Journal of Materials Science & Technology 64 (2021) 85–98

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Journal of Materials Science & Technology

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Research Article

Effect of aging treatment on microstructure and corrosion behavior of

Al-Zn-Mg aluminum alloy in aqueous solutions with different
aggressive ions
Pan Liu, Lulu Hu, Qinhao Zhang, Cuiping Yang, Zuosi Yu, Jianqing Zhang, Jiming Hu,
Fahe Cao ∗
Department of Chemistry, Zhejiang University, Hangzhou 310027, China

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

Article history: The microstructure and corrosion behavior of Al-Zn-Mg alloy (namely 7×××) after natural aging treat-
Received 14 May 2019 ment (NAT) and artificial aging treatment (AAT) in aqueous NaCl solutions containing different aggressive
Received in revised form 31 July 2019 ions have been investigated in current work. Results of microstructure characterization demonstrate that
Accepted 11 September 2019
the aging treatment has a great influence on the grain size and precipitates. The grain size is relatively
Available online 17 November 2019
sizeable and no evident precipitates are observed in alloy after NAT comparable with that after AAT.
The electrochemical corrosion behavior of alloy was studied by polarization curve and electrochemical
Keywords:
impedance spectroscopy (EIS). The corrosion potential (Ecorr ) of the aluminum alloy is more negative in
Al-Zn-Mg alloy
Aging treatment
3.5 wt.% NaCl containing 0.052 wt.% NaHSO3 solution than that in 3.5 wt.% NaCl solutions with or without
Microstructure 0.907 wt.% NaHCO3 . Charge transfer resistance (Rct ) results reveal that alloy after AAT has an enhance-
Corrosion behavior ment of corrosion resistance compare with that after NAT. With the immersion time increasing, mostly
Aggressive ion pitting spreads over the surface of the alloy only in NaCl solution, whereas exfoliation corrosion mainly
occurs in NaCl solutions containing NaHSO3 or NaHCO3 .
© 2019 Published by Elsevier Ltd on behalf of The editorial office of Journal of Materials Science &
Technology.

1. Introduction to properly understand the corrosion behavior and mechanism on

Aluminum (Al) alloys are extensively used in manufacture of
aircraft, vessel and locomotive owing to the high strength, satis-
factory thermal conductivity and impressive mechanical property
by adding different alloying elements into pure Al [1,2]. However,
the intermetallic strengthening precipitates cripple the corrosion
resistance of Al simultaneously. For instance, aluminum alloys
are extraordinary sensitive to salt fog, salt water spray and other
aggressive circumstances in general, which is prone to induce cor-
rosion initiation. Furthermore, pitting corrosion and exfoliation
corrosion are two main corrosion types of aluminum alloys, and the
exfoliation corrosion is widely regarded as the evolution of inter-
granular corrosion [3–5]. Consequently, these problems mentioned
above can greatly weaken intensity, fatigue properties and dramat-
ically shorten operation term and service life of aluminum alloys
[2,6]. Therefore, the corrosion of aluminum alloys is inevitable, and
∗ Corresponding author.
E-mail address: nelson cao@zju.edu.cn (F. Cao).
it is obvious imperative.
With the advance of measuring devices and testing methods,
numerous unexpected experimental conjectures and results in the
past were confirmed. The research works of aluminum alloys have
also acquired considerable progress. One of widely recognized
views about corrosion behavior of alloys is that the electrochemical
inhomogeneity discrepancies present between various intermetal-
lic particles (IMPs) and metal matrix [3,7–9]. For example, it was
reported by Li et al. [10] that aluminum alloy AA7150 possessed a
worse resistance to exfoliation corrosion after peaking-aging (T6)
due to the continuous and closely spaced distribution of MgZn2
precipitates at grain boundaries, in comparison to that under
over-aging (T73) and retrogression and re-aging (RRA), which was
usually regarded as the anodic path. In order to understand the
impact of intergranular Cu-rich particles on 2××× series aluminum
alloy, Bonfils-Lahovary et al. [11] incorporated copper species in
the amorphous alumina film to form structural defects. Results
indicated that Cu-rich precipitates corroded preferential along the
grain boundaries when the alloy was immersed in 1.0 mol L−1 NaCl
solution for 24 h. Another similar investigation in regards to the
impact of different aging treatments on 7055 alloy was studied by

https://doi.org/10.1016/j.jmst.2019.09.030
1005-0302/© 2019 Published by Elsevier Ltd on behalf of The editorial office of Journal of Materials Science & Technology.
86 P. Liu et al. / Journal of Materials Science & Technology 64 (2021) 85–98
Liu et al. [12]. It reported that the appropriate double-aging (DA)
and RRA could better promote the corrosion resistance than T6
when alloy was immersed in 3.5 wt.% NaCl solution for an acceler-
ating test. In the case of T6 temper, the oxide film broke down, and
continuous distribution of bare MgZn2 phase and coarse Al7 Cu2 Fe
could facilitate the development of pit cavity. Wang et al. [8]
reported that active MgZn2 particles, secondly Al2 MgCu and Mg2 Si
were main factors for the serious corrosion of 7A60 aluminum alloy,
while Al7 Cu2 Fe particles have little impact on pitting corrosion, and
the corrosion process of 7A60 alloy in 3.5 wt.% NaCl electrolyte solu-
tion consists of two distinguished stages based on electrochemical
impedance spectroscopy (EIS) and electrochemical noise (EN) tech-
niques results. Meanwhile, Chen et al. [13] studied the influence
of heat treatment on various properties of 7085 aluminum alloy.
Studied results demonstrated that high temperature and subse-
quent low temperature aging (HLA) played a role of decelerating
the enhancement of corrosion resistance and strength from alloy-
ing, whilst RRA as well as dual-retrogression and re-aging (DRRA)
improve the exfoliation corrosion resistance, and these behaviors
were rationalized by precipitates prevailed over matrix and grain
boundaries. Tang et al. [14] studied the continuous and discontin-
uous localized corrosion of 2××× series aluminum alloy. Results
showed that discontinuous localized corrosion event was more
common due to the Al2 Cu and Al-Cu-Fe-Mn-(Si) particles. In addi-
tion, the grain size is another significant factor for the corrosion of
alloys [15–19]. Tian et al. [20,21] revealed that grain size has, which
showed that the frequency of pitting current transients increased,
and peak value of current transients decreased simultaneously with
increasing ratios of the fine grain, while the number and volume
fraction of stable pits on alloy obviously decreased. Moreover, Ral-
ston and Davies et al. [17,22] studied the relationship between grain
size and corrosion rate of metals. Results depicted that the tendency
of corrosion rate decreased with the diminution of grain size in neu-
tral solution. What’s more, fine grain structures were beneficial to
create more reactive surfaces.
In this work, the impact of natural aging treatment (NAT)
and artificial aging treatment (AAT) on the microstructure and
corrosion behavior of Al-Zn-Mg alloy under different simulate
atmospheric environments was investigated, which was usually
used to manufacture parts of heavy equipment. To understand the
effect, of varied typical anions, microstructure characterization and
various electrochemical tests were implemented, and the relation-
ship between structure and evolution of corrosion resistance was
figured out.
2. Experimental
2.1. Materials and experimental set-up
The main alloying element of Al-Zn-Mg alloy in current work
was Zn (4.64 wt.%) and Mg (1.46 wt.%), and the trace element was
Zr (0.98 wt.%) and Si (0.06 wt.%) based on Energy Dispersive Spec-
trometer (EDS) data. A conventional three-electrode setup was
selected to perform all electrochemical experiments. The exam-
ined working electrodes were fabricated from Al-Zn-Mg alloy after
NAT and AAT and partly encapsulated with polyamide to avoid
crevice corrosion. An area of 1.0 cm2 was prepared to expose in
the experimental electrolyte solutions. Prior to the measurements,
in order to guarantee cleanish exposed surface of electrodes before
any immersion, working electrodes were subjected to ground pro-
cess with wet silicon carbide abrasive paper of increasing grain
size from 400 up to 1000 grit, successively, and subsequently pol-
ished with diamond suspension. Eventually, the exposed surface
was rinsed with distilled water, degreased with ethyl alcohol and
dried in cold air. The reference electrode used was a silver chloride
electrode, i.e., Ag(s)|AgCl(s)|Cl- (aq, saturated KCl), and platinum
sheet with a large area was chosen as the auxiliary electrode.
Three electrolyte solutions containing 3.5 wt.% NaCl solution (S1),
3.5 wt.% NaCl containing 0.052 wt.% NaHSO3 (S2), 3.5 wt.% NaCl con-
taining 0.907 wt.% NaHCO3 (S3) were chosen to simulate different
atmospheric environments by changing anions [23–25]. Besides,
it should be noted that the real service environments for alu-
minum alloy is quite complicated, which generally includes various
kinds of aggressive ions. To use 3.5 wt.% NaCl solution to sim-
ulate the marine atmosphere environment has been agreed by
many researchers, and numerous works for simulating the effect of
marine atmosphere environment on metal corrosion have been car-
ried out under such conditions as cited literatures above [23–25]. In
current work, the three solutions do not refer to three completely
identical service environments for Al-Zn-Mg aluminum alloy dur-
ing its application. Our idea is to extract three typical aggressive
ions with its suitable concentration based on literatures before
experiment, and investigate the single/ combined effect of these
aggressive ions on the corrosion behavior of Al-Zn-Mg aluminum
alloy. In addition, all solutions were prepared with deionized water
and were open under a natural condition.
2.2. Methods
2.2.1. Microstructure investigations
The microstructure of specimens after NAT and AAT treat-
ments were performed by electron back scatter diffraction (EBSD)
technique (NordlysNano, Oxford instruments, Inc., Britain) with
a TESCAN MAIA3 high resolution field emission scanning elec-
tron microscope (SEM), operated at the voltage of 20 kV and the
step size of around 4 ␮m. The results of EBSD were deeply pro-
cessed by Channel5 software for further analysis. Additionally, in
order to observe dispersed precipitates both in grain boundary and
matrix, test samples were thinned to 75 ␮m in thickness accurately,
stamped into 3 mm in diameter and further thinned and polished
by the mixed solution HNO3 :CH3 OH = 1:3 on a twin-jet electropol-
ishing device (RL-I, Ruiling Innovation, Inc., China) at a constant
current mode of 80 mA at around -30 ◦ . Well prepared samples
were characterized by utilizing FEI Tecnai G2 F20 S-TWIN transmis-
sion electron microscope (TEM) carried out at 200 kV. Moreover, in
order to describe the microstructures after the immersion at 12, 72
and 120 h under three different solutions and characterize compo-
sitions of corrosion products, Hitachi SU8010 SEM in the secondary
electron mode coupled with EDS was used and operated at 15 keV.
2.2.2. EIS measurements
Electrochemical impedance spectroscopy (EIS) was performed
to study the electrochemical behavior of the samples under two
aging conditions. The experiments were carried out by a Refer-
ence 600TM electrochemical workstation (Gamry Instruments, Inc.,
America) under open circuit potential (OCP) condition at ambient
temperature of 25 ◦ C, setting range of perturbation and frequency
of 10 mV and 105 -10−2 Hz, respectively. The 30 min OCP tests were
preceded by the conduct of EIS measurements to ensure the stable
potential. Considering the fast corrosion rate at initial immersion
stage, the measurement acquisitions were firstly performed every
4 h up for the immersion time of 12 h, and then changed into every
24 h for up to 120 h. The experimental data were analyzed by ZSim-
pWin analysis software with appropriate equivalent electric circuit
(EEC) models. The parameter values of EEC were acquired by fitting
the impedance function of non-linear least squares program.
2.2.3. Polarization curve measurements
Polarization curve measurements were conducted to determine
corrosion resistance in three simulated solutions. The experimental
measurements were performed at ambient temperature of 25 ◦ C
 P. Liu et al. / Journal of Materials Science & Technology 64 (2021) 85–98 87

Fig. 1. Typical microstructural images of Al-Zn-Mg aluminum alloy with two different treatments: (a) orientation map with NAT, (b) orientation map with AAT, (c) color
code acted on characterize crystallographic orientations on standard stereographic projection (different color represents diverse orientation projections: red is [0 0 1]; blue
is [1 1 1] and green is [1 0 1]) and distribution diagram of various grain diameter in Al-Zn-Mg aluminum alloy with NAT (d) and AAT (e), respectively.

by immersing the specimens into three different electrolytes with
Gamry Reference 600 electrochemical workstation in the applied
potential range from −250 mV to +1200 mV vs. OCP with a scan rate
of 1 mV s−1 after OCP was stable. Corresponding corrosion potential
(Ecorr ) and corrosion current density (icorr ) could be evaluated by
data obtained from polarization curves.
2.2.4. Bulk pH measurements
To illustrate changes in bulk pH values from initial stage to
120 h immersion. Variations in pH as a function of time for all the
investigated solutions were measured by using pH detector (Rex
Analytical Instruments, Inc., China). A commercial pH sensor was
calibrated in two universal buffer solutions firstly, which pH val-
ues were 6.86 and 9.18, respectively. Afterwards, we measured
three electrolyte solutions every 12 h for up to 120 h at ambient
temperature of 25 ◦ C in air.
3. Results
3.1. Microstructure and composition
Fig. 1(a) and (b) display the microstructures of Al-Zn-Mg alu-
minum alloy with NAT and AAT, respectively. The boundaries of
each grain, sub-grain and recrystallized- grain are legible, while
different kinds of grains are coded with diverse colors in terms of
its characteristic crystal orientation on account of [0 0 1] inverse
pole figure as standard presented in Fig. 1(c). It can be observed
that two different aging treatments after solution treatments lead
to a significant difference in grain size. Microstructures of samples
after NAT consists of anisometric coarse grains, which are along
the extruding direction, and a few recrystallized-grains well dis-
tribute in the metal matrix. Moreover, the range of grain diameter
is around 10−120 ␮m based on grain diameter distribution diagram
in Fig. 1(d) (especially in the range of 11–35 ␮m). However, as can
be seen in Fig. 1(b), the difference in size of the grains of Al-Zn-Mg
aluminum alloy after AAT is around 5−40 ␮m in Fig. 1(e) (mostly
in the range of 5–12 ␮m), mainly comprising of anisometric coarse
grains and a mass of fine sub-grains.
TEM was employed to characterize the microstructure, and the
corresponding results are shown in Fig. 2. Many dislocations can
be seen in intragranular areas of samples after NAT in Fig. 2(a)
and (b). Furthermore, no apparent precipitates are observed in
grain boundaries while a few speckle-like particles disperse well
in grains. Moreover, the samples after AAT are varied in com-
parison to NAT. A high-population density of round-shaped and
elongated IMPs is posed in grains and sub-grains, and relatively
sizeable IMPs distribute along grain boundaries in various shapes.
Besides, the distinct precipitate free zones (PZF) are additionally
seen along grain boundaries (Fig. 2(b) and (d)). Previous studies
[26,27] have reported the precipitation sequence of Al-Zn-Mg alloy
i.e., main ˛-supersaturated solid solution, Guinier-Preston zones
(GP zones) and then to form ␩’ phase. The great majority of ␩’
phase is a semi-coherent metastable MgZn2 phase, and eventu-
ally the ␩’ phase transforms into equilibrium  phase, i.e. MgZn2
phase. GP zones and ␩’ phase usually precipitate in intragranular
regions, while the  phase generally precipitate in grain bound-
aries. In addition, the structure of ␩’ and  phases are always easy
to distinguish from ˛-matrix phase, and the both are hexagonal
crystallographic microstructure. In order to identify the elements
and composites of those precipitates, the TEM/EDS measurements
were performed. The STEM-HAADF (scanning transmission elec-
tron microscope-high-angle annular dark field) images of samples
after NAT and AAT and the corresponding EDS analysis results are
displayed in Fig. 3. Due to in the difference of imaging patterns,
phase contrast of STEM-HAADF images reverses to TEM images.
The brighter contrast in STEM-HAADF images is relative to heav-
88 P. Liu et al. / Journal of Materials Science & Technology 64 (2021) 85–98
Fig. 2. TEM images of Al-Zn-Mg alloy with (a, b) NAT and (c, d) AAT conditions.
ier atomic compositions while the darker contrast signifies minor
ones [28–30]. Line scan mode was used for analyzing particles
elements, with the maximum resolution is around 0.102 nm. The
EDS results of TEM indicate that the main compositions are Al, Mg
and Zn, which can establish a consistent relation with EDS results
mentioned above. However, three obvious peaks are observed as
scanning through three brighter contrast precipitates for samples
after NAT in Fig. 3(a), which is likely to attribute to Al3 Zr dispersoid
combined with results of selected area electron diffraction (SAED)
[31]. Meanwhile, the results of the samples after AAT in Fig. 3(b)
show that the content of the brighter contrast precipitates is dif-
ferent from the darker ones. The brighter contrast phases are rich
in Mg and Zn, namely  phase or its analogues. In addition, the
darker contrast precipitates are of element comparable to that in
matrix, though the Al content decreases in intragranular regions,
which should be relative to more complex composites [32–34].
3.2. Corrosion behavior evolution
Immersion tests of Al-Zn-Mg alloy after NAT and AAT were per-
formed in S1, S2 and S3 solutions at ambient temperature of 25 ◦ C,
respectively. Fig. 4 presents the typical optical surface images of
the aluminum alloy after NAT during tests. Numerous bubbles are
produced and absorbed on the surface or in the vicinity of the alu-
minum alloy in S1 and S3 solutions, while few bubbles are observed
in S2 solution, indicating corrosion reaction mechanism is probably
different in solutions containing different cathodic anions. More-
over, an evident film covering on the surface of the alloy is observed
under S2 solution, which contributes to lose its metallic luster in
comparison to that under S1 and S3 solutions. The samples with
AAT show a similar bubble evolution behavior as the sample with
NAT as shown in Fig. 4, hence which are not exhibited here. Also,
Figs. 5 and 6 show the SEM images of the corroded surface mor-
phologies of samples with NAT and AAT immersed in S1, S2 and S3
solutions over 12, 72 and 120 h with the insets of higher magni-
fication of local micro-surface. Two typical corrosion forms can be
seen, that is pitting corrosion and exfoliation corrosion occur under
the three different solutions. Sparse pits having a small number of
branches are found on the surface of the alloy both with two aging
conditions at initial immersion stage in S1 solution, moreover, loose
and fine granular white particles are stacked over pits from a close
look. After 120 h corrosion (Figs. 5(g) and 6 (g)), the pits spread
over surface and their scale become large, and the size of the visi-
ble pits is comparable, ranging from a few to a dozen microns, while
the granular white particles gather together and grow up to form
dense flocculent corrosion products for sample with AAT in Fig. 6(g).
More serious corrosion phenomena are found at the NAT condi-
tion where corrosion products are changed to network plied on the
surface, the corresponding EDS analysis results of these corrosion
products are presented below. The five main elements like Al, Zn,
Mg, Si and O are detected from corrosion production during 120 h
under S1 solution, indicating that the corrosion products mainly
consist of oxide or hydroxide of Al, Zn, Mg and Si. Besides, chip-like
corrosion pits are apparently seen in S2 solution at the initial stage.
With the immersion time increasing, chip-like corrosion products
are changed to relatively honeycomb-like in Figs. 5(h) and 6 (h), and
 P. Liu et al. / Journal of Materials Science & Technology 64 (2021) 85–98 89

Fig. 3. STEM-HAADF images of the IMPs of samples after NAT (a) and AAT (b) with corresponding EDS results of precipitates.

it can be noted that a sizeable exfoliation region appears obviously, may contain aluminum sulphates except for substances mentioned
as a massive block of corrosion products is exfoliated from the sur- above in S2 solution. In addition, more severe corrosion occurs in
face (Fig. 5(h)). The results of EDS reveal that the corrosion products S3 solution in the case of samples after NAT compared with that
90 P. Liu et al. / Journal of Materials Science & Technology 64 (2021) 85–98
Fig. 4. Typical surface image of Al-Zn-Mg alloy after NAT immersed in (a) S1 solution, (b) S2 solution and (c) S3 solution at ambient temperature of 25 ◦ C during experiments.
after AAT, and some relatively loose tile-like exfoliated corrosion
products are scattered on the surface (12 h, in Fig. 5(c)). At the last
period of corrosion test (120 h, in Fig. 5(i)), a large chunks of cor-
rosion products appears and covers on the surface, which seems
like a block of lifted land after earthquake. Furthermore, the sur-
face of alloy looks like an arid field at a high magnification after the
immersion time of 120 h. However, no evident tile-like exfoliated
corrosion products are found for Al-Zn-Mg alloy with AAT, suggest-
ing that the alloy with AAT has a better corrosion resistance than
that of sample with NAT in S3 solution.
Considering the influence of pH change in experiment, since the
bubble evolution was observed in S1 and S3 solutions during the
immersion test, the bulk pH measurements were performed on the
three solutions at ambient temperature of 25 ◦ C in air. The results
are shown in Fig. 7. The bulk pH value of S1 solution (red line with
circle) keeps neutral at first, and then increases slightly with the
immersion time, and this may be attributed to the dissolution of
carbon dioxide from air in solution. What’s more, the pH value mea-
sured in S2 solution (green line with diamond) decreases mildly at
initial and then remains invariant, indicating hydrogen sulfite ion
hydrolyzes to form hydrogen ion in solution, which is very oppo-
site to results gained from S3 solution (blue line with square), i.e.,
bicarbonate radical ion hydrolyzes to alkalify solution. The order
of bulk pH is as follows: S3> S1 > S2, and no significant variation
of bulk pH value can be found, indicating the bulk pH of solution
remains relatively stable even obvious bubble evolution presences.
3.3. Corrosion electrochemical behavior
3.3.1. Polarization curve results
Potential dynamic polarization curves of the alloy under three
electrolyte solutions at ambient temperature of 25 ◦ C with a scan
rate of 1 mV s−1 are shown in Fig. 8. The similarly shape of polariza-
tion curves manifests the similar pattern of corrosion reactions goes
through. The cathodic current densities head towards a plateau
in three different solution for both samples with different aging
treatments, indicating that electrode reactions are controlled by
cathodic reactions at a potential negative far from Ecorr . Moreover,
the anodic current densities increase rapidly at a potential above
Ecorr , which could be explained that the compact oxide film on the
surface of aluminum alloy is inclined to broken, and many alu-
minum atoms are separated from the matrix lattice to the solution
by removing electrons. However, the trend slows down gradu-
ally with the potential increasing, which signifies the reactions are
under diffusion control. In addition, no evident passive region can
be seen from the anodic curves branch. It can be observed explicitly
that the values of Ecorr of samples in NAT are more negative than
that in AAT in all solutions. Another apparent result is the values
sequence of Ecorr for samples with both aging conditions are listed
as follows: S2 < S1 < S3.
3.3.2. EIS measurements
EIS measurements of alloy with NAT and AAT were performed
in S1, S2 and S3 solutions at ambient temperature of 25 ◦ C, respec-
tively, and tested at 4, 8, 12, 24, 48, 72, 96 and 120 h to estimate
the corrosion behavior as a function of immersion time. Represen-
tative EIS experimental results and corresponding fitting curves
using ZSimpWin analysis software are shown in Figs. 9 and 10. The
existence of unsteady state at initial immersion time contributes
to data points disperse especially in low-frequency regions. How-
ever, with increasing the immersion time up to 24 h, low-frequency
data points become regular gradually. Besides, the Nyquist plots
show the similar characters, i.e., capacitive impedance arcs appear
at high and middle frequency and inductive impedance arcs appear
at low frequency range. Nyquist plots of samples with NAT under
S1 solution present a slant angle at low frequency ranges, implying
diffusion process controls entire corrosion process rather than elec-
trochemical charge transfer controls in later period of immersion.
Moreover, the radius of Nyquist loop decreases over the immersion
time in S2 solution while it fluctuates in comparison to that in S1
and S3 solution, reflecting that Al-Zn-Mg alloy has the worse cor-
rosion resistance in S2 and more complicated factors in S1 and S3
solution. This encounter is consistent with results obtained from
the polarization curve measurements. In addition, it is notable that
the radius of capacitive impedance arcs in high and middle fre-
quency ranges is large and capacitive impedance arcs digress from
the feature of semicircle, so it is rational to believe that capacitive
impedance arcs in high and middle frequency ranges are overlaid
by more than one, i.e., the number of time constant is in excess of
one at this ranges (Figs. 9(a), (c), (e) and 10 (a), (c), (e)). According to
the previous literatures [35–37], the dielectric behavior of passive
film on Al-Zn-Mg alloy usually exhibits the capacitive impedance
arc of high frequency ranges, and low-frequency arc generally cor-
responds to the process of metal dissolution, such as metastable
or stable pitting corrosion. Furthermore, absorption of bubbles on
the surface and stratification caused by accumulation of corro-
sion products are normally related to the emergence of inductive
impedance arc in low frequency ranges [38–41]. On top of that, it
can be seen from experimental results that the radius of inductive
impedance arcs at low frequency regions presents same character
as capacitive impedance arcs, and the evident overlaid inductive
impedance arcs appear, indicating that more than one time con-
stant occur at low frequency ranges as well. Moreover, angle phase
plots signify information that ideal capacitance deviates to the cor-
responding electrochemical interface due to the maximum values
of phase angle are at most 90◦ .
The corresponding EEC models are provided in Fig. 11 using
ZSimpWin analysis software in order to further analyze the EIS
behavior of aluminum alloy immersed in three electrolytes for
different immersion time quantitatively. The definition of EEC ele-
ment is presented as follows: Rs is the solution resistance, CPEdl
is used to represent the non-ideality of double-layer capacitance,
 P. Liu et al. / Journal of Materials Science & Technology 64 (2021) 85–98 91

Fig. 5. SEM images of the microstructure of Al-Zn-Mg alloy after NAT immersed in (a, d, g) S1 solution, (b, e, h) S2 solution and (c, f, i) S3 solution at ambient temperature of
25 ◦ C for (a, b, c) 12, (d, e, f) 72 and (g, h, i) 120 h with corresponding EDS analysis of framed region, (A) S1/120 h, (B) S2/120 h, (C) S3/120 h. The insets are higher magnification
of micro-surface.
92 P. Liu et al. / Journal of Materials Science & Technology 64 (2021) 85–98

Fig. 6. SEM images of the microstructure of Al-Zn-Mg alloy after AAT immersed in (a, d, g) S1 solution, (b, e, h) S2 solution and (c, f, i) S3 solution at ambient temperature of
25 ◦ C for (a, b, c) 12, (d, e, f) 72 and (g, h, i) 120 h immersion with corresponding EDS analysis of framed region, (A) S1/120 h, (B) S2/120 h, (C) S3/120 h. The insets are higher
magnification of micro-surface.
 P. Liu et al. / Journal of Materials Science & Technology 64 (2021) 85–98
Rf is the resistance of film usually related to original passive film
and corrosion products, CPEhole is associated with hole capacitance,
Rhole is associated with hole resistance, two inductive elements L
with corresponding R occur to describe the corrosion behavior at
low frequency ranges. CPEct is capacitance associated with charge
transfer, Rct is charge transfer resistance, which is related to faradaic
process, i.e., corrosion reaction is controlled by charge transfer and
Ws is Warburg impedance. As can be seen in Figs. 9 and 10, the best
fitting line can be achieved using the corresponding EEC shown in
Fig. 11.
4. Discussion
4.1. Effects of microstructure of alloy on corrosion behavior
Aging can optimize strength, hardness and other performances,
while morphology and size and type of grain, volumetric fraction
and composition of precipitates, which associated with corro-
sion susceptibility and mechanical properties, are also significantly
influenced by aging condition [42,43]. It is generally accepted that
the grain boundaries and IMPs play a critical role in corrosion
behavior in the terms of microstructural scale. In the current work,
the microstructures of Al-Zn-Mg alloy with two aging conditions
are obviously different in grain size. The alloy with NAT contain-
ing more anisometric coarse grains, and a few fine grains suffers
more severe corrosion compared with samples with AAT, which
is composed with equiaxed grains and fine sub-grains. Although
the present work does not directly offer a conclusion for solid
relationship between grain size and corrosion resistance, some cor-
responding conclusions can be drawn according to experimental
data and literatures [15–18,44,45]. The refinement of grain further
facilitates to generate more uniform oxide layer, mostly ascribed
to a significant increment in the number and region covered by
grain boundaries. Ralston et al. [22] investigated the relationship
between grain size and corrosion rate among different metals, and
a linear regression function according to observation in all cases
was put forward by Eq. (1):
icorr = A + B × gs−0.5
where the constant A is likely correlated with the environment, B
is the material constant varying in composition and impurity level,
and gs represents the grain size. In view of this linear correlation,
icorr is negatively correlated with gs, and therefore, it is rational
to note that lower corrosion rate corresponds to grain size reduc-
tion, which is agreement with detailed experimental phenomena
of our work, i.e., the sample with NAT is inclined to be attacked and
Fig. 8. Typical polarization curves of Al-Zn-Mg alloy after (a) NAT and (b) AAT immersed in S1 solution (green line), S2 solution (red line) and S3 solution (blue line) at
ambient temperature of 25 ◦ C with a scan rate of 1 mV s−1 .
93
Fig. 7. Bulk pH evolution of S1 solution (red line with circle), S2 solution (green line
with diamond) and S3 solution (blue line with square) at ambient temperature of
25 ◦ C.
shows faintish corrosion resistance. Additionally, limited anodic
reactions rate is also related to grain refinement due to in the case
of these reactions are more rest upon ionic conductions than on
electronic conductions, which was investigated by Lee et al. [46].
As a result, these mentioned above indicates that refinement and
homogenization of grain can decrease susceptibility of Al-Zn-Mg
alloy for aggressive conditions.
Meanwhile, another vital factor connected with corrosion
behavior of metal is the difference of IMPs. The type and compo-
sition of precipitates are complicated in the terms of Al-Zn-Mg-Cu
alloys. Al3 Zr precipitates are commonly formed in Al-Zn-Mg alloys
with more than 0.15 wt.% Zr, which usually acts as nucleation sites
of ␩’ and  phase (MgZn2 ) during aging with relatively high melt-
ing point. A majority of references focused on reactivity of MgZn2
phase, for example, Deng et al. [31] reported that the values of
Ecorr of the PZF, stable MgZn2 phase and aluminum matrix are
−0.57, −0.86 and −0.68 V, respectively. Therefore, in the case of
(1)
MgZn2 phase, which acts as the anode and is easier to be attacked
in aggressive condition and induces occurrence of pitting corro-
sion depending on more negative potential than matrix nearby. As
presented in Fig. 2, Al-Zn-Mg alloy after AAT exhibits more pre-
cipitates both along grain boundaries and intragranular regions.
These outcomes seem paradoxical in the terms of electrochemi-
cal and immersion tests. However, it is worthy to note that these
precipitates distribute discontinuously and appear distribution fea-
94 P. Liu et al. / Journal of Materials Science & Technology 64 (2021) 85–98

Fig. 9. Representative Nyquist and Phase angle plots of the Al-Zn-Mg aluminum alloy with NAT under (a, b) S1 solution, (c, d) S2 solution and (e, f) S3 solution at ambient
temperature of 25 ◦ C for 4, 8, 12, 24, 48, 72, 96, 120 h, respectively. The colorful scattered symbols are experimental data and the corresponding fitting results are represented
by black solid lines.

ture alternating with brightness and darkness, whereas mostly it
displays decrease in the content of Al compared with the matrix
both in brighter and darker contrast precipitates, but a concurrent
increase in the content of Zn and Mg is observed in brighter con-
trast precipitates, and no evident increment of Zn and Mg is found
in darker contrast precipitates. Admittedly, the content of these
two elements to Al is lower than brighter contrast precipitates.
Therefore, a conclusion can be drawn combined with phenom-
ena mentioned above with results of TEM/EDS in Fig. 3, referring
to the composition of precipitates along grain boundaries is dif-
ference. Furthermore, electrochemical properties of MgZn2 phase
is correlated with alloying element, electrochemical activity of
MgZn2 phase decreases with content increment of Cu, and a con-
current decrease in Zn and Mg make the potential of MgZn2 phase
towards to noble. Moreover, the increasing content of Zn and Cu and
decreasing content of Mg would also shift MgZn2 phase towards
less anodic. In short, the difference of the content of Cu, Zn and Mg
in MgZn2 phase is the difference of potential between MgZn2 phase
and surrounding aluminum matrix, it determines whether they can
act as electrochemical units or not, whereas the effect of MgZn2
phase would be overwhelmed and even reversely protect matrix
from attacking by these factors. Additionally, sparser and strip-like
precipitates enhance restrain corrosion propagation by reducing
hydrogen concentration and further eliminate the negative impact
 P. Liu et al. / Journal of Materials Science & Technology 64 (2021) 85–98 95

Fig. 10. Representative Nyquist and Phase angle plots of the Al-Zn-Mg aluminum alloy with AAT under (a, b) S1 solution, (c, d) S2 solution and (e, f) S3 solution at ambient
temperature of 25 ◦ C for 4, 8, 12, 24, 48, 72, 96, 120 h, respectively. The colorful scattered symbols are experimental data and the corresponding fitting results are represented
by black solid lines.

on metal atom bonding [47]. The higher volume fraction of pre-
cipitates both in grain boundaries and intragranular regions may
contributes to weak the effect of galvanic coupling between grains
boundaries and alloy matrix. Otherwise, more dislocation lines and
loops spreading over the intragranular regions can be noted in alloy
with NAT, as the presence thereof in the microstructure may have
positive influence on the corrosion rate due to their disorder fea-
ture, which makes them as favorable places for corrosion attack,
thus they may have serious corrosion. Also, high density of dislo-
cation may inevitably accelerate increment of pits in depth with
spreading pits for coarse grain and hinder repassivation for alloy
at the later stage. Moreover, no obvious dispersoid posed in grain
boundaries strengthens the effect of galvanic coupling mentioned
above. As a result, in present work the finding is proposed, that the
corrosion resistance of Al-Zn-Mg alloy after AAT is better than that
after NAT. In addition, the electrochemical behavior and corrosion
resistance not merely depend on potential of precipitates, but result
from a synergistic effect of the grain size, precipitate composition
and distribution as well as other factors.
4.2. Effect of cathodic ions on electrochemical behavior
It is concluded from the experimental data that the Ecorr of alloy
with NAT is more negative than that with AAT, moreover, the evo-
lution of fitting values of the Rct with the immersion time in three
solutions is shown similarly. Compared with Al-Zn-Mg alloy with
96 P. Liu et al. / Journal of Materials Science & Technology 64 (2021) 85–98

Fig. 11. Equivalent circuit models used to fit EIS data under OCP condition at ambient temperature of 25 ◦ C. Rs is electrolyte solution resistance, CPEdl is double-layer
capacitance at high frequency, Rf is film resistance, CPEhole is associated with hole capacitance, Rhole is associated with hole resistance, CPEct is charge transfer capacitance at
low frequency, Rct is charge transfer resistance, Ws is Warburg impedance, L is the inductance for fitting dispersive inductive tails and R is corresponding resistance at low
frequency.

NAT, the Rct of that in AAT presents one order larger in value. Gener-
ally, the reciprocal of Rct is regarded as an important parameter for
characterizing the corrosion rate. Therefore, Rct is always taken to
illuminate the evolution of corrosion process and corrosion resis-
tance. In this work, Fig. 12 depicts the values of Rct collected from
the fitting results for S1, S2 and S3 solutions of different immersion
time. With respect to two aging conditions of alloy, the value of
Rct tends to decrease with ongoing immersion time in S2 solution.
Meanwhile, the value of Rct goes up and down as a function of time
in S1 and S3 solutions. In view of complicated EEC models make
the components of EEC favorable for interacting with each other
during fitting experimental results. Moreover, in the case of the
analysis results of SEM/EDS, component element of corrosion prod-
ucts on the surface in S2 solution contains sulfur, implying sulfur
involved in the reactions, which are varied from corrosion products
formed in S1 and S3 solutions. On the grounds of literature review
[48], in the case of the existence of defect, these areas are prone
to be attacked in the presence of chloride ion, thereby, this causes
high reactivity of localized oxide film to break, and fresh Al matrix
is exposed to the electrolyte solution. In neutral aerated solution,
most anodic reaction presents oxidation of matrix from Al to Al3+ ,
while dominant cathodic reaction contains reduction of dissolved
oxygen to form OH− , and then Al3+ combines with OH− to produce
aluminum hydroxides or oxides layer. Nevertheless, Al favors to
react with bisulfite ion (HSO3− ) to produce aluminum sulphates
easily caused by the sulfite and its analogues in solution, which
is mainly composed of Al2 (SO4 )3 ·16H2 O and Al3 (SO4 )2 (OH)5 ·9H2 O
[49]. Compared with aluminum hydroxides or oxides, aluminum
sulphates are more stable, due to the latter characterized by amor-
phous forms. However, aluminum hydroxides or oxides are prone
to further transform. Besides, double hydrolysis reaction is carried
out in S3 solution, and numerous of bubbles are posed in S1 and S3
solutions, whereas rare bubble is found in S2 solution during tests
as shown in Fig. 4. What’ more, the surface of alloy lost its metallic
luster under S2 solution as if it is covered by a passive film com-
pared with S1 and S3 solutions in Fig. 4, so it is rational to believe
that these bubbles promote lower stability of aluminum hydrox-
ides or oxides on the surface, which is consistent with variation
of the Rct value in different solutions. With the immersion time
increasing, the value of Rct in S2 solution shifts to small, indicating
less protection of the corrosion product layer. However, the data
obtained from EIS measurements merely reflect average informa-
tion on entire testing interface, that the alloy after AAT presents
superior corrosion resistance to that after NAT on a whole.
In summary, the better corrosion behavior of Al-Zn-Mg alloy is
gained with AAT than that with NAT. This good electrochemical
character is may attributed to more refinement and homogeniza-
tion of grain giving rise to the stronger protective layer of corrosion
products, which effectively restrains attack from aggressive ions
diffused from bulk solution to electrode interface. Although many
previous works have reported that the precipitation of ’ or  phase
in grain boundaries would increase susceptibility of alloy to severe
environment, the result of these work reflects that the corrosion
behavior of alloy is associated with various factors, which would
be overwhelmed if others act as domination. Moreover, the corro-
sion resistance is higher during 4 h especially in S2 solution than
that in S1 and S3 solution, and these phenomena are reverse after
a long period of immersion. Additionally, in order to simulate nat-
ural condition, dissolved oxygen did not deaerate before tests. As
a result, bubbles absorbing on the surface have a great effect on
EIS data. However, based on the analysis of SEM and EIS, it can be
found that Al-Zn-Mg alloy is inclined to induce localized pitting in
S1 solution, and serious exfoliation corrosion occurs in S2 and S3
solution especially with NAT.
 P. Liu et al. / Journal of Materials Science & Technology 64 (2021) 85–98
Fig. 12. Fitting values of Rct in EEC of Al-Zn-Mg alloy with NAT and AAT condi-
tions, immersed in (a) S1 solution, (b) S2 solution and (c) S3 solution at ambient
temperature of 25 ◦ C, respectively.
5. Conclusions
Microstructure and electrochemical behavior in the three sim-
ulated service environments as well as relationship between them
for Al-Zn-Mg alloy with NAT and AAT have been studied in this
work. Following conclusions can be reached through above several
aspects of research:
(1) The alloy after NAT is mainly consisted of anisometric coarse
grains and a few fine sub-grains, while the alloy after AAT is
composed of equiaxed grains and fine sub-grains, and the grain
size of each presents a great difference, the grain size of the
alloy in NAT is in the range of 11−35 ␮m relative to 5−12 ␮m of
that after AAT, and the ratios of coarse grains are higher in NAT.
A numerous MgZn2 phase both in intragranular regions, along
grain boundaries and in evident PZF zones are observed in alloy
97
after AAT, while Al3 Zr precipitates and numerous dislocations
are presented that with NAT.
(2) The alloy after NAT has the worse corrosion resistance, and
numerous bubbles are absorbed on the surface when the alloy
immersed in NaCl solutions with/without NaHCO3 . Localized
pitting corrosion occurs at initial immersion time, while pit-
ting corrosion spreads over the surface later. With respect to
NaCl solution, the corrosion behavior of the alloy is prone to
involve in serious exfoliation corrosion in solutions containing
additional NaHSO3 or NaHCO3 . The layer of corrosion products
formed in NaCl solution containing NaHSO3 offers the worse
protection from corrosion attack.
(3) Corrosion resistance of the alloy not merely depends on the
potential between matrix and precipitates, but associated with
a synergistic effect of the grain size, precipitates composition
and distribution, aggressive ion as well as other factors.
Acknowledgements
This work was financially supported by the National Key R&D
Program of China (No. 2017YFB0702302), the National Natural
Science Foundation of China (No. 51771174) and the National Mate-
rials Corrosion and Protection Data Center. F.H. Cao acknowledges
the assistant of Prof. J.F. Li and Dr. H. Ning from Central South Uni-
versity for TEM measurements.
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