376 DOI: 10.1002/maco.200604034
Corrosion Concepts
In this forum readers will be able to present practical problems
for discussion. It is envisaged that these contributions will
include not only discussion of general problems and incidents
of corrosion but that suggested remedies will also be presented
and discussed. It is hoped that this exchange of knowledge and
Corrosion resistance of steel with hot-dipped
galvanized zinc and zinc alloy coatings in
seawater
Hot-dipped galvanized zinc and zinc alloy coatings were used as
protective metallic coatings for steel structures in seawater in Chi-
na. Corrosion of the two coatings immersed in sea water in Qingdao
and Xiamen for 6 years were introduced and analyzed, which pro-
vides a basis for further development and applications of these coat-
ings in China. Tests proved that the anti-corrosion performance of
1 Introduction
Hot-dipped zinc coatings have already been used as protec-
tive metallic coatings for steel structures for a few decades
while the hot-dipped zinc alloy coatings were only developed
as metallic coatings in the last two decades [1, 2]. They are
still being developed and applied in China nowadays [3].
The application of these two coatings in marine environ-
ment in China should be based on their performance as deter-
mined from the long-term experimental data. In this study, ex-
periments were conducted to examine the performances of the
coatings. Results are expected to provide a basis for the selec-
tion and development of proper zinc alloy coatings for specific
environments in China.
2 Materials
2.1 The steel material
The base steel samples were made of 10# steel plates with a
2 mm thickness.
* Yantao Li. Jiangouo Liu, Jie Zhang
Institute of Oceanology, Chinese Academy of Sciences,
7 Nanhai Road, Qingdao, 266071 (P.R. China)
E-mail: ytli98@163.com
Shixian Chu
Qingdao Branch of Luoyang Ship Material Research Institute,
7 Nanhai Road, Qingdao, China, 266071 (P.R. China)
F 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Materials and Corrosion 2007, 58, No.
experience will become a permanent feature of this periodical.
We are particularly anxious that both Senior Scientists and
those with more practical experience will make use of this
forum to exchange information, problems and potential re-
medies.
Y. Li*, J. Liu, J. Zhang, and S. Chu
the hot-dipped low alloy zinc coatings (aluminum content less than
or equal to 10 wt%) is equal to or even lower than that of the pure
zinc sheet, while the performance of the hot-dipped high alloy zinc
coatings is higher than that of the pure zinc sheet. The hot-dipped
high alloy zinc coatings can be further developed for optimal per-
formance in the future.
2.2 The zinc/zinc alloy coatings
The compositions of different zinc/zinc alloy coating sam-
ples are shown in Table 1. The coatings containing less than
15 wt% aluminum (No. 5 to No. 8) are defined as low alloy
coatings. The coatings containing 15 wt% and more aluminum
are defined as high alloy coatings.
2.3 The hot-dip galvanizing process
The hot-dipped galvanized coatings were applied by a ty-
pical dry hot-dip galvanizing process.
The procedure is described below:
Pretreatment ! Cleaning ! Pre-Plating
! Hot-dip galvanizing ! Inspection
Three groups of pure zinc hot-dipped galvanized coatings
were separately applied following the manufacture procedure
in three typical professional plants, while another group of
parallel coating was applied in the laboratory following the
same procedure.
Only one group of zinc alloy coatings was applied in the
laboratory following the above procedure.
2.4 The dimensions of samples
The sizes of the steel samples with hot-dipped galvanized
pure zinc and zinc alloy coatings were 150
50
2 mm and
108
35
2 mm respectively.
www.wiley-vch.de/home/wuk
Materials and Corrosion 2007, 58, No. 5 Zinc alloy coatings in seawater 377

Table 1. Compositions of coatings (zinc bulk)

No Type of coating Aluminum Other elements No Type of coating Aluminum Other elements
(wt%) (wt%) (wt%) (wt%)
1 AnTa1 0.0 0.0 21 35A4M 35 4.5
2 HuSan2 0.0 22 35A4M1S 35 5.5
3 HuLao3 0.0 23 35A4M1.6S 35 6.1
4 Self-made4 0.0 24 35A10M 35 10.0
5 08A 0.1 0.0 25 35A10M1S 35 11.0
6 4A4M 4.5 4.5 26 35A10M1.6S 35 12.0
7 10A4M 10 4.5 27 55A 55 0.0
8 08A10A4M 11 4.5 28 55A1S 55 1.0
9 15A 15 0.0 29 55A1.6S 55 1.5
10 15A1S 15 1.0 30 55A4M 55 4.5
11 15A1.6S 15 1.5 31 55A4M1S 55 5.5
12 15A4M 15 4.5 32 55A4M1.6S 55 6.1
13 15A4M1S 15 5.0 33 55A10M 55 10.0
14 15A4M1.6S 15 6.0 34 55A10M1S 55 11.0
15 15A10M 15 10.0 35 55A10M1.6S 55 12.0
16 15A10M1S 15 11.0 36 A12S 87.4 12.6
17 15A10M1.6S 15 12.0 37 A0 99.8 0.2
18 35A 35 0.0
19 35A1S 35 1.0
20 35A1.6S 35 1.5
Note: The composition ratios of the alloy coatings are optimal according to the test results

The standard reference samples were preserved in the de-
siccator, and were used as references for the examination of
the tested sample surfaces after the experiment.
The thickness of each coating was measured using weight
methods or by magnetic thickness gauge (S2.310 Magnetic
Thickness Gauge, precision  2 lm, measurement error
3%). Results of the thickness measurement are shown in Ta-
ble 2 to Table 4.
3 Test condition and method
3.1 The test condition
3.1.1 Maidao sea area
Xiao Qingdao bay with the highest water temperature of
27  C, the lowest temperature of 1  C, and the annual average
temperature of 14  15  C. The seawater current flow is re-
latively steady with tide fluctuating current only.

Table 2. Six-year test of zinc and low alloy zinc coatings exposed in Qingdao sea area

No Class Type of Thickness Initial appearance In-test observation Final appearance Annual
samples (lm) after 6 years corrosion
rate (lm/a)
1 Pure zinc AnTa1 35  47 Uniformly grey white Black after 2 years, partial red rust covered 12
red rust appeared at 30% area
corners after 4 years
2 HuSan2 24  65 Uniformly grey white Black stain appeared red rust covered 90% 12
with crystal flower after 2 years, red rust area
stain appeared after
3 years
3 HuLao3 57  66 Uniformly grey white Red rust stain appeared local red rust covered 14
at crevices after 5 years 10% area
4 Self-made4 84  98 Uniformly grey white Black stain appeared red rust at crevices 16
after 2 years covering 1% total area
5 Low alloy 08A 55  58 Uniformly grey white Red rust appeared at local red rust covered 18
edges after 4 years 10% area
6 4A4M 16  30 Uniformly grey Red rust stain appeared dark red rust appeared 16*
in 10% area after in 90% area
2 years
7 10A4M 10  32 Uniformly grey Stain red rust appeared partial red rust 10*
in 5% area after appeared in 30% area
2 years
8 08A10A4M 36  98 Uniformly grey Crevice red rust Crevice red rust 12
appeared in 1% area appeared in 3% area
after 4 years
Note: 1) *The thickness of coatings was approximated, so the corrosion rate is only estimation;
2) Annual corrosion rate ¼ minimum thickness/test period (till the year before which red rust appeared)

www.wiley-vch.de/home/wuk
378 Li, Liu, Zhang, and Chu Materials and Corrosion 2007, 58, No. 5

Table 3. Five-year test of zinc and low alloy zinc coatings exposed in Xiamen sea area

No Class Type of Thickness Initial apperance In-test observation Final appearance Annual
samples (lm) after 5 years corrosion
rate (lm/a)

1 Pure zinc AnTa1 34  47 Uniformly grey white Red rust appeared red rust covered 17
underneath bio-layer 90% area
after 3 years
5 Low alloy 08A 55  58 Uniformly grey white Red rust covered Dark red rust covered 27
10% area under 80% area
bio-layer after 3 years
6 4A4M 16  30 Uniformly grey Red rust stain appeared Dark red rust covered 15*
under bio-layer after 90% area
2 years
7 10A4M 10  32 Uniformly grey Red rust stain appeared Dark red rust covered 15*
under bio-layer after 80% area
2 years
8 08A10A4M 36  98 Uniformly grey Red rust stain appeared Crevice red rust stain 18
at corners after 3 years covered 5% area
Note: 1) *The thicknesses of coatings are only approximations;
2) Annual corrosion rate ¼ minimum thickness/test period (till the year before which red rust appeared)

3.1.2 Xiamen sea area
The straits between Gulangyu Island and Xiamen, near
Kowloon estuary, with an annual average temperature of
21  C. The water current is higher [4].
3.2 The test method
life in seawater. According to the approximate corrosion rate
of the pure zinc coatings in seawater (Table 6), to achieve a 10-
year protective life, the thickness of zinc will have to increase
to be more than 120  160 lm in Qingdao area, and even
higher in Xiamen area.
The minimum thicknesses of hot-dipped pure zinc and zinc
alloy coatings for a 10-year protective life are shown in Ta-
ble 5.

The samples were inlayed in PVC shelves according to

Standard GB6384-86 and placed in floating rafts in each
sea area (or in a test pond) separately. The sample surfaces
were checked periodically every 1 or 2 years. Corrosion status
was recorded. The anti-corrosion life time of the coatings is
determined to be the year after which red rust first appeared.
The high aluminum alloy samples were immersed in the
seawater pond entirely.
4 Results
Results of the thickness measurements of the coatings and
the observations of the samples’ surface appearance during the
six years tests in Qingdao sea area and five to six years tests in
Xiamen sea area are presented in Table 2, Table 3 and Table 4
separately.
5 Discussion
5.1 Effect of coating thickness on the performance of the
coatings
As shown in Table 2, 3 and 4, for the same class of coatings
(pure zinc, low alloy or high alloy), the higher the coating
thickness, the better the anti-corrosion performance of the
samples with the coating, no matter where the samples
were exposed. The performance is enhanced with coating
thickness in Qingdao and Xiamen sea areas.
From the given observations, increasing the thickness of the
pure zinc coatings is the only way to increase their protective
5.2 Effect of the aluminum content on the performance of
the coatings
The effect of the aluminum composition on the anti-corro-
sion performance of the coatings does not seem to show a lin-
ear trend. When the aluminum content is less than 10%, the
anti-corrosion performance of low alloy zinc coatings is equal
or even poorer than that of the pure zinc coatings, even with
the presence of other alloying elements (Table 6). It may be
because that the self-closed corrosion product covering the
surface of the low alloy coatings is less compact than the clos-
ed surface shell on the surface of the pure zinc coatings [5].
The anti-corrosion performance of the high alloy zinc coat-
ings (presented in Table 4) is better than that of the pure zinc
coatings in Xiamen area. The annual corrosion rate of the
coatings containing 15% Al (15A4M1S, 15A10M, and
15A10M1S) is 2  3 times lower than that of the pure zinc
coatings. The corrosion rate of coatings containing 35% Al
(35A4M, 35A4M1.6S, and 35A10M1.6IS) is 2  3 times lo-
wer than that of the pure zinc coatings. The coatings contain-
ing 55% Al and other alloy elements (excluding 55A which
does not contain other alloying elements) performed better
than pure zinc coatings.
The effect of higher aluminum content improving the anti-
corrosion performance may be due to the reaction of sufficient
aluminum with other elements which result in self-passivity.
The self-closed passive film is probably a stronger barrier
against further corrosion than the self-closed film on pure
zinc surface, which is subject to further investigation in the
future.

www.wiley-vch.de/home/wuk
Materials and Corrosion 2007, 58, No. 5 Zinc alloy coatings in seawater 379

Table 4. Six-year test of high alloy zinc coatings exposed in Xiamen sea area

No Type of samples Thickness (lm) Initial appearance In-test observation Final Appearance Annual
after 6 years corrosion
rate (lm/a)

9 15A 50  70 Bright grey white Whiten after 2 years Red rust covered 10
30  40% area
10 15A1S 70  100 Bright grey Whiten after 2 years Red rust covered 5% area 14
11 15A1.6S 80  130 Uniformly grey Whiten after 2 years Red rust covered 2% area 16
12 15A4M 55  75 Uniformly grey Whiten after 2 years Red rust covered 11
20  40% area
13 15A4M1S 21  30 Uniformly grey Whiten after 2 years Red rust covered 4
15  35% area
14 15A4M1.6S 90  120 Uniformly grey Whiten after 2 years grey 13
15 15A10M 35  42 Uniformly grey Whiten after 2 years Red rust covered 7
30  35% area
16 15A10M1S 35  50 Uniformly grey Whiten after 2 years Red rust covered 5  10% 7
with granule area
17 15A10M1.6S 40  60 Uniformly bright grey Whiten after 2 years Red rust covered 8
white 30  35% area
18 35A 80  125 Uniformly grey Red rust stain covered Red rust covered 70% 80
5% area after 2 years area
19 35A10M1S 120  160 Uniformly grey Red rust stain covered Red rust covered 120
5% area after 2 years 40  80% area
20 35A10M1.6S 50  65 Uniformly grey Red rust stain covered Red rust covered 70% 50
5% area after 2 years area
21 35A4M 40  50 Uniformly grey white Grey after 2 years Red rust stain covered 8
2% area
22 35A4M1S 25  30 Uniformly grey white Red rust stain covered Red rust covered 25
2% area after 2 years 40  50% area
23 35A4M1.6S 27  40 Uniformly grey white Grey after 2 years Red rust covered 6
10  20% area
24 35A10M 30  40 Uniformly grey white Grey after 2 years Red rust covered 6
10  20% area
25 35A10M1S 22  45 Uniformly grey with Grey after 2 years Red rust covered 4
granule 10  15% area
26 35A10M1.6S 40  75 Uniformly grey with Grey after 2 years Red rust covered 5% area 8
granule
27 55A 55  75 grey Red rust stain covered Red rust covered 90% area 55
5% area after 2 years
28 55A1S 40  50 Uniformly silver white Grey after 2 years Red rust stain covered 8
2% area
29 55A1.6S 25  45 Uniformly silver white Grey after 2 years Red rust stain covered 5
2% area
30 55A4M 60  135 Non-uniformly grey Grey after 2 years Red rust stain covered 12
1% area
31 55A4M1S 39  55 Uniformly silver white Grey after 2 years Red rust stain covered 2% 8
area
32 55A4M1.6S 40  60 Uniformly silver white Grey after 2 years Red rust covered 1% area 8
33 55A10M 50  80 Uniformly grey Grey after 2 years Red rust covered 5% area 10
34 55A10M1S 50  65 Uniformly grey Grey after 2 years Red rust covered 5% area 10
35 55A10M1.6S 60  70 Uniformly coarse grey Grey after 2 years Stain red covered 1% area 12
36 A12S 17  25 Uniformly grey Red rust stain covered Red rust covered 90% area 17
with granule 5% area after 2 years
37 A0 502  75 Uniformly white Grey after 2 years Red rust stain covered 10
2% area
Note: Annual corrosion rate ¼ minimum thickness/test period (till the year before which red rust started to appear)

www.wiley-vch.de/home/wuk
380 Li, Liu, Zhang, and Chu
Table 5. Minimum thicknesses of hot-dipped zinc and zinc alloy coatings for a 10-year protective life
Sorts of samples Zn < 10%Al
Demanded thickness/ lm 160 180
Test sea area Qingdao Qingdao and Xiamen
5.3 Effect of other alloying elements on the corrosion
performance of the high alloy zinc coatings
The high alloy zinc (aluminum content > 15%) coatings
contain not only higher percentage of aluminum, but also
other elements. To investigate the effect of these other ele-
ments on the performance of the high alloy coatings, data ob-
tained in Xiamen sea area presented in Table 4 are used.
Both alloy coating 35A4M and alloy coating 35A contain
35 wt% aluminum; but 35A4M contains 4.5 wt% other alloy
elements while 35A does not (Table 1). During the test in Xia-
men sea area, the thickness of 35A4M (40  50 lm) was
much lower than that of 35A (80  125 lm), however after
six years exposure, only 2% area of the 35A4M surface
was covered by red rust dots at its corners; while 70% of
the 35A surface area was covered by red rust. The perfor-
mance of the thicker 35A coating is much worse than that
of the thinner 35A4M coating, which can only be interpreted
that the 4.5 wt% other alloying elements made a great im-
provement to the anti-corrosion resistance of 35A4M. The ef-
fect of the other alloying elements is stronger than that of the
thickness for these two alloys under this circumstances.
For the same reason, red rust appeared on the surface of
55A (55  75 lm thick) after only 1 year exposure, while
2% area of red rust appeared only at the corners of 55A1S
and 55A1.6S coatings (only 25  50 lm thick but containing
1.0 and 1.5 wt% other alloying elements) after 6 years expo-
sure.
The anti-corrosion performance of high alloy zinc coatings
depends not only on the thickness of the coatings, but also on
the alloy composition of the coatings.
5.4 Effect of environmental factor on performance of the
coatings
According to the test, for the same coatings, corrosion rate
in Xiamen area was higher than that in Qingdao area. The red
rust appeared one year earlier in Xiamen area than that in
Qingdao area. It can be interpreted that Xiamen seawater is
more corrosive than Qingdao seawater for these zinc coatings.
This may be due to the higher water temperature in the south
(Xiamen) therefore the marine biological effect is much
stronger.
Table 6. Zinc and zinc alloy coatings exhibiting good performance
Coatings series Zn < 10 wt% Al 15 wt% Al
Type of Hulao3 08A 15A1S 15A10M1S 35A4M
coatings Self-made4 08A10A4M 15A1.6S 15A4M1.6S
Corrosion 14  16 12  18 14  16 7  13
rate ( lm/a)
Test sea area Qingdao Qingdao and
Xiamen
Materials and Corrosion 2007, 58, No. 5
< 15%Al 35%Al > 55%Al A0
130 100 80 100
Xiamen
5.5 Optimal alloy composition of the coatings
To find an optimal alloy composition of the coatings, coat-
ings exhibiting good performance during the test are com-
pared. Eligible coatings are chosen from the tested zinc
and zinc alloy coatings (Table 2 to Table 4) based on the fol-
lowing criteria: less than 10% of the coating surface area was
covered by red rust after 6 years exposure. The selected coat-
ings and their annual corrosion rates are listed in Table 6.
The corrosion rate of low alloy zinc coatings containing less
than 10 wt% aluminum (12  18 lm/a) is close to that of the
pure zinc coatings (14  16 lm/a). For the coatings contain-
ing 15 wt% aluminum, only four elements alloy coatings
(15A10M1S and 15A4M1.6S) performed slightly better
than pure zinc coatings. High alloy zinc coatings containing
35 wt% aluminum performed much better after addition of
other elements (up to 8 lm/a). It can be further developed
in the future.
5.6 Corrosion mechanism
Almost all the red rusts were first found in crevices. It can
be interpreted that the medium in crevices was acidified,
which accelerated the zinc dissolution according to crevice
corrosion mechanism [6].
6 Conclusions
The following conclusions can be drawn from this study:
1) The corrosion resistance of hot-dipped zinc and zinc alloy
coatings in seawater in Xiamen and Qingdao areas is en-
hanced with the increase of the coatings thickness.
2) The corrosion resistance of hot-dipped high alloy zinc
coatings (aluminum content equal to or higher than
15wt%) depends not only on the thickness, but also on
the alloy composition. The corrosion resistance cannot
be improved with the increase of aluminum composition
unless other elements were added.
3) Xiamen seawater is more corrosive than Qingdao seawater
for the zinc coatings within the scope of this study.
35 wt% Al > 55 wt% Al
35A10M1.6S 55A1-1.6S 55A4M
55A4M1-1.6S 55A10M
55A10M1-1.6S
8  10 8  15 58 10  12
Xiamen
www.wiley-vch.de/home/wuk
Materials and Corrosion 2007, 58, No. 5 Zinc alloy coatings in seawater 381

7 Acknowledgements 8 References

This work was supported by the Development Project of
Qingdao Municipal Science and Technology (No.05-1-JC-
87) and the Key Project of Knowledge Innovation Program
(KIP),CAS (No.KZCX2-YW-210). The authors are grateful
to Dr. Yanxu Li (Department of Materials Science and Engi-
neering, McMaster University) for his valuable assistance and
helpful comments during the revision of this paper.
[1] P. R. Sere, M. Zapponi, C. I. Elsner, et al., Corrosion Science
1998, 40, 1711.
[2] G. Byrnes, Materials Performance 1885, 34, 44.
[3] Guocheng Gu, Bangjin Liu, The hot-dip coatings, Chemical in-
dustry Press Beijing, 1991.
[4] Dayang Liu, The Proceedings of the Chinese Association of
Corrosion and Protection, 1979.
[5] C. L. Kruse, Werkst. Korros. 1976, 27, 842.
[6] Metallic Corrosion Handbook, The Chinese Association of
Corrosion and Protection Shanghai; Shanghai Scientific &
Technical Publishers 1987.

(Received: September 18, 2006) W 4034

(Final Version: January 19, 2007)

www.wiley-vch.de/home/wuk