coatings
Article
Corrosion Behavior of the 2024 Aluminum Alloy in the
Atmospheric Environment of the South China Sea Islands
Jing Zhao 1 , Tongjun Zhao 2 , Yazhou Zhang 2 , Zhongtian Zhang 2 , Zehao Chen 2, *, Jinlong Wang 2
and Minghui Chen 2
Citation: Zhao, J.; Zhao, T.; Zhang, Y.;
Zhang, Z.; Chen, Z.; Wang, J.; Chen,
M. Corrosion Behavior of the 2024
Aluminum Alloy in the Atmospheric
Environment of the South China Sea
Islands. Coatings 2024, 14, 331.
https://doi.org/10.3390/
coatings14030331
Academic Editor: Ludmila B.
Boinovich
Received: 28 December 2023
Revised: 22 February 2024
Accepted: 29 February 2024
Published: 12 March 2024
Copyright: © 2024 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Coatings 2024, 14, 331. https://doi.org/10.3390/coatings14030331
1 Nuclear Power Institute of China, Chengdu 528208, China
2 Shenyang National Laboratory for Materials Science, Northeastern University, Shenyang 110819, China;
15040646273@163.com (T.Z.); 2210262@stu.neu.edu.cn (Y.Z.); 15633570693@163.com (Z.Z.);
wangjinlong@mail.neu.edu.cn (J.W.); mhchen@mail.neu.edu.cn (M.C.)
* Correspondence: chenzehao@mail.neu.edu.cn; Tel.: +86-24-23904856; Fax: +86-24-23893624
Abstract: The 2024 aluminum alloy, a structural material commonly used in aviation aircraft bodies,
is susceptible to serious corrosion in marine atmospheric environments. This paper comprehensively
studies the corrosion behavior of the 2024 aluminum alloy in the South China Sea atmosphere.
Weighing, morphology observation, phase analysis, electrochemical testing, and other methods were
used to study the corrosion law and corrosion mechanism of the 2024 aluminum alloy. The main
conclusions are as follows: At the initial stage of exposure, pitting corrosion occurred on the surface of
the 2024 aluminum alloy. After 3 months of exposure, the self-corrosion current density increased from
0.456 µA·cm−2 to 8.338 µA·cm−2 . After 6 months of exposure, the corrosion developed into general
corrosion. The main component of the corrosion product was Al2 O3 ·3H2 O. The product covered
the surface to form a loose corrosion product layer, which had an inhibitory effect on corrosion.
The self-corrosion current density was reduced to 2.359 µA·cm−2 . After 12 months of exposure, the
corrosion product layer fell off and became thinner, and the self-corrosion current density increased
to 2.849 µA·cm−2 . The corrosion kinetics conformed to the functional equation W = 0.00346t0.73891 ,
indicating that the corrosion products have a certain protective effect on the matrix.
Keywords: 2024 aluminum alloy; corrosion product; pitting corrosion; marine atmosphere
1. Introduction
Aluminum alloy is widely used as a structural material in the transportation field
due to its low density, favorable plasticity, and good corrosion resistance, especially high-
strength aluminum alloy, which is the main profile for manufacturing high-speed rail
car bodies and aircraft fuselages [1–4]. In recent years, the atmospheric environment,
faced by high-speed railways, airplanes, and other vehicles, has become increasingly
complex as the scope of construction of transportation facilities has become wider. Because
aluminum atoms have a relatively strong affinity for oxygen, self-passivation of aluminum
alloy can occur at room temperature, forming an oxide film with a thickness of several
nanometers on the surface [5–7]. Thus, in a general atmosphere, aluminum alloys are well
resistant to corrosion. However, in the marine atmosphere with high chloride ion content,
aluminum alloys are susceptible to corrosion, such as pitting corrosion, intergranular
corrosion, exfoliation, etc. [8], resulting in a serious decline in the mechanical properties
of aluminum alloys [9]. The service life of aluminum alloys is significantly shortened or
even fails prematurely. Therefore, the corrosion behavior of aluminum alloys in the marine
atmosphere has always been an important research direction [10–12].
Commonly, there are two types of atmospheric corrosion research methods: field
exposure and indoor accelerated testing [10,13–15]. The field exposure method involves
placing the samples in a realistic environment for experimentation; so, the data obtained
is very reliable. It has been an influential method for studying atmospheric corrosion.
https://www.mdpi.com/journal/coatings
Coatings 2024, 14, 331 2 of 14

Zhao Qiyue et al. [15] studied the corrosion behavior of the 7A85 aluminum alloy exposed
to the industrial-marine atmosphere for 5 years. They found that intergranular corrosion oc-
curred along the second phase of the alloy, and the mechanical properties of the aluminum
alloy decreased significantly.
The 2024 aluminum alloy belongs to the Al-Cu-Mg series of alloys, has a fine second
phase distributed internally, and is high-strength duralumin. Due to its good plasticity,
it is often used to make various high-load parts and components, such as aircraft skins,
spars, ribs, etc. It has been widely used as a structural material in civil and military aircraft
and is an indispensable and essential structural material in the aviation industry, but its
corrosion resistance is not universal. Marie-Laetitiade Bon-fils-Lahovary et al. [16] found
that aluminum in the 2024 aluminum alloy and the second phase forms a galvanic cell,
and an electrochemical reaction occurs in the corrosive medium to cause intergranular
corrosion. Zhang Sheng et al. [10] found that after exposure to the marine atmosphere of
the 2024-T4 aluminum alloy for 7 years, severe pitting and intergranular corrosion occurred
in the aluminum alloy. After 20 years of exposure, the aluminum alloy was exfoliated and
the main corrosion product was Al(OH)3 .
The South China Sea has extremely harsh corrosive environments because the average
temperature is 27 ◦ C and the highest temperatures exceed 35 ◦ C. The average value of
relative humidity (RH) is 77%, and the highest humidity is 85% [17–19]. The corrosivity of
the environment is CX, according to ISO 9223-2012 standard [20]. There are few reports
on the corrosion behavior of the 2024 aluminum alloy in the atmosphere of the South
China Sea using on-site exposure methods. Therefore, this paper presents a 12-month field
exposure experiment on the 2024 aluminum alloy in the atmospheric environment of the
South China Sea. The corrosion behavior of the 2024 aluminum alloy was characterized by
weighing, morphological observations, phase identification, electrochemical testing, and
other analytical methods, which provided data to support the corrosion protection design
of the aircraft fuselage and maintenance methods for the aircraft when parked. This study
offers new ideas and is therefore of crucial practical importance.

2. Materials and Methods

2.1. Materials
The samples used in the atmospheric corrosion test were processed by the Commercial
Aircraft Corporation of China. The dimensions of the samples were 150 mm × 75 mm × 5 mm.
The surface of the samples was refined with a roughness of Ra6.0. Then, samples were
placed into a mixture of ethanol and acetone (volume ratio 3:1), cleaned with an ultrasonic
cleaner to remove oil stains on the surface, and then the time was set to 30 min. The
chemical composition of the 2024 aluminum alloy is listed in Table 1. Environmental
characteristic parameters of the Xisha Islands are shown in Table 2.

Table 1. The chemical composition of the 2024 aluminum alloy (wt.%) [12,21,22].

Element Cu Mg Mn Cr Zn Al
Content 3.8–4.9 1.2–1.8 0.3–1.0 0.1 0.25 Bal.

Table 2. Environmental characteristic parameters of the Xisha Islands.

Average Average Sunshine Total Rainfall Surface Wetting Cl− Deposition

Temperature (◦ C) Humidity (%) Duration (h/a) (mm/a) Time (h/a) Rate (mg/100 cm2 ·d)
26–27 80 2800 1500 2628 1.0

2.2. Atmospheric Corrosion Test

First, the samples were numbered (01–36) by using an ink signature pen, and the
numbered side was defined as the reverse side. Then, the samples were weighed by the
electronic balance (SECURA225D-1CN, Sartorius, German with the precision of 0.1 mg)
Coatings 2024, 14, 331 3 of 14

and measured by the vernier caliper (precision 0.01 mm) to obtain the length, width, height,
and weight. Then, a photo of the front side of the samples was taken. The samples were
packaged and transported to the Paracel Islands for the exposure test. Finally, the samples
were firmly installed on the exposure test frame and then inclined at 45◦ to the horizontal
surface. The lengths of exposure time were 1, 2, and 3 weeks and 1, 3, 6, and 12 months,
and 3 parallel samples were retrieved each time. After retrieving the samples, the surface of
the samples was washed with distilled water and dried in an oven. After being dried, the
samples were weighed again. The added weight of the samples was calculated according
to the following formula:
m1 − m0
W= (1)
2( h × k + h × l + k × l )
In the formula, W is the weight gain per unit area (mg·cm−2 ), m1 is the weight when
the samples were retrieved (mg), m0 is the original weight of the samples (mg), and h, k, l
are the height, width, and length (cm) of the samples, respectively.

2.3. Morphology Observation

In this paper, the backscattered electron mode was used to analyze the cross-sectional
micromorphology. A scanning electron microscope (SEM, Inspect F50, FEI Co., Ltd.,
Hillsboro, OR, USA) with an accelerating voltage of 20 kV was used.

2.4. Phase Analysis

The X-ray diffractometer (XRD, CuKα radiation at 40 kV, 30 mA, SmartLab, Rigaku,
Japan) was used in this study. Cu was used as the target, the acceleration voltage was
40 kV, and the 2θ range was 10◦ to 90◦ , with a step of 0.02◦ /point.

2.5. Electrochemical Test

2.5.1. AC Impedance Test (EIS)
The test adopted a three-electrode system (CHI660E, ChenHua, Shanghai, China),
using a saturated calomel electrode as a reference electrode and a Pt electrode as an auxiliary
electrode. The test solution was 3.5 wt.% NaCl solution. The test solution was not deaerated.
Before the AC impedance test, we performed an open circuit potential test first and then
performed AC after the open circuit potential was stable. For the impedance test, the test
frequency range was 0.01 Hz~100 kHz and the disturbance voltage amplitude was 5 mV.

2.5.2. Polarization Test

After the AC impedance test, the samples were tested for the potential polarization
curve (CHI660E, ChenHua, China), and the test solution was 3.5 wt.% NaCl solution.
The test solution was also not deaerated, which adopted a three-electrode system, with a
scanning range of −0.3 V (vs. Eocp ) to +0.6 V (vs. Eocp ) and a scanning speed of 1 mV/s.

3. Results and Discussion

3.1. Corrosion Kinetics
The relationship between the weight gain per unit area of the samples in the outdoor
environment and the exposure time is shown in Figure 1. The figure shows that the weight
gain per unit area of the samples gradually increases with the prolongation of the exposure
time. This is due to the accumulation of corrosion products on the surface of the samples. In
the early exposure stage, the corrosion weight gain rate is relatively fast with the extension
of the exposure time. In the later stage, the corrosion weight gain rate begins to slow down.
When the exposure time reaches 12 months, the corrosion weight gain per unit area is
1.656 mg·cm−2 . Formula (2) was used to fit the weight gain scatter points, where A and n
are constants, and the fitting curve is shown in Figure 1, where the value of A is 0.00202. The
value of n is 0.7389, and the fitted correlation coefficient is 0.98995, indicating that the fitting
is reasonable. According to related literature, the power exponent n value in the power
function of corrosion kinetics is affected by material characteristics and environmental
 unit area is 1.656 mg·cm−2. Formula (2) was used to fit the weight gain scatter points, where
A and n are constants, and the fitting curve is shown in Figure 1, where the value of A is
Coatings 2024, 14, 331 4 of 14
0.00202. The value of n is 0.7389, and the fitted correlation coefficient is 0.98995, indicating
that the fitting is reasonable. According to related literature, the power exponent n value
in the power function of corrosion kinetics is affected by material characteristics and en-
factors. When
vironmental the value
factors. Whenofthe
n is lessof
value than
n is1, thethan
less corrosion product has
1, the corrosion a protective
product has a pro-effect
on
tective effect on the matrix; when the value of n is greater than 1, the corrosion producthave
the matrix; when the value of n is greater than 1, the corrosion product does not
protection.
does not have The corrosion
protection. kinetic
The power
corrosion exponent
kinetic powervalue of the
exponent samples
value of the in the outdoor
samples in
environment is 0.73891 because the value of n is less than 1; therefore,
the outdoor environment is 0.73891 because the value of n is less than 1; therefore, from the perspective
from
of
thecorrosion
perspectivekinetics, in thekinetics,
of corrosion outdoorinenvironment, the corrosion
the outdoor environment, theproducts
corrosionhave a certain
products
protective effect on the matrix.
have a certain protective effect on the matrix.
W
W==A𝑡Atn
(2)
(2)

Figure 1.
Figure 1.The
Therelationship between
relationship the the
between weight gain gain
weight per unit
per area
unitofarea
the of
samples in the outdoor
the samples en-
in the outdoor
vironment and the exposure time.
environment and the exposure time.

3.2. Surface
SurfaceMorphologies
Morphologies
The front macroscopicappearances
The front macroscopic appearancesofofthe thesamples
samples with
with different
different exposure
exposure timetime
lengths
lengths are shown in Figure 2. The figure shows that the surface
are shown in Figure 2. The figure shows that the surface of the samples is very of the samples is very
bright
bright
and and
has has a metallic
a metallic lusterluster
becausebecause
of theoffine
the lathe
fine lathe processing.
processing. AfterAfter outdoor
outdoor expo- for
exposure
1sure for 1the
week, week, the surface
surface of the samples
of the samples had scattered
had scattered white white
pittingpitting corrosion
corrosion products
products attached,
but the area was relatively small. Hence, the surface of the samples was stillwas
attached, but the area was relatively small. Hence, the surface of the samples still and
bright
still had a metallic luster. After 2 weeks of outdoor exposure, the number of whiteofspots
bright and still had a metallic luster. After 2 weeks of outdoor exposure, the number
whitethe
and spots and the
coverage coverage
area area Over
increased. increased.
time,Over
moretime, more
white white corrosion
corrosion productsproducts
occurred on
occurred on the surface of the samples, and the coverage area also began to increase. After
the surface of the samples, and the coverage area also began to increase. After 3 months of
3 months of exposure, the surface of the samples was no longer bright and completely lost
exposure, the surface of the samples was no longer bright and completely lost its metallic
its metallic luster. The initial scattered dots on the surface of the samples also turned into
luster. The initial scattered dots on the surface of the samples also turned into a thin layer
a thin layer of flakes. When the exposure time reached 6 months, the color of the samples’
of flakes. When the exposure time reached 6 months, the color of the samples’ surface
surface deepened, indicating that the corrosion products further accumulated on the sur-
deepened, indicating that the corrosion products further accumulated on the surface of
face of the samples and completely covered the test surface. When the exposure time
the samples and completely covered the test surface. When the exposure time reached
reached 12 months, the surface of the samples was entirely occupied by corrosion prod-
12 months, the surface of the samples was entirely occupied by corrosion products, and the
ucts, and the corrosion product layer cracked, resulting in an uneven surface of the sam-
corrosion product
ples. Therefore, thelayer cracked,
samples resulting
were darker in an uneven surface of the samples. Therefore,
in color.
the samples were darker in color.
The surface microstructure morphologies of the samples are shown in Figure 3, where
the red letters (a, b, c, d and e) in the figure are the scanning area of the energy spectrum.
After 1 week of exposure, scattered pitting corrosion appeared on the surface of the samples,
but the diameter of the pit was very small, about 14 µm, and there were corrosion products
in the pits. After 2 weeks of exposure, the diameter of the pits expanded to 20.5 µm. After
3 weeks of exposure, the diameter of the pits expanded further, and some of the pits were
connected to form a relatively large pitting area. When the exposure time reached 1 month,
the area where the pitting corrosion occurred was further enlarged, and at the same time,
the corrosion products adhered to the pitting area.
Coatings 2024,
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2024, 331x FOR PEER REVIEW 5 of 14
5 of 14

Coatings 2024, 14, x FOR PEER REVIEW 6 of 14

Figure 2.
Figure 2. The
The front
frontmacroscopic
macroscopicappearance
appearanceofof
the samples
the with
samples different
with exposure
different timetime
exposure lengths.
lengths.

The surface microstructure morphologies of the samples are shown in Figure 3,

where the red letters (a, b, c, d and e) in the figure are the scanning area of the energy
spectrum. After 1 week of exposure, scattered pitting corrosion appeared on the surface
of the samples, but the diameter of the pit was very small, about 14 µm, and there were
corrosion products in the pits. After 2 weeks of exposure, the diameter of the pits ex-
panded to 20.5 µm. After 3 weeks of exposure, the diameter of the pits expanded further,
and some of the pits were connected to form a relatively large pitting area. When the ex-
posure time reached 1 month, the area where the pitting corrosion occurred was further
enlarged, and at the same time, the corrosion products adhered to the pitting area.
The cross-sectional morphologies of the samples with different exposure time lengths
are shown in Figure 4. The white particles in the figure are the second phase in the alumi-
num alloy. The figure shows that pitting corrosion appeared on the surface of the samples
after 1 week of exposure. Then, after 2 weeks of exposure, the distribution density of pits
increased, and the distance between pits was relatively short. After reaching 3 weeks, the
diameter of the pits became larger and some pits tended to be connected to each other.
When the exposure time reached one month, due to the increase in the number of pits and
the enlargement of their diameters, some pits were connected to form a larger area of pit-
ting corrosion, and the gray areas in the figure are corrosion products. It can be seen that
the corrosion products are in the spots. Accumulation appeared in the pits and located
near the holes.

Figure3.3.The
Figure Thesurface
surfacemicrostructure
microstructuremorphologies
morphologiesof ofthe
thesamples
sampleswith
withdifferent
differentexposure
exposuretime
time
lengths: (a) 1 week, (b) 2 weeks, (c) 3 weeks, and (d) 1 month.
lengths: (a) 1 week, (b) 2 weeks, (c) 3 weeks, and (d) 1 month.
Coatings 2024, 14, 331 6 of 14

The cross-sectional morphologies of the samples with different exposure time lengths
are shown in Figure 4. The white particles in the figure are the second phase in the
aluminum alloy. The figure shows that pitting corrosion appeared on the surface of the
samples after 1 week of exposure. Then, after 2 weeks of exposure, the distribution density
of pits increased, and the distance between pits was relatively short. After reaching 3 weeks,
the diameter of the pits became larger and some pits tended to be connected to each other.
When the exposure time reached one month, due to the increase in the number of pits
and the enlargement of their diameters, some pits were connected to form a larger area of
pitting corrosion, and the gray areas in the figure are corrosion products. It can be seen that
Figure
the 3. Theproducts
corrosion surface microstructure morphologies
are in the spots. Accumulationof the samples in
appeared with
thedifferent
pits and exposure
located time
lengths: (a)
near the holes.1 week, (b) 2 weeks, (c) 3 weeks, and (d) 1 month.

Figure
Figure 4. 4.
TheThe cross-section
cross-section microstructure
microstructure morphologies
morphologies of the samples
of the samples with exposure
with different differenttime
exposure
time lengths:
lengths: (a) 1(b)
(a) 1 week, week, (b) 2(c)
2 weeks, weeks, (c) 3and
3 weeks, weeks,
(d) 1and (d) 1 month.
month.

More corrosion products accumulated, and the convex area thickened. As shown in
Figure 5, the white area on the surface of the samples further increased when the exposure
time reached 12 months, and cracks appeared in the white area.
The cross-sectional morphologies of the samples are shown in Figure 6. When the
exposure time reached 6 months, a relatively thick corrosion product layer formed on the
surface of the samples, but it was relatively loose and internally contained a lot of holes
and cracks. In addition, the corrosion product layer was uneven, and the surface was
undulated greatly. When the exposure time reached 12 months, the corrosion product
layer had obvious bulging, and part of the area was thinned due to the shedding of the
corrosion product.
 Coatings 2024, 14, x FOR PEER REVIEW 7 of 14

Coatings 2024, 14, 331 More corrosion products accumulated, and the convex area thickened. As shown in 7 of 14
Figure 5, the white area on the surface of the samples further increased when the exposure
time reached 12 months, and cracks appeared in the white area.

Figure 5. Surface morphologies of samples exposed for different long-term periods: (a) 6 months
and (b) 12 months.

The cross-sectional morphologies of the samples are shown in Figure 6. When the
exposure time reached 6 months, a relatively thick corrosion product layer formed on the
surface of the samples, but it was relatively loose and internally contained a lot of holes
and cracks. In addition, the corrosion product layer was uneven, and the surface was un-
dulated greatly. When the exposure time reached 12 months, the corrosion product layer
Figure5.5. Surface
Surface morphologies
morphologies ofofsamples exposed forfor
different long-term periods: (a) 6 months
Figure
had obvious bulging, and part ofsamples
the areaexposed
was thinned different
due to long-term periods:
the shedding of the(a)corro-
6 months and
and (b) 12 months.
(b) 12 months.
sion product.
The cross-sectional morphologies of the samples are shown in Figure 6. When the
exposure time reached 6 months, a relatively thick corrosion product layer formed on the
surface of the samples, but it was relatively loose and internally contained a lot of holes
and cracks. In addition, the corrosion product layer was uneven, and the surface was un-
dulated greatly. When the exposure time reached 12 months, the corrosion product layer
had obvious bulging, and part of the area was thinned due to the shedding of the corro-
sion product.

Figure 6.
Figure 6. The
The cross-sectional
cross-sectional morphologies
morphologiesof the
of samples exposed
the samples for different
exposed long-term
for different periods: periods:
long-term
(a) 6 months and (b) 12 months.
(a) 6 months and (b) 12 months.
3.3.Phase
3.3. Phase Analysis
Analysis
Energy spectrum analysis was utilized on the red-lettered area in the microscopic
Energy spectrum analysis was utilized on the red-lettered area in the microscopic
images. Table 3 shows that, after 2 weeks of outdoor exposure, corrosion products ap-
images. Table 3 shows that, after 2 weeks of outdoor exposure, corrosion products appeared
peared in the pits, but the amount was relatively small. The energy spectrum results con-
intain
thethe
pits, but theproducts
corrosion amount andwasthe
relatively
sample small. The
matrix, and energy
Table 3 spectrum
thatresults
showslong-term contain the
the periods:
weight
Figure 6. The cross-sectional morphologies of the samples exposed for different
corrosion
percentage products and the sample matrix, and Table 3 shows that the weight percentage of
(a) 6 months of
andoxygen was only 17.85%. When the exposure time reached 6 months, corro-
(b) 12 months.
oxygen was only
sion products 17.85%. When
accumulated on thethe exposure
surface of thetime reached
samples 6 months,
to form corrosion
a corrosion productproducts
accumulated on the surface of the samples to form a corrosion product layer; therefore, the
3.3. Phase Analysis
weight percentage
Energy spectrumof oxygen
analysisincreased to 70%.
was utilized on theThe phase analysis
red-lettered area inofthe
themicroscopic
corrosion product
powder on the surface of the samples exposed for 12 months in the
images. Table 3 shows that, after 2 weeks of outdoor exposure, corrosion productsoutdoor environment
ap-
was
peared in the pits, but the amount was relatively small. The energy spectrum results con- peaks
carried out. Figure 7 shows that the corrosion product has strong diffraction
generated by the matrix
tain the corrosion and
products Al2the
and ·3H2 O. matrix,
O3sample The resulting diffraction
and Table 3 shows peaks indicate
that the weight that the
main component
percentage of the
of oxygen wascorrosion
only 17.85%.product
When theis the monoclinic
exposure trihydrate
time reached 3 ·3H2 O. The
Al2 Ocorro-
6 months,
sion products
results accumulated
are consistent on the surface
with previous of the
studies samples
in the to form a corrosion product
field [23].

Table 3. Percentage of elements in the scanning area (wt.%).

Area O Al Mg Cu Mn
a 17.85 78.18 1.52 2.23 0.23
b 71.56 25.04 1.2 0.8 0.12
c 71.77 26.5 1.31 0.3 0.12
d 70.85 25.13 2.61 0.95 0.38
e 70.72 25.2 1.95 1.84 0.29
 Area O Al Mg Cu Mn
a 17.85 78.18 1.52 2.23 0.23
b 71.56 25.04 1.2 0.8 0.12
c 71.77 26.5 1.31 0.3 0.12
Coatings 2024, 14, 331 8 of 14
d 70.85 25.13 2.61 0.95 0.38
e 70.72 25.2 1.95 1.84 0.29

Figure 7.
Figure 7. XRD
XRD test
test results
resultsof
ofcorrosion
corrosionproducts
productsof
ofsamples
samplesafter
afterdifferent
differentexposure
exposuretimes:
times:6 6months
months (a)
(a) and 12 months (b).
and 12 months (b).

3.4. EIS Analysis

3.4. Analysis
The AC
The ACimpedance
impedance spectra of samples
spectra exposed
of samples to different
exposed lengthslengths
to different of time of in an
timeout-
in an
door environment
outdoor environment are shown in Figure
are shown 8. The8.larger
in Figure the impedance
The larger modulus
the impedance value, the
modulus value,
better
the the corrosion
better resistance.
the corrosion The figure
resistance. shows
The figurethat the initial
shows thatsamples havesamples
the initial an inductive
have an
arc in the low-frequency region, indicating that the 2024 aluminum alloy
inductive arc in the low-frequency region, indicating that the 2024 aluminum alloy is sensitive to Cl− is
and that ittoentered
sensitive Cl− and a small
that itpore corrosion
entered induction
a small period during
pore corrosion the test.
induction Theduring
period initial the
samples did not undergo pitting; therefore, the capacitive reactance arc
test. The initial samples did not undergo pitting; therefore, the capacitive reactance radius was the arc
largest, and the impedance modulus value was the largest. After exposure
radius was the largest, and the impedance modulus value was the largest. After exposure for 1 month,
the surface of the samples was pitted due to the erosion of Cl−; therefore, the capacitive
for 1 month, the surface of the samples was pitted due to the erosion of Cl− ; therefore,
reactance arc radius became smaller, and the impedance modulus became smaller. After
the capacitive reactance arc radius became smaller, and the impedance modulus became
exposure for three months, the capacitive reactance arc radius decreased, and the imped-
smaller. After exposure for three months, the capacitive reactance arc radius decreased, and
ance modulus value decreased. When the exposure time reached 6 months, the surface of
the impedance modulus value decreased. When the exposure time reached 6 months, the
the samples was covered by corrosion products generated by pitting corrosion. This had
surface of the samples was covered by corrosion
Coatings 2024, 14, x FOR PEER REVIEW
products generated by pitting9corrosion. of 14
a certain hindering effect on the diffusion of Cl− into the interior; therefore, the capacitive
This had a certain hindering effect on the diffusion of Cl− into the interior; therefore, the
reactance arc radius increased and the impedance modulus value increased. The increase
capacitive reactance arc radius increased and the impedance modulus value increased. The
in radius indicates an increase in corrosion resistance against a corrosive medium because
increase in radius indicates an increase in corrosion resistance against a corrosive medium
the thickness of the corrosion product layer increased. As a result, the path of inward dif-
because
fusionthe
of thickness
Cl− becameof the corrosion
longer. When theproduct
exposurelayer increased.
time reached As a result,
12 months, the path of
the corrosion
inward diffusion of Cl − became longer. When the exposure time reached 12 months, the
product layer began to fall off and thin, which weakened the barrier to Cl function. Hence,
−

corrosion productreactance
the capacitive layer began to fall
arc radius off andagain,
decreased thin, and
whichthe weakened the barrier
impedance modulus valueto Cl−
function. Hence, the capacitive reactance arc radius decreased again, and the impedance
decreased.
modulus value decreased.

Figure 8. The AC impedance spectra of samples exposed to different lengths of time outdoors: (a)
Figure 8. Thereactance
capacitive AC impedance spectra of
arc, (b) impedance samples
modulus exposed
value, and (c)tophase
different
angle. lengths of time outdoors:
(a) capacitive reactance arc, (b) impedance modulus value, and (c) phase angle.
Electrochemical analysis software was used to process the data. Based on the sensi-
tivity of aluminum alloys to Cl−, the equivalent circuit used for the initial samples is shown
in Figure 9, where Rs is the solution resistance, Q is the constant phase angle element
corresponding to the electric double layer, R1 is the resistance of the charge passing
through the surface oxide film, L is the equivalent inductance, and R2 is the corresponding
 Electrochemical analysis software was used to process the data. Based on the sensi-
tivity of aluminum alloys to Cl−, the equivalent circuit used for the initial samples is shown
in Figure 9, where Rs is the solution resistance, Q is the constant phase angle element
corresponding to the electric double layer, R1 is the resistance of the charge passing
Coatings 2024, 14, 331 9 of 14
through the surface oxide film, L is the equivalent inductance, and R2 is the corresponding
equivalent resistance [24–28]. Corresponding data are shown in Table 4.

TableElectrochemical
4. Electrochemicalanalysis software
parameters in the was used to
equivalent process
circuit the data. Based on the sensitiv-
diagram.
ity of aluminum alloys to Cl− , the equivalent circuit used for the initial samples is shown
in Figure 9, where Rs isRthe
Samples
s Q
solution resistance, Q is R1
n the constant
L
phase angle R2corre-
element
(Ω·cm
sponding to the electric 2 ) (×10
double layer,Ω
6
R1 cm
−1 −2
is the (kΩ·cm
) resistance of the)charge
2 (H·cm 2
passing (kΩ·cmthe
) through 2)

surface
Initialoxide film, L is
samples the equivalent
18.72 inductance,
52.1 and R18.36
0.81 2 is the corresponding
6.175 × 105 equivalent
2.1
resistance [24–28]. Corresponding data are shown in Table 4.

Figure
Figure 9.
9. Equivalent
Equivalent circuit
circuit diagram
diagram for
for the
the initial
initial state.
state.

TableFor one month after

4. Electrochemical exposure,
parameters in athe
pitequivalent
corrosioncircuit
structure occurred on the surface of the
diagram.
samples. The equivalent circuit used for the impedance spectrum of the samples is shown
Rs in Figure 10, where Q Rs is the solution R1 Q1 is the constant
resistance, L phase angleR2element
Samples n
(×106 Ω−to
(Ω·cm2 ) corresponding 1 ·cm−2 ) (kΩ · cm 2) (H · 2)
the electric double layer, R1 is the resistance corresponding(kΩ
cm ·cm2oxide
to the )
Initial samples 18.72 film, R2 is the52.1solution resistance 0.81in the pitting pit, Q2 is the6.175
18.36 constant 5
× 10 phase angle2.1element
Coatings 2024, 14, x FOR PEER REVIEWcorresponding to the non-Faraday process in the pitting pit, and R3 is the charge transfer 10 of 14
resistance when the metal anode at the bottom of the pitting pit is dissolved. The specific
For one month after exposure, a pit corrosion structure occurred on the surface of the
values of each equivalent element are shown in Table 5.
samples. The equivalent circuit used for the impedance spectrum of the samples is shown
Table 5. Electrochemical parameters in the equivalent circuit diagram.
in Figure 10, where Rs is the solution resistance, Q1 is the constant phase angle element
corresponding to Rsthe electric double
Q1 layer, R1 is theR1 resistance corresponding
Q2 to theRoxide
3
Samples
film, R2 is the(Ω·cm
solution resistance in the n 1
pitting pit, Q is R
the 2 constant phasenangle
2 element
2) (×106 Ω−1cm−2) (kΩ·cm2 2) (kΩ·cm2) (kΩ·cm 2)
corresponding to the non-Faraday process in the pitting pit, and R3 is the charge transfer
1 month 6.97 15.36 0.55 9.51 2.35 132.7 0.73 0.6
resistance when the metal anode at the bottom of the pitting pit is dissolved. The specific
3 months 7.93 4.716 0.84 4.58 3.74 60.61 0.79 1.91
values of each equivalent element are shown in Table 5.

Figure 10.
Figure 10. Equivalent
Equivalent circuit
circuit diagram
diagram for
for the
the specimens
specimens after
after three
three months
months of
of exposure.
exposure.

TableWhen exposed to parameters

5. Electrochemical the outdoor
in environment
the equivalent for 6 months,
circuit diagram.the samples were generally
corroded and the surface was covered with a corrosion product layer. Therefore, the
Rs equivalent
Q1 circuit adopted is shown R1 in Figure 11, where Rs Q2is the solution resistance
R3 and
Samples n1 R2 n
(Ω·cm2 ) 1 isΩthe·cm
(×Q10 6 −1 −2 )
normal (kΩ·cm2layer.
corrosion product ) For the phase (kΩ ·cm2 )element,2 R1 is the
angle ·cm2 )
(kΩtransfer
1 month 6.97 resistance
15.36 of the charge
0.55 in the corrosion
9.51 product,
2.35 Q2 is the constant phase
132.7 0.73 angle 0.6 element
3 months 7.93 4.716
corresponding 0.84
to the 4.58 layer, and
electric double 3.74 R2 is the 60.61 0.79
resistance corresponding 1.91to the
oxide film [29–31]. Corresponding data are shown in Table 6.
When exposed to the outdoor environment for 6 months, the samples were generally
Table 6. Electrochemical parameters in the equivalent circuit diagram.
corroded and the surface was covered with a corrosion product layer. Therefore, the
equivalent circuitRsadopted is shown
Q1 in Figure 11, where
R1 Rs is the
Q2solution resistance
R2 and
Samples n1 n2
(Ω·cm2) (×106 Ω−1cm−2) (kΩ·cm2) (kΩ·cm−2) (kΩ·cm2)
6 months 4.64 38.19 0.75 12.51 90.73 0.75 5.23

Coatings 2024, 14, 331
equivalent circuit adopted is shown in Figure 11, where Rs is the solution resistance and
Q1 is the normal corrosion product layer. For the phase angle element, R1 is the transfer
resistance of the charge in the corrosion product, Q2 is the constant phase angle element
corresponding to the electric double layer, and R2 is the resistance corresponding to the
oxide film [29–31]. Corresponding data are shown in Table 6. 10 of 14

Table 6. Electrochemical parameters in the equivalent circuit diagram.

Q1 is the normal Rcorrosion
s
product
Q1 layer. For the phase
R1 angle element,
Q2 R1 is the transfer
R2
Samplesof the charge
resistance in the corrosion n
product,
1 Q 2 is the constant nangle
phase 2 element
(Ω·cm2) (×106 Ω−1cm−2) (kΩ·cm2) (kΩ·cm−2) (kΩ·cm2)
corresponding to the electric double layer, and R2 is the resistance corresponding to the
6 months 4.64 38.19 0.75 12.51 90.73 0.75 5.23
oxide film [29–31]. Corresponding data are shown in Table 6.

Figure 11.
Figure 11. Equivalent
Equivalent circuit
circuit diagram
diagram for
for the
the specimens
specimens after
after six
six months
months of
of exposure.
exposure.

Table The polarization curves

6. Electrochemical of samples
parameters exposed circuit
in the equivalent to different lengths of time in an outdoor
diagram.
environment are shown in Figure 12, and the corresponding electrochemical parameters
Rs are shown Q1in Table 7. In addition, according R1 to the relevant
Q2 equation, the corrosion
R2 rate
Samples n1 n2
(Ω·cm2 ) was 106 Ω−1 ·cmin
(×calculated −2 )
the table [32]. The(kΩ ·cm2 )
self-corrosion (kΩ ·cm−2density
current ) (kΩ·cm
is an important 2)
indica-
6 months 4.64 tor for evaluating
38.19 the corrosion
0.75 resistance
12.51 of the samples.
90.73 The smaller0.75 the self-corrosion
5.23
current density, the better the corrosion resistance of the samples. When the self-corrosion
current density is the same, the higher the self-corrosion potential, the better the corrosion
The polarization
resistance curves
of the samples. Theof figure
samples exposed
shows thatto different
the lengths of
initial samples time
had no in an outdoor
pitting corro-
environment are shown in Figure 12, and the corresponding electrochemical
sion; therefore, the self-corrosion current density was the smallest. After one month of parameters
are shown in
exposure, theTable 7. Inofaddition,
surface the samplesaccording to the corrosion
had pitting relevant equation, the pits;
and pitting corrosion rate was
therefore, the
calculated in the table [32]. The self-corrosion current density is an important indicator for
evaluating the corrosion resistance of the samples. The smaller the self-corrosion current
density, the better the corrosion resistance of the samples. When the self-corrosion current
density is the same, the higher the self-corrosion potential, the better the corrosion resistance
of the samples. The figure shows that the initial samples had no pitting corrosion; therefore,
the self-corrosion current density was the smallest. After one month of exposure, the
surface of the samples had pitting corrosion and pitting pits; therefore, the self-corrosion
current density of the samples began to increase. After 3 months of exposure, the number of
pits increased, and the diameter of the pits further expanded. Therefore, the self-corrosion
current density continued to increase. When the exposure time reached 6 months, the
surface of the samples was covered by corrosion products generated by pitting corrosion.
The corrosion product layer had a hindering effect on the inward diffusion of Cl− and at
the same time, hindered the ion exchange process between the electrochemical corrosion
reaction area and the electrolyte liquid membrane; therefore, the self-corrosion current
density became smaller and the exposure time was longer. When it reached 12 months,
the corrosion product layer peeled off and thinned due to internal stress; therefore, the
hindering effect on the inward diffusion of Cl− and ion exchange began to weaken, and
the self-corrosion current density increased again.

Table 7. Electrochemical parameters corresponding to the polarization curve.

Samples Ecorr (mV vs. SCE) Icorr (µA/cm2 ) Corrosion Rate (µm/year)
Initial samples −629 0.456 4.97
1 month −592 1.387 15.12
3 months −593 8.338 90.88
6 months −619 2.359 25.71
12 months −555 2.849 31.05
 ated by pitting corrosion. The corrosion product layer had a hindering effect on the inward
diffusion of Cl− and at the same time, hindered the ion exchange process between the elec-
trochemical corrosion reaction area and the electrolyte liquid membrane; therefore, the
self-corrosion current density became smaller and the exposure time was longer. When it
Coatings 2024, 14, 331
reached 12 months, the corrosion product layer peeled off and thinned due to internal
11 of 14
stress; therefore, the hindering effect on the inward diffusion of Cl− and ion exchange be-
gan to weaken, and the self-corrosion current density increased again.

Figure 12.
Figure 12. The
The polarization
polarizationcurves
curvesofof samples
samples exposed
exposed to different
to different lengths
lengths of time
of time in anin an outdoor
outdoor environment.
environment.
3.5. Corrosion Mechanism
Table 7.
3.5.1. Electrochemical
The Initiation ofparameters corresponding to the polarization curve.
Pitting Corrosion
When
Samplesthe samples are(mV
Ecorr placed in an outdoor
vs. SCE) environment,
Icorr (µA/cm 2) the humidity
Corrosion in the air in the
Rate (μm/year)
marine atmosphere
Initial samples is relatively
−629 high, the air is filled
0.456 with small droplets,
4.97 and the droplets
contain1 corrosive anions (mainly Cl − ). The droplets condense on the surface of the samples,
month −592 1.387 15.12
Cl− is3adsorbed
months to the surface of the oxide film,
−593 and the following chemical
8.338 90.88 reaction occurs,
which6destroys
months and dissolves the oxide film on
−619 the surface of the samples.
2.359 25.71 In this process,
as the12oxide
monthsfilm dissolves and
−555 becomes thinner,
2.849 the impedance modulus
31.05 decreases, the
self-corrosion current density increases, and the corrosion resistance deteriorates.
3.5. Corrosion Mechanism
Al(OH)3 + Cl− → Al(OH)2 Cl + OH− (3)
3.5.1. The Initiation of Pitting Corrosion
When the samples are − the−humidity in the air in (4)
Al(placed
OH)2 Clin +
anCl
outdoor
→ Alenvironment,
(OH)Cl2 + OH
the marine atmosphere is relatively high, the air − is filled with small droplets, and the drop-
lets contain corrosive anionsAl(mainly
(OH)ClCl 2+ The→
−).Cl AlCl3 +
droplets OH− on the surface of the (5)
condense
samples,
AfterClthe
− is adsorbed to the surface of the oxide film, and the following chemical reac-
oxide film is dissolved, the substrate of the samples leaks out. Since the
equilibriumwhich
tion occurs, destroys
potential and than
is lower dissolves the oxideoxide
the adjacent film on the the
film, surface of the samples.
oxidation reaction In
of the
this process, as the oxide film dissolves and becomes thinner,
substrate as the anode is shown in Formula (7). The substrate continuously the impedance modulus
dissolves
decreases,
and formsthe self-corrosion
pitting pits. Thecurrent
reactiondensity increases,
continues and the
to occur, thecorrosion
diameterresistance dete- pits
of the pitting
riorates. larger, the number of pits increases, and the protective effect of the oxide film
becomes
continues to weaken. This stage is manifested by the disappearance of the low-frequency
inductive arc and the reduction of the impedance modulus, and the self-corrosion current
density becomes larger, indicating that the corrosion resistance of the samples continues
to deteriorate.
Al − 3e− → Al3+ (6)
O2 + 2H2 O + 4e− → 4OH− (7)
Rainfall wets the surface of the samples, which is conducive to the formation of an
electrolyte liquid film on the surface of the samples, and creates conditions for the occur-
rence of corrosion. Therefore, pitting corrosion occurs quickly on the surface. However,
sunlight exposure can also accelerate the evaporation of water in the electrolyte film on the
surface of the samples since electrochemical corrosion can only occur on the electrolyte film.
When the electrolyte liquid film decreases due to the accelerated evaporation of water, the
occurrence of electrochemical corrosion is hindered; therefore, electrochemical corrosion
cannot continue to occur. The pitting pits cannot continue to expand into the samples,
Coatings 2024, 14, 331 12 of 14

and it is difficult for intergranular corrosion to occur on the surface. As the exposure time
increases, the surface of the samples begins to enter a general corrosion stage. Therefore,
the electrolyte solution on the samples’ surface contains a large amount of Al3+ and OH
ions; the reaction between the two ions is shown in the Formula (8). The product Al(OH)3
will continue to react due to its instability, forming Al2 O3 ·3H2 O, which will accumulate on
the surface of the samples to form a corrosion product layer, blocking the inward diffusion
of Cl− and the ion exchange between the reaction area and the liquid membrane. Therefore,
the impedance modulus of the samples increases at this stage, the self-corrosion current
density decreases, and the corrosion resistance of the samples becomes better.

3.5.2. Spalling of the Corrosion Products

After a period of accumulation, the corrosion product layer gradually thickens, and
the internal stress continues to increase. Finally, the corrosion product layer falls off and
thins, which leads to a weakening of the inward diffusion of Cl− and ion exchange in the
reaction zone. Therefore, the impedance modulus decreases, the self-corrosion current
density increases, and the corrosion resistance of the samples deteriorates again.

Al3+ + 3OH− → Al(OH)3 (8)

2Al(OH)3 → Al2 O3 ·3H2 O (9)

4. Conclusions
Based on the above results, the following conclusions can be drawn:
The corrosion product weight gain and exposure time of the 2024 aluminum alloy
follow a power-law function. In the early stage, the aluminum alloy undergoes pit corro-
sion, generating some corrosion products, which then converge to form a loose corrosion
product layer. Then, pit corrosion transforms into general corrosion, and electrochemical
corrosion produces a large amount of Al(OH)3 , leading to the thickening of the loose
corrosion product layer. In the middle and later stages of corrosion, the outer layer of
corrosion products peeled off, leaving a dense stacked layer of corrosion products. The
electrochemical test results show that, as the exposure time increased, the capacitance arc
first contracts, then expands, and finally, contracts slightly. Correspondingly, the corrosion
current density of the 2024 aluminum alloy first decreased, then increased, and finally,
decreased again.

Author Contributions: Conceptualization, J.Z., T.Z. and Z.Z.; Methodology, T.Z., J.Z. and J.W.;
Investigation, T.Z., J.Z., Y.Z. and J.W.; Data curation, T.Z. and J.Z.; Writing—original draft preparation,
J.Z. and J.W.; Writing—review and editing, J.Z., Z.C. and M.C.; Visualization, J.W. and M.C. All
authors have read and agreed to the published version of the manuscript.
Funding: This project was financially supported by the National Natural Science Foundation of China
under Grant (51671053 and 51801021), the Fundamental Research Funds for the Central Universities
(No. N2302007), and the Ministry of Industry and Information Technology Project (No. MJ-2017-J-99).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data are contained within the article.
Conflicts of Interest: The authors declare that they have no known competing financial interests or
personal relationships that could have appeared to influence the work reported in this paper.

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