Powder Technology 162 (2006) 121 – 125

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Influence of pulsed arc parameters on powder production in ethanol

N. Parkansky a,*, G. Frenkel a, B. Alterkop a, R.L. Boxman a, S. Goldsmith a, Z. Barkay b,
Yu. Rosenberg b, O. Goldstein a
a
Electrical Discharge and Plasma Laboratory, Tel Aviv University, POB 39040, Tel Aviv 69978, Israel
b
The Wolfson Applied Materials Research Center, Tel Aviv University, POB 39040, Tel Aviv 69978, Israel

Received 16 February 2005; received in revised form 11 July 2005; accepted 25 October 2005
Available online 23 January 2006

Abstract

Powder consisting nickel and carbon particles were synthesized using a pulsed arc between Ni electrodes submerged in pure ethanol. The
ethanol was arc treated for 5 min with 20 and 40 As duration pulses, at a repetition rate of 100 Hz. The pulse energy was varied in a range of 7.7 –
192 mJ. Powder samples were obtained by extracting liquid from the treatment vessel after a pre-determined sedimentation time, or by allowing
the liquid to evaporate from the vessel, and collecting the residue. The samples were examined by HRSEM, EDX and XRD. Dependencies of the
particle structure and size distribution, and the powder production rate and composition, on the pulse energy and duration were studied.
The powder samples consisted of nickel and carbon particles. The surface of the nickel particle had a carbon coating. The Ni concentration
increased from 32% to 46%, and the C concentration decreased from 68% to 54%, when the pulse energy was increased from 7.7 to 100 mJ with
20 As pulses. For 40 As pulses the same changes of Ni and C concentrations were obtained when the pulse energy increased from 60 to 100 mJ.
The production rate of the Ni and C particles linearly increased with pulse energy.
The particle quantity and size distribution width increased with pulse energy. The maximum particle diameter increased from 70 to 550 nm
while its minimum diameter remained ¨ 50 nm when the pulse energy increased from 7.7 to 48 mJ with pulse duration of 20 As.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Discharge; Arc parameters; Powder

1. Introduction benzene was used for synthesis of amorphous carbon particles

Production of powders consisting of carbon and metallic
nano- and micro-particles excites considerable interest because
they are needed in micro-electronic devices, metallurgy, surface
modification, catalysis, biological labeling, photonics, and
information storage [1 –3]. Recently a technique based on an
arc discharge with C and Ni electrodes submerged in liquid was
developed [4,5]. Carbon nanoparticles with an onion-like
structure, i.e. ‘‘nano-onions’’ composed of concentric spherical
layers, were found after d.c. arcing in water with C electrode
pairs [4]. Carbon nano-onions and Ni and W nanoparticles
were produced by using pulsed arcs with Ni and W electrodes
submerged in ethanol [5]. The nano-onions typically had an
o.d. of 15– 20 nm, and the diameter of the interior void was
approximately 5– 8 nm. A similar technique based on d.c. arc
between Cu electrodes in ultrasonically irradiated liquid
* Corresponding author. Tel.: +972 3 6408176; fax: 972 3 6410189.
E-mail address: naump@eng.tau.ac.il (N. Parkansky).
0032-5910/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.powtec.2005.10.008
[6].
The influence of the pulsed arc parameters on the particle
production was not yet investigated. In this paper, we present
the influence of the pulse energy and duration on particle
structure and size distribution and on the powder production
rate and composition produced by pulsed arcing in ethanol with
Ni electrodes.
2. Experimental details
Pulsed arc was applied between two 99.5% Ni electrodes
submerged in 60 ml analytical (99.8%) ethanol contained in a
plastic cup [5]. One electrode with a 5
2.5 mm cross-section
was mounted on a vibrator, so as to periodically contact and
separate from another 80
5 mm plate electrode at a vibration
frequency of 100 Hz, vibration amplitude of ¨ 0.5 mm, for a
processing time of 5 min. The arcs were ignited by applying a
voltage between the electrodes from a charged capacitor—
current begins to flow upon contact, and an arc is ignited upon
122 N. Parkansky et al. / Powder Technology 162 (2006) 121 – 125

10
separation. The pulse energy W = (1/2)CU 2 (where C and U are
the capacitance and capacitor charge voltage, respectively) and
duration s were varied by varying U and C. Pulses with 20 As
pulse duration and 7.7, 22.7 and 48 mJ energy, and 40 As
duration and 30.7, 90.7, and 192 mJ were used. Five samples
were examined for each value of pulse energy, where each
sample was prepared by removing a small quantity of alcohol
0.1
(¨ 0.25 ml) from the cup using a pipette after arc treatment, and
transferring it to a glass microscope slide coated with ¨ 100 nm 48 mJ

N/∆d, 109*µm-1
Au film. The liquid was allowed to evaporate from the slide,
leaving a trace with average area A t ¨ 2 cm2. The samples were
examined by high-resolution scanning electron microscopy
(HRSEM). 22.7 mJ
The particle size distribution was determined from the
0.001
HRSEM micrographs at magnifications of 2000, 25,000,
60,000 and 100,000. Assuming that the particle spatial
distribution is uniform, the size distribution of the particles 7.7 mJ
produced during one pulse were calculated as follows: the
number of the particles N with diameters d in some specific
ranges yd = d max  d min in the micrograph area A were counted
and normalized according to the formula NA t/(ydAs), where s
0.00001
is the number of pulses during the arc processing. A final form 0 0.5 1 1.5 2
of the particle size distribution was determined after average of Particle diameter, µm
five samples.
In other tests, the liquid in the cup was allowed to evaporate, Fig. 2. Ni particle size distribution.
and the residue powders were collected and examined by X-ray
diffraction (XRD). XRD patterns of both the Ni electrodes and evaporation of the liquid. Assuming that the precipitate consists
powders produced, for comparison, by a pulsed submerged arc of carbon from ethanol and the electrode material (Ni), the
in water were also obtained and examined. carbon production rate at fixed discharge duration was deter-
XRD patterns were obtained using CuKa radiation in a h –h mined by using: (1) the difference between the precipitate weight
powder diffractometer equipped with a liquid nitrogen cooled and the total electrode mass loss, and, for control, (2) the powder
Ge solid-state detector. Then the powders were pressed into composition from EDX analysis and the total electrode mass
tablets with diameter of 4 mm and thickness of 2 mm. These loss. In the first case, the data of described above measurements
samples were analyzed by energy dispersive X-ray (EDX) to were used, while in the second case, EDX data on relative
determine the powder composition. contents of carbon and nickel in the precipitate were also used.
To determine the erosion rate, the Ni electrodes were weighed
before and after the arc treatment, and the weight difference was 3. Results
determined. The precipitate mass was determined by weighing
the cup before filling with ethanol, and after arc treatment and According to SEM and EDX analysis, the obtained powders
consisted of nickel and carbon [5]. A typical HRSEM

20
Ni erosion rate, mg/min

15
Anode

10 Cathode

0
0 50 100 150 200
Pulse energy, mJ
Fig. 1. HSEM micrograph of nanoparticles produced with Ni electrodes (pulse Fig. 3. Electrode erosion rate vs. pulse energy (pulse duration 40 As—hollow
energy—48 mJ, pulse duration—20 As). markers; pulse duration 20 As—solid markers).
 N. Parkansky et al. / Powder Technology 162 (2006) 121 – 125
30
Erosion and carbon production
25
rates, mg/min
20
15
10
5
0
0 50 100
Pulse energy, mJ
Fig. 4. Nickel and carbon component production rate vs. pulse energy (pulse
duration, 40 As—hollow markers; pulse duration, 20 As—solid markers).
micrograph of the produced particles is shown in Fig. 1. It is
seen that the particle spatial distribution on the substrate
surface was approximately uniform. Fig. 2 shows the particle
size distribution obtained from analysis of the HRSEM
micrographs. The particle number and the distribution width
increased with the pulse energy. The maximum diameter of the
particles increased from 700 nm to 2 Am when the pulse energy
increased from 7.7 to 48 mJ with a pulse duration of 20 As.
Only particles with diameters greater than ¨ 50 nm were
counted—smaller particles could not be differentiated from the
Au film grain structure.
The anode and cathode erosion rates as a function of the
pulse energy for 20 and 40 As pulse durations are shown in Fig.
3. The rate was nearly a linear function of discharge energy.
The anode erosion rate was greater than the cathode erosion
rate. Fig. 4 shows total (anode plus cathode) electrode erosion
rate and carbon production rate as a function of pulse energy.
The rates linearly increased with pulse energy.
Fig. 5 shows dependence of the precipitate composition (C
and Ni at.%) on pulse energy and duration. The Ni
concentration increased and the carbon concentration decreased
80
60
C & Ni at.%
40
20
0 50 100
Pulse energy, mJ
Fig. 5. Powder component concentration vs. pulse energy (pulse duration, 40
As—hollow markers; pulse duration 20, As—solid markers).
123
Ni
C
150 200
Fig. 6. Typical XRD pattern of produced powder. Sticks correspond to pure Ni
[JCPDS-International Center Diffraction Data, PDF card # 4-850].
with pulse energy. With 20 As pulses, the carbon concentration
decreased from 68% to 54% when the pulse energy was
increased from 7.7 to 100 mJ, while for 40 As pulses the same
change of carbon concentration was obtained when the pulse
energy increased from 60 to 100 mJ.
A typical XRD pattern is shown in Fig. 6. The lines were
substantially broadened, asymmetrical, and shifted to small
angles from the pure Ni spectra. An unidentified Bragg
diffraction line with a lattice spacing of 1.98 Å was observed
in most of the specimens as well, with no noticeable
dependence on the pulse energy. However, XRD patterns of
both the Ni electrodes and powders produced, for comparison,
by a pulsed submerged arc in water match well the reference
spectrum of pure Ni powder [JCPDS-International Center
Diffraction Data, PDF card # 4-850].
4. Discussion
The obtained results show that composition, size distribu-
tion and production rate of particles produced by a pulsed
discharge submerged in ethanol depend significantly on pulse
energy and duration. Pulse energy is expended on electrode
erosion and alcohol decomposition. The erosion products
presumably consist of metal vapor (ions and neutrals), liquid
and solid phases. Previous results [5] show that the obtained
Ni particles had, mainly, a spherical shape. Given that nickel
is ductile, it seems likely that the particles were produced
mainly from vapor or liquid phases, rather than by fracturing
of the solid electrodes. The width of the particle size
distribution increased with pulse energy. This dependence
may be connected with Ni vaporization increase at higher
pulse energy. If Ni concentration becomes higher by the
increased Ni vapor formation, then the coagulation of the Ni
particles is accelerated and, hence, their average size becomes
larger.
150 200 From Fig. 3 it is seen that the anode erosion rate is greater
than the cathode erosion rate. The discharge electrodes are
heated by accelerated charged particles, according to the
electric field direction: the anode by electrons and the cathode
124 N. Parkansky et al. / Powder Technology 162 (2006) 121 – 125
by ions. Electron mobility is greater than ions, and electron
heating of anode is greater than ion heating of cathode for short
pulses. The obtained dependencies of the powder production
on the pulse energy and duration (Fig. 4) can be understood as
follows. A pulse with energy W can vaporize electrode mass
Dm = aW/r, where a is the part of the pulse energy spent on the
powder production and r is the specific vapor energy (6480 and
840 J/g for nickel and ethanol, respectively). The number of the
pulses during time Dt is fDt, where f is the pulse repetition
frequency. Hence, mass DM = DmfDt will be vaporized during
treatment time Dt, and the production rate is given by:
DM f aW
GM ¼ ¼ f Dm ¼ ð1Þ
Dt r
The production rate is proportional to the pulse energy and
the pulse repetition frequency. In our experiments f = 100 Hz
and hence the production rate (mg/min) of nickel particles is
G M å 0.9aW, where W is in mJ. From the best fit to
experimental data we obtained an efficiency of a å 0.16, and
the dependence is G M [mg/min] = 0.15W [mJ] (see Fig. 4).
Now the production rate during the arc pulse, i.e. excluding
pauses between pulses, will be calculated. The net arc time is
DtV= (fs)Dt, and for our experiments Dt = 5 min and DtV= 0.6 and
1.2 s for s = 20 and 40 As, respectively. The net production rate
is given by
DM dM Dm aW
V¼
GM ¼ ¼ ¼ ð2Þ
DtV fs s rs
The net production rate of the nickel particles for our
experiments is G M V [mg/s] = 25W/s, where W is in mJ and the
pulse duration s in As. The net production rate is proportional
to the pulse energy and inversely proportional to the pulse
duration, i.e. G M
V is proportional to the pulse power P = W/s.
Fig. 7 shows that the experimental data agree well with Eq. (2).
It was shown experimentally (Fig. 4) that the carbon
production rate is much less than the nickel particle production
from the electrodes, even though the specific energy of
evaporation of ethanol is less by the factor ¨ 8 than that of
Ni. The reasons, apparently, are: (a) that only a small part of the
pulse energy is expended on the formation of the plasma
channel in the alcohol, in comparison with the energy
dissipated at the electrodes, and (b) the efficiency of the
alcohol decomposition and free carbon formation in the
considered conditions are low.
The XRD spectra showed that the produced powder
contained Ni particles with an FCC cubic structure. The line
shapes and their shift to smaller angles (compared to the pure
Ni powder spectrum) suggest that non-equilibrium nickel –
carbon solid solutions were formed. The nickel – carbon alloys
had an average lattice parameter of 3.5679 T 0.0006 Å. By
using the equation describing compositional variation in Ni– C
alloys at room temperature [7] we obtained that the lattice
parameter corresponds to a highly supersaturated phase with
5.5 at.% C, which is approximately twice the maximum
equilibrium solid solubility of carbon in nickel. Substantial
broadening of diffraction lines in Fig. 6 is caused by micro-
strains and the small size of constituent nanoparticles.
140
Ni&C net production rate, mg/s
120
100
80
60
40
20
0
0 50 100 150 200
Pulse energy, mJ
Fig. 7. Net production rate of Ni and C.
Formation of Ni – C non-equilibrium alloys leads to the line
broadening as well. It should be noted that no crystalline C
lines were observed in the XRD spectra, while EDX spectra
indicated that the C composition in the powder was in the range
of 50– 70 at.%. Thus apparently only a small fraction of the
carbon is incorporated within the Ni particles, while most of
the carbon is amorphous or nano-crystalline.
5. Conclusion
The obtained results showed that pulsed arc parameters
influence production rate and properties of the produced
powder and may be summarized as follows:
1. Production rate. The powder production rate increases
proportionally with the pulse energy. The nickel production
rate is larger by a factor of 3.6 than that of the carbon. The
net production rate of the nickel particles is proportional to
the pulse power. The powder production rate may be
increased by increasing pulse energy or frequency and by
decreasing the pulse duration. The production rate depends
on electrode polarities: the anode erosion rate is greater than
that of the cathode by a factor of 1.6.
2. The width of the particle size distribution function increases
with the pulse energy, e.g. by factor of ¨ 10 for 20 As pulses
when the energy increased from 7.68 to 48 mJ.
3. Carbon concentration in the produced powders decreases
with pulse energy, e.g. for 20 As pulses, from 67% to 54%
when the energy was increased from 7.68 to 48 mJ and for
40 As pulses from 30.7 to 192 mJ.
Acknowledgements
The authors gratefully acknowledge the financial support of
the Israel Academy of Sciences and Humanities.
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