrosion resistance of about 23 times more than that of gal-
vanized steel in most of the industrial and marine environments
[9]. Similarly, Galvalume show about 36 times better corrosion
resistance than galvanized steel in similar environments [10].
The increased corrosion resistance of Zn/Al coatings have been
attributed to the presence of passive Al-rich phase which occupies
a good part of the volume and the secondary barrier effect pro-
duced by their unique microstructure that lead to the development
of an adherent corrosion product over exposed areas [11]. In alloy
coatings such as Galvalume, the Al-rich phase occupies about 80
90% of the total volume while in Galfan about 4050% of the vol-
ume is occupied by similar phase [910]. Though the addition of
increased level of Al have remarkably improved the corrosion
resistance of these coatings, the sacricial or cathodic protection
capabilities of these coatings have been proportionately compro-
mised compared to the pure zinc coatings due to the reduced level
of zinc in the coatings, the most electrochemically active constitu-
ent in these coatings.
Steel industry was concerned about the relatively low level of
sacricial protection afforded by the ZnAl alloy coatings which
otherwise were excellent protective coatings. Though it is well

0010-938X/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.06.028
2430 R.P. Edavan, R. Kopinski / Corrosion Science 51 (2009) 24292442
known that even a limited amount of magnesium up to 0.1% signif-
icantly enhances the corrosion resistance of Zn5% Al alloy coating
(Super Zinc) compared to one without (Galfan) in both atmo-
spheric and aqueous environments [12], as conrmed by later
studies too [1316], the actual developments did not start till late
20th century. The rst breakthrough came in 1998 when Nisshin
steel introduced the rst ZnAlMg alloy coating known as
ZAM (1998) [1718]. ZAM not only retained the excellent corro-
sion resistance of ZnAl alloy but also showed considerably im-
proved cathodic protection due to the presence of magnesium in
the alloy. Mg exists as MgZn2 intermetallic in this alloy which is
also equally active as Mg [17]. The sacricial protection provided
by this coating is even better than that of zinc in most of the envi-
ronments. Since than most of the steel plants have produced a
range of ZnAlMg coatings the most notable being SuperDyma
(2002) [1923], MagiZinc [24] and ZMgEcoprotect [25]. All these
alloy coated steels are used to various extents in different parts of
the world.
The excellent corrosion resistance of ZnAlMg alloys containing
highly active Mg element, has been a subject matter of great interest
in the steel industry for quite sometime. Several mechanisms have
been proposed to explain the high corrosion resistance as well as
the cathodic protection capabilities of these coatings. The most
important mechanism appears to be that due to the cathodic protec-
tion of Al and Zn rich phases in the alloy coatings because of the
polarization of these phases by Mg and its intermetallics [26]. The
corrosion potential measurement of the alloy coatings before and
during the salt spray test have shown that Mg containing Zn alloys
are much more active than Mg free zinc alloys in chloride containing
environment. This active corrosion potential of Mg alloys are quite
stable and retained all through the test unlike pure Zn coatings
which showed considerable increase in the potential. The second
most important mechanism is the precipitation of alkali-resistant
Mg(OH)2 on the ZnAlMg alloy surface and its subsequent oxida-
tion. In an exhaustive study on the corrosion protection mechanism
of ZnMg alloys in chloride environment, it was shown [27] that all
the phases of the coating alloy were covered with a magnesium-
based oxide lm. The low corrosion rate of ZnMg alloys in atmo-
spheric conditions was attributed to the formation of this lm. It
was stable even after 28 days of exposure to humid air forming an
interlayer between dominantly zinc-based bulk corrosion products
and the metal surface. The lm is self repairing due to selective dis-
solution of magnesium from Mg-containing phases. X-ray photo-
electron spectroscopy and X-ray diffraction measurements carried
out on ZnMg coated corrosion test panels exposed to 5 wt.% sodium
chloride solution have conrmed the presence of magnesium oxide
(MgO), beside zinc oxide, zinc hydroxide and simonkolleite
(Zn5Cl2(OH)8H2O) on the surface [2829].
Magnesium oxide layer lm on the alloy surface has also been
found to hinder the oxygen reduction activity at (zinc and alumin-
ium) cathodes [27,29] probably because of a lower rate of electron
transfer connected to its good insulating properties. However, the
main role of the lm is seen in limiting the rate of the anodic reac-
tion by shifting the corrosion potential of ZnMg alloys close to the
reversible potential of zinc decreasing thus dropping the potential
across the metal/metal oxide interface and the overvoltage of the
anodic dissolution. Positive effect of magnesium disappeared when
the increasing content of magnesium in the metal structure caused
such a shift in the free corrosion potential that enabled water
reduction reaction. Therefore, the optimal corrosion protection of
ZnMg alloys in atmospheric conditions is related to combination
of relatively noble free corrosion potentials close to that of zinc
and the presence of magnesium-based lms with good stability
and barrier properties.
Magnesium present in the coating alloy also help stabilize zinc
hydroxides (the corrosion product of zinc) thus contributing in the
formation of the secondary barrier coating with aluminium corro-
sion products [2930]. It has been shown that Mg(OH)2 formed
from the initial corrosion of Mg, is gradually converted to more sol-
uble hydroxy carbonates by uptake of atmospheric carbon dioxide.
This lowers the surface pH sufciently to allow thermodynamically
general precipitation of insoluble corrosion products of Al and zinc
thereby retarding the overall corrosion reactions, leaving only
small traces of magnesium corrosion products behind [29]. In an
another study [31] it was shown that the articial rust particles
synthesized from aqueous solutions dissolving ZnCl2, AlCl3, and
MgCl2 consisted of mixed hydroxide chlorides of Zn(II), Al(III)
and Mg(II) [Zn(II)wAl(III)xMg(II)y](2w + 3x + 2y) + (OH)2w + 3x +
2y  z ClznH2O which appeared in form of plate particles. Their
ability to agglomerate in a dense, compact layer in the presence
of Mg salts is suggested to be the main reason for the enhanced
corrosion resistance of ZnAlMg alloys.
Sacricial metal coating such as zinc is well known for its excel-
lent synergy with the organic coatings [3233] to provide high
durable protective coating systems. Physical as well as the electro-
chemical properties of the metal coating, especially the corrosion
resistance and sacricial protection efciency of the coatings to
the base steel at the exposed areas, make a very signicant contri-
bution in this. These properties, being material specic, however,
change drastically from alloy to alloy. Each alloy coating has its
own unique features in terms of microstructure, exibility, bond-
ing, electrochemical characteristics and adhesion to organic coat-
ings which is completely different from the zinc coating.
Therefore, the type of the metal coated steel may have a strong
bearing on the durability and performance of pre-painted steel un-
der different application conditions.
Substrate induced changes in the performance of pre-painted
steels is a subject of great interest in coil industry for some time
and is the subject matter of this paper. For simplicity only a few
commercially available hot dip sacricial type metal coatings are
considered for this investigation along with a standard commercial
polyester paint system which is the work horse of the coil industry.
2. Experimental
Five different types of sacricial type hot dip coated steel sheets
(hereafter referred to as coated steel) were procured from different
commercial sources. These were zinc (type-A), Galvalume (type-B),
Galfan (type-C), ZAM (type-D) and SuperDyma (type-E), respec-
tively. The composition of these coatings are given in Table 1. All
the coated steel sheets were soft (commercial grade), non-skin
passed (as coated) and about 0.450.6 mm thick with a coating
thickness as shown in Table 2. Each of these coatings has its own
unique microstructure depending upon the alloy composition
and cooling conditions. It is worthwhile to mention here that
type-C and -D substrates were of marginally higher gauges and
high coating weights compared to other substrates. It is assumed
in this study that this will not alter drastically the physical proper-
ties of the coated and painted sheets and the high coating weight
will compensate for the sacricial protection at the cut edges. All
Table 1
Chemical composition of hot dip zinc alloy coatings used in the investigation.
Types Metal coatings Alloy composition, % by weight
Al Pb Si Mg Zn
A Zn coating 0.2 0.3 99.5
B Galvalume 55 1.6 43.4
C Galfan 5 0.12 94.5
D ZAM 6 3 91.0
E SuperDyma 11 0.2 3 85.8
 R.P. Edavan, R. Kopinski / Corrosion Science 51 (2009) 24292442
Table 2
Physical properties of the hot dip zinc alloy coatings used.
Type of coated steel Gauge, mm Coating weight, g/m2 (two sides)
A 0.45 210.34
B 0.46 165.35
C 0.60 270.00
D 0.60 338.60
E 0.46 188.40
Note: All the substrates were as coated, non-skin passed and also slightly aged.
the coated steel substrates were tested for the metal coating
weight by stripping the coating and weighing and the microstruc-
ture of the coatings were determined using optical microscope and
SEM.
Panels of 120  300 mm size were used for preparing painted
panels. All the panels were degreased, rinsed and dried before
painting using proprietary degreaser as per the recommendation.
Two sets of painted panels were prepared using the ve coated
steel substrates and were painted with a chrome and chrome free
paint system, respectively. The chrome paint system consisted of a
chrome-phosphate type conversion coating, about 5 lm epoxy
type chromate primer and about 18 lm of high durable polyester
top coat. The chrome free paint system consisted of a uorotitanate
based conversion coating, about 5 lm of an experimental polyester
based chrome free primer and about 18 lm of high Tg (the glass
transition temperature of the top coat was about 55) polyester
top coat. All the painted panels were prepared by bar draw down
technique and were cured in fast baking conditions to a peak metal
temperature (PMT) of about 232 C. These panels were used for all
physical and corrosion testing.
Both bare and painted steel substrates were also assessed for
their physical properties. The adhesion and exibility of the metal
coatings were determined by 180 bend test and impact resistance
as per the standard test procedures given in ASTM D653. The adhe-
sion and exibility of the paint systems were determined by cross
hatch/tape pull test, 180 bend test and reverse impact test as per
ASTM D3359, D4145 and D2794 standards, respectively. The wet
adhesion of the organic coatings over metallic substrates was
determined using a slightly modied ASTM D870 test. In this case
the painted panels with 1 mm square lattice pattern cut into the
paint lm were exposed to boiling water vapour (100 C) without
immersing in enclosed condition for 0.5 h and testing for adhesion
by reverse impact test on the lattice pattern. The adhesion of the
paint lms was determined by standard tape pull test on the de-
formed lattice area as in ASTM D2794.
Corrosion resistance of the bare and painted panels were deter-
mined by accelerated corrosion tests in the laboratory. Traditional
neutral salt spray test (ASTM B117) as well as cyclic corrosion test
(CCT-1, ISO 11997-1 cycle-A) were used for this purpose. The neu-
tral salt spray test consisted of exposure to a continuous neutral
salt fog at 35 C. The cyclic corrosion testing, CCT-1 is a three stage
cyclic corrosion test, with a 4 h of exposure to neutral salt fog, 2 h
of drying at 60 C and 2 h of exposure to 100% humidity at 50 C.
Standard proled panels were used for both the exposures with
the top edge protected with a silicon sealer. The panels were as-
sessed visually every 500 h for corrosion failure.
The atmospheric corrosion tests of the painted panels were car-
ried out at Akzo Nobel marine exposure site at Muriwai, New Zea-
land, under sheltered condition and only 14 months of exposure
was done at the time of submission of this paper. The corrosivity
of this sheltered exposure conditions have been rated to be C5+
as per the ISO 9223, a severe marine corrosion condition.
The metal coatings as well as the exposed painted panels were
also assessed for corrosion resistance using electrochemical tech-
2431
Coating thickness, lm 180 bend test Reverse impact test (J)
Cracking Peeling Cracking Peeling
14.6 3T 0 T <11 J 18 J
19 5T 0 T <5 J 18 J
24 0T 0 T 18 J 18 J
27 5 T (<50%) 0 T <5 J 18 J
15 >5 T (100%) 0 T <5 J 18 J
niques. A VoltaLab 40 electrochemical system was used for this
purpose. All the electrochemical measurements were made in
non-de-aerated aqueous 5% sodium chloride solution in a three
electrode glass cell at ambient condition (25 C). The EIS measure-
ments were performed under 10 mV sinusoidal perturbation at the
open circuit potential of the panels in the frequency range of
100 kHz to 10 mHz. The relative corrosion inhibition of different
substrates in 5% NaCl solution by chromate and Cr-free pigments
used for the primers were determined in a 1% of their solution.
3. Results
3.1. Properties of the bare substrates
The chemical composition of the metal coatings on the coated
steels used for this investigation are given in Table 1. Type-A coat-
ing is relatively a pure zinc coating, with only a very small amount
of aluminium (about 0.2%). Type-B and -C are ZnAl alloy coatings
with a composition of 55% of Al and 1.6% Si for B and 5% Al and 0.1%
Mg for type-C the rest being zinc. Type-D and -E coatings are based
on ZnAlMg alloys where D contained 6% Al and 3% Mg and E con-
tained 11% Al and 3% of Mg, respectively, in addition to zinc.
The microstructures of the ve metal coatings are shown in
Fig. 1. It is evident that each of these coatings has its own unique
microstructure depending upon the alloy composition. Except for
zinc coating (type-A, Fig. 1a) which contained small spangles (zinc
crystal) in a zinc matrix, all the alloy coatings had heterogeneous
microstructure. The predominant phases present on the surface
of the ZnAl binary alloys were zinc and aluminium rich phases,
the growth and distribution of which were dependent on the alloy
composition. In a type-B coating (Fig. 1b) the Al-rich phase was
present in the form of a dendritic network with the Zn rich phase
in the inter-dendritic region. About 80% of the type-B coating sur-
face was occupied by Al-rich phase. Type-C coating (Fig. 1c) which
has composition as that of the ZnAl binary eutectic alloy, the sur-
face predominantly contained ZnAl eutectic phase with little dis-
persion of primary zinc rich phase. The ZnAl eutectic consisted of
the Al-rich phase in ne lamellar form in a matrix of Zn rich phase.
In ZnAlMg alloys such as D and E, in addition to Zn and Al-rich
phases as in the previous alloys, also contained a Mg-containing
phase which is mostly present in the form of an intermetallic com-
pound (MgZn2). Type-D (Fig. 1d) alloy coating which had composi-
tion close to that of the ZnAlMg eutectic composition of Zn4%
Al3% Mg showed a microstructure predominantly containing
the ZnAlMgZn2 eutectic phase with occasional Al-rich phase.
Type-E alloy (Fig. 1e) with composition far from the ternary eutec-
tic, the microstructure consisted of a network of ZnAlMgZn2 eu-
tectic in relief pattern with the intermediate regions being lled
with Al-rich phase. The origin and distribution of the phases in
coating microstructures were mostly determined by the chemical
composition of the coatings as per the phase rule.
The physical properties of the untreated bare coated steel sub-
strates as determined from different tests are summarized in Table
2432 R.P. Edavan, R. Kopinski / Corrosion Science 51 (2009) 24292442

Fig. 1. Microstructure of the alloys of the coatings used in this investigation.

2. All the coatings were very adherent to the steel base under 180
bend and 18 J reverse impact without any peeling of the coatings.
The most ductile coating appeared to be C with very smooth sur-
face at the 0T bend and the impact dome with no cracking of the
coating. Type-A appeared to be the next best with no cracking at
3 T, followed by type-B at 5 T. Type-D showed about 50% cracking
at 5 T and type-E still showed 100% cracking at 5 T. Type-E ap-
peared to be the least ductile coating in this series, with very wide
cracks in the coating even at 5T bend. On the basis of the 180 bend
tests results on cracking, the ductility of the hot dip alloy coatings
can be ranked as: C > A > B > D > E.
Figs. 2 and 3 show the corrosion resistance of different metal /
alloy coatings as determined in the cyclic corrosion test (CCT-1)
and the electrochemical impedance spectroscopy (EIS), respec-
tively. Both the tests showed that type-B alloy was the most corro-
sion resistant and type-A the least. In cyclic corrosion conditions
such as in CCT-1, type-B was almost 6070 times more corrosion
resistant than that of type-A coating. Types-C, -D and -E alloys
were about 23 times, 12 times and 17 times more corrosion resis-
tant, respectively, than type-A coating. These results clearly
showed that the corrosion resistance of these alloy coatings were
predominantly dependent on the percentage of Al present in their
 R.P. Edavan, R. Kopinski / Corrosion Science 51 (2009) 24292442 2433

0.7 0.4

0.6
0.3
Corrosion rate, mm/year

Zi, kohms.cm2
0.5

0.4 0.2

0.3
0.1
0.2

0.1 0
0 0.2 0.4 0.6 0.8 1

0
Zr, kohms.cm2
A B C D E
Fig. 3. EIS-Nyquist plots of different coated steels in 5% sodium chloride solution
Fig. 2. Relative corrosion rates of different hot dip coated sheets as determined (where + is type-A,  type-B, } is type-C, 4 is type-D and h is type-E coated steels).
from the CCT-1 cyclic corrosion test.

strates (not included here). These results conrm that chromate

chemical composition, and the higher the better. The relative grad-
ing of these metal coatings on the basis of their corrosion resis-
tance was: B > E > D > C > A.
The corrosion resistance of type-B substrate in 5% NaCl solution
inhibited with none, chromate and Cr-free anti-corrosive pigments
is shown in Fig. 4. Substrate B showed considerable increase in cor-
rosion resistance when inhibited with chromate as compared to
Cr-free pigment. Similar trend was also observed for other sub-
is far superior corrosion inhibitor for type-B substrate than the
Cr-free anti-corrosive pigment in sodium chloride solution. The
Cr-free pigment used in this work had very little corrosion
inhibition.
The corrosion potential of each of these substrates were mea-
sured against the saturated calomel electrode for about half an
hour in 5% sodium chloride solution and the data are presented
in Fig. 5. The potential showed that type-B alloy was relatively

4
log Z, ohms.cm2

0
-3 -2 -1 0 1 2 3 4 5 6
log frequency, Hz

-20
Phase angle, degrees

-40

-60

-80

-100
-3 -2 -1 0 1 2 3 4 5 6
log frequency, Hz

Fig. 4. EIS-Bode plots of type-B bare substrate in 5% aqueous sodium chloride solution at 25 C containing none (4) and 1% chromate (j) and Cr free (N) anti-corrosive
pigments.
2434 R.P. Edavan, R. Kopinski / Corrosion Science 51 (2009) 24292442

-1040 bend test with type-B, -D and -E showing excellent adhesion with
no paint peeling at 18 J impact. Type-C showed not so satisfactory
Potential, mV (SCE)

-1060 performance (9 J) and type-A showed very poor performance (<9 J).
The results obtained for type-A and -C panels were signicantly
-1080
poor and not very typical of that is seen in the coil industry. This
-1100
may be due to the non-skin passed nature of these substrates
and chrome phosphate/uorotitanate based conversion coatings
-1120 used over these substrates in this investigation which might have
signicantly effected the results. Usually complex oxide based con-
-1140 version coatings are used over these substrates for coil applications
0 500 1000 1500 2000
which produce excellent results.
Time, s
Types-B, -D and -E coated sheets showed excellent wet adhe-
Fig. 5. Corrosion potential of the metal coatings in 5% sodium chloride solution sion resistance with a rating 0 and no paint peeling. Type-C
with respect to a saturated calomel electrode (where + is type-A,  is type-B, } is showed good to moderate wet adhesion with a rating of 1 and
type-C, 4 is type-D and h is type-E coated steels). 5% of paint peeling. Type-A showed very poor rating of about 5.
In general, it can be said that types-B, -D and -E showed excellent
dry and wet adhesion, type-C intermediate characteristics and
the most nobler of all the coatings in the series, followed by type-C,
type-A not so good properties. Based on these dry and wet adhe-
-E and -A in that order. Type-D was the most active of all coatings.
sion test results, the painted substrates can be categorised as:
The sacricial protection offered by these coatings to steel is
B D E > C > A.
dependent on their respective corrosion potential relative to steel.
On the basis of the above data, it appears that the maximum sacri-
cial protection to steel will be given by type-D coating and the 3.3. Corrosion resistance of the painted panels
least by type-B, coatings E, A and C being in the intermediate range.
The relative grading of the metal coatings on the basis of their rel- The results of the painted panels after exposure to neutral salt
ative sacricial protection capability to base steel will be: spray (ASTM B117), cyclic corrosion testing (CCT-1, ISO 11997-1
D > E > A > C > B. A) and natural exposure at Muriwai, New Zealand, are given in Ta-
bles 46. Only the results of the three important modes of corro-
3.2. Physical properties of the painted panels sion induced failures of the painted panels are considered here:
rust blistering on the intact painted areas, corrosion creep or
The physical properties of the painted coated steel panels are gi- undercutting at the defect or scribe and corrosion creep at cut
ven in Table 3. The standard dry adhesion of paint systems as edges. The blistering intensity/frequency and size are denoted by
determined by the cross hatch/tape pull test was good on all the D and S, respectively, in these tables in a scale of 05 where 0 is
substrates. No peeling of the paint was observed on any of the pan- no blistering and 5 is maximum as per the pictorial standard given
els from the square hatched area. This showed that both chrome in the Australian Standard AS 1580.481.1.9. Only average corrosion
and chrome free paint systems had reasonably good dry adhesion creep or undercutting at scribe (a linear cut through the paint lm
over each of these substrates. However, when it comes to dry adhe- introduced) and cut edges are reported here for each panel. The
sion of paint during compression bending and rapid deformations corrosion creep was measured in terms of the actual length of disb-
such as in roll forming or impact, different substrates showed dif- onded area in mm of the paint lm starting from the cut edges or
ferent level of adhesion. Two common tests used for assessing defect after exposure. Interestingly, the painted panels performed
paint adhesion on substrates under deformation are 180 bend test very differently in the neutral salt spray, cyclic corrosion test,
and the reverse impact test. Both these tests are considered as the CCT-1 and natural exposure.
routine tests for evaluating coil coatings. In the 180 bend test, The results of the salt spray and CCT-1 tests are summarized in
substrate types-B, -D and -E showed excellent paint adhesion with Tables 4 and 5, respectively. After 2000 h of exposure to salt spray
no paint peeling at 0T bend. Type-C was okay with only 3T while (ASTM B117), most of the painted panels except type-A showed
type-A with 4T. The reverse impact resistance of the paint systems excellent resistance to face blistering with either paint system.
on these substrates also followed similar trends as seen for the Type-A painted panel showed light blistering on the face in this
test in both cases. Panels were relatively more prone to blistering
in the cyclic corrosion test, CCT-1 than salt spray test for the same
Table 3
Physical properties of chrome and chrome free paint systems over different coated
duration of exposure for both paint systems. Low to light blistering
steel substrates. was observed on all the panels. It was relatively worse for the
chrome free paint system. Here too, type-A painted panels showed
Substrate Paint Paint Dry 180 Reverse Wet
types systems DFT adhesion bend impact test adhesion**
substantially higher blistering than others. Type-B panel with
(lm) test* test (J) chrome paint system showed the best blistering resistance, with
A Chrome 6 + 20 5B 2 T 13 J 2
almost no blistering. Type-D and -E painted panels showed low
B system 6 + 20 5B 0 T 18 J 0 blistering, followed by C which had low to medium blistering.
C 6 + 20 5B 1 T 13 J 1 The results of salt spray and CCT-1 tests are summarized below:
D 6 + 20 5B 0 T 18 J 0 Resistance to face blistering in salt spray:
E 6 + 20 5B 0 T 18 J 0
A Chrome 6 + 20 5B 2 T 13 J 2 Cr-system: B = D = E = C > A
B free 6 + 20 5B 0 T 18 J 0
Cr-free system: C = D = B > E > A
C system 6 + 20 5B 1 T 13 J 1
D 6 + 20 5B 0 T 18 J 0
E 6 + 20 5B 0 T 18 J 0 Resistance to face blistering in CCT-1 Test:
*
Dry adhesion test by ASTM D3359-02B.
**
Wet adhesion by boiling water test (13J) similar to ASTM D870. Rating scale used Cr-system: B = D = E > C > A
05, 0 being the best and 5 worst. Cr-free system: B > D = E > C > A
 R.P. Edavan, R. Kopinski / Corrosion Science 51 (2009) 24292442 2435

Table 4
Summary of the salt spray test results of the painted coated steel panels after 2000 h of exposure.

Panel Paint system Blistering (density, size) Corrosion product at 3T Cut edge corrosion creep, mm
Scale 05 (nilmax)
Scribe Face Bend (3T) Scribe Left Bottom Right Average
A Chrome system D0S0 D2S12 D2S12 0 0 3.5 3 7 4.5
B D2S2 D0S0 D2S23 3 0 20 12 50 27.3
C D0S0 D0S0 D1S2 0 0 6.5 2 6 4.8
D D0S0 D0S0 D1S2 2 0 2 1 2 1.7
E D0S0 D0S0 D2S2 2 0 2 3 3 2.7
A Chrome free system D0S0 D2S2 D2S1 2 0 5 10 9 8
B D4S3 D1S2 D2S1 5 5.5 68 72 75 71.7
C D2S2 D0S0 D1S1 0 0 11.7 13.5 10.5 11.9
D D0S0 D0S0 D1S1 3 0 3.7 2.5 3 3.1
E D2S1 D2S12 D2S1 2 0 9.3 5 9 7.7

Table 5
Summary of the cyclic corrosion test results of the painted coated steel panels after 2000 h of exposure.

Panel No. Paint system Blistering (density, size) Corrosion product at 3T Cut edge corrosion creep, mm
Scale 05 (nilmax)
Scribe Face Bend (3T) Scribe Left Bottom Right Average
A Chrome system D3S2 D3S2 D2S2 3 2 10.2 14.5 13.3 12.7
B D2S1 D1S1 D0S0 0 0 8 9.5 12.5 10
C D2S2 D23S2 D1S2 0 0 15 27 14 18.7
D D2S1 D2S1 D3S1 2 0 4.5 8 5.6 6.03
E D2S1 D2S1 D3S1 2 0 7.7 10 6 7.9
A Chrome free system D3S12 D4S12 D4S12 5 2 9 20.7 8 12.6
B D4S1 D4S2 D23S1 1 2 21 19.7 18 19.6
C D3S2 D4S2 D3S2 2 4.3 15 15.5 17 15.8
D D2S2 D23S12 D4S1 2 1.5 5.3 9 3.3 5.8
E D4S12 D3S12 D3S1 2 0.5 8 10.7 13 10.6

Table 6
Summary of the natural exposure test results of the painted coated steel panels at Muriwai, New Zealand, after 16 months of exposure in sheltered conditions.

Panel No. Paint system Blistering (density, D and size, S) Corrosion product 3T Cut edge corrosion creep, mm
Scale 05 (nilmax)
Scribe Face Bend (3T) Scribe Left Bottom Top Right Average
A Chrome system D3S2 D2S23 D3S2 0 1 3 5 1.5 5 3.6
B D0S0 D1S2 D0S0 0 0 0 1 0 2 0.8
C D0S0 D1S2 D0S0 0 0 3 4 3 9 4.8
D D0S0 D0S0 D0S0 0 0 0 0.5 0.5 0 0.3
E D0S0 D0S0 D0S0 0 0 0 0 0 0 0.0
A Chrome free system D3S2 D1S2 D3S2 4 0.5 3 5 1.5 2 2.9
B D0S0 D1S2 D0S0 0 0 1 2 2 6 2.8
C D0S0 D1S2 D2S2 0 0 1 10 2 1 3.5
D D2S1 D0S0 D3S2 2 0 1.5 2 1.5 1 1.5
E D0S0 D1S2 D2S1 0 0 2 2 1.5 1.5 1.8

The blistering at the bends appeared to follow very similar trends
as for the face in both the tests, except that the frequency of blis-
tering was marginally higher. Corrosion is also seen due to the
cracking of the paint lm at the bends. In salt spray test, type-A
and -C painted panels showed the best corrosion resistance, in
terms of deposition of the white corrosion products at the bends.
Types-B, -D and -E showed light white rusting at the bends. In
the cyclic corrosion test, on the other hand, types-B and -C showed
best results. White rusting were seen at the bends of panels A, D
and E. It appears that in cyclic corrosion test, CCT-1 painted panels
A, D and E are more prone to corrosion and developing white cor-
rosion product at bends than others. This is not evident at 500 h
but become more prominent after 1000 h of exposure. The chrome
free paint system was more prone to corrosion at bends than the
chrome ones on each of these substrates.
In the salt spray test (Table 4), type-D-painted panels exhibited
the best corrosion creep resistance with both chrome and chrome
free paint systems. Only very small corrosion creep was observed
at the cut edges of these panels. This was closely followed by E,
A and C painted panels in that order, with marginally more corro-
sion creeps. Type-B painted panel showed the least corrosion creep
resistance in this test, though it is well within the specication.
Interestingly, both Cr and Cr-free paint system showed similar
trend in this test except the fact the corrosion creep was substan-
tially higher for the Cr-free paint system. No red rusting was ob-
served at cut edges and only very little white corrosion product
was visible. The overall grading of the painted panels for edge cor-
rosion creep resistance in the salt spray test are:
Cr-system: D > E > A > C > B
Cr-free system: D > E = A > C > B
The edge corrosion creep resistance of painted panels changed
drastically in cyclic corrosion test, CCT-1 (Table 5). With the
2436 R.P. Edavan, R. Kopinski / Corrosion Science 51 (2009) 24292442

Cr-paint system, type-D still had the best corrosion creep resis- Table 7
tance followed closely by the type-E, both showing substantially Corrosion potential of painted and coated steel panels after different exposures in
aqueous 5% NaCl solution after 30 min of immersion.
low corrosion creep at the cut edges. The next best performance
was by type-B painted panel followed by type-C and -A panels, Types Metal Cr-paint system,corrosion Cr-free paint system,corrosion
respectively. In the Cr-free system, however, the trend remained coatings potential, mV (SCE) potential, mV (SCE)

same as that of the salt spray test. The performance of the painted Salt spray CCT-1 Salt spray CCT-1
panels with respect to corrosion creep resistance in the cyclic cor- A Zn coating 1078.50 984.93 1040.75 765.06
rosion test, CCT-1 can be, therefore, summarized as: B Galvalume 1007.35 941.06 994.06 993.37
C Galfan 1055.12 1014.56 1030.75 967.43
D ZAM 1135.46 1054.31 1079.55 950.06
Cr-system: D > E > B > C > A
E SuperDyma 1040.31 1065.68 1048.13 966.06
Cr-free system: D > E > A > C > B

Painted panels A and C showed small amount of red rusting at the

sures, however, showed some major changes. In these cases, the
bottom edge after 1500 h of exposure in the CCT-1 test. Same pan-
potential of type-A and -C panels showed major positive shift, indi-
els had not shown any red rusting even after 2000 h of exposure in
cating that the metal coatings on these panels have been consumed
the salt spray test. On the other hand panel B with the Cr-free paint
to a great extent. These potential scans clearly showed that CCT-1
system showed small amount of red rusting in salt spray test. Oth-
and natural exposure tests are considerably more aggressive than
ers did not show any red rusting in either of the tests.
the salt spray test.
After 2000 h of salt spray and CCT-1 tests, all the panels showed
The painted panels from accelerated and natural exposure tests
excellent corrosion creep resistance at the scribe, irrespective of
were also analysed for their barrier or pore resistance using EIS and
the type of the paint systems used. No signicant or measurable
the resulting spectra are given in Figs. 611. The results show that
corrosion creep was observed on any of the panels may be except
all panels, except B, tested in salt spray test (Figs. 6 and 7) retained
a few blistering.
most of their barrier resistance (high impedance values) for both
The natural exposure of the panels for 14 months at Muriwai,
Cr- and Cr-free paint systems even after 1000 h of exposure. The
New Zealand, under sheltered condition showed equally interest-
retention was quite high for the Cr-system and relatively low for
ing results (Table 6). Though this was an exposure only for a short
the Cr-free system. This indicates that very little degradation of
duration, still the test showed substantial corrosion creep at the
the paint systems might have taken place during the salt spray test.
cut edges because of the prevailing aggressive conditions. Type-A
The impedance of chrome paint system on A, C, D and E coated
panel with chromate based paint system, showed low to medium
steels were very close with little variations. On the other hand
facial blistering in this test, while others did not develop any face
blistering. With the Cr-free paint system, all the panels were al-
most blister free. Panel D was exceptionally good during this expo- 10
sure. Resistance to face blistering in natural exposure can be
9
summarized as:
8
Cr-system: B = D = E = C > A
log Z, ohms.cm2

7
Cr-free system: B = D = E = C = A
6
Interestingly, the corrosion creep at the cut edges observed in this
5
test were very similar to that seen in the cyclic corrosion test, CCT-
1, although at a much reduced rate. No measurable corrosion creep 4
was observed on the scribes of any of these panels. These results
3
were, however, different from those observed in the salt spray test.
This conrms the earlier ndings that the cyclic corrosion test 2
(CCT-1) replicates the failure modes of paint system more closely -3 -1 1 3 5
to that in the natural exposure conditions. On the basis of the nat- log f, Hz
ural exposure results, the relative corrosion creep resistance of
panels at the cut edges can be summarized as: 0

Cr-system: D E > B > A > C and -20

Phase angle [degrees]

Cr-free system: D E > A > B > C

-40
The corrosion potentials (vs. saturated calomel electrode, SCE) of
the Cr and Cr-free painted panels in 5% sodium chloride solution
after exposure to neutral salt spray test, CCT-1 and natural condi- -60
tions in Muriwai are given in Table 7. These potentials are signi-
cantly inuenced by the characteristics of the base metal and the -80
paint system and can be very helpful in understanding the corro-
sion pattern of the panels. Panels exposed to salt spray test showed
very similar trend as seen for the bare substrates except that they -100
-3 -1 1 3 5
are slightly shifted in the negative direction due to the inuence of
log f, Hz
the paint system. This conrmed that all exposed panels still
retained substantial amount of metal coatings even after 1000 h Fig. 6. EIS-Impedance and phase angle plots of chrome paint systems over different
of exposure and are capable of providing sacricial protection to substrates after 1000 h of salt spray test, ASTM B117 (where + is type-A,  is type-B,
steel against corrosion. Panels exposed to CCT-1 and natural expo- } is type-C, 4 is type-D and h is type-E painted and coated steel).
 R.P. Edavan, R. Kopinski / Corrosion Science 51 (2009) 24292442 2437

10 10

8 8

log Z, ohms.cm2
log Z, ohms.cm2

6 6

4 4

2
2 -3 -1 1 3 5
-3 -1 1 3 5
log f, Hz
log f, Hz

0 0

Phase angle [deg rees]

-20
-20
Phase angle [degrees]

-40

-40 -60

-80
-60

-100
-3 -2 -1 0 1 2 3 4 5
-80
log f, Hz

-100 Fig. 9. EIS-Bode Impedance and phase angle plots of chrome free paint systems
-3 -1 1 3 5 over different substrates after 1000 h of CCt-1 cyclic corrosion test (where + is type-
log f, Hz A,  is type-B, } is type-C, 4 is type-D and h is type-E painted and coated steel).

Fig. 7. EIS-Impedance plots of chrome free paint systems over different substrates
after 1000 h of salt spray test, ASTM B117 (where + is type-A,  is type-B, } is type- 10
C, 4 is type-D and h is type-E painted and coated steel).
9
8
log Z, ohms.cm2

10
7
6
8
5
log Z, ohms.cm2

4
6 3
2
-3 -1 1 3 5
4
log f, Hz

2 0
-3 -1 1 3 5
Phase angle [degrees]

log f, Hz -20

0 -40

-60
-20
Phase angle [degrees]

-80

-40
-100
-3 -1 1 3 5
-60 log f , Hz

Fig. 10. EIS-Bode Impedance and phase angle plots of chrome paint systems over
-80 different substrates after 14 months in natural exposure in Muriwai, New Zealand
(where + is type-A,  is type-B, } is type-C, 4 is type-D and h is type-E painted and
coated steel).
-100
-3 -1 1 3 5
log f, Hz the impedance of the chrome free paint system on the same sub-
Fig. 8. EIS-Impedance and phase angle plots of chrome paint systems over different
strates were substantially different. Type-B painted panels, which
substrates after 1000 h of CCT-1 cyclic corrosion test (where + is type-A,  is type-B, had very heterogeneous microstructure, registered very low
} is type-C, 4 is type-D and h is type-E painted and coated steel). impedance or barrier resistance for both types of paint systems
2438 R.P. Edavan, R. Kopinski / Corrosion Science 51 (2009) 24292442
10
9 painted panel A was of intermediate level. On the basis of these EIS
8
log Z, ohms.cm2
6 Cr-system: D E B A > C and
5
4 In the case of Muriwai unwashed natural exposure (Figs. 10 and
3 11), all the panels with Cr-paint system retained very high imped-
2
-3 -1 1 3
log f , Hz
0 tion of the paint system was much reduced. These EIS results for
Phase angle [degrees]
-20
-40
-60
-80
-100
-3 -1 1 3
log f, Hz
Fig. 11. EIS-Bode Impedance and phase angle plots of chrome free paint systems
over different substrates after 14 months in natural exposure in Muriwai, New
Zealand (where + is type-A,  is type-B, } is type-C, 4 is type-D and h is type-E
painted and coated steel).
in this test. The shift in the minima of the phase angle towards high
frequency region is an indicator to the corrosion creep happening
under the paint lm and the more the shift the higher the corrosion
creep. The phase angle shift in Figs. 6 and 7 suggest that paint lms
on substrate B is more prone to corrosion creep compared to others
under both paint systems. Based on these EIS results, the compar-
ative performance of paint systems on different substrates in salt
spray test can be summarized as below:
Cr-paint system: E = C P D > A  B
Cr-free paint system: C = D > A > E > B
The barrier or pore resistance of both Cr and Cr-free paint sys-
tems on all panels were signicantly low after 1000 h of CCT-1 test
(Figs. 8 and 9). This was irrespective of the coated substrates used
in this test. This shows that the degradation of the paint system
might have been more signicant in the cyclic corrosion test than
the salt spray test. Again the chrome paint system appeared to
have degraded relatively slowly compared to the chrome free paint
system in this test. Substrates appear to signicantly inuence the
degradation process of the paint system here too, but trends were
different from those seen in the salt spray test. In this case for
chrome paint system, highest impedance was registered on type-
D coated steel and lowest on C and A, others being in the interme-
diate range. For Cr-free paint system, the differences were not so
distinct. It appears that the presence of the chromate in the primer,
reduces the corrosion and the corresponding degradation of the
paint system considerably compared to the Cr-free primer. The
minima of the phase angle plots in Figs. 8 and 9 also underwent
considerable shift towards high frequency region due to corrosion.
These shifts suggested that under cyclic test conditions, the corro-
sion creep on pre-painted substrates D and E were least compared
to B and C for both types of paint systems. The performance of pre-
results the relative corrosion creep performance of pre-painted
panels in cyclic corrosion test can be graded as below:
Cr-free system: D > E A B > C
ance after 14 months of exposure, except for panel A which
5 showed very low value. In the case of the Cr-free system, all panels
except type-B showed high barrier resistance. These results are
very similar to that of the CCT-1 results, except that the degrada-
natural exposure are summarized below:
Cr-system: D E B C > A and
Cr-free system: A > D > C > E > B.
4. Discussion
The corrosion of painted and coated steel is a complex process
as it involves the degradation of both metallic and non-metallic
5 7 (especially polymeric) materials. The interactions of these materi-
als with the environments are, however, very different and may
also involve synergism, thus further complicating the degradation
process [3233]. The principal modes of corrosion failures ob-
served in normal outdoor applications are (a) blistering due to
rusting of the panel surface, (b) corrosion creep or undercutting
of the paint lm at the exposed cut edges and (c) corrosion creep
or undercutting at defects or damages in the paint lm. Below dif-
ferent aspects of these corrosion modes in the light of the above
ndings will be discussed.
Results of physical testing of the painted steels panels (Table 3)
show that there is a wide variation in the adhesive strength of the
paint systems on different coated steels. General adhesion of the
paint systems was good on all the coated steels as seen in the cross
hatch/tape pull test and coin scratch test. However, adhesion under
stressed conditions such as in compressive bend and rapid defor-
mation on impact, varied considerably from substrate to substrate.
Both Cr and Cr-free paint systems showed poor adhesion on rela-
tively pure zinc-coated (galvanized) steel (type-A). The same paint
systems showed better adhesion on alloy coatings rich in alumin-
ium such as BE. The adhesion of the paint systems were found to
increase with increasing aluminium content e.g. C compared to B.
These variations in the adhesive strength of paint systems on dif-
ferent metal coatings could be explained if we take into account
the interfacial composition of these systems. Observations made
during the tests have shown that peeling of paint lms usually oc-
cur at the metal coating/paint interface. The interface in this case
consists of conversion coatings, the chemical composition of which
is determined by the nature of the metal substrate and the chem-
ical treatment used. The composition of the conversion coating also
vary throughout the thickness of the coating, the closer to the me-
tal surface being rich in the respective metal oxides/hydroxides
while that away from the surface containing compounds from
the treating chemicals [3637]. Therefore, though similar conver-
sion coatings were used for all the substrates, the actual coatings
formed on these substrates vary substantially. These compositional
differences in the conversion coatings have very signicant inu-
ence over their properties too. Conversion coatings formed on A
and C which predominantly contained zinc compounds are not as
compact and adherent as those formed on aluminium rich coatings
 R.P. Edavan, R. Kopinski / Corrosion Science 51 (2009) 24292442
[3637], thus weakening the substrate/paint interface. This has
been attributed to the different electrical conductivities of the oxi-
des and their salts [38]. Zinc oxide and its salts which exhibit rel-
atively high conductivity inhibit clustering and compaction of its
products. On the other hand, aluminium oxides and its salt which
are mostly non-conducting and good insulators, allows faster clus-
tering and compaction. These characteristics of the conversion
coatings formed therefore signicantly inuence the adhesive
properties of the substrates. Zinc rich coatings such as A and C
therefore show relatively low adhesion for paints while the Al-rich
coatings B, D and E show good adhesion. Poor dry and wet adhe-
sion of paint systems seen on A and C type coated steels in 180
bend and reverse impact tests may be due to the above reasons.
Blistering due to corrosion of the painted and coated steels un-
der sheltered conditions is one of the very serious types of failures.
Earlier studies have identied that this kind of failure usually ini-
tiate through the localized de-adhesion of the paint system on
weaker areas on the painted surface followed by corrosion [17].
Considering the very similar nature of paint systems and conver-
sion coatings used for the same set of panels, the differences in
blistering might be due to the variations in the properties of the
coated steels. Both adhesion characteristics and corrosion resis-
tance of the metal coatings can signicantly inuence blistering
of paint lm in the corrosion test. The corrosion resistance of the
paint systems also signicantly inuence this process. These fac-
tors are considered in more details below.
In the previous paragraph it was explained that coated steel
such as B, C, D and E had better adhesion for paints compared to
pure zinc coating. The results from accelerated corrosion tests of
the substrates using the CCT-1 and EIS tests also show that the cor-
rosion resistance of the coated steel vary in the order of:
B > E > D > C > A. The corrosion resistance of the ZnAl alloy coat-
ings such as BE was much higher than that of the pure zinc coat-
ing (type-A) and the resistance increased as the Al content in the
alloy coatings increased. The coating with the largest amount of
Al (type-B) had the best corrosion resistance. The higher corrosion
resistance of the ZnAl alloy coatings are due to the better passiv-
ity of Al-rich coatings produced by aluminium oxides in corrosive
conditions. The solubility product of hydroxide of aluminium being
very low (1.3  1033 M4 at 25 C) compared to that of zinc
(3  1017 M3 at 25 C) and magnesium (5.61  1012 M3 at
25 C), Al-rich alloys passivate easily under the corrosive condi-
tions compared to pure zinc coatings [39]. Therefore corrosion
resistance of alloy coatings are better than that of the pure zinc
coating. And this is especially so in the case of B and C. Interest-
ingly ZnAl alloys containing Mg (such as D and E) also showed
good corrosion resistance in spite of the presence of highly active
Mg in the alloy. Mg appears to improve the corrosion resistance
by a dual mechanism. Mg in the alloy provides cathodic protection
to Al and Zn rich phases because of the polarization of these phases
to more negative potentials. The very negative corrosion potential
obtained for D and E alloy coatings containing Mg is strong evi-
dence to that (Fig. 7). The negative polarization of Al and Zn rich
phases present in alloy surface may initially increase the oxygen
reduction activity at the (zinc and aluminium rich phases) cath-
odes and the corrosion of the magnesium rich phase (MgZn2).
The products of these corrosion reactions, which in this case hap-
pen side by side, leads to the deposition of Mg(OH)2 on the entire
surface under the prevailing alkaline condition. The deposition of
alkali-resistant Mg(OH)2 on Zn- and Al-rich phases may consider-
ably reduce the overall oxygen reduction activity on these phases
in due course of time thus reducing the overall corrosion rate of
the alloy. Therefore, alloy coatings such as D and E containing
Mg rich phase show very good corrosion resistance in all the corro-
sion tests. The variations in blistering resistance of painted and
coated steel for same set of paint system in accelerated corrosion
2439
tests (ASTM B117 and CCT-1, ISO 11997-1 A) and natural exposure
(Tables 57) are mainly due to their differences in the adhesion
and corrosion resistance of the coated steels. Coated steels such
as B, D and E which have both good adhesion and corrosion resis-
tance showed almost blister free performance in all the exposure
tests including the natural exposure. Type-A which showed poor
paint adhesion and corrosion resistance showed poor blistering
resistance in these tests.
The corrosion resistance of the paint system is a function of the
total barrier resistance of the paint system (including conversion
coating, primer and top coat) [34] and corrosion inhibition ef-
ciency of the conversion coating and the primer. The chrome free
paint system used in this study had poor corrosion resistance com-
pared to the chromated one under similar circumstances. The cor-
rosion inhibition efciency of the anti-corrosive pigment used in
the Cr-free primer is very low (Fig. 4) as compared to the chromate.
The relatively lower blistering resistance seen for panels applied
with chrome free paint system in this study is mainly due to its
low corrosion resistance.
Painted zinc-coated steel (type-A) showed small amount of cor-
rosion at the bends in the salt spray and CCT-1 tests. Type-D and -E
also showed very small amount of white rusting at the bends. No
corrosion products were observed in the case of B and C. It appears
that these variations are due to differences in the ductility and cor-
rosion resistance of the of the coated steels depending upon the al-
loy composition of the coatings as explained earlier and mainly the
adhesion characteristics of the substrate for paints. Zinc coating
(type-A) has moderate exibility, low adhesion and very low corro-
sion resistance. Paint lm on type-A coated steel may usually crack
and lose adhesion during severe bending or deformation. Painted
zinc-coated steel, therefore, showed marginally high white corro-
sion at the bends in these tests. Type-D and -E alloy coatings on
the other hand, have good adhesion for paint systems and moder-
ate to high corrosion resistance. These coatings are, however,
tough due to the presence of MgZn2 phase (a relatively hard phase)
in the alloy matrix. Painted metal coatings such as these ones,
therefore, develop micro cracks during bending or deformation.
These cracks are also carried over to the paint lm adhering to
the surface thus exposing the substrate. Type-D and -E, therefore,
showed very small amount of white corrosion products at the
bends. Types-B and -C painted panels did not show any corrosion
at the bends. Type-B substrates have relatively low ductility, excel-
lent adhesion due to higher level aluminium in the coating and
very high corrosion resistance. The excellent adhesion of the paint
systems on these substrates and excellent corrosion resistance
more than compensates the relatively low exibility of the coating
in this case thus stopping blistering. On the other hand, type-C sub-
strates have moderate adhesion for paints and corrosion resistance
and excellent exibility due to the unique microstructure of the
coating. Zinc5% aluminium alloys coatings have composition
which is close to the eutectic composition and consists of Zn-
and Al-rich phases in a lamellar form through out the coating. As
both the alloy phases are very soft, the coatings show excellent
exibility. Therefore, type-C painted panel too showed no blister-
ing at the bends, though it has only moderate adhesion for paint
systems and corrosion resistance.
The resistance to corrosion creep or undercutting is considered
as one of the very important prerequisite for all painted steel appli-
cations. Corrosion creep usually occurs at break or defects in the
paint system or at the unprotected cut edges. Though similar ter-
minology is used to describe both failures, the morphology and
the mechanisms are completely different. The corrosion creep at
cut edges is considered a very serious problem in pre-painted
steels.
Both chromated and Cr-free types of paint systems showed
good resistance to corrosion creep at the scribe (paint defect) in
2440 R.P. Edavan, R. Kopinski / Corrosion Science 51 (2009) 24292442
all the tests. There was no measurable creep during the period of
the exposure. It has been shown that the corrosion creep at defects
such as at scribe occurs due to separation or shifting of the catho-
dic reaction from the metal surface at the scribe to underneath the
paint lm across the scribe [35]. Such transition is facilitated by
deposition of the corrosion products and consequent blockage of
all cathodic sites at the scribe during the corrosion process while
still maintaining a very active potential compared to the adjacent
painted areas [42]. Such cathodic reactions also give rise to electro
endosmosis of moisture through the paint lm due to negative
charge under the paint lm [35]. The undercutting of the paint
lm, therefore, takes place through a cathodic disbondment mech-
anism caused by alkali generated at the cathodic sites under the
paint lm during this process. The results from salt spray test
and cyclic corrosion tests such as CCT-1 and natural exposure show
that the extent of the corrosion creep in paint systems depend not
only on the adhesion of the paint system over the substrate, but
also on the electrochemical properties of the metal coating, nature
and efciency of corrosion inhibition by the primer and the barrier
resistance of the top organic coating. The salt spray test, with 100%
total wet time, the creep mechanism is dominated by the electro-
chemical properties of the metal coating and corrosion inhibition
by the primer. In chromated system, the inhibition of the corrosion
of the exposed metal surface being very good, no visible corrosion
creep was observed on most of the pre-painted steel except B with
large electrochemical heterogeneity. In Cr-free system, however,
the inhibition being relatively very poor, almost all panels showed
medium to large corrosion creep. In cyclic corrosion processes,
such as in CCT-1 and natural exposure, on the other hand, the total
wet time is considerably reduced (e.g. in CCT-1 it is about 50%). In
this case, the failure mechanism is dominated by the cyclic hygro-
thermal stresses in the coating which affects adhesion. The electro-
chemical properties of the substrates and corrosion inhibition,
though affects the corrosion creep mechanism, play only secondary
roles. Here, substrates with relatively poor adhesion characteris-
tics, such as A and C are prone to failure and showed considerably
high corrosion creep. Therefore, with a chromated primer, type
showed some corrosion creep in both CCT-1 and natural exposures.
With Cr-free primer, though all pre-painted steels showed some
amount of corrosion creep, it was largest for substrates A and C.
In natural exposure, the aggressivity of the environment being rel-
atively low compared to CCT-1, only type-A showed some amount
of corrosion creep others still being protected at this stage.
It has been widely accepted that the initiation and propagation
of the corrosion creep at the cut edges takes place by galvanic cor-
rosion mechanism, irrespective of the type of metal coatings used
[4041]. The creep is initiated by the accelerated corrosion of the
electrochemically active (sacricial) metal coating at the exposed
cut edges of the panels by the relatively noble steel base. The prop-
agation of corrosion creep is also galvanic, except that this mecha-
nism now takes place under the paint lm and a larger area of the
exposed panel surface is now involved. The electrolytes and corro-
sives required for the corrosion reaction is supplied by diffusion
through the paint lms from the surrounding atmosphere at the
advancing creep front.
Results of edge corrosion creep in the salt spray test as listed in
Table 4 show that it was least for D and max for B, the trend being:
D > E > A > C > B. This can be explained by taking into account the
electrochemical properties of the substrate and paint systems. In
a typical salt spray test which is completely static allowing no vari-
ations in the climatic conditions, the total wet time is 100%.
Though galvanic effect is the dominating factor in corrosion creep
mechanism at cut edges, the actual corrosion of the phases will dif-
fer from substrate to substrate. Galvanized steel which consists of
relatively pure zinc, corrosion of only zinc takes place all through
exposure. Such galvanic corrosions are normally considered as pri-
mary. In alloy coatings such as BE, where more than one electro-
chemically active phases are present as compared to steel,
however, the reaction are more complex. In such cases, it is the
most active phase present in the alloy coating which preferentially
corrodes [43]. For alloys B and C this phase has been identied to
the zinc rich phase. In the case of ZnAlMg alloys D and E, these
phases are the ZnMg2 intermetallics which are more active than
zinc. The relative corrosion of these phases will also be determined
by the level of polarization of steel surface achieved to provide pro-
tection against corrosion (cathodic protection). The creep initiates,
as has been described earlier, due to the primary galvanic effect be-
tween steel/sacricial coating. As Fig. 4 shows, coating D and E
have the best sacricial protection capabilities, followed by A and
C coated steels in that order. Type-B had the least sacricial protec-
tion capability. Moreover, under aerated humid conditions such as
that exist salt spray test, the Al-rich phase in alloy coatings present
in BE remains passive. This phase may in addition to steel, there-
fore, also contribute to the selective corrosion of zinc rich phase/
ZnMg2 during the initiation stage [44]. Once the delamination front
has moved to about 45 mm from the cut edge, the inuence of
steel base, however, decreases considerably because of the sharp
changes in the potential gradient across the panel surface. The gal-
vanic corrosion at this stage, therefore, will be more localized and
caused by the electrochemical heterogeneity of the coated steel
surface. The galvanic couple driving the delamination front will
be that due to the active zinc rich/ZnMg2 phase and the passive
Al-rich phase. Such galvanic corrosion mechanism is considered
as secondary as steel is no more active in this process. The rate
of propagation of the delamination front and extent of failure at
any time will be determined therefore by the type of electrochem-
ical heterogeneity of the metal coating, relative area of the anodic/
cathodic phases and the potential difference between these phases.
Therefore, pre-painted steels D and E which had the best sacricial
protection capabilities and also showed the best corrosion creep
resistance. A and C coated steels which had the next best sacricial
protection capabilities in that order, showed good corrosion creep
resistance close to that of D and E. The least corrosion creep resis-
tance was observed for B which had the least sacricial protection.
The high electrochemical heterogeneity (Fig. 1b) arising from the
two phase microstructure of the alloy coating B also contributes
to this. The relative corrosion creep resistance of painted steels re-
mained same for both chrome and chrome free paint systems in
salt spray test though the magnitudes were different. The corrosion
creep was signicantly low for chromate paint system because of
its relatively high corrosion inhibition capability and high for the
chrome free system with lower corrosion inhibition. The above re-
sults also show that the corrosion creep mechanism in salt spray
test is dominated by the electrochemical properties of the system.
The trends observed in the cyclic corrosion (CCT-1) and natural
exposure tests (Tables 5 and 6) were however different from that
seen in the salt spray test. Here, the relative corrosion creep resis-
tance for a Cr-paint system varied as D > E > B > C > A and that for
Cr-free paint system was D > E > A > C > B. Interestingly, panels B
and C with metal coatings having relatively poor sacricial protec-
tion, also showed good corrosion creep resistance. These coatings
had better paint adhesion than A as determined from physical test-
ing (Table 2). On the other hand, panel A of pure zinc coating with
very good sacricial protection capability, showed poor creep
resistance. Panel A had the least adhesion for paints. These results
show that the cut edge corrosion creep mechanism in pre-painted
steels under cyclic corrosive conditions such as CCT-1 and natural
exposure tests cannot be explained by the electrochemical mecha-
nism alone. The creep mechanism appears to be signicantly inu-
enced by the adhesion characteristics of the substrates too. A
model based on combining these two characteristics is shown pic-
torially in Fig. 12 and explained below.
 R.P. Edavan, R. Kopinski / Corrosion Science 51 (2009) 24292442
O2/ H2O
Hygro-thermal Stresses
Top coat
Corrosion product
Primer
Metal coating
Anode Cathode
Steel
Al 3+, Zn 2+, Mg2+ O2 + 2H2O 4OH-
Fig. 12. A schematics of the corrosion creep mechanism taking place on the painted
and coated steel sheet.
Paint adhesion play a very important role in cyclic corrosion
conditions, where the paint lms are subjected to repeated hygro-
thermal cyclic stresses during the wetdry cycle of the exposure.
This includes the natural exposure too which undergoes cyclic
changes during day and night conditions. Paint lms when ex-
posed to humid or wet condition such as during the salt fog and
humidity stages in CCT-1 test at 35 and 50 C, respectively, they in-
gress moisture. This ingress of moisture occurs by diffusion
through the free volume available in the polyester lm. Moisture
absorption in the paint lm changes its internal stresses both
tensile and compressive caused by wetting and drying of the lm
in cyclic testing [45]. As the paint lm absorbs water during the fog
and humidity cycle, it swells, causing compressive stresses in the
lm. When the paint lm dries in the dry stage (about 60 C), it
contracts, producing tensile stress. These compression and tension
forces have adverse effects on the lms cohesive integrity and on
its adhesion to the substrate. Of the two types of stresses, the ten-
sile stresses formed as the paint lm dries have greater effect.
Stress in paint systems is a dynamic phenomenon; it changes dras-
tically during water uptake and desorption [46]. The initial tensile
stresses (left over from shrinkage during lm formation) of the dry
lm decrease to zero as moisture is absorbed. Once the initial ten-
sile stresses have been negated by water uptake, further uptake
leads to build-up of compressive stresses. When the lm dries, ten-
sile (shrinkage) stresses redevelop, but to a lower degree than orig-
inally seen. Some degree of creep (permanent plastic yielding) has
also been observed due to breaking and reforming of bonds in the
paint lms. Similar observations were made by others too [47].
Hygrothermal stresses are related to ambient temperature [45]
as well as the glass transition temperature (Tg) of the paint system
[48], and the higher these temperatures the more the stresses.
Therefore, Hygroscopic stresses have a very real effect on coating
performance. Highly cross linked baked paint systems, which
develops high levels of internal stress during cure hygrothermal
stresses developed during water uptake or desorption can lead to
cracking or delamination. Investigation on both steel and zinc-
coated steel substrates have also shown that corrosion is slower
under complete wet conditions such as salt spray test where no
drying occurs. The corrosion is highly accelerated in wet/dry cyclic
testing. The transition zones between wet to dry and vice versa
that occurs in the cyclic test have been considered to be the most
corrosive due to thinner electrolyte layer, high amount of oxygen
transportation to the metal surface and high conductivity [49,50].
Therefore, the cyclic variations in the internal stresses of a paint
system can lead to localized mechanical disbondment of the paint
lm thus exposing the new metal areas for corrosion. The extent of
the inuence of these stresses to the paint system will depend
upon their relative adhesion (especially the wet adhesion) to the
substrate. The better the adhesion the lower the effect. Therefore,
the corrosion creep mechanism in the CCT-1 and natural exposure
tests is altered completely from that seen in the salt spray test.
From being a complete electrochemical mechanism as in salt spray
2441
test, is now changed to a mixed mechanism with substantial con-
tribution from both mechanical and electrochemical factors. The
overall performance of pre-painted steels, therefore, will not only
depend upon the electrochemical properties of the system but also
Cut
edge on adhesion characteristics. As the corrosion inhibition efciency
of the primer remains relatively same for a typical paint system,
the galvanic corrosion rate and therefore the paint undercutting
will be mainly determined by adhesion and electrochemical char-
acteristics of the metal coatings especially the galvanic or sacri-
cial protection. The overall corrosion creep under the paint lm
over Zn-alloy substrates, therefore may be low or high depending
upon the level of polarization of the steel i.e. cathodic protection.
The data in Table 3 show that the dry and wet adhesion of
chrome and chrome free paint systems were relatively poor on zinc
rich metal coatings such as type-A and -C, A being worse than C.
The adhesion of paint lms on aluminium rich coatings such as
B, D and E were, however, very good. Based on these results, the
relative adhesive strength of both types of paint lms on these me-
tal coatings were rated from high to low as: B = E = D > B > A. On
the other hand, the sacricial protection capability of the coated
steels varied as D > E > A > C > B. The overall corrosion creep exhib-
ited by these panels, therefore, will be determined by the interplay
of the adhesive and electrochemical properties and their relative
inuence. The best corrosion creep resistance was shown by the
type-D and -E painted panels which had best of both the proper-
ties. This was followed by B, A and C in the chrome system. In
the chrome free system, due to the relatively poor corrosion inhi-
bition by the chrome free primer, B showed relatively poor perfor-
mance compared to A, however better than C. From the above
discussion it is obvious that both physical as well as the electro-
chemical properties of the coated steel always transfer into their
painted products too thus signicantly inuencing their overall
weathering performance. The corrosion resistance of paint system,
especially that by the primer, further alters the mechanism espe-
cially by suppressing the electrochemical reactions and thus mod-
ifying the overall mechanism. Therefore selection of the coated
steel as well as the paint system is very critical for any painted
application.
The differences in the results in salt spray test and CCT-1 and
natural exposures are mainly because of the cyclic stress and relax-
ation of the paint lm. As the CCT-1 test replicates the wetdry cy-
cles reasonably well, the results from this test are very similar to
that of the natural exposure.
5. Conclusions
Painted coated steels containing ve different sacricial metal
coatings based on zinc, ZnAl and ZnAlMg alloys were assessed
for their corrosion performance in both accelerated and natural
environments. Their relative performance appeared to be strongly
linked with the physical as well as electrochemical characteristics
of the coated steel as well as the corrosion resistance paint system
used. Painted high corrosion resistant ZnAl alloy coated steels
gave more durable products than pure zinc-coated steel in this
study. The new ZnAlMg alloy coated steels showed remarkably
good blistering and edge corrosion creep resistance. The results
from the cyclic corrosion test such as CCT-1 (ISO 11997-1 A) were
more comparable to the natural exposure than those obtained
from the traditional salt spray test in this test series.
Acknowledgements
The authors would like to thank the management of Akzo Nobel
Pty Ltd., Sunshine, Australia for allowing to publish this paper in
Corrosion Science.
2442 R.P. Edavan, R. Kopinski / Corrosion Science 51 (2009) 24292442

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