Effects of Applied Voltages on Hydroxyapatite Coating of

Titanium by Electrophoretic Deposition

Xianwei Meng,1,2 Tae-Yub Kwon,1,3 Yunzhi Yang,4 Joo L. Ong,4 Kyo-Han Kim1,3
1

Institute for Biomaterials Research & Development, Kyungpook National University, Daegu, South Korea

Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, Peoples Republic of China

Department of Dental Biomaterials, College of Dentistry, Kyungpook National University, Daegu, South Korea

Department of Biomedical Engineering, University of Tennessee Health Science Center, Memphis, Tennessee

Received 25 March 2005; revised 1 October 2005; accepted 1 October 2005

Published online 16 December 2005 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/jbm.b.30497

Abstract: Hydroxyapatite (HA) coatings were deposited on titanium substrates by electrophoretic deposition (EPD) at constant voltage and dynamic voltage, respectively. Various
surface morphologies were observed under different type of voltages. Under a constant voltage
of 20 V, a dense HA coating could be prepared. Under a constant voltage of 200 V, big HA
particles were deposited and the coating was porous. Under a dynamic voltage, a continuous
gradient HA coating could be obtained. HA coatings were characterized with a eld emissionscanning electron microscopy (FE-SEM) and an X-ray diffraction (XRD). XRD indicated no
signicant HA decomposition when the coatings were sintered for 2 h at 800C. 2005 Wiley
Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 78B: 373377, 2006

Keywords:

hydroxyapatite; coatings; electrophoretic deposition; voltage; microstructure

INTRODUCTION
Hydroxyapatite (HA) coatings contribute excellent biocompatibility to implants, while titanium substrates provide favorable mechanical properties to the entire implant.15 To
obtain the maximum benet from such coatings, it is necessary to control the composition, thickness, and microstructures of the deposited HA layers.6 Among alternative coating
techniques, there is a growing interest in electrophoretic
deposition (EPD). EPD presents several advantages such as
ability to control thickness and morphology of the deposited
layer by controlling the electrochemical parameters, ability to
deposit relatively uniform coatings on complex shapes, a
higher deposition rate as compared with most coating process, and the low cost to purchase the equipment.7
The EPD process involves the migration and coagulation
of ceramic particles included in the suspension on the electrode surface by an impressing electric eld.8 Positively
charged particles undergo cataphoresis (deposition on the
cathode), whereas negatively charged particles undergo anophoresis (deposition on the anode).9 Parameters that determine the characteristics of this process are those related to the
suspension and the process, including physical parameters

such as the electrical nature of the electrodes and the electrical conditions (voltage/intensity relationship, deposition
times, etc.).10 Suspension for EPD is a complex system in
which each component has a substantial effect on EPD efciency.11 Once a well-dispersed suspension is prepared, the
applied voltage becomes a critical parameter.
The purpose of this study was to evaluate the effect of
applied voltages on HA coatings, by EPD process. By adjusting applied voltage, we could obtain HA coatings with
different microstructures.

MATERIALS AND METHODS

Substrate Treatment

In this study, titanium (Ti) sheets of 30 10 0.5 mm were

abraded with 600, 800, and 1000 grit SiC sandpapers. The
sheets were cleaned completely with distilled water and then
with alcohol for 10 min each, in an ultrasonic bath. The
substrates were etched in a solution containing nitric acid and
hydrouoric acid (3:1), rinsed with distilled water, and then
dried again.
Preparation of Suspensions

Correspondence to: K.-H. Kim (e-mail: kyohan@mail.knu.ac.kr)

2005 Wiley Periodicals, Inc.

Suspensions for EPD were prepared by ultrasonic agitation of

HA powder in ethanol. The HA concentration in the suspen373

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MENG ET AL.

Figure 1. Surface morphology by FE-SEM of coatings obtained at 0.1% HA particle concentration at

different applied voltage: constant voltage (a) 20 V, (b) 200 V during 10 min, and (c) dynamic voltage.
The magnication is 10,000.

sions was 0.1%. Polyvinyl alcohol (3%) and N,N-dimethylfrmamide (DMF) (10%) were added to the suspension for
adherence, strength, and crack-proof improvement.
Electrophoretic Deposition

A glass cell of 1000 cm3 equipped with two platinum counter

electrodes (3-cm apart) was used for deposition. The EPD
was done in pH 4.0 suspensions, at a constant voltage of 20
V, a constant voltage of 200 V, and a dynamic voltage
between 0 and 200 V, respectively, using a power supply
(HBPS-1A600V Hobang Electronics Co. Ltd., Korea). The
dynamic voltage process consisted of three increments, where
the primary voltage between 0 and 10 V was applied at a rate
of 0.0333 V/s, followed by a voltage between 10 and 50 V at
a rate of 0.1 V/s, with a nal voltage between 50 and 200 V
applied at a rate of 1 V/s. The green coatings were then air
dried for 24 h, before being sintered at a rate of 10C/min in
an argon atmosphere, and held at the temperature of 800C
for 2 h to allow densication of the coating.
The microstructure of the substrates, green HA coatings,
and sintered HA coatings were examined by FE-SEM (S4300, Hitachi, Japan). Samples sputter-coated with platinum
for FE-SEM were observed at 2000, 10,000, and
50,000 magnication. The sintered HA coatings were characterized by X-ray diffraction (XRD) (Xpert Pero MRD,
Philips, Holland), using Cu K radiation and grazing incidence 2 scans ( 1) from 20 to 60 at a speed of 0.08

s1. The generator tension is 40.0 kV, and the current is 30.0
mA. At least 5 samples were prepared for measurements, 4
samples for FE-SEM, and 3 for XRD.
RESULTS
Figure 1 shows the surface morphology of the HA coatings
deposited by EPD. Figure 1(a,b) is the representative surface
morphology of coatings deposited at a constant voltage of 20
and 200 V for 10 min, respectively. The HA coatings, obtained at a constant voltage of 20 V, were found to consist of
ne HA particles (150 200 nm in size), with a few large
particles sprinkled on these ne particles. The surface was
found to be uniform. For coatings prepared at a constant
voltage of 200 V, bigger particles (above 400 nm) were
observed. In addition to the big particles, surface porosities
greater than 500 nm in size were also noticed. Figure 1(c)
shows the representative surface morphology of coatings
deposited at dynamic voltage ranging from 0 to 200 V. The
HA coating obtained by dynamic voltage was observed to
consist of 300 400 nm particles and are uniform.
As shown in Figure 2(a c), continuously gradient coatings
were produced by applying dynamic voltage during EPD.
The coating layer closest to the substrate was found to be
dense, whereas the outer layer was found to be porous.
Figure 3 shows the microstructure of the coatings deposited at a constant voltage of 20 and 200 V, and a dynamic
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375

Figure 2. Surface morphology of the coating prepared by the dynamic voltage: (a) is the intermediate
coating nished the rst step, (b) is the intermediate coating nished the second step, (c) is the nal
coating. The magnication is 50,000.

voltage of 0 200 V. The coatings were sintered in an argon

atmosphere at 800C for 2 h, at a heating rate of 10C/min.
Sintered HA coatings turned to be denser and more adhesive
to the substrates than unsintered ones. As shown in Figure
4(b), big agglomeration and cracks can be found on the
sintered coatings obtained at a constant voltage of 200 V. The
coating exhibited bad sinterability. Figure 3(c) shows a FESEM micrograph of the sintered coatings deposited at a
dynamic voltage of 0 200 V. The coatings, obtained using
dynamic voltage, were found to be very uniform. Neither
crack nor big particles were found on the surface.
Figure 4 shows the XRD pattern of sintered HA coatings
on Ti substrate at dynamic voltage. The XRD pattern indicates well-dened peaks of HA, with no formation of other
crystalline phase.

DISCUSSION
Among other variables, during EPD, the electrophoretic velocity () is reported to be related to the applied voltage and
particle size, governed by the following equation:12

QE/4 r

(1)

where Q and r represent the charge and particle radius,

respectively. E is the potential difference applied to the
suspension of the electric eld, and is the suspension
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viscosity. The can be considered constant because the HA

particle concentration in suspension is relatively low. Under
this condition, the electrophoretic velocity is mainly a function of the electric eld and the particle size.
As the HA particles in the suspension used for EPD
usually have a distribution of particle sizes, particles with
different r value have different electrophoretic mobility,
thereby resulting in the segregation effects observed during
the EPD process, when E is constant. It is inferred that the
smallest particles gained the highest electrophoretic velocity,
accordingly, they are the rst to be deposited. This speculation corresponded to the deposits obtained at a constant
voltage of 20 V [Fig. 1(a)]. As the applied potential is
increased to 200 V [Fig. 1(b)], elctrophoretic velocity is
increased, thereby, bigger particles are deposited. Moreover,
fast deposition rate allow little time for the particles to rearrange, as a result, quite some bigger porosities are formed in
the microstruture.
It has been reported that a macroporous HA layer has a
similar crystalline morphology to that of bone apatite, so that,
the layer maintains a high potential for accommodating to
bone but low cohesive strength.1318 In this study, interesting
contraries are found on the coatings, those obtained at a
constant low voltage of 20 V produced high bond strength on
Ti substrates but low biocompatibility, while the coatings
obtained at a constant high voltage of 200 V yield low
adhesion to Ti substrates but satisfactory osteoinduction to
bone. In an attempt to optimize the coating property, appli-

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MENG ET AL.

Figure 3. Surface morphology by FE-SEM of sintered HA coatings at 800C, obtained by: (a) constant
voltage 20 V, (b) constant voltage 200 V, and (c) dynamic voltage 0 200 V. The magnication is
2000.

cation of dynamic voltage was evaluated in this study. It was

observed that small particles built up in the inner layer
densely and uniformly [Fig. 2(a,b)] and bigger particles
formed the outer porous layer [Fig. 2(c)]. This graded particle
size and difference in coating density on the inner and outer
layer were achieved as a result of electrophoretic velocity and
its dependence on electric eld and the particle size. It can be
deduced from Figure 2 and Eq. (1) that a continuously graded
HA coating was obtained using dynamic voltage.
Theories related to Eq. (1) helped explain the phenomenon
observed in this study, which told the production of a porous
and rough coating at a higher constant electric eld, and the
production of a dense coating of ner particle size at a lower
constant electric eld. In addition, using a dynamic voltage, a
continuous gradient HA coating was prepared.

HA coatings obtained on Ti with various applied voltages

were sintered at 800C for 2 h. Figure 3 shows the supercial
characteristics of the sintered coatings. Big deposited particles and higher porosity between particles in green coatings
are responsible for the cracks and big particles in the sintered
coating prepared at a constant voltage of 200 V. The coatings
obtained through dynamic voltage were observed to be free of
cracks. Good packing of submicron particles obtained at
dynamic voltage gets the credit.
It is also noted that high temperature treatment may lead to
the deterioration of desirable HA structures and thereby may
reduce the biocompatibility of the material.19 21 In this study,
all coatings showed well-dened peaks of HA (Fig. 4). The
black squares in the gure indicated standard HA peaks, with
no decomposition of HA observed. It was hence suggested
that EPD is a good processing method to form a HA coating.

CONCLUSIONS

Figure 4. XRD patterns of HA coatings on Ti at dynamic voltage after

sintered: (f) HA, (E) rutile.

Various microstructures of HA coatings on Ti can be prepared by EPD, using constant applied voltage and dynamic
applied voltage. The HA coating prepared at a constant low
voltage of 20 V consisted of ne HA particles and was dense.
The HA coating prepared at a constant high voltage of 200 V
consisted of big HA particles and was porous. The HA
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HA COATING OF Ti BY EPD

coating prepared at a dynamic voltage consisted of continuously gradient particles, with small particles building up the
inner layer while bigger particles forming the outer layer. The
deposits prepared using a dynamic voltage followed by sintering at 800C turned out a high packing of the HA particles.
In addition, coatings retained HA structure after sintering.
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