Int J Adv Manuf Technol (2007) 31: 682–687
DOI 10.1007/s00170-005-0241-4
ORIGINA L ARTI CLE
S. H. Choi . S. H. Ryu . D. K. Choi . C. N. Chu
Fabrication of WC micro-shaft by using electrochemical etching
Received: 21 December 2004 / Accepted: 19 August 2005 / Published online: 6 January 2006
# Springer-Verlag London Limited 2006
Abstract Tungsten carbide (WC) micro-shaft can be used
as various micro-tools for MEMS because of its high
rigidity and toughness. In this study, we performed
fabrication experiments of the WC micro-shaft using
electrochemical etching. H2SO4 solution was used as the
electrolyte because it can dissolve tungsten and cobalt
simultaneously. Optimal electrolyte concentration and ap-
plied voltage resulting in uniform shape, good surface
quality, and high material removal rate (MRR) of a work-
piece were experimentally selected. A straight micro-shaft
with 5 μm diameter and 3 mm length was obtained by
controlling the various machining parameters. Using the
fabricated micro-shafts as tools, we machined a high
quality micro-hole with 8 μm diameter and a micro-groove
with 9 μm width in stainless steel 304 (304 SS).
Keywords Electrochemical machining . Electrochemical
etching . Tungsten carbide
1 Introduction
The interest in micro/nano-technology has increased and
the market size for ultra-small parts required in MEMS/
NEMS has also increased. Micro-shaft and nano-tip fabri-
S. H. Choi (*) . C. N. Chu
School of Mechanical & Aerospace Engineering,
Seoul National University,
Seoul, South Korea
e-mail: sewany77@snu.ac.kr
Tel.: +82-2-8807147
Fax: +82-2-8877259
e-mail: cnchu@snu.ac.kr
S. H. Ryu
Department of Mechanical Engineering,
Chonbuk National University,
Jeonju, South Korea
D. K. Choi
Department of Precision Mechanical Engineering,
Kangnung National University,
Kangnung, South Korea
cation technology are needed to make the electrode or the
probe for electrochemical micro machining and micro-
scopes, respectively. Because it is difficult to make micro-
shafts smaller than 200 μm in diameter by conventional
processes, new micro-shaft fabrication technologies are
needed. Electrochemical machining is generally used as a
finishing process to improve the surface roughness of struc-
tures made of refractory hard metals. Also, micro electro-
chemical machining can be widely used in the fabrication of
micro nozzles, channels, various sensors and actuators in
MEMS/NEMS, and micro die/mold manufacture.
In electrochemical machining, the workpiece material is
removed by the anodic dissolution process in electrolytes
under an electric field. Electrochemical machining does not
need contact between tool and workpiece and thus neither
residual stress nor a heat-affected zone is generated on the
machined surface. Since the material is removed to a level
of an atomic unit, the surface quality of the machined
surface is also good. The electrochemical system can be set
up without special FAB or expensive equipment necessary
in sequential processes such as lithography [1].
Muller and Tsong [2] initially made a tungsten (W)
micro-probe for field ion microscopy (FIM) by electro-
chemical etching. Many researchers have studied micro-tip
manufacturing for the scanning tunneling microscope
(STM) and the atomic force microscope (AFM). Lim et
al. [3] reported the fabrication of a 50 μm diameter W
micro-shaft by the current density control. Generally,
tungsten or platinum (Pt) alloy tips have been used for the
probes, however, these materials are not sufficiently rigid
for repeatability and endurance assurance. Once deformed
by hard workpiece, W or Pt tools cannot perform to their
original ability, thus more rigid tools like tungsten carbide
(WC) are needed. WC micro-shafts have high rigidity and
hardness; therefore, they can be widely adopted as micro
punching tools or micro electrode tools for electrical
discharge machining and electrochemical machining.
Human et al. [4], Basu and Sarin [5], and Andersson and
Bergstrom [6] dealt with the electrochemical characteristics
of WC oxidation and the dissolution mechanism using
potential sweeping and microstructure analysis such as X-

ray diffraction (XRD) or X-ray photoelectron spectroscopy
(XPS).
In this study, by electrochemical etching of the rod
composed of WC with cobalt (Co) binder, a micro-shaft
having a diameter smaller than 10 μm was fabricated. The
electrolyte was selected considering the electrochemical
complexity of WC with Co. The shape, size, and surface
quality were investigated according to electrolyte concen-
tration, applied voltage, and etching time. In the finishing
process, the sludge generated was removed by dissolving
in an alkali solution. Under optimal machining conditions
based on the experimental data, a straight WC micro-shaft
with high aspect ratio and good surface quality was
fabricated. With the micro-shaft, micro-holes and micro-
grooves were machined on stainless steel 304 (304 SS) by
electrochemical etching with ultra short pulse voltage.
2 Electrochemical etching of WC
2.1 Material properties of WC
WC is widely used as tool material because of its high
rigidity, toughness, and good wear resistance. It is
commonly produced by powder metallurgy. High solubil-
ity of WC in Co at high temperature and good wetting of
WC in the liquid cobalt binder give excellent densification
during liquid phase sintering and result in a pore-free
structure. In this research, WC rod with 200 μm diameter
and 2.5 cm length were prepared for electrochemical
etching. Its mechanical properties include: density of
12.3 g/cm3, hardness of 87.5 HRA, yield strength of
4,600 N/mm2, and Young’s modulus of 460 kN/mm2. The
material is composed of 68 wt % WC, 28 wt % Co, and 4
wt % other material such as Ti.
2.2 Electrolyte selection
To fabricate the WC micro-shaft by electrochemical
etching, the electrolyte must be capable of dissolving
WC and Co composites simultaneously. H2SO4 solution or
mixed solution of NaCl with NaOH can dissolve the
materials [1]. However, the electrochemical behavior of
WC is quite different to that of pure W. This is specifically
seen in the WC dissolution rate, which rapidly decreases in
a neutral or alkali solution as Co increases [6]. Thus an
alkali solution such as NaCl with NaOH solution is not
suitable. H2SO4 solution can dissolve both W and Co
leaving the machined material with a good surface quality.
Therefore H2SO4 solution was selected as the electrolyte
for the WC micro-shaft dissolution.
2.3 Experimental set-up
The experimental processes consisted of etching WC rod in
an electrochemical cell, sludge removal, and measurement.
The schematic diagram of the electrochemical system for
683
the WC micro-shaft fabrication is shown in Fig. 1. The WC
specimen was attached to a jig that was chucked to the
precise feeding system. The z-axis was controlled by a
PMAC motion controller. In the acryl bath filled with
H2SO4 solution, the specimen was immersed 3 mm into the
electrolyte and connected to the anode of the DC power
supply. Pt wire was also immersed in the electrolyte and
connected to the cathode. The machining state such as
sludge formation and bubble generation was monitored by
a vision system. Porous sludge attached to the outside
surface of the specimen was subsequently removed by
ultrasonic cleansing or chemical dissolution. Finally, micro-
shaft shape, after sludge removal, was taken using scanning
electron microscopy (SEM).
2.4 Reactions at electrodes
The chemical reactions of WC with Co binder at the anode
of WC and the cathode of Pt in H2SO4 solution can be
described as follows [4–6].
Anodic reaction:
WC þ 5H 2 O ! WO 3 þCO 2 þ10H þ þ10e
(1)
WO 3 þ2H 2 O ! ðWO 3  2H 2 O Þ
Co þ WO 3 þH 2 O ! CoWO 4 þ2H þ þ2e

Co þ 2H 2 O ! CoðOH Þ2 þ2H þ þ2e

Co þ H 2 SO 4 ! CoSO 4 þ2H þ þ2e

Cathodic reaction:
2H þ þ2e
! H 2 (2)
As expressed in Eq. 1 at the anode, W in WC reacts with
H2O to form the oxidized WO3, which is then attached to
the specimen in the form of porous sludge. C in WC forms
CO2 gas and the generation of CO2 leads to porosity and
cracking in WO3 owing to the force of the escaping gas [5].
In a strong acid solution with less than pH 1, most WO3
combines with the water molecule and thus exists as the
hydrated form (WO3·2H2O) [6]. Some WO3 reacting with
Co and H2O produces CoWO4. The major part of the Co
Z Stage Controller PC
WC
Pt -+
DC
Power
H2SO4 Supply
Fig. 1 Schematic diagram of electrochemical etching system
684
reacts with the hydroxyl ion (OH–) to dissolve as a Co2+ ion,
and some of the Co remains as the oxidized layer with
CoWO4 or CoSO4 which forms on the specimen [4]. As
expressed in Eq. 2, at the cathode a proton (H+) in the
electrolyte gains an electron to reduce to a hydrogen gas (H2).
The Pilling Bedworth ratio (the ratio of the volume of
oxide formed to the volume of metal consumed) for W is
3.3 [5]. The formation of the W oxide layer was inferred
from observing the much larger volume of sludge than that
of the raw material, as shown in Fig. 2. From the analysis of
sludge components using energy dispersive spectroscopy
(EDS), it was shown that the ratio of Co is smaller in the
sludge than in the raw material. When the electrolyte was
not sufficiently supplied, the electrolyte color was con-
verted to red, which is the color of Co ions. From these
results, it was concluded that Co dissolved to form ions. The
bubble generations of CO2 at the WC anode and H2 at the Pt
cathode could be observed using the vision system.
3 Results and discussion
3.1 Etching characteristics according
to the electrolyte concentration
Experiments were performed to investigate the machining
characteristics according to H2SO4 solution concentration.
The electrolyte concentration varied from 0.5 M to 2.5 M in
0.5 M steps. Applied voltage was 4.1 V and the specimen
diameter was measured after 210 s of machining. As shown
in Fig. 3, the relationships between the electrolyte con-
centration and the diameter had a parabolic profile. In the
1.5 M electrolyte, diameter of the etched specimen had a
minimum value and material removal rate (MRR) was at a
maximum. On the other hand, the straightness and the
surface quality of the machined micro-shaft were not
distinctively different with respect to electrolyte concentra-
tions. The electrolyte concentration was set to 1.5 M
H2SO4 solution considering the machinability.
While MRR increased as electrolyte concentration
increased at low concentration, MRR dropped inversely
as electrolyte concentration was larger than 1.5 M. The
Fig. 2 Sludge growth on the specimen during WC etching
Fig. 3 Diameter of workpiece according to electrolyte concentra-
tion with applied voltage 4.1 V and machining time 210 s
change in the reaction rate according to concentration
change can be explained by the variation of ion activity. As
shown in Eq. 3, ion activity (a) can be expressed by the
activity coefficient (r) multiplied by the electrolyte con-
centration (m). In a dilute solution, the ion activity
increases with the nearly constant activity coefficient as
the concentration increases. However, in a thick solution
ion activity becomes small despite the large concentration.
The reason is that the probabilities of ionic interference and
the ionic association increase together with permittivity
reduction and thus activity coefficient drops as the elec-
trolyte concentration increases [7, 8]. Thus, ion activity and
dissolution rate have a maximum value at a certain
concentration, which is 1.5 M in this study.
a¼rm (3)
where a is the ion activity, r is the activity coefficient, and
m is the electrolyte concentration.
3.2 Etching characteristics according
to the applied voltage
Voltage between the tool and the workpiece critically
affects machining characteristics. When applied voltage
was lower than 2 V, MRR was very low and the workpiece
shape changed to a conical form as the shaft diameter
decreased; thus, it was difficult to make the micro-shaft
with a uniform diameter of less than 20 μm. In the region of
2∼3 V, chemical reactions rarely occurred due to the
hindrance of the tungsten or cobalt oxide generated. WC is
an alloy of various metals and each component has its own
passivity, thus the passive region has a wide range of
around 2∼3 V. Over 5 V, the shaft shape was not straight
and the surface was very rough because excessive bubble
generation leads to non-uniform dissolution.
Figure 4 represents the variation of the micro-shaft
diameter according to the applied voltage with the fixed
concentration of 1.5 M and machining time of 210 s. The
minimum diameter was obtained at about 4.0∼4.5 V. Over

Fig. 4 Diameter of workpiece according to applied voltage with
electrolyte 1.5 M H2SO4 and machining time 210 s
time, the shape of the shaft changed to a conical form and
thus it was impossible to get a shaft of uniform diameter at
applied voltage lower than 4.0 V. At low voltage the con-
centration of charge induced intensive dissolution at the
shaft end and a tapered shape of the shaft. However, at high
voltage excessive diffusion layers of dissolved ions hin-
dered chemical reaction at the shaft end [5]. This is because
the diffusion layers have a greater density than the
electrolyte and thus tend to sink downward. Therefore, an
inverse-tapered and uneven shape was obtained over 4.2 V.
Since charge concentration resulting from high activity in
that region lead to the rapid dissolution, necking occurred at
the interface between the electrolyte and the air in the region
of 4.7∼5 V. When 4.1 V was applied, the shape of the shaft
was entirely straight due to the balance obtained between
the effects of charge concentration and diffusion layers. The
applied voltage of 4.1 V was the local optimum with respect
to form accuracy, repeatability, and machinability.
3.3 Etching characteristics according
to the etching time
At 4.1 V applied voltage and 1.5 M H2SO4 solution,
variations of the shaft diameter and shape were experi-
mented with according to machining time. As shown in
Fig. 5, the removed volume was linearly proportional to the
machining time at less than 180 s. The uniform shape was
obtained without taper generation. A certain etching time
resulted in a straight micro-shaft with a certain diameter.
Regardless of the etching time, the deviation was within
5 μm. After 200 s, because of the electric charge concen-
tration at the shaft end, dissolution intensity occurred at the
end region so the machined shaft became conical with a
taper. When the etching time was longer than 220 s, the shaft
shape was converted to a sharp tip and the length of shaft was
rapidly shortened longitudinally.
3.4 Finishing of WC micro-shaft fabrication
The micro-shaft shape obtained at the 4.1 V applied
voltage, 1.5 M H2SO4 solution, and 210 s machining time
685
Fig. 5 Diameter of workpiece according to machining time with
electrolyte 1.5 M H2SO4 and applied voltage of 4.1 V
is shown in Fig. 6. The diameter of the manufactured
micro-shaft was 5 μm with 0.2 degree taper angle. The
straightness and surface quality of the acquired WC micro-
shaft were good.
The sludge generated on the specimen, composed of W
and Co oxide layers, was removed by immersing the shaft
in alkali solution. The sludge can be removed by ultrasonic
cleansing or by chemical dissolution. When we used the
ultrasonic cleansing, the machined micro-shaft occasion-
ally broke and the sludge could not be completely
removed. Therefore, this study used chemical dissolution
for the removal of the porous oxide layer. We selected the
NaOH as the cleansing solution because the sludge
components of WO3 and CoWO4 dissolve well in alkali
solution with high pH to form ions [6]. After electrochem-
ical etching, the specimen was immersed in 2 M NaOH
solution with the sludge being completely removed after
about 24 hours. Spectra of EDS show the variation of the
surface components of the original specimen after etching
and after sludge removal. Co reduction was observed and
we could infer from it that the generated oxide layer was
removed.
Fig. 6 WC micro-shaft with electrolyte 1.5 M H2SO4, applied
voltage 4.1 V, machining time 210 s, 3 mm length, 5 μm diameter,
and 0.2° taper angle. a Global shape. b Enlarged view of a
686
Power source
Tool Gap monitoring
module
module
Workpiece
X, Y, Z Stage
Controller
Fig. 7 Schematic diagram of ECM system
3.5 Electrochemical machining using the WC
micro-shaft
By applying the WC micro-shafts fabricated in this study as
micro electrode tools, a micro-hole and a micro-groove on
stainless steel (304 SS) were produced by electrochemical
machining. The experimental system consisted of an ECM
cell, a pulse generator, and a motion controller with
feedback system. To localize the electrochemical dissolu-
tion region near the micro-shaft end, a 304 SS workpiece
was laid very close to the tool end and voltage pulses of a
few tens of nanosecond duration were applied between the
micro-shaft electrode and the workpiece [9, 10]. Fig. 7 is
the schematic diagram of the ECM system.
The feed rate of the tool electrode was selected
considering the dissolution rate according to electrochem-
ical conditions. It was difficult to avoid mechanical contact
between the tool and the workpiece because of the very
small gap between them. When the tool and the workpiece
came into contact, the tool neither broke nor deformed due
to its high rigidity. Using the WC micro-shaft with 6 μm in
diameter, we machined a micro-hole with 8 μm in diameter
Fig. 8 Hole in 20 μm thick 304 SS with ϕ6 μm tool, 30 min
machining time, ϕ8.0 μm entrance, ϕ7.3 μm exit, and 1.0° taper
angle [10]
Fig. 9 Groove in 304 SS with ϕ7 μm tool, 10 min machining time,
9 μm width and 10 μm depth
on 304 SS foil with 20 μm thickness, as shown in Fig. 8.
The hole has a good roundness because of the straightness
of the micro-shaft. Fig. 9 shows the micro-groove with
9 μm in width and 10 μm in depth on 304 SS machined by
the 7 μm diameter WC micro-shaft. The machined groove
had a sharp edge and the surface quality was excellent.
From the above experiments, we found that by using the
WC micro-shaft as a tool, a high quality micro-hole and
micro-groove could be manufactured by electrochemical
process. The WC micro-shaft studied in this research can
be used as a valuable micro-tool for the fabrication of
various three dimensional microstructures.
4 Conclusions
The WC micro-shaft was fabricated by electrochemical
etching. Considering the complex material properties of
WC with Co binder, H2SO4 solution was used as an
electrolyte. Optimal conditions such as electrolyte concen-
tration, applied voltage, and machining time were selected
experimentally. With respect to micro-shaft shape, surface
quality, and machinability, 1.5 M H2SO4 solution and 4.1 V
applied voltage were local optimum conditions for micro-
shaft fabrication. After machining for 210 s, we could
fabricate the WC micro-shaft with good straightness and
surface quality with 5 μm diameter and 3 mm length. The
sludge generated on the specimen was removed by
immersing the shaft in NaOH solution. By using the
fabricated WC micro-shafts as tools, a micro-hole with
8 μm in diameter and a micro-groove with 9 μm in width
were machined on 304 SS by localized electrochemical
dissolution with a few tens of nanosecond pulses. It is
expected that various three dimensional microstructures
can be fabricated using the micro-shaft in an electrochem-
ical process.
Acknowledgement This research was supported by KISTEP
(Korea Institute of Science & Technology Evaluation and Planning)
through the Nanoscale Mechatronics & Manufacturing Program.

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