Corrosion Science 52 (2010) 534–539

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

The corrosion behaviour of Al–Zn–In–Mg–Ti alloy in NaCl solution

M.A. Jingling *, Wen Jiuba, L.I. Gengxin, X.V. Chunhua
School of Materials Science and Engineering, Henan University of Science and Technology, 48, Xiyuan Road, Luoyang, Hennan 471003, PR China

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

Article history: The corrosion behaviour of Al–5Zn–0.02In–1Mg–0.05Ti (wt.%) alloy was investigated by EIS, SEM and
Received 16 July 2009 EDX. The results show that there exist different corrosion stages of the alloy in 3.5% NaCl solution with
Accepted 7 October 2009 increasing time. At the initial stages, pits predominates the corrosion around precipitates with a typical
Available online 13 October 2009
inductive loop at low frequencies in EIS. In the late corrosion, a relative uniform corrosion predominate
the corrosion process controlled by the dissolution–precipitation of the In and Zn ions and characterized
Keywords: by the second capacitive loop at low frequencies in EIS. The mud structure appears on the corrosion sur-
A. Aluminium
face of the alloy.
B. SEM
B. X-ray diffraction
Ó 2009 Elsevier Ltd. All rights reserved.
C. Segregation

1. Introduction Electrochemical impedance spectroscopy (EIS) techniques have

Sacrificial anodes are the galvanic anodes that prevent corrosion
of steel when coupled. During cathodic protection, the sacrificial
anode, say aluminium, is ejected into the environment as its ions.
This process leads to impress electrons on the cathode, say steel
surface, suppressing oxidation of iron, i.e. the corrosion process
[1]. Aluminium alloys are preferentially selected for cathodic pro-
tection of steel objects due to high current efficiency, low specific
weight and low cost of the alloys. However, pure aluminium will
form a passive oxide film on its surface when it is exposed to aque-
ous environment, so the elements such as indium, zinc, and bis-
muth etc. should be added for activation the passive film [2–4].
The current efficiency of Al–Zn–In–Mg–Ti alloy was found to be
exceeding 90%, so this alloy became popular in China as sacrificial
anode materials [5]. But there are few data in the literature about
the corrosion behaviour about this alloy [6]. Numerous studies
have been carried out to study the corrosion behaviour of Al–Zn–
In alloys and find the activation action of indium and zinc in the
alloys [7,8]. The effects of Zn and In on Al activation was explained
taking into account the displacement reactions that produced In
accumulation and preferential Zn dissolution [9].
For Al–Zn–In–Mg–Ti sacrificial anode, the corrosion behaviour
is expected to be related to the multielement and the distribution
in the microalloy alloy. The elements may be either in solid solu-
tion or may be segregated as second-phase particles, intermetallic
compounds or inclusions. Both the initiation of attack and the
propagation of dissolution depend on local zones where the
enrichment of the alloying elements occur [10].
* Corresponding author. Tel.: +86 13698854177.
E-mail address: majingling.student@sina.com (M.A. Jingling).
been widely used to study the corrosion process of various metallic
materials [11,12]. EIS can characterize passive films formed on
pure metals or alloys. The passive films formation, dissolution,
and breakdown represent one of the most significant features with
respect to the corrosion behaviour [13]. The paper [6] investigated
the effects of Mg and Ti on microstructure and electrochemical
performance of Al–5Zn–0.02In–1Mg–0.05Ti (wt.%) alloy. This work
explored the corrosion behaviour of the alloy in 3.5 wt.% NaCl solu-
tion to gain a better understanding of the corrosion mechanism.
2. Experimental
2.1. Material preparation
The nominal compositions of alloy in present experiment are
5 wt.% Zn–0.02 wt.% In–1 wt.% Mg–0.05 wt.% Ti–Al, as showed in
Table 1. Raw materials are commercial pure aluminium, zinc, in-
dium, magnesium, titanium ingots (>99.9%) for casting the above
anode alloy. Raw material ingots were cut, dried, weighed the re-
quired amount of materials and melted in a graphite crucible in
ZGJL0.01-4C-4 vacuum induction furnace under argon atmosphere
at 760 °C. The molten alloy was poured in a preheated cast iron dye
of dimensions / 20  140 mm.
2.2. Electrochemical measurements
CHI660C electrochemical test system (CHI Company, USA).
Samples were cut transversely at ¢ 16  28 mm and then washed
with acetone, dried and weighed with 104 g accuracy. A saturated
calomel electrode (SCE) served as the reference electrode and a
mild steel was used as the cathode. Anode and cathode were

0010-938X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.10.010
 M.A. Jingling et al. / Corrosion Science 52 (2010) 534–539 535

Table 1 sample was taken out from the beaker one by one, respectively,
The nominal compositions of the alloy (wt.%). after immersing different time. The corrosion products of the sam-
Composition Zn In Mg Ti Al ples were clean-out in a solution of 2% CrO3 and 5% H3PO4 at 80 °C
Content 5.00 0.02 1 0.05 Bal. for about 5 min, then rinsed by ethanol. The corroded surface of the
samples in 3.5 wt.% NaCl solution at different immersion time was
examined using JSM-5610LV scanning electron microscope (SEM)
equipped with energy dispersive X-ray (EDX).
Table 2
Electrochemical performance of Al–5Zn–0.02In–1Mg–0.05Ti (wt.%) alloy.

Sample OCP V/SCE CCP V/SCE Efficiency (%) Capacity 2.4. EIS measurements
(Å h kg1)
Casting 1.122 1.079  1.091 91.5 2619 The samples were removed from the immersion solution (3.5%
NaCl) for different dipping times respectively to EIS tests. The EIS
measurements were carried out in 3.5% NaCl solution at room tem-
perature by CHI660A electrochemical measuring system. Imped-
immersed in artificial seawater at current density of 1 mA/cm2 for
ance spectra were obtained at open circuit potential with a 5 mV
10 days. The weight of the sample before and after the immersion
sine perturbation to the cell. The measuring frequency range was
of the galvanic system was measured after cleaning by standard
100 kHz–0.1 Hz. The exposed area of working electrode was
procedure according to the standard method GB/T17848-1999
1 cm2. The reference electrode was a saturated calomel electrode
[14]. After the test, the anode current efficiency and capacity were
and a graphite rod was used as counter electrode.
calculated based on the measurement of weight loss.

2.3. Immersion tests 3. Results and discussion

The samples of immersion tests were ground with emery paper 3.1. Electrochemical properties
(grade 400-800-1000-2000) and polished with 2.5 and 1.5 lm dia-
mond pastes. A few samples were immersed in 3.5% NaCl solutions Table 2 shows the electrochemical properties of Al–5Zn–
contained in a different beaker at the same time. The numbered 0.02In–1Mg–0.05Ti (wt.%) alloy. The current efficiency and capac-

Fig. 1. The SEM imagines of Al–5Zn–0.02In–1Mg–0.05Ti (wt.%) alloy before (a) and after immersed in 3.5%NaCl solutions for 2 min (b), for 5 h (c), for 10 h (d), for 3 d (e), (f) for
8 d.
536 M.A. Jingling et al. / Corrosion Science 52 (2010) 534–539
ity are 91.5% and 2619 Å h kg1, respectively. The protection po-
tential of steel cathode in seawater is 0.85 V (SCE) and the driving
potential is about 0.25 V, which confines the Open Circuit Potential
(OCP) and the Closed Circuit Potential (CCP) values of anode be-
tween 1.0 V and 1.2 V, so the OCP and CCP values of the alloy
can satisfy the cathodic protection needs.
3.2. Surface morphology of the corroded alloy
The microstructure of the alloy is shown in Fig. 1(a). The alloy
is mainly consisted of a-Al matrix with precipitates on continu-
ous or semi-continuous network of grain boundaries. Fig. 1(b–f)
show the representative corroded surface of the alloy at different
immersion time. No corrosion pit can be observed in Fig. 1(a).
After 2 min immersion, some pits become distinguishable pre-
senting a size of 3 lm in average (Fig. 1b), and the pits forma-
tion from the precipitates. For up to 5 h immersion (Fig. 1c),
the pits sizes are increase, but without any significant increase
in the pits number. In this case there is no other precipitate
on the metal surface. After 10 h immersion (Fig. 1d), special fea-
tures can be seen showing a mud structure in grain. Numerous
mud structures and pits cover the alloy surface after 3 d im-
mersed (Fig. 1e). Until 8d immersion in Fig. 2(f), the pits almost
spread around the all alloy surface, the mud structure also cover
the entire alloy surface.
3.3. EDX analysis of the alloy surface
Fig. 2 shows a semiquantitative EDX analysis on the original al-
loy surface in Fig. 1(a). The EDX result confirms that the a-Al ma-
trix at a location, the precipitates at position b and the grain
boundaries at position c all contain Al, Zn and Mg elements, but
the content of Zn and Mg of the precipitates is the highest than that
Fig. 2. SEM photograph and energy spectra analysis of Al–5Zn–0.02In–1Mg–0.05Ti alloy.
of the a-Al matrix and the grain boundaries. It has been docu-
mented that the main precipitate phase is MgZn2 particles in Al–
5Zn–0.03In–1Mg–0.05Ti alloy, and the corrosion potential of the
bulk MgZn2 is more negative than that of a-Al [10]. So MgZn2 pre-
cipitates can be acted as corrosion center and cause the initiation
and propagation of pitting corrosion. So some fits are show in
Fig. 1(b) at the initial stage of immersion. The amount of In and
Ti added in the alloy is so small that the phases containing In or
Ti phases can not be detected by EDX.
Fig. 3 shows an EDX analysis on the corroded surface of the al-
loy after 10 h immersion in Fig. 1(d). The EDX result indicates that
the grain with mud structure at position a, the grain boundary at
position b and the pit at position c all contain Al, Zn, Mg and In ele-
ments, but the content of In of the mud structure is the highest
than that of the pit and the grain boundary. There is not In element
on the original alloy surface in Fig. 2. This is because that the
amount of In added in the alloy is so small and not possible to de-
tect the In content considering the detection limit of EDX. So Fig. 3
shows that the In element of the alloy may involve the dissolution–
precipitation process and the precipitation of In should reach a
critical value that lead to the corrosion with the mud structure.
The mud structure of the alloy also can be possible explained by
considering passivation in the alloy as a dynamic process. The
oxide film is expected to dissolve and a fresh film is expected to
appear, though at a much slower rate. This is depending on the dis-
solved cations which might redeposit on the surface as hydroxides.
During the dissolution–precipitation process, the In ions are incor-
porated in the oxide film. Yet a further mechanism of incorporation
is at the flaws themselves: indium and zinc, being noble, may
become deposited on these sites. However, subsequently, they dis-
solve along with aluminium. Therefore, the new film formed on the
pits is entirely different from the film observed in the growing pits
of pure aluminium.
 M.A. Jingling et al. / Corrosion Science 52 (2010) 534–539 537

Fig. 3. SEM photograph and energy spectra analysis of Al–5Zn–0.02In–1Mg–0.05Ti alloy after corrosion 10 h.

1200 1200
(a) (b) experimental
fitting
800 800

400 0 h experimental 400

0 h fitting
0 0

0 400 800 1200 1600 2000 0 400 800 1200 1600 2000

1200 1200
(b) (d) 3d experimental
10 h experimental
10 h fitting 3d fitting
800 800

400 400

0
0

0 400 800 1200 1600 2000 0 400 800 1200 1600 2000

Fig. 4. EIS spectrums of Al–5Zn–0.02In–1Mg–0.05Ti alloy during immersion in 3.5% NaCl solution at the beginning (a), 5 min (b), 10 h (c), 3 d (d).
538 M.A. Jingling et al. / Corrosion Science 52 (2010) 534–539

Since passivation is a dynamic process involving dissolution and Table 3

precipitation, Zn2+ ions can become incorporated into A12O3 film. It EIS simulated values of Al–5Zn–0.02In–1Mg–0.05Ti alloy at different immersion
times.
shown earlier that ZnO forms the ZnAl2O4 phase, with Zn2+ in
interstitial positions [15]. For the above reasons, if ZnAl2O4 is as- Immersion time 0 5 min 10 h 8d
sumed to be formed, then the A12O3 film will have excess electrons Rs (X cm2) 15.42 7.76 7.20 7.40
and enhanced cationic mobility. The increase in electronic conduc- CPE1 (X-1 cm2 s1) 3.4  105 5.6  105 4.0  105 1.8  108
tivity reduces the field across the film, enhancing passivity. Thus n1 (0 < n < 1) 0.89 0.85 0.81 0.98
Rt (X cm2) 2702 1258 840 71.75
zinc reverts back the tendency of indium in the following ways: L (H cm2) 1.6  104 20.73
(1) by enhancing electron concentration and cation mobility and R1 (X cm2) 802 516.6
(2) by reducing the corrosion rate. CPE2 (X-1 cm2 s1) 5.5  103 9.93  105
n2 (0 < n < 1) 1 0.6
R2 (X cm2) 381.5 628.1
3.4. Electrochemical impedance spectroscopy (EIS) v 6.54  103 4.37  103 3.45  102 6.23  104

Fig. 4(a–d) show the EIS of the alloy obtained at different

immersion time for initial, 5 min, 10 h, and 3 d. The EIS varying
with the immersion time can be analyzed generally using equiva-
lent circuit as shown in Fig. 5 [16,17]. To obtain more precious fit-
ting results, the employed capacitance element (C) which shows
the double-layer capacitance is replaced by constant phase ele-
ment (CPE). The impedance of CPE is defined by the following
equation [18,19]:
ZðjxÞ ¼ ðY 0 Þ1 ðjxÞn
where Y0 is the CPE-constant, j the imaginary unit, n the CPE-power
(0 6 n 6 1) and x the angular frequency (x = 2pf, f is the fre-
quency). Obviously, the CPE is at pure capacitance when n is 1.
For a capacitance element, the derivation of n from the unit is due
to the heterogeneous effect.
A capacitive loop appears at the range of high frequencies at
early stage of immersion in Fig. 4(a). An equivalent circuit for sim-
ulating this process is shown in Fig. 5(a) and the fitting values of
impedance parameters are listed in Table 3. In Fig. 5(a), Rs repre-
sents the solution resistance, Rt and CPE1 are the charge-transfer
resistance and double-layer capacitance of the alloy surface. After
5 min immersion in Fig. 4(b), an inductive loop at low frequency
appears, and an equivalent circuit for simulating this process is
shown in Fig 5(b). The inductive loop may be represents the pitting
of the corroded morphology in Fig. 1(b). It has been documented
that the inductive loop is symbol of pitting in the pitting model
for Al alloys [20,21]. R1 and L are the corresponding parameters
for pitting. With increase of immersion time to 10 h, the EIS is
characterized by two capacitive loops at high and low frequencies
as well as an inductive loop at medium frequencies. An equivalent
circuit for simulating this process is shown in Fig 5(c). The second
capacitive loop in the EIS may be the consequence of a dissolution–
precipitation from In ions in corroded morphology (Fig. 1d). CPE2
and R2 represent corresponding parameters for the dissolution–
precipitation of In ions. After the immersion time of 3 d, a de-
pressed capacitive loop appears at high frequencies and the capac-
itive loop at low frequencies increases. This indicates that the
dissolution–precipitation increases, but the pitting decreases grad-
ually. In the case of the immersion moment, the equivalent circuit
is shown in Fig 5(d).
ð1Þ According to the above mentioned equivalent circuit, it can be
seen that the fitting results match the experimental data very well
in Fig 4(a–d). The simulation values obtained by ZSimpwin soft-
ware for the equivalent elements are shown in Table 3. The v2 is
the precision of the simulated data. It can be seen that the v2 val-
ues are small, reflecting the fact that the simulated data have good
agreement with the experimental ones. In general, the higher Rt re-
flects a lower corrosion since the exchange current is directly asso-
ciated with the electrochemical process of corrosion [22,23]. It can
be seen that the Rt reduces gradually with the immersion time.
This indicates that the corrosion process is more intense.
4. Conclusions
The corrosion behaviours of Al–5Zn–0.02In–1Mg–0.05Ti (wt.%)
alloy after different immersion times in 3.5% NaCl solution were
developed using EIS, SEM and EDX.
At the initial stage of immersion, the corrosion process is char-
acterized by a capacitive loop at high frequencies and an inductive
loop at low frequencies in EIS. Some pits present in the alloy sur-
face. It indicates that there exists pitting corrosion. With increase
of immersion time, the inductive loop disappears and the second
capacitive loop appears at low frequencies in EIS and a mud struc-
ture in grain can be seen. This shows the dissolution–precipitation

Fig. 5. Equivalent circuit of EIS of Al–5Zn–0.02In–1Mg–0.05Ti alloy during immersion different time: at the beginning (a), 5 min (b), 10 h (c), 3 d (d).
 M.A. Jingling et al. / Corrosion Science 52 (2010) 534–539
of In and Zn ions. The pitting predominates the mainly corrosion
process controlled by the activation of the precipitates particles
in the alloy at the initial stage of corrosion. At the late stage of cor-
rosion, the relative uniform corrosion predominates the mainly
corrosion process controlled by the dissolution–precipitation of
the In and Zn ions. The EIS results are in good agreement with
the SEM imagines.
Acknowledgments
This work was supported by Technology Creative programmer
of Henan for Excellent Talents (Grant No. 094200510019) and the
Natural Science Foundation of Hnnan Province, China (Grant No.
092300410132).
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