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WANG AND HU
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
15
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.
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
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HA PATTERNING
19
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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
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
23
WANG AND HU
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
References
1. Dearnley PA. A review of metallic, ceramic, and surfacetreated metals used for bearing surfaces in human joint
re-
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HA PATTERNING
ture 2000;404:56-59.
33. Trau M, Saville DA, Aksay IA. Assembly of colloidal
crystals
at
electrode interfaces. Langmuir 1997;13:6375- 6381.
34. Aizenberg J, Braun PV, Wiltzius P. Patterned colloidal
deposition controlled by electrostatic and capillary forces. Phys
Rev
Lett 2000;84:2997-3000.
35. Ozawa N, Yao T. Micropattern formation of apatite by
combination of a biomimetic process and transcription of resist
pattern. J Biomed Mater Res 2002;62:579-586.
36. Pancrazio JJ, Whelan JP, Borkholder DA, Ma W,
Stenger
DA.
Development and application of cell-based biosensors.
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