Applied Surface Science 349 (2015) 561–569

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Applied Surface Science

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

Stacked Bioglass/TiO2 nanocoatings on titanium substrate for

enhanced osseointegration and its electrochemical corrosion studies
D. Durgalakshmi, R. Ajay Rakkesh, S. Balakumar ∗
National Centre for Nanoscience and Nanotechnology, University of Madras, Guindy Campus, Chennai, India

a r t i c l e i n f o a b s t r a c t

Article history: We demonstrate an approach for Bioglass/TiO2 nanocomposites coatings onto the TiO2 nano-surfaces
Received 18 February 2015 formed by etching of CP-Ti. The coated surface is further covered with Bioglass fibres to enhance the rate
Received in revised form 20 April 2015 of apatite formation. Different concentrations of Bioglass/TiO2 composites are prepared by changing the
Accepted 20 April 2015
TiO2 concentration. The coating is performed by electrophoretic deposition technique, and it shows less
Available online 16 May 2015
concentration of TiO2 gives higher adhesion to the substrates. The in vitro electrochemical corrosion and
immersion studies confirm that the lower concentrations of TiO2 containing Bioglass/TiO2 composites
Keywords:
coated sample possesses higher corrosion resistance and bio-mineralization that is highly suitable for
Bioglass
TiO2 bone osseointegration applications.
Fibres © 2015 Elsevier B.V. All rights reserved.
Electrochemical corrosion
Biomineralization
Multilayer coating

1. Introduction
Titanium and its alloys have wide applications as artificial
implants in the field of dentistry and orthopaedic applications [1,2].
Since 1970s the application of Commercially pure Ti (CP-Ti) and its
alloys have become more widespread as they possess high strength,
low modulus, lower density, and a good combination of mechani-
cal and outstanding corrosion resistance [2,3]. The inability of these
implant surface to integrate with adjacent bone and tissues, results
in implant loosening, which subsequently leads to implant failure
and causes revision surgery is required [4,5]. The major reasons
for revision surgery are loosening, infection and dislocation [6]. In
most of the cases the revision surgery are not successful as primary
surgery, which leads to various health complication. To overcome
these issues, recently a bone mimetic and biocompatible coating
are being carried out to enhance osseointegration of the implant
[7].
Bioactive materials including hydroxyapatite (HA)
[Ca3 (PO4 )3 OH] have been preferred as coating material on
the implant surface due to their chemical, structural and biological
similarity with human bone and also due to their enhanced
osseointegration [8]. However, biodegradation of HA in the body is
a serious limitation. Biodegradation is a highly undesirable feature
∗ Corresponding author. Tel.: +91 9442617848; fax: +91 4422352494.
E-mail address: balasuga@yahoo.com (S. Balakumar).
for tissue engineering and also for any implant applications [9].
Bioactive glasses and related bioactive composite materials repre-
sent promising scaffolding materials, which are proven to be the
best alternatives to HA coatings [9]. Also, nano bioactive glasses are
expected to enhance the performance of the materials compared to
their micro sized material available in the market [10]. A common
characteristic of bioactive glasses is the time-dependent kinetic
modification of the surface that occurs upon implantation. During
in vivo, the surface forms a biologically active hydroxycarbonate
apatite (HCA) layer that facilitates the bonding interface with the
tissues. The HCA phase that forms on bioactive implants have
equivalent chemical and structural nature similar to the mineral
phase in bone [11]. In the present study Bioglass 45S5 system is
chosen to improve the osseointegration of the implant material,
as this material possesses both osteoconductivity and osteoinduc-
tivity properties [12–14]. Even though Bioglass 45S5 has superior
biocompatible properties it has poor mechanical properties and
hence it could not be used for high stress applications like hip and
knee joint prostheses. To overcome such drawbacks of Bioglass,
bioceramics/metal oxide or bioceramics/metal combinations are
preferred [15,16]. Such composites are expected to have improved
mechanical and chemical properties compared to pure bioceram-
ics. Titanium dioxide (TiO2 ) is one of the bioactive metal oxides
constituents which helps to enhance the mechanical and chemical
property of the HA [17]. When both TiO2 and Bioglass are present in
the nano level, it gives an added advantage to enhance the material
properties. Nanostructured materials with particle size/grain size

http://dx.doi.org/10.1016/j.apsusc.2015.04.142
0169-4332/© 2015 Elsevier B.V. All rights reserved.
562 D. Durgalakshmi et al. / Applied Surface Science 349 (2015) 561–569
less than 100 nm can significantly improve the bioactivity of the
implant and enhance the osteoblasts adhesion. This is because of
the collagen matrix, which is the building block of the bone in the
nano regime [18].
Electrophoretic Deposition (EPD) coating is an effective method
to fabricate ceramic coatings and also one of the attractive tech-
niques for nanostructural depositions from colloidal solutions
because of its high homogeneity. The greatest advantages for EPD
are less process time, perfect coating, inexpensive and also the pos-
sibility to obtain complex shapes [19]. Usually a trial and error
approach is done elsewhere for obtaining the coating, but it is very
tedious and less repeatability [16]. In our present work, we focused
on “Design of Experiments (DOE)” for obtaining the optimization
conditions for Bioglass/TiO2 nanocomposites coatings obtained
using the EPD technique [20]. In order to enhance the adhesion and
biocompatibility of the coating, pre-deposition surface treatment is
carried out. This treatment compresses the TiO2 formation on the
surface of CP-Ti by HF etching, followed by Bioglass/TiO2 coating
and thereafter over coating of the Bioglass fibres. The TiO2 surface
formed over CP-Ti enhances the surface roughness and improves
bonding with TiO2 /Bioglass coatings. The Bioglass fibres coated on
the composite coatings improve the rate of formation of HCA and
bone bonding nature of the coating.
2. Experimental techniques
2.1. Synthesis of Bioglass, TiO2 and composites
Calcium nitrate tetrahydrate, sodium hydroxide, tetra ethyl
ortho silicate (TEOS), orthophosphoric acid were procured from
Alfa Aesar, India and used as precursors for the synthesis of Bio-
glass 45S5. The Bioglass having weight percent composition (45%
SiO2 –24.5% Na2 O–24.5% CaO–6% P2 O5 ) was prepared by conven-
tional sol–gel process. The procedure involves mixing of tetra ethyl
ortho silicate (TEOS) and nitric acid (HNO3 ), followed by ethanol
for hydrolysis and stirred for 30 min to obtain the gel. The ratio of
TEOS:HNO3 :ethanol:water is 1:0.5:0.25:4. After complete gelation,
the following reagents were added in the interval of 30 min in the
order of sodium hydroxide, calcium nitrate and orthophosphoric
acid. The solution was stirred for 4 h to get a homogenous gel. The
sol was aged at a temperature of 70 ◦ C for 24 h, and then sintered
at 600 ◦ C for 2 h.
TiO2 nanoparticles were synthesized by the sol–gel technique
through an alkoxide reaction between titanium tetra isopropoxide
(TTIP) and glacial acetic acid in the presence of double distilled
water as a solvent. TTIP of 4.6 mL was added to 9.8 mL of glacial
acetic acid under vigorous stirring and thereafter 100 mL of water
was added drop wise to get a transparent solution. The solution is
then continuous stirred for 24 h to form a gel, which is then dried
at 60 ◦ C to get the nanoparticles of TiO2 .
Bioglass/TiO2 composites were prepared by mixing Bioglass and
TiO2 in the ratio of 1:0.25 (BGT1), 1:0.5 (BGT2) and 1:0.75 (BGT3).
In order to make the surface more bioactive in the presence of Bio-
glass, 1:1 ratio was not done in the present work. The weight ratio
of the powders were taken in grams and added to 20 mL of water
and stirred for 2 h to obtain a homogeneous mixture. The samples
were filtered and then dried in hot air oven at 100 ◦ C to obtain dry
powder of Bioglass/TiO2 composites.
2.2. Coating of composites and fibres on CP-Ti substrate
CP-Ti foils of purity 99.9% and thickness of about 0.25 mm Alfa
Aesar, India and used as substrate material. This foil was cut into
small pieces of dimensions 1 cm × 1 cm and were polished using
silicon carbide grits ranging from 600, 800, 1500 to 2000. These
samples were cleaned by ultrasonication with double distilled
water and acetone. In order to enhance the surface roughness of
the substrate, the sample surface were etched in 5% HF placed in
a glass petriplate. The etching reaction was allowed to take place
for about 10 min. The etched samples were further washed in dou-
ble distilled water and thereafter dried in ambient temperature.
For EPD coating technique, a DC power supply (Keithley 2200-72-
1 programmable power supply, USA) is used with the processing
condition at 90 V and isopropyl alcohol as electrolyte medium with
the composite particle loading of 0.2 gm/10 mL. Polyvinyl alcohol
(PVA) was used as binder with the loading weight of 0.05 gm/10 mL
[20].
For Bioglass fibres, the precursors of Bioglass were taken in mol%
and the solvent contains a mixture of ethanol and water in the ratio
of 1:1. 1 M HCl was added as a catalyst. This was considered as a
stock solution, from which 5 mL of BG was mixed with 2.5 mL of
water and 2.5 mL of ethanol. The solution is loaded into 2.5 mL sur-
gical syringe for electrospinning process. The drum collector setup
was used and an aluminium foil is placed onto the drum collector.
The coated samples were fixed on the surface of the aluminium
foil, facing upwards to receive the fibres. The distance between
the syringe and the collector surface was 12 cm. The solution flow
rate was optimized as 0.3 mL/h with the DC power supply of 15 kV.
In order to achieve densification in the coating, the sintering pro-
cess was carried out at the heating rate of 5 ◦ C/min up to 600 ◦ C in
vacuum condition and maintained at 600 ◦ C for 2 h.
2.3. Characterization techniques
The phase analysis of the sintered samples were investi-
gated by X-ray diffractometer (PANalytic, The Netherlands) using
monochromatic Cu K␣ ( = 1.5405 Å) with the 2 range from 10◦
to 80◦ at scanning speed of 0.5◦ /min. The sample composition
was characterized using X-ray photoelectron spectroscopy (XPS)
(Omicron Nanotechnology, Germany). The phase analysis of the
nanocomposites was analyzed using FTIR analyser using KBr as
a standard reference and the spectra were collected in the wave
number range 4000–400 cm−1 . The surface morphology and ele-
mental analysis were examined by Field emission scanning electron
microscopy (FESEM; Hitachi SU6600, Singapore). The samples were
coated with gold using ion sputtering techniques at atmospheric
pressure of 10 kg/m3 for 7 s in order to amplify the secondary elec-
tron signal.
A three-electrode cell arrangement was used for the electro-
chemical measurement with a saturated calomel electrode (SCE)
as a reference electrode and platinum wire as an auxiliary elec-
trode (ASTM G5-94). Hank’s simulating human body fluid (SBF)
(ASTM F2129-08) was used as an electrolyte and was prepared
using analytical grade chemicals and double distilled water. The pH
of the solution was precisely maintained at 7.4. Freshly prepared
solution was used for all experiments. Nitrogen gas, with a flow
rate of 150 mL/min, was purged through the electrolyte to attain
a deaerated atmosphere, and the temperature was maintained at
37 ◦ C (human body temperature). The electrochemical polarization
were measured using a potentiostat (Gill AC, ACM Instruments),
controlled by the sequencer software. The potentiodynamic polar-
ization was determined in a range of −750 mV to 2500 mV (vs. SCE)
at a scan rate of 0.166 mV/s. The impedance spectra were measured
followsed by polarization experiment with a frequency sweep from
104 Hz to 10−1 kHz on a logarithmic increment. 100 data points
were recorded for each experiment. The best fit circuit was identi-
fied based on the subsequent analysis of Nyquist, Bode phase and
Bode magnitude plots. Z view (V3.3) software was used for further
assistance in circuit fitting.
In order to understand the biocompatibility and biomineral-
ization of the coated substrates, it was immersed in Hank’s SBF
 D. Durgalakshmi et al. / Applied Surface Science 349 (2015) 561–569
Fig. 1. XRD spectra of Bioglass, nanoBioglass/TiO2 nanocomposites and titania show
that an increase in TiO2 percentage increases the intensity of TiO2 peak.
solution for 28 days, this solution is similar to the solution used
for corrosion studies. The procedure for immersion was followed
as prescribed by Kokubo et al. [21]. After 28 days, the immersed
samples were dried overnight at 80 ◦ C. The change in surface mor-
phology of the samples was observed by using FESEM and the
elemental confirmation was done with EDS. The phase analysis was
further confirmed by XRD.
3. Results and discussion
3.1. Structural characterization of Bioglass, TiO2 and
Bioglass/TiO2 nanocomposites powders
The XRD spectrum of sintered 45S5 Bioglass, Bioglass/TiO2
nanocomposites and TiO2 nanopowders are displayed in Fig. 1. The
XRD pattern of Bioglass samples showed a phase that had very
close similarity to sodium calcium silicate Na2 Ca2 Si3 O9 (JCPDS #
45-0550) which is a highly bioactive crystal phase of interest. The
titania peak is similar to the anatase crystal structure and well
matched with the JCPDS # 21-1274. The broad peak of TiO2 shows
a smaller crystallite size of the material. From the Scherrer formula,
the crystallite size of the TiO2 nanoparticles is found to be 4 nm. The
anatase titania coating on CP-Ti surface improves the osseointegra-
tion in vivo [22], leading to a higher antibacterial efficacy [23] and
also enhances the biological genetic effects [24]. In Bioglass/TiO2
nanocomposites, the intensity of the TiO2 peak is found to increase
with increase of TiO2 percentage, which proves that the composite
is well formed in the prepared ratio as expected.
The FTIR spectra of Bioglass/TiO2 nanocomposites are depicted
in Fig. 2. The spectra of BGT1 showed the typical bands for Bioglass
structure with broadening in their bands. The band at 900 cm−1
corresponds to Si O Si (tetrahedral) and the OH− stretching
Fig. 2. FTIR spectra of Bioglass/TiO2 nanocomposites shows that an increase in TiO2
increases the O Ti O stretching.
563
Fig. 3. XPS survey spectra of confirm the formation of Bioglass/TiO2 nanocompos-
ites.
band around 1800 cm−1 is observed in all three formulations. The
stretching band of C O is around 1400 cm−1 and the phosphate
peak P O is observed around 1250 cm−1 [25]. All the peaks men-
tioned above are the characteristic peaks of the Bioglass 45S5
system. As TiO2 percentage increases, the intensity of Ti O Ti band
at 565 cm−1 also increases gradually, which proves a better inter-
action between BG and titania nanocomposites [26].
3.2. Elemental confirmation of Bioglass/TiO2 nanocomposites
The elemental composition analysis at the outermost layer
(10 nm depth) of Bioglass/TiO2 nanocomposites was analyzed using
X-ray photoelectron spectroscopy (Fig. 3). The spectral evolution of
peaks around 531 eV, 347 eV, 350 eV, 287 eV, 132 eV, and 101 eV are
assigned to O 1s, Ca 2p3/2 , Ca 2p1/2 , C 1s, P 2p1/2 , and Si 2p binding
energies respectively. The broad peak around 497 eV is assigned
to Na KLL Auger transition. This elemental occurrence in all the
samples confirmed the presence of Bioglass 45S5 and it is in good
correlation with the reported literature [27]. One can see from the
spectra, more visible peaks of Na on the surface than that of Ca
and P, which is due to migration of Na+ ions from bulk to the sur-
face during glass formation by easily breaking the SiO Na+ bonds
during grinding as compared to the SiO Ca2+ bonds. Upon increas-
ing the TiO2 concentration in the nanocomposites, there occurs a
gradual increase in the TiO2 peak, which is marked in the survey
spectra. The binding energies 465 eV and 459 eV are assigned to Ti
2p1/2 and Ti 2p3/2 spin-orbital splitting in the Ti4+ oxidation state,
respectively [28]. The Ti peak has a higher intensity in BGT3 due to
its composite nature.
3.3. Morphological studies of etched CP-Ti, nanopowders and
coatings
Fig. 4 reveal the FESEM surface morphology of the etched sur-
face. The porous morphology is observed all over the sample
substrate. The cross section of the substrate reveals that the etchant
affects only the micrometre regime of the surface and the rest of
the substrate is not affected by the etching. These results further
confirm that the acid etched surface of the metal in nanoporous
structure will enhance the adhesion of the coatings [29]. The EDS
on the top surface confirms the Ti and O elemental formation.
The FESEM images of Bioglass, TiO2 nanopowders and their com-
posites are shown in Fig. 5. The Bioglass powders show a platelet
like structure with an average size of 75 nm whereas the TiO2
nanoparticles have a spherical morphology with the average size
∼10 nm. Depending upon the ratio of TiO2 in the formulation, there
is an increase in number of TiO2 spherical nanoparticles from BGT1
through BGT3 on to the surface of Bioglass platelet structure as
564 D. Durgalakshmi et al. / Applied Surface Science 349 (2015) 561–569

Fig. 4. FESEM images show (a) etched top surface, (b) its higher magnified image, (c) the substrate cross-section and (d) EDS confirmation of the Ti and O elemental formation
on the top surface after etching.

illustrated in Fig. 5(c). For higher concentration in BGT3, the platelet
structure is completely covered with spherical TiO2 nanoparticles.
In Bioglass/TiO2 nanocomposites, with respect to the concentra-
tion variation of TiO2 , the particles were found to be evenly spread
within the Bioglass, confirming the formation of composite mate-
rial.
Top surface and cross-section of the Bioglass/TiO2 nanocom-
posites decorated Bioglass fibres coated on CP-Ti substrates are
shown in Fig. 6. After coating and sintering of the material, the
surface morphology appears to be rough, which is highly suitable
for bone integration in vivo. A blend of platelet like structures
of Bioglass and TiO2 spherical cluster structures are also seen in
BGT1 (Fig. 6(a)) and BGT2 (Fig. 6(b)). The surface of BGT3 shown in
Fig. 6(c) is found to have a non-homogenous formation of material,
and this may be due to heavy particle loading during the coating
and sintering processes. BGT2 shows uniform coating and particle
loading in comparison to BGT3. In BGT1, there seems to be a good
adherence and no air gaps were found between the coating and the
substrate. Increasing concentration in the TiO2 percentage leads to
higher particle loading. Similar results were reported by Jonathan
et al. [30] when coating different ratios of Hydroxyapatite/TiO2 on
glass substrates. The Bioglass fibres are found to be well integrated
on the coated surface of BGT1 sample, whereas in BGT2, it is found
to be spread on the surface of the coating and in BGT3, it is fused
between the fibres. From the above morphological investigation
and results, one can see that in BGT1 the nano fibres are present on
the surface and gets integrated with the bone, thereby projecting
itself as a suitable candidate for bone osseointegration. Further, the
coating thickness of BGT1 is about 100 ␮m, which is an appreciable
limit for implant coatings [31].

Fig. 5. FESEM of (a) Bioglass, (b) TiO2 , (c) nanocomposites formation mechanism, (d) BGT1, (e) BGT2 and (f) BGT3.
 D. Durgalakshmi et al. / Applied Surface Science 349 (2015) 561–569
Fig. 6. FESEM of Bioglass fibre coated Bioglass/TiO2 nanocomposites on CP-Ti substrates top surface (a) BGT1, (b) BGT2, (c) BGT3 and cross-sections (d) BGT1, (e) BGT2, (f)
BGT3.
3.4. XRD confirmation of the Bioglass/TiO2 composite coatings
Fig. 7 shows the XRD spectra of etched CP-Ti surface and the
Bioglass/TiO2 nanocomposites coated surface. The pattern of the
coated samples reveals that the coating is not affected much due
to sintering. XRD of the etched surface of the substrates reveal
peaks similar to ˇ-titanium and rutile TiO2 with the JCPDS No. 89-
4913 and JCPDS No. 89-6975 respectively. After the coating and
sintering process, biocompatible Na2 Ca2 Si3 O9 peak [32] appears,
which proves the formation of Bioglass 45S5 fibres in addition to
the Bioglass coating over the surface. In BGT2 and BGT3, the spec-
tra appear to be a mixture of Bioglass, anatase TiO2 , rutile TiO2 and
ˇ-titanium peaks. The mixture of anatase and rutile TiO2 is highly
suitable for orthopaedic applications for its efficient antibacterial
and biocompatible properties [33]. From literature survey one can
see that it is important to have surface with Ti which can absorb
more OH molecules from the body fluid that favours the deposition
of bone-like apatite [34].
3.5. In vitro electrochemical studies
The etched CP-Ti and Bioglass/TiO2 nanocomposites coated
CP-Ti have been subjected to various electrochemical studies to
understand the corrosion and passive behaviour of the coated sub-
strates.
Fig. 7. XRD spectra of etched CP-Ti surface and Bioglass/TiO2 nanocomposites
coatings.
565
3.5.1. Potentiodynamic polarization studies
The passivation behaviour of etched CP-Ti and Bioglass/TiO2
nanocomposites coated CP-Ti substrates were analyzed by per-
forming potentiodynamic polarization studies Fig. 8. The rate of
corrosion of a material can be directly measured using corro-
sion current density (Icorr ) values. Icorr value is obtained by both
Tafel extrapolation method and Stern-Geary equation. Stern–Geary
equation is used, since the Tafel regions of the polarization curves
are not perfectly linear to predict accurate results. The Stern-Geary
equation [34,35] is given as,
ˇa ˇc
Icorr = (1)
2.303Rp (ˇa + ˇc )
For Tafel extrapolation method, the polarization curve is plotted
in the range of +100 mV to −100 mV with respect to the rest poten-
tial (Ecorr ) and analyzed using Gill AC analyzer software. Parameters,
such as Tafel slopes (ˇa ) and (ˇc ), corrosion potential (Ecorr ) and
the Icorr values are given in Table 1. The anodic branch of the
polarization curve exhibits an passivation–repassivation behaviour
for BGT1 and BGT2 samples. However, the active region of pas-
sivation curve of BGT1 is extended to lower current region and
Fig. 8. Potentiodynamic polarization curves of CP-Ti and Bioglass/TiO2 composite
coatings.
566 D. Durgalakshmi et al. / Applied Surface Science 349 (2015) 561–569
Table 1
Various polarization parameters and corrosion rates of etched CP-Ti and Bioglass/TiO2 composite coatings.
Material Ecorr (mV) Rp (k cm2 ) ˇc (mV) ˇa (mV)
CP Ti −301 165.33 53.000 55.00
BGT1 −285 185.55 27.006 30.77
BGT2 −235 0.39 27.341 35.488
BGT3 −239 1.22 82.220 53.078
competes similar as CP-Ti samples. There is a considerable shift
in Ecorr value towards noble region is observed for all the coated
samples. Whereas, with respect to Icorr , lower concentration BGT1
shows a small increment in corrosion protection and for higher con-
centrations Icorr is increased by one order tafel method and three
orders by Stern–Geary method. This indicates that higher parti-
cle loading diminishes the corrosion resistance of the coating. The
decrease in corrosion resistance due to heavy particle loading were
also observed by Sridhar et al. [36] when coated HA by EPD method
at higher voltage conditions. In our present study, higher particle
loading is also associated with the porous structure on the sur-
face of the coatings. Earlier reports suggests that as the pore size
increases the breakdown potential decrease and hence its corrosion
resistance decreases [36–38].
3.5.2. Electrochemical impedance spectroscopy
The electrochemical impedance spectroscopy (EIS) studies were
conducted to describe the electrochemical interface of the coated
substrates after polarization experiment in terms of an equiva-
lent circuit [39]. Fig. 9(a) and (b) shows the Nyquistic plot of the
etched CP-Ti and Bioglass/TiO2 composite substrates, respectively.
The plots are fitted with the prominent equivalent circuit, and the
circuit model corresponding to the fitted curve is shown in the inset
of Fig. 10(a) and (b). The corresponding fitted parameters are tab-
ulated in Table 2. The good agreement between experimental data
and the fitted data is revealed by the 2 value of about 10−3 [40].
This value is similar to earlier reports of surface films formed on tita-
nium alloys in SBF solutions [34,35]. The Nyquistic plot of etched
CP-Ti shows two semicircles representing the presence of RC cir-
cuits, which signifies passive layer formation on the surface. The
first RC shows the presence of pore resistance (Rpo ) and pore capac-
itance (Cc ), present in the CP-Ti surface. The second RC depicts the
resistance and double layer capacitance (Rct and Cc ) of CP-Ti sur-
face. When the electrolyte starts to diffuse through the coatings, Rct
and Cdl play a vital role in determining the corrosion resistance of
the coating [37].
On comparing the Nyquistic plot of Bioglass/TiO2 composite
coatings, Rpo decrease and increases from BGT1 to BGT3. The higher
Rpo and lesser Cc is observed in BGT1 samples. This shows the higher
corrosion resistance of BGT1 coatings. The Cdl value also exhibits an
increase and decrease pattern from BGT1 to BGT3. This variation is
directly related to the morphology of the samples. In BGT1, the
surface is completely covered without any gaps; the Bioglass/TiO2
nanocomposites were also evenly spread on the surface. In BGT2,
the surface is covered with agglomerated particles due to which
the corrosion resistance of the coating is very low. For BGT3, even
though there are pores on the surface which is covered with a
patched Bioglass fibre, the corrosion resistance of the coating is
high in comparison to BGT1.
The Bode phase and magnitude plots of etched CP-Ti and
Bioglass/TiO2 composite coatings are shown in Fig. 9(c) and (d)
respectively. For etched CP-Ti, it shows two humps at lower and
higher frequencies which results in two RC circuits and the lower
angle negative phase shift confirms the higher resistance of the
material. For Bioglass/TiO2 coating, the phase angle is higher for
BGT1 at high frequencies (102 Hz to 103 Hz). In BGT2 and BGT3,
Icorr (mA cm−2 ) Icorr (mA cm−2 ) (Tafel Corrosion rate
(Stern–Geary equation) extrapolation) mm/year (mils/year)
0.00007 0.000005 0.0007 (0.0274)
0.00003 0.000033 0.0003 (0.0115)
0.01725 0.000018 0.0001 (0.0060)
0.01150 0.001115 0.0096 (0.3817)
there is a sudden decrease in phase between 101 Hz and 10−1 Hz
frequencies, whereas in BGT1 there is a steady decrease, which
illustrates the EIS response of a highly protective coating. From the
bode magnitude plot (Fig. 9(d)) one can see that all the coated sub-
strates behave in the same way at lower frequencies (104 –103 Hz).
This is the characteristic response of electrolyte resistance Rs . For
BGT1, there is an increase in the in the log |Impedance|, at low fre-
quencies (10 Hz) and with a slight decrease at higher frequencies|,
which is due to the capacitance and resistance of the coated surface.
The same pattern is observed for the BGT2 and the BGT3 samples,
but however the log |Impedance| value is less compared to that of
BGT1.
The possible corrosion mechanism of Bioglass/TiO2 nanocom-
posite coatings is shown in Fig. 9(e). When immersed in solution,
the solution resistance (Rs ) is in the region between Hanks SBF solu-
tion and the fibre coatings. In BGT1, the Bioglass fibres are well
spread and the coating is also dense, which resists the solution to
penetrate inside the coating and hence it has a high pore resistance
and low capacitance. Due to the smaller air gap and higher adhe-
sion of the coating to the substrate, one gets high resistance when
the potential is increased. Hence, from the above results, BGT1 is
observed to be a better corrosion resistant material compared to
other Bioglass/TiO2 coatings.
3.6. Biomineralization studies
The ability of the biocompatibility and biomineralization of
the coated samples are tested by immersing the Bioglass/TiO2
nanocomposite coated substrates in SBF for 28 days. The change in
the surface morphology after immersion was imaged using FESEM
(Fig. 10(a)–(c)). In general, the bioactivity of an artificial material
to bond with bone is confirmed from the formation of apatite-like
phase on the surface of samples after immersion in SBF. In our
present study, it is observed that the surfaces of BGT1 and BGT2
samples are completely covered with the HCA layer. The Bioglass
fibres are found to get degraded after 28 days immersion in the SBF.
BGT3, forms micron level cracks throughout the sample surface.
These cracks are due to compressive stresses in the coatings [41]
and the stress is mainly attributed to the difference in the thermal
expansion co-efficient between the coated layers. The TiO2 sub-
strate which forms holes before and after immersion, leads to an
expansion of coating due to a higher absorption of the solution into
the air gaps in the coating. Further confirmation of HCA forma-
tion is found from the EDS. The elemental intensity of the graph is
presented in Fig. 10(d)–(f). The maximum intensity of the counts
are given below the respective EDS spectrum. All the graphs show
higher concentration of Ca and P element compared to other ele-
ments, which confirm the formation of HCA on the surface of the
samples. In higher concentrated TiO2 samples, a decrease in the
intensity of the Ca and P is observed thereby suppressing the HCA
formation.
The XRD patterns of the Bioglass/TiO2 coatings with various con-
centrations of TiO2 are presented in Fig. 11. The peaks are compared
with JCPDS # 86-1585 for ˇ-TCP (Tricalcium Phosphate) and JCPDS
# 9-432 for Hydroxyapatite (HA) respectively. From, Fig. 11, it is
clear that an increase in the concentration of TiO2 leads to decrease
 D. Durgalakshmi et al. / Applied Surface Science 349 (2015) 561–569 567

Fig. 9. (a) Nyquistic plot of etched CP-Ti sample with its equivalent circuit, (b) Nyquistic plot of Bioglass/TiO2 composite coatings with their equivalent circuit, (c) Bode plot
of etched CP-Ti, (d) Bode plot of Bioglass/TiO2 composite coatings, (e) corrosion mechanism of Bioglass/TiO2 composite coatings.

Fig. 10. FESEM of Bioglass/TiO2 nanocomposites coatings (a) BGT1, (b) BGT2 and (c) BGT3 and, EDS of (d) BGT1, (e) BGT2 and (f) BGT3 after immersed in SBF for 28 days.
568 D. Durgalakshmi et al. / Applied Surface Science 349 (2015) 561–569
Table 2
Parameters obtained after fitting the equivalent circuit to the EIS data for CP-Ti and Bioglass/TiO2 composite coatings.
Material Rs ( cm2 ) Rpo (×103  cm2 )
CP Ti 15.12 2.80
BGT1 102.3 0.66
BGT2 33.83 0.25
BGT3 51.01 0.31
Fig. 11. XRD spectra of Bioglass/TiO2 composite coatings after immersed in SBF for
28 days.
in the intensity of the HA and ˇ-TCP peaks and thus, confirming
that there is a decrease in bone like apatite formation as found
from FESEM immersion studies. Hence, BGT1 coating is proven to
enhance the osseointegration of the implant to the surrounding
bone.
In summation, the results indicates that, Bioglass/TiO2
nanocomposites coatings obtained by EPD method with the ratio
of 1:0.25 of Bioglass:TiO2 will be an aspiring solution for implant
applications. Previous literatures on Bioglass 45S5 for regenera-
tive applications and the application of this material in soft tissue
replacements as commercial products shows that this material
enhances the osseointegration in vivo [11,42–44]. However higher
the osseointegration of the coating leads to delimitation of the coat-
ing from the substrate. Considerable literatures are available for
Hydroxyapatite/TiO2 coating on implant surfaces and their results
shows that, TiO2 enhances the adhesion of the coating with the
implant surface [30,45–47]. Hence in our present study as per the
FESEM results, the surface having Bioglass fibres which is impreg-
nated inside the coated surfaces will enhance the osseointegration
of the coating and the middle composite layer containing the TiO2
will play the role of firm attachment of coating with the base sub-
strate. Also in the corrosion studies, the coating not only decreases
the corrosion resistance but also reduces the electric charge on
the surface by formation of apatite after implantation. Hence, this
results with is optimal composition coating of BGT1 with covered
Bioglass fibres will open up a promising avenues in the field of
Biomedical implant applications.
4. Conclusion
Micron size thickness of Bioglass/TiO2 nanocomposites coatings
on CP-Ti substrates were achieved using the EPD technique with
various concentrations of TiO2 . Further, Bioglass 45S5 fibres were
coated onto the surface of the nanocomposites coatings using
the electrospinning technique for enhancing the rate of osseoin-
tegration. Structural analysis of the prepared TiO2 nanoparticle
confirms the formation of the anatase phase and the Bioglass show
the presence of Na2 Ca2 Si3 O9 phase, which is highly bioactive and
Cc (␮F) Rct (×103  cm2 ) Rct (␮F) n 2
4.719 1.193 12.71 0.62 (6.81) 1.06 × 10−3
11.87 0.112 58.18 0.81 (6.96) 2.34 × 10−4
84.30 0.019 289.6 0.932 (10.58) 1.12 × 10−4
37.09 0.015 142.3 0.742 (5.13) 2.62 × 10−4
biocompatible in vivo osseointegration. An increase in the TiO2 con-
centration leads to heavy particles loading in the coated surface,
and formation of larger air gaps after sintering. This air gap was
formed due to the mismatch in the thermal expansion coefficient of
the coating and substrate, whereas minimal concentration of TiO2
limits the possibility of forming air gaps. The corrosion results show
that Bioglass with TiO2 in the ratio of 1:0.25 shows a higher cor-
rosion resistance and a passive layer formation compared to other
coated surfaces. This was due to the higher surface roughness and
air gaps formed due to agglomeration of the particles at a higher
concentration of TiO2 . This makes the SBF to penetrate inside the
coating and decreases the corrosion resistance. The biocompatibil-
ity and biomineralization of the coatings immersed in Hank’s SBF
for 28 days confirms the formation of HCA. Further due to higher
rate of biomineralization, the Bioglass fibres is expected to enhance
the osseointegration of the coatings in vivo at a higher rate.
Acknowledgements
One of the authors, D. Durgalakshmi, would like to acknowl-
edge Lady Tata Memorial Trust, Mumbai for providing the Junior
and Senior fellowships for carrying out this research work. All the
authors greatly acknowledge the NCNSNT instrumentation facili-
ties.
References
[1] M. Geetha, A.K. Singh, R. Asokamani, A.K. Gogia, Ti based biomaterials, the ulti-
mate choice for orthopaedic implants – a review, Prog. Mater. Sci. 54 (2009)
397–425.
[2] M. Long, H.J. Rack, Titanium alloys in total joint replacement – a materials
science perspective, Biomaterials 19 (1998) 1621–1639.
[3] J. Park, R.S. Lakes, Biomaterials: An Introduction, Springer Science & Business
Media, 2007, pp. 317–354.
[4] P.F. Sharkey, W.J. Hozack, R.H. Rothman, S. Shastri, S.M. Jacoby, Why are total
knee arthroplasties failing today? Clin. Orthop. Relat. Res. 404 (2002) 7–13.
[5] L. Ahnfelt, P. Herberts, H. Malchau, G.B.J. Andersson, Prognosis of total hip
replacement: a Swedish multicenter study of 4,664 revisions, Acta Orthop. 61
(1990) 2–26.
[6] J.C. Clohisy, G. Calvert, F. Tull, D. McDonald, W.J. Maloney, Reasons for revi-
sion hip surgery: a retrospective review, Clin. Orthop. Relat. Res. 429 (2004)
188–192.
[7] R.M. Streicher, M. Schmidt, S. Fiorito, Nanosurfaces and nanostructures for
artificial orthopedic implants, Nanomedicine (Lond.) 2 (2007) 861–874.
[8] A. Kolk, J. Handschel, W. Drescher, D. Rothamel, F. Kloss, M. Blessmann, M. Hei-
land, K.-D. Wolff, R. Smeets, Current trends and future perspectives of bone
substitute materials from space holders to innovative biomaterials, J. Cran-
iomaxillofac. Surg. 40 (2012) 706–718.
[9] Q. Chen, J.A. Roether, A.R. Boccaccini, N. Ashammakhi, R. Reis, F. Chiellini, Tissue
engineering scaffolds from bioactive glass and composite materials, Top. Tissue
Eng. 4 (2008) 1–27.
[10] E.M. Fernandes, R.A. Pires, J.O.F. Mano, R.L. Reis, Bionanocomposites from lig-
nocellulosic resources: properties, applications and future trends for their use
in the biomedical field, Prog. Polym. Sci. 38 (2013) 1415–1441.
[11] L.L. Hench, The story of Bioglass® , J. Mater. Sci. Mater. Med. 17 (2006) 967–978.
[12] H. Farnoush, F. Muhaffel, H. Cimenoglu, Fabrication and characterization of
nano-HA-45S5 bioglass composite coatings on calcium-phosphate containing
micro-arc oxidized CP-Ti substrates, Appl. Surf. Sci. 324 (2015) 765–774.
[13] C.-J. Shih, P.-S. Lu, C.-H. Hsieh, W.-C. Chen, J.-C. Chen, Effects of bioglass pow-
ders with and without mesoporous structures on fibroblast and osteoblast
responses, Appl. Surf. Sci. 314 (2015) 967–972.
[14] C. Berbecaru, H.V. Alexandru, A. Ianculescu, A. Popescu, G. Socol, F. Sima, I.
Mihailescu, Bioglass thin films for biomimetic implants, Appl. Surf. Sci. 255
(2009) 5476–5479.
[15] M. Mozafari, E. Salahinejad, V. Shabafrooz, M. Yazdimamaghani, D. Vashaee, L.
Tayebi, Multilayer bioactive glass/zirconium titanate thin films in bone tissue
engineering and regenerative dentistry, Int. J. Nanomed. 8 (2013) 1665–1672.
 D. Durgalakshmi et al. / Applied Surface Science 349 (2015) 561–569
[16] H.Y. Song, S.K. Sarkar, M.S. Kim, Y.K. Min, Y.H. Mo, B.T. Lee, Fabrication of bio-
glass infiltrated Al(2)O (3)-(m-ZrO (2)) composites, J. Mater. Sci. Mater. Med.
20 (2009) 265–269.
[17] P. Rajesh, C.V. Muraleedharan, M. Komath, H. Varma, Pulsed laser deposition
of hydroxyapatite on titanium substrate with titania interlayer, J. Mater. Sci.
Mater. Med. 22 (2011) 497–505.
[18] P. Fratzl, Collagen: Structure and Mechanics, Springer, New York, 2008.
[19] L. Besra, M. Liu, A review on fundamentals and applications of electrophoretic
deposition (EPD), Prog. Mater. Sci. 52 (2007) 1–61.
[20] D. Durgalakshmi, R.A. Rakkesh, C.A. Raja, S. Balakumar, Electrophoretic depo-
sition of Bioglass/TiO2 nanocomposite on CP-Ti substrates for biomedical
applications, Int. J. ChemTech Res. 7 (2015) 755–761.
[21] T. Kokubo, H. Takadama, How useful is SBF in predicting in vivo bone bioactiv-
ity? Biomaterials 27 (2006) 2907–2915.
[22] D.M. Dohan Ehrenfest, P.G. Coelho, B.-S. Kang, Y.-T. Sul, T. Albrektsson,
Classification of osseointegrated implant surfaces: materials, chemistry and
topography, Trends Biotechnol. 28 (2010) 198–206.
[23] A. Scarano, A. Piattelli, A. Polimeni, D. Di Iorio, F. Carinci, Bacterial adhesion on
commercially pure titanium and anatase-coated titanium healing screws: an
in vivo human study, J. Periodontol. 81 (2010) 1466–1471.
[24] V. Sollazzo, A. Palmieri, F. Pezzetti, A. Scarano, M. Martinelli, L. Scapoli, L.
Massari, G. Brunelli, E. Caramelli, F. Carinci, Genetic effect of anatase on
osteoblast-like cells, J. Biomed. Mater. Res. Part B 85 (2008) 29–36.
[25] J.E. Gough, I. Notingher, L.L. Hench, Osteoblast attachment and mineralized
nodule formation on rough and smooth 45S5 bioactive glass monoliths, J.
Biomed. Mater. Res. Part A 68 (2004) 640–650.
[26] A. Testino, I.R. Bellobono, V. Buscaglia, C. Canevali, M. D’Arienzo, S. Polizzi, R.
Scotti, F. Morazzoni, Optimizing the photocatalytic properties of hydrothermal
TiO2 by the control of phase composition and particle morphology. A systematic
approach, J. Am. Ceram. Soc. 129 (2007) 3564–3575.
[27] Q.Z. Chen, K. Rezwan, D. Armitage, S.N. Nazhat, A.R. Boccaccini, The sur-
face functionalization of 45S5 Bioglass® -based glass-ceramic scaffolds and its
impact on bioactivity, J. Mater. Sci. Mater. Med. 17 (2006) 979–987.
[28] R.A. Rakkesh, D. Durgalakshmi, S. Balakumar, Efficient sunlight-driven
photocatalytic activity of chemically bonded GNS–TiO2 and GNS–ZnO het-
erostructures, J. Mater. Chem. C 2 (2014) 6827–6834.
[29] K. Das, S. Bose, A. Bandyopadhyay, B. Karandikar, B.L. Gibbins, Surface coatings
for improvement of bone cell materials and antimicrobial activities of Ti
implants, J. Biomed. Mater. Res. Part B 87B (2008) 455–460.
[30] A.J. Nathanael, D. Mangalaraj, N. Ponpandian, Controlled growth and investiga-
tions on the morphology and mechanical properties of hydroxyapatite/titania
nanocomposite thin films, Compos. Sci. Technol. 70 (2010) 1645–1651.
[31] S. Lopez-Esteban, E. Saiz, S. Fujino, T. Oku, K. Suganuma, A.P. Tomsia, Bioactive
glass coatings for orthopedic metallic implants, J. Eur. Ceram. Soc. 3 (2003)
2921–2930.
569
[32] Q.Z. Chen, I.D. Thompson, A.R. Boccaccini, 45S5 Bioglass® -derived glass ceramic
scaffolds for bone tissue engineering, Biomaterials 27 (2006) 2414–2425.
[33] A. Simchi, E. Tamjid, F. Pishbin, A.R. Boccaccini, Recent progress in inorganic and
composite coatings with bactericidal capability for orthopaedic applications,
Nanomed.: Nanotechnol. Biol. Med. 7 (2011) 22–39.
[34] X.-B. Chen, Y.-C. Li, J.D. Plessis, P.D. Hodgson, C.E. Wen, Influence of calcium
ion deposition on apatite-inducing ability of porous titanium for biomedical
applications, Acta Biomater. 5 (2009) 1808–1820.
[35] M.G. Pujar, U. Kamachi Mudali, S.S. Singh, Electrochemical noise studies of the
effect of nitrogen on pitting corrosion resistance of high nitrogen austenitic
stainless steels, Corros. Sci. 53 (2011) 4178–4186.
[36] T.M. Sridhar, U. Kamachi Mudali, M. Subbaiyan, Preparation and characteri-
sation of electrophoretically deposited hydroxyapatite coatings on type 316L
stainless steel, Corros. Sci. 45 (2003) 237–252.
[37] K.H.W. Seah, R. Thampuran, S.H. Teoh, The influence of pore morphology on
corrosion, Corros. Sci. 40 (1998) 547–556.
[38] T. Raghu, S.N. Malhotra, P. Ramakrishnan, Corrosion behavior of porous sintered
type 316L austenitic stainless steel in 3% NaCl solution, Corrosion 45 (1989)
698–704.
[39] D. Durgalakshmi, M. Chandran, G. Manivasagam, M.S. Ramachandra Rao, R.
Asokamani, Studies on corrosion and wear behavior of submicrometric dia-
mond coated Ti alloys, Tribol. Int. 63 (2013) 132–140.
[40] M. Jamesh, T.S.N. Sankara Narayanan, P.K. Chu, Thermal oxidation of titanium:
evaluation of corrosion resistance as a function of cooling rate, Mater. Chem.
Phys. 138 (2013) 565–572.
[41] S.K. Misra, T. Ansari, D. Mohn, S.P. Valappil, T.J. Brunner, W.J. Stark, I. Roy,
J.C. Knowles, P.D. Sibbons, E.V. Jones, Effect of nanoparticulate bioactive glass
particles on bioactivity and cytocompatibility of poly (3-hydroxybutyrate)
composites, J. R. Soc. Interface 7 (2009) 453–465.
[42] V.M. Roriz, A.L. Rosa, O. Peitl, E.D. Zanotto, H. Panzeri, P.T. De Oliveira, Efficacy
of a bioactive glass ceramic (Biosilicate® ) in the maintenance of alveolar ridges
and in osseointegration of titanium implants, Clin. Oral Implants Res. 21 (2010)
148–155.
[43] A. Rainer, S.M. Giannitelli, F. Abbruzzese, E. Traversa, S. Licoccia, M. Trombetta,
Fabrication of bioactive glass-ceramic foams mimicking human bone portions
for regenerative medicine, Acta Biomater. 4 (2008) 362–369.
[44] G. Jell, M.M. Stevens, Gene activation by bioactive glasses, J. Mater. Sci. – Mater.
Med. 17 (2006) 997–1002.
[45] M. Zakeri, E. Hasani, M. Tamizifar, Mechanical properties of TiO2 -
hydroxyapatite nanostructured coatings on Ti-6Al-4V substrates by APS
method, Int. J. Min. Met. Mater. 20 (2013) 397–402.
[46] S.-H. Lee, H.-W. Kim, E.-J. Lee, L.-H. Li, H.-E. Kim, Hydroxyapatite-TiO2 hybrid
coating on Ti implants, J. Biomater. Appl. 20 (2006) 195–208.
[47] X.B. Zheng, C.X. Ding, Characterization of plasma-sprayed hydroxyapatite/TiO2
composite coatings, J. Therm. Spray Technol. 9 (2000) 520–525.