Materials Letters 60 (2006) 1575 – 1578

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Sol–gel derived hydroxyapatite/titania biocoatings on titanium substrate

Wei Xu a , Wangyu Hu a,⁎, Meiheng Li a , Cui'e Wen b
a
Department of Applied Physics, Hunan University, Changsha 410082, China
b
Faculty of Science and Technology, Deakin University, Geelong Vic 3217, Australia

Received 17 July 2005; accepted 22 November 2005

Available online 13 December 2005

Abstract

A simple sol–gel method was successfully developed for a hydroxyapatite (HA)/TiO2 double layer deposition on a pure titanium substrate.
Phase formation, surface morphology, and interfacial microstructure were investigated by differential scanning calorimetry analysis (DSC), X-ray
diffraction (XRD) and scanning electron microscopy (SEM). The TiO2 layer was coated by a spin coating method at a speed of 1500 rpm for 15 s,
followed by a heat treatment at 560 °C for 20 min. The HA film was subsequently spin coated on the outer surface at the same speed and then
heat-treated at difference temperatures. Results indicated that the HA phase began to crystallize after a heat treatment at 580 °C; and the
crystallinity increased obviously at a temperature of 780 °C. The HA film showed a porous structure and a thickness of 5–7 μm after the heat
treatment at 780 °C. SEM observations revealed no delamination and crack at the interfaces of HA/TiO2 and TiO2/Ti. The HA film with a porous
structure is expected to be more susceptible to the natural remodeling processes when it is implanted in a living body.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Titanium; Sol–gel preparation; Surfaces; Hydroxyapatite; Titania

1. Introduction advantages over other coating techniques, e.g. increased

Hydroxyapatite (HA) has many biological benefits such as
direct bonding to bone and enhancement of new bone formation
around it due to its chemical similarity with hard tissues [1–8].
Many methods including plasma-spraying, pulsed laser depo-
sition and electrophoretic deposition have been studied to
produce HA coatings over the last years [9–16]. However, of
these techniques only plasma-spraying [9] has achieved
commercial success. But a general limitation of plasma-
spraying is the inherent difficulty in microstructure control
and modification, which impedes this approach in achieving
optimum fixation with host tissues. Furthermore, methods such
as plasma spraying and electrophoresis may produce a highly
crystallized coating, and it is difficult to resorb in the body.
Lastly, the plasma spraying process requires an extremely high
temperature, which may be as high as 12000 °C.
In recent years, sol–gel technique has been developed to
synthesize HA [1–3,7,17,18]. This process offers lots of
homogeneity due to atomic level mixing; finer grain micro-
structure and lower temperature of the crystallization. Liu et al.
even synthesized HA at a temperature as low as 350 °C [12].
On the other hand, titania (TiO2) coatings, placed between the
HA and Ti, have been used to improve the bonding capability of
the HA layer with respect to the Ti and the corrosion resistance of
Ti. The corrosion resistance is known to increase with the
increasing of the thickness of the TiO2 coatings [2].
Pure titanium and some of its alloys, such as Ti–6Al–4V and
Ti–29Nb–13Ta–4.6Zr, have long been used as implant
materials in dental and orthopedic applications due to their
excellent mechanical properties and good corrosion resistance
[3,9,13,16]. In this investigation, we synthesized HA/TiO2
double layers coating on a pure Ti substrate by a sol–gel method
with simple procedures. The thickness of coatings can be
precisely tailored by adjusting the deposition parameters.
2. Experimental procedures

⁎ Corresponding author. Tel./fax: +86 731 8823971. The sol–gel process started with the preparation of a TiO2
E-mail address: wangyuhu2001cn@yahoo.com.cn (W. Hu). sol. A tetrabutylorthotitanate (C16H36TiO4) was first diluted
0167-577X/$ - see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2005.11.072
1576 W. Xu et al. / Materials Letters 60 (2006) 1575–1578

with absolute ethanol, and then a small amount of distilled water

mixed with diethanolamine (NH(CH2CH2OH)2) which was
used as catalyzer was added for hydrolysis, followed by
vigorous stirring for 24 h. At last, the mixed sol was aged for
24 h.
For the preparation of the HA sol, triethyl phosphite
(C2H5O3PO)) diluted with anhydrous ethanol was first
hydrolyzed for 24 h with distilled water under vigorous stirring.
A stoichiometric amount of 2 M calcium nitrate (Ca
(NO3)2·4H2O)) dissolved in anhydrous ethanol, was added
into the hydrolyzed phosphite sol which had been aged for 24
h (molar ratio Ca/P = 1.67). Vigorous stirring was continued for
4 h after the titration, and then aged for 24 h. As a result of the
above processes, a clear solution was prepared.
Prior to coating, the substrate of pure titanium was first
polished, and then cleaned in acetone for 10 min and in 40%
Fig. 2. DSC/TG curves of HA gel samples.
ethyl alcohol solution for 15 min, then rinsed in distilled water
for 20 min. The TiO2 layer was coated by a spin coating at a
peak at 530 °C is representative of the exothermic reaction indicating
speed of 1500 rpm for 15 s, followed by a heat treatment at 560 the formation of TiO2. Compared to the low exothermic peak at near
°C for 20 min. The HA film was subsequently spin coated at the 500 °C heating in N2, it can be concluded that some organic substances
same speed and heat-treated at 580 °C, and 780 °C, both for 20 are produced and fired in air around 500 °C, resulting in the releasing of
min. The process was repeated several times to get a thicker a large quantity of heat as indicated by the high exothermic peak at
coating. 530 °C. It can also be seen that there is a last broad exothermic peak in
The differential scanning calorimetry analysis (DSC), the range from 600 °C to 800 °C. TG curve of TiO2 gel sample heating
thermogravimetric analysis (TG), X-ray diffraction (XRD), in air can be divided into four stages. The first stage is from room
and scanning electron microscopy (SEM) were used for the temperature to 260 °C. The rate of weight loss is about 12%, which can
characterization of the dried gel and coated samples. be attributed to the result of the evaporation of the absorbed water in the
gel. The second stage is from 260 °C to 480 °C. The rate of weight loss
3. Results and discussion is about 33%, which is attributed to the combustion and carbonization
of organic substances. The third stage is from 480 °C to 600 °C. The
3.1. Thermal analysis rate of weight loss is about 15%, which is caused by the decomposition
of the residual organic materials and the transformation of the anatase
Differential scanning calorimetry analysis (DSC) and thermogravi- TiO2. No further weight loss can be observed in the last stage from
metric analysis (TG) were performed in the temperature range from 600 °C to 800 °C. It is due to the conversion of the anatase form of TiO2
room temperature to 800 °C with a heating rate of 10 K/min for both to the rutile form.
TiO2 and HA gels. Fig. 1 shows the DSC/TG curves of TiO2 gel Fig. 2 shows the DSC/TG curves of HA dried gel samples heating in
heating in flowing N2 and air, respectively. The DSC trace of the flowing air. The first endothermic peak appeared at 54 °C. It is due to
sample heating in flowing air has four exothermic peaks. There are two the evaporation of the absorbed water. The DSC curve also shows two
small exothermic peaks at 276 °C and 327 °C. The high exothermic

Fig. 3. XRD patterns of TiO2 gels (curves a, c and d) and coating (curve b). The
Fig. 1. DSC/TG curves of TiO2 gel samples (the broken line for gel heating in annealing temperatures were 800 °C, 560 °C, 340 °C, and 300 °C for (a), (b), (c),
flowing N2, the solid line for gel heating in flowing air). and (d), respectively.
 W. Xu et al. / Materials Letters 60 (2006) 1575–1578 1577

Fig. 4. XRD patterns of HA coatings at different temperatures.

exothermic peaks at 108 °C and 185 °C, which can be attributed to

nitrates and organic compounds decomposition. The endothermic peak
at 555 °C is representative of the endothermic reaction indicating the
crystallization of HA. The last endothermic peak is observed at 749 °C.
It is caused by the removal of residuals. The TG trace shows the total
weight losses of 42 mass% during heat treatment.

3.2. XRD analysis

The crystal structure of TiO2 gels and films was characterized

using XRD. Fig. 3(a)–(d) show the XRD patterns of TiO2 gels
(curves a, c and d), and a TiO2 coating with a pure Ti substrate
(curve b). The annealing temperatures were 800 °C, 560oC, 340 °C,
and 300 °C for (a), (b), (c), and (d), respectively. The film coated on
the Ti substrate through annealing at 560 °C (as shown in Fig. 3(b))
shows a sharp peak at 25.3° corresponding to the anatase phase,
indicating that the film prepared at this temperature is mainly
consisted of an anatase phase. The sharp peaks at 35.3°, 38.4° and
40.4° are attributable to the Ti substrate. It can be concluded that
TiO2 phase with an anatase structure is formed in this film. Fig. 3(a)
shows the phase transformation from anatase to rutile by annealing at
800 °C. The relatively sharp peaks can be explained by the high
crystallinity of the gel. The gels annealed at 340 °C or below are
found to be amorphous (as shown in curves (c) and (d)).
Fig. 6. SEM micrographs of HA films after heat treatments at different
temperatures (a) 580 °C and (b) 780 °C.
Fig. 4(a) and (b) shows the XRD patterns for the samples after HA
coating and the heat treatments at 780 °C and 580 °C, respectively.
Both traces show several major peaks, such as (002), (211), (112) and
(300), which are attributable to a HA structure. Fig. 4(b) shows that the
major phases of the sample are HA, titania and Ti substrate after heat
treatment at 580 °C. When the temperature increased to 780 °C, the
anatase phase of TiO2 transformed into a rutile phase. Also, CaO peak
can be observed in the sample after heat treatments at both
temperatures. CaO can be dissolved in the simulated body fluid
(SBF) due to its high solubility [13]. In the present study, the starting
temperature for the HA crystallite is 580 °C, which is much lower than
the temperature for plasma-spraying (6000 °C–12,000 °C).

Fig. 5. SEM micrograph of the surface of TiO2 film after heat treatment at Fig. 7. SEM micrograph for the cross-section image for the HA/TiO2 layers
560 °C. annealed at temperature of 780 °C.
1578 W. Xu et al. / Materials Letters 60 (2006) 1575–1578
3.3. SEM analysis
Fig. 5 shows the SEM photograph of the TiO2 film prepared at 560
°C. After heat treatment, the SEM image of TiO2 surface shows a
cracked structure. It can be seen that a number of islands separated by
large cracks on the surface. This is caused by the mechanical
constraints occurred during the heat treatment process. Such cracked
surface is beneficial to the adhesive strength between TiO2 and HA
layers. Because the HA gel can fill into the cracks and cover the surface
of TiO2 film. Therefore the high surface roughness of the TiO2 film
may improve the quality of the HA sol deposition during the spin-
coating process.
Fig. 6(a) and (b) shows the SEM images of the HA film after heat
treatment at different temperatures of 580 °C and 780 °C, respectively.
Fig. 7 shows the cross-section image of the HA/TiO2 layers of the
sample after heat treatment at the temperature of 780 °C. It can be seen
that the HA films of the outer surface shows a porous structure. There is
no cracks detectable in the HA porous structures. These pores on the
outer surface may be formed due to the decomposition of organic
materials during heat treatment. However, no pores can be found in the
inner TiO2 layer, as shown in Fig. 7. Moreover, there is no delamination
in either of the interfaces between layers of HA/TiO2 and TiO2/Ti,
suggesting that the adhesive strength between is very strong. It should
be noticed that the cross-section image of the HA film is dense and
uniform with a thickness of 5–7 μm. This thickness can be adjusted by
controlling the deposit times. SEM observations found out that the film
of the sample is rough and showing gray stains on the surface after heat
treatment at 580 °C (as shown in Fig. 6(a)). The porous structure of the
HA film is expected to be more susceptible to the natural remodeling
processes when it is implanted in a living body.
4. Conclusions
Sol–gel derived HA/TiO2 double layers were spin-coated on
Ti substrates successfully. The TiO2 layer was coated by a spin
coating at a speed of 1500 rpm for 15 s, followed by a heat
treatment at 560 °C for 20 min. The HA film was subsequently
spin coated at the same speed and heat treated at 580 °C and 780
°C. Results indicated that the HA phase began to crystallize
after a heat treatment at 580 °C; and the crystallinity increased
obviously at a temperature of 780 °C. The HA film showed a
porous structure and a thickness of 5–7 μm after heat treatment
at 780 °C. SEM observations found no delamination and crack
at the interfaces of HA/TiO2 and TiO2/Ti. The HA film with a
porous structure is expected to be more susceptible to the
natural remodeling processes when it is implanted in a living
body.
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