metals
Article
Actual Marine Atmospheric Pre-Corrosion Fatigue Performance
of 7075-T73 Aluminum Alloy
Laixin Shi 1, *, Lin Xiang 2, *, Jianquan Tao 2 , Qiang Chen 2 , Jun Liu 2 and Yong Zhong 2
Citation: Shi, L.; Xiang, L.; Tao, J.;
Chen, Q.; Liu, J.; Zhong, Y. Actual
Marine Atmospheric Pre-Corrosion
Fatigue Performance of 7075-T73
Aluminum Alloy. Metals 2022, 12, 874.
https://doi.org/10.3390/met12050874
Academic Editor: George
A. Pantazopoulos
Received: 10 April 2022
Accepted: 19 May 2022
Published: 21 May 2022
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Metals 2022, 12, 874. https://doi.org/10.3390/met12050874
1 College of Material Science and Engineering, Chongqing University of Technology,
Chongqing 400054, China
2 Southwest Technology and Engineering Research Institute, Chongqing 400039, China;
jarryallen@163.com (J.T.); 2009chenqiang@hfut.edu.cn (Q.C.); bvvh_liu@163.com (J.L.);
wanshi3816@163.com (Y.Z.)
* Correspondence: shilaixin2016@cqut.edu.cn (L.S.); xlin0731@163.com (L.X.);
Tel.: +86-15123376156 (L.S.); +86-18792897339 (L.X.)
Abstract: Actual marine atmospheric pre-corrosion behavior and its effect on the fatigue performance
of 7075-T73 aluminum alloy were studied by means of marine atmospheric outdoor exposure testing
and fatigue testing. The surface and cross-sectional microstructures of aluminum alloy specimens
after different numbers of days of exposure were analyzed. Localized pitting, and intergranular
and exfoliation corrosion occurred during the outdoor exposure of aluminum alloy specimens in
a marine atmosphere. The degree of severity of atmospheric corrosion increased with increasing
duration of exposure. The effects of Fe-rich constituent particles (Al23 CuFe4 ) and grain boundary
precipitates (MgZn2 ) on the marine atmospheric corrosion behavior were discussed. In addition,
when the exposure time was increased from 0 days to 15 days, the average fatigue life of aluminum
alloy specimens decreased dramatically from about 125.16 × 104 cycles to 16.58 × 104 cycles. As the
exposure time was further increased to 180 days, the average fatigue life slowly decreased to about
6.21 × 104 cycles. The fatigue fracture characteristics and the effect mechanism of marine atmospheric
pre-corrosion on the fatigue life of 7075-T73 aluminum alloy were also analyzed.
Keywords: 7075 aluminum alloy; outdoor exposure; actual marine atmosphere; pre-corrosion; fatigue
1. Introduction
The aluminum alloy 7075 has received a great deal of attention because of its outstand-
ing properties, which include low density and high strength; therefore, it has been used
widely as a structural material in the aircraft industry [1–6]. However, when aircraft are
in service, especially in marine atmospheric environments, the aluminum alloy structures
used inevitably suffer atmospheric corrosion damage, which could significantly degrade
the fatigue performance and reduce the service life of those structures [7–9]. Thus, a better
understanding of the effect of marine atmospheric corrosion on the fatigue performance of
7075 aluminum alloy would be vitally important and helpful in furthering research on the
service safety and life cycle of aircraft structures.
To date, many studies have been performed elucidating the effects of pre-corrosion on
the fatigue performance of 7075 aluminum alloy [10–22]. For instance, Sankaran et al. [12]
investigated the effects of pitting pre-corrosion on the fatigue behavior of aluminum alloy
7075-T6 using cyclic fog–dry salt spray tests, and found that the fatigue lives of aluminum
alloys could be dramatically reduced by pitting corrosion. Burns et al. [16] studied the
effect of EXCO solution pre-corrosion on the fatigue cracking of 7075-T6511 aluminum
alloy and reported that the substantial reduction in fatigue life due to pre-corrosion was
nearly independent of pre-corrosion time after an initial sharp degradation. Joshi et al. [19]
used constant stress amplitude fatigue tests to study the small crack growth behavior
of pre-corroded aluminum alloy 7075-T6 and found that small crack initiation life and
https://www.mdpi.com/journal/metals
 [19] used constant stress amplitude fatigue tests to study the small crack growth behavio
of pre-corroded aluminum alloy 7075-T6 and found that small crack initiation life and
crack growth life under salt water conditions were several times shorter than those unde
Metals 2022, 12, 874 2 of 10
ambient air. However, the investigations of the impact of pre-corrosion on the fatigue per
formance of 7075 aluminum alloy performed so far have mainly employed accelerated
corrosion methods to simulate atmospheric corrosion in the laboratory, seldom employ
crack growth life under salt water conditions were several times shorter than those under
ing marine atmospheric exposure tests, which in practice are more reliable and accurat
ambient air. However, the investigations of the impact of pre-corrosion on the fatigue
for evaluating actual marine atmospheric corrosion. Zhang et al. [23] performed atmos
performance of 7075 aluminum alloy performed so far have mainly employed accelerated
pheric exposure
corrosion methods to tests of epoxy
simulate primer-coated
atmospheric corrosion7075-T6 aluminum
in the laboratory, alloyemploying
seldom in a coastal envi
ronment
marine and foundexposure
atmospheric that the tests,
epoxy coating
which and anodic
in practice oxide
are more layer had
reliable lost theirfor
and accurate protectiv
ability after
evaluating 20 years
actual marine ofatmospheric
exposure. corrosion. Zhang et al. [23] performed atmospheric
exposureHowever,
tests of the
epoxy investigations
primer-coated that have aluminum
7075-T6 been performed
alloy inso far have
a coastal mainly focused on
environment
and found(peak-aged)
7075-T6 that the epoxy coating and
aluminum anodic
alloy, andoxide
havelayer had lost
seldom their protective
addressed 7075-T73 ability
(over-aged
after 20 years of exposure.
aluminum alloy, which may have a lower strength and better corrosion resistance than
However, the investigations that have been performed so far have mainly focused on
7075-T6 alloy [24]. In fact, to the best of our knowledge, the pre-corrosion fatigue perfor
7075-T6 (peak-aged) aluminum alloy, and have seldom addressed 7075-T73 (over-aged)
mance of bare 7075-T73 aluminum alloy exposed outdoors in an actual marine atmos
aluminum alloy, which may have a lower strength and better corrosion resistance than 7075-
phere
T6 alloyfor short
[24]. durations
In fact, such
to the best as several
of our daysthe
knowledge, remains unclear.
pre-corrosion In this
fatigue work, we investi
performance
gate
of barethe marinealuminum
7075-T73 atmospheric corrosion
alloy exposed behavior
outdoors in anof actual
bare marine
7075-T73 aluminum
atmosphere for alloy by
short durations such as several days remains unclear. In this work, we investigate the test site
means of outdoor exposure tests in an actual marine atmosphere at the Wanning
The fatigue
marine performance
atmospheric of behavior
corrosion atmospheric pre-corrosion
of bare aluminum
7075-T73 aluminum alloyalloy specimens
by means of with
outdoor
differentexposure
durations testsofin an actual
outdoor marine atmosphere
exposure at the Wanning
was also analyzed by means testofsite. The ampli
constant
fatigue performance
tude axial fatigue of atmospheric
tests. pre-corrosion
The corrosion aluminumand
characteristics alloy specimens
fatigue with different
fracture of pre-corrosion
durations of outdoor exposure was also analyzed by means of constant amplitude axial
aluminum alloy specimens were observed. In addition, the mechanisms of actual marin
fatigue tests. The corrosion characteristics and fatigue fracture of pre-corrosion aluminum
atmospheric corrosion and the effect of pre-corrosion on fatigue life are discussed.
alloy specimens were observed. In addition, the mechanisms of actual marine atmospheric
corrosion and the effect of pre-corrosion on fatigue life are discussed.
2. Experimental Procedure
2. Experimental
The aluminumProcedure
alloy specimens used in this work were cut from an extruded 7075
The aluminum alloy
T73 aluminum alloy sheet specimens
alongused
theinextrusion
this work were cut from
direction, an its
and extruded 7075-T73
chemical composition
aluminum alloy sheet along the extrusion direction, and its chemical composition
(wt.%) is indicated in Table 1. Figure 1 shows the geometry and dimensions (wt.%)
of the speci
is indicated in Table 1. Figure 1 shows the geometry and dimensions of the specimens
mens exposed to actual marine atmospheric environment. The average value of the yield
exposed to actual marine atmospheric environment. The average value of the yield strength
strength and tensile strengths of the 7075-T73 aluminum alloy specimens were measured
and tensile strengths of the 7075-T73 aluminum alloy specimens were measured to be about
to be
490 about
MPa and 490 MPa respectively.
562 MPa, and 562 MPa, respectively.

Table1.1.Chemical
Table Chemical composition
composition (wt.%)
(wt.%) of theof7075-T73
the 7075-T73 aluminum
aluminum alloy. alloy.

Element
Element Zn
Zn Mg
Mg Cu
Cu Fe Fe Ti Ti Si SiCr Cr
Mn Mn
Al Al
Weightfraction
Weight fraction (%) 5.57
(%) 5.57 2.58
2.58 1.51
1.51 0.140.140.0240.024
<0.05 <0.05
0.20 0.045
0.20 Bal.
0.045 Bal.

Figure1.1.Geometry
Figure Geometryand dimensions
and of the
dimensions of7075-T73 aluminum
the 7075-T73 alloy specimens.
aluminum alloy specimens.

All tests of outdoor exposure in actual marine atmosphere were carried out at Wanning
All tests of outdoor exposure in actual marine atmosphere were carried out at Wan
test site in China, which is close to the South China Sea. The average air temperature,
ning test site in China, which is close to the South China Sea. The average air temperature
relative humidity, and Cl− deposition rate at the Wanning test site can reach about 23.9 ◦ C,
relative
87.6% andhumidity, and Cl
14.5875 mg/(m deposition
2 −d), respectivelyrate at the
[23], Wanning
indicating thattest
thissite can reach
marine about 23.9 °C
atmosphere
87.6% and 14.5875
environment mg/(m by
is characterized 2 d),high
respectively
temperature, [23], indicating
high humidity, that this salt
and high marine atmospher
fog. The
environment
aluminum alloyisspecimens
characterized
were by high temperature,
installed on the test rack,high humidity,
which andsouth
was facing highatsalt
an fog. Th
angle of 45◦ and situated 350 m away from the coastline. The selected specimens were
Metals 2022, 12, x FOR PEER REVIEW 3 of 10

Metals 2022, 12, 874

aluminum alloy specimens were installed on the test rack, which was facing south at an
3 of 10
angle of 45° and situated 350 m away from the coastline. The selected specimens were
exposed to the actual marine atmosphere for 15, 30, 90 and 180 days, respectively. After
the outdoor exposure tests, the obtained atmospherically pre-corroded specimens were
exposed to the actual marine atmosphere for 15, 30, 90 and 180 days, respectively. After
withdrawn from the Wanning test site and kept in a desiccator (DZF-6020, Hefei Kejing
the outdoor exposure tests, the obtained atmospherically pre-corroded specimens were
Materials Technology Co., Ltd., Hefei, China). Afterwards, fatigue tests were carried out
withdrawn from the Wanning test site and kept in a desiccator (DZF-6020, Hefei Kejing
on the atmospherically
Materials Technology Co.,pre-corroded specimens
Ltd., Hefei, China). that had
Afterwards, been tests
fatigue exposed
werefor various
carried out ondura-
tion under constant amplitude axial loading on a QBG-50 fatigue testing
the atmospherically pre-corroded specimens that had been exposed for various duration machine (Chang-
chun Qianbang,
under Changchun,
constant amplitude axial China)
loadingin onlaboratory air at room
a QBG-50 fatigue testingtemperature to determine
machine (Changchun
their fatigue life. Sine wave load and a maximum cyclic stress (S
Qianbang, Changchun, China) in laboratory air at room temperature to determinewere max ) of 240 MPa theirap-
plied in all the fatigue tests. Moreover, the stress ratio (R) was set as
fatigue life. Sine wave load and a maximum cyclic stress (Smax ) of 240 MPa were applied 0.1 and the loading
in
frequency was about 80 Hz. The fatigue tests were repeated at least five
all the fatigue tests. Moreover, the stress ratio (R) was set as 0.1 and the loading frequency times for each
typeabout
was of marine
80 Hz.atmospherically
The fatigue testspre-corroded
were repeatedspecimen.
at least five times for each type of marine
In addition,
atmospherically selected as-received
pre-corroded specimen. (uncorroded) and atmospherically pre-corroded
In addition,
aluminum alloy selected
specimens as-received (uncorroded)ground,
were cross-sectioned, and atmospherically
polished and pre-corroded
then etched for
aluminum alloy specimens were cross-sectioned, ground, polished
microstructural observation using an optical microscope (OM, DMI5000M, Leica, and then etched for
Wetzlar,
microstructural
Germany) andobservation a scanningusing an optical
electron microscope
microscope (OM,Evo18,
(SEM, DMI5000M, Leica, Wetzlar,
Carl Zeiss, Germany)
Germany)
equippedand with a scanning electron spectroscopy
energy disperse microscope (SEM, Evo18,
(EDS). Carl Zeiss,
Selected samplesGermany)
were alsoequipped
cut from
with energy disperse spectroscopy (EDS). Selected samples were also
the as-received and pre-corroded specimens in order to analyze their surface morpholo- cut from the as-
received and pre-corroded specimens in order to analyze their surface
gies and fatigue fracture characteristics using SEM (secondary electron and backscatteredmorphologies and
fatigue
electron)fracture
and EDS.characteristics using
The thin foils SEMmechanically
were (secondary electron
thinnedandto abackscattered
thickness of electron)
100 μm be-
and EDS. The thin foils were mechanically thinned to a thickness of 100 µm before being
fore being twin-jet electro-polished in a solution consisting of 5% perchloric acid and 95%
twin-jet electro-polished in a solution consisting of 5% perchloric acid and 95% ethanol
ethanol for microstructural analysis of the as-received specimens using a transmission
for microstructural analysis of the as-received specimens using a transmission electron
electron microscope (TEM, JEM-2100, JEOL Ltd., Tokyo, Japan).
microscope (TEM, JEM-2100, JEOL Ltd., Tokyo, Japan).

3.3.Results
Resultsand
andDiscussion
Discussion
3.1.Microstructures
3.1. MicrostructuresofofAs-Received
As-Received7075
7075 Aluminum
Aluminum Alloy
Alloy
Figure
Figure22displays
displaysthe
the OM
OM microstructure
microstructure of of as-received
as-received 7075
7075 aluminum
aluminum alloy.
alloy. As in-
indicated, themicrostructure
dicated, the microstructurecontains
containsmany
many elongated
elongated grains
grains that
that areare parallel
parallel to the
to the extru-
extrusion direction
sion direction of aluminum
of the the aluminum alloy.
alloy. In addition,
In addition, several
several second-phase
second-phase constituent
constituent parti-
particles
cles can can be observed
be observed within
within thethe grain
grain or near
or near thethe grain
grain boundary.
boundary.

Figure2.2.OM
Figure OMmicrostructures
microstructuresofofas-received
as-received 7075
7075 aluminum
aluminum alloy.
alloy. Image
Image (b)(b) shows
shows thethe magnified
magnified
microstructureininthe
microstructure theframe
frame area
area ofof image
image (a).(a).

Figure
Figure33shows
showsthethesurface
surfacemorphology
morphology ofof thethe
as-received 7075
as-received aluminum
7075 aluminum alloy. It It
alloy.
can
canbe
beseen
seenthat
thatthe
theas-received
as-receivedalloy
alloysurface
surfaceisisfree
freefrom
fromcorrosion
corrosionand
andrelatively smooth.
relatively smooth.
Moreover,
Moreover,some
some second-phase
second-phase constituent
constituent particles
particles can also also be
be observed
observedon onthe
thealloy
alloysur-
surface. According to previous studies [25–27], the constituent particles in 7075
face. According to previous studies [25–27], the constituent particles in 7075 aluminum aluminum
alloy
alloymight
mightbebeFe-rich
Fe-richphase (Al
phase 23 CuFe
(Al 23CuFe4 or Al7 Cu
4 or Al 7Cu 2 Fe). The EDS results in Figure 3b further
2Fe). The EDS results in Figure 3b further
indicate that the chemical composition of these constituent
indicate that the chemical composition of these constituent particles waswas
particles Al23Al
CuFe 4 . 4.
23CuFe
Metals 2022, 12, x FOR PEER REVIEW 4 of 10
Metals 2022, 12,
12, 874
x FOR PEER REVIEW 4 of4 10
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Figure3.3.
Figure
Figure
3.Surface
Surfacemorphology
Surface morphology
morphology ofas-received
as-received
ofofas-received
7075
7075
7075
aluminum
aluminum
aluminum
alloy:
alloy:
alloy: (a)(a)
(a) secondary
secondary
secondary
electron
electron
electron
image
image
image
and
andand
(b) backscattered
(b) backscatteredelectron
electronimage.
image.
(b) backscattered electron image.

Figure444shows
Figure
Figure shows
shows the the
the TEM
TEM
TEM microstructure
microstructure
microstructure ofofofthe
the the 7075-T73
7075-T73
7075-T73 aluminum
aluminum
aluminum alloy.
alloy.
alloy. It clear
It isItclear
is is clear
thataaa lot
that
that lot of
offine
finesecond-phase
fine second-phaseprecipitates
second-phase precipitatesare
precipitates aredistributed
are distributed
distributed homogeneously
homogeneously
homogeneously within
within
within the the
the alu-
alu-
aluminum
minum alloy
minum alloymatrix.
alloy matrix.In
matrix. Inaddition,
In addition, aaacontinuous
addition, continuous
continuous chain ofofprecipitates
chain
chain can
ofprecipitates
precipitates also
can
can be
also
also observed
be be observed
observed
at
atthe
thegrain
the grainboundaries.
grain boundaries.
boundaries. The
Theelectron
Theelectron
electrondiffraction
diffractionpattern
diffraction pattern (Figure
pattern 4b)4b)
(Figure
(Figure reveals thatthat
reveals
4b) reveals the grain
the
that grain
the grain
boundary
boundary precipitates
boundary precipitates are
precipitatesare MgZn
areMgZn
MgZn (η) phase.
2 2 2(η)
(η)phase.
phase.

Figure 4. TEM microstructure of the 7075-T73 aluminum alloy: (a) bright-field image and (b) elec-
Figure4.4.TEM
Figure TEM microstructure
microstructure of 7075-T73
of the the 7075-T73 aluminum
aluminum alloy:
alloy: (a) (a) bright-field
bright-field image
image and and (b) elec-
(b) electron
tron diffraction pattern of grain boundary precipitates.
tron diffraction pattern of grain boundary precipitates.
diffraction pattern of grain boundary precipitates.
3.2.Corrosion
3.2. Corrosion Characteristics
3.2. CorrosionCharacteristics
Characteristics
Figure55shows
Figure showsthe thesurface
surfacemorphologies
morphologies ofof 7075
7075 aluminum
aluminum alloy
alloy specimens
specimens exposed
exposed
Figure 5 shows the surface morphologies of 7075 aluminum alloy specimens exposed
to
to marine
marine atmosphere
atmosphere for
for different
different numbers
numbers of of days.
days. After
After 15 15
daysdaysof of outdoor
outdoor exposure,
exposure,
to marine
somepits
atmosphere
pitswith
withvarious
varioussizes
for different
sizesandandirregular
numbers
irregularshapeshape
of days.
can
After 15 days of outdoor exposure,
some can bebe observed
observed ononthethe surface
surface of the
of the
some pits with various sizes and irregular shape can be observed on the surface of the
aluminum alloy specimen, suggesting that localized pitting corrosion has occurred. TheThe
aluminum alloy specimen, suggesting that localized pitting corrosion has occurred.
aluminum alloy
atmospheric specimen,
corrosion suggesting
products that localized pitting corrosion has occurred. The
atmospheric corrosion products ininthe thepitting
pitting corrosion
corrosion regions
regions cancanbe be
seenseen as having
as having a a
atmospheric
blackappearance
black corrosion
appearanceininthe theSEMproducts
SEMbackscattered in
backscattered the pitting
electron
electron corrosion
images
images regions
(Figure
(Figure can
5b,d).
5b,d). be
TheTheseen
EDS EDSas results a
having
results
black
showthat
show appearance
thatthese in
theseatmosphericthe SEM
atmosphericcorrosion backscattered
corrosionproducts electron
productsmainly mainlyimages (Figure
contain
contain thethe 5b,d).
elements
elements The EDS
O and
O and results
Al. Al.
show
According that tothese
the
According to the ratio atmospheric
ratio of Al to O, it can be deduced that the corrosion products of the 7075Al.
corrosion
O, it can beproducts
deduced mainly
that the contain
corrosion the elements
products ofO and
the
According
7075 aluminum
aluminum to the
alloyalloy ratio of Al
specimens
specimens to O, it can
suffering
suffering from be
fromdeduced
marine
marine that the corrosion
atmospheric
atmospheric products
pre-corrosion
pre-corrosion of the
mainly
mainly 7075
con-
aluminum
consist
sist of of
Al(OH) alloy
Al(OH) 3 specimens
3 [23]. suffering
[23].Furthermore,
Furthermore, as from marine
as shown
shown in
in Figure
Figureatmospheric
5c,d,
5c,d,somesome pre-corrosion
atmospheric
atmospheric mainly
corrosion
corrosion con-
sist of
products Al(OH)
might be[23]. Furthermore,
washed away by as shown
rainwater, in
andFigure
the
products might be washed away by rainwater, and the mud-crack characteristic can be
3 5c,d,
mud-crack some atmospheric
characteristic can corrosion
be
observed
productson
observed on the
thesurface
might be
surface ofofthe
washed remaining
away
the corrosion
by rainwater,
remaining corrosion products.
and After
the mud-crack
products. After30 30days of outdoor
characteristic
days can be
of outdoor
exposure,
observed on
exposure, the number
the thenumber and
surface size
andofsize of
the of the pits
remaining increase,
corrosion
the pits increase, and the mud-crack
products.
and characteristic
After 30characteristic
the mud-crack of
days of outdoor of
corrosion
exposure,product
corrosion the number
product surface
surfaceandbecomes
size ofmore
becomes obvious,
the pits
more increase,
obvious, as shown
and the
as shown in Figure
in Figure
mud-crack5e–h.When
5e–h. Whenthe theout- of
characteristic
outdoor
corrosion exposure
product time is increased to 90 days, the severity of the Figure
localized atmospheric
door exposure timesurface becomes
is increased to 90moredays,obvious,
the severityas shown
of theinlocalized 5e–h. When the
atmospheric out-
cor-
corrosion on the surface of the aluminum alloy specimens increases. The adjacent pits tend
door exposure
rosion time isofincreased
on the surface the aluminum to 90 days, the severityincreases.
alloy specimens of the localized atmospheric
The adjacent pits tend cor-
to interact with each other, and the size of the pits further increases, as shown in Figure 5i–l.
rosion
to on the
interact withsurface of theand
each other, aluminum
the size of alloy
thespecimens
pits furtherincreases.
increases,The adjacent
as shown pits tend
in Figure
5i–l. After 180
to interact withdays eachofother,
outdoor andexposure,
the size of most
the of thefurther
pits aluminum alloy specimen
increases, as shown surface
in Figure
5i–l. After 180 days of outdoor exposure, most of the aluminum alloy specimen surface
Metals 2022, 12, x FOR PEER REVIEW 5 of 10
Metals 2022, 12, 874 5 of 10

suffers from
After 180 atmospheric
days of outdoor corrosion. As indicated
exposure, most in Figure
of the aluminum 5m–p,
alloy the size
specimen of the
surface pits in-
suffers
creases significantly, which can be attributed to adjacent pits converging
from atmospheric corrosion. As indicated in Figure 5m–p, the size of the pits increases into larger pits.
Moreover, there are some newly formed small pits on the specimen surface.
significantly, which can be attributed to adjacent pits converging into larger pits. Moreover, It is worth
noting that,some
there are as shown
newlyin Figuresmall
formed 5, several corrosion
pits on pits are
the specimen distributed
surface. closenoting
It is worth to the Fe-rich
that,
constituent
as shown inparticles
Figure 5,(Al 23CuFe
several 4). Accordingly,
corrosion it can be close
pits are distributed inferred
to thethat the occurrence
Fe-rich constituent of
localized
particles pitting corrosion
(Al23 CuFe on the surface
4 ). Accordingly, it can beofinferred
7075-T73 aluminum
that alloyofspecimens
the occurrence exposed
localized pitting
tocorrosion
the marine on the surface of is
atmosphere 7075-T73
closelyaluminum
associatedalloy withspecimens exposed
the Fe-rich to the marine
constituent particles,
atmosphere
which is closely
might have higherassociated with the Fe-rich
electrochemical potential constituent
than the particles,
surrounding which might have
aluminum alloy
higher[25].
matrix electrochemical potential than the surrounding aluminum alloy matrix [25].

Figure 5. SEM secondary electron and backscattered electron images of the surface morphologies of
Figure 5. SEM secondary electron and backscattered electron images of the surface morphologies
7075 aluminum alloy specimens exposed outdoor for different numbers of days: (a–d) 15 days; (e–
of 7075 aluminum alloy specimens exposed outdoor for different numbers of days: (a–d) 15 days;
h) 30 days; (i–l) 90 days; (m–p) 180 days.
(e–h) 30 days; (i–l) 90 days; (m–p) 180 days.

Figure
Figure66 shows
shows thethecross-sectional
cross-sectional microstructures
microstructures of 7075
of 7075 aluminumaluminum alloy speci-
alloy specimens
mens subjected to outdoor exposure for different numbers of days.
subjected to outdoor exposure for different numbers of days. As indicated, there is As indicated, there
no is
noobvious
obvious corrosion
corrosion inin the
the as-received
as-received specimen
specimen (see
(see Figure
Figure 6a).6a). After
After 15 15 days
days of of outdoor
outdoor
exposure,
exposure,asasshown
shownin in Figure localizedintergranular
Figure 6b,f, localized intergranularcorrosion
corrosioncan canbebe seen
seen to to
havehave
occurredininthe
occurred thealuminum
aluminum alloy matrix,
matrix, and
andlamellar
lamellarcracks
cracksextend
extend along
alongthethe
elongated
elongated
grainboundary
grain boundaryparallel
parallel to
to the
the alloy
alloy surface.
surface. The
TheEDS
EDSresults
resultspresented
presented inin
Figure
Figure 6f 6f
show
show
that the intergranular corrosion products are also mainly
that the intergranular corrosion products are also mainly Al(OH) Al(OH) 3 . After 30 days of outdoor
3. After 30 days of out-
exposure,
door bothboth
exposure, the length and depth
the length of theof
and depth intergranular corrosion
the intergranular have increased
corrosion (see
have increased
Figure
(see Figure6c).6c).
With further
With furtherincreases in in
increases thethe
duration
duration of of
outdoor
outdoor exposure,
exposure,thethe
degree
degreeof of
severity of the intergranular corrosion progressively increases. When the duration of
severity of the intergranular corrosion progressively increases. When the duration of out-
Metals
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2022, 12,874
x FOR PEER REVIEW 6 6ofof1010

outdoor exposure
door exposure is increased
is increased to days,
to 180 180 days, the corrosion
the corrosion layers layers near
near the the surface
surface of the
of the alumi-
aluminum alloy specimens come apart and are even exfoliated (see Figure 6e),
num alloy specimens come apart and are even exfoliated (see Figure 6e), indicating that indicating
that exfoliation
exfoliation corrosion
corrosion is occurring.
is occurring.

Figure6.6. (a–e)
Figure (a–e) OM
OM and
and (f)
(f)backscattered
backscatteredelectron
electronimages forfor
images thethe
cross-sectional microstructures
cross-sectional of
microstructures
7075 aluminum alloy specimens subjected to outdoor exposure for different numbers of days: (a) 0
of 7075 aluminum alloy specimens subjected to outdoor exposure for different numbers of days:
days; (b,f) 15 days; (c) 30 days; (d) 90 days; (e) 180 days.
(a) 0 days; (b,f) 15 days; (c) 30 days; (d) 90 days; (e) 180 days.
As mentioned above, pitting, intergranular, and exfoliation corrosion may occur in
As mentioned above, pitting, intergranular, and exfoliation corrosion may occur in
the 7075-T73 aluminum alloy specimens exposed to the actual marine atmosphere at the
the 7075-T73 aluminum alloy specimens exposed to the actual marine atmosphere at the
Wanning test site, which has a high humidity and high chlorine ion (Cl−) concentration.
Wanning test site, which has a high humidity and high chlorine ion (Cl− ) concentration.
Under the conditions of the marine atmospheric environment, the oxide film on the sur-
Under the conditions of the marine atmospheric environment, the oxide film on the surface
face of the 7075 aluminum alloy specimen, especially close to the Fe-rich constituent par-
of the 7075 aluminum alloy specimen, especially close to the Fe-rich constituent particles,
ticles, might be damaged by electrolyte water films containing Cl−, and then the aluminum
might be damaged by electrolyte water films containing Cl− , and then the aluminum alloy
alloy matrix is exposed directly to marine atmosphere. Because the electrochemical poten-
matrix is exposed directly to marine atmosphere. Because the electrochemical potential of
tial of the Fe-rich constituent particles is different from that of the aluminum alloy matrix
the Fe-rich constituent particles is different from that of the aluminum alloy matrix [25],
[25], electrochemical reactions between them may occur. Compared with the Fe-rich con-
electrochemical reactions between them may occur. Compared with the Fe-rich constituent
stituent particles, the surrounding aluminum alloy matrix with lower electrochemical po-
particles, the surrounding aluminum alloy matrix with lower electrochemical potential
tential acts as an anode, and would be dissolved preferentially, leading to the occurrence
acts as an anode, and would be dissolved preferentially, leading to the occurrence of
of pitting corrosion.
pitting corrosion.
In addition, intergranular and exfoliation corrosion of the exposed 7075-T73 alumi-
In addition, intergranular and exfoliation corrosion of the exposed 7075-T73 aluminum
num alloy specimens might be related to the precipitates at the grain boundaries. As men-
alloy specimens might be related to the precipitates at the grain boundaries. As mentioned
tioned above, in the 7075-T73 aluminum alloy, the precipitates at the grain boundaries
above, in the 7075-T73 aluminum alloy, the precipitates at the grain boundaries were identi-
were identified as MgZn2 phase (see Figure 4). Under the action of corrosive media in the
fied as MgZn2 phase (see Figure 4). Under the action of corrosive media in the actual marine
actual marine atmosphere, an electrochemical corrosion system might be formed by the
atmosphere, an electrochemical corrosion system might be formed by the MgZn2 grain
MgZn2 grain boundary precipitates and the aluminum alloy matrix. It has been reported
boundary precipitates and the aluminum alloy matrix. It has been reported that MgZn2
that MgZn2 phase has a lower electrochemical potential than the aluminum alloy matrix
phase has a lower electrochemical potential than the aluminum alloy matrix [28]. There-
[28]. Therefore, in the above electrochemical corrosion system, the MgZn2 precipitates at
fore, in the above electrochemical corrosion system, the MgZn2 precipitates at the grain
the grain boundaries act as the anode and are dissolved preferentially, resulting in the
boundaries act as the anode and are dissolved preferentially, resulting in the occurrence
occurrence of intergranular corrosion. As the intergranular corrosion proceeds along the
of intergranular corrosion. As the intergranular corrosion proceeds along the elongated
elongated grain boundaries parallel to the specimen surface, the corrosion products will
grain boundaries parallel to the specimen surface, the corrosion products will accumulate
accumulate at the grain boundaries. The volume of corrosion products (Al(OH)3) will be
at the grain boundaries. The volume of corrosion products (Al(OH)3 ) will be larger than
larger than that of the consumed aluminum alloy matrix [29,30]. As a result, wedging
that of the consumed aluminum alloy matrix [29,30]. As a result, wedging force might be
force might be generated at the elongated grain boundaries, which could cause the rup-
generated at the elongated grain boundaries, which could cause the rupture and exfoliation
ture and exfoliation of the alloy surface. Accordingly, exfoliation corrosion occurs in the
of the alloy surface. Accordingly, exfoliation corrosion occurs in the 7075-T73 aluminum
7075-T73 aluminum alloy specimen subjected to outdoor exposure for 180 days, as shown
alloy specimen subjected to outdoor exposure for 180 days, as shown in Figure 6e.
in Figure 6e.

3.3. Fatigue Performance

Metals 2022, 12, 874 7 of 10
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3.3. Fatigue Performance

Figure 7 shows the average fatigue lives of the 7075-T73 aluminum alloy specimens
subjected to outdoor exposure in marine atmosphere for different numbers of days. The
maximum cyclic stress (Smax max)) was
was 240
240 MPa.
MPa. As As indicated,
indicated, the average fatigue life (Nff) of
the uncorroded aluminum
aluminum alloy
alloy specimens
specimenswas wasabout 125.16××1010
about125.16 4 cycles.
4 cycles. After
After15 15
days of
days
outdoor
of outdoorexposure, thethe
exposure, average
averageNf of
Nfthe pre-corroded
of the pre-corroded aluminum
aluminum alloyalloy
specimens
specimenshad had
sig-
nificantly
significantlydecreased
decreasedto to
about
about 16.58
16.58×× 4 cycles,
10410cycles, indicating
indicating that
thatlow-level
low-levelmarine
marineatmos-
atmo-
spheric corrosion damage was able to dramatically reduce
pheric corrosion damage was able to dramatically reduce the fatigue life the fatigue life of the 7075-T73
aluminum alloy specimens. After the initial sharp degradation, with increasing outdoor
exposure duration, the average fatigue life of of the
the aluminum
aluminum alloyalloy specimens
specimens still stillprogres-
progres-
sively decreased, but the rate of decrease became much smaller. Thus, the average average Nf of
4
pre-corroded
pre-corroded aluminum
aluminum alloy
alloy specimens
specimensdecreased
decreasedfrom fromabout 16.58×× 10 4 cycles to about
about16.58
6.21 ××10 4
104 cycles
cycleswhen
whennumber
numberofofdaysdaysofofexposure
exposureincreased
increasedfrom
from15 15to
to180.
180.

Figure 7. Average
Averagefatigue
fatiguelife
life(N
(Nf) of the
f ) of 7075
the aluminum
7075 alloy
aluminum specimens
alloy subjected
specimens to outdoor
subjected ex-
to outdoor
posure forfor
exposure different numbers
different numbers ofof
days.
days.

Figure 8 shows the fatigue fracture morphologies of 7075 aluminum alloy specimens
subjected to to outdoor
outdoor exposure
exposurefor fordifferent
differentnumbers
numbersofofdays.days.It can be seen
It can be seenthat,that,
in thein
the absence
absence of pre-corrosion,
of pre-corrosion, thethe fatigue
fatigue crackinitiated
crack initiatedatataa Fe-rich
Fe-rich constituent
constituent particle
(Al23 CuFe44) )near
23CuFe nearthethesurface
surfaceof of the
the aluminum
aluminum alloyalloy specimen,
specimen, as as shown
shown in in Figure
Figure 8a–c.
8a–c.
The Fe-rich constituent particles are harder than the aluminum alloy matrix and can give
rise to stress concentration. Thus, Thus, they
they could
could act
act as
as an
an initiation
initiation site
site for
for fatigue
fatigue cracking.
cracking.
After 15 days of outdoor exposure, the fatigue crack originated from a shallow localized
corrosion region near the corner of the pre-corroded aluminum alloy specimen, as shown
in Figure 8d–f. When the outdoor exposure duration increased to 180 days, the initiation
site of
site of the
thefatigue
fatiguecrack
crackrevealed
revealedanan irregular
irregulardeep
deeplocalized corrosion
localized corrosionfeature that that
feature was wasalso
situated near the corner of the alloy specimen, as shown in
also situated near the corner of the alloy specimen, as shown in Figure 8g–i. Figure 8g–i.
As can
As can be
be seen
seen from
from thethe experimental
experimental results,
results, marine
marine atmospheric
atmospheric corrosion
corrosion can can pen-
pen-
etrate the surface of aluminum alloy specimens and change the initiation
etrate the surface of aluminum alloy specimens and change the initiation site of fatigue site of fatigue
cracking. The
cracking. Thestress
stressconcentration
concentration caused
caused byby thethe generation
generation of localized
of localized atmospheric
atmospheric cor-
corrosion
rosion regions
regions during
during outdoor
outdoor exposure
exposure in the
in the marine
marine atmosphere
atmosphere couldcould significantly
significantly ac-
accelerate the initiation of fatigue cracks. Therefore, the fatigue life of
celerate the initiation of fatigue cracks. Therefore, the fatigue life of atmospherically pre- atmospherically
pre-corroded
corroded 7075-T73 7075-T73 aluminum
aluminum alloyalloy specimens
specimens withwith 15 days
15 days of exposure
of exposure was was dramati-
dramatically
cally reduced compared with that of the uncorroded specimens (see
reduced compared with that of the uncorroded specimens (see Figure 7). With the prolon- Figure 7). With the
prolongation of the duration of atmospheric pre-corrosion, the depth
gation of the duration of atmospheric pre-corrosion, the depth of the localized pre-cor- of the localized pre-
corroded
roded region
region increased
increased progressively,
progressively, as shown
as shown in Figure
in Figure 8d–i,
8d–i, whichwhichmightmight further
further in-
crease the severity of stress concentration and thus reduce the initiation time of fatigue
 Metals 2022, 12, 874 8 of 10
Metals 2022, 12, x FOR PEER REVIEW 8 of 10

increase the severity of stress concentration and thus reduce the initiation time of fatigue
cracking.
cracking.However,
However, the
the contribution
contribution ofof the
the increase
increaseininthe
thedepth
depthofoflocalized
localizedpre-corrosion
pre-corrosion
region
regionto
tothe
thedecrease
decrease in
in the fatigue life
life might
might be
beweaker
weakerthan
thanthat
thatofofthe
thegeneration
generationofofthe
the
localizedpre-corrosion
localized pre-corrosion region.
region. As a consequence,
consequence, the
the fatigue
fatiguelife
lifeofofthe
theatmospherically
atmospherically
pre-corroded 7075-T73
pre-corroded 7075-T73 aluminum
aluminum alloy
alloy specimens
specimensdecreased
decreasedslowly
slowlywhenwhenthe theduration
durationofof
outdoor exposure was increased from 15 days to 180
outdoor exposure was increased from 15 days to 180 days. days.

Figure 8. SEM secondary electron and backscattered electron images of fatigue fracture morpholo-
Figure 8. SEM secondary electron and backscattered electron images of fatigue fracture morpholo-
gies of 7075-T73 aluminum alloy specimens exposed outdoor for different days: (a–c) 0 days; (d–f)
gies of 7075-T73 aluminum alloy specimens exposed outdoor for different days: (a–c) 0 days;
15 days; (g–i) 180 days.
(d–f) 15 days; (g–i) 180 days.

4.4.Conclusions
Conclusions
(1)When
(1) Whenthe the 7075-T73
7075-T73 aluminum alloy alloy specimen
specimenwas wassubject
subjecttotooutdoor
outdoorexposure
exposureinin
actual marine
actual marine atmosphere
atmospherefor fora ashort duration
short duration (no(no
more thanthan
more 15 days), localized
15 days), pittingpitting
localized and
intergranular corrosion occurred near the alloy surface. The degree of severity
and intergranular corrosion occurred near the alloy surface. The degree of severity of ma- of marine
atmospheric
rine atmosphericcorrosion increased
corrosion increasedwithwith
increasing exposure
increasing duration.
exposure AfterAfter
duration. 180 days of
180 days
outdoor exposure, exfoliation corrosion also took
of outdoor exposure, exfoliation corrosion also took place. place.
(2)The
(2) Theformation
formation of of corrosion
corrosion pits
pits was
was mainly
mainlyattributed
attributedtotothetheanodic
anodicdissolution
dissolutionofof
the matrix around the Fe-rich constituent particles (Al 23 CuFe 4 ). The
the matrix around the Fe-rich constituent particles (Al23CuFe4). The intergranular intergranular corrosion
corro-
and exfoliation corrosion were mainly related to the preferential anodic dissolution of
sion and exfoliation corrosion were mainly related to the preferential anodic dissolution
MgZn2 (η) phase precipitates at the elongated grain boundaries of the aluminum alloy.
of MgZn 2 (η) phase precipitates at the elongated grain boundaries of the aluminum alloy.
(3) The fatigue cracking of the as-received (uncorroded) specimens was mainly initi-
(3) The fatigue cracking of the as-received (uncorroded) specimens was mainly initi-
ated near the Al23 CuFe4 particles, causing stress concentration. With increasing exposure
ated near the Al23CuFe4 particles, causing stress concentration. With increasing exposure
time, the fatigue life (Nf ) of the alloy specimens first decreased dramatically and then
time, the fatigue
continued life (Nmore
to decrease f) of the alloy specimens first decreased dramatically and then con-
slowly. The initial sharp decrease in Nf can be attributed to the
tinued to decrease
generation more slowly.
of a localized The initial
pre-corrosion region, sharp decrease
inducing moreinserious
Nf canstress
be attributed to the
concentration
generation of a localized pre-corrosion region, inducing more serious stress concentration
and thus significantly accelerating the initiation of fatigue cracking. The following slow
Metals 2022, 12, 874 9 of 10

and thus significantly accelerating the initiation of fatigue cracking. The following slow
decrease of Nf might be related to the increasing depth of the localized pre-corrosion region
with the prolongation of exposure time.

Author Contributions: L.S. and L.X. conceived, designed, and performed the experiments; L.S., L.X.,
J.T. and Q.C. analyzed the data; J.L. and Y.Z. contributed reagents/materials/analysis tools; L.S.
wrote the paper. All authors have read and agreed to the published version of the manuscript.
Funding: The work was supported by the Southwest Institute of Technology and Engineering
Cooperation Fund (Grant No. HDHDW5902020105) and the Basic and Advanced Research Project of
CQ CSTC (Grant No. cstc2018jcyjAX0035).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author. The data are not publicly available due to privacy.
Conflicts of Interest: The authors declare no conflict of interest.

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