Materials and Corrosion - Bernd Isecke, Michael Schütze, and Martin Stratmann

ISSN 0947 5117 MTCREQE 63 (5) 377468 (2012) Vol. 63 No.
5 May 2012
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Materials
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380
Contents 2012, 63, No. 5
Articles published on the web will

appear several weeks before the print
edition. They are available through:
wileyonlinelibrary.com
Contents
Cover:
The main image was taken by optical microscopy and shows a
polished 0.1 wt% well-dispersed MWCNT/AZ91 sample after
1 day immersion in 3.5% NaCl. The inset presents a SEM image
of pristine MWCNTs, which we postulate to act as electrodes in
the AZ91 composites. The evenly distributed corrosion pattern
in the main image indicates that with well-dispersed MWCNTs
in AZ91, formation of galvanic couples takes place everywhere
on the composite surface. The corrosion rate of the AZ91
composites with well dispersed MWCNTs is therefore strongly
increased compared to the composites with less well
dispersed MWCNTs and pure AZ91.
More detailed information can be found in: Q. Li, M. C. Turhan,
C. A. Rottmair, R. F. Singer, S. Virtanen, Influence of MWCNT
Dispersion on Corrosion Behaviour of their Mg Composites,
Materials and Corrosion 2012, 63, 384.
This study reports on the influence of

carbon nanotubes (CNT) dispersion on
corrosion behaviour of their Mg composites. Experiments revealed that the
corrosion rate is drastically increased
by adding CNTs to the magnesium alloy
due to galvanic coupling. Moreover, a
homogeneous CNT dispersion leads to
reduced corrosion resistivity. Surface
pre-treatment is also found to be
critical for the corrosion performance.
Laboratory exposures have been performed simulating a selective catalytic

reduction system with urea injection for
NOx reduction in diesel exhaust aftertreatment. The corrosion behaviour of
three ferritic and one austenitic stainless steel was examined. Results show
that cyclic interaction between high
temperature and condensation aggravates the corrosion compared to isothermal exposure at 4508C.
384-387
Influence of MWCNT dispersion on corrosion behaviour of their Mg composites
Q. Li, M. C. Turhan, C. A. Rottmair,
R. F. Singer and S. Virtanen
388-395
Corrosion of stainless steels in simulated diesel exhaust environment
with urea
J. Nockert, L. Nyborg and M. Norell
www.matcorr.com
381
This work studied the hot dip galvanizing behavior of three advanced high
strength steels annealed under different
protective atmosphere. Fourier transform infrared spectroscopy was employed to identify the different oxides
formed on steel surface during annealing, fitting well with the prediction
results from Thermo-Calc calculation.
Both the coating quality and the microhardness of the steels change with the
annealing atmosphere.
Hot dip galvanizing behavior of advanced high strength steel

F. Li, H. Liu, W. Shi, R. Liu and L. Li
-3
401-407
-4
Log(I(A/cm2)))
Corrosion behaviour of high-strength

galvanized steel wires under tensile
stress was investigated by electrochemical polarization and salt spray test
(SST) using simulated acid rain as
electrolyte. Electrochemical polarization and SST results showed corrosion
rate rose significantly with increasing
tensile stress.
396-400
-5
a
-6
b
-7
c
d
-8
e
-9
-0.7
Influence of tensile stress on corrosion

behaviour of high-strength galvanized
steel bridge wires in simulated acid
rain
-0.8
-0.9
-1.0
-1.1
-1.2
-1.3
W. J. Yang, P. Yang, X. M. Li and

W. L. Feng
E(mV/Ag/AgCl)
Materials commonly used in the automotive industry were assembled with

different combinations using various
joining techniques in order to evaluate
their corrosion performance as well
their mechanical properties after cyclic
accelerated corrosion tests. The results
indicated a relationship between the
corrosion inside the confined joint and
the decrease of the mechanical properties of the assemblies.
A zinc/silicon dioxide composite film

has been electrodeposited on carbon
steel surface via adding tetraethylorthosilicate (TEOS) in zinc nitrate
solution. Polarization curve results
showed that the composite film
obtained with the TEOS concentration
of 0.012 M possesses the best corrosion
resistance.
www.matcorr.com
408-415
Corrosion performance and mechanical properties of joined automotive
materials
N. LeBozec, A. LeGac and D. Thierry
416-420
A zinc/silicon dioxide composite film:
Fabrication and anti-corrosion characterization
Z. F. Lin, D. Zhang, Y. Wang and P. Wang
382
Corrosion behaviour of different tempers of Al-Zn-Mg-Cu-Zr-Sc alloy was

studied by potentiodynamic polarization, electrochemical impedance spectroscopy, optical microscopy and
transmission electron microscopy. AlZn-Mg-Cu-Zr-Sc alloy with over aged
treatment has an enhanced resistance
to exfoliation corrosion.
Influence of heat treatment on corrosion behaviour of AlZnMgCuZrSc

alloy
Y. P. Xiao, Q. L. Pan, W. B. Li, X. Y. Liu and
Y. B. He
-1.065
431-437
-1.070
a
Eocp(V/SCE)
Microbiologically influenced corrosion

(MIC) of Al-Zn-In-Sn sacrificial anodes
in marine sediment was investigated by
exposing samples to sulphate reducing
bacteria (SRB). Samples exposed to the
sterile marine sediment were used as
control. The results show that corrosion
can be increased sharply by the SRB
metabolic activity due to the cathodic
depolarization effect.
421-430
Effect of sulphate reducing bacteria

on corrosion of AlZnInSn sacrificial
anodes in marine sediment
-1.075
-1.080
-1.085
F. Liu, J. Zhang, S. Zhang, W. Li, J. Duan

and B. Hou
-1.090
The purpose of this study is to establish

a laboratory scale experimental setup
that can be used to study the kinetics of
the processes involved in copper corrosion of household plumbing systems
within a short period of time. The
developed setup offers a promising
alternative to studying copper corrosion
using experiments that last for just 24
hours instead of 6 months as with pipe
rig experiments.
Nanocrystalline nickel oxide particles

have been successfully prepared by a
simple, fast, economical and ecofriendly solution-combustion method.
The properties and behavior of the asprepared compound were examined by
different methods. As an application
part the corrosion behavior of Zn-NiO
composite coating was analysed by
Tafel, impedance and anodic polarization in aggressive medium.
Corrosion News
10
12
14
16
Time (days)
438-444
Alternative methods for copper corrosion studies in household plumbing
systems
A. Armanious and K Johannsen
445-455
Generation of nanocrystalline NiO
particles by solution combustion
method and its ZnNiO composite
coating for corrosion protection
K. G. Chandrappa, T. V. Venkatesha,
K. O. Nayana and M. K. Punithkumar
456-465
www.matcorr.com
384
DOI: 10.1002/maco.201006023
Materials and Corrosion 2012, 63, No. 5
Influence of MWCNT dispersion on corrosion behaviour

of their Mg composites
Q. Li*, M. C. Turhan, C. A. Rottmair, R. F. Singer and S. Virtanen
Carbon nanotubes (CNTs) have been demonstrated as good reinforcements to
improve mechanical properties of magnesium alloys. This study reports on the
influence of CNT dispersion on corrosion behaviour of their Mg composites.
Experiments revealed that the corrosion rate is drastically increased by adding
CNTs to the magnesium alloy due to galvanic coupling. Moreover, a
homogeneous CNT dispersion leads to reduced corrosion resistivity. Surface
pre-treatment is also found to be critical for the corrosion performance for both
1 and 5 wt% CNT composites.
1 Introduction
Carbon nanotubes (CNTs) have been considered as ideal
reinforcements for high strength and lightweight composites
due to their favourable geometrical and mechanical properties
[15]. While considerable research has been devoted to CNTpolymer composites [69], much less has been done in view of
embedding CNTs into metals. As one of the first groups to
produce CNT reinforced Mg AZ91 composites by a melt stirring
technique [10, 11], we demonstrated that by adding only 0.1 wt%
multiwall CNTs (MWCNTs), the mechanical properties of the
MWCNT/AZ91 composites can be increased up to 40% [10].
Additionally to the mechanical properties of MWCNT/AZ91,
we are also interested in the influence of CNTs on the corrosion
behaviour of Mg composites. Mg and its alloys have low corrosion
resistance, which limits their applications. Several studies
reported on the corrosion behaviour of AZ91 [12, 13] and
demonstrated that the alloy microstructure [14, 15] significantly
influences the corrosion resistance. However, the effect of
nanosize modifications such as CNTs on corrosion behaviour of
Mg alloys is rarely studied [1619]. In a first study of the corrosion
behaviour of a CNT/Mg alloy composite, a significant improvement of the corrosion behaviour of an Mg AZ91 alloy was found
by adding MWCNTs to the composite, along with increased
mechanical properties. This finding is quite surprising, as it can
be argued that MWCNTs may reduce the corrosion resistance due
to galvanic interactions between the cathodic MWCNT and the
Q. Li, C. A. Rottmair, R. F. Singer

Institute of Advanced Materials and Processes (ZMP), University of
Erlangen-Nuremberg, Dr.-Mack-Str. 81, 90762, Fuerth (Germany)
E-mail: qianqian.li@zmp.uni-erlangen.de
M. C. Turhan, S. Virtanen
Institute for Surface Science and Corrosion (LKO), University of
Erlangen-Nuremberg, Martensstrae 7, 91058 Erlangen (Germany)
2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
anodic Mg alloy matrix, similarly as reported for graphite or

carbon fibre reinforced Al and Mg [2022].
2 Experimental
To clarify the effect of CNT addition, we fabricated MWCNT/Mg
composites with different contents of MWCNTs (0.1, 1 and
5 wt%) by a melt stirring technique. MWCNTs (Baytubes1 C
150P) and magnesium alloy (AZ91, ECKA) were weighted into a
crucible which was placed into a furnace and heated up to 670 8C
under Argon atmosphere. After the alloy was molten, the melt
was stirred for 30 min at 350 rpm and cast into a cylindrical
mould. Samples without MWCNT were also produced as
reference material.
To reveal the influence of CNT dispersion on the corrosion
behaviour of the composites, samples containing 0.1 wt%
MWCNTs were produced using a two-step process. Before the
actual melting of the MWCNT/AZ91 mixture, a pre-dispersion
procedure was applied to break up big agglomerates of MWCNTs
and disperse them homogenously on the AZ91 chips. Details of
this process can be found elsewhere [10]. Afterwards, samples
were cut to cylindrical specimens ( 10 mm) and embedded in
resin. Their surfaces were polished and then immersed in 3.5%
NaCl solution for 1 day and investigated by optical microscopy.
For the corrosion tests, the cast samples were cut to
rectangular specimens (dimensions: 24 mm 7 mm 7 mm)
and were prepared with three different mechanical surface
finishing methods; mechanically ground, polished and etched.
The ground surfaces were prepared by simply using 1200 grit
emery paper. The polished ones were prepared with 6, 3 and 1 mm
aqueous diamond paste after mechanical grinding. Etched
surfaces were prepared by dipping the polished samples for 5 s
into 2.5 wt% H2SO4.
Corrosion tests were performed in 3.5% NaCl solution
(purity >99.5, pH 7) which was refreshed daily. For daily weight
loss measurement, samples were removed from NaCl solution
www.matcorr.com
and weight loss was recorded. The used NaCl solution was
collected and dried to investigate the residue under a scanning
electron microscope (SEM, Zeiss 1540ESB).
3 Results and discussion

For improved mechanical properties, a homogeneous dispersion
of CNTs in the material matrix is required. Without a
homogenous dispersion of the CNTs, their excellent properties
cannot be utilised and CNTs bundles act as defects rather than
reinforcements in the matrix. It is interesting to check the
influence of CNT dispersion on corrosion behaviour of CNT/
AZ91 composites. Figure 1ac displays optical micrographs of the
surfaces of 0.1 wt% MWCNT/AZ91 with pre-dispersion (Fig. 1a),
0.1 wt% MWCNT/AZ91 without pre-dispersion (Fig. 1b) and pure
AZ91 (Fig. 1c) after 1 day immersion in 3.5% NaCl. The effect of
CNT dispersion on the corrosion behaviour can be easily
observed. A bigger and more evenly distributed corrosion pattern
can be observed in Fig. 1a compared to a smaller corroded area in
Fig. 1b. With well-dispersed MWCNTs in AZ91, formation of
galvanic couples takes place everywhere on the composite
surface, hence strongly increasing the corrosion rate of the alloy.
Without pre-dispersion, the coupling effect only takes place at
MWCNT agglomerates (Fig. 1b). For the pure AZ91 alloy, the
Influence of MWCNT dispersion on corrosion of MWCNT/Mg composites
corrosion only takes place on a small area (at the right edge of the
pure AZ91 image) and the corrosion level after 1 day is quite low
compared to the MWCNT/AZ91 composites. Furthermore, Fig.
1d shows the weight loss for 5 wt% MWCNT/AZ91 composites
with and without pre-dispersion. Clearly, a much higher weight
loss of the dispersed CNT/AZ91 composite compared to the nondispersed sample is observed, confirming that the better the
dispersion, the worse the corrosion behaviour.
Additionally, we studied the effect of surface condition on the
corrosion rate. Clearly, surface pre-treatment is an important
factor influencing the corrosion behaviour of the composites.
Corrosion rates of the composites were between 5 and
9 g m 2 day 1 for the 1 wt% MWCNT composites and between
19 and 24 g m 2 day 1 for the 5 wt% MWCNT composites, which
are both significantly higher than the corrosion rate for pure
AZ91 (3 g m 2 day 1; Fig. 2). Since the observed gas evolution
during the experiments and the corrosion rate are proportional to
the MWCNT amounts in the Mg matrix, we attribute the
increased corrosion rate of the composites to a galvanic coupling
effect which can increase the dissolution of the Mg phase. Within
the 1 wt% MWCNT/AZ91 composites, the highest corrosion rate
was measured on the etched surface; while within the 5 wt%
MWCNT/AZ91 composites, the ground samples exhibited the
highest corrosion rate. The origin of the influence of the surface
Figure 1. Optical microscopy of polished 0.1 wt% MWCNT/AZ91 with (a) pre-dispersion process, (b) without pre-dispersion, (c) pure AZ91 sample
after 1 day immersion in 3.5% NaCl and (d) weight loss results of polished 5 wt% MWCNT/AZ91 composites (with/without pre-dispersed MWCNTs)
in 3.5% NaCl during 1 week
www.matcorr.com
385
386
Li, Turhan, Rottmair, Singer, and Virtanen
test and the residue was observed under SEM (shown in Fig. 3a).
The pattern in the circle (Fig. 3a) looks very different from Fig. 3b,
which presents a typical corroded AZ91 composite surface with
short, sharp and needle-shaped crystals. The material in the circle
has relatively long and cylinder shapes with a smooth surface,
which is more like pristine MWCNTs (Fig. 3c) and pre-dispersed
MWCNTs on AZ91 chips (Fig. 3d). Therefore, we assume that the
remnants are CNT-like material. This finding suggests that the
CNTs themselves are not dissolved, supporting the concept that
they act as local cathodes in the composite. More detailed
characterisation of the corrosion products and remnants, such as
Raman spectroscopy, will be carried out in the future.
4 Conclusions
Figure 2. Weight loss of AZ91 and MWCNT/AZ91 composites (1 and

5 wt%, without pre-dispersion) with different surface pre-treatments
(ground, polished and 2.5 wt% H2SO4 etched) over 7 days of immersion
in 3.5% NaCl
preparation on the corrosion behaviour in the present case is not

yet clear; this effect will be investigated in more detail in the
future.
The corrosion product of the 5 wt% MWCNT/AZ91 sample
in 3.5% NaCl solution was collected and dried after the corrosion
In this paper, the corrosion behaviour of MWCNT/magnesium

alloy AZ91 composites was studied. In contrast to a previous report
by Endo et al. [19], the present study clearly demonstrates the
deteriorating effect of CNTs as reinforcements on the corrosion
behaviour of the Mg alloy matrix. Dispersion of MWCNTs plays a
major role in corrosion of the AZ91 composites. A good dispersion
of MWCNTs leads to even higher corrosion rates on the composite
surface. In this case, galvanic coupling takes place at an increased
number of reaction sites, as bundles of CNTs are broken up to
smaller, more homogenously dispersed entities. Additionally, the
corrosion rate increases with increasing amount of MWCNTs in the
composites. This can be explained by a coupling effect between
cathodic MWCNTs and anodic Mg alloy.
Figure 3. SEM images of (a) dried corrosion residue of 5 wt% MWCNT/AZ91; (b) the typical corrosion pattern on a 5 wt% MWCNT/AZ91 composite;
(c) pristine MWCNT and (d) homogenously dispersed MWCNT on the surface of AZ91 chips [10]. Circle in (a) indicates a CNT-like area
www.matcorr.com
Acknowledgements: Financial support by the German Research

Foundation (DFG) under grant LI 1847/2-1 was gratefully
acknowledged. The authors also gratefully acknowledge the
support of the Cluster of Excellence Engineering of Advanced
Materials at the University of Erlangen-Nuremberg, which is
funded by the German Research Foundation (DFG) within the
framework of its Excellence Initiative under grant EXC 315-1.
We would like to thank Dorothea Amberger and Shi Feng for their
kind technical assistant. We appreciate Dr Jan Schwerdtfeger for
fruitful discussions and suggestions.
5 References
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[10] Q. Li, A. Viereckl, C. A. Rottmair, R. F. Singer, Comp. Sci.
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H. Muramatsu, Y. Shimizu, S. Morimoto, M. Terrones,
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(Accepted: January 7, 2011)
www.matcorr.com
W6023
387
388
DOI: 10.1002/maco.201005783
Corrosion of stainless steels in simulated diesel exhaust

environment with urea
J. Nockert, L. Nyborg and M. Norell*
Laboratory exposures have been performed simulating a selective catalytic
reduction (SCR) system with urea injection for NOx reduction in diesel exhaust
after-treatment. The corrosion behaviour of three ferritic and one austenitic
stainless steel was examined using X-ray photoelectron spectroscopy (XPS) and
Auger electron spectroscopy (AES). Continuous exposure to condensate did not
cause any corrosion. Results show that cyclic interaction between high
temperature and condensation aggravates the corrosion compared to
isothermal exposure at 450 8C. All ferritic alloys exhibited more or less the same
behaviour, while the austenitic steel performed better. In fact, the presence of
urea decreased the corrosion compared to the environment without urea. The
cyclic samples exposed with urea displayed iron sulphate on the surface. The
sulphate appeared to decrease the oxide thickness. A sulphur enrichment in the
form of sulphide also occurred in the inner chromium-rich oxides of all cyclically
exposed samples, both with and without urea. Thus, sulphidation is presumed to
be involved in the corrosion process.
1 Introduction
The most commonly used materials in automotive exhaust
systems used to be bare or aluminised carbon steel. Over the years
demands of longer service lifetime and decreased emissions have
led to higher demands on design and material selection. This has
in turn led to a gradual shift towards using stainless steel instead.
With the emission regulations becoming increasingly strict, the
carbon monoxide and hydrocarbon levels have been successfully
decreased and different methods for the reduction of NOx have
been developed. The aim of this study was to investigate the
performance of stainless steel for use in diesel exhaust gas aftertreatment systems for heavy-duty trucks using selective catalytic
reduction (SCR) for the reduction of NOx.
In SCR-systems a reducing agent is introduced into the
system upstream of the catalytic converter by means of an
aqueous solution of urea as ammonia source. The urea solution is
injected into the exhaust flow, where it vaporises and decomposes
into mainly ammonia and carbon dioxide, though also
intermediate compounds such as isocyanic acid will form. The
isocyanic acid can further decompose into ammonia. The
ammonia acts as reducing agent and reacts with the NOx on a
catalyst surface forming N2 and H2O, which are emitted with the
exhaust gases [1, 2].
J. Nockert, L. Nyborg, M. Norell
Department of Materials and Manufacturing technology, Chalmers
teborg (Sweden)
University of Technology, 41296 Go
E-mail: mats.norell@chalmers.se
The SCR-technique is quite new at this large scale and

therefore the corrosive impact is yet to be further investigated.
The environment in a catalytic converter has a complex nature.
Apart from the exhaust gases varying with the quality of the fuel,
and the injection of urea, there is a large temperature variation
ranging from the surrounding temperature when the engine is
switched off up to about 600 8C when the engine is running at
high load. This submits the material to thermal cycling, high
temperature corrosion when the engine is up in temperature and
also wet corrosion during the low temperature intervals related to
the formation of condensate.
Urea is not considered as being particularly corrosive in
itself, some of the by-products may, however, be more or less
aggressive [3, 4]. Most work done on corrosion involving urea is
linked to urea production or the fertiliser industry. During urea
synthesis for example the most critical stage from a corrosion
point of view is the intermediate formation of ammonium
carbamate, which is highly corrosive [2, 3]. Ammonium
carbamate is assumed to form only at high pressures, not likely
to arise in the type of systems here studied. In the fertiliser
industry urea is used for nitrogen containing products and has
here also been known to cause corrosion problems [5, 6].
Austenitic stainless steels are used for these two applications that
have similar conditions. The environment can be well controlled
for each stage of the process to an extent that would not be
possible for automotive applications. The processes sometimes
have high pressures, but there is no thermal cycling and generally
lower temperatures, up to about 250 8C [4], compared to diesel
exhaust systems where the temperature can reach 600 8C. Also,
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oxygen can be introduced to ensure the presence of a passive

layer. Thus, the situations will provide different challenges.
Investigations concerning the conditions in automotive
exhaust systems have been more focused on cars rather than
trucks. The studies often relate to either cyclic oxidation linked to
the thermal cycling of the system [7] or external corrosion due to
road salt [8, 9]. Many studies also address the effect of condensate
and thermal cycling, but mainly at lower temperatures and
without urea. Gumpel et al. [10, 11] have performed experiments
on stainless steel with synthetic condensates, where the focus has
been on lower temperatures up to 85 8C and acidic condensates
with both chlorides and active carbon. The samples were not
exposed to elevated temperatures. Thus, the combined effect of
high temperature exposure and condensate was not studied.
Michel et al. [12] have performed two different types of laboratory
experiments simulating the SCR environment. The first test
included direct spraying of urea solution onto cyclically heated
samples, resulting in carbonitriding. However, the procedure for
those experiments was not presented. The second experiment
involved the use of an artificial condensate of pH 4, which
takes into account exhaust gases dissolving in the condensate.
The test samples were cycled between dipping in condensate
and heating in a furnace at 300 8C. Higher number of cycles
gave more severe corrosion and the lowest alloyed ferritic
material performed worst. The study by Floyd et al. [13] mentions
problems involving urea and deposits on field components.
In their laboratory experiments on stainless steels cyclic tests
with urea solution were also performed, one simulating
condensation with a maximum temperature of 120 8C (initial
step 750 8C) and one where urea was sprayed onto samples
cyclically heated at temperatures between ambient and 650 8C.
The study used pH 910 urea solution as the synthetic
condensate. Most of these laboratory studies have been
performed in air, not taking the composition of the exhaust
gases into account. Neither do they present any particular
analyses of the corrosion products.
This study presents results from laboratory experiments
performed under controlled conditions in a rig simulating a
typical diesel exhaust system. The behaviour of four stainless
steels under the influence of simulated exhaust gas flow, urea
injection and thermal cycling, including the formation of a
condensate, has been studied through thorough analysis of
corrosion products. The focus has been on the situation for
materials at some distance from the urea injection point, just
before the catalyst itself.
Corrosion of stainless steels in diesel exhaust environment
Table 1. Nominal composition of alloys used in the experiments. The

designations given in bold letters are used in the article.
Alloy
EN
Fe
Cr
Ni
Mn ()
Mo
409
430Ti
304L
1.4512
1.4510
1.4513
1.4306/7
Bal.
Bal.
Bal.
Bal.
12
17
17
18
10
1
1
1
2
Others
Ti
using 1 mm diamond polishing liquid for a reproducible surface

roughness.
2.2 Furnace exposures
The difference in corrosion behaviour for the different alloys was
investigated under controlled conditions using a laboratory test
rig. This rig represents the part of the system immediately before
the catalytic converter with gas flow, injection of urea solution and
heating. A tube furnace was used (Fig. 1) for the simulation of an
exhaust after-treatment system. The gas flow through the system
was 13 mm/s and the temperature was 450 8C. A simplified gas
mixture was used, see Table 2, and the urea solution was
administered dropwise 7 mL/h by means of a nozzle entering the
tube furnace in a zone at about 300 8C resulting in immediate
vaporisation. The commercial 32.5 wt% urea solution AdBlue was
used and this solution was diluted (to 2.4 wt% urea) to achieve a
10% water vapour content in the gas mix.
In order to simulate the cyclical conditions under which an
after-treatment system works, when the engine is running and is
being switched off respectively, a second, water cooled, pipe kept
below 30 8C was attached to the furnace, see Fig. 1.
The sample holder was attached to a rod and the samples
could be moved between the heated and cooled zones at specific
intervals. For comparison, samples were exposed under three
different conditions; continuously hot, continuously cold and
cyclically. The different exposure times were 1 day (24 h), 1 week
(168 h) and 1 month (30 days) and the cycling was done according
to Table 3. To clarify the effect of urea, a 1 month exposure was
also done with all four alloys in the same gas mix and temperature
conditions, but with injection of water instead of urea solution.
The cycles were adjusted so that each exposure started and
ended in the hot zone. During the experiments the condensate
was collected and was found to have pH 3 despite the injection
of the urea solution, which has pH 910.
2.3 Analysis techniques
2 Experiments and analysis
The samples were first examined with a Zeiss Discovery V20

stereomicroscope to get an initial assessment of the overall
2.1 Material
For the purpose of studying the behaviour of ferritic stainless
steels in the simulated SCR-system three ferritic stainless steels
were selected and compared to an austenitic steel in the laboratory
tests. The material thickness was about 1 mm. The alloys and
their compositions are presented in Table 1.
The samples were cut in rectangular test pieces,
15 20 mm2 and polished on both surfaces with final step
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Figure 1. Laboratory setup of tube furnace and cooling section for

simulation of an after-treatment system.
389
390
Nockert, Nyborg and Norell
Table 2. Gas composition for laboratory experiments simulating diesel

exhaust gases
N2
O2
NO
NO2
H2O
84%
5.7%
0.2%
0.01%
10%
Propane
0.03%
SO2
0.01%
CO
0.05%
7 mL diluted urea solution/h
Table 3. Intervals for cycling of samples for the three test periods
1 day
1 week
1 month
1 h hot zone 6 h cold zone 17 h hot zone

6 h cold zone 18 h hot zone for 7 days
6 h cold zone 18 h hot zone on week days,
continuously hot on weekends for 30 days
morphology of oxide products formed. The 24 h- and 168 hsamples and thin oxide areas of the 1-month samples were then
analysed with X-ray photoelectron spectroscopy (XPS), while
multiple thick oxide areas of the 1-month samples were analysed
with Auger electron spectroscopy (AES) to achieve surface
analyses of the samples and subsequent depth profiles of the
oxides (through elemental analyses and argon ion etching).
The XPS used was a PHI 5500 instrument with an AlKa
X-ray monochromator and the AES used was a ThermoFisher
Microlab 350. Both techniques used argon ion etching for the
depth profiling with etch rates calibrated on Ta2O5. The results
were evaluated with PHI Multipak software for XPS and with
Avantage software for AES, using sensitivity factors given in the
softwares.
3 Results
Stereomicroscopy examination was carried out on the different
kinds of samples. From these investigations, the visual
impression was that the cyclically exposed samples generally
displayed the thickest oxide products with uneven oxidation
across their surfaces, while the continuously hot exposed ones
appeared to have more homogeneously thick and even oxides.
After 1 day both cyclic and continuously hot exposed samples of
all alloys appeared about the same with thin, even oxides. After
1 week the cyclic samples displayed areas with thicker oxides
appearing to be connected to drops of condensate, but on the
continuously hot samples thicker but more even oxide areas only
appeared to some extent after 1 month exposure. The
continuously cold exposed samples showed no sign of corrosion.
They were confirmed to experience condensation and XPS
analysis showed residue containing nitrogen and small amounts
of sulphur.
To demonstrate the different fundamental characteristics of
the continuously hot and cyclically exposed samples, a comparison between the surface appearances of 304L-samples exposed
for 1 month is illustrated in Fig. 2. The relatively smooth
appearance of the continuously hot exposed 304L can be seen
from Fig. 2a, while the much more heterogeneous surface
character for the cyclically exposed 304L sample is evident in
Fig. 2b. In the latter case, it appears that the surface is covered by
Figure 2. Optical stereomicrographs of 304L samples after

continuously hot (a) and cyclic (b) exposure for 1 month (30 days).
thicker oxide islands (see black arrows) with thinner oxide in

between. In fact, the three ferritic steels all showed similar surface
appearance as 304L with thicker oxide islands and thinner oxide
in between, see Fig. 3. The cyclically exposed samples also display
whitish crystal-like spots on part of their surfaces, as shown by
white arrows in Figs. 2 and 3.
From the above, it appears that the cyclic exposure is the most
severe one in terms of surface oxidation and corrosion attack. It
should also be noted that the surface appearance characteristics of
the samples showed evidence of corner and edge effects,
presumably because of influence of flow. From a lifetime point
of view it is important to address the worst scenario. In the
forthcoming presentation, the largest oxide thickness is therefore
considered to be a better measure of alloy performance than
surface fraction of the thicker oxide islands or the overall weight
gain. Furthermore, since the ferritic steels all show similar
behaviour also concerning oxide structure and thickness, the
effect of time and cyclic and hot exposure is interpreted from the
results of the 409 steel. To investigate the general difference in
oxidation behaviour over time and between continuously hot and
cyclically exposed samples, depth profiles were carried out on the
differently exposed samples.
After 1 day cyclic exposure all four alloys appeared more or
less the same and no specific surface morphology could be
observed. The oxides are thin, evenly distributed and the apparent
thickness can with the 409 steel as example, be estimated to about
30 nm from the XPS depth profile shown in Fig. 4a. This estimate
is done at the etch depth where the oxygen level has decreased to
half its maximum value. As can be seen from this depth profile, it
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Figure 4. XPS depth profiles of 409 samples subjected to cyclic

exposure for 1 day (a) and for 1 week (b). The latter profile is acquired on
a characteristic oxide island on the surface.
Figure 3. Optical stereomicrographs illustrating the overall corrosion

attack on 409 (a), 430Ti (b) and 1.4513 (c) after cyclic exposure for
1 month (30 days).
has already developed an outer Fe- and an inner Fe/Cr-oxide.

Carbon and surface sulphur in some form also appears to be
present.
After 1 week of cyclic exposure, most of the surface had a
smooth appearance with oxides not much thicker than after 1 day.
However, some oxide islands start to appear, see SEM micrograph
of a 409 sample in Fig. 5a. The presence of these oxide islands is
most pronounced for the ferritic steels. An example of an XPS
depth profile of the thickest oxide on 409 is shown in Fig. 4b, with
an apparent thickness estimated to about 3.5 mm. The oxide
consists of an outer Fe-oxide and an inner Fe/Cr-oxide, with
thicknesses that appear to be about 2.5 and 1 mm, respectively. In
the inner Fe/Cr-oxide small amounts of sulphur can be detected.
The main differences between the ferritic steels and 304L after
1 week are that 304L has less oxide islands of large thickness and a
higher chromium level in the inner oxide.
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An important finding is the presence of sulphur in the inner

part of the oxide. From high energy resolution analysis of the XPS
peak (S2p) of sulphur, its binding energy position is found be at
162 eV. This position is consistent with sulphide. Thus, it is
suggested that sulphide is formed at the inner oxide during the
cyclic exposure. This interpretation is applied to all observations
of sulphur at the inner oxides. Sulphur was also found to be
present on the top surface, but in the form of sulphate/sulphite as
evident from the binding energy position at about 170 eV.
After 1 month of cyclic exposure the difference in oxide
characteristics between the ferritic materials and the 304L is clear.
All the ferritic alloys have a surface morphology with significant
oxide islands covering part of the surface, as also indicated by
the optical stereomicroscopy performed (Figs. 2 and 3). The
thicknesses of these oxide islands range up to about 10 mm, while
the similar kind of oxide features on 304L are about 3 mm in
thickness. The overall appearance included both cracking and
spallation of oxide, see Fig. 5b. As for the 409, shown in Fig. 6,
also the 304L steel and the two other ferritic steels displayed an
inner chromium rich oxide with presence of sulphur in sulphide
state after the 1 month cyclic exposure. Despite the fact that the
other ferritic steels have somewhat higher chromium content,
they show about the same oxide thickness as 409 after the cyclic
exposure. The whitish spots, mentioned above, are indicated to
391
392
Figure 6. AES depth profile of 409 after 1-month cyclic exposure.
ferritic alloys. The oxides seem more evenly distributed after both
cyclic and continuously hot exposure compared to the condition
with urea present. Oxide spallation appeared on all cyclically
exposed ferritic alloys, most severely on 409, see Figs. 8a and c,
while the appearance of the thick oxide on austenitic 304L as seen
Figure 5. SEM micrographs of 409 samples subjected to cyclic exposure

for 1 week (a) and 1 month (b).
consist of iron sulphate by means of AES analysis. The sulphates

were up to 23 mm thick. For alloy 304L it was obvious that the
total sulphate/oxide thickness was similar to that of thick oxides
below thinner sulphates. A similar trend was noted for the ferritic
alloys. Actually, the same proportions of ironsulphuroxygen as
shown in the outermost 500 nm in Fig. 6 were found on top of all
thick oxides on cyclically exposed samples, even where whitish
deposits were not visible.
The XPS analyses confirm the impression that continuously
hot exposure results in significantly thinner oxides than cyclic
exposure. There seems to be no major difference in oxide
thickness between the different materials after 1 month of
continuously hot exposure. Typical depth profiles acquired on the
409 and 304L samples after 1 month are shown in Fig. 7. The
oxide thickness for both alloys can be seen to be about 22.5 mm,
i.e. considerably thinner than after cyclic exposure. Both the 409
and 304L show predominantly an outer Fe-oxide with an inner
Fe/Cr-oxide, but there are no signs of S in the inner oxides. The
chromium level in the inner part of the oxide is higher for the
304L steel. The much more extensive oxidation of the 409 during
the cyclic exposure seems to extend the thickness of the outer
Fe-oxide, while the inner part stays chromium-rich.
A reference experiment with water instead of urea was also
performed. The visual inspection showed severe corrosion of all
Figure 7. XPS depth profiles of samples of 409 (a) and 304(b) exposed
continuously for 1 month.
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in SEM (Fig. 8d)) did not differ significantly from the urea
condition. As can be seen in Figs. 6 and 9 the oxide composition is
about the same for both conditions, but the oxide thickness has
for 409 almost doubled with the removal of urea to become about
18 mm. It appears that the environment without urea causes more
Figure 9. AES profile of thick oxide on 409 after 1 month cyclic

exposure without urea.
severe corrosion than with urea. Furthermore, no whitish

sulphate-containing spots were observed on the surfaces of the
samples when water was injected instead of urea. Sulphur in
form of sulphide is however present in the chromium-rich inner
oxide, see Fig. 9, even more pronounced than for the urea
condition.
In conclusion, all ferritic alloys behaved more or less equally.
The two higher alloyed ferrites had maybe a little thinner oxides
than 409, but generally the thick oxide islands covering large parts
of the surface were up to about 10 mm for all three materials after
1 month cyclic exposure. The austenitic 304L behaved considerably better, with oxide islands of 3 mm in thickness. After
isothermal exposure at 450 8C for 1 month all four alloys
displayed oxides with thicknesses of about 2 mm, i.e. less oxide
growth than during cyclic exposure. After cyclic exposure without
urea addition, the 304L showed only small deviations from
experiments with urea, while the ferritic alloys exhibited a
significant increase in corrosion with oxide thicknesses up to
18 mm. For all experiments nitrogen was only detected as a
surface contaminant and not in any corrosion products.
4 Discussion
Figure 8. LOM micrographs of 409 (a) and 304L (b) and SEM
micrographs of 409 (c) and 304L (d) after 1 month cyclic exposure
without urea.
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The alloys studied are clearly more corroded after cyclic exposure
compared to after constant high temperature exposure. Condensation was observed on the samples exposed constantly in the
cold zone, but there was no sign of corrosion. Apparently the
stainless steels studied are not sensitive to the condensate formed
in this environment as long as they are kept at room temperature.
When the steels are kept isothermally at high temperature
(450 8C) and are not exposed to condensation a slow growing,
even oxide is formed. When the two conditions are combined into
the cyclic test mode, accelerated oxide growth occurs. The
combination of high temperature exposure and low temperature
intervals with condensation is obviously more aggressive to the
alloys than isothermal conditions. An outer more fast growing
Feoxide is formed and there is an inner Fe/Croxide with
presence of sulphur.
393
394
When the engine is switched off an acidic condensate is

formed, and even with the addition of urea solution, a base
with pH 910, the condensate is still acidic, pH3 in the case of
this study. Thus, the steels are exposed to a strongly acidic
environment at low temperatures. Despite high ammonia and
nitrogen content in the flow gases no nitrogen was found to have
diffused into the bulk metal, but was only detected as a
contaminant on the top surface. This suggests that in the part of
the catalytic system simulated here, at a distance from the injector
where the urea has decomposed and mixed with the exhaust
gases, sulphur is more involved in the corrosion process than the
urea derivates are. However, in a parallel study on austenitic
components tested close to the urea injection in engines no
sulphidation was observed, but large uptake of nitrogen.
There was no significant difference in corrosion resistance
between the ferritic alloys. The molybdenum in alloy 1.4513 is
primarily intended to increase the resistance against salts on the
outside of the exhaust system. It is further concluded that a
chromium content of 12 or 17% has not been critical for the
ferritic alloys in this study.
Temperature cycling in itself would suggest that ferritic
materials are to be preferred over austenitic ones due to smaller
difference in thermal expansion between bulk and oxide [7].
However, this is mostly true for higher maximum temperatures
and usually higher cycling frequencies than relevant for this
study. In these experiments the ferritic alloys performed worse
than the austenitic 304L, suggesting that the thermal cycling in
itself is not causing the aggressive situation. Thus, the conclusion
would be that the combination of high temperature oxidation and
low temperature condensation is so aggressive that higher alloyed
austenitic steel perform better than ferritic alloys. There are two
possibilities; either the condensate formed only becomes
aggressive at higher temperatures, e.g. when it is decomposed,
or the high temperature corrosion makes the steel more sensitive
to the condensate thus enabling wet corrosion. As the oxide has
the appearance of a high temperature oxide it should mostly have
grown in the hot zone. Therefore, it would appear as the
condensate formed becomes aggressive when heated.
Water vapour can cause rapid oxidation of chromia forming
steels. Several studies have been done on this effect [14, 15]
though mainly isothermally and at higher temperatures. This
effect might be active also at 450 8C. It would, however, affect the
samples held continuously hot as well as the cyclically exposed
ones. As the isothermal samples appeared to be less corroded
than the cyclic ones, despite a longer time at 450 8C, this effect is
most likely not the most important corrosion mechanism in this
system.
For almost all cyclic samples there was an enrichment of
sulphur in the inner chromium-rich oxide. Some samples
exhibited sulphur all through the oxide. Sulphide growth is
generally faster than oxide growth due to higher deviation from
stoichiometry. Sulphur was mainly found in two different sights,
in the form of sulphate on top of thick oxides on 1-month samples
with urea, sometimes seen as white spots, and in the inner
chromium-rich oxides for all cyclically exposed alloys both with
and without urea. Most studies on the effect of sulphur bearing
gases on stainless steels have been performed at higher
temperatures, 5501000 8C. They report sulphur penetration of
the oxide causing internal sulphidation. This is dependent on

temperature, atmosphere and the properties of the oxide [16] and
can in time lead to oxide failure. The permeability of chromia
varies, according to Young [17], with the content of other metal
species as well as sulphur partial pressure in the gas. Zheng and
Young [18] have shown that SO2 in the atmosphere affects the
permeability of the oxide to different gas species. Penetration
through the oxide can occur as ionic diffusion [19] or through
imperfections in the oxide [20, 21], possibly arising from thermal
cycling. In this study defects formed due to thermal cycling might
have enhanced the transportation of sulphur through the scale.
However, there was only 57 cycles/week. Instead, it is believed
that the most important effect of thermal cycling here was to
enable condensation, as indicated by the ample presence of
sulphur on the surfaces. Even a highly protective oxide will in
time experience sulphur penetration and sulphidation [19]. There
is also fairly high sulphur solubility in chromia [21], though most
studies mention sulphide formation beneath the oxide rather
than within the inner oxide layer as observed on all alloys in the
present study. The higher chromium content in the inner oxide of
the austenitic alloy could explain the better protection and slower
oxide growth compared to the ferritic alloys, in the presence of
sulphur. The alloy content of chromium alone seems less
important as the ferritic alloys perform similarly, whereas 304L
performs better than 403Ti with equivalent chromium content.
Concerning the outer sulphates, in cyclic exposures with urea the
total corrosion product thickness was unchanged with their
presence, i.e. the actual oxide thickness decreased in presence of
sulphate. Moreover, without urea no outer sulphate was observed
and the thickest oxides formed. This indicates that the outer
sulphates decrease the oxide growth. Sulphate formation on the
surface could according to Jardnas et al. [22] have a decreasing
effect on water induced chromium evaporation on 304L.
However, they did not find any sulphides in the inner oxides
and in this study the water vapour is not believed to have played a
major role. It is not clear by which mechanism the sulphate
formation possibly counteract the oxide growth.
Most of all, the results show that urea additions, do not
worsen the conditions for the stainless steels near the catalytic
converter, as with the removal of urea, the experiment showed
much more severe corrosion on all the ferritic materials with
thick fast growing oxides and substantial spallation.
5 Conclusions
(i) Small variations in corrosion behaviour between the
different ferritic alloys, while the austenitic 304L performed
considerably better.
(ii) At low temperature a condensate forms but no corrosion
occurs.
(iii) Thermal cycling with a condensation interval is more
aggressive to the steels than isothermal exposure at 450 8C.
(iv) Sulphur is enriched in the inner chromium rich oxides.
Sulphidation in the inner oxides appears to influence the
corrosion more than the urea while outer sulphates decrease
the oxide growth in cyclic exposures with urea.
www.matcorr.com
(v) More severe corrosion in the given atmosphere with only

water additions, than with urea. The urea seems to decrease
the aggressiveness of the atmosphere in this system.
Acknowledgements: This work was performed within the High

Temperature Corrosion Centre and was financed by the National
Swedish Energy Administration. The study was performed in
co-operation with Volvo Powertrain. The project is partly based on
an earlier project performed in co-operation with Swenox, which
was financed by the Swedish Agency for Innovation Systems
(VINNOVA). Special thanks are addressed to Dr. Anna Nafari and
Dr. Erik Strom who took part in earlier stages of this project and to
Urban Jelvenstam for technical support.
6 References
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[11] P. Gumpel, C. Hoffmann, N. Artl, 6th European Stainless
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1013, 2008, pp. 645651.
[12] B. Michel, S. Saedlou, J. M. Herbelin, P. O. Santacreu,
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and Market, Helsinki, Finland, June 1013, 2008, pp. 675
679.
[13] R. Floyd, A. Kotrba, S. Martin, K. Prodin, Material corrosion
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Vehicle Engineering Congress and Exhibition, Rosemont,
Illinois, USA, October 67, 2009.
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[16] B. Gleeson, Materials Solutions Conference 2001/John Stringer
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[17] D. J. Young, Int. J. Hydrogen Energy 2007, 32, 3763.
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April, NACE International, paper 236, 1990.
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(Received: May 4, 2010)
(Accepted: September 16, 2010)
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DOI: 10.1002/maco.201005905
Hot dip galvanizing behavior of advanced high strength steel

F. Li*, H. Liu, W. Shi, R. Liu and L. Li
This work studied the hot dip galvanizing behavior of three advanced high
strength steels annealed under different protective atmospheres. The coating
quality, surface oxides, and the mechanical property of steel matrix were
examined. The experimental results show that annealing atmosphere can
influence the galvanizability and thermodynamics calculation can predict the
surface selective oxidation. It was shown for the first time in this work that
annealing atmosphere may also influence the mechanical property of the steel
matrix.
1 Introduction
2 Experimental
To reduce the weight of automobile bodies, the use of advanced

high strength steels (AHSS) is increasing rapidly because of their
promising mechanical properties, such as dual phase (DP) steel,
and transformation induced plasticity (TRIP) steel. However, it
brings a challenge to galvanizers because alloying elements in
AHSS, such as Mn and Si, oxidized on steel surfaces during
recrystallization annealing prior to hot dip galvanizing. Oxides
formed on the steel surface will worsen the wettability of the steel,
resulting in bad coating with defects like bare spots.
In recent years, many scientists have done a great deal of
studies on this issue, and there are already many achievements.
Results of experiments with higher H2 content in annealing
atmosphere [1] or lower dew point [2] could improve the
wettability by reducing oxidation. However, some other
researches [35] pointed out that oxidation might transform
from external oxides to internal oxides, which made it possible to
get good coating surface of AHSS. Further, thermodynamics
calculations were also applied to predict the oxidation formed on
the surface of steel during the annealing [68].
In previous work, Liu et al. [9] showed the application of
Thermo-Calc software on the surface selective oxidation, the
problem is there is no experimental evidence to verify the
calculation results. Besides, there is no work paid attention to the
effect of surface segregation on the mechanical properties yet.
Therefore, this work studied the hot dip galvanizing behavior
of three steels annealed in different conditions, focusing on
verifying the Thermo-Calc simulation results and discussing the
effect of surface segregation on the hardness of experimental
steels.
Table 1 lists the chemical composition of experimental steel,

which were casted and rolled in laboratory, then cut in size
200 mm 100 mm 1 mm.
Experiments were done in three different annealing atmospheres. They are 5% H2N2 at dew point of 30 8C or 10 8C
and 40% H2N2 at dew point of 30 8C. After cleaning with
acetone, the samples were heated in the hot-dip galvanizing
simulator, at rate of 10 8C/s to 800 8C and hold for 120 s, then
cooled at 50 8C/s to 460 8C, temperature of zinc bath. The last
step consisted of dipping the sample into the Zn bath for 3 s, and
cooling to room temperature. The zinc bath contained 0.2 wt%
dissolved Al and was iron saturated.
There are two groups of samples, one was the galvanized
ones used for the coating quality assessment, while the other
group was without dipping used for surface oxides analysis and
mechanical properties test. FTIR (Fourier transform infrared
spectroscopy) was employed to identify the oxides formed on steel
surface during annealing. Because the samples are too undersized to take tensile test, only the microhardness of the cross
section was measured. For this, samples of 10 10 mm2 were
cut, mounted and polished. In order to minimize the error of
measurement, 5 measurements have been taken for each
polished but unetched sample.
F. Li, H. Liu, W. Shi, L. Li

School of Materials Science and Engineering, Shanghai University,
Shanghai (P. R. China)
E-mail: ashley415101@gmail.com
R. Liu
Technique Center of Ansteel, Ansteel Company, Anshan, Liaoning
(P. R. China)
3 Thermodynamic calculations
Thermo-Calc was employed to calculate the selective oxidation of
experimental steels when annealing at the continuous galvanizing simulator. In this calculation, matrix phases are defined from
TCFE4 database; while oxides and gas phase from SSUB
Table 1. Steel chemistry wt%
No.
Mn
Si
Cr
Al
Ti
1(DP)
0.11 1.72 0.38
0.055
2(DP)
0.12 1.62 0.3 0.39 0.045
3(TRIP) 0.41 1.61 0.55

1.5 0.12 0.031
Al/Mn Mn/Si
0.032
0.028
0.93
4.53
5.4
2.93
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Hot dip galvanizing behavior . . .
database. The calculation conditions should include the alloy

composition, total amount of system, total pressure and
annealing temperature, as well as the fraction (activities) of
hydrogen and water vapor. And each of hydrogen content and
water vapor content can be set as variable. So the influences of
hydrogen and dew point on selective oxidation can be predicted.
The concerning oxidation reactions are as follows,
Aldissolved H2 Ogas Al2 O3 s H2 g
(1)
Figure 1. Influence of dew point on selective oxidation of experimental

steels (annealing at 800 8C in N2 5%H2) a. Steel 1; b Steel 2; c Steel 3
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Sidissolved H2 Ogas SiO2 s H2 gas
(2)
Mndissolved H2 Ogas MnOs H2 gas
(3)
Crdissolved H2 Ogas Cr2 O3 s H2 gas
(4)
Al2 O3 s MnOs MnAl2 O4 s
(5)
Figure 2. Influence of annealing atmosphere on selective oxidation of

experimental steels (annealing at 800 8C at dew point of 30 8C)
a. Steel 1; b Steel 2; c Steel 3
397
398
Li, Liu, Shi, Liu and Li
Figure 3. Surface quality of coatings varied with the annealing atmosphere

Annealing atmosphere
Partial pressure of
oxygen (atm)
Steel 1 (DP)
Steel 2 (DP)
Steel 3 (TRIP)
108, 5%H2
2.38 1020
308, 5% H2
2.28 1023
308, 40% H2
3.57 1025
Fig.3a
Fig.3d
Fig.3g
Fig.3b
Fig.3e
Fig.3h
Fig.3c
Fig.3f
Fig.3i
4 Experimental results and discussions

4.1 Galvanizing properties
2MnOs SiO2 s Mn2 SiO4 s
(6)
MnOs SiO2 s MnSiO3 s
(7)
Figure 1 showed that whenever the dew point is 30 8C or

10 8C, on the surface of both steel 1 and steel 2, oxides such as
MnAl2O4, MnO, and Mn2SiO4 will form. Besides, since it
contains some Cr in steel 2, Cr2O3 could also be found. Oxides
formed on surface of steel 3 seem to be different, like Al2O3,
MnAl2O4, MnSiO3, and SiO2. Whats more, as shown in Fig. 2,
the content of oxides, which formed on the annealed steel 1 and
steel 2, decreased as the H2 content increased from 5 to 40%.
However, it seems that the H2 content played much less
significant role for steel 3.
Figure 3 shows pictures of galvanized panels prepared by hot-dip

simulator. The coating on steel 1 and steel 2 prepared at a 30 8C
dew point in N2 40%H2 was of reasonably good quality. The size
and number of bare spots increased as the annealing atmosphere
varied to DP 30 8C in N2 5%H2, and DP 10 8C in
N2 5%H2. That is, surface quality of steel 1 and 2 coatings
worsened with increasing the partial pressure of oxygen. However,
the trend of steel 3 is an exception. When annealed at 30 8C dew
point, with N2 5%H2, the coating quality on steel 3 substrate is
acceptable with only a few bare spots. Whether increasing the dew
point to 10 8C or the H2 content to 40%, some uncoated areas or
obvious more bare spots were obvious.
Clearly for DP steel (both steel 1 and steel 2), the coating
quality improved as the partial pressure of oxygen decreased.
Nevertheless, to TRIP steel (steel 3), the trend is different. The
coating on TRIP steel annealed in 5%H2 N2 atmosphere at dew
point of 10 8C presented the best appearance. The coating
surface worsened as the partial pressure of oxygen of annealing
atmosphere decreased. Mahieu et al. [4] pointed out that the
selective oxidation occurred on the surface of TRIP steel showed
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Hot dip galvanizing behavior . . .
type transformation. While the dew point of the atmosphere is

increased, external oxidation will become internal oxidation,
reducing the oxides on the surface of the substrate and improving
the wettability of the steel effectively.
4.2 Surface oxides analysis
Surface oxides formed on the steel sheets annealed under
DP 30 8C, 5%H2 N2 atmosphere, were examined using
FTIR. As shown in Fig. 4, some Fe2O3 can be detected on the
surface of the three steels. It is formed because of the air
contamination during sample transfer from the simulator.
For steel 1 and steel 2, the oxide was mainly Mn2SiO4,
MnSiO3, and SiO2. But in the calculation results, MnSiO3 is not
stable at higher dew point (higher than 40 8C), and there is no
SiO2 for steel 1 and 2. The precipitation of Mn2SiO4 will locally
consume oxygen, Si and Mn by reaction (2), (3), and (6) with the
mole ratio of MnO/SiO2 2. And, the diffusion of dissolved
oxygen, Si, and Mn will take some time. So MnSiO3 is formed for
kinetic reason rather than thermodynamic reason. SiO2 may form
during cooling of the samples to room temperature due to its
solubility product decreasing with temperature [10].
In addition, Cr2O3 could also be found on the surface of steel
2, because it contains 0.39 wt% Cr. According to the calculation
results of Fig. 1a and b, MnO may form for both steel 1 and steel 2
due to their Mn/Si (wt%) ratio is larger than 4. But it looks like
that FTIR detected MnO only on the surface of steel 2, which
maybe due to the small quantity of MnO for steel 1.
Owing to much more Al content, steel 3 exhibited
some Al2O3. Moreover, no Mn2SiO4 were detected on the steel
3 surface, which fitted with the Thermo-Calc calculation.
However, different from calculation, there is no MnAl2O4 in
Fig. 4. There might be two reasons for its absence:
(1) There is no FTIR data for MnAl2O4 yet.
(2) The Al2O3 tends to form internally, causing MnAl2O4 buried
under the steel surface.
In general, the thermodynamic predictions fitted well with the
FTIR results. Most of the oxides predicted by Thermo-Calc, like
MnO, SiO2, Cr2O3, Al2O3, MnSiO3, and Mn2SiO4 were detected
Figure 5. Microhardness of annealed samples
by FTIR, suggesting the applicability of this software on investigation of surface selective oxidation during hot-dip galvanizing.
However, Thermo-Calc can only predict the types and amounts of
oxides opt to form on steel surface and near surface area, but not
tell whether an oxide precipitates externally or internally.
4.3 Mechanical properties
Considering the conflict of heat treatment routines between the
continuous annealing and continuous hot-dip galvanizing, the
mechanical properties of AHS steel substrate should be tested.
From Fig. 5, steel 3 gains the highest strength and steel 2 gains
the lowest. In common sense, the hardness values should be close
to one another if the heat treatment and steel chemistry are the
same, no matter which of the annealing atmosphere is. However,
it is interesting to note in this work that only the case of steel 2
accords with it. Both steel 1 and steel 3 have a great variation of
microhardness. The varying hardness values reveal the inhomogeneity of the steel microstructure. As is known, during
annealing, alloy elements segregate to the surface area, causing
a gradient of alloy elements distribution from the surface to the
inner in the matrix. Consequently, nonuniform microstructure
formed during cooling. For steel 2, the inhomogeneity is not so
serious since it contains 0.39% Cr which is added to increase the
hardenability.
5 Conclusions
Systematic study of hot-dip galvanizing behavior of two DP
steels and one TRIP steel in H2N2 atmosphere with different
partial pressure of oxygen was carried out. The following
conclusions can be drawn from the findings in the present
study.
Figure 4. FTIR analyzes of various oxides on the annealed samples

(annealing atmosphere: 5%H2 N2 at dew point of 30 8C)
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1. The quality of coatings on DP steel substrates was acceptable

when the annealing atmosphere was at dew point of 30 8C
consisting of 40%H2N2. Coating quality deteriorated as the
partial pressure of oxygen of annealing atmosphere increased.
Different from DP steel, the quality of coatings on TRIP steel
was fair at dew point of 10 8C with 5%H2. Either decreasing
dew point or increasing H2 content, the selective oxidation
399
400
Li, Liu, Shi, Liu and Li
type might change from internal to external oxidation. Then

the coating surface will get worse.
2. FTIR analyses ensured accuracy and comparability of the
prediction results about the selective oxidation during the
annealing from Thermo-Calc calculation.
3. The mechanical property of annealed steel substrate varied
with the annealing atmosphere. The surface alloy elements
segregation might be responsible for it.
Acknowledgements: The authors are grateful to 973-Project
(No.2010CB630802) and NSFC (No.50934011 and No.50971137).
6 References
[1] I. Cvijovic, I. Parezanovic, M. Spiegel, Corros. Sci. 2006, 48,
980.
[2] E. De Bruycker, B. C. DeCooman, M. De Meyer, Steel Res. Int.

2004, 75, 147.
[3] S. H. Jeon, K. S. Shin, H. S. Sohn, D. R. Kim, Journal of the
Korean Institute of Metals and Materials 2008, 46, 427.
[4] J. Mahieu, S. Claessens, B. C. DeCooman, Metall. Mater.
Trans. A 2001, 32A, 2905.
[5] R. Khondker, A. Mertens, J. R. McDermid, Metall. Mater.
Trans. A 2007, 463, 157.
[6] I.-H. Jung, M. Paliwal, Y.-M. Kim, S.-K. Lee, J.-S. Kim, The
Asia-Pacific Galvanizing Conference, Lotte Hotel Jeju,
Korea, 2009.
[7] Y. Suzuki, T. Yamashita, Y. Sugimoto, S. Fujita, S. Yamaguch,
ISIJ Int. 2009, 49, 564.
[8] H. Liu, W. Shi, Y. He, L. Li, Surf. Interface Anal. 2010, 42,
1685.
[9] H. Liu, Y. He, L. Li, Appl. Surf. Sci. 2009, 256, 1399.
[10] S. Swaminathan, Doctoral thesis, Bochum University,
Germany 2007.
(Received: August 13, 2010)
(Accepted: November 16, 2010)
W5905
www.matcorr.com
DOI: 10.1002/maco.201005921
Influence of tensile stress on corrosion behaviour of highstrength galvanized steel bridge wires in simulated acid rain
W. J. Yang*, P. Yang, X. M. Li and W. L. Feng
Corrosion behaviour of the high-strength galvanized steel wires under tensile
stress was researched by electrochemical polarization and salt spray test (SST)
using simulated acid rain as electrolyte. Electrochemical polarization and SST
results showed corrosion rate rose significantly with increasing tensile stress;
white grains were observed by SEM after polarization, while cellular and
dendritic crystals appeared on the rust layer after SST. XRD and TG-DTA results
revealed (Zn(OH)2)3 ZnSO4 5H2O was the main corrosion product, and traces
of Fe2(SO4)2O 7H2O, Fe2(SO4)3, Fe2O3 H2O were also detected. A three-stage
corrosion process for the galvanized steel wires during SST was proposed.
1 Introduction
Both cable-stayed bridges and suspension bridges are popular
bridge styles for their elegancy, well dynamic stability, relative
light mass with a long span and other advantages [13]. Due to
cables in these bridges sustain most of the bridges loads, and
thus they play an important role in ensuring the bridges safety
operation [46]. However, due to bridge cables are usually exposed
to natural aggressive environment, steel wires in the cable are prone
to be seriously corroded especially in seashore and ocean area when
corrosive substances penetrate into the cable. Corrosion substances
in the cable will react with the steel wires electrochemically and
chemically when the electrolyte film formed in the oxygen content
environment. Besides, large amplitude and high frequency
vibrations induced by wind and alternating loads also account
for the deterioration and collapse of the bridges [79].
Much of the life expectancy of a bridge depends upon the
corrosion that it undergoes, but deterioration problems in bridge
cable wires tend to be unique, and the exact cause and
W. J. Yang, P. Yang, X. M. Li
College of Chemistry and Chemical Engineering, Chongqing University,
Chongqing 400044, (P. R. China)
E-mail: yangwj308@163.com
W. L. Feng
Key Laboratory for Optoelectronic Technology and Systems, Ministry of
Education; College of Optoelectronic Engineering, Chongqing University, Chongqing 400044, (P. R. China)
W. L. Feng
Department of Applied Physics, Chongqing University of Technology,
W. L. Feng
International Centre for Materials Physics, Chinese Academy of
Sciences, Shenyang 110016, (P. R. China)
www.matcorr.com
development mechanism are still not so clear. Whats more,

the stock of aging cable supported bridges is steadily increasing
and the effect of degradation processes such as fatigue and
corrosion has become an obvious problem for the cables, and
thus the reliability and lifespan of these bridges have been widely
concerned all over the world in recent years [1012]. Therefore,
intensive worldwide research work in this field have been carried
out on cable steel wire corrosion protecting, monitoring and
evaluating [1315]. It is well known that material properties,
structural geometries, maintenance and operational practices,
and local environment conditions all contribute to the bridge
cable wire corrosion problems. The authors [16, 17] conducted
accelerated corrosion of cables with intentional cuts and steel
wires under certain loads to observe their corrosion behaviour in
sodium chloride solutions. To make the corrosion mechanism of
the steel wires inside the cable clear, Hanmilton et al [14]
conducted field surveys of the specific environment that steel
wires exposed to inside the cable. Suzumura et al. [8] found
corrosion environments varied with position inside the cable:
wires were continuously wet at the side, wet at night and dry
during the day on the top, highly humid at the center, and soaked
in water at the bottom. In addition, acceleration test results
showed the steel wires were not corroded when kept with a lower
relative humidity (below 60%), but became corrosive with the
higher relative humidity. However, no research work have ever
been done using simulated acid rain as the electrolyte, which
models the atmospheric precipitation in a specific area, to
research the corrosion behaviour of the high-strength galvanized
steel bridge wires under certain tensile stress by electrochemical
and SST methods.
In the present work we observed the effect of tensile stress on
the corrosion behaviour of high-strength galvanized steel bridge
wires in simulated acid rain complementary using electrochemical polarization technique, scanning electronic microscope
(SEM), thermogravimetric and differential thermal analysis (TGDTA) and salt spray test (SST).
401
402
Yang, Yang, Li, and Feng
2 Experimental
2.1 The samples
Hot-dip galvanized steel wires (provided by Chongqing Wanqiao
Cable Co. Ltd, China) with a diameter of 5 mm, and zinc coating
thickness of about 42 mm, were used for corrosion tests. The steel
wire has a nominal tensile strength of 1570 MPa, and nominal
yield strength of 1330 MPa. The chemical composition of the
steel wire is given in Table 1.
Before electrochemical and accelerated corrosion testing the
galvanized steel wires were upset with upsetting machine. Then,
the steel wires were polished to mirror-like smooth surface with
emery paper (1200 grits), degreased by acetone, rinsed with
distilled water and dried using air blower. Afterwards, they were
fixed to the clamping fixture [21], and then different loads (300,
600, 900 and 1100 MPa) were respectively applied to the samples
using tensile testing machine (PC Controlled Electronic
Universal Test Machine CMT5105, Sans Epenet, China) through
the end-plates of the clamp fixture. The threaded-rod spacers were
then tightened in compression between the two end-plates until
the tensile load of the test machine was counteracted.
2.2 The simulated acid rain preparation
Figure 1. Profile of the electrochemical cell used for the

potentiodynamic polarization of the galvanized steel wires in
simulated acid rain
polarization test of the galvanized steel wires in the simulated

acid rain.
In order to investigate the effect of tensile stress on the
electrochemical corrosion behaviour of the galvanized steel wires, we
applied static load as 300 MPa, 600 MPa, 900 MPa and 1100 MPa
respectively to the steel wires, and then potentiodynamically
polarized in the simulated acid rain solution via Autolab PGSTAT30
(Eco Chemie, Netherlands). All the polarization tests were conducted
at room temperature, and scanned from -0.7V to -1.3V at a scanning
rate of 1 mV s1 after immersion in the electrolyte for 10 min.
Average chemical composition of the acid rain in Chongqing area

during 20022005 is given in Table 2. The simulated acid rain
solution was prepared using analytical reagent (NH4)2SO4,
Na2SO4,
CaCl2,
KNO3,
NaF,
MgSO4,
MgCl2 6H2O, CaNO3 4H2O, CaSO4 (purchased from Chongqing medicine Co., Ltd), and used as received. They were dissolved
in deionised water and adjusted with diluted sulfuric acid (10 wt.
%) to pH value as 4.5, gauged by pHS-25 pH-meter. The ions in
the simulated solution are twenty times denser than the ions in
natural acid rain [18, 19].
2.4 Salt spray test
2.3 Electrochemical polarization measurement
(a) Fog solution: simulated acid rain, 20 times the concentration

of the acid rain average chemical composition in Chongqing
area during 20022005 (see Table 2), pH 4.5;
(b) Chamber temperature: 35 28C
(c) Program: salt fog (12 hours), and then naturally kept for
another 12 hours.
Potentiodynamic polarization measurement was carried out

using a traditional three-electrode system, galvanized steel wires
as working electrode (working area: 3.14 cm2), a silver-silver
chloride (Ag/AgCl) electrode as reference electrode, and a Pt ring
as counter electrode (diameter 1.8 cm, width 1.0 cm). In addition,
a special cell was designed using polytetrofluoroethylene (PTFE).
Fig. 1 shows the profile of the cell used for electrochemical
The purpose of this experimental testing program was to observe

and analyze the corrosion process of the galvanized steel bridge
wires under different loads. A salt spray corrosion chamber YWX/
Q750C (Wuxi Sunan Experimental Equipment Co., Ltd, China)
was employed for salt spray testing. Fig. 2 shows the salt spray
chamber with pre-load specimens. The corrosion testing program
was a modification of ISO9227:2006(E). The following is a
summary of the conditions used:
Table 1. Chemical composition of the steel wires (mass percent):

Balance Fe
Element
Percent
Si
Mn
Cu
0.750.85 0.120.32 0.600.90 0.025 0.025 0.20
Table 2. Average chemical composition of the acid rain in Chongqing

area during 20022005 (milligrams per liter)
Ions

2
Cl NO
Mg2 K Na
NH
SO2
3 F
4 Ca
4
Concentration 18.79 1.16
3.6
0.39 2.78
4.49
0.33
0.84 0.56
Figure 2. Salt spray chamber with pre-load specimens
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Influence of tensile stress on corrosion of high-strength galvanized steel
-3
Specimens were removed after exposure time of 61 cycles,

cleaned as ASTM G1- 03 for other analyses and weighed after
drying. The difference between the initial and final mass was
reported as mass loss. The corrosion rates were determined by
applying the following equation proposed by the ASTM standard
G1- 03 [20].
Log(I(A/cm2)))
-4
Corrosion Rate K W=A t D mg dm2 day (1)
-5
a
-6
b
-7
c
d
-8
Where: K 2.40 106 D

t time of exposure (h)
A specimen area (cm2)
W mass loss after cleaning (g)
D density (g cm3)
-9
-0.7
-0.8
-0.9
-1.0
-1.1
-1.2
-1.3
E(mV/Ag/AgCl)
Figure 3. Polarization curves of the high-strength galvanized steel
wires under different tensile stresses/MPa (a, 0; b, 300; c, 600; d, 900; e,
1100) in simulated acid rain solution (pH 4.5)
2.5 Surface morphology characterization and corrosion

product analysis
The morphology of the specimens removed from the chamber
was observed by a scanning electron microscope (VEGA II LMU,
TESCAN, Czech) at 20 kV after rinsed with deionized water and
dried by flow air.
2.6 X-ray diffraction
X-ray diffraction analysis of the corrosion product scraped from
the steel wire was carried out with a Shimadzu XRD-6000 X-ray
diffractometer with Cu Ka radiation. The X-ray diffractometer
equipped with a diffracted beam graphite monochromator, tuned
to Cu Ka radiation, and a NaI scintillation detector. Diffraction
patterns were collected in reflection-mode geometry from 28 to
908 2u at a rate of 48 2u/min.
2.7 Thermogravimetric and differential thermal analysis
The TG-DTA curves were obtained by using a Shimadzu
DTG-60H instrument under flowing nitrogen atmosphere with
a heating rate of 58C/min. Approximately 6 mg corrosion product
was used in each case.
3 Results
Table 3. Corrosion parameters of the steel wires with different tensile

stresses polarized in the simulated acid rain (pH 4.5)
Stress ( MPa)
0
300
600
900
1100
Ecorr (V)
Rp (V cm2)
icorr (mA cm2)
0.949
0.832
0.890
0.841
0.863
16959
8582
7953
6615
6045
0.429
0.856
0.899
1.142
1.173
current by cathodic reactions within the applied potential range

(Fig. 3).
Fig. 4b shows the morphology of the galvanized steel wire
after polarization in the simulated acid rain (pH 4.5) under
1100 MPa. Compared with Fig. 4a (before corrosion) we can find
that micro-cracks appeared on the surface, and some white grainy
corrosion products situated at pits or cracks (see Fig. 4c, partial
enlarged detail of Fig. 4b). The phenomenon observed suggesting
that pitting corrosion occurred and some insoluable substances
formed during the polarization process.
3.2 Results of salt spray test
3.1 Electrochemical polarization measurement

High-strength galvanized steel wires were potentiodynamically
polarized in the simulated acid rain (pH 4.5) under different
tensile stresses (0, 300, 600, 900, 1100 MPa). Fig. 3 presents the
anodic and cathodic polarizations of the steel wires under various
loads in the simulated acid rain solution at room temperature.
Corrosion parameters of the polarization curves analyzed via
Autolab GPES software are presented in Table 3. The polarization
curves show that the corrosion rate (corrosion current density)
was higher under 1100 MPa and lower without tensile stress. This
feature implies that anodic dissolution of the steel wire was
accelerated with the increasing of tensile stress. The cathodic
branches of Tafel curves were linear, that is, there was no limiting
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3.2.1 Effect of tensile stress on mass loss

The specimens removed from the chamber after exposure time of
61 days were cleaned and dried according to ASTM G1-03 for
mass loss determination. Before the mass loss determination, the
galvanized steel wires under different tensile stresses were cut
into three 1.2 cm long pieces, and then average mass loss of the
steel wire under certain tensile stress was calculated from the
mass loss of every piece. Corrosion rate calculated from mass loss
represents the average quantity of the galvanized steel wires
corroded per square decimeter in a day time. It is an average value
but would not affect the evaluation of the effect of tensile stress on
the corrosion behaviour of the galvanized steel wires corroded in
the same period.
403
Figure 4. Surface morphologies of the galvanized steel wire: a, before corrosion; b, after electrochemical polarization under 1100 MPa in simulated
acid rain solution (pH 4.5); c, partial enlarged detail of b. Magnification 600 times
Fig. 5 shows the digital photos of the galvanized steel wires

under different tensile stress removed from the chamber after
exposure to SST for 61 days. It is notable that the most seriously
corroded steel wire was the one under 1100 MPa, whose much
surface area was covered with red rust compared to the ones
endured the load less than 1100 MPa. This feature suggested that
the micro surface structure of the high-strength galvanized steel
wire may be destructed by tensile stress, and hence facilitate the
corrosive ions like Cl, SO2
4 and other anions to react with the
fresh and more active zinc coating. Moreover, the larger the load the
faster the depletion process of the zinc coating, this is consistent
with the electrochemical polarization results of the steel wires
under different tensile stress in the simulated acid rain.
Mass loss versus tensile stress is plotted in Fig. 6. The plot
exhibits that mass loss of the steel wires has an increasing trend
with the increasing of tensile stress. This phenomenon indicates
that tensile stress can significantly promote the depleting process
of zinc coating, this is consistent with the results depicted above.
Depletion of the zinc coating will result in the deterioration of the
galvanic protection for the steel base, and even the collapse of the
steel wires [21].
3.2.2 Surface morphology observation after SST
Fig. 7a-7e are the surface morphologies of the rust layers on the
galvanized steel wires removed from the chamber after exposure
to salt spray test for 61 cycles.
It is interesting that the morphologies of the corrosion

products varied with the loads that the galvanized steel wires
endured. The corrosion product of the steel wire without any load
has a cellular structure (Fig. 7a). While under larger tensile
stresses, there are more dendritic crystals presented in the rust
layers (Fig. 7b-7e), and these rust layers seem to be less porous
compared with the rust layer in Fig. 7a. From the curve of mass
loss versus tensile stress (Fig. 6) we know that tensile stress plays
an important role in accelerating the corrosion process of the steel
wires. That is to say, active reaction sites may increase when the
galvanized steel wires endure larger tensile stress. Moreover, due
to Zn active sites worked as anodes of the corrosion cells situated
on the steel wire surface, this will result in the increasing of Zn
dissolution rate and further lead to the generating rate of crystal
nucleus much faster than their growing process. Thus, the
phenomenon of the rust layer structures varied with loads that the
galvanized steel wires endured depicted above appeared.
3.2.3 Corrosion products analysis
X-ray diffraction results of the corrosion products removed from
the galvanized steel wires enduring 1100 MPa after the test period
of 61 days are shown in Fig. 8. The most intense diffraction peaks
marked by a in the XRD pattern are mainly corresponding to
(Zn(OH)2)3 ZnSO4 5H2O. Besides, the less intense diffraction
peaks marked by b, c and d in the XRD pattern are
10
Mass loss (mg/dm2/d)
404
8
6
4
2
0
0
200
400
600
800
1000
Tensile stress (MPa)

Figure 5. Photos of the galvanized steel wires under different tensile
stress removed from the chamber after exposure to SST for 61 days
Figure 6. Mass loss of the galvanized steel wires under different tensile
stresses, exposure time of 61 days
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Figure 7. SEM micrographs of the rust layers on galvanized steel wires under different tensile stresses /MPa. a) 0; b) 300; c) 600; d) 900; e) 1100
corresponding to Fe2(SO4)2O 7H2O, Fe2(SO4)3 and Fe2O3 H2O

respectively. The appearance of Fe containing compounds in the
corrosion products revealed that local zinc coating depletion
occurred, and thus the steel base corroded without the sacrificial
zinc anode protection during the exposure period of 61 days.
Fig. 9 shows the TG-DTA results for the corrosion products
of the galvanized steel wires enduring 1100 MPa after exposed to
salt spray test for 61 days. A small endothermic peak was observed
at up to 48-C from the DTA versus temperature curve, and the
initial mass loss occurred in the range of 30-C70-C in the
corresponding TG versus temperature curve, indicating that

ZnSO4 5H2O begins to lose its adsorbed water and crystallization water, and convert to ZnSO4 H2O [22, 23]. Followed by
the dehydration of Fe2(SO4)2O 7H2O at 125-C200-C [20]. An
notable endothermic peak came forth at 264-C in the DTA curve
and an obvious mass loss occurred in the range of 240-C280-C,
indicating the conversion of ZnSO4 H2O to ZnSO4, and the
decomposition of Zn(OH)2 and Fe2O3 H2O [19]. When the
temperature increased higher than 500-C the third mass loss of
the decomposition of Fe2(SO4)3 and ZnSO4 occurred [12, 15, 21].
700
a: (Zn(OH)2)3ZnSO45H2O
b: Fe2(SO4)2O 7H2O
c: Fe2(SO4)3
d: Fe2O3H 2O
500
400
300
bb
200
cd c
b bc
d
a
d
c
100
0
7.0
10
20
30
40
50
6.0
-20
5.5
4.5
-40
4.0
70
80
90
2 ( degree)
Figure 8. XRD patterns of the corrosion products removed from the
galvanized steel wires after exposure to salt spray test for 61 days
www.matcorr.com
5.0
-30
-50
60
6.5
-10
-60
DTA
TG
TG(mg)
DTA(V)
Intensity (cps)
600
3.5
0
100
200
300
400
500
600
700
3.0
800
Temperature( )
Figure 9. TG-DTA curves of the corrosion products removed from the
galvanized steel wires
405
406
Figure 10. Three-stage corrosion process of the hot-dip galvanized steel wires during the period of SST
4 Discussion
5 Conclusions
Zinc coating of the hot-dip galvanized steel wires has a high

reactivity in the Cl containing simulated acid rain exposed to a
small polarization ( 100 mV) with the formation of grainy
corrosion products (Fig. 4). Moreover, thick rust layers formed
during the salt spray test period (Fig. 7a-7e). To depict the
corrosion behaviour of the hot-dip galvanized steel wires under
constant load in the simulated acid rain, a three-stage corrosion
process was proposed (Fig. 10).
In stage I, for the nonhomogeneity of the zinc coating,
electrochemical reactions occurred with the anodic dissolution of
Zn (Zn ! Zn2 2e) and cathodic evolution of hydrogen
(2H 2e ! H2). Zn2 diffused into the electrolyte layer and

reacted with SO2
4 , Cl and other ions in the electrolyte, Zn based
corrosion products precipitated at the reaction sites and gradually
expanded to the other recession places.
In stage II, corrosion products covered and expanded the
steel wire surface, resulting in the diffusion of H into the inner
zinc surface under the corrosion products difficult. Because of the
electrolyte layer on the hot-dip galvanized steel wires can be
continuously refreshed during the simulated acid rain spray test,
thats to say, the pH value in the outside layer is always lower than
that under the corrosion product, which will lead to the hydrolysis
of Zn2 to form Zn(OH)2 (Zn2 2H2O ! Zn(OH)2 2H)
[24]. And the lower pH value will also accelerate the migration
of Zn2 to the electrolyte layer, SO2
4 in the electrolyte layer then
reacts with Zn2 leading to the formation of ZnSO4. And further
formed Zn(OH)2)3 ZnSO4 5H2O (white rust) with the interaction of Zn(OH)2 and ZnSO4, which was confirmed by the XRD
analysis results.
In stage III, the corrosion products layer grew thicker, and
formed a barrier to the electrolyte solution. The hydrolysis of Zn2
resulted in the pH value near the interface decrease, which
contributed to the corrosion of the steel base with the depletion of
Zn coating. SO2
4 and other anions diffused through the barrier and
reached the interface area via the electric field force provided by the
corrosion cell, in which the steel base worked as anode. When those
anions reached the steel base area where the pH value was low
due to the hydrolysis of Zn2and Fe2, reacted with Fe2
and Fe2(SO4)3O 7H2O, Fe2(SO4)3, Fe(OH)3, Fe2O3 H2O and the
like (red rust) formed, XRD analysis proved this result.
1) Electrochemical polarization and mass loss results showed

corrosion rate of the hot-dip galvanized steel bridge wires in
the simulated acid rain could be significantly enhanced by
tensile stress.
2) XRD and TG-DTA characterization for the rust layers
exhibited that (Zn(OH)2)3 ZnSO4 5H2O (white rust) was
the main corrosion product, and a little amount
of Fe2(SO4)2O 7H2O, Fe2(SO4)3, Fe2O3 H2O (red rust) were
also detected.
3) A three-stage corrosion process for the hot-dip galvanized steel
bridge wires in the simulated acid rain under constant load
was proposed.
Acknowledgements: Support from the National Natural Science

Foundation of China (No.10476035) and from Natural Science
Foundation of Chongqing (No. 2004BB6056) is gratefully
acknowledged.
6 References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
M. Virlogeux, Eng. Struct. 1999, 21, 737.

W. E. Daniell, H. G. John, Eng. Struct. 2007, 29, 358.
M. Toshio, J. Wind Eng. Ind. Aerod. 2003, 91, 1393.
K. M. Mahmoud, Theor. Appl. Fract. Mec. 2007, 48, 152.
F. Rezaei, F. Sharif, A. A. Sarabi, S. M. Kasiriha, M. Rahmanian, E. Akbarinezhad, Mater. Corros. 2010, 61, 681.
D. Burton, D. Q. Cao, R. W. Tucker, C. Wang, J. Sound. Vib.
2005, 279, 89.
V. V. Dimitri, G. Stewart, E. Robert, Eng. Struct. 1998, 20,
1010.
K. Suzumura1, S. Nakamura, J. Mater. Civ. Eng. 2004, 16, 1.
S. Vincenzo, D. A. Piero, J. Wind Eng. Ind. Aerod. 2003, 91,
1285.
Q. H. Roger, P. B. David, K. Dyab, J. Bridge Eng. 1997, 2,
157.
K. Furuya, M. Kitagawa, S. I. Nakamura, K. Suzumura,
Struct. Eng. Int. 2000, 10, 189.
X. J. Wu, Y. H. Kang, H. G. Chen, Key Eng. Mater. 2004, 2, 1493.
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[13] L. Wei, R. Hunsperger, K. Folliard, M. Chajes, J. Barot, D.

Jhaveri, E. Kunz, Proc. SPIE. 1999, 3587, 28.
[14] H. R. Hanmilton, J. E. Breen, K. H. Frank, J. Struct. Eng.
1998, 3, 72.
[15] C. B. Scott, W. V. Garry, F. D. Paul, C. W. Alan, B. Raimondo,
J. Mater. Civ. Eng. 2000, 12, 33.
[16] S. Magaino, M. Soga, K. Sobue, A. Kawaguchi, N. Ishida, H.
Imai, Electrochim. Acta. 1999, 44, 4307.
[17] A. P. Yadav, H. Katayama, K. Noda, H. Masuda, A. Nishikata,
T. Tsuru, Electrochim. Acta. 2007, 52, 2411.
[18] R. Betti, A. C. West, G. Vermaas, Y. Cao, J. Bridge Eng. 2005,
10, 151.
[19] M. Xue, R. Chitrakar, K. Sakane, K. Ooi, S. Kobayashi, M.

Ohnishi, A. Doi, J. Solid State Chem. 2004, 177, 1624.
[20] G. Madhurambal, S. C. Mojumdar, S. Hariharan, P. Ramasamy, J. Therm. Anal. Calorim. 2004, 78, 125.
[21] P. Balaz, M. Balintova, Z. Bastl, J. Briancin, V. Sepelak, Solid
State lonics. 1997, 101, 45.
[22] R. V. Siriwardane, J. A. Poston, E. P. Fisher, M. S. Shen, A. L.
Miltz, Appl. Surf. Sci. 1999, 152, 219.
[23] D. Kuchar, T. Fukuta, M. S. Onyango, H. Matsuda, Desalination. 2007, 211, 144.
[24] A. P. Yadav, H. Katayama, K. Noda, H. Masuda, A. Nishikata,
T. Tsuru, Electrochim. Acta. 2007, 52, 3121.
(Received: August 31, 2010)
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W5921
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408
DOI: 10.1002/maco.201005888
Corrosion performance and mechanical properties of joined

automotive materials
N. LeBozec*, A. LeGac and D. Thierry
The automotive industry envisions that an optimized vehicle in terms of
performance and cost can be achieved only by using different materials at
different vehicle locations in order to utilize the functionality of the different
materials to a full extent. Currently, steel and aluminum are the most important
construction materials for the mass production of automotive structure.
However, other materials such as magnesium alloys and stainless steel are also
used. The use of dissymmetric assemblies of materials in the automotive
industry has also led to the development of joining technologies other than spot
welding and arc welding such as clinching, adhesive bonding, laser welding, and
MIG brazing. However, and despite the development of these new joining
technologies, there are still important gaps of knowledge with regards to the
corrosion performance of different joint populations using dissymmetric and
symmetric materials. Materials commonly used in the automotive industry
including steel and aluminum-based susbtrates were assembled with different
combinations using various joining techniques in order to evaluate their
corrosion performance as well their mechanical properties after cyclic
accelerated corrosion tests. The results indicated a relationship between the
corrosion inside the confined joint and the decrease of the mechanical
properties of the assemblies.
1 Introduction
The automotive industry envisions that an optimized vehicle in
terms of performance and cost can be achieved only by using
different materials at different vehicle locations in order to utilize
the functionality of the different materials to a full extent (weight
reduction, optimization of properties. . .). Currently, steel and
aluminum are the most important construction materials for the
mass production of automotive structures. The use of dissymmetric assemblies of materials in the automotive industry has
also led to the development of joining technologies other than
spot welding and arc welding such as clinching, adhesive
bonding, laser welding, and MIG brazing. The main objective of
joining is to make the joint as unobtrusive as possible. Ideally, the
joint would not result in local reduction of materials properties
nor introduce physical discontinuities. Realistically, very few
joining methods offer the potential of ideal joints. Most
common joining methods adversely affect materials properties by
excessive thermal exposure and create local discontinuities as the
N. LeBozec, A. LeGac, D. Thierry
French Corrosion Institute, 220 Rue Pierre Rivoalon, F-29200 Brest
(France)
E-mail: nathalie.lebozec@institut-corrosion.fr
result of the joint geometry. The choice of joining method is

generally a compromise of joint structural performance,
manufacturing speed, and cost [1]. The mechanical stability of
the joints is dependent on many parameters including the
robustness of the joining technique, the nature of assembled
materials in particular their corrosion resistance. Perforation
corrosion is probably the most important problem in automotive
corrosion when considering joined materials with overlap
configuration [2]. In order to assess the corrosion performance
and the mechanical properties, one of the major concerns is to
be able to design a relatively simple test panel assembly which
can accurately represent the inherently more complex features
within actual vehicles. A broad variety of test specimens has
been considered generally constructed by overlapping pairs of
sheets which are joined by spot welding, rivets, screws, or
clinches [310]. Among the different designs, overlapped
specimens [3, 58, 1014] closed to the lap-shear specimen
[15] may be used both to assess the corrosion resistance and to
evaluate the mechanical properties of the joints. The corrosion
resistance of lap joints and the effect of their mechanical
properties have been essentially studied in laboratory including
tests in solutions [6, 12, 13, 1618]. Couple of studies were
performed in accelerated corrosion tests such as salt spray,
GM9540P, CCTIV, or specific tests [3, 4, 1012, 1921]. Only few
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Corrosion performance and mechanical properties of joined automotive materials
studies related to field exposures in stationary sites [3, 5, 10, 22] or

on-vehicles [5, 19]. In particular, adhesive bonded aluminum
alloys have been quite intensively investigated in laboratory tests
to evaluate the performance of adhesives as well as the surface
treatment. However and despite the number of studies, the
relationship between corrosion and mechanical properties of
joined material is not always evident. Moreover, the variety of
panel designs simulating joined assemblies, of joining techniques as well as of assembled materials makes any comparison
very difficult. The aims of the present study were thus to assess
the corrosion performance of a large number of automotive
joined materials on their mechanical durability in order to
provide automotive designers and suppliers with a better
knowledge regarding the selection of appropriate materials and
the joining of dissimilar materials.
2 Experimental
2.1 Samples
The assembly consisted of two single panels of size
80 mm 10 mm joined together with an overlap of 25 mm as
shown in Fig. 1. Eight different substrates were assembled using
7 different joining technologies to produce 20 assemblies as
indicated in Table 1. Panels were spot welded using a medium
frequency welding equipment and electrodes with a diameter of
6 mm. The duration of the current flow was 240 ms. Arc welds
were achieved by cold metal transfer with a speed of 700 mm/
min. Laser welding was performed with a power of 4 kW, a speed
of 4 m/min and a gap of 0.2 mm. The material used for MIG
Brazing was CuSi3 alloy. The adhesive was a one component
epoxy based adhesive (Betamate 1060) cured at 180 8C. Materials
were clinched using a TOX system and the punch was made of
steel.
The specimens were then processed using normal procedure
in the production line of an automotive plant (degreasing,
phosphating, and ED-coating 1015 mm).
2.2 Accelerated corrosion test
The samples were exposed in an accelerated corrosion test called
N-VDA for durations up to 34 weeks with withdrawal of
samples after 12 and 17 weeks. N-VDA test is a new accelerated
corrosion test that has been developed by the German association
of automotive industry (VDA) together with the German steel
association (VDEh) in order to replace the test standard VDA 621415. It is indeed well known that VDA 621-415 test exaggerates
the corrosion of zinc coating and thus does not simulate onvehicle conditions [23]. As shown in Fig. 2, N-VDA test is based
on three different cycles which alternate during a week. In
particular, this test includes a freezing phase at 15 8C (cycle C)
and a lower salt concentration than in VDA 621-415 e.g., NaCl
1 wt% instead of 5 wt%.
Figure 1. Schematic representation of the assembly (top left) and photographs of different joined specimens
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409
410
LeBozec, LeGac and Thierry
Table 1. Combinations of materials and joining techniques
Assembly
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Material 1
Material 2
Joining technique
High strength carbon steel (HSCS)

HSCS
HDG 10 mm
Usibor AluSi 1500P
Usibor AluSi 1500P
Low carbon steel (CRS)
CRS
CRS
CRS
AA 6016
CRS
AA 6016
AA 6016
AA 6016
AA 6016
AA 5182
AA 5182
AA 5182
AA 5182
AM 50
HSCS
Hot Dip Galvanized (HDG) 10 mm
HDG 10 mm
HDG 10 mm
HDG 10 mm
HDG 10 mm
ElectroGalvanized Thin org coat (Gen 2) (EG)
EG
CRS
HDG10 mm
HDG 10 mm
HDG 10 mm
HDG 10 mm
EG
EG
HDG 10 mm
HDG 10 mm
EG
EG
AA 6016
Spot welding
Spot welding
Spot welding
Spot welding
Laser welding
MIG brazing
Spot welding
Laser welding
Spot welding
Arc welding
Adhesive clinching
Clinching
Adhesive clinching
Clinching
Adhesive clinching
Clinching
Adhesive clinching
Clinching
Adhesive clinching
Adhesive
Thickness in mm: C-steel, HDG: 0.8; HSCS: 1.3; Usibor AluSi: 1.2; EG: 0.9; AA6016, AA5182: 1.2, AM50: 3.
2.3 Evaluations
Before and after exposure to the accelerated corrosion test, the
samples were mechanically tested in order to evaluate the
influence of the corrosive environments on the mechanical
properties of the joints. Tensile testing was performed on a
Zwick Z100 tensile testing machine with 100 kN load capacity
at 22 8C and 50%RH. Tensile speed was 10 mm/min
using 50 mm long and 40 mm high self-tightening jaws.
Photographs of fracture surfaces were thereafter taken for visual

examination.
The extent of corrosion inside the confined overlapped area
was evaluated by measuring the deepest pits after removal of the
corrosion products according to ISO 8407. This was achieved
using an optical microscope Leica DM 2500M equipped with a
Mitutoyo micrometer gauge or using a Mitutoyo micrometer
gauge equipped with a sharp tip (for steel and zinc coated steel
panels).
Figure 2. Basic humidity and temperature subcycles of the new VDA test (according to VDEh)
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Failure mode of the adhesive was determined by image

analysis (Lucia software).
3 Results
3.1 Welded materials
Figure 3 presents the initial tensile strength of welded joint
specimens and their residual values as a function of exposure
time in N-VDA cyclic corrosion tests. The percentage of strength
loss induced by the corrosive test is also given.
Regarding the initial tensile strength, spot welded HSCS/
HSCS samples showed by far the highest peak load with a value of
25 kN while the other spot welded assemblies exhibited a
significantly lower tensile strength around 8 kN. For spot welded
specimens, the expected nugget pullout failure occurred. Arc
welded aluminum alloys to HDG exhibited a tensile strength of
the same range as spot welded assemblies (except HSCS/HSCS)
with a failure in the weld seam. Laser welded and MIG brazed
specimens presented a stronger joint with a peak load of 12 and
14 kN, respectively. Comparing assemblies which involve the
same combination of materials (e.g., Usibor AluSi/HDG and
CRS/EG), peak loads of the laser welded joints were higher than
those of spot welded joints (12 kN against 8 kN).
No significant influence of the exposure duration in N-VDA
test was observed on spot welded HSCS/HDG, HDG/HDG, and
Usibor AluSi/HDG assemblies despite a slight decrease of the
mechanical properties of HSCS/HDG after 34 weeks of exposure
(20%). In addition, no change of the failure mode was noticed on
these assemblies.
On the contrary, symmetric assemblies involving steel e.g.,
CRS and HSCS, were significantly affected by the exposure in
N-VDA with a total mechanical loss for CRS after 34 weeks of
exposure. Spot welded HSCS/HSCS lost about 60% of the

mechanical properties after 17 weeks of exposure with no change
when increasing the duration. However, this is given with an
important deviation as one of the samples was completely
dismantled after the test. Moreover, the failure mode changed
from pull out to interfacial failure. It can also be noted that the
residual tensile strength of HSCS/HSCS after 17 and 34 weeks
was in the range of the initial one of the other spot welded
assemblies. When CRS was welded to zinc coated steel (e.g., EG
or HDG) using spot welding, laser, or MIG techniques, the loss of
strength gradually increased with exposure time in N-VDA test to
reach important loss of about 90% after 34 weeks of exposure for
CRS/EG. The mechanical loss was less important in the case of
MIG brazed CRS/HDG after 34 weeks, showing a failure in CRS
base metal. No change of failure mode was observed on laser
welded Usibor/HDG while it failed in CRS base metal on CRS/
EG after 17 and 34 weeks. Arc welded 6016/HDG behaved quite
well during 17 weeks of exposure, while further exposure
durations resulted in complete dismantling of the assemblies
with an interfacial failure associated with the formation of deep
pits in aluminum panels (about 800 mm) and significant attack in
zinc coated steel (400 mm). Regarding the influence of the
welding process (laser or spot welding) of the Usibor AluSi/HDG
(A4 and A5) and CRS/EG (A7 and A8) assemblies, more strength
loss was generally measured on laser welded than spot welded
material, in particular for Usibor AluSi/HDG. As the initial
strength was higher for laser welded assemblies than for spot
welded specimens, the peak loads of laser and spot welded
specimens involving the same materials were however in the
same range after exposure to the corrosion tests.
In order to evaluate the influence of the corrosion inside the
confined overlap on the mechanical properties of the joints, the
strength loss was plotted as a function of the minimum
remaining thickness in the crevice for some assemblies on
Figure 3. Tensile test results on welded materials as a function of exposure time in N-VDA test. The strength loss is also given
www.matcorr.com
411
a)
12 weeks
17 weeks
b)
34 weeks
12 weeks
100
90
$+6&6+6&6
90
80
$+6&6+'*
80
70
A1
Strength loss (%)
Strength loss (%)
100
A1
60
50
40
30
20
A2
A1
A2
c)
20
17 weeks
70
$&56(*
A9
$&56(*/DVHU
A7
60
$&56&56
A6
50
40
A8
30
A9
A6
A8
A7
40
60
80
Remaining thickness (%)
12 weeks
A6
34 weeks
$&56+'*0,*
10
A2
17 weeks
A9
A8
A7
20
10
100
20
40
60
80
100
34 weeks
100
$+'*+'*
90
Strength loss (%)
412
$8VLERU+'*
80
$8VLERU+'* ODVHU
70
60
50
40
A5
30
A5
20
10
A3
0
0
A5
A4
A3A3
A4
20
40
60
80
100
A4
Figure 4. Strength loss as a function of the average remaining material thickness in overlapped area of spot welded, laser welded, and MIG brazed
assemblies after exposure in N-VDA test
Fig. 4. The percentage of remaining thickness was estimated

considering the initial material thickness and the deepest attacks
in the overlapped area in the vicinity of the joint (excluding the
edges). It should be underlined that the deepest attacks were
measured in steel panels when joined to zinc coated steel (Figs. 4a
and b) or in HDG substrate for assemblies A3, A4, and A5
(Fig. 4c). From Fig. 4, the strength loss has an obvious tendency to
increase while the remaining thickness of the materials decreases
with the exposure time in the accelerated corrosion test,
particularly for assemblies involving HSCS and CRS. The attack
of the material inside the lap in the vicinity of the weld would
indeed weaken the joint till a limit over which important or total
strength loss occurs. It should be emphasized that important edge
corrosion may also affect the mechanical properties of a joint after
long exposure durations particularly when considering carbon
steel. Thus, it may not be obvious to separate the contribution of
edge corrosion or corrosion in the confinement on the mechanical
properties of the joint. In the case of assemblies involving Usibor
AluSi and HDG (A4 and A5), the corrosion attacks did not appear
sufficient enough to induce significant strength loss on spot
welded joints (A4) while laser welded joints lost about 1530% of
initial strength with however much less corrosion attacks. The
influence of corrosion on the mechanical properties of this
assembly is not obvious. On spot welded HDG, the corrosion
attacks which reached about 50% of steel sheet locally did not
weaken the assembly significantly. Further exposure durations
would have been required to evaluate the influence of the
corrosion damage on the mechanical properties.
It can also be observed that the mechanical properties and
the corrosion resistance of steel were improved by coupling to
zinc coated steel: CRS/EG (A7) and HSCS/HDG (A2) versus
CRS/CRS (A9) and HSCS/HSCS (A1). This was explained by the
cathodic protection of zinc coating on the corrosion also observed
in previous studies as for example in ref. [4].
3.2. Clinched, adhesive bonded, and clinched materials
The tensile test results of adhesive bonded, pure clinched, and
clinch-bonded joints are presented in terms of maximum load
before and after exposure to N-VDA test in Fig. 5, together with
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Figure 5. Tensile test results on pure clinched and clinched and adhesive bonded materials as a function of exposure time in N-VDA test. The
strength loss is also given
the percentage of strength loss. Regarding the initial tensile

strength, the highest value was measured for the adhesive bonded
joint (A20) with a value of 19.5 kN. A typical load-displacement
curve of adhesive lap shear joint resulting in a pure cohesive
fracture of the adhesive was observed in agreement with previous
work [8]. Initial peak loads of clinch-bonded systems varied from
10 to 14 kN with a cohesive fracture of the epoxy resin, again
showing typical load-displacement curve of clinch-bonded joint
[8]. For similar combination of materials (e.g., AA6016/HDG,
AA6016/EG, AA5182/HDG, and AA5182/EG), the mechanical
strength of clinched samples was three to four times lower than
those with combined adhesive and clinched joints as expected.
After exposure to N-VDA test up to 34 weeks, no alteration of
the mechanical properties of pure clinched assemblies was
observed. After 12 and 17 weeks of exposure to the new VDA test,
the mechanical properties of clinched bonded specimens were
not affected as well, in exception for CRS/HDG joints which were
highly corroded and even failed without applying any tensile force
after 34 weeks of testing. Clinch-bonded specimens involving
AA6016 lost half of their initial strength while assemblies
involving AA5182 clinch-bonded did not lose as much of their
mechanical properties.
Wines also observed no significant effect of 480 h of neutral
salt spray on clinched preprimed HDG steel while clinch-bonded
specimens lost about 20% of their initial strength [8]. It has to be
underlined that even if the strength loss of the clinch-bonded
specimens was higher than the one of pure clinched samples, the
residual peak load of the clinch-bonded joints was still higher
than the one of the pure clinched tensile specimens. Strength loss
of AM50 bonded to AA6016 was similar after both 17 and
34 weeks of exposure i.e., about 30%.
As shown in Fig. 6, the strength loss of clinch-bonded
specimens seems to be related to the main fracture mode of the
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epoxy resin and particularly the percent of adhesive failure. This

is in good agreement with the work of Wilkinson and Ailor who
also observed that low bond strengths of aluminium/steel
assemblies exposed at atmospheric sites were connected by some
degree of adhesive failure [22]. Similar observations were drawn
by Lunder and coworkers when evaluating various surface
treatments prior to adhesive bonding on AA6060 in single lap
joint configuration [24]. The present results indicated a general
increase of the adhesive fracture with exposure time in the
accelerated corrosion test particularly for CRS/HDG joint (A11)
which showed 100% of adhesive fracture resulting in a complete
dismantlement of the joint after 34 weeks of test. Regarding joints
involving aluminum and galvanized steel, AA6016 presented a
higher degree of adhesive failure than AA5182, which obviously
induced a higher loss of strength.
Figure 7 shows a correlation between the loss of mechanical
properties and the corrosion attack in the 1200 mm thick
aluminum panel of the clinch-bonded joints. It has to be
underlined that aluminum alloy was more prone to corrosion
than galvanized steel (EG or HDG) panels they were assembled
to. This is in good agreement with the work of Townsend who
tested AA5182 riveted to electrogalvanized steel in different
accelerated tests [4]. In the case of assembly Nr 20 (AM50/
AA6016), magnesium alloys were significantly more attacked
than AA6016 as expected with about 600 mm of maximum depth
of attack against 50 mm in aluminum. The results of Fig. 7
indicated an increase in the corrosion attack with exposure time,
with a tendency for AA5182 to be more susceptible to pitting
corrosion than AA6016. Nevertheless, joined specimens involving AA6016 (e.g., A13 and A15) presented a more important
strength loss than similar joints with AA5182 (e.g., A17 and A19)
obviously connected to the mode of fracture (Fig. 5). Indeed, the
examination of the fractured surface revealed evidence of filiform
413
100
90
80
$
12 weeks
$&56+'*
17 weeks
$+'*
$(*
$(*
$$0
34 weeks
$+'*
$
Strength loss (%)
70
60
$
50
$
$
40
$
30
$
$
20
$
$
$
10
$
0
0
$
10
$
$
$ $
20
30
40
50
60
70
80
90
100
Percent of adhesive fracture (%)
Figure 6. Strength loss as a function of the percentage of adhesive fracture on adhesive bonded joints after exposure in N-VDA test
corrosion under the adhesive slightly more spread on AA6016.

The corrosion of the substrate would thus provide paths for
ingress of moisture to the substrate/adhesive interface and the
corrosion products might contribute to the loss of adhesion by
creating stresses as it was observed in previous studies [3, 23, 25].
For pure clinched specimens, no strength loss was observed
despite depth of attack up to 420 mm in the confined overlapped
area (see Table 2). It is likely that deeper attacks located close to the
clinch shall be formed in order to weaken the cohesion of
clinched joint. Additional exposure duration to N-VDA test
should thus have been performed. It can also be observed from
100
90
80
34 weeks
$+'*
17 weeks
$(*
12 weeks
$+'*
$(*
70
Strength loss (%)
414
A15
60
50
A13
40
A19
30
20
10
0
A15
A15
A19
A17 A19 A17

A13
A13
0
200
400
600
A17
Fig. 7 and Table 2 that after similar exposure durations, deeper

pits in aluminum were generally formed under the adhesive of
clinch-bonded joints than on pure clinched material.
4 Conclusions
Materials commonly used in the automotive industry were
assembled with different combinations using various joining
techniques in order to evaluate their corrosion performance as
well their mechanical properties. Steel-based materials included
carbon steel, high strength steel, Usibor AluSi, and zinc coated
steel. Light alloys covering two aluminum alloys 5182 and 6016
and magnesium alloy AM50 were selected. Joining techniques
integrated spot welding, laser welding, arc welding, MIG brazing,
clinching, and adhesive bonding with epoxy. In total, 20 different
assemblies were produced and characterized before being tested
in a cyclic accelerated corrosion test named N-VDA tests for
different exposure durations in order to assess the influence of
the corrosion on the mechanical properties of the different joints.
The loss of mechanical properties of welded joints exposed in
the accelerated corrosion test was related to the corrosion
degradation in the overlapped area which induced a modification
of the failure mode. Globally, the remaining thickness decreased
while the strength loss increased with the exposure time. No
Table 2. Maximum depth of attack in AA6016 clinched to zinc coated

steel after 34 weeks of exposure in N-VDA test
Assembly
800
1000
Max depth of attack (mm)
1200
Maximum depth of attack (m)
Figure 7. Strength loss as a function of the maximum depth of attack in

aluminum panels clinch-bonded after exposure in N-VDA test
A12:
A14:
A16:
A18:
6016/HDG
6016/EG
5182/HDG
5182/EG
420
350
330
280
www.matcorr.com
reduction in joint strength of spot welded HDG/HDG and Usibor

AluSi/HSG combinations was observed. The mechanical properties and the corrosion resistance of steel were improved by
coupling to zinc coated steel.
No reduction in joint strength was observed on any of the
clinched joints after 34 weeks of test. On the contrary, joints
involving adhesive presented increasing strength loss with
exposure time to the cyclic test. This was connected to an
increase of the degree of adhesive failure as a result of
environmental exposure generating corrosion of the substrate
that provided path for ingress of moisture to the substrate/
adhesive interface but also created stresses in the joint.
Acknowledgements: The authors acknowledge the technical and
financial support of Alcan, Arcelormittal group, BMW, Daimler,
Fiat, JFE Steel, PPG Industries, PSA and Renault.
5 References
[1] E. P. Patrick, M. L. Sharp, in: International Congress and
Exposition, SAE Technical Paper no. 920282, February 2428,
Detroit, Michigan 1992.
[2] S. Fujita, D. Mizuno, Corros. Sci. 2007, 49, 211.
[3] B. Chico, D. De La Fuente, M. Morcillo, J. A. Gonzalez, E.
Otero, J. Coat. Technol. 2003, 75, 43.
[4] H. E. Townsend, Corrosion 1996, 52, 66.
[5] C. De Medeiros, A. Berglund Ahman, D. Thierry, N.
Lebozec, RFCS Report EUR 21626 EN, 2005.
[6] J. P. Moran, M. W. Egbert, in: Conference Corrosion and
Corrosion Control of Aluminum and Steel in Lightweight Automotive Applications, March 2631, Orlando, USA 1995.
[7] W. King, G. Sowinski, E. T. Englehart, in: Automotive Engineering Congress and Exposition, SAE Technical Paper
no.750464, February 2428, Detroit 1975.
[8] B. L. Wines, in: International Congress and Exposition, SAE
Technical Paper no.890517, February 27March 3, Detroit,
Michigan 1989.
[9] G. J. Courval, J. Allin, D. P. Doylen, in: Proceedings of the 6th

Automotive Corrosion and Prevention Conference, SAE technical paper no.932357, 1993.
[10] W. J. Van Ooij, R. A. Edwards, G. L. Nelheisel, in: Proceedings
of the 5th Automotive Corrosion & Prevention Conference, 1991,
pp. 253264.
[11] L. Quintino, G. Pimenta, D. Iordachescu, R. M. Miranda,
N. V. Pepe, Mater. Manuf. Processes 2006, 21, 63.
[12] C. E. Caicedo-Martinez, J. Schoen, J. Vrenken, J. Bakels,
R. A. Brash, Corros. Manage. 2003, 55, 16.
[13] R. Akhter, K. G. Watkins, W. M. Steen, Mater. Lett. 1990, 9,
550.
[14] J. Wloka, H. Laukant, U. Glatzel, S. Virtanen, Corros. Sci.
2007, 49, 4243.
[15] K. L. Devries, P. Borgmeier, Testing of Adhesive Joints, ASM
Handbook Mechanical Testing and Evaluation, Vol. 8,
Materials Park, OH 2000, pp. 836844.
[16] H. N. McMurray, J. R. Searle, B. P. Wilson, D. A. Worsley, Br.
Corros. J. 2002, 37, 225.
[17] M. E. Somervuori, L.-S. Johansson, M. H. Heinonen, D. D.
H. Van Hoecke, N. Akdut, H. E. Hanninen, Mater. Corros.
2004, 55, 421.
[18] J. Senf, E. Broszeit, M. Gugau, C. Berger, in: Magnesium
Technology 2000, 2000 TMS Annual Meeting, March 1216,
Nashville, USA 2000, pp. 137142.
[19] G. Leijon, D. Persson, M. Ohman, C. Celsing, M. Larsson, A.
Melander, Report no. KIMAB-2006536, 2006.
[20] C. A. Gosselin, SAE Technical Papers no.850211, 1985.
[21] N. LeBozec, D. Thierry, Mater. Corros. 2010, 61, 845.
[22] T. L. Wilkinson, W. H. Ailor, in: Congress and Exposition Cobo
Hall, SAE Technical Paper no.780254, February 27March 3,
Detroit 1978.
[23] N. LeBozec, N. Blandin, D. Thierry, Mater. Corros. 2008, 59,
889.
[24] O. Lunder, B. Olsen, K. Nisancioglu, Int. J. Adhes. Adhes.
2002, 22, 143.
[25] T. V. Natale, in: International Congress and Exposition, SAE
Technical Paper no.880532, February 29March 4, Detroit,
Michigan 1988.
(Received: July 30, 2010)
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W5888
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416
DOI: 10.1002/maco.201005974
A zinc/silicon dioxide composite film: Fabrication and

anti-corrosion characterization
Z. F. Lin, D. Zhang*, Y. Wang and P. Wang
A zinc/silicon dioxide composite film has been electrodeposited on carbon steel
surface via adding tetraethylorthosilicate (TEOS) in zinc nitrate solution. The
advantage of this method is that the metal/inorganic composite film can be
fabricated without adding solid particles in solution. Polarization curve results
showed that the composite film obtained at a TEOS concentration of 0.012 M
had the best corrosion resistance. Electrochemical impedance spectroscopy
results indicated that this film had a corrosion protection effect in 3.5 wt%
sodium chloride solution for hundreds of hours. This kind of composite film can
be potentially applied as anti-corrosion coating for metal corrosion protection.
1 Introduction
The composite coatings of metal and alloy have various special
properties such as corrosion stability, wear resistance, friction
coefficient, self-lubrications, high temperature stability, and
improved catalytic activity [1, 2]. Electrodeposition is one of the
most common techniques for the fabrication of composite
coatings because it has the advantages of short processing time,
process simplicity, and better homogeneity [3, 4].
The common method for electrodeposited metal/inorganic
film is to add inorganic particles with micro or submicron size in
solutions [59]. However, this method requires the use of stable
suspensions of positively charged inorganic particles. It is
important to prevent particle agglomeration in the suspensions to
achieve a controlled deposition rate and uniform distribution of
particle size in the deposits. One of most common methods to
address this problem is the use of organics in solutions [1013].
The use of organic molecular could offer electrostatic stabilization
of inorganic particles in solutions as it could avoid the difficulties
related to the low thickness of the particles electric double layer in
solutions that leads to particle agglomeration and sedimentation
[14]. However, one of the disadvantages of this method is that the
system becomes more complex.
In this article, we use another novel method which is based
on manipulated electrosynthesis of particles by an electrochemical control of the pH at the electrode/solution interface to
Z. F. Lin, D. Zhang, Y. Wang, P. Wang

Key Lab of Corrosion Science, Shandong Province, Institute of Oceanology, Chinese Academy of Sciences, 7 Nanhai Road, Qingdao 266071
(P. R. China)
E-mail: zhangdun@qdio.ac.cn
Z. F. Lin
Graduate School of the Chinese Academy of Sciences, 19 (Jia) Yuquan
Road, Beijing 100039 (P. R. China)
fabricate composite coating with another material. The main

advantage of this method is that it avoids the problems related to
addition of other particles. Tetraethylorthosilicate (TEOS), which
acted as the precursor of particles, was added in zinc nitrate
solution to fabricate composite coatings. The fabrication of
composite film starts from hydrolysis of TEOS in solution and
then the sol is condensed to generate a silica film on the surface of
the electrode. Meanwhile, zinc ion is reduced to zinc to form
films on the electrode. Another advantage of this method is that
the quality of the composite film may be improved as the
hydrolysis product of TEOS may act as organic additive during
electrodeposition. It may have effective role on the microstructure
and the resultant properties of the composite film.
The objective of this investigation is to fabricate zinc based
composite films by electrodeposition. TEOS acted as an additive
to produce silicon dioxide in the films. The effect of various
concentrations of TEOS on the microstructure and anti-corrosion
properties of the resultant composite films were determined. This
was achieved by analyses using scanning electron microscope
(SEM) and X-ray diffraction (XRD) and the anti-corrosion
characterization was examined by polarization curves and
electrochemical impedance spectroscopy (EIS).
2 Material and methods

2.1 Materials
Sodium chloride and zinc nitrate were analytical grade and
purchased from Sinopharm Chemical Reagent Co., Ltd. TEOS
was analytical grade and purchased from Aldrich and used
without further purification. The water used in this investigation
was Milli-Q water (Millipore, USA).
The substrates used in the experiment were made of carbon
steel and the chemical composition (wt%) was 0.1 carbon, 0.4
manganese, 0.12 silicon, 0.02 sulfur, 0.05 phosphorus, and
balance was iron.
www.matcorr.com
In order to match the sample geometry to the specific

experimental requirements, two types of samples were applied.
Carbon steel rods mounted with epoxy resin were used for the
electrochemical measurements, maintaining a constant exposed
area (0.196 cm2) throughout the experiments. Carbon steel plates
were used for XRD, SEM, and energy dispersive spectrometer
(EDS) characterization, respectively. Prior to film deposition, the
plates and rods were grinded using emery papers (400, 800, and
1200 grits). Finally, all samples were rinsed in ethanol, clean
water, and finally dried at room temperature.
2.2 Fabrication of the composite films
The composite films were fabricated in 0.01 M zinc nitrate
solution containing different concentrations of TEOS. Electrodeposition experiment was carried out with a three-electrode cell.
Carbon steel electrode was used as working electrode. A silver/
silver chloride (Ag/AgCl) (3 M potassium chloride) and a
platinum wire electrode (CH Instruments, Inc.) were used as
reference electrode and counter electrode, respectively. All
potentials were reported versus the Ag/AgCl (3 M potassium
chloride) electrode. The applied potential was 1.2 V and the
deposition time was 20 min. During the electrodeposition
process, the temperature was maintained at 50 8C by a water
bath to make TEOS hydrolyzed completely.
2.3 Characterization
The phase content was determined by XRD with a diffractometer
(D/MAX-RB, Rigaku Corporation) using monochromeatized Cu
Ka radiation at a scanning speed of 1.28/min. The surface
morphologies and chemical composition of the deposited films
were studied using a field emission SEM (JSM-6700F, JEOL),
which was coupled with an EDS (OXFORD INCA Energy X-ray
Microanalysis system).
2.4 Electrochemical measurements
All the electrochemical experiments, including electrodeposition,
polarization curves, and EIS, were carried out by a computercontrolled electrochemical system (CHI 760C, CH Instruments
Inc.). Polarization curves were recorded in a potential range from
800 to 200 mV at a sweep rate of 1 mV/s. Sodium chloride
solution (3.5 wt%) was used as electrolyte. EIS experiments were
carried out at the frequencies from 105 to 101 Hz at open circuit
potential where the amplitude of the perturbation voltage was
5 mV. All the experiments were carried out at room temperature
and the test samples were immersed in 3.5 wt% sodium chloride
solution for a long time (30 min) to ensure stability of open circuit
potential.

3.1 Characterization of the film
Figure 1 shows the XRD patterns of composite films synthesized
with different TEOS concentrations. It can be observed in Fig. 1
www.matcorr.com
Figure 1. XRD patterns of the composite films fabricated by adding

different concentrations of TEOS: (a) 0, (b) 0.006, (c) 0.012, and
(d) 0.018 M
that most peaks of the product matched well with the hexagonal
structure of zinc oxide [JCPDS card no. 36-1451] in the absence of
TEOS. The peaks at 2u 31.80, 34.42, and 36.228 are assigned as
the (100), (002), (101) crystal faces of zinc oxide, respectively. The
intensity of the zinc oxide peaks decreased and some new peaks
appeared with the addition of TEOS, indicating that new products
were formed. Zinc oxide peaks disappeared when the concentration of TEOS were 0.012 and 0.018 M. These results suggest that
zinc oxide was hard to fabricate with dopant concentrations. The
peaks at 2u 36.30, 38.99, and 43.23 8 are assigned as the (002),
(100), (101) reflection lines of zinc [JCPDS card no. 04-0831],
respectively. Meanwhile, the wide hump in the range of 2u from
20 to 308 became more evident when TEOS was added, which can
be attributed to the fabrication of amorphous silica [15].
The fabrication of zinc oxide is generally based on the
generation of hydroxide ions (OH) at the surface of the electrode
by the cathodic reduction of an oxygen precursor in a zinc ion
solution. The reaction (1) occurs when nitrate radical (NO
3 ) is
used as oxygen precursors for zinc oxide electrodeposition [16].
The reaction of nitrate ion and hydroxide ions leads to zinc oxide
deposition on the surface of the cathode according to reaction (2).

NO
3 H2 O 2e ! NO2 2OH
(1)
Zn2 2OH ! ZnO H2 O
(2)
Tetraethylorthosilicate is an alkoxy silane with four alkoxyl

groups. It can form silicic acid in solution as a result of the
hydrolysis [17]. There are strong hydrogen bonds between
SiOH groups and silicic acid which could form molecular
network in solution. This network makes zinc ion difficult to get
hydroxy radical at the surface of the electrode. Thus, zinc oxide
was hard to form. For this reason, the content of zinc oxide in the
composite film decreased with increasing the TEOS concentration. There is no zinc oxide in the composite film when TEOS
concentration reached 0.012 M. It should be noted that at the
417
418
Lin, Zhang, Wang and Wang
same applied voltage (1.2 V), it was hard to obtain pure zinc film
when no TEOS was added. Thus, the network made zinc ion
reduced to zinc. Otherwise, silicic acid could form silicon dioxide
with catalyzation of hydroxy radical on the surface of the
electrode. Finally, a zinc/silicon dioxide composite film can be
obtained (reactions (35)).
SiOCH3 4 4H2 O ! SiOH4 4CH3 OH
OH
(3)
SiOH4 ! SiO2 2H2 O
(4)
Zn2 2e ! Zn
(5)
Potential is one of the most critical factors in electrodeposition. Various cathodic potentials were applied in this experiment.
However, it was found that a uniform film was hard to form even
at a potential of 1.15 or 1.25 V when other conditions were the
same. When the potential was higher than 1.2 V, the growth rate
of deposit was relatively low and it was hard to form uniform films
at the same time periods; when the potential is lower than 1.2 V,
there was aggregation of deposits and no uniform film could
form.
3.2 SEM and EDX analysis
The surface morphologies of the composite films coated on
carbon steel substrate were revealed by SEM, and their images are
shown in Fig. 2. As shown, the particles of the film surface
aggregated severely when no TEOS was added (Fig. 2a). This may
be originated from high surface energy of ZnO particles. This
surface morphology indicated that the film was not compact
when no TEOS was added. The film surface became compact with
TEOSs addition. However, when the TEOS concentration was
0.018 M, there were particle aggregations again at the surface of
the composite film (Fig. 2d).
Energy dispersive spectrometer technique was used to obtain
the elemental composition of the composite film. The results
confirmed the presence of zinc, silicon, and oxygen elements in
the film. The contents of silicon dioxide were 7.1 and 13.5% (atom
%) when the concentrations of TEOS were 0.012 and 0.018 M,
respectively.
3.3 Polarization curves measurements
Typical polarization curves of carbon steel and the samples with
different films are shown in Fig. 3. It can be observed that all the
films could reduce both the anodic and cathodic polarization
current densities, indicating that both anodic and cathodic action
processes of carbon steel could be inhibited due to the existence
of the composite film. As we know, the corrosion behavior of
coatings is severely affected by its quality. It should be noticed that
the composite film prepared with TEOS concentration of 0.012 M
presented better inhibition effect than other films although it had
familiar component as the film obtained at 0.018 M. When no
TEOS was added, the deposit was ZnO. It is a semiconductor and
the particle aggregated severely at the surface. Thus, its corrosion
resistance is not so good. When TEOS was added with the
concentration of 0.006 M, the hydrolyzation product of TEOS
made zinc oxide hard to form and the deposit was a composite of
zinc oxide, zinc, and silicon dioxide. When TEOS concentration
was 0.012 M, zinc oxide disappeared; also the film had a better
quality which can be seen from the surface morphology. The
optimal concentration of TEOS hydrolysis product made the zinc
Figure 2. SEM images of the composite films deposited in the solution containing 0.01 M zinc ion and (a) 0, (b) 0.006, (c) 0.012, and (d) 0.018 M TEOS
www.matcorr.com
Figure 3. Potentiodynamic polarization curves for the composite films

in 3.5 wt% sodium chloride solution (the deposition solution containing
0.01 M zinc ion and (a) 0, (b) 0.006, (c) 0.012, and (d) 0.018 M TEOS)
Figure 4. Representative Nyquist diagrams for carbon steel and the

samples with composite film exposed to 3.5 wt% sodium chloride
solution
deposited from solution more slowly and the proper content of

silicon dioxide in the composite film. So the film showed best
quality. As a result, it can provide a strong barrier effect against
aggressive ions during exposure to a corrosive environment.
However, when the content of TEOS was increased, particle
aggregations appeared at the surface of the coating (Fig. 2d).
Compared with the film prepared at 0.012 M, the particle
aggregation may attribute to more silicon dioxide in the film.
Possibly, it is the reason why the composite film prepared with a
concentration of 0.018 M had a poorer protection performance
than the film obtained at 0.012 M.
Figure 5. Electrical equivalent circuit for carbon steel and the samples
with composite film exposed to 3.5 wt% sodium chloride solution
3.4 EIS measurements

Electrochemical impedance spectroscopy has been used to
characterize the corrosion protection of coated samples [18]. In
this paper, EIS was used to investigate the long period protection
of c film the composite film prepared with TEOS concentration
of 0.012 M for other films were easily corroded after a few days
immersion in sodium chloride solution.
Figure 4 is a representative of the Nyquist diagrams of the
composite film directly exposed to the sodium chloride solution
(3.5 wt%) as a function of immersion time. A generally used
electrical equivalent circuit (Fig. 5) is proposed to fit the EIS
results, and the simulation results are listed in Table 1 (the
equivalent circuit consists of a electrolyte resistance, Rs, a film
constant phase element, Qf, a film resistance, Rf, a double layer
capacitance Cdl, a charge transfer resistance, Rct, in series with a
Warburg impedance, Zw, which characterizes diffusive limita-
tions through the corrosion product). In all cases, the set of

impedance spectra at different exposure times contains valuable
information concerning the kinetics of the corrosion process
occurring at the electrode surface [19]. In the range of high and
intermediate frequencies, Nyquist diagrams showed a complex
capacitive loop, which was attributed to charge transfer
associating with the effect of ionic double layer capacitance.
This can be related to the dynamic response of the active
dissolution of zinc [19]. While at low frequencies the impedance
behavior resembled the contribution of a diffusion process,
related mainly with the reduction of oxygen, as follows [20].
1=2O2 2H2 O 2e ! 2OH
E 0 0:401 V
(6)
Table 1. EIS data simulations for carbon steel and the samples with composite film exposed to 3.5 wt% sodium chlorine solution
Film
Exposure time (h)
Qf (S secn/cm2)
Rf (V cm2)
Cdl (F/cm2)
Rct (V cm2)
ZW (S sec1/2/cm2)
0.5
0.5
120
336
456
5.92E4
7.37E7
4.11E7
8.56E8
8.83E8
0.69
0.82
0.85
0.92
0.91
203.4
794.8
568.4
2268
3452
6.66E-5
2.10E-5
7.69E-6
6.18E-6
4.65E-6
84.4
331.5
222.6
658.5
932.4
0.0038
0.0015
0.0007
0.0004
0.0002
Carbon steel
Zn/SiO2
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419
420
Lin, Zhang, Wang and Wang
Zn 2OH ! ZnOH2 2e
ZnOH2 2H ! Zn2 2H2 O
E 0 1:248 V
Ksp 4:5 1017
(7)
(8)
It can be observed that the impedance of the film decreased

with immersion time within 120 h, which could be attributed to
the penetration process of the electrolyte in solution. However,
the impedance presented an increased trend with the immersion
time after 120 h at high frequencies, which was a result of
building-up of zinc corrosion products on the coating surface.
This trend was in accordance with the change of Rct and Rf. The
reduction of oxygen leads to local pH increase at the coating
surface and formation of a thin film of hydroxide on the surface.
The hydroxide film is the basis for further growth of corrosion
products which may be formed by one or more compounds such
as zinc oxide, zinc hydroxide, zinc carbonate, hydrozincite, and
simonkolleite [21]. These products have low solubility and could
protect the substrate. As a result, the corrosion rate of zinc in
chloride ion containing solution slows down [22]. It can be found
that the Warburg admittance of the film decreases as immersion
time increases from 0.5 to 456 h, which can result in lower
diffusion of reactant species through the corrosion product film
[20]. Therefore, this corrosion product layer develops a better
barrier against corrosion. This can be attributed to precipitation of
the corrosion products through porosities as time increases [23].
It should be noticed that after immersion in sodium chloride
solution for 456 h, the composite film was still intact. This means
the film could protect the substrate for hundreds of hours.
4 Conclusions
A zinc/silicon dioxide composite film has been fabricated on
carbon steel substrate from the mixed solution containing zinc
nitrate and TEOS by an electrodeposition method. The composite
film had different phases and surface morphologies when
different concentrations of TEOS were added in solutions.
Corrosion measurement results indicated that the film obtained
at a concentration of 0.012 M showed corrosion resistance for
hundreds of hours in 3.5 wt% sodium chloride solution. This can
be attributed to the compact surface and the proper component of
the composite film.
Acknowledgements: This work was supported by the National

Natural Science Foundation of China (grant no. 41076047),
Chinese Academy of Sciences (grant KZCX2-YW-205-03) and
Shandong Provincial Natural Science Foundation, China (grant

no. ZR2010DM004).
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[20] S. C. Chung, J. R. Cheng, S. D. Chiou, H. C. Shih, Corr. Sci.
2000, 42, 1249.
[21] V. Barranco, S. Feliu, Corr. Sci. 2004, 46, 2203.
[22] I. Suzuki, Corr. Sci. 1985, 25, 1029.
[23] M. Rahsepar, M. E. Bahrololoom, Corr. Sci. 2009, 51,
2537.
(Received: October 21, 2010)
(Accepted: December 14, 2010)
W5974
www.matcorr.com
DOI: 10.1002/maco.201005923
Influence of heat treatment on corrosion behaviour of

AlZnMgCuZrSc alloy
Y. P. Xiao*, Q. L. Pan, W. B. Li, X. Y. Liu and Y. B. He
Corrosion behaviour of different tempers (namely NA, UA, PA and OA) of
AlZnMgCuZrSc alloy was studied by potentiodynamic polarization,
electrochemical impedance spectroscopy (EIS), optical microscopy (OM) and
transmission electron microscopy (TEM). Over aged (OA) can decrease the
susceptibility to exfoliation due to the discontinuous distribution of the h
precipitates at the grain boundaries, cause a negative shift of the corrosion
potential (Ecorr), and lead to the prolonging of the time of the appearance of two
time constants in impedance diagrams. In addition, AlZnMgCuZrSc alloy
with over aged treatment has an enhanced resistance to exfoliation corrosion.
1 Introduction
AlZnMgCu alloys have been widely applied to airplane
structure due to their excellent combined properties, such as low
density, high elastic modulus, high ratio of strength to weight and
resistance to fatigue [13]. However, AlZnMgCu alloys are
sensitive to corrosion cracking in sodium chloride solution and
often exhibit different forms of corrosion, such as exfoliation
corrosion (EXCO), inter-granular corrosion (IGC) and stress
corrosion cracking (SCC), due to damp air and industrial waste
gas. Although complex addition of Sc and Zr can improve
markedly the strength of alloys of AlZnMgCu series, due to
the formation of Al3(Sc,Zr) dispersoid [4, 5], their sensitivity to
these types of corrosion cannot be suppressed. Therefore,
investigating their exfoliation corrosion properties would be very
important to their application. Many authors [68] reported that
the susceptibility of the AlZnMgCu alloys to corrosion can be
improved by developing new heat-treatment processes, such as
retrogression and re-aging (RRA) process and high-temperature
per-precipitation (HTTP) process. However, no detailed electrochemical investigation has been reported.
It is generally thought that exfoliation corrosion is developed
from inter-granular corrosion [1]. The corrosion product
accumulates in the grain boundary, resulting in a wedging force
Y. P. Xiao, Q. L. Pan, W. B. Li, X. Y. Liu, Y. B. He

School of Materials Science and Engineering, Central South University,
Changsha 410083, (P. R. China)
E-mail: xiaoyanping204@hotmail.com; xyp8659076@163.com
Q. L. Pan
Key Laboratory of Nonferrous Materials Science and Engineering of
Ministry of Education, Changsha 410083, (P. R. China)
W. B. Li
School of Civil Engineering, Hunan City University, Yiyang 413000,
(P. R. China)
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and lifts the alloy surface. According to Conde et al. [9], the intergranular corrosion is developed from a local corrosion cell, with
the copper-depleted precipitation-free zone (PFZ) along the grain
boundaries (GB) as the anode, and the grain particles (GP) and
the inter-metallic as the cathode for the AlCu alloys. Thus, the
exfoliation corrosion properties of the alloys are related with the
PFZ and precipitates at the grain boundaries. Meanwhile,
electrochemical impedance spectroscopy techniques (EIS) have
been widely used to study the corrosion process [1013]. Keddam
et al. [14] measured the electrode impedance of an aluminum
based alloy which showed exfoliation corrosion, they validated the
measured EIS data through Kramers-Kroning transforms and the
results show the EIS can detect the susceptibility to exfoliation of
the alloys accurately. In the previous study [15], we have reported
that the EIS can provide information on the exfoliation corrosion
susceptibility of AlZnMgCuZrSc alloy as a function of the
instants in impedance plots.
In this paper, we used the electrochemical technique and
morphology detected to study the exfoliation corrosion behavior
of AlZnMgCuZrSc alloy, tried to illustrate the effect of
aging treatment on corrosion process, and to find some regular
relationships between the exfoliation corrosion and the impedance spectra features and develop the electrochemical method
for evaluating exfoliation corrosion qualitatively.
2 Experimental methods
2.1 Materials
Exfoliation corrosion tests were carried out on the
AlZnMgCuZrSc alloy - chemical composition is shown
in Table 1 - with various aging treatments, as seen in Table 2. The
specimens used in the paper were cut from the alloy plate with a
thickness of 22.0 mm, and then mounted in epoxy with one
surface exposed. The exposed surface was grinded using abrasive
papers through 400-grade to 800-grade, polished with diamond
421
422
Xiao, Pan, Li, Liu and He
Table 1. Chemical composition of the studied alloy (wt.%)
Zn
Mg
Cu
Sc
Zr
Al
8.1
2.05
2.3
0.21
0.12
Bal
frequency, and ZView program was used for data fitting of

impedance spectra.

Table 2. Aging conditions of the studied alloys
3.1 Exfoliation corrosion behavior
Naturally aging
(NA)
Under aging
(UA)
Peak aging
(PA)
Over aging
(OA)
Room temperature/
one month
1208C/4 h
1208C/24 h
1208C/72 h
Accelerated exfoliation tests were performed according to EXCO

test standard of ASTM G34-01 [16]. The EXCO solution was
prepared as follows: 4.0 M NaCl 0.5 M KNO3 0.1 M HNO3.
Dissolve 234 g of NaCl, 50 g of KNO3 in water, and add 6.3 mL of
concentrated HNO3 (70 weight %). Dilute to 1 dm3. This solution
has an apparent pH of 0.4, and the solution temperature is
maintained at 25 38C using a thermostat. The electrolyte
volume-electrode surface area ratio is 15 mL/cm2, as defined by
the EXCO test. At intervals during the test, the specimens were
removed from the EXCO solution and the extent of the exfoliation
was assessed by comparing the surface appearance with standard
photographs given in ASTM G34-01. The sample was sectioned
and the depths of attack were measured under the optical
microscopy.
The exfoliation ratings for the studied alloy plate materials in the
EXCO test are shown in Fig. 1. The classification, N, indicates no
appreciable attack, P represents pitting corrosion and EA ED
describes a range from superficial to severe exfoliation. According
to this ranking, exfoliation developed most rapidly on the NA
specimens and the severity of attack was ranked in the order
NA > UA > PA > OA.
Fig. 2 shows the exfoliation corrosion morphologies of
AlZnMgCuZrSc alloy with various aging treatment. It is
found that most of the lifted surface layers on the alloy with the
NA and UA tempers are peeled off and raised to the upside of the
solution with gas blisters caused by electrochemical reaction
during the exfoliation process. The specimens with the NA and
UA tempers were more susceptible to exfoliation corrosion than
those with PA and OA tempers.
Fig. 3 illustrates the metallographic cross sections from the
specimens with various tempers. The depth of exfoliation
corrosion of the specimens can be obtained from this figure.
It is clear that the depth of corrosion attack was the greatest on the
NA tempers, and it was ranked in the order NA > UA > PA > OA.
Robinson et al. [17] reported that over aging has beneficial effect on
the susceptibility to exfoliation corrosion by reducing the rate of
inter-granular corrosion, which was in agreement with the
observation of the alloy metallographic cross sections.
2.3 Potentiodynamic polarization tests
3.2 Microstructure
Potentiodynamic polarization curves were carried out using the

Solartron 1286 electrochemical system. A saturated calomel
electrode (SCE) with a Luggin capillary was used as the reference
electrode, a large platinum sheet was served as the counter
electrode and 1 cm2 of the alloy under study was used as the
working electrode. The test solution was prepared as the same as
the EXCO testing solution. And the solution temperature was
maintained at 258C. The polarization is scanned potentiodynamically from 1.2 V to 0.4 V with the scan rate of 0.2 mV/s.
The usual precipitation sequence of the AlZnMgCu alloys can

be summarized as: Solid solution GP zones Metastable h
Stable h (MgZn2). In the peak aged (PA) AlZnMgCu series
paste, rinsed using acetone, degreased with de-ionized water and

dried in air.
2.2 Exfoliation test
2.4 Electrochemical impedance spectroscopy (EIS)

measurements
Electrochemical impedance spectroscopy (EIS) experiments were
collected at the open-circuit potential (OCP) using Solartron 1286
electrochemical system with all electrodes and solution the same
as those for potentiodynamic polarization curves tests. The
impedance spectra were obtained with a BSA-Zahner IM6 unit
using a frequency range from 100 kHz to 100 mHz. The
alternating voltage was applied directly between the working
electrode and counter electrode, and kept at a value that would not
cause more than 50 mV difference (peak to peak) across the cell.
The EIS tests were always conducted from high frequency to low
Figure 1. Surface ratings for AlZnMgCuZrSc alloys in the EXCO

test
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Effect of heat treatment on corrosion behaviour of AlZnMgCuZrSc alloy
Figure 2. Corrosion morphologies of AlZnMgCuZrSc alloys with (a) NA, (b) UA, (c) PA, (d) OA tempers after 72 h of immersion in EXCO solution
Figure 3. Metallographic cross sections of AlZnMgCuZrSc alloys with (a) NA, (b) UA, (c) PA, (d) OA treatments after 72 h of immersion in EXCO
solution
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423
424
Figure 4. TEM micrographs of the NA (a), UA (b), PA (c), OA (d) tempers of AlZnMgCuZrSc alloy
alloys, the h-phase is the main precipitate. However, for the overaging temper the main precipitate is the h-phase [1820].
The microstructures, examined through transmission
electron microscopy, are displayed in Fig. 4. It is obvious that
for the PA and OA temper, the precipitate, both dispersed in the
matrixes and distributed in the grain boundaries, was coarser in
size in comparison with those for the NA and UA temper. Those
coarse precipitates were more separated from each other thus
becoming less continuous phase and distributed in a wider zone
of grain boundaries. Due to the separated grain boundary
precipitates with large spacing, no continuous chimney existed
for IGC and EXCO. As a result, their susceptibility to IGC
and EXCO was decreased. Besides, it is worth noting that
the size of the matrix phase (Al3Zr) increases in the order
NA < UA < PA < OA, since it takes enough time to grow up
during the age treatment.
The following two function mechanisms on the localized
corrosion of Al alloys are widely accepted [21]. (1) Precipitate-free
zone (PFZ) and the distribution of the precipitates on the grain
boundaries are the main reasons for localized corrosion. Grain
boundaries with continuous h precipitates become the susceptive
anode channel, and the continuous h precipitates at the grain
boundary offer a path for IGC and EXCO. (2) There are potential
differences between the precipitates in the grain boundaries and
other electrodes around the grain boundaries, leading to the

anodic dissolution of the precipitates in the grain boundaries.
In the AlZnMgCuZrSc alloy studied in this paper, for
the UA and PA temper, due to the precipitates of h distributed
continuously at the grain boundary, there exists an active
corrosion path resulting from the galvanic reaction between
the anodic precipitates of h at the grain boundary and the alloy
base at their adjacent periphery, which leads to the great
susceptibility to IGC and EXCO. However, for the OA temper,
the precipitates of h at the grain boundary are distributed
discontinuously, and no continuous corrosion path exists in the
alloy. The size of the h precipitates, the spacing between the h
precipitates and the width of the PFZ were the largest, and the
susceptibility to IGC and EXCO was the lowest.
To explain the different corrosion susceptibility of the
AlZnMgCu alloy, besides the precipitate distribution at the
grain boundary, its electrochemical behaviour also should be
known. The equilibrium phase h (MgZn2) in the grain boundary,
PFZ and the alloy base of the aged AlZnMgCu alloy are,
respectively, 0.86, 0.57, 0.68V [22]. It is clearly seen that Ecorr of
the PFZ and the alloy base is positive with respect to that of the h
phase. Thus, the active compound MgZn2 acts as the anode to the
solid solution and PFZ at its periphery, leading to the anodic
dissolution of the h phase, and then inter-granular corrosion and
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0.0
with the corrosion current density by Faradays law [23]. It is

indicated that natural aged alloy is more susceptible to corrosion
than artificial aged alloy, and the corrosion susceptibility of the
AlZnMgCuZrSc alloys with different temper can be ranked
in the order NA < UA < PA < OA.
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-0.2
-0.4
-0.6
1$
8$
3.4 Electrochemical impedance spectroscopy analysis
3$
2$
-0.8
-1.0
-4
-3
-2
ORJL$FP
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Figure 5. Potentiodynamic polarization curves of AlZnMgCuZrSc

alloy with different tempers in the EXCO solution at 258C
exfoliation corrosion takes place. However, the alloy base at its

adjacent periphery is protected as a cathodic zone.
EXCO is a form of environmentally assisted subsurface
attack that proceeds along multiple narrow paths parallel to the
fabricated surface of the plate. Exfoliation corrosion has similar
characteristics to inter-granular corrosion. In fact, exfoliation
corrosion is developed from inter-granular corrosion. During
inter-granular corrosion, the corrosion product accumulates at
the grain boundary, resulting in a wedging force and finally lifting
the alloy surface. The wedging stress plays a significant role in the
development of the exfoliation. The OA aging treatment
decreased the susceptibility to IGC, and the susceptibility to
EXCO was also decreased.
3.3 Analysis of polarization curves
The polarization curves of AlZnMgCuZrSc alloy under
different tempers immersed in the EXCO test solution are shown
in Fig. 5. The corrosion potential (Ecorr), corrosion current density
(Icorr) and polarization resistance (Rp) derived from the
polarization curves, are summarized in Table 3. As shown in
Table 3, the corrosion potential Ecorr value of NA temper is
positive to that of artificial aged tempers, while the corrosion
current density Icorr value of the former is greater than that of the
latter and the polarization resistance Rp value of the latter is
greater than that of the former. Otherwise, the electrochemical
corrosion rate of AlZnMgCuZrSc alloys increases linearly
Table 3. Potentiodynamic polarization parameters of the

AlZnMgCuZrSc alloys with the test tempers in the EXCO solution
at 258C
Temper
Icorr (mA/cm2)
Ecorr (V)
Rp (V cm2)
2.246
1.477
1.352
0.886
0.473
0.492
0.507
0.546
6.9
10.5
14.5
18.4
NA
UA
PA
OA
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Fig. 6 illustrates the change of the impedance diagram observed

for AlZnMgCuZrSc alloys with various aging treatments in
a short immersion period. Two typical features can be obtained
from the diagrams. Firstly, at the beginning of the immersion in
EXCO solution, all impedance diagrams in Nyquist plot displayed
a capacitive loop in the high medium frequency range and an
inductive loop in the low frequency range. With prolonging the
immersion time, the radius of the capacitive loop decreased,
which indicated the decreasing of the corrosion rate during the
initial immersion time. This could be an indication for
appearance of pitting on the surface of the working electrode
[14, 18]. Secondly, the impedance diagram for the alloy in the NA
temper changed more fast than the other three tempers, which
indicated that the corrosion rate of the alloy in NA temper was the
greatest and it was ranked in the order NA > UA > PA > OA. The
result was in agreement with the observations of the surface
ratings.
The inductive behaviour of electrode impedance is often
explained by the relaxation phenomenon of the reaction
intermediates [14]. In fact, the origin of inductive features is
numerous. For example, when the electrode potential shifts
towards more anodic direction and if the time dependent change
of the electrode interface promotes the dissolution reaction (or
conversely the cathodic potential shifts to more cathodic process),
an inductive feature is expected. On the basis of the concept, it is
believed that the inductive loop is associated with the weakening
of the protective effectiveness of the aluminum oxide layer due to
the anodic dissolution of aluminum alloy. With prolonging the
immersion time, the surface oxide layer becomes progressively
less protective, due to the action of the aggressive anions in the
EXCO solution. Then the relaxation of weak points diminishes.
This explains why the inductive loop vanishes with the
immersion time in agreement with experimental observations.
The inductive loop shrinks with time, indicting that the surface is
attacked more severely with the immersion time.
Fig. 7 summarizes the evolution of Bode diagrams for
AlZnMgCuZrSc alloys after a long immersion period in
EXCO solution. According to these diagrams, one phenomenon
is pointed out. At the initial stage, there exists only one maximum
in Bode phase angle plots, indicating only one time constant,
while prolonging the immersion time, the appearance of another
maximum indicts two time constants. Moreover, the longer the
immersion time, the easier to distinguish the two time constants.
While for the alloys with different tempers, the instant of the
appearance of two time constants is different. For example, the
two time constants are clearly shown after 24 h of immersion
(Fig. 7 (a)) for the NA temper, while for the UA temper, the two
time constants can be shown after a longer immersion time with
36 h. For the PA and OA temper, the two time constants
associated with delamination do not appear until 48 h and 60 h of
425
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K
K
20
=LPRKPFP
=LPRKPFP
PLQ
K
K
16
10
10
20
30
10
20
=UHRKPFP
(a) NA
40
(b) UA
PLQ
K
K
40
30
=UHRKPFP
PLQ
K
K
30
20
=LPRKPFP
=LPRKPFP
426
20
10
0
0
20
40
60
80
100
=UHRKPFP
(c) PA
10
20
30
40
50
60
=UHRKPFP
(d) OA
Figure 6. Evolution of impedance diagram in a short immersion period: AlZnMgCuZrSc alloy with various aging treatments in EXCO
solution
immersion, respectively. According to Conde et al. [9, 13], the

onset of delamination marks the appearance of the two time
constants. The impedance technical can provide information on
the exfoliation susceptibility of aluminum alloys as a function of
the instant of appearance of the two time constants in impedance
plots. When the two time constants can be appreciated,
delamination has been initiated: the more clearly the two time
constants can be distinguished, the greater the delamination.
Hence, one can detect the exfoliation corrosion susceptibility of
the alloys according to the instant of the appearance of two time
constants. In this case, the exfoliation susceptibility for the NA
temper was the greatest, and the susceptibility can be ranked in
the order NA > UA > PA > OA, which was in agreement with the
observations of the surface ratings.
Fig. 9 is an equivalent circuit, which is obtained through the
structure of aluminum alloy electrode in Fig. 8 and fitting EIS
spectra in Fig. 5. There are thin aluminum film and corrosion
products on the surface of the working electrode after long
immersion. In an equivalent circuit, the three main parameters

introduced to characterize the impedance diagram are defined as
follows:
Rpo, the high frequency resistance corresponding to the electrolyte resistance through the pore (or lamella) due to the potential
and the current distribution, so called polarization resistance;
Rct, the charge interface resistance corresponding to the diameter
of the low frequency capacitive loop;
C2, double layer capacitance corresponding to interface capacitance connected in parallel to the charge interface resistance,
and may indicate approximately the expanded surface area of
the corroding electrode; thus can expect to indicate the corrosion
rate.
In this circuit, all capacitances are mathematically modeled
using a constant phase element (CPE) in order to obtain a better
simulation between the model and the experimental data. Then
www.matcorr.com
18 h
24 h
36 h
48 h
60
18 h
24 h
36 h
48 h
60 h
60
40
$QJOHGHJUHH
$QJOHGHJUHH
20
40
20
0
-2
-2
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(a) NA
36 h
48 h
60 h
72 h
84 h
60
$QJOHGHJUHH
$QJOHGHJUHH
40
(b) UA
24 h
36 h
48 h
60 h
72 h
84 h
60
/RJIUHTXHQF\+]
20
40
20
0
-2
-2
/RJIUHTXHQF\+]
/RJIUHTXHQF\+]
(c) PA
(d) OA
Figure 7. Evolution of impedance diagrams in Bode plot in a long immersion period: AlZnMgCuZrSc alloy with various aging treatments in
EXCO solution
the impedance is defined by the equation:

Z0
(1)
ZCPE
jvn
Where n can range between 0 and 1 (for a perfect capacitor),
and Z0 is a constant. For n 1, ZCPE represents an ideal
capacitance; n 0, a resistance; n 1, an inductance; and
n 0.5, a Warburg impedance.
original surface
pore
new inter-face
Based on the circuit, the typical EIS parameter can be worked

out, which are listed in Tables 47. In the equivalent circuit, C1
and C2 are expressed as the value of the outer layer capacitance
and double layer capacitance, respectively. The value of n2 shows
C1
Rs
C2
Rpo
Rct
grain
grain boundary
corrosion product
Figure 8. Structure of aluminum alloy after the occurrence of

exfoliation corrosion
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Figure 9. Equivalent electrical circuit for immersion of

AlZnMgCuZrSc alloy in the EXCO solution: Rs solution
resistance; C1 original surface layer capacitance; Rpo resistance of
the corrosion products; Rct charge transfer resistance; C2 double
layer capacitance
427
428
Table 4. The parameters of the EIS of NA with different immersion time
Time (h)
24
36
48
60
72
84
96
108
C1 (mF cm2)
n1
Rpo (V cm2)
C2 (mF cm2)
n2
Rct (V cm2)
5.266
4.983
4.756
4.059
3.925
3.853
3.154
2.910
0.8495
0.7497
0.7834
0.6255
0.6722
0.6744
0.7151
0.6942
6.812
6.989
7.012
6.548
7.304
6.937
7.105
7.092
5.559
5.073
4.628
4.234
3.886
3.571
3.790
3.832
0.8922
0.9784
0.8735
0.8181
0.8782
0.8037
0.8361
0.8913
12.35
15.43
20.15
22.50
26.44
25.76
28.61
28.67
Table 5. The parameters of the EIS of UA with different immersion time
Time (h)
36
48
60
72
84
96
108
C1 (mF cm2)
n1
Rpo (V cm2)
C2 (mF cm2)
n2
Rct (V cm2)
3.400
3.159
3.217
2.878
2.089
1.708
1.563
0.8628
0.8914
0.8806
0.7283
0.7859
0.7935
0.8169
9.893
8.707
8.004
7.346
10.11
9.687
11.39
4.256
4.349
4.011
3.667
3.523
3.469
3.397
0.9988
0.9748
0.9851
0.9752
0.9822
0.9351
0.9635
22.75
28.96
33.34
35.10
38.07
39.38
39.23
Table 6. The parameters of the EIS of PA with different immersion time
Time (h)
48
60
72
84
96
108
C1 (mF cm2)
n1
Rpo (V cm2)
C2 (mF cm2)
n2
Rct (V cm2)
2.279
2.114
1.529
1.049
1.255
0.836
0.7102
0.6162
0.6301
0.6118
0.6148
0.6073
10.295
13.34
14.02
17.18
16.09
16.91
3.942
3.719
3.229
3.287
3.283
3.285
0.9298
0.9591
0.9381
0.9563
0.9689
0.9674
27.22
35.06
45.75
51.66
50.96
52.31
Table 7. The parameters of the EIS of OA with different immersion time
Time (h)
60
72
84
96
108
C1 (mF cm2)
n1
Rpo (V cm2)
C2 (mF cm2)
n2
Rct (V cm2)
1.9623
1.8051
1.6597
1.1830
0.9848
0.6684
0.6801
0.6164
0.6389
0.6225
9.47
11.22
17.23
18.55
21.57
3.0195
2.8754
2.9735
2.8554
2.9772
0.9896
0.9121
0.9876
0.9850
0.9763
37.23
41.60
54.58
55.19
56.17
the degree of the smoothness on the surface of the electrode.

The value of n2 is close to 1.0 meaning smoothly electrode. This
is because the real area of the corroded electrode is varied in
the corrosion process, causing the deviation from smooth
electrode [24].
In this paper, the double layer capacitance (C2) and the
charge resistance (Rct) are used as parameters to characterize the
corrosion rate, and the double layer capacitance (C2) and the
charge resistance (Rct) are calculated from the Tables 47 as
shown in Fig. 10. It is apparent that the capacitance C2 of NA
temper is much higher than that of the artificial aged tempers. C2
is defined as the capacitance corresponding to the new interface
caused by the exfoliation corrosion. The NA temper is much more

sensitive to exfoliation corrosion than artificial aged tempers. It
shows that the capacitance C2 reflects the exfoliation corrosion
degree to some extent. Simultaneously, larger changes of C2 of
NA temper compared with artificial aged tempers may indicate
that NA temper is more sensitive to exfoliation corrosion. The
same results have also been reported [25, 26]. As seen from Fig. 10
(b), Rct with different tempers increases. After about 84 h
immersion time, it keeps at a stable value until to the last time.
In the EXCO solution, the presence of nitrate ions plays a
crucial role for the formation of exfoliation corrosion. In the
anodic dissolution process of iron, to be catalysed by nitrite, a
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60
a)
1$
1$
8$
8$
3$
3$
2$
2$
b)
1$
8$
3$
2$
Rct/ .cm2
& P)FP
2
20
40
20
40
60
80
100
120
20
40
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60
80
100
120
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Figure 10. Fitted (a) capacitance C2 and (b) resistance Rct of the AlZnMgCuZrSc alloy with NA, UA, PA and OA tempers
substance is formed spontaneously by a dismutation reaction of

nitrate itself [27]. Therefore, during the corrosion of
AlZnMgCuZrSc alloys in the EXCO solution, nitrite ion
plays an autocatalytic species. The overall corrosion process can
be summarized by

2Al 6H 3NO
3 3NO2 ! 2Al3 6NO2 3H2 O (2)
Consequently, the reaction rate will increase exponentially

with the immersion time. However, the concentration of the
proton and the nitrate ion in the EXCO solution also affect the
reaction rate of the reaction. When the proton comes to
exhaustion, the reaction rate will stop increasing. That can
explain the evolution of the Rct with the immersion time.
Furthermore, it can be seen from Fig. 10 (b) that the value of Rct
for NA temper is the lowest compared with that for artificial aged
tempers at the same immersion time. Thus, it is concluded that
when the immersion time reaches the same, the Rct can be
ranked in the order NA > UA > PA > OA, which indicates the
corrosion susceptibility can be ranked in the order
NA > UA > PA > OA [28].
4 Conclusions
The aims of this work were to evaluate the influence of
the aging treatment on the exfoliation behaviour of the
AlZnMgCuZrSc alloys, and to develop the relationship
between the exfoliation corrosion and the impedance spectra
features. The findings can be summarized as follows:
(1) The aging treatment strongly affects the exfoliation
behaviour of the samples: the samples in NA temper are
more susceptible to exfoliation corrosion than those aged
artificially. Moreover, with prolonging the artificially aging
time, the susceptibility to exfoliation corrosion decreases.
This behaviour is related with the grain boundary structure
and the electrochemical behaviour of the precipitates at the
grain boundaries.
(2) Ecorr of the PFZ and the alloy base is positive with respect to
that of the h phase, indicating that the h precipitates is more
www.matcorr.com
sensitive to corrosion than the alloy base. The preferential

corrosion of the h precipitates at the grain boundaries leads
the anodic dissolution of the grain boundary, and develop the
IGC and EXCO. For the OA temper, the h phases are
distributed discontinuously at the grain boundaries, and the
width of the PFZ is large, resulting to the less susceptibility to
the exfoliation corrosion.
(3) The potentiodynamic polarization measurements reveal
that Ecorr value for the OA temper is the most negative
(0.546 V), and Rp is the highest at 18.4 V cm2, while the Icorr
is the lowest. Thus, the OA temper is the least sensitive to
exfoliation corrosion.
(4) There are almost no distinct differences between naturally
aging and artificially aging about the shape of the impedance
diagrams. However, the instant of the appearance of two time
constants is different. For instance, for the NA temper, the
two time constants are clearly shown after 24 h of immersion,
with high exfoliation susceptibility, while for the OA temper,
the two time constants appear after 60 h of immersion,
showing lower exfoliation susceptibility.
(5) The EIS fitting results show that the corrosion rate increases
at the beginning of the exfoliation corrosion, then keeps at a
stable value until to the last time. This evolution can be
explained by the decrease of the concentration of the proton.
Acknowledgements: The authors gratefully acknowledge the
Electrochemical Workstation of the School of Materials Science
and Engineering, Central South University for support in
performing the measurements with electrolysis cell.
5 References
[1] A. Heinz, A. Haszler, C. Keidel, S. Moldenhauer, R. Benedictus, W. S. Miller, Mater. Sci. Eng. A 2000, 280, 102.
[2] L. L. Rokhlin, T. V. Dobatkina, N. R. Bochvar, J. Alloys Compd.
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[3] Z. M. Yin, Q. L. Pan, Y. H. Zhang, Mater. Sci. Eng. A 2000,
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[4] V. G. Davydov, T. D. Rostova, V. V. Zakharov, Yu. A. Filatov,

V. I. Yelagin, Mater. Sci. Eng. A 2000, 280, 30.
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[6] J. Lin, M. M. Kersker, 1992, US 5 108, 502.
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[11] F. H. Cao, Z. Zhang, J. X. Su, J. Q. Zhang, Mater. Corros.
2005, 56, 318.
[12] D. Tanguy, B. Bayle, R. Dif, Corros. Sci. 2002, 44, 1163.
[13] A. Conde, J. de Dambrenea, Corros. Sci. 2000, 42, 1363.
[14] M. Keddam, C. Kuntz, H. Takenouti, D. Schuster, D. Zuili,
Electrochim. Acta 1997, 42, 87.
[15] Y. P. Xiao, Q. L. Pan, W. B. Li, X. Y. Liu, Y. B. He, C. L. Li,
Mater. Corros. 2012, 63, 127.
[16] Standard test method for exfoliation corrosion susceptibility
in 2 and 7 series aluminum alloys (EXCO), ASTM
G34-01 2007.
[17] M. J. Robinson, N. C. Jackson, Corros. Sci. 1999, 41, 1013.

[18] F. H. Cao, Z. Zhang, J. F. Li, Y. L. Cheng, J. Q. Zhang, C. N.
Cao, Mater. Corros. 2004, 55, 18.
[19] A. F. Oliveira, Jr., M. C. de Barros, K. R. Cardoso, D. N.
Travessa, Mater. Sci. Eng. A 2004, 379, 321.
[20] D. Wang, Z. Y. Ma, J. Alloys Compd. 2009, 469, 445.
[21] J. F. Li, Z. Q. Zhang, S. C. Li, W. J. Chen, W. D. Ren, X. S.
Zhao, Corros. Sci. 2007, 49, 2436.
[22] Z. T. Wang, R. Z. Tian, Handbook of Aluminum Alloy and its
Working, Central South University Press, Changsha 2000.
[23] X. C. Liu, C. Q. An, Z. X. Cui, Metal Corrosion, National
Defence Industry Press, Beijing, 2002.
[24] E. B. Castro, C. A. Gervasi, Int. J. Hydrogen Energy 2000, 25,
1163.
[25] J. F. Li, Z. Q. Jia, C. X. Li, N. Birbilis, C. Cai, Mater. Corros.
2009, 60, 407.
[26] A. Conde, J. de Damborenea, Electrochim. Acta 1998, 43, 849.
[27] E. Stupnisek-Lisac, M. Karsulin, Electrochim. Acta 1984, 29,
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[28] J. W. Tang, Y. W. Shao, J. B. Guo, G. Z. Meng, F. H. Wang,
Corros. Sci. 2010, 52, 2050.
(Received: September 2, 2010)
(Accepted: October 11, 2010)
W5923
www.matcorr.com
DOI: 10.1002/maco.201005955
Effect of sulphate reducing bacteria on corrosion of

AlZnInSn sacrificial anodes in marine sediment
F. Liu, J. Zhang*, S. Zhang, W. Li, J. Duan and B. Hou
Microbiologically influenced corrosion (MIC) of Al-Zn-In-Sn sacrificial anodes in
marine sediment was investigated by exposing samples to sulphate reducing
bacteria (SRB). Samples exposed to the sterile marine sediment were used as
control. The results show that pitting corrosion occurs in both the sterile marine
sediment and the SRB-containing marine sediment. However, the corrosion can
be increased sharply by the SRB metabolic activity due to the cathodic
depolarization effect. In fact, the effect is based on the consumption of hydrogen
which probably results in the acceleration of galvanic corrosion between
corrosion products and metal substrate.
1 Introduction
With the development of marine industry, the corrosion of metal
structures in marine sediment has gradually been considered
[15]. Marine sediment can be seen as a kind of special soil, which
is covered and saturated by seawater [3]. Corrosion in marine
sediment is a complex phenomenon, which possesses the
corrosion characteristics of both soil and sea water [4]. Besides, a
variety of anaerobic microbe groups can live in marine sediment
owing to plenty of organisms and very rare oxygen in that
environment [5]. These microorganisms and their metabolic
activity often cause the formation of biofilms on metal structures
and can affect severely the kinetics of electrochemical corrosion
processes, leading to accelerating corrosion rate, assisting stress
corrosion and inducing pitting corrosion [610]. So MIC is one of
major corrosion factors in marine sediment.
SRB are considered as mainly aggressive microorganisms
under anaerobic or low dissolved oxygen concentration condition
[11]. They can use sulphate as a final electron acceptor for
degradation of organisms, resulting in the production of sulfide
ions, hydrogen sulfide and metal sulfides which are formed by
the precipitation of metallic ions with the sulfide ions [12, 13].
Currently, several mechanisms of the corrosion of metals induced
by SRB under anaerobic condition have been suggested, such as
the cathodic depolarization theory [14], the localized concentration cell corrosion mechanism [15], and the acid produced by
bacteria corrosion mechanism [16]. In addition, sulfides formed
by SRB metabolism can exhibit cathode properties in the galvanic

couple, so they play an important role in metal dissolution [17].
The high ability for complex-binding metal ions of extra cellular
polymeric substances (EPS) has also been reported as a
mechanism of SRB influenced corrosion [18]. Although considerable researches have been carried out about corrosion induced by
SRB in culture medium or sea water, rare studies about SRB
influenced corrosion in marine sediment have been reported.
Al sacrificial anodes are widely used for protection of steel
structures in marine environment due to their high theoretical
current efficiency, low active potential and low cost [19]. In marine
sediment environment, these sacrificial anodes may be attacked
by microbial activity [20]. The microbial fouling may further lead
to serious failure and loss of energy [21]. Some researchers have
investigated the corrosion analysis of Al-Zn-In sacrificial anodes
[22], and the biocidal activity of sacrificial anode [23], but the
influence of microbes on the performance of Al-Zn-In-Sn anodes
has not been reported.
Hence, in this paper, the influence of SRB on corrosion
behavior of AlZnInSn sacrificial anode in marine sediment
have been studied using galvanic corrosion test, electrochemical
impedance spectroscopy (EIS), scanning electron microscopy
(SEM) and energy dispersive spectroscopy (EDS). This work
might be helpful on getting a better insight of the evaluation of
the sacrificial anodes, which are applied in marine sediment, and
also controlling microbial fouling of the sacrificial anodes.
2 Material and methods

F. Liu, J. Zhang, W. Li, J. Duan, B. Hou
Institute of Oceanology, Chinese Academy of Sciences, Qingdao
266071, (P. R. China)
E-mail: zhangjie@ms.qdio.ac.cn
F. Liu, S. Zhang
College of Chemistry and Chemical Engineering, Chongqing University,
www.matcorr.com
2.1 Specimen preparation

Commercial AlZnInSn sacrificial anode plates composed of
the following elements with a mass ratio of 3.02% Zn, 0.022% In,
0.026% Sn, 0.056% Si, 0.079% Fe, 0.00024% Cu, and 96.80% Al
were used for this study. The work surfaces of all samples which
431
Liu, Zhang, Zhang, Li, Duan and Hou
were cut from the anode plates were treated according to GB

5776-86(China), abraded with emery papers up to grit size of
2000#, and degreased with ethanol using an ultrasonic bath. After
that they were rinsed with deionized water, and finally dried by
ethanol. Then they were kept in a silica gel desiccator and
sterilized by ultraviolet lamp for 30 min before test.
2.2 Bacteria and culture
The containers were conducted by KCl salt bridge. 50 mm

20 mm 5 mm samples were used as two working electrodes, the
electrodes were contacted with each other by copper conductor.
The work surface area of each sample is 24.5 cm2, and other
surface was sealed with epoxy resin. The galvanic current was
continuously monitored at interval time by a MS8218 digital
multimeter and the test lasted for 30 days.
2.5 Electrochemical experiments
The SRB were obtained from muddy sediment in Jiaozhou Bay of

Qingdao. Fresh marine sediment was added into a sterile modified
Postgates C (PGC) medium to enrich anaerobic bacteria in 20 ml
glass bottles with 15 ml culture medium. The bottles were sealed
with butyl rubber and aluminum lid, and all bottles were kept in a
constant temperature incubator at 308C. After 2 weeks, 100 ml
liquid medium containing bacterial species was inoculated to an
agar plate. The plate was put into an anaerobic box to cultivate
microbes under the carbon dioxide atmosphere. Colonies formed
in the plates were selected and inoculated into the PGC medium
again. The procedure was repeated until the colonies of single
bacterial strain were formed on the solid PGC medium. The
composition of the medium was the following: 0.5 g KH2PO4,
1 g NH4Cl, 0.06 g CaCl26H2O, 0.06 g MgSO47H2O, 6 ml 70%
sodium lactate, 1 g yeast extract, 0.3 g sodium citrate, 1000 ml
seawater from Qingdao offshore area. The pH value was
6.5 0.05.The medium was autoclaved at 1218C for 30 min. To
prepare the agar plate, 0.06 g (NH4)2Fe(SO4)26H2O and 1.5wt%
agar were added into 1 L PGC medium.
2.3 Test medium
The marine sediment used in the experiment was taken from
Jiaozhou Bay of Qingdao. The marine sediment was autoclaved at
1218C, then 400 ml was chosen as the sterile marine sediment by
adding 100 ml sterile modified medium, and 400 ml marine
sediment was used as SRB-containing marine sediment by adding
100 ml sterile modified medium inoculated with 8 ml of 5 days
cultured bacteria. The pH values of test medium are 7.5 0.05.
2.4 Galvanic corrosion test
All electrochemical tests were carried out in the cell with threeelectrode system consisting of a saturated calomel electrode (SCE)
as the reference electrode, a Pt-plate with an area of 4 cm2 as the
counter electrode and samples with 10 mm 10 mm surface
were used as working electrodes. For electrochemical studies,
samples were embedded in a mold of non-conducting epoxy resin
before abraded. The measurements were operated by a Parstat
2273 electrochemical analyzer system at 308C. The open circuit
potential (Eocp) and EIS measurements were performed in a cell
during 15 days. EIS tests were taken by 10 mV amplitude
sinusoidal voltage signal over the frequency ranging from
10 mHz to 100 kHz.
2.6 Surface analysis
SEM and EDS analysis were conducted at the surface of samples
for 15 days of exposure to the marine sediment without and with
SRB, respectively. The sample with bacteria was immersed for
2 hours in a 5% glutaraldehyde solution in order to fix the bacteria
to its surface, and then it was dehydrated using three kinds of
ethanol PBS solutions (15 min each): 50, 75 and 100%. The
sample without bacteria was also dehydrated using above
solutions. After that, the samples were taken to SEM and EDS
to investigate their morphology and chemical compositions.

3.1 Galvanic corrosion test
The curve of current density versus time is shown in Fig. 2. It was
observed that the sample in the biotic system acted as anode,
Galvanic corrosion test was carried out in a dual-compartment

cell at 308C. As shown in Fig. 1, the cell was constituted by two
500 ml containers, which were filled with the sterile marine
sediment and the SRB-containing marine sediment, respectively.
Amperemeter
KCl salt bridge
Biotic system
Working electrode
Conductor
Abiotic system
Working electrode
0 .8
0 .7
Current density A/cm 2
432
0 .6
0 .5
0 .4
0 .3
0 .2
0 .1
0
Hermetic cell
Figure 1. The setup of galvanic corrosion test
Hermetic cell
10
15
20
25
30
Time (days)
Figure 2. Time dependence of galvanic current
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Effect of sulphate reducing bacteria on corrosion of AlZnInSn
while the sample in the abiotic system acted as cathode. The

current density increased rapidly from the 1st to the 5th day,
indicating the corrosion rate of the sample increased, which is
possibly due to the increasing of active SRB during the
preliminary stage [24]. However, the current density decreased
quickly from the 5th to the 9th day, which was suggested that the
corrosion rate of the anode decreased during this period. The
reason was that a protective film of corrosion products was
formed on the anodic surface which could inhibit the erosion of
aggressive media [25]. After that, the current density increased
again from the 10th to the 12th day, indicating the corrosion rate of
the sample increased. It is supposed that the film of corrosion
products on the anodic surface gradually become loose and
porous as the time goes on, which can lead to the acceleration of
corrosion rate [26]. As can be seen, after 13 days, the current
density decreased again, and then weak and regular fluctuations
were observed. The decrease is most probably due to the
decreasing SRB populations during this stage. The oscillatory
behavior of the current density may be aroused by local corrosion
[27]. During this experiment, in the biotic system, the sample
always acted as anode, the corrosion process was accelerated.
While in the abiotic system, the sample always acted as cathode,
the corrosion process was inhibited.
lites [28]. After 7 days, the Eocp shifted in a positive direction from
1.090 to 1.074 V, the increase could be due to forming a thick
layer of corrosion products on the sample surface [25].
3.2.2 Electrochemical impedance spectroscopy
3.2.2.1 Control sample in the sterile marine sediment: Fig. 4A
shows the Nyquist plot obtained for the sacrificial anode
immersed in the sterile medium. From the Nyquist plot, a
capacitive semicircle appeared at high frequencies, which could
be attributed to the formation of a surface layer due to the
oxidation of metal and the precipitation of corrosion product. The
impedance represented by the diameter of the capacitive
semicircle decreased during the entire exposure time because
of the destruction of the sample surface. An inductive semicircle
could be obviously seen at middle frequencies, which may be
associated with the growth of pits in the initial stage [29]. After 9
days, the inductive semicircle disappeared probably owing to the
corrosion pits which had been formed [30]. The SEM image
(Fig. 5A) could also prove the pit initiation on the sacrificial anode
surface under sterile condition. At low frequencies, a small
capacitive loop appeared because of the evolution of the metallic
dissolution controlled by charge transfer processes.
3.2 Electrochemical measurements

3500
3000
2500
2000
-Zim()
3.2.1 Open circuit potential

Fig. 3 shows the variations of the open circuit potentials (Eocp) with
time for the sacrificial anode immersed in the sterile marine
sediment (a) and SRB-containing marine sediment (b), respectively. In the sterile medium, the Eocp keeps an almost stable value
of 1.073 V throughout the period of exposure, indicating the
kinetics of electrochemical processes of the sample surface was
relative stable. While the Eocp shifted in the negative direction from
1.070 to 1.090 V during the primary stage in the biotic medium.
The potential drop could be attributed to an increase of the
dissolution kinetics of the sample surface due to the synergy
between microbial metabolic activity and their corrosive metabo-
1500
1d
3d
5d
7d
9d
11d
13d
15d
(A)
1000
500
0
-500
-500
500
1000
1500
2000
2500
3000
3500
Zre()
-1.065
1500
-1.070
-Zim()
Eocp(V/SCE)
1000
-1.075
-1.080
-1.085
-1.090
500
1d
3d
5d
7d
9d
11d
13d
15d
(B)
0
0
10
12
14
16
Time (days)
500
1000
1500
Zre()
Figure 3. Time dependence of Eocp for samples immersed in sterile

marine sediment (a) and SRB-containing marine sediment (b) for
15 days
www.matcorr.com
Figure 4. Nyquist plots for samples immersed in sterile marine

sediment (A) and SRB-containing marine sediment (B)
433
434
Figure 5. SEM and EDS analysis for samples immersed in sterile marine sediment (A), (B) and SRB-containing marine sediment (C), (D)
3.2.2.2 Sample in the SRB-containing marine sediment: Fig. 4B

showed the Nyquist plot obtained for the sacrificial anode
immersed in the biotic medium. According to the Nyquist plot,
the variation of the EIS data showed a similar trend with the
abiotic medium. A capacitive semicircle appeared at high
frequencies because of the formation of a surface film on the
sample. It was considered that the film was formed by the
oxidation of metal, the adhesion of SRB and the accumulation of
corrosion products. At the beginning, the diameter of the
capacitive semicircle increased, which is probably due to the
growth of a heterogeneous surface film on the sample surface.
Subsequently, the decrease of the diameter is probably derived
from the disruption of the sample surface. Meanwhile, an
inductive semicircle appeared at middle frequencies, which
disappeared much earlier than that in the abiotic sediment. It can
be concluded that SRB play a significant role in the initiation and
propagation of local corrosion. Sheng et al. reported that SRB
could generate substantial hydrogen sulfide, which reacted with
metal ions to form metal sulfide, the compounds thus enhance
localized corrosion of the metal by inducing pitting corrosion [10].
A capacitive loop appeared at low frequencies in the Nyquist plot,
which related on the charge transfer processes.
3.2.2.3 Fitting analysis: The results of EIS were analyzed using
Zsimpwin software, the quality of the fit to the equivalent circuit
was based on the x2-value between the experimental data and the
fit results [31]. The EIS data for the sample immersed in the
sterile medium and the biotic medium could be fitted by two
equivalent circuits (Fig. 6). Model (A) is used for the sample
immersed in the abiotic medium from the 1st to the 9th day and
the biotic medium from the 1st to the 5th day. Model (B) is used for
the sample immersed in the abiotic medium from the 11th to
the 15th day and the biotic medium from the 7th to 15th day. As
shown in the two models, Rs is the solution resistance. Qf is
the capacitance of the surface film. The presence of CPE can be
interpreted by dispersion effects caused by roughness on the
sample surface [10]. The CPE impedance is described as:
n
ZCPE Y1
0 jv
0 < n < 1;
(1)
Y0 is a constant phase element and n is an empirical

exponent, the value of n can reflect the degree of heterogeneities
(A)
Qf
Rs
L pit
Cdl
R pit
Rct
Rf
(B)
Qf
C pit
Rs
C dl
Rf
R pit
R ct
Figure 6. Equivalent circuits for the analysis of EIS
www.matcorr.com
Table 1. Results of the fit with the equivalent circuit for samples immersed in sterile marine sediment
Time (d)
1
3
5
7
9
11
13
15
Rs
(Vcm2)
Qf
(F/cm2)
Rf
(Vcm2)
Lpit
(Hcm2)
Cpit
(F/cm2)
Rpit
(Vcm2)
Cdl
(F/cm2)
Rct
(Vcm2)
10.95
46.05
28.80
27.75
27.25
27.79
30.34
28.76
3.92 105
2.27 105
2.28 105
3.33 105
4.10 105
3.75 106
6.95 106
6.32 106
0.8315
0.8119
0.8077
0.7775
0.7749
1.0000
0.9274
0.9841
12.64
1.00 107
1.00 107
1232
1193
28
46
34
1045
160
67
52
65
1.07 105
8.86 106
2.16 105
1679
2270
1192
1271
1090
63
98
718
1.69 105
1.04 106
1.23 106
8.77 102
1.13 101
1.37 105
1.56 105
1.43 105
2121
1843
1227
793
765
955
910
72
on the sample surface [27]. Rf is the resistance of the surface

film. Lpit is the inductance of the pits. Cpit is the capacitance of the
pits. Rpit is the resistance of the pits. It can be used as a qualitative
measurement of the growth rates of pits [25]. Cdl is the
capacitance of the double layer. The double layer is formed as
ions from the marine sediment medium diffused to the sample
surface. Rct is the charge transfer resistance. It is a parameter
used to characterize the corrosion rate [24].
3.2.2.4 Comparison of fitting results in the sterile and SRBcontaining marine sediment: To compare the influence of SRB
on the sacrificial anode in marine sediment, the results of typical
equivalent parameters from the equivalent circuit models are
selected in Table 1 for the control sample and Table 2 for the
sample with SRB, respectively.
Under the abiotic condition, the value of n decreased from
0.8315 to 0.7749 during the first 9 days, and then the value of n
increased to 0.9841 for the later time. It is indicated that the
surface layer was becoming increasingly rough at first because of
the initiation of localized disruption of the sample surface [27],
after 9 days, the heterogeneity of the surface layer decreased with
exposure time due to the increasing thickness of the corrosion
products layer. At the same time, the value of n increased
continuously from 0.8424 to 0.9818 during the whole exposure
time under the biotic condition. It is suggested that the
heterogeneity of the surface film gradually diminished with
immersion time due to the distribution of biofilms and the
precipitation of corrosion products [24].
The value of Rpit for the control sample maintained at more
than 1000 Vcm2 from the 1st to the 9th day, but it reduced to
63 Vcm2 after 11 days. At the beginning of the experiment, the
initiation of the pits on the sample surface depends on the active

sites related on the enrichment of the alloying elements (such as
indium and zinc) [19], however, the growing rates of pits became
relatively slow because a protective film of corrosion products was
built on the sample surface, which could protect the sample from
aggressive media to some extent. About 9 days later, the corrosion
products film became loose and porous, served as strong
cathodes, and accelerated the active dissolution [32], thereby the
growth rates of pits increased greatly. Compared with the control
sample, the values of Rpit for the sample with SRB are much lower
in the whole experiment. It can be concluded that the growth rates
of pits can be greatly accelerated in the presence of SRB.
The Rct for the control sample decreased during the first 9
days, giving evidence to an increase of the dissolution of the
sacrificial anode. After that, it increased from the 9th to the 11th
day, but decreased rapidly from the 11th to 15th day. Such large
oscillations are probably owing to localized corrosion [27].
Compared to the control sample, the values of Rct in the SRBcontaining medium are much lower than those obtained in the
sterile medium during 15 days, which indicated that the
corrosion rate of the sample was accelerated with the growing
process of SRB. Furthermore, the oscillatory variety of the Rct for
the sample with SRB occurred earlier than that for the control
sample, It is reconfirmed that SRB can greatly enhance the
localized corrosion of the sacrificial anode.
3.3 Surface analysis
The results of the SEM and EDS analysis were shown in Fig. 5. A
narrow and deep pit could be seen on the sample surface without
SRB in Fig. 5A. Moreover, some tubercles were observed. The
Table 2. Results of the fit with the equivalent circuit for samples immersed in SRB-containing marine sediment
Time (d)
1
3
5
7
9
11
13
15
Rs
(V cm2)
Qf
(F/cm2)
Rf
(V cm2)
Lpit
(H cm2)
Cpit
(F/cm2)
Rpit
(V cm2)
Cdl
(F/cm2)
Rct
(V cm2)
10.07
18.89
22.58
22.56
21.81
24.10
24.43
22.54
5.23 105
4.04 105
3.69 105
5.65 106
2.28 105
3.23 105
1.91 105
5.69 106
0.8424
0.8121
0.8196
1.0000
0.8850
0.8509
0.9076
0.9818
287.40
575.80
2.09 105
27.94
108.40
124.80
106.00
19.14
9.23
15.12
29.91
1.61 105
7.42 106
1.07 101
1.28 105
1.53 105
196.90
723.50
715.20
971.90
928.90
291.10
714.20
49.40
3.31 101
24.74 102
1.81 106
1.29 105
3.46 102
1.14 105
7.16 102
2.27 105
419.70
67.28
942.30
60.69
179.60
858.30
239.50
594.40
www.matcorr.com
435
436
Table 3. EDS results for samples immersed in sterile marine sediment

and SRB-containing marine sediment
Reactions for the corrosion product:
Element/W%
Al
Fe
Zn
H2 O ! H OH
(4)
Abiotic system
Biotic system
12.47
15.30
9.94
14.65
69.20
63.97
4.17
1.91
4.22
4.17
Al3 3OH ! AlOH3 #
(5)
Mn nOH ! MOHn #
(6)
tubercles may be the result of the interaction between anodic

reaction and environment or between anodic and cathodic
reaction, which may act as a cathode in a galvanic couple and can
facilitate the initiation of pitting corrosion. While in Fig. 5C,
a larger local corrosion area was observed on the sample surface
with a large amount of SRB. Furthermore, some floccules with a
distinct structure could be found among the corrosion products.
The floccules were supposed to be EPS formed by SRB metabolic
activity. EPS could be helpful to create an inhomogeneous biofilm
on the metal surface, modify the physicochemical environment
and favor the electrochemical reactions that lead to critical
localized corrosion [7]. SEM images revealed the presence of
pitting morphologies on the sample immersed in the abiotic
medium as well as the biotic medium, but the local damage in the
biotic medium was more severe than that in the abiotic medium.
The EDS analysis (Fig. 5B and D) indicated that the surface film of
the sample immersed in both media is composed of C, O, Al, Fe
and Zn. However, the In and Sn elements were not detected, the
reason may be that the content of the elements in the surface film
is too low to be detected. It is considered that the main
components of the corrosion products are Al(OH)3 and Zn(OH)2.
The results of the EDS analysis were listed in Table 3. It showed
that the concentration of C and O in the surface film under the
SRB containing condition is higher than that under the sterile
condition, and it can further indicate the presence of bacterial
cells and EPS in the surface region. In addition, the concentration
of Al in the surface film under the SRB containing condition is
lower than that under the sterile condition, which suggests that
the corrosion rate of the sacrificial anode is accelerated by SRB. It
is noted that the surface analysis is consistent with the EIS result,
which showed that SRB colonization could greatly enhance the
corrosion of the sacrificial anode.
3.4 The hypothesis of corrosion mechanism
The local dissolution of the sacrificial anode has been widely
recognized to be an autocatalytic process of dissolution
redeposition. The re-precipitation of alloying elements, being
considerably nobler than Al, can form excellent micro-galvanic
corrosion couples that lead to the local degradation of the
sacrificial anode [33]. Based on the observation of EIS
measurements and EDS results, the possible electrochemical
reactions occurring during the sacrificial anode corrosion in the
marine sediment are as follows:
The anodic reaction:
AlM ! Al3 Mn 3 ne M : alloying elements
(2)
Al Mn ! Al3 M 3ne
(3)
The cathodic reaction:

H e ! Had
(7)
As the previous explanation in this paper, under the sterile

condition, pitting corrosion can be accelerated by the loose
corrosion products, which can create micro-corrosion cells with
metal substrate. Under the biotic condition, the EIS results and
surface analysis indicated SRB could further increase the
localized corrosion of the sacrificial anode. The possible reason
that the bacteria can accelerate the electrochemical corrosion
process is the cathodic depolarization effect. According to the
cathodic depolarization theory, the atomic hydrogen accumulated
at the cathode can be captured and utilized by SRB [14]. The
cathodic depolarization reaction formula is as follows:

SO2
4 8Had H ! HS 4H2 O
(8)
So the consumption of hydrogen by SRB may be the main

reason causing the increase of the sacrificial anode corrosion.
4 Conclusions
1. The variation of galvanic current reveals that the corrosion rate
of the sacrificial anode is accelerated by the metabolic activity
of SRB.
2. The results of EIS measurements and surface analysis show
pitting corrosion of the sacrificial anode in the marine
sediment without and with SRB during exposure time. In the
sterile marine sediment, the growth rates of pits can be
accelerated by the loose corrosion products, while the growth
rates of pits can be further enhanced by SRB in the biotic
marine sediment.
3. The corrosion rate of the sacrificial anode increases in the
presence of SRB because of the cathodic depolarization effect.
Acknowledgements: This study was supported by the National

Natural Science Foundation of China (No. 41006054) and the
Knowledge Innovation Program of the Chinese Academy of
Sciences (KZCX2-EW-205). The authors would like to acknowledge
Zibo Hongtai Antisepic Co., Ltd for Al-Zn-In-Sn sacrificial anode
plates.
5 References
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[21] W. G. Characklis, K. C. Marshall, A. Cunningham, Biofilms,
John Wiley & Sons, New York 1990.
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(Received: September 30, 2010)
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DOI: 10.1002/maco.201005796
Alternative methods for copper corrosion studies in

household plumbing systems
A. Armanious* and K Johannsen
Copper corrosion poses a serious challenge to the practice of using copper pipes
in household plumbing installations. Copper corrosion can cause health,
aesthetic and economic problems. Pipe rig experiments have always been used
to study copper corrosion. But the long duration of such experiments, which can
last for up to six months, makes them tedious and relatively expensive, thereby
limiting the progress of copper corrosion research. The purpose of this study is to
establish a laboratory scale experimental setup that takes less time and can be
used to study the kinetics of the processes involved in copper corrosion. The
developed setup offers a promising alternative to studying copper corrosion
using experiments that last for just 24 hours.
1 Introduction
Copper is the most commonly used pipe material in household
plumbing systems. Copper pipes are preferred due to their
workability, low toxicity, and antiviral and biocidal capabilities.
Nevertheless, copper corrosion poses a serious challenge to the
practice of using copper pipes. Corrosion of copper can cause
health, aesthetic and economic problems.
Copper corrosion is a complex phenomenon that comprises
a wide range of processes and sub-processes. Due to its
complexity, nearly every aspect of the system affects the final
copper concentration in tap water. Merkel and Pehkonen [1] tried to
sum up the parameters influencing general corrosion of copper
into two broad categories: internal and external parameters.
Internal parameters include material properties, surface properties and solid corrosion by-products. External parameters can be
grouped into three different categories: water composition
(inorganic and organics); water treatment (TOC removal, pH
adjustment, softening and corrosion inhibitors); and operational
conditions (consumption pattern, temperature and disinfection).
These factors affect, directly or indirectly, the processes governing
copper corrosion in water pipes.
Three sub-processes serve as the main controllers of copper
concentrations in tap water: metallic copper oxidation; soluble
copper fixation into scale; and solubility equilibrium. These subprocesses combine to determine the final copper concentration in
tap water and the composition of the scaly residue that covers the
inner surface of a copper pipe. The characteristics of the scale
generally change slowly, with higher rates for new pipes and very
A. Armanious, K. Johannsen
Institute of Water Resources and Water Supply, Hamburg University of
Technology, Schwarzenbergstrae 95, 21073 Hamburg, (Germany)
E-mail: antonius.armanious@env.ethz.ch
slow rates for aged pipes. In light of this, we can consider copper
corrosion in both long-term and short-term time spans [2]. In
the long-term, we are primarily concerned with the change in the
characteristics of the scale formed on the inner surface of the
copper pipes. Five copper minerals have been identified as, or
speculated to comprise, the main constituent of the scale layer:
cuprite (Cu2O); cupric hydroxide (Cu(OH)2); malachite
(Cu2(OH)2CO3); tenorite (CuO); and cupric phosphate
(Cu3(PO4)2) [213]. Of these five minerals, cuprite and malachite
have been more frequently detected and confirmed by analytical
methods like XDR or SEM. It is believed, however, that malachite
is the solid phase fraction responsible for governing copper
solubility in plumbing systems [8, 14]. This hypothesis is
supported by the results of Merkel and Pehkonen [1] where
malachite was the solid phase governing the equilibrium
concentration of copper even when detected in the form of very
small patches.
Over the short-term, we deal with the ongoing processes
during stagnation periods, which typically last for six to eight
hours in household plumbing systems. Previous research has
demonstrated that copper release during stagnation periods is a
non-equilibrium process. In other words, the kinetics of the
ongoing processes is essential to estimate copper levels in water
during stagnation.
Pipe rig experiments are commonly used to study copper
corrosion in plumbing systems. According to the German
standard DIN EN-15664-1 [15], pipe rig experiments usually last
for more than six months, in order to take into account the
variation of scale characteristics over time. Stagnation experiments are conducted at various stages of these six-month periods
to examine the copper release during stagnation. The long
duration of pipe rig experiments limits the number of studies that
can be conducted in the field of copper corrosion.
The objective of this study is to develop and optimise a
laboratory scale setup which can be used to investigate the
www.matcorr.com
Alternative methods for copper corrosion studies
As previously mentioned, malachite has been one of the most

commonly detected crystals in pipe scales [12, 58, 13]. In
addition, it is believed to be the solid phase fraction responsible
for governing copper solubility in plumbing systems [8, 14].
Therefore, we conducted the experiments in this study in the
presence of malachite-covered copper pipe pieces. We prepared
the malachite according to the method suggested and tested by
Merkel [14].
pieces were suspended in the reactor using Teflon tapes so as not

to obstruct the stirring fish. The reactor was always filled with the
same amount of water (900 ml) and the added copper pieces
always had the same surface area (447.4 cm2), which corresponds
to the surface area of ten copper pipe pieces, each with a length of
5 cm and an inner diameter of 13 mm. Figure 1 provides a
schematic diagram of the setup.
All the experiments lasted for 24 hours. DO and pH were
recorded just after the start of the experiment and at every
sampling event. Using syringes, samples were taken after 1, 3, 5,
and 24 hours, and also three additional samples were taken
between the 5th and 24th hour at different times. Before
withdrawing the sample from the reactor, the syringes were
used to introduce a volume of air equivalent to the volume of the
sample, so as to avoid creating vacuum pressure inside the
reactor. The samples were then acidified directly after sampling
using nitric acid (>65%) to pH 1, in order to prevent cupric ions
from precipitating. Acidifying the samples was also important to
convert all the cupric ions complexed with carbonates to free
cupric ions, thus allowing for further detection during the
photometric analysis of total cupric ions concentration. The
samples were also analysed later for cupric ions concentration,
and for phosphate concentration when needed.
2.2 Preliminary experiments
2.4 Chemical
We conducted a series of preliminary experiments to determine

the best sealing approach for ensuring a totally sealed reactor, and
to select an appropriate pH value. Our objective was to find a pH
value that would not be too low but would, at the same time,
produce detectable copper concentration variations in the water.
We decided to perform the experiments by adding 6 ml/l 0.1N
HCl, which led to a pH of 6.41 0.05 over a total of six
experiments.
In order to investigate the impact of the copper crystal
starting conditions and the possibility of reusing them, we
conducted two experiments with different starting conditions:
one with freshly prepared malachite-covered copper pieces and
another experiment with malachite-covered copper pieces that
had been aged in synthesised water for 24 hours. The results of
these experiments are presented later.
The following chemicals were used in the course of the

experimental work: sodium hydrogen carbonate NaHCO3 (p.a 99.7%., Riedlel-de Haen AG, Seelze/Germany); sodium dihydrogen phosphate hydrate NaH2PO4.H2O (p.a. - 99%, Merck,
Darmstadt/Germany); hydrochloric acid 0.1N HCl (Titrisol1
1.09973, Merck, Darmstadt/Germany); hydrochloric acid 25%
HCl (p.a., ROTH1, Karlsruhe/Germany); nitric acid 65% HNO3
(p.a., ROTH1, Karlsruhe/ Germany); ammonia 25% NH3 (p.a.,
ROTH1, Karlsruhe/ Germany); humic acid (ROTH1, Karlsruhe/ Germany); and sodium hypochlorite solution NaClO/
12%Cl (ROTH1, Karlsruhe/ Germany).
corrosion kinetics of copper in relatively short periods of time.

The new setup should produce results similar to those of
stagnation profiles in pipe rig experiments.
2 Materials and methods

As a first step, it was important to determine which copper solid
phase should be used in the laboratory experiments. The setup
also had to be optimised in order to ensure the reproducibility and
reliability of the results. Finally, we had to investigate corrosion
behaviour during the 24-hour stagnation periods under the
differing effects of a range of synthesised waters.
2.1 Malachite crystals
2.3 Experimental setup and procedure

We based our setup on one introduced by Merkel [14], which we
further developed, optimised and tested in this study. The setups
main element was an insulating flask filled with synthesised
water and in which the copper pieces were suspended. The flask
was connected to a WK 500 recirculating chillier (LAUDA,
Germany), in order to maintain the temperature at 25 8C. It had
three openings: one was used for the dissolved oxygen (DO)
probe; another one for a pH probe; and the last for sampling. In
order to ensure hermetic sealing that would prevent air exchange,
all the caps were fitted with Teflon tape and then sealed with
silicone. DO, pH probes and the sampling tubing were fitted
using silicone rings (Schott, Mainz/Germany) and then sealed
with silicone paste (Max Bahr, Hamburg/Germany). Copper
www.matcorr.com
Figure 1. Schematic diagram of the laboratory-scale setup
439
440
Armanious and Johannsen
Table 1. List of the conducted experiments and their characteristics
Water characteristics
Experiment
code
NaHCO3
0.1N HCl
DOC
NaH2 PO4 PO4
NaOCl Cl2
1 mmol/l
1 mmol/l
1 mmol/l
1 mmol/l
1 mmol/l
1 mmol/l
6 ml/l
6 ml/l
6 ml/l
6 ml/l
6 ml/l
6 ml/l
1 mg/l
3 mg/l
3 mg/l
3 mg/l
0.5 mg/l
2.5 Chemical analysis
M01
M02
M03
M03I
M03II
M04
four experiments, with one of them carried out in triplicate to

account for experimental accuracy and error range. The
experiment with no additives (dissolved organic carbon (DOC),
orthophosphate or free chlorine) is referred to as the control
experiment in the rest of the manuscript. Table 1 shows a list of
the experiments conducted.
DO and pH were measured using HQ40 (HACH Company,

Loveland/USA). For dissolved oxygen, an LDO101 probe (HACH
Company, Loveland/USA) was used. For pH, a PHC101 probe
(HACH Company, Loveland/USA) was used. Both cupric ions
and phosphate concentrations were determined by photometric
analysis using LP2W (Dr. Bruno Lange GmbH, Berlin/Germany).
3 Results and discussions
2.6 Copper analysis
3.1 Reproducibility of the results
The determination of cupric ions concentration was done using

Spectroquant1 14767-Fasttest (Merck KGaA, Darmstadt/Germany) at a wavelength of 588 nm (Filter, Dr. Bruno Lange GmbH,
Berlin/Germany). The procedure of the analysis was as follows:
first, two level green dosing spoons from Reagent Cu-1 were
added to 10 ml of the sample. Then the sample was shaken
vigorously and left for at least 10 minutes. After that the pH was
adjusted using a few drops of 25% ammonia to pH 10. Then 10
drops of Reagent Cu-2 were added to the sample. Afterwards, the
sample was well mixed and left for at least 5 minutes. Samples
from every experiment were done together, with a blank sample of
deionised water. All the reagents were added to the blank sample
in the same fashion as the experimental samples. Finally, light
absorption at 588 nm through a 10 mm cuvette (Type No. 100-0S,
Hellma1 GmbH, Mullheim/Germany) was measured. The
procedure followed in the analysis was based on the recommendations by Alex [16] and Dartmann [17].
3.1.1 Optimising experimental procedures

Two experiments were conducted: one for freshly prepared
malachite-covered pipe pieces; and one for pieces aged 24 hours
in synthesized water. Both experiments produced nearly identical
results in copper concentrations. We noted, however, a huge
difference in dissolved oxygen consumption and phosphate
concentrations between the two experiments. These differences
indicate that although the measured copper concentrations are
similar, the mechanisms behind them may differ. Therefore, all
experiments were conducted using freshly prepared pieces and all
the pieces were used for only one stagnation experiment.
2.7 Phosphate analysis
3.1.2 Variation range of the results

Experiments number M03, M03I and M03II were conducted to
look at the variation in results and the range of error. Figure 2
shows the average of all the results with standard deviation bars.
Based on these three experiments, all the results are considered
reproducible with a relatively limited variation.
Orthophosphate concentrations were determined using Spectroquant1 14848-Fasttest (Merck, Darmstadt/Germany) at a

wavelength of 695 nm (Filter, Dr. Bruno Lange GmbH, Berlin/
Germany). At first, 5 drops of the Reagent PO4-1 were added to a
5 ml sample. After mixing, one levelled blue micro-spoon
(provided with the test kit) from Reagent PO4-2 was added and
mixed vigorously. The samples were left until the reagent was
completely dissolved. A blank sample was always prepared
following the same procedure. Finally, light absorption at 695 nm
through a 10 mm cuvette (Type No. 100-0S, Hellma1 GmbH,
Mullheim/Germany) was measured.
3.1.3 Experimental limitations

Though the setup and the procedure of the stagnation
experiments were optimised to imitate the conditions in pipe
rig experiments, the sampling procedure still had an undesirable
effect on the DO of the water. For each sampling event an
equivalent volume of air was injected inside the reactor to avoid
generating vacuum pressure during sampling. Replacing water
by equal volume of air would eventually lead to an increase in DO
as a result of liquid gas equilibrium. This procedure might have
affected the pH of the water as well.
2.8 Conducted experiments
3.2 Control experiment (experiment code MO1)
In order to investigate the corrosion kinetics of copper under the

effects of a range of synthesised waters, we conducted a total of
Figure 3 shows the measured copper concentration and the

equilibrium concentrations with respect to different copper
www.matcorr.com
Figure 2. Average Cu(II), PO3

4 concentrations and DO consumption of
the experiments M03, M03I and M03II
Figure 4. Measured DO for experiment M01
Figure 3. Measured copper concentration and equilibrium

concentrations for experiment M01
crystals. The equilibrium concentrations were calculated using

Aqusim models according to the recorded experimental pH
values. It can be seen from the chart that the system can only be in
equilibrium with either malachite or tenorite, but not with cupric
hydroxide. It is more plausible to assume that the system is in
equilibrium with malachite as the copper pieces used were
covered with malachite. This observation supports the hypothesis
of Merkel et al. [8, 14] that malachite is the solid phase fraction
responsible for governing copper solubility in plumbing systems.
The profile of copper release is identical to that observed by
Merkel et al. [7] and Merkel [14] in the presence of malachite. The
rapid release of copper during the first 1 or 2 hours is attributed to
the oxidation of elemental copper. This assumed mechanism is
corroborated with the rate of oxygen consumption as seen in
Figure 4. The DO data indicate that there was hardly any more
oxidation going on after 5 hours of the experiment, although DO
concentration was round 6.5 mg/l. It has always been thought that
oxygen is the limiting factor in the oxidation process. Vargas et al.
[12] suggested that H ions concentration is the limiting factor for
the continuation of the oxidation process. However, this theory
might not be applicable in our case as it has been observed in
other experiments that oxidation of copper is still an ongoing
process at higher pH values. The most convincing reason is the
depletion of the elemental copper available for oxidation on the
surface of the copper pieces. This theory is supported by the fact
that the ratio of water volume to copper surface area is very large;
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thus all available elemental copper can be oxidised before the

dissolved oxygen is depleted.
Concurrently, the dissolution of malachite into the water
continues until copper concentration exceeds the equilibrium
concentration with respect to malachite. Once this occurs,
precipitation in the form of malachite crystals is initiated. The rate
of precipitation is dependent on how high the saturation index
(SI) of malachite is: the higher the SI the faster the precipitation
rate.
Until now we have only considered the processes of metal
oxidation and solubility equilibrium, but not copper fixation.
Copper fixation in the scale layer is expected to be of minor
consideration in this case, since the copper pieces used are
comparable to very old copper pipes, where the surface is nearly
totally covered with scale, thereby allowing for a very limited
likelihood of any more scale forming. This assumption was
proved to be true using computer models for the corrosion
process, data for which are not published here.
Figure 5 shows the stagnation curves of pipe rig experiments
by Merkel [2], according to the German standard DIN EN 15664-1
Figure 5. Copper concentrations during five days stagnation after

different aging periods [2]
441
442
[15] after 9, 10, 11, 13 and 14 weeks of operation. The longer the
operation time, the lower the peak of the stagnation curve; the
highest peak represents the 9-week stagnation curve and the
lowest peak represents the 14-week experiment. Merkel [2] also
found that malachite coverage of the copper surface increases
with operation time. In other words, the 14-week curve represents
the curve in the presence of the widest extension of malachite
scale coverage on the pipes internal surface. The stagnation
profile is very similar to the one obtained in both the control
experiment (Figure 3) and the chlorinated experiment (Figure 6 experiment M04). The main difference is the higher level of peaks
in the case of the laboratory scale experiments. Although the
difference in water characteristics between the laboratory scale
experiments and the experiments by Merkel [2] makes the results
incomparable, the higher peaking observed in the laboratory scale
experiments could be attributed to the difference in the ratio of
water volume to copper surface area. Hong et al. [3] observed an
increase in copper levels when the ratio between water volume
and copper surface area increased, which was concomitant with a
slower pH increase in the case of larger volumes. It was important
to point out this observation as it might be one of the main
challenges in applying the laboratory scale experiments as a
surrogate for pipe rig stagnation experiments.
Figure 7. Oxygen consumption for experiments M01, M02, M03 and

M04
3.3 Effects of DOC, phosphate and chlorine

Figures 6, 7, 8 and 9 show the results for all four synthesised
waters. All the experiments are discussed in details afterwards.
Figure 8. pH for experiments M01, M02, M03 and M04
3.3.1 Effects of DOC (experiment code MO2)

Previous research showed that, in most cases, the presence of
organic matter promotes the release of copper corrosion byproducts. Based on field measurements and laboratory experiments, Broo et al. [18, 19] concluded that the presence of natural
organic matter (NOM) leads to increases in copper release. They
attributed this increase to complexes formation. Similar results
were observed by Boulay and Edwards [20] and Edwards and
Sprague [21] when conducting pipe rig experiments. Edwards and
Sprague [21] attributed the increase in copper concentrations as
well to complexation of copper with the organic matter.
To investigate the effect of DOC on copper corrosion, 1 mg
TOC/l was added to water with the same characteristics as those
of the control experiment. Figures 6, 7 and 8 show two
Figure 9. Orthophosphate concentrations for experiment M03
Figure 6. Measured copper concentrations for experiments M01, M02,

M03 and M04
contradicting observations: lower and later peaking of copper

simultaneously with higher consumption of oxygen and
steeper pH increase. The fact that there was both higher oxygen
consumption (Figure 7) and a steeper increase in pH (Figure 8)
during the first few hours supports the theory of complexation
with humic acids. Still, humic acid complexation fails to explain
the observed copper release profile, as it would have been
expected to have a higher copper concentration over the whole
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period of stagnation. The only explanation that can solve this

conundrum is that the analytical method used for measuring
cupric ions concentration could not detect the ions that were
complexed with humic acids, which means that the actual cupric
ions concentration is higher than the one measured.
3.3.2 Effect of orthophosphate (experiment code MO3)
The effect of orthophosphate on copper release, as described in
the literature, was found to be inconsistent. Nevertheless, though
it is not fully clear, there is more understanding today about the
interaction of orthophosphates with copper corrosion. It used to
be commonly believed that on the addition of orthophosphate,
cupric phosphate (Cu3(PO4)2) precipitates, leading to the
reduction in copper solubility. Though cupric phosphate
precipitation was often hypothesised in the literature [6, 22], it
was only detected once by Edwards et al. [5] in a titration
experiment on the addition of orthophosphate at the concentration of 15.83 mg PO3
4 /l. This concentration is five times higher
than the common concentration used in drinking water. Cupric
phosphate was not detected by XRD analysis because the formed
scale was X-ray amorphous. The author assumed that it was
cupric phosphate based on wet chemistry analysis, which showed
a Cu: P ratio equal to 1.5 W0.06. Zhe et al. [10] questioned the
assumption that equilibrium concentration is determined based
on cupric phosphate equilibrium, stating that the literature
provides very limited evidence for the formation of cupric
phosphate in the pipe scales. Zhe et al. [10] and Dartmann et al.
[13] found that the measured copper concentrations were lower
than the equilibrium concentrations of cupric phosphate.
Dartmann et al. [13] deduced that phosphate is adsorbed on
the copper surface, blocking the active sites on the surface and
consequently leading to a decrease in oxygen consumption.
To investigate the effect of orthophosphate on copper
corrosion, an experiment was conducted with water containing
3 mg PO3
4 /l. The results (Figure 6) show that there was an
abatement in the peak of copper concentration. Meanwhile, the
cupric ions concentration stabilised at a clearly higher concentration compared to the control experiment. Equilibrium
concentrations with cupric phosphate were calculated using an
Aquasim model based on the measured pH and phosphate
concentrations. Equilibrium copper concentrations with cupric
phosphate were found to be higher than the measured cupric ions
concentration by about one order of magnitude, which initially
excludes the possibility of copper precipitation as cupric
phosphate. The other possible hypothesis is the sorption of
orthophosphate on the copper surfaces, thereby occupying sites
for both elemental copper oxidation and precipitation/dissolution. Although the observed copper profile is consistent with
Dartmanns et al. [13] theory of phosphate adsorption blocking the
active sites on the pipe surface, we did not observe any decrease in
oxygen consumption as it was observed by Dartmann et al. [13].
On the contrary, oxygen consumption slightly increased and pH
continued to increase until the end of the experiment (Figures 7
and 8). The drop in orthophosphate concentration seen in
Figure 9 suggests that the precipitation of phosphate promoted
copper precipitation one way or another. The only logical
explanation is that the precipitation of phosphate led to a
negatively charged copper surface. In turn, this charged surface
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attracted the positively charged cupric cations closer to the copper

surface, thus creating a sub-system close to the copper surface
with different ongoing processes. One suggested feature of this
sub-system is the oversaturation of cupric phosphate due to the
gathering of both the phosphate anions and cupric cations in a
very small volume. Consequently, cupric ions are incorporated in
the scale layer as cupric phosphate. As phosphate precipitates,
either in the form of cupric phosphate or any other form, it
occupies the active sites, allowing for no further precipitation of
cupric ions in any other form and thus leading to the stabilized
cupric ions concentration seen in Figure 6.
3.3.3 Effect of chlorination (experiment code MO4)
Although the effect of chlorine on copper corrosion has not been
as extensively studied, researchers have agreed on certain
observations. Hong et al. [3] and Boulay and Edwards [20]
observed a general trend of increase in copper release with an
increase in free chlorine concentration. The increase was
especially limited below pH 9.5. Hong et al. [3] mentioned that
HOCl attacks the copper surface and oxidises the available
elemental copper.
To investigate the effect of free chlorine on copper corrosion,
the water was spiked with 0.5 mg Cl2/l. As seen in Figures 6, 7
and 8, there is a great similarity in the profiles of Cu(II)T, oxygen
consumption and pH in both the control experiment and the
chlorinated water experiment. The chlorinated water had a higher
peak of cupric ions concentration while displaying slightly lower
oxygen consumption. This perplexing observation suggests that
free chlorine may act to oxidise elemental copper, thus leading to
rapid copper release. It is worth mentioning that although the
chlorinated water had a higher peak, it ended up having nearly the
same cupric ions concentration after roughly 18 hours of
stagnation. Spiking the water with 0.5 mg Cl2/l seems to be of
limited impact on copper release, which is in accordance with
Hong et al. [3] and Boulay and Edwards [20], who observed a
limited increase in copper release with chlorinated waters at pH
levels below 9.5.
3.4 Copper corrosion in the presence of malachite scale:
an overview
Using the laboratory scale setup, the copper release profile of the
control experiment was very similar to the results of pipe rig
experiments conducted by Merkel [2]. The observed results imply
that the same processes are taking place both in the pipe rig
experiments and in the laboratory scale experiments.
The addition of 1 mg TOC/l led to higher copper release, DO
consumption and pH increase over most of the stagnation period.
This increase was attributed to complexation of cupric ions with
humic acids. These observations were similar to those of Boulay
and Edwards [20] and Edwards and Sprague [21] when conducting
pipe rig experiments.
Spiking the synthesised water with 3 mg PO3
4 /l led to the
stabilisation of the copper concentration at a level clearly higher
than that of the control experiment. Although the observation
agrees with the conclusion of Dartmann et al. [13] that adding
phosphate would lead to higher copper levels (in the systems
where copper levels were already low before the addition of
443
444
phosphate), the mechanisms behind this increase in copper

concentration might be different from the mechanisms hypothesised by Dartmann et al. [13] in pipe rig experiments. It is believed
that phosphate is adsorbed on the copper surface leading to a local
over saturation with respect to cupric phosphate. The adsorption
of phosphates leads as well to occupying the active sites on the
copper surface, thus allowing for no further oxidation of copper or
precipitation of cupric species.
Adding 0.5 mg Cl2/l to the synthesised water led to a limited
increase in copper levels. Similar results were observed by Boulay
and Edwards [20] when conducting pipe rig experiments with
chlorine concentration of 0.7 mg Cl2/l at pH 7.0. The most
probable explanation for the slight increase in copper release
without the increase in oxygen consumption, or even with a slight
decrease in the oxygen consumption, is that chlorine acts as an
oxidising agent.
Overall, it can be confidently stated that the laboratory scale
experiments conducted in this study offer analogous results to
those obtained in previous studies using different experimental
methods, such as field data and pipe rig experiments. But still, in
order to extrapolate the calculated rates from laboratory scale
experiments to pipe networks, the effects of different ratios
between water volume and copper surface area need to be
investigated.
4 Conclusion
Although the laboratory setup we constructed achieved its
objectives, there remains room for improvement. First, the
sampling process introduces a volume of air to the setup, which
consequently affects the DO in the water and may affect pH as
well. Second, suspending the copper pieces using Teflon tapes
proved time consuming and inconvenient. The setup could be
improved by using a movable stopper on the top of the reactor,
which would shift downwards as samples are taken from the
reactor, thus leaving no air inside. This would ensure that
chemical reactions occur only in the liquid phase, the solid phase,
or in liquid-solid interaction.
Our experiments showed that laboratory scale experiments
result in similar copper release profiles compared to the pipe rig
experiments, but take far less time to conduct. By using waters
spiked with organic matter, phosphate and free chlorine, we
demonstrated that the laboratory scale experiments are a very fast
and practical method to study the mechanisms of copper
corrosion under different conditions.
As a next step, it is important to quantify the effect of the ratio
of volume to surface area on the copper corrosion. At a later stage
of research, parallel experiments, using both the laboratory scale

setup and pipe rig experiments, should be conducted using the
same water to look at the similarities and differences between the
two methods.
5 References
[1] T. Merkel, S. Pehkonen, Corros. Eng. Sci. Technol. 2006, 41,
21.
[2] T. Merkel, Wat. Sci. Technol. 2004, 49, 63.
[3] P. K. Hong, Macauley. Yeng-Yeng, Water Air Soil Pollut. 1998,
108, 457.
[4] D. A. Lytle, M. R. Schock, J. Water Supply Res. Technol. AQUA
2000, 49, 243.
[5] M. Edwards, K. Powers, L. Hidmi, M. Schock, Water Sci.
Technol. Water Supply 2001, 1(3), 25.
[6] M. Edwards, L. Hidmi, D. Gladwell, Corros. Sci. 2002, 44,
1057.
[7] T. Merkel, H.-J. Gro, G. Beuchle, W. Werner, E. Detscher, S.
Eberle, Water Sci. and Technol. 2002, 2(4), 119.
[8] T. Merkel, H.-J. Gro, W. Werner, T. Dahlke, S. Reicherter, G.
Beuchle, S. H. Eberle, Water Res. 2002, 36, 1547.
[9] J. J. Shim, J. G. Kim, Mater. Lett. 2004, 58, 2002.
[10] Y. Zhe, S. Pehkonen, Water Sci. Technol. 2004, 49(2), 73.
[11] B. Li, J. Qu, H. Liu, C. Hu, Chemosphere 2007, 68,
2153.
[12] I. T. Vargas, M. A. Alsina, P. A. Pasten, G. E. Pizarro, Corros.
Sci. 2009, 51, 1030.
[13] J. Dartmann, B. Sadlowsky, T. Dorsch, K. Johannsen, Mater.
Corros. 2010, 61, 189.
[14] T. Merkel, Ph.D. Thesis, Universitat Fridericiana Karlsruhe,
Germany, 2003.
[15] DIN EN 15664-1: Einfluss metallischer Werkstoffe auf Wasser fur den menschlichen Gebrauch -Dynamischer Prufstandversuch fur die Beurteilung der Abgabe von Metallen Teil 1: Auslegung und Betrieb. Juni 2008.
[16] T. Alex, Ph.D. Thesis, TU Hamburg-Harburg, Germany 2002.
[17] J. Dartmann, Ph.D. Thesis, TU Hamburg-Harburg,
Germany, 2005.
[18] A. E. Broo, B. Berghult, T. Hedberg, Corros. Sci. 1998, 40,
1479.
[19] A. E. Broo, B. Berghult, T. Hedberg, Water Sci. Technol. 1999,
40(9), 17.
[20] N. Boulay, M. Edwards, Water Resour. 2001, 35, 683.
[21] M. Edwards, N. Sprague, Corros. Sci. 2001, 43, 1.
[22] M. R. Schock, A. M. Sandvig, J. Am. Water Works Assoc. 2009,
101(7), 81.
(Received: May 20, 2010)
W5796
www.matcorr.com
DOI: 10.1002/maco.201005966
Generation of nanocrystalline NiO particles by solution

combustion method and its ZnNiO composite coating
for corrosion protection
K. G. Chandrappa, T. V. Venkatesha*, K.O. Nayana and
M. K. Punithkumar
The nanocrystalline nickel oxide (NiO) particles have been successfully
prepared by a simple, fast, economical, and eco-friendly solution-combustion
method using Ni(NO3)2 6H2O (oxidizer) and sugar (dextrose as fuel). The asprepared compound was calcined for an hour at different temperatures. The
synthesized NiO was characterized by XRD, TGA, SEM/EDX, TEM, XPS, FT-IR, and
UVVis spectral methods. The crystallite sizes of the NiO particles were
measured. Rietveld refinement of X-ray data matches the cubic structure with
space group of Fm3m (No. 225). The thermal behavior of as-prepared
compound was examined. Scanning electron micrographs show uniform cubic
like morphology of NiO and its chemical composition was measured. The TEM
results reveal that the particle sizes were in the order of 7080 nm. The red
shift was noticed in UVVis absorption spectra. As an application part the
ZnNiO composite coating was prepared by electrodeposition method and its
corrosion behavior was analyzed by Tafel, impedance and anodic polarization
in aggressive medium.
1 Introduction
Nanomaterials, especially metal oxides like TiO2, ZnO, CuO,
NiO, PdO, SnO2, Fe2O3, and WO3 etc, have received a
considerable attention over the last few years due to their
distinguished performance and potential applications in microelectronics, photocatalysis, magnetic devices, and powder
metallurgy [14]. These metal oxides exhibit better physical
and chemical properties different from conventional bulk
materials because of their size effect and have received increasing
technological interest in the field of chemical power sources since
1990 [5]. Among these oxides, NiO exhibits many applicable
configurations of nanostructures including nanotubules, nanowires, nanorings, nanorods, ordered hexagonal mesostructures
[610], nanosheets, nanoparticles, and hollow spheres [11, 12].
NiO is an important inorganic material and in nature, it occurs as
mineral bunsenite having cubic rock-salt (NaCl type) structure
with a0 4.195 A [13], and also it is available in two different
forms: pale apple green or jet black depending upon the
stoichiometry. The green phase is an insulator, but when there is a
K. G. Chandrappa, T. V. Venkatesha, K. O. Nayana, M. K. Punithkumar
Department of P.G. Studies and Research in Chemistry, School of
Chemical Sciences, Jnana Sahyadri Campus, Kuvempu University,
Shankaraghatta-577451, Karnataka (India)
E-mail: drtvvenkatesha@yahoo.co.uk
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deficiency of Ni2 ions (represented as Ni0.98 O1.00) it behaves like

a p-type semiconductor [14] with a band gap, 3.64.0 eV and
associated with complex band structure. The nanocrystalline NiO
has find applications in electrochromic coatings [15], p-type
transparent conducting films [16], smart windows [17], electrochemical supercapacitor [18], negative electrode of lithium-ion
batteries [19], catalyst [20], gas sensor [21], magnetic materials
[22, 23], active optical fibers [24], fuel cell electrodes [25, 26],
solar cells [27], ceramic, heterogeneous catalyst [28, 29], and
antiferromagnetic materials [30, 31].
Large numbers of preparation methods have been reported
in the literature. The NiO nanorings, nanosheets, nanorods, and
hollow spheres were prepared through thermal decomposition
where nanowires and ordered hexagonal mesostructures were
fabricated in solution assisted by surfactants [9, 11, 12, 3233].
The other methods are chemical liquid precipitation [34],
electrodeposition [35, 36], solgel [18], hydrothermal [37], laser
ablation [38], chemical vapor deposition [39, 40], chemical bath
deposition [41], evaporation [42], sputtering [43], thermal
decomposition [44], surfactant-mediated [45], polymer-matrix
assisted [46], microemulsion precipitation [47], co-precipitation,
solvothermal, electrospinning, pyrolysis [4851], and mechanochemical process [52]. Also, NiO has been successfully prepared
by template (hard template or soft template) control growth [53],
vaporsolid growth [54], solutionliquidsolid phase growth [55, 56],
microwave, and sonic irradiation methods [13].
445
446
Chandrappa, Venkatesha, Nayana, and Punithkumar
Most of the above methods for the synthesis of NiO

nanostructures are still limited to laboratory scale due to some
unresolved problems, such as strict experimental conditions,
tedious procedures, complex apparatus, low yield, and high cost.
Generally, the solution combustion synthesis (SCS) is employed
to prepare nano materials in larger scale. The SCS has been
successfully used to synthesize NiO [57], nanoscale Mg1xNixO
(0<x<1) solid solution and their structure, microstructure,
surface area, and magnetic properties were investigated [58]. The
quantitative effects of fuel on the synthesis of Ni/NiO particles by
SCS method using a microwave [59], nanosized ZnO/Carbon
composite for supercapacitor application [60], Ni-YSZ cermet
powders [61], layer structure of LiCoO2 for lithium ion battery
fabrication [62], and nanotitania thin films for dye-sensitized
solar cells which showed a high light-to-electricity conversion
yield [63] have been investigated. Technologically important giant
magneto resistant materials have also been prepared by SCS and
their properties have been studied [64]. This method produced
more homogeneous [65] and high purity crystalline material. The
extensive research carried out in the last 5 years emphasized the
solution combustion method capabilities for nanomaterials
synthesis.
In this paper, SCS method was used to synthesize nickel
oxide nanoparticle with nickel nitrate as oxidizer, dextrose as fuel,
and millipore water without using any templates, surfactant,
organic dispersant, and capping agent. In addition, the chemical
composition, morphology, thermal stability, and microstructure
were studied via XRD, TGA, XPS, SEM/EDX, TEM, FTIR, and
UVVis techniques. The synthesized NiO nanoparticle was
employed to generate ZnNiO composite thin film on mild steel
and its corrosion behavior was examined.
2 Experimental
2.1 Synthesis of NiO nanoparticles
The AR grade Ni(NO3)2 6H2O (s d fine Mumbai, 98%) and
dextrose (Merck, 98.5%) were used as metal nitrate and fuel,
respectively. The mixture in the ratio of 2:1 wt% (10 g 5 g)
were dissolved in 25 ml of millipore water (Elix, France) and
heated at 80 8C with uniform stirring for 30 min. The resulted
homogeneous solution was dehydrated slowly and gradually
converted into viscous before the formation of gel. The gel was
transferred to a silica crucible and placed in a preheated muffle
furnace at 100 8C. The gel boils and swelled into foam, ignites
with a flame which underwent a strong self-propogating
combustion reaction with the evolution of a large volume of
gases. The entire combustion process was completed by 5 min
giving black powder. The resulting black powder was highly
crystalline and the portion of the sample was calcined for an hour
in presence of air at different temperatures (200, 300, 500, and
700 8C). The similar set of experiments were conducted for
the preparation of NiO using 4:1 and 6:1 wt% ratio of
Ni(NO3)2 6H2O and dextrose and the samples were subjected
to calcination at different temperatures. Figure 1 shows the
scheme of synthesis of NiO using Ni(NO3)2 6H2O as oxidizer
and dextrose (sugar) as fuel.
Figure 1. Schematic diagram of SCS method for synthesis of NiO
2.2 Structural characterization

The X-ray diffraction (XRD) patterns (PANalytical Xpert pro
powder diffractometer, lKaCu1.5418 A8, scanning rate of 28/
minute with a 0.028 step size in the 2u range 10908 working at
30 mA and 40 kV) were recorded for all the samples and were
used for phase analysis and crystalline size determination. For
Rietveld refinement analysis, data were collected at a scan rate of
18/min with a 0.028 step size for 2u from 10908. The data were
refined using the FullProf Suite-2000 version. The crystalline size
was calculated from Debye Scherrers equation [66].
Kl
b cos u
(1)
where D is the diameter of the crystallite size (nm), K the

shape factor (the typical value is 0.9), l the X-ray wavelength (nm)
of incident beam, b is the broadening of the diffraction line
measured in radians at half of its maximum intensity (FWHM)
and u is the Braggs angle. Morphology and compositional
analysis was also confirmed by scanning electron microscope
(SEM, Philips XL 30) fitted with an energy dispersive X-ray
analyzer (EDX). Transmission electron microscopic (TEM,
Model: JEOL 2000 FX-II) study was carried out on the selected
samples to confirm the size of NiO particles in nanometer range.
The thermogravimetric analyses (TGA) were performed in the
temperature range of 251000 8C at a heating rate of 5 8C/min
under air atmosphere using a SDTA-85 1e from Mettler Toledo.
The X-ray photoelectron spectra (XPS) were recorded by ThermoScientific Multilab 2000 equipment employing Al Ka X-rays at
150 W. XPS binding energies were accurate within 0.1 eV.
Fourier transform infrared spectra (FT-IR) were recorded using a
Bruker FT-IR spectrometer (TENSOR 27). The UVVisible
absorption spectra were recorded by Elico SL 159 UVVis spectrophotometer. The NiO nanoparticles were dispersed in ethanol and
were sonicated for 10 min prior to UVVisible measurement, for
uniform dispersion. The electrochemical measurements at a
temperature of 25 2 8C were performed using the CHI660C
electrochemical work station (CH Instruments, USA).

3.1 X-ray diffraction studies
The powder XRD patterns of as-prepared NiO from 2:1 wt% ratio
of Ni(NO3)2 6H2O and dextrose and its calcined samples at
different temperatures are shown in Fig. 2. All the powder XRD
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Generation of N:O nanoparticles, Zn-NiO composite and its application
Berube and Esperance [67], where the texture coefficient (Tc) was
calculated by using the equation below:
P
I0hkl
Ihkl
Tc P

I0hkl
Ihkl
Figure 2. Powder XRD pattern of (a) as prepared NiO obtained from

2:1 wt% of Ni(NO3)2 6H2O and dextrose, calcined for 1 h at different
temperatures of (b) 200, (c) 300, (d) 500, and (e) 700 8C
patterns were indexed to pure cubic structure with lattice

parameter of 4.177 A8 and its space group: Fm3m (225). They are
matching with the standard JCPDS card no. 04-0835, indicating
that the NiO particles are crystalline with face center cubic
structure. In Fig. 2a and b, the five main peaks appeared at 2u
range of 44.3, 51.6, 76.2, 92.7, and 98.38 corresponding to
characteristic peaks of metallic nickel (JCPDS card no.04-0850).
The other small peaks appeared at 2u values of 37.2, 43.3, 62.8,
75.4, 79.4, and 95.18 corresponding to pure NiO phase. Figure
2be reveals that as calcination temperature increased from 200
to 700 8C, the diffracted lines became sharper. This inferred that
the non-crystalline NiO nanoparticles were gradually converted to
crystalline. The calculated crystallite size, based on XRD data, was
in between 18 and 62 nm (Table 1). Further the NiO particles
obtained from 4:1 and 6:1 wt% ratio of Ni(NO3)2 6H2O and
dextrose were calcined at different temperatures. All the
above samples resulted in similar XRD patterns (plots are not
shown).
The preferred orientation of the NiO phase was estimated
from the X-ray data according to the methodology developed by
(2)
where I(hkl) is the diffraction line intensity of the (hkl)

reflection of NiO powder, SI(hkl) is the sum of the intensities of
all the diffraction lines monitored. The Io refers to intensity of the
reference NiO sample (JCPDS card No. 04-0835). Figure 3 shows
the texture coefficient of NiO sample obtained from 2:1 wt% ratio
of Ni(NO3)2 6H2O and dextrose calcined at different temperatures for 1 h. It can be seen that the majority of the NiO crystallites
are oriented parallel to the (200) plane.
The structural parameters for all the calcined samples
were refined using Rietveld refinement method. All the NiO
nanoparticles were crystallized in the cubic (bunsenite) structure
with space group of Fm3m (No. 225). The refined structural
parameters for NiO nanoparticles calcined at 700 8C for 1 h are
given in Table 2. The observed lattice parameters agree well with
the reported data in the standard JCPDS card No. 04-0835. The
observed, calculated, and the difference XRD patterns are shown
in Fig. 4. There is a good agreement between the observed and
calculated patterns. Further, there is no appreciable change in the
lattice parameters of low temperature calcined samples.
3.2 Thermal analysis
The TGA in air atmosphere was conducted for as-prepared NiO
powder to examine its phase formation during calcinations. The
as-prepared sample was heated in alumina crucible at a scanning
rate of 58/min and in the temperature range of 251000 8C.
Table 1. Crystallite sizes obtained by powder XRD patterns for samples

calcined at different temperatures
Temperature
(8C)
Crystallite size (nm)

Family of crystallographic planes {hkl}
{111} {002} {022} {113} {222} {004} Average
As-prepared
200
300
500
700
21
15
39
47
43
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16
31
62
40
48
13
12
24
30
79
26
32
14
36
105
11
13
19
22
53
21
32
31
20
41
18
23
32
33
62
Figure 3. Texture coefficient of NiO nanoparticles obtained from

2:1 wt% ratio of Ni(NO3)2 6H2O and dextrose calcined at different
temperatures for 1 h
447
448
Table 2. Rietveld refined structural parameters for NiO nanoparticles synthesized by solution combustion method
Atoms
Ni1
O1
Oxidation state
Wyckoff notations
Biso
Occupancy
2
2
(4a)
(4b)
0.0000
0.5000
0.0000
0.5000
0.0000
0.5000
0.020
0.500
1
1
Crystal system Cubic, Space group Fm3m (No. 225).

); Cell volume 72.99(4) (A
3).
Lattice parameters, a 4.1792(1) (A
2
Rfactors, Rp 6.19, Rwp 7.97, x 1.05, RBragg 1.19, RF 0.912.
Figure 5 shows the TGA of NiO sample obtained from 2:1 wt%
ratio of Ni(NO3)2 6H2O and dextrose. The thermogram showed
two distinct weight change regions with respect to temperature.
Initially in the first step, there is a gradual weight loss up to
340 8C and the second region (between 360 and 570 8C) showed
increase in weight. In the first step, loss in the mass of sample is

due to the removal of crystalline water of Ni(NO3)2 6H2O and
its conversion to Ni atoms; decomposition of dextrose molecules
into CO2, CO, and charred carbon particles which occurred at
different manner ended up to about 340 8C. The formation of
Ni is attributed to the oxygen deficiency due to lack of oxygen
partial pressure in the vicinity of thermal decomposition of
dextrose moieties liberating CO2 and CO. Interestingly, it was
found that the weight loss due to decomposition of
Ni(NO3)2 6H2O and dextrose stops at about 340 8C and
significant weight gain occurs from 360 to 570 8C. It is likely
that the latter weight gain reaction could be the result of
formation of NiO/Ni nanocomposite which in turn further
oxidized (in air/O2) due to extended heating beyond 360 8C. The
temperature 570 8C indicated the completion of the oxidation
process of Ni to NiO. After 570 8C the thermogram shows a
parallel line with temperature axis indicating high stability of
NiO nanoparticles.
3.3 SEM/EDX and TEM analysis
Figure 4. Observed, calculated, and the difference X-ray diffraction

patterns for NiO sample obtained from 2:1 wt% of Ni(NO3)2 6H2O and
dextrose, calcined at 700 8C for 1 h
Figure 5. Thermograms of as prepared NiO particles obtained from

2:1 wt% ratio of Ni(NO3)2 6H2O and dextrose
The as-prepared compound resulted from 2:1 wt% ratio of

Ni(NO3)2 6H2O and dextrose was calcined for 1 h at 300, 500,
and 700 8C. The scanning electron micrographs of as-prepared
and calcined compounds are shown in Fig. 6. The SEM images of
NiO nanoparticles showed different morphologies. The SEM
images of as-prepared NiO compound exhibited irregular,
nonporous, and uniform flakes like structure (Fig. 6a), whereas
the calcined NiO at 300 8C showed uniformly distributed porous
structure (Fig. 6b). The sample calcination at 500 8C showed
dense structure and crystals of cubic appearance (Fig. 6c). Figure
6d corresponds to the SEM image of sample calcined for 1 h at
700 8C and this shows cubic crystals with non-porous structure.
The flakes like structure in as-prepared NiO converted to porous
structure at 300 8C. This porous structure is due to out flow of
combustion products like CO2, CO, and NO2- resulting from
decomposition of nitrate salts and combustion of dextrose. The
as-prepared sample heated at 500 8C for 1 h possesses less degree
of porosity with uniform dense structure due to the growth of
NiO particles. However, the particles are uniform in size with
spherical grains, which are well connected to porous structure,
which is an essential for device applications such as supercapacitors. As the heat treatment temperature increases,
the particles tend to grow as expected. For instance at 500 and
700 8C, the size of the grains grows in the range of 2333 and
3462 nm, respectively. Nevertheless, at 700 8C, the shape of the
particles is cubic in nature and shows non uniform grain
distribution.
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Figure 6. SEM pictures of (a) as-prepared NiO [2:1 wt% of Ni(NO3)2 6H2O and dextrose] and calcined at different temperatures of (b) 300, (c) 500,
and (d) 700 8C
The stoichiometry of the sample was examined by the EDX

spectrum as shown in Fig. 7. The EDX spectra of sample calcined
at 500 8C showed Ni and O signals. The inset in Fig. 7 shows the
ratio of nickel and oxygen ion concentration, with weight ratio of
79% Ni and 21% O. This result infers the presence of 100% NiO
in the calcined product obtained at 500 8C.
The TEM images of NiO nanoparticles were obtained
from 2:1 wt% ratio (Fig. 8a) and 4:1 wt% ratio (Fig. 8b) of
Ni(NO3)2 6H2O and dextrose calcined at 500 8C for 1 h. After the
heat treatment at 500 8C for 1 h, the size of NiO particles are in the
range of 2333 nm and these values are matching with the
crystallite size values calculated from Debye-Scherrer equation. It
can be observed that the size range of NiO nanoparticles was 70
80 nm and they were mainly present in cubic structure and well
crystallized. The circles in Fig. 8a and b emphasize the particles
having a clear cubic shape.
3.4 Chemical status of Ni, O and C atoms in the NiO
nanoparticles
The surface composition and chemical states of NiO samples
were studied by XPS spectra. Figure 9 shows the XPS spectra of
NiO nanoparticles obtained from 2:1 wt% of Ni(NO3)2 6H2O and
dextrose calcined at 500 8C for 1 h. It can be seen that the whole
region 01000 eV contains characteristic peaks of Ni2p, O1s, and
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Figure 7. EDX of NiO nanoparticles obtained from 2:1 wt% of

Ni(NO3)2 6H2O and dextrose calcined at 500 8C for 1 h
449
450
Figure 8. TEM images of NiO nanoparticles obtained from (a) 2:1 wt% of Ni(NO3)2 6H2O and dextrose, (b) 4:1 wt% of Ni(NO3)2 6H2O and dextrose
at 500 8C for 1 h. Circles emphasize the cubic feature of the nanoparticles
survey spectra (Fig. 9ac). The Ni2p signal could be deconvoluted

into six peaks (Fig. 9a). The binding energies at 853.6 and
854.7 eV are attributed to the Ni2p3/2 and the 872.1 and 878.7 eV
are attributed to Ni2p1/2 peaks, which are very close to the data for
Ni (2p) in NiO. The gap between Ni2p1/2 and Ni2p3/2 level was
17.5 eV, which is approximately the same as in standard spectrum
of Ni and the peak at 853.7 eV was assigned to Ni2 state in NiO,
and peak positions are also close to the value of pure NiO
(854.2 eV) with a little shift to the higher binding energy. The
peaks at 860.4 and 865.5 eV correspond to the satellite peaks of
Ni2p3/2 and Ni2p1/2, respectively. The O1s region was asymmetric (Fig. 9b), it indicates that at least two oxygen species are
present in vicinity of the region. The peak at about 529.0 eV was
due to oxygen present in the crystalline NiO nanoparticles,
Figure 9. Ni (2p) core level XPS of a pure NiO, (a) binding energy spectrum for Ni2p, (b) binding energy spectrum for O1s, and (c) survey spectra. Inset
shows the binding energy spectrum for C1s
www.matcorr.com
whereas the peak at about 531.4 eV was due to chemisorbed

oxygen caused by surface hydroxyl. The peak area of Ni(2p) and
O(1s) cores was measured and it was used to calculate the
chemical composition of the sample. The survey spectra of NiO
nanoparticles was shown in Fig. 9c, the binding energies reported
here are with reference to C(1s) at 284.5 eV and are accurate
within 0.1 eV. The Ni2p core level spectra consist of two
separated features 852.9 and 879.6 eV, the O1s line was located
at 528.2 eV and it is narrow, asymmetric in nature, and C1s peak
was visible and it is located at 285.6 eV. The main impurity
element is carbon, which was introduced in the form of CO and
CO2 gas products produced from decomposition of dextrose. The
quantification of the peaks giving the atomic ratio of Ni and O is
nearly 1:1. Thus the XPS results clearly proved that the sample is
composed of NiO.
3.5 FT-IR spectroscopy
The FT-IR spectra of as-prepared and calcined NiO powder for 1 h at
300 and 500 8C are shown in Fig. 10. The absorption band centered
at 3449 cm1 was attributed to the OH bond stretching vibrations
and the band near 1632 cm1 was assigned to HOH bending
vibrations. These vibrations are the evidence for the existence of
water in the as-prepared compound (Fig. 10a). It is interesting to
note the two weak bands at 2930 and 2853 cm1 in as-prepared and
calcined (300 8C) compound corresponding to the CH stretching
modes of dextrose carbon chain, which indicates that its molecules
were present on the surface of NiO nanoparticles. The band near at
2362 cm1 confirms the presence of bending vibrations of the
intercalated O C O species produced by the dextrose decomposition in the initial process of preparation. The weak bands at 664 and
761 cm1 appearing in IR spectrum of as-prepared and calcined
(300 8C) compound indicates the presence of stretching and
bending vibrations of the intercalated CO species and it disappears
upon thermal treatment as shown in Fig. 10c. Furthermore, the
strong absorption band around 431 cm1 was assigned to NiO
Figure 10. FT-IR spectra of (a) as prepared NiO obtained from 2:1 wt%
of Ni(NO3)2 6H2O and dextrose and calcined for 1 h at different
temperatures of (b) 300 and (c) 500 8C
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stretching vibration, indicating the presence of NiO structure

presented in calcined compounds (Fig. 10b and c). This indicates
the presence of NiO nanoparticles in calcined compounds.
3.6 UVVis spectroscopy
The UVVis spectra of as-prepared (generated from combustion
of 2:1 wt% of Ni(NO3)2 6H2O and dextrose) and calcined NiO
powder for 1 h at different temperatures of 200, 300, 500, and
700 8C are shown in Fig. 11. Also the as-prepared NiO samples
were calcined for different intervals of 2, 4, 6, 8, and 10 h at 100 8C
and their respective UVVis absorption spectra are shown in Fig.
12. For recording UVVis spectra, the sample of NiO solution was
prepared by ultrasonically dispersing them in absolute ethanol.
All the absorption peaks in Fig. 11 correspond to NiO sample
calcined at different temperatures showing the strong absorption
in the wavelength range of 289.9292 nm. As the temperature of
Figure 11. UVVis spectra of (a) as prepared NiO precursor obtained

from 2:1 wt% of Ni(NO3)2 6H2O and dextrose calcined at different
temperatures for 1 h (b) 200, (c) 300, (d) 500, and (e) 700 8C
Figure 12. UVVis spectra of NiO nanoparticles obtained from 2:1 wt%
of Ni(NO3)2 6H2O and dextrose calcined at 100 8C for different hours
(a) 2, (b) 4, (c) 6, (d) 8, and (e) 10 h
451
452
calcination raised to 200 8C the sample showed red shift

equivalent to 2 nm, whereas the temperature of calcination
raised to 300 8C the absorption peak appears at 291.4 nm.
However, the samples calcined at 500 and 700 8C show still less
wavelengths which appeared at 291.1 and 289.5 nm. It infers the
UV absorption oscillates between the wavelengths of 289.5
292 nm. The NiO particles growth will take place when the
sample is calcined up to 200 8C and the corresponding absorption
band (lmax) increases from 289.9 to 292 nm. The band gap (Eg) of
NiO nanoparticles was calculated by using the formula Eg hc/l,
where h Plancks constant, c velocity of light, and
l wavelength. It is noticed from Fig. 11ac that when the
temperature of calcination increased to 200 8C, the corresponding
band gap was 4.24 eV as against 4.27 eV of as-prepared NiO. There
is a small red shift in this region with the increase of particle size.
Figure 11df picturizes the UV absorption profiles generated for
the samples calcined at 300, 500, and 700 8C, the corresponding
band gap was found to be 4.254.28 eV. Figure 12 shows UV
absorption peaks for the samples calcined for different hours at
100 8C. It was noticed that all the absorption peaks appear at
almost the same wavelength of 291 nm and the corresponding
band gap will be 4.26 eV. It implies that the calcination time has
no effect on the optical absorption bands, whereas calcination
temperature influences the optical absorption a little.
4 Preparation of ZnNiO composite coating

The plating bath was prepared by dissolving 180 g/L ZnSO4, 30 g/
L Na2SO4, 10 g/L NaCl, 1.5 mM/L sodium lauryl sulfate (SLS)
(Himedia AR, India), and 1 g/L NiO in millipore water. The pH of
the solution was adjusted to 2.5. The operating parameters and
optimum bath composition are shown in Table 3. The bath
solution containing 1 g/L NiO particles of 33 nm size range was
prepared and stirred for 24 h. The mild steel plates (cathode) were
polished mechanically and degreased with trichloroethylene in a
degreaser plant followed by water wash. These plates were dipped
in 10% HCl for a few seconds and finally rinsed with water. The
zinc plate was used as anode and its surface was activated by
dipping in 5% HCl for a few seconds followed by water wash. The
electrodeposition was carried out at current density of 3 A/dm2
Table 3. Bath composition and operating parameters
Bath
composition
Concentration
Operating conditions
ZnSO4
Na2SO4
NaCl
SLS
NiO Particle
180 g/L
30 g/L
10 g/L
1.5 mM
1 g/L
Anode: Zinc plate (99.99% pure)

Cathode: Mild steel plate
Current density: 3 A/dm2
Plating time: 10 min
Stirring speed: 300 rpm
pH: 2.5, Temperature: 298 K
for 20 min under stirred condition with magnetic stirrer speed of

300 rpm. The coatings were characterized by SEM images and the
corrosion studies were carried out to examine the coatings of Zn
and ZnNiO.
The electrochemical measurements were performed using the
CHI660C electrochemical work station (CH Instruments USA).
For all (polarization, Tafel and EIS) measurements, a conventional
three-electrode cell with platinum as counter electrode, saturated
calomel as reference electrode, and specimen under investigation
as working electrode were used. The electrolyte was 3.5% NaCl
solution. The anodic polarization and the Tafel curves were
recorded at a sweep rate of 0.1 mV/s and 0.01 V/s, respectively in
3.5 wt% NaCl at room temperature using pure Zn and ZnNiO
composite coated specimens of 1 cm2 area. The electrochemical
impedance measurements for both pure Zn and composite coated
specimens were recorded using frequency response analyzer (FRA)
and the spectrum was recorded in the frequency range from
100 kHz10 mHz, and sinusoidal voltage excitation with amplitude
5 mV in 3.5 wt% NaCl. In order to establish the equilibrium
potential, the coated specimens were immersed in 3.5 wt% NaCl
solution for about 45 min before subjecting them to impedance
measurement. After each experiment, the impedance data were
displayed as Nyquist plot. The morphological study of coated
samples without and with NiO particles was undertaken by
scanning electron microscopy (SEM).
4.1 Surface morphology
Figure 13a and b shows the SEM images of pure zinc coated and
composite coated samples, respectively. The crystallite size
Figure 13. SEM images of (a) Zn and (b) ZnNiO composite coatings
www.matcorr.com
Figure 14. Anodic polarization curves of Zn coating and ZnNiO

composite in 3.5 wt % NaCl solution
(Scherrer equation) of the composite coated sample was smaller

than the pure zinc coated sample. In pure zinc coated sample, the
crystals of different size were oriented randomly and there was no
size uniformity (Fig. 13a). But in composite coated sample, more
uniform crystals were observed (Fig. 13b).
4.2 Electrochemical studies (corrosion rate
measurements)
4.2.1 Anodic polarization
The anodic polarization experiments were carried out for both Zn
and ZnNiO coatings and the curves are given in Fig. 14. For
generating ZnNiO composite coating the bath solution as in
Table 3, whereas for pure zinc coating the same bath solution
without NiO was employed. The polarization behavior of Zn and
ZnNiO coatings were examined in 3.5% NaCl solution in the
potential range 1.6 to 0.4 V. The curve (a) in Fig. 14 represents
the polarization behavior of bare zinc coating, whereas curve (b)
represents the polarization behavior of ZnNiO composite
coating generated from bath solutions (Table 3) showing larger
shift in potential toward positive direction or noble direction. This
shift of potential toward positive direction indicated the noble
character of ZnNiO composite coating than bare zinc coating.
The potential shift further indicates that there is a requirement of
high energy for the dissolution of zinc from ZnNiO composite
coating. Usually the bare zinc coating possesses defects, cracks,
gaps, crevices, and microholes, which were generally larger than
micron size. These microholes are the active sites for dissolution
of zinc during corrosion. During composite coating process, the
nanoparticles avoid the formation of these defects and also they
Figure 15. Tafel curves of Zn and ZnNiO coatings in 3.5 wt% NaCl
solution
enter and fill these holes [68]. Therefore, the anodic polarization
results indicated smaller anodic activity in composite coatings
than pure zinc coating. Hence, composites exhibit better
corrosion protection than bare zinc coating.
4.2.2 Corrosion rate by Tafel method
The anodic polarization profiles inferred the material dissolution
behavior in aggressive media. The Tafel plots were used to
quantify the polarization results and it gives corrosion rate
directly. The Tafel plots are shown in Fig. 15. The working
electrode used was bare zinc and composite coating. The
measurement was carried out in 3.5% NaCl solution. All the
results were measured at OCP of respective coatings. The Tafel
parameters and other electrokinetic parameters of coatings are
given in Table 4. The curve (a) in Fig. 15 represents the
polarization behavior of bare zinc coating and curve (b)
corresponds to ZnNiO coating. The corrosion potential value
of composite coating was slightly positive when compared to that
of bare zinc coating. This evidenced the noble character of
ZnNiO composite coating and the amount of NiO particles in
plating bath generated good deposit.
4.2.3 Electrochemical impedance studies
The impedance diagrams of composite coated and zinc coated
samples are shown in Fig. 16 and were displayed as typical
Nyquist plots (ZRe/ZIm). These Nyquist plots correspond to pure
zinc coating and ZnNiO coating immersed in non-deaerated
3.5% NaCl solution measured at the frequency range of 0.1 Hz
100 kHz. The Rp values of bare zinc and composite coating
Table 4. Values of corrosion parameters
Specimen
Zinc coating
ZnNiO coating
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Ecorr (V)
Icorr (mA/cm2)
ba (mv)
bc (mv)
Corrosion rate (mg/h)
1.041
1.020
48.00
6.229
18.109
22.449
4.502
1.824
58.56
7.599
453
454
Figure 16. Impedance spectra of (a) Zn and ZnNiO coatings in 3.5 wt% NaCl solution. (b) Equivalent circuit
Table 5. Electrochemical impedance analysis data
Specimen
Zinc coating
ZnNiO coating
Re (mV)
Cf (mF)
Rf (V)
Cdl (mF)
Rct (V)
CF (XmF)
RF (V)
Rp (kV)
0.0212
1.28 105
0.3611
0.3194
105.5
93.06
6.516
3.736
138.8
659.3
1806.0
482.90
227.1
917.5
0.471
1.669
sample in Table 5 indicated that the composite coating possesses

higher Rp than pure zinc coating and inferred higher protection
ability or higher corrosion resistance property.
5 Conclusions
In the present work, the nanosized NiO particles were
successfully generated by solution-combustion method using
2:1 wt% ratio of Ni(NO3)2 6H2O and dextrose without using
templates or surfactants. The size of NiO increased from 18 to
62 nm as calcinations temperature raises from 200 to 700 8C.
The Rietveld refinement method showed similar lattice
parameters for all NiO samples calcined at different temperatures. TGA revealed that the sample contains NO2- , CO, CO2, and
H2O. The EDX spectrum showed the presence of 100% NiO in
the calcined compound. The SEM analysis shows that the
particles morphology was cubic structure. The TEM images
confirmed the cubic shape of NiO nanoparticles and that they
are well crystallized in the nanosize of 7080 on nanometer
scale. XPS analysis showed that the NiO nanoparticles are
present in Ni2p, O1s, and trace amount of C1s. The FT-IR
spectrum shows the existence of OH-, CO2, and CO groups in
uncalcined sample. The band gap was higher for synthesized
NiO particles than their bulk counterparts. The ZnNiO
composite thin film was successfully generated on mild steel
and exhibited good corrosion resistance property than pure Zn
coating. Thus, the synthesis of NiO nanoparticles by solution
combustion method is simple, fast, economical, and ecofriendly in nature.
Acknowledgements: The authors thank Kuvempu University,

Karnataka, India for providing the lab facilities to bring about this
work, and thank Prof. M. S. Hegde, SSCU, for XPS measurements
and also Prof. A. J. Bhattacharyya, SSCU, for useful discussion,
IISc Bangalore. KGC and TVV thank, respectively the CSIR, for
SRF [Sanction No. 09/908(0002) 2K9-EMR-I], and DST, NewDelhi [No.S.R/S3/ME/014/2007], Government of India (GOI) for
research grant.
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(Received: October 11, 2010)
(Accepted: January 13, 2011)
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Industry Milestone: GEs Heavy
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during the steel production process and
new revenues generated by the sale of
some of the power plants electricity to the
local grid.
GEs fleet of heavy duty gas turbines
operating on low BTU fuels continues to
grow, as customers look to do more with
less.
GE Heavy Duty Gas Turbine Hours
Fired on Low BTU fuels
Experience by frame:
1 million hours on GE E-class turbines.
600,000 hours on GE B-class turbines.
400,000 hours on GE F-class turbines.
Experience by application:
450,000 hours at coal-based IGCC facilities.
860,000 hours at refineries.
700,000 hours at steel mills.
Experience by region/country:
250,000 hours at facilities operating
across Asia.
280,000 hours at facilities operating
across North America.
More than 1 million hours at facilities
operating across Europe.
For more information, please contact:
Andrew Williams, GE Corporate, Director
Media Relations Work Tel.: 1 212 850
5867, andrew. williams2@ge.com, www.
ge.com
CNE0812
www.matcorr.com
Books
Metallurgy and Corrosion Control in Oil
and Gas Production, Robert Heidersbach,
281 pages, 357 figures, 89 tables, John
Wiley & Sons, Hoboken, 2011, s 91,
ISBN: 978-0-470-24848-5
This extensive, large book, dealing

with a wide range of information, is a
timely contribution to the oil and gas
industry, an energy sector of the world
economy. The text is organized as a
practical guide for corrosion experts and
practitioners, as well for professionals
designing, constructing, operating and
maintaining facilities, installations and
equipment in oil and gas production. It
starts with a concise evaluation of the
critical aspects of costs, safety, environmental damage and corrosion control and
continues with the fundamentals of the
chemistry of corrosion, covering the electrochemical basics of the corrosion process
and its mechanisms. Corrosion rates are
measured by weight loss, depth of penetration and applying cathodic and anodic
polarization plots. The text proceeds into
the corrosive environments encountered in
the oil and gas fields, which are usually
contaminated with salty water. Water is not
soluble in hydrocarbon but a separate water
phase impacts on corrosion.
The core of this volume appears in
chapters 6 and 5 focusing on the principal
engineering materials for fabrication
of the equipment employed in the
production of oil and gas: steel, stainless
steel, Ni-based alloys, titanium, copper
and aluminum. Then, the common
forms of corrosion, affecting this materials and their equipment are presented,
following the classical, widely accepted
classification of Prof. M. Fontana,
www.matcorr.com
Corrosion News
described in his famous book Corrosion

Engineering.
The methods and techniques for
corrosion control are discussed in chapter
6 including protective coatings: metallic
and nonmetallic coatings, paints and
linings; water treatment and corrosion
inhibition; types of cathodic protection by
sacrificial anodes and impressed current.
The British, NACE, ASTM and API
standards, applied in corrosion control
procedures, are listed. Most current
standards can be downloaded from the
internet.
Chapter 7 is concerned with inspection, monitoring and testing procedures:
invasive and noninvasive, conventional
and modern; visual and instrumental;
gravimetric and electrochemical, laboratory and field; all clearly explained and
easy to follow. The book ends with chapter
8 on oilfield equipment for drilling
and exploration, oil and gas wells and
wellhead equipment; pumps, pipes, heatexchangers, storage tanks; pipelines and
flow lines, fittings such as bolting and
fasteners.
This volume mentions plenty of
standards, specifications and designations
set by international and national organizations (including their acronyms). They
focus on corrosion-resistant materials,
aspects of materials and corrosion testing,
protection and control. This is displayed
through the book chapters, and also
listed in the index, facilitating their
accurate identification. The emphasis is
on their application in the oil and gas
industry to solve corrosion problems of
materials, equipment, installations and
facilities.
The reviewers, as chemical engineers
and corrosion professionals active in
corrosion research and environmental
and industrial corrosion control could
benefit from reading the sections devoted
to inspection to determine the conditions
of the field and plant equipment and
corrosion monitoring to decide about the
effectiveness of the corrosion control
techniques implemented, followed by a
detailed description of the numerous
monitoring probes for different methods
and techniques including the demonstration of their insertion in the production
facilities and plants. Particular types of
corrosion are addressed: microbiologically
influenced corrosion (MIC), influence of
the flow regime in pipelines with introduction of suitable sensors, probes to

detect hydrogen penetration into steel and
more. . .
If a second edition will be published,
as this book and its subject deserve, it
would be useful to add:
A glossary of terms related to oil and gas
production, industrial materials and
equipment, corrosion, scale and petroleum industry maintenance.
A list of the main oil and gas journals
and the scientific and practical journals
of materials and corrosion.
A chapter or a paragraph on natural,
shale-gas production, describing the
actual problems related to well drilling
with the use of chemical additives, the
layers of steel and cement installed; the
hydraulic fracturing of the rock formation (called fracking) and the possible
contamination of deep water aquifer, to
assure a safe responsible operation.
This workable guide should be used
by engineers and professionals working in
the different fields of the petroleum
industry: drilling, producing wells, pipelines management, refineries operation,
fuel transportation and facilities maintenance. University teachers, scientists and
researchers and in particular their undergraduate and postgraduate students, preparing their graduate theses will benefit
from reading, employing and owing this
well-organized volume.
CBE0912
Benjamin Valdez Salas, Michael Schorr
Wiener
Kinetics of Chemical Reactions Decoding Complexity, Guy Marin, Gregory S.
Yablonsky, 446 pages, Wiley VCH, Weinheim, 2011, 79 s, ISBN-13: 978-3-52731763-9
457
458
Corrosion News
Beside of the thermodynamic possibility of occurring reactions the kinetic of

these processes is very important. This
book deals with the kinetic aspects in
theory, experiment and practice.
After introducing the reader in the
complexity, types and history of kinetics 11
well structured chapters provide a good
insight into this matter.
The chapter Chemical Reactions
and Complexity deals with elementary
reactions, the differences between various
rate calculations and dimensioning of
certain parameters.
Within the next chapter concepts and
realizations of kinetic experiments are
described, like requirements, balances,
reactor classification and analysis.
The following chapter deals with
basics and complexity of linear algebra
for chemical kinetics.
Two chapters on Steady-State Chemical Kinetics introduce to the Graph
Theory and the Machinery Analysis.
Here is described how complex mechanisms can be presented graphically, how
reaction rates and equations can be
derived as well as how mechanisms can
be revealed based on steady-state kinetic
data.
After a chapter on Linear and Nonlinear Relaxation dealing with closed
systems, general concepts and with simplifications of non-steady state models, the
steady-state and dynamics of nonlinear
mechanisms are described by incorporating critical phenomena, experimental
facts to create ideal simple models.
The chapter Kinetic Polynomials
presents the principles, derivation and
properties, classic approximations and
simplifications as well as the application
of kinetic-polynomial theory results.
The ninth chapter Temporal Analysis of Products: Principles, Applications
and Theory describes its operation,
principles and the position among other
kinetic methods. Some special thoughts
are dedicated to quantitative and qualitative analysis.
The book ends with two chapters on
Decoding the Past and . . .future.
Here historical discourses are made to
important discoveries in the past, like
such made by Guldberg and Waage as well
as Vant Hoff discussing the confusion and
the attempts to understand the achieve-
ments, followed by some philosophic

thoughts to future tackling of kinetic
aspects.
Each chapter is structured in an
introduction, specials paragraphs and
conclusions. This facilitates the understandability of this sometimes very complex content.
Finally, this book fulfills its aim to be
a systematic presentation of the addressed
matter for the broad variety of chemistry
lecturers and students, graduate students,
physical chemists, chemical engineering
students and lecturers, physics students
and chemical engineers.
CBE1012
R. Baler
Conferences
Intergalva 2012
June 1015, 2012, Paris (France)
Intergalva is organised by European
General Galvanizers Association (EGGA)
and hosted by Galvazinc. The conference
covers technical, commercial and environmental topics for the general (batch) hot
dip galvanizing industry.
It continues the series that began in
1950 and was last held in Madrid in 2009.
The must-attend event for the worldwide
galvanizing industry.
Features of Intergalva 2012:
3-day conference programme with
simultaneous translation from and into
many international languages
Visits to galvanizing plants in France
Extensive trade exhibition
Exciting social programme
Sightseeing tours for accompanying
persons
Who Should Attend:
Owners, operators and managers of
galvanizing plants
Users of galvanized products
Corrosion specialists
Everybody who has to specify corrosion
protection for steel
Suppliers of equipment and services to
the galvanizing industry
Suppliers of zinc and zinc alloys to the
galvanizing

European General Galvanizers Association
Maybrook House, Godstone Road,
Caterham, Surrey CR3 6RE, United Kingdom, Tel.: 441883 331277, Fax: 441883
331287, mail@egga.com, www.egga.
com
CCE1712
17th International Workshop on

Electromagnetic Nondestructive
Evaluation - ENDE 2012
July 26August 1, 2012, Rio de Janeiro
(Brazil)
This will be the 17th in a series of
international workshops. Its aim is to
bring together engineers and scientists
from universities, research institutions
and industry who are active in research,
development and industrial applications
of Electromagnetic Nondestructive Evaluation.
Topics:
As in previous ENDE workshops, the
programme will be comprised of invited
lectures by prominent, academic and
industrial experts and contributed oral
presentations on:
New developments in electromagnetic
NDE
Characterization of materials
Advanced sensors and their novel
industrial applications of NDE
Analytical and numerical modeling of
electromagnetic phenomena
Solutions to NDE inverse problems
NDE of cracks
NDE of residual internal stresses, phase
transformations, and microstructures
such as precipitation, voids, vacancies
and interstitials
Biomedical applications of electromagnetic NDE
Associacao Brasileira de Ensaios Nao
Destrutivos e Inspecao - ABENDI / Sede:
Avenida Onze de Junho, 1317 - Vila
Clementino - 04041-054 - Sao Paulo SP,
Tel.: 11 5586-3199, - Fax: 11 5581-1164 abendi@abendi.org.br, ende2012@metalmat.
ufrj.br, www.ende2012.metalmat.ufrj.br/
welcome.html
CCE1812
www.matcorr.com
Nanofair 2012
June 1213, 2012, Dresden (Germany)
Following the highly successful
Nanofair conferences of the last years
which attracted delegates from all over the
world Nanofair 2012 again will bring
together the international community
of science and industry. Already
started in 2002 Nanofair is the most
established conference on nanotechnology in Europe and among the premier
events worldwide.
Under the slogan New Ideas for
Industry Nanofair as an international
conference will present a vital platform
for the exchange of ideas and the generation of initiatives between science and
www.matcorr.com
Corrosion News
industry. The focus of the conference

will be on nanotechnology in the fields
of materials and surfaces, life sciences,
energy, electronics as well as nanoanalytics.
Plenary lectures by internationally
renowned speakers and contributed oral
presentations will offer delegates excellent
opportunities to become acquainted with
the latest developments in this diverse
field.
A comprehensive poster session will
complement the technical program. Sufficient time will be available for discussions
on challenges and solutions, new materials and processes as well as with cooperation partners. An exhibition running
concurrently to the conference offers
excellent opportunities to promote technical interchange of information and to

present the latest in equipment, services
and materials for commercializing R&D
results.
Dresden with its unique alliance of
large scientific research institutes of
Fraunhofer, Max-Planck, Leibniz and
Helmholtz Association and the Technical
University of Dresden is proud of being
the host of the conference.
Fraunhofer IWS, Dr. Andreas Leson,
Winterbergstr. 28, 01277 Dresden,
Germany, Tel.: 49 351 83391-3317,
Fax: 49 351 83391-3314, www.iws.
fraunhofer.de
CCE1912
459
460
Corrosion News
Calendar of Events
New Entry
Conference/Workshop/Symposium
Fair
Course
June 2012
4. 6.6.
Lviv (Ukraine)
10. 15.6.
Corrosion 2012XI. International

Conference and Exhibition
Ukrainian Association of Corrosionists

Prof. V. Pokhmurskii
Lviv
Ukraine
corrosion2012@ipm.lviv.ua
www.corrosion2012.ipm.lviv.ua
Intergalva 2012
European General Galvanizers Association

Caterham
United Kingdom
email: mail@egga.com
www.intergalva.com
Paris (France)
11. 14.6.
Naples (Italy)
11. 14.6.
Stockholm
(Sweden)
12. 13.6.
11th Quantitative InfraRed

Thermography QIRT 2012
Concrete Structures for

Sustainable Community
Swedish Cement and Concrete Research Institute

Stockholm
Sweden
fib@fibstockholm2012.se
www.cbi.se
Nanofair 2012
Fraunhofer IWS
Dresden
Germany
nanofair@iws.fraunhofer.de
www.nanofair.com
O&S International Trade Fair for

Surface Treatments and Coatings
Deutsche Messe
Messe Stuttgart
Germany
www.messe-stuttgart.de
Dresden
(Germany)
12. 14.6.
Stuttgart
(Germany)
13. 15.6.
Rome (Italy)
Department of Aerospace Engineering

Naples
Italy
www.qirt2012.unina.it
6th International Conference on

Composites in Construction
Engineering (CICE)
` di Roma
Sapienza Universita
Giorgio Monti
Roma
Italy
info.dist@unina.it
www.cice2012.it
www.matcorr.com
17. 20.6.
Corrosion News
ENDE 2012
Rio de Janeiro
(Brazil)
17. 20.6.
Brescia (Italy)
Bond in Concrete 2012: Bond,

Anchorage, Detailing
Department of Civil Engineering, Architecture,

Land and Environment (DICATA)
Brescia
Italy
secretary@bondinconcrete2012.org
www.bondinconcrete2012.org
Ancona (Italy)
2nd European Conference on

Nanofilms (ECNF 2)
18. 21.6.
NDT 2012 Conference
Canadian Institute for NDE

Hamilton
Canada
events@cinde.ca
www.events.cinde.ca
ACHEMA 2012
DECHEMA e.V.
Frankfurt am Main
Germany
achema@dechema.de
www.achema.de
17. 21.6.
VINF - Virtual Institute on Nano Films

Angleur
Belgium
www.ecnf.eu
Toronto
(Canada)
18. 22.6.
Frankfurt
(Germany)
24. 28.6.
Breda
(Netherlands)
ICCG9 - The 9th International

Conference on Coatings on Glass
and Plastics
ICCG
Karel Spee
Karel.spee@tno.nl
www.iccg9.eu
July 2012
3. 6.7.
Dresden
(Germany)
6th European Workshop on

Structural Health Monitoring
Paris (France)
4th International Congress on

Construction History
10. 13.7.
LATINCORR 2012
3. 7.7.
Lima (Peru)
www.matcorr.com
German Society for Nondestructive Testing

(DGZfP)
Berlin
Germany
tagungen@dgzfp.de
www.ewshm2012.com
Construction History Society
C/o Library and Information Services Manager
The Chartered Institute of Building
Berkshire
United Kingdom
secretary@constructionhistory.co.uk
NACE International
comitetecnico@latincorr2012.org
www.latincorr2012.org
461
462
Corrosion News
15. 20.7.
Denver (USA)
22. 25.7.
Karlsruhe
(Germany)
23. 27.7.
39th Annual Review of Progress in

Quantitative Nondestructive
Evaluation (QNDE)
9th fib International PhD Symposium

in Civil Engineering
JUNIOR EUROMAT
Lausanne
(Switzerland)
28. 29.7.
Wuyishan
(China)
5th International Conference

on new dimensions in bridges
Center for Nondestructive Evaluation

Ames, Iowa
USA
cnde@cnde.iastate.edu
www.qndeprograms.org/2012/Conference2012.html
Institute of Concrete Structures and Building Materials
Karlsruhe Institute of Technology (KIT)
Karlsruhe
Germany
fib-phd@imb.kit.edu
www.fib-phd.imb.kit.edu
Deutsche Gesellschaft fu
r Materialkunde e.V.
Niels Parusel
Frankfurt Germany
junior-euromat@fems.org
www.dgm.de
CI-Premier Pte Ltd
Singapore
john@cipremier.com
www.cipremier.com/page.php?422
August 2012
19. 24.8.
Prague
(Czech Republic)
29. 31.8.
Singapore
(Singapore)
63rd Annual Meeting of the

International Society of
Electrochemistry (ISE)
37th Conference on Our World

in Concrete & Structures
International Society of Electrochemistry

Lausanne
Switzerland
events@ise-online.org
www.ise-online.org
CI-Premier
Singapore
ci-p@cipremier.com
www.cipremier.com
September
2012
5. 7.9.
Oslo
(Norway)
9. 13.9.
Nordic Steel Construction

Conference (NSCC)
Norwegian Steel Association

Oslo
Norway
post@stalforbund.com
www.nordicsteel2012.com
EUROCORR 2012
Corrosion Association Turkey

Necil Kurtkaya
necil.kurtkaya@gmail.com
www.korozyondernegi.org.tr/en/
www.eurocorr2012.org
Istanbul
(Turkey)
10. 14.9.
GarmischPartenkirchen
(Germany)

Plasma Surface Engineering
ische Forschungsgesellschaft Du
Europa
nne
Schichten e.V.
Dresden
Germany
pse2012@efds.org
www.pse-conferences.net/pse2012.html
www.matcorr.com
16. 22.9.
Corrosion News
Corrosion Technology Week 2012
NACE
CaLae McDermott
calae.mcdermott@nace.org
Cement and Concrete Science 2012
Queens University Belfast

Roslyn Barnes
Belfast
Northern Ireland, U.K.
cement@qub.ac.uk www.qub.ac.uk
New Orleans
(USA)
17. 18.9.
Belfast
(Northern
Ireland, UK)
17. 19.9.
Belfast
(Northern
Ireland, UK)
17. 19.9.
ICDCS 2012 3rd International

Conference on Durability of
Concrete Structures
Secretariat, IcDcS 2012 centre for Built

Environment Research
Queens University Belfast
Roslyn Barnes
Belfast
Northern Ireland, U.K.
cber-events@qub.ac.uk
www.qub.ac.uk/sites/ccs2012/
Electrochemistry 2012
t Mu
Technische Universita
nchen
Germany
tg@gdch.de
electrochemistry2012@tum.de
www.gdch.de/electrochemistry2012
Mu
nchen
(Germany)
19. 21.9.
18th IABSE Congress
IABSE
ETH Zurich
Zurich
Switzerland
secretariat@iabse.org
www.iabse.org
Seoul (Korea)
19. 21.9.
Frankfurt
(Germany)
21. 23.9.
Wuhan (China)
25. 27.9.
Darmstadt
(Germany)
EFC Workshop: Beyond Single

Oxidants
DECHEMA e.V.
Xueqing Wu
Frankfurt am Main
Germany
wu@dechema.de
www.dechema.de

Problematic Soils
CI-Premier Pte Ltd

Singapore
john@cipremier.com
www.cipremier.com
MSE 2012 - Materials Science and

Engineering
r Materialkunde e.V.
Frankfurt
Germany
mse@mse-congress.de
www.mse-congress.de
IALCCE 2012 Third International

Symposium on Life-Cycle Civil
Engineering
University of Natural Resources and Life Sciences

Institute for Structural Engineering
Vienna
Austria
ialcce2012@boku.ac.at
www.ialcce2012.org
October 2012
3. 6.10.
Vienna (Austria)
www.matcorr.com
463
464
Corrosion News
7. 10.10.
Atlanta,
Titanium 2011 87th Annual

Conference and Exhibition of the
International Titanium Association
Georgia (USA)
10. 11.10.
Join-ex 2012
Schweitechnische Zentralanstalt (SZA)

Wien
Austria
martina.leibl@sza.info
www.sza.info
EuroBLECH 2012
EuroBLECH 2012
St Albans, Herts
Great Britain
info@euroblech.com
www.euroblech.com
Cellmat conference 2012
r Materialkunde e.V. DGM
Frankfurt
Germany
dgm@dgm.de
www.dgm.de
NUCPERF 2012
CEA Saclay
Gif sur Yvette
France
NUCPERF2012@cea.fr
www.NUCPERF2012.fr
IC-SDCI International Conference

on Sustainable Development
of Critical Infrastructure
IABSE
ETH Zurich
Zurich
Switzerland
secretariat@iabse.org
www.iabse.org
Vienna
(Austria)
23. 27.10.
International Titanium Association

Jennifer Simpson
Broomfield
USA
conference@titanium.org
www.titanium.org
Hannover
(Germany)
November
2012
7. 9.11.
Dresden
(Germany)
12. 15.11.
Cadarache
(France)
15.11.
Shanghai
(China)
18. 23.11.
Maragogi-Al
(Brazil)
28.11.
Paris (France)
10th Symposium on Electrochemical

Methods in Corrosion Research
(EMCR-2012)
3rd International Symposium
Coil coated steel
Dr. Oscar R. Mattos

Federal University of Rio de Janeiro
Brazil
www.sites.poli.usp.br/org/emcr2012/
Institut de la Corrosion
Brest
France
www.institut-corrosion.fr
tomas.prosek@institut-corrosion.fr
March 2013
17. 21.3.
CORROSION 2013
Orlando (USA)
NACE International
firstservice@nace.org
www.nace.org
www.matcorr.com
Corrosion News
April 2013
22. 24.4.
Tel-Aviv
(Israel)
International Federation
for Structural Concrete
fib-Symposium
ORTRA LTD.
Tel-Aviv
Israel
fib2013@ortra.com
www.fib2013tel-aviv.co.il
IABSE 2013 Spring Conference
IABSE
Dick Stoelhorst
Bergambacht
Nederland
www.iabse2013rotterdam.nl/index
May 2013
6. 8.5.
Rotterdam
(The Netherlands)
12. 16.5.
Karlsruhe
(Germany)
2nd International Conference on

Materials for Energy
Congress Office
Claudia Martz
DECHEMA e.V.
Frankfurt am Main
Germany
info@enmat.de
www.enmat.de
September
2013
1. 5.9.
EUROCORR 2013
cnico
Instituto Superior Te
Lisboa
Portugal
secretariat@eurocorr2013.org
www.eurocorr2013.org/
Intelligent Materials
r
Materialkunde e.V. DGM
Frankfurt
Germany
dgm@dgm.de
www.dgm.de
Estoril (Portugal)
25. 27.9.
Kiel (Germany)
September
2014
8. 12.9.
EUROCORR 2014
Pisa (Italy)
23. 25.9.
Darmstadt
(Germany)
www.matcorr.com
MSE 2014 - Materials Science and

Engineering
r Materialkunde e.V. DGM
Frankfurt
Germany
dgm@dgm.de www.dgm.de
465
Korrosionsnachrichten
Neues aus
nden und
Verba
Firmen
bernimmt Online-Datenbank
Wiley u
Structurae
Integration ins Angebot des Verlags

Ernst & Sohn
Structurae ist eine der fuhrenden OnlineDatenbanken fur Ingenieurbauwerke
(www.structurae.de). Die jetzt erfolgte
bernahme durch John Wiley & Sons,
U
Inc (NYSE: JWa, JWb), entspricht der
langfristigen Strategie des Verlagshauses,
die Angebote fur seine Zielgruppen in
Bezug auf Umfang und Wertigkeit kontinuierlich auszubauen. Adressaten in Forschung und Lehre sollen ebenso wie
professionelle Anwender durch die Inhalte
und Dienste der Wiley-Unternehmen jederzeit die optimale Unterstutzung fur ihre
Arbeit erhalten ob bei der Informationsbeschaffung, bei Lehr- und Lernmitteln
oder im Hinblick auf methodische Fragen.
Durch die Verbindung von Structurae mit den Angeboten unseres Berliner
Tochterunternehmens Ernst & Sohn, dem
fuhrenden Fachverlag fur die Baubranche
im deutschsprachigen Raum, schaffen wir
ein Portfolio, das Bauingenieuren, Architekten, Lehrenden und Praktikern der
Bauindustrie auf der ganzen Welt hochwertige, umfassende und losungsorientierte Ressourcen fur ihre tagliche Arbeit
bietet in Print-Produkten wie in OnlineAngeboten. Dabei bilden die Inhalte,
Werte und Kontakte beider Firmen die
Grundlage fur ein attraktives Leistungsspektrum, sagt Jon Walmsley, VP und
Managing Director, Physical Sciences,
Wiley-Blackwell.
Karin Lang, Geschaftsfuhrerin von
Ernst & Sohn, fugt hinzu: Diese Akquisition ist fur uns in zweierlei Hinsicht
strategisch bedeutsam. Zum einen stellt
sie eine magebliche Erweiterung unse-
www.matcorr.com
res Angebotes im Online-Bereich dar und

flankiert so die erfolgreichen PrintProdukte wie Beton-Kalender, StahlbauKalender und Titel wie Mechanised Shield
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Mit uber einer Million Seitenaufrufen pro Monat ist Structurae die weltweit grote Datenbank fur Ingenieurbauwerke. Sie ist in drei Sprachen
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Ressourcen verbinden und so diese einmalige Datenbank permanent weiterentwickeln und erganzen. Die User durfen
sich auf neue Produkte und Features
ebenso freuen wie auf praktische Losungsansatze fur den Alltag des Bauingenieurs.
Fur weitere Information wenden Sie
sich bitte an: Wilhelm Ernst & Sohn
Verlag fur Architektur und technische
Wissenschaften GmbH & Co. KG, Karin
Lang, Geschaftsfuhrerin, Rotherstrae 21,
10245 Berlin, Tel. 4930 47031 290, Karin.

lang@wiley.com, www.ernst-und-sohn.de
CND0712
Zink, ein nachhaltiger Werkstoff rlich - lebenswichtig Natu

vielseitig - recycelbar
Zink ist nicht nur der Basiswerkstoff fur
das Feuerverzinken, sondern ein naturlich vorkommendes Multitalent. Es ist fur
Menschen, Tiere und Pflanzen lebensnotwendig und wird in der Technik
vielfaltig eingesetzt.
Zink ist naturlich
Als ein naturlicher und wesentlicher
Bestandteil der Erdkruste und unserer
Umwelt kommt Zink in Gesteinen, Boden, Luft, Wasser und in der Biosphare
vor. Regen, Schnee, Eis, Sonne und Wind
bewirken die Erosion von zinkhaltigem
Gestein und Boden. Wind und Wasser
tragen kleinste Mengen von Zink in Seen,
Flusse und Meer. Zink kommt in unterschiedlicher Konzentration in der Natur
vor. Die Zinkmenge in der Erdkruste liegt
beispielsweise zwischen 10 und 300
Milligramm pro Kilogramm. Das Zinkvorkommen in Flussen variiert zwischen
weniger als 10 und mehr als 200 Mikrogramm pro Liter. Die Mengen variieren
nach Ort und Jahreszeit. So kommt es
beispielsweise im Herbst durch fallendes
Laub, das Zink enthalt, zu einem saisonalen Anstieg der Zinkwerte in Boden
und Wassern. Weltweit gibt es gigantische
Zinkvorkommen. Schatzungen zufolge
enthalt die erste Meile der Erdkruste
224.000.000 Millionen Tonnen Zink. Weitere 15 Millionen Tonnen befinden sich
im Meeresboden, und jede Kubikmeile
Meereswasser enthalt etwa 1 Tonne.
Zink ist lebenswichtig
Zink ist ein lebenswichtiges Spurenelement fur den Menschen. Es aktiviert
das Korperwachstum und ist unerlasslich
fur die korperliche und neurologische
Entwicklung von Kindern. Zink ist Bestandteil von uber 300 Enzymen und
beeinflusst die Hormone. Zudem beschleunigt Zink die Zellteilung und starkt
das Immunsystem. Zink ist notwendig fur
den Schutz des Korpers vor Krankheiten
und bei der Abwehr von Infektionen. Es
kann beispielsweise die Dauer und die
Schwere einer gewohnlichen Grippe
verringern und Durchfallerkrankungen
stoppen.
Zinkmangel ist ein Problem
Etwa ein Drittel der Erdbevolkerung
nimmt mit der Nahrung zu wenig Zink
auf.
Zinkmangel stellt eines der groten
Gesundheitsrisiken in Entwicklungslandern dar. Ein geschwachtes Immunsystem und eine erhohte Anfalligkeit fur
Durchfall und Erkrankungen wie Lungenentzundung und Malaria sind die Folge.
Zinkmangel beeintrachtigt zudem die
korperliche und geistige Entwicklung
von Kindern.
Auch fur Pflanzen ist Zinkmangel ein
Problem. Einer Studie der Ernahrungsund Landwirtschaftsorganisation der Vereinten Nationen (FAO) zufolge, weisen
etwa 50 Prozent der fur die Getreideproduktion landwirtschaftlich genutzten
Boden weltweit einen Zinkmangel auf.
Zinkmangel gilt als der kritischste Mikronahrstoffmangel bei Nutzpflanzen, da es
sich bei Zink um eines der acht Spurenelemente handelt, die Pflanzen fur ein
normales Wachstum benotigen. Obwohl
es nur in kleinen Konzentrationen benotigt wird, spielt Zink eine wichtige Rolle
bei Vorgangen wie der Photosynthese und
der Proteinsynthese.
Zink ist vielseitig
Zink wird unter anderem in der
Technik und Medizin verwendet. Eigenschaften wie die gute Formbarkeit,
die Legierungsfahigkeit, der niedrige
Schmelzpunkt, die Gieeigenschaften
und die Korrosionsbestandigkeit eroffnen
dem Metall Zink eine Fulle von Einsatzmoglichkeiten. Weltweit werden jahrlich
mehr als 11 Millionen Tonnen Zink
abgebaut. Rund 50 Prozent dieses Gesamtvolumens werden fur die verschiedenen Verzinkungsverfahren eingesetzt. Etwa 17 Prozent werden fur die Herstellung
von Messing und Bronze verwendet.
Weitere 17 Prozent gehen in die Produk-
tion zinkhaltiger Legierungen ein, hauptsachlich fur die Zinkdruckgussindustrie.

6 Prozent des weltweit eingesetzten Zinks
werden als Zinkblech an Dach und
Fassade sowie zur Entwasserung eingesetzt. Etwa die gleiche Menge wird fur die
Herstellung von Zinkverbindungen genutzt, aus denen unter anderem medizinische und kosmetische Produkte produziert werden.
Zink ist recycelbar
Zink kann beliebig oft ohne Qualitatsverlust recycelt werden. Mehr als 90 Prozent
der verfugbaren Zinkprodukte werden
heute recycelt. Etwa 60 Prozent des weltweit
produzierten Zinks werden derzeit aus
abgebauten Erzen gewonnen. Die verbleibenden 40 Prozent stammen aus wiederverwertetem Zink oder Sekundarzink. Der
Recyclinganteil erhoht sich entsprechend
der Zunahme der Zinkproduktion und
durch Innovationen bei Recyclingverfahren
in jedem Jahr. Die Zinkmengen, die zum
Recycling zur Verfugung stehen, variieren
bedingt durch die lange Lebensdauer zinkhaltiger Produkte, die nicht selten erst nach
weit uber 50 Jahren zum Recycling zur
Verfugung stehen.
Fazit
Zink ist ein naturliches und lebensnotwendiges Element. Aufgrund seiner
herausragenden Werkstoffeigenschaften
kann Zink vielfaltig in Medizin und
Technik eingesetzt werden. Zink ist
beliebig oft recycelbar und qualifiziert
sich als extrem nachhaltiges Metall.
Weitere Informationen enthalt die Broschure Zink - ein nachhaltiger Werkstoff der International Zinc Association,
die als Download unter www.goo.gl/
gw5bW zur Verfugung steht.
Abb. 1: Weltweite Zinkreserven 2009

(Quelle: USGS/ILZSG)
Abb. 2: Weltweit nachweisbarer Zinkmangel bei Menschen (Quelle: Black

et al, 2008)
sich bitte an: Industrieverband Feuerverzinken e.V., Holger Glinde, Sohnstr. 66,
40237 Dusseldorf, Tel.: 49 211/6907650,
Fax: 49 211/689599, holger.glinde@
feuerverzinken.com
CND0812
Ein starkes Trio DECHEMA in neuer

Struktur
Mit der Ausgrundung der DECHEMA
bergabe
Ausstellungs-GmbH und der U
des Karl-Winnacker-Instituts an die Stiftung DECHEMA-Forschungsinstitut ist
die Neustrukturierung der DECHEMA
vollzogen.
Kunftig arbeiten drei starke unabhangige Partner Seite an Seite, erklart
Prof. Dr. Kurt Wagemann, Geschaftsfuhrer
der DECHEMA e.V. Durch die Ausrichtung an den jeweiligen Kernkompetenzen konnen wir so noch besser fur
unsere Mitglieder, Partner und Kunden
aktiv sein. Die DECHEMA Gesellschaft
fur chemische Technik und Biotechnologie e.V. kummert sich weiterhin um die
Belange ihrer Mitglieder, betreut u.a. etwa
100 themenbezogene Gremien und ist
fur die Organisation von jahrlich 50
Tagungen, darunter auch den ACHEMAKongress, zustandig.
Die Stiftung DECHEMA-Forschungsinstitut wird sich zukunftig unter der
Leitung von Prof. Dr.-Ing. Michael Schutze
und PD Dr. Jens Schrader ganz auf die
Entwicklung nachhaltiger Technologien
konzentrieren. Dazu nutzen wir unsere
uber lange Jahre aufgebaute Kompetenz in
chemischer Technik, Elektrochemie, Werkstoffwissenschaften und Biotechnologie,
erklart Schutze. Wir danken allen
Stiftern, die diesen Schritt moglich
gemacht haben.
www.matcorr.com
Die Stiftung DECHEMA-Forschungsinstitut und die DECHEMA e.V. sind

Anteilseigner der DECHEMA Ausstellungs-GmbH. Diese organisiert zukunftig
die Ausstellung bei der weltweit groten
Chemiemesse ACHEMA und der in
Beijing stattfindenden AchemAsia. Wir
arbeiten daruber hinaus aber auch an der
Entwicklung neuer Themen im Ausstellungsbereich, erlautert Dr.-Ing. Thomas
Scheuring, Geschaftsfuhrer der DECHEMA Ausstellungs-GmbH. Durch die neue
Struktur eroffnen sich neue Handlungsspielraume, die wir nutzen wollen.
sich bitte an: DECHEMA e.V., Dr. Kathrin
Ruebberdt, Theodor-Heuss-Allee 25, 60486
Frankfurt, Tel.: 4969 7564-277, Fax
4969 7564-272, presse@dechema.de,
www.dechema.de
CND0912
cher
Bu
gkabelbru
cken - 40 Jahre
Schra
Erfahrung weltweit,
Holger Svensson, Verlag Ernst & Sohn,
2011, 458 Seiten, 1265 Abbildungen, mit 2
CDs, 129 Euro, ISBN-13: 978-3-43302977-0
Unter dem Titel Schragkabelbrucken

hat Holger Svensson seinen einzigartigen
Ruckblick auf 40 Jahre Grobruckenbau weltweit dokumentiert. Er selbst hat noch
bei Professor Leonhardt an der technischen Universitat Stuttgart studiert und
war seit 1972 im Ingenieurburo Leonhardt, Andra und Partner (LAP) fur
Entwurf und Prufung von Grobrucken,
insbesondere fur Schragkabelbrucken
zustandig.
www.matcorr.com
Der Autor hat das Buch in 7 Kapitel

unterteilt, die von der Einfuhrung in die
konstruktiven Grundlagen uber die Entwicklung von Schragkabelbrucken, Seile
und Kabel, Bemessung und Montage zu
Ausfuhrungsbeispielen und bis hin zum
Ausblick alle interessanten Fragen aus der
Welt der Schragkabelbrucken beantworten. Zahlreiche einzigartige Farbfotos und
Grafiken illustrieren das Buch, da getreu
berzeugung des Autors, ein gutes
der U
Bild mehr sagt als eine noch so gute
Beschreibung.
Im Kapitel 1 fuhrt Holger Svensson
seinen Leser neben den konstruktiven
Grundlagen in seine 10 wichtigsten
asthetischen Regeln fur das asthetische
Entwerfen von Brucken ein. Er pladiert
fur ein klares Tragsystem, gute Proportionen, gute Ordnung, gute Einpassung in
die Umgebung, geeignete Baustoffe,
durchdachte Farbgebung, Erkennbarkeit
des Kraftflusses, Beleuchtung und Einfachheit. Der Leser ist nun gespannt auf
das, was in den Hauptartikeln zur Entwicklung der Bauweise (Kapitel 2) mit
Stahl-, Beton- oder Verbundbalken, zu
Vor- und Nachteilen der verschiedensten
Kabel und Seilen (Kapitel 3) mit zahlreichen Anwendungsbeispielen, einschlielich der Kabeldynamik und der
Kabelmontage sowie zur Vorberechnung
der Brucke (Kapitel 4) als Gesamtsystem
bzw. der einzelnen Komponenten, z.B.
gegen Schiffsanprall folgt. Im Kapitel 5
wird die Montage der montagefreundlichen Schragkabelbrucken mit Blick auf
die Pylone und Balken aus allen Materialien systematisch dargestellt. Neben den
Verfahren werden auch die unterschiedlichsten Montagelastfalle betrachtet. Hohepunkt des Buches sind die reich
bebilderten Ausfuhrungsbeispiele (Kapitel 6) in allen Teilen der Welt. Dieses
Kapitel bietet nie dagewesene Einblicke in
Voruberlegungen, Aufbau und Bauausfuhrung konkreter Bruckenbauwerke. Die
Komplexizitat der Montagezustande ist
zum Teil bereits wahrend des Baus mit
berwachungssystemen verHilfe von U
folgt worden. Zur Ausfuhrung gehort
bei Holger Svensson z.B. auch die detaillierte Darstellung eines baubegleitenden
Messprogramms am Beispiel der Strelasundbrucke. Neben Wind, Temperatur
und statischen Belastungstests wurden
Pylon-, Seil- und Fupunktschwingungen
bergangskonstruktionen
sowie die U
messtechnisch uberwacht. Mit einem

kurzen Ausblick (Kapitel 7) auf die geplante Messinabrucke beschliet Holger
Svensson seinen auergewohnlich interessanten Ausflug durch sein Leben als
Schragkabelbruckenspezialist.
Das Buch mit seiner Fulle an Informationen uber Schragkabelbrucken, einschlielich zweier CD mit Vorlesungen,
ist ein Muss fur den Bucherschrank des
bruckeninteressierten Laien, des Studierenden und vor allem des Bruckenbauingenieurs.
CBD1012
R. Helmerich
Was ist falsch am falschen Rembrandt?
- Mit High-Tech den Ratseln der Kunstgeschichte auf der Spur, Horst Czichos,
Oliver Hahn, 223 Seiten, 185 Abbildungen, Carl Hanser Verlag, 2011, 24,90 s,
ISBN: 978-3-446-42636-8
In ihrem Buch stellen der langjahrige

Prasident der BAM, der Bundesanstalt
fur Materialforschung und prufung,
Prof. Horst Czichos und sein Mitarbeiter
Dr. Oliver Hahn fur den Laien sehr
anschaulich und doch wissenschaftlich
prazise den Zusammenhang zwischen
kulturhistorischen Werken und modernen Hi-Tech-Verfahren aus einem vollig
neuen Blickwinkel dar.
In funf Kapiteln beschreiben die
Autoren die Unterstutzung von konservatorischen Arbeiten und bei der Herkunftsanalyse mit den bei der BAM verfugbaren
Methoden. Die Themen reichen von der
Baudenkmalpflege, uber rontgenografische Analyse von antiken Bronzen bis
zur Pigmentanalyse z. B. zur Aufklarung
von Kunstfalschungen.
Gewusst, wie gemacht beschreibt
Untersuchungen zur Aufklarung historischer Herstellungstechniken z. B. von
griechischen und romischen Bronzen,
Damaszener Stahl, chinesischem Seidengewebe sowie von Farbmitteln in den

verschiedenen Zeiten.
Bei der Spurensuche in der Kulturgeschichte findet der Leser Informationen zur Materialforschung an historischen Artefakten und Dokumenten. Die
Autoren vermitteln u. a. Details zur
Himmelsscheibe von Nebra und den
Qumran-Schriftrollen vom Toten Meer.
Interessant sind auch Fakten zu zerstorungsfreien Untersuchungen von Silberstiftzeichnungen von Albrecht Durer, Hinterglasmalereien und Eisengallustinten,
die in alten Schriftstucken die dominierenden Schreibmittel waren. Besonders
die Silberstiftzeichnungen nahren Vermutungen zum eventuell doch vielfaltigeren Leben Durers.
Die Wiederherstellung von Kulturgutern und Architekturdenkmalen wird
im Kapitel Von der virtuellen zur materiellen Rekonstruktion behandelt. Anhand des Schadels eines Neandertalers
und des Kopfes der agyptischen Konigin
Teje werden technische Verfahren beschrieben, mit deren Hilfe die archaologischen Funde geordnet und rekonstruiert
werden konnen. Desweiteren ist ein
groer Teil dieses Kapitels der Wiederherstellung bedeutender Architekturdenkmale gewidmet.
Spezielle Beispiele zur Restaurierung
und Konservierung enthalt das Kapitel
Das Alte uber die Zeit retten. Neben
einer Fortsetzung der BaudenkmalpflegeThematik enthalt dieser Teil auch Beispiele zum Erhalt von Glasmalereien und
Juwelierplastiken (z. B. aus dem Grunen
Gewolbe in Dresden). Dabei wird auch auf
den Einfluss von Museumsluft und daraus resultierenden Auswirkungen auf die
Ausstellungsgestaltung eingegangen. Besonderes Augenmerk wird auf den so
genannten Tintenfra, einer von Eisengallustinten ausgehenden Gefahr fur alte
Papiere, gelegt.
Das Kapitel Echt oder unecht zeigt
Beispiele fur die Nutzung der Materialwissenschaft als Detektiv. So wird anhand
von speziellen Fallen gezeigt, mit welchen
Verfahren die Echtheit alter Beile, fernostlicher Bronzen und Meiner Porzellan
nachgewiesen werden kann. Spektakular
sind auch die Untersuchungen und
die daraus resultierenden Aussagen
zu einem Selbstbildnis von Rembrandt
und einer neuentdeckten Partitur einer
Sinfonie von Franz Schubert - mit welchem Ergebnis, sei an dieser Stelle nicht
verraten.
Das Buch beschreibt auf sehr interessante und gut illustrierte Weise, wie
speziell die BAM-Wissenschaftler in detektivischer Kleinarbeit Schritt fur Schritt
mit den ihnen zur Verfugung stehenden
Mitteln die Geheimnisse der Untersuchungsobjekte ergrunden und zur Losung
der Fragestellung beitragen. Die am Ende
jedes Kapitels aufgefuhrte Literatur bietet
ausreichend Quellen zum vertiefenden
Nachlesen. Letztendlich bietet dieses
Buch dem interessierten Leser eine
kurzweilige Lekture mit Hintergrunden
zu kulturhistorisch wertvollen Kunstwerken und diversen Analyseverfahren.
CBD1112
R. Baler
Veranstaltungen
Seminar: Geometrische
Produktspezifikationen GPS an
cken
Gussstu
11. 12.6.2012 in Essen (Deutschland)
Zunehmende Arbeitsteilung und Zusammenarbeit, z.B. mit Unterlieferanten,
Kunden und Lizenzpartnern im In- und
Ausland (Globalisierung, Outsourcing),
immer hoher werdende Qualitatsanforderungen und sich verscharfender Wettbewerbsdruck erfordern richtige, d.h.
funktions-, fertigungs-, pruf- und normgerechte, Ma-, Form- und Lagetolerierung. Dazu gibt es neue Normen. DIN
ISO 5458 Positionstolerierung, DIN ISO
2692 Maximum- bzw. Minimum-MaterialBedingung, DIN ISO 8015 Tolerierungsgrundsatz (Unabhangigkeitsprinzip) und
DIN 7167 Hullbedingung ohne Zeichnungseintrag, DIN ISO 1660 Profiltolerierung, DIN ISO 10135 Zeichnungseintragungen fur Gussstucke und DIN
ISO 8062 Toleranzen und Bearbeitungszugaben fur Gussstucke. Wie sind diese
Normen in welchen Fallen anzuwenden?
Wie toleriert man bei CAD-Modellen? Wie
sind die Hullbedingung , die Maximum-Material-Bedingung , die Minimum-Material-Bedingung und die
Wechselwirkungs-Bedingung anzuwenden? Wann genugen Matoleranzen
und wann und wie sind die Positions-
tolerierung und die Profiltolerierung anzuwenden? Was sind die Unterschiede

zwischen den DIN-ISO-Normen und der
Norm ASME Y 14.5 in den USA? Wie sind
Zeichnungen nach ASME Y 14.5 zu
interpretieren? Was ist in der Fertigung
zu beachten? Wie sind die Werkstucke zu
prufen? Warum ergeben sich mit der
Dreikoordinatenmesstechnik oft vollig
andere Messergebnisse als mit der konventionellen Messtechnik? Viele Zeichnungen sind unvollstandig und falsch
toleriert, weil Konstrukteuren und Zeichnern das notwendige Wissen uber die
Anwendung der Normen uber Form und
Lage fehlt. Erhohte Kosten und Schaden
sind die Folgen. Wie wird optimal toleriert? Das Seminar behandelt diese Fragen, zeigt einfache Regeln auf und
erlautert sie an Beispielen aus der Praxis.
Wenn vom Kunden die Fertigteil-Zeichnung gestellt wird, muss sie richtig
gelesen werden konnen, um daraus die
richtige Gussteil-Zeichnung ableiten zu
konnen. Die Regeln dazu werden behandelt. Die fur Gussteil-Zeichnungen
zusatzlichen, teilweise neuen Definitionen und Symbole (ISO 10135, ISO 80622) werden erklart und angewendet.
Interessenten wenden sich bitte an:
HAUS DER TECHNIK e.V., Hollestr. 1,
45127 Essen, Tel.: 49 201/18 03-1, Fax:
49 201/18 03-269, hdt@hdt-essen.de,
www.hdt-essen.de
CCD1412
Erstes Deutsches ElektrotauchlackForum 2012
12. 13.6.2012 in Wiesbaden
(Deutschland)
2004 lud die DFO zum Ersten
Deutschen Elektrotauchlack-Forum ein.
Das Forum wurde ein groer Erfolg
denn es gelang das, was von der Branche
schon lange gewunscht war. Es entstand
eine unabhangige Plattform fur den
unternehmensubergreifenden Informationsaustausch!
Wir wollen unserer Pionierrolle weiterhin gerecht werden. Das Erste
Deutsche Elektrotauchlack-Forum soll
in Zukunft ein Markenzeichen fur Innovationsgeist sein: So wie auf diesem
Forum konnen auf keiner vergleichbaren
Branchenveranstaltung in Deutschland
Fachinhalte dargestellt und diskutiert
werden.
www.matcorr.com
2012 wird die Veranstaltung zum

funften Mal durchgefuhrt.
DFO. e.V., Frau Dopheide, 41460 Neuss,
Europadamm 4, Tel.: 49 2131-40811-24,
Fax: 49 2131-40811-21, dopheide@dfoservice.de, www.dfo.info.de
CCD1512
Stahlbau-Kalender-Tag 2012
cken
Eurocode 3 und Bru
22.6.2012 in Stuttgart (Deutschland)
Der Stahlbau-Kalender 2012 beschaftigt sich als Schwerpunkt mit der neuen
europaischen Norm Eurocode 3 und dem
Thema Brucken.
Vorbereitend auf die Einfuhrung des
EC 3 werden die Grundnormen EN 1993
Teil 1-1 sowie EN 1993 Teil 1-5 uber
plattenformige Bauteile mit den zugehorigen Nationalen Anhangen vorgestellt.
Es folgen ausfuhrliche Kommentare zu
den Teilen 16, 18, 19 und 110. Die
Gesamtheit dieser Beitrage soll fur den
praktischen Nutzer ein besseres Verstandnis fur die neuen Normen vermitteln und
ihm bei der Einarbeitung helfen. Neben
allgemeinen Beitragen uber Lastannahmen sowie Korrosionsschutz liegt der
Schwerpunkt auf dem Thema Brucken
von der Gestaltung uber Fertigung und
Montage bis zu Seilen, Lagern und Fahrbahnubergangen.
Die Autoren des Stahlbau-Kalenders
erlautern im Rahmen des Seminars die
wesentlichen Inhalte ihrer Beitrage. Fur
die in der Praxis tatigen Ingenieure
eroffnet sich dadurch die Moglichkeit,
www.matcorr.com
sich aus erster Hand zu den Themen zu

informieren, Fragen zu stellen und mit
den Autoren zu diskutieren.
Universitat Stuttgart, Institut fur Konstruktion und Entwurf, Horsaal V47.03,
Pfaffenwaldring 47, 70569 Stuttgart,
Tel.: 49711-68566245, Fax: 4971168551018, stahlbaukalendertag@ke.unistuttgart.de, www.uni-stuttgart.de/ke
CCD1612
r
Internationale Fachmesse fu
chen und Schichten O&S
Oberfla
12. 14.6.2012 in Stuttgart
(Deutschland)
Das Konzept der O&S ist genauso
einfach wie erfolgreich: Alle Branchen.
Alle Materialien. Eine Messe. Ihre potenziellen Kunden finden alle Losungen zur
Oberflachenbehandlung an einem Ort:
Galvanotechnik, Reinigung und Vorbehandlung, Lackiertechnik, Industrielle
Plasma-Oberflachentechnik, Nanotechnologie, textile Werkstoffe, Analyse-, Messund Pruftechnik und viele weitere. Damit
ist die O&S der ideale Marktplatz fur alle,
die Losungen und Materialien der Oberflachenbehandlung innerhalb des gesamten Bearbeitungsprozesses wirkungsvoll
prasentieren wollen.
Aussteller profitieren von zahlreichen Fachbesuchern, die mit konkreten
Fragestellungen und festen Investitionsabsichten ihre Leistungen kennen lernen
ber 90% der Aussteller aus
mochten. U
2010 planen bereits eine erneute Teilnahme an der O&S 2012.
ber 21% der Fachbesucher komU

men aus dem Ausland, der Groteil aus
sterreich, Italien und
der Schweiz, O
Frankreich, aber auch Osteuropa.
Der Standort Stuttgart ist der ideale
Austragungsort der O&S. 90% der O&SAussteller aus 2010 beurteilen den Wirtschaftsstandort Baden-Wurttemberg fur
die Ausrichtung der Messe als uberdurchschnittlich gut. Nicht zuletzt, da ein
groer und wichtiger Teil der Branche
und ihrer Zielgruppe im suddeutschen
Raum sowie den direkten Anrainerlandern ansassig ist.
Die O&S ist ein Gemeinschaftsprojekt der Deutschen Messe, Hannover,
und der Landesmesse Stuttgart. Beide
Messegesellschaften sind seit langem
Ausrichter zahlreicher weltweiter Leitmessen und somit absolut erfahrene
Partner, wenn es um Bedurfnisse der
Aussteller geht.
Fur zusatzliches Besucherinteresse
und weitere Synergien auf Fachbesucherseite sorgen 2012 die parallel stattfindenden Veranstaltungen der UKIP-Media
Eventreihe European Automotive Components Expo, Automotive testing expo, Engine expo, Automotive interior
expo und Vehicle Dynamics Expo
sowie die LASYS Internationale Fachmesse fur Laser-Materialbearbeitung
(2012 zum zweiten Mal parallel zur
O&S).
Deutsche Messe AG, 30521 Hannover,
Tel.: 49 511 89-0, Fax: 49 511 89-32626,
www.messe.de, www.messe-stuttgart.de
CCD1712
Veranstaltungskalender
Neuer Eintrag
Konferenz/Workshop/Symposium
Messe
Kurs
Juni 2012
11. 12.6.
Essen
(Deutschland)
11. 12.6.
Berlin
(Deutschland)
11. 12.6.
Frankfurt
(Deutschland)
11. 13.6.
Berlin
(Deutschland)
12. 13.6.
Wiesbaden
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cken
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rtereipraxis fu
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tsoptimierung und
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geverfahren Werkstoffe und Fu

r die
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r
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Kooperation mit dem Fraunhoferr Werkstoffmechanik
Institut fu
in Freiburg
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Du
sseldorf
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7. 8.11.
Fachforum: Kunststoffe richtig

beschichten
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Ingenieurbau
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November
2012
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bendorf
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nchen
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2012
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19. Symposium Verbundwerkstoffe

und Werkstoffverbunde
r
Niels Parusel
Frankfurt
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chentage 2013
ZVO Oberfla
DGO Deutsche Gesellschaft

chentechnik e. V.
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r Oberfla
Hilden
info@dgo-online.de
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September
2013
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Materials and Corrosion - Bernd Isecke, Michael Schütze, and Martin Stratmann

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ISSN 0947 5117 MTCREQE 63 (5) 377468 (2012) Vol. 63 No.

Werkstoffe und Korrosion

Annual subscription rates 2012

Print & Electronic

Postage and handling charges included. All Wiley-VCH

ISSN 0947-5117 (Print)

Wileys Corporate Citizenship initiative seeks to address

Wiley-VCH Verlag GmbH & Co. KGaA, D-69451 Weinheim

Contents 2012, 63, No. 5

Articles published on the web will

This study reports on the influence of

Laboratory exposures have been performed simulating a selective catalytic

Wiley-VCH Verlag GmbH & Co. KGaA, D-69451 Weinheim

Contents 2012, 63, No. 5

Hot dip galvanizing behavior of advanced high strength steel

Corrosion behaviour of high-strength

Influence of tensile stress on corrosion

W. J. Yang, P. Yang, X. M. Li and

Materials commonly used in the automotive industry were assembled with

A zinc/silicon dioxide composite film

Wiley-VCH Verlag GmbH & Co. KGaA, D-69451 Weinheim

Contents 2012, 63, No. 5

Corrosion behaviour of different tempers of Al-Zn-Mg-Cu-Zr-Sc alloy was

Influence of heat treatment on corrosion behaviour of AlZnMgCuZrSc

Microbiologically influenced corrosion

Effect of sulphate reducing bacteria

F. Liu, J. Zhang, S. Zhang, W. Li, J. Duan

The purpose of this study is to establish

Nanocrystalline nickel oxide particles

Wiley-VCH Verlag GmbH & Co. KGaA, D-69451 Weinheim

Materials and Corrosion 2012, 63, No. 5

Influence of MWCNT dispersion on corrosion behaviour

Q. Li, C. A. Rottmair, R. F. Singer

2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

anodic Mg alloy matrix, similarly as reported for graphite or

Materials and Corrosion 2012, 63, No. 5

3 Results and discussion

Influence of MWCNT dispersion on corrosion of MWCNT/Mg composites

2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Li, Turhan, Rottmair, Singer, and Virtanen

Materials and Corrosion 2012, 63, No. 5

Figure 2. Weight loss of AZ91 and MWCNT/AZ91 composites (1 and

preparation on the corrosion behaviour in the present case is not

In this paper, the corrosion behaviour of MWCNT/magnesium

2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Materials and Corrosion 2012, 63, No. 5

Acknowledgements: Financial support by the German Research

Influence of MWCNT dispersion on corrosion of MWCNT/Mg composites

[8] Q. Li, M. Zaiser, V. Koutsos, Phys. Status Solidi A 2004, 201,

2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Materials and Corrosion 2012, 63, No. 5

Corrosion of stainless steels in simulated diesel exhaust

2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

The SCR-technique is quite new at this large scale and

Materials and Corrosion 2012, 63, No. 5

oxygen can be introduced to ensure the presence of a passive

Corrosion of stainless steels in diesel exhaust environment

Table 1. Nominal composition of alloys used in the experiments. The

using 1 mm diamond polishing liquid for a reproducible surface

2 Experiments and analysis

The samples were first examined with a Zeiss Discovery V20

Figure 1. Laboratory setup of tube furnace and cooling section for

2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim