Int J Adv Manuf Technol (2005) 26: 552–558
DOI 10.1007/s00170-003-2029-8
ORIGINAL ARTICLE
H. Chang · T.T. Tsung · L.C. Chen · Y.C. Yang · H.M. Lin · C.K. Lin · C.S. Jwo
Nanoparticle suspension preparation using the arc spray nanoparticle synthesis
system combined with ultrasonic vibration and rotating electrode
Received: 4 September 2003 / Accepted: 12 November 2003 / Published online: 24 November 2004
© Springer-Verlag London Limited 2004
Abstract This study aims to investigate the use of a new
nanoparticle preparation method, i.e., the arc spray nanoparticle
synthesis system (ASNSS) combined with ultrasonic vibration
and rotating electrode, to prepare TiO2 nanoparticle suspension.
For the proposed new method of nanoparticle suspension prep-
aration, this study has designed four different process modes of
experimentation for comparison, in order to obtain suspended
nanoparticles with smaller particle size and relatively good dis-
persion. This study discusses the process modes with differ-
ent settings of variables including peak current, pulse duration,
breakdown voltage, temperature of the dielectric fluid and am-
plitude of ultrasonic vibration, in order to determine the better
conditions for the preparation of TiO2 nanoparticles suspension.
The Transition Electron Microscope (TEM) image of the ex-
periment result shows that TiO2 nanoparticles prepared by the
ultrasonic vibration assisted vacuum arc spray process has an
average particle size of less than 10 nm.
H. Chang (u) · T.T. Tsung · Y.C. Yang
Department of Mechanical Engineering,
National Taipei University of Technology,
Taiwan, R.O.C.
E-mail: f10381@ntut.edu.tw
Tel.: 886-2-27712171 ext. 2035
Fax: 886-2-27317191
L.C. Chen
Institute of Automation Technology,
National Taipei University of Technology,
Taiwan, R.O.C.
H.M. Lin
Department of Materials Engineering,
Tatung University,
Taiwan, R.O.C.
C.K. Lin
Department of Material Science,
Feng Chia University,
Taiwan, R.O.C.
C.S. Jwo
Department of Air-Conditioning and Refrigeration Engineering,
National Taipei University of Technology,
Taiwan, R.O.C.
Keywords Nanoparticles suspension · Rotating electrode ·
Ultrasonic vibration · Vacuum arc spray process
1 Introduction
Nanomaterial is composed of particles with a grain size rang-
ing from 1 to 100 nm. Because of the quantum size effect, small
size effect, surface effect, and macroscopic quantum tunneling
effect in itself, nanomaterials can present many unique qualities.
Since nano-TiO2 possesses such characteristics as strong reduc-
tion and oxidation capability, high chemical stability, harmless
to the environment, and low prices, it can be used as a new type
of photocatalyst [1], and has many applications in areas such
as bacteria and fungus resistance, emission purification, air pu-
rification, water purification, self-cleaning, and photosynthesis.
Hence, TiO2 nanoparticle suspension has a great potential of be-
coming one of the star industries in the future.
Nanoparticle preparation methods are generally divided into
gas phase method, liquid phase method, and mechanical ball
milling method, which can be further divided into vacuum con-
densation method, gas condensation synthesis method, electron
beam or laser gas phase deposition method, sol-gel method, elec-
trochemical deposition method, etc. [2, 3].
The gas condensation method, however, can often result in
the loss of the various distinctive qualities of nanoparticles be-
cause the condensation process itself can cause nanoparticles to
aggregate. Using the basic principles of the gas condensation
method, this study has developed the vacuum arc spray nanopar-
ticle synthesis system (ASNSS) combined with ultrasonic vibra-
tion and rotating electrode, which includes four different types
of process modes, i.e., conventional vacuum arc spray, ultrasonic
vibration assisted, revolving electrode assisted, and vibro-rotary
assisted processes. In the experiment, the differences between
the TiO2 nanoparticles prepared by the four different process
modes are compared and the influence of various process vari-
ables on the preparation of TiO2 nanoparticles suspension is also
discussed. The experiment device mainly comprises a heating
system, an ultrasonic vibration system, a pressure control sys-

tem, and a temperature control system [4]. The particles thus
produced are dispersed in deionized water, which helps reduce
the aggregation phenomenon upon particle collection.
2 Theory analysis
The major principle of the nanoparticle synthesis system de-
veloped by this study is to use the rod for producing material
as electrodes and to place the two electrodes into the insulation
dielectric liquid, which is made of deionized water. A DC volt-
age ranging from tens to hundreds of volts is then provided be-
tween the electrodes. When the gap between the two electrodes
becomes sufficiently small, the magnitude of the electric field be-
tween the electrodes will surpass the insulation endurance of the
dielectric liquid, which will then lead to an insulation breakdown
and a plasma channel will thus be formed. Under high plasma
temperature, the insulation fluid surrounding the electrodes will
gasify and dilate, which will generate an ultra-high pressure, of
which the energy density can reach as high as 3 J/mm3 , a tem-
perature up to 40 000 K, and a pressure of 3000 bar.
Of all the processing capacity of the electric arc, 18% is used
to melt the cathode, 8% is used to melt the anode, and the re-
maining 74% is used to grow the electric arc. Throughout the
process, the ratio between energy density and electron number
density is held constant and is mainly subject to the following
two factors: (1) breakdown voltage, and (2) the thermal prop-
erty of the dielectric liquid. The energy density equation can be
expressed as follows [5]:


ρH U m i yi
= = H . (1)
ne 6.317 × 10 18 ye
In Eq. 1, ρH (J/cm3 ) denotes energy density, n e (electrons/
cm3 ) the electron number density, U the mean breakdown volt-
age, m i the particle mass, and yi the fraction of particle. As Eq. 1
shows, the energy density is proportional to the electron num-
ber density and mean breakdown voltage. Hence, it requires high
mean breakdown voltage to generate great energy density.
The growth of the nucleus determines the desired size of
the nanoparticles. The growth rate of the nucleus is controlled
primarily by the concentration of the vaporized metal and the
temperature of deionized water [6]. The temperature has a more
critical influence on the sizing of nanoparticles since the growth
rate of the nucleus is significantly affected by the metal trans-
fer frequency from the gaseous state (β) to solid state (α) on the
interface. The relationship of these parameters is shown in Eq. 2:
 
∆g
f β→α = ν exp − , (2)
kT
where ν is the vibration frequency of the atom, and ∆G is the
activation energy of diffusion.
Equation 2 indicates that when temperature drops, the growth
rate of the crystal nucleus will decrease rapidly. So, the most
effective way to check the growth of grains and acquire tiny
nanoparticles is a quick cooling.
553
Table 1. Adjustable range of ultrasonic system parameters
Ultrasonic frequency (kHz) Amplitude (µm) Rotary speed (rpm)
21.7 ∼ 18.5 0 ∼ 10 0 ∼ 500
This study integrates the ultrasonic vibration system with
electrode by tightening the screw that locks the end of the axis of
the ultrasonic system with the titanium rod. The oscillator used
in the ultrasonic system is a Lengevin-type piezoelectrical trans-
ducer with an input working power of 300 W. A motor-driven
timing belt is used to make sure that the axis of the ultrasonic vi-
bration and the electrode rotate at the set speed. Since the input
voltage of the ultrasonic vibration system is in direct proportion to
its amplitude, the amplitude of ultrasonic vibration can be altered
through voltage adjustment. In order for the ultrasonic vibration
to enhance the process of the vacuum electric arc, the end spot of
the titanium electrode has to be the resonance point. By adjust-
ing the frequency of the ultrasonic system, the end of the titanium
electrode can be made at exactly the position of half-wave, and
since it is the resonance point, the ultrasonic microjet can inject
into the cavitation bubble at a speed of approximately 110 m/s.
This generates a high-pressure injection effect, thereby achieving
the best result of ultrasonic vibration [7, 8]. The adjustable range
of the ultrasonic system variables is shown in Table 1.
3 Experiment design
The experiment device of the combined vacuum arc spray system
in this study is illustrated in Fig. 1. The main technique involved
in the process includes the use of the titanium bulk to be pro-
duced as the electrode and the integration of the device with an
ultrasonic vibrator, of which the electrode can revolve around
simultaneously. The experiment device mainly comprises a heat-
ing system, an ultrasonic system, a pressure control system, and
a temperature control system. Of which, the heating device can
provide a stable electric arc to serve as the needed heat source for
nanoparticle preparation. In addition, the system allows differ-
ent settings for important process variables such as peak current,
voltage, pulse duration, off time, and gap voltage. The ultra-
sonic system allows different settings of frequency, amplitude,
and rotation speed. With the help of the ultrasonic vibration,
the disturbance of the dielectric liquid can be increased and the
nanoparticles thus produced can quickly come out of the fusion
zone. In the meantime, the gasified metal can be quickly cooled
down. The pressure control system is used to maintain an ap-
propriate vacuum pressure inside the vacuum chamber, and uses
deionized water as the dielectric liquid. The temperature con-
trol system allows different cooling temperature settings, which
helps grain nucleation and prohibits the growth of grains. Hence,
smaller sized nanoparticle suspensions can be obtained.
For the preparation of finer and well-dispersed nanoparticles,
the experiment used four different process modes for compari-
son, as shown in Fig. 2. The four modes used are the conventional
554
Fig. 1. Schematic diagram of the ASNSS
combined with the ultrasonic vibration and
rotating electrode for nanomaterial produc-
tion
Fig. 2. The four different process modes adopted
vacuum arc spray process, ultrasonic vibration assisted vacuum
arc spray process, rotating electrode assisted vacuum arc spray
process, and vibro-rotary assisted vacuum arc spray process.
The influence of such process parameters as breakdown volt-
age, pulse duration, and temperature of the dielectric fluid, as
well as the amplitude of the ultrasonic system on the nanopar-
ticles prepared, is analyzed and compared through experimenta-
tion in order to identify the process conditions conducive to the
production of nanoparticles with smaller mean particle sizes.
4 Results and discussion
The particle size distribution of the TiO2 nanoparticle suspen-
sions prepared by different process modes, as measured by
HORIBA LB-500 particle size distribution analyzer, is shown
in Fig. 3. Figures 3a and 3b illustrate the relationship between
the peak current and the mean particle size under a breakdown
voltage of 220 V and 90 V, respectively. Under a preparation
condition with a breakdown voltage of 220 V, the size of the par-
ticles prepared by the vacuum arc spray (conventional) process
will increase as the current rises. Contrarily, the size of particles
prepared by the ultrasonic vibration assisted process decreases as
the current drops, but the particle size will begin to grow with
the increase of current as it reaches around 6 A. As Fig. 3a indi-
cates, the particles produced by the ultrasonic vibration assisted
process at a current of around 5.5 A are the smallest (∼ 50 nm) of
the four different process modes, while the mean particle sizes of
the particles prepared by the other three process modes all exceed
100 nm. The size of the particles prepared by the revolving elec-
trode assisted process (250 rpm) grows slowly with the increase
of current. But the influence of current on particle size is signifi-
cantly smaller by comparison. On the contrary, the size of the
particles prepared by the vibro-rotary assisted process slowly de-
creases as current rises, but will gradually increase as the current
goes up to 7 A. Under a preparation condition with a breakdown
voltage of 90 V, the vacuum arc spray (conventional) process
under a current of below 6 A cannot produce stably suspended
particles, and the mean particle size is the largest among the four
different process modes. The size of the particles prepared by the
ultrasonic vibration assisted process will decrease as the current
increases, but as the current reaches 6 A, the particle size will
start to grow with the increase of current. Both of the sizes of
the particles prepared by the revolving electrode assisted process
(250 rpm) and the vibro-rotary assisted process slowly decrease
as the current increases. In addition, all three processes of the ul-
trasonic vibration assisted process, revolving electrode assisted
process, and vibro-rotary assisted process under a current below
3 A, fail to produce stably suspended particles. As Fig. 3b indi-
cates, under a breakdown voltage of 90 V, all four process modes
produce particles with a mean size exceeding 150 nm. The com-
parison of Figs. 3a with 3b shows that finer TiO2 nanoparticles
can be obtained under greater breakdown voltages. Furthermore,
the Field Emission Scanning Electron Microscope (FESEM) is

Fig. 3. Relationship between the current and particle size under different
process modes with breakdown
used to observe the morphology of the particles produced by the
ultrasonic vibration assisted process under a current of 6 A. Fig-
ures 4a and 4b are the FESEM images under a current of 6 A and
with a breakdown voltage of 220 V and 90 V, respectively. As
Fig. 4a indicates, the particles are more or less in a round shape
with a mean size of 60 nm. In Fig. 4b, the mean particle size is
approximately 200 nm.
From the above experiment results and discussions, it is clear
that the ultrasonic vibration assisted vacuum arc spray process
can effectively enhance the capability of the vacuum arc spray
555
Fig. 4a,b. The FESEM image of ultrasonic vibration assisted process with a
current of 6 A and a breakdown voltage of a 220 V and b 90 V
system for the preparation of nano-level TiO2 nanoparticle sus-
pension. Ultrasonic vibration produces alternating pressure vari-
ation, which leads to increased hydrostatic pressure variation.
When the gap is widened, a large pressure drop causes more
molten metal to be removed from the crater [9, 10]. Since the
particles can be effectively removed from the crater, the proba-
bility of carbon deposition is reduced while the stability of the
arc is enhanced [11, 12]. In addition, the energy of the ultrasonic
vibration can generate minute disturbance and impact on the dis-
charge fusion zone, making the gasified metal easier to move
away from the fusion zone and quickly cooled down by the low-
temperature coolant surrounding it. In the meantime, this can
retard the growth stage of nanoparticles after nucleation when
the metal is solidifying. Hence, we will be able to obtain better
nano-level particles and better dispersed suspension.
Among the process variables, it is found that the pulse du-
ration can affect the arc temperature and crater radius. In order
to investigate the influence of pulse duration on the preparation
556

Fig. 5. Relationship between the pulse duration and mean particle size Fig. 6. Relationship between the current and mean particle size under ultra-
sonic vibration assisted process with varying amplitudes

of nanoparticles, the experiment selects the ultrasonic vibration

assisted process and sets the breakdown voltage at 220 V with
the pulse duration set at 2 µs, 4 µs, 25 µs, and 200 µs, respec-
tively. Figure 5 shows the changes between pulse duration and
particle size at a current of 2.25 A and 3.75 A, respectively. As
the figure indicates, when the current is 2.25 A, with pulse dura-
tion growing from 2 µs to 200 µs, the mean particle size of the
particles suspension will increase from 75 nm to 257 nm, while
under a current of 3.75 A with pulse duration growing from 2 µs
to 200 µs, the mean particle size of the suspended particles will
increase from 134 nm to 323 nm. Seen from Fig. 5, it is clear that
pulse duration has a great influence on the mean size of the par-
ticles produced. In other words, only with smaller pulse duration
will it be possible to obtain nano-level particles.
The amplitude of ultrasonic vibration is an important vari-
able in the ultrasonic system. In order to understand the influence
of amplitude on the preparation of nanoparticles, the experi-
ment selects the ultrasonic vibration assisted process and sets the
breakdown voltage at 220 V and pulse duration at 2 µs, in order
to find out the relationship between current and nanoparticle size
under varying amplitudes of ultrasonic vibration. The result is
summarized in Fig. 6. As the figure indicates, when the current is
below 8 A, the particles produced under an amplitude of 10 µm Fig. 7. Relationship between the temperature of the dielectric fluid and mean
particle size under ultrasonic vibration assisted process
have a mean size larger than those prepared under an amplitude
of 5 µm. But, when the current exceeds 8 A, the mean size of
the particles prepared under an amplitude of 5 µm may exceed breakdown voltage to constant. The temperature of the dielec-
that of particles prepared under an amplitude of 10 µm. As Fig. 6 tric fluid is set at 0◦ , 3◦ , 8◦ , 12◦ , and 19◦ , respectively, in order
reveals, with smaller amplitude and specific current, nano-level to identify the relationship between temperature of the dielectric
particles can be obtained. fluid and nanoparticle size. As Fig. 7 indicates, when the tem-
In order to understand the influence of the temperature perature is at 0◦ , the nanoparticles have a mean size of 70 nm,
change in the dielectric fluid on the preparation of nanoparticles, and the particle size will grow with the increase in the tempera-
the experiment selects the ultrasonic vibration assisted process ture. When the temperature is at 19◦ , the particle size of the
and sets such process variables as current, pulse duration, and nanoparticles prepared will grow to 231 nm.
 557

Table 2. Process variables contributing to the production of ideal nano- From the experiment results and discussions above, it is clear
particles that among the four different process modes, the ultrasonic vi-
bration assisted process produces nanoparticles with the small-
Process type Vibratory
est mean size ,and that process variables including breakdown
Breakdown voltage (V) 220
voltage, pulse duration, amplitude of ultrasonic system, and tem-
Peak current (A) 2.25 ∼ 6 perature of the dielectric fluid can all affect the preparation of
Pulse duration (µs) 2 nanoparticles. The nanoparticle suspension prepared under better
Off time (µs) 2 process variables identified throughout different sections in the
Pressure (Torr) 30
Temperature of dielectric liquid (◦ C) 0 experiment is summarized in Table 2. In other words, nanoparti-
Ultrasonic frequency (kHz) 19.7 cles with a mean particle size of below 100 nm can be prepared
Amplitude (µm) 5 using process variables within their respective scopes listed in
Table 2, and particles with the smallest mean size can be achieved
under a current of 4.5 A. Figure 8 is the particle size distribu-
tion derived from the HORIBA particle size distribution analyzer,
which indicates a mean particle size of 50.9 nm. Figure 9 is the
same nanoparticle suspension in TEM image, of which the mean
particle size is measured at 8.5 nm. The reason why the HORIBA
particle size distribution analyzer has derived a larger particle size
than that measured directly on TEM image is that the HORIBA
particle size distribution analyzer adopts the dynamic light scat-
tering principle, and thus some of the measurements represent the
particle size of aggregated or overlapping nanoparticles.

5 Conclusions
This study has successfully produced TiO2 nanoparticle suspen-
Fig. 8. TiO2 nanaoarticle size distribution under better process variables
sion using the self-developed combined vacuum arc spray sys-
tem, and has arrived at the following conclusions through the
experiment.
Ultrasonic vibration assisted process can enhance the ordi-
nary vacuum arc spray process and can successfully produce
nano-level particles. When under higher breakdown voltages and
specific currents, the particles produced can achieve a mean par-
ticle size of below 10 nm.
Smaller pulse duration can raise plasma temperature, and re-
duce the size of the crater, making the size of particles smaller.
When the pulse duration is reduced from 200 µs to 2 µs, the
mean size of the nanoparticles prepared will decrease from
257 nm to 75 nm.
The amplitude of ultrasonic vibration can affect the size of
particles prepared; nano-level particles can be prepared under
smaller amplitudes.
Lower temperatures of the dielectric fluid prohibit the growth
of grains, and thus are conducive to the preparation of smaller
sized nanoparticles. When the temperature of the dielectric fluid
is dropped from 19◦ to 0◦ , the mean size of the nanoparticles
prepared will decrease from 231 nm to 70 nm.

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