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WANG AND HU

Patterning hydroxyapatite biocoating by


electrophoretic
deposition
R. Wang, Y. X. Hu

Department of Metals and Materials Engineering, University of British Columbia, 309-6350


Stores Road,
Vancouver, BC Canada V6T 1Z4
Received 25 September 2002; revised 4 February 2003; accepted 20 March 2003
Abstract: Patterned bioceramic coatings may find
potential
applications in orthopedic implants and biosensors. In
this
study, various hydroxyapatite (HA) patterns were
created
on silicon and titanium substrates. Electrophoretic
deposition technique was used together with surface
patterning
of
the cathode specimen. When gold/palladium patterns
(hexagons, spherical dots, etc.) were created on the
cathode
surface, HA colloidal particles in ethanol would
preferentially deposit on the gold-coated area and form
patterns.
When silicon, instead of gold, was evaporated onto a
conducting cathode surface, HA mainly deposited on the
exposed area of the substrate. Detailed mechanisms for
form-

step
to
organize bone tissue, which is mechanically
anisotropic, so that a strong implant/bone interface can
be
achieved. However, a thin layer of hydroxyapatite
(HA) has been widely accepted as a biocoating to
enhance the osteoconductivity of titanium implants.2,4,11-13 One of the main problems with HA
coating is its mechanical integrity. Residual
stresses,
R. Wang is incumbent of the Canada Research Chair
in
Biomaterials.
Correspondence
to:
R.
Wang;
e-mail:
rzwang@interchange.
ubc.ca
Contract grant sponsor: Natural Sciences and
Engineering
Research Council of Canada
2003 Wiley Periodicals, Inc.

INTRODUCTION

Most dental and orthopedic implants are made


of
mechanically robust and bioinert metallic alloys
(e.g.,
titanium alloys, stainless steels, tantalum, and
cobaltchromium-molybdenum alloys). To increase the
bioactivity and/or to achieve a strong bone/implant
fixation, many surface modification techniques are
being
intensively studied.1-8 It has been reported that
proper surface topography could not only improve
the bone integration of implants,3,8 but could also
influence cell organization.5,9,10 This is the first

ing HA patterns may involve local concentration of the


electric field when a second metal is patterned on the
cathode. The difference in electric field across the two
metals
on
the cathode also enhances HA patterning through an
electrohydrodynamic process. This study demonstrated the
possibility and flexibility of electrophoretic deposition in
patterning charged particles onto a substrate. 2003
Wiley
Periodicals, Inc. J Biomed Mater Res 67A: 270-275, 2003
Key words: hydroxyapatite; patterning; electrophoretic
deposition; biomaterials

15

due to either specific processing techniques or


thermal
expansion mismatch, exist in many of the coating
methods and can cause coatings to crack or
debond
under external loading.14-20
Material surfaces can also regulate cell response.5,21,22 Compared with titanium, HA was reported to have higher affinity for osteoblast cell
attachment.23 In a recent in vitro study on the
interaction
between
human
osteoblasts
and
various
substrates,
Li
24
et al. also reported that substrates determined
both
cell shape and attaching mechanisms. This
observation, in addition to the cracking problems in
continuous HA coating and the cell-organizing effect by
grooved surfaces, led us to the idea of patterning
HA
on titanium surfaces. If HA coating could be
formed
into small and organized islands, residual stresses
and
cracking due to shrinkage and thermal mismatch
may
be reduced. Patterned HA could also promote cell
organization through contact guidance, topology,
and
its unique cell interactions.
This article presents the results of our first step
in
realizing the above idea, i.e., to pattern HA on
solid
substrates, including titanium. Electrophoretic
deposition (EPD) was used to deposit HA coatings. EPD
has been widely used to make continuous
ceramic
(including HA) coatings on substrates with complicated geometry.25,26 Positively charged HA
colloidal

WANG AND HU

HA PATTERNING

Figure 1. Schematic illustration of the EPD setup. The cathode shown here has Au dot arrays on a Si substrate. The
insert shows the steps of preparing Au (Au-40%Pd alloy)
patterned Si cathode.

particles are driven under an external electrical


field
to
the cathode where they form a thin coating. 27-30
The
purpose of this study was to assess the possibility
of
patterning HA through the use of patterned
metallic
cathodes.

MATERIALS AND METHODS


HA [Ca10(PO3)6(OH)2; Fisher Scientific, Fair Lawn, NJ],
with an average particle size of 0.2 ~ 0.5 microns, was
ultrasonically mixed in ethanol to make a 3 wt %
suspension.29 HA particles prepared in this manner have a
positive
surface charge.27,29,30 Coating was done by EPD at room
temperature (Fig. 1). A DC electric field of 5-100 V/cm
was
applied across two parallel electrodes that were 12 mm
apart
in HA suspension. Run times ranged from 15 s to 10
min.
The electrode plates were 20 X 20 mm in size, and
made
of either single-crystal silicon (Si) or titanium. The Si
electrodes were cut from a Si wafer (B-doped, P-type, (100)
Si;
WaferNet, San Jose, CA), whereas the titanium

electrodes
were made from Ti-6Al-4V alloy and had been
mechanically
polished down to 0.05 ^m with an alumina colloidal
suspension. The surfaces of the Si or titanium cathode
were
patterned using a gold/palladium alloy (Au-40%Pd
alloy),
and Si. The Au/Pd was sputter coated to about 3-nm
thick
with a vacuum sputtering machine (Denton DESK II;
Denton Vacuum, Moorestown, NJ), whereas Si was vapor deposited with a vacuum evaporator (JEOL JEE 4-B). Transmission electron microscope grids with various mesh
sizes,
and stencils with arrays of holes, were used as masks
(Fig.
1). After coating and removing the mask, islands of
target
material (in the shape of squares, hexagons, or circles)
patterned the cathode. The patterned cathodes were then
ultrasonically cleaned in acetone for 5 min before being
electrophoretically coated.
In a test to study the effect of cathode materials on
the
current density, a microampere meter was connected
to
the
circuit, and the current was measured when either Si or
a
fully Au-coated Si cathode was used.
Once EPD was done, the cathode was rinsed with
ethanol
and then air-dried. The HA coatings were first confirmed
with an X-ray diffractometer (Rigaku Rotaflex RU200BH,
50
kV,
100
mA,
scanning
speed
1/min).
A
stereomicroscope
was then used to examine the morphology of the
coating
at
low magnification, whereas a scanning electron
microscope
(Hitachi S-3000N) was used to examine the coating's
morphology at high magnification at the acceleration
voltage
of
20 kV. Elemental distributions on the surface of the
cathode
were mapped by energy dispersion X-ray spectroscopy
(EDX) (Noran Instruments, Middleton, WI).

RESULTS

Cathode materials dramatically affect coating

17

kinetics. Although a uniform layer of HA could be


coated
onto Si, Au/Pd fully coated Si, and titanium
cathode
surfaces, the thickness varies. Figure 2 shows the
variation of current density with the deposition time
at
the
given applied voltage of 10 V/cm. The current
density
decreases gradually with coating time on all the
tested
electrodes. However, it is about 25% higher on
the
Au/Pd-coated Si electrode than the noncoated Si
surface. The HA coating at 120 s was 5.7 microns
and
2.8
microns thick on the Au/Pd-coated Si surface and
Si
surface, respectively. No differences were found
between the X-ray diffraction patterns of HA before
and
after EPD.
Based on the above results, Si specimens were
patterned with Au/Pd to examine the possible
selective
deposition of HA by EPD. The Si specimens with
hexagonal Au/Pd patterns had a uniform HA layer

Figure 2. Current density versus EPD deposition time. (a)


Si cathode and (b) Au/Pd-coated Si cathode.

WANG AND HU

HA PATTERNING

19

WANG AND HU

Figure 3. Optical micrographs showing white HA patterns on gray substrates made by


EPD
technique.
(a,b)
Specimens
had
Au/Pd coating in hexagonal area, leaving the thin hexagonal boundaries and the wide
circular
boundary
with
exposed
Si
substrate before EPD. (c,d) Si wafer substrates had Si coated in square area (c) and
hexagonal
area
(d).
Note
the
reverse
HA
deposition on Au/Pd-coated and Si-coated substrates. EPD parameters: 7.5 V/cm, 120 s.

form on the Au/Pd coated area, leaving the


surrounding Si barely coated with HA particles. Typical
morphologies of the patterned HA coatings after 120
s
at
7.5 V/cm are shown in Figure 3(a,b). The
preferred
deposition of HA particles on the Au/Pd surface
was
further confirmed by EDX X-ray elemental
mapping.
Figure 4(a) shows a much stronger calcium signal
on
the hexagons than at the boundaries, whereas
Figure
4(b) demonstrates a higher Si signal at the
boundaries
than on the hexagons. Although the Au/Pd
patterns
in Figure 3 were made with a 75-and 200-mesh
microscope grid, we found patterns as small as 600
mesh

could also induce similar HA patterns.


As the spacing between the Au/Pd spots
increased
on a Si substrate, a thin noncontinuous layer of
HA
coating could form on the noncoated Si area (Fig.
5).
However, it is interesting to note that there was
an
obvious HA depletion zone surrounding each
Au/Pd
(and HA) dot where much less HA particles exist.
The
forming mechanism will be discussed later.
The Si-coated Si specimens had much different
properties from the other tests. The HA coating
primarily formed on the original, noncoated, surface
[Fig.
3(c,d)]. This can also be seen in the EDX X-ray
mappings [Fig. 4(c,d)]. The HA preferentially coated
the
single-crystal Si substrate, rather than square

HA PATTERNING

islands
of deposited Si, thus forming a pattern that is
opposite
to that on the Au/Pd-on-Si specimens (Figs. 3-5).
Similar results were found with the polished
titanium substrates. The locations where Au/Pd was
coated had more HA deposited, and the locations
where Si was deposited had less HA. In Figure 6,
Si
was patterned as hexagons onto a titanium
substrate.
After EPD, dense HA particles decorated the
titanium
boundaries (dark regions). Similar to the results
on
the
Si substrate with a large inter-spot distance (Fig.
5),
sparsely distributed HA particles were found in
the
Si-coated hexagons.

DISCUSSION

This pilot study demonstrates that HA can be


patterned on conductive surfaces using EPD,
provided
that proper conductive materials are patterned on
the
substrates. The potential application of this
technique
is an HA-patterned bioimplant that has certain
surface
topology and chemical modulation.

21

The
mechanisms
for
HA
pattern
formation
are
influenced by
the
conductivity
and
electrode
reaction
of
the cathode.
When
HA
particles are
ultrasonically
dispersed
in
alcohol, the
individual
particles
become positively
charged.27,29,3
0
The

WANG AND HU

<>
K

Si

500
pm

Figure 4. EDX X-ray mapping on HA patterned Si substrates. (a) and (b) are Ca and Si mappings of Figure 3(a); (c) and (d)
are Ca and Si mappings of Figure 3(c). In each micrograph, the brighter area corresponds to a higher concentration of the
labeled element. Note that the Ca patterns match the HA patterns in Figure 3.

positive
charge,
indicated
by positive zeta potential, is probably developed
because of the dissociation or ionization of HA
surface

Figure 5. HA spherical arrays formed on Au/Pd dots patterned on a Si cathode. The bright spherical dots are 12^mthick HA coatings. The gray area between the dots has
discontinuous HA particles. The dark ring surrounding each
bright dot is HA-depletion zone. EPD parameters: 7.5 V/cm,
180 s.

Figure 6. Scanning electron micrograph showing HA preferentially deposited on the titanium surface at hexagonal
boundaries (gray). The white hexagonal area was coated
with Si before EPD. Note that there are still HA aggregates
existing inside the Si-coated area. The specimen was tilted
by 35. EPD parameters: 7.5 V/cm, 120 s.

HA PATTERNING

groups.2627 Under an external electric field, the


charged particles are forced toward the cathode,
where they lose their charge and coagulate into a
dense coating. In this study, the EPD process has
obviously been affected by the patterns that were
created on the surfaces of the cathodes. It is easier
to
understand the Si-patterned Si system [Figs.
3(c,d)
and
6]. The thin vapor-deposited layer of Si was either
amorphous or polycrystalline. Therefore, the
noncovered single-crystal Si and titanium surfaces (Fig.
6)

23

were more conductive. It is interesting to notice


that
patterning Si with other conducting materials (Au,
Au/Pt) induces HA patterns to form. The detailed
mechanisms are elaborated below.
In studies on two-dimensional colloidal crystals
using EPD, Trau et al. 31 and Hayward et al. 32
reported
that when UV light was shined at an indium tin
oxide
anode of an EPD cell, polystyrene particles that
were
initially randomly dispersed on the anode's
surface
would assemble into two-dimensional crystals in
the
illuminated area. They used this phenomenon to
make
patterns, by selectively exposing parts of the
anode
to
UV light. When washed, the two-dimensional
crystals
that formed would adhere whereas the leftover
polystyrene particles would wash away. The
phenomenon
was attributed to the increase of current density
of
the
indium tin oxide electrode when it was
illuminated
by
UV light, which generates hole-electron pairs on
the
semiconductor surface and increases the rate of
charge
transfer between solution and the electrode.32
Polystyrene particles were swept into regions of higher
current density through an electrohydrodynamic
mechanism wherein gradients in current density, caused
by
either the presence of particles near the
electrode
surface or the patterning of electrodes, generate
convective flow across the electrode and drive the
particles
to
the area with higher current density.31,33 In the
present
study, charged HA particles started in a bulk
suspension rather than on the electrode surface. During
EPD,

WANG AND HU

they were driven to the cathode by external


potential.
In the case of homogeneous electrodes, the
coating
thickness would increase with the current density.
The
tests in Figure 2 show that a Au/Pd-covered Si
electrode has a current density that is 25% higher
than
that
of a Si electrode. Thus, when both Au/Pd and Si
are
cathodes in the same EPD system, there is a
higher
current density at the Au/Pd surface. This higher
current density induces a higher flux of HA
particles
toward the Au/Pd surface than the Si surface.
Once
the HA particles arrive at the electrode surface
(or
even near it), the electrohydrodynamic process
described by Trau et al.31 may further drive the
particles
from the Si surface to the Au surface, and thus
enhance the preferential deposition on Au. The later
mechanism is supported by Figure 5, where
circular
Au/Pd dots were deposited on Si at the inter-dot
distance of 2.5 times the dot diameter. After EPD,
an
HA depletion zone (~200 microns wide) exists
immediately outside the thick HA coating on the Au/Pd
surface. The Si area outside this depletion zone
has
an
HA coating that is discontinuous and much
thinner
than that on the Au surface. It is obvious that the
HA
particles in the depletion zone were swept to the
Au
surface through an electrohydrodynamic process.
It
is
uncertain how the electrostatic and capillary
forces
would affect the patterning of HA during the
process
of air-drying the samples.34
The idea of patterning HA mineral could bring a
new way of designing orthopedic implants.
Patterned
HA coatings many also be applied to the

HA PATTERNING

development
of biosensors where arrays of proteins and cells
are
being investigated.21,35,36 Future study will focus
on
how pattern size affects the residual stress in HA
coatings. The in vitro cell response to the
patterned
HA
islands is also another interesting topic. Although
our
experiments used flat Si and titanium substrates,
this
flexible technique could also be applied to a
curved
surface and other conducting materials. In
addition
to
HA, other materials such as proteins could be
deposited as well.

CONCLUSION

HA patterns could be created on Si and titanium


substrates through EPD. The key step is to first
make
the desired patterns on the cathode substrate
with
a
thin layer of another material so that electrical
current
density can be patterned across the surface
accordingly when placed in HA colloidal suspension. HA
particles preferentially deposit on areas with
higher
electric current density. This difference in electric
field
across the two metals on the cathode also
enhances
HA patterning through the electrohydrodynamic
process. The technique of patterning charged
particles
on
a substrate through EPD is expected to find
applications in bioimplants and biosensors.

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