JMEPEG ASM International

DOI: 10.1007/s11665-017-2730-7 1059-9495/$19.00

Effect of Carbon Nanotubes as Reinforcement

on the Mechanical Properties of Aluminum-Copper-
Magnesium Alloy
N.S. Anas, R.K. Dash, Tata N. Rao, and R. Vijay

(Submitted June 17, 2016; in revised form March 31, 2017)

Elemental powders of Al, Cu, Mg and x wt.% CNT (x: 0-2.5) were blended and milled in the high-energy
ball mill for 4 h. Milled powders of Al alloy-CNT composites were subsequently consolidated by upset
forging followed by hot extrusion. Even though the particle size of milled powders of Al alloy-CNT com-
posites decreased with the addition of CNT, there is no significant effect on crystallite size. Raman spectra
indicated that the nanocrystalline structure of CNT is retained after milling. Yield and ultimate tensile
strengths increased with CNT content and Al alloy-2.5 wt.% CNT exhibited an enhancement of 56 and
73%, respectively, when compared to Al alloy in solutionized condition. The improvement in mechanical
properties of Al alloy-CNT composites is due to ultra-fine grain size, finer second-phase precipitates and
uniform dispersion of CNT.

The aforementioned issues can be resolved by selecting proper

Keywords Al-Cu-Mg alloy, carbon nanotubes, composites, me-
chanical properties
1. Introduction
Aluminum (Al) alloys are being used as structural materials
in aerospace and defense industries due to light weight, good
ductility and high corrosion resistance. But, there is a need to
improve the strength and temperature capabilities of these
alloys. Many efforts are being made to improve the strength,
stiffness, creep resistance and wear properties. One of the
possible solutions that have been proposed to tailor and
improve mechanical properties of Al alloys is by developing Al
alloy matrix composites by dispersing hard particles, ceramics,
carbon fibers or whiskers in metal matrix (Ref 1-3).
Carbon nanotubes (CNT), a one-dimensional carbon nanos-
tructure, are also being considered as effective reinforcements
due to exceptionally high mechanical properties (Ref 4). The
sp2 hybridized carbon-carbon bonds offer them a YoungÕs
modulus of about 1 TPa and 100 GPa strength (Ref 5). The
mechanical properties of CNT-reinforced Al and its alloy
matrix composites can be improved if certain difficulties like
uniform dispersion of CNT in the metal matrix, bond strength at
the interface between CNT and matrix, and chemical stability of
CNT at elevated temperature are properly addressed (Ref 6).
N.S. Anas, International Advanced Research Centre for Powder
Metallurgy and New Materials (ARCI), Balapur, Hyderabad 500005,
India and School of Engineering Sciences and Technology, University
of Hyderabad, Gachibowli, Hyderabad 500046, India; R.K. Dash,
School of Engineering Sciences and Technology, University of
Hyderabad, Gachibowli, Hyderabad 500046, India; and Tata N. Rao
and R. Vijay, International Advanced Research Centre for Powder
Metallurgy and New Materials (ARCI), Balapur, Hyderabad 500005,
India. Contact e-mail: vijay@arci.res.in.
dispersion and consolidation methods. Different processing
methods, namely mechanical alloying/milling, metal infiltra-
tion, thermal spraying, sandwich processing, friction welding,
nanoscale dispersion methods, have been employed to produce
CNT-reinforced Al and its alloy composites. Among these,
mechanical milling followed by consolidation was favored due
to its solid state mixing, lower processing temperature and ease
of dispersion of CNT uniformly throughout the matrix (Ref 7-
12). Proper selection of consolidation technique is also an
important factor for enhanced strength levels of Al-CNT
composites because of the induced deformation during consol-
idation helps in the distribution and disentanglement of any
agglomerated CNT. Techniques that are being used for
consolidation of Al-CNT composites are hot rolling (Ref 7),
spark plasma sintering (SPS) (Ref 9), hot extrusion (Ref 10),
microwave sintering (Ref 15), hot isostatic pressing (HIP) (Ref
15), cold isostatic pressing (Ref 16), hot pressing (Ref 25), and
among these hot extrusion is selected for this study. It is
expected that the induced deformation during hot extrusion
promotes uniform dispersion of CNT, which helps to transfer
the load from Al matrix to CNT, thereby enhancing the strength
(Ref 26).
Yufeng et al. (Ref 13) synthesized 1 wt.% CNT-reinforced
Al6061 (Al-1 Mg-0.52Si-0.28Cu-0.27Fe) composites by semi-
solid processing of milled powders and reported that hardness
of Al6061-CNT composite increased by 28%. Age hardening
behavior of Al6063 (Al-0.85 Mg-0.2Si-0.19Cu-0.13Fe-
0.18Mn), Al6063 +CNT and Al6063 + Cu-coated CNTs pro-
cessed by high-energy ball milling and consolidation by
compaction and vacuum sintering at 560 C was studied by
Kashyap et al. (Ref 14). It has been found that the peak
hardening time decreased with CNT content. Cu-coated CNT-
reinforced Al6063 composite showed higher hardness as
compared to uncoated ones. Al-Aqeeli (Ref 15) prepared Al-
7Si-0.5 Mg alloy reinforced with (0-2 wt.%) CNT by mechan-
ical milling and compared the effect of three consolidation
techniques viz., SPS, microwave sintering and HIP on mechan-

Journal of Materials Engineering and Performance

ical properties. Higher hardness and improved density were
observed in SPS processed sample when compared to other
techniques. This can be attributed to the processing conditions
such as high applied current with simultaneous application of
pressure, high heating and cooling rates. Moreover, the grain
coarsening was minimized due to the fast processing in SPS.
The porosity of these composites increased with CNT content
due to agglomeration of CNT at large volume fractions.
Al-Cu-Mg alloys in wrought conditions, designated as 2xxx
series, have been considered as light alloy structural materials
(Ref 18). These alloys are strengthened by fine precipitates of hÕ
(CuAl2) and/or SÕ (Al2CuMg) phases in addition to solid
solution strengthening. Deng et al. (Ref 16) studied atomized
Al 2024 (Al-4.2Cu-1.47 Mg-0.56Mn-0.4Fe-0.27Si) blended
with 0-2 wt.% CNT by mechanical stirring in an ultrasonic
shaker and consolidated by cold isostatic pressing followed by
hot extrusion. The ultimate tensile strength (UTS) of these
composites increased up to 1 wt.% CNT and decreased with a
further increase in CNT content. Choi et al. (Ref 17) produced
Al 2024 alloy-CNT composites by hot rolling of ultra-fine
grained pre-alloyed powder milled with CNT in an attritor. The
increased strength was attributed to a combination of grain
refinement and particulate strengthening by the precipitates and
CNT.
Even though much of the research dealt with reinforcement
with CNT in commercial pre-alloyed powder (Ref 13-17), the
work related to the mechanical milling of the elemental
powders blended with CNT is limited. The advantage of using
elemental powders is that any composition that is needed can be
produced by mechanical milling. The present study is aimed at
understanding the effect of CNT dispersion in Al-Cu-Mg alloy
prepared by high-energy milling of respective elemental
powders and CNT.
2. Experimental Procedure
Elemental powders of Al (water atomized powder with
average particle size: 150 lm, 99.5% purity, SKMP Ltd, India),
Cu (electrolytic powder with average particle size: 45 lm,
98.8% purity MEPCO Ltd, India), and Mg (electrolytic powder
with average particle size: 450 lm, 97% purity, MEPCO Ltd,
India) to produce Al-4.4Cu-0.5 Mg (Al alloy) were blended
with 0-2.5 wt.% multi-walled carbon nanotubes (CNT) (CVD
processed powder with diameter: 20-30 nm and length: 1 lm,
98% purity, Bayer Material Science, Germany) and milled in a
high-energy horizontal attrition mill (Simoloyer CM08, Ger-
many) at 700 rpm for 4 h under argon atmosphere using
methanol as process control agent (PCA). Morphologies of the
raw materials used in the current research are shown in Fig. 1.
Milling was carried out in stainless steel vial using hardened
steel balls of 5 mm diameter with a ball to powder weight ratio
of 15. The processed composite powders were filled in
aluminum cans, degassed at 300 C and subsequently vac-
uum-sealed by crimping at a pressure of 4 9 106 kPa. The
crimped cans were consolidated by upset forging at 450 C,
350 MPa followed by hot extrusion at 550 C, 510 MPa with
an extrusion ratio of 16. Extruded samples were solutionized at
490 C for 2 h and water-quenched. Aging heat treatment
temperature and time (150 C, 4 h) was selected based on
isochronal and isothermal studies, and all the samples were age-
hardened at these conditions. The morphologies of milled
powders were observed using scanning electron microscope
(SEM: S-3400 N Hitachi), and particle size was estimated from
SEM images using image analysis software (IMAGEJ). Phase
analysis was carried out using x-ray diffractometer (BrukerÕs
D8 advance AXS diffractometer) having Cu-Ka radiation with
a scan rate of 0.1/s. Crystallite size was determined from XRD
high-intense peak using Williamson-Hall method (Ref 19).
Raman spectroscopy was carried out using Ar ion laser
(514 nm) in HORIBA Jobin-YvonÕs LabRAM HR. XRD on
bulk Al alloy-CNT composites was performed using Smart Lab
Microfocus x-ray Diffractometer, Rigaku, using Cu target with
a step size of 0.05. Transmission electron microscopy (Tecnai
G20, 200 kV) was carried out on Al alloy-CNT composites in
aged condition. The hardness of bulk samples was measured
using Vickers hardness tester (Walter UHL, VMHT). Tensile
properties were determined using the Universal testing machine
(INSTRON, Model No: 4483) on bulk samples as per ASTM
E8 standard with a strain rate of 5.5 9 104 s1 at room
temperature.
3. Results and Discussion
3.1 Milled Powders
Scanning electron micrographs of milled powders of Al
alloy-(0-2.5 wt.%) CNT composites are shown in Fig. 2. The
powder particles of Al alloy are observed to be predominantly
spherical with a lamellar structure resulting from deformation
and cold welding. The average particle size of milled powders
estimated using image analysis software as a function of CNT
content is shown in Fig. 3. It is observed that the average
particle size of Al alloy-CNT composites for a given milling
time of 4 h decreased with CNT content and reached a near
steady state beyond 2.0 wt.% CNT. During mechanical milling,
the ductile Al alloy undergoes severe plastic deformation and
eventually fractures due to work hardening. The new surfaces
created during fracture undergo cold welding immediately (Ref
20). During initial stages of milling, cold welding of particles
dominates, resulting in an increase in particles size, and on
further milling fracture dominates, thereby reducing the
particles size. Eventually, both cold welding and fracture reach
an equilibrium which results in nearly constant particles size.
When PCA is added to the powders during milling, it retards
the cold welding. Even though methanol was used as PCA
during milling (the quantity of methanol is same for all the
samples), the presence of CNT to Al alloy powder also acted as
PCA in retarding the cold welding of particles. At lower CNT
content, particle coarsening dominates due to the welding of
particles as effectiveness of CNT as PCA is less. With an
increase in CNT content, the effectiveness of CNT as a PCA
increases, leading to the reduction in particles size due to
retardation of cold welding.
X-ray diffraction patterns of milled powders of Al alloy-CNT
composites are shown in Fig. 4. All the peaks indexed to Al only.
There are no distinct carbon peaks corresponding to CNT. This is
due to the limitation of XRD instrument that could not detect the
low concentrations of CNT. It was also observed that the peak
broadening increased with CNT content. The Al peaks in all the
composites exhibited a constant peak shift of 0.0733 (inset of
Fig. 4a), which is due to the solid solution of Cu and Mg in Al. As
the peak shift in Al alloy-CNT composites is similar to that of
base alloy, it is reasonable to infer that the CNT have not gone into
Journal of Materials Engineering and Performance
Fig. 1 Morphology of the powders used for the study: (a) aluminum, (b) copper, (c) magnesium and (d) carbon nanotubes

Fig. 2 SEM images of Al alloy-(x wt.%) CNT composite powders milled for 4 h: (a) x = 0 (b) x = 0.5 wt.% (c) x = 1.0 wt.% (d) x = 1.5
wt.% (e) x = 2.0 wt.% and (f) x = 2.5 wt.%

solid solution. Similar observation was also reported by Busta-
mante et al. (Ref 8). Variation of crystallite size of Al alloy-CNT
composite powders milled for constant milling time of 4 h with
CNT content is shown in Fig. 5. It can be seen that there is no
appreciable change in crystallite size due to the addition of CNT.
It is known that mechanical milling induces severe plastic
deformation to the powders creating high dislocation densities.
At large strains, these dislocations tend to rearrange themselves to
form cells (Ref 20). Since the crystallite size has not changed
significantly, it is clear that the presence of CNT does not have
any influence on dislocations generation and dynamic recovery in
the Al alloy matrix.
Raman spectroscopy is used to find out the existence of
CNT in the Al alloy matrix and the defects induced to CNT due
to mechanical milling. This can be found qualitatively by
analyzing the D-band (scattering due to defect densities), G-
band (scattering due to CNTÕs graphitic sp2 structure) and 2D-
bands (overtone of D and G-bands) from the Raman spectra of
respective sample (Ref 21). Raman spectra obtained from as-
received CNT and Al alloy-CNT composites are given in

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Fig. 3 Variation of particles size of Al alloy-CNT composite milled
powders with CNT content
Fig. 4 XRD patterns of milled powders of Al alloy-CNT composite
powders
Fig. 5 Variation of crystallite size of Al alloy-CNT composite
milled powders with CNT content
Fig. 6. The as-received CNT exhibited intense G and D-bands
along with low-intensity 2D-band which indicate the CNT are
not defect-free. Even though there is no Raman shift in D-band
of Al alloy-CNT composites when compared to as-received
CNT, there is a clear shift of G-band of Al alloy-CNT
composites to higher frequencies by 35.91 cm1 and the shift is
constant irrespective of CNT content. This is due to the residual
stresses induced to the CNT during high kinetic processing.
Since the quantity of CNT (0-2.5 wt.%) was low in the
composites, the G- and D-bands are less intense and 2D-band
intensity of Al alloy-CNT composites was not clearly observed.
Another important parameter to check the structural stability of
CNT after mechanical milling is the intensity ratio of D-band to
G-band (ID/IG). The calculated ID/IG values of CNT along with
that of Al alloy-CNT composites are tabulated in Table 1. There
is no appreciable difference in the intensity ratio of Al alloy-
CNT composites with that of as-received CNT. This indicates
that the nanocrystalline structure of CNT is retained even after
4 h of high-energy milling.
3.2 Bulk Samples
As Al-Cu-Mg alloy is a precipitation hardenable alloy,
understanding of the hardening behavior is necessary so that
the same age hardening treatment can be applied to Al alloy-CNT
composites. In order to optimize the age hardening treatment
parameters to obtain the peak-aged condition, isothermal and
isochronal experiments were conducted on samples solutionized
at 490 C. Isochronal aging treatments were carried out at
different temperatures from 50 to 250 C at a constant hold time
of 2 h. Variation of hardness as a function of aging temperature is
shown in Fig. 7(a). The hardness of the alloy increased first,
reached a maximum value of 140 HV at 150 C and then
decreased with further increase in temperature. It is known that
the second-phase particles, which precipitated during cooling of
samples after hot extrusion, dissolve into matrix forming a
supersaturated solid solution during solution treatment (Ref 22).
When the Al alloy is aged at a temperature higher than ambient
conditions, i.e., artificial aging, the Cu atoms diffuse faster than at
room temperature (natural aging) and form clusters called GP
zones, which are coherent with Al lattice. With aging temperature
and time, the metastable phase subsequently evolves to fine h’’
Fig. 6 Raman spectra of Al alloy-x wt.% CNT composite powders
(x = 0-2.5)
Journal of Materials Engineering and Performance
Table 1 ID/IG of Al alloy-CNT composites
Sl No. Sample ID/IG

1 As-received CNT 1.4

2 Al alloy-0.5% CNT 1.41
3 Al alloy-1.0% CNT 1.52
4 Al alloy-2.5% CNT 1.54
5 Al alloy-2.0% CNT 1.37
6 Al alloy-2.5% CNT 1.35

(two layers of Cu atoms separated by three layers of Al) and hÕ

(body-centered tetragonal CuAl2) phases and eventually to
equilibrium h (tetragonal CuAl2) phase (Ref 23). During aging,
the hardness of the material increases due to the coherent h’’ and
semi-coherent hÕ phases and finally decreases due to the
conversion to incoherent h phase particles which are coarser in
size. The isochronal experiment carried out for 2 h resulted in
peak age temperature of 150 C that corresponds to the optimum
temperature, at which coherent precipitates of the right size,
adequate number density and volume fraction are formed. At
temperatures below 150 C, the number density of coherent
precipitates is less. At temperatures beyond 150 C, the precip-
itates coarsen and become incoherent with the matrix. So,
isothermal aging treatments were carried out at 150 C for aging
times from 0 to 10 h. Variation of hardness as a function of aging
time is shown in Fig. 7(b). The peak value of hardness was
obtained after 4 h of aging treatment. The peak age temperature
and time obtained from isochronal and isothermal studies are
150 C and 4 h, respectively. The aging treatments on Al alloy-
CNT composites were also carried out at the above-mentioned
temperature and time.
X-ray diffraction patterns of Al alloy-CNT composites in as- Fig. 7 Variation of hardness of Al alloy with aging conditions: (a)
solutionized condition are compared with those of specimens in isochronal treatment for 2 h and (b) isothermal treatment at 150 C
peak-aged condition (Fig. 8). In addition to Al peaks, the
CuAl2 peaks are identified in all the samples in peak-aged
condition. This is because of the precipitation of CuAl2 phase
when the samples are aged at 150 C for 4 h. CuAl2 peaks of
very low intensity are also observed even in as-solutionized
condition of Al alloy. The presence of Al4C3 phase was
detected in Al alloys containing CNT only. During high-energy
milling, the outer walls of CNT could be damaged and also be
truncated. This resulted in the amorphization of CNT at the
damaged ends (Ref 38). The high-temperature treatment during
the consolidation of milled powders (upset forging at 450 C
and extrusion at 550 C) accelerated the formation of Al4C3 at
the Al alloy matrix-CNT interface. The formation of Al4C3
phase was reported by other researchers as well, supporting the
observations made in this study (Ref 8, 9, 39).
Transmission electron microscopy (TEM) analysis was
performed on peak-aged Al alloy and Al alloy-2.5 wt.% CNT
composites to evaluate the size and structure of precipitates and
morphology of CNT. TEM image of Al alloy is shown in
Fig. 9(a). The precipitates are platelet-shaped, and the size of
the precipitates is 2.89 ± 0.83 nm in width and
12.32 ± 5.66 nm in length. The selected area diffraction pattern
(inset of Fig. 9(a)) indicated that the precipitates are of CuAl2. Fig. 8 XRD patterns of bulk Al alloy-(0.0, 1.5 and 2.5) wt.% CNT
The width and length distributions of precipitates are shown in composites in as-solutionized (S) and peak-aged (PA) conditions
Fig. 9(b) and (c), respectively. There is no evidence of the
precipitation of Al2CuMg phase. In the case of Al alloy-CNT
composites, in addition to precipitates, CNT were distributed The variation of the hardness of Al alloy-CNT composites in
uniformly and embedded firmly in the matrix (Fig. 10). No as-solutionized and peak-aged conditions with CNT content is
agglomeration of CNT was observed. shown in Fig. 11. The hardness of the samples in both

Journal of Materials Engineering and Performance

conditions increased with CNT content. All Al alloy-CNT
composites showed superior hardness than the Al alloy, and the
hardness of Al alloy-2.5wt.% CNT composites increased by 43
and 32% in as-solutionized and peak-aged conditions, respec-
tively, when compared to Al alloy. The increase in hardness in
composite materials with CNT content is due to increased
volume fractions of CNT in the matrix that resulted in increased
number of obstacles to dislocations motion. The difference in
hardness between as-solutionized and peak-aged conditions
maintained nearly the same with CNT content. It was reported
that yield and ultimate tensile strengths of Al-CNT composites
decreased at higher CNT content ( ‡ 1.5 wt.%) (Ref 7, 16, 24).
This is attributable to improper CNT dispersion resulting in
agglomeration of CNT at higher CNT content. But in the
present study, the hardness continued to increase even up to 2.5
wt.%, owing to the high-energy milling which evidently
Fig. 9 (a) TEM image of peak-aged samples of Al alloy with SAD patterns indicating CuAl2 precipitates, size distribution of precipitates: (b)
width and (c) length
resulted in a more homogenous dispersion of CNT in the
matrix. So the higher strength of the composites can be
attributed to (a) peak age hardening due to the formation of
metastable precipitates, (b) dispersion strengthening with the
uniform dispersion of CNTs in the Al alloy matrix accom-
plished by high-energy mechanical milling and (c) grain
boundary strengthening due to the presence of ultra-fine grains.
Engineering stress-strain curves of Al alloy-CNT compos-
ites at room temperature in solutionized as well as peak-aged
conditions are shown in Fig. 12(a) and (b). All Al alloy-CNT
composites showed distinctly different deformation behavior
when compared to Al alloy in both the conditions. The tensile
curves indicated that with the increase in CNT content (a) flow
stress increased and fracture strain decreased, (b) the work
hardening rate increased at low strains and decreased at high
strains and (c) the strain at which the flow stress dropped and
Journal of Materials Engineering and Performance
Fig. 10 TEM image of peak-aged samples of Al alloy-2.5 wt.%
composite
Fig. 11 Variation of hardness of Al alloy-CNT composites in as-so-
lutionized and peak-aged conditions
the magnitude of drop increased. Since the grain size in all the
materials is extremely fine (averaged about £ 336 nm), it is
clear that the increasing work hardening rate at low strains is
due to a large increase in the density of geometrically necessary
dislocations. The drop and a continued decrease in flow stress
at large strains are caused by strain softening. The strain
softening is considered to be due to the dominance of
annihilation of statistically stored dislocations over the dislo-
cation density at large strains. The annihilation of statistically
stored dislocations is promoted by ultra-fine grain structure
(Ref 30). The strain softening has been observed in other Al
alloy systems as well (i.e., Al7075, Al5083) (Ref 27-29). The
increase in strain with CNT content at which the drop in flow
stress occurred is due to the presence of higher number density
Journal of Materials Engineering and Performance
Fig. 12 Engineering stress-strain curves of Al alloy- CNT compos-
ites at room temperature: (a) as-solutionized condition and (b) peak-
aged condition
of CNT in the composites which seemed to be effective
obstacles for the movement of statistically stored dislocations.
The extent of the flow stress drop appeared to be related to the
ease with which the dislocations bypass the obstacles and get
annihilated at the nearest grain boundaries. The tensile behavior
of Al alloy-CNT composites in peak-aged condition is similar
to that of samples in solutionized condition.
Variation of yield and ultimate tensile strengths with CNT
contents is shown in Fig. 13(a) and (b). It is evident that the
samples with CNT exhibited superior strength than Al alloy.
Yield and ultimate tensile strengths of Al alloy-CNT compos-
ites in solutionized condition increased from 339 MPa (Al
alloy-without CNT) to 530 MPa (Al alloy-2.5 wt.% CNT
composite) and from 370 to 640 MPa, respectively. The
improvement in strengths (56% in yield strength and 73% in
ultimate tensile strength) is due to the reinforcement effect of
CNT. It can be seen that the strength exhibited by Al alloy-CNT
composites in the present study is higher when compared to the
work carried out by others (Ref 7, 8, 10, 16).
The strength of Al alloy-CNT composites is quantified by
considering the contributions made by solid solution strength-
ening, grain boundary strengthening, fine second-phase pre-
cipitate strengthening and dispersion strengthening by CNT.

Fig. 13 Variation of strength values of Al alloy-CNT composites:
(a) yield strength and (b) ultimate tensile strength
Thus, the yield strength of Al alloy-CNT composites can be
written as:
ry ¼ rm þ DrHP þ Drss þ Drppt þ DrCNT ðEq 1Þ
where ry is the yield strength, rm is the matrix strength of
Al, DrH-P is the Hall-Petch strengthening due to grain refine-
ment, Drss is the strengthening by solid solution, Drppt is the
fine second-phase precipitate strengthening and DrCNT is
strengthening by CNT dispersion.
The matrix strength (rm) was determined using the exper-
imental value of yield strength of Al alloy (without CNT) in as-
solutionized condition so that DrCNT is zero. And the
contribution made by precipitates (Drppt) in as-solutionized
condition is assumed to be negligible, because of the absence of
fine nanoscale CuAl2 precipitates after solutionizing and the
negligible contribution to the strength by the presence of
coarser undissolved CuAl2 (h) precipitates (420 nm). Based
on the above assumptions, Eq 1 can be rewritten as:
ryðsolÞ ¼ rm þ DrHP þ Drss ðEq 2Þ
where ry(sol) is the experimental yield strength in as-solution-
ized condition. DrH-P and Drss are estimated using equations
(Ref 31-34) given below:
DrHP ¼ ky d 1=2 ðEq 3Þ
Drss ¼ MGbe2=3
ss c
1=2
ðEq 4Þ
where ky is the Hall-Petch coefficient which is 0.13 MPam
(Ref 17, 35), d is the grain size, M is the mean orientation
factor, G is the shear modulus, b is the BurgerÕs vector, ess is
the lattice strain due to solid solution formation, and c is the
atomic fraction of solute atoms.
The bright- and dark-field TEM images along with the
matrix of grain size distribution of Al alloy-CNT composites in
as-solutionized condition are shown in Fig. 14. The average
grain size for Al alloy, Al alloy-1.5 wt.% CNT and Al alloy-2.5
wt.% CNT composites measured from TEM dark-field images
using image analysis software is 336, 225 and 193 nm,
respectively. It is observed that the matrix grain size of Al
alloy-CNT composites decreased with CNT content. The
presence of CNT at the grain boundaries retarded the grain
growth when exposed to higher temperatures during consoli-
dation (Ref 40). The calculated grain size-dependent strength
(DrH-P) using Eq 3 for the aforementioned samples is 224.3,
274.1 and 295.9 MPa, respectively. In the case of solid solution
strengthening, it is reported that the contribution to strength due
to the solid solution is 13.8 and 18.6 MPa per unit wt.% of Cu
and Mg, respectively (Ref 36). It is also considered that the
strength contribution due to solid solution follows a linear
relationship with concentration (Ref 27, 37). Even though the
concentration of Cu in the present study is 4.4 wt.%, the
microstructural examination followed by image analysis indi-
cated that 0.72 wt.% of Cu remained undissolved as coarse
CuAl2 particles and only 3.68 wt.% of Cu contributed to the
strength in as-solutionized condition. SEM image of Al alloy in
as-solutionized condition is shown in Fig. 15. The bright spots
are identified as undissolved CuAl2 particles. The weight
fraction of undissolved Cu corresponding to that of CuAl2
particles is estimated and is provided in Table 2. The strength
contribution due to solid solution (Drss) of Cu and Mg is
calculated to be 60.1 MPa. The matrix strength (rm) of Al alloy
is estimated using Eq 2 by subtracting DrH-P and Drss from
experimental yield strength (ry(sol)) and is 69.1 MPa. The
strength contribution due to the solid solution is assumed to be
constant for all Al alloy-CNT composites. The contribution to
strength by CNT (DrCNT) is calculated to be 58.9 and
109.5 MPa for 1.5 and 2.5 wt.% CNT, respectively.
The higher strength of Al alloy-CNT composites in peak-aged
condition is due to the presence of fine second-phase CuAl2
precipitates. Since there is no evidence of Al2CuMg precipitates, it
is reasonable to state that Mg is in solid solution and its
contribution to strength (Drss(Mg)) is 9.3 MPa. It is also observed
that the grain size remained unchanged after peak aging (150 C,
4 h). Therefore, the same rm and DrH-P values in solutionized
condition are used in peak-aged condition as well. So, the
strengthening contribution by fine precipitates (Drppt) is given by:


Drppt ¼ ryðageÞ  rm þ DrHP þ DrssðMgÞ ðEq 5Þ
where ry(age) is the experimental value of yield strength in
peak-aged condition. By using Eq 5, Drppt of Al alloy is esti-
mated to be 105.1 MPa. By following the same method,
Drppt of Al alloy-1.5 wt.% CNT and Al alloy-2.5 wt.% CNT
composites is found to be 98.5 and 94.1 MPa, respectively.
The relative contributions to the yield strength of Al alloy-
CNT composites (in peak-aged condition) by different mecha-
nisms are shown in Fig. 16.
Journal of Materials Engineering and Performance
Fig. 14 Bright- and dark-field TEM images along with matrix grain size distribution of bulk samples: (a), (b) and (c) Al alloy, (d), (e) and (f)
Al alloy-1.5 wt.% CNT composite and (g), (h) and (i) Al alloy-2.5 wt.% CNT composite

Variation of YoungÕs modulus and percentage elongation

with CNT content in as-solutionized and peak-aged conditions
is shown in Fig. 17(a) and (b). The YoungÕs modulus of all the
samples in as-solutionized conditions is constant and is about
75 GPa, whereas it slightly increased with CNT content in
peak-aged samples reaching a maximum value of 81 GPa at 2.5
wt.% CNT. YoungÕs modulus depends on the orientation of
CNT with respect to the loading direction. The variation of
YoungÕs modulus of Al-CNT composites will be high if CNTs
are positioned parallel to the loading direction, and it will be
low if CNT are aligned perpendicular to loading direction (Ref
26). A random orientation will give a medium value. Mechan-
ical milling and hot extrusion employed in the present study
might have aligned CNT to random orientation, and the
orientation of CNT did not change with solution treatment and
age hardening processes. Further study is needed to understand
the variation of YoungÕs modulus with CNT content in peak- Fig. 15 Al alloy in as-solutionized condition. Bright spots are iden-
aged condition. Even though the ductility of Al alloy-CNT tified as undissolved CuAl2 particles

Journal of Materials Engineering and Performance

Table 2 Estimation of undissolved Cu in as-solutionized Al alloy
No. of Average size, Volume percent of undissolved Weight percent of
Sample particles lm CuAl2 particles, % undissolved Cu, %

Al alloy solutionized at 500 C 742 0.42 0.86 0.72

Fig. 16 Contribution of various mechanisms to yield strength of Al

alloy-CNT composites in peak-aged condition

composites in as-solutionized and peak-aged conditions

decreased with CNT content, it is still within the accept-
able limit (>2% elongation) for many applications. This
reduction in ductility may be attributed to the increased void
nucleation sites with CNT content, which resulted in decreased
fracture strain.

4. Conclusions
Al alloy-x wt.% CNT (x: 0-2.5) composites were prepared
by high-energy ball milling and consolidated by upset forging
followed by hot extrusion. The conclusions made from the
study are given below:
1. Average particle size of milled powders decreased with
CNT content due to the retarded cold welding by the
presence of CNTs in the Al alloy.
2. There is no effect of CNT on crystallite size of milled
powders.
3. Nanocrystalline structure of CNT is retained in milled
powders of Al alloy-CNT composites even after high ki-
netic processing.
4. TEM analysis indicated that Al alloy-CNT composites
were strengthened by ultra-fine grains, fine CuAl2 precip-
itates, and uniform dispersion of CNT, which helps in the
effective load transfer from matrix to reinforcement.
5. The hardness of Al alloy-CNT composites increased with
CNT content and Al alloy-2.5 wt.% CNT exhibited 43
and 32% enhancement when compared to Al alloy in
Fig. 17 Variation of (a) YoungÕs modulus and (b) percentage elon-
gation with CNT content
solutionized and peak-aged conditions, respectively.
6. Both yield and ultimate tensile strengths of 590 and
677 MPa, respectively, are achieved with the addition of
2.5 wt.% CNTs to Al alloy in peak-aged condition.
7. The individual contributions to the strength of Al alloy-
CNT composites were evaluated.
Acknowledgments
Authors thank Nanomission, Department of Science and
Technology, Government of India for funding (No: SR/NM/NS-
102011G) the work. They express sincere thanks to Dr. A.V. Reddy
for his valuable suggestions and inputs. The help rendered by Mr.
Y. Sumanth, Mr. G.V.R. Reddy, Dr. B.V. Sarada, Dr. Joydip

Journal of Materials Engineering and Performance

Joardar, Mr. Ramesh Reddy, Dr. K. Satya Prasad and Mr. M. Rama
Krishna in carrying out this research work is acknowledged.
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