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Mechanical strength of carbon nanotubenickel nanocomposites

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2007 Nanotechnology 18 505704
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IOP PUBLISHING

NANOTECHNOLOGY

Nanotechnology 18 (2007) 505704 (6pp)

doi:10.1088/0957-4484/18/50/505704

Mechanical strength of carbon

nanotubenickel nanocomposites
Ying Sun, Jianren Sun, Miao Liu and Quanfang Chen
MEMS and Nanomaterials Lab, Mechanical, Materials and Aerospace Engineering
Department, University of Central Florida, Orlando, FL 32816-2450, USA
E-mail: qchen@mail.ucf.edu

Received 10 August 2007, in final form 17 October 2007

Published 20 November 2007
Online at stacks.iop.org/Nano/18/505704
Abstract
Carbon nanotubes (CNTs), including single-walled CNT (SWCNT) and
multi-walled CNT (MWCNT), have been regarded as the stiffest and
strongest materials ever developed and are promising reinforcement fillers for
developing nanocomposites. However, the scientific community has been
puzzled about the reinforcement efficiency. Here we report CNT-reinforced
nickel nanocomposites fabricated with an innovative electrochemical
co-deposition process for achieving good interfacial bonding between CNT
and metallic matrices. Test results show that Ni/SWCNT composite produces
a tensile strength as high as 2 GPa, which is more than three times stronger
than that of pure nickel. The mechanical strength of Ni/CNT nanocomposites
is dependent on CNT addition, while the fracture strain remains similar or
better than that of pure nickel. The good reinforcement of CNT/metal
nanocomposites is attributed to the good interfacial bonding as well as the
stiffer matrix nature.
(Some figures in this article are in colour only in the electronic version)

Since their discovery in the early 1990s [1], carbon nanotubes

(CNTs), including single-walled CNT (SWCNT) and multiwalled CNT (MWCNT), have been regarded as the stiffest
and strongest materials ever developed, mainly owing to the
perfect atomic arrangement and intrinsically strong in-plane
sp2 sp2 covalent bonding between carbon atoms. For example,
CNTs have a high Youngs modulus (1.01.8 TPa), high tensile
strength (30200 GPa) and high elongation at break (10
30%) [28]. In addition, CNTs have an extremely small size
(about 110 nm in diameter), high aspect ratio (>1000), high
structural and chemical stability, and remarkable electrical,
thermal and optical properties [9]. All these properties
make CNTs promising candidates as reinforcement fillers for
developing nanocomposites.
Most current studies on CNT-reinforced nanocomposite
have been focused on polymer base, including PMMA [10, 11]
and various types of epoxy resins [12, 13], and aim to replace
conventional carbon fiber with stronger CNTs to make polymer
composites stronger. However, the reinforcement efficiency
accomplished so far is not as good as predictions [314]
made with theoretical models including the law of mixture.
The under-accomplished reinforcement efficiency also occurs
0957-4484/07/505704+06$30.00

for CNT-reinforced ceramic nanocomposite [15, 16] as well

as for metallic nanocomposites [1719]. Various possible
reasons have been suggested to account for this underaccomplishment, including that: (1) carbon nanotubes do
not have good wetting on matrix materials and, therefore,
the interfacial bonding between a CNT and the matrix is
weak [2022]; (2) a soft matrix (polymer) could not prevent
robust CNTs from withdrawing [20, 22]; (3) the waviness of
CNTs in the composite limits their load bearing ability, as
predicted in their axial direction [23, 24]; (4) CNTs degrade
in ceramic and metallic composites due to high-temperature
sintering [17, 25, 26]. However, there seem to be no such
severe problems encountered in conventional carbon-fiber
reinforced composites. Therefore, there must be some unique
issues associated with CNT-reinforced composites.
The major apparent differences between CNTs and
conventional carbon fibers are the dimensions.
First,
conventional carbon fiber has a larger diameter, in a range
of a few micrometers to a few tens of micrometers. CNTs
have a diameter that is much smaller, in the range of one
to a couple of tens nanometers, or about a thousand times
smaller. Second, conventional carbon fibers can be made
1

2007 IOP Publishing Ltd Printed in the UK

Nanotechnology 18 (2007) 505704

Y Sun et al

Figure 1. Sketch of long carbon fiber reinforced composite (A) and short carbon nanotube reinforced composite (B) under tensile pressure.
Potential cracks in the matrix and the separation between the CNT and the matrix are sketched in (C).

infinitely long and CNTs are much shorter, in the range of a

few micrometers or down to the sub-micrometer range. As
a result, conventional carbon fibers are continuous within a
matrix, so each fiber fully supports the load that is applied. In
other words, conventional fibers can bear most of the applied
load and the deformation of the matrix is constrained within the
deformation range of the fibers (figure 1(A)), if a large volume
fraction is used. In contrast, CNTs are tiny short carbon fibers
that are trapped discontinuously within a matrix and load is
transferred indirectly to CNTs via the matrix, as sketched in
figure 1(B).
If a stress applied in the axial direction is denoted as ,
then the displacements of the CNT and the matrix within the
same length L CNT (figure 1(B)) are

L CNT = CNT L CNT = /E CNT L CNT

(1)

L M = M L CNT = /E M L CNT .

(2)

Table 1. Basic composition of the electrolyte for Ni deposition.

Nickel sulfate Boric acid Nickel chloride SDS
1

315 g l

35 g l

25 g l

Saccharine
1

0.1 g l

0.1 g l1

composites include powder sintering [19, 25, 26] and

electroless deposition plating [17, 18]. However, the powder
metallurgy may experience some difficulties in fabricating
CNT/metal composites, since the inevitable sintering at
elevated temperatures may degrade the properties of CNTs,
especially when a single-layered SWCNT is used. On the
other hands, it is difficult to fabricate a dense CNT/metallic
composite using the electroless deposition method.
In the present work, we report pulse-reverse controlled
electrochemical co-deposition of CNT-reinforced metallic
(Ni) nanocomposites. Electrochemical co-deposition has
been developed that eliminates unexpected influences on
composite properties during the fabrication process. First,
electrochemical deposition is a low-temperature process (at
about room temperature) so no diffusion or chemical reaction
is allowed between the CNT and the metallic matrix, and thus
the inherent properties of both the CNT and the matrix can
be preserved. Second, during the electroplating co-deposition
process, metallic ions and CNTs are driven towards the cathode
and deposit onto the cathode simultaneously. Since metallic
deposition on CNTs is an atomic-level process that involves
electron transport from cathode to metallic ions via CNTs, an
intimate bonding between the CNT and the metallic matrix
can be achieved. Moreover, the simultaneous co-deposition of
CNTs and metallic ions ensures the homogeneous dispersion
of CNTs within the metallic matrix.
The electrolyte for nickel electrochemical deposition was
a modified Watt bath solution, as shown in table 1. The
electrolyte for Ni/CNT is similar to that of table 1 but
mixed with CNTs. Purified SWCNTs and MWCNTs were
purchased from Nanostructured & Amorphous Materials Inc.
The diameter is about 12 nm for SWCNTs and 815 nm
for MWCNTs, respectively. The length is about 500 nm.
Carbon nanotubes were dispersed in deionized (DI) water
first, and an ultrasonic bath was used to break up nanotube
aggregates. Then the uniformly dispersed solutions were added
into the electrolyte with a concentration of 0.015 g/100 ml
and ultrasonic agitation was used to disperse it further for
20 min. The solutions could stay for about 2 h without visible
aggregation. A direct current (dc) density of 10 mA cm2 was
carried to deposit Ni/CNT nanocomposite. A scanning electron
microscopy (SEM) picture of deposited NiCNT is shown in
figure 2(A). This indicates that nickel nucleates and grows on
a CNT surface simultaneously. As the deposition continues,
nickel continues to grow to cover a CNT entirely in the axial

Therefore, the ratio of relative displacements between the

matrix and the CNT is

L M /L CNT = E CNT /E M  1.

(3)

Since Youngs modulus of a polymer matrix is very small

(about a few GPa) compared to a carbon nanotubes Youngs
modulus (about 1000 GPa), the difference in deformation
between the matrix and the CNT from equation (3) will be
about a few hundred times. For example, if the E M is
5 GPa (polymer) and E CNT is 1000 GPa, then the deformation
difference is 200 times! The consequence of the large
deformation difference is that the matrix surrounding the
CNT experiences extremely large distortion and thus a large
strain energy. If the distortion is larger than that of the
elongation at break of the matrix, then fracture is likely to occur
(figure 1(C)). On the other hand, if the distortion associated
strain energy is larger than the interfacial bonding energy, then
the CNT will eventually be pulled out (figure 3(C)). This may
explain to some extent why CNTs normally do not produce
higher strength in polymer-based composites. On the other
hand, if the difference in Youngs modulus between the matrix
and the CNT is small, then there should be less strain energy
produced. Therefore, for short CNT-reinforced composites, in
addition to the interfacial bonding, there may also be a stiffness
match related issue that needs to be addressed.
A metallic matrix may be well matched to CNTs, since
metals have a much larger stiffness than polymer counterparts
and a moderate elongation at break, as well as better interfacial
bonding if appropriate fabrication methods are used. The
CNT-reinforced metallic composite is still a new subject;
only a small number of studies have been reported to
date [1719, 25, 26]. The methods for fabricating CNT/metal
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Nanotechnology 18 (2007) 505704

Y Sun et al

Figure 2. Pictured: (A) dc electroplated Ni-covered CNTs; (B) morphology of pure nickel deposited using the pulse-reverse method;
(C) surface morphology of Ni/CNT composite fabricated using the pulse-reverse method.

SU-8 mold
Fracture on a specimen

Figure 3. (A) SEM picture of SU-8 mold (portion), (B) microscopic

picture of fractured sample (Ni/CNT, 0.4 mm 4 mm) after tensile
test.
Figure 4. Stressstrain of nickel, Ni/MWCNT and Ni/SWCNT
composites.

direction (figure 2(A)), as well as to thicken in the transverse

direction. However, the protruding Ni-covered CNTs are closer
to the anode, thus the nickel growing on CNTs is accelerated
due to the greater electric field. As a result, the density and the
surface roughness remain issues to be overcome.
A pulse-reverse electrochemical deposition process has
been developed to attempt to achieve uniform deposition of
the Ni/CNT nanocomposite. The pulse-reverse controlled
deposition was carried out galvanostatically using cathodic
square wave pulse signals periodically for both forward and
reverse (switching polarization from the cathode to the anode).
What happened was that a positive signal would deposit
nickel on the cathode while the reversed negative signal would
dissolve (trim) nickel off the top of protrusions, thus uniform
deposition can be achieved. A forward time period of 5 ms
and a reverse time period of 1ms were selected experimentally.
Both the forward and reverse peak current densities were
10 mA cm2 . The pH value of the electrolyte was adjusted
to 3.5, and the temperature was maintained at 60 C. The
resultant pure nickel fabricated using pulse-reverse deposition
is uniform on a surface, as shown in figure 2(B). The fabricated
Ni/CNT composite (figure 2(C)) indicates that the interspaces between deposited nickel covered CNT protrusions
(figure 2(A)) are filled completely with nickel (figure 2(C)),
thus a smooth surface has been formed. Similarly, Cu/CNT
composites were fabricated using a similar method.
The mechanical test sample was a dog-bone shape with
dimensions of 400 m in width and 4 mm in length. The samples were fabricated using a micro-electroforming method
a UV-LIGA (ultraviolet lithographie, galvanoformung and abformtechnik) process in which photolithography patterned micro SU-8 molds (figure 3(A)) were filled with deposited metals (Ni and Cu) and their composites. The fabrication pro-

cess started by evaporating a thin layer of copper on a silicon wafer as a seed layer. SU-8 photoresist was spin coated
and patterned to form micro-modes to define the dog-boneshaped samples. The thickness of the SU-8 mold was 100 m.
Both metals (Ni and Cu) and their composites (Ni/CNT and
Cu/CNT) were deposited into SU-8 molds using the abovementioned electrochemical deposition technique. The thickness was about 3040 m, as monitored by time control and
verified by SEM characterization. After deposition, the SU8 mold was removed by using a SU-8 remover and test samples were obtained after separation from the wafer substrate.
Tensile tests were performed using a Tytron 250 Microforce
Tester System (MTS, USA) under a constant loading rate of
10 N min1 .
The tensile strength tested sample was examined under a
microscope (figure 3(B)). This indicated that fracture did occur
within the gage length of the sample. The fracture propagates
at about 45 to the axial direction. These characteristics ensure
that the test is reliable, due to the fact that the ratio of gage
length to width is large (10:1).
Both the applied force and the resulting sample
deformation (displacement) were recorded automatically and
the engineering stress and strain were derived accordingly.
All samples, including pure metal (Ni) and the composites
(Ni/CNT), were deposited under the same conditions for the
purposes of comparison. The tested stressstrain curves of pure
nickel, MWCNT-reinforced nickel composite (Ni/MWCNT),
as well as SWCNT-reinforced nickel composite (Ni/SWCNT)
are represented in figure 4. The yield strength and the ultimate
strength of the as-deposited pure nickel were found to be
350 MPa and 625 MPa, respectively, which are comparable
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Nanotechnology 18 (2007) 505704

Y Sun et al

Nickel

Carbon

the bonding condition as well as the portion embedded in the

matrix. No rupture of CNTs can be identified, even though up
to 150 nm of the CNT pulled out. The average length of CNT
that pulled out is about 100 nm. Since the average length of the
CNTs was about 500 nm, therefore the embedded CNT length
is about 400 nm. This explains that a shorter embedded CNT
end has a smaller bonding energy, thus it is easily separated
from the matrix (figure 1(C)). Also, from figure 5(A) we can
learn that the CNTs were not well aligned, but fairly straight.
A high-resolution TEM image of a protrusion is shown in
figure 5(B). About ten layers of graphene can clearly be seen
in the lower portion of the protrusion. The upper portion of the
covered crystal material is nickel. The carbon map indicated
in figure 5(C) shows clearly that the carbon distribution
coincided with the distribution of MWCNTs (figure 5(B)).
Figure 5(D) is a nickel map, which indicates that nickel atoms
are not present on the exposed MWCNTs portion (figure 5(B)).
Therefore, an MWCNT was pulled out partially from the
nickel matrix. However, figure 5(D) does show a gradually
changed nickel distribution on a MWCNT, the sticky nature
of nickel bonded on CNTs. These are different from what
was reported for polymer-based composites [1013], as well
as metallic composites fabricated with powder metallurgy
sintering [25, 26], where a clearly separated boundary between
the CNTs and the matrix was identified. Since a MWCNT
has multiple layers of graphene and the inter-layer bonding is
weak (van der Waals force), it is possible that the exterior layer
may separate from the inner layers if the exterior layers bind
well with the nickel matrix. However, this is not the case for
Ni/SWCNT. As a result, Ni/MWCNT behaves with a relatively
low strength compared to that of Ni/SWCNT but with greater
strain at fracture, due to the inter-layer deformation-induced
resilience.
The influence of CNT addition to Ni/CNT nanocomposite
was examined and the results are plotted in figure 6. MWCNTs
were used for the study due to them being cost effective.
Figure 6(A) shows that, as the addition of MWCNTs in
electrolyte increases, the resultant tensile strength is increased
in a polynomial pattern. This is due to the fact that the
addition of more MWCNTs in the electrolyte would result in
more trapped MWCNTs in the Ni/MWCNT composite. On
the other hand, fracture strength versus MWCNT addition in

Figure 5. (A) TEM image of the fracture morphology. (B) An

individual protrusion which MWCNT is clear seen. (C) Carbon map
of (B). (D) Nickel map of (B).

to the reported data [27]. However, the composites exhibit

significantly higher strengths than that of pure nickel. The
yield strength and ultimate strength of Ni/MWCNT composites
is about 1290 MPa and 1715 MPa, respectively. In other
words, the ultimate strength of Ni/MWCNT is 270% higher
than that of pure nickel. For the Ni/SWCNT composite, the
yield strength and the ultimate strength are 1692 MPa and
1997 MPa, respectively. Therefore, the ultimate strength of
Ni/SWCNT is about 320% greater than that of pure nickel.
Also, as shown in figure 4, the Ni/WMNT composite has a
larger strain (2.4%) at fracture than that of pure nickel (1.7%),
while the Ni/SWCNT has a smaller strain (1.2%).
The fracture morphology of the tested sample (figure 3(B))
was characterized using high-resolution transmission electron
microscopy (HR-TEM); see figure 5. Figure 5(A) indicates that
the fracture surface (side view) consists of anchored CNTs.
The nickel matrix hold the CNTs on one side, depending on

Figure 6. (A) Tensile strength of Ni/MWCNT versus MWCNT addition in electrolyte. (B) Fracture strain of Ni/MWCNT versus MWCNT
addition in electrolyte.

Nanotechnology 18 (2007) 505704

Y Sun et al

the electrolyte behaves differently (figure 6(B)). This indicates

that, for small MWCNT addition in the electrolyte, the fracture
stain decreases (figure 6(B)) in comparison to that of pure
nickel. When MWCNT addition is larger than 90 mg l1 , the
fracture strain is similar or slightly greater than that of pure
nickel. The main difference between figures 4 and 6 is that the
CNT addition in figure 4 is greater.
In addition to Ni/CNT nanocomposites, we have also
tested Cu/CNT composites and the results show that
Cu/MWCNT produces a tensile strength of about 600 MPa,
or three times greater than that of the pure copper that was
tested. We attribute the difference in tensile strength between
Ni/CNT and Cu/CNT to the difference in stiffness between Ni
and Cu. Ni has a Youngs modulus of 207 GPa, while that
of copper is 110 GPa [27], or 1.88 times smaller than that
of nickel. Based on equation (3), the relative deformation
between Cu and CNT is much larger than that of Ni/CNT.
Therefore, Ni/CNT should produce at least 1.88 times smaller
relative deformation than that of Cu/CNT. The larger relative
deformation between Cu and CNT forms larger deformation
energy. If the accumulated deformation energy is larger than
the bonding energy between Cu and CNT, then the deformed
copper matrix will be the only load-bearing component and
fracture is suddenly inevitable. Since nickel is about two times
stiffer than copper, the tendency of accumulated strain energy
to reach the interfacial bonding energy between the nickel
matrix and the CNT is much smaller. From figure 6(A), for a
similar MWCNT addition the Ni/MWCNT produces a strength
of about 1300 MPa, which is about 2.1 times stronger that that
of Cu/MWCNT. Therefore the strength results agree well with
the stiffness difference. The extra is attributed to inherently
better interfacial bonding between the nickel and the carbon
nanotube [28].
Although Ni/CNT composite produces a strength as high
as 2 GPa, figure 5(B) shows that the fracture surface still
features partially pulled-out CNTs, and no broken CNTs can
be identified. Therefore, there is still some room for further
improvement in order to increase the strength by improving the
interfacial bonding strength. Future work will focus on surface
treatment of CNTs to increase interfacial bonding, as well as
studying alignment to increase the mechanical strength further.
As a summary, an innovative electrochemical codeposition method has been developed for fabricating uniform
and dense CNT/metal nanocomposites. A test method that
combines a microfabrication process and a microforce test
frame has been developed for characterizing the mechanical
strength of CNT/metal nanocomposites. Test results have
shown that the tensile strength of a CNT/Ni nanocomposite
is about 2 GPa, or more than a factor of three better than
that of pure metal. Meanwhile, the fracture strain of CNT/Ni
nanocomposites is similar to or better than that of pure nickel.
The strength of CNT/Ni nanocomposites is proportional to the
CNT addition. The good reinforcement of CNTs in metal
matrices is attributed to the good interfacial bonding as well
as to the stiffer nature of the matrices. In metal matrices, it is
difficult for CNTs to be deformed and pulled out of the matrix.

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Acknowledgment
This work was partially supported by the National Science
Foundation of USA.
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