CARBON 5 7 ( 2 0 1 3 ) 2 8 2 2 8 7

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Interface analysis of ultra-high strength carbon nanotube/

nickel composites processed by molecular level mixing

J.Y. Hwang a, B.K. Lim b, J. Tiley c, R. Banerjee d, S.H. Hong b,*

a
Carbon Convergence Materials Research Center, Korea Institute of Science and Technology, Jeonbuk 565-905, Republic of Korea
b
Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology, Daejeon 305-701, Republic of Korea
c
Materials and Manufacturing Directorate, Air Force Research Laboratory, Dayton, OH 45433, USA
d
Department of Materials Science and Engineering, University of North Texas, Denton, TX 76203, USA

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

Article history: Carbon nanotube (CNT) reinforced nickel matrix (CNT/Ni) composites exhibiting a yield
Received 8 July 2012 strength (YS) of 710 MPa, about 3.7 times higher than monolithic nickel, have been pro-
Accepted 4 January 2013 cessed by a molecular-level mixing process followed by spark plasma sintering (SPS). The
Available online 1 February 2013 enormous strength increase in these composites can be attributed to a homogeneous dis-
tribution of nanotubes in the nickel matrix coupled with the formation of well-bonded,
high strength, contaminant-free nanotube/nickel interfaces, as revealed by high-resolution
transmission electron microscopy. Such interfaces can effectively transfer load between
nanotubes and nickel matrix in the CNT/Ni composites.
2013 Published by Elsevier Ltd.

1. Introduction nanotubes in metal matrix composites processed via the

Carbon nanotubes (CNTs) have been used as a reinforcing
component in polymeric, metallic and ceramic matrices,
processed via a number of different routes [14]. Among
these composites, CNT/metal composites have attracted
considerable attention due to their attractive properties such
as high strength, enhanced thermal properties, low friction
coefficient and increased wear resistance [59]. However,
CNT/metal composites have not been widely investigated
due to several limitations such as poor inhomogeneous
dispersion of the CNTs, poor quality of the CNT/metal
interface, and difficulties in mass production [10,11]. There
are several papers focused on the critical understanding of
strengthening in CNT/metal composites [2,12,13]. Recently,
Bakshi et al. pointed out the strengthening mechanisms in
CNT/metal matrix composite, and discussed very significant
factors for high strength CNT/metal systems [2]. While
Cha et al. have reported a homogeneous distribution of
molecular level mixing process followed by SPS [6], the
interface between the metal matrix and the nanotube has
not been fully understood. Kim et al. have recently reported
that oxygen can significantly enhance the bonding across
the CNT/Cu interface and consequently enhance the YS,
based on results of X-ray spectroscopy and Fourier transform
infrared spectroscopy analysis [14,15]. This is important
considering the role of this interface in determining the
properties of such CNT/metal composites. Therefore, the
characterization of this interface at the highest possible
resolution is of prime importance but rather challenging.
The present work reports the processing and mechanical
properties of CNT/Ni composites, exhibiting an enormous
strength improvement while retaining reasonable ductility.
This investigation also focuses on a detailed structural
characterization of the CNT/Ni interface at high resolution
to determine the nature of this interface, formation of
intermediate reaction products, as well as the crystallo-

* Corresponding author: Fax: +82 63 219 8419.

E-mail address: shhong@kaist.ac.kr (S.H. Hong).
0008-6223/$ - see front matter 2013 Published by Elsevier Ltd.
http://dx.doi.org/10.1016/j.carbon.2013.01.075
 CARBON 5 7 (2 0 1 3) 2 8 228 7
graphic orientation relationship between the face-centered
cubic nickel and the carbon nanotubes.
2. Experimental
The CNT/Ni composite powders were fabricated via molecular
level mixing using multi-walled CNTs. Multi-walled CNTs,
produced by a chemical vapor deposition (CVD) process, with
an average diameter of about 10 nm and average length of a
few lm, were supplied by Hanhwa Nanotech Co., Ltd., S.
Korea. To fabricated CNT/Ni composite powders by molecular
level mixing process, the CNTs were purified and functional-
ized by using HF, acid solution mixture of H2SO4/HNO3. The
functionalized CNTs (diameter of 510 nm, length of
500 nm2 lm) were cleaned with distilled water and dried.
CNTNi precursor were prepared through a chemical reduc-
tion process, using hydrazine hydrate as reducing agent,
sodium hydroxide as oxidation agent and ethylene glycol as
solvent. The functionalized CNT were dispersed in ethylene
glycol solution by ultra-sonication and Ni(C2H3O2)24H2O
(Aldrich, 98% purity) was added in ethylene glycol. The CNT
solution was mixed with a Ni salt-solution and 2 M-NaOH
solution and hydrazine were injected into the mixed solution.
The mixed CNTNi solution was heated to 70 C and kept
30 min to complete CNT/Ni composite powder fabrication.
Fabricated CNT/Ni composite powers were separated from
remained chemicals and subsequently washed with ethanol
and dried. Finally, the reduction process of fabricated
CNT/Ni composite powders were performed in H2 + CO mixed
atmosphere for 2 hrs, at 400. The schematic steps of for
molecular level mixing process of CNT/Ni powders were pre-
sented in Fig. 1.
The volume fraction of CNTs was 6%. The CNT/Ni compos-
ite powders were pre-compacted in a graphite mold under a
pressure of 10 MPa. The pre-compacted powders were sin-
Fig. 1 Schematic diagram showing experimental steps for
molecular level mixing process of CNT/Ni powders.
283
tered by spark plasma sintering (SPS) at a temperature of
700 C for 1 min under vacuum (103 torr) employing a pres-
sure of 50 MPa. The heating rate was maintained at 100 C/
min.
Fig. 2 shows the microstructures of pure Ni powder and
CNT/Ni powder after molecular level mixing process. The
grain size of pure Ni powder is about 250 nm while CNT/Ni
powder has 150 nm grain size. The higher magnification im-
age taken from TEM observation was presented in inset in
Fig. 2b. The embedded CNT was marked with dotted circle
in the TEM microstructure. It was clearly observed in the Ni
particles. The diameter of pellet before machining for tensile
specimens was 23 mm with 1 mm thickness. The density of
the specimen was 98.9%, while the one of pure nickel was
98.2%. Dog-bone shaped sub-size specimens with gage length
of 9 mm and width of 2.5 mm based on the ASTM E8 M were
used for tensile test. Tensile tests were performed using an
INSTRON 5583 under a crosshead speed of 0.2 mm/min. The
tensile test was carried out under the 200 MPa pressure at
800 C.
Microstructural characterization with scanning electron
microscopy (SEM) was carried out using XL30FEG field emis-
sion SEM. Conventional and high-resolution transmission
electron microscopy (TEM) analysis was carried out using a
FEI TECNAI F20 field emission gun (FEG) TEM operating at
200 kV. TEM foils were prepared via jet-polishing techniques
and then ion milled using Gatan Duo Mill using 4 keV for
the further milling.
3. Results and discussion
The typical microstructures of the SPS processed pure Ni and
CNT/Ni composite obtained from TEM study are presented in
Fig. 3. The grain sizes after SPS process on the pure Ni and
CNT/Ni composites were 0.51 0.32 and 0.43 0.22 lm,
respectively. The CNT/Ni composite has slightly smaller grain
size compared to monolithic Ni.
Fig. 4a shows the true stressstrain curve of the CNT/Ni
composite, compared with monolithic Ni, produced by the
SPS process under similar conditions. The value of the yield
strength (YS), elastic modulus, and elongation for the samples
tested are given to Table 1. The YS of CNT/Ni composite, with
6 vol.% reinforcement, is 710 MPa, which is 3.7 times higher
than that of pure Ni fabricated by SPS process.
The overall microstructure, revealing the homogeneous
distribution of individual nanotubes within the nickel matrix,
is shown in the two bright-field TEM micrographs, Fig. 4b and
c. These two bright-field images have been acquired from two
different CNT/Ni TEM samples, prepared in different ways, to
achieve two different degrees of thinning. The low magnifica-
tion of the TEM image, shown in Fig. 4b, clearly shows that
CNTs are well dispersed in the Ni matrix and also appear to
be linked forming a network.
Interestingly, the stressstrain curve for the CNT/Ni com-
posite reveals three distinct regimes, which shows a different
behavior compared to the monolithic Ni counterpart. The
stressstrain curve shows a sharp increase (regime I) followed
by a slight decrease corresponding to regime II. The sharp
yield point observed in the case of the composite can be
284 CARBON 5 7 ( 2 0 1 3 ) 2 8 2 2 8 7

Fig. 2 (a) SEM images of pure Ni powders and (b) implanted CNTs in the Ni powders after molecular level mixing process. (c)
Higher magnification images obtained from TEM showing CNT in Ni powders and (d) its illustration.

attributed due to the homogenously distributed of CNTs in
the Ni matrix. Similar sharp yield points have been reported
in a number of CNT reinforced metal matrix composites such
as CNT/Cu, CNT/Al, and CNT/Mg [1517]. The addition of
6 vol.% of CNT results in 3.7 times increase of yield strength,
as compared to spark plasma sintered pure Ni, but there is
a compromise in terms of reduced ductility of the composite.
The drop of stressstrain curve corresponding to regime II is
possibly due to failure of CNTs at high strain prior to strain
hardening, but this needs to be further investigated. Despite,
the sub-micron grain size exhibited by this composite, as
shown in Fig. 3b and 4c, it is not possible to attribute the
experimentally observed enormous enhancement in strength
solely to grain size effects. From the grain size analysis, it is
hard to correlate with classical HallPetch equation to explain
the enormous increase of strength for the CNT/Ni composite.
Therefore, it is apparent that the strengthening in this
composite can be attributed primarily to the CNT
reinforcement in the Ni matrix. Furthermore, the interfacial
reaction should form during the molecular level mixing pro-
cess, which promote load transfer and improve the strength
in the composite. This phenomena is similarly observed and
discussed in other CNT/Al [2], CNT/Cu [14], and CNT/Mg
system [18].

Fig. 3 TEM bright field images of (a) pure Ni and (b) CNT/Ni composite processed by SPS sintering at 700 C.
 CARBON
Fig. 4 (a) Stressstrain curves of CNT/Ni composite and
pure Ni obtained from tensile test. Bright filed TEM images
of highlighted CNT region (b), and Ni matrix region (c) from
two different areas.
It is very important that the fracture surface of the tensile
sample to prove the distribution of CNTs in the powder.
Microstructure obtained the fracture surface shown in Fig. 5
revealed that CNTs were well distributed in the Ni grains.
5 7 (2 0 1 3) 2 8 228 7 285
Table 1 Mechanical properties of CNT/Ni composite and
pure Ni obtained from tensile test.
Y.S. (MPa) Elastic El. (%)
modulus (GPa)
Pure Ni 189 180 33.0
6 vol.% CNT/Ni 710 210 4.3
The dotted circles highlighted the CNTs clusters in Fig. 5a,
while the individual CNTs were indicated by arrows in Fig. 5b.
A more detailed analysis on the CNT/Ni interface is pre-
sented in Fig. 6. A relatively low magnification bright-field
TEM image is shown in Fig. 6a. The embedded CNTs within
the Ni matrix, are clearly visible in this relatively thin area
of the TEM sample. Fig. 6b and c show high-resolution TEM
images of an individual CNT embedded in the Ni matrix.
The CNT/Ni interface appears to be relatively sharp with an
abrupt transition from the lattice planes of FCC Ni to those
of the CNT, both of which are clearly visible in Fig. 6c.
A fast Fourier transform (FFT) equivalent to a local diffrac-
tion pattern of the high-resolution image is included as an in-
set in Fig. 6c. Fig. 6d shows a Fourier-filtered image of a
portion of the same interface as shown in Fig. 6c, viewed
along the h1 1 0i axis of FCC Ni region. From the FFT shown
as an inset in Fig. 6c, and the filtered image in Fig. 6d, the ori-
entation relationship between the CNT and Ni phases was
determined to be (0 0 0 2) planes of CNT parallel to (0 2 2)
planes of FCC Ni. The CNT/nickel interface plane appears to
be misoriented with respect to (0 0 0 2)CNT//(0 2 2)Ni planes
by a small angle of misorientation. Additionally, defects, pre-
sumably dislocations, are also clearly visible at the CNT/Ni
interface shown in Fig. 6d, marked with circles. These disloca-
tions are likely to be misfit dislocations and could potentially
aid in the strengthening process.
Interestingly, in case of some of the nanotubes reinforcing
the Ni matrix, nanocrystals of a second phase were observed
at the CNT/Ni interface, an example of which is shown in the
high-resolution TEM image in Fig. 7. These grains were typi-
cally less than 5 nm in size (see Fig. 7a). A higher magnifica-
tion image of one such nanocrystal is highlighted in Fig. 7b,
together with the corresponding Fourier-filtered image shown
as an inset. This nanocrystal exhibits a 2-fold symmetry that
appears to be a distorted form of the h0 1 1i zone axis of FCC
Ni. Interestingly, the structure of these nanocrystals appear
to be very similar to those reported previously in case of tem-
plated growth of nanocrystals on the surface of an aligned ar-
ray of CNTs by sputtering deposition of nickel.
Based on a combination of detailed high-resolution TEM
and atom probe tomography studies, the previous report
[19] identified these nanocrystals growing on the surface of
the CNTs, as the metastable hexagonal Ni3C phase. Interest-
ingly, with reference to the present observations, the filtered-
image shown as an inset in Fig. 7b shows a set of a and b
planes at an angle of 64, with the ratio between these inter-
planar spacings being a/b = 1.13, which can be consistently
indexed as the [1 2 13] zone axis of a hexagonal structure.
286 CARBON 5 7 ( 2 0 1 3 ) 2 8 2 2 8 7

Fig. 5 (a) SEM images showing the presence of CNT clusters in the fracture surface after tensile test, and (b) its higher
magnification image showing the individual CNTs.

Fig. 6 TEM images of (a) embedded CNT in the Ni matrix, (b) higher magnification of composite, (c) HRTEM images on the
CNT/Ni interface and its FFT in inset, and (d) Fourier-filtered image of the interface area.

Based on these results, we can conclude that these are likely
to be hexagonal Ni3C-type nanocrystals.
These nanocrystalline Ni grains were not homogeneously
distributed, but tend to occur near the defects at the CNT/Ni
interface (such as the ones shown in Fig. 6d). Thus, it appears
that these defect sites can act as potential heterogeneous
nucleation sites for the nanocrystalline Ni3C-type grains. Pre-
sumably, these defects could be generated during the function-
alizing of the nanotubes by acid treatment using the HF, and
H2SO4, and HNO3. Based on the observations presented in this
letter, it is likely that these defects potentially act as nucleation
sites for Ni3C-type nanocrystalline grains that form as a result
of a reaction between the CNT and the Ni matrix. Conse-
quently, a strong bond is formed between the matrix and nano-
tube resulting in enhanced mechanical properties, such as
high strength, of CNT/Ni composite.
 CARBON 5 7 (2 0 1 3) 2 8 228 7
Fig. 7 HRTEM images of (a) interface of CNT/Ni interface
showing the nanocrystals in the marked area, and (b)
highlighted region from one of the marked areas of interface
and its FFT image in inset.
4. Conclusions
We investigated the interface on the carbon nanotube/Ni
composites processed by molecular-level mixing process fol-
lowed by spark plasma sintering process by high resolution
transmission electron microscopy (HRTEM). The CNT/Ni com-
posites showed yield strength of 710 MPa, which was about
3.7 times higher than monolithic Ni fabricated by SPS process.
The CNT/Ni composite exhibited well distribution of CNTs
and good interfacial bonding which resulted in excellent
strengthening and evidence of effective load transferring via
CNT reinforcement in nickel matrix composite.
Acknowledgements
This work was financially supported by a grant (code
#:10K1501-00510) from Center for Nanostructured Materials
Technology under 21st Century Frontier R&D Programs of
the Ministry of Education, Science and Technology and the
Korea Institute of Science and Technology (KIST) Institutional
Program in Republic of Korea. It was also supported by a grant
(code No. FA2386-11-1-4008) from AOARD and partially
supported by U. S. Air Force Research Laboratory (AFRL ISES
Contract No. FA8650-08-C-5226).
287
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