Professional Documents
Culture Documents
5 May 2012
D 3716
Materials
5/2012
and
Corrosion
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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.
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
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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.
-3
401-407
-4
Log(I(A/cm2)))
396-400
-5
a
-6
b
-7
c
d
-8
e
-9
-0.7
-0.8
-0.9
-1.0
-1.1
-1.2
-1.3
E(mV/Ag/AgCl)
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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
-1.065
431-437
-1.070
a
Eocp(V/SCE)
421-430
-1.075
-1.080
-1.085
-1.090
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
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384
DOI: 10.1002/maco.201006023
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
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
wileyonlinelibrary.com
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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).
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
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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 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
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5 References
[1] Z. Yao, C. C. Zhu, M. Cheng, J. Liu, Comput. Mater. Sci. 2001,
22, 180.
[2] C. Li, T. A. Chou, J. Solids Struct. 2003, 40, 2487.
[3] M. M. J. Treacy, T. W. Ebbesen, J. M. Gibson, Nature (London)
1996, 381, 678.
[4] E. Wong, P. Sheehan, C. Lieber, Science 1997, 277, 1971.
[5] M. F. Yu, O. Lourie, M. J. Dyer, K. Moloni, T. F. Kelly, R. S.
Ruoff, Science 2000, 287, 637.
[6] J. N. Coleman, U. Khan, W. Blau, Y. K. Gunko, Carbon 2006,
44, 1624.
[7] E. T. Thostenson, Z. Ren, T. W. Chou, Comput. Sci. Technol.
2001, 61, 1899.
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DOI: 10.1002/maco.201005783
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
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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
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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390
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
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
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392
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 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
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.
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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.
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6 References
[1] H. L. Fang, H. F. M. DaCosta, Appl. Catal., B 2003, 46, 17.
[2] M. Koebel, E. O. Strutz, Ind. Eng. Chem. Res. 2003, 42,
2093.
[3] Stainless steel MayJune 2001, 7.
[4] R. Demuzere, Stainless steel Eur. 1991, 3, 55.
[5] H. Shaikh, R. V. Subba Rao, R. P. George, T. Anita, H. S.
Khatak, Eng. Failure Anal. 2003, 10, 329.
[6] M. Schorr, Stainless steel world (The Netherlands) 1998, 10,
21.
[7] L. Antoni, J. M. Herbelin, EFC-Workshop on Cyclic Oxidation
of High Temperature Materials: Mechanisms, Testing Methods,
Characterisation and Life Time Estimation, Frankfurt/Main,
Germany, 2526 Feb., 1999, pp. 187197.
[8] B. Won-Jin, Y. Kwi-Suba, P. Chan-Jin, R. Han-Jin, K. YoungHo, Corros. Sci. 2010, 52, 734.
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DOI: 10.1002/maco.201005905
1 Introduction
2 Experimental
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
Al/Mn Mn/Si
0.032
0.028
0.93
4.53
5.4
2.93
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(1)
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(2)
(3)
(4)
(5)
397
398
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
(6)
(7)
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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.
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6 References
[1] I. Cvijovic, I. Parezanovic, M. Spiegel, Corros. Sci. 2006, 48,
980.
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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,
Chongqing 400054, (P. R. China)
W. L. Feng
International Centre for Materials Physics, Chinese Academy of
Sciences, Shenyang 110016, (P. R. China)
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402
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
Element
Percent
Si
Mn
Cu
Ions
2
Cl NO
Mg2 K Na
NH
SO2
3 F
4 Ca
4
3.6
0.39 2.78
4.49
0.33
0.84 0.56
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-3
Log(I(A/cm2)))
-4
-5
a
-6
b
-7
c
d
-8
-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)
3 Results
Stress ( MPa)
0
300
600
900
1100
Ecorr (V)
Rp (V 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
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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
404
8
6
4
2
0
0
200
400
600
800
1000
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
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
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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
6 References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
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W5921
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DOI: 10.1002/maco.201005888
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
www.matcorr.com
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
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
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.
Figure 2. Basic humidity and temperature subcycles of the new VDA test (according to VDEh)
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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
Figure 3. Tensile test results on welded materials as a function of exposure time in N-VDA test. The strength loss is also given
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411
a)
12 weeks
17 weeks
b)
34 weeks
12 weeks
100
90
$+6&6+6&6
90
80
$+6&6+'*
80
70
A1
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
Remaining thickness (%)
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
Remaining thickness (%)
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
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
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413
100
90
80
$
12 weeks
$&56+'*
17 weeks
$+'*
$(*
$(*
$$0
34 weeks
$+'*
$
70
60
$
50
$
$
40
$
30
$
$
20
$
$
$
10
$
0
0
$
10
$
$
$ $
20
30
40
50
60
70
80
90
100
Figure 6. Strength loss as a function of the percentage of adhesive fracture on adhesive bonded joints after exposure in N-VDA test
34 weeks
$+'*
17 weeks
$(*
12 weeks
$+'*
$(*
70
Strength loss (%)
414
A15
60
50
A13
40
A19
30
20
10
0
A15
A15
A19
A17
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
Assembly
800
1000
1200
A12:
A14:
A16:
A18:
6016/HDG
6016/EG
5182/HDG
5182/EG
420
350
330
280
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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.
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W5888
415
416
DOI: 10.1002/maco.201005974
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
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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)
(2)
417
418
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)
(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
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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
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
Zn 2OH ! ZnOH2 2e
E 0 1:248 V
(7)
(8)
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.
5 References
[1] B. M. Praveen, T. V. Venkatesha, J. Alloy. Compd. 2009, 482,
53.
[2] L. M. Chang, J. H. Liu, R. J. Zhang, Mater. Corros. 2011, 62,
920.
[3] M. Quinet, F. Lallemand, L. Ricq, J. Y. Hihn, P. Delobelle, C.
Arnould, Z. Mekhalif, Electrochim. Acta 2009, 54, 1529.
[4] M. R. Majidi, K. Asadpour-Zeynali, B. Hafezi, Electrochim.
Acta 2009, 54, 1119.
[5] E. Rudnik, L. Burzynska, L. Dolasinski, M. Misiak, Appl. Surf.
Sci. 2010, 256, 7414.
[6] S. Cattarin, P. Guerriero, M. Musiani, Electrochim. Acta 2001,
46, 4229.
[7] B. Bozzini, B. Brevaglieri, P. L. Cavallotti, G. Giovannelli, S.
Natali, Electrochim. Acta 2000, 45, 3431.
[8] E. Pompei, L. Magagnin, N. Lecis, P. L. Cavallotti, Electrochim. Acta 2009, 54, 2571.
[9] X. K. Yang, Q. Li, S. Y. Zhang, X. K. Zhong, Y. Dai, F. Luo,
Mater. Corros. 2010, 61, 618.
[10] T. J. Tuaweri, G. D. Wilcox, Surf. Coat. Technol. 2006, 200,
5921.
[11] B. M. Praveen, T. V. Venkatesha, Appl. Surf. Sci. 2008, 254,
2418.
[12] X. Yang, Q. Li, S. Zhang, F. Liu, S. Wang, H. Zhang, J. Alloys
Compd. 2010, 495, 189.
[13] M. A. Pasquale, L. M. Gassa, A. J. Arvia, Electrochim. Acta
2008, 53, 5891.
[14] X. Xia, I. Zhitomirsky, J. R. McDermid, J. Mater. Process.
Technol. 2009, 209, 2632.
[15] N. Bogdanchikova, A. Pestryakov, M. H. Farias, J. A. Diaz, M.
Avalos, J. Navarrete, Solid State Sci. 2008, 10, 908.
[16] J. Elias, R. Tena-Zaera, C. Levy-Clement, J. Phys. Chem. C
2008, 112, 5736.
[17] Y. Gao, N. R. Choudhury, N. Dutta, J. Matisons, M. Reading,
L. Delmotte, Chem. Mater. 2001, 13, 3644.
[18] N. Tang, W. J. van Ooij, G. Gorecki, Prog. Org. Coat. 1997, 30,
255.
[19] F. Rosalbino, E. Angelini, D. Macci, A. Saccone, S. Delfino,
Electrochim. Acta 2009, 54, 1204.
[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
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DOI: 10.1002/maco.201005923
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
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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
Zn
Mg
Cu
Sc
Zr
Al
8.1
2.05
2.3
0.21
0.12
Bal
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
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.
3.2 Microstructure
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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
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0.0
3RWHQWLDO9
-0.2
-0.4
-0.6
1$
8$
3$
2$
-0.8
-1.0
-4
-3
-2
ORJL$FP
-1
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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425
PLQ
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
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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
(a) NA
36 h
48 h
60 h
72 h
84 h
60
$QJOHGHJUHH
$QJOHGHJUHH
40
(b) UA
24 h
36 h
48 h
60 h
72 h
84 h
60
20
40
20
0
-2
-2
(c) PA
(d) OA
Figure 7. Evolution of impedance diagrams in Bode plot in a long immersion period: AlZnMgCuZrSc alloy with various aging treatments in
EXCO solution
original surface
pore
new inter-face
C1
Rs
C2
Rpo
Rct
grain
grain boundary
corrosion product
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427
428
Time (h)
24
36
48
60
72
84
96
108
C1 (mF cm2)
n1
Rpo (V cm2)
C2 (mF cm2)
n2
Rct (V cm2)
5.266
4.983
4.756
4.059
3.925
3.853
3.154
2.910
0.8495
0.7497
0.7834
0.6255
0.6722
0.6744
0.7151
0.6942
6.812
6.989
7.012
6.548
7.304
6.937
7.105
7.092
5.559
5.073
4.628
4.234
3.886
3.571
3.790
3.832
0.8922
0.9784
0.8735
0.8181
0.8782
0.8037
0.8361
0.8913
12.35
15.43
20.15
22.50
26.44
25.76
28.61
28.67
Time (h)
36
48
60
72
84
96
108
C1 (mF cm2)
n1
Rpo (V cm2)
C2 (mF cm2)
n2
Rct (V cm2)
3.400
3.159
3.217
2.878
2.089
1.708
1.563
0.8628
0.8914
0.8806
0.7283
0.7859
0.7935
0.8169
9.893
8.707
8.004
7.346
10.11
9.687
11.39
4.256
4.349
4.011
3.667
3.523
3.469
3.397
0.9988
0.9748
0.9851
0.9752
0.9822
0.9351
0.9635
22.75
28.96
33.34
35.10
38.07
39.38
39.23
Time (h)
48
60
72
84
96
108
C1 (mF cm2)
n1
Rpo (V cm2)
C2 (mF cm2)
n2
Rct (V cm2)
2.279
2.114
1.529
1.049
1.255
0.836
0.7102
0.6162
0.6301
0.6118
0.6148
0.6073
10.295
13.34
14.02
17.18
16.09
16.91
3.942
3.719
3.229
3.287
3.283
3.285
0.9298
0.9591
0.9381
0.9563
0.9689
0.9674
27.22
35.06
45.75
51.66
50.96
52.31
Time (h)
60
72
84
96
108
C1 (mF cm2)
n1
Rpo (V cm2)
C2 (mF cm2)
n2
Rct (V cm2)
1.9623
1.8051
1.6597
1.1830
0.9848
0.6684
0.6801
0.6164
0.6389
0.6225
9.47
11.22
17.23
18.55
21.57
3.0195
2.8754
2.9735
2.8554
2.9772
0.9896
0.9121
0.9876
0.9850
0.9763
37.23
41.60
54.58
55.19
56.17
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60
a)
1$
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
,PPHUVLRQWLPHK
60
80
100
120
,PPHUVLRQWLPHK
Figure 10. Fitted (a) capacitance C2 and (b) resistance Rct of the AlZnMgCuZrSc alloy with NA, UA, PA and OA tempers
2Al 6H 3NO
3 3NO2 ! 2Al3 6NO2 3H2 O (2)
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
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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.
2004, 367, 10.
[3] Z. M. Yin, Q. L. Pan, Y. H. Zhang, Mater. Sci. Eng. A 2000,
280, 151.
429
430
W5923
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DOI: 10.1002/maco.201005955
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
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431
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.
Amperemeter
Biotic system
Working electrode
Conductor
Abiotic system
Working electrode
0 .8
0 .7
432
0 .6
0 .5
0 .4
0 .3
0 .2
0 .1
0
Hermetic cell
Hermetic cell
10
15
20
25
30
Time (days)
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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.
-Zim()
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()
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433
434
Figure 5. SEM and EDS analysis for samples immersed in sterile marine sediment (A), (B) and SRB-containing marine sediment (C), (D)
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)
(A)
Qf
Rs
L pit
Cdl
R pit
Rct
Rf
(B)
Qf
C pit
Rs
C dl
Rf
R pit
R ct
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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
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
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435
436
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
(5)
Mn nOH ! MOHn #
(6)
(2)
Al Mn ! Al3 M 3ne
(3)
(7)
SO2
4 8Had H ! HS 4H2 O
(8)
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.
5 References
[1] R. A. King, Mater. Perform. 1980, 19, 39.
[2] C. Batt, J. Dodson, M. Robinson, Br. Corros. J. 2002, 37, 194.
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W5955
437
438
DOI: 10.1002/maco.201005796
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
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2.4 Chemical
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439
440
Water characteristics
Experiment
code
NaHCO3
0.1N HCl
DOC
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
M01
M02
M03
M03I
M03II
M04
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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.
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443
444
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
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)
(Accepted: October 12, 2010)
W5796
www.matcorr.com
DOI: 10.1002/maco.201005966
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
www.matcorr.com
wileyonlinelibrary.com
445
446
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.
Kl
b cos u
(1)
www.matcorr.com
Berube and Esperance [67], where the texture coefficient (Tc) was
calculated by using the equation below:
P
I0hkl
Ihkl
Tc P
I0hkl
Ihkl
(2)
Temperature
(8C)
As-prepared
200
300
500
700
21
15
39
47
43
www.matcorr.com
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
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
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
www.matcorr.com
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
www.matcorr.com
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
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
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
www.matcorr.com
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
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
Figure 13. SEM images of (a) Zn and (b) ZnNiO composite coatings
www.matcorr.com
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
Specimen
Zinc coating
ZnNiO coating
www.matcorr.com
Ecorr (V)
Icorr (mA/cm2)
ba (mv)
bc (mv)
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
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
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.
6 References
[1] P. R. Andres, J. D. Bielefeld, J. I. Henderson, D. B. Janes,
V. R. Kolagunta, P. C. Kubiak, J. W. Mahoney, G. R. Osifchin,
Science 1996, 273, 1690.
[2] V. P. Kamath, J. Phys. Chem. B. 2002, 106, 7729.
[3] J. M. Thomas, J. Pure Appl. Chem. 1988, 60, 1517.
[4] J. A. A. J. Perenboom, P. Wyder, P. Meier, Phys. Rep. 1981,
78, 173.
[5] G. Xiao-yan, D. Jian-cheng, Mater. Lett. 2007, 61, 621.
[6] H. J. Liu, T. Y. Peng, D. E. Zhao, K. Dai, Z. H. Peng, Mater.
Chem. Phys. 2004, 87, 81.
[7] O. Yang, J. Sha, X. Y. Ma, D. R. Yang, Mater. Lett. 2005, 59,
1967.
[8] J. H. Liang, Y. D. Li, Chem. Lett. 2003, 32, 1126.
[9] B. Sumit, S. Ashwin, D. Aruna, P. M. Rao, Langmuir 2003,
19, 5522.
[10] W. Wang, Y. Liu, C. Xu, C. Zheng, G. Wang, Chem. Phys. Lett.
2002, 362, 119.
[11] Z. H. Liang, Y. J. Zhu, X. L. Hu, J. Phys. Chem. B 2004, 108,
3488.
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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
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kann beispielsweise die Dauer und die
Schwere einer gewohnlichen Grippe
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stoppen.
Zinkmangel ist ein Problem
Etwa ein Drittel der Erdbevolkerung
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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
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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-
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Bu
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Schra
Erfahrung weltweit,
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Nachlesen. Letztendlich bietet dieses
Buch dem interessierten Leser eine
kurzweilige Lekture mit Hintergrunden
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CBD1112
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Veranstaltungen
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Zunehmende Arbeitsteilung und Zusammenarbeit, z.B. mit Unterlieferanten,
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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-
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