Corrosion Science xxx (xxxx) xxxx

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

Macro-galvanic effect and its influence on corrosion behaviors of friction stir

welding joint of 7050-T76 Al alloy
Yong Chena, Yanqiu Wanga,b,*, Li zhouc, Guozhe Menga, Bin Liua, Junyi Wanga, Yawei Shaoa,
Jiantang Jiangd
a
Key Laboratory of Superlight Materials and Surface Technology (Harbin Engineering University), Ministry of Education, Harbin, 150001, China
b
Key Laboratory of Preparation and Application of Environmental Friendly Materials (Jilin Normal University), Ministry of Education, Changchun, 130103, China
c
Shandong Provincial Laboratory of Special Welding Technology, Harbin Institute of Technology at Weihai, Weihai, 264209, China
d
School of Materials Science and Engineering, Harbin Institute of Technology, Harbin, 150001, China

A R T I C LE I N FO A B S T R A C T

Keywords: The corrosion behavior of various zones of the 7050-T76 aluminum alloy friction stir welding (FSW) joint and
Al alloy their interaction were studied. The wire beam electrode (WBE) analysis reveals that heat-affected zone (HAZ)
Friction stir welding adjacent to nugget zone (NZ) receives the most intense negative current and thus presents the intensified sus-
Corrosion potential ceptibility to corrosion. Both pitting and intergranular corrosion are aggravated greatly in HAZ while suppressed
Galvanic corrosion
in base material (BM) when the whole FSW joint was put into NaCl solution, indicating the dominating influence
from macro-galvanic effect. The coupling relationship between macro-galvanic and micro-galvanic effects is
revealed based on the electrochemical analysis.

1. Introduction microstructure in FSW joints.

The development of friction stir welding (FSW) has greatly pro-
moted the fabrication of complicated components from aluminum
alloy, as the hot cracking sensitivity that derived in conventional
welding was substantially eluded [1]. Components fabricated from
7xxx and 2xxx Al alloys via FSW process have thus been widely used in
aircrafts, spacecrafts and ships in the past a few decades and excellent
mechanical properties were thereafter achieved [2]. Although FSW
endues the aluminum alloy in welding zone better retention of baseline
mechanical properties and fewer defects, comparing with the conven-
tional welding process, it still produces intensively modified micro-
structure quite different from that of the base materials and thus bring
out heterogeneity in FSW joints and the neighboring region. The pre-
sence of heterogeneous microstructure influences the performances of
the components including mechanical properties and corrosion re-
sistance as well [3–5]. Many studies noted that FSW structures exhibit
intensified susceptibility to localized corrosion (LC) to compare with
the base materials in local regions [6–16]. The aroused LC susceptibility
in joint then restricts the applications of FSW components that may
exposed to corrosive environment such as marine service and so on
[6,13]. It is thus of technical significance to investigate the corrosion
behavior and to address the influences from the modified
Many researches have been carried out to investigate the corrosion
behavior of the FSW joints [7–16] and some methods for improving the
corrosion resistance of local regions were developed [17–20]. The high
susceptibility of FSW joint is generally believed to originate from the
enhanced galvanic effect, either in micro scale that related to the mu-
tated microstructure in local regions, or in macro scale that related to
the microstructure heterogeneity that developed during the FSW pro-
cess. Micro-galvanic corrosion between the matrix and second phases,
grain boundaries (GBs) or precipitation free zones (PFZs) is common
mechanism for pitting and intergranular corrosion (IGC) in aluminum
alloys [13]. For instance, Al7Cu2Fe, one of commonly identified parti-
cles in aluminum alloys, can cause the dissolution of the surrounding
matrix and thus induce continuously accelerating pitting because of its
noble electrochemical potential and the initiative de-alloying process
[21]. Similarly, the presence of Al2Cu precipitate is believed the main
cause for the accelerated anodic-cathodic reactivity in 2xxx alloys [22].
The localized corrosion occurred at the GB/PFZ regions was attributed
to the non-uniform distribution of MgZn2 phase within the TMAZ in
FSW joint of AA7108-T79 alloy [23]. The mutation in microstructure
that occurs during the FSW can enhance the micro-galvanic effect and
thus leads to deteriorated corrosion resistance. For instance, previous
studies note that the enhanced corrosion susceptibility of local regions

⁎
Corresponding author at: Key Laboratory of Superlight Materials and Surface Technology (Harbin Engineering University), Ministry of Education, Harbin,
150001, China.
E-mail address: qiuorwang@hrbeu.edu.cn (Y. Wang).

https://doi.org/10.1016/j.corsci.2019.108360
Received 27 May 2019; Received in revised form 25 September 2019; Accepted 19 November 2019
0010-938X/ © 2019 Elsevier Ltd. All rights reserved.

Please cite this article as: Yong Chen, et al., Corrosion Science, https://doi.org/10.1016/j.corsci.2019.108360
Y. Chen, et al.
of FSW joints in most cases is correlated with wide PFZs and coarsened
precipitates such as η (MgZn2) and S(Al2CuMg)for 7075 Al alloy and
2024 Al alloy, respectively [24]. It was also noted that the corrosion
behavior of the FSW joint was largely determined by the distribution of
η phases that developed during the FSW process [23]. A most recent
study on 2014 Al alloy FSW joints demonstrated that, the grain re-
finement of Al matrix in the NZ was positive to the passivation and thus
improved the corrosion resistance [22]; meanwhile the grain coar-
sening of the Al matrix in the HAZ is negative to the passivation and
should be responsible for the reduction of the corrosion resistance [22].
Similar influence from grain refinement was also observed in AA6005
Al alloy FSW joints [25]. Additionally, reducing the size of second
phases was found beneficial to the passivation and thus can lead to
improved corrosion resistance [25–27].
In these previous studies, much attentions have been focused on the
localized corrosion in FSW and the micro-galvanic effect was specifi-
cally addressed considering the dispersoids, precipitates and micro-
chemistry in local regions. The interactions between welding zone and
the base materials, namely the macro-galvanic effects, however was
somewhat ignored. The circumstance deviates apparently from the re-
quirement from the actual service of components from the FSW process,
since the heterogeneous microstructure in FSW joints cause not only
micro-galvanic corrosion but also macro-galvanic effect that strides
across different regions. Wadeson [23] observed that the open circuit
potentials (OCP) and the corrosion resistance changed greatly with
various location across the thermo-mechanically affected zone (TMAZ)
of FSW joints of AA7108-T79 alloy. Bousquet revealed that the zone
close to TMAZ was the most corrosion susceptible region in FSW joint
fabricated from 2024-T3 alloy [3]. The increased susceptibility that
observed in this region was believed related to the macro-galvanic
coupling between the base material and the welded zone. Another study
also notes that the HAZ is the most corrosion susceptible zone for
AA2014 alloy [22]. Padgett depicted the difference in OCP between
sub-regions leads to significant macro-galvanic effect when the FSW
joint was exposed to aggressive environment [28]. This macro-galvanic
phenomenon was emphasized by Donford using the scanning reference
electrode technique on a FSW joint of aluminum alloy in 3.5 % NaCl
solution [29]. The investigation on corrosion behavior of FSWed
AA2024 and AA2195 alloys however indicated that the welding zone
and the base metal exhibits similar corrosion potentials [30].
Although the corrosion behavior was investigated considering the
galvanic effect in micro- and macro-scale as well, the study on corrosion
behavior of FSW joints remains inadequate. Specifically, the relevance
as well as the cause of macro/micro galvanic effect remain to be clar-
ified. The present work was inspired to investigate the corrosion be-
havior of FSW joints fabricated from 7050-T76 Al alloy, aiming to
clarify the interaction between galvanic effects in micro- and macro-
scale, and to address the cause that resulted in the microstructure
heterogeneity. The analysis based on wire electrode beam test and the
systematic comparison of corrosion configuration have revealed the
dominating influence of macro-galvanic effect on micro-galvanic effect.
The microstructure evolution combined with the redistribution of so-
lutes that occur during FSW process were observed to induce galvanic
effects both in micro- and macro-scales.
2. Experimental
2.1. Samples preparation
The raw material used in the current work was 7050-T76 Al alloy
plate, the nominal chemical composition of which is listed in Table 1.
The welding samples (250 mm × 75 mm × 6.8 mm in size) was cut
from the plate and cleaned thoroughly before putting into the FSW
process. During the FSW process, the rotation rate of the tool was set at
800 rpm and the traverse speed at 200 mm/min. The tilt angle of the
rotating tool was set at 2.5° with respect to the normal line of the
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Table 1
Chemical composition of 7050 aluminum alloy (wt.%).
Zn Cu Mg Fe Si Mn Zr Al
5.7-6.7 2.0-2.6 1.9-2.6 ≤0.15 ≤0.12 0.1 0.08-0.15 Balance
sample surface. The schematic drawing of the welding process is shown
in Fig. 1.
The joint was divided into the base material (BM), the heat-affected
zone (HAZ), the thermo-mechanically affected zone (TMAZ) and the
nugget zone (NZ) according to the characteristic microstructure ob-
served on the cross section. The advancing HAZ side is marked 'HAZ-A'
and the retreating HAZ side as 'HAZ-R'. The welded plate was naturally
aged for more than 3 months before putting into the subsequent testing.
Small samples that were supposed to represent the local characteristics
of each zone were cut respectively from the zones of BM, HAZ and NZ
according to microstructure regionalization.
2.2. Microstructure characterization
Metallographic observation was carried out on samples cut from the
joint transversely to welding direction. Samples were waterish grinded
using successively low-to-high grades of SiC abrasive paper and then
mechanically polished to mirror surface before etching in Keller’s re-
agent for 30 s.
Scanning electron microscope (SEM, FEI Quanta 200 F) equipped
with energy dispersive X-ray (EDS, EDAX Genesis 2000) was used, in
the mode of secondary electron (SE) imaging or backscattered electron
(BSE) imaging, to identify the distribution and composition of the
coarse dispersoids located in different zones, and to observe the mor-
phology of corroded samples.
Foils 80 μm in thickness were extracted from zone of NZ, BM and
HAZ (adjacent to TMAZ) respectively for TEM observing. The thin disc
samples 3 mm in diameter acquired from the foils were prepared by
twin jet electropolisher in a solution containing 30 vol.% nitric acid and
70 vol.% methanol at −25 °C. During TEM observation, bright field
(BF) images were taken to characterize the morphology, EDS-line
scanning or EDS-mapping was carried out to examine the micro-
chemistry in selected regions.
2.3. Corrosion test
Samples for open circuit potential (OCP) test and potentiodynamic
polarization (PDP) analysis were taken from the joint surface of each
zone and sealed by epoxy resin with area of 5 mm × 5 mm exposed,
then progressively ground to 2000 grit using SiC abrasive paper. The
PDP analysis was conducted in 3.5 % NaCl solution in the range −300
mV to 200 mV relative to the OCP with a scanning rate of 0.333 mV/s,
using a three-electrode system: a platinum auxiliary electrode, a satu-
rated calomel reference electrode (SCE) and a working electrode.
Samples were immersed in 3.5 % NaCl solution until the OCP was
stable, whereat the PDP test was started. The OCP test for samples
extracted from each zone (BM, HAZ and NZ) lasted for 1 h and the OCP-
time curves were recorded.
The immersion corrosion tests in 3.5 % NaCl solution were con-
ducted on the whole joint and the separated samples extracted from
HAZ according to ASTM G44. Intergranular corrosion (IGC) tests were
conducted on the samples extracted from each zone (BM, HAZ and NZ)
and the whole FSW joint via immersing in 57 g/L NaCl +10 ml/L H2O2
solution. The surface morphology or cross-sectional morphology of the
samples was observed using SEM after immersion corrosion and IGC
tests.
A wire beam electrode (WBE) was used for measuring the galvanic
current and corrosion potential of the upper-surface of FSW joint. The
WBE was composed of 30 micro electrode units each of them has an
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Fig. 1. Schematic diagram of friction stir welding. L for longitudinal (rolling), T for transverse and S for short-transverse direction of the raw plate, respectively.

Fig. 2. Diagrams of wire beam electrode used for measuring galvanic current and potential profile of the FSW joint surface (a), and for measuring galvanic current
and potential profile of the cross section of FSW joint (b).

exposed area of 2 mm × 5 mm, as shown in Fig. 2a. The WBE used for
measuring galvanic current and potential of the cross section of FSW
joint was composed of 30 × 3 micro electrode units, and each of them
was sealed by epoxy resin side by side with an exposed area 2 mm × 2
mm (Fig. 2b). The galvanic current and potential were recorded with an
interval of 9 s. The measurements were conducted in a thermostat bath
containing 3.5 % NaCl solution at 25 ± 1 °C.
3. Results
3.1. Microstructure of the FSW joint
The microstructure of the various zones of the FSW joint, namely
the BM, HAZ, TMAZ and NZ, was observed via metallurgical micro-
scope and the representative morphology was shown in Fig. 3. Fig. 3a
displays the 3D optical micrograph of the whole weld joint, revealing
the heterogeneous feature of the metallurgical structure in the FSW
joint. Fig. 3b shows that elongated grains 10∼15 μm in the width
distribute along the rolling direction of the plate, indicating the fibrous
characteristic of grains in the BM. Grains in HAZ are also fibrous but
larger (10∼25 μm in the width) than those in the BM (Fig. 3c), sug-
gesting that the grains within this zone coarsen slightly during the FSW
process. The intense temperature rise in HAZ induced by the friction-
stirring action is believed to cause the grain coarsening [10,15,19].
Metallograph in Fig. 3d reveals that elongated grains 5∼20 μm in the
width distribute along the rotating direction of welding tool in the
TMAZ, suggesting the severe deformation resulted from the stirring
action of the pin. The NZ, that located in the center zone of FSW joints,
consists of fine equiaxial grains 5−15 μm in the diameter, as seen in
Fig. 3e. These grains are reborn from the dynamic recrystallization
(DRX) that occurred in NZ [31]. Additionally, some fine particles are
observed to distribute linearly along the streamline of the matrix at the
bottom of NZ, as indicated by white arrows in Fig. 3f. Besides, the
grains in this region, 4−7 μm in the diameter, are obviously finer than
those in the center of NZ. The bottom of NZ has lower temperature rise
and shorter cooling time than the center of NZ and thus suffers lower
centrifugal force, which then leads to incomplete developed re-
crystallization [32].
The microstructure in samples extracted from various zones in the
joint were further examined via SEM observation using backscattered
electron (BSE) model. As demonstrated in Fig. 4, the segregation of
solutes outlines the grain boundaries (GBs) in all three zones. The shape
and size of grains displayed in SEM-BSE images are consistent with that
in metallograph. The SEM-BSE observation also reveals the morphology
and the distribution of dispersoids and precipitates. Precipitates a few
ten nanometers in diameter can be observed on GBs in the BM (Fig. 4a).

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Fig. 3. Optical observation of FSW joint of 7050-T76 Al alloy after etching in Keller’s reagent: (a) 3D image of the whole welded joint, (b) the BM, (c) the HAZ, (d) the
TMAZ, (e) the middle of NZ, (f) the bottom of NZ.

Comparative observation suggests that GB precipitates (GBPs) in HAZ
are apparently larger than those in BM, as shown in Fig. 4b. Precipitates
or solute segregation can also be recognized on GBs of recrystallized
grains in NZ (Fig. 4c), confirming the solutes’ enrichment. Dispersoids
can be observed in each zone but the morphology varies from zone to
zone. Precipitates are presumably believed to exist on the matrix;
however, they cannot be recognized via the SEM-BSE observation due
to the limitation in magnification.
SEM-EDS analysis was carried out to examine the composition of
dispersoids. Fig. 5 shows the micrographs and the EDS maps of the
particles in different zones on the upper surface of FSW joint. As shown
in Fig. 5a, dispersoids distribute along the rolling direction in the zone
of BM. The corresponding EDS maps demonstrate that these particles
are composed mainly of Al, Cu and Fe, and thus verified as Al7Cu2Fe
particles referring to previous studies [33,34]. The particles in HAZ and
NZ present the similar composition to those in BM (Fig. 5b and c), in-
dicating that Al7Cu2Fe particles retains in all zones of FSW joint despite
the FSW process. The morphology of Al7Cu2Fe dispersoids in HAZ
(Fig. 5b) is similar to that of particles in BM, however Al7Cu2Fe dis-
persoids in NZ present quite different morphology, as demonstrated in
Fig. 5c. The pre-existing Al7Cu2Fe particles in NZ were fragmented and
redistributed due to severe plastic deformation during FSW and the

Fig. 4. BSE images of microstructure in the various zones of FSW joint: (a) BM, (b) HAZ, (c) NZ.

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Fig. 5. EDS maps of dispersoids in various zones of FSW joint: (a) BM, (b) HAZ, (c) NZ.

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Fig. 6. TEM bright-field images of precipitates within the matrix or on GBs in various zones of FSW joint, taken along < 011 > Al: (a) and (b) BM, (c) and (d) HAZ, (e)
and (f) NZ.

Fig. 7. The 3D microhardness profile of the FSW joint of 7050-T76 Al alloy.

crushed particles distribute uniformly in the recrystallized matrix.
The precipitates, either within the matrix or on GBs were examined
via TEM observation and the BF images taken from representative site
of each zone are shown in Fig. 6. As exhibited in Fig. 6a and b, the
7050-T76 Al alloy, used as BM in the study, is found to contain high
density of disc-like η' or η phases (MgZn2) within the matrix together
with the coarsened precipitates on GBs. The similar characteristics are
also found in some previous studies [31,35,36]. These originally existed
precipitates, both within the matrix and on GBs, evolve dramatically
into coarsened ones in zone of HAZ (Fig. 6c and d), due to the strong
temperature rise induced by the frication and stirring within the zone.
In addition, PFZs in HAZ are obviously wider to compare with those in

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Y. Chen, et al.
Fig. 8. The distribution of solutes across representative GBPs in BM (a) and HAZ (b), obtained via EDS-line scanning in TEM analysis.
BM. The coarsening of precipitates contributes to the decreases of
hardness in HAZ, as demonstrated in Fig. 7, which is consistent with
that previously noted [37]. Fig. 6e shows that precipitate can hardly be
observed within grains in NZ. Also, the number of GBPs is much less
than that in HAZ and BM, as shown in Fig. 6f, despite the evident solute
segregation (as seen in Fig. 4c). The pre-existing precipitates are be-
lieved to dissolve now that exposed to the violently elevated tempera-
ture in the NZ. On the other hand, solutes can transfer quickly with
dislocations’ slipping and deposit eventually on the newly generated
GBs during the recrystallization [38]. Despite the re-dissolution and
segregation of solutes, precipitation can hardly occur in the NZ, either
within recrystallized grains or on GBs since the cooling is so quickly and
the temperature window for precipitation is very narrow. The climbing
back of microhardness observed in NZ (Fig. 7) is mainly attributed to
the grain refinement strengthening and the high sensitivity to natural
aging [6,37].
The coarsening of precipitates in HAZ is accompanied by the re-
distribution of solutes, especially the segregation of Cu into GBPs. EDS
analysis in Fig. 8 indicates that the content of Cu in GBPs in HAZ (up to
13.5 at.%) is much higher than that in BM (below 5.7 at.%). Similar
behavior of Cu enrichment in precipitates was previously observed in Al
alloys when exposed to elevated temperature [9]. The enrichment of Cu
in GBPs inevitably leads to Cu’s depletion in the PFZ since the short-
range diffusion in local region can be evident [39]. Although the de-
pletion of Cu can hardly be recognized by the EDS analysis, it can
contribute to the decrease in corrosion potential. On the other hand, the
enrichment of Cu into η/η’ precipitates within the matrix can also be
evident since the diffusion of Cu can be evidently accelerated when
elevated temperature (200 ∼ 300 °C) emerges in HAZ [40]. This en-
richment of Cu into η/η’ phases depletes Cu in the matrix.
As mentioned in Fig. 3f, some fine particles are found to distribute
linearly at the bottom of NZ, which then was further examined. Fig. 9a
shows the cross-sectional micrograph of NZ. A representative zone,
labeled as A in Fig. 9a, was selected to further examine the micro-
structure in the bottom of NZ. The TEM image in Fig. 9c presents the
characteristics of fine uniaxial grains as well as the fine particles dis-
tributed along GBs. The EDS maps of various elements suggest that the
particle labeled as B is rich in Cu and Fe and thus determined to be
Al7Cu2Fe dispersoids. The Al7Cu2Fe dispersions observed here on GBs
in NZ are smaller in size than those observed in HAZ and BM (Fig. 4).
These fine particles are believed to be fragmentized from pre-exiting
Al7Cu2Fe dispersoids and then accumulate along the treamline of alloy
during the FSW. The schematic diagram showed in Fig. 9b [41,42]
reflects the material flow in FSW process, in which the accumulation of
fragmentized dispersoids can be inferred. The particle marked C mainly
contains elements of Mg, Zn, Cu indicating the presence of η phase.
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3.2. Corrosion behavior of the FSW joint
3.2.1. Corrosion behavior of the various zones of the joint
The electrochemical corrosion behavior of different zones of FSW
joint, namely BM, HAZ and NZ, was evaluated separately via the testing
on samples that extracted from various zones of joint. The OCP and PDP
curves of BM, HAZ, and NZ zone are shown in Fig. 10a and 10b, re-
spectively. The OCP of sample extracted from BM, HAZ and NZ is
around -0.51 V, -0.55 V and -0.53 V respectively. The fluctuation of
OCP is intense in case of BM sample but much slighter for HAZ and NZ
sample. PDP curves test from samples extracted from different regions
presents similar overall profile (Fig. 10b). The cathodic current density
was approximately 6☓10−6A·cm-2 for each region despite the diversity
in the microstructure. This similarity in PDP indicates similar corrosion
behavior for these three regions in FSW joint when tested separately.
The HAZ sample shows the lowest corrosion potential while the BM
possesses the highest one; this is compatible with the sequence that
observed in OCP.
The IGC behavior of samples extracted from the zones of BM, HAZ
and NZ was examined by immersing these samples individually into
IGC solution. The cross-section of samples immersed for 6 h was ob-
served using SEM and the representative morphology is shown in
Fig. 11. Attacking along GBs together with the spalling of grains can be
observed on the corroded surface of each sample, which suggests that
all zones in FSW joint are susceptible to IGC when put into IGC test
individually. The susceptibility, however, is different for these three
regions. The IGC is around 60, 140 and 110 μm in depth for the samples
extracted from BM, HAZ and NZ, respectively, indicating that the HAZ
exhibits the highest susceptibility and the BM exhibits the lowest.
The IGC susceptibility is dominated by the micro galvanic effect that
induced by the inhomogeneous distribution of solutes within the
narrow regions along GBs. The intense temperature rise in HAZ during
FSW can induce GBPs’ coarsening and the solutes’ segregation to GBs,
as the EDS analysis suggested (as seen in Fig. 8). The coarsening of GBPs
and the resulted depletion of Cu in adjacent regions leads to increased
potential difference between the matrix and the GBs and thereafter
enhanced the local micro galvanic effect. Similar phenomenon was
previously observed in 7075 alloy in Mahoney’s research [39]. The
research notes that the precipitate coarsening and resulted Cu depletion
along GBs promoted by the thermal excursion during welding should
contribute to the enhanced sensitivity to IGC [43]. On the other hand,
the intense thermal-mechanical process in the center region of FSW,
namely the NZ, induces sufficient recrystallization and the accom-
panying redistribution of solutes. Especially, the deposition of solutes
on GBs is evident in NZ, as indicated in the Fig. 4. The increased dif-
ference in solute content between the GBs and grain interior then in-
duces aggravated corrosion along GBs.
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Fig. 9. Metallographic image of the cross-section of NZ (a), schematic diagram of flow model of plastic material in the NZ (b), TEM image of zone A in the bottom of
NZ and the EDS maps of various elements (c).

Fig. 10. OCP-time curves (a) and potentiodynamic polarization curves (b) tested on the separated samples extracted from BM, HAZ and NZ of FSW joint, respectively.

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Y. Chen, et al.
Fig. 11. The cross-sectional morphology of the various separated zones after IGC immersion test for 6 h in 57 g/L NaCl +10 ml/L H2O2 solution.
3.2.2. Corrosion behavior of the whole FSW joint
3.2.2.1. The three-dimensional potential profile of FSW joint. The 3D OCP
profile of the FSW joint was figured out based on the WEB testing. As
shown in Fig. 12, the HAZ presents the lowest OCP (−580 mV, vs.
SCE), which is apparently lower than that of BM (−500 mV, vs. SCE)
and NZ (−530 mV, vs. SCE) suggesting the highest corrosion
susceptibility. In addition, OCP as low as −580 mV is also observed
at the bottom of NZ, which is similar to that observed in Paglia’s
research [9]. The OCP of HAZ tested in the whole joint is apparently
lower than that tested in the separated HAZ sample, while the OCP of
BM tested in the whole joint is higher than that tested in the separated
BM sample. This oppositely directed shift in OCP in HAZ and BM
suggests a macro-galvanic effect that spans across the different zones in
FSW joint.
The 3D morphology of the FSW joint after immersing for 3 h in NaCl
solution is shown in Fig. 13. It can be seen that the white corrosion
products cover some local zones of the joint, indicting the preferential
occurrence of corrosion in HAZ and the bottom of NZ. It is obvious that
the distribution of preferential corrosion is highly consistent with the
distribution of low potential regions that shown in the 3D potential
profile (Fig. 12). This consistency in distribution also suggests an effect
of macro galvanic.
3.2.2.2. Macro-galvanic corrosion effect. The WEB was employed to test
the local OCP and galvanic current and to examine the macro-galvanic
Fig. 12. The 3D OCP profile of the FSW joint after immersing in 3.5 % NaCl solution.
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effect spanning across zones of FSW joint. Fig. 14 shows the variation of
OCP and galvanic current over time at various zones. The potential of
the BM fluctuates in the range of -460～-510 mV (vs. SCE) while the
potential of the NZ fluctuates slightly and keeps at the level of around
−530 mV (vs. SCE). The HAZ presents the lowest potential and
specifically very low potential of −580 mV is observed in the narrow
regions adjacent to NZ, as seen in Fig. 14a. The potential in the center of
NZ is near to that of BM, but slightly lower in the boundary regions in
both sides. The potential of each region fluctuates slightly as the test
proceeds, but doesn’t vary apparently all through the test. The galvanic
current increases first to a peak level and then decreases slightly and
remains at a level all through the test (Fig. 14b). A strong negative
current as high as 0.03 mA·cm−2 is observed at the narrow region along
HAZ/NZ boundaries on both sides, revealing the intense anodic effect.
The lower potential together with the strong negative current in these
boundary regions suggest an evident and long-lasting macro galvanic
effect that occurs in the FSW joint.
The surface morphology of the post-immersed FSW joint is shown in
Fig. 15. Apparently, serious corrosion is located at the regions 10 mm
from the center, which is corresponding to the HAZ that possesses the
lowest potential. Meanwhile, white spots 50 ∼ 200 μm in diameter can
be observed in NZ, which are actually corrosion pits. Obvious change
can hardly be observed in the region of BM, which suggests that this
region is protected from corrosion. The distribution of corrosion on the
whole welded joint is highly consistent with the distribution of the
Y. Chen, et al.
Fig. 13. The 3D morphology of the FSW joint immersed in 3.5 % NaCl solution for 3 h. The corrosion products were not removed before observation.
lowest potential and negative galvanic current regions in Fig. 14. This
indicates a dominating influence from macro-galvanic effect on the
corrosion when the whole FSW joint is exposed to the corrosive en-
vironment.
In-situ SEM observation was carried out to record the pitting evo-
lution and reveal the influence of macro-galvanic effect in different
zones of FSW joint. Fig. 16 shows the surface morphology of the dif-
ferent zones of the whole FSW joint and separated HAZ sample after
immersion. It can be seen that few pitting can be observed in the BM of
whole-Joint before the immersion proceeds to 2 h. Very small corrosion
pits with diameter below 1 μm can be observed after immersing for 0.5
h in the BM, indicating the initiation of pitting at the early stage. These
pits develop very slowly as time prolongs, as shown in the first line of
Fig. 16. The corrosion in HAZ however is quite different. Severe pitting
can be observed in HAZ after the whole FSW joint was immersed for
only 0.5 h. Besides the matrix adjacent to Al7Cu2Fe dispersoids, pits are
also observed in adjacent matrix, which can be related to the coarsened
η’/η precipitates (seen in Fig. 6c and 6d). The pitting in HAZ develops
continuously as the immersion proceeds with a lot of corrosion products
generated. Additionally, a few cracks shape up on the matrix around the
Al7Cu2Fe particles when the immersion time is prolonged to 6 h. The
corrosion behavior in HAZ that observed on the whole FSW joint is
quite different from that occurs in the separated HAZ sample (shown in
the last line of Fig. 16), where pitting initiates only at sites of Al7Cu2Fe
particles and develops much more slowly. The difference in corrosion
behavior of HAZ, in separated sample and in whole joint, indicates the
evident influence from the macro galvanic effect. Pitting can also be
recognized in region of NZ when the FSW joint was immersed for 0.5 h,
as shown in the third line of Fig. 16, which indicates that the suscept-
ibility to pitting is higher in the NZ than in the BM, but far below that in
HAZ.
The IGC behavior of the whole FSW joint was examined via the
immersion test in the 57 g/L NaCl +10 ml/L H2O2 solution. The
Fig. 14. Variation curves of local OCP (a) and galvanic current (b) with the immersing time in 3.5 % NaCl solution.
10
Corrosion Science xxx (xxxx) xxxx
morphology observed on the corroded surface and cross-section are
shown in Fig. 17. Characteristics of IGC can be observed on the cor-
roded surface in region of BM, but can hardly be observed on the ap-
positional cross-section (displayed in the left column of Fig. 17), in-
dicating the slight IGC in the BM. Obvious characteristics of IGC are
seen on both the surface and the cross section in zone of HAZ (shown in
the middle column of Fig. 17) indicating the severe IGC in the zone. The
IGC is found to extend horizontally along the grain boundaries; and
that, the depth of IGC reaches to about 200 μm. The propagation of
corrosion along GBs together with spalling is also observed in the re-
gion of NZ, as shown in the right column of Fig. 17. The depth of IGC in
the NZ is about 110 μm and the sectional profile is of semi-ellipse shape,
which is different from that in HAZ. To compare Fig. 17 with Fig. 11, it
can be found that the susceptibility to IGC decreases apparently in BM,
decreases slightly in the NZ but intensifies evidently in HAZ, when the
FSW joint was put into immersion test as whole. The change of IGC
susceptibility in the two cases suggests the significant influence from
the macro galvanic effect.
4. Discussion
As the BM in this study, the 7050-T76 Al alloy contains high density
of η'/η (Mg(Zn, Cu, Al)2) [31], as demonstrated in Fig. 6a and b. These
precipitates coarsen in HAZ (Fig. 6c and d) but dissolve in NZ (Fig. 6e
and f) due to stirring-induced temperature rise in local regions. The
enrichment of copper into precipitates, either in matrix within grains or
on GBs, accompanied by the intense coarsening, occurs due to the
temperature rise in HAZ. The migration of copper results in the de-
pletion of Cu in the matrix, which then induces the decrease in OCP in
HAZ (Figs. 10 and 12) since the electrode potential of Cu is much higher
than that of aluminum [44,45]. For the NZ, the dissolution of pre-
cipitates releases Mg, Zn and Cu simultaneously into the matrix, which
results in a moderate potential between that of HAZ and BM due to the
Y. Chen, et al. Corrosion Science xxx (xxxx) xxxx

Fig. 15. The surface morphology of the whole FSW joint after immersion in 3.5 % NaCl solution for different duration.

combined effect from Mg/Zn and Cu on the corrosion potential. The the oxygen reduction and diffusion. For this particular case, all of their
lower OCP detected in the bottom of NZ (as seen in Fig. 12) can be corrosion rates are determined by oxygen diffusion and the ratio of
attributed to the solute segregation to GBs that related to the stirring- anodic area to cathodic area [46,47]:
induced dynamic recrystallization. Icorr1 = IL (1)
From the typical polarization curves of those separated zones
(Fig. 10b), it can be seen that all of the potentiodynamic polarization Ia1 A
γ= =1+ 2
curves present the same overall shape with a cathodic plateau related to Icorr1 A1 (2)

Fig. 16. SEM morphology of the separated HAZ sample and the different zones in the whole FSW joint, after immersing in 3.5 % NaCl solution for different duration.

11
Y. Chen, et al. Corrosion Science xxx (xxxx) xxxx

Fig. 17. Surface and cross-sectional morphology of BM, HAZ and NZ after the whole FSW joint was immersed in 57 g/L NaCl +10 ml/L H2O2 solution for 6 h for IGC
test.

A2 is also enhanced by macro-galvanic effect. Therefore, pitting corrosion

Ia1 = Ig (1 + )
A1 (3) also occurs at the region that is not adjacent to the Al7Cu2Fe phase, as
shown in Fig. 16. For IGC process, IGC in the cathodic region (BM) is
where γ is the contact corrosion effect, Ia1 is the anode dissolves current greatly suppressed while IGC in the anodic region (HAZ) is enhanced
density after contact, Icorr1 is the anode dissolves current density before greatly. As a brief summary, the micro-galvanic corrosion induced by
contact, A1 is the area of lower potential, A2 is the area of higher po- heterogeneous microchemistry is greatly enhanced by the macro-gal-
tential, IL is limited diffusion current density, Ig is the measured value of vanic effect across the whole FSW joint.
galvanic current.
According to Eqs. (1)–(3), if the cathodic reaction is fully controlled
5. Conclusions
by diffusion-reaction during corrosion, the effect of impurity phase on
the corrosion rate can be neglected. In other words, the cathodal im-
(1) The pre-existing microstructure mutates greatly when the 7050-T76
purity phase Al7Cu2Fe in different zones has little influence on accel-
Al alloy was subjected to FSW process. Precipitates in HAZ coarsen
erating corrosion of the metallic matrix due to their small area
evidently, and this induces enrichment of Cu in precipitates but
(equivalent to A2). This can be further demonstrated by the fact that
depletion in the matrix. Precipitates’ dissolving as well as DRX in-
there is no serious pitting between Al7Cu2Fe and matrix from SEM
duce solute segregation on the recrystallization GBs in NZ. Al7Cu2Fe
observation (Fig. 16). However, when the area of BM is considered as
dispersoids in NZ are fragmented and located at the recrystalliza-
A2 (which is far larger than that of Al7Cu2Fe phase) and the area of HAZ
tion GBs.
as A1, the macro-galvanic corrosion rate of HAZ (Ia1) will be greatly
(2) The HAZ has the lowest OCP and the BM presents the highest one,
accelerated according to Eq. (3).
according to OCP test on the separately extracted samples as well as
From Eq. (3), the corrosion rate Ia1 is proportional to the Ig when the
the test on the whole joint. The difference in potential thus induce
area of A1 and A2 is constant. That is, the galvanic current is propor-
intensive macro-galvanic effect between the different zones in the
tional to the corrosion rate. The larger negative galvanic current in the
joint; the boundary region of HAZ adjacent to NZ receives the most
HAZ close to NZ indicates a higher corrosion rate, leading to severe
intense negative current and thus presents the highest susceptibility
corrosion (Figs. 15–17). Therefore, both pitting corrosion and IGC in
to corrosion.
HAZ were promoted greatly by the macro-galvanic effect. Pitting cor-
(3) The pitting, basically induced by Al7Cu2Fe dispersoids, aggravates
rosion in 7xxx Al alloy by itself is generally induced by the micro-gal-
greatly when the whole joint is exposed to immersion test. The
vanic effect between the second particles (Al7Cu2Fe) and the adjacent
coarsened MgZn2 precipitates cannot induce pitting in the case of
aluminum matrix, in which Al7Cu2Fe phase serves as cathode and the
separately extracted HAZ, however they can induce severe pitting
surrounding matrix as anode [17]. IGC in 7xxx Al alloy is generally
when the joint is put into immersion test as a whole.
induced by the micro-galvanic effect between precipitates on GBs and
(4) The macro-galvanic effect greatly aggravates IGC in HAZ but ap-
matrix/PFZ, where precipitates serve as anode and the surrounding
parently suppresses IGC in BM, and it has a slight influence on IGC
matrix/PFZ as cathode. However, both of these micro-galvanic effects
in NZ.
can be influenced by the macro-galvanic effect induced by the potential
(5) The pitting and IGC resulted from micro-galvanic corrosion will
difference between various zones of the FSW joint. The HAZ adjacent to
change greatly by macro-galvanic effect, both in intensity and in
NZ that presents the lowest potential serves as the anodic region, and
path. The macro-galvanic effect is believed more dominating com-
the BM that presents the highest potential serves as the cathodic region.
paring with the micro-galvanic effect for corrosion of FSW weld-
Therefore, an intense current in the HAZ/NZ boundary was induced
ment.
once the FSW joint was immersed into NaCl solution as a whole. This
macro-galvanic current can be merged into the current of micro-gal-
vanic corrosion, and thus leads to enhanced corrosion. For pitting Data availability statement
process, beside the susceptibility related to Al7Cu2Fe phase, the micro-
galvanic corrosion induced by the coarsened anodic MgZn2 precipitates The raw/processed data required to reproduce these findings cannot

12
Y. Chen, et al.
be shared at this time as the data also forms part of an ongoing study.
Declaration of Competing Interest
The authors declare that there are no conflicts of interest to this
work.
Acknowledgments
The authors wish to acknowledge the financial supports from the
National Natural Science Foundation of China (No. 51971073,
51771061 and U1737206), the Fundamental Research Funds for the
Central Universities (No. HEUCFG201838), the Open Project Program
of Key Laboratory of Preparation and Application of Environmental
Friendly Materials (Jilin Normal University), Ministry of Education,
China (No. 2017012)
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