Journal of Colloid and Interface Science 375 (2012) 102–105

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Journal of Colloid and Interface Science

www.elsevier.com/locate/jcis

Alternating current electrophoretic deposition (EPD) of TiO2 nanoparticles

in aqueous suspensions
A. Chávez-Valdez, M. Herrmann, A.R. Boccaccini ⇑
Institute of Biomaterials, Department of Materials Science and Engineering, University of Erlangen-Nuremberg, 91058 Erlangen, Germany

a r t i c l e i n f o a b s t r a c t

Article history: TiO2-nanostructured coatings from aqueous suspensions have been successfully prepared by the applica-
Received 27 December 2011 tion of alternating current (AC) instead of direct current (DC) during electrophoretic deposition (EPD). No
Accepted 18 February 2012 organic additives in suspension were required for successful EPD. The quality of the AC-EPD TiO2 coatings
Available online 3 March 2012
in terms of homogeneity and extent of microcracking, upon drying, observed by SEM, was superior to that
of DC-EPD coatings made from the same type of suspensions. The main difference between AC- and DC-
Keywords: EPD was the suppression of bubble formation. The absence of water electrolysis at the electrodes can be
Electrophoretic deposition
explained by the particular distribution of the electric field during AC mode, which prevents the nucle-
TiO2 nanoparticles
Alternating current
ation of bubbles. The preparation of TiO2 coatings from aqueous suspension and without the aid of
Coatings organic stabilizers opens the possibility for co-deposition of sensitive materials such as biomolecules
and even cells for biomedical applications, given the high biocompatibility of TiO2. The deposition of
TiO2 coatings from aqueous suspensions is also attractive from environmental and economical points
of view.
Ó 2012 Elsevier Inc. All rights reserved.

1. Introduction the formation of gas bubbles in the deposits is eliminated or dras-

Titanium dioxide is a very important material for numerous
applications such as photocatalysis, sensors, biomedical coatings,
solar cells, and memory devices [1–4]. In the biomedical field, tita-
nia is mainly used as coating for orthopedic implants due to its
proven biocompatibility and anti-bacterial properties [5–7]. Elec-
trophoretic deposition (EPD) is a widely used technique for the
preparation of coatings that can be applied with any powder mate-
rial that can be suspended in a suitable solvent [7]. EPD enables
coatings to be obtained on both planar and complex shape sub-
strates, such as fibers and porous materials [7–10]. The EPD tech-
nique is based on the movement of charged particles in a stable
suspension upon the application of an electric field [11], whereby
organic solvents such as acetone or alcohols are usually preferred
over water because of the reactions at the electrodes that occur
at very low voltages in case of aqueous suspensions [8]. However,
the use of aqueous medium not only has economical advantages
limiting the environmental problems related to the use of organic
solvents [11] but also allows the deposition of sensitive materials
(such as biomolecules and biological entities) [12–18]. One solu-
tion to overcome the problem of water electrolysis is the use of
alternating current (AC) instead of direct current (DC) in EPD.
The use of AC leads to very low decomposition of water, and thus,
tically minimized [19].
Several investigations have reported on the EPD of TiO2 nano-
particles using organic suspensions [20–23] or mixtures of organic
solvents and water [24–28], but there has been no previous work,
to the authors’ knowledge, on the EPD of TiO2 from pure water
suspensions, that is, without added organic solvents. The EPD of
TiO2 nanoparticles without the addition of stabilizers and using
water–ethanol mixtures has been achieved at low voltages [24].
Also, the EPD of TiO2 without bubble formation has been possible
by using mixed water–alcohol suspensions with the addition of
compounds such as (C2H5)4NOH and Tiron molecule [25,26]. The
addition of ethanol reduces the zeta potential but prevents water
electrolysis. The preparation of TiO2 coatings from aqueous sus-
pensions with the addition of stabilizers such as carboxylic acids
and NaOH has also been reported [27]. In these investigations,
DC-EPD has been applied and the use of water and different addi-
tives has led to porosity in the coatings.
In this research, the preparation of TiO2 coatings from suspen-
sions of TiO2 nanoparticles in water without the addition of organic
stabilizers has been achieved by AC-EPD. Although the application
of AC-EPD is rapidly emerging [29], surprisingly, there have been
no previous reports in the literature on AC-EPD of TiO2 in water.
2. Materials and methods

⇑ Corresponding author. Fax: +49 9131 8528602. The suspensions for EPD were prepared using fresh deionized
E-mail address: aldo.boccaccini@ww.uni-erlangen.de (A.R. Boccaccini). water and commercially available TiO2 nanoparticles (P25, Evonik

0021-9797/$ - see front matter Ó 2012 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2012.02.054
 A. Chávez-Valdez et al. / Journal of Colloid and Interface Science 375 (2012) 102–105
Industries, particle size of 21 nm) in the concentration of 1 wt.%.
The suspensions were magnetically stirred for 5 min followed by
15 min ultrasonification, subsequently followed by 5 min of stir-
ring. The zeta potential of these TiO2 nanoparticles in water has
been documented in the literature [30]. In this work, the nanopar-
ticles acquired a positive surface charge at pH  4 and deposited
on the cathode. The substrates used as electrodes were planar
316 L stainless steel foils separated by a distance of 1 cm in the
AC-EPD cell. For AC-EPD tests, a programmable function generator
(HP 3314A) was used to generate the asymmetric AC signal. A
Piezo Driver/Power amplifier (PZD 700A) with a maximum voltage
of 700 V in DC or peak AC was used to amplify the signal. The signal
was monitored with a digital oscilloscope (Fluke). Different fre-
quencies from 30 to 1000 Hz, peak-to-peak voltages from 5 to
20 V, and times from 1 to 5 min were considered to obtain electro-
phoretic coatings. The waveform of the asymmetrical signal was of
rectangular shape, and the asymmetry factor of the signal used was
set to 4. For comparison purposes, the same conditions were used
for the same suspensions in conventional DC-EPD experiments. To
prepare samples for SEM observations, TiO2-coated foils were bent
and the coatings were detached from the substrates. The top sur-
face and cross-section of deposits were analyzed by SEM (Quanta
200, FEI) equipped with secondary electron and back-scattered
electron detectors. A working distance of 10.8 mm and voltage of
20 kV were used. The deposition yield (deposited mass/covered
area) was evaluated for AC-EPD coatings in dependence of varying
deposition time, frequency, and voltage.
3. Results and discussion
Fig. 1 shows the surface SEM images of coatings obtained by AC-
EPD at 5 V and 1000 Hz frequency during 5 min and by continuous
DC-EPD at 5 V during 1 min. The different quality of the deposits, in
(A)
1 mm
(B)
1 mm
Fig. 1. AC-EPD (A and A0 ) and DC-EPD (B and B0 ) TiO2 coatings obtained at 5 V showing different extent of microcracking formation (images at different magnifications).
(Deposition times were 5 min and 1 min for AC-EPD and DC-EPD, respectively.)
103
terms of microstructural homogeneity, can be observed in Fig. 1A
and B for AC- and DC-EPD coatings, respectively. The AC coating
shows a very homogeneous and smooth microstructure with lim-
ited surface damage, while the DC coating shows considerable
damage due to the gas bubble formation in aqueous suspensions,
which occurs even at short deposition times of 1 min. The different
extent of microcracking can be clearly appreciated by direct com-
parison of the images in Fig. 1A0 and B0 . AC-EPD coatings show
some small cracks on the surface which occur during the drying
stage of nanoparticulate coatings but the surface quality is similar
to that of DC-EPD coatings obtained from organic solvents, for
example, in acetylacetone (see Refs. [20,31,32]). On the other hand,
in addition to exhibiting greater extent of microcracking, DC-EPD
coatings show also localized damage, which is ascribed to the ef-
fect of water electrolysis. Microcracking and hydrolysis in continu-
ous DC-EPD coatings thus have a detrimental effect on the deposit
surface quality and structural integrity, and the pores formed will
reduce the mechanical properties of the deposits. It is unlikely that
such relatively large microcracks will be closed during a post-EPD
high-temperature sintering stage.
Increasing the voltage was seen to increase the amount and size
of cracks in the coatings in AC and DC fields, as shown in Fig. 2. In
AC-EPD coatings (Fig. 2A and A0 ), some cracks were visible on the
surface when using 10 V and deposition time of 5 min but no other
structural damage was observed, for example, due to electrochem-
ical reactions at the electrodes. The degree of severity of bubble
formation and cracking in coatings obtained by DC-EPD at 10 V
can be appreciated in Fig. 2B and B0 .
The suppression of bubble formation during AC-EPD can be ex-
plained by considering the distribution of electric field between
the positive and negative side of the rectangular signal during alter-
nating current mode, so that the amount of bubbles generated is less
in AC fields than when using DC fields, as discussed by Neirinck et al.
[19]. They demonstrated the suppression of bubble formation in
(A’)
100 µm
(B’)
100 µm
104 A. Chávez-Valdez et al. / Journal of Colloid and Interface Science 375 (2012) 102–105

(A) (A’)

1 mm 100 µm

(B) (B’)

1 mm 300 µ m
Fig. 2. AC-EPD (A and A0 ) and DC-EPD (B and B0 ) coatings obtained at 10 V during 5 and 1 min, respectively, showing marked differences in the extent of microcracking and
structural damage (images at different magnifications).

Al2O3 coatings in AC-EPD from aqueous suspensions. Also, the fre-
quency of the AC signal has an effect on the bubble formation.
Increasing the AC signal frequency means that the complete cycle
of the wave will repeat a higher number of times per time unit, so
there will be a higher number of periods of ‘‘on’’ and ‘‘off’’ current
during deposition. Therefore, the absence of bubble formation dur-
ing AC fields may be ascribed to the fact that the reaction of water is
minimized and the nucleation of bubbles can be prevented, as re-
flected in the microstructures of the AC coatings.
Fig. 3 shows the deposition yield curves for coatings obtained by
AC-EPD at different conditions. Fig. 3a shows the deposition yield
increasing with increasing deposition time and voltage at a fixed
frequency of 500 Hz. The deposition yield increases linearly with
time at each applied voltage, which is expected at low deposition
times. This is a typical behavior in DC-EPD [11]. Fig. 3b shows the
increasing trend of deposition yield with increasing deposition time
at different applied frequencies and at a fixed voltage of 10 V. As in
regular DC-EPD, the deposition yield increases linearly with time.
It is also seen that deposition slightly increases as the frequency in-
creases up to 500 Hz. Using higher frequencies (1000 Hz) results in
lower deposition yield considering that the direction of the electric
field is reversed every millisecond and deposition starts to slow
down. This effect could be due to particle inertia; however, a quan-
titative confirmation of this phenomenon was not further attempted
here. Thus, the selection of frequency in AC-EPD will have to con-
sider both aspects related to the final coating quality, that is, highest
possible suppression of bubbles and adequate deposition yield.
Fig 4 shows cross-section morphologies of TiO2 coatings
produced by AC-EPD from nanocrystalline titania particles in aque-
ous suspension (AC frequency of 1000 Hz). For comparison, SEM

6 4
(a) Fixed Frequency 500 Hz
20 V (b) Fixed Voltage 10 V
5
Deposition yield (mg/cm 2)

Deposition yield (mg/cm2)

3 500 Hz
4 30 Hz
1000 Hz

3 10 V
2

2
1
1 5V

0 0
1 3 5
1 3 5
Time (min) Time (min)

Fig. 3. Deposition yield for AC-EPD coatings showing the expected increased deposition with time at fixed frequency or voltage.
 A. Chávez-Valdez et al. / Journal of Colloid and Interface Science 375 (2012) 102–105 105

(a ) (b)

50 µm 20 µm

Fig. 4. Cross-section areas of TiO2 electrophoretic coatings obtained by AC-EPD (5 V, 5 min, 1000 Hz frequency); (a) as-deposited and (b) presintered at 550 °C. (In (a), the
deposit was purposely detached from the substrate to prepare the cross-section image.)

images of ‘‘green’’ deposits (as-deposited) and after heat treatment Acknowledgment

at 550 °C are shown. From microstructural SEM observations of
deposits obtained at different EPD conditions, 5 min was chosen A. Chavez gratefully acknowledges Conacyt, Mexico, for finan-
as the optimum deposition time at deposition voltage of 5 V and cial support (Grant Number 146879).
frequency of 1000 Hz. The cross-section of the green coating shows
a thickness of approximately 16 lm. After the presintering treat- References
ment at 550 °C, the TiO2 layer has a thickness of approximately
10 lm, and it exhibits a uniform microstructure well bonded to [1]
[2]
the planar stainless steel substrate. [3]
The present results thus confirm one of the main benefits of [4]
using AC-EPD, namely it enables to work with aqueous suspen-
[5]
sions at relatively high voltages, which is not possible with DC- [6]
EPD due to water electrolysis. DC-EPD from aqueous suspensions [7]
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[8]
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[9]
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[13]
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[20]
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[21]
Alternating current electrophoretic deposition has been shown [22]
to be a very convenient technique to produce homogeneous nano-
structured TiO2 coatings based on water suspensions (no organic [23]
additives), with similar microstructural quality to coatings ob- [24]
tained from organic suspensions. Conventional DC-EPD led to
TiO2 coatings showing structural damage due to the gas bubble for- [25]
[26]
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deposition times. The distribution of the electric field during alter-
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[29]
that usually occur at very low voltages in DC-EPD. The economical [30]
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the opportunity for co-deposition of sensitive materials (e.g., bio- [31]
active molecules, biological entities) from aqueous suspensions
[32]
will expand applications of TiO2 coatings in the biomedical field
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