Journal of Alloys and Compounds 622 (2015) 725–733

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

Fabrication of Al5083 surface composites reinforced by CNTs and cerium

oxide nano particles via friction stir processing
S.A. Hosseini a, Khalil Ranjbar a,⇑, R. Dehmolaei a, A.R. Amirani b
a
Department of Materials Science and Engineering, Faculty of Engineering, Shahid Chamran University of Ahvaz, Iran
b
12th Ghaem Street, Bld. Hashemzadeh, Shahrak Golestan, Tehran, Iran

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

Article history: In the present investigation, friction stir processing (FSP) was utilized to incorporate Multi Walled Carbon
Received 13 June 2014 Nano Tubes (MWCNT) and nanosized cerium oxide particles into the matrix of Al5083 alloy to form
Received in revised form 2 October 2014 surface reinforced composites. The effect of these nanosized reinforcements either separately or in the
Accepted 29 October 2014
combined form, on microstructural modification, mechanical properties and corrosion resistance of
Available online 7 November 2014
FSPed Al5083 surface composites was studied. A threaded cylindrical hardened steel tool was used with
the rotation speeds of 600 and 800 rpm and travel speeds of 35 and 45 mm/min and a tilt angle of 5°.
Keywords:
Mechanical properties and corrosion resistance of FSPed samples were evaluated and compared with
Al5083 alloy
Friction stir processing
the base alloy. The maximum tensile strength and hardness value were achieved for the hybrid composite
Carbon Nano Tubes containing a mixture of CNTs and cerium oxide in the volume ratio of 75–25, respectively, whereas a
Cerium oxide significant increase in pitting resistance of the base alloy was obtained when cerium oxide alone was
Pitting resistance incorporated. The corrosion behavior of the samples was investigated by potentiodynamic polarization
tests and assessed in term of pitting potential and passivation range. Microstructural analysis carried
out by using optical and electron microscopes showed that reinforcements are well dispersed inside
the nugget zone (NZ), and remarkable grain refinement is gained. The study was aimed to fabricate sur-
face composites with improved mechanical properties and corrosion resistance simultaneously.
Ó 2014 Elsevier B.V. All rights reserved.

1. Introduction particles and the substrate in the near surface layer of the pro-
cessed metallic substrate. It is believed that FSP can improve and
Friction stir processing (FSP) is a new solid-state process used to modify the various properties such as yield and tensile properties
modify the surface and microstructure of metallic materials [1–3]. [6–8], fatigue [9,10], wear and hardness [11,12], and corrosion
It is actually based on the basic principle of friction stir welding resistance [13].
(FSW) [4], where a rotating tool with a specially designed pin Carbon Nano-Tubes (CNTs) have been increasingly used as rein-
and shoulder is inserted inside a monolithic metallic substrate forcement materials in metals due to their low density and very
and traversed along the desired path on the surface of the sub- high theoretical strength [14,15]. There are few studies focusing
strate. The frictional heating and severe plastic deformation on fabrication of aluminum alloy composites reinforced with CNTs
imposed by the rotating tool result in a significant evolution in via FSP [8,16,17]. Al5083 is one of Al–Mg alloys with excellent
the local microstructure which is composed of three distinct zones, combination of low density, high specific strength, good formabil-
namely: the heat affected zone, the thermomechanically affected ity, and great corrosion resistance in sea water, hence it is widely
zone (TMAZ), and the NZ also called the stir zone. The most intense used in automobile and transportation industries, aerospace and
plastic deformation and high temperature is experienced by NZ marine applications. These properties can further be improved
and the grain refinement is achieved in this zone due to dynamic when reinforced with CNTs and oxide particles. Liu et al. [8]
recrystallization [5]. Further, FSP can be used to produce surface inserted CNTs into the holes which were pre-machined on the
composite, by incorporating reinforcing particles into the surface. plates of A1016 commercial aluminum before FSP. Tensile strength
Reinforcing particles are introduced into a hole or groove on the and hardness in NZ improved after processing more than two
surface and the rotation of the pin promotes intermixing of times with increasing of CNTs content. Reinforcement of Al5083
by various oxide particles is also reported. Shahraki et al. [18]
⇑ Corresponding author. Tel.: +98 6113330020 19x5682; fax: +98 6113336642. reported that mechanical properties of the composite Al5083–
E-mail address: [email protected] (K. Ranjbar). ZrO2 fabricated by FSP, have improved. In a similar work,

http://dx.doi.org/10.1016/j.jallcom.2014.10.158
0925-8388/Ó 2014 Elsevier B.V. All rights reserved.
726 S.A. Hosseini et al. / Journal of Alloys and Compounds 622 (2015) 725–733

incorporation of fullerene into Al5083 resulted in grain refinement

and remarkable hardness increase [19]. Fabrication of Al5083 sur-
face composites by incorporation of silicon carbide reinforcing par-
ticles also reported [3,11]. In this case, by uniform distribution of
SiC particles resulted in significant hardness improvement. Mosta-
fapour et al. [20] studied the effect of the hybrid ratio on mechan-
ical, microstructural and wear properties of surface hybrid
nonocomposites of Al2O3/Graphite/Al5083 fabricated by FSP. They
Shoulder and
threaded pin
reported that hybrid ratio is a designing factor and a graphite Groove filled with
hybrid ratio of 50% resulted in a better combination of wear and reinforcement powder
tensile properties. However, reinforcing materials may not have
the same effect on corrosion resistance of the matrices, since they
may operate as active cathodic sites [21]. Nevertheless, it has been
FSPed Composite
shown that, cerium oxide dispersion improves corrosion resistance Region
in aluminum matrices [22–24]. It seems they act as effective catho-
dic inhibitors and suppressing the cathodic reaction of corrosion
process.
Fig. 2. Schematic illustration shows the FSP method with its different elements.
In the present investigation, FSP method was used to fabricate
Al5083 metal matrix composites reinforced with CNTs and cerium
oxide particles. An effect of these reinforcing materials either sep- CNTs/Al5083 and the hybrid composites of CNTs/CeO2/Al5083 which contain
arately or in the combined form has not been reported so far. Con- reinforcements in the volume ratios of 25, 50 and 75 respectively. Fig. 2 shows
sidering the unique properties of CNTs including its high strength, the schematic view of the FSP tool and grooved plate. FSP tool was made of H13
hot working tool steel which had been heat treated to surface hardness of 52
and the positive effect of cerium oxide on corrosion resistance of HRC. Cylindrical concave shoulder had the diameter of 18 mm, and threaded pin
aluminum matrices, combined with high strength to weight ratio had the length and the diameter of 4.5 and 6 mm respectively. The filled grooves
of Al5083 and its corrosion resistance, there is still a large scope first were closed by a pinless shoulder to prevent powder from spattering during
to increase the strength and corrosion resistance of this matrix the process. Then, a pin is attached to the shoulder and plunged into the plate
and traveled along the closed groove. All samples were subjected to three passes
by utilizing these properties.
of FSP for homogeneous dispersion of reinforcement. The first two passes were per-
formed at rotational speed of 800 rpm and traveling speed of 35 mm/min, whereas
2. Material and methods the last pass was done at 600 rpm and traveling speed of 45 mm/min. For all the
passes a tool tilt angle of 5° were maintained throughout the process. Fig. 3 a shows
The sheet of 5 mm thickness with its chemical composition corresponds to alu- the appearance of a typical FSPed plate.
minum alloy of Al5083 base alloy in annealed condition was used. Its chemical Microstructural observations were performed by using optical and field emis-
composition is given in Table 1. The sheet was cut as rectangular samples of sion scanning electron microscopes (FESEM) model RIGMA/VP- ZESIS and model
5  100  250 mm3. Commercially available cerium oxide particles of 99% pure VEGA-TESCAN equipped with an energy dispersive X-ray spectroscopy (EDS). Sam-
and average particle size of 30 nm and the MWCNTs (after words called CNTs) with ples were cut from the cross section of processed samples, polished and electro
the purity of 99.9%, axial length of 10–20 lm a nominal outer diameter of 10–20 nm etched with Barker’s reagent (6 ml HBF4 and 94 ml H2O). Grain size measurement
were used as reinforcement. The micrographs of these reinforcements are shown in was carried out using an image analyzer.
Fig. 1. The reinforcements mixed with acetone to form a paste and packed into the Tensile specimens with 8 mm gage length were prepared longitudinally from
groove of 1.2 mm width and 2 mm depth which had been pre-machined on surface NZ after machining the processed samples down to 3 mm thickness. This is shown
of the samples. Samples with different composition were FSPed and compared with in Fig. 3b. All the tensile testing was performed at a strain rate of 30  10 3 s 1 uti-
as received base Al5083 alloy. They are noted as FSPed base alloy, CeO2/Al5083, lizing SANTAM electronic tensile machine. The hardness profile along the thickness
cross section of FSPed samples was also determined by a microhardness test using a
Table 1 Vickers indenter at the load of 200 g and dwell time of 15 s. The average hardness
Chemical composition of the base alloy Al5083 sued in this study. value is reported based on these measurements.
To conduct the potentiodynamic polarization tests, samples were cut from NZ
Elements Zn Cu Ti Si Cr Fe Mn Mg Al and prepared according to the ASTM-G3 standard. All corrosion tests were
Wt.% 0.061 0.06 0.04 0.22 0.11 0.4 0.4 4.51 Bal. conducted in a 3.5% NaCl solution prepared by dissolving 35 g of NaCl in double dis-
tilled water, at a scan rate of 0.5 mV/s using an AUTO LAB potentiostat–galvanostat

Fig. 1. Scanning electron micrographs of reinforcements, (a) CNTs, and (b) cerium oxide particles.
 S.A. Hosseini et al. / Journal of Alloys and Compounds 622 (2015) 725–733 727

reinforcements of CNTs and cerium oxide particles were intro-

a duced and processed. In all cases, a good bonding between NZ
and TMAZ was attained and no cracks or voids were observed. Uni-
form distribution of reinforcement in NZ was carefully studied
after applying every pass of FSP. It was found that by increasing
the number of passes it is possible to get better distribution of rein-
forcements. This importance is presented in Fig. 6a–c for the com-
posites of CeO2/Al5083, CNTs/Al5083 and CNTs/CeO2/Al5083,
20 mm respectively. Another typical microstructural feature in FSP is the
appearance of onion rings which is the characteristic of materials
flow. An indication of good material mixing in the NZ is that rings
b are very close together and no island (unmixed regions) formed
between the rings. Micrographs in Fig. 7a and b reveal the effect
of number of passes on homogeneity of the microstructure in NZ
for the composite CNTs/Al5083. In the former micrograph, still
there are unmixed and unaffected grains whereas in the latter,
these features are vanished and rings are very uniform and closely
spaced. An interface between NZ and base alloy in the same com-
posite is shown in Fig. 7c, indicating sound bonding.
10 mm

3.2. Mechanical properties

Fig. 3. Micrographs showing, (a) NZ of an FSPed plate, and (b) specification of
tensile specimen prepared longitudinally from the NZ.
3.2.1. Tensile test
model AUT8491.Temperature and the pH of the electrolyte was maintained at 25 °C Tensile testes were performed inorder to determine the yield
and 7, respectively. An electrochemical cell consisted of platinum as auxiliary elec- strength, tensile strength and elongation of Al5083 base alloy
trode, saturated calomel as reference electrode, and the samples taken from NZ as FSPed with or without reinforcement particles. Effect of CNTs and
working electrode, was used. Before each polarization, the sample was immersed in
cerium oxide incorporation in combined form on tensile behavior
the test solution for 30 min. at the open circuit potential (OCP), allowing the system
to stabilize. An exposure area of 17.5 mm2 from NZ was subjected to the corrosion was first investigated in order to get optimum ratio. Fig. 8a shows
tests and the rest of the areas were covered with epoxy. The i-corrosion was calcu- the typical stress–strain curves of the tensile tested hybrid com-
lated using Tafel extrapolation. posites contain CNTS and cerium oxide. Tensile strength was
increased with increase of CNTs, but, the maximum tensile
3. Results and discussion strength of 396 MPa was achieved for composite FSPed with CNTs
and cerium oxide particles in the volume ratio of 75–25 respec-
3.1. Microstructure tively. It is corresponding to 42% increase in tensile strength of
base alloy. So, this composition was found to be the optimum
Fig. 4a represents the optical micrograph of the as received base and its hardness and corrosion behavior was evaluated and com-
alloy sample and Fig. 4b represents the macrograph of the same pared with other compositions. A graphical comparison of all ten-
which is subjected to FSP but with no reinforcement. In the latter sile tested compositions is made in Fig. 8b. From this figure it can
case, there is a clear grain structure modification and refinement be derived that, tensile strength of FSPed composites is enhanced
where grain size of the matrix is reduced and transformed to a significantly as compared to as received base alloy. In a similar
more homogeneous, equiaxed and smaller ones in NZ. The average manner, elongation was reduced. It was also shown that CNTs as
grain size of the as received base alloy matrix before FSP treatment a reinforcement has more impact on mechanical properties than
was 21 lm, which is reduced to 6.31 lm after treatment. Grains in cerium oxide particles. Moreover, incorporation of cerium oxide
the NZ were further reduced to 3.98 lm by the addition of CNTs as nano particles also improved the strength of the base alloy. Thus,
shown in Fig. 5a. This indicates that, plastic deformation and tem- it can be concluded that, strength of Al5083 base alloy was
perature rise had been sufficiently high by FSP to cause dynamic increased when it was subjected to FSP either with or without
recrystallization and grain refinement [5]. Grains are also reinforcement.
deformed and elongated in an upward flowing pattern at interface
or transition between base and NZ as shown in Fig. 5b and c. This 3.2.2. Strengthening mechanisms
zone is also called the TMAZ, where deformation strain and The improvement in mechanical properties of aluminum com-
frictional heat are not sufficient to cause grain reduction. posites is believed to be due to different mechanisms. First is the
Likewise, similar microstructural evolution was observed when Orowan mechanism [25,26], where the motion of the dislocations

a b

50 µm 50 µm

Fig. 4. Optical micrographs of the base alloy Al5083, (a) before FSP, and (b) after FSP.
728 S.A. Hosseini et al. / Journal of Alloys and Compounds 622 (2015) 725–733

a b
NZ

TMAZ
50 µm 50 µm

1 mm

c
NZ

TMAZ

50 µm

Fig. 5. Micrograph is showing the NZ of the composite CNTs/CeO2/Al5083 at the center and its corresponding features at, (a) NZ, (b) interface with up word flowing pattern of
NZ, and, (c) interface at higher magnification. The volume ratio of CNTs to cerium oxide in the composite is 75:25.

a b

5µm 5µm

c
CNTs

CeO2

200 nm

Fig. 6. Scanning electron micrographs show the location and distribution of reinforcements in the matrix of Al5083 composites after third pass, (a) CeO2/Al5083, (b) CNTs/
Al5083, and (c) CNTs/CeO2/Al5083 surface composite shown in Fig. 5.

is inhibited by nanometer sized particles and carbon nanotubes [26], which results in increase and punching of dislocations at
provided they are closely spaced. The second mechanism is consid- the interface, leading to work hardening of the matrix. The third
ered to be due to the large coefficient of thermal expansion mis- mechanism is the shear lag mechanism where load is transferred
match between the aluminum matrix and the reinforcements from the matrix to the reinforcement by interfacial shear stress,
 S.A. Hosseini et al. / Journal of Alloys and Compounds 622 (2015) 725–733 729

a a

Stress (MPa)
Un-FSPed Grains

25CNT/75CeO2/Al5083
50CNT/50CeO2/Al5083
75CNT/25CeO2/Al5083

100 µm

Strain

b
b

Stress (MPa)
Base alloy Al5083
FSPed Base alloy
CeO2/Al5083
75CNT/25CeO2/Al5083
CNT/Al5083
100 µm

Strain
c
Base Metal Fig. 8. Typical stress–strain curves of the tensile tested specimens: (a) hybrid
composites contain CNTs and cerium oxide, and (b) all the tensile tested
compositions.

cerium oxide which have coefficient of thermal expansion of

Interface
1  10 6 K 1 and 8.26  10 6 K 1, respectively. The difference in
the coefficients of thermal expansion between the matrix and rein-
forcing particles, coupled with the temperature change during pro-
NZ
cessing, can create residual plastic strain in the matrix around the
particles resulting in generation of dislocation. The dislocation
100 µm density and its effect on strengthening depend upon reinforcement
surface area. George et al. [26] reported that in the case of CNTs
due to its smaller diameter, dislocation density generation and
Fig. 7. Micrographs reveal the effect of no. of passes on homogeneity of the
thereby its strengthening effect is higher. Moreover, Al6(Mn,Fe)
microstructure in the NZ for the composite CNTs/Al5083, (a) after two passes, (b)
after three passes. In former case, still there are un-effected regions left between the intermetallic was also detected in matrix (see Fig. 9). So, it can
rings, whereas in the latter case microstructure is more uniform although rings are be expected that all these mechanisms to be operative up to some
clearly visible and, (c) sound bounding at the interface between the base metal and extent in the FSPed composites. However, strengthening from
the same composite. grain size refinement is very apparent among other mechanisms.
This claim can further be verified while observing the uniform
provided there is a good interfacial bonding between the matrix distribution of high strength CNTs and cerium oxide particles
and reinforcement, as recently reported by Bradbury et al. [27] which are obtained by three passes of FSP and their pinning effect
for Al/MWCNTs composites. Liu et al. [8] found shear lag mecha- on grain growth of the aluminum alloy matrix during recrystalliza-
nism very effective in improving the strength of FSPed MWCNTs/ tion, leading to grain refinement in the NZ. The pinning effect of
Al composites. Additionally, in Al5083 alloy, there are large inter- nanosized reinforcements, on restriction of the grain growth in
metallic particles such as Al6(Mn,Fe) which are not dissolved in Al matrices is previously stated [8,18]. It is also reported that, mul-
NZ and get fragmented during FSP [28,29]. They play the role of tiple pass FSP, can create more uniform distribution of reinforce-
fine reinforcement particles when uniformly distributed in NZ, ments [12,17]. Fig. 6a and b shows the distribution of cerium
and can be considered as another strengthening mechanism. In oxide particles and CNTs following three subsequent passes of
the present study, both nanosized cerium oxide particles and CNTs FSP, respectively. Distribution of reinforcements in combined form
are distributed in matrix. On the other hand, grain refinement was is also shown in Fig. 6c. In all cases, the clustering of reinforce-
achieved in all the FSPed composites. Of course, there exists a ments was reduced considerably by two passes and further
significant mismatch between aluminum matrix and CNTs, as well reduced by third pass.
as cerium oxide particles. Aluminum has a greater coefficient of The other possible mechanisms which affect the strengthening
thermal expansion, i.e. 23.6  10 6 K 1, with respect to CNTs and of these composites could be the formation of Al4C3 compound by
730 S.A. Hosseini et al. / Journal of Alloys and Compounds 622 (2015) 725–733

25 µm

Fig. 9. Distribution of intermetallic Al6(Mn,Fe) phase and cerium oxide particles in the matrix of composite CeO2/CNTs/Al5083 contains equal amount of reinforcement and
their corresponding spectra analyzed by SEM–EDX, (a) SEM micrograph of particles, (b) SEM–EDX analysis corresponding to Al6(Mn,Fe) phase which is fragmented and re-
distributed after subjecting to FSP. These gray particles are marked by a solid arrow, and, (c) SEM–EDX analysis of cerium oxide particles which are bright and are shown by a
dashed arrow.

interfacial reaction between matrix and CNTs, and the CNTs short- et al. [30]. They showed that CNTs were cut short after FSP, but
ening during FSP. In fact, further work is required to investigate the effect of CNTs shortening was more pronounced when more
these influences. than three passes were applied and the strength reduced signifi-
Although CNTs shortening and grain refinement affect the com- cantly. Liu et al. [17] also shown that, CNTs are cut short due to
posite strengthening in opposite ways, in the present study, this mechanical milling and FSP, but still improved the strength
affect was not seen, because only three passes were applied. This because of their pinning action on grain boundaries. They obtained
behavior is expected to occur more often in multi-pass FSPed com- maximum yield and tensile strengths after three passes of FSP,
posites. Analysis of carbon nanotube shortening and composite beyond which more shortening of CNTs occurred. Thus, in the pres-
strengthening in carbon nanotube/aluminum composites fabri- ent study, CNTs shortening which is also expected to occur, further
cated by multi-pass friction stir processing is reported by Liu is acting to hinder the grain growth of the matrix.
 S.A. Hosseini et al. / Journal of Alloys and Compounds 622 (2015) 725–733 731

In the present study, it seems several strengthening effects are and grain growth inhibition due to distribution and location of
simultaneously present. The major mechanisms contributing to the CNTs (Fig. 6b), contribute more to hardness than other mecha-
strengthening can be suggested as: nisms. Morisada et al. [32] also reported a similar effect of
MWCNTs on grain refinement and hardness in the MWCNTs/
1. Grain size refinement strengthening due to dynamic recrystalli- AZ31 surface composites.
zation of FSP and effect of reinforcements on retarding the grain
growth. 3.4. Fractography
2. Orowan strengthening, since reinforcements are in nano scale
and uniformly distributed. Fig. 11 shows the fractographs of fracture surfaces of the tensile
3. The dislocation strengthening originating basically from the tested samples. The fracture surface of as the received base alloy is
large coefficient of thermal expansion mismatch between the shown in Fig. 11a. Micrograph indicates a typical ductile failure
matrix and the reinforcements. described by deep, large and uneven dimples. In the FSPed sample
4. Shear lag or load transfer strengthening, where load is trans- (Fig. 11b), dimples are more uniform but still large and deep. In the
ferred from the low strength matrix to the strong CNTs, and former case, presence of large second phase particles at the core of
5. Second phase intermetallic strengthening which are frag- the dimples and their fracture is shown. Dimples are known to be
mented and distributed in matrix due to FSP. This is considered created by the nucleation, growth, and coalescence of microvoids,
to have least impact among others. and microvoids are generated at the locations such as interface
between second phase particles, and reinforcements. So it is
expected that in FSPed composites with fine reinforcing particles,
3.3. Microhardness
the number of voids and dimples to be increased. Micrographs of
the CeO2/Al5083 and CNTs/Al5083 composites are presented in
Microhardness profiles of the composites along the thickness
Fig. 11c and d respectively. The fracture surface of these FSPed
cross section treated after three passes of FSP are shown in
reinforced composites exhibited large number of shallower and
Fig. 10. It clearly shows that microhardness value of the FSPed base
smaller dimples. It is true because of their higher hardness and
alloy without reinforcement was increased as compared with the
strength and thereby their lower ability to be deformed plastically.
as-received alloy, expected to be due to grain refinement and also
These observations are consistent with the tensile test results. In a
due to fragmentation and distribution of second phase intermetal-
study by Liu et al. [8] it was shown that the fracture mode was
lic particles. The increase in hardness values was evidently higher
transformed to brittle one when CNTs was increased to 6 vol.%.
in composites reinforced with CNTs and cerium oxide particles
Presence of the reinforcements at the core of dimples and their
either separately or in combined form. This is firstly because of
fracture revealed that the failing was initiated from the reinforce-
direct strengthening imparted to matrix by these strong and hard
ment, and no voids or cracks were observed at the interface
reinforcements which act to hinder dislocation movement. Here,
between reinforcement/matrix. Esawi et al. [33] in a similar con-
the impact will be more pronounced since reinforcements are in
clusion reported that CNTs are the nucleation sites for void forma-
nano scale and well distributed by FSP. Secondly, it is due to the
tion only during tensile testing.
effect of microstructural modification in NZ. It is known that grain
size refinement can enhance the hardness according to Hall–Petch
3.5. Corrosion behavior
relation. It is also believed that homogeneous distribution of nano-
sized reinforcement, results in pinning of dislocations and retard-
In order to better understand the corrosion behavior of the base
ing grain growth [26,31]. Similar to the results of tensile
alloy as well as FSPed composites, potentiodynamic polarization
strengths, a maximum hardness value of 173 VHN was obtained
tests were carried out. The results are presented by potentiody-
for the composites containing CNTs and cerium oxide mixture in
namic polarization curves in Fig. 12. The corrosion potential (Ecorr),
the volume ratio of 75–25, respectively. That means it is more than
pitting potential (Epit) as well as the corrosion current density (icorr)
twice harder than the base alloy which possesses a hardness of less
derived from these curves are also summarized in Table 2. In gen-
than 80 VHN. Indeed, for the FSPed composites with higher weight
eral, the corrosion resistance of aluminum and its alloys originates
ratios of reinforcements, agglomeration can take place which dis-
from the tightly bonded oxide film formed on the surface when it is
turbs the uniform distribution of particles and makes the differ-
exposed to air or water. This oxide film may fail when it is exposed
ence in hardness profile. In these cases, the role of reinforcement
to salt water or alkaline solutions, since film may dissolve and
and their distribution have also to be taken into account. In the
result in a localized corrosion or pits. Pits can initiate as a result
present study, evidence shows that grain refinement due to FSP
of the difference in corrosion potential within a localized galvanic
cell at the alloy surface at locations such as phase boundaries,
insoluble intermetallic compounds, interface regions between
matrix and inclusions and reinforcements. A critical potential
called (Epit) is defined in order to quantify the resistance of mate-
rial to pitting corrosion. At this potential, localized breakdown of
Hardness (HV)

Base alloy Al5083 oxide film is initiated. Similarly a repassivation or protection

FSPed Base alloy potential is defined which represents the minimum potential at
CeO2/Al5083
75CNT/25CeO2/Al5083 which existing pits can propagate, but new pits cannot form.
CNT/Al5083 Indeed, material with higher (Epit) is more resistant to pitting cor-
rosion. Furthermore, the difference between (Epit) and (Ecorr) in a
given environment is considered as the margin of safety and is also
used as a measure of the susceptibility to localized corrosion [34].
Considering this, a comparison was made between the corrosion
response of base alloy as well as FSPed composites based on icorr
Distance from center (mm)
and Epit Ecorr values. It was found that, FSPed base alloy has lower
Fig. 10. Microhardness profiles along the thickness cross section of the base alloy icorr and negligible passive range than un-FSPed one, hence
and FSPed specimens. relatively better corrosion response due to the effect of grain
732 S.A. Hosseini et al. / Journal of Alloys and Compounds 622 (2015) 725–733

a b

20 µm 20 µm

c d

20 µm 20 µm

Fig. 11. SEM fractographs of tensile fractured surfaces of, (a) base alloy Al5083, (b) FSPed base alloy, (c) CNTs/Al5083, and, (d) 75% CNTs/25% CeO2/ Al5083, where highest
tensile strength and hardness was achieved. Ductile fracture characteristic are observed for all specimens except for the specimen shown in last fractograph.

incorporated composite (CeO2/Al5083) i.e. the lowest icorr, the

highest Epit and the longest passive range Epit – Ecorr. In this partic-
ular composite, pitting resistance was significant as compared with
other corrosion tested specimens. This behavior is shown in Fig. 11
and Table 2 as well. The improved pitting resistance is definitely
attributed to the effect of cerium oxide, which is considered as
E (VSCE)

Base alloy Al5083 an effective cathodic inhibitor in aluminum matrix. Ashraf et al.
FSPed Base alloy [23,24] reported a similar positive effect of cerium oxide on corro-
CeO2/Al5083 sion behavior of aluminum matrix, when they melted aluminum
75CNT/25CeO2/Al5083 ingot and added cerium oxide to the melt by stirring. It is believed
CNT/Al5083 that cerium oxide in aluminum matrix can suppress the corrosion
reactions by creating barrier to supply oxygen and electrons from
the aluminum matrix to corrosion medium [36].
On the other hand, the composite containing CNTs showed the
Log icorr (Acm-2)
highest icorr and almost no passive range, hence relatively poor pit-
ting resistance as compared to other tested samples. Here, it seems
Fig. 12. Potentiodynamic polarization curves of the base alloy as well as FSPed
specimens in 3.5% NaCl solution.
the formation of microgalvanic couples between the matrix and
CNTs plays the main role, since CNTs are cathodic with respect to
aluminum matrix. A similar effect is reported by Turhan et al.
Table 2
[21] and Aung et al. [37] in Mg-CNTs composites. Furthermore,
The summary of potentiodynamic polarization test results conducted in a 3.5% NaCl as stated in the earlier section, grain size was reduced in CNTs con-
solution at room temperature. taining composites, due to the pinning action of CNTs on grain
Ecorr (mV) icorr (A/cm2) Epit (mV) Epit Ecorr (mV)
boundaries. Hence, grain boundary areas were increased which
facilitated the nucleation and growth of corrosion pits. However,
Base alloy Al5083 673 3.550  10 6 673
more studies are required to explore the corrosion behavior of
FSPed base alloy 658 2.035  10 6 658
CeO2/Al5083 1180 1.671  10 7 650 530 Al-metal matrix composites reinforced by CNTs under FSP
75CNTs/25CeO2/Al5083 706 5.77  10 6 706 treatment.
CNTs/Al5083 713 7.80  10 6 713

4. Conclusions

refinement as well as uniform distribution and fragmentation of Metal matrix surface composites based on Al5083 containing
intermetallic particles induced by FSP. Indeed, a large volume frac- reinforcements of CNTs and cerium oxides either individually or
tion of grain boundaries is created by this process which helps for in hybrid form were fabricated via FSP. Microstructural features,
better adherence of passive films as it is reported by Argade et al. mechanical properties, and corrosion behavior of these composites
[35]. The best corrosion response was obtained for cerium oxide in NZ were evaluated. Three passes of FSP were applied for all
 S.A. Hosseini et al. / Journal of Alloys and Compounds 622 (2015) 725–733 733

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