Corrosion Science xxx (xxxx) xxx–xxx

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

A study on corrosion behavior of friction stir welded and tungsten inert gas
welded AA2014 aluminium alloy
⁎
Sunil Sinhmar , Dheerendra Kumar Dwivedi
Mechanical & Industrial Engineering Department, Indian Institute of Technology Roorkee, Roorkee 247667, Uttarakhand, India

A R T I C L E I N F O A B S T R A C T

Keywords: The present study comprises the comparison of the electrochemical behavior of friction stir weld (FSW) joint and
Aluminium tungsten inert gas (TIG) weld joint of AA2014 using immersion test, potentiodynamic polarization test and
Welding electrochemical impedance spectroscopy (EIS). Weld thermal cycles and microhardness were correlated with
Pitting corrosion corrosion behavior of the weld joints. TIG weld joint showed lower corrosion resistance than FSW joint. Heat
Polarization
affected zone was the most corrosion susceptible region in both type of weld joints. Optical microscopy, FESEM,
EIS
TEM and XRD analysis were performed to discuss the corrosion behavior in light of the microstructure.

1. Introduction Corrosion resistance of AA2014 aluminium alloy is very poor and

2xxx series heat treatable aluminium alloys have copper as their
major alloying element. AA2014 aluminium alloy is a widely used alloy
of this series owing to its high strength to weight ratio. AA2014 alu-
minium alloy is preferably used in aerospace industry. Welding of this
alloy is difficult due to the tendency of welding defects formation.
Fusion welding of Al–Cu alloys mainly produces porosity and cracks
[1]. Solid state welding like friction stir welding can produce sound
weld joint of AA2014 aluminium alloy at optimized process parameters.
Although, the fusion welding of aluminium alloy is a big challenge,
however, tungsten inert gas welding has been used for last many years.
Double sided TIG welding was used for joining of thick aluminium alloy
plates [2]. Friction stir welding is a new welding technique as compared
to the TIG welding and it was invented in 1991 at ‘The welding institute
(TWI)’ in UK [3]. Friction stir welding uses a non-consumable rotating
tool plunged into abutting surfaces of the plates to be welded. The
movement of the tool causes plastic deformation which results in to the
welding. Temperature rise is due to the combined effect of the frictional
heat produced by shoulder and plastic deformation caused by pin of the
tool. The temperature rise in FSW remains below the melting point of
the alloy, whereas TIG welding causes melting of the material in fusion
zone. Different zones formed during the FSW are nugget zone (NZ) –
region which stirred by pin and experiences recrystallization and plastic
deformation, thermo-mechanical affected zone (TMAZ) – region which
experience only plastic deformation, heat affected zone (HAZ) – region
which experience only change in microstructure due to thermal cycle,
and base metal (Fig. 1a). Similarly, zones formed during the TIG
welding are fusion zone (FZ), HAZ and base metal (Fig. 1b).
most of the time it is susceptible to the pitting corrosion. Non-uni-
formity in the microstructure of this alloy is the major reason for poor
corrosion resistance. The chemical composition of AA2014 is given in
Table 1. AA2014 mainly contains θ phase (Al2Cu) within the matrix and
at the grain boundaries. Welding results into the change in micro-
structure and creates various zones having different grain sizes and
precipitates. These variations reduce corrosion resistance of the alloy.
Corrosion behavior of the friction stir welded AA2A14 aluminium
alloys was investigated in EXCO (exfoliation corrosion) solution using
various electrochemical measurements [4]. Authors studied the effect
of immersion time and different phases on the corrosion behavior of the
alloy and found that the corrosion attack was increasing with the time.
Water cooled friction stir welding was used to suppress the corrosion
attack on the AA2014 aluminium alloy [5]. Authors reported that the
formation of Al2Cu precipitate was responsible for accelerating the
corrosion reaction. Non-uniform distribution of MgZn2 was responsible
for the localized intergranular corrosion of thermo-mechanical affected
zone of friction stir welded AA7108 [6]. A network of intergranular
precipitates was found to be responsible for severe corrosion in heat
affected zone of AA2024 FSW joint [7]. Potentiodynamic polarization
and EIS (electrochemical impedance spectroscopy) corrosion tests were
performed to investigate the corrosion behavior of FSW joint of thick
plates of 2219-O aluminium alloy and it was found that the presence of
Cu in coarse intermetallics was responsible for poor corrosion resistance
[8]. EIS study was performed on the friction stir processed/welded
aluminium alloys and it was found that the second phase particles
lowered the corrosion resistance of the alloy [9,10]. Comparative study
of the corrosion behavior of FSW joint and TIG weld joint was

⁎
Corresponding author.
E-mail address: sun25.dme2014@iitr.ac.in (S. Sinhmar).

https://doi.org/10.1016/j.corsci.2018.01.012
Received 22 August 2017; Received in revised form 9 January 2018; Accepted 18 January 2018
0010-938X/ © 2018 Elsevier Ltd. All rights reserved.

Please cite this article as: Sinhmar, S., Corrosion Science (2018), https://doi.org/10.1016/j.corsci.2018.01.012
S. Sinhmar, D.K. Dwivedi Corrosion Science xxx (xxxx) xxx–xxx

Fig. 1. Schematic of (a) FSW, and (b) TIG weld joint

cross section showing different zones formed during
welding.

Table 1 Table 2
Chemical composition (wt%) of AA2014. Tool dimensions and FSW process parameters.

Alloy Cu Si Fe Mn Mg Zn Al Tool dimensions FSW parameters

AA2014 4.8 0.97 0.7 0.38 0.54 0.25 Balance Shoulder Pin shape Pin Pin Rotational Traverse Tool
diameter diameter length speed speed tilt
(mm) (mm) (mm) (rpm) (mm/ angle
performed on AA2024 and AA6061 aluminium alloys and it was found min) (°)
that phase transformation caused by the high heat input during the TIG 18 Cylindrical M6 5.7 931 41 1.5
welding lead to the more corrosion [11,12]. Metal inert gas weld joint (threaded)
of AA6xxx also showed lower corrosion resistance compared to the FSW
joint [13]. HAZ was the most corrosion susceptible region in the TIG
weld joint of AA2219. It was attributed to the segregation and reversion Table 3
of second phase (Al2Cu) along the grain boundary [14]. TIG welding process parameters.
As the AA2014 is a very important aluminium alloy from the
Welding Voltage (V) Welding speed Shielding gas Gas flow rate
commercial point of view, so it is essential to study the corrosion be- current (A) (mm/min) (l/min)
havior of this alloy. FSW and TIG welding are the two major joining
techniques uses for this alloy. Corrosion behavior of the FSW joint of 150 12 150 Ar 15
AA2014 was studied in the literature but same for TIG welding alone
and comparative study of FSW and TIG weld joint of AA2014 is not
welding along with schematic of the position of thermocouples. Sam-
available to the author’s knowledge. Although heat input during the
ples from transverse cross-section were polished on SiC papers up to
welding is a very important factor, but comparative weld thermal cycles
2000 grit and then followed by rough and fine cloth polishing using
for both welding techniques in correlation with corrosion behavior has
heavy magnesium oxide powder slurry. Keller’s etchant (2.5 ml of
not been reported. The present study investigates the corrosion beha-
HNO3, 1.5 ml HCl, 1.0 ml of HF and 95 ml of distilled water) was ap-
vior of AA2014 correlating with microstructure (including precipitate
plied on the polished samples for 25 s to reveal the grain boundaries.
reversion and coarsening) and weld thermal cycle history.
Optical microscopy was performed on Dewinter LT-23B microscope
and ‘Image J’ software was used to calculate the average grain size of
2. Experimental procedure each zone of the weld joints. Field emission scanning electron micro-
scopy (FESEM) and energy dispersive X-ray spectroscopy (EDS) were
As received AA2014-T651 aluminium alloy plates were used for the used for micro analysis of elements present in the different phases. X-
FSW and TIG welding. Plate dimensions were ray diffraction (XRD) with CuKα radiation was used to analyze the
70 mm × 27.5 mm × 6 mm and 100 mm × 27.5 mm × 6 mm for FSW phases of the joints. Transmission electron microscopy (TEM) was used
and TIG welding, respectively. Abutting surfaces were properly cleaned on the electron transparent foils of the joints for profound study.
using acetone before the welding. An indigenous modified vertical Microhardness study of the both weld joints was performed using
milling machine (15 HP) was used for the FSW. Plates were properly Vicker’s microhardness tester. Load, dwell time and distance between
clamped in the fixture before starting of the welding. The non con- two consecutive indentations were 100 g, 10 s and 0.5 mm, respec-
sumable tool of ‘H13 steel’ having a cylindrical threaded pin of Inconel tively. The temperature was measured during welding using K-type
was used for the FSW. Rotational and traverse speeds were 931 rpm and thermocouples. Thermocouple wires were inserted into the drilled holes
41 mm/min, respectively. Tool dimensions and friction stir welding of 1.5 mm diameter and 3 mm depth at the bottom side of the plates to
parameters are given in Table 2. Axial force (F) during FSW was 3.5 kN be welded. A special backing plate with slots was prepared to accom-
and concavity (α) at the shoulder of FSW tool was 5°. modate the thermocouple wires. The locations of the holes were kept at
Double sided TIG welding was carried out on ‘EWM Triton 180 AC/ 5 mm and 10 mm distance from the weld center line in both the welding
DC hightec welding’ machine without using any filler material. Process techniques. Thermocouple wire was not kept in the center of the weld
parameters used for the TIG welding are given in Table 3. Samples were because the moving pin of the FSW tool and melting in TIG welding
extracted for various testing and characterization after performing both could have destroyed the wire.
types of welding. Fig. 2 is showing the plates welded using FSW and TIG Corrosion behavior of the upper surface of weld joints obtained

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S. Sinhmar, D.K. Dwivedi
through both welding techniques was studied via immersion test, po-
tentiodynamic polarization (Tafel) test and electrochemical impedance
spectroscopy. Samples for each corrosion test were polished up to the
mirror finish. All the corrosion tests were performed in aerated 3.5%
NaCl solution and at room temperature. Samples were immersed for
30 days during the immersion test and the solution was changed on
alternate days. The extent of attack of the corrosion on the surface of
immersed samples was analyzed using optical microscopy. Gamry’s
‘1000 interface’ potentiostat was used for the electrochemical study.
Software used for the Tafel polarization and EIS testing were DC105
and EIS300, respectively. Exposed area for the electrochemical tests
was kept 0.15 cm2 and remaining portion of the samples was masked. A
horizontal electrolytic cell of glass with three electrode setup was used
for the electrochemical corrosion testing. Saturated calomel electrode
(SCE), graphite electrode and weld joint sample (to be corrosion tested)
were the reference electrode, counter electrode and working electrode,
respectively. Open circuit delay (OCD) time was kept 1800s. Process
parameters for the Tafel polarization test were: potential range
−0.25 V to +0.25 V with respect to open circuit voltage (OCV) and a
scan rate of 1 mV/s. EIS study was performed at a frequency range of
10 kHz to 0.01 Hz at open circuit potential with AC amplitude of 10 mV.
3. Results and discussion
3.1. Microstructure
The optical microstructure of the FSW and TIG weld joints are
shown in Figs. 3 and 4, respectively. The microstructure of the weld
joints mainly comprises α-Al matrix grains and Al2Cu precipitates.
Nugget zone (Fig. 3a) is showing the finer grains compared to the heat
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Corrosion Science xxx (xxxx) xxx–xxx
Fig. 2. Images of (a) friction stir welded, and (b) TIG
welded plates along with schematic of position of
thermocouples in weld plates during (c) friction stir
welding, and (d) TIG welding.
affected zone (Fig. 3b). Average grain size of α-matrix in nugget zone
and heat affected zone of FSW joint was 14.7 ± 2.02 μm and
134.35 ± 16.23 μm, respectively. Plastic deformation and dynamic
recrystallization produced by the FSW tool pin in nugget zone resulted
in refined grain structure. Average grain size of α-matrix in fusion zone
(Fig. 4a) and heat affected zone (Fig. 4b) of TIG weld joint was
99.7 ± 13.84 μm and 185.5 ± 35.55 μm, respectively. The equiaxed
dendritic microstructure was observed in fusion zone after the solidi-
fication of the material (Fig. 4a). The large difference in the grain sizes
of respective regions was observed in the both welding techniques.
These microstructure variations are expected to alter the various
properties of the joints and will be discussed in the below given sec-
tions.
Field emission scanning electron microscope (FESEM) images of
both types of weld joints are given in Fig. 5. EDS analysis of the pre-
cipitates present on the surface of nugget zone and fusion zone sug-
gested the presence of Al2Cu (Fig. 5a and b). Presence of the Al2Cu
precipitates was confirmed by the XRD analysis of FSW and TIG weld
joints in Fig. 6. Fine Al2Cu precipitates (average size 1.12 ± 0.18 μm)
and coarse precipitates (average size 3.51 ± 0.40 μm) were observed
in the nugget zone and fusion zone, respectively (Fig. 5a and b). The
average size of the coarse precipitates distributed within the grains of
HAZ of FSW and TIG weld joints were 3.51 ± 0.40 μm (Fig. 5c) and
3.80 ± 0.69 μm (Fig. 5e), respectively. Magnified view of precipitates
present at the grain boundary of the heat affected zone of FSW (Fig. 5c)
and TIG (Fig. 5e) weld joints are shown in Fig. 5d and f, respectively.
3.2. Weld thermal cycle and heat generation
The microstructure of the weld joint is significantly affected by the
S. Sinhmar, D.K. Dwivedi
weld thermal cycle during the welding [15]. Maximum temperature
observed near the nugget zone (5 mm away from the center of the weld)
and HAZ (10 mm away from the center of the weld) of FSW joint
(Fig. 7a) was 374 °C and 355 °C, respectively. Similarly, maximum
temperature observed near the fusion boundary (5 mm away from the
center of the weld) and HAZ (10 mm away from the center of the weld)
of TIG weld joint (Fig. 7b) was 703 °C and 544 °C, respectively. Thus,
temperature observed in the TIG welding was higher than the friction
stir welding.
Major heat generation occurs mainly due to the friction between
shoulder-workpiece interfaces and plastic deformation during friction
stir welding. FSW tool pin also participates in the heat generation but to
less extent as compared to the shoulder. Many studies have been per-
formed to investigate the heat generation in FSW [16–18]. Some re-
searchers considered only role of the shoulder in heat generation, while
others considered the effect of both shoulder and tool pin. The present
study considers the role of the pin along with the shoulder for heat
generation during FSW. The formula used for heat generation in friction
stir welding is [19]:
2 F
Qfsw = μω 2 [(RS3 − RP3)(1 + tan α ) + RP3 + 3RP2 HP ]
3 vRS
where, Qfsw is the heat input (kJ/mm) during friction stir welding, μ is
the friction of coefficient, ω is the angular velocity (rad/s), F is axial
load (kN), RS is radius of shoulder (m), RP is radius of tool pin (m), HP is
the height of tool pin (m), v is the traverse speed (mm/s) and α is the
concavity of the shoulder (degree).
The formula for the heat input during the TIG welding is:
V×I
Qtig = η ×
vs
where, Qtig is the heat input (kJ/mm) during TIG welding, η is the arc
efficiency, V is the voltage (volt), vs is the welding speed (mm/s) and I
is the current (ampere). Different values of arc efficiency were calcu-
lated in literature [20,21]. The value of arc efficiency used in this work
was 0.78 [22]. Different parameters used for heat input calculation are
shown in Table 4. Total heat input calculated during TIG welding was
4
Corrosion Science xxx (xxxx) xxx–xxx
Fig. 3. Optical microstructure of (a) nugget zone, (b)
heat affected zone of FSW joint.
slightly lower than the FSW joint.
3.3. Microhardness
Microhardness testing results of the FSW and TIG weld joints are
shown in Fig. 8. Maximum microhardness observed in FSW and TIG
weld joints were 128 HV and 113 HV, respectively. Friction stir weld
joint showed higher hardness compared to the TIG weld joint. Both
weld joints showed higher hardness in nugget (FSW) and fusion zone
(TIG) compared to the heat affected zone. The small grain size of the α-
Al matrix of the nugget zone (Fig. 5a) contributed to higher hardness
(Hall-Petch relationship) of the joint [7]. Weld thermal cycle indicates
that HAZ of TIG weld joint (Fig. 7b) was experienced higher peak
temperature than HAZ of FSW joint (Fig. 7a). Generally, Guinier-Pre-
ston (GP) zone precipitates dissolve above 200 °C. Therefore, as the
temperature increases, the fine Al2Cu precipitates also get dissolve and
segregate at grain boundaries, which in turn reduces the hardness of
HAZ [14].
3.4. Corrosion testing
Corrosion behavior of the friction stir weld and TIG weld joint was
investigated using immersion test, Tafel test (direct current based test)
and electrochemical impedance spectroscopy (alternate current based
test). Optical images of the corroded surface of both weld joints after
30 days immersion in 3.5% NaCl solution are shown in Fig. 9. Corrosion
attack sites were fewer in nugget zone (Fig. 9a) compared to the HAZ of
FSW joint (Fig. 9b) as well as both zones of TIG joint (Fig. 9c and d).
Severe corrosion attack was observed in TIG weld joint, especially in
heat affected zone (Fig. 9d). Black circles in Fig. 9d are indicating se-
vere corrosion sites in the heat affected zone of TIG weld joint.
Potentiodynamic polarization corrosion test was performed on FSW
and TIG weld joint and Tafel curve (Fig. 10) was obtained. Corrosion
potential of each zone of FSW and TIG weld joint observed from the
Tafel curve is shown in Table 5. More negative value of corrosion po-
tential shows less corrosion resistance. In the present study, the
Fig. 4. Optical microstructure of (a) fusion zone, and
(b) heat affected zone of TIG weld joint.
S. Sinhmar, D.K. Dwivedi Corrosion Science xxx (xxxx) xxx–xxx

Fig. 5. SEM images of (a) nugget zone with EDS, (b)

fusion zone with EDS, (c) HAZ of FSW joint, (d) mag-
nified view of the grain boundary area shown in rec-
tangle in ‘c’, (e) HAZ of TIG weld joint, and (f) magnified
view of the grain boundary area shown in square in ‘e’.

corrosion potential of the nugget zone of FSW joint showed lower ne- Electrochemical impedance spectroscopy (EIS) is a most reliable
gative value compared to the other zones in case of both weld joints. non-destructive electrochemical technique [23]. Information revealed
Hence, the corrosion resistance of the nugget zone and HAZ of FSW by EIS technique are more than the potentiodynamic polarization test.
joint was higher than the TIG weld joint. This technique provides an average electrochemical response across the

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S. Sinhmar, D.K. Dwivedi
Fig. 6. XRD patterns of different zones of FSW joint and TIG weld joint.
entire exposed area. In the present study, EIS confirmed the results
obtained from immersion test and potentiodynamic polarization test. It
provides information on the capacitive performance of the material.
Loops formed in Nyquist plot are classified according to the frequency
range and the number of loops indicates the number of time constants.
High frequency loops can be attributed to the formation of oxide film on
the surface of the sample and called capacitive loop. Presence of in-
termediate frequency loop can be attributed to the relaxation process
into the oxide film and called inductive loop. The low frequency loop is
associated with the dissolution of the material and called second ca-
pacitive loop. Low frequency loop occurs in aggressive electrolytic so-
lution. EIS data obtained for the both types of weld joints is shown in
Fig. 11. Nyquist plot (Fig. 11a) is showing real and imaginary im-
pedance on the x and y-axis, respectively. This is a high frequency
single time constant capacitive loop. The plot shows impedance along
with frequencies at some particular points. The diameter of the loop
indicates the corrosion resistance of the different zone of FSW and TIG
weld joint. The larger diameter of the loop shows the more impedance
and hence higher corrosion resistance. Nugget zone of the FSW weld
joint showed larger loop as compared to the remaining zones. Thus, the
corrosion resistance of this zone was higher than other zones. Fig. 11b is
showing the bode plot of impedance with respect to frequency. The
impedance was stable at low frequency, but it was reduced at high
frequency. The equivalent circuit given in Fig. 11c was used to fit the
data. Constant phase elements (CPE) were used in the equivalent circuit
model. Simple elements like an inductor, resistor or capacitor generally
do not describe the frequency dispersion revealed at the electrolyte/
electrode interface. This frequency dispersion can be attributed to the
capacitive dispersion and is expressed by the constant phase element.
The constant phase element behavior can be attributed to the surface
roughness, inhomogeneity or porosity related to the electrode geometry
[24]. Extracted EIS data from the equivalent circuit is shown in Table 6,
where Rs is the solution resistance, Rp is the polarization resistance, Yo
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Corrosion Science xxx (xxxx) xxx–xxx
is the admittance which becomes capacitor, resistor or inductor at
n = 1, 0, −1 respectively, and n is the deviation of the capacitance of
the circuit from the ideal capacitor. The value of n less than 1 indicates
frequency dependent capacitor which shows the characteristic behavior
of an oxide film. Table 6 shows the polarization resistance of the nugget
zone of FSW joint was higher than the other zones of FSW (HAZ) and
TIG (FZ and HAZ) weld joints, whereas, the value of Yo was lower than
the other zones. These parameters (Rp, Yo) suggest that the FSW joint
offers higher corrosion resistance than the TIG weld joint. Solution
resistance (Rs) was nearly same for all the samples and it was negligible
as compared to the polarization resistance (Rp).
Corrosion occurs due to the potential difference between anode and
cathode. Furthermore, higher difference leads to more corrosion [25].
Anode represents a more active (more negative potential) material,
whereas cathode represents a noble (more positive potential) material.
Basic corrosion reactions of the Aluminium in aqueous solution are
given as [26]:
– Anodic reaction:
Al → Al3 + + 3e− (1)
– Cathodic reaction:
3
3H+ + 3e− → H2
2 (2)
Evolution of hydrogen gas from reduction reaction was observed on
the cathode during the potentiodynamic electrochemical test.
Dissolution of the aluminium occurs when it acts as anode compared to
the surrounding material or adjacent particles. The extent of dissolution
depends upon many factors such as temperature, type of electro-
chemical solution etc. Corrosion potential and polarization resistance
obtained from the potentiodynamic and EIS tests are shown in Fig. 12,
respectively. Results obtained from both tests suggested higher corro-
sion resistance of the FSW joint compared to the TIG weld joint. HAZ
zones of the both weld joints were more susceptible to the corrosion
than the nugget and fusion zone. These results were in agreement with
findings of the immersion test. Corrosion attack in Fig. 9b (FSWHAZ)
and Fig. 9d (TIGHAZ) was more compared to Fig. 9a (FSWNZ) and
Fig. 9c (TIGFZ), respectively.
Similarly, pitting corrosion behavior was studied in cases of both
weld joints after the potentiodynamic polarization test (Fig. 13). Pits
were observed in the nugget zone (Fig. 13a) and HAZ (Fig. 13b) of FSW
joint. Some trenching (dissolution of surrounding material of particle)
along with the pits was also observed in fusion zone (Fig. 13c) and HAZ
(Fig. 13d) of TIG weld joint. The growth of the trenches over the time
also results into the pits [27,28]. Pitting within the grain boundary can
also be observed in the HAZ of the TIG weld joint. More severe pitting
corrosion was experienced by the TIG weld joint compared to the FSW
joint.
AA2014 aluminium alloy contains Al2Cu as major precipitate and
Fig. 7. Graphs showing temperature profile of dif-
ferent zones of (a) FSW joint, and (b) TIG weld joint.
S. Sinhmar, D.K. Dwivedi Corrosion Science xxx (xxxx) xxx–xxx

Table 4
Process parameters used for heat input calculation.

FSW TIG

ω (rad/s) RS (m) RP (m) HP (m) F (kN) μ α V (volt) I (A)

Parameters 97 9 × 10−3 3 × 10−3 5.7 × 10−3 3.5 0.3 5° 12 150

Heat input, 1st pass (kJ/mm) – 0.56
Total heat input (kJ/mm) 1.16 1.12

Fig. 8. Showing microhardness variation along the cross-section of FSW joint and TIG
weld joint.
the electrochemical potential of the aluminium matrix is more active
(anode) compared to the Al2Cu precipitate (cathode), which in turn
leads to the dissolution of the aluminium matrix [29]. The proposed
mechanism of pitting is schematically shown in Fig. 14. The potential
difference between the aluminium matrix and Al2Cu precipitate is large
which led to the corrosion of α-Al matrix adjacent to the Al2Cu pre-
cipitate and resulted in pit formation. The grain size of the α-Al matrix
of nugget zone (Fig. 3a) and HAZ (Fig. 3b) of FSW joint was finer as
compared to the fusion zone (Fig. 4a) and HAZ (Fig. 4b) of TIG weld
joint. Small grain size provided the large grain boundary area and fa-
cilitated more passivation which in turn reduced the corrosion current.
Thus, nugget zone showed more passivation than the fusion zone of TIG
weld joint. These results are in agreement with Ralston et al. [30] who
showed that the small grain size of aluminium led to more passivation
which in turn improved the corrosion resistance of the material. Pas-
sivation due to the grain refinement and its effect on corrosion were
reported elsewhere and described schematically [31]. The finer grain
size of the nugget zone of FSW joint corresponded to higher corrosion
resistance, whereas largest grain size of the heat affected zone of TIG
weld joint among all the zones corresponded to the lower corrosion
resistance. Hence, corrosion resistance can be related with the refine-
ment of microstructure, which in turn reduces the corrosion reactivity
by improving the passivation.
Presence of intermetallic particles/precipitates in the micro-
structure of aluminium alloys affects the mechanical as well as corro-
sion behavior. Copper deleteriously affects the corrosion performance
of the alloy by forming a galvanic cell of copper rich zone and copper
depleted zone [32]. In AA2014 aluminium alloy, Al2Cu forms a gal-
vanic cell with the Al- matrix due to the large potential difference. So,
this is the preferential site for corrosion reaction to occur. The positive
potential of the Al2Cu precipitate compared to the Al-matrix favors the
reduction reaction to occur. Welding process changes the micro-
structure in the nugget zone/fusion zone of the weld joint. Most of the
time grain coarsening occurs in the heat affected zone (Figs. Figure 3b
and Figure 4b) along with the reversion of precipitates due to thermal

Fig. 9. Micrographs of weld joints subjected to im-

mersion test (a) nugget zone, (b) HAZ of FSW joint,
(c) fusion zone, and (d) HAZ of TIG weld joint.

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S. Sinhmar, D.K. Dwivedi Corrosion Science xxx (xxxx) xxx–xxx

Fig. 10. Potentiodynamic polarization curves of different zones of (a) FSW joint, and (b) TIG weld joint.

Table 5 Table 6
Results obtained from Potentiodynamic polarization test of FSW and TIG weld joints. EIS data of FSW and TIG weld joint extracted from the equivalent circuit.

FSW NZ FSW HAZ TIG FZ TIG HAZ Rs (Ω) Rp (Ω cm2) Yo (Ω−1 cm−2 sn) n

Ecorr (mV) −659 −675 −692 −741 FSW NZ 14.76 3270 1.16 × 10−5 0.92
FSW HAZ 15.30 2152 2.126 × 10−5 0.84
TIG FZ 15.71 1920 6.76 × 10−5 0.89
cycles of the welding. Size of the precipitates in nugget zone of FSW TIG HAZ 15.65 1579 6.78 × 10−5 0.89

joint (Fig. 5a) was finer as compared to the fusion zone of TIG weld
joint (Fig. 5b) due to the plastic deformation and dynamic re-
of coarse precipitates and precipitate free zone (PFZ) with the corrosion
crystallization occurred during the friction stir welding. This size dif-
susceptibility of the material [33]. In both types of welding, heat af-
ference in precipitates is evident from Fig. 15. The TEM micrographs of
fected zone experienced dissolution and coarsening of the precipitates.
nugget and fusion zone along with the selected area diffraction (SAD)
However, the peak temperature experienced was more in case of the
pattern (Fig. 15b) taken from nugget zone of FSW joint are shown in
TIG weld joint, which resulted into the more coarsening of precipitates
Fig. 15a and c, respectively. Plane (310) observed from the SAD pattern
within grains and at the grain boundary of the heat affected zone
ring was corresponding to the Al2Cu precipitates and it is in agreement
(Fig. 5e and f).
with the XRD analysis (Fig. 6). Previous studies correlated the presence
Microhardness profile of the both weld joints is showing that the

Fig. 11. EIS test results of FSW and TIG weld joint as (a) Nyquist plot, (b) bode plot, and (c) equivalent circuit for fitting the EIS data.

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S. Sinhmar, D.K. Dwivedi
Fig. 12. Polarization resistance and corrosion potential of different zones of FSW and TIG
weld joints.
heat affected zone was the weakest part in the joints (Fig. 8). Micro-
hardness was also correlated with the corrosion susceptibility elsewhere
and weakest part showed lowest corrosion resistance [34]. In the pre-
sent case, heat affected zone of TIG weld joint was the weakest part and
showed highest corrosion susceptibility. Increase in the size of pre-
cipitates led to the softening of the HAZ. Similarly, coarse precipitates
were also responsible for the poor corrosion resistance of the weld joint
[35]. The corrosion potential of the both weld joints was more negative
in the low hardness region (Fig. 16).
Weld thermal cycle affected the corrosion behavior of the weld
joints by altering the microstructure. The rise in temperature at 5 mm
and 10 mm distance from the weld center can be noticed from Fig. 7.
Coarsening of the strengthening precipitates is a function of tempera-
ture which further depends upon the distance from the center of the
weld [36]. High temperature retention for a longer period in case of TIG
9
Corrosion Science xxx (xxxx) xxx–xxx
weld joint (Fig. 7b) caused reversion and coarsening of precipitates and
α-Al matrix (Fig. 5b and e). Furthermore, the higher temperature ex-
perienced during TIG welding compared to the friction stir welding led
to the sensitization of microstructure and the presence of Cu was in-
creased at grain boundary in form of coarse Al2Cu precipitates (Fig. 5f).
Hence, the corrosion resistance of the FSW joint was higher as com-
pared to the TIG weld joint of AA2014.
4. Conclusions
A thorough study of the electrochemical behavior of friction stir
welded and TIG welded joints of AA2014 has been performed. Major
conclusions drawn from the study are:
1. Finer Al-matrix grains of the nugget zone of FSW joint showed more
passivation and improved corrosion resistance, whereas, larger Al-
matrix grain size along with coarse precipitates in the HAZ of the
TIG weld joint reduced the passivation and hence, showed poor
corrosion resistance.
2. Presence of Al2Cu precipitates was mainly responsible for accel-
erating the anodic-cathodic reactivity in both weld joints.
3. Higher temperature experienced during TIG welding resulted into
the sensitization of microstructure, which in turn reduced corrosion
resistance.
4. FSW joint showed higher microhardness than the TIG weld joint and
this was also correlated with the corrosion behavior of the weld
joints. It was found that the weakest part showed poor corrosion
resistance.
5. Immersion test, potentiodynamic polarization test and EIS test re-
sults of FSW joint showed higher corrosion resistance than the TIG
weld joint of AA2014.
Fig. 13. FESEM images of corroded surfaces of (a)
nugget zone, (b) HAZ of FSW joint, (c) fusion zone,
and (d) HAZ of TIG weld joint after potentiodynamic
polarization test.
S. Sinhmar, D.K. Dwivedi
Fig. 14. Schematic of different stages of pitting process in a material having matrix as anode and precipitates as cathode.
Fig. 15. Showing (a) TEM micrograph of nugget zone of FSW joint, (b) SAD pattern of nugget zone shown in ‘a’, and (c) TEM micrograph of fusion zone of TIG weld joint.
Fig. 16. Microhardness and corrosion potential of different zones of FSW and TIG weld
joints.
Acknowledgements
The authors gratefully thank the Council of Scientific and Industrial
Research (CSIR), New Delhi, India for financially supporting this entire
research work under the scheme of CSIR sponsored research project
sanction no. 22(0636)/13/EMR-II dated 31.10.2013.
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