Materials Science and Engineering C 25 (2005) 541 – 547

www.elsevier.com/locate/msec

Bioceramic coating of hydroxyapatite on titanium substrate

with Nd-YAG laser
Gary J. Cheng a,*, Daniel Pirzada a, M. Cai b, Pravansu Mohanty c, Amit Bandyopadhyay a
a
School of Mechanical and Materials Engineering Washington State University, Pullman, WA 99164, USA
b
Physics Department Washington State University, Pullman, WA 99164-2814, USA
c
Department of Mechanical Engineering, University of Michigan - Dearborn, Dearborn, MI, USA

Received 27 September 2004; received in revised form 19 April 2005; accepted 3 May 2005
Available online 24 June 2005

Abstract

The ability to bond to bone tissue is a unique property of bioactive ceramics. Hydroxyapatite (HAp) is one of the potential bioceramics
candidates due to its superior bio-compatibility. Significant effort has been devoted to coat HAp ceramics on metallic substrates. Most of
these processes, such as ion-beam sputter coating, thermal spraying, and flame spraying, are high temperature line of sight processes, which
suffer from undesirable phase formation and weak metal/HAP bonding strength. This paper presents a unique process to coat HAp powders
on titanium substrates at low temperature and enhance the coating/substrate interface by laser surface engineering. Nd-YAG laser transmits
HAp powders and the laser power is absorbed by titanium substrate to produce a thin layer of molten region. During coating process, HAp
powders are kept at low temperature before they are entrapped in metallic layer. Scanning electron microscope (SEM) was used to investigate
the microstructure of coating; the chemical composition of the coating is determined by energy dispersive spectrometry (EDS). Mechanical
properties of the interface between coating and Ti substrate were investigated by nanoindentation.
D 2005 Elsevier B.V. All rights reserved.

1. Introduction such as poor osteoinductive properties. This results in one of

Hydroxyapatite, a bioactive ceramic, is compatible with
various tissue types and can adhere directly to osseous, soft,
and muscular tissue without an intermediate layer of
modified tissue [1 –4]. HAp also displays an outstanding
osteoconductivity — a property of a material that encour-
ages bone to form, to lie closely, or to adhere to its surface
[4]. This is especially useful for an implant where fast
healing is required. Despite HAp’s excellent properties as a
biomaterial, the inherent mechanical properties of HAp –
specifically brittleness, low tensile strength, and poor impact
resistance – have restricted it from many load-bearing
applications [5].
Ti and its alloys have been used in several implant
applications. However, they suffer certain disadvantages,
* Corresponding author. Tel.: +1 509 335 7711.
E-mail address: cheng1@wsu.edu (G.J. Cheng).
0928-4931/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.msec.2005.05.002
the prominent failure mechanisms in total joint replacement
— aseptic loosening of the implant due to stress shielding.
One way to avoid aseptic loosening is to incorporate porous
coated materials. These materials encourage in-growth of
mineralized tissue from the surrounding bone into the
implant’s pore spaces and improves biological fixation [6].
Therefore, the concept of applying HAp onto metallic
implants as a surface coating was developed, where the
HAp-coated implant combined the good strength and
ductility of the metal with the excellent biocompatibility
and bioactivity of the HAp [7,8].
Musculoskeletal disorders and bone deficiencies have
been established as among the most important human health
conditions that exist today, costing society an estimated
$254 billion every year, and afflicting 1 out of 7 Americans.
As these conditions are prevalent in the older population, it
is expected that the number of individuals presenting with a
bone deficiency will increase even higher over the coming
years, as our population as a whole ages. It is projected that
542 G.J. Cheng et al. / Materials Science and Engineering C 25 (2005) 541 – 547
0.20
HAP
0.15
Absorbance
0.10
0.05
0.00
400 500 600 700 800 900
Wavelength (nm)
Fig. 1. Spectrum of HAp at UV-Near Infrared range.
the number of people over age 50 will double between 1990
and 2020. Metallic implants are currently being used as
load-bearing implants, and polymer, ceramic, or composite
implants are typically used as non-load-bearing implants.
HAp coatings were first introduced in the mid-1980s for
improving the fixation between the bone and the implant
[9,10]. Various methods have been used to deposit HAp
coatings, for example dip coating– sintering [11,12], immer-
sion coating [13,14], electrophoretic deposition [15], sol-
ution deposition [16], ion-beam sputter coating [17] and
dynamic mixing [18], thermal spraying techniques such as
plasma spraying [19,20], flame spraying [21], and high-
velocity oxy-fuel (HVOF) combustion spraying [22].
Detailed descriptions of these methods have been given
by Lacefield [11] and Berndt et al [8]. A comparison of
these methods has also been made by Jaffe and Scott [16].
Most of the coatings made by those methods suffer from
weak coating adherence to the substrate, thickness non-
uniformity, and non-stoichiometric composition of the
coatings. Dip coating/sintering, for example, can degrade
mechanical properties of metal implants and lead to low
bond strength and impurity of HAp [12 – 15]. Electro-
phoretic deposition has the same problems as dip coating/
sintering, also leads to nonuniform thickness of HAp,
shrinkage and cracking due to the densification during
(a)
Laser scanning
direction
Entrapped HAp -powder
Molten metal Metallic substrate
Fig. 2. Schematic representation of monolayer HAp ceramic coating on Ti substrates. (a) Laser coating of HAp powders. (b) Composite microstructure
Monolayer porous coating after laser coating.
sintering [15]. In hot isostatic pressing, the encapsulating
materials react with the HAp coating and it is difficult to
seal borders on implants of complex shapes. In solution
deposition, maximum thickness of 20 Am limits its use as a
primary mode of fixation. Sputter-deposited coatings have
good adherence properties, however the deposition rate is
slow [17]. Plasma spraying is the major method commer-
cially available for coating implant devices with HAp due to
its reproducibility and economic efficiency. However, coat-
ing produced by this method presents poor coating/substrate
adherence and is lack of uniformity in terms of both
morphology and crystallinity [19,20]. Therefore, there is
indeed a need for the development of new alternative
techniques to produce better coating.
1000
In this work, a unique process is presented to coat HAp
powders on titanium substrates at low temperature by laser
surface engineering (LSE). Nd-YAG laser will transmit HAp
powders and laser energy will be absorbed by titanium
substrate and Ti powders. The transmission of the HAp
powder to the Nd-YAG laser reduces the thermal effect on
HAp and minimized probability of phase transformation.
Because the replaced ceramic powder precursor is entrapped
into a thin layer of molten substrate, these coatings are
metallurgically bonded, providing a sound and adherent
interface between the coating and substrate. It has advan-
tages over, conventional methods such as plasma spraying.
2. Coating schemes
By LSE, a pre-placed powder precursor, including Ti and
HAp powder, will be scanned with Nd-YAG laser. HAp
powders are entrapped in a thin layer of the molten metal to
produce a laser-melt zone of desired composition. The
density of HAp can be controlled by the HAp concentration
in the precursor. The absorption of metal to laser is the
highest in infrared range, while HAp is transparent to
infrared light but opaque to UV light. The spectrum of HAp
has been plotted in Fig. 1, where the absorption coefficient
of HAp to Nd-YAG laser is very small. Laser penetrates the
HAp powders and heats the metal powders and substrate.
Laser heating conditions are carefully chosen so that the
peak temperature of metal is slightly higher than the melting
(b)
Metallic substrate
 G.J. Cheng et al. / Materials Science and Engineering C 25 (2005) 541 – 547
temperature of Ti. Since HAp does not absorb laser, HAp
powders will stay at low temperature before they are
entrapped into metallic layer and form a strong metallurgical
bonding with metallic substrate. In the current study, pure Ti
powders were used to improve the wetability and adherence
of the coating on titanium substrate. Fig. 2 illustrates a
schematic of the coating process. The coating microstructure
consists of three layers — a metal layer, a molten zone (a
dense composite coating), and a less dense HAp coating
near surface.
3. Experimental method
HAp powders and pure Ti powders are used as a
precursor for coating. Thin plate of Titanium (10mm

10mm) is spray-coated with mixture of the precursor and
organic solvent (acetone). After drying the sample, organic
solvent is removed and thin layer of HAP is pre-coated on
the substrate. A 100W continuous wave Nd:YAG laser
(1064 nm wavelength) equipped with X – Y table is
employed for laser-assisted HAp coating.
After coating, the sample is cut in thickness direction for
microstructure and mechanical properties characterization.
SEM investigations of the microstructure of coating were
carried out in a JOEL microscope operating at 15 kV.
Chemical composition of the coating is analyzed by EDS
attached to the SEM. Before the spectrum analysis on the
HAp coating, a calibration process is conducted on
calibration material (Al –Cu alloy). Calibrations are per-
formed with the lowest low-energy and highest high-energy
peaks available. The process is to iterate the adjustment of
the gain and offset controls of the pulse processor until the
spectrum comes into alignment. The offset and gain control
of the pulse processor is adjusted until the low-energy
(copper) peak and high-energy (Aluminum) peak reach the
correct energy respectively. Once the calibration shows a
close match between the actual and measured peaks (high
and low energy), the intermediate peaks are also calibrated.
The calibration preferences are saved. After the X-ray
spectrum is properly calibrated, spectra of the interested
area are acquired. The element labels and KLM markers
Fig. 3. Cross-sectional SEM micrograph of HAp coated Ti6a14V substrate using an Nd:YAG laser with power of 100W and scanning velocity of 1 mm/s.
543
are displayed in proximity to each peak. Manually defined
region of interest (ROI) markers are overlaid for each peak.
The intensities are integrated counts in the element ROIs.
A full-width at half-maximum (FWHM) value is calculated
for each peak. A background subtraction is then performed
on the spectrum. At the end, a qualitative analysis on the
spectrum to integrate counts in the element ROIs for
relative intensities, and a probability of each element is
obtained.
The mechanical properties of the coating are investigated
in the following aspects: (a) the measurement of hardness
and modulus by nanoindentation and (b) the determination
of the interfacial toughness of this HAp/Ti substrate system
by Vickers indentation. The indentation unit is a Hysitron
Triboscope coupled with a Park Autoprobe scanning probe
microscope. The indentations were made with cube corner
diamond indenter (90- included angle) to induce plasticity at
small depths. The load was applied normal to the HAp/Ti
interface. The indents were made using a constant loading
rate of 50 AN/s to a maximum load of 500 AN. Elastic
properties and hardness were inferred from the load-
displacement curves [23,24].
4. Results and discussion
4.1. Microstructure
Fig. 3 represents a typical cross sectional microstructure
of a HAP coating on Ti substrate. The coating consists of
three layers. The top layer is a less dense HAp coating. The
less dense and porous HAp layer is preferred for cell
growth by forming a strong bonding between HAp and
body cell. The mid-layer is a composite structure where
HAp powders are entrapped in Ti molten zone. The density
of HAp decreases with the depth increasing. The SEM
micrographs in Fig. 4 further reveal the HAp entrapped Ti
matrix composite structure on the interface of HAp coating
and Ti substrate. It can be seen in Fig. 4(a) that HAp
powders are entrapped in Ti molten zone forming a
composite structure with a solid HAp/Ti bonding. Fig.
4(b) shows another region with a further depth from the
HAp coatings
HAp powders entrapped in
molten zone
Ti Substrate
544 G.J. Cheng et al. / Materials Science and Engineering C 25 (2005) 541 – 547

Fig. 4. The SEM micrograph and chemical analysis by EDS on the cross-section of coating (a) HAp/Ti composites at interface, (b) HAp/Ti composites with
depth increasing, (c) Titanium substrate.

surface than Fig. 4(a). Similar to Fig. 4(a), HAp/Ti 4.2. Chemical composition
composite structures were also found in Fig. 4(b), however
the density of HAp is less than that in Fig. 4(a). The Hydroxyapatite (HAp), Ca10(PO4)6(OH)2, is an impor-
substrate layer of Ti, is shown in Fig. 4(c). tant biomaterial and its biocompatibility relies on the
 G.J. Cheng et al. / Materials Science and Engineering C 25 (2005) 541 – 547 545

Modulus Profile
180
position of HAp can be minimized by controlling the laser
heating condition, in which Ti substrate is heated just
above the melting point.
160

4.3. Mechanical properties

140
4.3.1. Elastic modulus
E (GPa)

Fig. 5 shows the elastic modulus calculated from

120
nanoindentation test of HAp coating along thickness
direction. It can be seen from Fig. 5 that porous HAp
100 coatings near the top surface has low elastic modulus. The
elastic modulus increases gradually with depth and becomes
80
almost constant at the thickness bigger than 150 nm from
the surface. It should be noted that the constant modulus
(about 120¨160GPa) is higher than the elastic modulus of
60 Ti substrate (106GPa). This is attributed to the HAP/Ti
0 100 200 300 400 500
composite structure and the fine Ti grain structure after LSE
Displacement (nm)
treatment. The elastic moduli of the interface of HAp/Ti
Fig. 5. The elastic constant results of the HAp coating on Titanium substrate
from nanoindentation test.

(a) Hardness Profile

chemical integrity. One important and strongly regulated 10

quality indicator of HA is molar ratio of Ca/P. In this study,

EDS is used for chemical analysis on micro-scale. The area
8
ratio of the characteristic X-rays is used to evaluate the the
relevant amounts of the existing elements. EDS in Fig. 4(a)
shows the chemical compositions of HAp particle and Ti 6
H (GPa)

substrate. Based on the quantitative EDS analysis process

described in Section 3, integrate counts in the element
ROIs are obtained for relative probability of each element 4

(Ca and P). The results of the relative intensity of HAp

elements reveal that molar ratio of Ca / P is about 1.636, 2
which is very closed to the Ca / P molar ratio in
Ca10(PO4)6(OH)2 : 1.666. The HAp particles survived
LSE treatment on the surface. From EDS in Fig. 4(b), 0
the Ca / P molar ratio of the particle is about 1.68, which is 0 100 200 300 400 500
Displacement (nm)
also closed to the molar ratio of Ca / P in HAp. The
chemical composition of Ti matrix defined by EDS in Fig. (b)
4(a) is the same with that in Fig. 4(c). It is seen from Fig. 4 5.5
(a) and (b) that the chemical composition of HAP is
5.0
maintained after laser coating. This is important because it
insures that biocompatibility of HAp does not degrade 4.5
Hardness (GPa)

during the laser irradiation. As discussed previously, this is

expected because most of the heat is absorbed by titanium 4.0

substrate. Heating and cooling rate in laser irradiation 3.5

substrate
process is extremely fast (¨104 – 5 K/s). The specific heat
of HAp is much less than that of titanium. Therefore, HAp 3.0
particles do not have time to reach high temperature before surface
2.5
they cool down. The thermal decomposition of HAp
largely depends on the coating conditions. Generally, the 2.0
decomposition temperature is ¨900 – 1200 -C. The melting 0 5 10 15 20 25
temperature of Titanium is ¨1600 -C [25]. Due to the fast Distance from surface (µm)
cooling of laser irradiation and large specific heat of Fig. 6. The hardness results of the HAp coating on Titanium substrate from
Hydroxyapatite, the majority of heat will be dissipated in nanoindentation test. (a) Hardness distribution near the coating surface. (b)
air and Titanium substrate mostly. The thermal decom- Hardness from nanoindentation at a larger depth scale.
546 G.J. Cheng et al. / Materials Science and Engineering C 25 (2005) 541 – 547
show the same trend at difference points. This implies a
uniform coating using LSE technique.
4.3.2. Hardness
Fig. 6(a) shows the hardness profile from nanoindenta-
tion test of HAp coating along thickness direction. The
hardness data is used qualitatively to compare the mechan-
ical properties of the coatings at the interface. Fig. 6(a)
shows the hardness of many points on the coating surface.
Near the top surface, porous HAp coatings has low
hardness. The hardness is highest right below the porous
coatings. This very high hardness (7¨9GPa) corresponds
well to the high dense HAp coatings achieved (Fig. 4). The
hardness decreases slightly with further depth increasing.
Fig. 6(b) shows hardness from nanoindentation at a larger
depth scale. It shows that the hardness of HAp/Ti interface
decrease continuously to 2.5¨3GPa with depth beyond 10
Am. This is because HAp density decrease with depth. Also,
heating/cooling rate close to the surface is higher, which
results in crystalline reaction products and phase(s) formed
at the ceramic/metal interface. The gradually decreased
nanoscale hardness values around the HAP/Ti coating imply
a strong interface between HAP coating and Ti substrate.
This is because HAP particles are entrapped to Ti molten
layer forming metallurgical bonding. The LSE is a non-
equilibrium synthesis involving high cooling rates, which
produce metastable phases by exceeding the solid-solubility
limit beyond the equilibrium phase diagram [25]. This
results in a wide variety of microstructures with novel
properties, including crystalline reaction products and
phases on HAp/Ti interface. These microstructure features
suggest strong ceramic/metal interface within the coating
region.
Vikers – Microhardness tests were performed to see
potential failure in the coating. The loadings were applied
normal to the coating surface. The hardness value is in the
range of 230¨260 HV. Fig. 7 shows an impression of
indentation after microhardness testing. There is no apparent
Fig. 7. Image of indentation after microhardness testing with loading
applied normal to the coating surface.
crack on the edges and corners of the indent. This is because
the ductility of the coating is enhanced by the HAp/Ti
composite structure. This HAp/Ti composite structure is
expected to have a relatively larger fracture toughness and
good resistance to crack growth than a sharp HAp coating
and Titanium substrate interfacial structure. Further inves-
tigations will be conducted to compare the interfacial
fracture toughness of the presented coating and other
coatings techniques, such as plasma coating. The interfacial
fracture toughness is implied using the following equation:
n
o
KIC ¼ 0:016Tð E=Hv Þ1=2 T P= C 3=2
where K IC : fracture toughness, E: Young’s modulus, H v :
Vickers hardness, P: the load and C: the half crack size.
4.4. What is anticipated?
Laser surface engineering coatings of HAp on Ti
substrate are expected to have the following features:
1) Low temperature coating is realized. HAp is transparent to the
selected wavelength. Therefore, temperature of the coating
process could be controlled such that most of the heat goes to
the metal/ceramic interface to generate a thin molten layer to
entrap HAp particles. Cooling of this molten metal pool is
significantly faster (in a few seconds) and therefore, the HAp
powders could be kept at low temperature to reduce the chances
of phase transformation of HAp.
2) Coating with designed HAp density is realized. Based on a
multiple-layer laser coating process, the porosity and density of
HAp can be controlled on each monolayer. Therefore, the
multiple-layer coating will have tailored porosity and HAp
density as a whole. Micro-porous coatings will generate better
cell anchorage due to higher specific surface area of these
coatings and increase implant/tissue bonding strength.
3) Strong metal/HAp interface is obtained. Because the replaced
ceramic powder precursor is entrapped with a thin layer of the
molten substrate to produce a laser-melt zone, these coatings are
metallurgically bonded, providing a sound and adherent inter-
face between the coating and substrate.
4) Novel microstructure and functional coating could be obtained.
Laser-surface modification is a non-equilibrium synthesis
involving high heating/cooling rates, which produce metastable
phases by exceeding the solid-solubility limit beyond the
equilibrium phase diagram. This could lead to very fine Ti
grain structure. The HAp and Ti form a composite coating
structure. However, the HAp/Ti interfacial structure is unknown
and should be investigated in the future. Moreover, it is
expected that the fine phases formed at the ceramic/metal
interface due to high cooling rate can further reduce the chances
of crack propagation [22].
5) It is a flexible manufacturing method. The laser beam has an
excellent spatial resolution that makes it ideal for depositing
coating on miniature-sized components. Laser with fiber-optic
beam delivery provides limitless opportunities to synthesize
and/or fabricate such a coating into various shapes and sizes,
thereby making it even more functional for commercial
applications.
 G.J. Cheng et al. / Materials Science and Engineering C 25 (2005) 541 – 547
5. Conclusions
A unique process is presented in this paper to coat HAp
powders on Ti substrates at low temperature by laser surface
engineering. HAp has very low absorption to Nd-YAG laser,
therefore most laser power is transmitted and scattered by
HAp powders and finally absorbed by Ti powders and Ti
substrate. During this fast heating and cooling process, HAp
powders are kept in low temperature. SEM investigations
reveal three layered structure formed during LSE: porous
HAp layer, dense HAp/Ti bonded structure layer and Ti
substrate. Chemical analysis of the coating by EDS shows
that the Ca / P molar ratio is well maintained throughout the
cross-section of the coating interface. Nanoindenation
further proves that a strong interface with good interfacial
mechanical properties has been achieved by using LSE
technique. The interface structure produced by LSE has a
fairly high toughness and good resistance to crack growth,
which implies the potential application in bioengineering. It
can also be expected that LSE can be used as a further
modification procedure to enhance HAp/metal interface
produced by other methods.
Acknowledgements
The authors would like to thank Prof. Dave Bahr and Mr.
Kevin Morasch from Washington State University, School
of Mechanical and Materials Engineering, for helping on
nanoindentation testing and valuable discussions. Financial
support from Office of research, Washington State Univer-
sity and National Science Foundation is also appreciated.
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