Surface & Coatings Technology 337 (2018) 12–23

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Surface & Coatings Technology

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

Surface modification of Al6061 by graphene impregnation through a T

powder metallurgy assisted friction surfacing
Abhishek Sharma, Shiwendu Sagar, Raju Prasad Mahto, Baidehish Sahoo, Surjya Kanta Pal,
⁎
Jinu Paul
Department of Mechanical Engineering, Indian Institute of Technology, Kharagpur 721302, India

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

Keywords: Impregnation and homogeneous distribution of nanomaterials on metallic surfaces have always been a challenge
Friction surfacing for researchers in recent times. In the present work, authors demonstrate a surface modification of Aluminium by
Aluminium graphene impregnation through a novel powder metallurgy assisted friction surfacing (PMAFS) process. This
Graphene modified friction surfacing technique involves two stages. In the first stage, an Aluminium-graphene composite
Surface composites
tool is fabricated through a powder metallurgy route. In the second stage, this consumable tool is utilized for FS
Powder metallurgy
to obtain a composite coating layer on Aluminium surface. Experimental results show that the surface composite
prepared by this modified friction surfacing technique does have impregnated graphene successfully in Al ma-
trix. The obtained surface composites were characterized by using SEM, TEM, and XRD. Morphology and da-
mage to graphene are studied by using Raman spectroscopy. Nanoindentation study was conducted for a various
set of processing parameters with variation in graphene content. Further, the influence of graphene percentage
and processing parameters on mechanical properties and microstructural changes were also studied. Composites
prepared at relatively lower tool rotational speed with low content of graphene in the tool is found to have
optimum mechanical properties with a homogeneous distribution of graphene in Al substrate. The nano-hard-
ness of the surface composite is increased by 100% after impregnation of graphene nano platelets (GNP) with an
optimum set of parameters.

1. Introduction and various properties of a composite depend mainly on following

In the last decade, various researchers established several surface
modification techniques for aluminium alloys such as plasma electro-
lytic oxidation [1], anodic oxidation treatment method [2], EDM [3],
rubbing technique [4], Laser surface alloying [5], etc. All these pro-
cesses aim to improve the wear and corrosion resistance of Al alloys for
certain specific applications. Another promising surface modification
technique is the fabrication of surface composites. Surface composites
prepared by reinforcing micro and nano particles in the aluminium
matrix offer both a scientific challenge as well as an industrial need in
the manufacturing of various mechanical components. Though various
methods are developed to fabricate Al composite with different re-
inforcements, the homogeneous dispersion of reinforcing particles re-
mains a challenge for the scientists and researchers. The difference in
density of Al and reinforcements leads to agglomeration and finally
results in deterioration of strength. The processing temperature and the
formation of intermetallic compounds during the fabrication of Al
composite also deteriorate the properties in certain cases. The strength
factors: i) reinforcement ii) size of reinforcement iii) method of re-
inforcement impregnation in the matrix.
Graphene, with outstanding tensile properties of 130 GPa and
Young's modulus of 1 TPa, is an excellent reinforcement in composites
[6,7]. It is one atom thick planar sheet of sp2 bonded carbon atoms
densely packed in a honey comb crystal lattice [8,9]. Several methods
were used by researchers to impregnate graphene homogeneously in Al
matrix to enhance the mechanical and thermal properties of the com-
posite [6,10–18]. Due to ultrahigh strength and multiple wrinkled
structures of graphene nano flakes, the Al-GNP composite possesses
increased strength and excellent ductility [14]. Large surface area of
graphene provides a wide contact between the matrix and reinforce-
ment which results in better load transfer and ultimately increases the
strength [11].
Friction surfacing (FS) is a solid state coating technique with ap-
plication mainly in corrosion protection and hardfacing [19–21]. The
process consists of forcing the consumable rod of coating material on
the substrate and move it parallel to the substrate surface while

⁎
Corresponding author.
E-mail address: jinu.paul@mech.iitkgp.ernet.in (J. Paul).

https://doi.org/10.1016/j.surfcoat.2017.12.059
Received 20 September 2017; Received in revised form 5 December 2017; Accepted 23 December 2017
Available online 26 December 2017
0257-8972/ © 2017 Elsevier B.V. All rights reserved.
A. Sharma et al.
Fig. 1. (a &b) Morphology of GNP and Al powder respectively (c & d) Schematic of FS tool (e) Flow diagram of PMAFS process.
simultaneously rotating it and applying load. Friction surfacing is
known for its ability to produce homogeneous and fine grain coatings
with hard second phase particles. The main advantage of the process is
that the temperature generated during the coating is well below the
melting point, and thus the formation of intermetallic compounds can
be avoided [20,22,23]. The process becomes eco-friendly and cheap as
it does not require any external heat source.
In the present study, surface modification of Al6061 is carried out
by impregnation of GNP in the Al matrix through a powder metallurgy
assisted friction surfacing method. Friction surfacing is mainly used as
coating technique, but few modification in the process makes it an ef-
fective surface modification technique. A consumable Al-GNP compo-
site tool is fabricated via powder metallurgy route, and the so devel-
oped tool was utilized for friction surfacing.
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Surface & Coatings Technology 337 (2018) 12–23
2. Experimental details
2.1. Raw material and FS tool fabrication
As received GNP's (Fig. 1(a), United Nanotech Innovations (India))
of size 5–10 nm with 5 μm lateral dimension and 3–10 layers is mixed
in 2.5 wt% and 5 wt% with 98% extra pure aluminium fine powder
(Fig. 1(b), Loba Chemie (India)) of size ~20 μm. The mixing is carried
out in a high-speed planetary ball mill at 380 rpm for 60 minutes with a
ball to powder ratio of 5:1. The as-mixed powder is cold compacted
(250 Mpa) in a cylinder die (die steel) to form a cylindrical billet of
dimension 25 mm diameter and 13 mm height. The green samples are
then sintered under argon atmosphere in a tubular sintering furnace at
a temperature of 600 ± 20 °C with a heating rate of 15 °C/min fol-
lowed by soaking for 60 minutes. The sintered samples are then fixed in
a slot which is fabricated in a solid Al6061 consumable rod using a push
A. Sharma et al. Surface & Coatings Technology 337 (2018) 12–23

Fig. 2. Schematic representation of tool assembly.

fit or shrink fit (interference 0.002 mm) such that the Al6061 con-
sumable rod and sintered sample becomes a single unit (Fig. 1(c & d)).
It is then used as a tool for fabrication of surface composite using FS
(Fig. 1(e)). Fig. 2 shows the assembly of powder composite in Al rod to
use it as an FS tool.
2.2. Friction surfacing methodology
FS is carried out at a constant 5 kN axial load by using a vertical axis
end mill at a tool rotational speed of 550 rpm and 1120 rpm. The tool
traverse speed is 120 mm/min over an Al6061 substrate of 5 mm
thickness. These process parameters during FS are selected after several
hit and trials conducted to obtain the desired surface composite.
Various notations used to denote composites fabricated at different
process parameters are listed in Table 1.
The overall process of FS involved here consists of three basic
stages:
(i) Heat-up-stage: The rotating Al/GNP tool made up of powder
metallurgy process is brought into contact with the Al6061 substrate,
and an axial compressive load of 5 kN is applied.
(ii) Dwelling: After achieving the desired axial force the tool is made
to rotate without any traverse motion so as to generate the temperature
sufficient to bring the material in a plastic state. Due to the relative
motion of tool and substrate, heat is generated at the interface. This
heat generation increases the temperature of the contributing rubbing
interfaces and consequently leads to the decrease in flow stress of the
material. Eventually, the Al/GNP tool is unable to withstand the ap-
plied axial compressive force and tends to plastically deform and start
impregnating in the substrate along with some flash generation. This
phenomenon is accomplished by the combined effect of frictional shear
stresses (experienced by the tool) and mechanical mixing (on the sub-
strate). The frictional shear stress deforms the tool, and the GNP par-
ticles are detached from the tool and transferred to the substrate. Due to
frictional heat, the softening of the substrate also takes place which
ultimately assists in mechanical mixing and dispersion of these parti-
cles. The mechanism of material transfer during the process is shown
schematically in Fig. 3.
(iii) Traverse: The 3rd stage involves the linear motion of tool along
with rotation. The traverse speed and rotational speed both come into
the scene and increases the heat generation due to increased frictional
resistance. The third stage is immediately followed by the tool removal,
and the contact between tool and substrate is broken.
2.3. Characterization of the surface composites
The samples were adequately polished (on cross section) primarily
on the progressive grades of emery paper (220, 400, 600, 800, 1000 &
1200) before characterization and mechanical testing. The paper po-
lished surface is then fine cloth polished by using HIFIN diamond
compounds (Geologist's syndicate, India).The fine polished samples are
then etched using Keller's reagent before the microstructural examina-
tion. The microstructural characterization is carried out on the cross
section and within 30–50 (μm) proximity of the processing surface as
shown in Fig. 1s (Supplementary information). The GNP distribution in
the matrix of both tool (Al/GNP sintered composite) and surface com-
posite (Friction surfaced) was examined by scanning electron micro-
scopy (Zeiss) and field emission scanning electron microscopy (Mer-
lin).The EDAX analysis was also carried out with 20 kV power source.
The interface bonding of GNP and Al matrix in the surface composite
was examined by high-resolution transmission electron microscopy
(Jeol). X-Ray Diffraction (XRD) (PANalytical XPERT PRO) with CuKα of
2θ range 20°–80°) analysis was conducted to identify the different in-
termetallic compounds and phases formed both in FS tool and surface
composite. Nanoindentation was performed at the cross-section of the
tool and surface composite by using Nano-Triboindenter (Hystiron, TI
950) under a load of 5000 μN with Berkovich tip. Ten readings for each
sample were taken within 1 mm proximity of the processed surface. The
indents are separated by a distance of 50 μm (horizontally) in order to
cover the maximum length of the sample and to avoid overlapping of
indents. Duration of loading, dwelling, and unloading was kept to be
10 s each. Reduced Young's modulus results were also recorded during
the test. Raman spectrometry (Jobin Yvon Horiba, T64000) with ex-
citation by Argon-Krypton mixed ion gas laser was performed for both
the tool and surface composite to study the morphology and level of
defects in GNP. Fig. 4 shows the schematic of observed surfaces for
various characterization and analyses.
3. Results and discussion
3.1. Surface profile and finishing
Fig. 5 shows the surface generated from the proposed methodology
at 550 rpm tool rotational speed and 120 mm/min traverse speed. The
sample selection scheme is also shown in Fig. 5. The surface shows a
rough profile with very less flash generation. The rough surface may be

Table 1
Notations of various composites fabricated at different process parameters.

Composite type Description Notation

Surface composite Surface composite fabricated at 550 rpm using 2.5% GNP tool Al-2.5GNP/550 rpm
(formed by friction surfacing) Surface composite fabricated at 550 rpm using 5% GNP tool Al-5GNP/550 rpm
Surface composite fabricated at 1120 rpm using 2.5% GNP tool Al-2.5GNP/1120 rpm
Surface composite fabricated at 1120 rpm using 5% GNP tool Al-5GNP/1120 rpm
Powder composite Powder composite fabricated with 2.5%GNP Al-2.5GNP powder composite
(formed by powder compaction) Powder composite fabricated with 5%GNP Al-5GNP powder composite

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A. Sharma et al. Surface & Coatings Technology 337 (2018) 12–23

Fig. 3. Schematic representation of material transferring mechanism

in powder metallurgy assisted FS.

attributed to the lower tool rotational speed and less plunge depth due
to low applied axial load [24,25]. The friction generated at lower tool
rotational speed and the significantly low applied load is maybe not
sufficient to deform the material plastically and maintain the flow of
material along the processing direction and ultimately results in the
poor surface finish. Fig. 5 also shows the sticking of tool material in the
substrate during the tool withdrawal (at the end of the process). This
behavior of tool material sticking can be attributed to the sudden de-
crease in applied axial load at the end of the processing due to tool
removal.

3.2. Distribution of GNP in powder composite

Fig. 6(a & b) shows SEM micrographs of the ball milled compacted
powder composite with 2.5 wt% GNP and 5 wt% GNP, respectively.
Micrographs show the homogeneous dispersion of GNP in both the
composites. The wrinkled morphology of GNP was retained as it is even
after ball milling as shown in Fig. 6(c & d). Fig. 6(e & f) shows the Al- Fig. 5. Surface profile generated after PMAFS.
2.5GNP sintered composite and Al-5GNP sintered composite,

Fig. 4. Sample profiles for various analyses.

15
A. Sharma et al.
Fig. 6. SEM micrograph of FS tool (a) 2.5% GNP green compacted (b) 5% GNP green compacted (c) high magnification image of (a) (d) High magnification image of (b) (e) 2.5% GNP
Sintered composite (f) 5% GNP Sintered composite. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
respectively. The GNP is observed on the surface of Al powder because
of shearing mode created between Al powder and GNP by dominantly
planetary ball milling [8,26]. EDAX analysis in Fig. 2s (Supplementary
information) confirms the presence of GNP in the composite.
3.3. Nanoindentation
Fig. 7(a–b) shows the variation of nano-hardness with GNP content
for the powder composite, whereas Fig. 7(c–d) shows the variation of
nano-hardness in case of the processed surface composite. Among the
mechanical properties which can be evaluated by a nanoindentation
test, the elastic modulus (E) and the hardness (H) are extremely normal.
In the present study, the Oliver and Pharr method [27] was used for
measuring these properties. This method is grounded on the analyses of
unloading behavior of the load-displacement curve. The observed
average area of indent in the study is 25.85 ( ± 9.69) μm2. It can be
perceived from the Fig. 7(a–b) that GNP shows an excellent reinforcing
effect at optimum process parameters and content on the nano-hardness
of the GNP/Al alloy nano composite. With the introduction of 2.5 and
5.0% GNP in powder composite, the hardness increases from 0.77 GPa
to 1.07 GPa. The gain in strength with the increase of GNP content in
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Surface & Coatings Technology 337 (2018) 12–23
powder composite has been reported by many researchers in previous
studies [12,13,15,28,29]. The increase in hardness with the GNP con-
tent is attributed to the astonishing mechanical properties of the re-
inforced GNPs which provides high resistance force for deforming
during indentations. Also, apart from the strengthening provided by the
Al-GNP interface, some strengthening mechanism also exists in the
matrix surrounding the GNP. This strengthening is an outcome of in-
terface layers/loops exist in the matrix surrounding the particle. Wu
et al. [30] characterizes these interface layers in various regions namely
region I, II and III with the region I farthest from the particle and region
III being closest to the particle. In region I only grain refinement is the
strengthening mechanism whereas in region II and III elemental diffu-
sion, Orowan strengthening mechanism, dislocation strengthening, etc.
are the primary strengthening mechanism. When the inter-particle
distance is small, there is overlapping of the regions belonging to the
two particles, causing the strengthening effect to be more pronounced
in the interface layers. Fisher et al. [31] also reported the closed loops
in the matrix around the particle and the back stress from the closed
loops increases the effective residual stress in the matrix surrounding
the GNP. These residual stresses and subsequent strengthening by
various mechanisms around the periphery of the GNP lead to the
A. Sharma et al.
Fig. 7. Micrographs of (a) nano hardness of powder composite, (b) L-D curves of powder composite, (c) nano hardness of processed composites, (d) L-D curves of the processed composite.
increased localized hardness of the matrix. Thus, even if the indenter is
not striking at the Al-GNP interface, the increased value of hardness as
compared to unreinforced aluminium is obtained due to the presence of
GNP in the matrix. The strengthening mechanisms of powder composite
in the present study are stress transfer and dislocation strengthening.
Since the powder composite are fabricated at solid state sintering, the
effect of grain refinement is negligible. The stress transfer between Al
matrix and GNP largely depends on the interfacial bonding. Also, the
GNP possesses the wrinkled feature (Fig. 6), which is encouraging for
the formation of mechanical bonding between Al matrix and GNPs. This
excellent mechanical bonding effectively transfers the load from the
ductile Al matrix to the hard GNPs, resulting in the increase of hard-
ness. The existence of large mismatch of thermal expansion coefficient
in Al matrix and GNPs leads to the formation of dislocations. The hard
GNPs restrict the motion of these dislocations and cause the increase in
dislocation density finally resulting in dislocation strengthening. Al-
though, the hardness increases by 39% on increasing the GNP content
from 2.5 to 5.0%, negligible change in the ductility is noticed
(Fig. 7(b)).The excellent ductility due to the addition of GNPs is also
reported by various researchers making GNP as the potential re-
inforcement for Al-based alloys [29].
The strengthening mechanism of GNP reinforcement in the surface
composite is supposed to be associated with the outstanding mechanical
properties and the exceptional structured characteristic of graphene,
and to the good bonding interfaces among graphene and Al matrix. Fine
precipitate strengthening or the Orowan strengthening mechanism is
the primary mechanism for the strengthening of Al composite [9].
These GNP precipitates restrain the dislocation motion and material
failure during loading. In addition to strengthening due to reinforce-
ments, the FS also offers the grain refinement due to dynamic re-
crystallization. Thus, with the reduction in grain size due to FS, the
strength of the composite also increases. The combined effect of Or-
owan strengthening and grain refinement results in the excellent
properties of the fabricated surface composite. However, the impreg-
nation of GNP varies with the process parameters and strength of the
powder composite and is discussed here in detail.
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Surface & Coatings Technology 337 (2018) 12–23
The variation of nano-hardness is quite complicated in case of sur-
face composite (Fig. 7(c & d)). Surface composite of Al-2.5GNP/
550 rpm shows a remarkable increase in hardness of 100% as compared
to as received Al, whereas at same tool rotational speed of 550 rpm the
composite Al-5GNP/550 rpm shows negligible change in the hardness
value relative to as received Al alloy. This unusual behavior due to
change in GNP content can be attributed to the insufficient impregna-
tion of GNP in Al matrix at lower tool rotational speed due to the sig-
nificantly higher strength of the composite at 5% GNP content
(Fig. 7(a)). Owing to the higher strength of Al-5GNP the disintegration
of GNP from the powder composite and consecutive impregnation in Al
substrate during FS is restricted. Also, during FS at lower tool rotational
speed the frictional shear stress offered to the powder composite is also
very less which resist the easy disintegration of powder composite. With
the reduction in volume fraction of GNP in Al-5GNP/550 rpm, the
number of Al/GNP interfaces also decreases. Since the load sharing
capacity of the composite is determined by the number of interfaces and
interfacial bonding between the particle and matrix, it also decreases,
and thus the hardness remains almost unchanged. Apart, from hard-
ness, the reduced Young's modulus obtained in case of Al-2.5GNP/
550 rpm is 25% greater than that obtained at Al-5GNP/550 rpm.
Composites fabricated at a processing speed of 1120 rpm shows an
opposite trend relative to the composites fabricated at 550 rpm. Here,
the insufficient amount of GNP impregnation is observed at 2.5% GNP
content. The higher frictional shear stress due to high tool rotational
speed (1120 rpm) and low strength of powder composite fabricated
with 2.5% GNP results in effortless consumption of powder composite.
Due to this easy and rapid consumption of tool the GNP particles are not
able to impregnate up to a sufficient depth inside the substrate. Instead,
the particles are just agglomerated on the surface with very weak me-
chanical bonding and improper interface between GNP and matrix. This
phenomenon ultimately reduces the final volume fraction of GNP im-
pregnated in the substrate. At higher tool rotational speed the frictional
shear stress is pronounced [32]. Also, due to low strength of powder
composite, the resistance offered by the substrate decreases to a greater
extent. This combined effect of lower resistance due to reduced strength
A. Sharma et al.
and lower frictional force results in insufficient heating of the substrate
during FS. The insufficient heating diminishes the plastic flow of im-
pregnated GNP and ultimately results in agglomeration of the re-
inforcement. The combined effect of above phenomenon ultimately
drastically reduces the hardness of the Al-2.5GNP/1120 rpm composite.
In case of Al-5GNP/1120 rpm, a significant increase in hardness of
65% relative to as received Al is noticed. Due to the greater strength
possessed by powder composite containing 5% GNP, the tool disin-
tegration/consumption is not that easy as in case of Al-2.5GNP/
1120 rpm. This greater strength makes the powder composite to pro-
vide resistance against sliding on Al alloy during FS and in this phe-
nomenon generates a heat sufficient to create a good interfacial
bonding between Al matrix and GNPs. The higher strength of powder
composite also restricts the disintegration of the composite at higher
tool rotational speed during friction surfacing and allowing the im-
pregnation of a greater amount of GNP deeper inside the Al matrix. This
phenomenon explains the considerable increase in hardness of Al-
5GNP/1120 rpm surface composite.
Fig. 7(c & d) also shows the variation of hardness and Young's
modulus of Al6061 aluminium alloy friction surfaced by a tool made up
of pure Al powder. At the same process parameters as that used for GNP
impregnation, the pure Al reinforced surface composite shows a mar-
ginal change in hardness and Young's modulus. Due to this marginal
change, the effect of Al powder in GNP impregnated surface composites
can be neglected. The surface composite does not show any significant
improvement/degradation of properties due to the presence of Al
powder. This phenomenon can be attributed to the very low tensile
strength of Al (310 MPa) as compared to GNP (1 TPa). Due to such a
low strength possessed by Al powder, its contribution in strengthening
can be neglected, and it is assumed that the strengthening behavior of
surface composites is entirely due to restricting dislocation motion by
GNP and dynamic recrystallization due to friction surfacing.
This nanoindentation behavior of surface composite assists in se-
lecting the optimum critical parameters (hardness of powder composite
and tool rotational speed) for the successful impregnation of GNP in the
Al matrix.
3.4. Distribution of GNP in surface composite
Fig. 8(a–d) shows the SEM micrographs of Al-2.5GNP/550 rpm, Al-
5GNP/550 rpm, Al-2.5GNP/1120 rpm and Al-5GNP/1120 rpm, re-
spectively obtained at the cross-section. All the micrographs show that
GNP is well distributed in the Al matrix with interparticle distance of
~ 94 μm (Fig. 3s, supplementary information). The porosity observed in
various composites is attributed to the inherited porosity of powder
composite in the overall process. Fig. 8(c & d) shows the higher mag-
nification micrographs of the surface composites and morphology of
GNP in the composite. The best distribution of GNP is obtained at Al-
2.5GNP/550 rpm surface composite. Also, the wrinkled morphology of
GNP is retained in the surface composite. The homogeneous distribu-
tion of GNP in Al-2.5GNP powder composite contributes towards the
homogeneous distribution of GNP in the surface composite. The lower
strength of Al-2.5GNP powder composite (Fig. 7(a)) allows the tool
consumption at an optimum rate and thus assist in the uniform dis-
tribution of GNP. However in the case of Al-5GNP/550 rpm (Fig. 8(b))
the tool disintegrate at Al substrate in a non-uniform manner due to
higher hardness of Al-5GNP powder composite (Fig. 7(a)) and hence the
impregnation of GNP is less uniform.
Fig. 8(e) shows the SEM micrograph of Al-2.5GNP/1120 rpm sur-
face composite. High magnification image (Fig. 8(g)) shows the wrin-
kled morphology of incorporated GNP particle. The higher tool rota-
tional speed offers a higher frictional shear stress to the Al/GNP
particles in powder composite. This higher frictional shear stress in-
creases the rate of disintegration of the tool during friction surfacing on
the Al substrate which ultimately leads to the lesser volume fraction of
GNP particle impregnated in the surface composite. The lower strength
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Surface & Coatings Technology 337 (2018) 12–23
of Al-2.5GNP powder composite also contributes towards the increased
rate of tool disintegration at higher tool rotational speed. In Al-5GNP/
1120 rpm surface composite the combination of higher tool rotational
speed and higher strength of Al-5GNP powder composite is achieved.
Thus, higher tool rotational speed increases the rate of tool disin-
tegration due to higher frictional shear stress, while the higher strength
of Al-5GNP powder composite resists the easy fragmentation of tool.
These opposite tendencies result in the uniform distribution of GNP in
Al matrix with an excellent bonding between the GNP and Al matrix
(Fig. 8(f & h)). Fig. 8(i) shows the point EDAX analysis of Al-2.5GNP/
1120 rpm surface composite. The presence of GNP in the matrix is
confirmed by the fraction of carbon. Since the samples are kept in the
open atmosphere before SEM analysis, the layer of Al2O3 is deposited
on the aluminium surface. The presence of Oxygen in EDAX analysis is
justified by the formation of this Al2O3 on the aluminium surface. The
elemental mapping (on the 20 μm scale) conducted for Al-2.5GNP/
550 rpm surface composite reveals the aerial distribution of Carbon as
2% along with some oxygen is shown in Fig. 4s (supplementary in-
formation).
3.5. Transmission electron microscopy (TEM) analysis
Observation by TEM shows the crystallinity of GNP, as well as the
interaction with aluminium matrix. The TEM analyses of samples pos-
sessing best mechanical properties are presented here. Fig. 9(a) presents
bright field TEM images of GNP corresponding to Al-2.5GNP/550 rpm
surface composite. Fig. 9(b & C) shows the SAED pattern and high
magnification of Fig. 9(a) respectively. It can be found from Fig. 9(a)
that the GNP is successfully embedded in the Al matrix without any
formation of Al4C3 between Al matrix and GNP. SAED pattern
(Fig. 9(b)) confirms the signature of GNP. The hexagonal pattern re-
veals the six-fold symmetry of carbon atoms arranged in graphene
plane, representing good crystallinity of the GNP [26]. A high magni-
fication HRTEM image in Fig. 9(c) displays the interface between the
impregnated GNP and Al matrix. A transition zone (encircled and
magnified in inset), indicates the intercalation between atoms of carbon
and aluminium. The existence of transition zone shows a strong alu-
minium-GNP bond without any formation of aluminium carbide. This
bonding further reveals the existence of strengthening mechanism such
as a thermal mismatch between aluminium and GNP, effective transi-
tion layers to transfer of load from aluminium to the reinforcement and
interaction with dislocations [15]. Along with strongly bonded inter-
face, Fig. 9(c) also represents the single layer stacking in GNP. The
individual single atomic carbon layers (corresponding to monolayer
graphene) can be easily identified, suggesting that the composite truly
contains some single layer graphene. Since the graphene has a tendency
to restack and form graphitic structure due to van der Walls interaction.
Thus, layered graphene restacking containing several individual
monolayers is also present, where the adjacent line distance appears
equal to 0.30 nm ( ± 0.1) corresponding to the d spacing of (002)
crystal plane of graphite (Fig. 9(c)). Similarly, Fig. 9(d) reveals the
distribution of GNP in Al matrix for Al-5GNP/1120 rpm surface com-
posite, whereas Fig. 9(e) represents a single GNP particle with de-
formation band (encircled) in Al-5GNP/1120 rpm surface composite.
Fig. 9(f) represents the rectangular area marked in Fig. 9(e), whereas
Fig. 9(g) represents the encircled region of Fig. 9(e). A well-defined
interface between GNP and Al matrix can be also visualized from
Fig. 9(f) indicating strong bonding between GNP and Al matrix.
Fig. 9(g) shows the magnified image of deformation band present in the
composite. During the fabrication of composite, Al grains undergo
plastic deformation due to high heat generation during friction surfa-
cing. When the stress concentration in the deforming grain is sufficient
to activate the slip in the adjacent grain (having unfavorably oriented
slip system) a piling up of dislocation takes place in the deforming grain
which leads to macroscopic yielding [8,33]. This phenomenon involves
the strain gradient which facilitates the displacement of the adjacent
A. Sharma et al. Surface & Coatings Technology 337 (2018) 12–23

Fig. 8. SEM micrograph of (a) Al-2.5GNP at 550 rpm, (b) Al-

5GNP at 550 rpm, (c)High magnification image of (a), (d) high
magnification image of (b), (e) Al-2.5GNP at 1120 rpm, (f) Al-
5GNP at 1120 rpm, (g) high magnification image of (e), (h) high
magnification image of (f), (i) EDAX of blue spot in fig (g). (For
interpretation of the references to color in this figure legend, the
reader is referred to the web version of this article.)

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A. Sharma et al. Surface & Coatings Technology 337 (2018) 12–23

Fig. 9. Bright field TEM micrographs of (a) Al-2.5GNP/550 rpm

(b) SAED pattern of fig (a), (c) high magnification image of (a),
(d & e) Al-5GNP/1120 rpm, (f) high magnification image of
rectangular region in (e), (g) High magnification image of en-
circled region in (e).

20
A. Sharma et al.
Fig. 10. XRD micrographs of powder and surface composites.
grains. This extent of shear localization in the matrix leads to the for-
mation of highly localized deformation bands. Due to the high specific
surface area of GNP, it may restrict the mass flow in Al matrix, resulting
in substantial reduction of plastic strain to failure of the Al/GNP surface
composite.
3.6. Phase analysis
Fig. 10 shows the XRD patterns of different powder and surface
composites. The major peaks of Al are observed at 38.3°, 44.6°, 65.1°,
and 78.2° corresponding to the (111), (200), (220), and (311) planes of
Al. The low-intensity peak at 26.5° confirms the presence of GNP in
powder composite. This peak corresponds to (002) plane of graphene.
However, the peak of GNP is not observed in case of surface composite
due to the low volume fraction of GNP impregnated in the substrate.
The peaks of intermetallic compounds such as Al2O3, Mg2Si and Al4C3
are also absent. The absence of peaks corresponding to intermetallic
compounds may be due to the low volume fraction of intermetallic in
the surface composite. Another possible reason for the absence of peaks
corresponding to intermetallic compounds is the lack of any reaction
between the GNP and Al.
3.7. Damage to GNPs
Raman spectroscopic analysis was conducted to analyze the damage
to the GNP during fabrication of both powder and surface composite.
The defects or degree of the disorder often improves the performance of
the component when used in practical application [34]. For example, to
avoid the slip between the graphitic plane and matrix material, or-
ientation disorder is advantageous [34,35]. It also improves the me-
chanical strength of the composite [35]. For the present study, the
21
Surface & Coatings Technology 337 (2018) 12–23
Fig. 11. Raman spectrum of powder and surface composites.
analysis area was selected randomly as GNP is distributed homo-
geneously throughout the composites. The Raman spectra (Fig. 11)
show the sharp and strong graphitic (D and G) peaks in both powder
and surface composite fabricated at different parameters. The single
photon emission process which is also termed as first-order Raman
scattering and produced by tangential stretching (E2g) mode of the
graphite plane results in G band at ~1598 cm− 1 [36]. However,
second-order Raman scattering due to the double resonance of single
phonon for sp2 carbon results in a D band around ~1353 cm− 1. The
defects in hexagonal graphitic structure due to in-plane vibrations re-
sults in activation of D band in Raman spectra [34]. The 2D peak at
around ~2688 cm− 1 is a result of two-phonon Raman process depen-
dent upon the π-band of the electronic structure of graphite. The 2D
peak reveals important information regarding the stacking structure of
graphite. The intensity of 2D peak shows the number of layers in the
structure and the layer stacking along c axis [16]. The intensity ratio of
D band and G band (ID/IG) indicates the structural defect and degree of
disorder in the structure [37,38].
As seen from the Fig. 11, the surface composites exhibit a higher
intensity of D band relative to the powder composite. This higher D
band intensity indicates towards the increase in defects especially the
edge defect. Due to FS, the edge of the crystal structure undergoes a
transition from zigzag to arm chair which is indicated by high-intensity
D band of surface composites. The D band appears in case of powder
composites also, but it is due to non-uniformity and roughness in edge
structure. The higher ID/IG in case of the surface composite is also at-
tributed to the generation of edge defect due to the impregnation of
GNP in Al matrix with the folded edges embedded inside the Al grains
as seen from the SEM micrographs (Fig. 8) [37]. The embedded GNP in
Al matrix experiences stresses due to the large difference of coefficient
of thermal expansion between GNP and Al matrix. This increase in
stress further increases the intensity of D band, and ultimately the ratio
of ID/IG increases. Friction surfacing at 1120 rpm tool rotational speed
with 5% GNP tool obtains a higher ID/IG ratio relative to the ID/IG ratio
obtained with 2.5% GNP tool. This high ID/IG ratio is attributed to the
higher heat generation at 1120 rpm with 5% GNP tool. High tool ro-
tational speed contributes towards this high heat generation due to
friction. At high tool rotational speed, low strength Al-2.5GNP disin-
tegrates readily due to high frictional shear stress experienced during
FS. Thus, the heat generation is comparatively less than the case of Al-
5GNP. An entirely reverse trend has been observed when FS is carried
out at tool rotational speed of 550 rpm. The reverse trend is attributed
to the reduced volume fraction of the impregnated GNP in the Al-
5GNP/550 rpm surface composite relative to Al-2.5GNP/550 rpm. With
the reduction in volume fraction of GNP corresponding edge defects are
also reduced which ultimately reduces the D band intensity in Al-
A. Sharma et al.
5GNP/550 rpm composite. Owing to the decreased D band intensity,
the ID/IG ratio also decreases. The decreased volume fraction of GNP is
attributed to the higher strength of the tool containing 5% GNP. This
higher strength resists the tool disintegration at lower tool rotational
speed.
The intensity ratio of the 2D band and G band (I2D/IG) is almost
identical for the powder composites and surface composite. The max-
imum I2D/IG ratio is observed for the surface composite fabricated at
1120 rpm with 5% GNP tool. This high I2D/IG ratio is attributed to the
high heat generation as explained earlier. Due to this high heat gen-
eration, the material flow stress decreases and leads to softening of Al
substrate which in turn causes the homogeneous distribution of GNP
particles [39]. During this phenomenon, the GNP particles exfoliate
easily and result in higher I2D/IG ratio. A linear red shift is observed in
the 2D band in case of surface composites. This red shift may be due to
increase in anharmonic coupling of phonons and increased thermal
expansion in the lattice at a higher temperature during fabrication [40].
4. Conclusions
Fabrication and characterization of aluminium-graphene surface
composites were discussed. The impregnation of GNP in aluminium
substrate is carried out by using modified friction surfacing method
involving FS tool made up of powder metallurgy process. Significant
improvement in surface properties of Aluminium was achieved through
impregnation of graphene nanoplatelets. The depth of graphene im-
pregnated and mechanical bonding of GNP with Al depends largely
upon the processing parameters (tool rotational speed) and also on the
strength of modified FS tool. There exists a best processing condition
(2.5% GNP, 550 rpm & 120 mm/min) where the excellent surface
hardness (100% of as received Al) was achieved. The fraction of GNP
impregnation is closely associated with the tool hardness.
The increase in surface hardness is attributed to the various
strengthening mechanism due to the presence of GNP in an aluminium
matrix. Successful impregnation of GNP with two-stage homogeneous
distribution in Al matrix is visualized by FE-SEM micrographs. The
presence of residual stress in GNP is visualized and analyzed by Raman
spectroscopy. Nanoindentation studies which enable the evaluation of
surface properties up to a maximum depth of 0–1 μm, revealed that the
surface hardness of GNP impregnated Al6061 is more than the as-re-
ceived Al alloy only with a particular set of processing parameters. Also,
non-stringent control over the processing parameter leads to dete-
rioration of surface properties of the composite. XRD analysis reveals
the non-existence of any intermetallic compound during processing.
The absence of intermetallic compound is further confirmed by SAED
analysis. Such Graphene impregnated Al surface composite have ap-
plication in the areas where excellent wear resistance along with
toughness is the primary requirement. The proposed approach of sur-
face modification through powder metallurgy assisted FS provides a
path to a broad new class of graphene-based surface composites and
their use in a variety of industrial applications.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.surfcoat.2017.12.059.
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