Copyright 2006 American Scientic Publishers

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Printed in the United States of America

Journal of
Nanoscience and Nanotechnology
Vol. 6, 16, 2006

Surface Modication by Electric

Discharge Implemented with Electrodes
Composed of Carbon Nanotubes
H. Y. Miao,1 J. T. Lue,2
and M. S. Ouyang3
1

Department of Information Technology, Ling Tung University, Taichung, Taiwan

Department of Physics and 3 Department of Engineering and System Science,
National Tsing Hua University, Hsin Chu, Taiwan

In this work the electric discharge machining (EDM) implementing with multi-wall carbon nanotubes
(MWCNT) as a miniscule electrode for pursuing precise surface modication was studied. The
excellent upright growth of carbon nanotubes on copper based alloy substrates by a radio frequency
(RF) assisted hot lament chemical vapor deposition (HFCVD) method suggests us to exploit MWCNTs as the miniature electrodes for discharge machining. The results reveal that the electrodes are
much endurable to be distorted even when the spoiling rates for the polishing of n-type Si wafer
(of 10 100
-cm) are up to 30 nm/min with. It is expected that MWCNTs can be applied to
non-conventional material processing especially in miniature discharge machining.

Keywords: Surface Modication by CNTs, EDM (Electric Discharge Machining), Hot-Filament

CVD, Bulk Alloy Substrate.

2. EXPERIMENTAL DETAILS

Since the early 1990, the discovery of CNTs (carbon nanotubes)1 has intrigued a great interest of research all over
the world to study this one-dimensional new material. The
structure, mechanical, thermal2
3 and electrical4
5 properties of carbon nanotubes were fully studied. Both computer simulation and experimental results demonstrated
that both SWCNTs (single-wall carbon nanotubes) and
MWCNTs possess a high rigidity and well conduction
of heat and electricity. Especially, the inheriting of a
high aspect ratio of CNTs leads to a large electric eld
enhancement for electron emission at low applied electric elds. Recently, it is largely demanded to develop
a precise micro-electric discharge machining (EDM) process to produce tungsten wire electrodes as tiny as 2 m
in diameter79 by using etching or wire electric discharge guiding (WEDG) method to control the precision
of work-pieces. On taking the advantages of the straight
up-right, durability and strong electron eld emission, we
exploit the multi-wall carbon tubes grown on copper based
alloys to replace the micro sized electrodes for surface
polishing.

The copper and iron based alloys were employed as the

catalyzed substrates to grow the multi-wall carbon nanotubes by a microwave/radio-frequency assisted HFCVD
method.10
11 The scanning electron microscopy (SEM)
images as shown in Figure 1 indicate the well-aligned
MWCNTs grown on the substrate with a composition of
(Cu-70 wt%, Fe-10 wt%, Co-10 wt%, and Ni-10 wt%).
The diameter of the CNTs is about 110 nm with a height
of 3 m. The metal particles embedded in the tip of nanotubes composed of more than 65% of Cu with the rest of
Fe, Co, Ni, and W as analyzed by an electron probe X-ray
micro-analyzer (EPMA). Figure 1(c) expresses the metallic
root of the MWCNT grown from the bulk alloy substrate
that reveals much robust than those grown from Si substrates, which were deposited with a thin catalyst lm.1214
Moreover, the higher content of the Cu element in the
substrate, the higher electric and heat conduction to the
tip of MWCNTs. The prevailing characteristics of MWCNTs over other materials that are valuable to be dictated
for electric discharge are the resistivity of 104 -cm, the
maximum current density of 1013 A/m2 , and a Youngs
modulus of 1.28 Tpa.15
The main aim of this study is to understand the IV
characteristics of MWCNTs grown on alloy substrates.

Author to whom correspondence should be addressed.

J. Nanosci. Nanotechnol. 2006, Vol. 6, No. 4

1533-4880/2006/6/001/006

doi:10.1166/jnn.2006.151

RESEARCH ARTICLE

1. INTRODUCTION

Surface Modication by Electric Discharge Implemented with Electrodes Composed of Carbon Nanotubes

Miao et al.

(a)

(b) Applied Voltage

600

(a)

210 s 140 s

Time

Fig. 2. (a) The schematic diagram of the electronic circuit to perform

the micro-EDM process that generates the desired on and off cycles.
(b) The clocks showing the electric on-off time durations generated.

RESEARCH ARTICLE

(a)

(b)

(b)

(c)
Fig. 1. The MWCNTs grown on alloy substrates by a dc bias 450 V
induced by the rf eld for (a) upright features, (b) cross view for the piled
tubes showing a size of 110 nm in diameter, 3 m in length, with metal
particles embedded in the tip, respectively. And (c) clearly indicates a
root of one carbon nanotube grown from the alloy substrate.

Fig. 3. The current and voltage (IV) characteristics for (a) the leakage current test of Cu-based alloy substrate, (b) the eld emission of
MWCNTs grown on the alloy substrate.

J. Nanosci. Nanotechnol. 6, 16, 2006

Miao et al.

Surface Modication by Electric Discharge Implemented with Electrodes Composed of Carbon Nanotubes

The eld emission was measured under a vacuum of

106 torr with a Teon spacer of 150 m and a Mo
(thickness of 3 m) coated glass plate displaying as
the anode.16 The eld emission properties do not follow the Fowler-Nordheim equation but comply with the
metal-semiconductor tunneling theory.17
18 The circuit for
performing the micro-EDM is shown in Figure 2 where the
integrated circuit SG3524 produces the controlling square
clocks which are amplied by the high voltage transistor
IRF640 to control the switching voltage for embarking the
discharge electrodes D6 to start or close. The photo coupler TLP250 isolates the controlling gate from the power
output to immunize the noise feedback. Variable resistance
R7 controls the demanded current during EDM. The EDM
tests for an un-polished n-type Si wafer were carried out
under an environment of, in a vacuum of 103 torr, in air,
or in a deionized water with a resistivity of 18 M, separately. The morphologies and microstructure of the EDM

results were checked by a SEM (JEOL 6500F), and the

wall structure and bonding strength of MWCNTs were
examined by the Micro-Raman spectroscopy.

3. RESULTS AND DISCUSSION

The currentvoltage (IV) characteristic of the raw alloy
substrate before CNT growth as shown in Figure 3(a) illustrates that the leakage current is below 0.025 A/cm2 at
an applied voltage of 1000 V which is much smaller than
the eld emission current for the MWCNTs grown on the
alloy substrate as shown in Figure 3(b). The threshold voltage required is 2.5 V/m that is smaller than that emitted from the MWCNTs grown on Si wafer1214 or from
those grown on non-Cu based metallic alloy.19
20 We tacitly assumed that the lowering down of the threshold voltage is attributed to the high electric and heat conduction of
copper and the high aspect ratio of the well-aligned MWCNTs grown in this HFCVD method. The pillar structure
of the MWCNTs as grown deeply from the alloy substrate
makes the robust MWCNTs to be featured with durability
for repeatedly discharge testing at high voltages.
The SEM images as shown in Figure 4 examine the surface morphology of the Mo-plated glass anode after the
(a)

RESEARCH ARTICLE

(a)

(b)

(b)
Fig. 4. The SEM micrographs of the surface of the Mo-coated glass
after EDM process for (a) the highlight view, and (b) the exaggerated
view of a single spot.

J. Nanosci. Nanotechnol. 6, 16, 2006

Fig. 5. (a) The IV characteristic for the eld emission of for the electrode composed of the MWCNTs as the cathode and the n-type Si wafer
as the anode. (b) The exaggerated SEM picture of the silicon surface
from a point in the inset after one EDM process.

Surface Modication by Electric Discharge Implemented with Electrodes Composed of Carbon Nanotubes

discharge. The Mo lm of 3 m thickness was etched

to form island-like structure of about 22 m in diameter
as shown in Figure 4(a). Figure 4(b) clearly indicates a
transparency-ring of glass surrounding the Mo islands. It is
conjectured that this phenomenon embodies in the numerous transient pulse current to burn numerous point-like
area of Mo and aggregated to form Mo islands. The source
of transient pulse current might be arisen from the eld
evaporation of the MWCNT tip under some high values of
applied voltages.
Replacing the anode by the unpolished n-type silicon
wafer with a resistivity of 10 100 -cm, a sharp increase
of current density caused by the arc discharge at applied
voltage 600 V occurs as shown in Figure 5(a). The threshold voltage increases to 3 V/m resulting from the larger
resistance of the Si electrode than the Mo electrode. Therefore the resistivity of the work piece also plays an essential
role for successfully machined even implemented with the
same MWCNT cathode.
The SEM micrograph as shown in Figure 5(b) clearly
reveals a burned trace of diameter 120 nm corresponding
to the size of MWCN tubes. The inset is the reduced

Miao et al.

(a)

(b)

(a)

RESEARCH ARTICLE

(c)

(b)
(d)

Fig. 6. The surface modications of the n-type Si substrate (a) before

and (b) after the electric discharge machining (EDM) under a pressure
of 103 torr, respectively.

Fig. 7. The SEM photographs for (a) the highlight of the MWCNTs
cathode after nano-scale EDM processes, the exaggerated pictures at
(b) at area B, (c) at area C, and (d) at area D, respectively.

J. Nanosci. Nanotechnol. 6, 16, 2006

Miao et al.

Surface Modication by Electric Discharge Implemented with Electrodes Composed of Carbon Nanotubes
(a)

(b)
Fig. 8. The micro-Raman spectra of the MWCNTs electrode after nanoscale EDM process.

RESEARCH ARTICLE

magnication (2000) of the discharge area illustrating

numerous burn points. To perform the electric discharge
machining (EDM), the output pulse generated from the
electronic circuit is shown in Figure 2(b). The surface
modications of the n-type Si substrate before and after
the electric discharge machining (EDM) under a pressure of 103 torr are shown in Figures 6(a) and 6(b)
respectively. A nano-scaled EDM polishing process for
20 minutes clearly shows the improvement of the surface
roughness to be about 600 nm. The surface-eliminating
rate is 30 nm/min for implementing the MWCNTs cathode
in the nano-scale EDM polishing process.
A highlight on the surface of the MWCNTs cathode
after EDM process is expressed in Figure 7. Due to the
non-perfect atness of the electrode surface, the discharge
chance of each nanotube at repeatedly EDM process is not
equal. Area A indicates the trace of the sputtered MWCNTs by the high energy EDM sparks. The SEM micrograph
Figure 7(b) corresponds to the exaggerated white area B

(c)

Fig. 10. (a) The erosion of the MWCNT cathode after the EDM process
with the gap embedded in air discharged at low voltages, (b) same condition as (a) while discharge at high voltages, and (c) with the electrode
gap embedded in de-ionized water, respectively.

Fig. 9. The Micro-Raman spectra of the MWCNTs electrode after low

applied voltage repeated EDM processes.

J. Nanosci. Nanotechnol. 6, 16, 2006

caused by the more often discharge process. Figure 7(c) is

the less discharged MWCNTs at area C while Figure 7(d)
corresponds to the Teon covered area D without participating in EDM process. The MWCNTs are toppled over
and piled up without bending after the discharge.
5

RESEARCH ARTICLE

Surface Modication by Electric Discharge Implemented with Electrodes Composed of Carbon Nanotubes

A typical Micro-Raman spectrum of MWNTs indicates

two characteristic peaks. The G-line peak at 1580 cm1
corresponds to the high-frequency Raman-active E2g mode
of graphite. The strong and broad D-line at 1350 cm1 and
a weak D - band at around 1621 cm1 was sophistically
attributed to disorder-induced carbon features arising from
nite particle size effect or lattice distortion.21
22 Another
prospect of the origins of the D-line is attributed to defects
in the curved graphite sheets, tube ends, and nite size
crystalline domains of the tubes.23
24 This reveals that, in
the structure, defect elements of graphite layers are more
than perfect elements, which is the main cause that makes
the prole and the structure not being sharp. Figure 8
shows the Micro-Raman spectrum of the MWCNTs electrode after the nano-scale EDM process exhibiting those
the peaks of G band and D band both decrease gradually
after repeatedly arc discharge. The deeper the etched area
the more diminishing of the D and G intensities resulting
in the catastrophic broke of the sp2 bonds to become the
graphite-like structure by the discharge. At the test of a
lower discharge voltage (e.g., 400 V), only the weak bonds
of MWCNTs are burned out leading to a sharper Raman
spectrum as shown in Figure 9.
Different dielectric materials embedded in the discharge
gap results in different distortion of the MWCNTS as
shown in Figure 10. The outlooks of the MWCNTs after
the DEM with the gap lled with air at low and high voltages are shown in Figures 10(a) and 10(b), respectively.
At low applied voltages, the air rarely ionized to affect
the shapes of the MWCNT electrode as shown the pit-like
in Figure 7(a). Increasing the applied voltage, the carbon
tubes are twisted by the airow generated by the explosion
of arc discharge as shown in Figure 10(b). The CNTs even
twisted and conjunct together at the tips by the whirlpool
of the water stream for the electrodes embedded in deionized water as shown in Figure 10(c).

4. CONCLUSION
The well-aligned MWCNTs grown on copper based alloy
by the radio frequency biased HFCVD method developed
in our laboratory can be readily implemented as the cathode for micro-electric discharge machining. The etching

Miao et al.

rate for surface modication can be up to 30 nm/min

without seeing appreciable deterioration of the electrodes.
Various outlooks of the MWCNTs after EDM with the
electrodes embedded in different dielectric uids are
examined.

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Received: 1 July 2005. Revised/Accepted: 16 December 2005.

J. Nanosci. Nanotechnol. 6, 16, 2006