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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


the prominent failure mechanisms in total joint replacement
Hydroxyapatite, a bioactive ceramic, is compatible with — aseptic loosening of the implant due to stress shielding.
various tissue types and can adhere directly to osseous, soft, One way to avoid aseptic loosening is to incorporate porous
and muscular tissue without an intermediate layer of coated materials. These materials encourage in-growth of
modified tissue [1 –4]. HAp also displays an outstanding mineralized tissue from the surrounding bone into the
osteoconductivity — a property of a material that encour- implant’s pore spaces and improves biological fixation [6].
ages bone to form, to lie closely, or to adhere to its surface Therefore, the concept of applying HAp onto metallic
[4]. This is especially useful for an implant where fast implants as a surface coating was developed, where the
healing is required. Despite HAp’s excellent properties as a HAp-coated implant combined the good strength and
biomaterial, the inherent mechanical properties of HAp – ductility of the metal with the excellent biocompatibility
specifically brittleness, low tensile strength, and poor impact and bioactivity of the HAp [7,8].
resistance – have restricted it from many load-bearing Musculoskeletal disorders and bone deficiencies have
applications [5]. been established as among the most important human health
Ti and its alloys have been used in several implant conditions that exist today, costing society an estimated
applications. However, they suffer certain disadvantages, $254 billion every year, and afflicting 1 out of 7 Americans.
As these conditions are prevalent in the older population, it
is expected that the number of individuals presenting with a
* Corresponding author. Tel.: +1 509 335 7711. bone deficiency will increase even higher over the coming
E-mail address: cheng1@wsu.edu (G.J. Cheng). years, as our population as a whole ages. It is projected that
0928-4931/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.msec.2005.05.002
542 G.J. Cheng et al. / Materials Science and Engineering C 25 (2005) 541 – 547

0.20
sintering [15]. In hot isostatic pressing, the encapsulating
materials react with the HAp coating and it is difficult to
HAP
seal borders on implants of complex shapes. In solution
0.15 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
Absorbance

0.10 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
0.05
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
0.00 techniques to produce better coating.
400 500 600 700 800 900 1000
In this work, a unique process is presented to coat HAp
Wavelength (nm)
powders on titanium substrates at low temperature by laser
Fig. 1. Spectrum of HAp at UV-Near Infrared range. surface engineering (LSE). Nd-YAG laser will transmit HAp
powders and laser energy will be absorbed by titanium
the number of people over age 50 will double between 1990 substrate and Ti powders. The transmission of the HAp
and 2020. Metallic implants are currently being used as powder to the Nd-YAG laser reduces the thermal effect on
load-bearing implants, and polymer, ceramic, or composite HAp and minimized probability of phase transformation.
implants are typically used as non-load-bearing implants. Because the replaced ceramic powder precursor is entrapped
HAp coatings were first introduced in the mid-1980s for into a thin layer of molten substrate, these coatings are
improving the fixation between the bone and the implant metallurgically bonded, providing a sound and adherent
[9,10]. Various methods have been used to deposit HAp interface between the coating and substrate. It has advan-
coatings, for example dip coating– sintering [11,12], immer- tages over, conventional methods such as plasma spraying.
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 2. Coating schemes
plasma spraying [19,20], flame spraying [21], and high-
velocity oxy-fuel (HVOF) combustion spraying [22]. By LSE, a pre-placed powder precursor, including Ti and
Detailed descriptions of these methods have been given HAp powder, will be scanned with Nd-YAG laser. HAp
by Lacefield [11] and Berndt et al [8]. A comparison of powders are entrapped in a thin layer of the molten metal to
these methods has also been made by Jaffe and Scott [16]. produce a laser-melt zone of desired composition. The
Most of the coatings made by those methods suffer from density of HAp can be controlled by the HAp concentration
weak coating adherence to the substrate, thickness non- in the precursor. The absorption of metal to laser is the
uniformity, and non-stoichiometric composition of the highest in infrared range, while HAp is transparent to
coatings. Dip coating/sintering, for example, can degrade infrared light but opaque to UV light. The spectrum of HAp
mechanical properties of metal implants and lead to low has been plotted in Fig. 1, where the absorption coefficient
bond strength and impurity of HAp [12 – 15]. Electro- of HAp to Nd-YAG laser is very small. Laser penetrates the
phoretic deposition has the same problems as dip coating/ HAp powders and heats the metal powders and substrate.
sintering, also leads to nonuniform thickness of HAp, Laser heating conditions are carefully chosen so that the
shrinkage and cracking due to the densification during peak temperature of metal is slightly higher than the melting

(a) (b)

Laser scanning
direction
Entrapped HAp -powder

Molten metal Metallic substrate 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.
G.J. Cheng et al. / Materials Science and Engineering C 25 (2005) 541 – 547 543

temperature of Ti. Since HAp does not absorb laser, HAp are displayed in proximity to each peak. Manually defined
powders will stay at low temperature before they are region of interest (ROI) markers are overlaid for each peak.
entrapped into metallic layer and form a strong metallurgical The intensities are integrated counts in the element ROIs.
bonding with metallic substrate. In the current study, pure Ti A full-width at half-maximum (FWHM) value is calculated
powders were used to improve the wetability and adherence for each peak. A background subtraction is then performed
of the coating on titanium substrate. Fig. 2 illustrates a on the spectrum. At the end, a qualitative analysis on the
schematic of the coating process. The coating microstructure spectrum to integrate counts in the element ROIs for
consists of three layers — a metal layer, a molten zone (a relative intensities, and a probability of each element is
dense composite coating), and a less dense HAp coating obtained.
near surface. 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
3. Experimental method of the interfacial toughness of this HAp/Ti substrate system
by Vickers indentation. The indentation unit is a Hysitron
HAp powders and pure Ti powders are used as a Triboscope coupled with a Park Autoprobe scanning probe
precursor for coating. Thin plate of Titanium (10mm  microscope. The indentations were made with cube corner
10mm) is spray-coated with mixture of the precursor and diamond indenter (90- included angle) to induce plasticity at
organic solvent (acetone). After drying the sample, organic small depths. The load was applied normal to the HAp/Ti
solvent is removed and thin layer of HAP is pre-coated on interface. The indents were made using a constant loading
the substrate. A 100W continuous wave Nd:YAG laser rate of 50 AN/s to a maximum load of 500 AN. Elastic
(1064 nm wavelength) equipped with X – Y table is properties and hardness were inferred from the load-
employed for laser-assisted HAp coating. displacement curves [23,24].
After coating, the sample is cut in thickness direction for
microstructure and mechanical properties characterization.
SEM investigations of the microstructure of coating were 4. Results and discussion
carried out in a JOEL microscope operating at 15 kV.
Chemical composition of the coating is analyzed by EDS 4.1. Microstructure
attached to the SEM. Before the spectrum analysis on the
HAp coating, a calibration process is conducted on Fig. 3 represents a typical cross sectional microstructure
calibration material (Al –Cu alloy). Calibrations are per- of a HAP coating on Ti substrate. The coating consists of
formed with the lowest low-energy and highest high-energy three layers. The top layer is a less dense HAp coating. The
peaks available. The process is to iterate the adjustment of less dense and porous HAp layer is preferred for cell
the gain and offset controls of the pulse processor until the growth by forming a strong bonding between HAp and
spectrum comes into alignment. The offset and gain control body cell. The mid-layer is a composite structure where
of the pulse processor is adjusted until the low-energy HAp powders are entrapped in Ti molten zone. The density
(copper) peak and high-energy (Aluminum) peak reach the of HAp decreases with the depth increasing. The SEM
correct energy respectively. Once the calibration shows a micrographs in Fig. 4 further reveal the HAp entrapped Ti
close match between the actual and measured peaks (high matrix composite structure on the interface of HAp coating
and low energy), the intermediate peaks are also calibrated. and Ti substrate. It can be seen in Fig. 4(a) that HAp
The calibration preferences are saved. After the X-ray powders are entrapped in Ti molten zone forming a
spectrum is properly calibrated, spectra of the interested composite structure with a solid HAp/Ti bonding. Fig.
area are acquired. The element labels and KLM markers 4(b) shows another region with a further depth from the

HAp coatings

HAp powders entrapped in


molten zone

Ti Substrate

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.
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 crack on the edges and corners of the indent. This is because
uniform coating using LSE technique. the ductility of the coating is enhanced by the HAp/Ti
composite structure. This HAp/Ti composite structure is
4.3.2. Hardness expected to have a relatively larger fracture toughness and
Fig. 6(a) shows the hardness profile from nanoindenta- good resistance to crack growth than a sharp HAp coating
tion test of HAp coating along thickness direction. The and Titanium substrate interfacial structure. Further inves-
hardness data is used qualitatively to compare the mechan- tigations will be conducted to compare the interfacial
ical properties of the coatings at the interface. Fig. 6(a) fracture toughness of the presented coating and other
shows the hardness of many points on the coating surface. coatings techniques, such as plasma coating. The interfacial
Near the top surface, porous HAp coatings has low fracture toughness is implied using the following equation:
hardness. The hardness is highest right below the porous n  o
coatings. This very high hardness (7¨9GPa) corresponds KIC ¼ 0:016Tð E=Hv Þ1=2 T P= C 3=2
well to the high dense HAp coatings achieved (Fig. 4). The
hardness decreases slightly with further depth increasing. where K IC : fracture toughness, E: Young’s modulus, H v :
Fig. 6(b) shows hardness from nanoindentation at a larger Vickers hardness, P: the load and C: the half crack size.
depth scale. It shows that the hardness of HAp/Ti interface
decrease continuously to 2.5¨3GPa with depth beyond 10 4.4. What is anticipated?
Am. This is because HAp density decrease with depth. Also,
heating/cooling rate close to the surface is higher, which Laser surface engineering coatings of HAp on Ti
results in crystalline reaction products and phase(s) formed substrate are expected to have the following features:
at the ceramic/metal interface. The gradually decreased
nanoscale hardness values around the HAP/Ti coating imply 1) Low temperature coating is realized. HAp is transparent to the
a strong interface between HAP coating and Ti substrate. selected wavelength. Therefore, temperature of the coating
process could be controlled such that most of the heat goes to
This is because HAP particles are entrapped to Ti molten
the metal/ceramic interface to generate a thin molten layer to
layer forming metallurgical bonding. The LSE is a non- entrap HAp particles. Cooling of this molten metal pool is
equilibrium synthesis involving high cooling rates, which significantly faster (in a few seconds) and therefore, the HAp
produce metastable phases by exceeding the solid-solubility powders could be kept at low temperature to reduce the chances
limit beyond the equilibrium phase diagram [25]. This of phase transformation of HAp.
results in a wide variety of microstructures with novel 2) Coating with designed HAp density is realized. Based on a
properties, including crystalline reaction products and multiple-layer laser coating process, the porosity and density of
phases on HAp/Ti interface. These microstructure features HAp can be controlled on each monolayer. Therefore, the
suggest strong ceramic/metal interface within the coating multiple-layer coating will have tailored porosity and HAp
region. density as a whole. Micro-porous coatings will generate better
Vikers – Microhardness tests were performed to see cell anchorage due to higher specific surface area of these
potential failure in the coating. The loadings were applied coatings and increase implant/tissue bonding strength.
normal to the coating surface. The hardness value is in the 3) Strong metal/HAp interface is obtained. Because the replaced
ceramic powder precursor is entrapped with a thin layer of the
range of 230¨260 HV. Fig. 7 shows an impression of
molten substrate to produce a laser-melt zone, these coatings are
indentation after microhardness testing. There is no apparent 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,
Fig. 7. Image of indentation after microhardness testing with loading thereby making it even more functional for commercial
applied normal to the coating surface. applications.
G.J. Cheng et al. / Materials Science and Engineering C 25 (2005) 541 – 547 547

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