j m a t e r r e s t e c h n o l .

2 0 2 0;9(5):11201–11219

Available online at www.sciencedirect.com

https://www.journals.elsevier.com/journal-of-materials-research-and-technology

Original Article

Study on heat treatment to improve the

microstructure and corrosion behavior of ZK60
magnesium alloy

Zhen Li a , Zeyin Peng a , Yubing Qiu a,b,∗ , Kai Qi a , Zhenyu Chen a,c , Xingpeng Guo c,d,∗
a School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, PR China
b Key Laboratory of Material Chemistry for Energy Conversion and Storage (Huazhong University of Science and Technology), Ministry of
Education, Wuhan 430074, PR China
c Hubei Key Laboratory of Materials Chemistry and Service Failure, Wuhan 430074, PR China
d School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, PR China

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

Article history: The effects of different heat treatments on the microstructure and corrosion behavior of
Received 16 January 2020 an as-cast ZK60 magnesium alloy were investigated by microscopic analyses, weight loss
Accepted 1 August 2020 tests, hydrogen evolution tests, and electrochemical measurements. The results indicate
Available online 19 August 2020 that solution treatment (T4) could result in the dissolution of most of the second-phase par-
ticles and make the alloying elements (Zn and Zr) distribute uniformly. However, new tiny
Keywords: second phase particles re-precipitated during aging treatment (T6). The as-cast and heat-
ZK60 magnesium alloy treated ZK60 alloys displayed filiform-like corrosion morphologies with different initiation
Heat treatment and propagation features in the early corrosion period, and they gradually developed corro-
Microstructure sion pits. Their corrosion rates showed similar change tendencies, and the T4-treated ZK60
Corrosion behavior alloy exhibited the best anti-corrosion performance owing to it having the weakest micro-
galvanic effect. The relationship between the alloys’ microstructures and their corrosion
features was analyzed, and the involved mechanism was examined.
© 2020 The Author(s). Published by Elsevier B.V. This is an open access article under the
CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

specific strength [5–9]. In recent years, ZK60 (typical Mg–Zn–Zr)

1. Introduction alloys have greatly attracted the attention of researchers. How-
ever, their weak corrosion resistance is still a restraining factor
Magnesium (Mg) is the lightest structural metal and has
when they are applied in corrosive environments.
high specific strength and specific stiffness. Because of these
Some researchers have tried to improve the corrosion
properties, Mg alloys have received widespread attention in
resistance of ZK60 alloys by surface modification methods,
recent years [1–4]. Among the different Mg alloys, Mg–Zn–Zr
including micro-arc oxidation (MAO) [10–12], ions implanta-
series alloys are widely used for automobile panels, aircraft
tion [13,14], hydrothermal treatment [15,16], and conversion
envelopes, and biomaterials due to their superior strength and
coatings [17–19]. However, in addition to the surface modifica-
tion, improving the corrosion resistance of the ZK60 substrates
is still necessary to enhance the overall protection perfor-
∗ mance of the alloys. According to the studies on Mg alloys
Corresponding authors.
E-mail: qiuyubin@mail.hust.edu.cn (Y. Qiu).
https://doi.org/10.1016/j.jmrt.2020.08.004
2238-7854/© 2020 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
11202 j m a t e r r e s t e c h n o l . 2 0 2 0;9(5):11201–11219
[20–26], the grain size [20], texture [21], alloying elements [22],
intermetallic particles, and second phases [23] of the alloys
can influence the alloys’ corrosion behavior [24–26]. However,
the corresponding research on ZK60 alloys is still limited.
In recent years, the corrosion resistance of ZK60 alloys has
been improved in some studies by microstructure modifica-
tion through heat treatment [27,28], deformation processing
[29–31], and the addition of alloying elements [32–34]. Based on
the findings of these studies, grain refinement, the evolution
of a nobler texture, and the small size and uniform distribu-
tion of second-phase particles may promote the formation
of a reasonably consistent protective layer on the surface of
ZK60 alloys to improve their corrosion resistance. Moreover,
the change in the nobility of the newly formed second phases
may enhance the micro-galvanic corrosion and degrade the
corrosion resistance of the alloys. These studies focused on the
effect of various treatments on the microstructure and the cor-
rosion behavior of ZK60 alloys, but the relationship between
them is still not clearly understood.
Until now, a unified conclusion has not been reached on the
effect of alloying element Zr on the corrosion of Zr-containing
Mg alloys. Neil et al. [35] attributed the attack in the center
region of grains to the presence of Zr-rich regions and Zr-rich
intermetallic particles. On the contrary, other studies found
that the presence of Zr-rich areas within the center of grains
resulted in higher corrosion resistance of these regions com-
pared with the other parts of the grains [36,37]. Moreover, a fine
distribution of Zr particles in Mg alloys can lead to better pro-
tection due to the stable oxide film on the alloys surface [38].
In this case, if the Zr-rich regions in ZK60 alloys are dissolved
back into the Mg matrix, a more homogenous Zr-distribution
may decrease the cathodic sites within the center region of
the grains, and consequently, a more stable oxide film will
be formed, increasing the corrosion resistance of the region.
However, the corresponding research has not been reported.
Heat treatment is an effective way to adjust the alloy
phases and composition distributions, which can have a
significant influence on the corrosion of Mg alloys [39–42].
However, relevant research on the heat treatment of ZK60
alloys is still lacking. In recent years, Chen et al. [43] reported
that T5 treatment enhanced the corrosion resistance of an
extruded ZK60 alloy due to the formation of small and uni-
formly distributed MgZn phases. Therefore, heat treatment is
likely to increase the corrosion resistance of ZK60 alloys by
adjusting the distribution of Zr and second-phase particles.
In this study, a commercial as-cast ZK60 alloy was selected
as test material, and different heat treatments—solution
treatment (T4) and aging treatment (T6)—were employed to
investigate their effects on the microstructure and corrosion
behavior of the ZK60 alloy. The microstructure of the as-cast
ZK60 alloy before and after heat treatments was character-
ized by various microscopic analyses. The corrosion behavior
of the alloy in 0.1 M NaCl was investigated using electrochem-
ical measurements, weight loss tests, and hydrogen evolution
tests. The relationship between the microstructure and the
corrosion features of the ZK60 alloy was analyzed, and the
involved mechanism was studied. This work will help clar-
ify the effect of microstructure on the corrosion behavior of
ZK60 alloys. It can also provide a reference for microstruc-
Table 1 – Chemical composition of the as-cast ZK60 alloy
(wt. %).
Zn Al Fe Ni Cu Zr Mg
5.80 <0.01 <0.01 <0.01 <0.01 0.57 Bal.
Table 2 – Heat treatment conditions of the as-cast ZK60
alloy.
Conditions Parameters
As-cast –
T4 515 ◦ C 2 h water quenching
T6 515 ◦ C 2 h water quenching + 160 ◦ C 24 h air cooling
ture modification to improve the corrosion resistance of the
alloys.
2. Experimental
2.1. Materials and solutions
A commercial as-cast ZK60 alloy ingot was employed as the
test material. Table 1 presents the chemical composition of
the alloy, which was obtained by inductively coupled plasma-
atomic emission spectrometry (ICP-AES) analysis. The as-cast
ZK60 ingot was sectioned to test samples (10 × 10 × 10 mm3 )
for all of the experiments. The heat treatments of the ZK60
alloy were conducted under N2 atmosphere protection, and
their specified conditions are listed in Table 2. The solutions
used in this work were prepared with analytical grade reagents
and distilled water. The test solution was 0.1 M NaCl under
open-air condition, which was controlled at 25 ± 1 ◦ C with a
water bath.
2.2. Microstructure characterization
For metallographic observation, the test specimens were
ground to 2000 grit SiC paper, polished with 3 ␮m diamond
paste, and then etched by a solution containing 1.5 g picric
acid, 25 mL ethanol, 5 mL acetic acid, and 10 mL water. The
metallographic morphologies were characterized via scan-
ning electron microscopy (SEM, Quanta 200) coupled with
energy-dispersive X-ray spectroscopy (EDX, EDAX-Genesis)
and transmission electron microscopy (TEM). Using EDX, the
element content of the second-phase particles and the lin-
ear element distribution of the test samples were analyzed.
X-ray diffraction (XRD, Philips, model PW1830) was utilized to
confirm the phase structure of the specimens. The TEM sam-
ple was firstly mechanically grounded to a thickness of about
20 ␮m, and then ion milled at 4 keV and 4◦ , cooled by liquid
nitrogen. TEM observations were carried out with an FEI Talos
F200X transmission electron microscope operated at 200 kV.
Scanning Kelvin probe force microscopy (SKPFM, SPM-9700)
was used to measure the relative Volta potential differences
among different microstructural constituents to show their
relative nobility; meanwhile, the corresponding topography
maps of the same area were also obtained.
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(5):11201–11219
Fig. 1 – Schematics of the hydrogen evolution test system.
2.3. Weight loss tests
The specimens (10 × 10 × 10 mm3 ) were ground to 2000 grit SiC
paper, cleaned in distilled water and ethanol, dried with cool
air, and then immersed in 0.1 M NaCl solution for different
times. After taken out of the solution, the specimens were
immersed in a solution of 180 g CrO3 with 1000 mL of reagent
water for 10 min to remove the corrosion products. Accord-
ing to [44,45], the obtained average weight loss rate of the test
samples (W, mg cm−2 h−1 ) can be converted to an average
corrosion rate Pw (mm/y) using Eq. (1):
Pw = 3.65 × 24 × W/,
where  is the metal density (g/cm3 ). For the as-cast ZK60 alloy,
 = 1.8 g/cm3 ; thus, Eq. (1) becomes:
Pw = 48.67W.
At least three parallel tests were carried out for each test
condition to ensure the reliability of the test data.
2.4. Hydrogen evolution tests
Fig. 1 presents the schematic of the hydrogen evolution test
system, in which the plug-in sample (10 × 10 × 10 mm3 ) was
prepared based on [46]; the evolved hydrogen was collected
in the burette to obtain its volume (VH , mL cm−2 ) at different
times (t). The hydrogen evolution test for different samples
was repeated at least three times in this study. The hydrogen
evolution rate (vH , mL cm−2 day−1 ) at different times is calcu-
lated through the differentiation of the VH –t data. According
to [44,45], vH is also converted to the corresponding corrosion
rate, PH (mm/y), using Eq. (3):
PH = 2.2vH
2.5. Electrochemical measurements
A typical three-electrode system was used in the electrochem-
ical tests, including a saturated calomel reference electrode
(SCE), a platinum (Pt) counter electrode, and a test sample
working electrode. The working electrode (10 × 10 × 10 mm3 )
was sealed by epoxy resins (working area = 1.0 cm2 ), which was
11203
ground to 2000 grit SiC paper and rinsed in distilled water
and ethanol before the electrochemical tests. After immersion
in 0.1 M NaCl solution at 25 ◦ C for different times, the elec-
trochemical impedance spectroscopies (EIS) and polarization
curves were measured, separately using a CS 350 Corrtest elec-
trochemical workstation. The potential scanned toward the
positive direction with a rate of 0.5 mV/s in the polarization
curve measurements. Based on [44,45], we also applied the
cathodic Tafel extrapolation method to estimate the corrosion
current density (icorr , mA cm−2 ) and the cathodic Tafel slope
(bc , mV/Dec). The corresponding corrosion rate (Pi , mm/y) is
converted by the equation Pi = 22.06icorr , according to [45,47].
The EIS measurements were performed at free corrosion
potential (Ecorr ) with the AC voltage amplitude ±10 mV in the
frequency range of 100 kHz to 0.05 Hz. All the EIS results were
fitted using Zview2.0 software. All the electrochemical tests
under different conditions were repeated at least three times
to ensure the accuracy of the results.
2.6. Corrosion morphology observation
The corrosion morphology of the etched samples immersed
in 0.1 M NaCl for different times was characterized by SEM
(Quanta 200) to observe the corrosion development in the early
immersion period (0–2 h). The corrosion morphology of the
samples immersed in 0.1 M NaCl for three days (with corrosion
products removed) was characterized by SEM (Quanta 200) and
a 3D microscope system (KEYENCE VHX-1000) to observe the
(1)
corrosion pits and their depth.
3. Results
(2) 3.1. Microstructure of the ZK60 alloys
Fig. 2 presents the back-scattered electron (BSE) SEM micro-
graphs of the as-cast, T4-treated, and T6-treated ZK60 alloys.
The microstructure of the as-cast ZK60 alloy was composed
of ␣-Mg phase and some large second-phase particles, which
were mainly deposited along the grain boundaries (Fig. 2a–b).
The element distribution of the as-cast ZK60 was not homo-
geneous because the brighter areas contained more elements
of higher atomic weight than the darker regions in the BSE-
SEM images; a similar element distribution was found in
Mg–Zn–Y–Zr alloy in [48]. After the T4 treatment at 515 ◦ C
for 2 h, most of the second-phase particles were dissolved in
the matrix (Fig. 2c–d), which would transform into a super-
saturated solid solution, as reported in [49], and only a small
amount of tiny particles distribute unevenly in the matrix and
grain boundaries (Fig. 2d). Furthermore, the element distribu-
tion of the T4-treated alloy was more uniform (Fig. 2c and d).
(3) In the T6-treated alloy (Fig. 2e and f), more second- phase par-
ticles occurred again. Nevertheless, they were more tiny and
homogeneous than those in the as-cast alloy (Fig. 2e), which
may help to improve the alloy corrosion resistance as reported
for the case of the heat-treated WE43 Mg alloy in [50].
Block-shaped, globular, and rod-like particles existed on
the grain boundaries or in the matrix of the T6-treated alloy
(Fig. 2f). Table 3 presents the EDX point analysis results of these
particles. The rod-like (point 1) and globular (point 2) particles
11204 j m a t e r r e s t e c h n o l . 2 0 2 0;9(5):11201–11219

Fig. 2 – BSE–SEM micrographs of the ZK60 alloys: (a, b) as-cast; (c, d) T4-treated; (e, f) T6-treated.

Fig. 3 presents the XRD diffraction patterns of the ZK60

Table 3 – EDX analysis results of the second phase
particles in Fig. 2f. alloys after different heat treatments. The patterns indicate
that the primary second phase was MgZn2 in the three ZK60
Particles Mg (at.%) Zn (at.%) Zr (at.%)
alloys, and no Zr-rich phase was detected probably because
1 41.6 57.8 0.6 of the low Zr content in the alloys. From the change in the
2 55.2 44.8 / diffraction peak intensity in Fig. 3b, it can be concluded that
3 56.9 17.3 25.8 most of the second-phase particles in the as-cast ZK60 alloy
were dissolved into the Mg matrix in the T4 treatment and
re-precipitated during the aging process, which is consistent
on the grain boundaries mainly contained Mg and Zn, while
with the SEM results in Fig. 2.
the block-like particles (point 3) in the matrix were rich in Zr.
Even though some [51,52] reported that there were lamel-
It is difficult to precisely determine the chemical composition
lar MgZn phase and MgZn2 phases in the cast ZK60 alloy, the
of these particles by EDX; thus, we temporarily denote them
diffraction peaks in Fig. 3b just indicates the presence of the
as Mgx Zny and Zr-rich phase in Fig. 2f.
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(5):11201–11219 11205

Fig. 3 – (a) XRD patterns of the ZK60 alloys and (b) the partial magnification.

Fig. 4 – TEM micrograph of the as-cast ZK60 alloy and the corresponding SAED patterns (a–c) of the second phase particles.

MgZn2 phase in the as-cast ZK60 alloy. To further verify the
second phase in the as-cast ZK60 alloy, Fig. 4 presents the
TEM micrograph of the as-cast ZK60 alloy and the selected
area electron diffraction (SAED) patterns of the second-phase
particles. Block-shaped, globular, and short rod second-phase
particles were observed in Fig. 4, and their SAED patterns in
Fig. 4a–c proved that they were MgZn2 [53]. No MgZn phase
was found in the as-cast ZK60 alloy.
After the T4 treatment, most of the MgZn2 phase was dis-
solved in the Mg matrix; thus, its diffraction peaks nearly
disappeared (Fig. 3b). However, the MgZn2 phase formed dur-
ing solidification had a high melting point and high stability; it
is difficult for this phase to be completely dissolved during the
T4 treatment [53]. Therefore, the MgZn2 phase is still indicated
in the XRD pattern of the T4-treated ZK60 alloy (Fig. 3b).
11206 j m a t e r r e s t e c h n o l . 2 0 2 0;9(5):11201–11219

Fig. 5 – BSE–SEM micrographs and corresponding EDX linear scanning analysis results of the ZK60 alloys: (a, b) as-cast; (c, d)
T6-treated.

Fig. 6 – Sketch map for the microstructural change in the ZK60 alloys: (a) as-cast; (b) T4-treated; (c) T6-treated.

After the T6 treatment, the diffraction peak intensity of
MgZn2 increases again, but their shape and position are dif-
ferent from those of the as-cast alloy (see Fig. 3b), suggesting
that a different MgZn2 phase was formed during the aging
treatment. According to [54–59], when aged at 120–260 ◦ C, ˇ1
and ˇ2 are considered as the main precipitate phase in Mg–Zn
alloys, and their structure is similar to that of the Laves phase
(MgZn2 ). The ˇ2 phase formed during the overaging process
can be excluded because the T6 treatment condition in this
work is much different from the condition of the overaging
process. Thus, apart from the residual granulate-like MgZn2
phase after the T4 treatment, the rod-like ˇ1 phase and block-
like Zr-rich particles (see Fig. 2f and Table 3) were newly formed
during the aging process in the T6-treated ZK60 alloy.
To further verify the effect of the heat treatment on the
element distribution, Fig. 5 presents the EDX linear scanning
analysis results of the ZK60 alloys. The element distribution
of the as-cast ZK60 was not uniform, as shown in Fig. 5a and
b; the Zr and Zn contents were relatively higher in the light-
colored grain region (denoted as the Zr-rich region), and the
dark grain boundary region had a relatively higher Mg con-
tent. Here, the “grain boundary region” of the as-cast ZK60
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(5):11201–11219
Fig. 7 – SKPFM topography maps (a, c, e) and corresponding potential maps (b, d, f) of the ZK60 alloys: (a, b) as-cast; (c, d)
T4-treated; (e, f) T6-treated.
is denoted as the areas between the Zr-rich region, i.e., the
dark areas in Fig. 2b. The results in Fig. 5c and d indicate that
the distributions of Zr and Zn were uniform in the T6-treated
ZK60 alloy, which is consistent with the BSE–SEM analysis
results in Fig. 2e and f. Moreover, the element distribution
in the T4-treated ZK60 alloy was more uniform than that in
the T6-treated ZK60 alloy (Fig. 2c and d). Thus, the heat treat-
ment makes the distribution of the alloying elements more
homogeneous in the ZK60 alloys.
Based on the above results, Fig. 6 presents a sketch map to
describe the microstructural change in the ZK60 alloys after
different heat treatments. The heat treatment improves the
distribution of the alloying elements and second phases in
the ZK60 alloys, which may cause a more homogeneous elec-
trochemical activity in their microstructures, consequently
weakening the micro-galvanic corrosion effect [60].
Fig. 7 shows the surface topography and potential maps of
the as-cast, T4-treated, and T6-treated ZK60 alloys obtained
by SKPFM analysis, while Fig. 8 gives the Volta potential pro-
files along the lines in the potential maps. The results in Fig. 7
generally indicate that the bright second-phase particles had
much higher potential than the surrounding Mg matrix, and
the potential distribution of the Mg matrix may become more
uniform after the heat treatment.
The detailed potential profiles in Fig. 8a, c, and d reveal
that the maximum relative potential difference between the
second-phase particle and the Mg matrix was about 681 mV,
254 mV, and 451 mV for the as-cast, T4-treated, and T6-treated
ZK60 alloy, respectively. The central area of grains in the as-
cast ZK60 alloy (Zr-rich region) exhibited relatively higher
11207
potential than the grain boundary regions (Fig. 8b), probably
due to the presence of more Zr and Zn contents in these areas
(Fig. 5b). However, this potential difference was nearly absent
in the T4- and T6-treated ZK60 alloys (Fig. 8c and d) because
of their uniform element distribution in the Mg matrix. The
heat treatment decreased the potential difference between
the second-phase particle and the Mg matrix, and a uniform
potential distribution was formed in the Mg matrix, which
would reduce the micro-galvanic corrosion in the ZK60 alloys.
In this case, the T4-treated alloy should have relatively bet-
ter corrosion resistance than the as-cast and T6-treated ZK60
alloys.
It should be noted that the grain size of the as-cast
ZK60 alloy was about 20–40 ␮m (Figs. 2b and 8b) and
increased slightly after the T4 and T6 treatments (Fig. 2).
However, the potential difference in the heat-treated alloys
decreased according to the results in Fig. 8, indicating that
the microstructural change after the heat treatments did not
increase the micro-galvanic effect of the alloys. According to
[61], the galvanic effect of the intermetallic particles and the
segregated alloying elements in the grain boundary zones are
the decisive factors affecting the corrosion resistance of Mg
alloys. Therefore, we did not consider the influence of the grain
size in this study.
3.2. Weight loss and hydrogen evolution tests
Fig. 9 shows the corrosion rates (PW ) of the as-cast, T4-
treated, and T6-treated ZK60 alloys after they were immersed
in 0.1 M NaCl solution for different times, denoted as Pw as−cast ,
11208 j m a t e r r e s t e c h n o l . 2 0 2 0;9(5):11201–11219
Fig. 8 – Volta potential profiles along the lines in the SKPFM maps of the ZK60 alloys: (a, b) as-cast; (c) T4-treated; (d)
T6-treated.
Fig. 9 – Corrosion rates obtained from weight loss tests of
the as-cast, T4-treated, and T6-treated ZK60 alloys after
immersion in 0.1 M NaCl solution for different times at
25 ◦ C.
Pw T4 , and Pw T6 , respectively. The Pw as-cast at 24 h was about
3.5 ± 0.1 mm/y, which is similar to that of a cast ZK60 in 0.9%
NaCl (4.6 ± 0.6 mm/y) reported by Merson et al. [62]. However,
as illustrated in Fig. 9, the Pw value of the three alloys signif-
icantly decreased with time in 0–72 h, and increased slightly
after 72 h, suggesting that the T4 and T6 heat treatments did
not change the general corrosion behavior of the alloy. The
Pw order of the three ZK60 alloys was Pw as-cast > Pw T6 > Pw T4 in
0–72 h, and it became Pw as-cast ≈ Pw T6 > Pw T4 in 72–96 h, indicat-
ing that the T6-treated ZK60 alloy showed a lower corrosion
rate in the corrosion period of 0–72 h and the T4-treated ZK60
alloy exhibited the best corrosion resistance.
Fig. 10 presents the hydrogen evolution test results of
the as-cast, T4-treated, and T6-treated ZK60 alloys in 0.1 M
NaCl to elucidate the detailed changes of their corrosion
rates with time; the VH –t curve in Fig. 10a is differentiated
to obtain the vH at different times, and then PH is calcu-
lated using Eq. (3). The VH as-cast at 24 h (Fig. 10a) was about
0.7 ± 0.03 mL/cm2 , which is close to that of an extruded ZK60
in 0.1 M NaCl (∼0.5 mL/cm2 ) recently reported in [30]. As shown
in Fig. 10b, the PH as-cast value increased quickly in the ini-
tial period (0–1.5 h) and decreased with time until t = 48 h
(1.5–48 h), then it increased again in 48–72 h, suggesting that
there may be different corrosion stages in the test period. The
PH T4 and PH T6 values also exhibited similar change tendencies,
but the three corrosion periods were about 0–18 h, 18–52 h, and
52–72 h. Furthermore, the PH order of the three ZK60 alloys
was PH as-cast > PH T6 > PH T4 in the period of about 0–2 h and it
became PH as-cast ≈ PH T6 > PH T4 after 5 h. Thus, the inhibition in
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(5):11201–11219
Fig. 10 – (a) VH –t and (b) PH –t curves of the as-cast, T4-treated, and T6-treated ZK60 alloys measured by the hydrogen
evolution test in 0.1 M NaCl.
the hydrogen evolution process on the T6-treated alloy only
occurred in the early corrosion period (0–2 h), but that on the
T4-treated alloy was maintained throughout the test period.
These results may be related to the change in the surface con-
ditions of these ZK60 alloys, which is discussed later.
3.3. Electrochemical tests
3.3.1. Potentiodynamic polarization curves
Fig. 11 presents the polarization curves of the as-cast, T4-
treated, and T6-treated ZK60 alloys after immersion in 0.1 M
NaCl for different times and the changes in their corrosion
rates (icorr and Pi ) with time. The polarization curves in Fig. 11
generally show similar characteristics. Their cathodic sides
are controlled by the hydrogen evolution reaction, and their
anodic branches display the active dissolution of Mg with
a so-called breakdown potential (except t = 2 h) owing to the
breakdown of the oxide film on these alloys; this observation
is similar to those reported in [63,64].
The heat-treated alloys, especially the T4-treated alloy,
exhibited a more positive Ecorr compared with the as-cast
alloy, and the Ecorr values of the two alloys generally became
more positive with increasing immersion time (Fig. 11a–e).
These results, combined with the change in the anodic polar-
ization curves in Fig. 11, imply that the anodic process on
the heat-treated alloys was impeded. The icorr and Pi val-
ues in Fig. 11f are much smaller than the Pw (Fig. 9) and PH
(Fig. 11b) values. Similar results from other Mg alloys have
been discussed in detail in [44,45]. However, they displayed
a similar change tendency. The icorr and Pi of the three ZK60
alloys (Fig. 11f) also exhibited three corrosion periods: 0–2 h,
2–24 h, and 24–72 h. Generally, Pi as-cast > Pi T6 > Pi T4 in 0–24 h,
and Pi as-cast ≈ Pi T6 > Pi T4 after 24 h. These results also indicate
that the corrosion resistances of the heat-treated ZK60 alloys
were improved, and the T4-treated ZK60 alloy had the best cor-
rosion resistance. Their specific change with time is discussed
later.
3.3.2. EIS results
Fig. 12 shows the Nyquist diagrams of the as-cast, T4-, and
T6-treated ZK60 alloys after their immersion in 0.1 M NaCl for
11209
different times and the change of their 1/Rp (polarization resis-
tance) as a function of time. The EIS results of the T4- and
T6-treated ZK60 alloys show similar features compared with
those of the as-cast alloy, i.e., two capacitive loops in the high-
frequency region and an inductive loop in the low-frequency
region, except those at 0.5 h, as shown in Fig. 12a, where there
is no inductive loop. The capacitive loops are related to the
processes in the surface film and the electrical double layer
[57], and the inductive loop is attributed to the initiation of
the localized corrosion on the surface of the as-cast ZK60 alloy
according to [65–67]. Here, the disappearance of the inductive
loop implies a higher stability of the oxide films on the T4- and
T6-treated alloys compared with that on the as-cast alloy in
the initial immersion period (0–0.5 h). With increasing immer-
sion time, the low-frequency inductive loop appears on the T4-
and T6-treated alloys (see Fig. 12b–d), indicating that localized
corrosion occurred on their surface.
Fig. 13 presents the equivalent circuits to fit the EIS results
in Fig. 12 [68–70]; here, Rs represents the solution resistance;
Rct represents the charge transfer resistance. CPEdl is the con-
stant phase element (CPE) to describe the electrical double
layer; Rct and CPEdl are used to describe the high-frequency
capacitive loop; Rf and CPEf represent the surface film resis-
tance and the CPE for the surface film, respectively, which are
used to describe the medium-frequency capacitance loop; RL
and L denote equivalent resistance and inductor, respectively,
to describe low-frequency inductive behavior [66]. The fitting
curves fit the raw data, as displayed in Fig. 12, and Table 4 lists
the obtained fitting results. Based on the methods in [65,69],
the fitting curves are extrapolated to the zero-frequency limit
to obtain the polarization resistance (Rp ). Therefore, we can
present 1/Rp –t curves (Fig. 12f) to indicate the change in cor-
rosion rate with time.
The Rf , Rct , and Rp values of the T4- and T6-treated ZK60
alloys (except the Rf of the T6-treated) are much larger than
those of the as-cast ZK60 alloy in the initial period (0.5 h,
Table 4), demonstrating that the heat-treated alloys had a
more protective oxide film to inhibit their corrosion. The 1/Rp –t
curves (Fig. 12f) show similar change tendencies compared
to the icorr –t curves (Fig. 11f), further proving that the T4
and T6 heat treatments improved the corrosion resistance of
11210 j m a t e r r e s t e c h n o l . 2 0 2 0;9(5):11201–11219

Fig. 11 – Polarization curves of the as-cast, T4-, and T6-treated ZK60 alloys after immersion in 0.1 M NaCl solution for
different times: (a) 0.5 h, (b) 2 h, (c) 24 h, (d) 48 h, and (e) 72 h; (f) changes in the icorr and Pi with time (25 ◦ C).

the as-cast ZK60 alloy, especially in the corrosion period of
0–24 h. In general, the T4-treated ZK60 alloy had the best anti-
corrosion performance. The difference in CPEdl , CPEf , RL , and
L among the three ZK60 alloys and the change of the param-
eters with the corrosion time may be closely related to the
surface layer of the ZK60 alloys [69,71], which is discussed
later.
3.4. Corrosion morphology
Fig. 14 gives the BSE–SEM morphologies of the etched as-cast,
T4-, and T6-treated ZK60 samples immersed in 0.1 M NaCl
for 10 min to clarify the initiation of corrosion on their sur-
face. In the as-cast alloy (Fig. 14a), black corrosion products
only occurred near the second-phase particles and mainly in
the grain boundary regions rather than in the central region
of the grains; this suggests that the corrosion on the as-cast
ZK60 might have originated from the areas adjacent to the
second phases in the grain boundary regions. However, for the
T4- and T6-treated ZK60 alloys, their corrosion originated not
only from the second-phase particles but also from the cen-
tral region of the grains (Fig. 14b–c). These changes could be
related to the difference between the microstructures of the
as-cast and treated alloys.
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(5):11201–11219 11211

Fig. 12 – Nyquist plots of the as-cast, T4-, and T6-treated ZK60 alloys after immersion in 0.1 M NaCl for different times: (a)
0.5 h, (b) 2 h, (c) 24 h, (d) 48 h, and (e) 72 h; (f) 1/Rp –t curves at 25 ◦ C.
11212 j m a t e r r e s t e c h n o l . 2 0 2 0;9(5):11201–11219

Fig. 13 – Equivalent circuits used to fit the EIS results in Fig. 11: (a) with low-frequency inductive loop; (b) without
low-frequency inductive loop.

Table 4 – EIS fitting results for the as-cast, T4-, and T6-treated ZK60 alloys immersed in 0.1 M NaCl for different times.
Alloy Time Rs Rct CPEdl -T CPEdl -P Rf CPEf -T CPEf -P RL L
(h) ( cm2 ) ( cm2 ) ␮F cm−2 Hz1−n1 /n1 ( cm2 ) ␮Fcm−2 Hz1−n2 /n2 ( cm2 ) (H cm2 )

as-cast 0.5 32 25 22.26 0.87 759 15.90 0.69 1360 2359

2 65 14 66.56 0.87 502 20.75 0.96 1224 1143
24 40 179 37.75 0.79 1546 21.90 0.88 5865 16588
48 27 57 37.19 0.81 1453 48.30 0.87 3429 9781
72 27 34 38.13 0.83 1390 59.00 0.88 3557 9029
T4-treated 0.5 28 3217 11.13 0.93 1671 1510.44 0.64 – –
2 25 53 47.22 0.83 1351 40.90 0.88 3076 7272
24 25 275 15.76 0.89 2018 81.10 0.82 3472 4250
48 27 261 51.57 0.81 1717 18.21 0.86 5291 16141
72 27 153 48.43 0.82 1643 16.35 0.82 4250 10452
T6-treated 0.5 23 2065 12.33 0.93 610 2780.32 0.74 – –
2 27 28 74.52 0.84 982 82.67 0.94 2613 4727
24 27 129 18.64 0.92 1773 42.54 0.89 3028 4247
48 26 96 48.33 0.82 1469 32.78 0.86 3895 11233
72 30 103 43.72 0.82 1338 13.76 0.89 3963 13755

Fig. 14 – BSE–SEM morphologies of the etched ZK60 alloys after immersion in 0.1 M NaCl for 10 min: (a) as-cast; (b)
T4-treated; (c) T6-treated.

Fig. 15 shows the BSE-SEM morphologies of the etched as-
cast, T4-, and T6-treated ZK60 samples immersed in 0.1 M
NaCl for 2 h to depict the development of corrosion on their
surfaces. The as-cast ZK60 exhibited filiform-like corrosion
(Fig. 15a–b). The filaments on the as-cast ZK60 propagated
mainly in the grain boundary regions (i.e., the dark areas
between the Zr-rich regions) and gradually toward the center
region of the grains (Fig. 15a and b). However, the T4- and T6-
treated ZK60 alloys displayed different features of the filiform
corrosion (Fig. 15c and f) [72]; their filaments spread to dif-
ferent directions and even through the grains, but they never
crossed each other. The grain boundaries and second phases
seemed to have little influence on the development of the cor-
rosion filaments. The initiation and propagation features of
the corrosion filaments on the T4- and T6-treated ZK60 alloys
were quite different from those of the filaments on the as-
cast ZK60 alloy. According to [73,74], these differences could
be attributed to the quantity and size of the second phases and
the distribution of alloying elements in these alloys, which is
discussed later.
Fig. 16 presents the SEM corrosion morphologies of the
ZK60 alloys immersed in 0.1 M NaCl for three days with the cor-
rosion products removed. For the three ZK60 alloys, increasing
corrosion time, the corrosion filaments gradually developed
to the entire surface. Meanwhile, much larger corrosion pits
occurred on the as-cast alloy compared with the T4- and
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(5):11201–11219 11213

Fig. 15 – BSE–SEM morphologies of the etched ZK60 alloys immersed in 0.1 M NaCl for 2 h: (a, b) as-cast; (c, d) T4-treated; (e,
f) T6-treated.

T6-treated alloys. To characterize the development of cor-
rosion pits, we selected the deepest pit on the three ZK60
alloys and measured their 3D morphologies and depth pro-
files. The results (Fig. 17) generally indicate different local
corrosion characteristics of the test alloys [75]. Denser and
deeper (∼150 ␮m) corrosion pits were observed on the as-
cast ZK60 alloy (Fig. 17a and b), while corrosion pits with
depths of only ∼80 ␮m (Fig. 17c and d) and ∼110 ␮m (Fig. 17e
and f) occurred on the T4- and T6-treated alloys, respec-
tively. The local corrosion on the heat-treated ZK60 alloys was
much slighter than that on the as-cast ZK60 alloy, and the
T4-treated alloy exhibited the best local corrosion resistance
performance.
11214 j m a t e r r e s t e c h n o l . 2 0 2 0;9(5):11201–11219

Fig. 16 – SEM corrosion morphologies of the ZK60 alloys immersed in 0.1 M NaCl for three days: (a) as-cast; (b) T4-treated; (c)
T6-treated (with corrosion products removed).

In the case of the heat-treated ZK60 alloys, the heat treat-

4. Discussion
4.1. Effect of heat treatment on the filiform corrosion
of the ZK60 alloys
According to [4,76,77], a partly protective and non-uniform
MgO/Mg(OH)2 oxide film existed on the as-cast ZK60 alloy in
neutral 0.1 M NaCl. The film around the second phase had
more imperfections to be easily broken under Cl− attack [78].
In contrast, the film at the center region of the grains
(Zr-rich area) was more stable than that at the adjacent Mg
matrix in the grain boundary regions (Fig. 8a and b) [36,79].
Therefore, the second-phase particles in the grain bound-
aries and the Zr-rich area within the grains with higher Volta
potentials (Figs. 7 and 8) all acted as micro-galvanic cathodes
compared to the Mg matrix in the grain boundary regions. The
micro-galvanic corrosion was initiated in the areas around the
discontinuous second phases in the grain boundary regions
(see Fig. 14a) owing to the strong galvanic effect between the
second phase and Mg matrix, where the anodic and cathodic
reactions are Reactions (4) and (5) [80], respectively.
Because the Zr-rich area within the grains was more stable
than the Mg matrix (Fig. 8a and b), the corrosion preferably
propagated in the grain boundary regions in the initial period
to display filiform-like characteristics, as shown in Fig. 15a and
b. In NaCl solution, Cl− may be enriched around the anode
areas to attack and break the oxide film [81]. Meanwhile, the
activated cathodes behind the anodes may provide the driving
force for the development of the corrosion filaments. Then,
the precipitations of Mg(OH)2 (Reaction (6)) [80] will cover the
surface of the active cathodes behind the anodes, so that the
cathodes gradually become inert. The second phases in the
grain boundaries and the Zr-rich region within the grains had
an essential influence on the initiation and propagation of the
corrosion filaments on the as-cast ZK60 alloy.
Mg → Mg 2+ + 2e− (anodicreaction)
2H2 O + 2e− → H2 (g) + 2OH− (cathodicreaction)
Mg 2+ + 2OH− → Mg(OH)2 (corrosionproductformation)
ments improved the distribution of the alloying elements and
second phases (Figs. 2 and 5), resulting in a decrease in the
potential difference between the second phases and the Mg
matrix and the uniform potential distribution in the Mg matrix
(Fig. 8). Consequently, the T4- and T6-treated ZK60 alloys dis-
played more homogeneous electrochemical activity in their
microstructures, so that the micro-galvanic effect was weak-
ened, and a more uniform and more stable oxide film was
formed on the alloys surfaces. In this case, the heat-treated
ZK60 alloys showed a much smaller PH (Fig. 10b), icorr and Pi
(Fig. 11f), and 1/Rp (Fig. 12f) and a much larger Rct and Rf (except
the T6-treated alloy, Table 4) compared with the as-cast ZK60
alloy in the initial corrosion period (0.5 h). The disappearance
of the low-frequency inductive loop in the EIS diagrams of the
heat-treated ZK60 alloys (t = 0.5 h, Fig. 12a) also implies that
the alloys had a more stable oxide film. Their CPEf values are
two orders of magnitude larger than that of the as-cast ZK60
alloy (t = 0.5 h, Table 4), suggesting that a much thinner oxide
film was formed on the heat-treated ZK60 alloys.
Because of the weak micro-galvanic effect in the T4- and
T6-treated alloys, filiform corrosion could be initiated from
both the region adjacent to the second-phase particles in
grain boundaries and the center region of the grains (Fig. 14b
and c), depending on the stability of the oxide film in these
areas under Cl− attack. Moreover, because of the more homo-
geneous electrochemical activity in these heat-treated ZK60
alloys, the corrosion filaments could propagate through the
grains in various directions, and their microstructures showed
little influence on the filament growth directions. These fili-
form corrosion features are similar to those reported for other
Mg alloys [72,82,83]. In [72], the existence of Cl− was found
to have a significant influence on the filiform corrosion of
Mg–3Zn alloys, and the anodic Reaction (4) could accelerate
the filament growth, during which the anodes and cathodes
in the micro-galvanic cells transferred dynamically. However,
the detailed mechanism for the propagation of the corrosion
filaments is still not clearly understood.
(4)
In general, the heat treatments changed the microstruc-
ture of the as-cast ZK60 alloy, especially the size and number of
the second-phase particles and the distribution of the alloying
(5)
elements. This resulted in different initiation and propaga-
tion features of the filiform corrosion in the early corrosion
(6) period. By comparing their corrosion rates (PW , PH , and Pi )
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(5):11201–11219 11215

Fig. 17 – 3D corrosion morphologies of the ZK60 alloys immersed in 0.1 M NaCl for three days: (a, b) as-cast; (c, d) T4-treated;
(e, f) T6-treated (with corrosion products removed).

and EIS results (Rct and Rf ) in this period, we can further ver-
ify the effect of the heat treatments on the filiform corrosion
development rate.
4.2. Effect of heat treatment on the change of corrosion
rate of ZK60 alloys
According to the above discussion, the T4- and T6-treated
ZK60 alloys had more stable oxide films on their surfaces.
This inhibited the anodic corrosion process more than it did
the cathodic process, so that the Ecorr of the alloys moved
positively in the initial corrosion period (0–0.5 h, Fig. 11a).
Meanwhile, the corrosion rate (PH , Pi , and 1/Rp ) order of the
alloys is as follows: as-cast alloy » T6-treated alloy > T4-treated
alloy (Figs. 10b, 11f, and 12f). In this period, filiform corrosion
was initiated on the three ZK60 alloys (Fig. 14), and the fila-
ments began to develop; therefore, the filament growth rates
of the alloys should have the same order. In the T6-treated
alloy, the re-precipitated second-phase particles decreased
the stability of the oxide film, and the filiform corrosion of
the alloy was thus accelerated.
After the initial period, the broken oxide film on the ZK60
alloys steadily increased with the growth of the corrosion fil-
aments (Fig. 15), and this promoted the anodic and cathodic
11216 j m a t e r r e s t e c h n o l . 2 0 2 0;9(5):11201–11219
corrosion processes, as shown in Fig. 11a–b. Therefore, the cor-
rosion rates (PH , Pi , and 1/Rp ) of the three ZK60 alloys increased
quickly in 0.5–2 h (Figs. 10b, 11f, and 12f), while the Rct and
Rf of the alloys (t = 2 h, Table 4) decreased significantly. How-
ever, the corrosion rate order of the alloys was still the same
as that in the initial period (0–0.5 h), implying that the fila-
ment propagation on the heat-treated alloys was also impeded
in this period. The increase in the broken oxide film may be
the reason no Ebreak occurs in the anodic polarization curve
when t = 2 h (Fig. 11b). The increase in the broken oxide film
also enlarged the reactive areas to increase CPEdl and CPEf
but decreased the RL and L of the as-cast ZK60 alloy (0.5–2 h,
Table 4). Meanwhile, the CPEf values of the heat-treated ZK60
alloys decreased significantly to be approximate to that of the
as-cast ZK60 alloy (0.5–2 h, Table 4). The PH –t curves in Fig. 10b
indicate that this quick development period for the as-cast
ZK60 alloy was about 0–2.0 h, but that for the heat-treated
alloys was prolonged to about 0–18.0 h. This result also sug-
gests that the more stable oxide film on the heat-treated alloys
inhibited the development of the corrosion filaments on the
alloys surfaces.
After this quick development period, with the growth of
the corrosion filaments, most parts of the surface of the three
ZK60 alloys would be gradually corroded and covered with
a black Mg(OH)2 precipitate [73], which may be the reason
Ebreak occurs again in the curve (Fig. 11c and d). In this case,
the anodic corrosion process on the three ZK60 alloys was
inhibited significantly, so that the Ecorr values of the alloys
move positively (Fig. 11c–d) and the alloy corrosion rates were
reduced, implying a corrosion inhibition period. Furthermore,
the growth of the corrosion filaments and the increase in the
corrosion product layer will decrease the broken oxide film
and the reactive area; therefore, the CPEdl values of the alloys
decreased in this period (2–24 h, Table 4). However, the CPEf
values displayed different changes, which may be related to
the different areas and thicknesses of the corrosion prod-
uct layers on the three ZK60 alloys. Even though PW , PH , Pi ,
and 1/Rp gave different corrosion inhibition periods for the
three ZK60 alloys, which should result from the difference
between the test methods, they still correspond to the fol-
lowing order: as-cast alloy > T6-treated alloy > T4-treated alloy,
and the difference among them decreases apparently. These
results suggest that the effect of the heat treatment weakens
moving across the as-cast alloy, the T6-treated alloy, and then
the T4-treated alloy, while the effect of the corrosion product
layer increases.
After this corrosion inhibition period, the corrosion rate
(PW , PH , Pi , and 1/Rp ) of the three ZK60 alloys increased again,
and their order became as-cast alloy ≈ T6-treated alloy > T4-
treated alloy. However, corrosion pits occurred in this period
(Figs. 16 and 17), suggesting a pitting corrosion period. The
pitting corrosion resistance order is as-cast alloy < T6-treated
alloy < T4-treated alloy, which may be closely related to the
size and number of the precipitation phases in the ZK60 alloys.
With the growth of the corrosion filaments, the corrosion pits
can be generally formed under the second-phase particles
to produce an occluded environment covered by the second-
phase particles and Mg(OH)2 precipitate [84]. The solution in
the occluded corrosion pit will be alkalized (pH ≈ 10.5) through
the dissolution of Mg(OH)2 . Meanwhile, Cl− will migrate in due
to the charge neutralization and become enriched at the pit
bottom. These effects will accelerate the anodic process in the
corrosion pits to make them develop deeply [85]. In this case,
the heat treatments improved the microstructure of the heat-
treated ZK60 alloys to inhibit the corrosion pit development,
and the T4-treated ZK60 alloy exhibited the best pitting corro-
sion resistance. Moreover, the increase in the anodic process
also made the Ecorr of the alloys negative (Fig. 11e) and made
their general corrosion rates increase again, while Rt , Rf , and Rp
decreased in this period (24–72 h, Table 4). However, their CPEdl
and CPEf values did not display a consistent change tendency,
which may be related to the different changes in the alloys
corrosion product layers and the different developments of
the corrosion pits in this period.
Based on the above discussion, the three ZK60 alloys
showed the same corrosion types, and their general corro-
sion rates (PW , PH , Pi , and 1/Rp ) displayed similar change
tendencies with increasing corrosion time. Thus, the T4 and
T6 treatments did not change the alloys corrosion behavior
but improved their resistance to general corrosion and pit-
ting corrosion; this was due to the more stable oxide film and
weak micro-galvanic effect on the heat-treated alloys. The
uniform distribution of alloying elements and the occurrence
of a small quantity of small-sized second-phase particles in
the microstructure are the vital properties behind the excel-
lent corrosion resistance of the T4-treated ZK60 alloy.
5. Conclusions
The microstructure of the as-cast ZK60 alloy comprised ␣-
Mg phase; large second-phase particles (MgZn2 ), which were
mainly deposited along the grain boundaries; and a Zr-rich
region occurring in the central area of the grains. This resulted
in a strong micro-galvanic effect in the alloy. The T4 treatment
could dissolve most of the second-phase particles and make
the elements more evenly distributed in the matrix; however,
new tiny second phase particles re-precipitated during the T6
treatment process, resulting in weak micro-galvanic effect in
the T4- and T6-treated ZK60 alloys.
The three ZK60 alloys displayed similar filiform corrosion
morphologies in the early corrosion period, but the initiation
and propagation features of the corrosion filaments were quite
different. The filiform corrosion of the as-cast ZK60 originated
from areas adjacent to the second phase in grain bound-
aries, first propagated in the grain boundary regions (i.e., the
areas between the Zr-rich regions), and then gradually devel-
oped to the center region of the grains. For the heat-treated
ZK60 alloys, the filiform corrosion originated from the areas
in grains and grain boundaries, and the grain boundaries and
second-phase particles had little influence on the propagation
of the corrosion filaments.
The as-cast and heat-treated ZK60 alloys showed the same
corrosion types, and their general corrosion rates (PW , PH , Pi ,
and 1/Rp ) displayed similar change tendencies with increasing
corrosion time. The T4- and T6-treated ZK60 alloys generally
exhibited better anti-corrosion performance than the as-cast
ZK60 alloy, especially in the early corrosion period (0–2 h) and
the pitting corrosion period. This was due to their improved
microstructures, which produce stable oxide films and a weak
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(5):11201–11219
micro-galvanic effect. The T4-treated ZK60 alloy had the best
corrosion resistance; even so, the pitting corrosion on the ZK60
alloys should still be given more attention.
Conflicts of interest
The authors declare no conflicts of interest
Acknowledgments
The authors thank for the analysis support of Key Labora-
tory of Material Chemistry for Energy Conversion and Storage
and the Analytical and Testing Center, Huazhong University of
Science and Technology. We thank LetPub (www.letpub.com)
for its linguistic assistance during the preparation of this
manuscript.
references
[1] Liu DX, Yang DL, Li XL, Hu SW. Mechanical properties,
corrosion resistance and biocompatibilities of degradable
Mg–RE alloys: a review. J Mater Res Technol 2019;8:1538–49.
[2] Yang Z, Li JP, Zhang JX, Lorimer GW, Robson J. Review on
research and development of magnesium alloys. Acta Metall
Sin (Engl Lett) 2008;21:313–28.
[3] You SH, Huang YD, Kainer KU, Hort N. Recent research and
developments on wrought magnesium alloys. J Magnesium
Alloy 2017;5:239–53.
[4] Esmaily M, Svensson JE, Fajardo S. Fundamentals and
advances in magnesium alloy corrosion. Prog Mater Sci
2017;89:92–193.
[5] He YB, Pan QL, Qin YJ, Liu XY, Li WB, Chiu YL, et al.
Microstructure and mechanical properties of ZK60 alloy
processed by two-step equal channel angular pressing. J
Alloy Compd 2010;492:605–10.
[6] Dharmendra C, Rao KP, Jain MK, Prasad YVRK. Role of
loading direction on compressive deformation behavior of
extruded ZK60 alloy plate in a wide range of temperature. J
Alloy Compd 2018;744:289–300.
[7] Figueiredo RB, Langdon TG. Achieving superplastic
properties in a ZK10 magnesium alloy processed by
equal-channel angular pressing. J Mater Res Technol
2017;6:129–35.
[8] Sarraf SAT, Langdon TG. Properties of a ZK60 magnesium
alloy processed by high-pressure torsion. J Alloy Compd
2014;613:357–63.
[9] Wang W, Zhang WC, Chen WZ, Cui GR, Wang E. Effect of
initial texture on the bending behavior, microstructure and
texture evolution of ZK60 magnesium alloy during the
bending process. J Alloy Compd 2018;737:505–14.
[10] Xiong Y, Lu C, Wang C, Song RG. The n-MAO/EPD bio-ceramic
composite coating fabricated on ZK60 magnesium alloy
using combined micro-arc oxidation with electrophoretic
deposition. Appl Surf Sci 2014;322:230–5.
[11] Pan YK, Chen CZ, Wang DG, Yu X. Microstructure and
biological properties of micro-arc oxidation coatings on ZK60
magnesium alloy. J Biomed Mater Res B Appl Biomater
2012;100:1574–86.
[12] Hua YL, Zhang ZG, Li W. Microstructure and degradation
properties of C-containing composite coatings on
magnesium alloy wires treated with micro-arc oxidation.
Surf Coat Technol 2016;291:70–8.
11217
[13] Zheng Y, Li Y, Chen JH, Zou ZY. Surface characteristics and
corrosion resistance of biodegradable magnesium alloy ZK60
modified by Fe ion implantation and deposition. Progress
Nat Sci: Mater Int 2014;24:547–53.
[14] Jamesh MI, Wu GS, Zhao Y, McKenzie DR, Bilek MM, Chu PK.
Effects of zirconium and oxygen plasma ion implantation on
the corrosion behavior of ZK60 Mg alloy in simulated body
fluids. Corros Sci 2014;82:7–26.
[15] Xia KD, Pan H, Wang TL. Effect of Ca/P ratio on the structural
and corrosion properties of biomimetic Ca–P coatings on
ZK60 magnesium alloy. Mater Sci Eng C 2017;72:676–81.
[16] Xu RZ, Shen Y, Zheng JS, Wen Q, Li Z, Yang XB, et al. Effects
of one-step hydrothermal treatment on the surface
morphology and corrosion resistance of ZK60 magnesium
alloy. Surf Coat Technol 2017;309:490–6.
[17] Riaz U, Rahman Z, Asgar H, Shah U, Shabib I, Haider W. An
insight into the effect of buffer layer on the electrochemical
performance of MgF2 coated magnesium alloy ZK60. Surf
Coat Technol 2018;344:514–21.
[18] Wang B, Huang P, Ou CW, Li KK, Yan B, Lu W. In vitro
corrosion and cytocompatibility of ZK60 magnesium alloy
coated with hydroxyapatite by a simple chemical conversion
process for orthopedic applications. Int J Mol Sci
2013;14:23614–28.
[19] Liu QL, Wang XD, Wang XK, Yan XW, Ma XJ. Study of high
emittance chemical conversion coatings for magnesium
alloys. Surf Eng 2014;30:48–52.
[20] Parfenov EV, Kulyasova OB, Mukaeva VR, Mingo B, Farrakhov
RG, Cherneikina YaV, et al. Influence of ultra-fine grain
structure on corrosion behaviour of biodegradable Mg–1Ca
alloy. Corros Sci 2020;163:1–13.
[21] Xin RL, Luo YM, Zuo AL, Gao JC, Liu Q. Texture effect on
corrosion behavior of AZ31 Mg alloy in simulated
physiological environment. Mater Lett 2012;72:1–4.
[22] Gusieva K, Davies CHJ, Scully JR, Birbilis N. Corrosion of
magnesium alloys: the role of alloying. Int Mater Rev
2015;60:169–94.
[23] Song YW, Han EH, Shan DY, Yim CD, You BS. The role of
second phases in the corrosion behavior of Mg–5Zn alloy.
Corros Sci 2012;60:238–45.
[24] Feng H, Liu SH, Du Y, Lei T, Zeng RC, Yuan TC. Effect of the
second phases on corrosion behavior of the Mg–Al–Zn alloys.
J Alloy Compd 2017;659:2330–8.
[25] Jia RL, Zhang M, Zhang LN, Zhang W, Guo F. Correlative
change of corrosion behavior with the microstructure of
AZ91 Mg alloy modified with Y additions. J Alloy Compd
2015;634:263–71.
[26] Song GL, Atrens A, Dargusch M. Influence of microstructure
on the corrosion of diecast AZ91D. Corro Sci 1998;41:249–73.
[27] Choi HY, Kim WJ. Effect of thermal treatment on the
bio-corrosion and mechanical properties of ultrafine-grained
ZK60 magnesium alloy. J Mech Behav Biomed Mater
2014;37:307–22.
[28] Li X, Jiang JH, Zhao YH, Ma AB, Wen DJ, Zhu YT. Effect of
equal-channel angular pressing and aging on corrosion
behavior of ZK60 Mg alloy. Trans Nonferrous Met Soc China
2015;25:3909–20.
[29] Orlov D, Ralston KD, Birbilis N, Estrin Y. Enhanced corrosion
resistance of Mg alloy ZK60 after processing by integrated
extrusion and equal channel angular pressing. Acta
Materialia 2011;59:6176–86.
[30] Sarraf HT, Sarraf SAT, Poursaee A, Langdon TG.
Electrochemical behavior of a magnesium ZK60 alloy
processed by high-pressure torsion. Corro Sci
2019;154:90–100.
[31] Mostaed E, Hashempour M, Fabrizi A, Dellasega D, Bestetti
M, Bonollo F, et al. Microstructure, texture evolution,
mechanical properties and corrosion behavior of ECAP
11218 j m a t e r r e s t e c h n o l . 2 0 2 0;9(5):11201–11219
processed ZK60 magnesium alloy for biodegradable
applications. J Mech Behav Biomed Mater 2014;37:307–22.
[32] Baek SM, Kim B, Park SS. Influence of intermetallic particles
on the corrosion properties of extruded ZK60 Mg alloy
containing Cu. Metals 2018;8:323–32.
[33] Biancardi OV, Rosa VL, Abreu LB, Tavares APR, Corrêa RG,
Cavalcanti PH, et al. Corrosion behavior of as-cast ZK60 alloy
modified with rare earth addition in sodium sulfate medium.
Corro Sci 2019;158,
http://dx.doi.org/10.1016/j.corsci.2019.108092.
[34] Zhang TT, Cui HW, Cui XL, Zhao ET, Feng R, Pan YK.
Investigations on microstructures, mechanical and corrosion
properties of Mg–5.5Zn–0.8Zr alloys with Sm addition. Mater
Res Express 2019;6,
http://dx.doi.org/10.1088/2053-1591/ab1530.
[35] Neil WC, Forsyth M, Howlett PC, Hutchinson CR, Hinton
BRW. Corrosion of magnesium alloy ZE41 – the role of
microstructural features. Corros Sci 2009;51:387–94.
[36] Ben-Hamu G, Eliezer D, Shin KS, Cohen S. The relation
between microstructure and corrosion behavior of
Mg–Y–RE–Zr alloys. J Alloys Compd 2007;431:269–76.
[37] Chang JW, Guo XW, Fu PH, Peng LM, Ding WJ. Relationship
between heat treatment and corrosion behavior of
Mg–3.0%Nd–0.4%Zr magnesium alloy. Nonferr Metal Soc
2007;17:1152–7.
[38] Chang JW, Guo XW, He SM, Fu PH, Peng LM, Ding WJ.
Investigation of the corrosion for Mg–xGd–3Y–0.4Zr (x = 6, 8,
10, 12 wt.%) alloys in a peak-aged condition. Corros Sci
2008;50:166–77.
[39] Wang ZC, Yu L, Jia F, Song GL. Effect of additives and heat
treatment on the formation and performance of electroless
nickel–boron plating on AZ91D Mg alloy. J Electrochem Soc
2012;159:406–12.
[40] Zhou W, Shen T, Aung NN. Effect of heat treatment on
corrosion behavior of magnesium alloy AZ91D in simulated
body fluid. Corros Sci 2010;52:1035–41.
[41] Chowdary S, Dumpala R, Anand Kumar S, Kondaiah VV.
Influence of heat treatment on the machinability and
corrosion behavior of AZ91 Mg alloy. J Magnesium Alloy
2018;6:52–8.
[42] Li JR, Jiang QT, Sun HY, Li YT. Effect of heat treatment on
corrosion behavior of AZ63 magnesium alloy in 3.5 wt.%
sodium chloride solution. Corros Sci 2016;111:288–301.
[43] Chen J, Tan L, Yang K. Effect of heat treatment on
mechanical and biodegradable properties of an extruded
ZK60 alloy. Bioact mater 2017;2:19–26.
[44] Shi ZM, Liu M, Atrens A. Measurement of the corrosion rate
of magnesium alloys using Tafel extrapolation. Corros Sci
2010;52:579–88.
[45] Atrens A, Song GL, Liu M, Shi ZM, Cao FY, Dargusch MS.
Review of recent developments in the field of magnesium
corrosion. Adv Eng Mater 2015;17:400–53.
[46] Shi ZM, Atrens A. An innovative specimen configuration for
the study of Mg corrosion. Corros Sci 2011;53:226–46.
[47] Zhao MC, Schmutz P, Brunner S, Liu M, Song G, Atrens A. An
exploratory study of the corrosion of Mg alloys during
interrupted salt spray testing. Corro Sci 2009;51:1277–92.
[48] Song YW, Shan DY, Chen RS, Han EH. Effect of second phases
on the corrosion behavior of wrought Mg–Zn–Y–Zr alloy.
Corros Sci 2010;52:1830–7.
[49] El-Morsy AW, Farahat AIZ. Effect of aging treatment on the
damping capacity and mechanical properties of Mg–6Al–1Zn
alloy. Scientific World J 2015;6:1–8.
[50] Chu PW, Marquis EA. Linking the microstructure of a
heat-treated WE43 Mg alloy with its corrosion behavior.
Corro Sci 2015;1:94–104.
[51] He YB, Pan QL, Liu XY, Li WB. Microstructure evolution of
ZK60 magnesium alloy during Homogenization. J Aeronaut
Mater 2011;31:14–20.
[52] Ma YL, Zuo RL, Tang AT, Zhang J, Pan FS. Analysis of
microstructure of as-cast ZK60 magnesium alloy. J
Chongqing Univ 2004;27:52–6.
[53] He YB, Pan QL, Qin YJ. Effect of heat treatment on
microstructure and mechanical properties of wrought ZK60
magnesium alloy. Heat Treatment Metals 2011;36:52–7.
[54] Yuan YG, Ma AB, Gou XF. Effect of heat treatment and
deformation temperature on the mechanical properties of
ECAP processed ZK60 magnesium alloy. Mater Sci Eng A
2016;677:125–32.
[55] Wei LY, Dunlop GL, Westengen H. The intergranular
microstructure of cast Mg–Zn and Mg–Zn–Rare earth alloys.
Metall Mater Trans A 1995;26:1947–55.
[56] Wei LY, Dunlop GL, Westengen H. Precipitation hardening of
Mg–Zn and Mg–Zn–RE alloys. Metall Mater Trans A
1995;26:1705–16.
[57] Clark JB. Transmission electron microscopy study of age
hardening in a Mg–5wt.% Zn alloy. Acta Metall
1965;13:1281–9.
[58] Zhang SQ, Luo ZP. Study of the quasicrystal and crystal
phases in the MB25 magnesium alloy. J Instrum Anal
1994;6:35–7.
[59] Gao X, Nie JF. Characterization of strengthening precipitate
phases in a Mg–Zn alloy. Scripta Mater 2007;56:645–8.
[60] Galicia G, Pebere N, Tribollet B, Vivier V. Local and global
electrochemical impedances applied to the corrosion
behavior of an AZ91 magnesium alloy. Corro Sci
2009;51:1789–94.
[61] Song GL, Xu ZQ. Effect of microstructure evolution on
corrosion of different crystal surfaces of AZ31 Mg alloy in a
chloride containing solution. Corro Sci 2012;54:97–105.
[62] Merson D, Vasiliev E, Markushev M, Vinogradov A. On the
corrosion of ZK60 magnesium alloy after severe plastic
deformation. Lett Mater 2017;7:421–7.
[63] Song YW, Shan DY, Chen RS, Han EH. Investigation of surface
oxide film on magnesium lithium alloy. J Alloys Comp
2009;29:1039–45.
[64] Song GL, Unocic KA. The anodic surface film and hydrogen
evolution on Mg. Corros Sci 2015;9:758–65.
[65] Song GL, Atrens A, John DS, Wu X, Nairn J. The anodic
dissolution of magnesium in chloride and sulphate
solutions. Corros Sci 1997;39:1981–2004.
[66] Cao CN, Zhang JQ. An introduction of electrochemical
impedance spectroscopy. Beijing: Science Press; 2002.
[67] Song YW, Han EH. The effect of Zn concentration on the
corrosion behavior of Mg–xZn alloys. Corros Sci
2012;65:322–30.
[68] Shi ZM, Cao FY, Song GL, Atrens A. Low apparent valence of
Mg during corrosion. Corros Sci 2014;88:434–43.
[69] King AD, Birbilisa N, Scully JR. Accurate electrochemical
measurement of magnesium corrosion rates; a combined
impedance, mass-loss and hydrogen collection study.
Electrochim Acta 2014;121:394–406.
[70] Baril G, Galicia G, Deslouis C, Pebere N, Tribollet B, Vivier V.
An impedance investigation of the mechanism of pure
magnesium corrosion in sodium sulfate solutions. J
Electrochem Soc 2007;154:108–13.
[71] Gomes MP, Costa I, Pebere N, Rossi JL, Tribollet B, Vivier V. On
the corrosion mechanism of Mg investigated by
electrochemical impedance spectroscopy. Electrochim Acta
2019;306:61–70.
[72] Wang HX, Song YW, Yu J, Shan DY, Han EH. Characterization
of filiform corrosion of Mg–3Zn Mg alloy. J Electrochem Soc
2017;164:574–80.
 j m a t e r r e s t e c h n o l . 2 0 2 0;9(5):11201–11219
[73] Song YW, Han EH, Shan DY. Corrosion characterization of
Mg–8Li alloy in NaCl solution. Corros Sci 2009;51:1087–94.
[74] Neil WC, Forsyth M, Howlett PC, Hutchinson CR, Hinton
BRW. Corrosion of heat treated magnesium alloy ZE41.
Corros Sci 2011;53:3299–308.
[75] Liang SQ, Guan DK, Tan XP. The relation between heat
treatment and corrosion behavior of Mg–Gd–Y–Zr alloy.
Mater Des 2011;32:1194–9.
[76] Atrens A, Song GL, Shi ZM, Soltan A, Johnston S, Dargusch
MS. Understanding the corrosion of Mg and Mg alloys.
Encyclopedia Interfacial Chem 2018:515–34.
[77] Song YW, Han EH, Dong KH, Shan DY, Yim CD, You BS.
Microstructure and protection characteristics of the
naturally formed oxide films on Mg–xZn alloys. Corros Sci
2013;72:133–43.
[78] Lindström R, Johansson LG, Thompson GE, Skeldon P,
Svensson JE. Corrosion of magnesium in humid air. Corros
Sci 2004;46:1141–58.
[79] Kaya A, Ben-Hamu G, Eliezer D, Shin KS, Kohen S. Corrosion
and oxidation of alloys of the Mg–Y–Zr-REM system. Met Sci
Heat Treat 2006;48:518–23.
11219
[80] Dinodi N, Shetty AN. Electrochemical investigations on the
corrosion behavior of magnesium alloy ZE41 in a combined
medium of chloride and sulphate. J Magnesium Alloys
2013;1:201–9.
[81] Hara N, Kobayashi Y, Kagaya D, Akao N. Formation and
breakdown of surface films on magnesium and its alloys in
aqueous solutions. Corros Sci 2007;49:166–75.
[82] Schmutz P, Guillaumin V, Lillard RS, Lillard JA, Frankel GS.
Influence of dichromate ions on corrosion processes on pure
magnesium. J Electrochem Soc 2003;150:99–110.
[83] Williams G, Grace R. Chloride-induced filiform corrosion of
organic-coated magnesium. Electrochim Acta
2011;56:1894–903.
[84] Song GL, Dargusch M. Influence of microstructure on the
corrosion of die cast AZ91D. Corros Sci 1998;41:249–73.
[85] Zeng RC, Zhang J, Huang WJ, Kainer KU, Blawer C, Dietzel W,
et al. Review of studies on corrosion of magnesium alloys.
Trans Nonferrous Met Soc China 2006;16:763–71.