Carbon 43 (2005) 1716–1721

www.elsevier.com/locate/carbon

The preparation of multi-walled carbon nanotubes with a

Ni–P coating by an electroless deposition process
Feng Wang a, Susumu Arai a,*
, Morinobu Endo b

a
Department of Chemistry and Material Engineering, Faculty of Engineering, Shinshu University,
4-17-1 Wakasato, Nagano-shi, Nagano 380-8553, Japan
b
Department of Electrical and Electronic Engineering, Faculty of Engineering, Shinshu University,
4-17-1 Wakasato, Nagano-shi, Nagano 380-8553, Japan

Received 26 November 2004; accepted 8 February 2005

Available online 13 March 2005

Abstract

The multi-walled carbon nanotubes (MWCNTs, mean diameter: 100–200 nm) with nickel–phosphorous (Ni–P) coatings were
obtained by an electroless deposition process. To prepare the MWCNTs covered with continual Ni–P layers, a pre-treatment pro-
cedure comprised of acid-cleaning, sensitization and activation has been developed. The resulting MWCNTs have a uniform distri-
bution of the Ni–P layers coated on the MWCNTs with the fibrous appearance maintained. X-ray diffraction (XRD) and
transmission electron microscopy (TEM) observations revealed that the as-coated MWCNTs were comprised of the amorphous
Ni–P layers and inner carbon nanotubes covered with the Ni–P layers. These amorphous Ni–P-coated MWCNTs were used as pre-
cursors for preparing MWCNTs with nanocrystalline Ni–P(crystalline Ni and Ni3P intermetallic compound) layers by the heat-
treatment above 400
C, which were determined by differential scanning calorimeter (DSC) and XRD studies. The results of this
work provide an effective electrochemical method for preparing powdery MWCNTs with Ni–P layer as new composite materials
from the aqueous solution.
 2005 Elsevier Ltd. All rights reserved.

Keywords: Carbon nanotube; Carbon/carbon composites; Coating; Electrochemical treatment; Microstructure

1. Introduction carbon nanotubes (MWCNTs) show promise as new

Carbon nanotubes (CNTs) are promising raw materi-
als for the industrial application due to their outstand-
ing physical and electrical properties such as high
tensile strength and high elastic modulus, high thermal
conductivity and electric conductivity [1,2]. Significant
interest has been recently focused on carbon nanotube
composites that enhance mechanical and electrical char-
acteristics more than those of the host materials. Partic-
ularly, metal composites incorporating multi-walled
*
Corresponding author. Tel.: +81 26 269 5413; fax: +81 26 269 5432.
E-mail addresses: wangf@gipwc.shinshu-u.ac.jp (F. Wang), arai-
sun@gipwc.shinshu-u.ac.jp (S. Arai).
CNT-composite materials exhibiting improved and un-
ique functionality. Concretely, metal-coated MWCNTs
increase surface active sites to improve weak interfacial
bonding between nanotubes and resins [3] with the
intrinsic properties of nanotubes maintained. As re-
ported previously [4–6], moreover, the MWCNTs with
metal coatings have significant potential for a fabrica-
tion of new powdery metal-MWCNT composites, thus
extending the application fields of MWCNTs.
Nickel–phosphorous (Ni–P) layers have been
adopted for an increasing number of CNT-applications
in the recent decade. Electroless deposition is an effective
approach for the preparation of the MWCNTs with Ni–
P layers. To form continual Ni–P layers firmly attached

0008-6223/$ - see front matter  2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2005.02.015
 F. Wang et al. / Carbon 43 (2005) 1716–1721 1717

on MWCNTs, it would be indispensable to increase the chemical method to prepare the powdery MWCNTs
catalyzation sites (which promote the electroless deposi- with metal layers.
tion) on the nanotube surface, and to improve the inter-
facial adhesion between MWCNTs and metal layers.
Therefore, an appropriate pre-treatment of MWCNTs 2. Experimental
is required prior to the electroless deposition process.
The pre-treated nanotubes are considered to undergo The MWCNTs used in the present study were synthe-
Ni–P layers more efficiently, when immersed to the plat- sized via catalyst-assisted chemical vapor deposition
ing bath containing metal source and reducing agent. (CVD) process (Showa Denko Co. Ltd.) [8]. They were
However, MWCNTs have a propensity to aggregate then heat-treated at 2800
C in an argon flow for 30 min.
into packed ropes or entangled networks due to strong Fig. 1 shows the pristine MWCNTs of 100–200 nm in
inter-tube van der Waals attraction, which hinders hom- diameter and of 20 lm in average length.
ogenously distribution of metal layers on individual The plating bath used contained 0.1 M NiSO4 Æ 6-
nanotubes. The present study has tried to develop an H2O, 0.2 M NaH2PO2 Æ H2O, 0.5 M C6H5Na3O7, and
optimum pre-treatment procedure for an ideal electro- 0.5 M (NH4)2SO4. All solutions were prepared using
less deposition, which makes Ni–P layers to be homo- deionized water and reagent grade chemicals.
geneously deposited on the surface of individual To impart the catalytic sites on the surface of
MWCNTs. Firstly, we conducted the cleaning and sur- MWCNTs for the electroless Ni–P deposition,
face modification of the pristine MWCNTs using con- MWCNTs need to be pre-treated through acid-cleaning
centrated nitric acid. Subsequently, sensitization and (purification and surface modification), sensitization
activation (so-called
two-step process) of the acid-trea- and activation. Fig. 2 shows the process sequence of
ted MWCNTs were carried out to endow the nanotube electroless Ni–P deposition on MWCNTs including
surface with the catalyzation effect promoting the subse- the pre-treatment. Firstly, MWCNTs were cleaned in
quent electroless Ni–P deposition. To prevent the aggre- 12.8 M concentrated HNO3 for 12 h, and washed thor-
gation of the treated MWCNTs in the aqueous oughly with deionized water. The cleaning process by
solutions, a cationic polymer was employed as a dispers- nitric acid eliminates the residual metal catalyst parti-
ing agent. cles from the MWCNTs as-prepared by the CVD
The Ni–P layers formed by electroless deposition can process [9], which prevents the side-effect originating
be identified as a metastable phase from the viewpoint of from the catalyst particles in the subsequent electroless
thermodynamics, which is converted into a more stable
crystalline phase by heat-treatment. As a significant
application of such thermodynamically metastable prop-
erties of amorphous alloys, a previous study has reported
a novel fabrication method of nanocrystalline alloys by
an appropriate heat-treatment [7]. Based on this, we have
further prepared the MWCNTs with nanocrystalline Ni–
P layers by the heat-treatment of the amorphous Ni–P-
coated MWCNTs. The nano-crystallization process
was observed through differential scanning calorimeter
(DSC) and X-ray diffraction (XRD) measurements.
In this study, we designed an advantageous pre-treat-
ment procedure allowing preparation of MWCNTs with
Ni–P coatings by an electroless deposition process. These
coated carbon nanotubes then were also characterized by
several techniques including scanning electron micro-
scope, X-ray diffracmeter and transmission electron Fig. 1. SEM image of pristine multi-walled carbon nanotubes
microscope. Our study provided an effective electro- (MWCNTs).

Fig. 2. Schematic illustration of the procedure of electroless Ni–P deposition on MWCNTs: (a) acid-cleaning, (b) sensitization, (c) activation, and
(d) electroless deposition.
1718 F. Wang et al. / Carbon 43 (2005) 1716–1721
deposition. Moreover, the acid-cleaning process slightly
modifies the surface of MWCNTs to enhance the inter-
facial adhesion between the MWCNTs and metal layers
[10].
Next, the cleaned MWCNTs were sensitized in the
aqueous solution containing 8.9 · 10 3 M SnCl2 and
2.4 · 10 3 M HCl for 10 min. Subsequently, the sensi-
tized MWCNTs were activated in an aqueous solution
containing 1.2 · 10 3 M PdCl2 and 1.2 · 10 2 M HCl
for 30 min, followed by washing thoroughly with deion-
ized water. In the ‘‘two-step’’ method, the sensitization
process leads to the adsorption of Sn2+ on the nanotube
surface, while the activation process forms fine Pd parti-
cles on the nanotube surfaces through the displacement
reaction of Sn2+ with Pd2+. The resulting Pd particles
serve as seeds for catalytic nucleation centers.
Finally, the pre-treated MWCNTs were immersed in
the electroless Ni–P plating bath (a beaker of 200 cm3)
with stirring magnetically. On each step of pre-treatment
and subsequent electroless deposition, the MWCNTs
were dispersed by adding 1.25 · 10 6 M poly(diallyl-
dimethylammonium chrolide) solution (PDMA, mean
molecular weight: 400 000, Aldrich) in the aqueous solu-
tions. The electroless Ni–P deposition was conducted at
the temperature of 60
C for 30 min. Then, the resulting
MWCNTs with Ni–P layers were filtered, washed well
with deionized water, and dried at room temperature
in a vacuum desiccator.
The chemical composition of the Ni–P layers was
identified by energy dispersive X-ray spectroscopy
(EDS) analysis (Noran, Instrument, Inc.). The morpho-
logical features of the MWCNTs with Ni–P layers were
investigated by field emission scanning electron micros-
copy (FE-SEM, HITACHI S-4100). The phase struc-
tures of the MWCNTs with Ni–P layers were
determined by X-ray diffractometry (XRD, RIGAKU
RINT2200V/PC) and high-resolution transmission elec-
tron microscopy (HR-TEM, JEOL JEM-2000FE). A
differential scanning calorimeter (DSC, Seiko DSC-
200) was used to investigate the transformation of the
phase structures up to 450
C. The DSC measurements
were carried out under nitrogen atmosphere to prevent
the oxidation of the samples. To characterize the struc-
Fig. 3. SEM images of Ni–P-coated MWCNTs by the electroless deposition: (a) low magnification (b) higher magnification.
tural variation with temperature by XRD analysis, the
sample was heat-treated under argon atmosphere at
200–480
C for 60 min, where the heating rate was
10
C/min.
3. Results and discussion
3.1. Morphological features of composites
Although the pristine MWCNTs are black powders,
the obtained MWCNTs with Ni–P layers prepared by
the electroless deposition showed gray color, remaining
powdery state. Fig. 3(a) shows the morphological fea-
tures of the coated MWCNTs observed by the FE-
SEM measurement. The appearance of the coated
MWCNTs is fibrous (300–400 nm in diameter), and
the electrolessly deposited Ni–P layers are homoge-
nously distributed on the individual nanotubes. This
clearly indicates the validity of the above pre-treatment
procedure for the electroless deposition on MWCNTs.
The SEM image with higher magnification (Fig. 3(b))
shows the further morphological features that the sur-
face of the coated MWCNTs is relatively smooth, and
the thickness of the electroless deposition layer covering
the inner nanotube is about 90 nm.
3.2. Phase structures of composites
The results of the EDS analysis indicate that the P
content in the electroless deposition layers is about
19–21 at.%. The phase structures of the as-coated
MWCNTs have been determined by the XRD analysis.
Fig. 4 illustrates the XRD patterns of (a) the pristine
MWCNTs and (b) the as-coated MWCNTs with Ni–P
layers. In the diffraction pattern (Fig. 4(a)) of the pris-
tine MWCNTs, a sharp and intense peak at
2h = 26.42
and several small peaks are observed, which
correspond to (0 0 2), (1 0 0), (1 0 1), (0 0 4) and (1 1 0)
planes of graphitized MWCNTs, respectively. In the
case of the as-coated MWCNTs, a new broad peak
other than the (0 0 2) diffraction peak of graphitized
MWCNTs is clearly observed at around 45
, which orig-

VGCF (002)
VGCF (100)
VGCF (101)
Intensity (CPS)
VGCF (002)
20 30 40
Diffraction Angle, 2θ (°)
Fig. 4. XRD patterns of following samples: (a) the pristine MWCNTs
and (b) the as-coated MWCNTs.
inates from the electrolessly deposited Ni–P layers. The
results of the EDS and XRD analyses clearly reveal that
the introduction of Ni–P layers onto the surfaces of
MWCNTs are accomplished by the electroless deposi-
tion, and the phase structure of the deposited Ni–P lay-
ers is an amorphous state. These results of this work are
in good agreement with those reported by other
researchers [11]. The amorphous state of the Ni–P layers
is largely attributed to the distortion of crystalline lattice
of Ni caused by P atoms.
The phase structure of the as-coated MWCNTs has
been also confirmed by TEM investigation. Fig. 5 shows
Fig. 5. TEM image of as-coated MWCNTs and the electron diffrac-
tion pattern, which was selectively taken on the edge of MWCNTs
with Ni–P layers.
F. Wang et al. / Carbon 43 (2005) 1716–1721 1719
the representative TEM image of the MWCNTs with
Ni–P layers and the electron diffraction pattern, which
was selectively taken on the edge of MWCNTs with
Ni–P layers (circular point). The TEM image clearly
indicates that the Ni–P layer almost uniformly covers
VGCF (004)
VGCF (110)
the nanotube surface, the phase structure of which is
an amorphous state without any trace of crystalline
phases. The electron diffraction pattern is a broad ring
(a) characteristic of an amorphous phase. From these re-
sults, the as-coated MWCNTs have been confirmed to
be the MWCNTs with the amorphous Ni–P layers.
3.3. Nanocrystalline process of Ni–P-coated
(b) MWCNTs upon heat-treating
In order to observe the nano-crystallization process,
50 60 70 80 90 the MWCNTs with amorphous Ni–P layers were ther-
modynamically analyzed by the DSC method. In addi-
tion to the DSC measurement, the XRD analysis was
also performed to determine the phase transformation.
For the preparation of the XRD samples, the as-coated
MWCNTs were heat-treated at several different temper-
atures of 200–480
C for 60 min (under argon, the heat-
ing rate is 10
C/min).
Fig. 6 shows the DSC curve of the Ni–P-coated
MWCNTs at 10
C/min. Two exothermic peaks have
been observed in the DSC curve. The very broad peak
observed in the region of 110–300
C might be related
to the short-range atomic movements and primary crys-
tallization of crystalline Ni [12]. Although being still in
amorphous state, the matrix of the Ni–P layers might al-
ready contain a small amount of fine crystallite [13]. The
359°C
10°C/min
Heat flow
100 150 200 250 300 350 400 450
Temperature (°C)
Fig. 6. DSC curve of as-coated MWCNTs with amorphous Ni–P
layers.
1720 F. Wang et al. / Carbon 43 (2005) 1716–1721

sharp peak observed at 359
C shows the major crystal-

lization of an intermetallic compound of Ni3P. It should
be noted that no exothermic or endothermic peaks relat-
ing to the MWCNTs are observed in the DSC curve,
since the graphitized MWCNTs are thermodynamically
stable under the heat-treatment condition up to 500
C
in the nitrogen atmosphere, even in the air [14].
The variations of XRD peaks of the Ni–P-coated
MWCNTs by the heat-treatments are shown in Fig. 7.
The XRD pattern of the as-deposited sample afforded
only a broad peak showing the amorphous phase struc-
ture. At the temperature up to 330
C, the Ni peaks
gradually became sharp through the release of lattice
stress in the Ni–P layers. When the heat-treatment tem-
perature reached 400
C, the diffraction peaks corre-
sponding to the Ni3P intermetallic compound appeared
accompanying the fcc Ni-peaks. This means that the
heat-treatment at 400
C causes the transformation of
Fig. 8. TEM image and the electron diffraction pattern of Ni–P-coated
the amorphous Ni–P-coated MWCNTs to the crystal- MWCNTs under heat-treatment at the temperature of 400
C.
line structure.
Fig. 8 shows the TEM image of the MWCNTs with
4. Conclusion
crystalline Ni–P layers after the heat-treatment at
400
C. Clearly, the nanocrystalline structure of the
The MWCNTs with Ni–P layers have been success-
Ni–P-coated MWCNTs has been observed, and the
fully synthesized by an electroless deposition process
grain size is estimated to be around 10 nm. The corre-
combined with the developed pre-treatment (acid-clean-
sponding electron diffraction pattern shows a polycrys-
ing, sensitization, and activation). The microstructures
talline structural feature, which is in agreement with
of the metal–nanotube composites were characterized
the results of the XRD analysis. These results have dem-
by the FE-SEM, XRD and HR-TEM measurements,
onstrated that the MWCNTs with nanocrystalline Ni–P
and the nano-crystallization process of the Ni–P layers
layers can be prepared by the heat-treatment using the
by the heat-treatment has been evaluated using the
MWCNTs with amorphous Ni–P layers as the
DSC and XRD analyses. The results have clearly indi-
precursors.
cated that the obtained MWCNTs have a uniform
distribution of the Ni–P layers with the fibrous
appearance maintained, and are comprised of the amor-
phous Ni–P layers (the average thickness: 90 nm) and
• °• Ni
Ni
3P the inner MWCNTs covered with the Ni–P layers. It has
been found that the heat-treatment can convert the
amorphous Ni–P-coated MWCNTs into the MWCNTs
with nanocrystalline Ni–P (Ni and Ni3P intermetallic
compound) layers. The results of this work have demon-
•
Intensity ( CPS)

• strated the effectiveness of an electroless deposition on

° ° ° °
the preparation of MWCNTs with the Ni–P layers.
° ° •
(e)
° ° ° ° (d) Acknowledgments
•
(c) This research was supported by the CLUSTER of the
Ministry of Education, Culture, Sports, Science and
(b) Technology, Japan. We thank Mr. Yoshinari Misaki
(a) of Tokyo Metropolitan University for assisting in
TEM observation.
40 42 44 46 48 50 52 54
Diffraction angle 2θ
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