Applied Surface Science 255 (2009) 3927–3932

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Surface characterisation and electrochemical behaviour of porous titanium

dioxide coated 316L stainless steel for orthopaedic applications
S. Nagarajan, N. Rajendran *
Department of Chemistry, MIT Campus, Anna University, Chennai 600 044, India

A R T I C L E I N F O A B S T R A C T

Article history: Porous titanium dioxide was coated on surgical grade 316L stainless steel (SS) and its role on the
Received 12 March 2008 corrosion protection and enhanced biocompatibility of the materials was studied. X-ray diffraction
Received in revised form 8 October 2008 analysis (XRD), atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, scanning
Accepted 8 October 2008
electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX) were carried out to characterise
Available online 1 November 2008
the surface morphology and also to understand the structure of the as synthesised coating on the
substrates. The corrosion behaviour of titanium dioxide coated samples in simulated body fluid was
Keywords:
evaluated using polarisation and impedance spectroscopy studies. The results reveal that the titanium
Titanium dioxide
dioxide coated 316L SS exhibit a higher corrosion resistance than the uncoated 316L SS. The titanium
Stainless steel
Polarisation dioxide coated surface is porous, uniform and also it acts as a barrier layer to metallic substrate and the
Electrochemical impedance spectroscopy porous titanium dioxide coating induces the formation of hydroxyapatite layer on the metal surface.
Hydroxyapatite ß 2008 Elsevier B.V. All rights reserved.

1. Introduction is to deposit a protective bioactive ceramic coating layer on the

Biomedical prosthetic devices are used in human body to carry
out the functions that are no longer performed by the original
human parts. Metals are used in the human body mainly for
orthopaedic purposes and their degradation by wear and corrosion
must be negligible so that they can be used for various practical
applications [1]. Among the various metallic materials that are
used for orthopaedic devices, 316L stainless steel (SS) is one of the
most commonly used. It is frequently employed for temporary
devices in orthopedic surgery because of its low cost and
acceptable biocompatibility [2]. However, under some conditions
this alloy suffers localised corrosion and releases significant
quantities of iron to its neighbouring tissue thus inducing fibrosis
around the implant [3]. To overcome this problem the prostheses
should possess and also ensure high mechanical resistance. In
addition to this, the prostheses should also have high corrosion
resistance and at the same time the best adhesion to the tissue so
that a stable biological bond with the bone is formed.
Various surface modification techniques have been developed
in recent times to improve the corrosion resistance and
biocompatibility of the metals. One of the most effective methods
* Corresponding author. Tel.: +91 44 2251 6141; fax: +91 44 2223 2403.
E-mail addresses: nrajendran@annauniv.edu, snograj@gmail.com
(N. Rajendran).
metal surface. Various ceramic coatings have been identified to
induce bioactivity on the metallic prosthesis [4,5]. Different types
of ceramic coatings have been used including titanium dioxide,
calcium phosphate and silica based glasses [6–8]. In recent years,
titanium dioxide thin films on metallic implants, as a composite
material have received great attention in the field of orthopaedics
because of its excellent mechanical, osteoconductive and corrosion
resistant properties. Titania ceramics finds application in porous
cell carrier material due to its good permeability and high
biocompatibility which is also useful to serve in enhancing cell
vitality [9,10]. Coating metallic prosthesis with bioactive ceramic
could be a route to combine both mechanical resistance and
bioactivity in one material.
Many attempts have been made in this direction by using
different coating techniques such as plasma spray, electrophoresis,
electrochemical deposition, blast coating, ion beam sputtering etc.
[11,12]. All these methods have significant limitations such as low
bond strength in the coatings, transformation of phases in the
coated material or huge cost of the equipment. Among the
unconventional techniques of deposition for such coatings directly
from gas and liquid phases, the most important techniques are
metallo-organic chemical vapour deposition method and sol–gel
method [13]. Sol-gel is a versatile technique for ceramic oxide
preparation. The sol–gel deposition procedure requires relatively
lower temperature and fewer equipments as compared to the
chemical vapour deposition and therefore it is considerably less

0169-4332/$ – see front matter ß 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2008.10.058
3928 S. Nagarajan, N. Rajendran / Applied Surface Science 255 (2009) 3927–3932

expensive. The most important advantage of the sol–gel method is earlier report [15]. Potentiodynamic polarisation studies were
the possibility of controlling the microstructure in the coating carried out for the test specimens in SBF. The potentiostat (model
films, which is not possible in conventional coating methods [14]. PGSTAT 12, AUTOLAB, the Netherlands B.V) was controlled by a
In the present investigation, an attempt has been made to personal computer. A dedicated software (GPES Version 4.5) was
deposit porous titanium dioxide coatings on 316L SS with two used for conducting the polarisation experiments. The potential
main objectives: (a) reduction of corrosion of the substrate in the applied on the working electrode was at a scan rate of
body. (b) Stabilisation of the implant and allowing the growth of 0.167 mV s 1. In order to test the reproducibility of the results,
hydroxyapatite on the coated surface. The performance of the the experiments were performed in triplicate.
coated metal was evaluated by various surface techniques and also Electrochemical impedance spectroscopy measurements were
by carrying out in vitro experiment. carried out using a frequency response analyser (FRA), which
included a potentiostat model PGSTAT 12. Impedance spectra were
2. Experimental procedure acquired in the frequency range of 40 kHz to 0.01 Hz with a 10 mV
amplitude sine wave generated by the FRA.
Titanium isopropoxide (TIP), triethanolamine (TEA), ethanol
(EtOH) and polyethylene glycol (PEG) were used as the starting 3. Results and discussion
materials. The relative volume ratio of each chemical in the sol was
3:1:20: 0.5 (TIP:TEA:EtOH:PEG). Introduction of titanium isoprop- 3.1. Surface characterisation
oxide in ethanol induces immediate precipitation due to the highly
reactive nature of the alkoxide and therefore to avoid this The X-ray diffraction pattern of the titanium dioxide coated 316L
triethanolamine has been added as a stabilising agent for SS shows (Fig. 1) strong diffraction peaks at 2u values 25.3, 37.8, 48,
hydrolysis. The mixture was initially stirred with 10 ml of ethanol
followed by the addition of titanium isopropoxide and PEG. The
stirring of the solution was continued for 30 min then the
remaining ethanol was added and the mixture was further stirred
for 3 h at room temperature. The pretreatment of the substrate
surfaces is very important for obtaining a uniform porous coating
and keeping this in mind the 316L SS electrodes (composition
given in Table 1) of 10 mm  20 mm  2 mm samples were
mechanically polished from 120 to 1000 grit silicon carbide
(SiC) papers followed by diamond paste to get mirror finish. The
substrate then was washed thoroughly with running distilled
water, rinsed and ultrasonically degreased with acetone and then
finally it was dried. These substrates were then dip coated with the
sol solution with a withdrawal speed of 1 cm/min. Sol–gel titanium
dioxide coating thus obtained on surgical grade 316L SS was later
dried and sintered at 450 8C for 1 h.
X- ray diffraction patterns were recorded with a Pan Analytical Fig. 1. X-ray diffraction pattern of TiO2 coated on 316L SS.

xpert-pro diffractometer using Cu Ka radiation, with 40 KV and

30 mA, at a scan rate of (2u) 0.028 min 1. The surface morphology
was studied using atomic force microscopy (AFM) technique. The
nanosurf easy scan 2 (Nanosurf AG, Grammetstrasse 14, CH-4410
Liestal, and Switzerland) instrument was used to record AFM. The
images were acquired by contact mode using silicon nitride
cantilevers with a spring constant of 0.15 N/m at a resonance
frequency of 13 kHz. All the images were recorded under air
atmosphere at room temperature. FTIR spectra were collected in
the 400–4000 cm 1 range on a Thermo Electron Corporation USA.
The surface morphology of porous titanium dioxide film was
studied using scanning electron microscopy (SEM) on a Hitachi
Model-S 3400.
A conventional three-electrode cell was used for all the
electrochemical measurements. A saturated calomel electrode
(SCE) was used as a reference electrode, platinum foil acts as a
counter electrode and the test material was taken as the working
electrode. The electrolyte used for electrochemical and immersion
test is Simulated Body Fluid (SBF). The preparation of SBF and the
procedure for conducting the in vitro test was adopted using an

Table 1
Chemical composition of 316L stainless steel (wt.%).

Alloy Main alloying elements (wt.%)

Cr Ni Mo N C Mn
Fig. 2. AFM image of TiO2 coated on 361L SS (a) topographic image (b) line profile
316L SS 17.20 12.60 2.40 0.02 0.03 1.95
from section analysis.
 S. Nagarajan, N. Rajendran / Applied Surface Science 255 (2009) 3927–3932 3929

and 55.1 corresponding to the planes of (1 0 1), (0 0 4), (2 0 0),

(2 1 1). These peaks are the characteristic peaks of titanium dioxide
present on the surface of the substrate. From the diffraction peaks
the crystalline phase was identified as the anatase phase. The
average grain size of titanium dioxide was calculated using
Scherrer’s equation dhkl = kl/(B cos (2u)) [16]. The calculated
crystallite sizes were in the range of 30–40 nm. Earlier reports
indicated that on increasing the thermal treatment, the crystallite
size also increases [17]. Due to the porous nature of the coatings, the
X- ray diffraction pattern in our present study was dominated by the
peaks originating from the substrate. The strong signal observed at
2u values of 74.68, 50.76 and 43.56 corresponds to the planes (2 2 0),
(2 0 0) and (1 1 1) of cubic centric Cr0.19 Fe0.7 Ni0.11, respectively [18].
The atomic force microscopic (AFM) image of the titanium Fig. 3. FTIR spectra of (a) TiO2 coated 316L SS (b) TiO2 coated 316L SS surface
immersed for 7 days in SBF.
dioxide coating on the 316L SS substrate is shown in Fig. 2a. The

Fig. 4. SEM- EDAX analysis of (a), (b) uncoated 316L SS, (c), (d) TiO2 coated and (e), (f) TiO2 coated 316L SS surface immersed 7 days in SBF solution.
3930 S. Nagarajan, N. Rajendran / Applied Surface Science 255 (2009) 3927–3932
topography image revealed that the coatings were fine and porous
in nature. The thicknesses of titanium dioxide coatings were
measured before and after the thermal treatments were 873 and
787 nm, respectively. The result reveals that the coating 100 nm
were reduced after thermal treatment and this is attributed to the
evaporation of the solvent and organic compounds. The particle
size in the coating should neither be small nor should they
agglomerate to produce uneven surfaces. The surface roughnesses
of the coated film were calculated. The mean (Ra) and root mean
square (Rrms) roughness values were obtained from the area shown
in Fig. 2a, the Rrms value of the film was 6.4 nm. Fig. 2b shows the
AFM line profile of the surface of the titanium dioxide thin films.
The line profile of the AFM image suggests that the curvature of the
particles on the surface is important with respect to the bioactivity.
Nanometer and sub micrometer pores were produced in these
films since the surfactant contained in the gel films which
decomposes completely at higher temperature. The porous surface
microstructure thus developed in titanium dioxide thin films was
attributed to the characteristics of the used surfactant [19].
3.2. In vitro characterisation
For an artificial material the most essential requirement for
bonding to living tissues is the natural generation of bone like
apatite on its surface in the physiological environment. An initial
evaluation of a material may be obtained by in vitro experiment; in
which the surface formation of apatite is examined in simulated
body fluid [20]. The FTIR spectrum of the titanium dioxide film is
shown in Fig. 3a. The coating exhibits a strong broad band in the
range of 400–900 cm 1. The presence of broad band in this region
could be attributed to the formation of Ti–O and Ti–O–Ti bonds in
the development of the titanium dioxide network of the film [21].
The cause of peak broadening related to the Ti–O bond might arise
from the amorphous nature of the titanium dioxide thin film due to
the incorporation of carbon or hydroxyl groups in to the Ti–O bond
network. In addition, the broad band around 3000–3800 cm 1
corresponds to the O–H stretching vibration of the coatings. The
FTIR method is sensitive to the vibration modes which are the
characteristics for the constituent molecular groups, permitting
the detection of hydroxyapatite and its growth on the material
surface [22]. Fig. 3b shows the titanium dioxide coated 316L SS that
were soaked in SBF for 7 days. The corresponding bands originating
from 600 to 500 cm 1 and 1100–950 cm 1 were related to the
presence of phosphate groups in the substrate. The broad band
with small shoulder over the region of 1500–1400 cm 1 together
with an absorption band at 869 cm 1 suggests the incorporation of
carbonate groups in the apatite crystals. The above observations
clearly reveal that the growth layer was essentially the carbonated
apatite, resembling to that of human mineralised tissues [23].
Fig. 4(a, b) shows SEM micrographs of the uncoated 316L SS the
surface was uniform in nature. However, the pure titanium dioxide
coated 316L SS film exhibited a porous film with no cracks and
granular in nature. The homogeneous microstructure of the large
pores were surrounded by small pores, while large pores remain
open and the smaller pores were fully or partially closed with the
titanium dioxide grains. The dark spots originated from the pores,
with pore openings of around 3 mm diameter. The pores and their
opening were distinguishable with nonporous area over the
surfaces. This is possibly due to the lateral and longitudinal
inhomogeneity in the distribution of the template to titanium
dioxide weight ratio with in these areas [24]. A similar effect was
observed earlier for titanium dioxide coated films by Bu et al. [25].
The EDAX spectrum shown in Fig. 4(d, e) shows the peaks
corresponding to the uncoated 316L SS and titanium dioxide
coated 316L SS. It can be noticed from the EDAX spectrum no peaks
Fig. 5. Cyclic polarisation curves for uncoated and TiO2 coated 316L SS.
corresponding to any impurities of the element. The titanium
dioxide 316L SS substrate the peak corresponding to Ti Ka was
observed at 4.5 KeV, it reveals that the titanium dioxide presence
on the 316L SS surface and also this analysis also helps to know the
purity of the coating.
Fig. 4c shows the SEM image obtained for the coated specimen
soaked in SBF for 7 days, which reveals that the surface of the film
was covered by a new layer of material that appears to be
constituted by capsule shape crystallites. The in vitro bioactivity
study shows that the soaking of these sol–gel coating in a SBF
solution leads to the formation of a new layer on the coating
surface. This new layer corresponds to an apatite like structure and
it was constituted by small crystallites [26]. The in vitro test clearly
reveals that the coated induces the formation of semi crystalline
hydroxyapatite rich layer on the substrate surface as a result of the
chemical reaction of the particles with the surrounding body fluid.
The apatite particles with sizes of about 1 mm were dispersed on
the surface. The pores observed on the coated substrate were
covered by a new layer, which plug the macro pores. The anatase
was necessary to induce easy deposition of apatite on the titanate
gel in SBF [27]. The corresponding EDAX spectrum (Fig. 4f) shows
Ca and P, together with a significant decrease of Ti percentage. The
increasing concentration of Ca and P indicates the formation of an
apatite like material on the surface.
3.3. Electrochemical characterisation
Fig. 5 shows the potentiodynamic cyclic polarisation curves of
the titanium dioxide coated and uncoated 316L SS substrate
immersed in SBF solution. The polarisation curve of titanium
dioxide coated 316L SS substrate was appreciably different from
that of the uncoated stainless steel substrate indicating that the
titanium dioxide coating produces an effect on the corrosion
behaviour. The titanium dioxide coating reduces the passive
current density (icorr) with respect to the uncoated 316L SS, as
detailed in Table 2. It is possible that the sol–gel coating acts as an
Table 2
Corrosion characteristics of uncoated and TiO2 coated 316L SS in SBF solution.
Sample OCP (mV) Eb (mV) Ep (mV) DE Corrosion rate
(mmpy 10 3)
Uncoated 326 220 245 465 18.09
TiO2 coated 252 308 58 366 1.27
 S. Nagarajan, N. Rajendran / Applied Surface Science 255 (2009) 3927–3932
active site blocker and thus reducing the effective electroactive
area. A plausible explanation is that the adhesion and deduction of
the coatings depends upon the stress generated in the film
thickness due to the successive application of sol and thermal
treatments [28]. The break down potential (Eb) of the coated 316L
SS is higher than that the uncoated 316L SS. The break down
potential reaches a value of 308 mV thus providing a wide passivity
range for the coated 316L SS in comparison with the uncoated
substrate. The break down potential of the coated 316L SS related
to oxygen evolution in the metal coating interface, from the
electrolyte may be accessed through pores or diffusion through the
film, which leads to the blistering of the coating [1].
The repassivation potential (Ep) was determined for the
titanium dioxide coated and uncoated 316L SS from the polarisa-
tion curves. The repassivation potential for the uncoated 316L SS
was found to be 245 mV, whereas for the titanium dioxide coated
substrate it was 98 mV, respectively. The difference between the
break down potential (Eb) and the repassivation potential (Ep) for a
given system is defined as the relative corrosion resistance
(DE = Eb Ep). The magnitude of DE is often considered as an
indicator of corrosion resistance of the materials, that is, the higher
the DE value, the lower the corrosion resistance of the material
[29]. The mean value of DE for 316L SS was found to be 465 mV,
whereas the titanium dioxide coated substrate exhibits lower DE
Fig. 6. Impedance spectrum of uncoated, TiO2 coated and TiO2 coated 316L SS
surface immersed for 7 days in SBF solution (a) bode phase angle and (b) bode
impedance plot.
3931
values (366 mV). Thus the lower DE values reflect the enhanced
corrosion resistance of the substrate. The electrochemical reaction
between the interface of the coating and the substrate, results in
the formation of an oxide layer, which acts as a passivation layer
thus enhancing the corrosion resistance [30].
The Electrochemical impedance spectroscopic (EIS) studies were
carried out for the coated specimens in order to evaluate the
formation of new apatite layer and their protective properties. Fig. 6
shows bode plots which represent the uncoated, titanium dioxide
coated and the coated specimen immersed in SBF solution for 7 days.
Bode diagram shows a difference in corrosion resistance between
uncoated and titanium dioxide coated substrate. The uncoated 316L
SS (Fig. 6a) shows a gradual decrease in the phase angle from 08 at
highest frequency and approaches 758 at intermediate frequency
and remains constant at particular frequency region. This behaviour
confirms that the passive film over the surface is insulative and
protective by nature. The titanium dioxide coated substrate shows
significant shift in the phase angle, at higher frequency region and
the phase angle is close to 108 and gradually decreases to the value of
158 and remains seemingly stable for a short range of frequency,
thus making a plateau. At near low frequency region, the phase angle
gradually decreases and attains a minimum value of 608. This
behaviour confirms the presence of titanium dioxide coated layer
present on the substrate. The titanium dioxide coated 316L SS
soaked SBF in for 7 days shows distinct behaviour on comparison
with uncoated and titanium dioxide coated 316L SS. At a high
frequency region the phase angle was observed to be at 458
whereas in the low frequency region a new time constant with
distinct phase angle behaviour is observed. The maximum phase
angle value was observed approximately at 508. This pattern is
similar to that has been ascribed to the presence of porous layer
followed by an initiation of a new layer [31]. The porous layer
associated with the titanium dioxide coating and the growth of a
new layer can be associated to the apatite growth. The formation of a
new layer is the characteristic of a phase angle shift at low
frequencies. This shift in the phase angle can be attributed to a
growth of apatite over the porous layer [32].
The EIS spectra were analysed with an equivalent circuit and
the curve fitting was performed for all the substrates which shows
an excellent agreement between the experiments and the fitting.
The fitted values and the circuit elements are given in Table 3 and
are presented in Fig. 7. From Table 3, the lower resistance values for
the uncoated 316L SS indicate that the susceptibility towards the
Fig. 7. Equivalent circuit diagram for (a) uncoated (b) TiO2 coated and (c) TiO2
coated 316L SS surface immersed for 7 days in SBF.
3932 S. Nagarajan, N. Rajendran / Applied Surface Science 255 (2009) 3927–3932
Table 3
Impedance parameter for uncoated, TiO2 coated and TiO2 coated 316L SS immersed 7 days SBF solution.
Rs (V cm2) Qa (mF cm 2
) na Ra (kV cm2)
Uncoated 316L SS 216 – – – –
TiO2 coated 197 – – – 29.05
TiO2 coated 7 days immersion 13 0.95 0.82 96
corresponding ions present in the electrolyte can attack on the
surface and this attributed to the thinning of the passive film. It is
to be noted here that the resistance of the titanium dioxide coated
substrate has a higher value and it is consistent with the insulating
nature of the coatings. The surface indicates that the barrier effect
on the films remains unaltered, which impedes the ingress of
anions in the electrolyte from attacking metal-titanium dioxide
interface. Titanium dioxide coated substrate after immersion of 7
days shows a three-time constant, which can be attributed to the
formation of a new apatite layer from the interaction of solution
ion with the titanium dioxide coating. The increase in the
capacitance values of the apatite layer is indicative of a growth
in the layer. The interaction of solutions are generally identified by
a phase shift at higher frequency region which can be attributed to
a physical change in the porous coating due to the interaction of
the solution ions present in the solution [33]. The Fig. 7a shows that
the fitted equivalent circuit obtained for 316L SS is Rs (RbQb), where
Rs, Rb and Qb represents the solution resistance, charge transfer
resistance and double layer capacitance of barrier layer of stainless
steel. Fig. 7(b, c) shows the equivalent circuit of Rs (RcQc) (RbQb) and
Rs (RaQa) (RcQc) (RbQb) for titanium dioxide coated substrate and
titanium dioxide coated substrate was immersed in 7 days in SBF
solution, respectively. Where Rc and Ra represents the charge
transfer resistance of the TiO2 coated and formed apatite layer, Qc
and Qa are the double layer capacitance of coated and apatite layer.
4. Conclusions
Surface characterisation studies reveals a continuous and porous
titanium dioxide coating on the 316L SS. Electrochemical character-
isation results for titanium dioxide coated samples shows a
reduction of passive current densities and improved corrosion
protection potential, when compared to uncoated substrate in the
SBF solution. In vitro responses of coated samples show fast hydroxy
apatite growth. These coatings impede strongly the ion release and
avoid biotoxicity. The above results indicate that the porous titanium
dioxide coatings can be deployed and act as a viable alternative for
improved corrosion resistance and also it enhances the biocompat-
ibility of the implant devices. This coating may be used as an
alternate in permanent orthopaedic appliances, providing a compe-
titive alternative related to conventional Co–Cr and Ti alloys.
Qc (mF cm 2
) nc Rc (kV cm2) Qb (mF cm 2
) nb Rb (V cm2)
– – 26.83 0.77 76
0.63 235 14.65 0.86 216
0.91 0.61 409 37.08 0.64 53
Acknowledgement
One of the authors S. Nagarajan is grateful to the Council of
Scientific and Industrial Research (CSIR), New Delhi, India for the
financial assistance.
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