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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 for tissue engineering and also for any implant applications [9].
Bioactive glasses and related bioactive composite materials repre-
Titanium and its alloys have wide applications as artificial sent promising scaffolding materials, which are proven to be the
implants in the field of dentistry and orthopaedic applications [1,2]. best alternatives to HA coatings [9]. Also, nano bioactive glasses are
Since 1970s the application of Commercially pure Ti (CP-Ti) and its expected to enhance the performance of the materials compared to
alloys have become more widespread as they possess high strength, their micro sized material available in the market [10]. A common
low modulus, lower density, and a good combination of mechani- characteristic of bioactive glasses is the time-dependent kinetic
cal and outstanding corrosion resistance [2,3]. The inability of these modification of the surface that occurs upon implantation. During
implant surface to integrate with adjacent bone and tissues, results in vivo, the surface forms a biologically active hydroxycarbonate
in implant loosening, which subsequently leads to implant failure apatite (HCA) layer that facilitates the bonding interface with the
and causes revision surgery is required [4,5]. The major reasons tissues. The HCA phase that forms on bioactive implants have
for revision surgery are loosening, infection and dislocation [6]. In equivalent chemical and structural nature similar to the mineral
most of the cases the revision surgery are not successful as primary phase in bone [11]. In the present study Bioglass 45S5 system is
surgery, which leads to various health complication. To overcome chosen to improve the osseointegration of the implant material,
these issues, recently a bone mimetic and biocompatible coating as this material possesses both osteoconductivity and osteoinduc-
are being carried out to enhance osseointegration of the implant tivity properties [12–14]. Even though Bioglass 45S5 has superior
[7]. biocompatible properties it has poor mechanical properties and
Bioactive materials including hydroxyapatite (HA) hence it could not be used for high stress applications like hip and
[Ca3 (PO4 )3 OH] have been preferred as coating material on knee joint prostheses. To overcome such drawbacks of Bioglass,
the implant surface due to their chemical, structural and biological bioceramics/metal oxide or bioceramics/metal combinations are
similarity with human bone and also due to their enhanced preferred [15,16]. Such composites are expected to have improved
osseointegration [8]. However, biodegradation of HA in the body is mechanical and chemical properties compared to pure bioceram-
a serious limitation. Biodegradation is a highly undesirable feature 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
∗ Corresponding author. Tel.: +91 9442617848; fax: +91 4422352494. the nano level, it gives an added advantage to enhance the material
E-mail address: balasuga@yahoo.com (S. Balakumar). 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 samples were cleaned by ultrasonication with double distilled
implant and enhance the osteoblasts adhesion. This is because of water and acetone. In order to enhance the surface roughness of
the collagen matrix, which is the building block of the bone in the the substrate, the sample surface were etched in 5% HF placed in
nano regime [18]. a glass petriplate. The etching reaction was allowed to take place
Electrophoretic Deposition (EPD) coating is an effective method for about 10 min. The etched samples were further washed in dou-
to fabricate ceramic coatings and also one of the attractive tech- ble distilled water and thereafter dried in ambient temperature.
niques for nanostructural depositions from colloidal solutions For EPD coating technique, a DC power supply (Keithley 2200-72-
because of its high homogeneity. The greatest advantages for EPD 1 programmable power supply, USA) is used with the processing
are less process time, perfect coating, inexpensive and also the pos- condition at 90 V and isopropyl alcohol as electrolyte medium with
sibility to obtain complex shapes [19]. Usually a trial and error the composite particle loading of 0.2 gm/10 mL. Polyvinyl alcohol
approach is done elsewhere for obtaining the coating, but it is very (PVA) was used as binder with the loading weight of 0.05 gm/10 mL
tedious and less repeatability [16]. In our present work, we focused [20].
on “Design of Experiments (DOE)” for obtaining the optimization For Bioglass fibres, the precursors of Bioglass were taken in mol%
conditions for Bioglass/TiO2 nanocomposites coatings obtained and the solvent contains a mixture of ethanol and water in the ratio
using the EPD technique [20]. In order to enhance the adhesion and of 1:1. 1 M HCl was added as a catalyst. This was considered as a
biocompatibility of the coating, pre-deposition surface treatment is stock solution, from which 5 mL of BG was mixed with 2.5 mL of
carried out. This treatment compresses the TiO2 formation on the water and 2.5 mL of ethanol. The solution is loaded into 2.5 mL sur-
surface of CP-Ti by HF etching, followed by Bioglass/TiO2 coating gical syringe for electrospinning process. The drum collector setup
and thereafter over coating of the Bioglass fibres. The TiO2 surface was used and an aluminium foil is placed onto the drum collector.
formed over CP-Ti enhances the surface roughness and improves The coated samples were fixed on the surface of the aluminium
bonding with TiO2 /Bioglass coatings. The Bioglass fibres coated on foil, facing upwards to receive the fibres. The distance between
the composite coatings improve the rate of formation of HCA and the syringe and the collector surface was 12 cm. The solution flow
bone bonding nature of the coating. 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
2. Experimental techniques
vacuum condition and maintained at 600 ◦ C for 2 h.
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 and sintering processes. BGT2 shows uniform coating and particle
structure is completely covered with spherical TiO2 nanoparticles. loading in comparison to BGT3. In BGT1, there seems to be a good
In Bioglass/TiO2 nanocomposites, with respect to the concentra- adherence and no air gaps were found between the coating and the
tion variation of TiO2 , the particles were found to be evenly spread substrate. Increasing concentration in the TiO2 percentage leads to
within the Bioglass, confirming the formation of composite mate- higher particle loading. Similar results were reported by Jonathan
rial. et al. [30] when coating different ratios of Hydroxyapatite/TiO2 on
Top surface and cross-section of the Bioglass/TiO2 nanocom- glass substrates. The Bioglass fibres are found to be well integrated
posites decorated Bioglass fibres coated on CP-Ti substrates are on the coated surface of BGT1 sample, whereas in BGT2, it is found
shown in Fig. 6. After coating and sintering of the material, the to be spread on the surface of the coating and in BGT3, it is fused
surface morphology appears to be rough, which is highly suitable between the fibres. From the above morphological investigation
for bone integration in vivo. A blend of platelet like structures and results, one can see that in BGT1 the nano fibres are present on
of Bioglass and TiO2 spherical cluster structures are also seen in the surface and gets integrated with the bone, thereby projecting
BGT1 (Fig. 6(a)) and BGT2 (Fig. 6(b)). The surface of BGT3 shown in itself as a suitable candidate for bone osseointegration. Further, the
Fig. 6(c) is found to have a non-homogenous formation of material, coating thickness of BGT1 is about 100 m, which is an appreciable
and this may be due to heavy particle loading during the coating 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) 561–569 565
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 3.5.1. Potentiodynamic polarization studies
The passivation behaviour of etched CP-Ti and Bioglass/TiO2
Fig. 7 shows the XRD spectra of etched CP-Ti surface and the nanocomposites coated CP-Ti substrates were analyzed by per-
Bioglass/TiO2 nanocomposites coated surface. The pattern of the forming potentiodynamic polarization studies Fig. 8. The rate of
coated samples reveals that the coating is not affected much due corrosion of a material can be directly measured using corro-
to sintering. XRD of the etched surface of the substrates reveal sion current density (Icorr ) values. Icorr value is obtained by both
peaks similar to ˇ-titanium and rutile TiO2 with the JCPDS No. 89- Tafel extrapolation method and Stern-Geary equation. Stern–Geary
4913 and JCPDS No. 89-6975 respectively. After the coating and equation is used, since the Tafel regions of the polarization curves
sintering process, biocompatible Na2 Ca2 Si3 O9 peak [32] appears, are not perfectly linear to predict accurate results. The Stern-Geary
which proves the formation of Bioglass 45S5 fibres in addition to equation [34,35] is given as,
the Bioglass coating over the surface. In BGT2 and BGT3, the spec-
ˇa ˇc
tra appear to be a mixture of Bioglass, anatase TiO2 , rutile TiO2 and Icorr = (1)
2.303Rp (ˇa + ˇc )
ˇ-titanium peaks. The mixture of anatase and rutile TiO2 is highly
suitable for orthopaedic applications for its efficient antibacterial For Tafel extrapolation method, the polarization curve is plotted
and biocompatible properties [33]. From literature survey one can in the range of +100 mV to −100 mV with respect to the rest poten-
see that it is important to have surface with Ti which can absorb tial (Ecorr ) and analyzed using Gill AC analyzer software. Parameters,
more OH molecules from the body fluid that favours the deposition such as Tafel slopes (ˇa ) and (ˇc ), corrosion potential (Ecorr ) and
of bone-like apatite [34]. the Icorr values are given in Table 1. The anodic branch of the
polarization curve exhibits an passivation–repassivation behaviour
3.5. In vitro electrochemical studies for BGT1 and BGT2 samples. However, the active region of pas-
sivation curve of BGT1 is extended to lower current region and
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 Fig. 8. Potentiodynamic polarization curves of CP-Ti and Bioglass/TiO2 composite
coatings. 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) Icorr (mA cm−2 ) Icorr (mA cm−2 ) (Tafel Corrosion rate
(Stern–Geary equation) extrapolation) mm/year (mils/year)
competes similar as CP-Ti samples. There is a considerable shift there is a sudden decrease in phase between 101 Hz and 10−1 Hz
in Ecorr value towards noble region is observed for all the coated frequencies, whereas in BGT1 there is a steady decrease, which
samples. Whereas, with respect to Icorr , lower concentration BGT1 illustrates the EIS response of a highly protective coating. From the
shows a small increment in corrosion protection and for higher con- bode magnitude plot (Fig. 9(d)) one can see that all the coated sub-
centrations Icorr is increased by one order tafel method and three strates behave in the same way at lower frequencies (104 –103 Hz).
orders by Stern–Geary method. This indicates that higher parti- This is the characteristic response of electrolyte resistance Rs . For
cle loading diminishes the corrosion resistance of the coating. The BGT1, there is an increase in the in the log |Impedance|, at low fre-
decrease in corrosion resistance due to heavy particle loading were quencies (10 Hz) and with a slight decrease at higher frequencies|,
also observed by Sridhar et al. [36] when coated HA by EPD method which is due to the capacitance and resistance of the coated surface.
at higher voltage conditions. In our present study, higher particle The same pattern is observed for the BGT2 and the BGT3 samples,
loading is also associated with the porous structure on the sur- but however the log |Impedance| value is less compared to that of
face of the coatings. Earlier reports suggests that as the pore size BGT1.
increases the breakdown potential decrease and hence its corrosion The possible corrosion mechanism of Bioglass/TiO2 nanocom-
resistance decreases [36–38]. 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
3.5.2. Electrochemical impedance spectroscopy spread and the coating is also dense, which resists the solution to
The electrochemical impedance spectroscopy (EIS) studies were penetrate inside the coating and hence it has a high pore resistance
conducted to describe the electrochemical interface of the coated and low capacitance. Due to the smaller air gap and higher adhe-
substrates after polarization experiment in terms of an equiva- sion of the coating to the substrate, one gets high resistance when
lent circuit [39]. Fig. 9(a) and (b) shows the Nyquistic plot of the the potential is increased. Hence, from the above results, BGT1 is
etched CP-Ti and Bioglass/TiO2 composite substrates, respectively. observed to be a better corrosion resistant material compared to
The plots are fitted with the prominent equivalent circuit, and the other Bioglass/TiO2 coatings.
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 3.6. Biomineralization studies
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- The ability of the biocompatibility and biomineralization of
nium alloys in SBF solutions [34,35]. The Nyquistic plot of etched the coated samples are tested by immersing the Bioglass/TiO2
CP-Ti shows two semicircles representing the presence of RC cir- nanocomposite coated substrates in SBF for 28 days. The change in
cuits, which signifies passive layer formation on the surface. The the surface morphology after immersion was imaged using FESEM
first RC shows the presence of pore resistance (Rpo ) and pore capac- (Fig. 10(a)–(c)). In general, the bioactivity of an artificial material
itance (Cc ), present in the CP-Ti surface. The second RC depicts the to bond with bone is confirmed from the formation of apatite-like
resistance and double layer capacitance (Rct and Cc ) of CP-Ti sur- phase on the surface of samples after immersion in SBF. In our
face. When the electrolyte starts to diffuse through the coatings, Rct present study, it is observed that the surfaces of BGT1 and BGT2
and Cdl play a vital role in determining the corrosion resistance of samples are completely covered with the HCA layer. The Bioglass
the coating [37]. fibres are found to get degraded after 28 days immersion in the SBF.
On comparing the Nyquistic plot of Bioglass/TiO2 composite BGT3, forms micron level cracks throughout the sample surface.
coatings, Rpo decrease and increases from BGT1 to BGT3. The higher These cracks are due to compressive stresses in the coatings [41]
Rpo and lesser Cc is observed in BGT1 samples. This shows the higher and the stress is mainly attributed to the difference in the thermal
corrosion resistance of BGT1 coatings. The Cdl value also exhibits an expansion co-efficient between the coated layers. The TiO2 sub-
increase and decrease pattern from BGT1 to BGT3. This variation is strate which forms holes before and after immersion, leads to an
directly related to the morphology of the samples. In BGT1, the expansion of coating due to a higher absorption of the solution into
surface is completely covered without any gaps; the Bioglass/TiO2 the air gaps in the coating. Further confirmation of HCA forma-
nanocomposites were also evenly spread on the surface. In BGT2, tion is found from the EDS. The elemental intensity of the graph is
the surface is covered with agglomerated particles due to which presented in Fig. 10(d)–(f). The maximum intensity of the counts
the corrosion resistance of the coating is very low. For BGT3, even are given below the respective EDS spectrum. All the graphs show
though there are pores on the surface which is covered with a higher concentration of Ca and P element compared to other ele-
patched Bioglass fibre, the corrosion resistance of the coating is ments, which confirm the formation of HCA on the surface of the
high in comparison to BGT1. samples. In higher concentrated TiO2 samples, a decrease in the
The Bode phase and magnitude plots of etched CP-Ti and intensity of the Ca and P is observed thereby suppressing the HCA
Bioglass/TiO2 composite coatings are shown in Fig. 9(c) and (d) formation.
respectively. For etched CP-Ti, it shows two humps at lower and The XRD patterns of the Bioglass/TiO2 coatings with various con-
higher frequencies which results in two RC circuits and the lower centrations of TiO2 are presented in Fig. 11. The peaks are compared
angle negative phase shift confirms the higher resistance of the with JCPDS # 86-1585 for ˇ-TCP (Tricalcium Phosphate) and JCPDS
material. For Bioglass/TiO2 coating, the phase angle is higher for # 9-432 for Hydroxyapatite (HA) respectively. From, Fig. 11, it is
BGT1 at high frequencies (102 Hz to 103 Hz). In BGT2 and BGT3, 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 ) Cc (F) Rct (×103 cm2 ) Rct (F) n 2
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