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NANO

LETTERS

Carbon Nanotubes Loaded with


Magnetic Particles

2005
Vol. 5, No. 5
879-884

Guzeliya Korneva, Haihui Ye, Yury Gogotsi,*, Derek Halverson,


Gary Friedman, Jean-Claude Bradley, and Konstantin G. Kornev|
Chemistry Department, Department of Materials Science and Engineering, and
Department of Electrical and Computer Engineering, A. J. Drexel Nanotechnology
Institute, Drexel UniVersity, 3141 Chestnut Street, Philadelphia, PennsylVania 19104,
and TRI/Princeton, 601 Prospect AVenue, P. O. Box 625, Princeton, New Jersey 08542
Received February 15, 2005; Revised Manuscript Received March 14, 2005

ABSTRACT
We describe a simple and versatile technique to produce magnetic tubes by filling carbon nanotubes (CNTs) with paramagnetic iron oxide
particles (10 nm diameter). Commercial ferrofluids were used to fill CNTs with an average outer diameter of 300 nm made via chemical vapor
deposition into alumina membranes. Transmission electron microscopy study shows a high density of particles inside the CNT. Experiments
using external magnetic fields demonstrate that almost 100% of the nanotubes become magnetic and can be easily manipulated in magnetic
field. These one-dimensional magnetic nanostructures can find numerous applications in nanotechnology, memory devices, optical transducers
for wearable electronics, and in medicine.

1. Introduction. The unique physicochemical properties of


carbon nanotubes1 have stimulated the search for possible
applications in different areas of engineering.2-6 Especially,
electrical properties of CNTs are very attractive, but all
attempts to make CNTs magnetic7,8 have had limited success.
The nanotubes containing magnetic particles did not show
useful magnetic properties because the amount and location
of magnetic material inside the tube was difficult to control.
Other techniques, which have been used to produce magnetic
needles, are expensive and time-consuming,9 leading to a
low yield. While increasing the magnetization, it is also
important to prevent nanoneedles from agglomerating when
a magnetic field is not applied. Encapsulating paramagnetic
particles into CNTs makes paramagnetic needles and allows
for control of their movement.
The phenomenon of spontaneous penetration of fluids into
wettable capillaries is taken as a guiding idea to load the
nanotubes with magnetic nanoparticles. As known from
everyday experience, when a capillary is set in contact with
a wetting fluid, the fluid spontaneously penetrates inside.
This method of filling nanotubes with molten metals was
suggested long ago.10-12 The drawback of using the melts
in the way suggested in refs 10-12 is that it is timeconsuming, includes the quite tedious and unpredictable step
of nanotube opening, and, at the end, the filling efficiency
* Corresponding author. E-mail: gogotsi@drexel.edu, Phone: (215) 8956446, FAX: (215) 895-1934.
Chemistry Department, Drexel University.
Department of Materials Science and Engineering, Drexel University.
Department of Electrical and Computer Engineering, Drexel University.
| TRI/Princeton.
10.1021/nl0502928 CCC: $30.25
Published on Web 03/30/2005

2005 American Chemical Society

is too low to consider this method for large scale production.


Ferrous metals, which are of interest for magnetic applications, have high melting points (1535 C for Fe, 1453 C
for Ni, and 1495 C for Co),13 and their melts react with
carbon. To avoid these shortcomings, we suggest a threestep protocol which consists of (1) synthesis of CNTs by
the method of noncatalytyic chemical vapor deposition
(CVD) into the pores of an alumina template (this method
provides tubes with open ends and they will be free of
ferromagnetic catalyst particles); (2) filling of nanotubes with
suspensions of functional nanoparticles; (3) separation of
nanotubes from alumina membrane. Step three can be made
before step two. Then the individual nanotubes are filled with
a suspension in a similar way.
It has been previously demonstrated that CVD nanotubes
produced by template synthesis can be filled with water,3,14
glycerin, ethylene glycol,15 hydrocarbons, and other liquids.
However, filling nanotube channels with particle-loaded
fluids or colloidal solutions has not been previously reported,
although, a recent demonstration using a Coulter counter16
shows that particulate flow inside nanotubes is possible. The
dragging of nanoparticles into the nanotubes is mostly
affected by the process of enforcement of the fluid body as
a whole continuum.17
The objectives of this work are to use commercially
available ferrofluids to fill the CNTs, evaporate the carrying
fluid from the tubes, and produce magnetic nanotubes.
2. Materials and Experimental Details. In all experiments we used carbon nanotubes produced in our laboratory
by the CVD technique. The nanotubes were formed in the

Figure 1. Filling of carbon nanotubes. First method. Alumina membrane with carbon nanotubes produced by CVD (a) is brought in
contact with ferrofluid (b). Ferrofluid invades pores (c). Carrying fluid is dried to leave only magnetic particles in CNTs (d). Alumina
membrane is dissolved in NaOH to produce magnetic CNTs (e). Second method. Alumina membrane with carbon nanotubes produced by
CVD (f) is dissolved in NaOH to produce individual CNTs (g). Droplet of ferrofluid is deposited atop nanotube layer (h). Ferrofluid fills
nanotubes, then carrying fluid is evaporated and nanotubes are left with magnetic particles inside.

straight cylindrical pores connecting both faces of the


alumina membrane. The alumina template Anodisc of 13 mm
in diameter was purchased from Whatman. The pore diameter
and thickness of the membrane determine the dimensions
of the nanotubes. In our experiments, the pore size was 300
nm in average, and the membrane thickness was 60 m. The
synthesis of CNT by CVD is described in detail in refs 18
and 33. The resulting CNTs have open ends from one or
both sides, and their walls are highly disordered and
hydrophilic to allow water to invade the tubes.3,14,19 This
makes it possible to fill the nanotubes with both organicand water-based ferrofluids. To fill the CNTs with magnetic
particles, we used the following commercially available
ferrofluids: water based (EMG 508) and organic based
(EMG 911) (Ferrotec Corporation) which carry magnetite
(Fe3O4) particles with a characteristic diameter of 10 nm.
Samples were characterized by transmission electron
microscopy (TEM) using a JEOL JEM-2010F (operated at
200 kV) with a point-to-point resolution of 0.23 nm. The
TEM samples were prepared by dispersing the nanotubes in
2-propanol and then placing them onto a copper grid coated
with a lacy carbon film. Images of nanotubes in experiments
with external magnetic field of strength 0H ) 0.011-0.012
T (0 is the permeability of vacuum) were taken on a Leica
DM LFS microscope with a Leica HCX APO 63/0.90
U-V-I water immersion lens and a MagnaFire SP model
S99805 camera.
3. Results and Discussion. 3.1. Filling of CNT with
Magnetic Particles. The procedure of nanotube filling with
ferrofluid is shown schematically in Figure 1. Two different
methods have been used. The first method assumes filling
nanotubes in the alumina membrane, while the second
method deals with filling nanotubes released from the
membrane.
Filling tubes in alumina membranes. Upon deposition of
a droplet of ferrofluid onto the membrane, the fluid invaded
the pores. To control the magnetic anisotropy of prepared
magnetic CNTs, we also applied a magnetic field. A
permanent magnet (0H 0.4 T) was mounted underneath
the membrane. Even without a field, the penetration occurs
almost instantaneously. An applied magnetic field only
880

Figure 2. TEM images of CNTs filled with organic-based


ferrofluid EMG 911. (a) CNTs filled with ferrofluid in magnetic
field. Nanotubes are embedded in alumina, which can be seen in
the lower left corner. (b) High-resolution TEM image of a fragment
of the nanotube, filled with magnetite particles without applied
magnetic field. The particles are agglomerated inside the nanotube.

increases the rate of penetration, because it creates an


additional force to direct magnetic nanoparticles toward the
magnet, i.e., into the tubes. The effect of field-induced
acceleration, however, is insignificant at the fields used in
our experiments. After evaporation of the carrying liquid at
room temperature, the membrane was broken into tiny pieces
and dispersed in 2-propanol for the TEM examination. TEM
micrographs show the typical distribution of magnetic grains
inside the nanotubes (Figure 2). During the processing, the
Nano Lett., Vol. 5, No. 5, 2005

Figure 3. TEM image of a released tube filled without magnetic field. The closed tip of the nanotube shown is revealed after dissolution
of the aluminum template in NaOH followed by sonicating, filtering, and rinsing in the alcohol. This image shows high density of particles
inside the nanotube even after several hours processing.

magnetic particles deposited outside the nanotubes were


washed out, while the particles deposited inside were held
by adhesion forces. Statistical analysis of a large number of
tubes showed that nanoparticles fill the nanotubes equally
with and without magnetic field. This suggests that filling
is primarily driven by capillary forces.
Filling released nanotubes. In a second technique, the
alumina template after preparation of the CNT by the CVD
method was dissolved in 4.0 M NaOH. After sonication, the
solution was vacuum filtered through the polyester nucleopore membrane (Osmonic Corp.) with the pore size of 0.2
m. Then the filtrate was dispersed in toluene. In the next
step, a few milliliters of solution containing CNTs dispersed
in toluene was filtered again by using a similar polyester
membrane. After filtration, the residue was rinsed with
alcohol and distilled water, and then dried. Typically, a gray
area of concentrated nanotubes appeared on the substrate after
drying. A drop of ferrofluid was deposited on that gray spot.
Again, after complete evaporation of the solvent, the substrate
was rinsed with alcohol, immersed into a small vial and 5
mL of alcohol was added. The vial was put into a sonicator
and the deposit was removed from the membrane. This
dispersion was analyzed by TEM (Figures 3 and 4).
As shown, both approaches give similar results: the
nanotubes are filled with magnetic nanoparticles. The density
of magnetic grains is so high that it can be probed by a
variety of macroscopic techniques, including optical microscopy, SEM and TEM. Suspended in liquids, magnetic
nanotubes follow the change of the direction of applied
magnetic field. Figure 5 shows the typical behavior of a
suspension of magnetic nanotubes in water placed in a
magnetic field of 0H ) 0.01 T. Magnetic nanotubes can be
oriented in the plane of a silicon wafer with gold electrodes
(Figure 5 a,b) or can be forced to stand normally to the wafer
surface (Figure 5c). In the field, the nanotubes form long
chains with lengths greater than the widths of the golden
islands, 25 m. As seen from that panel, all nanotubes are
sensitive to the application of magnetic field, independent
of whether they are on an Au or Si surface. In particular, all
nanotubes seen in the camera align perpendicularly to the
wafer (Figure 5c). This proves that we have an almost 100%
yield of magnetic nanotubes after filling. Single nanotubes
could also be manipulated, e.g., positioned between two gold
electrodes using dielectrophoresis as described in ref 20.
Nano Lett., Vol. 5, No. 5, 2005

Figure 4. Filling of released nanotubes. TEM image of (a) part of


the branched CNT, and (b) CNTs with open ends, filled with
magnetic particles from water-based ferrofluid EMG 508. This
image shows that the nanoparticles are collected inside the CNT
and form quite dense structure. Attached to the walls of the CNT
by adhesion forces, the particles stay intact after processing.

3.2. Nanotube Magnetization. Average magnetic properties


of the nanotubes filled with the magnetic particles were
measured using an alternating gradient magnetometer (AGM
by Princeton Measurements Inc.). Membranes with the filled
nanotubes were rinsed with toluene to remove ferrofluid
particles from the surface of the membrane. Pieces of the
membrane were cut out and their areas were measured under
the microscope. An example of the magnetization curve for
a sample of area 5.9177 10-6 m2 is given in Figure 6.
Using the total magnetization value of this sample of M )
9.138351 10-8 Am2 for the applied field of 0.007 T, the
881

Figure 6. Typical magnetization curve of a nanotube membrane


loaded with magnetic nanoparticles without a magnet.

10-20 Am2 for each particle at this field obtained from


the vendor, the nanotubes are estimated to contain approximately 7 104 magnetic nanoparticles. Taking the
volume of each nanoparticle to be dg3/6 ) 5.24 10-25
m3 and the average volume of the nanotubes to be Ld2/4
) 8.84 10-19 m3, where L is the tube length, one results
in the estimated 11% filling of the nanotube volume by the
magnetic nanoparticles.
An independent analysis of the nanotube magnetic moments can be carried out using experiments on a suspension
of magnetic nanotubes in a rotating magnetic field. In this
experiment, the CNTs were released by dissolving the
membrane. The resulting CNT suspension was subjected to
a uniform rotating magnetic field of 0.007 T, and the steadystate CNT rotation was observed.
With respect to a stationary reference frame, the angle
between the direction of the external field H and the reference
axis X changes with time as ) t (Figure 5b). Assuming
that the nanotube magnetization direction coincides with the
nanotube axis and denoting the angle between the magnetization and field direction as , we can write the following
equation for tube rotation21
(-) ) 0mH sin

Figure 5. Manipulation of magnetic nanotubes by magnetic field.


(a) and (b) magnetic CNTs are oriented along in the plane of
supporting wafer, 0H ) 0.01 T; (c) magnetic nanotubes frozen in
applied magnetic field perpendicular to the wafer 0H ) 0.03 T.
(Inset) Schematic of orientations of applied field H and magnetization m with respect to nanotube axis. All vectors are assumed to
lie in one plane.

average magnetic moment of the filled nanotubes at that field


is found using the formula

where prime denotes the time derivative, and is the friction


coefficient of the tube,22
) L3/(3ln(L/de) - 3A)

m ) M(d )/(4pA)

(3)

(4)

(1)

where A is the sample area, d ) 300 nm is the nanotube


diameter, and p ) 0.25 is the fraction of the membrane area
occupied by the nanotubes. This gives the average nanotube
magnetic moment of 4.37 10-15 Am2 for the external field
of 0.007 T. Using the value of the magnetic moment of 4.48
882

A)0.8

Here de is the tube external diameter, and is the fluid


viscosity. As can be seen from eq 2, there is a solution )
constant which disappears as the frequency of the field
approaches the critical frequency:
cr ) 0 mH/

(2)

Thus, by observing the frequency up to which CNT rotation


is synchronized with the field rotation, it is possible to
estimate the nanotube magnetic moments at the given
magnitude of the rotating field. However, due to dispersion
of the CNT length and magnetic moments, different CNTs
lose their synchronization with the field at different frequenNano Lett., Vol. 5, No. 5, 2005

cies. We experimented with a water-based suspension of


CNTs in a field of 0.007 T. The critical frequency was found
to vary between fcr ) 6-10 Hz. Taking these values, the
magnetization is estimated through the formula
m ) cr /0 H ) 2fcr L3 [(3ln(L/de) - 2.4) 0 H]-1
(5)
where L ) 10-15 m, de ) 300 nm, and 0 H ) 0.007 T.
The rotational experiments give m ) 5 10-15 - 2 10-14
Am2, which is slightly higher, but is otherwise in good
agreement with the magnetic moment obtained from the
membrane magnetization measurements by AGM. The
rotational field experiments also demonstrate that the produced magnetic nanotubes are highly responsive to the
applied field typical in MEMS applications.
It is worthwhile to compare the energy of dipole-dipole
interactions with respect to the energy of thermal excitations.
The minimum energy of two needle-like magnets corresponding to their parallel orientation is estimated to be Edd
) 0m2/L2de 10-18 - 10-17 J, which is much greater than
the energy of thermal excitations, Et ) T 10-21 J. This
estimate may explain why the CNT needles are prone to
forming chains as seen in Figures 5a,b.
4. Potential Applications. The proposed approach allows
magnetic nanotubes to inherit paramagnetic nature of encapsulated magnetic particles, yet become much more
responsive to an applied field. Even without extra treatment,
our magnetic nanoneedles stay separated in suspension. In
contrast, ferromagnetic needles, e.g., -Fe2O3, of the same
length (but with a much smaller aspect ratio) and same
concentration require some extra treatment to prepare stable
suspensions. Given the high magnetization that we can
achieve and the compatibility of CNTs with many polymeric
materials, the magnetic nanotubes are a highly attractive
multifunctional material. They can be added to polymers to
produce composites with aligned paramagnetic needles,
arranged in a variety of patterns on a surface or incorporated
into polymer fibers. The list of applications of magnetic
nanotubes can be extended to include materials for wearable
electronics,23-25 cantilever tips in magnetic force microscopes,26 magnetic stirrers in microfluidic devices, or magnetic valves in nanofluidic devices.27 Use of these tubes as
connecting pipes in nanofluidic devices has already been
demonstrated.28 Experiments shown in Figure 5c suggest the
use of these magnetic nanotubes instead of nanoposts in
fluidic chips for DNA separation.29,30 That is, one can apply
magnetic field to freeze nanotubes and to vary the intertube
spacing in order to unravel DNA coils and separate them as
described in refs 29-32. Thus, the versatile technique
suggested in this paper offer an opportunity to make a step
toward the nanoengineering of complex multifunctional
nanosystems.
One of the most attractive applications is using the
magnetic CNTs as capsules or nanosubmarines for magnetically guided drug delivery to desired locations in the body,
as well as for diagnostics without surgical interference. Other
particulate fluids, e.g., solutions of quantum dots or polymer
Nano Lett., Vol. 5, No. 5, 2005

particles can be used as well. In our previous studies, we


demonstrated that not only water,3,14 but a large number of
organic fluids including glycerin, alcohols, benzene, and
cyclohexane can be encapsulated into the same kind of
nanotubes. These liquids can be used as carriers for some
other particulate and emulsion systems or biopolymer solutions for nanotube filling. We have also demonstrated selective sealing of tube tips with polypyrrole by using bipolar
electrochemistry,33 making closed capsules for liquid delivery.
5. Conclusions. We have demonstrated a relatively simple,
inexpensive, reproducible, scalable, and fast method of filling
the carbon nanotubes with functional nanoparticles, in
particular, with magnetic nanograins. This technique opens
an opportunity for engineering magnetic nanotubes based on
the phenomenon of spontaneous penetration of wetting fluids
into capillaries. The magnetization of magnetic CNTs is
controlled by the number of encapsulated nanograins and
thus can be made very magnetic. In our experiments, for
example, the number of magnetic grains in the tubes varies
between N 104-105. The filled nanotubes follow the
applied magnetic field, thus manifesting their magnetic
nature. Thus we showed that the yield of magnetic nanotubes
after wet filling was close to 100%. Controllable manipulation of magnetic nanotubes with micromagnets points to a
straightforward way for utilization of these nanoneedles in
different nanofluidic and electronic devices.
Generally, the paper provides a procedure of making
nanotubes functional. Other particulate fluids, emulsions, and
polymer solutions can be used to fill nanotubes and transform
them into multifunctional nanostructures.
Acknowledgment. The authors thank Dr. P. G. Ndungu,
Dr. S. Babu, Dr. B. M. Kim, and D. Mattia for help in carbon
nanotube preparation and study. The appreciation of Drexel
University group is extended to NTI and NSF NIRT for
financial support.
Supporting Information Available: Windows Media
Player movie showing the motion of CNT filled with
magnetic nanoparticles in rotating magnetic field of 0H )
0.007 T, and frequency of f ) 1 Hz. This material is available
free of charge via the Internet at http://pubs.acs.org.
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NL0502928

Nano Lett., Vol. 5, No. 5, 2005